United States
Environmental Protection
Agency
Effluent Guidelines
Division (WH-552)
Washington DC 20460
EPA 440/1-84/067
August 1984
Development Final
Document for
Effluent Limitations
Guidelines and
Standards for
Battery Manufacturing
Point Source Category
Volume I
Subcategories:
Cadmium
Calcium
Leclanche
Lithium
Magnesium
Zinc
-------
VOLUME I
DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
BATTERY MANUFACTURING
POINT SOURCE CATEGORY
William Ruckelshaus
Administrator
Jack E. Ravan
Assistant Administrator
Office of Water
Edwin Johnson, Director
Office of Water Regulations and Standards
Jeffery D. Denit, Director
Effluent Guidelines Division
Ernst P. Hall, P.E., Chief
Metals and Machinery Branch
Mary L. Belefski
Project Officer
September, 1984
U.S. Environmental Protection Agency
Effluent Guidelines Division
Office of Water Regulations and Standards
Washington, D.C. 20460
-------
-------
CONTENTS
SECTION TITLE PAGI
I SUMMARY AND CONCLUSIONS 1
II RECOMMENDATIONS 11
III INTRODUCTION 71
Legal Authority 71
Guideline Development Summary 73
Industry Description 79
Industry Summary 97
Industry Outlook 107
IV INDUSTRY SUBCATEGORIZATION 137
Subcategorization 137
Final Subcategories And Production
Normalizing Parameters 145
Operations Covered Under Other
Categories 152
V WATER USE AND WASTE CHARACTERIZATION 159
Data Collection And Analysis 159
Cadmium Subcategory 173
Manufacturing Processes 175
Water Use, Wastewater Character-
istics, and Wastewater Discharge 181
Wastewater Treatment Practices and
Effluent Data Analysis 187
Calcium Subcategory 189
Manufacturing Processes 190
Water Use, Wastewater Character-
istics, and Wastewater Discharge 191
Wastewater Treatment Practices and
Effluent Data Analysis 192
Leclanche Subcategory 193
Manufacturing Processes 194
Water Use, Wastewater Character-
istics, and Wastewater Discharge 198
Wastewater Treatment Practices and
Effluent Data Analysis 201
Lithium Subcategory 202
Manufacturing Processes 203
Water Use, Wastewater Character-
istics, and Wastewater Discharge 204
Wastewater Treatment Practices and
Effluent Data Analysis 207
111
-------
CONTENTS
SECTION
VI
VII
TITLE
Magnesium Subcategory
Manufacturing Processes
Water Use, Wastewater Character-
istics, and Wastewater Discharge
Wastewater Treatment Practices and
Effluent Data Analysis
Zinc Subcategory
Manufacturing Processes
Water Use, Wastewater Character-
istics, and Wastewater Discharge
Wastewater Treatment Practices and
Effluent Data Analysis
SELECTION OF POLLUTANT PARAMETERS
Verification Parameters
Specific Pollutants Considered for
Regulation
CONTROL AND TREATMENT TECHNOLOGY
End-of-Pipe Treatment Technologies
Major Technologies
1. Chemical Precipitation
2. Chemical Reduction of Chromium
3. Cyanide Precipitation
4. Granular Bed Filtration
5. Pressure Filtration
6. Settling
7. Skimming
Major Technology Effectiveness
L & S Performance
LS & F Performance
Minor Technologies
8. Carbon Adsorption
9. Centrifugation
10. Coalescing
11. Cyanide Oxidation By Chlorine
12. Cyanide Oxidation By Ozone
13. Cyanide Oxidation By Ozone With
UV Radiation
14. Cyanide Oxidation By Hydrogen
Peroxide
15. Evaporation
16. Flotation
17. Gravity Sludge Thickening
18. Insoluble Starch Xanthate
PAGE
208
209
211
215
215
217
223
235
419
419
465
495
495
496
496
498
504
505
509
511
514
518
518
529
533
533
536
538
539
541
542
543
543
547
549
551
IV
-------
CONTENTS
SECTION TITLE PAGE
19. Ion Exchange 551
20. Membrane Filtration 554
21. Peat Adsorption 556
22. Reverse Osmosis 557
23. Sludge Bed Drying 560
24. UHrraf iltration 562
25. Vacuum Filtration 564
26. Permanganate Oxidation 566
In-Process Pollution Control Techniques 567
VIII COST OF WASTEWATER CONTROL AND TREATMENT 643
Cost Estimation Methodology 643
Cost Estimates For Individual Treatment
Technologies 651
Treatment System Cost Estimates 666
Nonwater Quality Environmental Aspects 674
IX BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY 725
AVAILABLE
Technical Approach To BPT 725
Selection of Pollutant Parameters
for Regulation 729
Cadmium Subcategory 729
Calcium Subcategory 735
Leclanche Subcategory 737
Lithium Subcategory 742
Magnesium Subcategory 747
Zinc Subcategory 751
Application of Regulation in Permits 757
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY 817
ACHIEVABLE
Technical Approach To BAT 817
Regulated Pollutant Parameters 819
Cadmium Subcategory 819
BAT Options Summary 819
BAT Option Selection 821
Regulated Pollutant Parameters 826
BAT Effluent Limitations 826
Calcium Subcategory 827
Technology Options Summary •827
Option Selection 829
Pollutant Parameters Selected for
Effluent Limitations 830
Leclanche Subcategory 830
-------
CONTENTS
SECTION TITLE PAGE
Technology Summary 830
Pollutant Parameters Selected
for Effluent Limitation 830
Effluent Limitations 830
Lithium Subcategory 831
'Technology Options Summary 831
Option Selection 834
Pollutant Parameters Selected 835
Effluent Limitations 835
Magnesium Subcategory 835
Technology Options Summary 836
Option Selection 839
Pollutant Parameters Selected 840
Effluent Limitations 840
Zinc Subcategory 841
BAT Options Summary 841
BAT Option Selection 845
Pollutant Parameters for Regulation 847
BAT Effluent Limitations 848
XI NEW SOURCE PERFORMANCE STANDARDS 925
Technical Approach to NSPS 925
Cadmium Subcategory 925
New Source Performance Standards 926
Calcium Subcategory 926
New Source Performance Standards 926
Leclanche Subcategory 926
New Source Performance Standards 927
Lithium Subcategory 927
New Source Performance Standards 927
Magnesium Subcategory 928
New Source Performance Standards 928
Zinc Subcategory 928
New Source Performance Standards 929
XII PRETREATMENT STANDARDS 967
Technical Approach To Pretreatment 969
Cadmium Subcategory 970
Pretreatment Selection r 970
Pollutant Parameters for Regulation 971
Pretreatment Effluent Standards 971
Calcium Subcategory 971
Pretreatment Selection 972
Pretreatment Effluent Standards 972
Leclanche Subcategory 972
vi
-------
CONTENTS
SECTION TITLE PAGE
Pretreatment Selection 972
Pollutant Parameters for Regulation 972
Pretreatment Effluent Standards 973
Lithium Subcategory 973
Pretreatment Selection 973
Pollutant Parameters for Regulation 973
Pretreatment Effluent Standards 974
Magnesium Subcategory „ 974
Pretreatment Selection 974
Pollutant Parameters for Regulation 975
Pretreatment Effluent Standards 975
Zinc Subcategory 976
Pretreatment Selection 976
Pollutant Parameters for Regulation 977
Pretreatment Effluent Standards 977
XIII BEST CONVENTIONAL POLLUTANT CONTROL 1057
TECHNOLOGY
XIV ACKNOWLEDGEMENTS 1059
XV BIBLIOGRAPHY 1061
XVI GLOSSARY 1071
CONVERSION TABLE 1087
vii
-------
TABLES
Number Title
III-l Survey Summary 108
III-2 Battery General Purposes and Applications 109
III-3 Anode Half-Cell Reactions HO
III-4 Cathode Half-Cell Reactions 110
III-5 Consumption of Toxic Metals in Battery Manufacture 111
III-6 Battery Manufacturing Category Summary 112
III-7 Raw Materials Used in Lithium Anode Battery
Manufacture 113
IV-1 Subcategory Elements And Production Normalizing
Parameters (PNP) 154
IV-2 Operations At Battery Plants Included In Other
Industrial Categories (Partial Listing) 156
V-l Screening and Verification Analysis Techniques 238
V-2 Screening Analysis Results - Cadmium Subcategory 244
V-3 Screening Analysis Results - Calcium Subcategory 248
V-4 Screening Analysis Results - Leclanche Subcategory 252
V-5 Screening Analysis Results - Lithium Subcategory 256
V-6 Screening Analysis Results - Magnesium Subcategory 261
V-7 Screening Analysis Results - Zinc Subcategory 266
V-8 Verification Parameters 271
V-9 Cadmium Subcategory Process Elements {Reported
Manufacture) 273
V-10 Normalized Discharge Flows-Cadmium Subcategory
Elements 274
V-l1 Pollutant Concentrations In Cadmium Pasted And 275
viii
-------
TABLES
jmber Title Page
Pressed Powder Anode Element Waste Streams
-12 Pollutant Mass Loadings In The Cadmium Pasted And
Pressed Powder Anode Element Waste Streams 276
-13 Pollutant Concentrations In The Cadmium Electro-
deposited Anode Element Waste Stream 277
-14 Pollutant Mass Loadings In The Cadmium Electro-
deposited Anode Element Waste Streams 278
-15 Pollutant Concentrations And Mass Loadings In
The Cadmium Impregnated Anode Element Waste
Streams 279
-16 Pollutant Concentrations In The Nickel Electro-
deposited Cathode Element Waste Streams 280
-17 Pollutant Mass Loadings In The Nickel Electro-
deposited Cathode Element Waste Streams 281
-18 Pollutant Concentrations In The Nickel Impregnated
Cathode Element Waste Streams 282
-19 Pollutant Mass Loadings In The Nickel Impregnated
Cathode Element Waste Streams 283
-20 Statistical Analysis (mg/1) Of The Nickel
Impregnated Cathode Element Waste Streams 284
'-21 Statistical Analysis (mg/kg) Of The Nickel
Impregnated Cathode Element Waste Streams 285
'-22 Pollutant Concentrations In The Floor And
Equipment Wash Element Waste Streams 286
r-23 Pollutant Mass Loadings In The Floor And Equipment
Wash Element Waste Streams 287
r-24 Pollutant Concentrations In Employee Wash1
Element Waste Streams 288
r-25 Pollutant Mass Loadings In Employee Wash
Element Waste Streams 289
-------
TABLES
<
Number Title Page
V-26 Mean Concentrations And Pollutant Mass Loadings
In The Cadmium Powder Element Waste Streams 290
V-27 Cadmium Subcategory Effluent Flow Rates
From Individual Plants 291
V-28 Statistical Analysis (mg/1) of the Cadmium
Subcategory Total Raw Waste Concentrations 292
V-29 Treatment In Place At Cadmium Subcategory Plants 293
V-30 Performance Of Alkaline Precipitation, Settling
And Filtration - Cadmium Subcategory 294
V-31 Performance Of Settling - Cadmium Subcategory 295
V-32 Cadmium Subcategory Effluent Quality (From Dcp) 296
V-33 Normalized Discharge Flows - Calcium Subcategory
Elements 297
V-34 Pollutant Concentrations In The Heat Paper
Production Element Waste Stream 298
V-35 Pollutant Mass Loadings In The Heat Paper
Production Element Waste Stream 299
V-36 Treatment In Place At Calcium Subcategory Plants 300
V-37 Effluent Characteristics From Calcium Subcategory
Manufacturing Operations - Dcp Data 301
V-38 Leclanche Subcategory Elements (Reported
Manufacture) 302
V-39 Normalized Discharge Flows Leclanche Subcategory
Elements 303
V-40 Pollutant Concentrations In The Cooked Paste
Separator Element Waste Streams 304
V-41 Pollutant Mass Loading In The Cooked Paste
Separator Element Waste Streams 305
-------
TABLES
Number Title Page
V-42 Pollutant Concentrations In The Paper Separator
(With Mercury) Element Waste Streams 306
V-43 Pollutant Mass Loadings In The Paper Separator
{With Mercury) Element Waste Streams 307
V-44 Normalized Flow Of Ancillary Operation
Waste Streams 308
V-45 Pollutant Concentrations In The Equipment
And Area Cleanup Element Waste Stream 309
V-46 Pollutant Mass Loadings In The Equipment
And Area Cleanup Element Waste Streams 310
V-47 Statistical Analysis (mg/1) Of The Equipment
And Area Cleanup Element Waste Streams 311
V-48 Statistical Analysis (mg/kg) Of The Equipment
And Area Cleanup Element Waste Streams 312
V-49 Statistical Analysis (mg/1) Of The Leclanche
Subcategory Total Raw Waste Concentrations 313
V-50 Treatment In Place At Leclanche Subcategory Plants 314
V-51 Leclanche Subcategory Effluent Quality (From Dcp) 315
V-52 Treatment Effectiveness At Plant B (Treatment
Consists Of Skimming and Filtration) 316
V-53 Normalized Discharge Flows Lithium Subcategory
Elements . 317
V-54 Pollutant Concentrations In The Iron Bisulfide
Cathode Element Waste Stream 318
V-55 Pollutant Mass Loadings In The Iron Bisulfide
Cathode Element Waste Stream 319
V-56 Pollutant Concentrations in The Lithium Scrap
Bisposal Waste Stream 320
V-57 Treatment In Place At Lithium Subcategory Plants 321
XI
-------
TABLES
Number Title
V-58 Effluent Characteristics Of Iron Bisulfide Cathode
Element Waste Stream After Settling Treatment- 322
V-59 Normalized Discharge Flows - Magnesium S.ubcategory
Elements . • 323
V-60 Pollutant Concentrations In the Developer Solution
Of The Silver Chloride Reduced Cathode Element
Waste Stream • 324
V-61 Magnesium Subcategory Process Wastewater Flow Rates
From Individual Plants (Dcp Data) 325
V-62 Treatment In Place At Magnesium Subcategory Plants 326
V-63 Zinc Subcategory Process Elements (Reported
Manufacture) 327
V-64 Normalized Discharge Flows - Zinc Subcategory
Elements 329
V-65 Observed Flow Rates For Each Plant In The Zinc
Subcategory 331
V-66 Pollutant Concentrations In The Zinc Powder -
Wet Amalgamated Anode Element Waste Streams 332
V-67 Pollutant Mass Loadings In The Zinc Powder -
Wet Amalgamated Anode Element Waste Streams 333
V-68 Statistical Analysis (mg/1) Of The Zinc Powder -
Wet Amalgamated Anode Element Waste Streams 334
V-69 Statistical Analysis (mg/kg) Of The Zinc Powder -
Wet Amalgamated Anode Element Waste Streams 335
V-70 Pollutant Concentrations In The Zinc Powder -
Gelled Amalgam Anode Element Waste Streams 336
V-71 Pollutant Mass Loading In The Zinc Powder -
Gelled Amalgam Anode Element Waste Stream 337
V-72 Statistical Analysis (mg/1) Of The Zinc Powder -
Gelled Amalgam Anode Element Waste Streams 338
XII
-------
Number Title Page
V-73 Statistical Analysis (mg/kg) Of The Zinc Powder -
Gelled Amalgam Anode Element Waste Streams 339
V-74 Pollutant Concentrations In The Zinc Oxide
Powder - Pasted Or Pressed, Reduced Anode Element
Waste Streams 340
V-75 Pollutant Mass Loadings In The Zinc Oxide Powder -
Pasted or Pressed, Reduced Anode Element Waste
Streams 341
V-76 Statistical Analysis (mg/1) Of The Zinc Oxide
Powder - Pasted Or Pressed, Reduced Anode Element
Waste Streams 342
V-77 Statistical Analysis (mg/kg) Of The Zinc Oxide
Powder - Pasted Or Pressed, Reduced Anode Element
Waste Streams 343
V-78 Pollutant Concentrations In The Spent Amalgamation
Solution Waste Stream 344
V-79 Pollutant Concentrations In The Zinc Electro-
deposited Anode Element Waste Streams 345
V-80 Pollutant Mass Loadings In The Zinc Electro-
deposited Anode Element Waste Streams 346
V-81 Normalized Flows Of Post-Formation Rinse
Waste Streams 347
V-82 Pollutant Concentration In The Silver Powder
Pressed And Electrolytically Oxidized Cathode
Element Waste Streams 348
V-83 Pollutant Mass Loadings In The Silver Powder
Pressed and Electrolytically Oxidized Cathode
Element Waste Streams 349
V-84 Statistical Analysis (mg/1) Of The Silver Powder
Pressed And Electrolytically Oxidized Cathode
Element Waste Streams 350
V-85 Statistical Analysis (mg/kg) Of The Silver 351
xiii
-------
TABLES
Number Title
Powder Pressed And Electrolytically Oxidized
Cathode Element Waste Streams
V-86 Pollutant Concentrations In The Silver Oxide
(Ag2O) Powder-Thermally Reduced And Sintered,
Electrolytically Formed Cathode Element Waste
Streams 352
V-87 Pollutant Mass Loadings In The Silver Oxide (Ag20)
Powder-Thermally Reduced And Sintered, Electro-
lytically Formed Cathode Element Waste Streams 353
V-88 Pollutant Concentrations In The Silver Peroxide
(AgO) Powder Cathode Element Waste Streams 354
V-89 Pollutant Mass Loadings In The Silver Peroxide
(AgO) Powder Cathode Element Waste Streams 355
V-90 Statistical Analysis (mg/1) Of The Silver Peroxide
(AgO) Powder Cathode Element Waste Streams 356
V-91 Statistical Analysis (mg/kg) Of The Silver
Peroxide (AgO) Powder Cathode Element Waste
Streams 357
V-92 Production Normalized Discharges From Cell Wash
Element 358
V-93 Pollutant Concentrations In The Cell Wash
Element Waste Streams (mg/1) 359
V-94 Pollutant Mass Loadings In The Cell Wash
Element Waste Streams (mg/kg) 360
V-95 Statistical Analysis (mg/1) Of The Cell Wash
Element Waste Streams 361
V-96 Statistical Analysis (mg/kg) Of The Cell Wash
Element Waste Streams 362
V-97 Pollutant Concentrations In The Electrolyte
Preparation Element Waste Streams 363
V-98 Pollutant Mass Loadings In,The Electrolyte 364
xiv
-------
TABLES
Number Title Page
Preparation Element Waste Streams
V-99 Pollutant Concentrations In The Silver Etch
.Element Waste Streams 365
V-100 Pollutant Mass Loadings In The Silver Etch
Element Waste Streams 366
V-101 Pollutant Concentrations In The Laundry Wash
And Employee Shower Element Waste Streams 367
V-102 Pollutant Concentrations In The Mandatory
Employee Wash Element Waste Streams 368
V-103 Pollutant Mass Loadings In The Mandatory
Employee Wash Element Waste Streams 369
V-104 Pollutant Concentrations In The Reject Cell
Handling Element Waste Streams 370
V-105 Pollutant Concentrations In The Reject Cell
Handling Element Waste Streams 371
V-106 Pollutant Mass Loadings In The Reject Cell
Handling Element Waste Streams 372
V-107 Pollutant Concentrations In The Floor Wash
Element Waste Stream 373
V-108 Pollutant Mass Loadings In The Floor Wash
Element Waste Stream 374
V-109 Pollutant Concentrations In The Equipment
Wash Element Waste Streams 375
V-110 Pollutant Mass Loadings In The Equipment
Wash Element Waste Streams 376
V-111 Statistical Analysis (mg/1) Of The Equipment
Wash Element Waste Streams 377
V-112 Statistical Analysis (mg/kg) Of The Equipment
Wash Element Waste Streams 378
xv
-------
TABLES
Number Title
V-113 Pollutant Concentrations In The Silver Powder
Production Element Waste Streams 379
V-114 Pollutant Mass Loadings In The Silver Powder
Production Element Waste Streams 380
V-115 Pollutant Concentrations In The Silver Peroxide
Production Element Waste Streams 381
v"-116 Pollutant Mass Loadings In The Silver Peroxide
Production Element Waste Streams 382
y-117 Statistical Analysis (mg/1) Of The Zinc
Subcategory Total Raw Waste Concentrations 383
/-118 Treatment In Place At Zinc Subcategory Plants 384
7-119 Treatment Practices And Effluent Quality At
Zinc Subcategory Plants 385
7-120 Performance Of Sulfide Precipitation -
Zinc Subcategory 386
/-121 Performance of Lime, Settle, And Filter -
Zinc Subcategory 387
f-122 Performance of Amalgamation - Zinc Subcategory 388
?-123 Performance Of Skimming, Filtration, Amalgamation
And Carbon Adsorption - Zinc Subcategory 389
?~124 Performance Of Settling, Filtration And Ion
Exchange - Zinc Subcategory 390
rl~l Priority Pollutant Disposition - Battery
Manufacturing 488
'1-2 Other Pollutants Considered For Regulation 493
rll-l pH Control Effect On Metals Removal 592
'I1-2 Effectiveness Of Sodium Hydroxide For Metals
Removal 592
xvi
-------
TABLES
umber Title Page
'II-3 Effectiveness Of Lime And Sodium Hydroxide For
Metals Removal 593
'II-4 Theoretical Solubilities of Hydroxides and Sulfides
of Selected Metals in Pure Water 593
pII-5 Sampling Data From Sulfide Precipitation-
Sedimentation Systems 594
'II-6 Sulfide Precipitation-Sedimentation Performance 595
rII-7 Ferrite Co-Precipitation Performance 596
11-8 Concentration of Total Cyanide 596
rII-9 Multimedia Filter Performance 597
rll-10 Performance of Sampled Settling Systems 597
^11-11 Skimming Performance 598
^11-12 Selected Partition coefficients 599
fII-13 Trace Organic Removal by Skimming
API Plus Belt Skimmers 600
ai-14 Combined Metals Data Effluent Values (mg/1) 600
fII-15 L&S Performance - Additional Pollutants 601
f11-16 Combined Metals Data Set - Untreated Wastewater 601
fll-17 Maximum Pollutant Level In Untreated Wastewater -
Additional Pollutants 602
fll-18 Precipitation-Settling-Filtration (LS&F)
Performance Plant A 603
/II-19 Precipitation-Settling-Filtration (LS&F)
Performance-Plant B 604
/II-20 Precipitation-Settling-Filtration (LS&F)
Performance-Plant C 605
xvii
-------
TABLES
Number Title Page
VII-21 Summary of Treatment Effectiveness 606
VII-22 Treatability Rating of Priority Pollutants
Utilizing Carbon Adsorption 607
VI1-23 Classes of Organic Compounds Adsorbed On Carbon 608
VII-24 Activated Carbon Performance (Mercury) 609
VI1-25 Ion Exchange Performance 609
VII-26 Membrane Filtration System Effluent 610
VII-27 Peat Adsorption Performance - 610
VII-28 Ultrafiltration Performance 611
VII-29 Process Control Technologies In Use At Battery
Manufacturing Plants 612
VIII-1 Cost Program Pollutant Parameters 677
VII1-2 Treatment Technology Subroutines 678
VII1-3 Wastewater Sampling Frequency 679
VIII-4 Waste Treatment Technologies For Battery 680
Manufacturing Category
VII1-5 Lime Additions For Lime Precipitation 681
VIII-6 Reagent Additions For Sulfide Precipitation 682
VIII-7 Neutralization Chemicals Required 683
VIII-8 Water Treatment Component Costs - Hydroxide 684
Precipitation And Settling
VIII-9 Water Treatment Component Costs - Sulfide 685
Precipitation And Settling - Batch
VIII-10 Water Treatment Component Costs - Sulfide 686
Precipitation And Settling - Continuous
XVI11
-------
TABLES
Number Title
VIII-11 Water Treatment Component Costs - Mixed
Filtration 687
VII1-12 Water Treatment Component Costs - Membrane
VIII-13
/III-14
fIII-15
fIII-16
/III-17
/III-18
VIII-19
VIII-20
VIII-21
VIII-22
/III-23
[X-l
rx-2
IX-3
IX-4
IX-5
Filtration
Water Treatment Component Costs - Reverse Osmosis
Water Treatment Component Costs - Vacuum Filtration
Water Treatment Component Costs - Holding And
Settling Tanks
Water Treatment Component Costs - pH Adjustment
Water Treatment Component Costs - Aeration
Water Treatment Component Costs - Carbon
Adsorption
Water Treatment Component Costs - Chrome
Reduction
Nonwater Quality Aspects Of Wastewater Treatment
Nonwater Quality Aspects Of Sludge And Solids
Handling
Battery Category Energy Costs and Requirements
Wastewater Treatment Sludge RCRA Disposal Costs
Flow Basis For BPT Mass Discharge Limitations -
Cadmium Subcategory
Cadmium Subcateqory BPT Effluent Limitations:
Pasted And Pressed Powder Anodes
Electrodeposited Anodes
Impregnated Anodes
Nickel Electrodeposited Cathodes
688
689
690
691
692
693
694
695
696
697
698
699
758
759
760
761
762
xix
-------
TABLES
Number Title Page
IX-6 Nickel Impregnated Cathodes 763
IX-7 Cell Wash 764
IX-8 Electrolyte Preparation 765
IX-9 Floor And Equipment Wash 766
IX-10 Employee Wash 767
IX-11 Miscellaneous Wastewater Streams 768
IX-12 Cadmium Powder Production 769
IX-13 Silver Powder Production 770
IX-14 Cadmium Hydroxide Production 771
IX-15 Nickel Hydroxide Production 772
IX-16 Comparison Of Actual To BPT Annual Flow At
Cadmium Subcategory Plants 773
IX-17 Flow Basis For BPT Mass Discharge Limitations -
Calcium Subcategory 774
Calcium Subcategory BPT Effluent Limitations;
IX-18 Heat Paper Production And Cell Testing 775
Leclanche Subcateqory BPT Effluent Limitations;
IX-19 Foliar Battery Miscellaneous Wash 776
Lithium Subcategory BPT Effluent Limitations;
IX-20 Flow Basis For BPT Mass Discharge Limitations -
Lithium Subcategory 777
IX-21 Iron Disulfide Cathodes 778
IX-22 Lead Iodide Cathodes 779
xx
-------
Number
IX-23
IX-24
IX-25
IX-26
IX-27
IX-28
IX-29
IX-30
IX-31
IX-32
IX-33
IX-34
IX-35
IX-36
IX-37
IX-38
IX-39
IX-40
IX-41
TABLES
Title
Heat Paper Production
Miscellaneous Wastewater Streams
Air Scrubbers
Flow Basis For BPT Mass Discharge Limitations -
Magnesium Subcategory
Magnesium Subcategory BPT Effluent Limitations:
Silver Chloride Cathodes, Chemically Reduced
Silver Chloride Cathodes, Electrolytic
Floor And Equipment Wash
Cell Testing
Heat Paper Production
Air Scrubbers
Flow Basis For BPT Mass Discharge Limitations -
Zinc Subcategory
Zinc Subcategory BPT Effluent Limitations;
Wet Amalgamated Powder Anodes
Gelled Amalgam Anodes
Zinc Oxide Anodes, Formed
Electrodeposited Anodes
Silver Powder Cathodes, Formed
Silver Oxide Powder Cathodes, Formed
Silver Peroxide Cathodes
Nickel Impregnated Cathodes
Pag<
780
781
782
783
784
785
786
787
788
789
790
791
792
793
794
795
796
797
798
XXI
-------
Number
IX-42
IX-43
IX-44
IX-45
IX-46
IX-47
IX-48
IX-49
IX-50
IX-51
IX-52
X-l
X-2
X-3
X-4
X-5
X-6
X-7
TABLES
Title
Cell Wash
Electrolyte Preparation
Silver Etch
Employee Wash
Reject Cell Handling
Floor And Equipment Wash
Miscellaneous Wastewater Streams
Silver Peroxide Production
Silver Powder Production
Comparison Of Actual To BPT Annual Flow At Zinc
Subcategory Plants
Sample Derivation Of The BPT 1-Day Cadmium
Limitation For Plant ¥
Process Element Flow Summary - Cadmium Subcategory
Process Element Wastewater Summary - Cadmium
Subcategory
Summary Of Treatment Effectiveness Cadmium
Subcategory
Pollutant Reduction Benefits of Control Systems
Cadmium Subcategory - Total
Pollutant Reduction Benefits Of Control Systems
Cadmium Subcategory - Direct Dischargers
Cadmium Subcategory BAT Effluent Limitations?
Electrodeposited Anodes
Impregnated Anodes
Pag*
799
800
801
802
803
804
805
806
807
808
809
850
851
853
854
855
856
857
XXI1
-------
Number
X-8
X-9
X-10
X-ll
X-12
X-13
X-14
X-15
X-16
X-17
X-18
X-19
X-20
X-21
X-22
X-23
X-24
TABLES
Title
Nickel Electrodeposited Cathodes
Nickel Impregnated Cathodes
Cell Wash
Electrolyte Preparation
Employee Wash
Miscellaneous Wastewater Streams
Cadmium Powder Production
Silver Powder Production
Cadmium Hydroxide Production
Nickel Hydroxide Production
Summary Of Treatment Effectiveness - Calcium
Subcategory
Pollutant Reduction Benefits Of Control Systems
Calcium Subcategory - Total
Pollutant Reduction Benefits Of Control Systems
Leclanche Subcategory
Leclanche Subcategory BAT Effluent Limitations:
Foliar Battery Miscellaneous Wash
Process Element Flow Summary Lithium Subcategory
Summary Of Treatment Effectiveness Lithium
Subcategory
Pollutant Reduction Benefits of Control Systems
Lithium Subcategory
Lithium Subcateqory BAT Effluent Limitations:
Paae
858
859
860
861
862
863
864
865
866
867
868
869
870
871
872
873
874
X-25 Lead Iodide Cathodes 876
xxiii
-------
lumber
1-26
C-27
C-28
C-29
C-30
;-3i
:-32
,-33
;-34
-35
-36
-37
-38
-39
-40
-41
-42
-43
TABLES
Title
Iron Disulfide Cathodes
Miscellaneous Wastewater Streams
Process Element Flow Summary - Magnesium Subcategory
Summary Of Treatment Effectiveness - Magnesium
Subcategory
Pollutant Reduction Benefits Of Control Systems -
Magnesium Subcategory
Magnesium Subcategory BAT Effluent Limitations:
Silver Chloride Cathodes - Chemically Reduced
Silver Chloride Cathodes - Electrolytic
Cell Testing
Floor And Equipment Wash
Process Element Flow Summary - Zinc Subcategory
Manufacturing Element Wastewater Summary - Zinc
Subcategory
Summary Of Treatment Effectiveness - Zinc Subcategory
Pollutant Reduction Benefits Of Control Systems
Zinc Subcategory - Total
Pollutant Reduction Benefits Of Control Systems
Zinc Subcategory - Direct Dischargers
Zinc Subcategory BAT Effluent Limitations:
Wet Amalgamated Powder Anodes
Gelled Amalgam Anodes
Zinc Oxide Anodes, Formed
Electrodeposited Anodes
Pag
876
877
878
879
880
882
882
883
883
884
885
888
889
890
891
892
893
894
XXIV
-------
Number
X-44
X-45
X-46
X-47
X-48
X-49
X-50
X-51
X-52
X-53
X-54
X-55
X-56
XI-1
XI-2
XI-3
XI-4
XI-5
XI-6
XI-7
XI-8
TABLES
Title
Silver Powder Cathodes, Formed
Silver Oxide Powder Cathodes, Formed
Silver Peroxide Cathodes
Nickel Impregnated Cathodes
Cell Wash
Silver Etch
Employee Wash
Reject Cell Handling
Floor And Equipment Wash
Miscellaneous Wastewater Streams
Silver Peroxide Production
Silver Powder Production
Battery Category Costs
Cadmium Subcategory New Source Performance
Standards
Electrodeposited Anodes
Impregnated Anodes
Nickel Electrodeposited Cathodes
Nickel Impregnated Cathodes
Cell Wash
Electrolyte Preparation
Employee Wash
• Miscellaneous Wastewater Streams
Pag<
895
896
897
898
899
900
901
902
903
904
905
906
907
931
932
933
934
935
936
937
938
XXV
-------
Number
XI-9
XI-10
XI-11
XI-12
XI-13
XI-14
XI-15
XI-16
XI-17
XI-18
XI-19
XI-20
XI-21
XI-22
XI-23
XI-24
XI-25
TABLES
Title
Cadmium Powder Production
Silver Powder Production
Cadmium Hydroxide Production
Nickel Hydroxide Production
Leclanche Subcategory New Source Performance
Standards :
Foliar Battery Miscellaneous Wash
Lithium Subcategory New Source Performance
Standards :
Lead Iodide Cathodes
Iron Disulfide Cathodes
Miscellaneous Wastewater Streams
Air Scrubbers
Magnesium Subcategory New Source Performance
Standards :
Silver Chloride Cathodes - Chemically Reduced
Silver Chloride Cathodes - Electrolytic
Cell Testing
Floor And Equipment Wash
Air Scrubbers
Zinc Subcateqory New Source Performance Standards:
Zinc Oxide Anodes, Formed
Electrodeposited Anodes
Silver Powder Cathodes, Formed
Pag
939
940
941
942
943
944
945
946
947
948
949
950
951
952
953
954
955
XXVI
-------
Number
XI-26
XI-27
XI-28
XI-29
XI-30
XI-31
XI-32
XI-33
XI-34
XI-35
XI-36
XII-1
XII-2
XII-3
XII-4
XII-5
XII-6
XII-7
XII-8
XII-9
TABLES
Title
Silver Oxide Powder Cathodes, Formed
Silver Peroxide Cathodes
Nickel Impregnated Cathodes
Cell Wash
Silver Etch
Employee Wash
Reject Cell Handling
Floor And Equipment Wash
Miscellaneous Wastewater Streams
Silver Peroxide Production
Silver Powder Production
Pollutant Reduction Benefits Of Control Systems
Cadmium Subcategory - Indirect Dischargers
Cadmium Subcategory Pretreatment Standards For
Existing Sources:
Electrodeposited Anodes
Impregnated Anodes
Nickel Electrodeposited Cathodes
Nickel Impregnated Cathodes
Cell Wash
Electrolyte Preparation
Employee Wash
Miscellaneous Wastwater Streams
Pagj
956
957
958
959
960
961
962
963
964
965
966
978
979
980
981
982
983
984
985
986
xxvii
-------
Number
XII-10
xii-n
XXX-12
XII-13
XII-14
XII-15
XII-16
XII-17
XII-18
XII-19
XII-20
XII-21
XII-22
XII-23
XIJ-24
XII-25
XII-26
XII-27
TABLES
Title
Cadmium Powder Production
Silver Powder Production
Cadmium Hydroxide Production
Nickel Hydroxide Production
Cadmium Subcategory Pretreatment Standards For
New Sources:
Electrodeposited Anodes
Impregnated Anodes
Nickel Electrodeposited Cathodes
Nickel Impregnated Cathodes
Cell Wash
Electrolyte Preparation
Employee Wash
Miscellaneous Wastwater Streams
Cadmium Powder Production
Silver Powder Production
Cadmium Hydroxide Production
Nickel Hydroxide Production
Pollutant Reduction Benefits Of Control
Systems Calcium Subcategory - Total
Pollutant Reduction Benefits Of Control Systems
Leclanche Subcategory
Leclanche Subcategory Pretreatment Standards
For Existing Sources:
Pag
987
988
989
990
991
992
993
994
995
996
997
998
999
1000
1001
1002
1003
1004
xxvi i i
-------
TABLES
Number Title Page
XII-28 Foliar Battery Miscellaneous Wash 1005
Leclanche Subcategory Pretreatment Standards
For New Sources;
XI1-29 Foliar Battery Miscellaneous Wash 1006
XI1-30 Pollutant Reduction Benefits Of Control Systems
Lithium Subcategory 1007
Lithium Subcategory Pretreatment Standards For
Existing Sources;
XI1-31 Lead Iodide Cathodes 1009
XII-32 Iron Disulfide Cathodes 1010
XI1-33 'Miscellaneous Wastewater Streams 1011
Lithium Subcategory PretreatmentStandards For
New Sources;
XI1-34 Lead Iodide Cathodes 1012
XII-35 Iron Disulfide Cathodes 1013
XI1-36 Miscellaneous Wastewater Streams 1014
XII-37 Pollutant Reduction Benefits Of Control Systems
Magnesium Subcategory 1015
Magnesium Subcategory Pretreatment Standards
ForExisting Sources;
XII-38 Silver Chloride Cathodes - Chemically Reduced 1017
XI1-39 Silver Chloride Cathodes - Electrolytic 1018
XII-40 Cell Testing 1019
XI1-41 Floor And Equipment Wash 1020
Magnesium Subcateqory Pretreatment Standards
For New Sources;
-------
Number
XII-42
XII-43
XII-44
XII-45
XII-46
XII-47
XII-48
XII-49
XII-50
XII-51
XII-52
XII-53
XII-54
XII-55
XII-56
XII-57
XII-58
XII-59
XII-60
XII-61
TABLES
Title
Silver Chloride Cathodes - Chemically Reduced
Silver Chloride Cathodes - Electrolytic
Cell Testing
Floor And Equipment Wash
Pollutant Reduction Benefits Of Control Systems
Zinc Subcategory - Indirect Dischargers
Zinc Subcategory Pretreatment Standards For
Existing Sources:
Wet Amalgamated Powder Anodes
Gelled Amalgam Anodes
Zinc Oxide Anodes, Formed
Electrodeposited Anodes
Silver Powder Cathodes, Formed
Silver Oxide Powder Cathodes, Formed
Silver Peroxide Cathodes
Nickel Impregnated Cathodes
Cell Wash
Silver Etch
Employee Wash
Reject Cell Handling
Floor And Equipment Wash
Miscellaneous Wastewater Streams
Silver Peroxide Production
Page
1021
1022
1023
1024
1025
1026
1027
1028
1029
1030
1031
1032
1033
1034
1035
1036
1037
1038
1039
1040
XXX
-------
Number
XII-62
XII-63
XII-64
XII-65
XII-66
XII-67
XII-68
XII-69
XII-70
XII-71
XII-72
XII-73
XII-74
XII-75
XII-76
TABLES
Title
Silver Powder Production
Zinc Subcategory Pretreatment Standards For New
Sources:
Zinc Oxide Anodes, Formed
Electrodeposited Anodes
Silver Powder Cathodes, Formed
Silver Oxide Powder Cathodes, Formed
Silver Peroxide Cathodes
Nickel Impregnated Cathodes
Cell Wash
Silver Etch
Employee Wash
Reject Cell Handling
Floor And Equipment Wash
Miscellaneous Wastewater Streams
Silver Peroxide Production
Silver Powder Production
Page
1041
1042
1043
1044
1045
1046
1047
1048
1049
1050
1051
1052
1053
1054
1055
XXXI
-------
FIGURES
Number Title Pag
III-l Theoretical Specific Energy As a Function of
Equivalent Weight and Cell Voltage For Various
Electrolytic Couples 11
III-2 Performance Capability of Various Battery Systems 11
II1-3 Cutaway View of An Impregnated Sintered Plate
Nickel-Cadmium Cell 11
III-4 Cutaway View of A Cylindrical Nickel-Cadmium
Battery 11
III-5 Cutaway View Of Lead Acid Storage Battery 11
III-6 Cutaway View of Cylindrical Leclanche Cell 11
III-7 Exploded View of A Foliar Leclanche Battery Used
In Film Pack 121
III-8 Cutaway View of Two Solid Electrolyte Lithium
Cell Configurations 12'
II1-9 Cutaway View of A Reserve Type Battery 12:
111-10 Cutaway View of A Carbon-Zinc-Air Cell 12:
III-ll Cutaway View of An Alkaline-Manganese Battery 1 2<
111-12 Cutaway View of A Mercury-Zinc (Ruben) Cell 12!
111-13 Major Production Operations in Nickel-Cadmium
Battery Manufacture , 121
111-14 Simplified Diagram Of Major Production
Operations In Lead Acid Battery Manufacture 12"
111-15 Major Production Operations In Leclanche
Battery Manufacture 12£
III-l6 Major.Production Operations in Lithium-Iodine
Battery Manufacture 12S
III-17 Major Production Operations In Ammonia-Activated
Magnesium Reserve Cell Manufacture 130
xxxii
-------
FIGURES
Number Title Page
II1-18 Major Production Operations In Water-Activated
Carbon-Zinc-Air Cell Manufacture 131
111-19 Major Production Operations In Alkaline-Manganese
Dioxide Battery Manufacture 132
II1-20 Simplified Diagram of Major Operations In Mercury-
Zinc (Ruben) Battery Manufacture 133
II1-21 Value of Battery Product Shipments 1963-1977 134
111-22 Geographical-Regional Distribution Of Battery
Manufacturing Plants 135
IV-1 Summary Of Category Analysis 157
V-l Generalized Cadmium Subcategory Manufacturing
Process 391
V-2 Cadmium Subcategory Analysis 392
V-3 Production Of Cadmium Electrodeposited Anodes 394
V-4 Production Of Cadmium Impregnated Anodes 395
V-5 Production Of Nickel Electrodeposited Cathodes .396
V-6 Production Of Nickel Impregnated Cathodes 397
V-7 Generalized Calcium Subcategory Manufacturing
Process 398
V-8 Calcium Subcategory Analysis 399
V-9 Generalized Schematic For Leclanche Cell
Manufacture 400
V-10 Leclanche Subcategory Analysis 401
V-l1 Generalized Lithium Subcategory Manufacturing
Process 402
V-l2 Lithium Subcategory Analysis 403
xxxiii
-------
FIGURES
Number Title
V-13 Generalized Magnesium Subcategory Manufacturing
Process 404
V-14 Magnesium Subcategory Analysis 405
V-15 Generalized Zinc Subcategory Manufacturing
Processes 406
V-16 Zinc Subcategory Analysis 407
V-17 Production Of Zinc Powder-Wet Amalgamated
Anodes 409
V-18 Production Of Zinc Powder - Gelled Amalgam Anodes 410
V-19 Production Of Pressed Zinc Oxide Electrolytically
Reduced Anodes 411
V-20 Production Of Pasted Zinc Oxide Electrolytically
Reduced Anodes ' 412
V-21 Production Of Electr©deposited Zinc Anodes 413
V-22 Production Of Silver Powder Pressed Electrolytically
Oxided Cathodes 414
V-23 Production Of Silver Oxide (Ag2O) Powder Thermally
Reduced Or Sintered, Electrolytically Formed
Cathodes 415
V-24 Chemical Treatment Of Silver Peroxide Cathode
Pellets 416
V-25 Production Of Pasted Silver Peroxide Cathodes 417
VII-1 Comparative Solubilities Of Metal Hydroxides And
Sulfides As A Function Of pH 613
VII-2 Lead Solubility In Three Alkalies 614
VII-3 Effluent Zinc Concentrations vs. Minimum
Effluent pH 615
XXXIV
-------
FIGURES
Number Title Page
VII-4 Hydroxide Precipitation Sedimentation Effectiveness
Cadmium 616
VII-5 Hydroxide Precipitation Sedimentation Effectiveness
Chromium 617
VI1-6 Hydroxide Precipitation Sedimentation Effectiveness
Copper 618
VI1-7 Hydroxide Precipitation Sedimentation Effectiveness
Lead 619
VI1-8 Hydroxide Precipitation Sedimentation Effectiveness
Nickel and Aluminum 620
VI1-9 Hydroxide Precipitation Sedimentation Effectiveness
Zinc 621
VII-10 Hydroxide Precipitation Sedimentation Effectiveness
Iron 622
VII-11 Hydroxide Precipitation Sedimentation Effectiveness
Manganese 623
VII-12 Hydroxide Precipitation Sedimentation Effectiveness
TSS 624
VII-13 Hexavalent Chromium Reduction With Sulfur Dioxide 625
VII-14 Granular Bed Filtration 626
VII-15 Pressure Filtration 627
VI1-16 Representative Types Of Filtration 628
VI1-17 Activated Carbon Adsorption Column 629
*
VI1-18 Centrifugation 630
VI1-19 Treatment Of Cyanide Waste By Alkaline
Chlorination 631
VI1-20 Typical Ozone Plant For Waste Treatment 632
xxxv
-------
FIGURES
VII-21
VII-22
VII-23
VI1-24
VII-25
VII-26
VII-27
VII-28
VII-29
VII-30
VIII-1
VIII-2
VIII-3
VIII-4
VIII-5
VIII-6
VIII-7
VIII-8
VIII-9
VIII-10
UV-Ozonation
Types Of Evaporation Equipment
Dissolved Air Flotation
Gravity Thickening
Ion Exchange With Regeneration
Simplified Reverse Osmosis Schematic
Reverse Osmosis Membrane Configurations
Sludge Drying Bed
Simplified Ultrafiltration Flow Schematic
Vacuum Filtration
Simplified Logic Diagram System Cost Estimation
Program
Simple Waste Treatment System
Predicted Precipitation And Settling Costs •-
Continuous
Predicted Costs For Precipitation And Settling
Batch
Chemical Precipitation And Settling Costs
Predicted Costs Of Mixed-Media Filtration
Membrane Filtration Costs
Reverse Osmosis Or Ion Exchange Investment Costs
Reverse Osmosis Or Ion Exchange Labor
Requirements
Reverse Osmosis Or Ion Exchange Material Costs
Paqe
633
634
635
636
637
638
639
640
641
642
700
701
702
703
704
705
706
707
708
709
XXXV1
-------
FIGURES
Number Title . Page
VIII-11 Reverse Osmosis or Ion Exchange Power Requirements 710
VII1-12 Vacuum Filtration Investment Costs 711
VJII-13 Vacuum Filtration Labor Requirements 712
VII1-14 Vacuum Filtration Material Costs 713
VIII-15 Vacuum Filtration Electrical Costs . 714
VIII-16 Holding Tank Investment Costs 715
VIII-17 Holding Tank Electrical Costs , 716
VII1-18 Holding Tank Labor Requirements 717
VII1-19 Neutralization Investment Costs 718
VIII-20 Neutralization Labor Requirements 719
VIII-21 Carbon Adsorption Costs 720
VII1-22 Chemical Reduction Of Chromium Investment Costs 721
VII1-23 Annual Labor For Chemical Reduction Of Chromium 722
VII1-24 Costs For Vapor Compression Evaporation 723
IX-1 Cadmium Subcategory BPT Treatment 810
IX-2 Calcium Subcategory BPT Treatment 811
IX-3 , Leclanche Subcategory BPT Treatment 812
IX-4 Lithium Subcategory BPT Treatment 813
IX-5 Magnesium Subcategory BPT Treatment 814
IX-6 Zinc Subcategory BPT Treatment 815
X-l Cadmium Subcategory BAT Option 1 Treatment 908
X-2 Cadmium Subcategory BAT Option 2 Treatment 909
xxxvi i
-------
FIGURES
Number Title Page
X-3 Cadmium Subcategory BAT Option 3 Treatment 910
X~4 Cadmium Subcategory BAT Option 4 Treatment 911
X-5 Calcium Subcategory BAT Option 1 Treatment 912
X-6 Calcium Subcategory BAT Option 2 Treatment 913
X-7 Lithium Subcategory BAT Option 1 Treatment 914
X-8 Lithium Subcategory BAT Option 2 Treatment 915
X-9 Lithium Subcategory BAT Option 3 Treatment 916
X-10 Magnesium Subcategory BAT Option 1 Treatment 917
X-11 Magnesium Subcategory BAT Option 2 Treatment 918
X-12 Magnesium Subcategory BAT Option 3 Treatment 919
X-13 Zinc Subcategory BAT Option 1 Treatment 920
X-14 Zinc Subcategory BAT Option 2 Treatment 921
X-15 Zinc Subcategory BAT Option 3 Treatment 922
X-16 Zinc Subcategory BAT Option 4 Treatment 923
xxxvi i i
-------
SECTION I
SUMMARY AND CONCLUSIONS
Background
Pursuant to Sections 301, 304, 306, 307, 308, and 501 of the
Clean Water Act, EPA collected and analyzed data for plants in
the Battery Manufacturing Point Source Category. There are no
existing effluent limitations or performance standards for this
industry. This document and the administrative record provide
the technical bases for promulgating effluent limitations for
existing direct dischargers using best practicable and best
available technology (BPT and BAT). Effluent standards are
promulgated for existing indirect dischargers (PSES), and new
sources, for both direct dischargers (NSPS) and indirect
dischargers (PSNS).
Battery manufacturing encompasses the production of modular
electric power sources where part or all of the fuel is contained
within the unit and electric power is generated directly from a
chemical reaction rather than indirectly through a heat cycle
engine. There are three major components of a cell — anode,
cathode, and electrolyte — plus mechanical and conducting parts
such as case, separator, or contacts. Production includes
electrode manufacture of anodes and cathodes, and associated
ancillary operations necessary to produce a battery.
This volume {Volume I) of the development document specifically
addresses the cadmium, calcium, Leclanche, lithium, magnesium,
nuclear, and zinc subcategories. Volume II addresses the lead
subcategory of the battery manufacturing point source category.
Section III of both volumes provides a general discussion of all
battery manufacturing.
Subcategorization
The category is subcategorized on the basis of anode material and
electrolyte. This Subcategorization was selected because most of
the manufacturing process variations are similar within these
subcategories and the approach avoids unnecessary complexity.
The data base includes the following seven subcategories which
are included in this volume:
• Cadmium » Magnesium
• Calcium • Nuclear
• Leclanche • Zinc
* Lithium
-------
The nuclear subcategory was considered in the data base, but was
not considered for regulation because production had ceased and
was not expected to resume.
Within each subcategory, manufacturing process operations (or
elements) were grouped into anode manufacture, cathode
manufacture, and ancillary operations associated with the
production of a battery. The development of a production
normalizing parameter (pnp) for each element was necessary to
relate water use to various plant sizes and production
variations. The pnp was, in general, the weight of anode or
cathode material, or weight of cells produced.
Data
The data base for these seven subcategories of the battery
manufacturing category includes 69 subcategory specific plants
which employed over 12,000 people. Of the 69 plants in the
subcategories in this volume, 10 discharge wastewater directly tc
surface waters, 33 discharge wastewater to publicly owned
treatment works (POTW), and 26 have no discharge of process
wastewater. Data collection portfolios (dcp) were sent to all
known battery companies in the U.S. and data were requested for
1976. Data were returned by 100 percent of the companies in
these seven subcategories. The data base includes some data for
1977 and 1978.
Water is used throughout battery manufacturing to clean battery
components and to transport wastes. Water is used in the
chemical systems to make most electrodes and special electrode
chemicals; water is also a major component of most electrolytes
and formation baths. A total of 31 plants from the seven
subcategories covered in this volume were visited prior to
proposal for engineering analysis, and wastewater sampling was
conducted at 19 of these plants. These visits enabled the Agency
to characterize about 30 specific wastewater generating processes
for the seven subcategories, select the pollutants for
regulation, and evaluate wastewater treatment performance in this
category. Since proposal one additional battery manufacturing
site was visited in order to collect additional information for
the Leclanche subcategory.
The most important pollutants or pollutant parameters generated
in battery manufacturing wastewaters are (1) toxic metals —
arsenic, cadmium, chromium, copper, lead, mercury, nickel,
selenium, silver, and zinc; (2) nonconventional pollutants —
aluminum, cobalt, iron, manganese, and COD; and (3) conventional
pollutants — oil and grease, TSS, and pH. Toxic organic
pollutants generally were not found in large quantities although
some cyanide was found in a few subcategories. Because of the
-------
amount of toxic metals present, the sludges generated during
wastewater treatment generally contain substantial amounts of
toxic metals.
Current wastewater treatment systems in the battery manufacturing
category range from no treatment to sophisticated physical
chemical treatment (although frequently not properly operated)
combined with water conservation practices. Of the 69 plants
covered in this document, 33 percent of the plants have no
treatment and do not discharge, 9 percent have no treatment and
discharge, 10 percent have only pH adjust systems, 12 percent
have only sedimentation or clarification devices, 17 percent have
equipment for chemical precipitation and settling, 9 percent have
equipment for chemical precipitation, settling and filtration,
and 10 percent have other treatment systems. Even though
treatment systems are in place at many plants, however, the
category is uniformly inadequate in wastewater treatment
practices. The systems in place are generally inadequately
sized, poorly maintained, or improperly operated (systems
overloaded, solids not removed, pH not controlled, etc.).
Wastewater Treatment
The control and treatment technologies available for this
category and used as the basis for the regulation include both
in-process and end-of-pipe treatments. In-process treatment
includes a variety of water flow reduction steps and major
process changes such as: cascade and countercurrent rinsing (to
reduce the amount of water used to remove unwanted materials from
electrodes); consumption of cleansed wastewater in product mixes;
and substitution of nonwastewater-generating forming (charging)
systems. End-of-pipe treatment includes: hexavalent chromium
reduction; chemical precipitation of metals using hydroxides,
carbonates, or sulfides; and removal of precipitated metals and
other materials using settling or sedimentation; filtration; and
combinations of these technologies. While developing the
regulation, EPA considered the impacts of these technologies on
air quality, solid waste generation, water scarcity, and energy
requirements.
The effectiveness of these treatment technologies has been
evaluated and established by examining their performance on
battery manufacturing and other similar wastewaters. The data
base for hydroxide precipitation-sedimentation (lime and settle)
technology is a composite of data drawn from EPA sampling and
analysis of copper and aluminum forming, battery manufacturing,
porcelain enameling, and coil coating effluents. A detailed
statistical analysis done on the data base showed substantial
homogeneity in the treatment effectiveness data from these five
categories. This supports EPA's technical judgment that these
-------
wastewaters are similar in all material respects for treatment
because they contain a range of dissolved metals which can be
removed by precipitation and solids removal. Electroplating data
were originally used in the data set, but were excluded after
further statistical analyses were.performed. Following proposal,
additional battery manufacturing lime and settle technology
effluent data was obtained from battery plants primarily to
evaluate treatment effectiveness for lead. Precipitation-
sedimentation and filtration technology performance is based on
the performance of full-scale commercial systems treating
multicategory wastewaters which also are essentially similar to
battery manufacturing wastewaters.
The treatment performance data is used to obtain maximum daily
and monthly average pollutant concentrations. These
concentrations (mg/1) along with the battery manufacturing
production normalized flows (I/kg of production normalizing
parameter) are used to obtain the maximum daily and monthly
average values (mg/kg) for effluent limitations and standards.
The monthly average values are based on the average of ten
consecutive sampling days. The ten-day average value was
selected as the minimum number of consecutive samples which need
to be averaged to arrive at a stable slope on a statistically
based curve relating one-day and 30-day average values and it
approximates the most frequent monitoring requirement of direct
discharge permits.
Treatment Costs
The Agency estimated the costs of each control and treatment
technology using a computer program based on standard engineering
cost analysis. EPA derived unit process costs by applying plant
data and characteristics (production and flow) to each treatment
process (i.e., metals precipitation, sedimentation, mixed media
filtration, etc.). The program also considers what treatment
equipment exists at each plant. These unit process costs were
added for each plant to yield total cost at each treatment level.
In cases where there is more than one plant at one site, costs
were calculated separately for each plant and probably overstate
the actual amount which .would be spent at the site where one
combined treatment system could be used for all plants. These
costs were then used by the Agency to estimate the impact of
implementing the various options on the industry. For each
control and treatment option considered the number of potential
closures, number of employees affected, and the impact on price
were estimated. These results are reported in the EPA document
entitled, Economic Impact Analysis of Effluent Limitations and
Standards for the Battery. Manufacturing Industry (EPA 440/2-84-
002).
-------
Regulation
On the basis of raw waste characteristics, in-process and end-of-
pipe treatment performance and costs, and other factors, EPA
identified and classified various control and treatment
technologies as BPT, BAT, NSPS, PSES, and PSNS. The regulation,
however, does not require the installation of any particular
technology. Rather, it requires achievement of effluent
limitations and standards equivalent to those achieved by the
proper operation of these or equivalent technologies.
Except for pH requirements, the effluent limitations for BPT,
BAT, and NSPS are expressed as mass limitations — a mass of
pollutant per unit of production (mg/kg). They were calculated
by combining three figures: (1) treated effluent concentrations
determined by analyzing control technology performance data/ (2)
production-weighted wastewater flow for each manufacturing
process element of each subcategory/ and (3) any relevant process
or treatment variability factor (e.g., mean versus maximum day).
This basic calculation was performed for each regulated pollutant
or pollutant parameter and for each wastewater-generating process
element of each subcategory. Pretreatment standards — PSES and
PSNS — are also expressed as mass limitations rather than
concentration limits to ensure a reduction in the total quantity
of pollutant discharges.
BPT - In general, the BPT level represents the average of the
best existing performances of plants of various ages, sizes,
processes or other common characteristics. Where existing
performance is uniformly inadequate, BPT may be transferred from
a different subcategory or category. In balancing costs in
relation to effluent reduction benefits, EPA considers the volume
and nature of existing discharges, the volume and nature of
discharges expected after application of BPT, the general
environmental effects of the pollutants, and cost and economic
impact of the required pollution control level.
EPA is promulgating BPT mass limitations for existing direct
discharges in the cadmium and zinc subcategories. These
limitations are based on model end-of-pipe treatment consisting
of oil skimming when required and chemical precipitation and
settling. The pollutant parameters selected for limitation at
BPT for the cadmium subcategory are: cadmium, nickel, zinc,
cobalt, oil and grease, total suspended solids (TSS), and pH.
The pollutant parameters selected for limitation at BPT for the
zinc subcategory include: chromium, mercury, silver, zinc,
manganese, oil and grease, TSS and pH.
Eight cadmium and zinc battery plants in the data base are direct
dischargers. Implementation of BPT limitations will remove
-------
140/470 kilograms (309,000 pounds) per year of toxic metals and
203,500 kilograms (447,700 pounds) per year of conventional and
other pollutants from the estimated raw waste generation. The
Agency estimates that capital costs above equipment in place for
these plants will be $0.161 million ($1983) and total annual
costs will be $0.061 million ($1983). The economic impact
analysis concluded that there are no potential plant closures or
employment effects associated with compliance with this
regulation. If compliance costs were passed on to consumers,
price increases would be no higher than 0.3 percent for battery
products in these subcategories. There are no balance-of-trade
effects. The Agency has determined that the effluent reduction
benefits associated with compliance with BPT limitations justify
the costs.
No BPT limitations are promulgated for the calcium, Leclanche,
lithium, and magnesium subcategories. There are no direct
dischargers in the calcium and Leclanche subcategories, and low
flows and toxic pollutant loads do not justify national
limitations for the lithium and magnesium subcategories.
BAT - The BAT level represents the best economically achievable
performance of plants of various ages, sizes, processes or other
shared characteristics. As with BPT, where existing performance
is uniformly inadequate, BAT may be transferred from a different
subcategory or category. BAT may include feasible process
changes or internal controls, even when not common industry
practice. In general, in process technologies causing an average
87 percent reduction in wastewater flow are the basis for BAT
limitations.
In developing BAT, EPA has given substantial weight to the
reasonableness of costs. The Agency considered the volume and
nature of discharges, the volume and nature of discharges
expected after the application of BAT, the general environmental
effects of the pollutants, and the costs and economic impacts of
the required pollution control levels. Despite this
consideration of costs, the primary determinant of BAT is still
effluent reduction capability.
The direct dischargers are expected to move directly to
compliance with the BAT limitations from existing treatment
because the flow reduction used to meet BAT limitations would
allow the use of smaller — and less expensive — chemical
precipitation and settling equipment than would be used to meet
BPT limitations without any flow reduction. The pollutant
parameters selected for limitation at BAT for the cadmium
subcategory include: cadmium, nickel, zinc and cobalt. The
pollutant parameters selected for limitation at BAT for the zinc
-------
subcategory include: chromium, mercury, silver, zinc and
manganese.
Implementation of the BAT limitations will remove annually an
estimated 141,000 kilograms (310,100 pounds) of toxic metals and
212,150 kilogram (466,700 pounds) per year of other pollutants
from estimated raw waste generation at a capital cost above
equipment in place of $0.31 million and a total annual cost of
$0.09 million in 1983 dollars. The Agency projects no plant
closures, employment impacts, or foreign trade effects and has
determined that the BAT limitations are economically achievable.
No BAT limitations are promulgated for the calcium, Leclanche,
lithium and magnesium subcategories for reasons discussed under
BPT.
NSPS - NSPS (new source performance standards) are based on the
best available demonstrated (BDT), including process changes, in
plant controls, and end-of-pipe treatment technologies which
reduce pollution to the maximum extent feasible.
For new source direct dischargers, NSPS are promulgated for the
cadmium, calcium, Leclanche, lithium, magnesium, and zinc
subcategories. No discharge of process wastewater is promulgated
for the calcium, and Leclanche (all processes but foliar battery
miscellaneous wash) subcategories based on treatment using the
end-of-pipe control technology and water reuse. Standards based
on flow reduction and end-of-pipe treatment are promulgated for
the cadmium, Leclanche (foliar battery miscellaneous wash),
lithium, magnesium, and zinc subcategories. EPA does not believe
that NSPS will pose a barrier to entry for new direct sources.
PSES - PSES (pretreatment standards for existing sources) are
designed to prevent the discharge of pollutants which pass
through, interfere with, or are otherwise incompatible with the
operation of publicly owned treatment works (POTW). Pretreatment
standards are technology-based and analogous to the best
available technology for removal of toxic pollutants.
For existing indirect dischargers, PSES are promulgated for the
cadmium, Leclanche, magnesium and zinc subcategories. The
standards promulgated are mass based and for the cadmium and zinc
subcategories are equivalent to the BAT limitations. A standard
based on flow reduction and the treatment effectiveness of lime,
settle, and filter technology as end-of-pipe treatment is
promulgated for the foliar battery miscellaneous wash element of
the Leclanche subcategory. A standard based primarily on the
treatment effectiveness of lime and settle technology as end-of-
pipe treatment is promulgated for the magnesium subcategory. No
discharge of process wastewater achieved by treatment using the
-------
end-of-pipe control technology and water reuse is promulgated for
the other processes in the Leclanche subcategory.
No PSES standards are promulgated for the calcium and lithium
subcategories because low flows and toxic pollutant loads do not
justify developing national standards.
Implementation of the PSES will remove annually an estimated
54,450 kilograms (119,800 pounds) of toxic pollutants and 133,450
kilograms (293,600 pounds) of other pollutants at a capital cost
above equipment in place of $1.075 million and an annual cost of
$0.354 million in 1983 dollars. The Agency has concluded that
PSES is economically achievable.
PSNS - Like, PSES, PSNS (pretreatment standards for new sources)
are established to prevent the discharge of pollutants which pass
through, interfere with, or are otherwise incompatible with the
operation of the POTW. New indirect dischargers, like new direct
dischargers, have the opportunity to incorporate the best
available demonstrated technologies.
For PSNS the promulgated standards are mass based and equivalent
to the NSPS technology. EPA does not believe that PSNS will pose
a barrier to entry for new indirect sources.
BCT - BCT effluent limitations for the cadmium and zinc
subcategories are deferred pending adoption of the BCT cost test.
Energy and Nonwater Quality Environmental Impacts
Eliminating or reducing one form of pollution may cause other
environmental problems. Sections 304(b) and 306 of the Act
require EPA to consider the nonwater quality environmental
impacts (including energy requirements). In compliance with
these provisions, the Agency considered the effect of this
regulation on air pollution, solid waste generation and energy
consumption. The Administrator has determined that the impacts
identified below are justified by the benefits associated with
compliance with the limitations and standards.
Imposition of BPT, BAT, NSPS, PSES, and PSNS will not create any
substantial air pollution problems because the wastewater
treatment technologies required to meet these limitations and
standards do not cause air pollution.
EPA estimates that battery manufacturing plants generated 18,960
kkg (87,000 tons) of solid wastes per year from manufacturing
process operations, and an indeterminate amount of solid waste
from wastewater treatment because of the variable technologies
currently practiced. The solid wastes that would be generated at
-------
battery manufacturing plants by lime and settle treatment
technologies are believed to be nonhazardous under Section 3001
of the Resource Conservation and Recovery Act (RCRA). Only
wastewater treatment sludge generated by sulfide precipitation
technology, and wastewater treatment sludges containing mercury
are likely to be hazardous under the regulations implementing
subtitle C of RCRA.
EPA estimates that the achievement of BPT effluent limitations
for the cadmium and zinc subcategories will result in a net
increase in electrical energy consumption of approximately 0.02
million kilowatt-hours per year. The BAT effluent technology are
projected to increase electrical energy consumption by 0.04
million kilowatt hours per year. BPT. The energy requirements
for NSPS and PSNS are estimated to be similar to energy
requirements for BAT and PSES.
-------
10
-------
SECTION II
RECOMMEN0ATIONS
1. EPA has divided the battery manufacturing category into
eight subcategories for the purpose of effluent limitations and
standards. These subcategories are;
• Cadmium • Lithium
• Calcium • Magnesium
• Lead • Nuclear
• Leclanche » Zinc
2. These subcategories have been further subdivided into
process .elements specific to basic manufacturing operations
within the subcategory and the promulgated regulations are
specific to these elements. The nuclear subcategory is excluded
from regulation since there are no currently operating plants and
there are no known plans to resume production. The lead
subcategory {Subcategory C) is the subject of Volume II and is
not considered here.
3. The following effluent limitations are promulgated for
existing sources.
A. Subcategory A - Cadmium
(a) BPT Limitations
(1) Subpart A - Pasted and Pressed Powder Anodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 0.92 0.41
Nickel 5.18 3.43
Zinc 3.94 1.65
Cobalt 0.57 0.24
Oil and Grease 54.0 32.4
TSS 111.0 52.65
pH Within the range of 7.5 - 10.0 at all times
11
-------
(2) Subpart A - Electrodeposited Anodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1", 000,000 Ib of cadmium
Cadmium 237.0 104.6
Nickel 1338.2 885.2
Zinc 1017.6 425.2
Cobalt 146.4 62.7
Oil and Grease 13940.0 8364.0
TSS 28577.0 13592.0
pH Within the range of 7.5 - 10.0 at all times
(3) Subpart A - Impregnated Anodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 339.3 149.7
Nickel 1916.2 1267.5
2inc 1457.1 608.8
Cobalt 209.6 89.8
Oil and Grease 19960.0 11976.0
TSS 40918.0 19461.0
pH Within the range of 7.5 - 10.0 at all times
12
-------
(4) Subpart A - Nickel Electrodeposited Cathodes
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum
any one
for
day
Maximum
monthly
for
average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium
Nickel
Zinc
Cobalt
Oil and
TSS
pH
Grease
193,
1092
830
1 19
1 1380
23329
Within the range of 7.5 -
85
722
347
51
6828
11095
10.0
.4
.6
. 1
.2
.0
.5
at
all times
(5) Subpart A - Nickel Impregnated Cathodes
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum
monthly
for
average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium
Nickel
Zinc
Cobalt
Oil and grease
TSS
pH
557.6
3148.8
2394.4
344.4
32800.0
67240.0
246,
2082,
1000,
147,
19680,
31980,
Within the range of 7.5 - 10.0 at all times
13
-------
(6) Subpart A - Miscellaneous Wastewater Streams
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Cadmium
Nickel
Zinc
Cobalt
Oil and Grease
TSS
pH
6.29 2.77
35.54 23,50
27.02 11.29
3.89 1.66
370.20 222.12
758.91 360.94
Within the range of 7.5 - 10.0 at all
times
(7) Subpart A
Cadmium Powder Production
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any oneday
Maximum
monthly
for
average
Metric Units - njg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
Cadmium
Nickel
Zinc
Cobalt
Oil and
TSS
pH
Grease
22,
126,
95,
13,
1314,
2693,
34
14
92
80
0
0
Within the range of 7.5 -
9.86
83.44
40.08
5.91
788.4
1281.2
10.0 at all times
14
-------
(8) Subpart A - Silver Powder Production
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Cadmium 7.21 3.18
Nickel 40.70 26.92
Silver 8.69 3.61
Zinc 30.95 12.93
Cobalt 4.45 1.91
Oil and Grease 424.0 254.4
TSS 869.2 413.4
pH Within the range of 7.5 - 10.0 at all times
(9) Subpart A - Cadmium Hydroxide Production
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
Cadmium 0.31 0.14
Nickel 1.73 1,14
Zinc 1.31 0.55
Cobalt 0.19 0.08
Oil and Grease 18.0 10.8
TSS 36.9 17.6
pH Within the range of 7.5 - 10.0 at all times
15
-------
(10) Subpart A - Nickel Hydroxide Production
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
Cadmium 37.4 16.5
Nickel 211.2 139.7
Zinc 160.6 67.1
Cobalt 23.1 9.9
Oil and Grease 2200.0 1320.0
TSS 4510.0 2145.0
pH Within the range of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
(b) BAT Limitations
(1) Subpart A - Electrodeposited Anodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 11.95 5.27
Nickel 67.49 44.64
Zinc 51.32 21.44
Cobalt 7.38 3.16
16
-------
(2) Subpart A - Impregnated Anodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 68.0 30.0
Nickel 384.0 254.0
Zinc 292.0 122.0
Cobalt 42.0 18.0
(3) Subpart A - Nickel Electrodeposited Cathodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium 11.22 4.95
Nickel 63.36 41.91
Zinc 48.18 20.13
Cobalt 6.93 2.97
17
-------
(4) Subpart A - Nickel Impregnated Cathodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium 68.0 30.0
Nickel 384.0 254.0
Zinc 292.0 122.0
Cobalt 42.0 18.0
(5) Subpart A - Miscellaneous Wastewater Streams
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Cadmium 0.79 0.35
Nickel 4.47 2.96
Zinc 3.40 1.42
Cobalt 0.49 0.21
(6) Subpart A - Cadmium Powder Production
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property ; any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
Cadmium 2.23 0.99
Nickel 12.61 8.34
Zinc 9.59 4.01
Cobalt 1.38 0.59
18
-------
(7) Subpart A - Silver Powder Production
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Cadmium 1.09 0.48
Nickel 6.16 4.08
Silver 1.32 0.55
Zinc 4.69 1.96
Cobalt 0.67 0.29
(8) Subpart A - Cadmium Hydroxide Production
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
Cadmium 0.05 0.02
Nickel 0.27 0.18
Zinc 0.20 0.09
Cobalt 0.03 0.01
19
-------
(9) Subpart A - Nickel Hydroxide Production
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
Cadmium 5.61 2.48
Nickel 31.68 20.96
Zinc 24.09 10.07
Cobalt 3.47 1.49
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
20
-------
B.Subcategory B - Calcium
(a) BPT Limitations
[Reserved]
(b) BAT Limitations
(Reserved]
C. Subcategory C - Lead
(See Battery Manufacturing Document - Volume II)
D. Subcategory D - Leclanche
(a) BPT Limitations
[Reserved]
(b) BAT Limitations
[Reserved]
E. Subcategory E - Lithium
(a) BPT Limitations
[Reserved J
(b) BAT Limitations
[Reserved]
F. Subcategory F - Magnesium
(a) BPT Limitations
[Reserved]
(b) BAT Limitations
[Reserved]
21
-------
G, Subcategory G - Zinc
(a) BPT Limitations
{1} Subpart G - Wet Amalgamated Powder Anodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium 1.67 0.68
Mercury 0.95 0.38
Silver 1.56 0.65
Zinc . 5.55 2.32
Manganese 2.58 1.10
Oil and Grease 76.0 45.6
TSS 155.8 74.1
pH Within the range of 7.5 - 10.0 at all times
(2) Subpart G - Gelled Amalgam Anodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium 0.30 0.12
Mercury 0.17 0.07
Silver 0.28 0.12
Zinc 0.99 0.42
Manganese 0.46 0.20
Oil and Grease 13.6 8.16
TSS 27.9 13.26
pH Within the range of 7.5 - 10.0 at all times
22
-------
(3) Subpart G - Zinc Oxide,. Formed Anodes
BPT Effluent Limitations
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium
Mercury
Silver
Zinc
Manganese
Oil and Grease
TSS
PH
62,9 25.7
35.8 14.3
58.7 24.3
208.8 87.2
97.2 41.5
2860.0 1716.0
5863.0 2789.0
Within the range 7.5 - 10.0 at all
times
(4) Subpart G - Electr©deposited Anodes
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Chromium
Mercury
Silver
Zinc
Manganese
Oil and Grease
TSS
PH
1404
798,
1308,
4657,
2169
63800
130700
Within the range of 7.5 -
574.0
319.0
543.0
1946.0
925.0
38280.0
62210.0
10.0 at all times
23
-------
(5) Subpart G - Silver Powder, Formed Cathodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property : any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/l,QOO,QOO Ib of silver applied
Chromium 86.2 35.3
Mercury 49.0 19.6
Silver 80.4 33.3
Zinc 286.2 119.6
Manganese 133.3 56.8
Oil and Grease 3920.0 2350.0
TSS 8036.0 3822.0
pH Within the range of 7.5 - 10.0 at all times
(6) Subpart G - Silver Oxide Powder, Formed Cathodes
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 57.7 23.6
Mercury 32.8 13.1
Silver 53.7 22.3
Zinc 191.3 79.9
Manganese 89.1 38.0
Oil and Grease 2620.0 1570.0
TSS 5370.0 2554.0
pH Within the range of 7.5 - 10.0 at all times
24
-------
(7) Subpart G - Silver Peroxide Cathodes
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Chromium
Mercury
Silver
Zinc
Manganese
Oil and Grease
TSS
PH
• mg/kg
- lb/1,
of silver applied
000,000 Ib of silver applied
13
7
12
45
21
628
1287
8
85
9
8
4
,0
0
5,
3.
5,
19,
9,
377,
612,
65
14
34
2
1 1
0
0
Within the range of 7.5 - 10.0 at all times
{8} Subpart G - Nickel Impregnated Cathodes
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Chromium
Mercury
Nickel
Silver
Zinc
Manganese
Oil and Grease
TSS
pH
Within
721 .
410,
3149,
672,
2394,
1115,
32800,
67240.0
the range
6
0
0
4
4
2
,0
295,
164,
2083,
279,
1000,
475,
19680,
31980,
of 7.5 - 10.0 at all times
25
-------
(9) Subpart G - Miscellaneous Wastewater Streams
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 3.85 1.58
Cyanide 2.54 1.05
Mercury 2.19 0.88
Nickel 16.82 11.12
Silver 3.59 1.49
Zinc 12.79 5.34
Manganese 5.96 2.54
Oil and Grease 175.20 105.12
TSS 359.16 170.82
pH Within the limits of 7.5 - 10.0 at all times
(10) Subpart G - Silver Etch
BPT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 21.6 8.84
Mercury 12.3 4.91
Silver 20.2 8.35
Zinc 71.7 30.0
Manganese 33^. 4 14.3
Oil and Grease 982.0 589.2
TSS 2013.1 957.5
pH Within the range of 7.5 - 10.0 at all times
26
-------
(11) Subpart G - Silver Peroxide Production
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
mpn t h1y aver age
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Chromium
Mercury
Silver
Zinc
Manganese
Oil and Grease
TSS
PH
23,
13,
21 ,
76,
35
1044,
2140
9,
5
8,
31
15
627
1018
40
22
88
8
1
0
0
Within the range of 7.5 - 10.0 at all times
(12) Subpart G
- Silver Powder Production
BPT Effluent Limitations
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver
powder produced
Chromium
Mercury
Silver
Zinc
Manganese
Oil and grease
TSS
PH
9.33
5.30
8.69
30.95
14.42
424.0
869.0
3
2
3
12
6
254
413
82
12
61
93
15
4
4
Within the range 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
27
-------
(b) BAT Limitations
(1) Subpart G - Wet Amalgamated Powder Anodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lbs/1,000,000 Ibs of zinc
Chromium 0.24 0.099
Mercury 0.14 0.055
Silver 0.23 0.093
Zinc 0.80 0.34
Manganese 0.37 0.16
(2) Subpart G - Gelled-Amalgam Anodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium 0.030 0.012
Mercury 0.017 0.007
Silver 0.028 0.012
Zinc 0.099 0.042
Manganese 0.046 0.020
28
-------
(3) Subpart G -
Zinc Oxide Formed Anodes
BAT Effluent Limitations
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Chromium
Mercury
Silver
Zinc
Manganese
mg/kg of zinc
- lb/1,000,000 Ib of zinc
9.53
5.42
8.89
31 .64
14.74
3,
2,
3
13
90
17
68
22
6.28
(4) Subpart G -
Electrodeposited Anodes
BAT Effluent Limitations
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Chromium
Mercury
Silver
Zinc
Manganese
mg/kg of zinc deposited
- lb/1,000,000 Ib of zinc deposited
94.47
53.68
88.03
313.46
146.00
38.65
21 .47
36.50
130.97
62.26
29
-------
(5) Subpart G - Silver Powder Formed Cathodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 13.07 5.35
Mercury 7.43 2.97
Silver 12.18 5.05
Zinc 43.36 18.12
Manganese 20.20 8.61
(6) Subpart G - Silver Oxide Powder Formed Cathodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day month 1 y average
Metric Units - mg/kg of silver applied
English .Units - lb/1,000,000 Ib of silver applied
Chromium 8.73 3.57
Mercury 4.96 1.99
Silver 8.14 3.37
Zinc 28.98 12.11
Manganese 13.50 5.76
30
-------
(7) Subpart G - Silver Peroxide Cathodes
BAT Effluent Limitations
Pollutant or
Pollutant , Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 2.09 0.87
Mercury 1.19 0.48
Silver 1.95 0.81
Zinc 6.95 , 2.90
Manganese 3.24 1.38
(8) Subpart G - Nickel Impregnated Cathodes
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Chromium 88.0 36.0
Mercury 50.0 20.0
Nickel 384.0 254.0
Silver 82.0 34.0
Zinc 292.0 122.0
Manganese 136.0 58.0
31
-------
(9) Subpart G - Miscellaneous Wastewater Streams
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.57 0.23
Cyanide 0.38 0.16
Mercury 0.32 0.13
Nickel 2.48 1.64
Silver 0.53 0.22
Zinc 1.88 0.79
Manganese 0.88 0.37
(10) Subpart G - Silver Etch
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 3.27 1.34
Mercury 1.86 0.74
Silver 3.05 1.26
Zinc 10.86 4.54
Manganese 5.06 2.16
32
-------
(11) Subpart G - Silver Peroxide Production
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property . any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Chromium 3.48 1.42
Mercury 1 .98 0.79
Silver 3.24 1.34
Zinc 11.55 4.83
Manganese 5.38 . 2.29
(12) Subpart G - Silver Powder Production
BAT Effluent Limitations
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Chromium 1.41 0.58
Mercury • 0.80 0.32
Silver 1.32 0.55
Zinc 4.69 1.96
Manganese 2.18 0.93
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
33
-------
4. The following standards are promulgated for new sources.
A. Subcategory A - Cadmium
(1) Subpart A - Electrodeposited Anodes - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 7.03 2.81
Nickel 19.33 13.01
Zinc 35.85 14.76
Cobalt 4.92 2.46
Oil and Grease 351.5 351.5
TSS 527.3 421.8
pH Within the range of 7.5 - 10.0 at all times
(2) Subpart A - Impregnated Anodes - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 40.0 16.0
Nickel 110.0 74.0
Zinc 204.0 84.0
Cobalt 28.0 14.0
Oil and Grease 2000.0 2000.0
TSS 3000.0 2400.0
pH Within the range of 7.5 - 10.0 at all times
34
-------
(3) Subpart A - Nickel Electrodeposited Cathodes - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
mo n t h 1 y average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium
Nickel
Zinc
Cobalt
Oil and Grease
TSS
pH
6.60
18.15
33.66
4,62
330.0
495.0
Within the range of 7.5
2
12
13
2
330
396
64
21
86
31
0
0
- 10.0 at all times
(4) Subpart A - Nickel Impregnated Cathodes - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
mpnt hly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium
Nickel
Zinc
Cobalt
Oil and grease
TSS
pH
40.0
110.0
204.0
28.0
2000.0
3000.0
Within the range of 7.5
16.0
74.0
84.0
14.0
2000.0
2400.0
10.0 at all times
35
-------
(5) Subpart A - Miscellaneous Wastewater Streams - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Cadmium 0.47 0.19
Nickel 1.28 0.86
Zinc 2.38 0.98
Cobalt 0.33 0.16
Oil and Grease 23.3 23.3
TSS 35.0 28.0
pH Within the range of 7.5 - 10.0 at all times
(6) Subpart A - Cadmium Powder Production - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
Cadmium 1.31 0.53
Nickel 3.61 2.43
Zinc 6.70 2.76
Cobalt 0.92 0.46
Oil and Grease 65,70 65.70
TSS 98.55 78.84
pH Within the range of 7.5 - 10.0 at all times
36
-------
(7) Subpart A - Silver Powder Production - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Cadmium 0.64 0.26
Nickel 1.77 1.19
Silver 0.93 0.39
Zinc 3.27 1.35
Cobalt 0.45 0.22
Oil and Grease 32.10 32.10
TSS 48.15 38.52
pH Within the range of 7.5 - 10.0 at all times
(8) Subpart A - Cadmium Hydroxide Production - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day mon t n1y average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
Cadmium 0.028 0.011
Nickel 0.077 0.051
Zinc 0.142 0.058
Cobalt 0.019 0.009
Oil and Grease 1.40 1.40
TSS 2.10 1.68
pH Within the range of 7.5 - 10.0 at all times
37
-------
(9) Subpart A - Nickel Hydroxide Production - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
Cadmium 3,30 1.32
Nickel 9.08 6.11
Zinc 16.83 6.93
Cobalt 2.31 1.16
Oil and Grease 165.0 ' 165.0
TSS 247.5 198.0
pH Within the range of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
B. Subcategory B - Calcium
There shall be no discharge of wastewater pollutants from any
battery manufacturing operations.
C. Subcategory C - Lead
(See Battery Manufacturing Document - Volume II)
D, Subcategory D - Leclanche
(1) Subpart D - Foliar Battery Miscellaneous Wash - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Mercury 0.010 • 0.004
Zinc 0.067 0.030
Manganese 0.019 0.015
Oil and Grease 0.66 0.66
TSS 0.99 0,79
pH Within the range of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
38
-------
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
E. Subcategory E - Lithium
(1) Subpart E - Lead Iodide Cathodes - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
Chromium
Lead
Iron
TSS
pH
23.34
17.66
75.70
946.2
Within the range of 7.5
9.46
8.20
38.48
756.96
10.0 at all times
(2) Subpart E - Iron Disulfide Cathodes - NSPS
Pollutant
Pollutant
Property
or
Maximum
any one
for
day
Maximum for
monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib of iron disulfide
Chromium
Lead
Iron
TSS
pH
2.79
2.11
9.05
113.1
Within the range of 7.5
1 .13
0.98
4.60
90.5
10.0 at all times
39
-------
(3) Subpart E - Miscellaneous Wastewater Streams - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.039 0.016
Lead 0.030 0.014
Iron 0.129 0.066
TSS 1.62 1.30
pH Within the range of 7.5 - 10.0 at all times
(4) Subpart E - Air Scrubbers NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
TSS 434.0 207.0
pH Within the range of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
40
-------
F. Subcategory F - Magnesium
(1) Subpart F - Silver Chloride Cathodes - Chemically
Reduced - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Lead 22.93 10.65
Silver 23.75 9.83
Iron 98.28 49.96
TSS 1228.5 982.8
COD 4095.0 1999.0
pH Within the range of 7.5 - 10.0 at all times
(2) Subpart F - Silver Chloride Cathodes - Electrolytic
- NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Lead 40.6 18.9
Silver 42.1 17.4
Iron 174.0 88.5
TSS 2175.0 1740.0
COD 7250.0 3540.0
pH Within the range of 7.5 - 10.0 at all times
41
-------
(3) Subpart I - Cell Testing - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Lead 19.5 7.89
Silver 15.3 6.31
Iron 63.1 32.1
TSS 789.0 631.2
COD 2630.0 1290.0
pH Within the range of 7.5 - 10.0 at all times
(4) Subpart F - Floor and Equipment Wash - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Lead 0.026 0.012
Silver 0.027 0.011
Iron 0.112 0.057
COD 4.70 2.30
TSS 1.41 1.13
pH Within the range of 7.5 - 10.0 at all times
42
-------
(5) Subpart F - Air Scrubber - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
TSS
PH
8467.0 4030.0
Within the range of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other
than those battery manufacturing operations listed above.
G. Subcategory G - Zinc
(1) Subpart G - Zinc Oxide Formed Anodes - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium
Mercury
Silver
Zinc
Manganese
Oil and Grease
TSS
pH
4.55 1.97
2.82 1.19
4.55 1.97
0.87 0.39
6.50 4.98
216.7 216.7
325.0 260.0
Within the limits of 7.5 - 10.0 at
all times
43
-------
(2) Subpart G - Electrodeposited Anodes - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Chromium 45.09 19.54
Mercury 27.91 11.81
Silver 45.09 19.54
Zinc 8.59 . 3.86
Manganese 64.41 49.38
Oil and Grease 2147.00 2147.00
TSS 3220.50 2576.40
pH Within the limits of 7.5 - 10.0 at all times
(3) Subpart G - Silver Powder Formed Cathodes - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 6,24 2.70
Mercury 3.86 1.63
Silver 6.24 2.70
Zinc 1.19 0.53
Manganese 8.91 6.83
Oil & Grease 297.00 297.00
TSS 445.5 356.40
pH Within the limits of 7.5 - 10.0 at all times
44
-------
(4) Subpart G - Silver Oxide Powder Formed Cathodes - NSPS
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Chromium
Mercury
Silver
Zinc
Manganese
Oil & Grease
TSS
pH
mg/kg of silver applied
- lb/1,000,000 Ib of silver applied
4.17 1.81
2.58 1.09
4.17 1.81
0.79 0.36
5.96 4.57
198.5 198.5
297.8 238.2
Within the limits of 7.5 - 10.0 at
all times
(5> Subpart G - Silver Peroxide Cathodes - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
month1y average
Metric Units
English Units
Chromium
Mercury
Silver
Zinc
Manganese
Oil & Grease
TSS
pH
- mg/kg of silver applied
- lb/1,000,000 Ib of silver
1 .00
0.62
1 .00
0.19
1 .43
47.6
71 .4
Within the limits of 7.5 -
applied
0.43
0.26
0.43
0.09
1 .09
47.6
57.1
10.0 at all tim
45
-------
(6) Subpart G - Nickel Impregnated Cathodes ~ NSPS
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Chromium
Mercury
Nickel
Silver
Zinc
Manganese
Oil & Grease
TSS
pH
mg/kg of nickel applied
- lb/1,000,000 Ib of nickel applied
42.0 18.2
26.0 11.0
42.0 18.2
42.0 18.2
8.0 3.6
60.0 46.0
2000.0 2000.0
3000.0 2400.00
Within the limits of 7.5 - 10.0 at
all times
(7) Subpart G - Miscellaneous Wastewater Streams - NSPS
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
Chromium
Cyanide
Mercury
Nickel
Silver
Zinc
Manganese
Oil & Grease
TSS
pH
mg/kg of cells produced
- lb/1,000,000 Ib of cells produced
0.27
0.039
0.17
0.27
0.27
0.05
0.39
12.90
19.35
Within the limits of 7.5
0,
0,
0,
0,
0,
0,
0,
12,
15,
12
016
07
12
12
02
30
90
46
- 10.0 at all times
46
-------
(8) Subpart G - Silver Etch - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day mpnt h 1 y aye ra ge
Metric Units - mg/kg
English Units - lb/1
Chromium
Mercury
Silver
Zinc
Manganese
Oil & Grease
TSS
of silver processed
,000,000 Ib of silver
1.56
0.97
1.56
0.30
2.23
74.40
11 1 .60
processed
0.68
0.41
0.68
0.13
1 .71
74.40
89.28
pH Within the limits of 7.5 - 10.0 at all times
(9) Subpart G - Silver Peroxide Production - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property ; any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Chromium 1.66 0.72
Mercury 1.03 0.44
Silver 1.66 , 0.72
Zinc 0.32 0.14
Manganese 2.37 1.82
Oil & Grease 79.10 79.10
TSS 118.65 94.92
pH Within the limits of 7.5 - 10.0 at all times
47
-------
(10) Subpart G - Silver Powder Production - NSPS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/l,OOQ,000 Ib of silver powder produced
Chromium 0.67 0.29
Mercury 0.42 0.18 ;
Silver 0.67 0.29
Zinc 0.13 0.06
Manganese 0.96 0.74
Oil & Grease 32.10 32.10
TSS 48.15 38.52
pH Within the limits of 7.5 - 10.0 at all times
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
5. The following pretreatment standards are promulgated for
existing sources.
A. Subcategory A - Cadmium
(1) Subpart A - Electr©deposited Anodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 11.95 5.27
Nickel 67.49 44.64
Zinc 51.32 21.44
Cobalt 7.38 3.16
48
-------
(2) Subpart A - Impregnated Anodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 68.0 30.0
Nickel 384.0 254.0
Zinc 292.0 122.0
Cobalt 42.0 18.0
(3) Subpart A - Nickel Electrodeposited Cathodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium 11.22 4.95
Nickel 63.36 41.91
Zinc 48.18 20.13
Cobalt 6.93 2.97
(4) Subpart A - Nickel Impregnated Cathodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium 68.0 30.0
Nickel 384.0 254.0
Zinc 292.0 122.0
Cobalt 42.0 18.0
49
-------
(5) Subpart A - Miscellaneous Wastewater Streams - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day mon t h 1 y aver age
Metric Units - mg/kg of cells produced
English Units - lb/1,OQO,OQQ Ib of cells produced
Cadmium 0.79 0.35
Nickel 4.47 2.96
Zinc 3.40 1.42
Cobalt 0.49 0.21
(6) Subpart A - Cadmium Powder Production - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
Cadmium 2,23 0.99
Nickel 12.61 8.34
Zinc 9.59 4.01
Cobalt 1.38 0.59
(7) Subpart A - Silver Powder Production - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Cadmium 1.09 0.48
Nickel 6.16 4.08
Silver 1.32 0.55
Zinc 4.69 1.96
Cobalt 0.67 0.29
50
-------
(8) Subpart A - Cadmium Hydroxide Production - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
Cadmium 0.05 0.02
'Nickel 0.27 0.18
Zinc 0.20 0.09
Cobalt 0.03 0.012
(9) Subpart A - Nickel Hydroxide Production - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
Cadmium 5.61 2.48
Nickel 31.68 20.96
Zinc 24.09 10.07
Cobalt 3.47 1.49
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
B. Subcategory B - Calcium
[Reserved]
C. Subcategory C - Lead
(See Battery Manufacturing Document-Volume II)
51
-------
D. Subcategory D - Leelanche
(1) Subpart D - Foliar Battery Miscellaneous Wash - PSES
Pollutant or
Pollutant Maximum for Maximum-for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Mercury 0.01 0.004
Zinc 0.067 0.030
Manganese 0.019 0.015
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other than
those battery manufacturing operations listed above.
E. Subcategory E - Lithium
[Reserved]
52
-------
F. Subcategory F - Magnesium
(1) Subpart F - Silver Chloride Cathodes - Chemically
Reduced - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lbs/1,000,000 Ibs of silver processed
Lead 1032.36 491.60
Silver 1007.78 417.86
(2) Subpart F - Silver Chloride Cathodes - Electrolytic - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Lead 60.9 29.0
Silver 59.5 24.7
(3) Subpart F - Cell Testing - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Lead 22.1 10.5
Silver 21.6 8.9
53
-------
(4) Subpart F - Floor and Equipment Wash - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Lead 0.039 0.018
Silver 0.038 0.015
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other
than those battery manufacturing operations listed above.
G. Subcategory G - Zinc
(1) Subpart G - Wet Amalgamated Powder Anode - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium 0.24 0.099
Mercury 0.14 0.055
Silver 0.23 0.093
Zinc 0.80 0.34
Manganese 0.37 0.16
54'
-------
(2) Subpart G - Gelled Amalgam Anodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lbs/1,000,000 Ibs of zinc
Chromium 0.030 0.12
Mercury 0.017 0.006
Silver 0.028 0.012
Zinc 0.099 0.042
Manganese 0.046 0.020
(3) Subpart G - Zinc Oxide Formed Anodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium 9.53 3.90
Mercury 5.42 2.17
Silver 8.89 3.68
Zinc 31.64 13.22
Manganese 14.74 6.28
(4) Subpart G - Electrodeposited Anodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Chromium 94.47 38.65
Mercury 53.68 21.47
Silver 88.03 36.50
Zinc 313.46 130.97
Manganese 146.00 62.26
55
-------
(5) Subpart G - Silver Powder Formed Cathodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 13.07 5.35
Mercury 7.43 2.97
Silver 12.18 5.05
Zinc 43.36 18.12
Manganese 20.20 8.61
(6) Subpart G - Silver Oxide Powder Formed Cathodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 8.73 3.57
Mercury 4.96 1.99
Silver 8.14 3.37
Zinc 28.98 12.11
Manganese 13.50 5.76
(7) Subpart G - Silver Peroxide Cathodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 2.09 0.87
Mercury 1.19 0.48
Silver 1.95 0.81
Zinc 6.95 2.90
Manganese 3.24 1.38
56
-------
(8) Subpart G - Nickel Impregnated Cathodes - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Chromium 88.0 36.0
Mercury 50.0 20.0
Nickel 384.0 254.0
Silver 82.0 34.0
Zinc 292.0 122.0
Manganese 136.0 58.0
(9) Subpart G - Miscellaneous Wastewater Streams - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.57 0.23
Cyanide 0.38 0.16
Mercury 0.32 0.13
Nickel 2.48 1.64
Silver 0.53 0.22
Zinc 1.88 0.79
Manganese 0.88 0.37
57
-------
(10) Subpart G - Silver Etch - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day -monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 3.27 1.34
Mercury 1.86 0.74
Silver 3.05 1.26
Zinc 10.86 4.54
Manganese 5.06 2.16
(11) Subpart G - Silver Peroxide Production - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Chromium 3.48 1.42
Mercury 1 .98 0.79
Silver 3.24 1.34
Zinc 11.55 4.83
Manganese 5.38 2.29
58
-------
(12) Subpart G - Silver Powder Production - PSES
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Chromium 1.41 0.58
Mercury 0.80 0.32
Silver 1.32 0.55
Zinc 4.69 1.96
Manganese 2.18 0.93
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operation other
than those battery manufacturing operations listed above.
6. The following pretreatment standards are promulgated for
new sources.
A. Subcategory A - Cadmium
(1) Subpart A - Electrodeposited Anodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 7.03 2.81
Nickel 19.33 13.01
Zinc 35.85 14.76
Cobalt 4.92 2.46
59
-------
(2) Subpart A - Impregnated Anodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
Cadmium 40.0 16.0
Nickel 110.0 74.0
Zinc 204.0 84.0
Cobalt 28.0 14.0
(3) Subpart A - Nickel Electrodeposited Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium 6.60 2.64
Nickel 18.15 12.21
Zinc 33.66 13.86
Cobalt 4.62 2.31
(4) Subpart A - Nickel Impregnated Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Cadmium 40.0 16.0
Nickel 110.0 74.0
Zinc 204.0 84.0
Cobalt 28.0 14.0
60
-------
(5) Subpart A - Miscellaneous Wastewater Streams -PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property _ any one day _ monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Cadmium 0.47 0.19
Nickel 1.28 0.86
Zinc 2.38 0.98
Cobalt 0.33 0.16
(6) Subpart A - Cadmium Powder Production - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
Cadmium 1.31 0.53
Nickel 3.61 2.43
Zinc 6.70 2.76
Cobalt 0.92 0.46
(7) Subpart A - Silver Powder Production - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Cadmium 0.64 0.26
Nickel 1.77 1.19
Silver 0.93 0.39
Zinc 3.27 1.35
Cobalt 0.45 0.22
61
-------
(8) Subpart A - Cadmium Hydroxide Production - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly aver age
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
Cadmium 0.028 0.011
Nickel 0.077 0.051
Zinc 0.142 0.058
Cobalt 0.019 0.009
(9) Subpart A - Nickel Hydroxide Production - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
Cadmium 3.30 1.32
Nickel 9.08 6.11
Zinc 16.83 6.93
Cobalt 2,31 1.16
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operations other than
those battery manufacturing operations listed above.
B. Subcategory B - Calcium
There shall be no discharge of wastewater pollutant from any
battery manufacturing operations.
C. Subcategory C - Lead
(See Battery Manufacturing Document-Volume II)
62
-------
D. Subcategory D - Leclanche
(1) Subpart D - Foliar Battery Miscellaneous Wash - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Mercury 0.010 0.004
Zinc 0.067 0.030
Manganese 0.019 0.015
There shall be no discharge allowance for process wastewater
pollutants from any battery manufacturing operations other than
those battery manufacturing operations listed above.
E. Subcategory E - Lithium
(1) Subpart E - Lead Iodide Cathodes - PSNS
<
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
Chromium 23.34 9.46
Lead 17.66 8.20
•v
(2) Subpart E - Iron Disulfide Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib of iron disulfide
Chromium 2.79 1.13
Lead 2.11 0.98
63
-------
(3) Subpart E - Miscellaneous Wastewater Streams - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.039 0.016
Lead 0.030 0.014
There shall be no discharge allowance for process wastewater
pollutants from any bettery manufacturing operations other than
those battery manufacturing operations listed above.
F. Subcategory F - Magnesium
(1) Subpart F - Silver Chloride Cathodes - Chemically
Reduced - PSNS
«
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Lead 22.93 10.65
Silver 23.75 9.83
(2) Subpart F - Silver Chloride Cathode - Electrolytic - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Lead 40.6 18.9
Silver 42.1 17.4
64
-------
(3) Subpart F - Cell Testing - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000/000 Ib of cells produced
Lead 19.5 7.89
Silver 15.3 6.31
(4) Subpart F - Floor and Equipment Wash - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Lead 0.026 0.012
Silver 0.027 0.011
There shall be no discharge allowance for process wastewater
pollutants from any bettery manufacturing operations other than
those battery manufacturing operations listed above.
65
-------
G. Subcategory G - Zinc
(1) Subpart G - Zinc Oxide Formed Anodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Chromium 4.55 1,97
Mercury 2.82 1.19
Silver 4.55 1.97
Zinc 0.87 0.39
Manganese 6.50 4.98
(2) Subpart G - Electrodeposited Anodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Chromium 45.09 19.54
Mercury 27.91 11.81
Silver 45.09 19.54
Zinc 8.59 3.86
Manganese 64.41 49.38
66
-------
(3) Subpart G - Silver Powder Formed Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 6.24 2.70
Mercury 3.86 1.63
Silver 6.24 2.70
Zinc 1.19 0,53
Manganese 8.91 6.83
(4) Subpart G - Silver Oxide Powder Formed Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 4.17 1.81
Mercury 2.58 1.09
Silver 4.17 1.81
Zinc 0.79 0.36
Manganese 5.96 4.57
(5) Subpart G - Silver Peroxide Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day month 1y average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Chromium 1.00 0.43
Mercury 0.62 0.26
Silver 1.00 0.43
Zinc 0.19 0.09
Manganese 1.43 1.09
67
-------
(6) Subpart G - Nickel Impregnated Cathodes - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Chromium 42.0 18.2
Mercury 26.0 11.0
Nickel 42.0 18.2
Silver 42.0 18.2
Zinc 8.0 3.6
Manganese 60.0 46.0
(7) Subpart G - Miscellaneous Wastewater Streams - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.27 0.12
Cyanide 0.039 0.016
Mercury 0.17 0.07
Nickel 0.27 0.12
Silver 0,27 0.12
Zinc 0.05 0.02
Manganese 0.39 0.30
68
-------
(8) Subpart G - Silver Etch - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthiy average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
/
Chromium 1 .56 0.68
Mercury 0.97 0.41
Silver 1.56 0.68
Zinc 0.30 0.13
Manganese 2.23 1.71
(9) Subpart G - Silver Peroxide Production - PSNS
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver peroxide produced
Chromium 1.66 0.72
Mercury 1 .03 0.44
Silver 1.66 0.72
Zinc 0.32 0.14
Manganese 2.37 1.82
69
-------
(10) Subpart G - Silver Powder Production - PSNS
Pollutant or
Pollutant "Maximum for Maximum for
Property / monthly average
Metric Units - rag/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Chromium 0.67 0.29
Mercury 0.42 0.18
Silver • 0.67 0.29
Zinc 0.13 0.06
Manganese 0.96 0.74
There shall be no discharge allowance for process wastewater
pollutants from-any bettery manufacturing operations other than
those battery manufacturing operations listed above.
7. Effluent limitations based on the best conventional
pollutant control technology are reserved at this time.
70
-------
SECTION III
INTRODUCTION
This section provides an overview of the legal background of the
Clean Water Act, and of the technical background of the battery
category. Volumes I and II include general information for the
entire category in this section. Volume I also includes a brief
technical description of the cadmium, calcium, Leclanche,
lithium, magnesium and zinc subcategories, whereas only the lead
subcategory is discussed in Volume II.
LEGAL AUTHORITY
This report is a technical background document prepared to
support effluent limitations and standards under authority of
Sections 301, 304, 306, 307, 308, and 501 of the Clean Water Act
(Federal Water Pollution Control Act, as Amended, (the Clean
Water Act or the Act). These effluent limitations and standards
are in partial fulfillment of the Settlement Agreement in Natural
Resources Defense Council, Inc. v. Train, 8 ERC 2120 (D.D.C.
1976), modified 12 ERC 1833 (D.D.C. 1979), modified by orders
dated October 26, 1982, August 2, 1983 and January 6, 1984. This
document also fulfills the requirements of sections 304(b) and
(c) of the Act. These sections require the Administrator, after
consultation with appropriate Federal and State Agencies and
other interested persons, to issue information on the processes,
procedures, or operating methods which result in the elimination
or reduction of the discharge of pollutants through the
application of.the best practicable control technology currently
available, the best available technology economically achievable,
and through the implementation of standards of performance under
Section 306 of the Act (New Source Performance Standards).
Background
The Clean Water Act
The Federal Water Pollution Control Act Amendments of 1972
established a comprehensive program to restore and maintain the
chemical, physical, and biological integrity of the Nation's
waters. By July 1, 1977, existing industrial dischargers were
required to achieve effluent limitations requiring the
application of the best practicable control technology currently
available (BPT), Section 301(b)(1)(A); and by July 1, 1983, these
dischargers were required to achieve effluent limitations
requiring the application of the best available technology
economically achievable which will result in reasonable
further progress toward the national goal of eliminating the
71
-------
discharge of all pollutants (BAT), Section 301(b)(2)(A). New
industrial direct dischargers were required to comply with
Section 306 new source performance standards (NSPS), based on
best available demonstrated technology; and new and existing
sources which introduce pollutants into publicly owned treatment
works (POTW) were subject to pretreatment standards under
Sections 307(b) and (c) of the Act. While the requirements for
direct dischargers were to be incorporated into National
Pollutant Discharge Elimination System (NPDES) permits issued
under Section 402 of the Act, pretreatment standards were made
enforceable directly against any owner or operator of any source
which introduces pollutants into POTW (indirect dischargers).
Although section 402(a)(1) 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 3Q4(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 Councilt
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
72
-------
"toxic" pollutants, including the 65 "priority" pollutants and
classes of pollutants which Congress declared "toxic" under
Section 307(a) of the Act. Likewise, EPA's programs for new
source performance standards and pretreatment standards are now
aimed principally at toxic pollutant controls. Moreover, to
strengthen the toxics control program, Section 304(e) of the Act
authorizes the Administrator to prescribe best management
practices (BMPs) to prevent the release of toxic and hazardous
pollutants from plant site runoff, spillage or leaks, sludge or
waste disposal, and drainage from raw material storage associated
with, or ancillary to, the manufacturing or treatment process.
In keeping with its emphasis on toxic pollutants, the Clean Water
Act of 1977 also revises the control program for nontoxic
pollutants. Instead of BAT for conventional pollutants
identified under Section 304(a)(4) (including biochemical oxygen
demand, suspended solids, fecal coliform and pH), the new Section
301(b)(2)(E) requires achievement by July 1, 1984, of effluent
limitations requiring the application of the best conventional
pollutant control technology (BCT). The factors considered in
assessing BCT for an industry include the costs of attaining a
reduction in effluents and the effluent reduction benefits
derived compared to the costs and effluent reduction benefits
from the discharge of publicly owned treatment works (Section
304(b)(4)(B). The cost methodology for BCT has not been
promulgated and BCT is presently deferred. For nontoxic,
nonconventional pollutants, Sections 301(b)(2)(A) and (b)(2)(F)
require achievement of BAT effluent limitations within three
years after their establishment or July 1, 1984, whichever is
later, but not later than July 1, 1987.
GUIDELINE DEVELOPMENT SUMMARY
The effluent guidelines for battery manufacturing were developed
from data obtained from previous EPA studies, literature sear-
ches, and a plant survey and evaluation. Initially, information
from EPA records was collected and a literature search was
conducted. This information was then catalogued in the form of
individual plant summaries describing processes performed,
production rates, raw materials utilized, wastewater treatment
practices, water uses and wastewater characteristics.
In addition 'to providing a quantitative description of the
battery manufacturing category, this information was used to
determine if the characteristics of the category as a whole were
uniform and thus amenable to one set of effluent limitations and
standards. Since the characteristics of the plants in the data
base and the wastewater generation and discharge varied widely,
the establishment of subcategories was determined to be
73
-------
necessary. The initial subcategorization was made by using
recognized battery type as the subcategory description:
Lead Acid . Carbon-Zinc (Air)
Nickel-Cadmium (Wet Process) . Silver Oxide-Zinc
Nickel-Cadmium (Dry Process) . Magnesium Cell
Carbon-Zinc (Paper) . Nickel-Zinc
Carbon-Zinc (Paste) . Lithium Cell
Mercury (Ruben) . Mercury (Weston)
Alkaline-Manganese . Lead Acid Reserve
Magnesium-Carbon . Miniature Alkaline
To supplement existing data, EPA sent a data collection portfolio
(dcp) under authority of Section 308 of the Federal Water
Pollution Control Act, as amended, to each known battery
manufacturing company. In addition to existing and plant
supplied information (via dcp), data were obtained through a
sampling program conducted at selected sites. Sampling consisted
of a screening program at one plant for each listed battery type
plus verification at up to 5 plants for each type. Screen
sampling was used to select pollutant parameters for analysis in
the second or verification phase of the program. The designated
priority pollutants (65 toxic pollutants) and typical battery
manufacturing pollutants formed the basic list for screening.
Verification sampling and analysis was conducted to determine the
source and quantity of the selected pollutant parameters in each
subcategory.
Conventional nomenclature of batteries provided little aid in
development of effluent limitations and standards. SIC groupings
are inadequate because they are based on the end use of the
product, not composition of the product, or manufacturing
processes. Based on the information provided by the literature,
dcp, and the sampling program, the initial approach to
subcategorization using battery type was reviewed. Of the
initial 16 battery types no production of mercury (Weston) cells
was found. The miniature alkaline type was dropped because it is
not a specific battery type but merely a size distinction invol-
ving several battery types (e.g., alkaline-manganese, silver
oxide-zinc, and mercury-zinc (Ruben)). In addition to the
original battery types, the dcp disclosed seven additional
battery types (silver chloride-zinc, silver oxide-cadmium,
mercury-cadmium, mercury and silver-zinc, mercury and cadmium-
zinc, thermal, and nuclear). Nuclear batteries, however, have
not been manufactured since 1978. Since they constitute a
distinct subcategory, they have been included in the
subcategorization discussion, but are not otherwise considered in
battery documents. Mercury and silver-zinc batteries have not
been manufactured since 1977, but do not constitute a single
subcategory and therefore will be discussed where appropriate.
74
-------
The other five additional battery types are considered in the
battery documents.
An analysis of production methods, battery structure and electro-
lytic couple variations for each battery type revealed that there
are theoretically about 600 distinct variations that could
require further subgrouping. Based on dcp responses and plant
visits, over 200 distinct variations have been positively
identified. Because of the large number of potential subgroup-
ings associated with subcategorization by battery type, a
subcategorization basis characterizing these variations was
sought. Grouping by anode material accomplishes this objective
and provides the following subcategories:
Anode Material Designation for Battery Documents*
Cadmium Anode Cadmium
Calcium Anode Calcium
Lead Anode Lead
Zinc Anode, Acid Electrolyte Leclanche
Lithium Anode Lithium
Magnesium Anode Magnesium
Zinc Anode, Alkaline Electrolyte Zinc
Radioisotopes Nuclear
*A11 subcategories except for lead are discussed in detail in
Volume I and the lead subcategory is discussed in Volume II.
As discussed fully in Section IV, the zinc anode is divided into
two groups based on electrolyte type because of substantial
differences in manufacture and wastes generated by the two
groups. As detailed in Sections IV and V, further segmentation
using a matrix approach is necessary to fully detail each
subcategory. Specific manufacturing process elements requiring
control for each subcategory are presented in Section IV followed
by a detailed technical discussion in Section V.
After establishing subcategorization, the available data were
analyzed to determine wastewater generation and mass discharge
rates in terms of production for each subcategory. In addition
to evaluating pollutant generation and discharges, the full range
of control and treatment technologies existing within the battery
manufacturing category was identified. This was done considering
the pollutants to be treated and the chemical, physical, and
biological characteristics of these pollutants. Special
attention was paid to in-process technologies such as the
recovery and reuse of process solutions, the recycle of process
water, and the curtailment of water use.
75
-------
The information as outlined above was then evaluated in order to
determine what levels of technology were appropriate as a basis
for effluent limitations for existing sources based on the best
practicable control technology currently available (BPT) and best
available technology economically achievable (BAT). ' Levels of
technology appropriate for pretreatment of wastewater introduced
into a publicly owned treatment works (POTW) 'from both new and
existing sources were also identified as were the new source
performance standards (NSPS) based on best demonstrated control
technology, processes, operating methods) or other alternatives
(BDT) for the control of direct discharges from new sources.
Sources of Industry Data
Data on battery manufacturing were gathered fromJ literature
studies, previous industry studies by the Agency, plant surveys
and evaluations, and inquiries to waste treatment equipment
manufacturers. These data sources are discussed below.
Literature Study - Published literature in the form of books,
reports, papers, periodicals, and promotional materials was
examined. The most informative sources are listed in Section XV.
The material research covered battery chemistry, the man-
ufacturing processes utilized in producing each battery type,
waste treatment technology, and the specific market for each
battery type.
EPA Studies - A previous preliminary and unpublished EPA study of
the battery manufacturing segment was reviewed. The information
included a summary of the industry describing: the manufacturing
processes for each battery type; the waste characteristics
associated with this manufacture; recommended pollutant
parameters requiring control; applicable end-of-pipe treatment
technologies for wastewaters from the manufacture of each battery
type; effluent' characteristics resulting from this treatment; and
a background bibliography. Also included in these data were
detailed production and sampling information on approximately 20
manufacturing plants.
Plant Survey and Evaluation - The initial collection of data
pertaining to facilities that manufacture batteries was a two-
phased operation. First, a mail survey was conducted by EPA. A
dcp was mailed to each company in the country known or believed
to manufacture batteries. This dcp included sections for general
plant data, specific production process data, waste management
process data, raw and treated wastewater data, waste treatment
cost information, and priority pollutant information based on
1976 production records. A total of 226 dcp were mailed. From
this survey, it was determined that 133 companies were battery
manufacturers, including full line manufacturers and assemblers.
76
-------
Of the remaining 93 data requests that were mailed, 9 companies
were no longer manufacturing batteries, 15 were returned as
undeliverable, and 69 companies were in other business areas.
For clarification, the following terminology is used throughout
the battery manufacturing documents. Battery manufacturing sites
are physical locations where battery manufacturing processes
occur. Battery plants are locations where subcategory-specific
battery manufacturing processes occur. Battery facilities are
locations where final battery type products or their components
are produced and is primarily used for economic analysis of the
category. In the survey, some plants responded with 1977 or 1978
data, and some provided 1976 data although production has
subsequently ceased. Table III-l (page 108) summarizes the
survey responses received in terms of number of plants that
provided information in each subcategory. Another column was
added to include information obtained in the survey, by phone or
by actual plant visit, that a plant was no longer active in a
subcategory. The total number of plant responses is larger than
the 133 company responses, since many companies own more than one
plant and information was requested on each site owned or
operated by the company. Also, some sites manufacture batteries
in more than one subcategory; four are active in three
subcategories and nine are active in two subcategories. Due to
changes in ownership and changes in production lines, the number
of companies and the number of plants and sites active in the
category often vary. The result is that about 230 sites are
currently included in this category. All information received
was reviewed and evaluated, and will be discussed as appropriate
in subsequent sections.
The second phase of the data collection effort included visiting
selected plants, for screening and verification sampling of
wastewaters from battery manufacturing operations. The dcp
served as the major source in the selection of plants for
visitation and sampling. Specific criteria used for site
selection included:
1. Distributing visits according to the type of battery manu-
factured.
2. Distributing visits among various manufacturers of each bat-
tery type.
3. Selecting plants whose production processes .were .represen-
tative of the processes performed at many plants for each
subcategory. Consideration was also given to the under-
standing of unique processes or treatment not universally
practiced but applicable to the industry in general.
77
-------
4. A plant's knowledge of its production processes and waste
treatment system as indicated in the dcp.
5. The presence of wastewater treatment or water conservation
practices.
Prior to proposal 48 plants were visited and a wastewater
sampling program was conducted at twenty-four of these plants.
The sampling program at each plant consisted of two activities:
first, the collection of technical information, and second, water
sampling and analysis. The technical information gathering
effort centered around a review and completion of the dcp to
obtain historical data as well as specific information pertinent
to the time of the sampling. In addition to this, the following
specific technical areas were covered during these visits.
1. Water use for each process step and waste constituents.
2. Water conservation techniques.
3. In-process waste treatment and control technologies.
4. Overall performance of the waste treatment system and future
plans or changes anticipated.
5. Particular pollutant parameters which plant personnel
thought would be found in the waste stream.
6. Any problems or situations peculiar to the plant being
visited.
All of the samples collected were kept on ice throughout each day
of sampling. At the end of each day, samples were preserved
according to EPA protocol and sent to laboratories for analysis
per EPA protocol. Details of this analysis and of the overall
sampling program results are described in Section V of this
document.
After proposal, EPA made a second intensive study of lead battery
manufacturing (lead subcategory) and foliar battery manufacturing
(Leclanche subcategory). Seventeen additional lead plants were
visited and five were sampled. One foliar plant was also
visited. Plant supplied data from 65 lead plants was updated
using an industry survey form. This additional data is reported
in Section V (Volume I for the Leclanche subcategory and Volume
II for the lead subcategory).
Waste Treatment Equipment Manufacturers - Various manufacturers
of waste treatment equipment were contacted by phone or visited
78
-------
to determine cost and performance data on specific technologies.
Information collected was based both on manufacturers' research
and on in-situ operation at plants that were often not battery
manufacturers but had similar wastewater characteristics
(primarily toxic metal wastes).
Utilization of Industry Data
Data collected from the previously described sources are used
throughout this report in the development of a base for BPT and
BAT limitations, and NSPS and pretreatment standards. Previous
EPA studies and information in the literature provided the basis
for the initial battery subcategorization discussed in Section
IV. This subcategorization was further refined to an anode
grouping basis as the result of information obtained from the
plant survey and evaluation. Raw wastewater characteristics for
each subcategory presented in Section V were obtained from
screening and verification sampling because raw waste information
from other sources was so fragmented and incomplete that it was
unusable. Selection of pollutant parameters for control {Section
VI) was based On both dcp responses and plant sampling. .These
provided information on both the pollutants which plant personnel
felt would be in their wastewater discharges and those pollutants
specifically found in battery manufacturing wastewaters as the
result of sampling. Based on the selection of pollutants
requiring control and their levels, applicable treatment
technologies were identified and then studied and discussed in
Section VII of this document. Actual waste treatment
technologies utilized by battery plants (as identified in dcp and
seen on plant visits) were also used to identify applicable
treatment technologies. The cost of treatment (both individual
technologies and systems) based primarily on data from equipment
manufacturers is contained in Section VIII of this document.
Finally, dcp data and sampling data are utilized in Sections IX,
X, XI, XII, and XIII (BPT, BAT, NSPS, Pretreatment, and BCT, res-
pectively) for the selection of applicable treatment systems and
the presentation of achievable effluent levels and actual
effluent levels obtained for each battery subcategory discussed
in the two volumes.
INDUSTRY DESCRIPTION
Background
The industry covered by this document makes modular electric
power sources where part or all of the fuel is contained within
the unit. Electric power is generated directly from a chemical
reaction rather than indirectly through a heat cycle engine.
Batteries using a radioa.ctive decay source where a chemical
reaction is part of the operating system were considered.
79
-------
Historical - Electrochemical batteries and cells were assembled
by Alessandro Volta as early as 1798. His work establishing the
relationship between chemical and electrical energy came 12 years
after the discovery of the galvanic cell by Galvani, and 2000
years after the use of devices in the Middle East, which from
archeological evidence, appear to be galvanic cells. Volta used
silver and zinc electrodes in salt water for his cells. Soon
after Volta's experiments, Davy, and then Faraday, used galvanic
cells to carry out electrolysis studies. In 1836 Daniell
invented the cell which now bears his name. He used a copper
cathode in copper sulfate solution separated by a porous cup from
a solution of zinc sulfate in dilute sulfuric acid which
contained the amalgamated zinc anode. In 1860, Plante presented
to the French Academy of Sciences the lead acid storage battery
he had developed, and in 1868 Leclanche developed the forerunner
of the modern dry cell. Leclanche used an amalgamated zinc anode
and a carbon cathode surrounded by manganese dioxide and immersed
both in an ammonium chloride solution. The portable dry cell was
developed in the late 1880s by Gassner who prepared a paste
electrolyte of zinc oxide, ammonium chloride and water in a zinc
can, inserted the carbon rod and manganese dioxide, then sealed
the top with " plaster of Paris. The cell was produced
commercially. Several other acid-electrolyte cells using
amalgamated zinc anodes and carbon or platinum cathodes saw
limited use prior to 1900.
Lalande and Chaperon developed a caustic soda primary battery
about 1880 which was used extensively for railroad signal
service. Amalgamated zinc anodes and cupric oxide cathodes were
immersed in a solution of sodium hydroxide. A layer of oil on
the surface of the electrolyte prevented evaporation of water,
and the formation of solid sodium carbonate by reaction of carbon
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 manufactured today, a large volume of. research is being
directed toward making it a workable automotive power source.
The system consists of iron anodes, potassium hydroxide
electrolyte, and nickel hydroxide cathodes. The iron powder was
packed in flat "pockets" of nickel-plated steel strips. The
nickel hydroxide, with layers of nickel flakes to improve
conductivity, was packed in tubes of nickel-plated steel strips.
The batteries were rugged and could withstand more extensive
charge-discharge cycling than lead acid storage batteries. Their
greater cost kept them from replacing lead acid batteries.
Another cell only recently displaced from the commercial market
is the Weston cell. For decades the Weston cell, consisting of
80
-------
an amalgamated cadmium anode and a mercurous sulfate cathode in a
cadmium sulfate solution, was used as a voltage reference
standard in industrial instruments. Introduction of new solid
state devices and circuits has displaced the Weston cell from
most of its former industrial applications, and it is no longer
commercially available.
New battery systems are introduced even today. In the past
decade implantable lithium batteries have been developed for
heart pacemakers, tens of thousands of which are in use. Huge
development programs have been funded for electric powered
automobiles. The liquid sodium-liquid sulfur system is one of
the new "exotic" systems being studied. Advancing technology of
materials coupled with new applications requirements will result
in development of even newer systems as well as the redevelopment
of older systems for new applications. Figure III-l (page 114),
graphically illustrates the amplitude of systems in use or under
development in 1975 for rechargeable batteries. This plot of
theoretical specific energy versus equivalent weight of reactants
clearly shows the reason for present intensive developmental
efforts on lithium and sodium batteries, and the Edison battery
(Fe/NiOOH) and the zinc-nickel oxide battery.
Battery Definitions and Terminology - Batteries are named by
various systems. Classification systems include end-use, size,
shape, anode-cathode couple, inventor's name, electrolyte type,
and usage mode. Thus a flashlight battery (end-use), might also
be properly referred to as a D-Cell (size), a cylindrical cell
(shape), a zinc-manganese dioxide cell (anode-cathode couple), a
Leclanche cell (inventor), an acid cell (electrolyte type), and a
primary cell (usage mode), depending on the context. In the
strictest sense, a cell contains only one anode-cathode pair,
whereas a battery is an assemblage of cells connected in series
to produce a greater voltage, or in parallel to produce a greater
current. Common usage has blurred the distinction between these
terms, and frequently the term battery is applied to any finished
entity sold as a single unit, whether it contains one cell, as do
most flashlight batteries, or several cells, as do automobile
batteries. In these documents the marketed end product is
usually referred to as a battery. Manufacturing flow charts and
construction diagrams reveal the actual assembly details.
In the battery documents, the terms "battery" and "cell" are used
only for self-contained galvanic devices, i.e., those devices
which convert chemical energy to electrical energy and which do
not require a separate chemical reservoir for operation of the
device. Cells where one of the reacting materials is oxygen
supplied by the atmosphere in which the cell operates are
included as well as cells which contain all of the reacting
chemicals as part of the device. In some literature, reference
81
-------
is made to electrolysis cells or batteries of electrolysis cells.
Those devices are for chemical production or metal winning and
are not covet eel by this discussion. Fuel cells, although
functioning as galvanic devices, must be supplied with the
chemical energy from an external source, and are not considered
in this document.
The essential parts of an electrochemical cell designed as a
portable source of electrical power are the same regardless of
the size of the unit. From the smallest cell used in a watch to
the massive storage batteries used in telephone branch exchanges
there is an anode, sometimes called the negative plate, a
cathode/ also called the positive plate, and electrolyte. The
anode and cathode are referred to by the general term electrodes.
One or both electrodes consist of a support or grid which serves
as a mechancial support and 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, 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
82
-------
battery the operating voltage must be substantially less than the
open-circuit or no-load voltage. A power curve is sometimes used
to characterize battery performance under load, but because the
active materials are being consumed, the power curve will change
with time. Because batteries are self-contained power supplies,
additional ratings of specific energy and energy density must be
specified. These are commonly measured in units of
watthours per pound and watthours per cubic foot, respectively.
These latter measures characterize the total energy available
from the battery under specified operating conditions and allow
comparison of the ability of different battery systems to meet
the requirements of a given application. Figure III-2 (page 115)
illustrates how these measures of performance are used to compare
battery systems with each other and with alternative power
sources.
The suitability of a battery for a given application is
determined not only by its voltage and current characteristics,
and the available power and energy. In many applications,
storage characteristics and the length of time during which a
battery may be operational are also important. The temperature
dependence of battery performance is also important for some
applications. Storage characteristics of batteries are measured
by shelf-life and by self-discharge, the rate at which the
available stored energy decreases over time. Self-discharge is
generally measured in percent per unit time and is usually
dependent on temperature. In some battery types, self-discharge
differs during storage and r.se 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 be useful however, in considering groups for
which the general purpose and primary performance requirements
are similar. Such groups are shown in Table III-2 (page 110).
The requirements for a flashlight battery are: low cost, long
shelf life, suitability for intermittent use, and moderate
operating life. The household user expects to purchase
replacement cells at low cost after a reasonable operating life,
but does expect long periods before use or between uses.
An automobile battery must be rechargeable, produce large
currents to start an engine, operate both on charge and discharge
over a wide temperature range, have long life, and be relatively
83
-------
inexpensive when replacement is necessary. The user looks for
high power density, rechargeability, and low cost.
Standby lighting, and life raft emergency radio beacons represent
two similar applications. For standby lighting power in
stairways and halls, the battery is usually a storage battery
maintained in a constant state of readiness by the electrical
power system and is activated by failure of that primary system.
Such a battery system can be activated and then restored to its
original state many times and hence can be more expensive and can
have complex associated equipment. Weight is no problem, but
reliable immediate response, high energy density and power
density are important. The emergency radio beacon in a life raft
is required to be 100 percent reliable after storage of up to
several years. It will not be tested before use, and when
activated will be expected to operate continuously until
completely discharged. Light weight may be important. Instan-
taneous response is not a requirement although a short time for
activation is expected.
Remote location operation such as arctic meteorological stations
and orbiting spacecraft requires very high reliability and long
operating life. Cost is usually of no consequence because the
overall cost of launching a satellite or travel to a remote
location overshadows any possible battery cost. Rechargeability
is required because solar cells (solid state devices producing
small electrical power levels directly from solar illumination)
can be used to recharge the batteries during sunlight periods to
replace the energy used in brief periods of high power demand for
transmissions or satellite equipment operation. High power
density for meteorological stations and high specific power for
satellites is therefore more important than high energy density
or high specific energy because the rechargeability requirement
means energy can be replaced. Additional requirements are
reliable operation over a wider range of temperatures than is
usually experienced in temperate earth regions, and sealed
operation to prevent electrolyte loss by gassing on charge
cycles.
Voltage leveling and voltage standards are similar. Voltage
leveling is a requirement for certain telephone systems. The
batteries may be maintained in a charged state, but voltage
fluctuations must be rapidly damped and some electrochemical
systems are ideally suited to this purpose. An additional
requirement is the provision of standby power at very stable
voltages. Such operation is an electrochemical analogue of a
surge tank of a very large area, maintaining a constant liquid
head despite many rapid but relatively small inflows and
outflows. The use of batteries for secondary voltage standards
requires stability of voltage over time and under fluctuating
84
-------
loads. Though similar to the voltage leveling application, the
devices or instruments may be portable and are not connected to
another electrical system. Frequently power is supplied by one
battery type and controlled by a different battery type. Usually
cost is a secondary consideration, but not completely ignored.
For secondary voltage standards, wide temperature ranges can
usually be avoided, but a flat voltage-temperature response is
important over the temperature range of application. Power and
energy density as well as specific power and energy also become
secondary considerations in both of these applications.
Battery Function and Manufacture
The extremely varied requirements outlined above have led to the
design and production of many types of batteries. Because
battery chemistry is the first determiner of performance,
practically every known combination of electrode reactions has
been studied - at least on paper. Many of the possible electrode
combinations are in use in batteries today. Others are being
developed to better meet present or projected needs. Some have
become obsolete, as noted earlier. Short discussions on the
electrochemistry of batteries, battery construction, and battery
manufacturing are presented to help orient the reader.
Battery Chemistry - The essential function of the electrodes in a
battery is to convert chemical energy into electrical energy and
thereby to drive electrical current through an external load.
The driving force is measured in volts, and the current is
measured in amperes. The discrete charges carrying current in
the external circuit, or load, are electrons, which bear a
negative charge. The driving force is the sum of the
electromotive force, or EMF, of the half-cell reactions occurring
at the anode and the cathode. The voltage delivered by a cell is
characteristic of the overall chemical reaction in the cell. The
theoretical open-circuit (no-load) voltage of a cell or battery
can be calculated from chemical thermodynamic data developed from
nonelectrochemical experiments. The cell voltage is related to
the Gibbs free energy of the overall chemical reaction by an
equation called the Nernst equation. The variable factors are
temperature and concentration of the reactants and products.
Voltages (or more properly the EMF) of single electrode reactions
are often used in comparing anodes of cathodes of different types
of cells. These single electrode (or half-cell) voltages are
actually the voltages of complete cells in which one electrode is
the standard hydrogen electrode having an arbitrarily assigned
value of zero. In all such calculations, equilibrium conditions
are assumed.
85
-------
In this brief discussion, only the net half-cell reactions are
discussed. The very complex subject of electrode kinetics,
involving a study of exactly which ionic or solid species are
present and in what quantities, can be found in any of several
electrochemistry textbooks.
The anode supplies electrons to the external circuit - the half-
cell reaction is an oxidation. The cathode accepts electrons
from the external circuit - the reaction is a reduction. Half-
cell reactions can occur in either forward or reverse direction,
at least in theory. Some, however, cannot be reversed in a
practical cell. Tables III-3 and III-4 (page 110) show the
reactions as they are used in practical cells for delivery of
power. In those cells that are rechargeable, charging reverses
the direction of the reaction as written in the tables.
Most of the battery systems currently produced are based on
aqueous electrolytes. However, lithium and thermal batteries,
and at least one magnesium cell, have nonaqueous electrolyte.
Because lithium reacts vigorously with water, organic or non-
aqueous inorganic electrolytes are usually, but not always, used
with this very high energy anode metal. Thermal batteries are
made with the electrolyte in a solid form and are activated by
melting the electrolyte with a pyrotechnic device just prior to
use. One type of magnesium reserve cell uses a liquid ammonia
electrolyte which is injected under pressure just prior to use.
In aqueous systems, any of the anode reactions can be coupled
with any of the cathode reactions to make a working cell, as long
as the electrolytes are matched and the overall cell reaction can
be balanced at electrical neutrality. As examples:
Leclanche:
anode: Zn < > Zn+2 + 2e (acid)
cathode: 2e + 2MnO2 + 2NH4C1 + Zn+z < > MN2O3 + H2O + Zn(NH3)2Cl2(acid)
cell: Zn + 2Mn02 + 2NH4C1 < > Mn2O3 + H2O + Zn(NH3)2Cl2
Alkaline Manganese;
anode: Zn + 20H- < > Zn(OH)2 + 2e (alkaline)
cathode: e + MnO2 + H2O < > MnOOH + OH- (alkaline)
.e + MnOOH- + H20 < > Mn(OH)2 + OH- (alkaline)
cell: Zn + MnO2 + 2H2O <-—> Zn(OH)2 + Mn(OH)2
86
-------
One essential feature of an electrochemical cell is that all
conduction within the electrolyte must be ionic. In aqueous
electrolytes the conductive ion may be H+ or OH~. In some cases
metal ions carry some of the current. Any electronic conduction
between the electrodes inside the cells constitutes a short
circuit. The driving force established between the dissimilar
electrodes will be dissipated in an unusable form through an
internal short circuit. For this reason, a great amount of
engineering and design effort is applied to prevent formation of
possible electronic conduction paths and at the same time to
achieving low internal resistance to minimize heating and power
loss.
Close spacing of electrodes and porous electrode separators leads
to low internal electrolyte resistance. But if the separator
deteriorates in the chemical environment, or breaks under
mechanical shock, it may permit electrode-electrode contact
resulting in cell destruction. Likewise, in rechargeable cells,
where high rates of charging lead to rough deposits of the anode
metal, a porous separator may be penetrated by metal "trees" or
dendrites, causing a short circuit. The chemical compatibility
of separators and electrolytes is an important factor in battery
design.
Long shelf life is frequently a requirement for batteries. Shelf
life is limited both by deterioration of battery separators and
by corrosion (self-discharge) of electrodes which decreases the
available electrical energy and may also result in other types of
cell failure. As an example, corrosion of the zinc anode in
Leclanche cells may result in perforation of the anode and
leakage of the electrolyte. Compatability of the active material
of the electrodes in contact with the electrolyte to minimize
these self-discharge reactions is an electrochemical engineering
problem. Two of the approaches to this problem are outlined
here.
Some applications require only one-time use, and the electrolyte
is injected into the cell just before use, thereby avoiding long
time contact of electrode with electrolyte. The result is a
reserve battery. One reserve battery design (now abandoned) used
a solid electrolyte and the battery was constructed in two parts
which were pressed together to activate it. The parts could be
separated to deactivate the battery. Up to 25 cycles of
activation-deactivation were reported to be possible. Reserve
batteries are usually found in critical applications where high
reliability after uncertain storage time justifies the extra
expense of the device.
In other applications, long shelf life in the activated state is
required. This allows repeated intermittent use of the battery,
87
-------
but is achieved at the price of somewhat lower certainty of
operation than is provided by reserve cells. Special fabrication
methods and materials then must be used to avoid self-discharge
by corrosion of the anode. In Leclanche cells, the zinc is
protected from the acid electrolyte by amalgamating it; in some
magnesium cells a chemical reaction with the electrolyte forms a
protective film which is subsequently disrupted when current is
drained; in some lithium batteries, the very thin film formed by
chemical reaction with electrolyte conducts lithium ions at a
rate sufficiently high to be usable for power delivery. All
three types of cells require the use of specific chemicals and
special assembly techniques.
Operation of cells in the rechargeable mode places additional
constraints oh the chemical components and construction
materials. In aqueous-electrolyte cells, vented operation may be
possible, as with lead acid automotive and nickel cadmium
batteries. Or, the cells may be sealed because remote operation
prevents servicing and water replacement. Cells with liquid
organic or inorganic electrolyte also are sealed to prevent
escape of noxious vapors. Organic liquids used in cells manufac-
tured in the U. S. today include: methyl formate, acetonitrile,
methyl acetate, and dioxolane. Inorganic liquids include thionyl
chloride and ammonia.
Sealed operation of rechargable cells introduces two major
problems relating to pressure buildup that must be accommodated
by design and materials. Pressure changes normally occur during
discharge-charge cycling and must be accommodated by the battery
case and seal designs. Many applications also require cells to
accept overcharging. In nickel-cadmium cells, the oxygen or
hydrogen pressure would build to explosive levels in a short time
on overcharge. As a result, cells are designed with excess
uncharged negative material so that when the nickel electrode is
completely charged, the cadmium electrode will continue to
charge, and oxygen evolved at the nickel electrode will migrate
under pressure to the cadmium and be reduced before hydrogen
evolution occurs. A steady state is reached where continuous
overcharge produces no harmful effects from pressure and no net
change in the composition of electrodes or electrolytes. The
excess uncharged negative material ensures that hydrogen is not
evolved. Oxygen recombination is used because the alternative
reaction of hydrogen recombination at an excess uncharged
positive electrode proceeds at very low rates unless expensive
special catalysts are present.
Cell reversal is the other operational phenomenon requiring
chemical and electrochemical compensation. Cell reversal occurs
when a battery of cells is discharged to a point that one cell in
the battery has delivered all of its capacity (i.e., the active
88
-------
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 than ambient
temperature. For some high-power drain applications such as
prime mover power plants and central station power, it is
feasable to build a high-temperature system to take advantage of
the improved electrode kinetics and reduced electrolyte
resistance. Of course the kinetics of corrosion processes are
also enhanced, so additional materials problems must be overcome.
For the majority of cells that must be operated at a temperature
determined by the environment, the only practical way to achieve
greater power outputs is to increase the active surface area of
the electrodes. The usual approach to increasing surface area is
to subdivide the electrode material. Powdered or granular active
material is formed into an electrode with or without a structural
support. The latter may also function, as a current collector.
The limitation to increasing the surface area is the fact that a
mass of finely divided active material immersed in electrolyte
will tend to lose surface area with time, a phenomenon similar to
Ostwald ripening of silver halide photograph emulsion. The
89
-------
smaller particles, which provide the large surface area, dissolve
in the electrolyte, and the larger particles grow even larger.
The nature of the electrolyte and active mass is the main
determinant of the extent of this phenomenon.
A further limitation to the power drain available from porous
electrodes results from a phenomenon called concentration
polarization. Total ampere-hours available are not affected by
this process, but the energy delivered is limited. In a thick
porous body such as a tube or pocket type electrode, the
electrolyte within the narrow, deep pores of the electrode can
become overloaded with ionic products of electrode reaction or
depleated of ions required for electrode reaction. For instance,
at the negative plate of a lead-acid battery, sulfate ions are
required for the reaction:
Pb + S04 < > PbS04 + 2e
When an automotive battery is fully charged the concentration of
sulfuric acid, hence sulfate ions, is very high. Large currents
can be sustained for sufficient time to crank a cold engine until
it starts. However, when the battery is "low" (i.e. the sulfate
ion concentration throughout the battery is low) sufficient
sulfate ions are initially present in the pores of the negative
plate to sustain the negative plate reaction for a brief period
of cranking the engine, then the sulfate is so drastically
depleted that the cranking current cannot be sustained. If the
battery is allowed to "rest" a few minutes, the rather slow
process of diffusion will replenish sulfate ions in the interior
of the pores and in effect return to effective use that "deep"
surface area. The battery appears to come to "life" again.
Cranking currents will again deplete the supply of ions and the
battery is "dead." If a "light" load, such as a radio is placed
on the nearly "dead" battery the diffusion process may be able to
supply sufficient ions on a continuing basis so that the battery
appears to be functioning normally.
The above example is familiar to many people. Similar phenomena
occur in any battery with porous electrodes. In some primary
batteries the discharge products may increase in concentration to
a point of insolubility and permanently block off active material
surface. Thus a battery may deliver significantly fewer
ampere-hours to a predetermined cut-off voltage when used at the
C/2 ampere rate than, at the C/20 ampere rate where C is the
theoretical ampere-hour capacity of the battery and the numerical
denominator is in hours.
Concentration polarization also limits the rate at which
rechargeable batteries can be charged. Use of higher charging
voltages to shorten the recharge time can result in gassing
90
-------
(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 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 II1-12 (pages 116-125) are drawings or cutaway views of
these 10 batteries. Figures 111-13 through 111-20 (pages 126-
133) 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
91
-------
them active. As noted earlier, anodes are metals when they are
in their final or fully charged form in a battery. Some anodes
such as lithium anodes, and zinc anodes for some Leclanche cells,
are made directly by cutting and drawing or stamping the pure
metal sheet. Lithium, because of its flexibility, is either
alloyed with a metal such as aluminum, or is attached to a grid
of nickel or other rigid metal. Drawn sheet zinc anodes are
rigid enough to serve as a cell container.
Zinc anodes for some alkaline-manganese batteries are made from a
mixture of zinc powder, mercury, and potassium hydroxide. Zinc
is amalgamated to prevent hydrogen evolution and thus, corrosion
at the anode.
Anodes for most lead-acid batteries and some nickel-cadmium cells
are prepared from a paste of a compound of the anode metal (lead
oxides or cadmium hydroxide, respectively). Additives may be
mixed in, and then the paste is applied to a support structure
and cured.
The techniques for preparing the compounds of the anode metal may
be unique to the battery manufacturing process. For pocket-type
nickel cadmium batteries, cadmium metal is oxidized in a high
temperature air stream, then hydrated to cadmium hydroxide.
Graphite, to increase conductivity, and iron oxide, to keep the
cadmium in a porous state during cycling, may be mixed into the
cadmium hydroxide.
Organic expanders, lampblack, and barium sulfate are added to the
paste mixture for lead-acid battery anodes. The expanders
maintain the lead in a porous state during charge-discharge
cycling. The organic expanders coat the lead particles,
preventing agglomeration. Barium sulfate holds the lead grains
apart. Lampblack aids in the formation step.
In addition to physically applying the active material to the
support structure as a metal or compound, some anode active
materials are prepared from soluble metal compounds. High-rate
nickel-cadmium battery anodes are prepared by impregnating a
porous nickel plaque with a solution of cadmium nitrate. The
plaque is transferred to an alkali solution or is made the
cathode of an electrolysis cell. Either technique precipitates
the cadmium as the hydroxide which is subsequently converted to
metallic cadmium in the forming step.
To sum up, the active mass for anodes is usually prepared as the
massive metal, finely divided metal, finely divided metal
compound, or as a soluble salt of the metal which is precipitated
onto a carrier or support structure. In most batteries, there is
an additional support structure, such as the paste for the
92
-------
negative active mass of a lead-acid battery which is pressed into
a grid of lead or a lead alloy. Different types of nickel-
cadmium batteries exemplify three approaches to fabrication of
anodes. As noted above, the cadmium for pocket type anodes is
admixed with other materials then loaded into the pockets of a
perforated nickel or steel sheet. The method of precipitating an
insoluble cadmium compound from a solution of a soluble cadmium
salt in the pores of a porous powder metallurgical nickel plaque
was also described above. For some cells, highly porous cadmium
powder is mixed with cadmium compounds and pasted onto a support
structure. Chemical production of anode active materials which
are specifically used for batteries, is considered part of
battery manufacturing. This process is usually considered as an
ancillary operation.
The final step in anode preparation for many types of batteries
is formation, or charging, of the active mass. The term
"formation" was first used to describe the process by which
Plante plates were prepared for lead-acid batteries. In that
process, lead sheet or another form of pure lead was placed in
sulfuric acid and made anodic, generating a surface layer of lead
sulfate, then cathodic, reducing that layer to lead which
remained in the finely divided state. Repeated cycling generated
a deep layer of finely divided lead for the anodes. Few lead-
acid anodes are made that way today, but the term "formation" has
remained to designate the final electrochemical steps in
preparation of electrodes for any type of battery.
Formation may be carried out on individual electrodes or on pairs
of electrodes in a tank of suitable electrolyte, e.g. sulfuric
acid for lead-acid battery plates, or potassium hydroxide for
nickel-cadmium battery electrodes. Formation of anodes by
themselves requires an inert, gassing, counter-electrode. More
often the electrodes for a battery are formed in pairs. The
cathodes are arranged in the tank in opposition, to the anodes or
are interspaced between the anodes. Frequently, electrodes are
formed in the cell or battery after final assembly. However the
electrodes are physically arranged, current is passed through the
electrodes to charge them. For some battery types, charge-
discharge cycling up to seven times is used ,to form the
electrode.
Primary battery anodes are almost always prepared in the active
form, and require no formation step. Rechargeable battery anodes
almost always go through a formation step.
Cathodes
Cathode active materials are never metals despite the common
usage of the metal type to designate the cathode active material.
93
-------
"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 to 30 percent free lead)
referred to by industry as "leady oxide," which is produced by
the ball mill or Barton process. This leady oxide is used for
both the anode and the cathode. Chemical production of cathode
active materials which are used specifically for batteries is
considered part of battery manufacturing usually as an ancillary
operation.
Manganese dioxide for Leclanche cells and alkaline-manganese
cells is mixed with graphite to increase conductivity. For
Leclanche cells, the mixture may be compacted around the carbon
cathode rod, or is poured into the cell as a loose powder and
compacted as the carbon rod is inserted. For alkaline-manganese
cells, analagous procedures are used except that the cathode
94
-------
active material takes the shape of a cylinder sgair.et the «•»?.) 1 <->f
the nickel-plated steel can and no carbon rod is used. In the
foliar-cell Leclanche battery the manganese dioxide is printed
onto a conducting plastic sheet. The other side of the sheet
bears the zinc anode film to produce a bipolar electrode.
.(Bipolar electrodes perform the same function as an anode and
cathode of two separate cells connected in series.)
The magnesium-ammonia reserve battery uses a different type of
cathode structure. A glass fiber pad containing the meta-
dinitrobenzene (mDNB), carbon, and ammonium thiocyanate is placed
against a stainless steel cathode current collector. Activation
of the battery causes liquid ammonia to flood the cell space,
saturate the pad, and dissolve the dry acidic salt (ammonium
thiocyanate) and the cathode active material (m-DNB). The m-DNB
functions as a dissolved cathodic depolarizer.
The cathode active material for the carbon-zinc (air) cell is
oxygen from the air. Therefore, the principal function of the
cathode structure is to provide a large area of conductive carbon
surface in the immediate vicinity of the electrolyte-air contact
region. Air must have free access through the exposed pores of
the rigid structure. Electrolyte in the wetted surface pores
must have a continuous path to the body of the electrolyte to
provide the ionic conduction to the anode. The porous carbon
body is wetproofed on the electrolyte surface to prevent deep
penetration and saturation or flooding of the pores by
electrolyte.
The mercury-zinc cell uses a compacted cathode active material.
Mercuric oxide mixed with graphite is pressed into pellets for
use in miniature cells, or is pressed directly into the cell
case.
In sum, cathode fabrication almost always includes a rigid,
current-carrying structure to support the active material. The
active material may be applied to the support as a paste,
deposited in a porous structure by precipitation from a solution,
fixed to the support as a compacted pellet, or may be dissolved
in an electrolyte which has been immobilized in a porous inert
structure.
The formation step for cathodes of rechargeable batteries is much
the same as that for anodes. Nickel cathodes may be formed
outside or inside the assembled cell in a potassium hydroxide
electrolyte. Lead cathodes for lead-acid batteries are handled
in a manner similar to that used to make anodes, except they
remain in the lead peroxide state after forming. For some cell
types, chemical processes rather than electrolysis are used to
95
-------
form nickel hydroxide and silver oxide cathodes or reactive
materials prior to physical application to the electrode support.
Ancillary Operations
Ancillary operations are all those operations unique to the
battery manufacturing point source category which are not
included specifically under anode or cathode fabrication. They
are operations associated mainly with cell assembly and battery
assembly. ' Also chemical production for anode or cathode active
materials used only for batteries (discussed above) is considered
an ancillary operations.
Cell assembly is done in several ways. The electrodes for
rectangular nickel cadmium batteries are placed in a stack with a
layer of separator material between each electrode pair and
inserted into the battery case. Almost all lead-acid batteries
are assembled in a case of hard rubber or plastic with a porous
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 positioned, electrolyte is applied to it
before the next electrode is placed. When the battery is
completed the entire assembly is sandwiched between two thin
aluminum sheets. Assembly is completely automated. The
resulting six-volt battery is about three inches by four inches
by three-sixteenths of an inch thick and has high specific power
and power density. Shelf life is several years and operating
lifetime depends on drain rate.
96
-------
A contrasting battery is the carbon-zinc (air) cell. The cast
amalgamated zinc anodes positioned on each side of a porous
carbon air electrode are attached to the cover of the cell. Dry
potassium hydroxide and lime are placed in the bottom of the cell
case, the cover is put in place and sealed, and a bag of
dessicant is placed in the filler opening. The cell is shipped
dry and the user adds water to activate it. This cell has a very
low power density but a very long operating life.
Ancillary operations for this document, beside specific chemical
production, include some dry operations as well as cell washing,
battery washing, the washing of equipment, floors and operating
personnel. Because the degree of automation varies from plant to
plant for a given battery type, the specific method of carrying
out the ancillary operations is not as closely identifiable with
a battery type as are the anode and cathode fabrication
operations.
INDUSTRY SUMMARY
The battery manufacturing industry in the United States includes
about 250 plants operated by about 130 different companies. In
all, the industry produced approximately 1.8 million tons of
batteries valued at 2.1 billion dollars in 1976, and employed
over 33 thousand workers. As Figure II1-21 (page 134) shows, the
value of industry products has increased significantly in recent
years. This growth has been accompanied by major shifts in
battery applications, and the emergence of new types of cells and
the decline and phase - out of other cell types as commercially
significant products. Present research activity in battery
technology and continuing changes in electronics and
transportation make it probable that rapid changes in battery
manufacture will continue. The rapid changes in battery
manufacturers is reflected in the age of battery manufacturing
plants. Although a few plants are more than 60 years old,
battery manufacturing plants are fairly new with over half
reported to have been built in the past twenty years. Most have
been modified even more recently. Figure 111-22 (page 135)
displays where battery plants are located throughout the U.S. and
within EPA regions.
Plants commonly manufacture a variety of cells and batteries dif-
fering in size, shape, and performance characteristics. Further,
a significant number of plants produce cells using different
reactive couples but with a common anode material, (e.g.,
mercury-zinc and alkaline manganese batteries both use a zinc
anode). Thirteen plants currently produce cells or batteries
using two or more different anode materials and therefore are
considered in two or more subcategories. Some battery
manufacturing plants purchase finished cell components and
97
-------
assemble the final battery products without performing all of the
manufacturing process steps on-site. Other plants only
manufacture battery components, and perform battery manufacturing
process operations without producing finished batteries.
Finally, some battery plants have fully integrated on-site
production operations including metal forming and inorganic
chemicals manufacture which are not specific to battery
manufacturing.
The reactive materials in most modern batteries include one or
more of the following toxic metals: cadmium, lead, mercury,
nickel, and zinc. Cadmium and zinc are used as anode materials
in a variety of cells, and lead is used in both the cathode and
anode in the familiar lead-acid storage battery. Mercuric oxide
is used as the cathode reactant in mercury-zinc batteries, and
mercury is also widely used to amalgamate the zinc anode to
reduce corrosion and self discharge of the cell. Nickel
hydroxide is the cathode reactant in rechargeable nickel cadmium
cells, and nickel or nickel plated steel may also serve as a
support for other reactive materials. As a result of this
widespread use, these toxic metals are found in wastewater
discharges and solid wastes from almost all battery plants.
Estimated total annual consumption of these materials in battery
manufacture is shown in Table III-5 (page 111). Since only lead-
acid batteries are reclaimed on a significant scale, essentially
all of the cadmium, mercury, nickel, and zinc consumed in battery
manufacture will eventually be found in liquid or solid wastes
either from battery manufacturers or from battery users.
Water is used in battery manufacturing plants in preparing
reactive materials and electrolytes, in depositing reactive
materials on supporting electrode structures, in charging
electrodes and removing impurities, and in washing finished
cells, production equipment and manufacturing areas. Volumes of
discharge and patterns of water use as well as the scale of
production operations, wastewater pollutants, and prevalent
treatment practices vary widely among different battery types,
but show significant similarities among batteries employing a
common anode reactant and electrolyte. Table III-6 (page 112)
summarizes the characteristics of plants manufacturing batteries
in each of the groups discussed in the battery documents based on
anode and electrolyte. The cadmium,, calcium, Leclanche, lithium,
magnesium and zinc subcategories are discussed below.
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 $100 million in 1977.
Silver-cadmium battery manufacture is limited in terms of product
weight amounting to less than one percent of the amount of
98
-------
nickel-cadmium batteries manufactured. Small quantities of
mercury-cadmium batteries are manufactured for military and
industrial applications. Presently 10 plants are manufacturing
batteries in the cadmium subcategory. Total annual production is
estimated to be 5251 metric tons (5790 tons) of batteries with
three plants producing over 453.5 metric tons (500 tons) of
batteries, and one producing less than 0.907 metric ton (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
<18,925 1/hr (<5,000 gal/hr) while two plants have no process
wastewater flows. Normalized process wastewater flows based on
the total weight of cadmium anode cells produced vary from 0 to
782 I/kg (94 gal/lb) and averages 148 I/kg (18 gal/lb), with the
subcategory having a median flow of 49 I/kg (6 gal/lb). The
substantial variations shown in wastewater discharges from these
plants reflect major manufacturing process variations, especially
between batteries using pressed or pasted electrodes and sintered
electrodes. These are addressed in detail in Section V. The
most significant use of process water in cadmium anode battery
manufacture is in the deposition of electrode active materials on
supporting substrates and in subsequent electrode formation
(charging) prior to assembly into cells. These operations 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 8 of 9 plants which indicated process
wastewater discharge; two plants also indicated the use of
coagulants, and seven plants use pH adjustment. Two plants
indicated the use of material recovery, five plants have sludges
hauled by a contractor and one plant has its sludge landfilled.
On-site observations at several plants indicate that the
treatment provided is often rudimentary and of limited
effectiveness. Battery process wastewater discharges from five
cadmium anode battery manufacturing plants in the data base flow
directly to surface waters, and four plants discharge to munici-
pal sewers. Recently, one direct discharge plant in the data
base has added additional treatment including 100 percent recycle
and has no discharge of wastewater. Currently there are three
plants which moved their operations to other plants, three plants
with no discharge to navigable waters of the United States and
99
-------
four plants which discharge wastewater to surface waters.
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, whereas 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.
Calcium Subcategory
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 plants was not
determined since one plant which produced no process wastewater
reported that thermal cell production data were not available.
The other two plants, however, showed total thermal battery
production amounting to less than 23 metric tons (25 tons).
Total employment for the three plants manufacturing in the
calcium subcategory is estimated to be 240.
Process water use and discharge in this subcategory are limited.
Two plants discharge wastewater to municipal sewers and one plant
reports no discharge of wastewater. Wastewater discharge is
reported from the process operation whi.ch is involved in
producing the reactive material used to heat the cell for
activation, and for testing the cells. The cell anode, cathode,
TOO
-------
and electrolyte are all produced by 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.
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 an acidic (chloride) electrolyte and a zinc anode.
Among carbon-zinc air batteries, only "dry" cells which use
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 rec-
tangular nine-volt transistor batteries, various rectangular lan-
tern batteries, and flat sheet batteries for photographic appli-
cations. 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 (e.g., cooked paste, un-
cooked paste, pasted paper).
Major raw materials used in the manufacture of batteries in this
subcategory include zinc, mercury, carbon, manganese dioxide, am-
monium chloride, zinc chloride, silver chloride, paper, starch,
flour, and pitch or similar materials for sealing cells.
101
-------
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 plants 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 set-
ting 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). Twelve plants reported zero
discharge of process wastewater. The maximum reported volume of
process wastewater per unit of production (weight of cells pro-
duced) 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. Significant flow rate variations
among plants in this subcategory are attributable to manufactur-
ing process differences, to variations in equipment cleanup
procedures employed, and the degree of water conservation prac-
ticed at each plant.
The most significant pollutants in waste streams from plants in
this subcategory are mercury, 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
one plant reports the use of settling tanks. Treatment by
adsorption is reported by one plant, and three plants report pH
adjustment; Some plants discharge without treatment, and the use
of contractor hauling for disposal of some waste streams is
common.
Lithium Subcategory
This subcategory encompasses the manufacture of batteries that
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
102
-------
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 plants 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 for washing reactive mater-
ials or for air pollution control and area cleanup. One plant
also reports process water use in manufacturing reactive mater-
ials 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 expec-
ted to vary considerably in their chemical composition because of
the widely varying raw materials and processes used. Raw
materials reported to be used in lithium anode battery
manufacture are shown in Table III-7 (page 113).
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 subcategory. 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 the plants
in this subcategory are limited to settling and pH adjustment.
Three plants report pH adjustment of process wastewater while one
103
-------
plant reports only filtration. Two plants report no discharge of
wastewater, four plants discharge to a municipal sewer, and one
plant discharges to surface waters.
Magnesium Subcategory
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 because of 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 and separator processing in the production of silver
chloride cathodes, fume scrubbers, battery testing, and activator
manufacture for thermal batteries. Floor and equipment wash
process water was also reported. Process wastewater from only
two 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 on the basis of
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
104
-------
is 670 1/hr (180 gal/hr), which is 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 pH adjustment, settling, and filtration, which is
practiced at two plants. One plant utilizes pH adjustment and
filtration, and one plant uses filtration only.
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 sizes, 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, 17 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 16 plants currently producing these batteries, 5
manufacture more than one type of battery in this subcategory.
Employment for this subcategory is estimated to be 4,680.
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
105
-------
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 used in cell electrolytes (which may also
include zinc oxide and mercuric oxide) and as reagents in various
process steps. Steel is used in cell cases, and paper and
plastics are used 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, floor and equipment cleaning, and sinks and showers.
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 (12 plants). Sulfide
precipitation is practiced at two sites, oil skimming is
practiced at one plant, and carbon adsorption is practiced at two
plants. One plant has upgraded its system to include ion
exchange and metals recovery. Several plants employ amalgamation
with zinc for the removal of mercury from process waste streams
from this subcategory. Most treatment is performed as
pretreatment for discharge to POTW since 11 plants discharge to
106
-------
municipal sewers. Three plants discharge to surface waters and
two of the active plants have no wastewater discharge.
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 occurred in recent years and which are
anticipated in the near future are creating strong demand for
existing battery products and for new ones.
The advent of transistor electronics, and subsequently of
integrated circuits, light emitting diodes, and liquid crystal
devices has resulted in the development of innumerable portable
electronic devices such as radios, calculators, toys, and games,
which are powered by batteries. This has resulted in the
development of new mass markets for cells in small sizes and has
led to the rapid commercialization of new cell types. The
extremely low power drains of some digital electronic devices
have created markets for low power, high energy density, long
life cells and have resulted in the commercial development of
silver oxide-zinc and lithium batteries. Solid state technology
has also reduced or eliminated markets for some battery types,
most notably mercury (Weston) cells which were widely used as a
voltage reference in vacuum tube circuits. Continued rapid
change in electronics and growth in consumer applications are
anticipated with corresponding change and growth in battery
markets.
In transportation technology and power generation, tightening
fuel supplies and increasing costs are directing increased
attention toward electrical energy storage devices. The
development and increasing use of battery powered electric
automobiles and trucks are creating an increasing market for
large battery sizes with high energy and power densities.
Increasing application of batteries for peak shaving in
electrical power systems is also an anticipated development
creating higher demand for batteries in larger sizes.
In summary, while, as with Lalande, Edison and Weston cells in
the past, some battery types may become obsolete, the overall
outlook is for growth in the battery industry. Increased
production of many current products and the development of new
battery types are likely. Based on general industry patterns,
conversion of battery plants from one type of product where
demand for specific battery types is not strong to another is
more likely than plant closings.
107
-------
TABLE III-l
DCP EFFORT SUMMARY
SUBCATEGORY NUMBER OF PLANTS NUMBER OF PLANTS
(Information Received) (Currently Active)
Cadmium
Calcium
Lead
Leclanche
Lithium
Magnesium
Nuclear
Zinc
13
3
186*
20
7
8
1
17
10
3
167*
19
7
8
0
16
Totals 255 228
Total Number of Plant Sites in Category - 230.
*Includes plate manufacturers and assemblers.
108
-------
TABLE II1-2
BATTERY GENERAL PURPOSES AND APPLICATIONS
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
PBXs
regulated power supplies
109
-------
TABLE I I I- 3
ANODE HALF-CELL REACTIONS (electrolyte)
Cd + 20H- < --- > Cd(OH)2 + 2e (alkaline)
Ca < --- > Ca+2 + 2e (nonaqueous inorganic)
Pb + H2S04 < --- > PbSO* + 2H+ •«- 2e (acidic)
Zn <~ — > Zn+2 + 2e (acidic)
Li < --- > L1 + + e (molten salt, organic, nonaqueous inorganic)
Mg < --- > Mg+2 + 2e (sea water)
Zn + 20H- < --- > Zn(OH)2 + 2e (alkaline)
TABLE I I 1-4
CATHODE HALF-CELL REACTIONS (electrolyte)
e + NiOOB + HZO < --- > Ni(OH)2 + OH- (alkaline)
4e + Ag2O2 + 2H2O < --- > 2Ag + 4OH- (alkaline)
2e •*• Ag2O + HZ0 < --- > 2Ag + 2OH- (alkaline)
2e + HgO + H2O < --- > Hg + 2OH- (alkaline)
2e + Pb02 + SO*-2 + 4H+ < --- > PbSO* + 2H2O (acid)
2e + 2Mn02 + 2NH4C1 + Zn+2 < --- > Mn2O3 + H20 + Zn(NH3)2Cl2 (acid)
2e + 2AgCl + Zn*2 < --- > 2Ag + ZnCl2 (acid)
e + TiS2 + Li* < --- > TiS2sLi (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 + HZ0 < --- > MnOOH + OH- (alkaline)
e + MnOOH * H20 < --- > Mn(OH)2 + OH- (alkaline)
8e ••- m-C6H
+ 6NH3 + Mg(OH)2 (ammonia)
2e + PbCl2 < --- > Pb + 2C1- (sea water)
e + CuCl < --- > Cu + Cl- (sea water)
e + AgCl < --- > Ag + Cl- (sea water)
4e + O2 + 2H2O < --- > 4OH- (alkaline)
no
-------
Table II1-5
CONSUMPTION OF TOXIC METALS IN BATTERY MANUFACTURE*
METAL ANNUAL CONSUMPTION
Metric Tons Tons
Cadmium 730 800
Lead 980,000 1,080,000
Mercury 670 740
Nickel 1,200 1,300
Zinc 27,000 29,000
* Based on 1976 data provided in dcp. Numbers shown are sums of
provided data. Because response to the raw materials questions was
incomplete, actual consumption will be higher by 10 to 20 percent.
111
-------
TABLE 111-6
BATTER* MANUFACTURING CATEGORY SUHMARY
(TOTAL DATA BASE)
Batteries
Subcategory Manufactured
Estimated Estimated
Number of Total Annual Production Total Number Discharges
Total
Process.rtastewater Flow
(tons) of Employees Direct POTtfZero 1/yr (106) [Ral/yr (1Ub)j
Cadmium
Calcium
Lead
Leclanche
/
-* Lithium
—j,
K>
Magnesium
Zinc
Nickel-Cadmium
Silver Cadmium
Mercury Cadmium
Thermal
Lead Acid
Caroon Zinc
Carbon Zinc, Air
Depolarized
Silver Chloride-
Zinc
Lithium
Thermal
Magnesium Carbon
Magnesium Reserve
Thermal
Alkaline Manganese
13
3
186
20
7
8
17
5,250
<23
1 , 300, 000
108,000
<23
1,220
23,000
(5,790)
«25)
(1,430,000)
(119,000)
«25)
( 1 , 340)
(25,000)
2,500 5(4) 1
240
18,745 - 12
4,200 0
400 1
350 1
4,680 3
4
2
117
8
4
3
11
4(5)1
1
57
12
2
4
3
748
0.13
7,106
16.7
0.36
3.91
60.3
(198)
(0. 034)
(1,877)
(4.41)
(0.095)
(1.03)
(15.9)
Silver OKide-Zinc
Mercury Zinc
Carbon Zinc-Air
Depolarized
Nickel Zinc
TOTALS
2542
1,437,516 (1,581,180)
31,115 22(21) 149 83(84) 7,935.40
(2,096.469)
NOTES:
direct discharge plant changed to zero discharge after data was collected.
does not include nuclear subcategory (1 plant).
-------
TABLE II1-7
RAW MATERIALS USED IN LITHIUM
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
113
-------
^
tt"
X
>-*
0
EC
u
z
ui
u
0.
(I)
J
<
u
£
a
o
u
i
H
3000
2000
1000
800
700
600
SOO
400
300
200
100
-U/S
,Li/CI2
,l\!a/AIR
,Li/FeS2
-Li/Se
-LiVGuS
-Li/FeS
'Na/S
-e H2O
Zn/NiOOH-
Fe/NiOOH-
TYPE OF ELECTROLYTES
© MOLTEN SALT OR CERAMIC
O AQUEOUS
O ORGANIC
O MOLTEN SALT AND AQUEOUS
Cd/NiOOH'
Pb/PbO2"
10
20 40 60 60 tOO
EQUIVALENT WEIGHT, G/EQUIVALENT
ZOO
300 4OO
FIGURE lli-1
THEORETICAL SPECIFIC ENERGY AS A FUNCTION OF EQUIVALENT WEIGHT AND
CELL VOLTAGE FOR VARIOUS ELECTROLYTIC
COUPLES
114
-------
1000
SPECIFIC ENERGY, W-HR/KG
10 100
1000
too
m
j
O
0.
u
H
u
u
Q.
tn
— 1000
COMBUSTION
ENGINES
HEAVY
DUTY
LECLANCHE
LOW-DRAIN
LECLANCHE
0.4
6 10 20 40 60 100
SPECIFIC ENERGY WATT HOURS/LB
ZOO 400
1000
FIGURE 111-2
PERFORMANCE CAPABILITY OF VARIOUS BATTERY SYSTEMS
115
-------
TERMINA
VENT CAP
BAFFLE.
NEGATIVE PLATE
(CADMIUM ANODE)
SEPARATOR
POSITIVE PLATE
(NICKEL CATHODE)
CELL JAR
CELL COVER
•TERMINAL COMB
PLATE TABS
6-9
INCHES
FIGURE Ili-3
CUTAWAY VIEW OF AN IMPREGNATED SINTERED PLATE NICKEL-CADMIUM CELL
(SIMILAR IN PHYSICAL STRUCTURE TO SOME
SILVER OXIDE-ZINC AND NICKEL-ZINC CELLS)
116
-------
NICKEL-PLATED
STEEL COVER
NICKEL-PLATED
STEEL CASE
NICKEL POSITIVE
CONTACT LUG
NYLON GASKET-
SEAL
POLYETHYLENE-
INSULATOR
POLYETHYLENE
INSULATOR
POSITIVE PLATE
(NICKEL CATHODE)
,SEPARATOR
NICKEL NEGATIVE
CONTACT LUG
NEGATIVE PLATE
(CADMIUM ANODE)
FIGURE 111-4
CUTAWAY VIEW OF A CYLINDRICAL NICKEL-CADMIUM BATTERY (SIMILAR IN
PHYSICAL STRUCTURE TO CYLINDRICAL LEAD ACID BATTERIES)
117
-------
VENT PLUGS
CONTAINER
NEGATIVE PLATE
TAPERED
TERMINAL
POSTS
POST STRAP
COVER
PLATE LUGS
POSITIVE
PLATE
SEPARATORS
ELEMENT RESTS
SEDIMENT SPACE
FIGURE IiI-5
CUTAWAY VIEW OF LEAD ACID STORAGE BATTERY
118
-------
METAL CAP-
-METAL COVER
ZINC CAN
(ANODE)
SEPARATOR
METAL BOTTOM
H3fj
<.
i
i
i
\ w
I
;
i
^
55
r~»
-
-'
•"
&
BOTTOM INSULATOR-
INSULATINO WASHER
SUB SEAL
CARBON ELECTRODE
{CATHODE)
t-9
INCHES
MANGANESE DIOXIDE
MIX (DEPOLARIZER)
COMPLETE CELL
FIGURE 111-6
CUTAWAY VIEW OF A CYLINDRICAL LECLANCHE CELL (SIMILAR IN PHYSICAL
STRUCTURE TO SOME CARBON-ZINC-AIR AND SILVER CHLORIDE-ZINC DRY CELLS)
119
-------
NEGATIVE END (-)
MANGANESE
DIOXIDE
ZINC
CONNECTOR
(CONDUCTIVE SHEET)
ALUMINUM COVERED WITH CONDUCTIVE
PLASTIC BEARING A PATCH OF ZINC ON
THE UNDERSIDE (ALUMINUM WRAPS
AROUND ALUMINUM AT OTHER END)
DUPLEXES
(CONDUCTIVE PLASTIC-
UPPER SIDE MANGANESE
DIOXIDE, LOWER SIDE ZINC)
SEPARATOR CONTAINING
ELECTROLYTE
ADHESIVE AROUND EDGE
OF SEPARATOR
MANGANESE DIOXIDE ON
CONDUCTIVE PLASTIC ON ALUMINUM
POSITIVE END (+)
COMPLETED BATTERY
ASSEMBLED ON CARD
WITH CONTACT HOLES
THICKNESS, 1/4 INCH
FIGURE III-7
EXPLODED VIEW OF A FOLIAR LECLANCHE BATTERY USED IN FILM PACK
120
-------
POLYESTER
JACKET
CATHODE CURRENT
COLLECTOR
ANODE CURRENT
COLLECTOR
DEPOLARIZER
LITHIUM ANODE
FLUOROCARBON
PLASTIC JACKET
PLASTIC LAYERS SEPARATE
DEPOLARIZER FROM CASE
LITHIUM ENVELOPE AND
FLUOROCARBON PLASTIC JACKET
SEPARATE DEPOLARIZER FROM CASE
FIGURE IH-8
CUTAWAY VIEW OF TWO SOLID ELECTROLYTE
LITHIUM CELL CONFIGURATIONS
121
-------
GAS GENERATOR
TOP CAP
DRIVE DISK
ACTIVATOR
CUP
OUTER
CASE
BATTERY
ASSEMBLAGE
LANCE
ELECTROLYTE
RESERVOIR
-BULKHEAD
QUAD RING
3 INCHES
B-C SECTION
TERMINAL PLATE
A SECTION
EXAMPLE SHOWN FOR LIQUID-AMMONIA-ACTIVATED MAGNESIUM RESERVE BATTERY;
CATHODE - CARBON DEPOLARIZED META-DIN1TROBENZENE
ANODE - MAGNESIUM
ELECTROLYTE - DRY AMMONIUM THIOCYANATE ACTIVATED BY LIQUID AMMONIA
FIGURE Hl-9
CUTAWAY VIEW OF A RESERVE TYPE BATTERY ("A" SECTION AND "B-C"
SECTION CONTAIN ANODE AND CATHODE)
122
-------
FILLER
TUBE CAP
FILLER TUBE
FOR WATER
SOLID CAUSTIC SODA
CYLINDRICAL
ZINC ANODE
CARBON CATHODE
MIXTURE OF
PELLETED LIME
AND GRANULAR
CAUSTIC SODA
FIGURE 111-10
CUTAWAY VIEW OF A CARBON-ZINC-AIR CELL
123
-------
ONE PIECE COVER
(+) PLATED STEEL
ELECTROLYTE-
POTASSIUM HYDROXIDE
CATHODE-MANGANESE
DIOXIDE MIX
SEPARATORS -
NON WOVEN FABRIC
INSULATING TUBE -
POLYETHYLENE COATED
KRAFT
METAL SPUR
INSULATOR -
PAPERBOARD
METAL WASHER
CAN -STEEL
CURRENT COLLECTOR -
BRASS
ANODE - AMALGAMATED
POWDERED ZINC
JACKET -
TIN PLATED
LITHOGRAPHED
STEEL
SEAL - NYLON
INNER CELL BOTTOM -
STEEL
PRESSURE SPRING -
PLATED SPRING STEEL
RIVET - BRASS
OUTER BOTTOM (-)
PLATED STEEL
FIGURE 111-11
CUTAWAY VIEW OF AN ALKALINE-MANGANESE BATTERY
(SIMILAR IN PHYSICAL STRUCTURE TO CYLINDRICAL
MERCURY-ZINC BATTERIES)
124
-------
CELL. CAN
ANODE CAP
CATHODE
(MERCURIC)
OXIDE MIX
ANODE
(AMALGAMATED
ZINC)
FIGURE 111-12
CUTAWAY VIEW OF A MERCURY-ZINC (RUBEN) CELL (SIMILAR IN PHYSICAL
STRUCTURE TO ALKALINE-MANGANESE AND SILVER OXIDE-ZINC BUTTON CELLS)
125
-------
POSITIVE PLATE PROCESS
NICKEL
POWDER'
a t
NICKEL
•STRIP
SINTERED
STRIP
RAW
MATERIALS-
IMPREGNATION
METAL
SCREEN
BRUSH
u
RAW
MATERIALS
NEGATIVE
PLATE
PROCESS
FORMATION
SEPARATOR-
1
• NICKEL PLATED
STEEL CASE
ASSEMBLY
POTASSIUM HYDROXIDE
SODIUM HYDROXIDE
WATER
ELECTROLYTE
ADDITION
TEST
T
PRODUCT
FIGURE 111-13
MAJOR PRODUCTION OPERATIONS IN NICKEL-CADMIUM BATTERY MANUFACTURE
126
-------
LEAD-
LEAD OXIDE,
SULFURIC •
ACID
LEADY OXIDE
PRODUCTION
MIXER
PASTING
MACHINE
WITH DRYER
CURING OF
PLATES
SEPARATORS
STACKER
WELD
ASSEMBLED
ELEMENTS
BATTERY CASE
AND COVER
PIG LEAD OR
SHEET LEAD
GRID
MANUFACTURE
PRODUCT
FIGURE 111-14
SIMPLIFIED DIAGRAM OF MAJOR PRODUCTION
OPERATIONS IN LEAD ACID BATTERY MANUFACTURE
127
-------
r
WATER, STARCH,
ZINC CHLORIDE,
MERCUROUS CHLORIDE,
AMMONIUM CHLORIDE
ADDITION
OF PASTE
.ZINC CANS
»r*l - -~"»-"-»^ ••«••• f , „
DEPOLARIZER
(MANGANESE DIOXIDE
+ CARBON BLACK)
ELECTROLYTE•
(AMMONIUM CHLORIDE +
ZINC CHLORIDE + WATER)
CARBON ROD
DEPOLARIZER AND
ELECTROLYTE ADDED
|
•CARBON ROD
-PAPER LINED
ZINC CANS
SUPPORT
WASHER ADDED
r±iE
PASTE
SETTING
zt
CELL
SEALED
_J
CRIMP
TEST AND
FINISH
___—- ALTERNATE PRODUCTION STEPS
AGE AND
TEST
PRODUCT
FIGURE 111-15
MAJOR PRODUCTION OPERATIONS IN LECLANCHE BATTERY MANUFACTURE
128
-------
IODINE-
POL Y-2-VINYL-PYRIDINE-
CATHODE
MIX
ELECTROLYTE
LITHIUM-
DEGREASE
ANODE
CELL CASE,
CONTACTS,
SEALS
ASSEMBLY
TEST
PRODUCT
FIGURE 111-18
MAJOR PRODUCTION OPERATIONS IN
LITHIUM-IODINE BATTERY MANUFACTURE
129
-------
CARBON-
DE1ON1ZE
WATER
SLURRY
PREPARATION
MAGNESIUM
STRIP
DRY
PUNCH
PUNCH
CATHODE
ANODE
ASSEMBLY
AMMONIA
-AMMONIUM-
TH1OCYANATE
PRODUCT
FIGURE 111-17
MAJOR PRODUCTION OPERATIONS IN AMMONIA-ACTIVATED MAGNESIUM
RESERVE CELL MANUFACTURE
130
-------
CONTAINER
LIME.
CAUSTIC
POTASH •
DRY ELECTROLYTE
PLACED IN
CONTAINER
MANGANESE
DIOXIDE
GRAPHITE
CHARCOAL
POWDER
POROUS ACTIVATED
CARBON
ELECTRODE
ELECTRODE
INSERTED
ZINC-
MERCURY-
AMALGAMATED
ZINC ELECTRODE
INSERTED
ZINC
ELECTRODE
SEALED
TEST AND
PACK
PRODUCT
FIGURE 111-18
MAJOR PRODUCTION OPERATIONS IN WATER ACTIVATED
CARBON-ZINC-AIR CELL MANUFACTURE
131
-------
BINDER,
CARBON &
MANGANESE
DIOXIDE
ZINC a
MERCURY
FORMED INTO
CATHODE
POTASSIUM HYDROXIDE,
WATER 8e BINDER
CONTAINER
PRODUCED
CATHODE
INSERTED
SEPARATOR
INSERTED
ELECTROLYTE
ANODE
ANODE
INSERTED
CURRENT
COLLECTOR
RIVET AND
SEAL INSERTED
CRIMP
N>
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
-------
MERCURIC
OXIDE
GRAPHITE
MANGANESE
DIOXIDE
SODIUM
HYDROXIDE
WATER
ZINC
MERCURY
AMALGAM
TOP AND
GASKET ADDED
I
CELL. CRIMPED
AND WASHED
FIGURE 111-20
SIMPLIFIED DIAGRAM OF MAJOR OPERATIONS IN MERCURY-ZINC (RUBEN)
BATTERY MANUFACTURE
133
-------
2800
U>
3400
ZOOO
in
K
O
a
u.
o
in
z
0
i 1600
I
III
Q.
I
U)
h.
O
U
3
I ZOO
800
400
63
•FROM U.S. DEPT. OF COMMERCE DATA
1977 CENSUS OF MANUFACTURERS
FIGURE 111-21
VALUE OF BATTERY PRODUCT SHIPMENTS 1963-1977*
-------
• 10 OR MORE PLANTS
• S-S PLANTS
A 1-4 PLANTS
•BASED ON TOTAL OF 2S3 PLANTS; PLANTS
M MULTIPLE SUBCATEGOR1ES COUNTED
MORE THAN ONCE,
i—X EPA REGIONS
FIGURE 111-22
GEOGRAPHICAL REGIONAL DISTRIBUTION OF BATTERY MANUFACTURING PLANTS
-------
136
-------
SECTION IV
INDUSTRY SUBCATEGORIZATION
Subcategorization should take into account pertinent industry
characteristics, manufacturing process variations, water use,
wastewater characteristics, and other factors which are important
in determining a specific grouping of industry segments for the
purpose of regulating wastewater pollutants. Division of the
industry segment into subcategories provides a mechanism for
addressing process and product variations which result in
distinct wastewater characteristics. Effluent limitations and
standards establish mass limitations on the discharge of
pollutants and are applied, through the permit issuance process,
to specific dischargers. To allow the national standard to be
applied to a wide range of sizes of production units, the mass of
pollutant discharge must be referenced to a unit of production.
This factor is referred to as a production normalizing parameter
and is developed in conjunction with subcategorization.
In addition to processes which are specific to battery
manufacturing, many battery plants report other process
operations. These operations, generally involve the manufacture
of battery components and raw materials and may include
operations not specific to battery manufacture. These operations
are not considered in this document.
SUBCATEGORIZATION
*
Factors Considered
After examining the nature of the various segments of the battery
manufacturing category and the operations performed therein, the
following subcategorization factors were selected for evaluation.
Each of these factors is discussed in the ensuing paragraphs,
followed by a description of the process leading to selection of
the anode subcategorization.
1. Waste Characteristics
2. Battery Type
3. Manufacturing Processes
4. Water Use
5. Water Pollution Control Technology
6. Treatment Costs
7. Effluent Discharge Destination
8. Solid Waste Generation and Disposal
9. Size of Plant
10. Age of Plant
11. Number of Employees
12. Total Energy Requirements (Manufacturing Process
137
-------
and Waste Treatment and Control)
13. Nonwater Quality Environmental Aspects
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 as a logical basis for
subcategorization. This basis has two significant shortcomings.
First, batteries of a given type are often manufactured using
several different processes with very different wastewater
generation characteristics. Second, it was found that batteries
of several types were often manufactured at a single site with
some process operations (and resultant wastewater streams) common
to the different battery types. Since modification of battery
type subcategories to reflect all process variations and product
combinations results in over 200 subcategories, battery type was
found to be unacceptable as the primary basis for
subcategorization. Battery type is, however, reflected to a
significant degree in manufacturing process considerations and in
anode metal.
Manufacturing Processes - The processes performed in the
manufacture of batteries are the sources of wastewater
generation, and thus are a logical basis for the establishment of
subcategories. In this category, however, similar processes may
be applied to differing raw materials in the production of
different • battery types yielding different wastewater
characteristics. For example, nickel, cadmium and zinc
electrodes may all be produced by electrodeposition techniques.
Further., the number of different manufacturing process sequences
used in producing batteries is extremely large although a smaller
number of distinct process operations are used in varying com-
binations. As a result of these considerations, neither overall
process sequence nor specific process operations were found to be
suitable as primary bases for subcategorization. However,
process variations that result in significant differences in
wastewater generation are reflected in the manufacturing process
elements for which specific discharge allowances were developed
within each subcategory.
Water Use - Water use alone is not a comprehensive enough factor
upon which to subcategorize because water use is related to the
various manufacturing processes used and product quality needed.
While water use is a key element in the limitations and standards
138
-------
established, it is not directly related to the source or the type
and quantity of the waste. For example, water is used to rinse
electrodes and to rinse batteries. The amounts of water used for
these processes might be similar, but the quantity of pollutants
generated is significantly different.
Water Pollution Control Technology, Treatment Costs, and Effluent
Discharge Destination - The necessity for a subcategorization
factor to relate to the raw wastewater characteristics of a plant
automatically eliminates certain factors from consideration as
potential bases for subdividing the category. Water pollution
control technology, treatment costs, and effluent discharge
destination have no effect on the raw wastewater generated in a
plant. The water pollution control technology employed at a
plant and its costs are the result of a requirement to achieve a
particular effluent level for a given raw wastewater load. The
treatment technology does not affect the raw wastewater
characteristics. Likewise, the effluent discharge destination
does not affect the raw wastewater characteristics.
Solid Waste Generation and Disposal - Physical and chemical solid
waste characteristics generated by the manufacture of batteries
can be accounted for by subcategorization according to battery
type since this determines some of the resultant solid wastes
from a plant. Solid wastes resulting from the manufacture of
batteries includes process wastes (scrap and spent solutions) and
sludges resulting from wastewater treatment. The' solid waste
characteristics (high metals content), as well as wastewater
characteristics, are a function of the specific battery type and
manufacturing process. However, not all solid wastes can be
related to wastewater generation and be used for developing
effluent limitations and standards. Also, solid waste disposal
techniques may be identical for a wide variety of solid wastes
but cannot be related to pollutant generation. These factors
alone do not provide a sufficient base for subcategorization.
Size of Plant - The size of a plant is not an appropriate
subcategorization factor since the wastewater characteristics per
unit of production are essentially the same for different size
plants that have similar processing sequences. However, the size
of a plant is related to its production capacity. Size is thus
indirectly used to determine the effluent limitations and
standards since these are based on production rates. But, size
alone is not an adequate subcategorization parameter because the
wastewater characteristics of plants are also dependent on the
type of processes performed.
Age of Plant - While the relative age of a plant may be important
in considering the economic impact of a regulation, it is not an
appropriate basis for subcategorization because it does not take
139
-------
into consideration the significant parameters which affect the
raw wastewater characteristics. In addition, a subcategorization
based on age would have to distinguish between the age of the
plant and the age of all equipment used in the plant which is
highly variable. Plants in this industry modernize and replace
equipment relatively frequently, and changes of subcategories
would often result. Subcategorization using this factor is
therefore infeasible.
Number of Employees - The number of employees in a plant does not
directly provide a basis for subcategorization since the number
of employees does not reflect the production processes used, the
production rates, or water use rates. Plants producing batteries
varied widely in terms of number of production employees. The
volume and characteristics of process wastewater was found to not
have any meaningful relationship with plant employment figures.
Total Energy Requirements - Total energy requirements were
excluded as a subcategorization parameter primarily because
energy requirements are found to vary widely within this category
and are not meaningfully related to wastewater generation and
pollutant discharge. Additionally, it is often difficult to
obtain reliable energy estimates specifically for production and
waste treatment. When available, estimates are likely to include
other energy requirements such as lighting, air conditioning, and
heating energy.
Nonwater Quality Environmental Aspects - Nonwater quality
environmental aspects may have an effect on the wastewater
generated in a plant. For example,,wet scrubbers may be used to
satisfy air pollution control regulations. This could result in
an additional contribution to the plant's wastewater flow.
However, it is not the primary source of wastewater generation in
the battery manufacturing category, and therefore, not acceptable
as an overall subcategorization factor.
Unique Plant Characteristics - Unique 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 do not necessarily have similar processes and, consequently
may have different wastewater characteristics. However, process
water availability may be a function of the geographic location
of a plant, and the price of water may necessitate individual
modifications to procedures employed in plants. For example, it
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
140
-------
plants that have access to plentiful water supplies and thus,
constitute a basis for effluent control rather than for
subcategorization.
A limitation in the availability of land space for constructing a
waste treatment facility may in some cases affect the economic
impact of a limitation. However, in-process controls and water
conservation can be adopted to minimize the size and thus land
space required for the treatment facility. Often, a compact
treatment unit can easily handle wastewater if good in-process
techniques are utilized to conserve raw materials and water.
Subcategorization Development
After reviewing and evaluating data for this category, the
initial battery type subcategorization was replaced by the anode
material, electrolyte approach. This development is discussed
below in detail.
Upon initiation of the study of the battery manufacturing
category, published literature and data generated in a
preliminary study of the industry were reviewed, and a
preliminary approach to subcategorization of the industry was
defined. This approach was based on electrolytic couples (e.g.
nickel-cadmium and silver oxide-zinc) and recognized battery
types {e.g. carbon-zinc, alkaline manganese, and thermal cells).
The weight of batteries produced was chosen as the production
basis for data analysis. This approach provided the structure
within which a detailed study of the industry was conducted, and
was reflected in the data collection portfolio used to obtain
data from all battery manufacturing plants. In addition, sites
selected for on-site data collection and wastewater sampling were
chosen to provide representation of the significant electrolytic
couples and battery types identified in the data collection
portfolios.
As discussed in Section III, the preliminary review of the
category resulted in the identification of sixteen distinct
electrolytic couples and battery types requiring consideration
for effluent limitations and standards. A review of the
completed dcp returned by the industry revealed four additional
battery types requiring study but did not initially result in any
fundamental change in the approach to subcategorization.
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. The
determination was made that further breakdown of the original
battery type subcategories would be required to encompass
141
-------
existing and possible manufacturing process and product
variations. The number of subcategories ultimately required
using this approach was likely to approach 200. This approach
was likely to result in redundant regulations and possible
confusion about applicability in some cases.
Review of dcp responses and on-site observations at a number of
plants revealed that there was substantial process diversity
among plants producing a given battery type, and consequently
little uniformity in wastewater generation and discharge. For
most cell types, several different structures and production
processes were identified for both anode and cathode, and it was
observed that these could be combined into many variations. The
data also revealed that not all plants performed all process
operations on-site. Some battery manufacturing plants produced
cell electrodes or separators which were not assembled into
batteries within the plant, and others purchased some or all of
the components which were used in producing the finished
batteries shipped from the plant. To reflect these differences
in manufacturing processes it would have been necessary to divide
the preliminary battery type subcategories into approximately 200
subcategories to accommodate those presently existing and into
nearly 600 subcategories to encompass all of the obvious
variations possible in new sources.
The data obtained from the industry also showed that most
production operations are not separated by battery type.
Manufacture of more than one battery type at a single location is
common, and some production operations are commonly shared by
different battery types. Raw material preparation, cell washes,
and the manufacture of specific electrodes (most often the anode)
are often commonly performed for the production of different
battery types. Production schedules at some of these plants make
the association of production activity (and therefore wastewater
discharge) in these operations with specific battery types
difficult.
Many operations are intermittent and variable, and there is often
a considerable lag between the preparation of raw materials and
components, and the shipment of finished batteries. The
redundant inclusion of production operations under several
different battery types is undesirable in any case.
Subcategorization of the battery category was re-evaluated and
redefined in light of the industry characteristics discussed
above. In the development of the final subcategorization
approach, objectives were to:
142
-------
1. Encompass the significant variability observed in
processes and products within battery manufacturing
operations
2. Select a subcategorization basis which yielded a
manageable number of subcategories for the promulgation
of effluent limitations and standards
3. Minimize redundancy in the regulation of specific
process effluents
4. Facilitate the determination of applicability of
subcategory limitations and standards to specific
plants
5. Subcategorize so that, to the maximum extent possible,
plants fall within a single subcategory
Available data show that where multiple cell types are produced,
and especially where process operations are common to several
types, the cells frequently have the same anode material. As a
result, cell anode was considered as a subcategorization basis.
Significant differences in wastewater volume and characteristics
between plants producing zinc anode cells with alkaline
electrolytes and Leclanche cells necessitated further
subcategorization based on cell electrolyte. Subcategorization
on these bases yielded eight subcategories: cadmium, calcium,
lead, Leclanche, lithium, magnesium, nuclear, and zinc. The lead
subcategory is discussed specifically in Volume II of the
Development Document for Effluent Limitations Guidelines and
Standards for the Battery Manufacturing Point Source Category.
These subcategories preserve most of the recognized battery types
within a single subcategory and greatly reduce the redundancy in
covering process operations. They also limit the number of
plants producing batteries under more than one subcategory to
thirteen. Recognized battery types which are split under this
approach are carbon-zinc air cells which are manufactured with
both alkaline and acidic electrolytes, and thermal batteries
which are produced with calcium, lithium, and magnesium anodes.
In both cases, however, significant variations in process water
use and discharge exist within the preliminary battery type
subcategories, and these are reflected in the breakdown resulting
from anode based subcategorization. In most cases where process
operations are common to multiple battery types, the processes
fall within a single subcategory. Where plants produce batteries
in more than one subcategory, manufacturing processes are
generally completely segregated.
143
-------
Identification of these anode groups as subcategories for
effluent limitations purposes was also favored by an examination
of wastewater characteristics and waste treatment practices. In
general, plants manufacturing batteries with a common anode
reactant were observed to produce wastewater streams bearing the
same major pollutants (e.g. zinc and mercury from zinc anode
batteries, cadmium and nickel from cadmium anode batteries). As
a result, treatment practices at these plants are similar.
A battery product within a subcategory is produced from a
combination of anode manufacturing processes, cathode
manufacturing processes and various ancillary operations (such as
assembly associated operations, and chemical powder production
processes specific to battery manufacturing). Within each group
(anode, cathode, or ancillary) there are numerous manufacturing
processes or production functions. These processes or functions
may generate independent wastewater streams with significant
variations in wastewater characteristics. To obtain specific
waste characteristics for which discharge allowances could be
developed, the following approach was used (Figure IV-1, page
157). Individual process waste streams (subelements) can be
combined to obtain specific flow and waste characteristics for a
manufacturing process or function with similar production
characteristics which generates a process wastewater stream.
Some manufacturing processes are not associated with any
subelements; these 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 for a
nickel-cadmium battery. One method of producing this cathode is
by sintering nickel paste to a support structure and impregnating
nickel salts within the pores of the sintered nickel. Several
process waste streams can be associated with this manufacturing
process such as, electrode rinse streams, spent solution streams,
and air scrubber wastewater streams. All of these subelements
are related to production of nickel impregnated cathodes, which
is the element. At the element level, flows and pollutant
characteristics can be related to production. Elements are
combined or can be combined in various ways at specific plants at
the subcategory level. Wastewater treatment can be related to
this level which is considered the level of regulation. The
detailed information which 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.
144
-------
FINAL SUBCATEGORIES AND PRODUCTION NORMALIZING PARAMETERS
The final approach to subcategorization based on anode reactant
material and electrolyte composition yielded the following
subcategories:
. . Cadmium . Magnesium
- Calcium . Nuclear
Leclanche . Zinc
Lithium
Specific elements within each subcategory and corresponding
production normalizing parameters are summarized in Table IV-1
(page 154). 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 considered as individual elements for discharge
limitations under this subcategory.
Characteristics of each of the process elements discussed above
resulted 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 plants. The selected 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
145
-------
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 plants would render this production normalizing
parameter 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
others indicated the production of finished batteries from elec-
trodes processed at other locations. For such plants 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 differ-
ent 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
wastewater discharge is associated with the reactive materials,
the use of battery weight as a production normalizing parameter
for all operations would not result in uniform application of
effluent limitations and standards to plants in this subcategory.
146
-------
Since most of the wastewater discharge volume associated with
electrode production results from depositing materials on or re-
moving 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 always available. The difficulty results from the fact that
the electrodes generally have significant porosity and irregular
surfaces, and it is the total wetted surface rather than the sim-
ple projected area which determines the volume of wastewater gen-
erated. Since this area could not be readily determined,
electrode surface area was not chosen as the production
normalizing parameter for these operations.
Total electrode weights were found to be less desirable .than
active material weights because the use of process water is
involved primarily with the active materials. Since most
electrodes produced in this subcategory include nonreactive
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 the relationship between wastewater volume and the weight of
reactive materials in the electrode.
Electrical capacity of the battery should, in theory, correspond
closely to those characteristics of cell electrodes most closely
associated with process water use and discharge during
manufacture. The electrical capacity of cells is determined by
the mass of reactive materials present, and the processing of
reactive 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. Although the number of employees would be
a suitable basis for limiting discharges from employee showers
and hand washes, battery weight was chosen instead to achieve
uniformity with other ancillary wastewater sources and to
minimize the number of production normalizing parameters to be
applied.
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
147
-------
depolarize^, 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 two ancillary elements. One
for the manufacture of reactive material used to heat the cell to
its operating temperature upon activation (heating component
production), and one to test the cells manufactured for leaks.
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, for cathode
manufacture, it is the weight of reactive cathode material in the
cells, and for cell testing is the weight of cells produced.
Leclanche Subcateqory
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 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 pro-
duced in manufacturing processes in which water use is limited,
and the volume of process wastewater produced is small.
In addition to equipment wash and cleaning operations,
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
148
-------
Paste
Cooked
Uncooked
Pasted Paper
With Mercury
Without Mercury
Amalgamation
Mercury in electrolyte
Mercury in separator
The most significant elements in this subcategory are the
separator processes. Pasted paper can be manufactured at the
battery plant 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. Information on 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, equipment and
area cleanup operations, and foliar battery miscellaneous wash.
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 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 cannot be readily determined
for cell cathodes and for anodes prepared using powdered zinc.
In addition, there is little 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 discharges from pasted paper separator production,
or from the manufacture of cells containing pasted paper
separators. It is subject to variability, however, due to the
varying amounts of paste applied, and 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.
149
-------
Lithium Subcateffory
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 currently
manufactured use an aqueous electrolyte. The manufacture of
thermal batteries 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 where lithium is formed. 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 the 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 involved with the complete
cell assembly (testing and cell wash), with all production areas
(air scrubbers), 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 Subcateqory
This subcategory which addresses cells with magnesium anodes,
includes 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
150
-------
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 which 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. The weight of batteries produced is selected as the
production normalizing parameter for cell testing and cell
separator processing operations, floor and equipment area
maintenance, and assembly area air scrubbers.
Nuclear Subcateqory
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
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 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 production activity, the production
normalizing parameter is the total weight of batteries produced.
151
-------
For one ancillary operation where the etching of silver foil is
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 containing 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 plant 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. 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 cannot be readily determined.
Because some electrodes include nonreactive 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 are not presently available. The number 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 156).
Below, they are generally discussed in reference to all the
subcategories. Specific operations are discussed in Section V.
152
-------
Battery manufacturing plants 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 plants 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. They may however, be
addressed by effluent limitations and standards promulgated for
other industries.
153
-------
TABLE IV-1 SUBCATEGORY ELEMENTS AND PHOOUCTIOH NORMALIZING PARAMETERS (PHP)
SUSCATEGORY
Cadmium Anodes
Cathodes
Ancillary
Calcium Anodes
Cathodes
Ancillary
ELEMENT PNP
P«st«d and Presttd Powder Weight if Ctdmiura
EkclrodtptsHed in Anode
Impregnated
Silver Powder Pressed Weight of Silver
in Cathode
Pressed in Cethode
Nickel Pressed Powder Weight of Nickel
Nickel Electrodeposited Applied
Nickel Impregnated
Cell Wish Weight of Cells
Electrolyte Preparation Produced
Floor and Equipment Wash
Employee Wash
Cadmium Powder Production Weight of Cadmium
Powder Produced
Powder Produced
Cadmium Hydroxide Production Weight of Cadmium
Used
Nickel Hydroxide Production Weight of Nickel
Used
Vapor Deposited Weight of Calcium
Calcium Chiomate Weight of Reactive
Tungstic Oxide Material
Potassium Bichromate
Heating Component Production Total Weight of
Heal Paper Reactants
Heat Pellet
Cell Testing Weight of Cells
Produced
Plating NA
SUBCATEGORy
Ledincbe Anodei
Cathodes
Ancillary
ELEMENT PMP
Zinc Powder Weljht »f Cells
Produced
jumped NA
drawn
Maniantu Oioside-Pcessed WtiglM of CcHt
mercury
•electrolyte with
mercury
•gelled electrolyte
with mercury
Patted Manganese Dioxide
Cuban (Porous!
Silver Chloride
Cooked Paste Produced
Separator
Separator Weight of Dry
Pasted Paper with mercury Pasted Material
Separator NA
Patted Paper Wo mercury
Equipment uid Weight of Cells
Area Cleanup Produced
Miscellaneous Wash
-------
SUBCATEGORY
Lithium Anodes
Cathodes
Ancillary
Magnesium Anodes
Cathodes
Ancillary
NA - Not Applicable to Battery Ma
ELEMENT PNP
Formed and Stamped Weight of Lithium
Sulfur Dioxide Weight of Reactive
Iodine Material
Iron Disulfide
Lithium Perchlorate
Titanium OKultide
Thionyl Chloride
Lead Iodide
Heating Component Production Weight of Reactants
Heat Paper
Heat Pellets
Lithium Scrip Disposal Weight of Cells
Cell Testing Produced
Cell Wash
Floor and Equipment Wash
Air Scrubbers
Sheet Magnesium NA
stamped
formed
fabricated
Magnesium Powder Weight of Magnesium
Used
Silver Chloride - Weight of Depolarizer
Chemically Reduced Material
Silver Chloride -
Electrolytic
Copper Chloride
Copper Iodide
Lead Chloride
Silver Chloride
Vanadium Pentoxide
Carbon
M-Dinitrobenzene
Heating Component Production Weight of Reactants
Heat Paper
Heat Pellets
Cell Testing Weight of Cells
Separator Processing Produced
Floor and Equipment Wash
Air Scrubbers
nufacturing Category
SUBCATEGORY
Zinc Anodes
Cathodes
Ancillary
ELEMENT PNP
Cast or Fabricated Weight of Zinc
Wet Amalgamated
Zinc Powder -
Gelled Amalgam
Zinc Powder -
Dry Amalgamated
Zinc Oxide Powder -
Pasted or Pressed
Zinc Oxide Powder -
Pasted or Pressed, Reduced
Zinc Electrodeposrted Weight of Zinc
Deposited
Porous Carbon Weight of Carbon
Manganese Dioxide - Weight of Manganese
Carbon Dioxide
Mercuric Oxide (and Weight of Mercury
mercuric oxide -
manganese dioxide carbon)
Mercuric Oxide - Weight of Mercury
Cadmium Oxide and Cadmium
Silver Powder Pressed Weight of Silver
Silver Powder Pressed Applied
and Electrolytically
Oxidized (Formed)
Silver Oxide
Powder - Thermally
Reduced or Sintered,
Electrolytically Formed
Silver Oxide Powder
Silver Peroxide Powder
• Nickel Impregnated and Weight of Nickel
Formed Applied
Cell Wash Weight of Cells
Electrolyte Preparation Produced
Mandatory Employee Wash
Reject Cell Handling
Floor and Equipment Wash
Silver Etch Weight of Silver
Processed
Silver Peroxide Production Weight of Silver in
Silver Peroxide
Produced
Silver Powder Production Weight of Silver
Powder Produced
-------
TABLE IV-2
OPERATIONS AT BATTERY PLANTS INCLUDED IN OTHER
INDUSTRIAL CATEGORIES
(Partial Listing)
Plastic and Rubber Case Manufacture
Cell Containers and Components:
A. Forming
B. Cleaning and Deburring
C. Metal Surface Treatment (e.g., Plating, Chromating, etc.)
Retorting, Smelting and Alloying Metals
Inorganic Chemical Production (Not Specific to Battery
Manufacturing)
Pasted Paper Manufacture (Without Mercury)
156
-------
SUBCATEGORY
REGULATION
r
ANODE MANUFACTURE
rT 4
CATHODE MANUFACTURE
I — — i
II
II
ANCILLARY OPERATIONS
I
L
ELEMENT
I
tm
, J
!•«
, J
••••
k
•
<••••
ELEMENT ' 1
1 1
J
«M
, 1
••
1 1
1 1
1 1
ELEMENT
1
•••
'•
••«•
'
•••
mm
ELEMENT
^H
ELEMENT ' *
II
1
••
i t
m mm
i i
mmm
II
II
1 1
ELEMENT
j
••• Mi
I
•••» «i
•••• •
ELEMENT '
J
•••M
i j
••
i
. _J
INDIVIDUAL PROCESS WASTEWATER STREAMS (SUBELEMENTS)
MANUFACTURING PROCESS
OPERATIONS—
DETERMINATION OF
FLOWS AND POLLUTANT
CHARACTERISTICS
GENERATION OF
WASTEWATER
POLLUTANTS
FIGURE IV-1 SUMMARY OF CATEGORY ANALYSIS
-------
158
-------
SECTION V
WATER USE AND WASTEWATER CHARACTERIZATION
This section describes the collection, analysis, and
characterization . of data that form the basis for effluent
limitations and standards for the battery manufacturing category,
and presents the results of these efforts. Data were collected
from a number of, sources including published literature, previous
studies of battery manufacturing, data collection portfolios
(dcp) mailed to all known battery manufacturers, and on-site data
collection and sampling at selected facilities. Data analysis
began with an investigation of the manufacturing processes
practiced, the raw materials used, the process water used and the
wastewater generated in the battery category. This analysis was
the basis for subcategorization and selection of production
normalizing parameters (pnp) discussed in detail in Section IV.
Further analysis included collecting wastewater samples and
characterizing wastewater streams within each subcategory.
DATA COLLECTION AND ANALYSIS
The sources of data used in this study have been discussed in
detail in Section III. Published literature and previous studies
of the category provided a basis for initial data collection
efforts and general background for the evaluation of data from
specific plants. The dcp sent to all known battery manufacturing
companies provided the most complete and detailed description of
the category which could be obtained. Dcp were used to develop
category and subcategory data summaries and were the primary
basis for the selection of plants for on-site sampling and data
collection. Data from plant visits were used to characterize raw
and treated wastewater streams within the category and provide an
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 evaluation of the available information from published-
literature and previous studies was used as the basis for
developing the dcp format which structured the preliminary data
base for category analysis. This initial effort included the
definition of preliminary subcategories within the battery
manufacturing category. These subcategories were expected to
differ significantly in manufacturing processes and wastewater
discharge characteristics. Consequently on-site data collection
and wastewater sampling were performed for each subcategory.
Specific sites for sampling were selected on the basis of data
obtained from completed dcp. For each subcategory, screening
159
-------
samples were collected and analyzed for all priority pollutants
and other selected parameters. The results of these screening
analyses, plus the dco data, were evaluated ho select significant
pollutant parameters within each subcategory for verification
sampling and analysis.
Data Collection Portfolio
The data collection portfolios (dcp) were used to obtain
information about production, manufacturing processes, raw
materials, water use, wastewater discharge and treatment,
effluent quality, and presence or absence of priority pollutants
in wastewaters from battery manufacturers.
The dcp requested data for the year 1976, the last full year for
which production information was expected to be available. Some
plants provided information for 1977 and 1978 rather than 1976 as
requested in the dcp. All data received were used to
characterize the category.
For data gathering purposes, a list of companies known to
manufacture batteries was compiled from Dun and Bradstreet Inc.
SIC code listings, battery industry trade association membership
lists, listings in the Thomas Register, and lists of battery
manufacturers compiled during previous EPA studies. These
sources included battery distributors, wholesalers, corporate
headquarters and individual plants. The lists were screened to
identify corporate headquarters for companies manufacturing
batteries and to eliminate distributors and wholesalers. As a
result, 226 dcp were mailed to each corporate headquarters, and a
separate response was requested for each battery manufacturing
plant operated by the corporation. Following dcp distribution,
responses were received confirming battery manufacture by 133
companies operating at 235 manufacturing sites. For the
subcategories which are the subject of this volume, responses
were received from about 50 sites. Because of the dynamic nature
of battery manufacturing these numbers may vary since some sites
have consolidated operations, some have closed, and new sites may
have opened.
Specific information requested in the dcp was determined on the
basis of an analysis of data available from published literature
and previous EPA studies of this category, and consideration of
data requirements for the promulgation of effluent limitations
and standards. This analysis indicated that wastewater volumes
and characteristics varied significantly among different battery
types according to the chemical reactants and electrolyte used,
and that raw materials constituted potential sources of sig-
nificant pollutants. In addition, batteries of a given type are
commonly produced in a variety of sizes, shapes, and electrical
160
-------
capacities. Available data also indicated that processes could
vary significantly in wastewater discharge characterisitcs.
As a result of these considerations, the dcp was developed so
that specific battery types manufactured, manufacturing processes
practiced, and the raw materials used for each type could be
identified. Production information was requested in terms of
both total annual production (Ib/yr) and production rate (lb/-hr).
Water discharge information was requested in terms of gallons per
hour. The dcp also requested a complete description of the
manufacturing process for each battery type, including flow
diagrams designating points and flow rates of water use and
discharge, and type and quantity of raw materials used. Chemical
characteristics of each process wastewater stream were also
requested.
Basic information requested included the name and address of the
plant and corporate headquarters, and the names and telephone
numbers of contacts for further information. Additionally, the
dcp included a request for a description of wastewater treatment
practices, water source and use, wastewater discharge
destination, and type of discharge regulations to which each
plant was subject. Since the wastewaters at each plant had not
been analyzed for the priority pollutants, the dcp asked whether
each priority pollutant was known or believed to be present in,
or absent from, process wastewater from the plant.
Of the 69 confirmed battery manufacturing plants which are the
subject of this volume, all returned either a completed dcp or a
letter with relevant available information submitted in lieu of
the dcp. This level of response was achieved through follow-up
telephone and written contacts after mailing of the original data
requests.
The quality of the responses obtained varied significantly.
Although most plants could provide most of the information
requested, a few indicated that available information was limited
to the plant name and location, product, and number of employees.
These plants were generally small and usually reported that they
discharged no process wastewater. Also, process descriptions
varied considerably. Plants were asked to describe all process
operations, not just those that generated process wastewater. As
a result approximately 40 percent of the plants submitting dcp
indicated that certain process operations did not generate
wastewater. In some dcp specific process flow rates conflicted
with water use and discharge rates reported elsewhere in the dcp.
Specific process flow information provided in the dcp was
sufficient to characterize flow rates for most process elements
for each subcategory. These data were augmented by data from
plant visits and, where appropriate, by information gained in
161
-------
follow-up telephone and written contacts with selected plants.
Raw waste chemical analysis was almost universally absent from
the dcp and had to be developed almost entirely from sampling at
visited plants and data from previous EPA studies.
Upon receipt, each dcp was reviewed to determine plant products,
manufacturing processes, wastewater treatment and control
practices, and effluent quality (if available). Subsequently,
selected data contained in each portfolio were entered into a
computer data base to provide identification of plants with
specific characteristics (e.g. specific products, process
operations, or waste treatment processes), and to retrieve basic
data for these plants. The dcp data base provided quantitative
flow and production data for each plant. This information was
used to calculate production normalized flow values as well as
wastewater flow rates for each manufacturing process element in
each subcategory. The data base was also used to identify and
evaluate wastewater treatment technologies and in-process control
techniques used.
Plant Visits and Sampling
Thirty-two battery manufacturing plants were visited as part of
the data collection effort for the subcategories in this volume,
including one following proposal. At each plant, information was
obtained about the manufacturing processes, raw materials,
process wastewater sources (if any), and wastewater treatment and
control practices. Wastewater samples were collected at 19
plants.
The collection of data on priority, conventional and
nonconventional pollutants in waste streams generated by this
category was accomplished using a two-phase sampling program.
The first phase, screening, was designed to provide samples of
influent water, raw wastewater and treated effluent from a
representative plant in each subcategory. Samples from the
screening phase were analyzed and the results evaluated to
determine the presence of pollutants in a waste stream and their
potential environmental significance. Those pollutants found to
be potentially significant in a subcategory were selected for
further study under the second, or verification, phase of the
program. This screening-verification approach allowed both
investigation of a large number of pollutants and in-depth
characterization of individual process wastewater streams without
incurring prohibitive costs.
Sampling and Analysis Procedures
Sampling procedures were applied for screening and verification
sampling programs. For screening, plants identified as being
162
-------
representative of the subcategory in terms of manufacturing
processes, raw materials, products, and wastewater generation
were selected for sampling. Where possible, plants with multiple
products or processes were chosen for screening. The screening
program was designed to cover battery types under the initial
subcategorization.
Screening samples were obtained to characterize the total process
wastewater before and after treatment. All screening was
performed according to EPA protocol as documented in Sampling and
Analysis Procedures for Screening of Industrial Effluents for
Priority Pollutants, April 1977. Only the combined raw waste
stream and total process effluent were sampled. At plants that
had no single combined raw waste or treated effluent, samples
were taken from discrete waste sources and a flow-proportioned
composite was used to represent the total waste stream for
screening.
Asbestos data were collected from selected plants as part of a
separate screening effort using self-sampling kits supplied to
each selected plant. The sampling protocol for asbestos was
developed after the initial screening efforts had been completed.
Consequently, asbestos data on plant influent, raw wastewater,
and effluent for each subcategory was not necessarily collected
from the same plants involved in the initial screening.
Plants were selected for verification sampling on the basis of
the screening results. Those plants within a subcategory that
demonstrated effective pollutant reductions were specifically
identified for sampling in order to evaluate wastewater treatment
and control practices within the industry. For the subcategories
containing a relatively small number of plants and relatively few
types of wastewater treatment and control practices, the
selection of plants for sampling was based primarily on
production, manufacturing processes, and wastewater generation.
Initially, each potential sampling site was contacted by
telephone to confirm and expand the dcp information and to
ascertain the degree of cooperation which the plant would
provide. The dcp for the plant was then reviewed to identify (a)
specific process wastewater samples needed to characterize
process raw waste streams and wastewater treatment performance
and (b) any additional data required. Each plant was 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. In these cases, plans
for sampling the site were discontinued. For plants chosen for
sampling, a detailed sampling plan was developed on the basis of
163
-------
the preliminary plant visit identifying sampling locations, flow
measurement techniques, sampling schedules, and additional dajba
to be collected during the sampling visit.
Sample points were selected at each plant to characterize a
process wastewater from each distinct process operation, the
total process waste stream, and the effluent from wastewater
treatment. Multiple wastewater streams from a single process
operation or unit, such as the individual stages of a series
rinse, were not sampled separately but combined as a flow-
proportioned composite sample. In some cases, wastewater flow
patterns at specific plants did not allow separate sampling of
certain process waste streams, and only samples of combined
wastewaters from two or more process operations were taken.
Where possible, chemical characteristics of these individual
waste streams were determined by mass balance calculations from
the analyses of samples of other contributing waste streams and
of combined streams. In general, process wastewat'er samples were
obtained before any treatment, such as settling in sumps,
dilution, or mixing that would change its characteristics. When
samples could not be taken before treatment, sampling conditions
were carefully documented and considered in the evaluation of the
sampling results.
As a result of the sampling visits approximately 200 raw waste
samples were obtained characterizing wastewater sources
associated with over 30 different battery manufacturing process
elements for the subcategories in this volume. In addition,
samples were obtained from plant water supplies. Samples were
also taken for analysis which either characterized wastewater
streams from sources other than battery manufacturing that were
combined for treatment with battery manufacturing wastes or
characterized wastewater at intermediate points in treatment
systems that used several operations.
Samples for verification were collected at each site on three
successive days. Except if precluded by production or wastewater
discharge patterns, 24-hour flow proportioned composite samples
were obtained. Composite samples were prepared either by using
continuously operating automatic samplers or by compositing grab
samples obtained manually at a rate of one per hour. For batch
operations composites were prepared by combining grab samples
from each batch. Wastewater flow rates, pH, and temperature were
measured at each sampling point hourly for continuous operations.
For batch operations, these parameters were measured at the time
the sample was taken. At the.end of each sampling day, composite
samples were divided into aliquots and taken for analysis of
organic priority pollutants, metals, TSS, cyanide, ammonia, and
oil and grease. Separate grab samples were taken for analysis of
volatile organic compounds and for total phenols because these
164
-------
parameters would not remain stable during compositing. Composite
samples were kept on ice at 4°C during handling and shipment.
Analysis for metals was by plasma arc spectrograph for screening
and by atomic absorption for verification. Analysis for organic
priority pollutants was performed by gas chromatograph-mass
spectrometer for screening. For verification analysis, gas
chromatograph-mass spectrometer (GCMS) and gas chromatograph were
used for organic priority pollutant analysis as required by EPA
protocol. All sample analyses were performed in accordance with
the EPA protocol listed in Table V-l (page 238).
The sampling data provided wastewater chemical characteristics as
well as flow information for the manufacturing process elements
within each subcategory. Long-term flow and production values
from the dcp data base or average flow and production values
obtained during sampling were used as a basis for calculating a
production normalized flow for each process element. A single
value for each plant that most accurately represented existing
plant operations was used to avoid excessively weighting visited
plants (usually three days of values) in statistical treatment of
the data.
Mean and median statistical methods were used to characterize
each process element production normalized flow and wastewater
characteristics. The mean value is the average of a set of
values, and the median of a set of values is the value below
which half of the values in the set lie.
All data was used to determine total process element and
subcategory wastewater discharge flows. For plants that did not
supply process wastewater discharge flows, but did provide
production data, the mean of the individual production normalized
flow values was used.
Screening Analysis Results
The results of screening analysis for each subcategory are
presented in Tables V-2 through V-7 (pages 244-266). Pollutants
reported in the dcp as known or believed to be present in process
wastewater from plants in the subcategory are also indicated on
these tables. In the tables, ND indicates that the pollutant was
not detected and NA indicates that the pollutant was not
analyzed. For organic pollutants other than pesticides, the
symbol * is used to indicate detection at less than or equal to
0.01 mg/1, the quantifiable limit of detection. For pesticides
(pollutants 89-105), the symbol ** indicates detection less than
or equal to the quantifiable limit of 0.005 mg/1. For metals,
the use of < indicates that the pollutant was not detected by
analysis with a detection limit as shown. The analytical methods
used for screening analysis could not separate concentrations of
165
-------
certain pollutant parameter pairs, specifically polllutants
numbered 72 and 76, 78 and 81, and 74 and 75. These pollutant
pairs will have the same reported concentrations. Alkyl
epoxides, and xylenes were not analyzed in any samples because
established analytical procedures and standards were not
available at the time of analysis. 2,3,7,8-Tetrachlorodibenzo-p-
dioxin (TCDD) was not analyzed because of the hazard in
laboratory analysis associated with handling TCDD standards. In
the screening analysis tables dioxin is listed as not detected
because analysis could not be done for this pollutant. Analysis
of asbestos was accomplished using microscopy. Results of
asbestos analysis are reported as fibers being present or absent
from a sample. The symbol + is used to indicate the presence of
chrysotile fibers. Nonvolatile organic pollutants were not
analyzed for one zinc subcategory screening sample 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 initial product type subcategories.
Selection Of Verification Parameters
Verification parameters for each subcategory were selected based
on screening analysis results, presence of the pollutants in
process waste streams as reported in dcp, and a technical
evaluation of manufacturing processes and raw materials used
within each subcategory. Criteria for selection of priority and
conventional pollutants included:
1. Occurrence of the pollutant in process wastewater from
the subcategory may be anticipated because the
pollutant is present in, or used as, a raw material or
process chemical. Also the dcp priority pollutant
segment indicated that the pollutant was known or
believed to be present in process wastewaters.
2. The pollutant was found to be present in the process
wastewater at quantifiable limits based on the results
of screening analysis. If the presence of the
pollutant was at or below the quantifiable limit, the
other criteria were used to determine if selection of
the parameter was justified.
3. The detected concentrations were considered significant
following an analysis of the ambient water quality
criteria concentrations and an evaluation of
concentrations detected in blank, plant influent, and
effluent samples.
The criteria were used for the final selection of all
verification parameters, which included both toxic and
conventional pollutant parameters. An examination was made of
166
-------
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. Table V-8
(page 271) is a summary of the verification parameters selected
for all the subcategories.
Cadmium Subcateqory. The following 16 pollutant parameters were
selected for further analysis in this subcategory:
44. methylene chloride 126. silver (for silver cathodes only)
87. trichloroethylene 128. zinc
118. cadmium ammonia
119. chromium cobalt
121. cyanide phenols (4AAP)
122. lead oil and grease
123. mercury TSS
124. nickel pH
The organic pollutants dichlorobromomethane and bis(2-
ethylhexyl)phthalate were all detected in screening raw waste
samples at concentrations 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 detected in screening but
was not selected for verification sampling because the presence
of chloroform was attributed to the influent water. Toluene was
detected at 0.025 mg/1 in the effluent but was not chosen for
verification because this pollutant was not related to any
manufacturing process. All other organic priority pollutants
detected in screening analysis 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, was not known to
be used as a raw material and was therefore not selected. Copper
was detected at a concentration above the limit of detection in
only the influent sample. Because copper was not associated with
any manufacturing process in the subcategory, it was not selected
for verification. Although silver was not detected in screening,
it was selected as a verification parameter for process
wastewaters associated with silver cathode production because
silver was used as a raw material. All other metal priority
pollutants detected in screening analysis for this subcategory
were selected for verification. Cyanide was also selected for
verification because it was detected in screening and it was
reported as a pollutant known to be present in battery
wastewaters in the dcp data.
167
-------
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
analysis. 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 Subcateqory. The following 18 pollutant parameters
selected for further analysis in this subcategory:
were
14. 1,1,2-trichloroethane
23. chloroform
44. methylene chloride
66. bis(2-ethylhexyl)ogtgakate
116. asbestos
118. cadmium
119. chromium
120. copper
122. lead
124. nickel
126. silver
128. zinc
cobalt
iron
manganese
oil and grease
TSS
pH
Three organic priority pollutants, pentachlorophenol, di-n-butyl
phthalate, and toluene were detected in screening samples at
concentrations below the analytical quantification limit of 0.01
mg/1 and were not selected for verification because there was no
reason why these pollutants should be present as a result of the
manufacturing processes in this subcategory. All other organic
priority pollutants detected in screening analysis for this
subcategory were selected for verification.
The metal priority pollutants, antimony, arsenic, beryllium,
mercury, selenium, and thallium, were not quantifiable in
screening analysis and are not known to result from any
manufacturing process in this subcategory. Consequently, they
were not selected for verification. All other metal priority
pollutants were detected in screening and were selected for
verification. In addition, asbestos, reported as a raw material
in this subcategory and detected in screening samples, was
included for verification.
A number of nonconventional pollutants were detected in screen-
ing, but not included in verification analysis. Cobalt, iron,
and manganese were detected during screening and were included as
verification parameters. In addition, the conventional pollu-
168
-------
tants total suspended solids, oil and grease, and pH were
included in verification analysis.
Leclanche Subcategory. The following 16 pollutant parameters
were selected for further analysis in this subcategory:
70. diethyl phthalate 124. nickel
114. antimony 125. selenium
115. arsenic 128. zinc
11.8. cadmium manganese
119. chromium phenols (4AAP)
120. copper oil and grease
122. lead TSS
123. mercury pH
Twelve organic priority pollutants were detected at
concentrations less than the quantification levels in screening
samples for this subcategory. Nine of these pollutants,
1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane,
dichlorobromomethane, chlorodibromomethane, phenol, bis(2-
ethylhexyl)phthalate, 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, di-n-octyl phthalate, and
toluene, were reported as known or believed to be present in
process wastewater in the dcp data. Methylene chloride was
reported as known to be present and was used in the manufacturing
process by one plant. This plant also reported, however, that
use of this material had been discontinued. Di-n-octyl phthalate
was reported as believed to be present in process wastewater by
one plant. Toluene was reported as believed to be present in
process wastewater by two plants. Their presence cannot be
traced to any use in battery manufacturing processes, and is
believed to be due to on-site plastics processing and vapor
degreasing operations which are not regulated as part of the
battery manufacturing category. On the basis of these
considerations, none of these 12 pollutants were included in
verification analyses. Chloroform was detected in screening at
the quantifiable limit in the raw waste but was not selected for
verification because the influent sample concentration of this
pollutant was greater than the raw waste concentration. Diethyl
phthalate was the only organic priority pollutant 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 not found in screening samples because
169
-------
arsenic was reported as believed to be present in process
wastewater by four plants in this subcategory, is a highly toxic
pollutant, and is 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
therefore included in verification analyses. All other metal
priority pollutants which were detected in screening were
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. The following 18 pollutant parameters were
selected for further analysis in this subcategory:
14. 1,1,2-trichloroethane 124. nickel
23. chloroform 126. silver
44. methylene chloride 128. zinc
66. bis(2-ethylhexyl)phthalate cobalt
116. asbestos iron
118. cadmium manganese
119. chromium oil and grease
120. copper TSS
122. lead pH
Screening analysis for this subcategory encompassed waste streams
resulting from the manufacture of cathodes and heating elements
for thermal batteries. The selection of verification parameters
for this subcategory is based on the screening results as well as
a review of raw materials and dcp information for all process
elements.
Wet scrubbers used in sulfur dioxide and thionyl chloride cathode-
manufacture serve to control emissions of vapors of these
materials. The resultant wastewater consequently will contain
sulfurous and hydrochloric acids, but no priority pollutants.
Neutralization and recycle of the scrubber wastes will result in
the presence of sodium sulfite and sodium chloride as well as
sodium sulfate resulting from oxidation of the sulfite. Lithium
scrap disposal is expected to produce a waste containing lithium
and iron, but no significant concentrations of priority
pollutants. On the basis of these considerations, screening
results for this subcategory are believed to identify all of the
priority pollutants appropriate for verification sampling and
control in this subcategory.
170
-------
Three organic priority pollutants, toluene, 1,1,1-trichloroethane
and butyl benzyl phthalate were detected in screening samples at
concentrations less than the quantifiable limit of 0.01 mg/1 and
were not selected for verification analysis. All other organic
priority pollutants detected in screening analysis for this sub-
category were selected for verification analysis.
The metal priority pollutants, antimony, arsenic, beryllium,
mercury, selenium, and thallium were not quantifiable in
screening analysis and are not known to result from any
manufacturing process in this subcategory. Consequently, they
were not selected for verification. All other metal priority
pollutants were detected in screening and were selected for
verification. In addition, asbestos is reported as a raw
material and was detected in screening samples. It was therefore
selected for verification.
A number of nonconventional pollutants were detected in screening
but were not selected for verification analysis. Cobalt, iron,
and manganese were detected at significant concentrations and
were selected for verification. In addition, the conventional
pollutants, oil and grease, total suspended solids and pH were
selected for verification analysis.
Magnesium Subcategory. The magnesium subcategory is unique in
the sense that manufacturing process elements and types of
pollutants generated vary from plant to plant. Consequently, one
set of parameters cannot be used to represent total screening for
the subcategory. All manufacturing processes, production
quantities and raw materials used, as well as priority pollutant
segments of dcp from all plants in this subcategory were
examined. On this basis, three process elements were selected
for wastewater screening analysis. For the heat paper production
process element, eighteen pollutant parameters were selected for
verification as discussed under the calcium subcategory (pages
189-193). Each of the silver chloride cathode processes was
sampled separately. Screening analysis results will be used for
verification because at present, production in this process
element is limited.
Zinc Subcategory. The following 33 pollutant parameters were
selected for further analysis for this subcategory:
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
38. ethylbenzene* 124. nickel
44. methylene chloride 125. selenium*
55. naphthalene* 126. silver
171
-------
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
sites. Because screening and verification parameter selection
was 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.
172
-------
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, TSS and pH were selected as verification
parameters.
Verification Data. Under the discussions and analysis for each
subcategory, verification parameter analytical results are
discussed and tabulated. Pollutant concentration (mg/1) and mass
loading (mg/kg) tables are shown for each sampled process. In
the tables 0.00 indicates no detection for all organic pollutants
except cyanide. For organic pollutants other than pesticides,
the symbol * is used to indicate detection at less than or equal
to 0.01 mg/1, the quantifiable limit of detection. For
pesticides (pollutants 89-105), the symbol ** indicates detection
less than or equal to the quantifiable limit of 0.005 mg/1. For
the metals and cyanide, total phenols, and oil and grease, 0.000
indicates the pollutant was not detected above the quantifiable
limit. When samples were flow proportionally combined for a
process, the values shown are calculated, and 0.0000 indicates
that the pollutant was detected in at least one sample of the
combined process wastewater stream. For chemical analysis, the
*'s are calculated as positive values which cannot be quantified,
but for statistical analysis are counted as zeroes.
CADMIUM SUBCATEGORY
This subcategory includes the manufacture of all batteries
employing a cadmium anode. Three battery types, mercury-cadmium,
silver-cadmium, and nickel-cadmium batteries, are included.
Nickel-cadmium batteries, however, account for over 99 percent of
the total mass of cadmium anode batteries produced. Manufacturing
plants in the subcategory vary significantly in production volume
and in raw materials, production technology, wastewater genera-
tion, and in wastewater treatment practices and effluent quality.
There are 13 plants in the data base for the subcategory. Three
of the 13 plants have closed, but moved the production to
existing plants. Nine of the remaining ten plants manufacture
cells based on the nickel-cadmium electrolytic couple. One of
these nine plants also produces silver-cadmium batteries. The
tenth plant manufactures mercury-cadmium cells, although
production at that plant is reported to be sporadic and quite
small in volume.
173
-------
Annual production reported in the subcategory totaled 4800 metric
tons of batteries in 1976. Using the latest available data at the
first writing of this document (1976-1979), estimated annual
production for each battery type was:
Battery Type Estimated Annual Production
kkg tons
nickel-cadmium 5242 5780
silver-cadmium 8.6 9.5
mercury-cadmium 0.045 0.05
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 kkg (980 tons) contained pasted or
pressed powder electrodes. The remainder of the nickel cadmium
batteries produced contained sintered electrodes. Plant pro-
duction rates range 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 producers of cadmium subcategory batteries also
manufactured 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 sub-
categories at only one of these plants, however. Production in
other subcategories produces process wastewater at only two other
cadmium subcategory plants, and wastewater 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.
Geographically, plants in the cadmium anode subcategory are
dispersed throughout the United States. There are two active
plants 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. The oldest manufacturing plant is reported to be only 15
years old.
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 plants, and nickel was reported as a raw material by
eleven of thirteen plants supplying data in the subcategory. Of
the remaining two plants, one produced only mercury-cadmium
batteries and the other produced nickel-cadmium batteries, but
obtain processed electrode material from another site. Cadmium
174
-------
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 is some-
times added to nickel cathodes as an aqueous solution in
impregnation operations as is nickel nitrate. Nickel hydroxide
is used in producing 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 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 com-
ponents. 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 desirable 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.
Manufacturing processes differ widely within the subcategory.
This results in corresponding differences in process water use
and wastewater discharge. A total of 16 distinct manufacturing
process operations or process elements were identified. These
operations are combined in various ways by manufacturers in this
subcategory and they provide a rational basis for effluent
limitations. Following a discussion of manufacturing processes
used in the subcategory each of these process elements is
discussed in detail to establish wastewater sources, flow rates,
and chemical characteristics.
Manufacturing Processes
As shown in the generalized process flow diagram of Figure V-l,
(page 391), the manufacture of batteries in this subcategory
comprises the preparation and formation of the anode and cathode,
assembly of these components into cells and batteries, and
175
-------
ancillary operations performed in support of these basic
manufacturing steps. Three distinct process elements for the
production of anodes, five for the manufacture of cathodes, and
eight different wastewater generating ancillary operations are
practiced 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 273). This table also lists the eight ancillary
operations that have been observed to involve water use and
wastewater discharge. The X's entered in the table under each
anode type and after each cathode type and ancillary operation
identify reported use of the designated manufacturing 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 provided
the framework for analysis of wastewater generation and control
in this subcategory. Several operations involve two or more
distinct process wastewater sources which must be considered in
evaluating wastewater characteristics. The relationship between
the process elements and discrete wastewater sources observed at
cadmium subcategory plants is illustrated in Figure V-2 (page
392) .
Anode Operations
Except for one plant, which obtains electrodes produced at
another plant, all manufacturers use cadmium or cadmium salts to
produce anodes. Three general methods for producing these anodes
are currently used, and they 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
precipitation of cadmium hydroxide from a cadmium salt solution.
Impregnated anodes are manufactured by impregnation of cadmium
solutions into porous structures and subsequent precipitation of
cadmium hydroxide in place.
Pasted and Pressed Powder - To make cadmium pasted and pressed
anodes, cadmium hydroxide is physically 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 (a) pressing
to form a button or pellet, or (b) pasting on a supporting grid.
176
-------
The charged state for these anodes is achieved in present
practice by formation after cell assembly.
One plant reports the manufacture of cadmium hydroxide on-site
for use in battery manufacture. Because 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 to be a separate
ancillary operation.
Formation of these anodes outside the battery case is not
presently practiced in the United States but is anticipated in
the near future by one manufacturer.
Electrodepos i ted - Electrodeposited anodes are produced by
electrochemically precipitating cadmium hydroxide from nitrate
solution onto the support material. (Neither in this discussion
nor subsequent discussion of electrodeposited nickel cathodes
does the term "electrpdeposit" mean deposition of metal as the
term is used in electroplating practice. "Electrodeposited" as
used in the , application of active material to anode or cathode
supports actually means "electrochemically precipitated." The
material deposited is a Jiydroxide. ) When the appropriate weight
of cadmium hydroxide has been deposited, the deposited material
is subjected to trharge and discharge cycles 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 derived from 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. Figure V-3 (page 394)
is a process flow diagram of anode production by cadmium
electrodeposition.
Impregnated - A third method of cadmium anode manufacture
involves submerging porous sintered nickel stock in an aqueous
solution of cadmium salts and precipitating 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 and is then
rinsed. 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
177
-------
generally followed by rinsing. Figure V-4 (page 395) is a
process flow diagram of anode production by cadmium impregnation.
Cathode Operations
Three of the five cathode manufacturing process elements are for
producing nickel cathodes. The other two are for producing
silver cathodes and mercury cathodes.
Nickel Pressed Powder Cathodes - Pressed powder cathodes,
including cathodes commonly described as "pocket plates" in the
literature, are made by blending solid powdered materials 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 used in 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. These cathodes in the unformed
(divalent) state, are assembled into batteries with unformed
anodes.
Nickel Electrodeposited - Sintered nickel grids prepared by
either the slurry or dry methods are used as the substrate upon
which nickel hydroxide is electrodeposited. (See discussion of
the use of "electrodeposited" under Anode Operations.) Nickel
powder in either a slurry or dry form is layered on nickel-plated
steel which passes through a furnace for sintering. 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 and electrochemically formed. After
formation is completed, the cathodes are removed from the tank
for subsequent rinsing and the spent formation caustic is dumped.
Figure V-5, (page 396) is a process flow diagram of cathode
production by electrodeposition.
Nickel Impregnated - The remaining method of nickel cathode
manufacture requires submerging porous sintered stock in an
aqueous solution of nickel salts. The product is next immersed
in a caustic solution to precipitate the nickel as nickel
hydroxide. The material is subsequently rinsed to remove
caustic, excess nitrate, and poorly adherent particles. The
178
-------
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 the cathode material is cleaned to remove
excess deposited material. The electrodes are then formed, or
they are 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. 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.
Figure V-6 (page 397) is a flow diagram of the process for
producing impregnated nickel cathodes. Nickel hydroxide washed
off the impregnated stock during 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.
Silver Powder Pressed - The production of silver cathodes begins
with preparing a silver powder which is then sintered. The
metallic silver cathodes which result are assembled into cells
and batteries with unformed cadmium anodes. The resulting
batteries are shipped in the unformed state.
Mercury Oxide Powder Pressed - Mercury cathodes are produced by
physical compaction of mercuric oxide.
Assembly
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
179
-------
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.
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 may be achieved.
Separators in open, pasted and pressed powder (pocket plate)
cells are frequently narrow plastic or hard rubber rods but may
be corrugated, perforated plastic sheets. In cells using
sintered electrodes, a variety of separator materials are used
including woven or nonwoven synthetic fabrics, sheet resin, and
cellophane. A three-layer separator comprised of a layer of
cellophane between two nylon layers is frequently used. In
sealed cells, separators are often made of felted nylon.
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 performance. 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
release gas 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 they open only when abnormal conditions cause
pressures to rise above normal limits.
Ancillary Operations - In addition to the basic electrode
manufacture and assembly steps, a number of wastewater generating
process operations or supporting functions are required for the
production of cadmium subcategory batteries. These wastewater
generating ancillary operations discussed under "Process Water
Use" includes: (1) washing assembled cells; (2) preparing
electrolyte solutions; (3) cleaning process floor areas and
equipment; (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. Ancillary operations such
as welding and drilling or punching which do not generate
wastewater are not discussed in this section.
180
-------
Water Use, Wastewater Characteristics/ and Wastewater
Discharge
Process Water Use
Process water is used in many of the operations performed in the
manufacture of batteries in this subcategory. Flow rates are
sometimes high. Process wastewater is discharged from most
plants and usually it results from several different manufac-
turing processes. Because of the large number of different
wastewater producing operations in the subcategory and the
variety of operations that are combined at an individual plant,
plant wastewater discharges are observed to vary widely in flow
rate and in chemical characteristics. Wastewater treatment
practices and effluent quality also vary significantly within the
subcategory. However, the flow rates and chemical charac-
teristics of wastewater from specific process operations
performed at different sites are generally similar. Observed
differences can usually be accounted for by variations in plant
water conservation practices.
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 summarized in Table V-10 (page
274). This table also presents the production normalizing
parameters upon which the reported flows are based and which were
discussed in Section IV, and the annual raw waste volume for each
process. The water use and wastewater discharge from these
process operations varies from 1 liter per kilogram of cadmium
used for the manufacture of cadmium hydroxide production to 1640
liters per kg of impregnated nickel for sintered impregnated
electrodes.
Process Wastewater Characteristics
Anode Operations - Cadmium Pasted and Pressed Powder Anodes
Preparation of the solid active materials is not included in this
process group.
Only limited discharge of process water is associated with
production of pasted and pressed cadmium powder anodes. The only
wastewater discharge from anode production is process area
maintenance. Two plants (A and B) use water to clean floors and
equipment. The wastewater was sampled at Plant A. The analyses
are presented in Table V-ll (page 275). Table V-12 (page 276)
shows the pollutant mass loadings in the clean-up wastewater
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. However,
181
-------
anticipated production changes by at least one manufacturer to
include formation of anodes outside the cell could introduce an
additional wastewater source for this process element.
Cadmium Electrodeposited Anode - The wastewater resulting from
cadmium anode electrodeposition was sampled at one plant allowing
pollutant characterization and confirmation of the information
provided in dcp. 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 wastewater 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
wastewater streams discussed above. Table V-13 and V-14 (pages
277 and 278) show the pollutant concentrations and mass loadings
for this process sequence.
Cadmium Impregnated Anode - There are seven points of wastewater
discharge in the process sequence including (1) sintered stock
preparation clean-up; (2) cadmium impregnation rinses; (3)
impregnation caustic removal; (4) electrode cleaning waste
discharge; (5) soak water discharge; (6) formation caustic
removal; and (7) post-formation rinse.
Analytical results from the second and third sampling days are
presented in Table V-15 (page 279) to characterize the raw
wastewater from the- cadmium impregnation process. Sampling
results from the first day are excluded because the impregnation
process did not operate on that day. All wastewater streams were
sampled except sintered stock preparation clean-up and the
formation caustic dump on the third day. The spent formation
caustic wastewater 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. Wastewaters from
anode cleaning, which are included in the analyses shown, were
not observed at all sites producing impregnated cadmium anodes.
In evaluating the data in Table V-15 it should be noted that the
wastewater characteristics for the impregnation rinse on day 3
are not considered representative of the normal process dis-
charge. The data for day 2 (columns 1 and 3) are considered to
provide the best available characterization of the total raw
waste from this process operation.
Cathode Operations - Nickel Pressed Powder Cathodes - No
wastewater discharge was reported from manufacturing cathodes in
182
-------
this group except for effluent from the production of nickel
hydroxide by chemical precipitation at one plant. The
precipitation process is addressed as a separate ancillary
operation in this subcategory.
Nickel Electrodeposited Cathodes - Wastewater 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-16 (page 280)
presents the verification analysis results of the post-formation
rinse discharge (on a daily basis). Table V-17 (page 281)
presents the daily pollutant mass loadings based on the weight of
active nickel applied to produce the cathode.
Nickel Impregnated Cathode - A total of eleven different sources
of process wastewater are associated with this variation of
nickel cathode manufacture. These wastewater sources include:
(1) nickel paste clean-up; (2) spent impregnation caustic; (3)
impregnation rinses; (4) impregnation scrubbers (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. Any
wastewater generated as a result of nickel hydroxide recovery is
also attributable to this process element.
Seven plants reported the manufacture of impregnated nickel
cathodes. One of these subsequently moved their production. Of
the remaining six plants, four plants, A, B, C, and D, were
visited for on-site data collection and wastewater sampling.
These plants collectively produced all of the wastewater streams
identified. Total wastewater discharges from nickel cathode
production were characterized for each day of sampling at each
plant by summing the discrete wastewater streams characterized
above. Th/is approach was required because wastewater 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-18 (page 282). Table V-19 (page 283) presents
corresponding pollutant mass loadings. Statistical analyses of
these data are presented in Table V-20 and V-21 (pages 284 and
285) .
Silver Powder Pressed Cathode - No process wastewater is
generated in producing silver powder pressed cathodes. Waste-
water does result from the production of silver powder used in
183
-------
these electrodes. This discharge source is discussed separately
as an ancillary operation under the zinc subcategory.
Mercuric Oxide Cathode - No process wastewater discharge is
reported from production of mercuric oxide cathodes in the
cadmium subcategory.
Ancillary Wastewater Generating 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 plants produce comparable products without the
need for cell washing. The quantity of water used to wash cells
ranges from 3,032 to 15,746 liters per day (7521 I/day mean).
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). The discharge flow rate reported by plant B, however,
reflects the combined wastewater from cell washing and floor area
clean-up.
The cell wash wastewater at these plants was not sampled and no
historical sampling data specifically representing wastewater
from the wash operations was provided. However, no additional
raw 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 wastewater 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-93 and V-
94 (pages 359 and 360), 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
requires pumps and other equipment which are intermittently
cleaned. Two plants reported wastewater discharge from electro-
lyte 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 wastewater stream. The only raw
materials involved are potassium hydroxide and lithium hydroxide
which are not expected to contribute any priority pollutants to
184
-------
the wastewater stream. The volume and pollutant loads
contributed by this wastewater sourc? are minimal.
Floor and Equipment Wash - Some plants use water for floor and
equipment maintenance in process and assembly areas. Three
plants in the data base reported using water for this purpose in
the cadmium subcategory. 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
electrodeposition 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-22 (page 286). In addition, Table V-23
(page 287) 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 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-24 (page 288) 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
assembling batteries. The other two samples were taken during
the first shift when the number of employees washing their hands
was approximately fifteen times greater. Table V-25 (page 289)
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.
i
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 charac-
terized by sampling. The resulting concentrations together with
corresponding pollutant mass loadings based on the total dis-
charge flow are shown in Table V-26 (page 290).
185
-------
Silver Powder Production - Silver powder used specifically for
battery cathodes is produced primarily for silver oxide-srinr
batteries, but also for silver-cadmium batteries. Discussion of
this operation is under ancillary operations in the zinc sub-
category, on page 234. Results of analysis of wastewater samples
collected on three successive days are presented in Table V-113
(page 379). Production normalized discharge volumes and
corresponding pollutant mass loading for each sampling day are
shown in Table V-114 (page 380).
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.
This operation was observed during data collection for this
study, but the resultant wastewater discharge was not
characterized by sampling. However, characteristics of the
resultant effluent as supplied by the plant are presented in
Table V-32 (page 296). Pollutant wastewater characteristics from
this process are similar to nickel impregnated cathodes.
Cadmium Hydroxide Production - Cadmium hydroxide for battery
manufacture is produced by thermal oxidation of cadmium to
cadmium oxide, addition of nickel sulfate, hydration of cadmium
oxide to the hydroxide, and drying of the product. Process
wastewater results only from the contamination of seal cooling.
As discussed for nickel hydroxide production, this operation was
observed but its wastewater was not characterized by sampling.
Wastewater from cadmium hydroxide production is combined with
other process wastewater streams prior to treatment. Reported
characteristics of the resultant effluent are presented in Table
V-32 (page 296). Pollutant wastewater characteristics from this
process are similar to impregnated anodes.
Total Process Wastewater Discharge and Characteristics
•
Water use and wastewater discharge are observed to vary widely
among cadmium subcategory plants with process wastewater flow
rates ranging from 0 to 450,000 I/day. Individual plant effluent
flow rates are shown in Table V-27 (page 291). Most of the
observed wastewater flow variation may be understood on the basis
of manufacturing process variations. Plants with different
process sequences produce different volumes of process waste-
water. 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,
186
-------
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.
Total process wastewater flow and characteristics were determined
for four plants in the cadmium subcategory which were sampled.
These characteristics, reflecting the combined raw wastewater
streams from all cadmium subcategory process operations at each
site on each of three days of sampling, are summarized
statistically in Table V-28 (page 292). Prevailing discharge and
treatment patterns in this subcategory generally preclude
directly sampling a total raw wastewater stream because
wastewaters from individual process operations are often treated
or discharged separately. In other cases, individual process
wastewaters are mixed with other wastewater streams such as non-
contact cooling wastewater and electroplating wastewater prior to
combination with other cadmium subcategory wastewater streams.
Consequently, the total process wastewater characteristics shown
in Table V-28 were determined for each plant by mass balance
calculations from analyses of wastewater samples from individual
process operations.
As Table V-28 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 varia-
tions, 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.
Wastewater Treatment Practices and Effluent Data Analysis
Reported treatment applied to cadmium subcategory process
wastewater (Table V-29, page 293) shows that all but one of the
plants which produce process wastewater provide settling for the
removal of suspended solids and metal precipitates. Filtration
for further pollutant removal was provided at four sites.
Despite this apparently high level of treatment, on-site
observations at visited plants revealed that th«=> treatment
nominally employed was often marginal in its design and
operation. An analysis of the treatment in place was done for
both active and inactive plants which submitted process
information. Some of these plants were visited and sampled,
others provided effluent data, and others just reported what
treatment was in place.
At one plant which was visited, "settling" was found to occur in
sumps in process areas which were observed to provide only
187
-------
limited retention time at average flow rates. The effectiveness
of these sumps was further reduced by the fact that they were
subject to very high surge flows during which essentially no
settling occurred. Finally, several of these sumps were almost
completely filled with accumulated solids so that essentially no
further settling out could occur. The results of sampling and
analysis at this site (Table V-2, page 244) confirmed the
extremely high (41 and 46 mg/1) effluent concentrations of
cadmium and nickel shown in this plant's dcp (Table V-32, page
296).
At another plant which was visited for sampling and on-site data
collection, segregated cadmium subcategory process wastewater
streams were treated in batch systems providing pH adjustment,
settling, and filtration. Although the obvious deficiencies in
treatment at the first plant were not noted at this site, the
general level of control maintained over treatment system
operation was inadequate as shown by the highly variable effluent
performance observed by sampling. Analysis results shown for
this plant in Table V-30, Treatment System I and II (page 294),
indicate a number of irregularities characteristic of inadequate
treatment plant performance. For example, effluent metals
sometimes exceeded raw wastewater values even though TSS values
were low. This indicates that the metals were not precipitated.
Similarly, finding treated TSS levels above raw TSS levels may
indicate poor treatment operation.
A third cadmium subcategory plant was visited for sampling
treated process wastewater in a settling lagoon after separate
treatment of some wastewater streams in settling tanks. At this
plant, however, neither pH adjustment nor the use of settling
aids (coagulants or flocculants) was practiced. As the analysis
of data from this plant (Table V-31, page 295) shows, the
effluent pH was consistently outside the optimum range for
treatment of these wastes.
Effluent concentration data provided in dcp from cadmium
subcategory plants which are presented in Table V-32 (page 296)
were evaluated in the light of the on-site observations and
sampling results discussed above. Plants D and A (Table V-32)
were visited for sampling, and are discussed. Plants E and F (no
longer active), and H (Table V-32) did not provide sufficient
information to allow a definitive evaluation of treatment system
operating parameters. Plants E and H used the equivalent of
chemical precipitation and settling technology. Plant F used
precipitation and settling followed by ion exchange.
Plant B (Table V-32) which was visited, but not sampled,
practices combined treatment of cadmium subcategory process
188
-------
wastewater and of other similar wastewaters. The treatment
provided included pH adjustment, settling in a lagoon, sand
filtration and final pH adjustment. At this site a large volume
of noncontact cooling water from cadmium subcategory processes
was also discharged to treatment, increasing the mass of
pollutants in the effluent attributable to cadmium anode battery
manufacture by a factor of nearly two. Since the initial
collection of data, this plant has upgraded its wastewater
treatment and control plants to provide additional treatment and
complete recycle of all process wastewater. As a result, this
plant is presently achieving zero discharge of process wastewater
pollutants.
Plant C (Table V-32) has chemical precipitation, settling and
filter technology in place; however, from the data submitted,
proper pH control was not maintained.
The two remaining active cadmium subcategory plants and one
inactive plant achieved zero discharge of process wastewater by
in-process control techniques or process variations which
eliminated the generation of process wastewater.
After evaluating all dcp and plant visit effluent data, the
conclusion is made that although plants which discharge have
treatment equipment in place, the operation and maintenance of
these systems are generally inadequate for treating cadmium
subcategory pollutants.
CALCIUM SUBCATEGORY
This subcategory covers the manufacture of calcium anode thermal
batteries for military applications. These batteries are de-
signed for long term inactive storage followed by rapid activa-
tion and delivery of relatively high currents for short periods
of time. These characteristics are achieved by the use of solid
electrolytes which at the moment of use are heated to above their
melting point to activate the cell. Heat is supplied by chemical
reactants incorporated as a pyrotechnic device in the cell.
Because calcium, the cell anode material, reacts vigorously with
water, water use is avoided as much as possible in manufacturing
these batteries. Production volumes are generally small and
manufacturing specifications depend 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.
Calcium anode batteries are produced at three plants. All
production is governed by military specifications, and products
from different plants are not, in general, interchangeable.
189
-------
Specific raw materials used in manufacturing these batteries
differ somewhat from plant to plant although the use of calcium,
iron, lithium and potassium chlorides, calcium chromate,
zirconium, barium chromate, and asbestos is common to all
manufacturers of these batteries. Other raw materials used are:
silica, kaolin, glass fiber, and potassium dichromate. 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;
Manufacturing Processes
To manufacture calcium anode thermal batteries cell anodes,
depolarizers, electrolytes, and the cell activators (heating
elements) are prepared. These elements are assembled with
current collectors, insulators, initiators, and containers into
cells and multicell batteries. A generalized process flow
diagram is shown in Figure V-7 (page 398). The relationship
between the process elements and discrete wastewater sources
reported at battery plants is illustrated in Figure V-8 (page
399).
Anode Operations
Calcium anode material is generally produced by vapor deposition
of calcium on a substrate of metal such as nickel or iron which
serves both as a current collector and support for the calcium
during cell operation.
Cathode Operations
Cathodic depolarizers for calcium anode cells include calcium
chromate, tungstic oxide, and potassium dichromate. They are
incorporated into the cells in one of several ways including
impregnation of fibrous media, pelletization of powders, and
glazing. Electrolyte is incorporated into cells similarly - some
cell designs even combine the depolarizer and electrolyte.
Almost all cells in production at the time of the survey used a
lithium chloride-potassium chloride eutectic mixture as the
electrolyte.
One form of cell uses a fibrous medium to immobilize the
electrolyte. The fibrous medium, such as glass tape, is
impregnated by dipping it in a fused bath of electrolyte,
depolarizer, or a mixture of electrolyte and depolarizer. The
impregnated material is allowed to cool and then is cut to shape
for the specific cell design. Alternatively, the depolarizer or
electrolyte may be ground to powder, mixed with a binder such as
190
-------
kaolin or silica, and pressed to form a pellet of suitable size
and shape. In general, pellets containing the depolarizer con-
tain electrolyte as weii to ensure adequate conductivity, and
multilayer pellets containing both depolarizer and electrolyte
layers are produced. Pellets are also produced which are a
homogeneous mixture of electrolyte and depolarizer throughout.
Ancillary Operations
Heating Component Operations. The heating component containing
highly reactive materials is an essential part of a thermal cell.
Two basic types of heating components are reported to be in use:
heat paper containing zirconium powder and barium chromate; and
heat pellets containing iron powder and potassium perchlorate.
To produce heat paper, zirconium powder, barium chromate (which
is only sparingly soluble), and asbestos or other inorganic
fibers are mixed as an aqueous slurry. The slurry is passed
through a filter screen 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 then is discharged.
Heat pellets are prepared by mixing potassium perchlorate and
iron powders and pressing the mixture to form a pellet. Heat
paper is nonconductive 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
part of the cathode current collector as well as the source of
heat to activate the cell.
Battery Assembly - Assembly of batteries from these components
frequently involves the creation of stacked multicell 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.
Cell Testing - After assembly the cells are hermetically sealed,
and may be immersed in a water bath to test for leakage.
i
Water Use, Wastewater Characteristics, and Wastewater
Discharge
Process Water Use
The manufacturing of calcium anode batteries produces little
wastewater since most of the production processes involved are
dry. As mentioned earlier, the limited use of water is due to
the vigorous reaction of calcium with water and the safety
problems inherent to this reaction.
191
-------
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-33 (page 297).
This table also presents the production normalizing parameters
upon which the reported flows are based, and the annual raw waste
volume for each process. Heat paper production in the calcium
subcategory as well as the lithium and magnesium subcategory is
similar. For this reason data for developing the normalized flow
was combined. Annual raw waste volumes from heat paper
production are separate for each subcategory.
Process Wastewater Characteristics
Anode and Cathode Operations - No process wastewater discharge is
reported from the production of anodes and cathodes in the
calcium subcategory.
Ancillary Operations - Heating Component Production - (Heat
Pellet Production) No process wastewater discharge is reported
from the production of heat pellets. (Heat Paper Production)
This process is the major wastewater generating operation in this
subcategory. The production normalizing parameter for this
process is the weight of reactants used (barium chromate and
zirconium). Sampling data from plants A and B characterizing
this wastewater stream are presented in Table V-34 (page 298).
As shown in the table, the major pollutants are chromium (from
the barium chromate) and total suspended solids. The pollutants
mass loadings for this waste stream are shown in Table V-35 (page
299). The two plants have similar wastewaters, but plant B has
much higher concentrations of the pollutants as well as a
substantially higher production normalized wastewater discharge.
The latter fact indicates less efficient deposition of the
reactants on the heat paper filter substrate at plant B than at
plant A.
Cell Testing - At plant A, cell testing produces about 50 gallons
of wastewater per year and water use for washing containers is
equally small. These operations are considered to contribute no
significant amounts of priority pollutants to the wastewater
discharge and were not specifically sampled.
Wastewater Treatment Practices and Effluent Data Analysis
Present treatment practice at calcium subcategory plants is
limited to settling as is shown in Table V-36 (page 300).
Process wastewater is either contract removed or discharged to a
POTW. One plant reports no process wastewater from the
manufacture of calcium subcategory batteries.
192
-------
Effluent characteristics reported by one plant in this
subcategory are presented in Table V-37 (page 301). Data
reported by this plant are specifically for the effluent from
heat paper production.
LECLANCHE SUBCATEGORY
This subcategory covers 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. Cells with silver
chloride cathodes, however, comprise less than 0.01 percent of
the total production in the subcategory.
There are several distinct variations both in form and in
manufacturing process for the Leclanche cell, with corresponding
differences in process water use and wastewater discharge. Most
of the production is in the form of standard, round "dry cells,"
but other shapes are produced for special purposes, flat cell
batteries, foliar film pack batteries, and air-depolarized
batteries.
Wastewater discharge results only from separator production and
from cleanup of miscellaneous equipment. After a discussion of
the manufacturing processes employed in the subcategory, the
process elements that produce wastewater are discussed in greater
detail. The available data regarding specific wastewater
sources, flow rates, and chemical characteristics is presented
followed by a discussion of treatment in place and effluent
characteristics.
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). Annual production for
1982 was received on one plant which had not changed
significantly from the data submitted earlier.
193
-------
Geographically, plants in the Leclanche subcategory are in the
eastern United States, with the single exception of a plant in
Texas. There are eight active plants 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 plants ranges from three years to
many decades.
Manufacturing Processes
As shown in the generalized process flow diagram of Figure V-9
(page 400), the manufacture of batteries in this subcategory
comprises the preparation of the anode and cathode, the prepa-
ration or application of the separator, assembly of these
components into cells and batteries, and ancillary operations
performed in support of these basic manufacturing steps.
The observed variations in anode, cathode and separator
manufacture and the combinations of these processes carried out
at existing plants together with ancillary operations that were
observed to generate wastewater are shown in Table V-38 (page
302). These variations provide the framework for analysis of
process wastewater generation in the Leclanche subcategory as
indicated in Figure V-10 (page 401). These tables and figures
have been revised following an evaluation of comments received
and a plant visit made after proposal concerning foliar battery
production. Specific changes are detailed below. Of thirteen
identified process elements in this subcategory, only five
generate process wastewater. Three of these were characterized
by wastewater sampling at two plants in the subcategory.
Wastewater discharge from the fourth element is believed to be
similar in character, and is eliminated by recycle in present
practices. Wastewater discharge from the fifth element is
believed to be similar in character to the sampled wastewaters
for equipment and area cleanup.
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, 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.
Anode Operations
194
-------
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 other form
of zinc sheet metal anode is a flat zinc plate.
Preparation of powdered zinc anodes for foliar cells 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 Operations
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 on a
conductive substrate. These cathode types are combined with zinc
anodes and electrolyte to make cells with a variety of con-
figurations and performance characteristics.
Manganese Dioxide - 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 plants discontinued operations during 1979,
leaving 13 active plants. Based on survey and visit data, the
raw materials added to the manganese dioxide ore to make a
cathode may include acetylene black, carbon black, graphite,
magnesium oxide, mercury, and ammonium chloride. Typically,
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 - Porous carbon cathode manufacture consists of:
blending carbon, manganese .dioxide, and water; molding the
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".
195
-------
Silver Chloride - 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.
Pasted Manganese Dioxide - For the pasted MnO2 cathode a paste
consisting of manganese dioxide, carbon, and latex is applied to
a conducting film. The steps used to prepare this film are
similar to the steps described above for the zinc powder anode.
The cathode paste material is applied on the film in rectangular
spots, directly opposite the anode spots.
Ancillary Operations
Separator Operations - Separators are used to isolate the cathode
from the anode, while providing an ionically conductive path
between them. Separators consist of gelled paste, treated paper,
or plastic sheet.
Cooked Paste Separator. In cells using cooked paste, the
temperature is elevated to set the paste. 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 gel. After the paste is set, the can is removed from
the hot water bath and final assembly operations are conducted.
One plant reported producing "cooked" paste separator cells.
Uncooked Paste Separator. Some paste formulations are used which
set at room temperature. The paste formulation includes zinc
chloride, ammonium chloride, mercuric chloride, cornstarch, and
flour. The paste is held in cold storage until it is injected
into the zinc anode cans. After the insertion of the compressed
cathode, the paste is allowed to set. Then final assembly
operations are performed to prepare the cells for shipping.
One plant manufactures carbon-zinc cells with an uncooked paste
separator. Two plants produce uncooked paste separator material
for use in silver chloride-zinc cells. Flour, zinc chloride and
ammonium chloride are used in formulating the separator paste.
Pasted Paper (With Mercury) Separator. Pasted paper separators
are made by blending a paste-like material; applying it to 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.
196
-------
The manufacture of pasted paper separator material containing
mercury is specific to battery manufacturing and is included
under battery manufacturing, when pre-pasted paper is purchased
by the cell assembler, the separator material is inserted, as
purchased, directly into the zinc can, followed by cathode mix.
Pasted Paper (Without Mercury) Separator - Some of the Leclanche
cell manufacturers use pre-pasted paper separator material which
does not contain mercury. Manufacture of the paper separator
material which does not contain mercury is not specific to the
battery industry because the product has other industrial uses in
addition to Leclanche cell manufacturing.
Cell Assembly - Cell assembly processes differ for paper
separator cells, paste cells, flat cells, carbon cathode cells,
silver chloride cathode cells, and pasted cathode cells. To make
paper separator cells, a pre-coated paper separator is first
inserted into the zinc can. The depolarizer mix and carbon rod
(current collector) are put in 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, the paste mixture is poured into a zinc
can. The depolarizer-electrolyte mix, molded around a central
carbon rod, is pushed into the paste. 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.
Flat cell production includes 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.
Duplex electrodes and depolarizer-electrolyte cakes are stacked
with a paper separator in between and a plastic sleeve around the
four sides and overlapping the top and bottom of the cell. The
cells 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.
To assemble porous carbon cathode cells, the porous carbon
"agglo" cathode is inserted into the zinc anode container. An
197
-------
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.
The pasted Mn02 cathode foliar cell is assembled by interleafing
separator sheets between 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, some
equipment cleanup practices cannot be associated with production
of only one of the major cell components, anode, cathode, or
separator operations. They include the clean-up of equipment
used in assembling cells, employee handwash in the production
area, as well as the preparation and delivery of electrolyte.
Foliar Battery Miscellaneous Wash - Foliar battery production
equipment and cleanup practices are separated out from the other
Leclanche subcategory equipment and area cleanup practices.
Although these practices are similar, unique physical dimensions
of the foliar battery and product quality requirements make the
water use requirements different from the other batteries
produced in this subcategory.
Water Use, Wastewater Characteristics, and Wastewater
Discharge
Process Water Use
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.
Mean and median normalized discharge flows from both dcp and
visit data for each of the wastewater producing elements included
in this subcategory are summarized in Table V-39 (page 303).
This table also presents the production normalizing parameters
upon which the reported flows are based and which were discussed
in Section IV, and the annual raw waste volume for each process.
198
-------
Process Wastewater Characteristics
Anode and Cathode Operations - There is no process wastewater
associated specifically with Leclanche anode or cathode
manufacture.
Ancillary Operations - Cooked Paste Separator - The source of
direct process wastewater discharge from making cooked paste
separators 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 waste from the operating machinery. Wastewater from the
paste separator manufacture was sampled at the only plant
reporting the use of this process. The only source of direct
process discharge is from the hot bath paste setting. At this
plant, no wastewater was discharged from either the paste
preparation or paste clean-up operations, due to in-process
controls. The paste preparation water supply tank held water
previously used for cleaning. The sources of water reused in
mixing the paste included 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 cathode 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
contacted the paste was collected for reuse in paste formulation,
and this closed system limits mercury contamination of the
wastewater.
Total discharge production normalized flows 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 included
wastewater from each of the three discharge sources. The
analytical results are presented in Table V-40 (page 304). Table
V-41 (page 305) presents the pollutant mass loadings based on the
weight of finished cells for each of the three sample days.
Pollutants found in this flow-proportioned combined stream are
mercury, manganese and zinc, TSS and oil and grease.
Uncooked Paste Separator - The only source of wastewater
discharge from the preparation of uncooked paste is paste tool
cleaning. The wastewater stream from tool cleaning estimated at
less than 5 liters per day was not sampled. The paste does not
contain mercury, and zinc is the only toxic pollutant expected to
be found in the wastewater.
Pasted Paper With Mercury Separator - The only source of
wastewater discharge during manufacture of pasted paper (with
199
-------
mercury) is hand washing and washing of equipment used -to handle
the paste.
Wastewater from the manufacture of paper separators with mercury
was sampled. The measured flows ranged from 0.11 to 0.17 I/kg of
applied dry paste material (0.14 I/kg mean). The analytical
results for this waste stream are presented in Table V-42 (page
306). Table V-43 (page 307) 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 production areas.
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 was considerable variability in
pollutant concentrations during the three sampling days because
of the sporadic 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 - Because this, product is
not unique to the manufacture of batteries, the wastewater
generated is riot included in the battery category.
Cell Assembly - No wastewater discharge is attributed to cell
assembly. All wastewaters generated during cell assembly are
allocated to separator preparation or to equipment and area
cleaning.
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: electrolyte preparation equipment wash, electrode
preparation equipment wash, cathode carrier wash, miscellaneous
equipment wash, and hand washing. Out of the nineteen active
Leclanche plants, twelve reported no discharge of process
wastewaters. One of the nineteen did not report data on flow or
discharge. The six remaining plants reported both water use and
water discharge. All six reported wastewater discharge from
equipment and area cleanup. Plants A, E and F reported
wastewater from electrolyte preparation equipment wash; plant D
200
-------
reported wastewater from electrode preparation equipment wash;
plant B reported wastewater from cathode carrier wash; and Plant
C reported wastewater from hand wash and miscellaneous equipment
wash.
Table V-44 (page 308) indicates the best available information on
equipment and area cleanup wastewater discharges for the nineteen
active 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-45
(page 309). Table V-46 (page 310) presents pollutant mass loads
expressed as milligrams discharge per kilogram of cells produced.
Table V-47 presents statistics based on the values in Table V-45,
and Table V-48 (page 312) presents statistics based on the values
in Table V-46.
Foliar Battery Miscellaneous Wash - After receiving comments
defining the differences of foliar battery production, the
comments were evaluated, a visit was made to a foliar battery
plant, and additional data on specific water use requirements
were received. Although the chemical characteristics of the
battery and the wastewater generating processes for equipment
cleaning are similar to the other Leclanche plants, the physical
configuration of the product creates unique problems. Minute
quantities of impurities in the water can cause product failures.
For this reason, separate flows were obtained for this process.
Data received indicates that the production normalized flow is
0.132 liters per kilogram of cells produced. Wastewater
characteristics are believed to be similar to those in Table V-45
because raw materials used are the same and washing practices are
similar.
Total Process Wastewater Characteristics
Total process wastewater flow and characteristics were determined
for two plants in the Leclanche subcategory which were sampled.
These characteristics, which reflect the combined raw wastewater
stream at each site on each of three days of sampling, are
summarized statistically. The statistical summary of total
process wastewater characteristics from Leclanche subcategory
plants is presented in Table V-49 (page 313).
Wastewater Treatment Practices and Effluent Data Analysis
201
-------
Twelve plants do not discharge any wastewater. Five of the 19
active plants in the Leclanche subcategory have wastewater
treatment systems. Two plants discharge without treatment.
Table V-50 (page 314) summarizes treatment in place for this
subcategory. The most frequent technique was filtration, which
was reported at four plants. Three plants reported pH
adjustment, two reported coagulant addition, one reported
skimming, and one reported carbon adsorption.
Table V-51 (page 315) shows reported effluent quality at the
Leclanche plants. Comparing this table with the treatment system
information 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.
The treatment effectiveness at one plant was determined by
sampling on three days. The results of sampling presented in
Table V-52 (page 316) show that the skimming and filtration
effectively lower oil and grease and TSS. However, because the pH
was not controlled at the optimum level (8.8-9.3), zinc and
manganese levels actually were higher after treatment than
before. This indicates improper operation of the system.
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 con-
siderably 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.
Seven plants reported the manufacture of a total of eight
different types of batteries within this subcategory. Because
lithium battery technologies are rapidly changing, production
patterns are also undergoing rapid change. Three of the 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 for any single year. Based on the submitted figures,
production ranges from less than 50 kg per year (100 Ibs/yr) to
14 kkg/yr (15.5 tons/yr) and in employment from 4 to 175. One
plant accounts for more than half of the total subcategory
output. However, several plants reported only prototype, sample,
or startup production with larger scale operations anticipated in
the future. In the data base, lithium subcategory production is
202
-------
heavily concentrated in the northeastern U.S. with one plant in
EPA Region 1, two in Region III and three in Region II. The
other producer was a small operation in Region IX.
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.
Manufacturing Processes
The manufacture of batteries in this subcategory is illustrated
in the generalized process diagram shown in Figure V-l1 (page
402). The manufacture of lithium anodes generally involves only
mechanical forming of metallic lithium to the desired
configuration. 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. Cell assembly techniques differ with
specific cell designs. 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, cathode depolarizer, and electrolyte
discussed above. The relationship between the process elements
and discrete wastewater sources reported at battery plants is
illustrated in Figure V-l2 (page 403).
Anode Operations
All cells manufactured in this subcategory employ a metallic
lithium anode. The anode is generally prepared from purchased
lithium sheet or foil by mechanical forming operations only,
although one plant 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 nonreactive 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 (nonthermal) lithium cells are designed do not
necessitate maximized anode surface areas.
Cathode Operations
Iodine Cathodes - 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
203
-------
is solid lithium iodide which forms at the interface between the
anode and depolarizer after assembly of the cell.
Iron Bisulfide Cathodes - Iron disulfide is used as a depolarizer
in thermal batteries which use lithium anodes.
Lead Iodide Cathodes - This cathode is reported to be a mixture
oflead iodide, lead sulfide and lead. Fume scrubbers are used
in the production areas.
Lithium Perchlorate Cathodes - Manufacture of this type of
cathode was reported only on a small scale in sample quantities.
Manufacturing process details were not supplied.
Sulfur Dioxide Cathodes - The manufacture of cathodes for cells
using sulfur dioxide depolarizer begins with the preparation of a
porous carbon electrode structure. Binders such as teflon may be
added to a carbon paste which is applied to a metallic grid. T^e
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 added to the cells, and they
are sealed.
Thionyl Chloride Cathodes - Production of cells using thionyl
chloride as the depolarizer is similar to that discussed above
for sulfur dioxide depolarized cathodes except that the organic
electrolyte acetonitrile is not used.
Titanium Bisulfide Cathodes - 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.
Water Use, Wastewater Characteristics, and Wastewater
Bischarqe
Process Water Use
As previously indicated, water use and process wastewater
discharge in this subcategory is quite limited. Three of seven
plants in the subcategory reported process wastewater discharges.
These ranged from 3.9 1/hr to 150 1/hr. Mean and median
normalized discharge flows from both dcp and visit data for each
of the wastewater producing elements included in this subcategory
are summarized in Table V-53 (page 317). This table also
presents the production normalizing parameters upon which the
reported flows are based and which were discussed in Section IV,
and the annual raw waste volume for each process.
204
-------
Process Wastewater Characteristics
Anode Operations - There is no process wastewater associated
specifically with lithium anode manufacture.
Cathode Operations - There is no process wastewater associated
with the manufacture of the following cathodes: iodine, lithium
perchlorate, and titanium disulfide.
Lead Iodide Cathodes - The manufacture of lead iodide cathodes
generates process wastewater from equipment cleaning. This
process is separated from the ancillary floor and equipment wash
because of the presence of lead. This process was not
specifically sampled, however pollutant concentrations are
expected to be similar to those in the iron disulfide process.
Iron Disulfide Cathodes - The manufacture of iron disulfide
cathodes generates process wastewater. In the manufacture of
iron disulfide cathodes, process wastewater is generated. The
chemical analysis data for process wastewater from the
manufacture of iron disulfide cathodes at Plant A are presented
in Table V-54 (page 318). The corresponding mass loadings for
this stream are shown in Table V-55 (page 319).
Sulfur Dioxide Cathodes - The manufacture of sulfur dioxide
cathodes does not generate wastewater in the actual production
operations, but wastewater results from air scrubbers used to
control sulfur dioxide emissions. Wastewater from the scrubbers
is included under ancillary operations.
Thionyl Chloride Cathodes - The manufacture of thionyl chloride
cathodes is reported to generate two process wastewater streams
resulting from wet air pollution control scrubbers . and from
washdown of spilled materials. Wastewater discharge from spills
occurs only when there are accidents and since none occurred this
process stream could not be sampled. Wastewater generated from
air scrubbers is included under ancillary operations.
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. The
sampling analysis data and the corresponding mass loadings for
the wastewater stream produced by heat paper production are
listed in Tables V-34 and V-35 (Pages 298 and 299) which were
discussed in the calcium subcategory. (Heat Pellet Production) -
No process water use or discharge is generated from this process
which is usf-d in the manufacture of thermal batteries. Heat
205
-------
pellet production is identical to that discussed under the
calcium subcategory discussion.
Cell Washing - Following assembly lithium cells can be washed.
Wastewater is discharged from this process. Washing lithium
cells was reported to produce process wastewater at one plant.
The total volume of wastewater was about 55 gallons per week, and
was periodically discharged. The production normalized discharge
volume is 0.929 I/kg of cells produced. No priority pollutant
chemical characteristics were .reported by the plant and the
operation was not characterized by sampling.
Cell Testing - After assembly, thermal cells may be immersed in a
water bath to test for leakage. The contents of this bath may be
discharged on an infrequent basis. Wastewater from testing of
thermal cells is identical to that for calcium anode thermal
batteries which was discussed on page 192.
Scrap Disposal - Lithium scrap is disposed of 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. Plant A disposes of
scrap lithium off-site with a single aeration process in a
settling tank. The plant reported that the resulting wastewater
will be contract hauled, although no removal of material from the
disposal tank had yet occurred. A sample was taken from the tank
to obtain representative wastewater characteristics for a scrap
disposal dump. The sample analysis data are presented in Table
V-56 (page 320) .
Floor and Equipment Wash - A negligible amount of water is used
for floor and equipment wash.
Air Scrubbers - Wastewater is generated from air scrubbers
located in various process areas in this subcategory. One plant
reports an air scrubber discharge flow of 3.9 liters per hour,
but completely recycles the scrubber water and did not report
wastewater discharge. Another plant reported a discharge of 56.8
1/hr. Other plants also produce scrubber wastewater but did not
report the volume of this wastewater stream. Scrubber discharges
in this process element are not characterized in dcp data or in
sampling because they are not believed to contribute any
significant priority pollutants to the total wastewater
discharge. The wastewater discharges from sulfide dioxide
cathode production area scrubbers will contain primarily
sulfurous acid and sodium sulfite (resulting from the addition of
sodium hydroxide to the scrubber water). The wastewater
discharges from thionyl chloride cathode production area
scrubbers are expected to contain hydrochloric and sulfurous
acids and sodium chloride and sodium sulfite derived from
206
-------
dissolution of thionyl chloride and reaction with sodium
hydroxide added to the scrubber solutions. Exposure to and
contamination by other pollutants will, in general, be minimal.
Elimination of discharge can be accomplished either by
elimination of the use of wet scrubbers or by treatment and
recycle of the scrubber wastewater.
Total Process Wastewater Discharge and Characteristics
Water use and wastewater discharge are observed to be variable
depending upon the particular processes used to manufacture
different types of batteries. Also the total wastewater
discharged, about 350,000 1/yr is low when compared to other
battery subcategories. For the purposes of treatment the types
of wastewater streams generated need to be considered. The heat
paper production wastewater stream, as discussed under the
calcium subcategory, contains hexavalent chromium.
The wastewaters from cathode operations (iron disulfide and lead
iodide) contain metals, and the cell testing, lithium scrap
disposal, and floor and equipment wash will also .contain metals.
The scrubber wastewaters contain limited amounts of pollutants.
More detailed data on process wastewater and effluent
characteristics are limited in this subcategory because of the
present levels of production which are low.
Wastewater Treatment Practices and Effluent Data Analysis
Two plants reported zero discharge of wastewater and one plant
contract hauled wastewater from one wastewater stream.
Wastewater treatment practices within this subcategory are
limited to pH adjustment and settling as shown in Table V-57
(page 321). Two plants reported pH adjustment of process
wastewater while one plant reported only settling. Effluent
monitoring data were submitted by only one plant. These data
characterized the settled wastewater discharge resulting from
heat paper production. They have been presented in Table V-37
(page 301) and discussed under the calcium subcategory. Treated
effluent data were obtained by sampling one additional wastewater
stream in the lithium subcategory. Wastewater resulting from the
manufacture of iron disulfide cathodes was sampled after
treatment in a settling tank which provided a short retention
time for the removal of suspended solids. Analysis results for
this wastewater stream are presented in Table V-58 (page 322).
Several metals values (0.9 mg/1 of lead and 43.5 mg/1 of iron)
indicate that additional treatment can be used for these
wastewaters.
207
-------
MAGNESIUM SUBCATEGORY
The magnesium subcategory includes manufacturing operations used
to produce cells combining magnesium anodes with cathodes of
different materials. Many of the cell types produced are reserve
cells which are activated by electrolyte addition or by a
chemical reaction which raises the cell temperature to the
operating level.
Total 1976 annual production of batteries in this subcategory as
reported in dcp was 1220 kkg (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
was comprised of a variety of magnesium reserve cells generally
intended for seawater activation.
Eight plants reported production of batteries in this
subcategory. Two of the eight plants account for 84 percent of
the total production. These two plants manufacture magnesium-
carbon batteries as does the third largest plant. None of these
magnesium-carbon plants reported the generation of any battery
manufacturing wastewater.
Six of the eight plants manufacturing magnesium anode batteries
report production in other battery manufacturing subcategories as
well. Magnesium-carbon battery production is co-located with
Leclanche subcategory production at two of the three plants where
magnesium-carbon batteries are produced. This association is
logical since cathode materials and cell assembly techniques are
quite similar for these cell types. Other subcategories produced
at the same site as magnesium subcategory production include the
cadmium subcategory, lead subcategory, lithium subcategory, and
zinc subcategory. In most cases, magnesium subcategory
production accounts for less than 30 percent of the total weight
of batteries produced at the plant.
A number of different process operations in the subcategory are
observed to yield process wastewater. These wastewater streams
differ significantly in flow rates and chemical characteristics.
Because of the limited use of water and wastewater discharge
associated with magnesium subcategory operations, wastewater from
magnesium subcategory production is combined with wastewaters
from other subcategories at only one plant. Since no production
operations are common at that site, segregation of wastewaters at
that plant is feasible.
Geographically, producers in this subcategory are scattered. One
plant is located in each of the U.S. EPA Regions I, III, VI and
208
-------
VIII, two in Region IV, and two in Region V. No two plants are
located in the same state.
Manufacturing Process
The manufacture of magnesium anode batteries is illustrated in
the generalized process flow diagram of Figure V-13 (page 404).
Anode manufacture generally requires 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, as well as
processes involving chemical treatment operations. Heating
components (heat paper) are manufactured at one plant for
assembly into magnesium anode thermal batteries. One plant
reported testing assembled cells with a subsequent wastewater
discharge. The relationship between the process elements and
discrete wastewater sources reported at battery plants is
illustrated in Figure V-14 (page 405).
Anode Operations
Anodes used in this subcategory are mechanically formed metallic
magnesium, except for thermal cells where the anode is magnesium
powder. In magnesium-carbon cells, the anode may be 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 of the cells.
The chromate conversion coating on the magnesium anode serves to
suppress parasitic chemical reactions during storage, and to
reduce self-discharge of these cells. One plant reported no
generation of wastewater from chromating. 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. As discussed in Section IV these operations
are not included in the battery manufacturing category.
Cathode Operations
Carbon Cathodes - 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 be in the form of a
solid inserted in the center of a formed magnesium can, or it may
be a carbon cup within which 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 of the depolarizer mix.
209
-------
Magnesium perchlorate electrolyte may also be added tc this
mixture before assembly into the cell.
Copper Chloride Cathodes - 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.
Copper Iodide Cathodes - The manufacture of this cathode type
involves mixing cuprous iodide, sulfur, and carbon and then
sintering the mixture. The sintered material is subsequently
ground, and then pressed on a supporting copper grid to form the
cathode which is dipped in an aqueous alcohol solution prior to
insertion in the battery.
Lead Chloride Cathodes - Lead chloride cathodes are reported to
be produced by pressing lead chloride on a copper screen.
m-Dinitrobenzene Cathodes - Cathodes in which this material
serves as the depolarizer are produced by mixing m-dinitrobenzene
with carbon or graphite, ammonium thiocyanate, and glass fiber.
The mixture is subsequently molded or pasted to produce a thin
sheet which is in contact with a flat stainless steel current
collector in the assembled cell.
Silver Chloride Cathodes - Three different processes are reported
for producing silver chloride cathodes for use in reserve cells:
pellet formation, silver reduction, and the electrolytic
oxidation of silver.
Silver chloride cathodes are produced by one manufacturer by
forming silver chloride powder into pellets which are sub-
sequently 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 such as hydroquinone, sodium thiosulfate, or
paramethylaminophenol sulfate (ELON) to reduce the surface to
metallic silver.
In the third method, 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.
Vanadium Pentoxide Cathodes - Vanadium pentoxide, used as the
depolarizer in magnesium anode thermal batteries, is blended with
electrolyte (lithium chloride and potassium chloride) and kaolin
210
-------
as a dry powder and pressed to form pellets which are used in
cell assembly.
Cell Assembly
Details of cell assembly processes vary significantly among the
different types of cells manufactured in this subcategory. 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 cylindrical carbon
cathode cup and placement of cathode mix in the annular space
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. It is pumped into the
cells at the time of activation of the battery. In magnesium
anode thermal batteries solid electrolyte is incorporated into
pellets containing the depolarizer. In seawater activated cells,
the saline seawater itself serves as the electrolyte. No
electrolyte is added during assembly of the cells.
Ancillary Operations
Five ancillary operations which produce wastewater were
identified within the magnesium subcategory. The operations are
discussed below.
Water Use, Wastewater Characteristics, and Wastewater
Discharge
Process Water Use
Process water use varies considerably among manufacturers in this
subcategory. As shown in the preceding manufacturing process
discussion, most process operations are accomplished without the
use of process water. In addition, many of the cell types
produced use nonaqueous electrolytes or they are shipped without
electrolyte. Me'an and median normalized discharge flows from
both dcp and visit data for each of the wastewater producing
elements included in this subcategory are summarized in Table
V-59 (page 323). This table also presents the production
normalizing parameters upon which the reported flows are based
and which were discussed in Section IV, and the annual raw waste
volume for each process.
211
-------
Wastewater Characteristics
Anode Operations - The only wastewater generating processes
involved in anode manufacturing are the cleaning and chromating
of magnesium anodes. The wastewaters produced by these metal
finishing processes are not included in the battery manufacturing
category.
Cathode Operations - As stated previously, there are seven
different cathodes which are used in the production of magnesium
anode batteries. The manufacture of six of these cathode types -
carbon, copper iodide, copper chloride, lead chloride, m-
dinitrobenzene and vanadium pentoxide - produces no wastewater.
The production of silver chloride cathodes generates wastewater.
Silver Chloride Cathodes - Pellet. The formation of silver
chloride powder into pellets is a dry operation.
Silver Reduction. The rinsing step following reduction generates
wastewater, as do periodic dumps of spent developing solutions.
Following the first rinse, the cathodes are either dipped in
acetic acid and rinsed, or are just rinsed again, generating
additional wastewater. Pollutant concentrations found in the
waste streams from the silver chloride reduction process at Plant
A are shown in the screening analysis, Table V-6 (page 261). As
shown in the table, silver is the only priority pollutant at
significant concentration levels. The total phenols
concentration found is believed to not represent the true level
of phenolic materials present because of the masking effect of
the developer formulation and the analytical procedure used.
This judgment is made on the basis of the chemical constituents
in the developer solution.
Normalized wastewater flow from this process was 4915 I/kg.
Rinse water flow from this process was found to be excessive (not
adequately controlled) and exceeded the normalized flow
previously confirmed by the plant (3310 I/kg), for 1976 data.
Since flow was not controlled at the time of sampling, concen-
trations of pollutants in the total process are substantially
lower than separate samples from each process step. Evidence of
this is shown in the separate sample taken of the developer
solution displayed in Table V-60 (page 324). Concentrations of
pollutants, particularly metals and COD are significantly reduced
by dilution as a result of excess usage of process water.
Electrolytic Oxidation. Process wastewater results from rinsing
the electrolytic silver chloride. The electrolytic oxidation of
silver foil to silver chloride in hydrochloric acid also produces
wastewater. Plant A uses this method to manufacture silver
chloride cathodes. Normalized wastewater flow from the rinsing
212
-------
operation and from the dumps of spent hydrochloric acid was
measured at 145 I/kg. Flow from this process was adequately
controlled and was appreciably lower than the normalized flow
previously confirmed by the plant (1637 I/kg) for 1976 data.
Plant A did not report any wastewater characteristics for the
electrolytic forming stream, but it was characterized by
sampling. The screening sample in Table V-6 (page 261) presents
the pollutant characteristics of the waste stream from rinsing
the product and of the spent hydrochloric acid discharged. The
only toxic pollutant found significant concentrations was silver.
Cell Assembly - None of the cell assembly processes were reported
to generate process wastewater.
Ancillary Operations - Several ancillary operations within this
subcategory produce wastewater. Among these operations are
heating element manufacture, glass bead separator processing,
floor and equipment washing, cell testing, and fume scrubbing.
Heating Component Production - (Heat Paper Production)
Magnesium anode thermal batteries are activated by heat generated
in a chemically reactive element (heat paper) incorporated within
the cell structure. The production of heat paper for magnesium
batteries is identical to the production of heat paper for
calcium batteries. Barium chromate, zirconium, and fibers (such
as asbestos) are the raw materials used in the process. The
production of the heating component generates process wastewater
as was described for the calcium subcategory. The pollutant
characteristics of the heat paper manufacturing wastewater stream
along with their corresponding pollutant mass loadings are
presented in the discussion of calcium batteries and are
displayed in Tables V-34 and V-35 (pages 298 and 299). At Plant
A which produces heat paper within the magnesium subcategory, the
volume of process wastewater is 308.1 I/kg. (Heat Pellet
Production) - Although not reported in this subcategory, heat
pellets are manufactured for thermal batteries. No process
wastewater is generated from this process. Production is
identical to that discussed under the calcium subcategory.
Glass Bead Separators - One manufacturer of silver chloride
magnesium batteries uses glass beads as a separator material.
These beads are etched with ammonium bifluroide and hydrofluoric
acid. The rinse following this etch step is a source of
wastewater. The plant reported 9.1 1/hr of wastewater generated
and gave the following sampling data:
Pollutant mg/1
Aluminum 1 .8
Ammonia-nitrogen 17.7
213
-------
Since this process is not presently active, no further discussion
of waste characteristics is necessary.
Floor and Equipment Washing — The removal of contaminants from
production area floors and process equipment is frequently
required for hygiene and safety. This may be accomplished by dry
techniques such as sweeping and vacuuming but may also require
the use of water in some instances. Two plants in this
subcategory reported floor washing and indicated a resultant
process wastewater discharge. At one plant that reported washing
floors intermittently, the washing operation used about 38 I/day
of water. The discharge was not characterized in the dcp or in
sampling because the operation is sporadic, and also because the
floor areas would be contaminated with pollutants from another
subcategory. As in other subcategories, this wastewater source
may be eliminated by the use of dry floor cleanup techniques.
Cell Testing - 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. Plant A utilizes a cell
testing process in which a water solution of 5% sodium and
magnesium salts is used to activate lead chloride magnesium
reserve cells. No samples were taken and the plant did not
report any data on the cell testing stream. The only major
constituents of the wastewater are expected to be sodium,
magnesium, chloride, and lead. This operation has a flow of 52.6
liters per kilogram of batteries produced.
Fume Scrubbing - Wastewater is discharged from fume scrubbers on
dehumidifiers used to dry manufacturing areas. Process
wastewater is also reported from the use of scrubbers on vent
gases from drying blended electrolyte and depolarizer for use in
magnesium anode thermal batteries. The wet scrubbers serve to
control emissions of potassium chloride and lithium chloride
electrolyte from the drying process, and these salts are
consequently present .in the scrubber discharge. The
concentrations of these pollutants were not reported in dcp data
and were not determined in sampling. However, elimination of
this discharge by treatment and recycle is feasible as
demonstrated in other industrial categories. This has been
partially accomplished at Plant A, which by replacement of the
original once-through scrubber with a recirculating scrubber,
substantially lowered its discharge flow from 1652 I/kg to 206.5
I/kg.
Total Process Wastewater Discharge and Characteristics
214
-------
Process operations which result in battery manufacturing
wastewater are reported at four of the eight plants in the
subcategory. Total process wastewater flow rates are reported to
range from 0 to 42,000 I/day (11,100 gal/day). 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-61 (page 325).
Actual water use and wastewater discharge are observed to be
variable depending upon the particular processes used to
manufacture different types of batteries. About 1.5 million 1/yr
is discharged by plants in this subcategory. For the purposes of
treatment the types of wastewater streams generated need to be
considered. The heat paper production wastewater stream, as
discussed under the calcium subcategory, contains hexavalent
chromium. The wastewaters from the silver chloride cathode
processes contain metals and COD, and the cell testing and floor
and equipment wastewaters also contain metals. The scrubber
wastewaters contain limited amounts of pollutants. More detailed
data on process wastewater and effluent characteristics are
limited in this subcategory because of the present levels of
production which are low.
Wastewater Treatment Practices and Effluent Data Analysis
Present wastewater treatment practice within this subcategory is
limited. Treatment practices at most plants are limited to pH
adjustment and removal of suspended solids. One plant reported
the use of settling tanks followed by filtration for this
purpose. Treatment in place at magnesium subcategory plants is
summarized in Table V-62 (page 326). No effluent analyses
specifically characterizing treated wastewater from this
subcategory were supplied in the dcp.
ZINC SUBCATEGORY
Five battery product types: carbon-zinc-air, alkaline manganese,
mercury-zinc, silver oxide-zinc, and nickel-zinc are manufactured
within the zinc subcategory. Silver oxide-zinc cells are
produced using two different oxides of silver, silver oxide
(monovalent) and silver peroxide. Many produce more than one
type of cell. Wastewater treatment practices and effluent
quality are highly variable.
There are 17 plants in the data base for this subcategory. One
plant has ceased production. During the years 1976-1979 when the
data base was established, annual production in the subcategory
is estimated to have been 22,300 kkg (24,500 tons), and is broken
down among battery types as shown below:
215
-------
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
17800
2010
•1240
1230
0.23
19600
2210
1360
1350
0.25
Geographically, active plants in the zinc subcategory are
concentrated primarily in the eastern and central EPA Regions.
There are five plants in EPA Region IV, four plants in Region V,
two plants each in Regions I, II, and VII, and one plant in
Region VIII.
Although there were some variations in raw materials with
manufacturing process and product variations, many of the raw
materials used in producing zinc anode batteries were common to
all plants. Mercury is used to produce cathodes and for
amalgamation.
All batteries manufactured in this subcategory use an amalgamated
zinc anode. The zinc is amalgamated to reduce anode corrosion
and self-discharge of the cell. The electrolyte is an aqueous
alkaline solution - usually potassium or sodium hydroxide. The
zinc anodes differ considerably in physical configuration and in
production technique depending upon the desired operational
characteristics of the cells. This subcategory includes
batteries manufactured for a variety of applications requiring
different performance characteristics and physical dimensions.
Six different cathode depolarizers are used in zinc anode cells:
porous carbon, manganese dioxide, mercuric oxide, mercuric oxide
and cadmium oxide, silver, and silver oxide. Cathodes for using
these depolarizers may require several different production
techniques.
Steel is used in cell cases, and paper and plastics are used in
cell separators and insulating components. Other raw materials
are discussed under the processes they are used in.
Manufacturing processes differ widely within the subcategory.
This results in corresponding differences in process water use
and wastewater discharge. A total of 25 distinct manufacturing
process operations or process elements were identified. These
operations are combined in various ways by manufacturers in this
subcategory and they provide a rational basis for effluent
limitations. Following a discussion of manufacturing processes
used in the subcategory, each of the wastewater producing process
elements is discussed in detail to establish wastewater sources,
flow rates, and chemical characteristics.
216
-------
Manufacturing Processes
The manufacture of zinc subcategory batteries is represented by
the generalized process flow diagram presented in Figure V-15
(page 406). The anode and cathode variations observed in this
subcategory and the ancillary operations which generate process
wastewater were the basis for analysis of process wastewater
generation as illustrated in Figure V-16 (page 407). As shown in
the figure, several distinct wastewater streams frequently result
from a single process operation or element.
i
Not all operations shown on this diagram are performed at each
plant in the subcategory. In some cases, the order in which they
are performed may be different, 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 plants some of-these production steps
are accomplished without generating a wastewater stream. The
specific operations performed by these "dry" techniques differs
from site to site and each of the indicated wastewater sources
was observed at one or more plants in the subcategory.
In this part, manufacturing operations for all anode and cathode
elements, wet or dry, are described. No ancillary operations are
described. Under "Process Water Use" ancillary operations which
generate process wastewater are described along with the
wastewater flows and characteristics.
Anode Operations
Zinc anodes used in these cells usually corrode by reactions with
the cell electrolyte. When these reactions occur hydrogen gas is
evolved. The rate of hydrogen evolution on zinc in the cell is
reduced by zinc anode amalgamation, thus reducing anode
corrosion. 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 of powdered zinc are thereby increased compared to
the requirement for sheet zinc, 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 choice of amalgamation techniques which may be
used as well as the severity of mercury pollutant discharge
problems encountered.
217
-------
Amalgamation is accomplished by one of six different techniques
which are discussed in the description of each anode
manufacturing process. The choice of technique depends on the
anode configuration and the preference of the manufacturer.
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 subcategory.
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 amalgamated 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. Two plants in the data survey
reported using cast anodes for carbon-zinc-air cell manufacture.
Zinc Powder - Wet Amalgamated Anode - Wet amalgamation of zinc
powder is used by plants 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. Later, 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
carboxymethylcellulose (CMC) are commonly added to the dry
amalgamated zinc powder to aid in compaction of the anode in the
cells. 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.
Figure V-17 (page 409) is a schematic diagram of the zinc powder-
wet amalgamation process. Six plants in the data base reported
using wet amalgamated powdered zinc processes for anode
formulation. Two plants have discontinued these operations.
Zinc Powder - Gelled Amalgam Anode - The gelled amalgam process
results in a moist anode gel in a single operation. The
production of gelled amalgam, illustrated in Figure V-18 (page
410), 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 carboxymethylcellulose or carboxypolymethylene, is blended
in the amalgam mixture to achieve the appropriate gel charac-
teristics. Three plants produce gelled amalgam.
Zinc Powder - Dry Amalgamated Anode - In the dry amalgamation
process zinc powder and metallic mercury are mixed for an
extended period of time to achieve amalgamation. To control
218
-------
mercury vapor exposure of production workers, the mixing is
commonly performed in an enclosed vented area separate from the
material preparation areas. Discussions with industry personnel
have indicated that this process is less costly than wet
amalgamation and has resulted in satisfactory anode performance.
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 - Zinc oxide and
mercuric oxide are mixed in a slurry. The mixture is 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, to be later formed by the customer. Only one
plant reported manufacturing slurry . pasted anodes which are
assembled with uncharged cathodes to produce cells to be later
charged by the customer. No plants reported manufacturing zinc
oxide anodes pressed from dry powder and shipped unformed.
However, similar . operations were reported in the cadmium
subcategory and by analogy such an operation might be expected in
the future with zinc oxide and will fall into this process
element.
Zinc Oxide Powder - Pasted or Pressed, Reduced Anodes - Anodes in
this group are produced by 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
metallic zinc and to reduce mercuric oxide to mercury which
amalgamates with the active zinc. After completion of formation,
the anode material is rinsed to remove residual caustic.
The pressed powder technique- for zinc anode formulating,
illustrated in Figure V-19 (page 411), requires preparation of 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 to the grids. The grids are held in place by
separate molds. The grids and the powder mixture are compressed
together 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 is illustrated in Figure V-20
(page 412). A slurry of zinc oxide and mercuric oxide, is
prepared with water or dilute potassium hydroxide. A binding
agent such as CMC may be added to the slurry. The slurry is
layered onto a silver or copper screen and the material is
219
-------
allowed to dry prior to formation. The dried plates are immersed
in a potassium hydroxide solution and formed against either
positive electrodes or nickel dummy electrodes. After formation,
the anodes are thoroughly rinsed to assure removal of potassium
iiydroxide. The plaques are dried and later compressed to
eliminate irregularities such as jagged edges. Four plants
reported using the pressed powder or pasted slurry technique
followed by reduction for zinc anode manufacture.
Electrodeposited Zinc Anode - In this process zinc is
electrodeposited on a grid and rinsed prior to amalgamation by
immersion in a solution of mercuric salts. Afterwards, the
plaques are either immediately dried, or rinsed and then dried.
(In this process the term electrodeposition is used in the
conventional sense - powdery zinc metal deposits on the grid.)
The most common grid materials used in the electrodeposition
process are 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. After completion of the rinse
operation, the prepared plaques are dipped in an acidic solution
containing mercuric chloride. Mercury is reduced and deposited
on the surface where it forms an amalgam with the zinc. The
amalgamated plaques are either rinsed and subsequently dried or
immediately dried following amalgamation. Figure V-21 (page 413)
is a schematic diagram of the entire electrodeposition process.
Cathode Operations
Depolarizers used in this subcategory are primarily metal oxides
which are purchased from manufacturers of inorganic chemicals.
In some cases depolarizer material is chemically prepared on-site
because special characteristics are required for battery
manufacture. Preparation of such special depolarizer materials
is considered a battery manufacturing operation. Commercially
available depolarizer materials may also be prepared on site at
battery plants in processes equivalent to those used in inorganic
chemicals manufacturing operations. Preparation of depolarizer
materials which are commercially available is not considered a
battery manufacturing operation. Ten distinct cathode
manufacturing processes a're observed in this subcategory.
Porous Carbon Cathode - Porous carbon cathodes are used in air
depolarized cells. They are produced by blending carbon,
manganese dioxide and water, then pressing and drying the mixture
to produce an agglomerated cathode structure or "agglo." The
220
-------
agglo serves as a current collector for the cathode reaction and
as a porous medium to carry atmospheric oxygen to the electro-
lyte. CuiiLi-ui ul Liie porosity and surface characteristics of the
agglo is essential since the cathode structure must permit free
flow of oxygen through the pores, but prevent flooding of the
pores by 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 agglos are assembled with cast
zinc anode plates to produce carbon-zinc air cells.
Manganese Dioxide-Carbon Cathode - Cathodes in this group are
produced by blending manganese dioxide with carbon black,
graphite, Portland cement, and for some special cells, mercuric
oxide. Typically the cathode mixture is inserted in steel cans
along with separator material. Electrolyte solution consisting
of potassium hydroxide is subsequently added to the partly
assembly 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.
Mercuric Oxide (And Mercuric Oxide-Manganese Dioxide Carbon)
Cathodes - The manufacturing process for mercuric oxide cathodes
is 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. Four plants
produce this cathode for mercury (Ruben) cells. Production at
one plant was stopped after submittal of dcp.
Mercuric Oxide-Cadmium Oxide Cathode - 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 powered smoke detectors .to provide a warning of impending
battery failure. Production of this type of cathode was reported
by one plant in the subcategory.
Silver Powder Pressed Cathode. The manufacture of pressed silver
powder cathodes begins with the production of silver powder which
is prepared on-site by electrodeposition. See "Ancillary
Operations Producing Wastewater". The resultant powder is
221
-------
pressed on the surface of a silver screen or other support and
sintered to achieve mechanical integrity. These electrodes may
then be assembled with unformed (oxidized) zinc anodes and the
resultant batteries charged prior to use.
Silver Powder Pressed and Electrolytically Oxidized Cathode -
These cathodes are made from silver powder which is 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-22 (page 414) is a schematic
diagram of this process. Three plants reported pressing silver
powder on grids to produce sintered plates which are subsequently
formed.
Silver Oxide (Aq ? 0) Powder Pressed Cathode - Cathodes using
silver oxide powder are prepared 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. Four plants
reported manufacturing cathodes in this element.
Silver Oxide (Ag?0) Powder - Thermally Reduced or 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-23 (page 415) is a
schematic diagram of this process. Two plants reported using
this process.
Silver Peroxide (AgO) Cathodes - The production of silver
peroxide cathodes begins with the oxidation of silver oxide to
produce silver peroxide. See Ancillary Operations Generating
Wastewater. Two preparation processes are in current practice
222
-------
for preparing cathodes from the silver peroxide. 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 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 to metallize the surface. Figure V-24
(page 416) is a schematic diagram of the process involving
chemical treatment of silver peroxide pellets.
In another method currently used, silver peroxide cathodes are
produced by 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. Figure V-25 (page 417) is a schematic
diagram of this process.
Nickel Impregnated and Formed Cathodes - Nickel hydroxide
cathodes used in this subcategory are prepared by sintering,
impregnation and formation processes as described for the cadmium
subcategory.
Process Integration - The different process operations discussed
above may in principle be combined in many ways for the
manufacture of batteries. Table V-63 (page 327) presents the
combination of anode and cathode manufacturing processes observed
in the subcategory at the present time. Of seventeen distinct
process operations or functions identified in the subcategory for
anode and cathode manufacture, eight are reported to result in
process wastewater discharges. An additional eight ancillary
process operations which produce wastewater are discussed later
under "Ancillary Operations Generating Wastewater". All sixteen
of these discharge sources were represented in sampling at zinc
subcategory plants.
Water Use, Wastewater Characteristics, and Wastewater
Discharge
Process Water Use
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 summarized in Table V-64 (page
329). This table also presents the production normalizing
parameters upon which the reported flows are based and which were
discussed in Section IV, and the annual raw waste volume for each
223
-------
process. The water use and wastewater discharge from these
process operations varies from less than 1 I/kg of production
normalizing parameter for several processes to 3190 I/kg of
deposited zinc for electrodeposited zinc anode manufacture.
Observed flow rates for process wastewater at each zinc
subcategory plant are displayed in Table V-65 (page 331).
Wastewater Characteristics
Anode Operations - Zinc Cast or Fabricated Anode - No process
wastewater is generated in processing anodes by this procedure.
Zinc Powder - Wet Amalgamated Anode - There are four sources 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) ranged
from 1.4 to 10,900 liters per day at the seven plants which
reported using the wet amalgamation process (2890 I/day mean).
The production normalized discharge from both dcp and visit data
ranges from 0.69 to 10.09 I/kg (3.8 I/kg mean). The final
amalgam rinse with alcohol is generally retained and reused until
ultimately contractor removed.
The wastewaters from wet amalgamation processes at two plants
were sampled. The normalized discharge flow during sampling
ranged from 1.88 to 6.82 I/kg (4.2 I/kg mean). The entire
amalgamation process wastewater was sampled at both plants.
Wastewater from amalgam preparation and equipment cleaning was
combined. Another wastewater stream at one plant resulted from
reprocessing amalgamated material. During the sampling visit
amalgam that had been previously stored was being reprocessed
intermittently throughout the three sample days. The mercury
concentration in the wastewater from the "virgin" amalgam process
is substantially greater than that of the reprocessed amalgam
since no additional mercury is mixed into the latter material.
Table V-66 (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. The tank was
manually scraped to remove the residue from the mixer and the
remaining material was washed from the tank with a hose. This
cleaning procedure increased the volume of water used in the
amalgamation process and contributed 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.
224
-------
Table V-67 (page 333) presents the pollutant mass loading in the
amalgamation samples taken daily at both Plants B and A. The
range, mean, and medium values in units of mg/1 and mg/kg are
presented in Tables V-68 and V-69 (pages 334 and 335),
respectively.
Zinc Powder, Gelled Amalgam Anode - No wastewater discharge
results directly from 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-70
(page 336) presents the analysis results of these wastewater
streams. The discharge flows on a daily basis range from 0.21 to
1.67 I/kg (0.69 I/kg mean). The discharge flows measured at
Plant B include the combined wastewater from equipment and floor
area 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 wastewater 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 wastewater streams
include TSS, mercury, and zinc which result from the removal of
residual amalgam in the cleaning of utensils and equipment. In
addition, spills resulting from the bulk handling of raw
materials for 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 wastewater stream were not measured
directly but were determined by mass balance using two wastewater
samples representing wastewater resulting from scrap cell de-
activation and the mixed scrap cell deactivation and amalgamation
wastewater. On the first day extremely high zinc concentrations
in the scrap cell deactivation wastewater prevented accurate
determination of zinc concentrations in the amalgamation waste
stream.
Another parameter present in significant concentrations in the
anode room floor wash samples taken at Plant A was arsenic. The
source of this pollutant is unknown although it may be a trace
225
-------
contaminant of the zinc used in the amalgamation process. The
wastewater streams generated from washing the amalgamation
equipment and the floor areas are highly alkaline as a result of
the potassium hydroxide addition to gelled amalgam formulation
and the inclusion of utensil wash water from electrolyte
preparation.
Table V-71 (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-72 and V-73 (pages 338
and 339) for both mg/1 and mg/kg analysis results, respectively.
Dry Amalgamated Zinc Powder Anodes - This process is a dry
operation and involves no process wastewater discharge.
Zinc Oxide Powder, Pasted or Pressed Anodes - 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.
Zinc Oxide Powder, Pasted or Pressed, Reduced Anodes - The only
source of wastewater discharge is the post-formation rinse
operation. Since the raw materials are comparable for the powder
and the slurry techniques of preparing the plaques, the pollutant
characteristics for the rinse water discharges are similar. The
normalized discharge flow 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). The rinse wastewater stream was
sampled at two of these plants, 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.
The analysis results for each sample day from Plants A and B are
presented in Table V-74 (page 340). Table V-75 (page 341)
presents the pollutant mass loadings from anode preparation on a
daily basis. Tables V-76 and V-77 (pages 342 and 343) show the
statistical analysis of the raw wastewater data in units of mg/1
and mg/kg, respectively.
Zinc Electrodeposited Anodes - The process wastewater associated
with the manufacture of electrodeposited anodes are: (1) post-
electrodeposition rinses, (2) amalgamation solution dump, and (3)
post-amalgamation rinse.
Two plants (A and B) in the data base used the electrodeposition
process. 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. Only the first two wastewater
226
-------
streams were sampled at Plant A because that plant does not
require a rinse tollowing 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) 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 plants results
from post-electrodeposition rinsing. The most significant
pollutant in the sampled rinse wastewater stream is zinc
particles. Poorly adherent zinc particles are removed from the
product by rinsing, and by compressing the deposited material
between the rinses.
The other wastewater stream at Plant A which is associated with
the zinc electrodeposition process is the amalgamation solution
dump. At this plant, the amalgamation solution is dumped after
sixteen hours of operation of a single electrodeposition line.
Table V-78 (page 344) presents the chemical characteristics of
two batch dumps of the spent amalgamation solution. The re-
sulting normalized discharge flow averages one liter per kilogram
of zinc applied. Table V-79 (page 345) 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 wastewater
streams. In addition, the pollutant mass loadings on each sample
day are presented in Table V-80 (page 346).
Cathode Operations - Porous Carbon Cathode - No wastewater is
discharged from this operation at either of the two plants
reporting the manufacture of porous carbon cathodes.
Manganese Dioxide-Carbon Cathode - The processes used to
formulate the cathode material do not generate any wastewaters.
Mercuric Oxide (And Mercuric Oxide-Manganese Dioxide-Carbon)
Cathodes - The cathode formulation process generates no process
wastewater since the blended and pelletized materials are in dry
powdered forms.
Mercuric Oxide-Cadmium Oxide Cathode - No process wastewater is
generated from this process since the materials are combined in a
dry powdered state, and further processing is executed under dry
conditions.
227
-------
Silver Powder Pressed Cathode - No process water is used and no
wastewater discharge results from the production ot these
cathodes. ;
Silver Powder Pressed and Electrolytically Oxidized Cathodes -
Three plants reported pressing silver powder on grids to produce
sintered plaques which are subsequently formed. The post-
formation rinse was the only source of wastewater and was sampled
at both Plants A and B. Table V-81 (page 347) 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 normalized flow is 196.25 I/kg. Analysis results are
presented in Table V-82 (page 348).
Table V-83 (page 349) presents the daily pollutant mass loadings
of both plants and statistical analysis in units " of mg/1 and
mg/kg are presented in Table V-84 and V-85 (pages 350 and 351),
respectively.
Silver Oxide (Ag20) Powder Pressed Cathodes - No wastewater is
generated from this process since the materials are combined in
the dry powdered state and further processing, involving
pelletizing and insertion into the cell container, is done under
dry conditions.
Silver Oxide (Ag20) Powder - Thermally Reduced or Sintered,
Electrolytically Formed Cathode - The normalized wastewater-flow
rates for the two plants using this process 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).
Two samples were taken at Plant B 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-86 (page 352) and the pollutant mass loading estimates
are presented in Table V-87 (page 353). 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. This
• 228
-------
wastewater 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 wastewater 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 (AgO) Cathodes - Process wastewater 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
flows ranged from 5.5 to 22.4 I/kg. Table V-88 (page 354)
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 through the
three sampling days due to the batch nature of the processes and
the one-hour sampling interval.
The only wastewater from the slurry pasting process is from the
clean-up of utensils used to mix the slurry and apply the
material to a support.
Plant C reported manufacturing reinforced silver peroxide
cathodes. The wastewater was sampled at this plant. The
normalized discharge flow for the sample day was 76.0 liters per
kilogram of silver processed. This flow varied according to the
operator's discretion in the amount of water used to wash the
utensils. Table V-88 (page 354) presents the results of analysis
of the wastewater from the utensil wash operation at Plant C.
Table V-89 (page 355) presents the pollutant mass loadings in the
process wastewater 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 wastewater streams resulting from both pellet
chemical treatment and slurry application on support material are
summarized in the statistical analyses presented in Tables V-90
and V-91 (pages 356 and 357).
Nickel Impregnated Cathodes - Discussion of wastewaters from
manufacture of impregnated nickel cathodes is under the cadmium
229
-------
subcategory. Table V-18 (page 282) and Table V-19 (page 283)
present the results of the analyses in terms of concentrations
and mass loadings; corresponding statistical analyses are
presented in Tables V-20 (page 284) and V-21 (page 285).
Ancillary Operations Generating Wastewater - Only wastewater
generating ancillary operations are described in this part. Dry
ancillary operations such as soldering, punching, or shearing are
not described.
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 to minimize the probability
of corrosion of the battery case, contacts, or devices into which
the battery is placed. 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 plants
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 containing chromic acid) 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 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. 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 was sampled. The fourth cell wash group uses freon
to clean cell surfaces. Two plants presently use freon in the
230
-------
cell wash operations. Wastewaters were not sampled at these two
plants. 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 or
during sampling visits. Table V-92 (page 358) presents the
normalized discharge flows from cell wash operations at Plants A-
G. Based on these data, after deleting an abnormally high flow
of 34.1 I/kg, the range is 0.09 to 4.21 I/kg of finished cells
(1.13 I/kg mean). The large observed variations in discharge
from cell wash operations may be related primarily to differences
in plant water conservation practices although cell size and
plant specific washing procedures were also observed to have an
influence. Table V-93 (page 359) 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 wastewater
streams from cell wash operations that were sampled at each plant
are combined on a flow-proportioned daily basis to achieve
complete plant-by-plant raw wastewater characterizations from
cell washing. Table V-94 (page 360) presents the pollutant mass
loadings on a daily basis for each plant. Statistical summaries
are presented in Tables V-95 and V-96 (pages 361 and 362). The
normalized discharge flows range from 0.085 to 1.8 I/kg of cells
produced. 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 - The electrolytes used in cells in this
subcategory are primarily aqueous solutions of potassium or
sodium hydroxide, but may in some cases contain zinc oxide as
well. In general, they are added to the batteries in solution
form during cell assembly and must first be prepared from
purchased solid constituents. The preparation of these elec-
trolyte 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.
Nine plants reported using water to formulate electrolyte
solution. One plant reported using sodium hydroxide solution as
a substitute electrolyte for potassium hydroxide solution in the
manufacture of certain cells. Two plants 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.
231
-------
Table V-97 (page 363) presents the analytical results of the
wastewater stream sampled at Plant A. The measured flow is 0.37
I/kg 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). The observed
pollutant mass loadings of the sampled wastewater stream at Plant
A as presented in Table V-98 (page 364) do not contribute
substantially to the total cell manufacture raw waste.
Silver Etching - 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 removal. 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.
The wastewater stream was sampled at Plant A. The process is
conducted on an intermittent basis depending on the production of
silver oxide-zinc cells requiring the etched material. The
observed discharge flow is 49.1 I/kg of silver processed. Tables
V-99 and V-100 (pages 365 and 366) 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 plants require the employees to wash before each
work break and at the end of each work day. Since process
materials are removed during the wash operation, the resultant
wastewater stream is considered process wastewater from the zinc
subcategory. Two plants (A and B) reported mandatory employee
washing. Employee wash wastewater from both plants was sampled.
The composited sample taken at Plant B is a combination of waste-
waters generated from washing clothes previously worn by
manufacturing process employees and from employee showers. A
flow measurement was not obtained due to pipe inaccessibility.
The analytical results are presented in Table V-101 (page 367).
The employee wash wastewater was separately sampled at Plant A.
The observed discharge flow is 0.27 I/kg of finished cells.
Table V-102 (page 368) presents the analytical results of the
wash wastewater stream. The most significant pollutants are
suspended solids and oil and grease which are probably due to the
employees handling both process materials and lubricated
machinery. Table V-103 (page 369) presents the pollutant mass
232
-------
loadings of the employee wash wastewater 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 cannot be repaired, it is
scrapped. The disposal techniques used by the zinc subcategory
cell manufacturers differ according to whether the materials
composing the rejected cells require deactivation. By submerging
certain cells in water, the active materials are discharged to
reduce 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 I/kg of finished cells (0.01 I/kg mean). 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
I/kg of finished cells. Table V-104 (page 370) presents the
analysis results of the reject cell handling wastewater stream.
The significant pollutants are silver, zinc, and mercury.
The reject cell wastewater was also sampled at Plant B. Analy-
tical results for Plant B only are presented in Table V-105 (page
371). This wastewater stream is characterized, by a low discharge
flow (0.003 I/kg). The most significant pollutants observed are
suspended solids, zinc, and mercury which are constituents of the
alkaline cells being processed. Table V-106 (page 372) presents
the pollutant mass loadings from the data obtained from sampling
the reject cell wastewater at Plant B.
Floor Wash and Equipment Wash - Some plants maintain process
floor areas and equipment by using water to remove wasted process
materials and other dirt. 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 require
water 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. 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 0.030 I/kg of cells produced.
Table V-107 (page 373) presents the analytical results of the
wastewater resulting from the floor wash operation at Plant A.
Table V-108 (page 374) 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
233
-------
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.
Four plants in the data base reported usina wahpr to c
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 wastewater at Plants A
and B. At these two plants, the observed discharges averaged 5.1
I/kg and 9 I/kg of cells produced. The significant pollutants in
the equipment wash wastewater streams at Plant B include
suspended solids, zinc, and mercury which result from the
formation operation. Table V-109 (page 375) 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. The same table shows the analytical
results from the sample, visit of Plant A. The wastewater at this
plant is generated from equipment wash operations and occasional
employee hand washing. The observed flow is 5.1 I/kg of cells
produced. The significant pollutants in this wastewater stream
are suspended solids, mercury, and zinc which result from process
material contamination. Table V-110 (page 376) presents the
pollutant mass loading calculated from the analytical data from
Plants A and B. Statistical summaries of both the concentration
and loading data are presented in Table V-111 and V-112 (pages
377 and 378), 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 from 19.8 to 23.7 I/kg (21.2
I/kg mean). The results of analyses of samples from this
wastewater source are presented in Table V-113 (page 379). Table
V-114 (page 380) presents corresponding pollutant mass loading
data.
Silver Peroxide Production - Silver peroxide is produced from
silver oxide or silver nitrate by two chemical oxidation
processes. The results of analysis of wastewater samples from
234
-------
peroxide production are presented in Table V-115 (page 381) and
corresponding pollutant mass loadings in Table V-116 (page 382).
Total Process Wastewater Discharge and Characteristics
Wastewater discharge from zinc subcategory manufacturing
operations varies between 0 and 26,000 1/hr (7,000 gal/hr). The
variation may be understood primarily on the basis of the
variations among these plants in the mix of production operations
used, and also on the observed differences in water conservation
practices in the subcategory.
Total process wastewater flow and characteristics were determined
for eight plants in the zinc subcategory which were sampled.
These characteristics, reflecting the combined raw wastewater
streams from all zinc subcategory process operations at each site
on each of up to three days of sampling, are summarized
statistically in Table V-117 (page 383). Prevailing discharge
and treatment patterns in this subcategory generally preclude
directly sampling a total raw wastewater stream because
wastewaters from individual process operations are often treated
or discharged separately. Consequently, the total process
wastewater characterisics shown in Table V-117 were determined
for each plant by mass balance calculations from analyses of
wastewater samples from individual process operations.
As Table V-117 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.
Wastewater Treatment Practices and Effluent Data Analysis
The plants in this subcategory reported the practice of numerous
wastewater treatment technologies (Table V-118, page 384)
including pH adjustment, sulfide precipitation, carbon
adsorption, amalgamation, sedimentation, and filtration. Several
indicated the recovery of some process materials from wastewater
streams. In addition to the wastewater treatment systems
reported in dcp, a complete system combining in-process controls
with ion exchange and wastewater recycle has been installed at
one plant, which will ultimately eliminate the discharge of
wastewater effluent. Process changes at another plant have also
eliminated process wastewater discharge since the data presented
in the dcp were developed. Many of the technologies practiced
235
-------
(e.g., amalgamation and carbon adsorption) are aimed specifically
at the removal of mercury. Effluent data and on-site
observations at plants in the zinc subcategory reveal that most
of the technologies employed are not effectively applied for the
reduction of pollutant discharges. In some cases, such as
amalgamation, this is due to treatment system design and the
inherent limitations of the technologies employed. In others,
such as sulfide precipitation, failure to achieve effective
pollutant removal results from specific design, operation, and
maintenance deficiencies at the plants employing the
technologies.
An analysis of the treatment in place was done for all plants
which submitted process information. Some of these plants were
visited and sampled, others provided effluent data, and others
just reported what treatment was in place.
As shown in Table V-119 (page 385), plants submitted limited
data. Only four plants submitted data on pH which could be
related to treatment performance, however the effectiveness could
not be substantiated by this data alone.
At plant A which was visited with sulfide precipitation,
settling, and filtration it was observed that the plant did not
operate the precipitation system at optimum pH values. The
results of sampling for this plant are shown in Table V-120 (page
386). In this same table the sampling data for plant B are also
shown. Observations made during the plant visit indicated that
nonprocess streams were mixed with battery process water, severly
overloading the treatment system. Additionally, the system was
not consistently operated at optimum pH values, and the treatment
tanks were long overdue for sludge removal.
Another plant which was sampled had chemical precipitation,
settling and filtration technology. As shown in Table V-121
(page 387), this plant had four separate treatment systems to
treat wastewaters from the zinc subcategory. Observation made
during sampling, however indicated that the systems were
inadequately maintained. pH was not controlled properly and
excessive accumulations of sludge from previously treated batches
of wastewater were in the settling tanks.
Observations at two plants with settling and amalgamation in
place revealed that the treatment systems were crude in design
and operability. Sampling results for these two plants are in
Table V-122 (page 388).
At another plant having skimming, filtration, amalgamation and
carbon adsorption in place, the equipment was designed and
236
-------
operated inadequately. Sampling results for this plant are shown
in Table V-123 (page 389).
One plant had just installed a settling, filtration and ion
exchange treatment system. Because the system had just been
installed and was not in full operation prior to sampling, the
results shown in Table V-124 {page 390) could not be evaluated.
After evaluating all dcp and plant visit effluent data, the
conclusion is made that although plants which discharge have
treatment equipment in place, the operation and maintenance of
these systems are generally inadequate for treating zinc
subcategory pollutants.
237
-------
IABLB V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQOES
03
Pollutants
Screening Analysis
Methodology
Verification Analysis
Methodology
1. Acenapbtbene
2, Acrolein
3. Aery Ion it rile
4 . Benzene
5 . Benzidine
6, Carbon Tetrachloride
{ Tetrachloromethane)
7 . chlorobenzene
8. 1,2,ft-i:richlorobenzene
9. Hexachlorobenzene
10, 1,2-Dichloroethane
11. 1,1,1-lrichloroethane
12. Hexachloroe thane
13. 1, 1-Dichloroethane
1«U 1,1,2-lrichloroethane
15. 1,1,2, 2-Tetrachloroethane
16. chloroettoane
17. Bis (Chloromethyl) Ether
18. Bis (2-Chloroethyl) Ether
19. 2-Cbloroethyl Vinyl Ether (Mixed)
20. 2-Chloronaphthalene
21. 2,4,6-Trichlorophenol
22. Parachlorometa cresol
23. Chloroform (Trichloromethane)
2ft. 2-Chlorophenol
25. 1 , 2 -D ic hlorobenzene
26. 1,3-Dichlorobenzene
27 . . 1 , H-Dichlorobenzene
28. 3,3-Dichlorobenzidine
29. 1,1 -Dichloroethylene
30. 1,2-Trans-Dichloroethylene
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP VP; L-L Extract; GC, BCD
SP VP: L-L Extract; sc, BCD
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP VPJ L-L Extract; SC, BCD
-------
ho
U)
TABLE V-1
SCREENING MD VERIFICATION ANALYSIS TECHNIQUES
Screening Analysis Verification Analysis
Pollutants Methodology Methodology
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
11.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55,
56.
57.
58.
59.
60.
2 » 4-Da.chlorophenoI
1 , 2-Dichloropropane
1 » 2-Dichloropropylene
(1 , 2-Dichloropropene}
2, 4-Dimethylphenol
2»fl-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 (Dichloromethane)
Methyl chloride (Chloromethane
Methyl Bromide (BroraomethaneJ
Bromoform (Tribromomethane)
Dichlorobrompmethane
Irichlorofluoromethane
Dichlorodifluoromethane
Chi or od ibromome than e
Hexachlozobutadiene
Hexachlorocyclopentadiene
Isophorone.
Naphthalene
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
2, 4-Dinitrophenol
4, 6-Dinitro-o-cresol
SP
SP
SP
SP VP: GC - FID
SP
SP
SP
SP
SP SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP SP
SP SP
SP
SP
SP
SP
SP
-------
NS
-P-
O
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Screening Analysis Verification Analysis
Pollutants Methodology Methodology
61. N-Nitrasodimethylamine
62. N-Nitrosodiphenylamine
63. N-Nitroaodi-N-Propylamine
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-Benzantbracene
(Benzo (a) Anthracene)
73. Benzo (a) Pyrene (3, 4- Benzo- Pyrene)
74. 3, 4-Benzofluorantnene
75. 1 1, 12-Benzofluoranthene
(Benzo (k) Fluoranthene)
76. chrysene
77. Acenaphthylene
78. Anthracene
79. 1 , 12-Benzoperylene
(Benzo (qhi)-Perylene)
80. Fluor ene
81. Phenantbrene
82. 1,2,5,6-Dibenzathracene
(Dibenzo (a,h) Anthracene)
83. Indeno (1,2, 3-cd) Pyrene
(s,3-0-Phenylene Pyrene)
84. Pyrene
85. letrachloroethylene
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
VP: GC, ID
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
Pollutants
Screening Analysis
Methodology
Verification Analysis
Methodology
86. loluene
87. Trichloroethylene
88. Vinyl Chloride (Chloroethylene)
89. Aldrin
90. Dieldrin
91. Chlordane
(technical Mixture and Metabolites}
92. 4,4-DDT
93, 4,4-DDE (p,p'-DDX)
94. 4,4-DDD (p,p'-TDE)
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptachlor
101. Heptachlor Epoxide
(BHC-Hexachlorocyclohexane)
102. Alpha-BHG
103. Beta-BHC
104. Gamma-BBC (Lindane)
105. Delta-BBC
(FCB-Polychlorinated Biphenyls)
106. PCB-1242 (Aroclor 1242)
107. PCB-1254 (Aroclor 1254J
108. PCB-1221 (Aroclor 1221)
109. PCB-1232 (Aroclor 1232)
110. PCB-1248 (Aroclor 1248)
111. PCB-1260 (Aroclor 1260)
112. PCB-1016 (Aroclor 1016)
113. loxaphene
114. Antimony
115. Arsenic
SP VP: L-L Extract; SC, FID
SP VP: L-L Extract; 3C, BCD
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
SP
-------
TABLE V-1
SCREENING ftND VERIFICATION ANALYSIS TECHNIQUES
Pollutants
Screening Analysis
Methodology
Verification Analysis
Methodology
•P-
to
116. Asbestos
117. Beryllium
118. Cadmium
119. Chromium
Hexavalent chromium
120. Copper
121, Cyanide
Cyanide Amenable to
122. Lead
123. Mercury
124. Nickel
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,4,8-Tetrachlorodibenzo-
P-Dioxin (TCDD)
Aluminum
Fluorides
Iron
Manqanese
Phenols
Phosphorous Total
Oil 6 Grease
1SS
IDS
pH Minimum
pH Maximum
Temperature
40CFR
Chlorination
136
ICAP
I CAP
ICAP
ICAP
: Dist./col.
ICAP
SP
SP
SP
SP
SP
ICAP
SP
40CFR 136: AA
40CFR 136: AA
40CFR 136; Colorimetric
40CFR 136: AA
Mea. 40CFR 136: Dist./col. Mea.
40CFR 136: Dist./col. Mea.
40CFR 136:AA
IJOCFR 136 :AA
40CFR 136:AA
40CFR 136:AA
Dist./I.E.
40CFR 136:AA
40CFR 136:AA
ttOCFR 136
SM: Dig/SnC!
ttOCFR 136: Dist./I.E.
HQCFR 136
40CFR 136
Electrochemical
Electrochemica1
-------
TABLE V-1
SCREENING AND VERIFICATION ANALYSIS TECHNIQUES
HOCFR 136: Code of Federal Regulations, Title tO, Part 136.
SP ~ Sam{3ling_and Analysis .Procedures for Screenin!| of Indus-trial Effluents for Priority Pollutants,
WTs. EPA, March, 1977, Revise! April, 1977.
VP ~" Analytical Methods^ for the yfri|jLcation Phase of BAT Review,
U.S. EPA, June, 1977T""
SM ~ Standard. Methods, 14th Edition.
ICAP - Inductively coupled Argon Plasma.
AA - Atomic Absorption.
L-L Extract; GC, BCD - Liquid-Liquid Extraction/Gas Chromatography, Electron Capture Detection.
Diq/Snd, - Digestion/Stannous Chloride.
Filt./Grav. - Filtration/Gravimetric
Freon Ext. - Freon Extraction
Dist./col. Mea. - Distillation/pyridine pyrazolone colorimetric
Dist./l.E. - Distillation/Ion Electrode
GC-FID - Gas Chromatography - Flame loaization Detection.
SIE - Selective Ion Electrode
-------
TABLE V-2
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.
11.
42.
43.
44.
45.
46.
CADMIUM
DCP Data
KTBP, BTBP
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride
chlorobenzene
1,2,4 Trichlorobenzene
Hexachlorobenzene
1, 2 Dichloroethane
1,1,1 Irichloroethane
Hex achl or oe thane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetrachloroethane
Chloroethane
Bis Chloromethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinyl Ether
2-Chloronaphthalene
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
Ethylbenzene
Fluoranthene
4 Chlorophenyl Phenyl Ether
4 Bromophenyl Phenyl Ether
Bis (2 Chloroisopropyl) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride
Methyl chloride
Methyl Bromide
SUBCATEGORY
Plant Raw
Influent Haste
Cone. Cone.
mcr/1 mq/1
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
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
Effluent
Cor.c.
mcr/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
Analysis
Blank
Cone.
mq/1
ND
ND
ND
ND
NA
NA
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
-------
TABLE V-2
SCREENING ANALYSIS RESULTS
NJ
-!>•
Cn
47.
48.
19.
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.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
CADMIUM
DCP Data
KTBP, BTBP
Erorcoform
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromomethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2 Nitzophenol
4 Nitre phenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Nitrosodimethylamine
E-Nitrosodiphenylamine
N-Nitrosodi-N-propylamine
Pentachlorophenol
Phenol 0,2
Eis (2-Ethylhexyl) Phthalate
Butyl Eenzyl Phthalate
Di-N-butyl Phthalate
Di-N-octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthracene
Benzo (A) Pyrene
3,4 Benzof luoranthene
11, 12-Benzof luoranthene
Chrysene
Acenaphthylene
Anthracene
1,1 2-Benzoperylene
Fluorene
Phenanthrene
1,2,5,6 Dibenzanthracene
Indenopyrene
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene 0,1
Vinyl Chloride
Aldrin
Dieldrin
chlordane
4,4 DDT
SOBCATE3ORY
Plant
Influent
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
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/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
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
ND
ND
ND
ND
0.025
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
ND
ND
ND
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
NA
NA
NA
NA
NA
ND
*
ND
ND
NA
NA
NA
NA
-------
TABLE V-2
SCREBKHJG ANALYSIS RESOKTS
OS
CADMIOM SUBCATE6OHY
DCP Data Plant Raw
KTBP, BfBP Influent Haste
Cone. cone.
ma/1 ma/1
93. 4,4 DDE
94. 4,4 DDD
95. Alpba-Endosalfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Beptacblor
101. Beptacblor Ep oxide
102. Alpha-BBC
103. Beta-BBC
104. Gamma -EHC (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. loxaphene
114. Antimony 1,0
115. Arsenic 1,0
116. Asbestos
117. Beryllium
118. Cadwiun 4,0
119. Chromium 2,0
120. Copper
121. cyanide 1,0
122. Lead
123. Mercury
124. Nickel 7,0
125. Selenium
126. Silver
127. Thallium
128. Zinc
129. 2,3,7,8 1CDD (Dioxin)
130, xylenes
131. Allcyl Epoxides
Aluirinum - -
Ammonia - -
Barium - -
Boron - -
Calcium - -
cobalt
Fluoride - -
Gold
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
HO
ND
NA
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
+
<0.001
0.009
0.007
0.010
0.020
0.020
0.0003
0.005
ND
<0.001
ND
0.090
ND
NA
NA
<0.090
0.12
0.020
<0.080
18.0
<0.002
1.20
<0.001
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
+
<0.01
70.0
0.08
0.09
0.07
0.40
0.0003
100.0
ND
<0.01
ND
<0.5
ND
NA
NA
<0.90
5.76
<0.06
<0.08
<50.0
<0.02
1.15
ND
Effluent
Cone.
mg/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
NA
<0.01
100.0
0.05
0.09
0.04
0.04
0.0003
70.0
ND
<0. 1
ND
<0.5
ND
NA
NA
<0.90
3.57
<0.06
<0.08
<50.0
<0.02
1.15
ND
Analysts
Blank
Cone.
BW/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
SA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
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
-------
TABLE V-2
SCREENING ANALYSIS RESaLTS
CADMIUM SUBCATEGORY
DCP Data Plant
KTBP, BTBP Influefit
Cone.
__ mq/1
Iron - - <0,1
Haqnesium
Manganese
Molybdenum
Oil and Grease
Phenol a (Total)
Phosphorus
Sodium
Strontium
1SS
Tin
litanium
Vanadium
Yttriuir
7.8
0.03
<0.006
6.0
<0.005
MO
8.8
NA
<5.0
0.05
<0.006
<0.002
<0.002
Raw
Haste
Cone.
BHJ/1
1.00
7,00
0.10
<0.06
<5.00
<0.005
0.05
400.0
NA
368.0
0.30
<0.06
<0.02
<0.02
Effluent
Cone.
pg/1
<1.00
7.00
0.09
<0.06
<5.00
0.009
ND
510.0
NA
338.0
<0.08
<0.06
<0.02
<0.02
Analysis
Blank
Cone.
mg/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
±NA
NA
ND
Not detected
ISA Not analyzed (includes Xylenes 6 Alkyl Epoxid.es since laboratory analyses were not finalized for these
parameters).
KTBP Known to be present indicated by number of plants.
BTBP Eelieved to be present indicated by number of plants.
-,- Kot investigated in DCP survey.
* Indicates <0.01 m«r/l.
** Indicates <0.005 mg/1.
+ For asbestos analysis} indicates presence of chrysotile fibers.
-------
TABLE V-3
SCREENING ANALYSIS RESULTS
(S3
•P-
00
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.
CALCIUM SUBCATEGORY
DCP Data
KTBP, BTBP
Acenapbthene
Acrolein
Acrylontrile
Benzene
Benzidine
Carbon Tetrachloride'
Chlorobenzene
1,2,4 Trichlorobenzene
Hexachlorobenzene
1,2 Dichloroethane
1,1,1 Trichloroethane
Hexach lor oe thane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetrachloroethane
Chloroethane
Bis Chloromethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinyl Ether
2-Chloronapthalene
2,4,6 Irichlorophenol
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
Ethylbenzene
Fluor an tbene
4 Chlorophenyl Phenyl Ether
Plant
Influent
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
0.055
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Raw
Haste
Cone.
mq/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.
mq/1
NA
ND
ND
ND
ND
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
NA
ND
NA
NA
NA
NA
ND
NA
NA
-------
TABLE V-3
SCREENING ANALYSIS RESULTS
N>
11.
42.
43.
44.
us.
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.
CALCIUM SUBCATEGORY
DCP Data
KTBP. BTBP
4 Bromophenyl Phenyl Ether
Bis (2 Chloroisopropyl) Ether
Bis (2 Chloroethoxy) Methane
Methylene Chloride
Methyl Chloride
Methyl Bromide
Bromoform
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromome thane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2 Nitrophenol
4 Nitrophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Nitroscdimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-N-propylamine
Pentachlorophenol
Phenol
Bis (2-Ethylhexyl) Phthalate
Butyl Eenzyl Phthalate
Di-N-butyl Phthalate
Di-N-octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthracene
Benzo (A) Pyrene
3,4 Benzofluorathene
11, 12-Benzofluoranthene
Chrysene
Acenaphthylene
Anthracene
1, 12-Eenzoperylene
Fluorene
Plant
Influent
Cone.
mq/l
ND
ND
ND
0.011
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
COnc.
mg/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
ND
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
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
TABLE V-3
SCREENING ANALYSIS RESDLTS
Oi
O
81.
82.
83.
814.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122.
123.
CALCIUM SUBCATEGORX
DCP Data
KTBP, BTBP
Phenanthrene
1,2,5,6 Dibenzanthcacene
Indenopyrene
Pyrene
Tetrachloroethylene
Toluene
Tr ichl oroe thy lene
Vinyl Chloride
Aldrin
Dieldrin
Chlordane
4,4 DDI
H,H DDE
4,4 DDD
Alpha-Endosulfan
Beta-Endosul fan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
Heptachlor Epoxide
Alpha-BHC
Beta-EHC
Gamma-BBC (Lindane)
Delta-BHC
PCE-1242
PCB-1254
PCB-1221
PCB-1232
PCE-1248
PCB-1260
PCE-1016
Toxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadmium
Chromium 0,2
Copper
Cyanide
Lead
Mercury
Plant
Influent
Cone.
mcj/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
<0.005
<0.005
ND
<0.001
0.001
0.005
0.068
ND
0.025
<0.001
Raw
Haste
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
<0.005
<0.005
+
<0.001
0.002
2.06
0.118
ND
0.044
<0.001
Analysis
Blank
Cone.
mq/1
NA
NA
NA
NA
ND
ND
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
NA
NA
NA
NA
NA
NA
NA
-------
TABLE V^
SCREENING ANALYSIS RESULTS
Ui
124.
125.
126.
127.
128.
129.
130.
131.
CALCIUM SUBCATEGORY
DCF Data
KTBPA__BTBP
NicJcel
Selenium
Silver
Thallium
Zinc
2,3,7,8 TCDD (dioxin)
Xylenes
Alkyl Epoxides
Aluminum -,-
Ammonia -,-
Barium -,-
Boron -»-
Calcium -,-
Cobalt -,-
Fluoride - ,-
Sold -,-
Iron -,-
Magnesium -,-
Manganese -,-
Molybdenum -,-
Oil and Grease -,-
Phenols (Total) -,-
Phosphorus -f—
Sodium -,-
Strontium -,-
TSS -,-
Tin -»-
Titanium -,-
Vanadium -,- •
Yttrium -,-
Plant
Influent
Cone.
mg/1
0.060
<0.005
0.003
<0.050
0.018
ND
NA
NA
0.086
NA
0.016
0.040
15.*J
0.011
1.7
NA
0.091
3.U7
0.007
<0.00t
ND
ND
ND
5.73
NA
ND
0.012
0.001
0.030
<0.001
Raw
Waste
Cone.
mg/1
0.067
<0.005
0.012
<0.050
0.0«5
ND
NA
NA
0.10H
HA
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
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
8D Not detected
NA Not analyzed (includes Xylenes 5 Alkyl Epoxides since laboratory analyses
were not finalized for these parameters).
KTBP Known to be present indicated by number of plants.
ETBP Believed to be present indicated by number of plants.
-,- Not investigated in DCP survey.
* Indicates S 0.01 mg/1.
** Indicates < 0.005 mg/1.
+ For asbestos analysis; indicates presence of chrysotile fibers.
-------
TABLE V-4
SCREENING ANALYSIS RESDLTS
to
Ui
DCP
KTBP,
1. Acenaphthene
2. Acrolein
3. Acrylonitrile
4. Benzene
5. Benzidine
6. Carbon Tetrachloride
7. Chlorobenzene
8. 1,2,4 Trichlorobenzene
9. Hexachlorobenzene
10. 1, 2 Dichloroethane
11. 1,1,1 Trie hloroethane
12. Hexachloroethane
13. 1,1 Dichloroethane
14. 1,1,2 Trichloroethane
15. 1,1,2,2 Tetrachloroethane
16. chloroethane
17. Bis Chloromethyl Ether
18. Bis 2-Chloroethyl Ether
19. 2-Chloroethyl Vinyl Ether
20. 2-Chloronaphthalene
21. 2,4,6 Trichlorophenol
22. Farachlorometacresol
23. Chloroform
24. 2 Cblorophenol
25. 1,2 Dichlorobenzene
26. 1,3 Dichlorobenzene
27. 1,4 Dichlorobenzene
28. 3,3 Dichlorobenzidine
29. 1,1 Dichloroethylene
30. 1,2 Trans-Dichloroethylene
31. 2,4 Dichlorophenol
32. 1,2 Dichloropropane
33. 1,2 Dichloropropylene
34. 2,4 Dimethylphenol
35. 2,4 Dinitrotoluene
36. 2,6 Dinitrotoluene
37. 1,2 Diphenylhydrazine
38. Ethylbenzene
39. Fluoranthene
40. 4 Chlorophenyl Phenyl Ether
41. 4 Bromophenyl Phenyl Ether
42. Bis (2 Chloroisopropyl) Ether
43. Bis (2 Chloroethoxy) Methane
44. Methylene Chloride 1
45. Methyl Chloride
LECLANCHE SUBCATEGORY
Data Plant
BTBP Influent
Cone.
mcr/1
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
,0 *
ND
Raw
Haste
Cone.
mcj/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
Analysis
Blank
Cone.
mq/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
-------
TABLE V-H
SCREENING ANALYSIS RESULTS
Ui
OJ
LECLANCHE SOBCATEGORX
DCP Data Plant Raw
KTBP, BTBP Influent Waste
Cone. Cone.
mq/1 mg/1
46.
in.
48.
49,
50.
51.
52.
53.
54.
55.
56.
57.
5fi.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
Methyl Bromide
Bromoform
Dichlor obromome thane
Tr ichl o r of luorontethane
Dichlozodifluoromethane
Chlorodibromomethane
Hexach lor obutad iene
Hexachlorocyclopentadiene
Igophorone
Naphthalene
Nitrobenzene
2 Nitrophenol
4 Nitzophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Nitrosodiwethylamine
B-Nitrosodiphenylamine
N-Nit ro sodi-N- propyl ami ne
Pentachlorophenol
Phenol
Bis (2-Ethylhexyl) Phthalate
Butyl Benzyl Phthalate
Dl-N-butyl Phthalate
0i-H-octyl Phthalate 0,1
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthraeene
Benzo (A) Pyrene
3,4 Benzofluoranthene
11, 12-Benzofluoranthene
chrysene
Acenaphthylene
Anthracene
1, 12-Benzoperylene
Fluorene
Phenanthrene
1,2,5,6 Dibenzanthracene
Indenopyrene
Pyrene
letrachloroethylene 0,1
toluene 0, 2
Irichloroethylene 0, 1
Vinyl Chloride 0,1
Aldrin
Dieldrin
Chlordane
ND
8D
*
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
0.016
*
ND
ND
ND
ND
ND
SO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SD
ND
ND
ND
Analysis
Blank
Cone.
mq/1
ND
ND
ND
ND
ND
ND
NA
m
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
-------
TABLE V-«
SCRSBNIH3 ANALYSISRESPMS
92. 4,4 DDT
93. 4,4 DDE
94. 4,4 ODD
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endesulfan sulfate
98. Endrin
99. Endrin Aldehyde
100. fleptacnlor
101. Heptachlor Epoxide
102. ftlphaBBC
103. EetaBHC
104. GammaBBC (Lindane)
105. DeltaBHC
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 ICDD (Dioxin)
130. Xylenes
131. Alkyl Epoxides
Aluirinurr
Ammonia
Barium
Boron
Calcium
Cobalt
LECLANCHE SOBCATE30BY
DCP Data plant
KTBP, BTBP Influent
Cone.
mcf/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0,3 ND
0,4 ND
ND
<0.001
0,5 <0.002
1,2 <0.005
4,2 <0.009
ND
4,3 <0.02
5,1 0.020
1,3 <0.005
1,0 ND
<0.001
ND
0,2 0.080
ND
NA
NA
<0.09
-,- NA
-,- 0.010
-,- 0.100
-,- 52.000
-,- <0.002
Raw
Haste
Cone.
mct/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.00
ND
ND
<0.01
0.10
0.20
1.00
0.018
0.018
6.00
4.00
ND
<0.01
ND
2000.0
ND
NA
NA
<0.09
ND
0.40
2.00
150.0
<0.02
Analysis
Blank
cone.
BKf/1
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
HA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
TABLE V-4
SCREENING ANALYSIS RESULTS
LECLANCHE SUBCATE30RY
DCP Data Plant Raw
KTBP, BTBP Influent
cone.
mg/1
Fluoride - - 1.200
Gold
Iron
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium
Yttrium
ND
<0. 10
7. 500
0.02
<0.006
ND
1.600
0.2HO
66.00
HA
ND
<0.008
-------
TABtE V-5
SCREENING ANALYSIS RESPWS
1, Acenaphthene
2. Acrolein
3. Acrylonitrile
t). Benzene
5. Benzidine
6. Carbon letrachloricle
7. Chlorobenzcne
8. 1,2,4 iriehlorobenzene
9. Rexachlorobenzene
10. 1,2 Dicbloroethane
11. 1,1,1 sziehloroethane
12. Hexachloroethane
13. 1,1 Dichloroethane
14. 1,1,2 Triehloroethane
15. 1,1,2,2 Tetrachloroethane
16. Chlozoethane
17. Bis Chloromethyl Ether
18. Bis 2-Chloroethyl Ether
19. 2-Chloroethyl Vinyl Ether
20. 2-Chlozonaphthalene
21. 2,4,6 irichlorophenol
22. Paraehlorametacresol
23. Chloroform
24. 2-Chlorophenol
25. 1,2 Dichlorobenzene
26. 1,3 Dichlorobenzene
27. 1,4 Dichlorobenzene
28. 3,3 Dichlorobenziatre
29. 1,1 Dichloroethylene
30. 1,2 Trans-Diehloroethylene
31. 2,4 Dichlorophenol
32. 1,2 Dichloropropane
33. 1,2 Oichloropropylene
34. 2,4 Dimethylphenol
35. 2,4 Dinitrotoluene
36. 2,6 Dinitrotoluene
MTHIDH SCJBCATESOKY
Plant Raw*
Influent Haste
DCP Data Cone. Cone.
KTBP, BIBP ma/1 ma/1
ND
ND
ND
ND
ND
ND
ND
ie ND
ND
ND
( SD
ND
ND
! ND
:hane ND
ND
ir ND
ler ND
Ither ND
ND
ND
ND
0.055
ND
ND
ND
ND
: ND
ND
lylene 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
Analysis Raw2
Blank Haste
Cone. Cone.
mg/1 mcr/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
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
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mer/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
-------
TA'BLE v-5
SCREENING ANALYSIS RESULTS
N>
37. 1,2 Diphenylhydrazine
38. Ethylbenzene
39. Fluoranthene
HQ. 1 Chlorophenyl Phenyl Ether
11. 1 Bromophenyl Phenyl Ether
12. Bis (2-Chloroisoprop
13. Bis (2-Chloroethoxy)
11. Methylene Chloride
15. Methyl chloride
16. Methyl Bromide
17. Bromoform
18. Dichloxobromomethane
19. Trichlorofluoromethane
50. Dichloxodifluoromethane
51. Chlorodibromomethane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
51. Isophorone
55. Naphthalene
56. Nitrobenzene
57. 2 Nitrophenol
58. 1 Nitrophenol
59. 2,1 Dinitrophenol
60. 1,6 Dinitro-o-cresol
61. N-Nitrosodimethylamine
62. B-Nitrosodiphenylamine
63. N-Nitrosodi-N-propylamine
61. 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
71. 3,1 Eenzofluoranthene
75. 11, 12-Eenzofluoranthene
DCP Data
KTBPt BTBP
!
Ether
Ether
•1) Ether
Methane
,e
ne
liene
e
,e
.mine
thalate
e
ene
LITHIUM SUBCATEGORY
Plant Raw1
Influent Waste
Cone. Cone.
mq/1 mq/1
ND
ND
ND
ND
ND
ND
ND
0.011
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
0.011
" ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
0.021
ND
*
ND
ND
ND
ND
ND
ND
ND
Analysis Raw2
Blank Waste
Cone. Cone.
mq/1 mg/1
NA
ND
NA
NA
NA
NA
NA
*
ND
ND
ND
ND
ND
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
ND
ND
ND
ND
ND
ND
ND
0.016
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
Analysis
Blank
Cone.
mq/1
NA
ND
NA
NA
NA
NA
NA
*
ND
ND
ND
ND
ND
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
-------
TABLE V-5
SCREENING ANALYSIS RESPLTS
Ui
OO
76. Chryaene
77. Acenaphthylene
78. Anthracene
79. 1,12-Benzoperylene
80. Fluorene
81. Phenanthrene
82. 1,2,5,6 Dibenzanthracene
83. Indenopyrene
84. Pyrene
85. letrachloroethylene
86. Toluene
87. Trichloxoethylene
88. Vinyl Chloride
89. Aldrin
90. Dieldrin
91. Chlordane
92. H,H DDJ
93. H,H DOS
94. 4,4 ODD
95. Alpha-Endosulfan
96. Beta-Endosulfan
97. Endosulfan Sulfate
98. Endrin
99. Endrin Aldehyde
100. Heptacblor
101. Heptachlor Epoxide
102. Alpba-BHC
103. Beta-BHC
10Q. Gamma-BBC (Lindane)
105. Delta-BHC
106. PCB-1242
107. PCB-1254
108. PCB-1221
109. PCB-1232
110. PCB-1218
111. PCB-126Q
112. PCB-1016
113. foxaphene
L1THIOH SUBCATEGORX
Plant Raw*
influent Haste
DCP Data Cone. Cone.
KfBP, BTBP mq/1 mq/1
NO
ND
ND
ND
ND
ND
.cene 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
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mq/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
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
Raw*
Haste
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
Analysis
Blank
cone.
mg/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
HD
ND
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
ND
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
-------
TAB!,! 7-5
SCREENING ANALYSIS RESULTS
Ui
LITHIUM SUBCATE6ORY
Plant Raw1
Influent Waste
DCP Data Cone. Cone.
KTBP, BTBP mq/1 BKj/1
111.
115.
116.
117.
118.
119.
120.
121.
122.
123.
121.
125.
126.
127.
128.
129.
130.
131.
Antimony <0,005
Arsenic <0.005
Asbestos NA
Eeryllium <0.001
Cadirium 0,1 0.001
Chromium 0,1 0.005
Copper ' 0.068
Cyanide ND
Lead 0,1 0.025
Mercury <0.005
Hickel 0.060
Selenium <0.005
Silver 0.003
Thallium <0.050
Zinc 0.018
2,3,7,8 TCDD (Dioxin) ND
Xylenes NA
Alky! Epoxides NA
Aluminum - - 0.086
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
Sold
Iron
Lithium
Magnesium
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Phosphorus
Sodium
Strontium
TSS
Tin
Titanium
Vanadium -
Yttrium
NA
0.016
0.040
15. H
0.011
1.7
NA
0.091
<0.050
3.«7
0.007
<0.001
ND
ND
0.00
5.73
NA
ND
0.012
0.001
0.030
<0.001
<0.005
<0.005
630+
<0.001
0.002
2.06
0.118
0.00
0.00
<0.005
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
<0.050
3.66
0.008
<0.001
0.00
0.00
0.00
6.06
NA
21.0
0.006
0.001
0.030
<0.001
Analysis Raw*
Blank Waste
Cone. Cone.
mg/1 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
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
<0.005
<0.005
2.4+
<0.001
0.025
0.015
0.109
0.14
4.93
<0.001
0.235
<0.005
0.001
<0.050
0.473
ND
NA
NA
0.287
NA
0.059
0.193
22.8
0.176
3.05
NA
54.9
<0.050
3.78
1.60
0.021
ND
ND
1.56
6.44
NA
39.0
0.023
0.001
0.035
0.023
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
-------
TABLE V-5
ANALYSIS RESULTS
LITHIUM SUBCATEGORY
ND Not detected
Nft Not analyzed (includes Xylenes 6 Alkyl Epoxides since laboratory
analyses were not finalized for these parameters).
KTBP Known to be present indicated by number of plants.
BlBP Believed to be present indicated by number of plants.
-»- Sot investigated in DCP survey.
* Indicates <0.01 mg/1.
*» Indicates <0.005 mg/1.
1. Heat Paper Production wastewater
2. Cathode Process Wastewater
+ For asbestos analysis; indicates presence of cbrysotile fibers
-------
TABLE V-6
SCREENING ANALYSIS RESULTS
ho
ON
MAGNESIUM SUBCATEGORY
DCP Data Plant Raw
KTBP, BTBP Influent Wast«
Cone . Cone . 1 /
mg/1 mg/1
1 . Acenaphthene
2. Acrolein
3. Acrylonitrile
4. Benzene
5. Benzidine
6. Carbon Tetrachloride
7. Chlorobenzene
8. 1,2,4 Trichlorobenzene
9. Hexachlorobenzene
10. 1,2 Dichloroethane
11. 1,1,1 Trichloroethane
12. Hexachloroethane
13. 1,1 Dichloroethane
14. 1,1,2 Trichloroethane
15. 1,1,2,2 Tetrachloroethane
16. Chloroethane
17. Bis Chloromethyl Ether
18. Bis 2-Chloroethyl Ether
19. 2-Chloroethyl Vinyl Ether
20. '2-Chloronaphthalene
21. 2,4,6 Trichlorophenol
22. Parachlorometacresol
23. Chloroform
24. Chlorophenol
25. 1,2 Dichlorobenzene
26. 1,3 Dichlorobenzene
27. 1,4 Dichlorobenzene
28. 3,3 Dichlorobenzidine
29. 1,1 Dichloroethylene
30. 1,2 Trans -Dichloroethylene
31. 2,4 Dichlorophenol
32. 1,2 Dichloropropane
33. 1,2 Dichloropropylene
34. 2,4 Dimethylphenol
35. 2,4 Dinitrotoluene
36. 2,6 Dinitrotoluene
37. 1,2 Diphenylhydrazine
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
0.013
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.038
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
ND
ND
ND
ND
NA
ND
ND
NA
NA
ND
ND
NA
ND
ND
ND
ND
ND
ND
ND
NA
NA
NA
*
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
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
0.380
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Raw
Waste
Cone . 2/
mg/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.155
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Raw
Waste
Cone . 3/
ms/1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.140
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-------
TABLE V-6
SCREENING ANALYSIS RESULTS
DCP
KTBP,
38. Ethylbenzene
39. Fluoranthene
40. 4 Chlorophenyl PhenyL Ether
41. 4 Bromophenyl Phenyl Ether
42. Bis (2 Chloroisopropyl) Ether
43. Bis (2 Chloroethoxy) Methane
44. Methylene Chloride
45. Methyl Chloride
46. Methyl Bromide
47. Bromoform
48. Dichlorobromomethane
49. Trichlorofluoromethane
50. Dichlorodifluoromethane
51. Chlorodibromomethane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
54. Isophorone
55. Naphthalene
56. ' Nitrobenzene
57. 2 Nitrophenol
58. 4 Nitrophenol
59. 2,4 Dinitrophenol
60. 4,6 Dinitro-o-cresol
61. N-Nitrosodimethylamine
62. N-Nitrosodiphenylaraine
63. N-Nitrosodi-N-propylamine
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 Benzof luoranthene
MAGNESIUM SUBUATEGURY
Data Plant Raw
BTBP Influent Waste
Cone . Cone . 1 /
ng/1 mg/1
ND
ND
ND
ND
ND
ND
0.011
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
NA
NA
NA
NA
NA
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
Analysis
Blank
Cone.
OR/1
ND
NA
NA
NA
NA
NA
*
ND
ND
ND
ND
ND
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
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
Raw
Waste
Cone . 2/
ng/l~
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
Conc.3/
rag/1
ND
ND
ND
ND
ND
ND
0.011
ND
ND
ND
0.026
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.051
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
-------
TABLE V-6
SCREENING ANALYSIS RESULTS
MAGNESIUM SUBCATEGORY
DCP Data Plant Raw
KTBP, BTBP Influent Waste
Cone . Cone . 1 /
mg/1 mg/1
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
11,1 2-Benzof luoranthene
Chrysene
Acenaphthylene
Anthracene
1 , 1 2-Benzoperylene
Fluorene
Phenanthrene
1,2,5,6 Dibenzanthracene
Indenopyrene
Pyrene
Tetrachloroethylene
Toluene
Trlchloroethylene
Vinyl Chloride
Aldrin
Dieldrin
Chlordane
4,4 DDT
.4,4 DDE
4,4 ODD
Alpha-Endosulfan
Beta-Endosulfan
Endosulfan Sulfate
Endrin
Endrin Aldehyde
Heptachlor
Heptachlor Epoxide
Alpha -BHC
Beta-BHC
Gamma -BHC (Lindane)
Delta-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
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
Analysis
Blank
Cone.
mg/1
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
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Plant
Influent
Cone.
rag/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
Raw
Waste
Cone . 2/
rag/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
Raw
Waste
Cone . 3/
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
-------
TABLE V-6
SCREENING ANALYSIS RESULTS
MAGNESIUM SUBCATJSGORY
DCP Data Plant Raw
KTBP, BTBP Influent Waste
Cone . Cone . 1 /
rag/1 mg/1
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
129.
PCB-1016 ND
Toxaphene ND
Antimony <0.005
Arsenic <0.005
Asbestos 1,0 ND
Beryllium <0.001
Cadmium 0, 1 0. 001
Chromium 1,2 0.005
Copper 0. 068
Cyanide ND
Lead 0.025
Mercury 0. 001
Nickel 0.060
Selenium <0. 005
Silver 0. 003
Thallium <0.050
Zinc 0.018
2, 3, 7, 8-tetrachlorodibenzo- ND
p-dioxin (TCDD)
Aluminum - - 0. 086
Ammonia
Barium
Boron
BOD
Calcium
Chlorides
Cobalt
COD
Iron
Magnes turn
Manganese
Molybdenum
Oil and Grease
Phenols (Total)
Sodium
Tin
NA
0.016
0.040
NA
15.4
NA
0.011
NA
0.091
3.47
0. 007
<0.001
ND
ND
5.73
0.012
ND
ND
<0.005
<0.005
+
<0.001
0.001
2.06
0.118
ND
0.044
0.001
0.067
<0. 005
0.012
<0.050
0.045
ND
0.104
NA
2.67
0.116
NA
15.9
NA
0.006
ND
0.122
3.66
0.008
0.001
ND
ND
6.06
0.006
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
Plant
Influent
Cone.
ND
ND
<0.015
<0.015
+
0.001
<0.005
<0. 01
0.015
ND
<0.050
<0.0003
<0.050
<0.015
< 0.002 4/
<0.015 ~
0.066
ND
0.300
<0.050
0.013
<0.020
<1 . 000
6.460
17.0
<0.005
<5.00
0.064
2.210
<0.010
<0.010
<0. 500
<0.020
24.500
<0.010
Raw
Waste
Cone .21
ND
ND
<0.015
<0.015
+
<0.001
<0.005
<0.01
0.011
ND
<0.050
<0. 0003
<0.050
<0.015
0.039 4/
<0.015 ~
0.035
ND
0.260
2.013
0.015
<0.020
40. 268
6.720
54. 309
<0.005
140.0
<0.030
2.380
<0.010
<0.010
<0.500
0.001
300.0
<0.010
Raw
Waste
Cone . 3/
mg/1
ND
ND
<0.015
<0.015
4.
<0.001
<0,005
0.088
0.180
ND
<0.050
<0.0004
<0.050
<0.015
0.248 4/
<0.015 ~
0.130
ND
0.270
0.004
0.015
<0.020
NA
7.740
2010.0
X0.005
NA
0.560
2.470
0.014
<0.010
<0.500
0.004
24.60
<0.010
-------
TABLE V-6
SCREENING ANALYSIS RESULTS
DCP
MAGNESIUM SUBCATEGORY
Data Plant Raw Analysis
KTBP, BTBP Influent Waste Blank
Titanium
TOG
TSS
Vanadium
Yttrium
Cone . Cone . 1 / Cone .
mg/1 mg/1 mg/1
0.001 0.001 NA
NA NA NA
ND 21.0 NA
0.030 0.030 NA
<0.001 0.001 NA
Plant
Influent
Cone.
mg/1
-------
TABLE V-7
SCREENING ANALYSIS RESOLTS
ZINC SUBCATEGORY
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
Acenaphtbene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon Tetrachloride
Chlorobenzene
1,2,4 Trichlorobenzene
Hexachl or obenzene
1,2 Dichloroethane
1,1,1 Irichloroethane
Hexachloroe thane
1,1 Dichloroethane
1,1,2 Trichloroethane
1,1,2,2 Tetrachloroethane
Chi or oe thane
Bis Chloromethyl Ether
Bis 2-Chloroethyl Ether
2-Chloroethyl Vinyl Ether
2 -Chi or onaphthalene
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
Ethylbenzene
Fluoranthene
4 Chiorophenyl Phenyl Ether
4 Bromophenyl Phenyl Ether
DCP Data Plant
KTBP, BTBP Influent
Cone.
mg/1
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
1,0 ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.086
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Raw
Haste
Cone.
mg/1
NA
ND
ND
*
NA
ND
ND
NA
NA
ND
4.2
NA
0.018
ND
ND
ND
ND
ND
ND
NA
NA
NA
ND
NA
NA
NA
NA
NA
0.64
0.016
ND
ND
ND
NA
NA
NA
NA
*
NA
NA
NA
Effluent
Cone.
mg/1
ND
ND
ND
*
ND
ND
ND
ND
ND
ND
6.4
ND
0.079
*
ND
ND
ND
ND
ND
ND
*
ND
ND
*
ND
ND
ND
ND
0.42
ND
NA
ND
ND
ND
ND
ND
ND
0.032
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
ND
NA
NA
NA
NA
NA
ND
ND
NA
ND
ND
NA
NA
NA
NA
ND
NA
NA
NA
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
Raw
Haste
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
Effluent
Cone.
ng/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
NA
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
NA
NA
NA
NA
ND
NA
NA
NA
NA
NA
ND
ND
ND
ND
ND
NA
NA
NA
NA
ND
NA
NA
NA
-------
TABLE V-7
SCREENING ANALYSIS RESULTS
,ZINC SUBCATEGORY
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
81
82
Eis (2 Chlorcisopropyl) Ether
Eis (2 Chloroethoxy) Methane
Methylene Chloride
Methyl Chloride
Methyl Bromide
Brorcoform
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromomethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2 Nitrophenol
4 Nitrophenol
2,4 Dinitrophenol
4,6 Dinitro-o-cresol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-N-propylamine
Pentachlorophenol
Phenol
Bis (2-Ethylhexyl) Phthalate
Butyl Benzyl Phthalate
Di-N-Butyl Phthalate
Di-N-octyl Phthalate
Diethyl Phthalate
Dimethyl Phthalate
1,2 Benzanthracene
Eenzo (A) Pyrene
3,4 Benzofluoranthene
11, 12-Eenzofluoranthene
Chrysene
Acenaphthylene
Anthracene
1,1 2-Benzoperylene
Fluorene
Phenanthrene
1,2,5,6 Dibenzanthracene
DCP Data Plant
KTBP, BTBP Influent
Cone.
mg/1
ND
ND
1,1 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
Raw
Haste
Cone.
mg/1
NA
NA
0.35
ND
ND
ND
ND
ND
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
NA
NA
NA
Effluent
Cone.
mg/1
ND
ND
8.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.190
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
Analysis
Blank
Cone.
mg/1
NA
NA
ND
ND
ND
ND
ND
ND
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
NA
NA
NA
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
Raw
Waste
Cone.
mg/1
ND
ND
0.022
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.040
ND
0.012
*
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
*
ND
ND
*
ND
Effluent
Cone.
mg/1
ND
ND
0.031
ND
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
ND
ND
ND
ND
ND
Analysis
Blank
Cone.
mg/1
NA
NA
0.018
ND
ND
ND
ND
ND
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
NA
NA
-------
TABLE V-7
SCREENING ANALYSIS RESULTS
ZINC SUBCATEGORX
CO
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
11U
115
116
117
118
119
120
121
122
123
Indenopyrene
Pyrene
TetrachJ
Toluene
Trichlcj
Vinyl chloride
Aldrin
Dieldrin
Chlordane
4,4 DDT
4,4 DDE
4,4 ODD
Alpha-Endo
Beta-Endos
Endosulfan
Endrin
Endrin Aid
Heptachlor
Heptachlor
Alpha-EHC
Beta-BHC
Gamma-BHC
Delta-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
Toxaphene
Antimony
Arsenic
Asbestos
Eeryllium
Cadirduro
Chromium
Copper
Cyanide
Lead
Mercury
DCP Data Plaat
KTBP, BTBP Influent
Cone.
mg/1
ie ND
ND
lethylene ND
0,1 ND
.hylene 2,0 ND
•ide ND
ND
ND
ND
ND
ND
ND
iulfan ND
ilfan ND
Sulfate ND
ND
*yde ND
ND
Epoxide ND
ND
ND
[Lindane) ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1,0 ND
1,0 ND
ND
<0.001
0,1 <0.002
5,0 <0.005
<0.006
1,2 ND
0,1 <0.02
12,0 0.0060
Raw
Haste
Cone.
mg/1
NA
NA
0.025
0.11
0.39
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
0.07
ND
ND
<0.001
0.16
2.13
0.078
ND
<0.02
110
Effluent
Cone.
mg/1
ND
ND
*
0.055
0.045
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
<0.001
<0.002
<0.005
0.047
ND
<0.02
0.06
Analysis
Blank
Cone.
mg/1
NA
NA
ND
ND
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
NA
NA
NA
NA
NA
NA
NA
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
<0.001
<0.002
0.020
0.030
<0.005
<0.02
0.100
Raw
Haste
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
0.060
0.020
0.100
0.001
0.100
0.800
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
<0.001
0.030
0.020
0.100
0.001
0.100
0.800
Analysis
Blank
Cone.
mg/1
NA
NA
ND
ND
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
NA
NA
NA
NA
NA
NA
NA
-------
TABLE V-7
SCREENING ANALYSIS RESULTS
r>
o
124 Nickel
125 Selenium
126 Silver
127 Thallium
128 Zinc
129 2,3.7,8 1CDD (Dioxin)
130 Xylenes
131 Alkyl Epoxides
Aluminum
Ammonia
Barium
Boron
Calcium
Cobalt
Fluoride
Gold
Iron
Magnesium
Manqanese
Molybdenum
Oil (, Grease
Phenols (Total)
Phosphorus
sodium
Strontium
1SS
Tin
Titanium
Vanadium
Xttrium
ZINC SUBCATEGORY
DCP Data
KTBP, BTBP
1,0
6,0
13,2
" t~~
~t~
~"*~
— ,-
""*"*
— t -
— ,~
"~,~
— ,—
~» ~
— ,-
~~f ~"
~»~
~ * *"
~«~
~"» ~
~ * ""
~"# **
— ,~
~»~
~»~
~ »~
Plant
Raw
Influent Waste
Cone.
mg/1
<0.005
ND
<0.001
ND
0.170
NA
NA
NA
0,068
NA
0.026
<0.05
<5.0
<0.005
1.10
ND
0.17
2.600
-------
TABLE V-7
SCREENING ANALYSIS RESULTS
ZINC SUBCATEGORY
NO Not detected.
MA Net analyzed (includes Xylenes and Alky! Epoxides since laboratory analyses were not finalized for
these parameters).
KTBP Known to be present indicated by number of plants.
B1BP Believed to be present indicated by number of plants.
-«- Not investigated in DCP survey.
• Indiactes <0.01 mq/1.
*• Indicates SO.005 ng/1.
-------
TABLE V-8
VERIFICATION PARAMETERS
S3
11
13
14
23
29
30
38
44
55
64
66
70
85
86
87
1U
115
116
118
119
.12 a
121
122
123
1?«
125
126
PARAMETERS
1,1,1 -Trichloroethane
1, 1-Dichloroethane
1,1 , 2-lrichloroethane
Chloroform
1.1 -Dichloroethvlene
1,2 Trans-dichloroethylene
Ethylbenzene
Methylene Chloride
Naphthalene
Pentachloiophenol
Bis (2-ethyl hexyl) Phthalate
Diethyl Phthalate
Tetrachloroethylene
Toluene
Trichloroethylene
Antimony
Arsenic
Asbestos
Cadiriuro
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
CADMIUM
SUBCATEGORY
X
X
X
X
X
X
X
x
CALCIDM
SUBCATEGORY
X
X
X
x •
X
X
X
X
X
X
X
LECLANCHE
SUBCATEGORY
x
X
X
X
X
X
X
X
x
X
LITHIUM
SUBCATEGORY
x
X
X
X
X
X
X
X
X
X
X
MAGNESIUM
SUBCATEGORY
x
X
X
X
X
X
X
X
X
TC
X
ZINC
SUBCATEGORY
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 V-8
VERIFICATION PARAMETERS
CADMIUM
PARAMETERS SOBCATEGORX
to
^J
to
128 Zinc
Aluminurr
Ammonia
Barium
Cobalt
COD
Fluoride
Iron
Manganese
Phenols (Total)
Oil 6 Grease
TSS (Total Suspended Solids)
PH
X
X
X
X
X
X
X
CALCIUM LECLANCHE LITHIUM
SUBCATEGORY SOBCATEGORY SOBCATE30RY
X XX
X X
X X
X XX
X
X XX
X XX
X XX
MAGNESIUM
SUBCATEGORY
X
X
X
X
X
X
X
X
X
X
X
X
ZINC
SUBCATEGORY
X
X
X
X
X
X
X
X
X
-------
to
^4
CO
TABLE V-9
CADMIUM SUBCATEGOR? PROCESS ELEMENTS
(Reported Manufacture)
Anodes
Cathodes
Mercuric Oxide
Powder Pressed
Silver Powder
Pressed
Kickel
Powder Pressed
nickel Electro-
deposited
Kickel Impregnated
Cadmium Pasted
and Pressed
Powder
Cadmium
Electrodeposited
Cadmium
Impregnated
AncMJary_geeration8
Cell Hash
Electrolyte
Preparation
floor and Equipment
hash
Employee Hash
Cadmium Powder
Production
Silver Powder Production
Mickel Hydroxide Pro-
duction
Cadmium Hydroxide Pro-
duction
-------
£-
TABLE V-10
NORMALIZED DISCHARGE FLOWS
CADMIOM SOBCATEGORY ELEMENTS
Elements
Anodes
Fasted 6 Pressed
Powder
Electrodeposited
Impregnated
Cathodes
Nickel Electrode-
posited
Nickel Impregnated
flnci11ary_pEerations
Cell Wash
Electrolyte Prepa-
ration
Floor and Equipment
Wash
Employee Wash
Cadmium Powder
Production
Silver Powder
Production
Cadmium Hydroxie
Production
Nickel Hydroxide
Mean
Discharge
(I/kg)
2.
697.
998.
569.
1640.
4.
0.
12.
1.
65.
21.
0.
110.
7
0
0
0
0
93
08
0
5
7
2
9
0
Median
Discharge
(I/kg)
1.0
697.0
998.0
569.0
1720.0
3.33
0.08
2.40
1.5
65.7
21.2
0.9
110.0
Total Production
Raw Waste Normalizing
Volume (1/yr) Parameter
(10*)
0
.948
80.9
179
0
274
4
0
7
0
27
.6
.680
.2
.71
.037
.78
.068
.0
0.80
1
170
.6
.0
Weight
Weight
Weight
Weight
weight
Weight
Weight
Weight
Weight
Height
Weight
Weight
Weight
of
of
of
of
of
of
of
of
of
of
of
of
of
Cadmium
Cadmium
Cadmium
Nickel
Nickel
Applied
Applied
Cells Produced
Cells Produced
Cells Produced
Cells Produced
Cadmium
Silver
Cadmium
Nickel
Powder Produced
Powder Produced
Used
Used
Production
-------
TABLE V-11
POLLUTANT CONCENTRATIONS IN CADMIUM PASTED AND
PRESSED POWDER ANODE ELEMENT WASTE STREAMS
mg/1
Temperature (Deg CJ 29.0 29-0 31^0
44 Methylene chloride 0.00 0.00 0.00
87 Trichloroethyiene 0.00 0.00 0.00
118 Cadmium 285.0 365.0 151.0
119 Chroirium, Total 0.011 0.000 0.000
Chromium, Hexavalent 0.000 0.000 0.000
121 Cyanide, Total 0.101 0.000 9.45
Cyanide, Amn. to Chlor. 0.099 0.000 9.40
122 lead 0.050 0.000 0.02
123 Mercury 0.000 0.000 0.000
124 Nickel 40.50 2.780 13.50
128 Zinc 0.530 0.350 0.350
Ammonia 2.90 0,67 , 1.15
Cobalt 0.000 0.000 0.000
Phenols, Total 0.042 0.013 0.062
Oil 6 Grease 5.0 1960.0 500.0
Total Suspended Solids 808. 1036.0 1270.0
pH, minimum 10.0 9.6 9.0
pH, maximum 10.0 9.6 9.0
-------
TABLE V-12
POLLUTANT MASS LOADINGS IN THE CADMIUM PASTED
AND PRESSED POWDER ANODE
ELEMENT WASTE STREAMS
tng/kg
Flow (I/kg)
Temperature (Deg C)
44 Methylene chloride
87 Trichloroethylene
118 Cadirium
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 8 Grease
Total Suspended Solids
pH, minimum
pH, maximum
1.533
29.0
0.00
0.00
437.0
0.017
0.000
0.155
0.152
0.077
0.000
62.1
0.813
4.446
0.000
0.064
7.67
1239.0
10.0
10.0
1.781
29.0
0.00
0.00
650.0
0.000
0.000
0.000
0.000
0.000
0.000
4.952
0.623
1.193
0.000
0.023
3491.0
1845.0
9.6
9.6
2.680
31.0
0.00
0.00
404.6
0.000
0.000
25.32
25.19
0.054
0.000
36.18
0.938
3.082
0.000
0.166
1340.0
3403.0
9.0
9.0
-------
TABLE V-13
POLLUTANT CONCENTRATIONS IN THE CADMIUM ELICTRODEPOSITED
ANODE ELEMENT WASTE STREAMS
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 Einc
Ammonia
Cobalt
Phenols, Total
Oil 6 Grease
Total Suspended solids
pH, minimum
pB, maximum
mg/1
24.6
0.00
*
108.2
0.000
0.000
0,021
I
0,000
0.0006
0.080
0.009
2.27
0.000
0.012
5.1
187.7
2.9
11.9
21.6
0.00
*
129.5
0.001
0.000
0.020
I
0.000
0.0003
0.081
0.006
2.49
0.000
0,012
5,1
177.6
4.5
11.8
24.7
*
*
46.17
0.0000
0.000
0.024
I
0.0000
0.0006
0.048
0.002
4.07
0.000
0.012
5.5
14.9
3.7
11.7
I - Interference
* - < 0.01
-------
TABLE V-14
POLLUTANT MASS LOADINGS IN THE CADMIUM ELECTRODEPOSIT1D
ANODE ELEMENT WASTE STREAMS
to
*^j
oo
mg/kg
Flow (I/kg)
Temperature (Deg C)
14 Methylene chloride
87 Trichloroethylene
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to chlor.
122 lead
123 Mercury
12* Nickel
128 Zinc
Ammonia
Cqbalt
Phenols, Total
Oil 8 Grease
Total Suspended Solids
pH, minimum
pH, maximum
691.0
21.6
0.00
0.068
71700.0
0.000
0.000
11.28
I
0.000
0.1128
55.28
6.01
1566.0
0.000
8.21
3190.0
129600.0
2.9
11.9
697.0
21.6
0.00
0.069
90200.0
0.123
0.000
14.12
I
0.000
0.2116
58.31
1.182
1731.0
0.000
8.29
3518.0
123700.0
4.5
11.8
697.0
24.7
0.00
0.070
32160.0
0.093
0.000
16,53
I
0,093
0.3939
33.63
1.542
2835.0
0.000
8.29
3815.0
10100.0
3.7
11.7
I - Interference
-------
TABLE V-15
POLLUTANT CONCENTRATIONS AND MASS LOADINGS IN THE CADMIUM IMPREGNATED
ANODE ELEMENT WASTE STREAMS
mg/1
m
-------
TABLE V-16
POLLUTANT CONCENTRATIONS IN THE NICKEL ELECTRODEPOSITED
CATHODE ELEMENT WASTE STREAMS
mg/1
00
o
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 Hercury
124 Nickel
128 Zinc
Ammonia
cobalt
PhenoIs, Tota1
Oil 6 Grease
Total Suspended Solids
PH, minimum
pH, maximum
11.0
0.00
0.00
0.048
0.000
0.000
0.042
0.042
0.000
0.0160
1.980
0.000
0.00
0.000
0.006
1.0
0.0
7.1
7.1
12.0
*
0.00
0.090
0.000
0.000
0.040
0.016
0.000
0.000
6.01
0.000
0.00
0.250
0.042
2.0
5.0
5.2
5.8
10.0
0.00
0.00
0.013
0.007
0.000
0.011
0.000
0.000
0.0320
1.550
0.000
0.00
0.053
0.014
2.0
0.0
7.0
7.2
* - < 0.01
-------
TABLE V-17
POLLUTANT MASS LOADINGS IN THE NICKEL ELECTRODEPOSITED
CATHODE ELEMENT WASTE STREAMS
mg/kg
00
Flow (I/kg)
Temperature (Deg C)
44 Methylerie chloride
87 Trichloroethylene
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to Chior.
122 lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended solids
pH, minimum
pH, maximum
97.7
11.0
0.00
0.00
4.688
0.000
0.000
4. 102
4.102
0.000
1.563
193.4
0.000
0.000
0.000
0.586
97.7
0.000
7.1
7.1
416.3
12.0
0.042
0.00
37.47
0.000
0.000
16.65
6.66
0.000
0.000
2502.0
0.000
0.000
104.1
17.49
833.0
2082.0
5.2
5.8
1167.0
10.0
0.00
0,00
15.17
8.17
0.000
12.84
0.000
0.000
37.34
1809.0
0.000
0.000
61.9
16.34
2334.0
0.000
7.0
7.2
-------
TABLE V-18
POLLUTANT CONCENTRATIONS IN THE NICKEL IMPREGNATED
CATHODE ELEMENT WASTE STREAMS
Temperature (Deg C)
«*4 Methylene chloride
87 Trichloroethylene
118 Cadndiarr
119 Chromium, Total
Chrcmium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to
Chior.
^ 122 lead
oo 123 Mercury
N> 124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil 6 Grease
Total Suspended
Solids
pH, rrinimum
pH, maximum
28.6
0.00
*
79.2
0.178
0.0000
0.025
0.018
0.010
0.0009
514.0
0.015
8.64
0.000
0.007
27.6
1163.0
4.1
13.1
PLANT A
16.7
0.00
*
25.16
0.086
0.0000
0.033
0.016
0.000
0.0113
189.2
0.027
9.39
0.000
0.006
7.4
341.9
4.0
13.0
mg/1
PLANT C PLANT D PLANT B
30.2 51.5
* 0.00
* #
10.73 0.020
0.045 0.049
0.0000 0.000
0.023 0.046
0.017 0.046
0.000 0.000
0.0004 0.0012
120.1 21.10
0.055 0,120
9.03 8.46
0.000 0.264
0.006 0.008
6.2 1.0
185.2 2690.0
5.2 9.7
12.8 12.0
38.7 43.9 16.0 16.0 71.9 69.9
* * 0.00 0.00 0.00 0.00
0.00 * * * 0.00 0.00
0.039 0.142 0.026 0.004 13.38 0.772
0.138 0.109 0.000 0.000 0.002 0.002
I I 0.000 0.000 0.0000 0.0000
0.072 0.008 0.000 0.000 0.286 0.051
0.008 0.000 0.000 0.000 0.000 0.000
0.020 0.000 0.000 0.000 0.000 0.000
0.0003 0.0274 0.000 0.000 0.000 0.000
9.19 44.71 59.00 1.960 199.2 14.45
0.324 0.027 0.220 0.150 0.303 0.712
8.14 3.46 NA NA 86.6 18.92
0.209 1.275 4.700 0.081 0.101 0.001
0.024 0.013 0.015 0.000 0.025 0.086
1.3 6.9 2.4 3.0 6.1 6.1
644.0 92.5 96.0 28.0 87.9 64.8
6.5 8.0 7.7 8.5 1.0 1.0
10.0 11.5 10.9 10.5 14.0 14.0
I - Interference
NA - Not Analyzed
* - < 0.01
-------
TABLE V-19
POLLUTANT MASS LOADINGS IN THE NICKEL IMPREGNATED
CATHODE ELEMENT WASTE STREAMS
•O
X
Flow (1/kq)
Temperature (Deg C)
44 Methylene chloride
87 Trichloroethylene
118 Cadwiuui
119 Chrcmium, Total
Chrotrium JHexavalent
121 Cyanide, Total
Cyanide, Amn. to
chlor.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil 6 Grease
Total Suspended
solids
pH, (Finimurn
pH, maximum
1817.0
) 28.6
0.00
0.00
143900.0
323.4
nt 0.0000
H5.13
32.71
18.17
1.635
933938.0
81.8
15700.0
0.000
12.72
50100.0
2113000.0
4.1
13.0
PLANT A
1630.0
16.7
0.00
0.00
41500. 0
1140.2
1621.0
30.2
0.00
0.00
17390.0
72.9
0.0000 0.0000
53.8
26.08
0.000
18.42
308396.0
44.01
15310.0
0.000
9.78
12060.0
557000.0
4.0
13.0
37.28
27.56
0.000
0,618
194682.0
89.2
14640.0
0.000
9.73
10050.0
300200,0
5.2
12.8
1363.
51.
0.
0.
27.
66.
0.
62.
62.
0.
1.
28759.
163.
11530.
359.
10.
1363.
3666000.
9.
12.
0
5
00
00
26
8
000
7
7
000
636
0
6
0
8
90
0
0 1
7
0
mg/kg
PLANT C
1954.0
38.7
0.00
0.00
76.2
269.7
I
140.7
15.63
39.08
PLANT D
1638.0
43.9
0.00
0.00
232.6
1-78.5
I
13. 10
0.000
0.000
0.586 44.88
17957.0
633.0
15190.0
408.1
46.90
2540.0
258000.0
6.5
10.0
73235.0
44.23
5670.0
2088.0
21.29
11300.0
151500.0
8.0
11.5
1934.0
16.0
0.00
0.00
50. 1
0.000
0.000
0.000
0.000
0.000
0.000
114106.0
425.5
NA
9090.0
29.01
4642.0 1
185700.0 11
7.7
10.9
3869.
16.
0.
0.
15.
0.
0.
0.
0.
0.
0.
75fl3.
580.
0 228.
0 71.
00 0.
00 0.
48 3050.
000 0.
PLANT B
3
9
00
00
0
457
000 0.0000
000 65.
000 0.
000 0.
000 0.
0 45177.
0 69.
NA 19770.
313.
0.
1610.
1000.
8.
10.
4 23.
000 5.
0 1293.
0 20080.
5 1.
5 14.
3
0000
000
000
0
2
0
06
71
0
0
0
0
197.3
69.9
0.00
0.00
152.3
0.395
0.0000
10.06
0.0000
0.000
0.000
2851.0
140.5
3733.0
0.197
16.97
1204.0
12790.0
1.0
11.0
I - Interference
NA - Net Analyzed
-------
TABLE 7-20
STATISTICAL ANALYSIS (mg/1) OF THE NICKEL IMPREGNATED
CATHODE ELEMENT WASTE STREAMS
CO
•P-
Temperature (Deg C)
44 Methylene chloride
87 Irichloroethylene
118 Cadmium
119 chromium. Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 lead
123 Mercury
124 Nickel
128 Zinc
Ammania
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
NIMOM
16.0
0.00
0.00
0.004
0.000
0.0000
0.000
0.000
0.000
0.0000
1.960
0.027
3.46
0.000
0.000
1.0
28.0
1.0
10.0
MAXIMUM
71.9
*
*
79.2
0.178
0.0000
0.386
0.046
0.02
0.0274
514.0
0.712
86.6
4.700
0.086
27.6
2690.0
9.7
14.0
1
MEAN MEDIAN VAL
38.3
*
*
12.98
0.061
0.0000
0.054
0.011
0.000
0.0042
117.3
0.198
19.08
0.663
0.019
6.8
539.0
5.6
12.2
34.5
0.00
*
0.457
0.047
0.0000
0.029
0.004
0.000
0.0004
51.85
0.135
8.55
0.091
0.008
6.1
140.6
5.9
12.4
10
3
7
10
8
8
8
5
2
6
10
10
8
7
9
10
10
10
10
*
ZEROS
0
7
3
0
2
0
2
2
8
4
0
0
0
3
1
0
0
0
0
*
PTS
10
10
10
10
10
8
10
10
10
10
10
10
10
10
10
10
10
10
10
* - < 0.01
-------
TABLE V-21
STATISTICAL ANALYSIS (mg/kg) OF THE NICKEL
IMPREGNATED CATHODE ELEMENT WASTE STREAMS
MINIMUM
MAXIMUM
MEAN
MEDIAN
00
Ui
Flow (I/kg)
Temperature (Deg C)
44 Methylene Chloride
87 irichloroethylene
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 6 Grease
Total suspended solids
pH, minimum
pH, maximum
197.3
16.0
0.00
0,00
15.48
0.000
0.000
0.000
0.000
0.000
0.0000
2851.0
44.01
3733.0
0.000
0,000
1204.0
12790.0
1.0
10.0
3869.0
71.9
0.00
0.00
143900.0-
323.4
0.000
140.7
62.7
9.08
44.88
934000.0
633.0
19770.0
9090.0
46.90
50100.0
3666000.0
9.7
14.0
1625.0
38.3
0.00
0.00
20640,0
105.2
0.000
42.84
16.47
5.73
6,78
172700.0
227.1
12780.0
1228.0
16.30
10630.0
838000.0
5.6
12.2
1634.0
34.4
0.00
0.00
192.5
69.9
0.000
41.36
7.82
0.000
0.617
59300.0
114.9
14915.0
168.2
11.81
7350.0
243000.0
5.9
12.4
-------
TABLE V-22
POLLUTANT CONCENTRATIONS IN THE FLOOR
AND EQUIPMENT WASH ELEMENT WASTE STREAMS
mg/1
Temperature (Deg C) 16.0
44 Methylene chloride NA
87 Trichloroethylene NA
118 Cadmium 29.20
119 Chromium, Total 0.081
Chromium, Hexavalent 0.000
121 Cyanide, Total NA
Cyanide, Amn. to Chlor. NA
122 Lead 0.000
123 Mercury 0.000
124 Nickel 9.08
128 Zinc 12.90
Ammonia NA
Cobalt 5.040
Phenols, fotal NA
Oil & Grease NA
Total Suspended solids NA
pH, minimum 7.9
pB, maximum 7.9
NA - Not Analyzed
-------
TABLE V-23
POLLUTANT MASS LOADINGS IN TH1 FLOOR AND
EQUIPMENT WASH ELEMENT WASTE STREAMS
mg/kg
Flow (I/kg) 0.246
Temperature fDeg C) 16.0
4*» Methylene chloride NA
87 Irichloroethylene NA
118 cadmium 7.18
119 Chromium, Total 0.020
Chromium, Hexavalent 0.000
121 Cyanide, Total NA
Cyanide, Amn. to Chlor. NA
122 Lead 0.000
123 Kercury 0.000
124 Nickel 2.232
128 Zinc 3.171
Ammonia NA
Cobalt 1.239
Phenols, Total NA
Oil 6 Grease NA
Total Suspended Solids NA
pH, minimum 7.9
pH, maximum 7.9
NA - Sot Analyzed
-------
TABLE V-2H
POLLUTANT' CONCENTRATIONS IN EMPLOYEE WASH
ELEMENT WASTE STREAMS
mg/1
oo
00
Temperature (Deg C)
4t Methylene chloride
87 Trichloroethylene
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
12« Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended solids
pH, minimum
pH, maximum
31.0
0.00
0.00
0.002
0.000
0.000
0.000
0.000
0.00
0.000
0.000
0.190
0.00
0.000
0.007
1.0
0.0
7.3
7.3
32.0
0.00
0.00
0.130
0.000
0.000
0.030
0.025
0.00
0.000
0. 130
0.200
0.00
0.000
0.010
212.0
280.0
6.8
6.8
32.0
0.00
0.00
0.076
0.000
0.000
0.036
0.036
0.00
0.000
0.260
0.050
0.00
0.000
0.000
288.0
312.0
7.9
7.9
-------
TABLE V-25
POLLUTANT MASS LOADINGS IN EMPLOYEE WASH
ELEMENT WASTE STREAMS
mg/kg
00
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 S Grease
Total suspended solids
pH, minimum
pH, maximum
1.475
31.0
0.00
0.00
0.003
0-000
0.000
0.000
0.000
0.000
0.0000
0.000
0.280
0.000
0.000
0.010
1.H75
0.000
7.3
7.3
1.475
32.0
0.00
0.00
0.192
0.000
0.000
0.044
0.037
0.000
0.0000
0.192
0.354
0.000
0.000
0,015
312.6
412.9
6.8
6.8
1.475
32.0
0.00
0.00
0.112
0.000
0.000
0.053
0.053
0.000
0.0000
0.383
0.074
0.000
0.000
0.000
424.7
460.1
7.9
7.9
-------
TABLE V-26
MEAN CONCENTRATIONS AND POLLUTANT MASS LOADINGS
IN THE CADMIUM POWDER ELEMENT WASTE STREAMS
Mean
(mg/1)
Mean
(mg/kg)
Flow (I/kg)
Temperature (Deg C)
44 Methylene chloride
87 Irichloroethylene
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
121 Cyanide, Total
Cyanide, Amn. to Chior.
122 Lead
123 Mercury
124 Nickel
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended solids
pH, minimum
pH, maximum
21.9
0.00
0.00
177.3
0.004
0.000
0.026
0.000
0.000
0.0077
0.062
4274.0
5.16
0.000
0.022
4.4
17.5
1.3
3.3
65.7
21.9
0.00
0.00
11650.0
0.263
0.000
1.708
0.000
0.000
0.506
4.073
280800.0
339
0.000
1.445
298.1
1150.0
1.3
3.3
-------
TAILS V-27
CADMIUM SOBCATIGORY EFFLUENT FLOW RATES
FROM INDIVIDUAL PLANTS
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
-------
TABLE V-28
STATISTICAL ANALYSIS (mg/lj OF THE CADMIUM SDBCATEGORY TOTAL
RAH HASTE CONCENTRATIONS
vo
NS
Temperature (Deg C)
44 Methylene chloride
87 Trichloroethylene
118 eadiriu»
119 Chromium, Total
Chromium, Hexavalent
121 cyanide. Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
126 Silver*
128 Zinc
Ammonia
Cobalt
Phenols, Total
Oil & Grease
Total Suspended Solids
PH Minimum
pH Maximum
MINIMUM
MAXIMUM
MEAN
MEDIAN
t
VAL
ff
ZEROS
14,0
0.00
0.00
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.570
0.000
0.000
1.94
0.000
0.000
0.8
13.0
1.0
2,5
66.8
0.027
*
186.5
0.756
0.000
0.364
0.354
0.400
0.0250
281.2
13.90
2489.0
80.8
1.572
0.080
20.2
2290.0
7.1
14.0
29.6
*
*
37.06
0.198
0.000
0.079
0.040
0,161-
0.003
61.8
8.467
270.4
15.17
0.390
0.018
7.2
325.1
3.4
11.6
25.4
*
*
17.27
0.086
0.000
0.023
0.000
0.123
0.0004
19.20
9.89
0.150
6.69
0.047
0.0049
5.7
72.0
2.6
12.9
12
6
9
11
12
0
9
8
3
8
12
3
11
9
7
10
11
12
12
12
0
6
3
1
0
12
2
3
1
4
0
1
1
0
5
1
0
0
0
0
I
PIS
12
12
12
12
12
12
11
11
4
12
12
4
12
9
12
11
11
12
12
12
+ - Not a cadmium subcategory verification parameter, analyzed only where silver cathodes produced
* - < 0,01
-------
TABLE V-29
TREATMENT IN-PLACE AT CADMIUM SUBCATEGORY. PLANTS
JMN3LID TREATMENT IN-PLACE DISCHARGE I/
A Settling lagoon; material recovery D
B Lagooning, sand filter, pH adjust D (Zero)
(Replaced by additional treatment
and 10Oil recycle)
C pH adjust, coagulant addition, I
clarifier, filtration
D Settling, pH adjust, in-process Cd, I
Ni recovery
E Lagooning - offsite Zero 2/
F None Zero
G none Zero 2/
H pH adjust, clarification, D 2/
ion exchange ~
I ph adjust I
J 1) pH adjust, coagulant addition, clari-
fication, sand filtration D
2} Ion exchange
K Settling I
L pH adjust, settling, filtration D
M None Zero
J/ I = Indirect
D = Direct
J/ No longer active in the cadmium subcategory.
-------
TABLE V-30
PERFORMANCE OF ALKALINE PRECIPITATION, SETTLING
AND FILTRATION - CADMIUM SUBCATESORY.
TREATMENT SYSTEM I
Pollutant or
Pollutant Property
118 Cadmium
124 Nickel
128 Zinc
cobalt
Oil and Grease
TSS
Concentrations (mg/1)
Day
Raw
0.026
59.0
0.220
4.700
2.4
96.0
7.7-10.9
1
Treated
0.490
1.760
0.0160
0.020
1.2
0.00
8.9
Day
Raw
0.004
1.960
0.150
0.081
3.0
28.0
8.5-10.5
2
Treated
0. 140
0.800
0.000
0.024
0.0
0.0
8.5-10.5
TREATMENT SYSTEM II
Concentration (mg/1)
Day 1 Day 2 Day 3
Raw Treated Raw Treated Raw Treated
118 Cadmium
124 Nickel
126 Silver
128 Zinc
cobalt
Oil & Grease
TSS
pH
0.000
0.610
12.00
0.180
0.000
NA
27.0
2.0-2.6
0.030
• 0.620
0.220
1.400
2.200
NA
51.0
6.7-11.4
0.007
1.500
24.10
0.440
2.700
NA
23.0
2.2-2.5
0.008
0.550
0.240
3.100
2.700
NA
216.0
9.2
0.000
0.570
13.90
0.380
0.000
NA
13.0
2.1-2.5
0.010
0.500
0.270
2.800
3.000
NA
18.0
9.9
NA - Not Analyzed
-------
TABLE V-31
PERFORMANCE OF SETTLING - CADMIUM SUBCATEGORY
Pollutant
or Pollutant Property
Concentration (mg/1)
Ul
118 Cadmium
124 Nickel
128 Zinc
Cobalt
Oil and Grease
TSS
PH
Day 1
0.100
0.820
2.000
0.000
1.0
11.0
11-12
Day 2
0.061
0.800
0.150
0.000
2.0
8.0
11.1-12.3
0.250
1.000
1.970
0.012
3.0
10.0
11.1-12.5
-------
TABLE V-32
CADMIUM SUBCATESORY EFFLUENT QUALITY
(FROM DCP)
TOTAL DISCHARGE
FLOW
vfl
SLANT
ID NO.
A
E
C
D
E
*
G+
C++
HH
1/hr
114
114000*
27250
23160*
23
7880
4630
7040
49500
pH oilSGrease
(gal/hr) (mg/1)
(30)
(30000)
(7200) 7-14
(8760) 12.4 3
(6.1)
(2081) 7.5
(1220)
(1860)
TSS Cd
(mg/1) (mg/1)
1.1
0.01
8. 1
150 41.0
0.1
0.04
0.26
3.73
Co Ni
(mg/1) (mg/1)
6.7
0.034
18.5
46.0
<0.08
0.09
0.08 0.54
0.34
3.06
Ag Zn
(mg/1) (mg/1)
<0.02
75
* - Combined discharge includes wastewater from other subcategories and categories.
+ - Effluent from pH adjustment and clarification
++ - Effluent from ion exchange
-------
TABLE V-33
NORMALIZED DISCHARGE FLOWS
CALCIUM SUBCATEGORr ELEMENTS
Elements
Heat Paper
Production
Cell Testinq
Mean
Discharge
(1/kq)
115.4
0.014
Median
Discharge
(I/kg)
24.1
0.014
Total
Raw Waste
Volume (1/yr)
1.3 x 105
200
Production
Normalizing
Parameter
Weights of Reactants
Weights of Cells Produced
to
-------
TABLE V-34
POLLUTANT CONCENTRATIONS IN THE
HEAT PAPER PRODUCTION ELEMENT WASTE STREAM
mg/1
00
Temperature (°C)
14 1»1»2-trichloroethane
23 Chloroform
44 Methylene Chloride
66 Eis (2-ethylhexy) Phthalate
116 Asbestos*
118 Cadmium
119 Chromium
120 Copper
122 Lead
124 Nickel
126 Silver
128 Zinc
Cobalt
Iron
Manganese
Oil 6 Grease
Total Suspended Solids
pH» Minimum
pH» Maximum
Plant B
20
0.00
*
0.00
0.00
0.0
0.000
120.0
0.150
0.000
0.000
0.000
0.110
0.000
0.520
0.021
0.0
715.0
2.9
4.7
Plant A
17
0.013
0.038
0.14
0.024
630.0
0.002
2.064
0.118
0.044
0.067
0.012
0.045
0.006
0.122
0.008
0.0
21.0
6.2
6.2
+ Chrysotile fibers - millions of fibers/liter
* <0.01
-------
TABLE V-35
POLLUTANT MASS LOADINGS IN THE
HEAT PAPER PRODUCTION ELEMENT WASTE STREAM
Plant B
mg/kg
Plant A
Flow (I/kg)
Temperature (°CJ
14 1,1,2-trichloroethane
23 Chloroform
Hit Methylene Chloride
66 Bis (2-ethylhexy) Phthalate
116 Asbestos*
118 Cadmium
119 Chromium
120 Copper
122 Lead
124 Nickel
126 Silver
128 Zinc
Cobalt
Iron
Manganese
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
99.9
20
0.00
0.00
0.00
0.00
0.0
0.000
12000.0
15.0
0.000
0.000
0.000
11.0
0.000
51.9
2.10
0.0
71400.0
2.9
4.7
14.0
17
0.182
0.532
0.196
0.336
8820.0
0.028
28.90
1.652
0.616
0.938
0.168
0.630
0.084
1.708
0.112
0.0
294.0
6.2
6.2
Chrysotile fibers - millions of fibers/kg
-------
TABLE V-36
TREATMENT IN-PLACE AT CALCIUM SUBCATEGORY PLANTS
EL ANT,. ID TREATMENT IN-PLACE DISCHARGE I/
A pH adjust, settling I
B None Zero
C None I
w V I = Indirect
o —
o
-------
TABLE V-37
EFFLUENT CHARACTERISTICS FROM CALCIUM SUBCATEGORY
MANUFACTURING OPERATIONS -DCP DATA
PLANT A
Flow Rate Cd Ba Cr
1/hr mg/1 mg/1 tng/1
1385.+ 0.01 20.0 0.20
+ - Intermittent flow, average is <15 1/hr on a monthly basis
u>
o
-------
TABLE V-38
LECLANCHE SOBCATEGORy ELEMENTS
(Reported Manufacture)
Anodes
Zinc
Zinc sheet Metal Powder
Cathodes
(and cooked Uncooked- Paper Separator Plastic
Electrolyte Paste Paste Prepared On or Separator
Form] Separator Separator off-Site
KnOj, Cathode X
(and
Electrolyte
with Mercury)
KnO, CathodesXX X :rr=
(and
Electrolyte
without. Mercury)
KnO, Cathode X X
(and Gelled
Electrolyte
viith_Mercuryrj
Carbon X
Cathode
Silver X
Cathode
fasted X
MnOg_Cathode
Ancillary Operations
Equipment X
Area Cleanup
-------
LO
o
OJ
TABLE V-39
NORMALIZED DISCHARGE FLOWS
LECLANCHE SUBCATEGOR* ELEMENTS
Mean Median
Discharge Discharge
Elements (1/kg) (I/kg)
ancillary operations
Separator 0.0» 0.04
Cocked Paste
Separator nil nil
Uncooked Paste
Separator 0.1 4 . 0.14
Total
Raw Waste
Volume (1/yr)
(10«l
3.2
nil
0.015
Production
Normalizing
Parameter
Weight of Cells Produced
Weight of Cells Produced
Weight of Dry Paste
Pasted Paper with
Mercury
Iquipwent and Area
Cleanup
0.38
9.65
Materials
Weight of Cells Produced
U-
-------
TABLE V-40
POLLUTANT CONCENTRATIONS IN THE COOKED PASTE
SEPARATOR ELEMENT WASTE STREAMS
mg/1
OJ
o
p*
Temperature (Deg C)
70 Diethyl phtbalate
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended solids
PH» Minimum
pH» Maximum
59.9
*
0.000
0.000
0.000
0.042
0.000
0.030
0.000
0.0060
0.000
0.000
0.110
0.130
0.011
13.0
119.0
5.1
6.8
59.9
*
0.000
0.000
0.016
0.001
0.000
0.083
0.000
0.1600
0.051
0.000
94.0
5.48
0.009
39.0
41.0
5.1
6.8
59.9
*
0.000
0.000
0.021
0.004
0.000
0.130
0.000
0.1500
0.097
0.000
148.0
14.20
0.009
11.0
62.0
5.9
6.3
* - < 0.01
-------
TABLE V-41
POLLUTANT MASS LOADINGS IN THE COOKED PASTE SEPARATOR
ELEMENT WASTE STREAMS
mg/kg
u>
o
Ul
Total
Bexavalent
Flow (I/kg)
Temperature (Deg C)
70 Diethyl phthalate
111 Antimony
115 Arsenic
118 Cadmium
119 Chromium,
Chromium,
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
0.0*7
59.9
0.00
0.000
0.000
0.001
0.000
0.000
0.004
0.000
0.0003
0.002
0.000
4.011
0.140
0.001
0.613
5.615
5.1 .
6.8
0.045
59.9
0.00 '
0.000
0.000
0,001
0.000
0.000
0.004
0.000
0.0072
0.002
0.000
4.228
0.246
0.000
1.754
1.844
5.1
6.8
0.025
59.9
0.00
0.000
0.000
0.001
0.000
0.000
0.003
0.000
0.0038
0.002
0.000
3.750
0.360
0.000
0.279
1.571
5.9
6.3
-------
TABLE V-42
POLLUTANT CONCENTRATIONS IN THE PAPER
SEPARATOR (WITH MERCURY) ELEMENT WASTE STREAMS
mg/1
u>
o
Temperature (Deg C)
70 Diethyl pbthalate
114 Antiirony
115 Arsenic
118 Cadmium
119 Chroirium, Total
chr one ium, Hexavalent
120 Copper
122 lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
31.0
*
0.000
0.000
0.470
0.000
0.000
0.110
0.070
0.4000
0.140
0.000
1.160
1.150
0.011
16.0
140.0
8.3
.8.3
31.1
*
0.000
0.000
0.015
0.000
0.000
0.081
0.000
0.1600
0.020
0.000
0.410
1.250
0.090
7.0
7.0
7.5
8.5
30.0
*
0.000
0.000
0.024
0.000
0.000
0.085
0,000
0. 1400
0.027
0.000
0.230
0.430
0.046
83.0
96.0
8.5
8.6
* - < 0.01
-------
TABLE V-43
POLLOTANT MASS LOADINGS IN THE PAPER
SEPARATOR (WITH MERCURY) ELEMENT »ASTE STREAMS
mg/kg
CO
o
Flow (I/kg)
Temperature (Deg C)
70 Diethyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
12*» Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
0.109
31.0
0.00
0.000
0.000
0.051
0.000
0.000
0.012
0.008
0.0436
0.015
0.000
0.126
0.125
0.001
1.740
15.23
8.3
8.3
0.174
31.1
0.00
0.000
0.000
0.003
0.000
0.000
0.014
0.000
0.0278
0.003
0.000
0.071
0.218
0.016
1.218
1.218
7.5
8.5 l
0.152
30.0
0.00
0.000
0.000
0.004
0.000
0.000
0.013
0.000
0.0228
0.004
0.000
0.035
0.065
0.007
12.64
14.62
8.5
8.6
-------
TABLE V-44
NORMALIZED FLOW OF ANCILLARY OPERATION WASTE STREAMS
SAMPLING
PLANT DATA MEAN SURVEY
KO. VALUE, 1/lcq DATA, I/kg
1 - 0.05
2 0
3 0
4 0
5(B) 0.01 0.04
6 0
7 0
8 0
o 10 - 0
00 11 - 0
12(C) 0.01
13 (D) - 6.37
14 0
15 0
16 (E) - 0.44
17 - 0.44
18 - 0
19 0
-------
TABLE V-45
POLLUTANT CONCENTRATIONS IN THE EQUIPMENT AND AREA CLEANDP
ELEMENT WASTE STREAMS
mg/1
PLANT B
PLANT C
PLANT E»/
PLANT B»/
PLANT D
Temperature (Deg CJ
70 Diethyl phthalate
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Hanqanese
Phenols, Total
Oil & Grease
Total Suspended solids
pH, Minimum
pH, Maximum
59.9
*
0.000
0.070
0.036
0.250
0.000
0.220
0.070
I
0.780
0.070
220.0
140.0
0.059
33.0
2610.0
7.5
10.4
43.3
*
0.000
0.090
0.020
0.130
0.000
0.160
0.000
I
0.220
0.090
325.0
3.82
I
482.0
4220.0
7.5
10.4
60.0
*
0.000
0.640
0.088
2.880
0.000
3.220
0.940
I
10.10
0.600
680.0
383.0
I
36.0
14230.0
8,5
9.7
31.0
*
0.000
0.000
0.054
0.014
0.000
0.094
0.000
0.0170
0.5670
0.000
98.0
33.89
0.056
9.80
357.2
6.2
8.6
30.5
*
0.000
0.000
0.043
0.022
0.000
0.770
0.000
0.0300
0.334
0.000
42.44
21.82
0.253
438.5
395.0
6.1
9.0
30.1
*
0.000
0.000
0.189
0.283
0.000
0.108
0.000
0.0310
0.369
0.000
33.83
13.30
0.044
96.1
471.1
6.1
8.7
117.0
1640.0
0.033
410.0
0.03
1.42
0.0070
24.6
I - interference
* - < 0.01
i/- Dcp data
-------
TABLE V-46
POLLUTANT MASS LOADINGS IN THE EQUIPMENT AND AREA CLEANUP
ELEMENT WASTE STREAMS
rag/Jcg
o
Flow (1/kq)
Temperature (Deg C)
70 Diethyl 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 8 Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
0.008
59.9
0.00
0.000
0.001
0.000
0.002
0.000
0.002
0.001
I
0.007
0.001
1.840
1.171
0.000
0.276
21.83
7.5
10. 1
PLANT B
0.011
43.3
0.00
0.000
0.001
0.000
0.001
0.000
0.002
0.000
I
0.002
0.001
3.553
0.042
I
5.270
46.14
7.5
10.4
0.011
60.0
0.00
0.000
0.007
0.001
0.032
0.000
0.036
0.011
I
0.114
0.007
7.66
4.316
I
0.406
160.4
8.5
9.7
0.010
31.0
0.00
0.000
0.000
0.001
0.000
0.000
0.001
0.000
0.0000
0.006
0.000
0.981
0.339
0.001
0.098
3.576
6.2
8.6
PLANT C
0.010
30.5
0.00
0.000
0.000
0.000
0.000
0.000
0.001
0.000
0.0000
0.003
0.000
0.431
0.222
0.003
4.458
4.016
6.1
9.0
PLANT EM
0.010 0.44
30.1
0.00
0.000
0.000
0.002
0.003
0.000
0.001
0.000
0.0000 51.5
0.004
0.000
0.339 722.0
0.133
0.000
0.962
4.718
6.1
8.7
PLANT
0.04
0.001
16.4
PLANT D
6.3
0.1.
9.0
0.0
157.0
I - Interference
J/- Dcp data
-------
TABLE V-47
STATISTICAL ANALYSIS (mg/1) OP THE EQUIPMENT AND AREA CLEANUP
ELEMENT HASTE STREAMS
Temperature (Deg C)
70 Dietljyl phthalate
11« Antimony
115 Arsenic
118 Cadmium
119 Chrcntium, Total
Chromium, Hexavalent
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manqanese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
MINIMUM
30.1
*
0.000
0.000
0.020
0.014
0.000
0.094
0.000
0.0170
0.007
0.000
33.83
3.820
0.044
9.80
357.2
6.1
8.6
MAXIMUM
60.0
*
0.000
0.640
0.189
2.880
0.000
3.220
0.940
117.0
10.10
0.600
1640.0
383.0
0.253
482.0
14230.0
8.5
10.4
MEAN
45.1
*
0.000
0.133
0.072
0.597
0.000
0.650
0.1490
19.76
1.768
0.127
431.0
99.3
0.103
160.0
3714.0
7.0
9.5
MEDIAN
37.1
*
0.000
0.035
0.049
0.190
0.000
0.134
0.000
0.0320
0.369
0.035
272.5
27.86
0.058
36.00
1541.0
6.9
9.4
f
VAL
6
6
0
3
6
6
0
6
3
6
7
3
8
6
4
7
6
6
6
ZEROS
0
0
6
3
0
0
6
0
4
0
0
3
0
0
0
0
0
0
0
PfS
6
6
6
6
6
6
6
6
7
6
7
6
8
6
4
7
6
6
6
* - SO.01
-------
TABLE V-48
STATISTICAL ANALYSIS (mg/kg) OP THE EQUIPMENT AND AREA CLEANUP
ELEMENT WASTE STREAMS
MINIMUM
MAXIMUM
MEAN
MEDIAN
How (I/kg)
Temperature (Deg C)
70 Diethyl phthalate
111 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
122 lead
123 Mercury
121 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
oil & Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
0.008
30.1
0.00
0.000
0.000
0.000
0.000
O.OQO
0.001
0.000
0.000
0.002
0.000
0.339
0.0tt2
0.000
0.098
3.576
6.1
8.6
0.011
60.0
0.00
0.000
0.007
0.002
0.032
0.000
0.036
0.190
51.5
0.114
0.007
722.0
4.316
0.003
157.0
160. 4
8.5
10.4
0.010
45.1
0.00
0.000
0.001
0.001
0.007
0.000
0.007
0,029
10.09
0.026
0.001
94.2
1.037
0.001
24.07
40.11
7.0
9.5
0.010
37.1
0.00
0.000
0.000
0.000
0.002
0.000
0.001
0.000
0.0005
0.006
0.000
2.697
0.281
0.001
0.962
13.27
6.9
9.4
-------
TABLE V-49
STATISTICAL ANALYSIS (mg/1) OF THE LECLANCHE SOBCATESORX TOTAL
RAW WASTE CONCENTRATIONS
00
Flow (I/day)
Temperature (Deg C)
70 Diethyl phthalate
111 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 copper
122 Lead
123 Mercury
121 Nickel
125 Selenium
128 Zinc
Manganese
Phenols, Total
oil fi Grease
Total Suspended Solids
PH, Minimum
pH, Maximum
MINIMUM
636.0
30.1
*
0.000
0.000
0.016
0.013
0.000
0.095
0.000
0.0111
0.086
0.000
30.57
5.155
0.006
10.2
341.7
5.1
8.6
MAXIMUM
5880.0
59.9
*
0.000
0.197
0.173
0.889
0.000
1.081
0.289
0.1287
3.177
0.185
311.8
127.7
0.236
391.8
1420.0
6.2
10.4
MEAN
2640.0
55.3
*
0.000
0.038
0.062
0.207
0.000
0.263
0.051
0.0788
0.764
0.035
119.3
36.62
0.061
109.5
1150.0
5.7
9.5
MEDIAN
1920.0
43.8
*
0.000
0.005
0.041
0.033
0.000
0.099
0.003
0.0742
0.318
0.005
98.2
21.60
0.031
56.8
464.3
6.0
9.4
t
VAL
6
6
6
0
3
6
6
0
6
3
6
6
3
6
6
6
6
6
6
6
I
ZEROS
0
0
0
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
* - SO.01
-------
TABIiE V-50
TREATMENT IN-PLACE AT
LECLANCHE SUBCATEGORY PLANTS
S3S2-IB TRgATMEMJig-gl^gg DISCHARGE I/
A None 1
B None Zero
C None I
D None Zero
E Grease trap, sand filter, activated I
carbon; retention and reuse of paste
area clean-up water in paste pre-
paration
F None Zero
G Retention and reuse of paste appli- Zero
cation washwater, contract removal of
other wastes
H None Zero
I None Zero
J None Zero
K None Zero
L None I
M pH adjust, coagulant addition, vacuum I
filtration
N Settling, skimming I 2/
O None Zero
P None Zero
Q Chemical reduction, pH adjust, coagu- I
lant addition, pressure filter
R chemical reduction, pH adjust, coagu- I
lant addition, pressure filter
S None Zero
T None Zero
J/ I = Indirect
D = Direct
2/ Production discontinued
-------
TABLE V-51
LICLANCHE SUBCATEGORY EFFLUENT QUALITY
(FROM DCP)
PLANT_J[ PLANT E
flow, l/J?q 6.37 6.37
flow, 1/hr 2168 83
Cil S Grease 24.6
lead 0.03
u>
u^ Kercury 1.42 3.15
Kickel 0.007
Zinc - 658.0
-------
TABLE V-52
TREATMENT EFFECTIVENESS AT PLAHT B
(TREATMENT CONSISTS OF SKIMMING AND FILTRATION)
118 Cadmium
119 chromium
120 copper
122 Lead
123 Mercury
124 Nickel
128 Zinc
Manqanese
Oil 6 Grease
TSS
PH
Day 1
Raw
Haste
0.012
0.000
0.078
0.000
0.130
0.034
85.00
2.97
Treated
Effluent
0.018
0.000
0.002
0.000
0.011
0.038
118.0
11.30
13.0
119.0
5.1-6.8
4.2
10.0
6.2-7.0
mg/1
Haw
Haste
0.016
0.004
0.083
0.000
0.160
0.054
94.0
5.48
39.0
41.0
5.1-6.8
Day 2
Treated
Effluent
0.005
0.000
0.000
0.000
0.007
0.054
103.0
8.53
4.8
4.0
6.2-7.0
Day 3
Raw
Haste
0.021
0.004
0.130
0.000
0.150
0.097
148.0
14.20
11.0
62.0
5.9-6.3
Treated
Effluent
0.004
0.000
0.007
0.000
0.100
0.076
115.0
8.51
3.5
1.0
5.6-5.9
-------
TABLE V-53
NORMALIZED DISCHARGE FLOWS
LITHI0M S0BCATEGORY ELEMENTS
Elements
Cathodes
lead Iodide
Iron Disulfide
Knc illary. ceerations
Beat Paper
Production*
lithium Scrap
Dispcsal
Cell Testing
Cell Hash
Air Scrubbers
floor and Equipment Hash
Mean
Discharge
(I/kg)
63.08
7.54
115.4
nil
0.011
0.929
10. 5S
0.091
Median
Discharge
(I/kg)
63.08
7.54
24.1
nil
0.014
0.929
10.59
0.09«
total
Raw Waste
Volume (1/yr)
(10«)
0.020
0.17
0.038
nil
0.0002
0.013
0.11
0.0013
Production
Normalizing
Parameter
Height of Lead
Weight of Iron Disulfide
Weight of Reactants
Weight of Cells Produced
Weight of Cells Produced
Weight of Cells Produced
Height of Cells Produced
Weight of cells Produced
Same as for calcium subcategory
-------
TABLE V-54
POLLOTANT CONCENTRATIONS IN
THE IRON DISULFIDE CATHODE
ELEMENT WASTE STREAM
mg/1
Temperature (°C) 18.0
14 1,1,2-trichloroethane 0.00
23 Chloroform 0.012
44 Methylene Chloride 0.91
66 Bis (2-ethylhexyl) phthalate 0.013
116 Asbestos 2.44
118 Cadmium 0.025
119 Chromium 0.015
120 Copper 0.109
w 122 Lead 4.94
oo 124 Nickel 0.235
126 Silver 0.001
128 Zinc 0.473
Cofcalt 0.176
Iron 54.9
Lithium 0.00
Manganese 1.60
Oil & Grease <5.0
Total Suspended Solids 39.0
pH, Minimum 5.6
pH, Maximum 5.8
-------
TABLE V-55
POLLUTANT MASS LOADINGS IN
THE IRON DISULFIDE CATHODE
ELEMENT WASTE STREAM
fc
mg/kg
Flow (I/kg) 7.51
Temperature (°C) 18.0
14 1,1,2-trichloroethane 0.00
23 Chloroform 0.090
44 Methylene Chloride 0.121
66 Bis (2-ethylhexyl) phthalate 0.098
116 Asbestos 18.1+
118 Cadmium 0.189
119 Chromium 0.113
120 Copper 0.822
122 Lead 37.2
124 Nickel 1.77
126 Silver 0.007
128 Zinc 3.57
Cobalt 1.23
Iron 411.0
Lithium 0.00
Manganese 12.1
Oil & Grease 0.0
Total Suspended Solids 294.0
pfi. Minimum 5.6
pB, Maximum 5.8
+ Chrysotile fibers - millions of fibers/kg
-------
TABLE V-56
POLLUTANT CONCENTRATIONS IN THE
LITHIUM SCRAP DISPOSAL WASTE STREAM
mg/1
14 1,1,2-trichloroethane *
23 Chloroform . *
HH Methylene Chloride 0.00
66 Bis(2-ethylhexyl)phthalate 0.00
116 Asbestos NA
118 Cadmium 0.000
119 Chrcndum 0.013
120 Copper 0.025
122 Lead 0.000
ro 124 Nickel 0.22
0 126 Silver 0.000
128 Zinc 0.12
Cobalt 0.000
Iron 52.00
lithium 0.59
Manqanese 0.032
Oil & Grease 1.0
Total Suspended Solids 69.0
pH, Minimum 5.7
pH» Maximum 5.7
* - <0.01
NA - Not analyzed
-------
TABLE V-57
TREATMENT IN-PLACE AT LITHIUM STOCATEGORY PLANTS
jLfl|jT_ID TREATMENT IN-PLACE DISCHARGE I/
A None I
B None Zero
C pH adjust, settling I
D Filtration I
E pH adjust I
NS F Settling; contract haul Zero
~* pH adjust D
G None Zero
V I = Indirect
D = Direct
-------
TABLE V-58
EFFLUENT CHARACTERISTICS OF IRON DISOLFIDE
CATHODE ELEMENT WASTE STREAM
AFTER SETTLING TREATMENT
mg/1
14 1,1,2-trichloroethane NA
23 Chloroform NA
44 Methylene chloride NA
66 Bis (2-ethylhexyl) phthalate NA
116 Asbestos NA
118 Cadmium 0.000
119 Chromium 0.021
120 Copper 0.092
w 122 L€ad 0.920
{S 124 Nickel 0.058
126 Silver 0.000
128 Zinc 0.250
Cobalt 0.000
Iron 43.5
lithium 0.00
Manganese 0.980
Cil & Grease NA
lotal Suspended solids NA
NA - Not Analyzed
-------
TABLE V-59
NORMALIZED DISCHARGE FLOWS
MAGNESIUM SOECATEGORY. ELEMENTS
CO
K>
CO
Elements
Cathodes
Mean
Discharge
(I/kg)
Silver Chloride 4915.0
Cathode-Cheirically
Reduced
Silver Chloride
Cathode-Electro-
lytic
Ancillary
Operations
Air Scrubbers
Cell lestinq
Separator
Processing
Floor and Equipment
Wash
Beat Paper
Production*/
145.0
206.5
52.6
*-'
0.094
115.4
Median
Discharge
(I/kg)
4915.0
145.0
206.5
52.6
i/
0.094
24.1
Total Production
Raw Waste Normalizing
Volume (1/yr) Parameter
0.65 Weight of Silver Processed
0.11 Weight of Silver Processed
0.45 Weight of Cells
0.091 Weight of Cells
0 Weight of Cells
0.013 Weight of Cells
Produced
Produced
Produced
Produced
0.26 Weight of Reactants
J/ Cannot be calculated from present information.
jj/ Same as for calcium subcategory.
-------
TABLE v-60
POLLUTANT CONCENTRATIONS IN THE DEVELOPER SOLUTION OF THE SILVER
CHLORIDE REDUCED CATHODE ELEMENT WASTE STREAM
23. chloroform 0.091
66. bis(2-ethylhexyl)phthalate *
86. toluene 0.0190
114. antimony <0.015
115. arsenic <0.015
117. beryllium <0.001
118. cadmium <0.005
119. chromium <0.010
120. copper 0.022
121. cyanide <0.010
122. lead 0.170
123. mercury <0.0003
124. nickel <0.050
125. selenium <0.015
126. silver 0.340
127. thallium <0.015
ro 128. zinc 0.049
•^ aluminum 0.200
ammonia 60.0
barium 0.008
boron 0.038
BOD 1200.0
calcium 4.160
chlorides 1100.0
cobalt <0.005
COD 4100.0
iron 0.064
magnesium 2.640
manganese <0.010
molybdenum <0.010
oil and grease <0.500
phenols (total) 0.040
sodium 7000.0
tin » <0.010
titanium <0.050
TOG 1200.0
TSS 21.0
vanad ium <0.00 5
yttrium '" ~""~
-------
to
01
TABLE V-61
MAGNESIUM SUBCATEGORY PROCESS
WASTEWATER FLOW RATES FROM
INDIVIDUAL FACILITIES
Plant ID Flow Rate
d/day)
A 4. 1 8 x 1 0
B 0
C 872
D 0
E 2990
F +
G 0
H 0
+ Not Available
-------
to
TABLE V-62
TREATMENT IN-PLACE AT MAGNESIUM SUBCATEGORY PLANTS
iLANT^IP
A
B
C
D
I
F
G
H
TREATMENT IN-PLACE
None
pH adjust, settling, filtration
None
pH adjust, filtration
pB adjust, settling, clarification,
filtration
Filtration
None
None
DISCHARGE
Zero
D 2/
Zero
I
I 3/
I 3/
Zero
Zero
J/ I = Indirect
D = Direct
2/ Not presently active in this subcategory.
J/ Wastewater combined from more than one subcategory
-------
TABLE V-63
ZINC S0BCW1GORX PROCESS ELEMENTS
(REPORTED MASUFACTORE)
Zinc Anodes
Zinc Powder
Cathodes
Cast or
Fabricated
Porous Carbon (A
-------
TABLE V-63
ZINC SOBCATEGORY PROCESS ELEMENTS
(Reported Manufacture)
Zinc Anodes
Zinc Powder Pasted or zinc Oxide Powder
Cast or Wet Gelled Dry Pressed on Pasted or Electro-
Cathodes Fabricated Amalgamated Amalgam Amalgamated Grid Pressed-Reduced deposited
Silver Peroxide Powder XX X
Nickel-sintered, Impregnated
and Formed X
Operations
cell wash
w Electrolyte Preparation
OD silver itch
Mandatory Employee-fcash
Be.iect Cell Handling*
floor Wash
Equipment Wash
Silver Pcwder Production
Silver Percixd£ Production
-------
TABLE V-6«
NORMALIZED DISCHARGE FLOWS
ZINC SUBCATEGORY ELEMENTS
CO
VO
Elements
Mean
Discharge
(I/kg)
Median
Discharge
(I/kg)
Total Production
Raw Waste Normalizing
Volume (1/yr) Parameter
(10*)
Anodes
Zinc Powder-Wet 3.8
Amalgamated
Zinc Powder-Gelled 0.68
Amalgam
Zinc Oxide Powder- 1U3.0
Pasted or Pressed
Reduced
Zinc Electrodeposited 3190.0
2.2
0.68
117.0
3190.0
Cathodes
Silver Powder Pressed 196.0
and Electrclytica11y
Oxidized
Silver Oxide (Ag20) 131.0
Powder-Therma11y
Reduced or Sintered,
Electrolytica11y
Formed
Silver Peroxide 31.1
Powder
Kickel Impregnated 1640.0
and Formed
196.0
131.0
12.8
1720.0
5.60
0.«75
4.86
15.60
Weight of Zinc
Weight of Zinc
Weight of Zinc
Weight of Zinc Deposited
7.90
0.066
0.230
nil
Weight of silver Applied
Weight of Silver Applied-
Weight of Silver Applied
Weight of Nickel Applied
-------
TABLE V-6<4
NORMALIZED DISCHARGE FLOWS
ZINC S0BCATEGORY ELEMENTS
Mean
Discharge
Elements (I/kg)
flnci_11arymQ|:eration3
Cell Kasn 1.13
Electrolyte 0.12
Preparation
Silver Etch H9.1
Mandatory Employee 0.27
Hash
Be-ject Cell Handling 0.01
floor and Equipment Hash 7.23
Silver Peroxide 52.5
Production
Silver Powder 21.2
Production
Median
Discharge
(I/kg)
0.335
0
t»9.1
0.27
0.002
7.23
52.2
21.2
Total Production
Raw Waste Normalizing
Volume (1/yr) Parameter
19.11
1.26
0.003
2.61
0,022
1.42
0.365
0.800
Weight of Cells Produced
Weight of Cells Produced
Weight of Silver Processed
Weight of Cells Produced
Weight of Cells Produced
Weight of Cells Produced
Height of silver in Silver
Peroxide Produced
Weight of Silver Powder
Produced
-------
TABLE V-65
OBSERVED FIOW RATES FOR
EACH PLANT IN THE ZINC SUBCATEGORy
OJ
Observed Flow
Rate (I/day)
Plant ID
A
B
C
D
E
F
G
H
I
J
K
L
H
N
0
P
* - Data Not Available
DCP Data
+
25432.2
3494.2
+
16118.2
4008.0
77516.8
144000.0
0
16.0
27500.0
10900.8
0
22619.2
4542.4
21206.4
Mean Visit
Data
3772.5
101892.2
27271.2
23305.5
54186.1
11506.4
9687.1
13471.6
-------
TABLE V-66
POLLUTANT CONCENTRATIONS IN THE ZINC POHDER-HET
AMALGAMATED ANODE ELEMENT HASTE STREAMS
Temperature (Deg C) 14.0
11 1,1,1-Tricbloroethane *
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 Pentachlorophenol , NA
66 Bis(2-ethylhexyl) phthalate NA
70 Dlethyl phthalate 0.00
85 Tetracbloroethylene *
86 Toluene 0.00
87 Trichloioethylene 0.00
111* . Antimony 0.000
115 Arsenic 0.080
118 Cadmium 0.002
119 Chromium, Total 0.140
Chromium, Hexavalent 0.110
120 Copper 0.006
121 Cyanide, Total 0.000
Cyanide, Amn. to Chlor. I
122 lead 0.000
123 Mercury I
12ft Nickel 0.000
125 Selenium 0.000
126 Silver 0.000
128 Zinc 35.30
Aluminum 0.000
Aramcnia NA
lion NA
Manqanese 0.030
Phenols, Total 0.088
Oil & Grease 2.0
Total Suspended Solids 0.0
pH, Minimum 8.8
pH, Maximum 8.8
PLANT A
mg/1
PLANT B
21.0
*
0.00
0.00
0.00
0.00
0.00
*
NA
NA
0.00
0.00
0.00
0.00
0.000
0.140
0.006
0.210
0.140
0.010
0.027
I
0.000
I
0.000
0.000
0.000
22.00
0.000
NA
NA
0.055
0.055
2.8
32.0
8.2
8.5
18.0
*
0.030
*
*
0^00
*
*
NA
NA
*
0.00
0.00
*
0.000
0.080
0.000
0.034
0.030
0.011
0.000
I
0.000
I
0.000
0.000
0.000
47.40
0.000
NA
NA
0.090
0.110
9.2
25.0
8.4
8.8
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.041
NA
NA
NA
0.00
0.000
0.000
0,000
0.003
0.000
0.036
0.000
0.000
0.000
0.600
0.000
NA
0.0220
450.0
NA
NA
NA
0.040
0.000
10.0
5.0
4.3
6.5
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
*
NA
NA
NA
*
0.000
0.000
0,000
0.005
0.000
0.021
0.000
0.000
0.000
0.5000
0.000
NA
0.0140
1050.0
NA
NA
NA
0.030
0.000
9.0
5.0
4.3
6.5
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.070
NA
NA
NA
0.00
0.000
0.000
0.000
0.018
0.000
0.000
0.000
0.000
0.000
0.2600
0.000
NA
0.0200
206.0
NA
NA
NA
0.010
0.000
22.0
5.0
4.3
6.5
I •"• Interference
NA - Not Analyzed
* - <0.01
-------
TABLE V-67
POLLUTANT MASS LOADINGS IN THE
ZINC POWDER-WET AMALGAMATED
ANODE ELEMENT WASTE STREAMS
PLANT A
mg/kg
PLANT B
CO
u>
Flow (1/kq) 5.168
Temperature (Deg C) 14.0
11 1,1,1-frichloroethane 0.00
13 1,1-Dichloroethane 0.00
29 1,1-Dicbloroethylene 0.00
30 1,2-lrans-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 letrachloroethylene 0.00
86 Toluene 0.00
87 Trichloroethylene 0.00
114 Antimony 0.000
115 Arsenic 0.413
118 Cadmium 0.010
119 Chromium, Total 0.724
Chromium, Hexavalent 0.568
120 Copper 0.031
121 Cyanide, Total 0.000
Cyanide, Amn. To Chlor. I
122 lead 0.000
123 Mercury I
124 Nickel 0.000
125 Selenium 0.000
126 Silver 0.000
128 Zinc 182.4
Alundnum 0.000
Ammonia NA
Iron NA
fManganese 0.155
Phenols, Total 0.455
Oil 6 Grease 10.34
Total suspended Solids 0.000
pH, Minimum 8.8
PH, Maximum 8.8
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
0.000
0.955
0.041
1.432
0.955
0.068
0.184
I
0.000
I,
0.000
0.000
0.000
150.0
0.000
NA
NA
0.375
0.375
19.09
218.2
8.2
8.5
6.82
18.0
0,00
0.205
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.546
0.000
0. 232
0.205
0.075
0.000
I
0.000
I
0.000
0.000
0.000
323.2
0.000
NA
NA
0.614
0.750
62.7
170.5
8.4
8.8
2.379
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.09R
NA
NA
NA
0.00
0.000
0.000
0.000
0.007
0.000
0.086
0.000
0.000
0.000
1 .427
0.000
NA
0.0520
1071.0
NA
NA
NA
0.095
0.000
23.79
11.90
ft. 3
6.5
1.8P4
28.0
0.00
NA
NA
Nft
NA
0.00
NA
NA
0.00
NA
NA
NA
0.00-
0.000
0.000
0.000
0.009
0.000
0.040
0.000
0.000
0.000
0.942
0.000
NA
0.0260
1079.0
NA
NA
NA
0.057
0.000
16.96
9.42
4.3
6.5
2.159
28.0
0.00
NA
NA
NA
NA
0.00
NA
NA
0.151
HA
NA
NA
0.00
0.000
0.000
0.000
0.039
0.000
0.000
0.000
0.000
0.000
0.5616
0.000
NA
0.0430
444.7
NA
NA
NA
0.022
0.000
47.49
10.70
4.3
6.5
I - Interference
NA - Nat Analyzed
-------
TABLE V-68
STATISTICAL ANALYSIS (mg/1) OF THE
ZINC POHDER-HET AMALGAMATED ANODE
ELEMENT HASTE STREAMS
to
11
13
29
30
3 8
tn
55
64
66
70
85
86
87
11 4
115
118
119
120
121
122
123
124
125
126
128
Temperature (Deg C)
1 , 1 , 1 -Trichloroethane
1,1 -Diehloroethane
1,1 -Dichloroethylene
1 , 2-Tran3-dichloroethylerie
Ethylbenzene
Hethylene chloride
Naphthalene
Pentaeblorophenol
Bis(2-etbylhejtyl)phthalate
Diethyl phthalate
letrachloroethylene
Toluene
Tricolor oethylene
Antimony
Arsenic
Chromium, Total
Chromium, Hexavalent
Copper
Cyanide, Total
Cyanide, Amn. to Chlor.
lead
Mercury
Nickel
Seleniuir
Silver
Zir.c
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Gil 6 Oreaae
Total Suspended solids
pH, Minimum
pH, Maximum
INIMOM
14.0
0.00
0.00
0.00
0.00
0.00
0.00
*
NA
*
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.003
0.000
0.000
0.000
0.000
0.000
0.260
0.000
0.000
0.000
22.00
0.000
NA
NA
0.010
0.000
2.0
0.0
64.3
6.5
MAXISOM
28.0
*
0.030
*
*
0.00
*
*
NA
0.070
*
»
0.00
*
0.000
0.140
0.006
0.210
0.140
0.036
0.027
0.000
0.000
0.6000
0.000
0.000
0.0220
1050.0
0.000
NA
NA
0.090
0.110
22.0
32.0
3.8
8.8
MEAN
22.6
*
0.010
*
*
0.00
*
*
NA
0.037
*
*
0.00
#
0.000
0.050
0.001
0.068
0.047
0.014
0.005
0.000
0.000
0.1533
0.000
0.000
0.0093
301.8
0.000
NA
NA
0.043
0.042
9.2
12.0
6.4
7.6
MEOIAN
24.5
*
0.00
0.00
0.00
0.00
0.00
*
NA
0.041
0.00
0.00
0.00
0.00
0.000
0.040
0.000
0.026
0.015
0.011
0.000
0.000
0.000
0.5000
0.000
0.000
0.0070
126.7
0.000
NA
NA
0.035
0.027
9.1
5.0
6.3
7.5
tit
VAL ZEROS PTS
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
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
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
0
3
0
1
0
0
NA - Not Analyzed
* - <0.01
-------
TABLE V-69
STATISTICAL ANALYSIS (mg/kg) OP THE
ZINC POWDER-WET AMALGAMATED
ANODE ELEMENT HASTE STREAMS
Minimum
Maximum
Mean
Median
u?
w
ui
Flow (I/kg)
Temperature (Deq. C)
11 1,1,1-lrichloroethane
13 1,1-Diehloroethane
29 1,1-Dicnloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
61 Pentachlorophenol
66 Eis(2-ethylbexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichlozoethylene
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
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
1.884
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
0.00
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.007
0.000
0.000
0.000
0.000
0.000
0.5616
0.000
0.000
o.ooo
150.0
0.000
NA
NA
0.022
0.000
10.34
0.000
4.3
6.5
6.82
28.0
0.00
0.205
0.00
0.00
0.00
0.00
0.00
NA
0.151
0.00
0.00
0.00
0.00
0.000
0.055
0.041
1.432
0.955
0.086
0.184
0.000
0.000
1.427
0.000
0.000
0.0520
1979.0
, 0.000
NA
NA
0.614
0.750
62.7
218.2
8.8
8.8
4.205
22.6
0.00
0.068
0.00
0.00
0.00
0.00
0.00
NA
0.083
0.00
0.00
0.00
0.00
0.000
0.319
0.009
0.407
0.288
0.050
0.031
0.000
0.000
0.977
0.000
0.000
0.0202
692.0
0.000
NA
NA
0.220
0.263
30.07
70.1
6.4
7.6
3.774
24.5
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
0.098
0.00
0.00
0.00
0.00
0.000
0.207
0.000
0. 135
0.102
0.054
0.000
0.000
0.000
0.9420
0.000
0.000
0.0130
384.0
0.000
NA
NA
0.125
0.188
21.44
11.35
6.3
7.5
NA - Not Analyzed
-------
TABLE V-70
POLLUTANT CONCENTRATIONS IN THE ZINC
POWDER-GELLED AMALGAM ANODE ELEMENT
HASTE STREAMS
PLANT A
tng/1
PLANT B
OS
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Diehloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylfaenzene
44 Methylene chloride
5 5 Naphthalene
6ft Pentachlorophenol
66 Bis(2-ethylhexyl)phthalate
70 Diethyl phthalate
8 5 Tetrachloroethylene
86 Toluene
87 Irichlorbethylene
11ft 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
12 5 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum
pH, maximum
I - Interference
Nri - Sot Analyzed
* - < 0.01
21.0
*
NA
HA
NA
NA
0.00
NA
0.00
0.014
NA
NA
NA
*
0.000
1.060
0.080
0.000
0.000
0.670
NA
NA
0.000
I
0.000
NA
0.000
1100.0
NA
10.90
NA
0.110
0.003
33.0
97.0
13.2
13.5
26.0
NA
NA
NA
NA
NA
NA
NA
0.00
0.013
NA
NA
NA
NA
0.000
1.050
0.120
0.040
0.000
0.540
NA
NA
0.000
I
0.000
NA
0.000
750.0
NA
5.30
NA
3.420
NA
NA
100.0
13.2
13.2
22.0
0.025
NA
NA
NA
NA'
0.00
NA
0.00
0.042
NA
NA
NA
*
0.000
0.810
0.071
0.068
I
0.620
NA
NA
0.000
I
0.000
NA
0.000
440.0
NA
4.70
NA
4,650
0.000
26.0
NA
12.9
13.4
16.0
*
*
0.00
0.00
0.00
0.023
0.00
0.042
0.011
0.00
*
*
*
0.000
0.000
0.063
0.021
0.000
0.101
0.001
0.005
0.102
0.814
0.010
NA
0.0100
NA
3.130
11.55
0.522
2.086
0.000
7.8
413.5
NA
NA
15.0
*
NA
NA
NA
NA
0.00
NA
0.00
*
NA
NA
NA
0.00
0.000
0.080
0.006
0.014
0.000
0.081
0.005
0.005
0.000
0.4700
0.025
NA
0.0020
133.0
NA
1.57
NA
0.170
0.000
6.0
257.5
NA
NA
16.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
*
NA
NA
NA
*
0.000
0.07Q
0.008
0.005
I
0.054
0.000
0.000
0.000
0.5000
0.000
NA
0.0130
17.60
NA
0.17
NA
0.210
0.100
0.0
545.0
NA
NA
-------
TABLE V-71
P3LLOTANT MASS LOADINGS IN THE
ZINC POWDER-GELLED AMALGAM
ANODE ELEMENT WASTE STREAMS.
PLANT A
mg/kg
PLANT B
to
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dicbloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
3 8 Ethylbenzene
ftft Methylene chloride
55 Naphthalene
6 tt Pentachlorophenol
66 Bis (2-ethylhejcyl) phthalate
70 Diethyl phthalate
85 Tetracbloroethylene
86 Toluene
87 Trichloroethylene
11 ft Ant intcny
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
128 Zinc
Aluminum
Ammonia
Iron
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended solids
pH, minimum
pH, maximum
0.228
21.0
0.00
RA
NA
NA
NA
0.00
NA
0.00
0.003
NA
NA
NA
0.00
0.000
0.242
0.018
0.000
0.000
0.153
NA
NA
0.000
I
0.000
NA
250.7
NA
2.370
NA
0.025
0.001
7.52
22.11
13.2
13.5
0.212
26.0
NA
NA
NA
NA
NA
NA
NA
0.00
0.003
NA
NA
NA
NA
0.000
0.223
0.025
0.0080
0.000
0.115
NA
NA
0.000
I
0.000
NA
159.1
NA
1.124
NA
0.725
NA
NA
21.21
13.2
13.2
0.314
22.0
0.00
NA
NA
NA
NA
NA
NA
0.00
0.013
NA
NA
NA
0.00
0.000
0.255
0.022
0.021
I
0.195
NA
NA
0.000
I
0.000
NA
138.3
NA
1.477
NA
1.462
0.000
8.17
NA
12.9
13.4
0.646
16.0
0.00
0.00
0.00
0.00
0.00
0.015
0.00
0.027
0.007
0.00
0.00
0.00
0.00
0.000
0.000
0.040
0.013
0.000
0.065
0.001
0.003
0.066
0.5260
0.007
0.041
NA
2.024
7.47
0.337
1.349
0.000
5.02
267.3
NA
NA
1.077
15.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.000
0.086
0.006
0.015
0.000
0.087
0.005
0.005
0.000
0.5060
0.027
NA
143.3
NA
1.692
NA
0.183
0.000
6.46
277.4
NA
NA
1.668
16.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.000
0.117
0.013
0.008
I
0.090
0.000
0.000
0.000
0.8340
0.000
NA
29.35
NA
0.283
NA
0.350
0.167
0.000
909.0
NA
NA
I - Interference
NA - Not Analyzed
-------
TABLE V-72
STATISTICAL -ANALYSIS (mg/1) OP THE ZINC
POHDER-GELLED AMALGAM ANODE
ELEMENT HASTE STREAMS
00
MINIMUM
Temperature (Deg C) 15.0
11 1,1,1-Trichloroethane 0.00
13 1,1-Diehloroethane *
29 1,1-Dicbioroethylene 0.00
30 1,2-Trans-diehloroethylene 0.00
38 Ethylbenzene 0.00
41 Methylene chloride 0.00
55 Naphthalene 0.00
61 Pentaeblorophenol 0.00
66 Bis(2-ethylhexyl) phthalate *
70 Diethyl phthalate 0.00
85 letraebloroethylene *
86 Toluene *
87 Tricbloroethylene 0.00
111 Antimony 0.00
115 Arsenic 0.000
118 Cadmium 0.006
119 Chromium, Total 0.000
Chromium, Hexavalent 0.000
120 Copper 0.054
121 Cyanide, Total 0.000
Cyanide, Amn. to Chlor. 0.000
122 lead 0.000
123 Mercury 0.4700
121 Nickel 0.000
125 Selenium 0.063
126 Silver 0.0000
128 Zinc 17.60
Aluminum 3.130
Ammonia 0.17
Iron 0.522
Manqanese 0.110
Phenola, Total 0.000
Oil 6 Grease . 0.000
Total Suspended solids 97.0
pH, minimum 12.9
pH» maximum 13.2
NA - Not Analyzed
* - SO.01
MAXIMUM
26,0
0.025
*
0.00
0.00
0.00
0.023
0.00
0.012
0.012
0.00
*
*
*
0.00
1.060
0.120
0.063
0.000
0.670
0.005
0.005
0. 102
0.8111
0.025
0.063
0.0130
1100.0
3.130
11.55
0.522
1.650
0.100
33.0
515.0
13.2
13.5
MEAN
20.3
0.005
*
0.00
0.00
0.00
0.005
0.00
0.007
0.013
0.00
*
*
*
0.00
0.512
0.058
0.025
0.000
0.311
0.002
0.003
0.017
0.5918
0.006
0.063
0.0012
188.1
3.130
5.61
0.522
1.711
0.021
14.6
282.6
13.1
13.1
MEDIAN
18.5
*
*
0.00
0.00
0.00
0.00
0.00
0.00
0.012
0.00
*
*
*
0.00
0.115
0.067
0.017
0.000
0.321
0.001
0.005
0.000
0.5000
0.000
0.063
0.0010
111.0
3.130
5.00
0.522
1.118
0.000
7.77
257.5
13.2
13.1
1
VAL
6
1
1
0
0
0
1
0
1
6
0
1
1
1
0
5
6
5
0
6
2
2
1
3
2
1
3
5
1
6
1
6
2
1
5
3
3
t
ZEROS
0
1
0
1
1
1
1
1
5
0
1
0
0
1
6
1
0
1
1
0
1
1
5
0
4
0
3
0
0
0
0
0
3
1
0
0
0
I
PTS
6
5
1
1
1
1
5
1
6
6
1
1
1
5
6
6
6
6
1
6
3
3
6
3
6
1
6
5
1
6
1
6
5
5
5
3
3
-------
LO
LO
VD
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 Napthalene
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 fi Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
TABLE V-73
STATISTICAL ANALYSIS (mg/kg) OF THE
ZINC POWDER-GELLED AMALGAM ANODE
ELEMENT WASTE STREAMS
MINIMUM
MAXIMUM
MEAN
MEDIAN
0.212
15.0
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
0.000
0.000
0.006
0.000
0.000
0.000
0.065
0.000
0.000
0.5060
0.000
.0.040
0.000
29.35
2.024
0.283
0.337
0.025
0.000
0.000
21.21
12.9
13.2
1.668
26.0
0.00
0.00
0.00
0.00
0.00
0.015
0.00
0.027
0.013
0.00
0.00
0.00
0.00
0.000
0.255
0.040
0.021
0.000
0.005
0.020
0.005
0.066
0.834
0.027
0.040
0.0220
250.7
2.024
7.47
0.337
1.462
0.167
8.17
909.0
13.2
13.5
0.691
20.3
0.00
0.00
0.00
0.00
0.003
0.003
0.00
0.004
0.004
0.00
0.00
0.00
0.00
0.000
0. 154
0.021
0.011
0.000
0.002
0.117
0.003
0.011
0.622
0.006
0.040
0.0050
144.1
2.024
2.402
0.337
0.682
0.033
5.436
299.4
13.1
13.4
0.480
18.5
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
0.000
0.170
0.020
0.011
0.000
0.001
0.102
0.003
0.000
0.5260
0.000
0.040
0.0010
144.3
2.024
1.584
0.337
0.538
0.000
6.46
267.3
13.2
13.4
-------
TABLE V-74
POLLUTANT CONCENTRATIONS IN THE
ZINC OXIDE POWDER-PASTED OR PRESSED,
BIDUCED ANODE ELEMENT HASfE STREAMS
PLANT A
PLANT B
mg/1
-P-
o
Temperature (Deg C)
11 1,1,1-Tricoloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylerie
38 Ethylfcenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
S5 Tetrachloroethylene
66 Toluene
£7 Iriehloroethylene
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 2inc
Aluminum
Ammonia
Iron
Hanqanese
Phenols, Total
Oil £ Grease
Total Suspended Solids
pB, Minimum
pH, Maximum
15.0
0.00
0.00
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0,00
0.00
0.00
0.000
0.080
0.071
0.025
0.000
0.300
NA
NA
0.078
0.1000
0.000
0.000
0.1200
53.00
0.000
NA
NA
0.010
NA
NA
122.0
11.9
11.9
13.0
*
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.110
0.058
0.059
I
0.610
NA
NA
0.140
0.1600
0.023
0.000
0.2700
129.0
0.480
NA
NA
0.006
NA
NA
96.0
11.H
11.1
15.0
0.00
*
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.000
0.011
0.000
0.000
0.000
NA
NA
0.000
0.000
0.000
0.000
0.000
0.280
0.000
NA
NA
0.000
NA
HA
5.0
9.tt
9.4
10.0
0.00
*
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.000
0.03*
0.000
0.000
NA
NA
NA
NA
0.0140
0.050
0.000
0.000
2.840
NA
NA
NA
0.000
NA
NA
5.0
9.4
9.4
I - Interference
NA - Not Analyzed
* - < 0.01
-------
TABLE V-75
POLLUTANT MASS LQADINSS IM THE ZINC
OXID1 POWDER-PASTED OR PRESSED, REDUCED
ANODE ELEMENT WASTE STREAMS
PLANT A
mg/kg
PLANT 8
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 Etfaylbenzene
44 Methylene chloride
55 Naphthalene
61 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
10 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
chrooiium, Hexavalent
120 copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 selenium
126 Silver
128 Zinc
Aluirinum
Ammonia
Iron
Manganese
Phenols, Total
oil 6 Grease
Total Suspended solide
pH, Minimum
pH, Maximum
81.9
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
0.000
6.56
5.818
2.019
0.000
24.58
NA
NA
6.39
8.20
0.000
0.000
9.83
4343.0
0.000
NA
NA
0.819
NA
NA
10000.0
11.9
11.9
151.0
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
0.000
16.65
8.78
8.93
I
92.4
NA
NA
21.20
24.22
3.482
0.000
40.88
19530.0
72.7
NA
HA
0.908
NA
NA
14530.0
11.4
11.4
315.4
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
0.000
0.000
3.470
0.000
0.000
0.000
NA
NA
0.000
0.0000
0.000
0.000
0.0000
88.3
0.000
NA
NA
0.000
NA
NA
1577.0
9.4
9.4
239.2
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
0.000
0.000
8.13
0.000
0.000
NA
NA
NA
NA
3.349
11.96
0.000
0.0000
679.0
NA
NA
NA
0.000
NA
NA
1196.0
9.9
9.4
I - Interference
NA - Not Analyzed
-------
TABLE V-76.
STATISTICAL ANALYSIS (mg/1) OF THE
ZINC OXIDE POHDER-PASTED OR PRESSED,
REDUCED ANODE ELEMENT HASTE STREAMS
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dicbloroethane
29 1,1-Dichloroethylene
30 1,2-Irans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis (2-ethylhexyl)phthalate
70 Diethyl phthalate
85 Tetracbloroethylene
_p» 86 Toluene
to 87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadir.ium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Ann. To Chlor.
122 lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluirinun
Ammonia
Iron
Manqanese
Phenols, Total
oil & Grease
Total Suspended solids
pH, Minimum
pH, Maximum
INIMOM
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
0.000
0.000
0.011
0.000
0.000
0.000
NA
NA
0.000
0.0000
0.000
0.000
0.000
0.280
0.000
NA
NA
0.000
NA
NA
5.0
NA
NA
MAXIMUM
15.0
*
*
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.110
0.071
0.059
0.000
0.610
NA
NA
0.140
0.1600
0.050
0.000
0.2700
129.0
0.080
NA
NA
0.010
NA
NA
122.0
MA
NA
HEAN
12.9
*
*
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.047
0.044
0.021
0.000
0.303
NA
NA
0.073
0.0685
0.018
0.000
0.0975
16.30
0.160
NA
NA
0.004
NA
NA
57.0
NA
NA
MEDIAN
14.0
0.00
*
0.00"
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.010
0.046
0.013
0.000
0.300
NA
NA
0.078
0.0570
0.012
0.000
0.0600
27.92
0.000
NA
NA
0.003
NA
NA
50.5
NA
NA
1
VAL
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
f
ZEROS
0
3
2
4
4
4
3
4
4
2
4
4
2
0
2
3
1
1
1
2
4
2
0
2
•
prs
NA - Not Analyzed
* - <0.01
-------
TABLE V-77
STATISTICAL ANALYSIS (mg/Jtf) OF THE ZINC
OXIDE POWDER-PASTED OR PRESSED, REDUCED
ANODE ELEMENT WASTE STREAMS
Minimum
Maximum
Mean
Median
OJ
•P-
LO
Flow a/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-lran3-dichloroethylene
3 8 Ethylbenzene
44 Methylene chloride
55 Napthalene
64 Pentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Diethyl phthalate
8 5 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Bexavalent
120 Copper
121 cyanide. Total
Cyanide, Amn. to chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 2inc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil S Grease
Total suspended solids
pH, Minimum
pH, Maximum
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
0.000
0.000
3.470
0.000
0.000
0.000
NA
NA
0.000
0.0000
0.000
0.000
0.0000
88.3
0.000
NA
NA
0.000
NA
NA
1196.0
9.4
9.4
315.4
15.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
1.262
0.00
0.000
16.7
8.78
8.93
0.000
92.4
NA
NA
21.20
24.22
11.96
0.000
40.88
19530.0
72.7
NA
NA
0.908
NA
NA
14530.0
11.9
11.9
197.0
12.9
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.375
0.00
0.000
5.80
6.55
2.745
0.000
38.98
NA
NA
9.20
8.94
3.861
0.000
12.68
6160.0
24.22
NA
NA
0.432
NA
NA
6830.0
10.5
10.5
195.3
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.120
0.00
0.000
3.28
6.98
1.024
0.000
24.58
NA
NA
6.39
5.772
1.741
0.000
4.917
2511.0
0.000
NA
NA
0.410
NA
NA
5787.0
10.4
10.4
NA - Not Analyzed
-------
TABLE V-78
POLLUTANT CONCENTRATIONS IN THE
SPENT AMALGAMATION SOLUTION
WASTE STREAM
mg/1
Co
-P-
Temperature (Deg C)
11 1,1,1-Irichloroethane
13 1,1-Dichloroethane
29 1,1-Dicbloroethylene
30 1,2-Trans-dichloroethylene
3 8 Etbylbenzene
M Methylene chloride
55 Naphthalene
6H lentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
111 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 6 Grease
Total suspended Solids
pH, Minimum
pH, Maximum
16,0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
13.10
0.000
3.390
NA
NA
68.0
53000.0
8.84
0.000
0.2800
1300,0
0.300
0.14
NA
0.8HO
NA
NA
160.0
1.3
1.3
10.0
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
0.000
15. 10
0.000
0.300
NA
NA
16.1*0
30000.0
9.10
0.000
0.0460
1200.0
0.450
0.14
NA
0.980
NA
NA
11.0
1.0
1.0
NA - Not Analyzed
-------
TABLE V-79
POLLUTANT CONCENTRATIONS IN THE
ZINC ELECfRODEPOSITED ANODE ELEMENT
WASTE STREAMS
mg/1
Ui
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Diehloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
3 8 Ethylbenzene
44 Methylene chloride
55 Napthalene
64 Pentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Diethy1 phthalate
85 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
111 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
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended solids
pH, Minimum
pH, Maximum
9.0
0,00
0.00
*
0.00
0.00
0.00
0.00
MA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.016
0.000
0.012
0.010
0.005
0.039
30.78
0.005
0.000
0.0651
12.15
0.000
1.40
NA
0.000
0.007
1.0
10.1
9.3
12.2
10.0
0,00
0.00
*
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.006
0.000
0.020
0.005
0.005
0.000
0.0000
0.000
0.000
0.0310
12.20
0.000
0.28
NA
0.000
0.000
7.6
10.0
10.5
12.1
7.0
0.00
0.00
*
0.00
0.00
0.00
*
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.013
0.000
0.008
0.005
0.005
0.007
13.35
0.004
0.000
0.4298
12.43
0.000
0.28
NA
0.000
0.000
4. 1
3.4
9.6
12.2
NA - Not Analyzed
* - < 0.01
-------
TABLE V-8Q
POLLUTANT MASS LOADINGS IN THE ZINC
ELECTRODEPOSITED ANODE ELEMENT
WASTE STREAMS
mg/kg
u>
•P*
ON
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Diehloroethane
29 1,1-Dichloroethylene
30 1,2-Irans-dichloroethylene
3 8 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl)phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Triehlcroethylene
111 Antimony
115 Arsenic
118 Cadnr.iun
119 Chroirium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Ann. to Chior.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Slujrinum
Ammonia
Iron
Manganese
Phenols, Total
Oil and Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
1658.0
9.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
•NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
72.7
0.000
55.72
46.56
23.28
183.8
143400.0
23.90
0.000
303.4
56600.0
0.811
6520.0
NA
2.271
32.59
4660.0
46990.0
NA
NA
5370.0
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
0.000
0.000
0.000
32.21
0.000
107.4
26.84
26. 8H
0.000
0.0000
0.000
0.000
166.4
65500.0
0.000
1503.0
NA
0.000
0.000
40800.0
53680.0
10.5
12.1
4874.0
7.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.017
61.9
0.000
39.62
24.36
24.36
35.47
65100.0
19.68
0.000
2095.0
60600.0
0.973
1364.0
NA
2.120
0.000
2000.0
16590.0
NA
NA
NA - Not Analyzed
-------
TABLE V-81
NORMALIZED FLOWS OF POST-FORMATION
RINSE WASTE STREAMS
fcASTE STREAM
PLANT ID
I/kg
PLANT MEAN
Post-formation Rinsing
A
A
A
B
B
C
Mean
Median
79.7*
1135.5*17
100.9*
262.6
341.8
+
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 variability in floor area maintenance water use.
-------
TABLE V-82
POLLOTANT CONCENTRATIONS IN THE SILVER
POH0ER PRESSED AND ELECTROLYTICAIJaf OXIDIZED
CATHODE EtEMENT HASTE STREAMS
PLANT A
PIAOT B
mg/1
11
13
29
30
3 8
44
55
64
66
.70
8 5
86
87
114
115
118
119
120
121
122
123
124
125
126
128
Temperature (Deg C)
1,1,1-Trichloroethane
1,1-Dichloroethane
1,1-Dichl0Eoethyletie
1,2-Trans-dicbloroefchylene
Ethylbenzene
Metbylene' chloride
Naphthalene
Pentachlorophenol
Bis (2-ethylhexyl) phthalate
Dietbyl phthalate
Tetrachloroethylene
Toluene
Triehloroethylene
Antimony
Arsenic
Cadmium
Chrctnium, Total
Chromium, Hexavalent
Copper
Cyanide, Total
Cyanide, Amn. to Chlor.
Mercury
Nickel
Selenium
silver
2inc
Aluainum
Ammonia
Iron
Manganese
Phenols, , Total
Oil 5 Grease
Total Suspended Solids
pi. Minimum
pH, Maximum
NA - Mot Analyzed
* - < 0.01
14.0
0.00
0.00
0.00
0.00
0.00
41
*
NA
NA
*
0.00
0.00
*
0.000
0.110
0.082
0.007
I
1.210
NA
NA
0.690
0.0600
0.250
0.000
0.640
235.0
0.000
NA
NA
0.009
NA
NA
362.0
10.6
11.8
15.0
*
0.00.
0.00
0.00
0.00
*
*
NA
NA
0.00
0.00
*
*
0.000
0.000
0.008
0.007
0.000
4.110
NA
NA
0.200
0.0090
0.050
0.000
0.3200
29.40
0.000
NA
NA
0.024
NA
NA
86.0
11.8
11.8
15.0
*
0.00
0.00
0.00
0.00
*
*
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.065
11.60
0.000
1.730
NA
NA
0.820
0.0170
0.590
0.000
1.480
59.0
1.440
NA
NA
0.040
NA
NA
217.0
10.6
10.6
15.0
0.00
*
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.000
0.055
0.000
0.000
0.000
NA
NA
0.000
0.0110
0.048
0.000
3.880
0.000
0.000
NA
NA
0.000
NA
NA
5.0
11.0
11.0
15.0
0.00
*
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.000
0.004
0.000
0.000
0.000
NA
NA
0.000
0.0710
0.000
0.000
3.200
0.000
0.000
NA
NA
0,008
NA
NA
49.0
10.8
11.0
-------
TABLE V-83
POLLUTANT MASS LOADINGS IN THE SILVER
POWDER PRESSED AND ILECTFOLfTICALLf OXIDIZED
CATHODE ELEMENT »ASTE STREAMS
PLANT A
PLANT B
mg/kg
\o
Flow (I/kg}
Temperature (Deg C)
11 1,1,1-Tricbloroethane
13 1,1-Diehloroethane
29 1,1-Diebloroethylene
30 1,2-Trans-dicnloroethylene
3 8 Ethylbenzene
44 Methylene chloride
55 Napththalene
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
Oils S Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
79.7
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.040
0.00
0.00
0.00
0.000
8.77
6.53
0.558
I
96.4
NA
NA
54.98
4.781
19.9
0.000
51.00
18730.
0.000
NA
NA
0.717
NA
NA
28850.0
10.6
11.8
1136.0
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
0.000
0.000
9.08
7.95
0.000
4670.0
NA
NA
227.1
10.22
56.78
0.000
363.4
33380.
0.000
NA
NA
27.25
NA
NA
97700.0
11.8
11.8
100.9
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
0.000
0.000
6.56
1171.0
0.000
477.4
NA
NA
82.8
1.716
59.55
0.000
149.4
5955.
488.1
NA
NA
4.037
NA
NA
21900.0
10.6
10.6
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
o.oo
0.000
0.000
14.45
0.000
0.000
0.000
NA
NA
0.000
2.889
12.61
0.000
1019.0
0.000
0.000
NA
NA
0.000
NA
NA
1313.0
11.0
11.0
341.8
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
0.000
0.000
1.367
0.000
0.000
0.000
NA
NA
0.000
24.27
0.000
0.000
1093.0
0.000
0.000
NA
NA
2.735
NA
NA
16750.0
10.8
11.0
I - Interference
NA - Not Analyzed
-------
TABLE V-84
STATISTICAL ANALYSIS (mg/1) OF TOE
SILVER POHDER PRESSED MID ELECTROLYTICALLlf
OXIDIZED CATHODE ELEMENT WASTE STREAMS
Ul
o
temperature (Deg C)
11 1,1, 1 -iriehloroethane
13 1,1-DicM.oroethane
29 1,1 -Die hloroethylene
30 1 , 2-Trans-dicliloroethyler,e
38 Ethylbenzene
I* Methylene chloride
55 Naphthalene
64 Eentachlorophenol
66 Bis p-ethylhexyl) phthalate
70 Diethyl phthalate
85 letrachloroethylene
8 6 Toluene
87 Trichlczoethylene
114 antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 copper
121 cyanide, Total
Cyanide, ftmn. to Chlor.
122 lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Ammonia
Iron
Manganese
Phenols, Total
oil & Grease
Total Suspended solids
pH, Minimum
pH, Maximum
IHIMDM
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
HA
0.00
0.00
0.00
0.00
0.000
0.000
0.004
0.000
0.000
0.000
NA
NA
0.000
0.0090
0.000
0.000
0.3200
0.000
0.000
NA
HA
0.000
NA
NA
5.0
10.6
10.6
MAXIMUM
15.0
*
*
0.00
0.00
0.00
*
*
HA
NA"
*
0.00
*
*
0.000
0.110
0.082
11.60
0.000
4.730
NA
NA
0.820
0.0710
0.590
0.000
3.880
235.0
ft. 440
NA
NA
0.040
NA
NA
362.0
11.8
11.8
MEAN
15.0
*
*
0.00
0.00
0.00
*
*
NA
NA
*
0.00
*
*
0.000
0.020
0.043
2.323
0.000
2.010
NA
NA
0.342
0.0336
0.188
0.000
1.904
64.7
0,888
NA
NA
0.016
NA
m
143.8
11.0
11.2
MEDIAN
15.0
0.00
0.00
0.00
0.00
0.00
*
*
NA
NA
0.00
0.00
*
0.00
0.000
0.000
0.055
0.007
0.000
1.210
NA
NA
0.200
0.0170
0.050
0.000
1.480
29.40
0.000
NA
NA
0.009
NA
NA
86.0
10.8
11.0
f
VAL
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
Q
5
5
5
*
ZEROS
0
3
3
5
5
S
2
2
2
0
1
5
0
2
4
f
PIS
5
5
5
5
5
5
5
5
4
5
5
5
5
5
5
5
5
5
5
5
NA - Not Analyzed
* - <0.01
-------
TABLE V-85
STATISTICAL ANALYSIS (mg/kg) OF THE
SILVER POWDER PRESSED AND ELECTROLYTICALLY
OXIDIZED CATHODE ELEMENT WASTE STREAMS
Flow (I/kg)
Temperature (Deg C)
11 1,1.1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dicbloroethylene
, 30 1,2-Tran3-dichloroethylene
36 Ethylbenzene
i»i» Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl)Phthalate
70 Diethyl Phthalate
8 5 Tetrachloroethylene
86 Toluene
87 Trichloroethylene
11 a 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 5 Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
MINIMUM
MAXIMUM
MEAN
MEDIAN
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
0.000
0.000
1.367
0.000
0.000
0.000
NA
NA
0.000
1.716
0.000
0.000
51.00
0.000
0.000
NA
NA
0.000
NA
NA
1313.0
10.6
10.6
1136.0
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
0.000
8.77
14.45
1171.0
0.000
4667.0
NA
NA
227.1
24.27
- 59.55
0.000
1094.0
33380.0
448.1
NA
NA
27.25
NA
NA
97650.0
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
0.000
1.753
7.60
235.9
0.000
1048.0
NA
NA
73.0
8.775
29.77
0.000
535.3
11610.0
89.6
NA
NA
6.95
NA
NA
33290.0
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
0.000
0.000
6.56
0.558
0.000
96.4
NA
NA
54.98
4.781
19.92
0.000
363.4
5955.0
0.000
NA
NA
2.735
NA
NA
21900.0
10.8
11.0
NA - Not Analyzed
-------
TABLE V-86
POLLUTANT CONCENTRATIONS IN THE SILVER
OXIDE (Ag20) POHDER-TBERMALLY REDOCED AND
SINTERED, ELECTROLmCALLY FORMED CATHODE ELEMENT
WASTE STREAMS
Ui
NS
mg/1
Temperature (Beg CJ
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene "
Hit Methylene chloride
55 Naphthalene
64 Pentacbloropbenol
66 Bis(2-ethylhexylJ phthalate
70 Diethyl phthalate
85 letrachloroethylene
86 loluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Cbronium, Hexavalent
120 Copper
121 Cyanide, lotal
Cyanide, Amn. to Chlor.
122 lead
123 Mercury
124 NicJsel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Wienols, Total
Oil 6 Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
10,0
0.00
*
*
0.00
0.00
*
*
NA
NA
*
0.00 .
0.00
0.00
0.000
0.000
0.000
0.010
0.000
0.002
0.006
0.000
0.000
0.0130
0.000
0.000
0.3000
0.017
0.350
0.84
NA
0.000
0.004
12.0
6.1
12.4
12.4
16.0
0.00
0.00
*
0.00
0,00
0.00
*
NA
NA
*
0.00
0.00
0.00
0.000
0.000
0.000
0.007
0.000
0.000
0.000
0.000
0.000
0.0200
0.000
0.000
16.70
0.011
0.000
0.28
NA
0.000
0.017
9.3
1.0
9.0
9.0
NA - Hot Analyzed
* - < 0.01
-------
TABLE V-8?
POLLUTANT MASS LOADINGS IN THE SILVER
OXIDE (Ag2O) POWDER-THERMALLY REDUCED AND
SINTERED, ELECTROLYTICALLY FOKMED CATHODE ELEMENT
WASTE STREAMS
ntg/kg
Flow (I/kg)
temperature (Deg C)
11 1,1.1-Tzichloroet.hane
13 1,1-Dichloroethane
29 1»1~Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
HI Methylene chloride
55 Naphthalene
64 Pentacblorophenol
66 Bis (2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetracbloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Color.
122 lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluirinum
Ammonia
Iron
Manganese
Phenols, Total
Oil 6 Grease
Total Suspended Solids
pH, Minimum
pH, Maximum
437.4
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
0.000
0.000
0.000
4.374
0.000
0.875
2.621
0.000
0.000
5.686
0.000
0.000
131.2
7.4»
153.1
367.4
HA
0.000
1.750
5250.0
2668.0
12.4
12.4
100.9
16.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.707
0.000
0.000
0.000
0.000
0.000
2.019
0.000
0.000
1686.0
1.110
0.000
28.26
NA
0.000
1.716
939.0
100.9
9.0
9.0
NA - Not Analyzed
-------
TABLE V-88
POLLUTANT CONCENTRATIONS IN THE SILVER
PEROXIDE (AgO) POWDER CATHODE ELEMENT WASTE STREAMS
PLANT C
PLANT B
Dig/I
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Die hloroetbane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Etbylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
6 6 Bis{2-ethylbexyl}phthalate
70 Diethyl phthalate
85 Tetraebloxoethylene
86 Toluene
87 Trichloroethylene
111 antimony
115 Arsenic
118 Catoiuni
119 Chromium, Total
Chromium, Hexavalent
120 Capper
121 Cyanide, Total
Cyanide, Ann. 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
* - S to 0.01
i - Invalid Analysis
38.0
0.00
0.00
*
0.00
0.00
0.00
*
NA
NA
*
0.00
0.00
0.00
0.000
0.000
0.000
0.008
0.000
0.013
0.007
0.000
0.000
0.0070
0.008
0.000
45.20
0.450
0.000
1.10
SA
0.000
0.000
16.0
620.0
9.0
9.0
NA
0.00
0.00
0«00
0.00
0.00
*
*
NA
NA
0.00
0.00
0.00
0.00
0.000
i
5.99
0.220
I
0.000
NA
NA
0.000
I
0.000
i
71.0
0.014
0.000
NA
HA
0.000
NA
NA
310.0
10.0
11.0
NA
*
0.00
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
i
2.250
0.088
I
0.000
NA
NA
0.000
I
0.000
i
48.60
0.050
0.000
NA
NA
0.000
NA
NA
178.0
11.0
13.0
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
0.000
i
3.380
0. 160
I
0.000
NA
NA
0.000
I
0.000
i
8.80
0.030
3.560
NA
NA
0.000
NA
NA
730.0
10.0
13.0
-------
TABLE V-89
POLLtJTANT MASS LOADINGS IN THE SILVER
PEROXIDE (AgO) POWDER CATHODE ELEMENT WASTE STREAMS
PLANT C
PLANT B
mg/kg
CO
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dicnloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
3 8 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, Ann. to Chlor.
122 Lead
123 Mercury
124 Ntckel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil 6 Grease
Total suspended solids
pH, Minimum
pH, Maximum
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
0.000
0.000
0.000
0.606
0.000
0.984
0.530
0.000
0.000
0.5300
0.606
0.000
3422.0
34.07
0.000
83.3
NA
0.000
0.000
1211.0
46930.0
9.0
9.0
5.539
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
0.000
i
33.18
1.219
I
0.000
NA
NA
0.000
I
0.000
i
393.3
0.078
0.000
NA
NA
0.000
NA
NA
1717.0
10.0
11.0
22.35
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
0.000
i
50.30
1.967
I
0.000
NA
NA
0.000
I
0.000
i
1086.0
1.118
0.000
NA
NA
0.000
NA
NA
3978.0
11.0
13.0
10.42
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
0.000
i
35.22
1.667
I
0.000
NA
NA
0.000
I
0.000
i
91.7
0.313
37.10
NA
NA
0.000
NA
NA
7610.0
10.0
13.0
I - Interference
NA - Not Analyzed
i - Invalid Analysis
-------
TABLE V-90
STATISTICAL ANALYSIS (mg/1) Of THE
SILVER PEROXIDE (AgO} POHDER CATHODE
ELEMENT HASTE STREAMS
KENIMOM MAXIHOM
MEAN
MEDIAN
*
VAL
t
ZEROS
*
PIS
CO
m
ON
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 Diethy1 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 6 Grease
Total Suspended solids
pH, Minimum
pH, Maximum
38.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
HA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.008
0.000
0.000
0.007
0.000
0.000
0.0070
0.000
0.000
8.80
0.011
0.000
1.10
NA
0.000
0.000
T6.0
178.0
9.0
9.0
3.80
*
0.00
*
0.00
0.00
*
*
NA
NA
*
0.00
0.00
0.00
0.000
0.000
5.990
0.220
0.000
0.013
0.007
0.000
0.000
0.0070
0.008
0.000
71.0
0.150
3.560
1.10
NA
0.000
0.000
16.0
730.0
11.0
13.0
3.08
*
0.00
*
0.00
0.00
*
*
NA
HA
*
0.00
0.00
0.00
0.000
0.000
2.905
0.119
0.000
0.003
0.007
0.000
0.000
0.0070
0.002
0.000
43.40
0.136
0.890
1.10
NA
0.000
0.000
16.0
459.5
10.0
11.5
3.80
0.00
0.00
0.00
0.00
0.00
*
*
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
2.815
0.124
0.000
0.000
0.007
0.000
0.000
0.0070
0.000
0.000
46.90
0.040
0.000
1.10
HA
0.000
0.000
16.0
465.0
10.0
12.0
1
1
0
1
0
0
2
2
1
0
0
0
0
0
3
4
0
1
1
0
0
1
1
0
4
4
1
1
0
0
1
4
4
4
0
3
4
3
4
4
2
2
3
4
4
4
4
1
1
0
1
3
0
1
4
0
3
1
0
0
3
0
4
1
0
0
0
0
4
4
4
4
4
1
4
4
1
4
1
1
4
1
4
1
4
4
4
1
4
1
1
4
4
4
NA - Not Analyzed
* - < 0.01
-------
TABLE V-91
STATISTICAL ANALYSIS (mg/kg) OF THE
SILVER PEROXIDE (AgO) POWDER
CATHODE ELEMENT WASTE STREAMS
CO
Flow (I/kg)
Temperature (Deg C)
11 1,1,1-lrichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
3 8 Ethylbenzene
44 Methylene chloride
55 Naphthalene
61 Pentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Dietbyl pbthalate
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
121 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil C Grease
Total Suspended -Solids
pH, Minimum
PH, Maximum
MINIMUM
5.539
38.0
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.606
0.000
0.000
0.530
0.000
0.000
0.5300
0.000
0.000
91.7
0.078
0.000
83.3
NA
0.000
0.076
1211.0
'717.0
9.0
9.0
MAXIMUM
MEAN
MEDIAN
75.7
38.0
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
50.29
1.967
0.000
0.984
0.530
0.000
0.000
0.5300
0.606
0.000
3442.0
34.07
37.10
83.3
NA
0.000
0.076
1211.0
46930.0
11.0
13.0
28.50
38.0
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
29.67
1.365
0.000
0.246
0.530
0.000
0.000
0.5300
0.151
0.000
1248.0
8.89
9.27
83.3
NA
0.000
0.076
1211.0
15060.0
10.0
11.5
16.39
38.0
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
34.20
1.443
0.000
0.000
0.530
0.000
0.000
0.5300
0.000
0.000
740.0
0.715
0.000
83.3
NA
0.000
0.076
1211.0
5792.0
10.0
12.0
NA - Hot Analyzed
-------
TABLE V-92
PRODUCTION NORMALIZED DISCHARGES
FEOM CELL HASH ELEMENT
KASTE
STBEAM
Cell Wash
fcastewater
u>
U1
c»
PLANT
ID
A
B
C
D
E
P
6
RANGE
I/kg
DCP
DATA
I/kg
4.21
+
0.334
MEAN
I/kg
MEAN
SAMPLING
DATA
I/kg
0.088
1.62
0.315
0.209
MEDIAN
I/kg
.088-1.21
1.13
0.310
* - Abnormally high flow (34.1 I/kg) deleted from consideration,
-------
WBI£ V-93
fouaum ooMZflRAHONS w THE
CeU. HfSSH ELHCff HASTE STRAWS
•temperature (Deg C)
13 1,1-DiddOTOethans
29 14-DieWoroethylene
30 l,2-Trans-didilotDetlvl«K
33 Ethylbenzene
44 Methylena chloride
55 Naphthalene
64 fentachlorqphenol
66 als(2-«thjrlhesvl) phthalate
70 Methyl phthaist
35 Uetrachlaroethylene
86 Tbliene
87 Triehloroettylene
114 Antiseoy
US Arsenic
HB Ca4nun
119 Qjrunitm, Tbtal
Chromlun, Hewvalent
120 Ctfper
121 Cyani
-------
RXUTWOT WSS UWJDWS IN TIE
mi wan asar vtss. sums
SOWSG
euwr B
rawr
PUHTC
•Rnpatature {Oeg C)
11 1,1,1-Trichtaoethane
13 1,1-Dkhksroethane
29 1,1-DicWofaethylene
30 1,2-Tcans-dicM.oroethylfim
38 EUiylibenaens
44 ftethylene chlori*
55 tfaphthalere
64 Bentaehloncehenol
66 Bia(2-«thyUiexfl) phttelate
70 Olettiyl phthalat
85 TtetmchtaoetJ^lena
86 Tbluene
87 Ttlchloroeths'teie
114 Antimony
115 Arsenic
118 Gidnlum
119 ChroniuiK, Tbtal
Chrcmium, Hexavalent
120 dagger
121 Cyanide, fatal
Cyanide, tab to Chlor.
122 tead
123 Mercury
124 Nickel
125 Seleniun
126 Silver
128 Zinc
Aluminas
Rumania
Iron
Wrngmese
Phenols, Tbtal
Oil & Grease
•total 9uspe«Jea Solids
rH, Mij:iinuii
pHf ifexinun
I - Interference
NA - (tot Analyzed
* - £0.01
i - Invalid Analysis
0.194
29.9
0.001
NA
KA
NA
m
0.00
KA
0.00
0.007
NA
NA
HA
0.002
0.000
0.000
0.001
0.006
0.000
0.053
NA
HA
0.002
0.0040
0.471
m
o.oooo
0.711
NA
0.282
NA
3.417
0.003
8.02
4.189
8.9
11.4
0.224
30.3
0.001
KA
KA
KA
KA
0.00
HA
NA
0.025
HA
KA
KA
0.00
0.000
0.000
0.000
0.008
0.000
0.063
KA
KA
0.005
0.0050
1.457
HA
0,0000
0.826
KA
1.878
KA
5.394
0.004
16.06
11.65
8.0
11.0
0.220
31.1
0,004
HA
HA
KA
KA
0,00
KA
0.00
0.005
KA
KA
NA
0.00
0.000
0.000
0.002
0.032
0.000
0.139
NA
NA
0.030
0.0650
5.373
KA
0,0000
2.734
NA
0.495
HA
15.33
0.003
10.97
35.53
9.7
11.9
0.575
KA
0.00
0.00
0.00
0.00
0.00
0,00
0.00
KA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.005
5.571
4.949
0.019
0.008
I
0.000
o.ssao
0.121
0.000
0.0100
0.247
0.000
m
KA
0.039
0.051
1.726
18.99
NA
KA
0.295
58.0
0.00
0.00
0.00
0.00
0.001
0.00
0.007
NA
NA
0.00
0.00
0.001
0.00
0.000
0.020
0.053
21.58
17.45
0.055
0.005
I
0.003
1.576
0.454
0.013
0.3970
3.759
0.049
NA
HA
0.179
0.007
8.77
4.046
KA
KA
0.603
56.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
HA
0.00
0.00
0.00
0.00
0.000
o.ooo
0.008
9.29
9.05
0.006
0.010
I
0.000
0.802
0,211
0.000
0.0200
0.428
0.000
HA
KA
0.090
0.013
6.64
0.000
KA
NA
0.085
34.0
0.00
KA
HA
NA
NA
0.00
NA
KA
0.014
KA
NA
KA
0.00
0.000
0.000
0.001
21.81
I
0.032
0,332
0.332
0.000
I
0,399
NA
0.0010
1.567
HA
HA
HA
1.261
0.000
8.96
2.470
S.g
5.8
0.039
34.0
0.00
NA
NA
KA
NA
0.00
KA
KA
0.005
KA
HA
KA
0.00
o.ooo
0.000
0.001
22.59
I
0.048
0.643
0.438
0.000
I
0.772
KA
0.0010
2.938
NA
KA
HA
3.429
o.ooo
18.31
3.393
6.4
6.4
0.090
34.0
0.00
NA
KA
KA
NA
0.00
KA
NA
0.003
HA
HA
HA
0.00
0.000
o.ooo
0.001
28.56
I
0.039
0.189
0.189
0.000
I
0.616
KA
0.0010
2.640
KA
KA
HA
2.263
0.000
12.03
3.772
5.8
5.8
1.485
KA
0.00
o.oo
0.00
0,00
0.00
0.00
0.00
NA
KA
0.00
0,00
0.00
0.00
0.000
i
0.152
0.038
0.000
0.153
HA
HA
O.OOO
0.3010
1.307
1
0.732
2.817
0.000
KA
KA
0.093
NA
HA
43.73
8.0
11.5
1.562
NA
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
HA
0.00
0.00
0.00
0.00
0.000
i
0.156
0.003
0.000
0.122
NA
KA
0.000
0.915
1.071
i
0,4061
3.463
0.000
KA
KA
0.146
HA
KA
53.62
7.5
11.9
1.804
KA
0.00
0.01
0.00
0.00
0.00
0.00
0.00
NA
HA
0.00
0.00
0.00
0.00
0.000
t
0.223
0.046
0.000
0.217
NA
m
0.000
0.736
0.902
1
0.4690
2.590
0.000
HA
HA
0.107
KA
HA
51.74
7.5
12.0
-------
TABLE V-95
STATISTICAL ANALYSIS (mg/1) OF THE
CELL WASH ELEMENT WASTE STREAMS
U>
Ov
MINIMUM
11
13
29
30
38
44
55
61
66
70
85
86
87
114
115
118
119
120
121
122
123
124
125
12fi
128
Temperature (Deg CJ
1,1, 1-lrichloroethane
1, 1-Dichloroethane
1, 1-Dichloroethylene
1 , 2-Trans-dichloroethylene
Ethylbenzene
Methylene chloride
naphthalene
Pentachlorophenol
29,9
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Bis (2-ethylhexyl) phthalateO. 011
Diethyl phthalate
Tetrachloroethylene
Toluene
Trichloroe thylene
Antimony
Arsenic
Cadmium
Chrcmium, Total
Chrcnium, Hexavalent
copper
Cyanide, Total
Cyanide, Amn. to Chlor.
Lead
Mercury
Nickel
Selenium
silver
zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
oil S Grease
Total Suspended Solids
pB, Minimum
PH, Maximum
*
0.00
0.00
0.00
0.000
0.000
0.002
0.002
0.000
0.010
0.014
2.100
0.000
0.0191
0.210
0.000
0.0000
0.430
0.000
1.46
MA
0.059
0.000
3,0
0.0
5.8
5.8
MAXIMUM
58.0
0.016
*
*
*
0.004
*
0.023
0.00
0.161
*
*
0.004
0.012
0.000
0.067
0.181
318.0
59.14
0.629
7.20
4.900
0.136
5.343
24.39
0.046
1.345
32.90
0.166
8.37
NA
69.6
0.088
205.0
161.3
9.7
12.0
MEAN
32.3
0.002
*
*
*
0.001
*
0.004
0.00
0.069
*
*
0.001
0.001
0.000
0.007
0.047
77.1
9.19
0.254
2.208
3.633
0.015
1.019
4.967
0.015
0.2030
9.99
0.028
1.03
NA
15.89
0.020
72.2
40.3
7.5
9.7
MEDIAN
34.0
*
*
*
*
0.00
0.00
*
0.00
0.046
*
*
0.00
*
0.000
0.000
0.010
4.913
0.000
0.229
1.059
3.900
0.000
0.4081
2.682
0.000
0.0160
3.675
0.000
2.25
NA
7.70
0.015
49.8
31.3
7.5
11.4
I
VAL
8
9
4
4
3
1
4
5
0
6
6
2
1
8
0
1
12
12
3
12
6
3
4
9
12
1
9
12
1
3
12
6
9
11
9
9
*
ZEROS
0
3
2
2
3
5
8
1
2
0
0
4
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
9
12
12
9
12
6
3
12
9
12
3
12
12
6
3
12
9
9
12
9
9
NA - Not Analyzed
* - < 0.01
-------
V-96
STATISTICAL ANALYSIS (Big/kg) OF THE CELL WASH ELEMENT WASTE STREAMS
to
Flow (I/Kg)
Temperature (Deg CJ
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
3 8 Ethylbenzene
44 Methylene chloride
5 5 Napthalene
64 pentaehlorophenol
66 Bis(2-ettoylhexyl) phthalate
70 Diethyl phthalate
8 5 Tetrachloroethylene
86 Toluene
87 Trichloraethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chrcnivw,, Total
Chromium, 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
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended Solids
pH, Minimum
pB, Maxinum
M1NIKOW
0.085
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
0.000
0.000
0.000
0.003
0.000
0.006
0.005
0.189
0.000
0.0010
0.121
0.000
0.0000
0.247
0.000
0.282
ISA
0.039
0.000
1.726
0.000
5.8
5.8
MAXIHOM
1.804
58.0
0.004
0.00
0.00
0.00
0.001
0.00
0,007
0.00
0.024
0.00
0.00
0.001
0.00
0.000
0.020
0.223
28.56
17.45
0.217
0.643
0.438
0.030
1.576
5.37
0.013
0.7320
3.759
0.049
1.878
NA
15.33
0.051
18.31
53.6
9.7
12.0
MEAH
0.602
32.3
0.001
0.00
0.00
0.00
0.00
0.00
0.001
0.00
0.010
0.00
0.00
0.00
0.00
0.000
0.002
0.050
9.13
3.494
0.079
0.198
0.319
0.003
0.5510
1.202
0.004
0.1690
2.060
0.008
0.885
m
2.646
0.009
10.15
19.43
7.5
9.7
MEDIAN
0.260
34.0
0.00
0.00
0.00
0.00
0.00
0.00
0,00
0.00
0.006
0.00
0.00
0.00
0.00
0.000
0.000
0.003
2.808
0.000
0.054
0.099
0.332
0.000
0.5580
0.756
0.000
0.0060
2.615
0.000
0.495
NA
0.720
0.003
8.86
7.92
7.5
11.4
NA - Not Analyzed
-------
TABLE V-97
POLLUTANT CONCENTRATIONS IN THE ELECTROLYTE
PREPARATION ELEMENT HASTE STREAMS
mg/1
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
UH Methylene chloride 0.00
55 Naphthalene 0.00
61 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
11
-------
TABLE V-98
POLLUTANT MASS LOADINGS IN THE ELECTROLYTE
PREPARATION ELEMENT WASTE STREAMS
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 Ithylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl} phthalate
70 Diethyl phthalate
85 letrachloroethylene
86 Toluene
87 Tricfaloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 chromium. Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Ann. to Chlor,
122 lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manqanese
Phenols, lotal
Oil 6 Grease
Total Suspended Solids
pR, Minimum
pH, Maximum
mg/kg
0.365
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
0.000
i
0.000
0.000
0.000
0.000
NA
NA
0.000
0.0146
0.080
i
0.2884
7.01
0.000
NA
NA
0.000
NA
NA
25.55
12.8
12.8
NA - Not Analyzed
i - Invalid Analysis
-------
TABLE V-99
POLLUTANT CONCENTRATIONS IN THE SILVER
ETCH ELEMENT WASTE STREAMS
mg/1
Temperature (Deg C) 10.0
11 1,1,1-Trichloroethane 0.00
13 1,1-Dichloroethane 0.00
29 1,1-Dichloroethylene *
30 1,2-Trans-dichloroethylene 0.00
38 Ethylbenzene 0.00
44 Metbylene chloride 0.00
55 Naphthalene 0.00
6H Pentachlorophenol NA
66 Eis (2-ethylhexyl) phthalate NA
70 Diethyl phthalate 0.00
85 Tetrachloroethylene 0.00
86 Toluene 0.00
87 Trichloroethylene 0.00
eo 111 Antimony 0.000
cr> 115 Arsenic 0.000
<•" 118 Cadmium 0.040
119 Chromium, Total 0.009
Chromium, Hexavalent 0.000
120 Copper 0.088
121 Cyanide, Total 0.010
Cyanide, Amn. to Chlor. 0.000
122 Lead 0.047
123 Mercury 0.0090
121 Nickel 0.000
125 Selenium 0.000
126 Silver 36.30
128 Zinc 1.060
Aluminum 0.650
Ammonia 2.00
Iron NA
Manganese 0.013
Phenols, Total 0.011
Oil 6 Grease 0.000
Total Suspended Solids 7.0
pH, Minimum 2.6
pH, Maximum 3.6
NA - Not Analyzed
* - < 0.01
-------
TABLE V-100
POLLUTANT MASS LOADINGS IN THE
SILVER ETCH ELEMENT WASTE STREAMS
Plow (1/Jcg)
Temperature (Deg C)
11 1,1,1-Trichloroethane
13 1,1-Dichloroethane
29 1,1-Dichloroethylene
30 1,2-Trans-dichloroethylene
38 Etbylfcenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetracbloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, ftmn. to Chior.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammcnia
Iron
Manganese
Phenols, Total
Oil 6 Grease
Total Suspended solids
pH, Minimum
pH, Maximum
ng/kf
19.04
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
RA
0.00
0.00
0.00
0.00
0.000
0.000
1.962
0.441
0.000
4.316
0.490
0.000
2.305
0.4414
0.000
0.000
1780.0
51.99
31.88
98.1
NA
0.638
0.539
0.000
343.3
2.6
3.6
NA - Not Analyzed
-------
TABLE V-101
POLLUTANT CONCENTRATIONS IN THE LAUNDRY WASH
AND EMPLOYEE SHOWER ELEMENT HASTE STREAMS
mg/1
Temperature (Deg C) 27.0 28.0 30.0
11 1,1,1-frichloroethane * * *
13 1,1-Dichloroethane 0.00 0.00 0.00
29 1,1-Dichloroethylene 0.00 0.00 0.00
30 1,2-lrans-dichloroethylene 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
64 Pentachlorophenol NA NA NA
66 Bis (2-ethylhexyl) phthalate NA MA NA
70 Diethyl phthalate * * *
85 letrachloroethylene 0.00 0.00 0.00
86 loluene 0.00 0.00 0.00
87 irichloroethylene * * *
114 Antimony NA 0.000 0.000
115 Arsenic NA 0.000 0.000
118 Cadmium NA 0.071 0.100
119 Chromium, Total NA 0.000 0.000
Chromium, Hexavalent NA 0.000 0.000
120 Copper NA 0.230 0.450
121 Cyanide, Total 0.030 0.014 0.000
Cyanide, Amn. to Chlor. Ill
122 lead NA 0.000 0.043
123 Mercury NA 9.40 I
124 Nickel NA 0.000 0.025
125 Selenium NA 0,000 0.000
126 Silver NA 1.460 0.4300
128 Zinc NA 0.820 1.220
Aluminum NA 0.160 0.160
Ammonia NA NA MA
Iron NA NA NA
Manganese NA 0.350 0.400
Phenols, Total 0.190 0.053 0.081
Oil 6 Grease 270.0 5.2 14.0
Total Suspended Solids 42.0 72.0 23.0
pH, Minimum 4.7 6.4 5.5
pH, Maximum 7.7 7.2 6.9
I - Interference
NA - Not Analyzed
* - < 0.01
-------
TABLE V-102
POIiOTAOT CONCENTRATIONS IN THE
HANDATOBX EMPWXEE HASH ELEMENT HASTE
STREAMS
00
temperature (Deg C) 17.0
11 1,1,1 - Trichloroethane 0.00
13 1,1 - Dichloroethane NA
29 1,1 - Dichloroethane NA
30 1,2 - Trans-dichloroethylene NA
3 8 Ethylfcenzene NA
«H Methylene chloride 0.00
55 Naphthalene NA
64 Pentachlorophenol 0,00
66 Bis (2-etbylhexyl)phthalate *
70 Diethyl phthalate NA
85 letrachloroethylene NA
86 Toluene NA
87 Trichloroethylene 0.00
114 Antimony 0.000
115 Arsenic 0.000
118 Cadntium 0.000
119 Chromium, Total 0.000
Chromium, Hexavalent 0.000
120 Copper 0.027
121 Cyanide, Total 0.000
Cyanide, Amn. to Chlor. 0.000
122 lead 0.000
123 Mercury 0.0000
121 Nickel 0.000
125 Selenium NA
126 Silver 0.0000
Zinc 0.100
Aluminum NA •
Ammonia 6.23
Iron NA
Manqanese 0.230
Phenols, Total 0.022
Oil 6 Grease 8.3
Total Suspended Solids 133.3
pH, Minimum MA
pH, Maximum NA
mg/1
29.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
*
NA
NA
NA
0.00
0.000
0.000
0.000
0.000
0.000
0.014
0.000
0.000
0.000
0.0000
0.000
NA
0.0000
0.150
NA
0.73
NA
0.095
0.035
2.0
84,0
NA
NA
26.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
*
NA
NA
NA
0.00
0.000
0.000
0.000
0.000
0.000
0.024
0.000
0.000
0.000
0.0000
0.000
NA
0.0000
0.150
NA
0.13
NA
0.360
I
42.0
55.0
NA
NA
I - Interference
NA - Not Analyzed
* - < 0.01
-------
TABLE V-103
POLLOTAOT MASS LOADINGS IN
THE MANDATORY EMPLOYEE WASH ELEMENT
- WASTE STREAMS
mg/kg
Flow (1/kq) 0.266
Temperature 17.0
11 1,1,1-Trichloroethane 0.00
13 1,1-Dichloroethane NA
29 1,1-Dichloroethylene NA
30 1,2-Trans-dichloroethylene NA
38 Ethylbenzene NA
«tt Methylene chloride 0.00
55 Naphthalene NA
6H Pentachlorophenol 0.00
66 Bis (2-ethylhexyl)phthalate 0.00
70 Diethyl phthalate NA
65 Tetrachloroethylene NA
86 Toluene HA
87 Trichloroethylene NA
111 Antimony 0.000
115 Arsenic 0.000
118 Cadmium 0.000
119 Chroirium, Total 0.000
Chromium, Hexavalent 0.000
120 Copper 0.007
121 Cyanide, Total 0.000
Cyanide, Amn. to chlor. 0.000
122 lead 0.000
123 Mercury 0.0000
124 Nickel 0.000
125 Selenium NA
126 Silver 0.0000
128 Zinc 0.027
Aluminum NA
Ammonia 1.657
Iron Nft
Manqanese 0.061
Phenols, Total 0.006
Oil & Grease 2.208
Total Suspended Solids 35.46
pH, Minimum . NA
pH, Maximum NA
0.266
29.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
NA
0.000
0.000
0.000
0.000
0.000
0.004
0.000
0.000
0.000
0.0000
0.000
NA
0.0000
0.040
RA
0.19H
NA
0.025
0.009
0.532
22.34
NA
NA
0.266
26.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
NA
0.000
0.000
0.000
0.000
0.000
0.006
0.000
0.000
0.000
0.0000
0.000
NA
0.0000
o.ono
NA
0.035
NA
0.096
I
11.17
14.63
NA
NA
I - Interference
NA - Not Analyzed
-------
TABLE V-104
• POLLUTANT CONCENTRATIONS IN THE REJECT CELL
HANDLING ELEMENT HASTE STREAMS
mg/1
Temperature (Deg C) NA
11 1,1,1 - TrichloEoethane WA
13 1,1 - Diehloroethane NA
29 1,1 - Dichloroethylene NA
30 1,2 - Trans-dichloroethylene NA
38 Ethylfcenzene NA
4i| 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
w 115 Arsenic NA
^ 118 Cadmium 0.023
119 Chromium, Total 0.095
Chromium, Hexavalent NA
120 Copper 5.460
121 Cyanide, Total NA
Cyanide, Ann. to Chior. NA
122 lead 0.311
123 Mercury 17.00
124 Nickel 0.571
125 Selenium NA
126 Silver 3.590
128 Zinc 156.0
Aluminum 106.0
Ammonia NA
Iron 0.565
Manqane se 0.175
Phenols, Total NA
Oil 5 Grease NA
Total Suspended Solids NA
pH, Minimum NA
PH, Maximum NA
NA - Not Analyzed
-------
TABLE V-105
POLLUTANT CONCENTRATIONS IN THE REJECT
CELL HANDLING ELEMENT HASTE STREAMS
mg/1
to
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
61 Pentacblorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 letrachloroethylene
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
Alunrinum
Ammonia
Iron
Manganese
Phenols, Total
Oil 6 Grease
Total Suspended Solids
pH, minimum
pH, maximum
18.0
*
NA
NA
NA
MA
0.00
NA
0.00
0.038
NA.
NA
NA
0.00
0.000
0.100
0.000
0.000
0.000
0.076
0.096
0.008
0.057
0.1700
0.007
NA
0.0000
730.0
NA
5.57
NA
0.021
0.000
13.3
762.0
NA
NA
19.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.078
NA
NA
NA
0.00
0.000
0.190
0.000
0.016
I
0.300
0.000
0.000'
0.000
1,000
0.070
NA
0.0000
495.0
NA
8.89
NA
0.150
0.000
6.0
500.0
NA
NA
18.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
*
NA
NA
NA
0.00
0.000
0. 150
0.000
0.009
0.000
0.320
0.069
0.000
0.000
0.3700
0.180
NA
0.0000
206.0
NA
1.370
NA
0.290
0. 120
19.0
1310.0
NA
NA
I - Interference
NA - Not Analyzed
* - < 0.01
-------
TABLE V-106
POLLUTANT MASS LOADINGS IN THE REJECT
CELL HANDLING ELEMENT WASTE STREAMS
Flow (1/kq) 0.003
Temperature (Deg C) 18.0
11 1,1,1 - Irichloroethane 0.00
13 1,1 - Dichloroethane NA
29 1,1 - Dichloroethylene NA
30 1,2 - Trans-dichloroethylene NA
38 Ethylbenzene NA
««» Methylene chloride 0.00
55 Naphthalene NA
61 Pentachlorophenol 0.00
66 Bis(2-ethylhexyl) phthalate O.OQ
70 Diethyl phthalate NA
85 letrachloroethylene NA
86 Toluene NA
87 Trichloroethylene 0.00
11t Antimony 0.000
115 Arsenic 0.000
118 Cadmium 0.000
119 Chromium, Total 0.000
Chromium, Hexavalent 0.000
120 Copper 0.000
121 Cyanide, Total 0.000
Cyanide, Amn. to Chlor. 0.000
122 lead 0.000
123 Mercury 0.0010
124 Nickel 0.000
125 Selenium NA
126 Silver 0.0000
128 Zinc 1.995
Aluminum NA
Ammonia 0.015
Iron NA
Manganese 0.000
Phenols, Total 0.000
Oil 6 Grease 0.036
Total Suspended Solids 2.082
PH, minimum " NA
FH» maximum NA
mg/kg
0.002
19.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.000
0.000
0.000
0.000
I
0.001
0.000
o.'ooo
0.000
0.0020
0.000
NA
0.0000
0.902
NA
0.016
NA
0.00
0.00
0.011
0.911
NA
NA
0.003
18.0
0.00
NA
NA
NA
NA
0.00
NA
0.00
0.00
NA
NA
NA
0.00
0.000
0.000
0.000
0.000
0.000
0.001
0.000
0.000
0.000
0.0010
0.001
NA
0.0000
0.563
NA
O.OOiJ
NA
0.001
0.000
0.052
3.580
NA
NA
I - Interference
NA - Not Analyzed
-------
TABLE V-107
POLLUTANT CONCENTRATIONS IN THE
FLOOR WASH ELEMENT WASTE STREAM
U3
--J
Temperature (Deg C)
11 1.1.1 - Trichloroethane
13 1,1 - Dictoloroethane
29 1,1 - Dichloroethylene
30 1,2 - Trans-dichloroethylene
38 Ethylfcenzene
ill Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2~ethylhexyl) phthalate
70 Diethyl phthalate
8 5 Tetrachloroethylene
8 6 Toluene
87 Trichlozoethylene
11ft. Antimony
115 Arsenic
118 Cadmium
119 Chrciriuro, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to chlor.
122 lead
123 Mercury
124 Nickel
125 selenium
126 Silver "
128 Zinc
Alujrinun
Ammonia
Iron
Manganese
Phenols, Total
Oil & Grease
Total Suspended solids
PH, minimum
pH, maximum
mg/1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.000
0.000
o.oto
0.350
0,000
0.230
NA
NA
(4.130
I
0.380
0.000
U9.50
600.0
5.830
120.0
NA
0.3UO
NA
NA
2800.0
NA
NA
I - Interference
NA - Sot Analyzed
-------
TABLE V-108
POLLOTANf MASS LOADINGS IN THE
FLOOR HAS! ELEMENT HASTE STREAM
W
11
13
29
30
38
44
55
64
66
70
8 5
86
87
111
115
118
119
120
121
122
123
12«
125
126
128
Plow (I/kg)
Temperature (Deg C)
1,1,1 - Tricbloroetbane
1,1 - Dichloroethane
1,1 - Dichloroethylene
1,2 - Trans-dichloroethylene
Ethylfcenzene
Metbylene chloride
Naphthalene
Pentachlorophenol
Bis (2-ethylhexyl) phthalate
Diethyl phthalate
Tetrachloroethylene
Toluene
Iriehloroethylene
Antimony
Arsenic
Chromium, Total
Chromium, Hexavalent
Copper
Cyanide, Total
Cyanide, Amn. to Chlor.
lead
Mercury
Nickel
Selenium
Silver
Zinc
Aluminum
Ammonia
Iron
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended Solids
pH, minimum
pH, maximum
I - Interference
KA - Not Analyzed
mg/kg
0.296
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
HA
NA
NA
0.000
0.000
0.012
0.103
0.000
0.068
NA
NA
1.221
I
0.112
0.000
14.6H
177.4
1.72W
35.48
NA
0.101
NA
KA
828.0
NA
NA
-------
TABLE V-109
POItUlANT CONCENTRATIONS IN THE EQUIPMENT•WASH ELEMENT WASTE STREAMS
PLANT B
mg/1
PLANT A
Us
Temperature (Deg C)
11 1,1,1 - Triehloroethane
t3 1,1 - Oichloroethane
29 1,1 - Diciiloroethylene
30 1,2 - Irans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentacblorophenol
66 Bis (2-ethylhexylJ phthalate
70 Diethyl phthalate
85 Tetractoloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Ann. to Chior.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, lotal
oil £ Grease
lotal Suspended solids
PH, minimum
pH, maximum
18.8
0.00
*
0.00
0.00
0.00
0,00
0.00
NA
NA
*
0.00
*
0.00
0.000
0.006
0.188
0.000
0.000
0.005
NA
NA
0.005
0.1188
0.128
0.000
0.0344
8.03
0.124
NA
NA
0.020
NA
NA
51.5
12.0
12.2
10.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
*
0.00
0.000
0.100
0,015
0.000
I
NA
NA
NA
NA
0.4000
0.020
0.050
0.0000
0.660
NA
NA
NA
0.000
NA
NA
112.0
11.8
11.8
50.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
*
0.00
*
0.00
0.000
0.090
0.021
0.012
0.000
0.026
NA
NA
0.000
0,0380
0.038
0.070
0.3500
1.UOO
0.000
NA
NA
0.020
NA
NA
68.0
12.0
12.2
NA
*
0.00
0.00
0.00
*
*
*
NA
NA
*
0.00
0.00
0.00
0.000
0.000
0.02«
0.011
0.000
0.042
NA
NA
0.000
0.2200
0.100
0.000
0.960
1.790
0.000
NA
NA
0.072
NA
NA
98.0
5.6
6.5
I - Interference
NA - Not Analyzed
* - < to 0.01
-------
TABLE V-110
POIKJTANT MASS LOADINSS IN fBB EQUIPMENT WASH EtEMENT WASTE STREAMS
PLANT B
P1ANT A
mg/kg
to
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 Ethylfcenzene
44 Metbylene chloride
55 Naphthalene
61 Pentachlorophenol
66 Bis(2-etbylhexyl) 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, fimn. to Chlor.
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 silver
128 2inc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
oil 6 Grease
Total Suspended Solids
pH, minimum
pH, maximum
16.64
18.8
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.097
3.131
0.000
0.000
0.084
NA
NA
0.083
1.977
2.131
0.000
0.5730
133.7
2.057
KA
NA
0.337
NA
NA
856.0
12.0
12.2
6.79
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
0.000
0.679
0.102
0.000
I
NA
NA
NA
NA
2.717
0.136
0.340
0.000
4.484
NA
NA
NA
0.000
NA
NA
761.0
11.8
11.8
3.470
50.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.312
0.073
0.042
0.000
0.090
NA
NA
0.000
0.1320
0.132
0.243
1.214
4.857
0.000
'NA
NA
0.069
NA
NA
235.9
12.0
12.2
5.090
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
0.000
0.000
0.122
0.056
0.000
0.214
NA
NA
0.000
1.120
0.509
0.000
4.887
9.111
0.000
NA
NA
0.366
NA
NA
498.8
5.6
6.5
I - Interference
NA - Not Analyzed
-------
TABLE V-111
STATISTICAL ANALYSIS (mg/1) OF THE EQUIPMENT HASH ELEMENT WASTE STREAMS
OJ
Temperature (Deg C)
11 1,1,1 - Trichloroethane
13 1,1- Dichloroethane
29 1,1 - Dichloroethylene
30 1,2 - irans-dichloroethylene
38 Ethylfcenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylfaexyl) phthalate
70 Diethyl phthalate
85 letrachloroethylene
86 Toluene
87 Trichloroethylene
114 Antimony
115 Arsenic
118 Cadirium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chlor.
122 Lead
123 Mercury
121 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
Oil 5 Grease
Total Suspended Solids
pH, minimum
pH, maximum
UNI MUM
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
0.000
0.000
0.015
0.000
0.000
0.005
NA
NA
0.000
0.0380
0.020
0.000
0.0000
0.660
0.000
NA
NA
0.000
NA
NA
51.4
5.6
6.5
MAXIMOM
50.0
*
*
0.00
0.00
*
*
*
NA
NA
*
0.00
*
0.00
0.000
0.100
0.188
0.012
0.000
0.042
NA
NA
0.005
0.4000
0.128
0.070
0.960
8.03
0.124
NA
NA
0.072
NA
NA
112.0
12.0
12.2
MEAN
19.3
*
*
0.00
0.00
*
*
*
NA
NA
*
0.00
*
0.00
0.000
0.0«9
0.062
0.006
0.000
0.024
NA
NA
0.002
0.1942
0.072
0.030
0.3361
2.971
0.041
NA
NA
0.028
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
0.000
0.048
0.023
0.006
0.000
0.026
NA
NA
0.000
0.1694
0.069
0.025
0.1922
1.595
0.000
NA
NA
0.020
NA
NA
83.0
11.9
12.0
f
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
1
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
NA - Not Analyzed
* - < 0.01
-------
TABLE V-112
STATISTICAL ANALYSIS (mg/kg) OF THE EQUIPMENT HASH ELEMENT HASTE STREAMS
MINIMUM
MAXIMUM
MEAN
MEDIAN
CO
«-J
00
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 Ethylhenzene
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
Chrcmium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn. to Chior.
122 lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manqanese
Phenols, Total
Oil & Grease
Total Suspended Solids
pH, minimum •
pH, maximum
3.470
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
0.000
0.000 .
0.073
0.000
0.000
0.084
NA
NA
0.000
0.1320
0.132
0.000
0.0000
4.484
0.000
NA
NA
0.000
NA
NA
235.9
5.6
6.5
16.64
50.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.679
3.131
0.056
0.000
0.214
NA
NA
0.083
2.717
2.131
0.340
4.887
133.7
2.057
NA
NA
0.366
NA
NA
856.0
12.0
12.2
8.00
19.3
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.272
0.857
0.024
0.000
0.129
NA
NA
0.028
1.486
0.727
0.146
1.668
38.03
0.686
NA
NA
0.193
NA
NA
587.9
10.4
10.7
5.942
18.8
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.205
0.112
0.021
0.000
0.090
NA
NA
0.000
1.548
0.322
0.121
0.894
6.98
0.000
NA
NA
0.203
NA
NA
630.0
11.9
12.0
NA - Not Analyzed
-------
TABLE V-113
POLLUTANT CONCENTRATIONS IN THE SILVER POWDER
PRODUCTION ELEMENT HASTE STREAMS
mg/1
Temperature {Deg C)
11 1,1,1 - Iriehloroethane
13 1,1 - Dichloroethane
29 1,1 - Dichloroethylene
30 1,2 - Trans-dichloroethylene
38 Ethylkenzene
1H Methylene chloride
55 Naphthalene
6i| Pentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Dlethyl phthalate
8 5 Tetracbloroethylene
86 Toluene
87 irichloroethylene
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
Manqanese
Phenols, Total
Oil 6 Grease
Total Suspended solids
PH, minimum
pH, maximum
14.0
0.00
0.00
0.00
0.00
0.00
*
0.00
NA
MR
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.700
0.000
4.350
NA
NA
0.160
0.0080
0.610
0.000
12.00
0.180
3.400
NA
MA
0.110
NA
NA
27.0
2.0
2.6
15.0
0.00
0.00
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.007
1.520
0.000
10.50
NA
NA
0.280
0.0000
1.450
0.000
24.10
0.440
12.00
NA
NA
0.078
NA
NA
23.0
2.2
2.5
14.0
0.00
0.00
0.00
0.00
0.00
*
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
0.000
0.000
0.580
0.000
4.370
NA
NA
0.000
0.0000
0.570
0.000
13.90
0.380
0.180
NA
NA
0.100
NA
NA
13.0
2.1
2.5
NA - Not Analyzed
* - < 0.01
-------
TABLE V-11*
POLMJTANT MASS LOADINGS IN T8E SILVER POHDER
PRODOCTION ELEMENT HASTE STREAMS
mg/kg
oo
o
Flow (I/kg)
Temperature (Deg C)
11 1,1,1 - Trichloroethane
13 1,1 - Dicnloroethane
29 1r1 - Dichloroethylene
30 1,2 - Irans-dichloroethylene
3 8 Ethvlfcenzene
44 Methylene chloride
5 5 Naphthalene
64 Eentachlorophenol
66 Bis (2-ethylhexyl) phthalate
70 Diethyl phthalate
85 Tetrachloroethylene
86 Toluene
87 Irichloroethylene
11 ft Antimony
115 Arsenic
118 Cadmium
119 Chromium, Total
Chrcmium, Hexavalent
120 copper
121 Cyanide, Total
Cyanide, Ann- to Chlor.
122 lead
123 Mercury
12H Nickel
125 Selenium
126 Silver
128 2inc
Aluminum
Ammonia
Iron
Manganese
Phenols, Total
oil & Grease
Total Suspended solids
pH, minimum
pH, maximum
23.72
14.0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HA
NA
0.00
0,00
0.00
0.00
0.000
0.000
0.000
16.60
0.000
103.1
NA
NA
3.794
0.1897
14.46
0.000
284.5
4.268
80.6
NA
MA
2.608
NA
NA
641.0
2.0
2.6
20.14
15.0
0.00
0.00
0.00
a. oo
0.00
0.00
0.00
NA
NA
0,00
0.00
0.00
0.00
0.000
0.000
0.141
30.61
0.000
211.5
NA
NA
5.64
0.0000
29.20
0.000
485.4
8.86
241.7
NA
NA
1.571
NA
NA
463.3
2.2
2.5
19.80
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
0.000
0.000
0.000
11.48
0.000
86.6
HA
NA
0.000
0.0000
11.29
0.000
275.2
7.52
9.50
NA
NA
1.980
NA
NA
257.4
2.1
2.5
HA - Not Analyzed
-------
TABLE V-115
POLLUTANT CONCENTRATIONS IN THE
SILVER PEROXIDE PRODUCTION ELEMENT WASTE STREAMS
mg/1
Temperature (Deg C) NA
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 *
55 Naphthalene 0.00
64 Pentachlorophenol NA
66 Eis (2-ethylhexyl) phthalate NA
70 Diethyl pbthalate 0.00
85 Tetracbloroethylene 0.00
86 loluene 0.00
87 Trichloroethylene 0.00
114 Antimony 0.000
115 Arsenic 5.910
w 118 Cadmium 0.000
2 119 Chromium, Total 0.090
Chromium, Hexavalent I
120 Copper 0.000
121 Cyanide, Total NA
Cyanide, Amn. to Chior. NA
122 lead 0.000
123 Mercury 0.0370
124 Nickel 0.000
125 Seleniw 4.800
126 Silver 0.770
128 Zinc 0.075
Aluminum 0.000
Ammonia NA
Iron NA
Manganese 0.000
Phenols, Total NA
Oil & Grease NA
Total suspended Solids 31.0
pH, Minimum 11.0
pH, Maximum 12.5
I - Interference
NA - Not Analyzed
* - < 0.01
-------
TABLE V-116
POLLUTANT MASS LOADINGS IN THE
SILVER PEROXIDE PRODUCTION ELEMENT HASTE STREAMS
LO
oo
N>
Flo« (1/kq)
Temperature (Deg C)
11 1,1,1-Irichloroethane
13 1,1-Dichloroethane
29 1,1-Dicbloroethylene
30 1,2-Trans-dichloroethylene
38 Ethylbenzene
44 Methylene chloride
55 Naphthalene
64 Pentachlorophenol
66 Bis(2-ethylhexyl) phthalate
70 Diethyl phthalate
85 52trachloroethylene
86 Toluene
87 Srichloroethylene
111 Antimony
115 Arsenic
118 Cadnium
119 Chromium, Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
Cyanide, Amn, to Chlor.
122 lead
123 Mercury
12U Nickel
125 Selenium
126 Silver
128 Zinc
Alurninum
Ammonia
Iron
Manqanese
Phenols, lJtal
Oil & Grease
Total suspended solids
pB, Minimum
pH, Maximum
I - Interference
NA - Not Analyzed
mg/kf
14.28
NA
0.00
0.00
0.00
0.00
0.00
0.043
0.00
NA
NA
0.00
0.00
0.00
0.00
0.000
84.
-------
TABLE V-117
ANALYSIS (mg/i) OP THE
ZINC StIBCATIGORY TOTAL SAW WASTE CONCENTRATIONS
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 Trictoloroethylene
114 Antimony
(jj 115 Arsenic
00 118 Cadmium
w 119 chromium. Total
Chromium, Hexavalent
120 Copper
121 Cyanide, Total
. Cyanide, Ann. to Chlor.
122 Lead
123 Mercury
124 Hickel
125 Selenium
126 Silver
128 Zinc
Aluminum
Ammonia
Iron
Manqanese
Phenols, Total
Oil & Grease
Total Suspended Solids
PH, Minimum
pi!, Maximum
MINIMUM
7.1
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
*
0.00
0.00
0,00
0.00
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.0007
0.000
0.000
0.0000
0.026
0.000
0.15
0.099
0.000
0.000
0.5
3.4
1.0
9.8
MAXIMUM
30.0
7.79
0.033
1.187
0.030
*
0.649
0.031
*
3.816
*
0.046
0.204
0.723
0.130
0.148
0.460
30.00
0.000
2.881
0.106
0.005
0.196
29.98
20.29
0.012
12.20
156.9
2.109
7.98
4.000
58.67
3.570
31200.
6460.0
10.8
13.5
MEAN
23.8
0.340
0.002
0,079
0.002
*
0.028
*
*
0.632
*
0.003
0.014
0.032
0.006
0.034
0.064
2.901
0.000
0.464
0.011
0.002
0.031
3.409
2.300
0.001
1.830
31.21
0.466
2.60
2.639
5.661
0.352
2230,0
636.0
6.7
11.9
MEDIAN
16.8
*
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.028
0.00
0.00
0.00
0.00
0.000
0.004
0.014
0.036
0.000
0.103
0.001
0.000
0.000
0.1085
0.064
0.000
0. 1243
13.30
0.148
1.10
3.819
0.069
0.016
13.9
80.2
7.9
12.1
i
VAL
19
12
7
5
2
2
10
7
1
8
7
3
7
10
1
13
18
21
0
22
8
5
10
21
22
3
16
23
12
9
3
21
15
16
23
20
20
ZEROS
0
11
8
10
13
13
13
8
7
0
B
12
8
13
22
9
5
2
20
0
5
7
12
0
0
13
7
0
3
0
0
2
1
0
0
0
0
PTS
,19
23
15
15
15
15
23
15
8
8
15
15
15
23
23
22
23
23
20
22
13
12
22
21
22
16
23
23
15
9
3
23
16
16
23
20
20
* - < 0.01
-------
TABLE V-118
TREATMENT IN-PLACE AT ZINC SUBCATEGORY PLANTS
IlilELIS TREATMENT IN-PLACE DISCHARGE V
A Chemical reduction I
B pH adjust, settling, filtration D
C Settling, pH adjust, in-process Cd, I
Ni recovery
D Settling D
E Filtration, carbon adsorption, D
lagooning
F None Zero
G None Zero
H pH adjust, settling Zero 2/
w I pH adjust I ""
4> J Skimming, sand filter, amalgamation, I
carbon adsorption
K pH adjust, coagulant addition, sulfide I
precipitation, clarification
L pH adjust, coagulant addition, sulfide I
precipitation, clarification
M None I
. N Settling, sand filtration, carbon I
adsorption
O Chemical reduction, settling I
P chemical reduction, settling I
Q Settling (upgraded to settling, I
filtration, ion exchange, metal
recovery)
J/ I * Indirect
D * Direct
2/ Not presently active in this subcategory
-------
TABLE V-119
PRACTICES AND EFIUHHT QUALTn AT ZDC SUBCA3EHMK PLANE EFFUENT ANALYSIS
PUOT ID Treatnent Cd
A pH Adjust Settle-
Filter
B Settle 0.20
C Settle 0.10
PtltHr-Carbon ND
MsocptLon
^ D Sklnrillter-Carbon
E pH Adjust-Chem
Precipitation
Settle-Filter
F pH Mjust-Oiem
Precipitation-Settle
G None
H Filter-Carbon
Adsorption
J flnalganation-Settle
K Settle
Cr Cu
0.8
Cn
0.10
0.21
8.
10.
<0.005 0.047
0.0403
Pb Hg
0.04
1.0 0.005
0.01 0.8
10.
0.01
0.0017 10.
0.0086
0.20
0.01
0.13
0.0005 ND
Ag
Zn NH
1.3
2.0
Fe
TSS
0.16 0.02 274.
10.
.37
2.1
0.70
0.74
0.03
0.076 3.99
0.011 0.33 0.005 1.24 0.291 8.
0.006 0.19 <0,005 0.143 0.194 15.
10.
pH
30. 6.0-9.5
2.52 0.84
10. 0.50 10.
4.1
2.9 92.
0.281 200.
11.7
0.235
11.2
8.2
ND - Not Detected
-------
00
TABLE V-120
PERFORMANCE OF SUWIDE
PRECIPITATION ZINC SOBCATEGORY
Plant A
Plant B
118
119
120
121
122
123
124
126
128
Pollutant
Pollutant
Cadrrium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Silver
Zinc
Iron
Manqanese
or Day 1
Parameter
Haw
Waste
0.000
2H.HO
0.097
0.015
0.000
I
0.430
0.000
13.30
NA
1.500
Oil 8 Grease 31220.0
1SS
1700.0
pH Minimum 7.8
cl-l Maximum
I
NA
9.8
(mg/1)
Day 2
(mg/1)
Raw
Effluent Haste
0.000
0.210
0.014
0.000
0.000
0.000
0.075
0.012
26.50
HA
1.890
7.0
5.0
6.8
6.9
0.000
30.00
0.500
0.000
0.000
0.2654
0.800
0.000
40.00
4.000
30.00
3340.0
4600.0
7.8
9.8
Effluent
0.000
1.000
0.000
0.000
0.000
0.0197
0.000
0.000
7.00
2.000
0.900
14.0
26.0
7.0
7.0
Zinc
Subcat
Only
(mg/1)
Effluent
0.000
0.005
0.032
0.032
0.000
I
0.035
0.013
0.100
NA
0.760
2.9
26.0
6.8
7.3
Combined Wastes
(Including HgO
Production)
(«g/i)
Raw
Waste Effluent
0.160 0.000
2.130 0.000
0.078 0.047
0.000 0.053
0.000 0.000
110.0 0.060
0.000 0.000
0.088 0.000
21.00 0.226
2.06 62.8
0.450 0.377
6.7 380.0
270.0 380.0
- _
*** ""*
Analytical Interference
Not Analyzed
-------
TABLE V-121
PERFORMANCE OF LIME, SETTLE, AND
FILTER - ZINC SUBCATESORY
TREATMENT SYSTEM I
TREATMENT SYSTEM II
to
QO
118 Cadmium
119 Chromium (Total)
120 copper
121 Cyanide
122 Lead
123 Mercury
121 Nickel
126 Silver
128 Zinc
Iron
Manganese
cil 6 Grease
1SS
pH minimum
pH ffaximum
Day 1
Raw
Waste
0.026
0.000
NA
0.000
NA
0.000
59.0
NA
0.220
NA
NA
2.4
96.0
7.7
10,9
Effluent
0.490
0.000
NA
0.000
NA
0.000
1.760
NA
0.016
NA
NA
1.2
0.0
8.9
8.9
Raw
Waste
0.004
0.000
NA
0.000
NA
0.000
1.960
NA
0.150
NA
NA
3.0
28.0
8.5
10.5
Day 2
Effluent
0.140
0.000
NA
0.000
NA
0.000
0.800
NA
0.000
Nfi
NA
0.0
0.0
8.5
10.5
Day
Raw
Waste
2.040
0.081
NA
0.000
NA
100.0
1100.0
NA
9.26
NA
NA
1.5
401.0
2.1
2.1
3
Effluent
0.067
0.006
NA
0.000
NA
0.000
0.500
NA
0.000
NA
NA
1.5
0.0
9.8
9.8
Day
Raw
Haste
0.071
0.025
0.300
NA
0.078
0.100
0.000
0.120
53.0
NA
0.010
NA
122.0
11.9
11.9
2
Effluent
0.012
0.014
0.081
NA
0.000
0.074
0.000
0.025
9.57
NA
0.210
NA
30.0
11.9
11.9
Day
Raw
Waste
0.058
0.059
0.610
NA
0,140
0.160
0.023
0.270
129.0
NA
0.006
NA
96.0
11.4
11.4
3
Effluent
0.004
0.018
0.200
HA
0.000
0.080
0.020
0.007
7.02
NA
0.000
NA
32.0
9.4
9.9
TREATMENT SYSTEM III
TREATMENT SYSTEM IV
118 Cadirium
119 Chromium (Total)
120 Copper
121 Cyanide
122 Lead
123 Mercury
124 Nickel
126 Silver
128 Zinc
Iron
Manqanese
Oil 6 Grease
1SS
pH minimum
pH maximum
Day
Raw
Haste
0.000
0.700
4.35
NA
0.160
0.008
0.610
12.00
0.180
NA
0.110
NA
27.0
2.0
2.6
1
Effluent
0.029
0.020
26.8
NA
0.000
0.000
0.620
0.220
1.410
NA
0. 160
NA
51.0
6.7
11.4
Day
Raw
Waste
0.007
1.520
10.50
NA
0.280
0.000
1.450
24.10
0.440
NA
0.078
NA
23.0
2.2
2.5
2
Effluent
0.008
0.059
29.90
NA
0.000
0.000
0.550
0.240
3.090
NA
0.010
NA
216.0
9.2
9.2
Day
Raw
Waste
0.000
0.580
4.370
NA
0.000
0.000
0.570
13.90
0.380
NA
0.100
NA
13.0
2.1
2.5
3
Effluent
0.011
0.018
15.30
NA
0.000
0.030
0.500
0.270
2.840
NA
0.090
NA
18.0
9.9
9.9
Raw
Waste
0.008
0.007
4.110
NA
0.200
0.009
0.050
0.320
29.40
NA
0.024
NA
86.0
11.8
11.8
Effluent
0.000
0.005
0.100
NA
0.000
0.008
0. 130
0.042
1.180
NA
0.011
NA
17.0
9.2
9.2
-------
TABLE V-122
PERFORMANCE OF AMALGAMATION - ZINC SUECATEGORY
mg/1
Plant A
Day 2 Day 3
118 Cadmium 0.008 0.007
119 Chrarium 0.018 0.006
120 Copper 0.110 0.200
122 Lead 0 0.036
123 Mercury 0.083 0.370
124 Nickel 0.015 0.019
126 Silver 0 0
128 Zinc 190..0 64.0
Manganese 0.20 0.15
Oil 8 Srease 5.7 0
ISS 395.0 370.0
OJ
00
00 Plant B
Before Amalgamation After Amalgamation
118 Cadmium 0.008 0.0
119 Chromium 15.10 15.60
120 Copper 0.300 0.720
122 Lead 016.40 7.88
123 Mercury 30000.0 2600.0
124 Nickel 9.10 7.30
126 Silver 0.046 0.120
128 Zinc 1200.0 870.0
Manqanese 0.980 12.60
Oil & Grease NA 14.0
ISS 11.0 220.0
pH .1.0 1.6
NA - Not analyzed
-------
TABLE V-123
PERFORMANCE OF SKIMMING, FILTRATION, AMALGAMATION,
AND CARBON ADSORPTION - EINC S0BCATIGORY
u>
00
118 Cadn-iura
119 Chromium
120 Copper
122 Lead
123 Mercury
121 Nickel
126 Silver
128 Zinc
Manganese
Oil 6 Grease
1SS
PH
Day 1
0.110
0.061
0.420
0.0
I
0.500
0.0
736.0
4.60
58.0
100.0
12.8 - 13.6
mg/1
Day 2
0.078
0.017
0.500
0.0
I
1.29
0.0
480.0
9.60
69.0
9.0
11.8 - 13.2
Day 3
0.010
0.004
0.330
0.0
I
0.82
0.0
455.0
7.10
37.0
69.0
11.4 - 13.2
I - Analytical interference
-------
TABLE V-124
PERFORMANCE OP SETTLING, FILTRATION AND ION
EXCHANG1 - ZINC SUBCATEGORY
mg/1
Day 2 Day 3
118 Cadmium 0.026 0.024
119 Chroiritun 0.027 0.036
120 Copper 0.033 0.042
122 Lead 0.0 0.0
123 Mercury 0.021 0,059
124 Nickel 0.0 0.0
126 Silver 1.13 0.880
128 Zinc 0.94 0.59
Manganese 0.007 0.005
TSS 36.0 44.0
pH 12.1 12.6
-------
ELECTROLYTE RAW
MATERIALS
Id
Q
ELECTROLYTE
PREPARATION
WASTEWATER
ANODE
PREPARATION
ANODE
CATHODE
CATHODE
PREPARATION
g<
s
s
WASTEWATER
CELL
WASH
WASTEWATER
PRODUCT
FLOOR
AND EQUIPMENT
WASH
WASTEWATER
EMPLOYEE
WASH
WASTEWATER
SPECIAL
CHEMICALS
AND
METALS
PRODUCTION
WASTEWATER
FIGURE V-l
GENERALIZED CADMIUM SUBCATEGORY MANUFACTURING PROCESS
391
-------
Grouping
Anode
Manufacture
FIGURE V-2
CADMIUM SUBCATEGOKf ANALYSIS
Element Specific Wastewater Sources (Subelements)
Pasted and Pressed Powder , Process Area Clean-up
Blectrodeposited
Impregnated
Cathode
Manufacture
Silver Powder Pressed
Nickel Pressed Powder
Nickel Electrodepositsed
Nickel Impregnated
Ancillary
Operations
Mercuric Oxide Powder
Pressed
Cell Wash
Product Rinses
Spent Caustic
Scrubbers
Sintered Stock Preparation Clean-up
Inpregnated Rinses
Spent Impregnation Caustic
Product Cleaning
Pre-forroation Soak
Spent Formation Caustic
Post-formation Rinse
No Process Wastewater
No Process Wastewater
Spent Caustic
Post-formation Rinse
Sintered Stock Preparation Clean-up
Impregnation Rinses
Inpregnation Scrubbers
Product Cleaning
Impregnated Plague Scrub
Pre-formation Soak
Spent Formation Caustic
Post Formation Rinses
Inpregnation Equipment Wash
Nickel Recovery Filter Wash
Nickel Recovery Scrubber
No Process Wastewater
Cell Wash
392
-------
Grouping
Ancillary
Operations
FIGURE V~2
CADMIUM SUBCMEGOm? ANALYSIS
Element Specific Wastewater Sources (Subelements)
Electrolyte Preparation . Equipment Wash
Floor and Equipment Wash
Employee Wash
Cadmium Powder Production
Floor and Equipment Wash
Employee Wash
Product Rinses
Scrubber
Silver Powder Production . Product Rinses
Nickel Hydroxide Production . Product Rinses
Cadmium Hydroxide Production . Seal Cooling Water
393
-------
CADMIUM NITRATE,
HYDROGEN PEROXIDE
SOLUTION
PREPARATION
SCRUBBERS
GRID-
ELECTRO-
DEPOSITION
WASTEWATER
WATER'
RINSE
RINSE WASTEWATER
DISCHARGE
CAUSTIC SOLUTION
FORMATION
CAUSTIC SOLUTION PROCESS
"REUSE OR DISCHARGE
WATER-
RINSE
RINSE WASTEWATER
DISCHARGE
FINISHED ANODES
• •»' TO ASSEMBLY
FIGURE V-3
PRODUCTION OF CADMIUM ELECTRODEPOSITED ANODES
394
-------
SINTERED
STOCK
PREPARATION
WASTEWATER
CADMIUM NITRATE.
SINTERED GRIDS-
CAUSTIC SOLUTION-
WATER.
SOLUTION
PREPARATION
IMPREGNATION
SCRUBBERS
IMMERSION
RINSE
WASTEWATER
TO 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-4
PRODUCTION OF CADMIUM IMPREGNATED ANODES
395
-------
NICK.E1. Nil KATfc,
COBALT NITRATE
GRIDS
*
CAUSTIC
SOLUTION
WATER
SOLUTION
PREPARATION
I
ELECTRODE-
POSITION
1
FORMATION
1
RINSE
CAUSTIC SOLUTION PROCESS
REUSE OR DISCHARGE
RINSE WASTEWATER
DISCHARGE
FINISHED CATHODES
TO ASSEMBLY
FIGURE V-5
PRODUCTION OF NICKEL ELECTRODEPOSITED CATHODES
396
-------
NICKEL NITRATE,
COBALT NITRATE
SOLUTION
PREPARATION
SCRUBBERS
T
SINTERED GRIDS'
CLEAN-UP
WASTEWATER DISCHARGE
IMPREGNATION
WASTEWATER
CAUSTIC SOLUTION-
IMMERSION
WASTER'
I
RINSE
WATER-
TO REUSE OR SPENT
CAUSTIC DISCHARGE
CLEANING
CAUSTIC SOLUTION
FORMATION
WATER-
RINSE
RINSE WASTGWATER
DISCHARGE
TO REUSE OR RINSE
WASTEWATER DISCHARGE
SPENT CAUSTIC
DISCHARGE
RINSE WASTEWATER
DISCHARGE
TO ASSEMBLY
FINISHED
CATHODES
FIGURE V-6
PRODUCTION OF NICKEL, IMPREGNATED CATHODES
397
-------
BLEND DEPOLARIZER
AND ELECTROLYTE
HEATING
COMPONENT
PREPARATION
DEPOLARIZER
PREPARATION
WASTEWATER
ASSEMBLY
T
ANODE
MANUFACTURE
SHIP
CELL
TESTING
WASTEWATER
FIGURE V-7
GENERALIZED CALCIUM SUBCATEGORY MANUFACTURING PROCESS
398
-------
Grouping
Anode
Manufacture
Cathode
Manufacture
Ancillary
FIGURE V-8
CALCIUM SUBCATEGORY ANALYSIS
Element
Vapor Deposited
Fabricated
Calcium Chroraate
Tungstic Oxide
Potassium Bichromate
Heating Component Production:
Heat Paper
i
Heat Pellet
Cell Tasting
Specific Wastewater Sources
(Subelements)
. No Process Wastewater
. No Process Wastewater
. No Process Wastewater
. No Process Wastewater
. No Process Wastewater
Slurry Preparation
Filtrate Discharge
. No Process Wastewater
. Leak Testing
399
-------
ELECTROLYTE
RAW
MATERIALS
SEPARATOR
RAW
MATERIALS
i
ELECTROLYTE
FORMULATION
i
SEPARATOR
PREPARATION
WASTEWATER
ZINC
, i
| ANODE
! Mff"T*JttL
! FORMING
ANODE
A
i
SSEMBL
i
CATHODE RAW
MATERIALS
*
CATHODE
PREPARATION
f
PRODUCT
MISCELLANEOUS TOOLS
AND EQUIPMENT FROM
ALL OPERATIONS
EQUIPMENT
AND AREA
CLEANUP
WASTEWATER
• OPERATION NOT REGULATED IN BATTERY
MANUFACTURING POINT SOURCE CATEGORY
FIGURE V-9
GENERALIZED SCHEMATIC FOR LECLANCHE CELL MANUFACTURE
400
-------
FIGURE V-10
IBCLANCHE SUBCMBGOm ANALYSIS
Grouping
Anode
Manufacture
Cathode
Ancillary
Operations
Element
Zinc Powder
Manganese Dioxide - Pressed
- Electrolyte with Mercury
- Electrolyte without
Mercury
- Gelled Electrolyte with
Mercury
Carbon (Porous)
Silver Chloride
Manganese Dioxide - Pasted
Separators
Cooked Paste
tticooked Paste
Pasted Paper with Mercury
Equipment and Area
Cleanup
Specific Wastewater Sources
. No Process Wastewater
. No Process Wastewater
Foliar Battery
Miscellaneous Wash
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
Miscellaneous Equipment and
Area Wash
401
-------
ANODE
MANUFACTURE
HEATING COMPONENT
PREPARATION
(THERMAL CELLS ONLY)
DEPOLARIZER
PREPARATION
WASTEWATER
BLEND
DEPOLARIZER
ELECTROLYTE
ELECTROLYTE
WASTEWATER
LITHIUM SCRAP
DISPOSAL
WASTEWATER
PRODUCT
•" 1* WASTEWATER
FLOOR AND
EQUIPMENT
WASH
WASTEWATER
AIR SCRUBBERS
• WASTEWATER
FIGURE V-11
GENERALIZED LITHIUM SUBCATEGORY MANUFACTURING PROCESS
402
-------
FIGURE V-12
LITHIUM sroc&TEGoror ANALYSIS
Grouping
Anode
Manufacture
Cathode
Manufacture
Element
Formed and Stamped
Specific Wastewater Sources
(Subelements)
. No Process Wastewater
Ancillary
Operations
Iodine
Iron Bisulfide
lead Iodide
Lithium Perchlorate
Sulfur Dioxide
iMonyl Chloride
Titanium Disulfide
Heating Component Production:
Heat Paper
Heat Pellets
Lithium Scrap Disposal
Cell "testing
Floor and Equipment Wash
Mr Scrubbers
Cell Wash.
Ho Process Wastewater
Product Treatment
Equipment Wash
No Process Wastewater
Spills*
Spills*
No Process Wastewater
Filtrate Discharge
Slurry Preparation
No Process Wastewater
Scrap Disposal
'Leak Ttesting
Floor and Equipment Wash
Slowdown from various
production areas
Cell Wash
* - Wastewafcer discharged from air scrubbers for the manufacture of
these cathodes is included with ancillary operations.
403
-------
WASTEWATER
1 ANODE |
| METAL j
I FORMING 1
1 - - n
i
J CLEAN St I
1 CHROMATE •
1 . 1
ELECTROLYTE
PREPARATION
f
WASTEWATER
ANOC
>E
CELL
TEST
1
SEPARATOR uifiCTc-waTFR DEPOLARIZER
PREPARATION ^WASTEWATER PREPARATION
"1
ASSE
i
PROI
'
CATHODE
«BLY MANUFACTURE
I ». v
HEATING
COMPONENT PREP, WAS"
(THERMAL CELLS
ONLY)
3UCT
WASTEWATER
SUPPORT
WASTEWATER
WASTEWATER
WASTEWATER
-OPERATIONS NOT REGULATED IN BATTERY
MANUFACTURING POINT SOURCE CATEGORY
FIGURE V-13
GENERALIZED MAGNESIUM SUBCATEGORY MANUFACTURING PROCESS
-------
FIGURE V-14
MAGNESIUM SUBCATEGORY ANALYSIS
Grouping
Anode
Manufacture
Cathode
Manufacture
Ancillary
Operations
Element
Magnesium Powder
Carbon
Copper Chloride
Copper Iodide
Lead Chloride
M-Dinitrobenzene
Silver Chloride -Chemically
Reduced
Silver Chloride-Electro-
lytic
Silver Chloride
Vanadium Pentoxide
Heating Conponent
Production:
Heat Paper
Heat Pellets
Cell Testing
Separator Processing
Floor and Equipment Wash
Air Scrubbers
Specific Wastewater Source
(Subelements)
. 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
No Process Wastewater
Filtrate
Slurry Preparation
No Process Wastewater
Activation of Sea-Water
Reserve Batteries
Etching Solution
Product Rinsing
Floor and Equipment Wash
Blowdown front Various
Production Areas
405
-------
ANODE RAW
MATERIALS
CATHODE RAW
MATERIALS
I
AMALGAMATION
WASTEWATER
ELECTROLYTE
RAW MATERIALS
CHEMICAL
PREPARATION
OF
DEPOLARIZER
WASTEWATER
mi !••
ANODE
PREPARATION
WASTEWATER
ANODE
FORMATION
WASTEWATER
SPECIAL
CHEMICALS,
METALS
PRODUCTION
CATHODE
PREPARATION
WASTEW
ELECTROLYTE
PREPARATION
ANODE
-*•
WASTEWATER
CATHODE
FORMATION
ASSEMBLY
EMPLOYEE
WASH
WASTEWATER
CATHODE
WASTEWATER
~i
REJECTS
CELL WASH
WASTEWATER
i
REJECT CELL
HANDLING
WASTEWATER
I
PRODUCT
FLOOR AND
EQUIPMENT
WASH
WASTEWATER
SILVER
ETCH
WASTEWATER
FIGURE V-15
GENERALIZED ZINC SUBCATEGORY MANUFACTURING PROCESSES
406
-------
FIGURE V-16
ZINC SUBCATEGORY 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 Amalgam Rinses
Floor Area and Equipment Clean-up
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
Silver Powder Pressed and
Electrolytically Oxidized
(Formed)
No Process Wastewater
No Process Wastewater
Post-formation Rinse
407
-------
Grouping
Cathode
Manufacture
(Contd.)
Ancillary
Operations
FIGURE V-16
ZINC SUBCATEGORY ANALYSIS
Element
Silver Oxide (Ag20)
Powder
Specific Wastewater Sources
. No Process Wastewater
Silver Oxide (Ag20)
Powder - Thermally Reduced
or Sintered, Electrolytically.
Stormed
Silver Peroxide (AgO) Powder .
Nickel Impregnated and Formed
Cell Wash
Electrolyte Preparation
Silver Etch
Mandatory Employee Wash
Reject Cell Handling
Floor Wash and 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
Analysis (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 and Equipment Wash
Product Rinse
Product Rinses
Spent Solution
408
-------
ZINC, MERCURY
SOLUTION
MIX
WATER
RINSE
RINSE WASTE WATER
DISCHARGE
METHANOL
METHANOL
RINSE
CONTRACTOR REMOVAL
OF SPENT METHANOL
DRY
DRY POWDERED
AMALGAM
-ft*- TO ASSEMBLY
FIGURE V-17
PRODUCTION OF ZINC POWDER - WET AMALGAMATED ANODES
409
-------
ZINC, MERCURY,
ELECTROLYTE
MIX
I
GELLING AGENT
BLEND
TO ASSEMBLY
WATER
EQUIPMENT
AND FLOOR
AREA WASH
WASH WASTEWATER
DISCHARGE
FIGURE V-18
PRODUCTION OF ZINC POWDER GELLED AMALGAM ANODES
410
-------
ZINC OXIDE AND
MERCURIC OXIDE
POWDERS
MIX
BINDING AGENT
BLEND
GRIDS
PRESS ON
GRIDS
CAUSTIC SOLUTION
ELECTROLY-
TICALLY
REDUCED
WATER
RINSE
RINSE WASTEWATER
DISCHARGE
DRY
FINISHED ANODES
TO ASSEMBLY
FIGURE V-19
PRODUCTION OF PRESSED ZINC OXIDE ELECTROLYTICALLY REDUCED ANODES
411
-------
ZINC OXIDE, MERCURIC
OXIDE SLURRY
MIX
BINDING AGENT
BLEND
GRIDS
LAYER ON
GRIDS
CAUSTIC SOLUTION
ELECTRO-
LYT1CALLY
REDUCED
WATER
RINSE
RINSE WASTEWATER
DISCHARGE
DRY
COMPRESS
FINISHED ANODES
HP""- TO ASSEMBLY
FIGURE V-20
PRODUCTION OF PASTED ZINC OXIDE ELECTROLYTICALLY REDUCED ANODES
.412
-------
ZINC CAUSTIC
SOLUTION
SOLUTION
PREPARATION
GRIDS
ELECTRODE-
POSITION
I
WATER
RINSE
MERCURIC CHLORIDE
ACIDIC SOLUTION
I
AMALGAMATION
DRY
RINSE WASTEWATER
DISCHARGE
SPENT AMALGAMATION
SOLUTION DISPOSAL
WATER
i
RINSE
I
RINSE WASTEWATER
DISCHARGE
DRY
FINISHED ANODES
TO ASSEMBLY
FIGURE V-21
PRODUCTION OF ELECTRODEPOSITED ZINC ANODES
413
-------
SILVER POWDER
MIX
GRIDS
PRESS
ON GRIDS
CAUSTIC SOLUTION
WATER
ELECTRO-
LYTICALLY
FORMED
I
RINSE
RINSE WASTEWATER DISCHARGE
1
DRY
FINISHED CATHODES
• TO ASSEMBLY
FIGURE V-22
PRODUCTION OF SILVER POWDER PRESSED ELECTROLYTICALLY OXIDIZED
CATHODES
414
-------
SILVER OXIDE
POWDER, WATER
GRIDS
MIX
I
LAYER ON
GRIDS
SINTER
CAUSTIC SOLUTION
ELECTROLY-
TICALLY
FORMED
WATER
I
RINSE
TO RESERVOIR OR SPENT
CAUSTIC DISCHARGE
RINSE WASTEWATER
DISCHARGE
WATER
SOAK
SOAK WASTEWATER
DISCHARGE
WATER
EQUIPMENT
AND FLOOR
AREA WASH
DRY
WASH WASTEWATER
DISCHARGE
FINISHED CATHODES
>
TO ASSEMBLY
FIGURE V-23
PRODUCTION OF SILVER OXIDE (Ag2O) POWDER THERMALLY REDUCED OR
SINTERED, ELECTROLYTICALLY FORMED CATHODES
415
-------
SILVER PEROXIDE
POWDER
PELLET1ZE
I
SOLUTION
CHEMICAL
TREATMENT
I
RINSE WASTEWATER
DISCHARGE
WATER
RINSE
CONTAINERS
I
RINSE WASTEWATER
DISCHARGE
DRY AND PLACE
IN CONTAINER
METHANOL-HYDRAZINE
SOLUTION ^
I
CHEMICAL
TREATMENT
I
CONTRACTOR REMOVAL
OF SPENT SOLUTION
METHANOL
METHANOL
RINSE
I
CONTRACTOR REMOVAL
OF METHANOL
DRY
FINISHED CATHODES
TO ASSEMBLY
FIGURE V-24
CHEMICAL TREATMENT OF SILVER PEROXIDE CATHODE PELLETS
416
-------
SILVER PEROXIDE POWDER
AND WATER
BINDING AGENT
GRIDS
WATER
EQUIPMENT
WASH
MIX
BLEND
LAYER ON
GRIDS
DRY
FINISHED CATHODES
TO ASSEMBLY
WASH WASTEWATER
DISCHARGE
FIGURE V-25
PRODUCTION OF PASTED SILVER PEROXIDE CATHODES
417
-------
CO
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The priority, nonconventional, and conventional pollutant
parameters that are to be examined for possible regulation were
presented in Section V. Data from plant sampling visits, and
results of subsequent chemical analysis were presented and
discussed. Pollutant parameters were selected for verification
according to a specified rationale.
Each of the pollutant parameters selected for verification
analysis is discussed in detail. The selected priority
pollutants are presented in numerical order and are followed by
nonconventional pollutants and then conventional pollutants, both
in alphabetical order. The final part of this section sets forth
the pollutants which are to be considered for regulation in 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 271) 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.
1,1,1-Trichloroethane(11). 1,1,1-Trichloroethane is one of the
two possible trichlorethanes. It is manufactured by
hydrochlorinating vinyl chloride to 1,1-dichloroethane which is
then chlorinated to the desired product. 1,1,1-Trichloroethane
is a liquid at room temperature with a vapor pressure of 96 mm Hg
at 20°C and a boiling point of 74°C. Its formula is CC13CH3. It
is slightly soluble in water (0.48 g/1) and is very soluble in
organic solvents. U.S. annual production is greater than one-
third of a million tons. 1,1,1-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
419
-------
human health from the toxic properties of 1,1,1-trichloroethane
ingested through the consumption of water and fish, the ambient
water criterion is 18.4 mg/1. The criterion is based on bioassy
for possible carcinogenicity.
No detailed study of 1,1,1-trichloroethane behavior in POTW is
available. However, it has been demonstrated that none of the
organic priority pollutants of this type can be broken down by
biological treatment processes as readily as fatty acids,
carbohydrates, or proteins.
Biochemical oxidation of many of the organic priority pollutants
has been investigated, at least in laboratory scale studies, at
concentrations higher than commonly expected in municipal
wastewater. General observations relating molecular structure to
ease of degradation have been developed for all of these
pollutants. The conclusion reached by study of the limited data
is that biological treatment produces a moderate degree of
degradation of 1,1,1-trichloroethane. No evidence is available
for drawing conclusions about its possible toxic or inhibitory
effect on POTW operation. However, for degradation to occur a
fairly constant input of the compound would be necessary.
Its water solubility would allow 1,1,1-trichloroethane, present
in the influent and not biodegradable, to pass through a POTW
into the effluent. One 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.
1,1-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-dichloroethane 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.
420
-------
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 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 based on the non-threshold assumption for
this chemical. However, zero level may not be attainable at the
present time. Therefore, the levels which may result in
incremental increase of cancer risk over the lifetime are
estimated at 10~7. 10~6, and 10~5. The corresponding recommended
criteria are 0.000019 mg/1, 0.00019 mg/1, and 0.0019 mg/1.
No data are available regarding the behavior of chloroform in a
POTW. However, the biochemical oxidation of this compound was
studied in one laboratory scale study at concentrations higher
than these expected to be contained by most municipal
wastewaters. After 5, 10, and 20 days no degradation of
chloroform was observed. The conclusion reached is that
421
-------
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.
1,1-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 32°C,
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 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-
trichloroethylene 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 due to exposure to 1,1-dichloroethylene
through ingestion of water and contaminated aquatic organisms,
the ambient water concentration should be zero based on the
nonthreshold assumption for this chemical. However, zero level
may not be attainable at the present time. Therefore, the levels
which may result in incremental increase of cancer risk over the
lifetime are estimated at 10~5, 10~6 and 10~7. The corresponding
recommended criteria are 0.00033 mg/1, 0.000033 mg/1 and
0.0000033 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
422
-------
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.
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-1,2-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
423
-------
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.
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
constituent 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 1.4 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 ethylbenzene. 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
424
-------
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
depressant. There is also evidence that the compound causes,
heart failure when large amounts are inhaled.
Methylene chloride does produce mutation in tests for this
effect. In addition a bioassay recognized for its extremely high
sensitivity to strong and weak carcinogens produced results which
were marginally significant. Thus potential carcinogenic effects
of methylene chloride are not confirmed or denied, but are under
continuous study. Difficulty in conducting and interpreting the
test results from the low boiling point (40°C) of methylene
chloride which increases the difficulty of maintaining the
compound in growth media during incubation at 37°C; and from the
difficulty of removing all impurities, some of which might
themselves be carcinogenic.
For the protection of human health from the potential
carcinogenic effects due to exposure to methylene chloride
through ingestion of contaminated water and contaminated aquatic
organisms, the ambient water concentration should be zero based
on the nonthreshold assumption for this chemical. However, zero
level may not be attainable at the present time. Therefore, the
levels which may result in incremental increase of cancer risk
over the lifetime are estimated at 10~s, 10~6 and 10~7. The
corresponding recommended criteria are 0.0019 mg/1, 0.00019 mg/1,
and 0.000019 mg/1.
425
-------
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 CJOH8.
As such it is properly classed as a polynuclear aromatic
hydrocarbon (PAH). Pure naphthalene is a white crystalline solid
melt-ing at 80°C. For a solid, it has a relatively high vapor
pressure (0.05 mm Hg at 20°C), and moderate water solubility (19
mg/1 at 20°C). Naphthalene is the most abundant single component
of coal tar. Production is more than a third of a million tons
annually in the U.S. About three fourths of the production is
used as feedstock for phthalic anhydride manufacture. Most of
the remaining production goes into manufacture of insecticide,
dyestuffs, pigments, and Pharmaceuticals. Chlorinated and
partially hydrogenated naphthalenes are used in some solvent
mixtures. Naphthalene is also used as a moth repellent.
Naphthalene, ingested by humans, has reportedly caused vision
loss (cataracts), hemolytic anemia, and occasionally, renal
disease. These effects of naphthalene ingestion are confirmed by
Studies on laboratory animals. No carcinogenicity studies are
available which can be used to demonstrate carcinogenic activity
for naphthalene. Naphthalene does bioconcentrate in aquatic
organisms.
There are insufficient data on which to base any ambient water
criterion.
Only a limited number of studies have been conducted to determine
the effects of naphthalene on aquatic organisms. The data from
those studies show only moderate toxicity.
Naphthalene has been detected in sewage plant effluents at
concentrations up to 0.022 mg/1 in studies carried out by the
U.S. EPA. Influent levels were not reported. The behavior of
naphthalene in POTW has not been studied. However, recent
426
-------
studies have determined that naphthalene will accumulate in
sediments at TOO 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 (C6C15OH) 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 competitive 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
Pentachlorophenol, interpretation of data is frequently
uncertain. Occupational exposure observations must be examined
carefully because exposure to pentachlorophenol is frequently
accompanied by exposure to other wood preservatives.
Additionally, experimental results and 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.
427
-------
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
pentachlorophenol ingested through water and through contaminated
aquatic organisms, the ambient water quality criterion is
determined to be 1.01 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, including 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.
i
The low water solubility and low volatility of pentachlorophenol
lead to the expectation that most of the compound will remain in
the sludge 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.
Phthalate Esters (66-71). Phthalic acid, or 1,2-
benzenedicarboxylic acid, is one of three isomeric
benzenedicarboxylic acids produced by the chemical industry.
The other two isomeric forms are called isophthalic and
terephthalic acids. The formula for all three acids is
C«H4(COOH)2. Some esters of phthalic acid are designated as
428
-------
priority pollutants. They will be discussed as a group here, and
specific properties of individual phthalate esters will be
discussed afterwards.
Phthalic acid esters are manufactured in the U.S. at an annual
rate in excess of 1 billion pounds. They are used as
plasticizers - primarily in the production of polyvinyl chloride
(PVC) resins. The most widely used phthalate plasticizer is bis
(2-ethylhexyl) phthalate (66) which accounts for nearly one-third
of the phthalate esters produced. This particular ester is
commonly referred to as dioctyl phthalate (DOP) and should not be
confused with one of the less used esters, di-n-octyl phthalate
(69), which is also used as a plasticizer. In addition to these
two isomeric dioctyl phthalates, four other esters, also used
primarily as plasticizers, are designated as priority pollutants.
They are: butyl benzyl phthalate (67), di-n-butyl phthalate (68),
diethyl phthalate (70), and dimethyl phthalate (71).
Industrially, phthalate esters are prepared from phthalic
anhydride and the specific alcohol to form the ester. Some
evidence is available suggesting that phthalic acid esters also
may be synthesized by certain plant and animal tissues. The
extent to which this occurs in nature is not known.
Phthalate esters used as plasticizers can be present in
concentrations up to 60 percent of the total weight of the PVC
plastic. The plasticizer is not linked by primary chemical bonds
to the PVC resin. Rather, it is locked into the structure of
intermeshing polymer molecules and held by van der Waals forces.
The result is that the plasticizer is easily extracted.
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
429
-------
toxicity in animals is greater for the lower molecular weight
esters than for the higher molecular weight esters.
Orally administered phthalate esters generally produced enlarging
of liver and kidney, and atrophy of testes in laboratory animals.
Specific esters produced enlargement of heart and brain,
spleenitis, and degeneration of central nervous system tissue.
Subacute doses administered orally to laboratory animals produced
some decrease in growth and degeneration of the testes. Chronic
studies in animals showed similar effects to those found in acute
and subacute studies, but to a much lower degree. The same
organs were enlarged, but pathological changes were not usually
detected.
A recent study of several phthalic esters produced suggestive but
not conclusive evidence that dimethyl and diethyl phthalates have
a cancer liability. Only four of the six priority pollutant
esters were included in the study. Phthalate esters do
bioconcentrate in fish. The factors, weighted for relative
consumption of various aquatic and marine food groups, are used
to calculate ambient water quality criteria for four phthalate
esters. The values are included in the discussion of the
specific esters.
Studies of toxicity of phthalate esters in freshwater and salt
water organisms are scarce. Available data show that adverse
effects on freshwater aquatic life occur at phthalate ester
concentrations as low as 0.003 mg/1.
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 it
is expected that they will be biochemically oxidized to a lesser
extent than domestic sewage by biological treatment in POTW. On
the same basis it is expected that di-n-octyl phthalate will not
be biochemically oxidized to a significant extent by biological
treatment in a POTW. An EPA study of seven POTW revealed that
for all but di-n-octyl phthalate, which was not studied, removals
ranged from 62 to 87 percent.
No information was found on possible interference with POTW
operation or the possible effects on sludge by the phthalate
esters. The water insoluble phthalate esters - butyl benzyl and
430
-------
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 DOP, in the plastics industry where it is
the most extensively used compound for the plasticization of
polyvinyl chloride (PVC). Bis(2-ethylhexyl) phthalate has been
approved by the FDA for use in plastics in contact with food.
Therefore, it may be found in wastewaters coming in contact with
discarded plastic food wrappers as well as the PVC films and
shapes normally found in industrial plants. This priority
pollutant is also a commonly used organic diffusion pump oil
where its low vapor pressure is an advantage.
For the protection of human health from the toxic properties of
.bis(2-ethylhexyl) phthalate ingested through water and through
contaminated aquatic organisms, the ambient water quality
criterion is determined to be 15 mg/1. If contaminated aquatic
organisms alone are consumed, excluding the consumption of water,
the ambient water criteria is determined to be 50 mg/1.
Although the behavior of bis(2-ethylhexyl) phthalate in POTW has
not been studied, biochemical oxidation of this priority
pollutant has been studied on a laboratory scale at
concentrations higher than would normally be expected in
municipal wastewater. In fresh water with a nonacclimated 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.
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
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.
431
-------
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 350 mg/1. -If contaminated aquatic organisms
alone are consumed, excluding the consumption of water, the
ambient water criterion is 1800 mg/1.
Although the behavior of diethyl 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 79, 84, and 89 percent of theoretical was observed
after 5, 5, and 20 days, respectively. Based on these data it is
expected that diethyl phthalate will be biochemically oxidized to
a lesser extent than domestic sewage by biological treatment in
POTW.
Dimethyl phthalate (71). In addition to the general remarks and
discussion on phthalate esters, specific information on dimethyl
phthalate (DMP) is provided. DMP has the lowest molecular weight
of the phthalate esters - M.W. = .194 compared to M.W. of 391 for
bis(2-ethylhexyl)phthalate. 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 finishes for exterior metal siding. Coil
432
-------
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 313 mg/1. If contaminated aquatic
organisms alone are consumed, excluding the consumption of water,
the ambient water criterion is 2900 mg/1.
Based on limited data and observations relating molecular
structure to ease of biochemical degradation of other organic
pollutants, it is expected that dimethyl phthalate will be
biochemically oxidized to a lesser extent than domestic sewage by
biological treatment in POTW.
Tetrachloroethylene(85). Tetrachloroethylene (CC12CC12), 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.
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 should be zero based on the
nontheshold assumption for this chemical. However, zero level
may not be attainable at the present time. Therefore, the levels
which may result in incremental increase of cancer risk over the
lifetime are estimated at 10-5, 10-*, and 10~7. 'The
433
-------
corresponding recommended criteria are 0.008 mg/1, 0.0008 mg/1
and 0.00008 mg/1.
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 toluol, methylbenzene, methacide, and
phenylmethane. It is an aromatic hydrocarbon with the formula
CeH5CH3. 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 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.
434
-------
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 14.3
mg/1. If contaminated aquatic organisms alone are consumed,
excluding the consumption of water, the ambient water criterion
is 424 mg/1. Available data show that adverse effects on aquatic
life occur at concentrations as low as 5 mg/1.
Acute toxicity tests have been conducted with toluene and a
variety of freshwater fish and Daphnia maqna. 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.
Only one 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 the theoretical 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. Based
on study of the limited data, it is expected that toluene will be
biochemically oxidized to a lesser extent than domestic sewage by
biological treatment 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. The EPA studied toluene removal in seven POTW. The
removals ranged from 40 to 100 percent. Sludge concentrations of
toluene ranged from 54 x 10~3 to 1.85 mg/1.
Trichloroethylene(87). Trichloroethylene (1,1,2-trichloro-
ethylene 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
435
-------
tetrachloroethane by treatment with lime in the presence of
water.
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 limited. 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
in vitro Fischer rat embryo cell system (FT 706) that is used for
identifying carcinogens. Severe and persistant 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 should be zero based on the nonthreshold assumption
of this chemical. 'However, zero level may not be attainable at
the present time. Therefore, the levels which may result in
incremental increase of cancer risk over the lifetime are
estimated at 10~5. 10~6 and 10~7. The corresponding recommended
criteria are 0.027 mg/1, 0.0027 mg/1 and 0.00027 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 limited data for
aquatic life show that adverse effects occur at concentrations
higher than those cited for human health risks.
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
436
-------
to ease of degradation, the conclusion is reached that TCE would
undergo little or no biochemical oxidation 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 nonmetal or metalloid, is a silvery white ,
brittle, crystalline solid. Antimony is found in small ore
bodies throughout the world. Principal ores are oxides of mixed
antimony valences, and an oxysulfide ore. Complex ores with
metals are important because the antimony is recovered as a by-
product. Antimony melts at 631°C, and is a poor conductor of
electricity and heat.
Annual U.S. consumption of primary antimony ranges from 10,000 to
20,000 tons. About half is consumed in metal products - mostly
antimonial lead for lead acid storage batteries, and about half
in nonmetal products. A principal compound is antimony trioxide
which is used as a flame retardant in fabrics, and as an
opacifier in glass, ceramics, and enamels. Several antimony
compounds are used as catalysts in organic chemicals synthesis,
as fluorinating agents (the antimony fluoride), as pigments, and
in fireworks. Semiconductor applications are economically
significant.
Essentially no information on antimony - induced human health
effects has been derived from community epidemiology studies.
The available data are in literature relating effects observed
with therapeutic or medicinal uses of antimony compounds and
industrial exposure studies. Large therapeutic doses of
antimonial compounds, usually used to treat schistosomiasis, have
caused severe nausea, vomiting, convulsions, irregular heart
action, liver damage, and skin rashes. Studies of acute
industrial antimony poisoning have revealed loss of appetite,
diarrhea, headache, and dizziness in addition to the symptoms
found in studies of therapeutic doses of antimony.
For the protection of human health from the toxic properties of
antimony ingested through water and through contaminated aquatic
organisms the ambient water criterion is determined to be 0.146
mg/1. If contaminated aquatic organisms alone are consumed,
excluding the consumption of water, the ambient water criterion
is determined to be 45 mg/1. Available data show that adverse
effects on aquatic life occur at concentrations higher than those
cited for human health risks.
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,
437
-------
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
nonmetal or metalloid. Elemental arsenic normally exists in the
alpha-crystalline metallic form which is steel gray and brittle,
and in the beta form which is dark gray and amorphous. Arsenic
sublimes at 615°C. Arsenic is widely distributed throughout the
world in a large number of minerals. The most important
commercial source of arsenic is as a by-product from treatment of
copper, lead, cobalt, and gold ores. Arsenic is usually marketed
as the trioxide (As203). Annual U.S. production of the trioxide
approaches 40,000 tons.
The principal use of arsenic is in agricultural chemicals
(herbicides) for controlling weeds in cotton fields. Arsenicals
have various applications in medicinal and veterinary use, as
wood preservatives, and in semiconductors.
The effects of arsenic in humans were known by the ancient Greeks
and Romans. The principal toxic effects are gastrointestinal
disturbances. Breakdown of red blood cells occurs. Symptoms of
acute poisoning include vomiting, diarrhea, abdominal pain,
lassitude, dizziness, and headache. Longer exposure produced
dry, falling hair, brittle, loose nails, eczema, and exfoliation.
Arsenicals also exhibit teratogenic and mutagenic effects in
humans. Oral administration of arsenic compounds has been
associated clinically with skin cancer for nearly a hundred
years. Since 1888 numerous studies have linked occupational
exposure to, and therapeutic administration of arsenic compounds
to increased incidence of respiratory and skin cancer.
For the maximum protection of human health from the potential
carcinogenic effects due to exposure to arsenic through ingestion
of water and contaminated aquatic organisms, the ambient water
concentration should be zero based on the nonthreshold assumption
of this chemical. However, zero level may not be attainable at
the present time. Therefore, the levels which may result in
incremental increase of cancer risk over the lifetime are
estimated at 10~5, 10~6 and 10~7. The corresponding recommended
criteria are 2.2 x TO-7 mg/1, 2.2 x TO-6 mg/1, and 2.2 x 10-5
438
-------
mg/1. If contaminated aquatic oraanisms alone are consumed,
excluding the consumption of water, the water concentration
should be less than 1.75 x 10-4 mg/I to keep the increased
lifetime cancer risk below 10-5. Available data show that
adverse effects on aquatic life occur at concentrations higher
than those cited for human health risks.
A few studies have been made regarding the behavior of arsenic in
POTW. One EPA survey of 9 POTW reported influent concentrations
ranging from 0.0005 to 0.693 mg/1; effluents from 3 POTW having
biological treatment contained 0.0004 - 0.01 mg/1; 2 POTW showed
arsenic removal efficiencies of 50 and 71 percent in biological
treatment. Inhibition of treatment processes by sodium arsenate
is reported to occur at 0.1 mg/1 in activated sludge, and
1.6 mg/1 in anaerobic digestion processes. In another study
based on data from 60 POTW, arsenic in sludge ranged from 1.6 to
65.6 mg/kg and the median value was 7.8 mg/kg. Arsenic in sludge
spread on cropland may be taken up by plants grown on that land.
Edible plants can take up arsenic, but normally their growth is
inhibited before the plants are ready for harvest.
Asbestos(116). Asbestos is a generic term used to describe a
group of hydrated mineral silicates that can appear in a fibrous
crystal form (asbestiform) and, when crushed, can separate into
flexible fibers. The types of asbestos presently used
commercially fall into two mineral groups: the sepentine and
amphibole groups. Asbestos is minerologically stable and is not
prone to significant chemical or biological degradataion in the
aquatic environment. In 1978, the total consumption of asbestos
in the U.S. was 583,000 metric tons. Asbestos is an excellent
insulating material and is used in a wide variety of products.
Based on 1975 figures, the total annual identifiable asbestos
emissions are estimated at 243,527 metric tons. Land discharges
account for 98.3 percent of the emissions, air discharges account
for 1.5 percent, and water discharges account for 0.2 percent.
Asbestos has been found to produce a significant incidence of
disease among workers occupationally exposed in mining and
milling, in manufacturing, and in the use of materials containing
the fiber. The predominant type of exposure has been inhalation,
although some asbestos may be swallowed directly or ingested
after being expectorated from the respiratory tract. Non-
cancerous asbestos disease has been found among people directly
exposed to high levels of asbestos as a result of excessive work
exposure; much less frequently, among those with lesser exposures
although there is extensive evidence of pulmonary disease among
people exposed to airborne asbestos. There is little evidence of
disease among people exposed to waterborne fibers.
439
-------
Asbestos at the concentrations currently found in the aquatic
environment does not appear to exert toxic effects on aquatic
organisms. For the maximum protection of human health from the
potential carcinogenic effects of exposure to asbestos through
ingestion of water and contaminated aquatic organisms, the
ambient water concentration should be zero based on the
nonthreshold assumption of this substance. However, zero level
may not be attainable at the present time. Therefore the levels
which may result in incremental increase of cancer risk over the
life time are estimated at 10-5, 1O-6 and 10-7. The
corresponding recommended cirteria are 300,000 fibers/1 , 30,000
fibers/1, and 3,000 fibers/1.
The available data indicate that technologies used at POTW for
reducing levels of total suspended solids in wastewater also
provide a concomitant reduction in asbestos levels. Asbestos
removal efficiencies ranging from 80 percent to greater than 99
percent have been reported following sedimentation offwastewater.
Filtration and sedimentation with chemical addition'(i.e., lime
and/or polymer) have achieved even greater percentage removals.
Cadmium(ITS). Cadmium is a relatively rare metallic element that
is seldom found in sufficient quantities in a pure state to
warrant mining or extraction from the earth's surface. It is
found in trace amounts of about 1 ppm throughout the earth's
crust. Cadmium is, however, a valuable by-product of zinc
production.
Cadmium is used primarily as an electroplated metal, and is found
as an impurity in the secondary refining of zinc, lead, and*
copper.
Cadmium is an extremely dangerous cumulative toxicant, causing
progressive chronic poisoning in mammals, fish, and probably
other organisms.
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.
440
-------
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 through
to the POTW effluent. Only 2 of the 189 POTW allowed less than
20 percent pass through, and none less than 10 percent pass
through. POTW effluent concentrations ranged from 0.001 to
1.97 mg/1 (mean 0.028 mg/1, standard deviation 0.167 mg/1).
Cadmium not passed through the POTW will be retained in the
sludge where it is likely to build up in concentration. Cadmium
contamination of sewage sludge limits its use on land since it
increases the level of cadmium in the soil. Data show that
cadmium can be incorporated into crops, including vegetables and
grains, from contaminated soils. Since the crops themselves show
no adverse effects from soils with levels up to 100 mg/kg
cadmium, these contaminated crops could have a significant impact
on human health. Two Federal agancies have already recognized
the potential adverse human health effects posed by the use of
sludge on cropland. The FDA recommends that sludge containing
over 30 mg/kg of cadmium should not be used on agricultured land.
Sewage sludge contains 3 to 300 mg/kg (dry basis) of cadmium
(mean = 10 mg/kg). The USDA also recommends placing limits on
the total cadmium from sludge that may be applied to land.
Chromium(119). Chromium is an elemental metal usually found as a
chromite (FeO»Cr203). The metal is normally produced by reducing
the oxide with aluminum. A significant proportion of the
chromium used is in the form of compounds such as sodium
dichromate (Na2Cr04), and chromic acid (Cr03) - both are
hexavalent chromium compounds.
441
-------
Chromium is found as an alloying component of many steels and its
compounds are used in electroplating baths, and as corrosion
inhibitors for closed water circulation systems.
The two chromium forms most frequently found in industry
wastewaters are hexavalent and trivalent chromium. Hexavalent
chromium is the form used for metal treatments. Some of it is
reduced to trivalent chromium as part of the process reaction.
The raw wastewater containing both valence states is usually
treated first to reduce remaining hexavalent to trivalent
chromium, and second to precipitate the trivalent form as the
hydroxide. The hexavalent form is not removed by lime treatment.
Chromium, in its various valence states, is hazardous to man. It
can produce lung tumors when inhaled, and induces skin
sensitizations. Large doses of chromates have corrosive effects
on the intestinal tract and can cause inflammation of the
kidneys. Hexavalent chromium is a known human carcinogen.
Levels of chromate ions that show no effect in man appear to be
so low as to prohibit determination, to date.
The toxicity of chromium salts to fish and other aquatic life
varies widely with the species, temperature, pH, valence of the
chromium, and synergistic or antagonistic effects, especially the
effect of water hardness. Studies have shown that trivalent
chromium is more toxic to fish of some types than is hexavalent
chromium. Hexavalent chromium retards growth of one fish species
at 0.0002 mg/1. Fish food organisms and other lower forms of
aquatic life are extremely sensitive to chromium. Therefore,
both hexavalent and trivalent chromium must be considered harmful
to particular fish or organisms.
For the protection of human health from the toxic properties of
chromium (trivalent) ingested through water and contaminated
aquatic organisms, the recommended water qualtiy criterion is 170
mg/1. If contaminated aquatic organisms alone are consumed,
excluding the consumption of water, the water criterion for
trivalent chromium is 3,443 mg/1. The ambient water quality
criterion for hexavalent chromium is recommended to be identical
to the existing drinking water standard for total chromium which
is 0.050 mg/1.
Chromium is not destroyed when treated by POTW (although the
oxidation state may change), and will either pass through to the
POTW effluent or be incorporated into the POTW sludge. Both
oxidation states can cause POTW treatment inhibition and can also
limit the usefulness of municipal sludge.
442
-------
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
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.
443
-------
Copper(120). Copper is a metallic element that sometimes is
found free, as the native metal, and is also found in minerals
such as cuprite (Cu20), malechite [CuC03»Cu(OH)2], azurite
[2CuC03»Cu(OH)2], chalcopyrite (CuFeS2), and bornite (CusFeS4).
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.
The recommended criterion to protect freshwater aquatic life is
0.0056 mg/1 as a 24-hour average, an'd 0.012 mg/1 maximum
concentration at a hardness of 50 mg/1 CaC03. For total
recoverable copper the criterion to protect freshwater aquatic
life is 5.6 x 10-3 mg/1 as a 24-hour average.
Copper salts cause undesirable color reactions in the food
industry and cause pitting when deposited on some other metals
such as aluminum and galvanized steel.
Irrigation water containing more than minute quantities of copper
can be detrimental to certain crops. Copper appears in all
soils, and its concentration ranges from 10 to 80 ppm. In soils,
copper occurs in association with hydrous oxides of manganese and
iron, and also as soluble and insoluble complexes with organic
444
-------
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).
Copper which does not pass through the POTW will be retained in
the sludge where it will bui-ld 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.
445
-------
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 relationslhip 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 noncumulative
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
nontoxic thiocyanate and eliminate it. However, if the quantity
of cyanide ingested is too 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 con-
centration, 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
446
-------
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.
Persistance 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 POTW 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 pretreat-
ment regulations were put in force. Concentrations fell from
0.66 mg/1 before, to 0.01 mg/1 after pretreatment was required.
Lead (122). Lead is a soft, malleable, ductile, bluish-gray,
metallic element, usually obtained from the minerals galena (lead
sulfide, PbS), anglesite (lead sulfate, PbS04), or cerussite
(lead carbonate, PbC03). Because it is usually associated with
the minerals 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.
447
-------
Lead is widely used for its corrosion resistnace, 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. Mutagenicity data are not available for
lead.
For the protection of human health from the toxic properties of
lead ingested through water and through contaminated aquatic
organisms, the ambient water criterion is 0.050 mg/1. Available
data show that adverse effects on aquatic life occur at
concentrations as low as 7.5 x 10~4 mg/1 of total recoverable
lead as a 24-hour average with a water hardness of 50 mg/1 as
CaC03.
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 lead is normally
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.
448
-------
Mercury. Mercury (123) is an elemental metal rarely found in
nature as the free metal. Mercury is unique among metals as it
remains a liquid down to about 39 degrees below zero. It is
relatively inert chemically and is insoluble in water. The
principal ore is cinnabar (Hg_S).
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 aquati'c
organisms the ambient water criterion is determined to be
0.000144 mg/1.
Mercury is not destroyed when treated by a POTW, and will either
pass through to the POTW effluent or be incorporated into the
POTW sludge. At low concentrations it may reduce POTW removal
efficiencies, and at high concentrations it may upset the POTW
operation.
The influent concentrations of mercury to POTW have been observed
by the EPA to range from 0.0002 to 0.24 mg/1, with a median
concentration of 0.001 mg/1. Mercury has been reported in the
literature to have inhibiting effects upon an activated sludge
POTW at levels as low as 0.1 mg/1. At 5 mg/1 of mercury, losses
of COD removal efficiency of 14 to 40 percent have been reported,
while at 10 mg/1 loss of removal of 59 percent has been reported.
Upset of an activated sludge POTW is reported in the literature
to occur near 200 mg/1. The anaerobic digestion process is much
less affected by the presence of mercury, with inhibitory effects
being reported at 1365 mg/1.
449
-------
In a study of 22 POTW having secondary treatment, the range of
removal of mercury from the influent to the POTW ranged from 4 to
99 percent with median removal of 41 percent. Thus significant
pass through of mercury may occur.
In sludges, mercury content may be high if industrial sources of
mercury contamination are present. Little is known about the
form in which mercury occurs in sludge. Mercury may undergo
biological methylation in sediments, but no methylation has been
observed in soils, mud, or sewage sludge.
The mercury content of soils not receiving additions of POTW
sewage sludge lie in the range from 0.01 to 0.5 mg/kg. In soils
receiving POTW sludges for protracted periods, the concentration
of mercury has been observed to approach 1.0 mg/kg. In the soil,
mercury enters into reactions with the exchange complex of clay
and organic fractions, forming both ionic and covalent bonds.
Chemical and microbiological degradation of mercurials can take
place side by side in the soil, and the products - ionic or
molecular - are retained by organic matter and clay or may be
volatilized if gaseous. Because of the high affinity between
mercury and the solid soil surfaces, mercury persists in the
upper layer of soil.
Mercury can enter plants through the roots, it can readily move
to other parts of the plant, and it has been reported to cause
injury to plants. In many plants mercury concentrations range
from 0.01 to 0.20 mg/kg, but when plants are supplied with high
levels of mercury, these concentrations can exceed 0.5 mg/kg.
Bioconcentration occurs in animals ingesting mercury in food.
Nickel(124). Nickel is seldom found in nature as the pure
elemental metal. It is a relatively plentiful element and is
widely distributed throughout the .earth's crust. It occurs in
marine organisms and is found in the oceans. The chief
commercial ores for nickel are pentlandite [(Fe,Ni),S8], and a
lateritic ore consisting of hydrated nickel-iron-magnesium
silicate.
Nickel has many and varied uses. It is used in alloys and as the
pure metal. Nickel salts are used for electroplating baths.
The toxicity of nickel to man is thought to be very low, and
systemic poisoning of human beings by nickel or nickel salts is
almost unknown. In nonhuman 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.
450
-------
Nickel salts can kill fish at very low concentrations. However,
nickel has been found to be less toxic to some fish than copper,
zinc, and iron. Nickel is present in coastal and open ocean
water at concentrations in the range of 0.0001 to 0.006 mg/1
although the most common values are 0.002 - 0.003 mg/1. Marine
animals contain up to 0.4 mg/1 and marine plants contain up to
3 mg/1. Higher nickel concentrations have been reported to cause
reduction in photosynthetic activity of the giant kelp. A low
concentration was found to kill oyster eggs.
For the protection of human health based on the toxic properties
of nickel ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 0.0134
mg/1. If contaminated aquatic organisms are consumed, excluding
consumption of water, the ambient water criterion is determined
to be 0.100 mg/1. Available data show that adverse effects on
aquatic life occur for total recoverable nickel concentrations as
low as 0.0071 mg/1 as a 24-hour average.
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.
451
-------
Nickel is found in nearly all soils, plants, and waters. Nickel
has no known essential function in plants. In soils, nickel
typically is found in the range from 10 to 100 mg/kg. Various
environmental exposures to nickel appear to correlate with
increased incidence of tumors in man. For example, cancer in the
maxillary antrum of snuff users may result from using plant
material grown on soil high in nickel.
Nickel toxicity may develop in plants from application of sewage
sludge on acid soils. Nickel has caused reduction of yields for
a variety of crops including oats, mustard, turnips, and cabbage.
In one study nickel decreased the yields of oats significantly at
100 mg/kg.
Whether nickel exerts a toxic effect on plants depends on several
soil factors, the amount of nickel applied, and the contents of
other metals in the sludge. Unlike copper and zinc, which are
more available from inorganic sources than from sludge, nickel
uptake by plants seems to be promoted by the presence of the
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 nonmetallic
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, xerography, 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.
452
-------
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 determined to be 0.010
mg/1. Available data show that adverse effects on aquatic life
occur at concentrations higher than that cited for human
toxicity.
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 a potential hazard
for humans or other mammals 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 large number of organisms. Upon ingestion
by humans, many silver salts are absorbed in the circulatory
system and deposited in various body tissues, resulting in
generalized or sometimes localized gray pigmentation of the skin
and mucous membranes know as argyria. There is no known method
for removing silver from the tissues once it is deposited, and
the effect is cumulative.
Silver is recognized as a bactericide and doses from 0.000001 to
0.0005 mg/1 have been reported as sufficient to sterilize water.
The criterion for ambient water to protect human health from the
toxic properties of silver ingested through water and through
contaminated aquatic organisms is 0.050 mg/1.
The chronic toxic effects of silver on the aquatic environment
have not been given as much attention as many other heavy metals.
Data from existing literature support the fact that silver is
very toxic to aquatic organisms. Despite the fact that silver is
nearly the most toxic of the heavy metals, there are insufficient
data to adequately evaluate even the effects of hardness on
silver toxicity. There are no data available on the toxicity of
different forms of silver.
453
-------
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.
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, concentrations in ambient water
should not exceed 5 mg/1. Available data show that adverse
effects on aquatic life occur at concentrations as low as 0.047
mg/1 as a 24-hour average.
Toxic concentrations of zinc compounds cause adverse changes in
the morphology and physiology of fish. «Lethal concentrations in
the range of 0.1 mg/1 have been reported. Acutely toxic
concentrations induce cellular breakdown of the gills, and
possibly the clogging of the gills with mucous. Chronically
toxic concentrations of zinc compounds cause general enfeeblement
and widespread histological changes to many organs, but not to
gills. Abnormal swimming behavior has been reported at
0.04 mg/1. Growth and maturation are retarded by zinc. It has
been observed that the effects of zinc poisoning may not become
apparent immediately, so that fish removed from zinc-contaminated
water may die as long as 48 hours after removal.
454
-------
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 usefulness of municipal sludge.
In slug doses, and particularly in the presence of copper,
dissolved zinc can interfere with or seriously disrupt the
operation of POTW biological processes by reducing overall
removal efficiencies, largely as a result of the toxicity of the
metal to biological organisms. However, zinc solids in the form
of hydroxides or sulfides do not appear to interfere with
biological treatment processes, on the basis of available data.
Such solids accumulate in the sludge.
The influent concentrations of zinc to POTW facilities has been
observed by the EPA to range from 0.017 to 3.91 mg/1, with a
median concentration of 0.33 mg/1. Primary treatment is not
efficient in removing zinc; however, the microbial floe of
secondary treatment readily adsorbs zinc.
In a study of 258 POTW, the median pass through values were 70 to
88 percent for primary plants, 50 to 60 percent for trickling
filter and biological process plants, and 30-40 percent for
activated process plants. POTW effluent concentrations of zinc
ranged from 0.003 to 3.6 mg/1 (mean = 0.330, standard deviation =
0.464) .
455
-------
The zinc which does not pass through the POTW is retained in the
sludge. The presence of zinc in sludge may limit its use on
cropland. Sewage sludge contains 72 to over 30,000 mg/kg of
zinc, with 3,366 mg/kg as the mean value. These concentrations
are significantly greater than those normally found in soil,
which range from 0 to 195 mg/kg, with 94 mg/kg being a common
level. Therefore, application of sewage sludge to soil will
generally increase the concentration of zinc in the soil. Zinc
can be toxic to plants, depending upon soil pH. Lettuce,
tomatoes, turnips, mustard, kale, and beets are especially
sensitive to zinc contamination.
Aluminum. Aluminum is a nonconventional pollutant. It is a
silvery white metal, very abundant in the earths crust (8.1
percent), but never found free in nature. Its principal ore is
bauxite. Alumina (A1203) is extracted from the bauxite and
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 nonmagnetic. It can be formed,
machined or cast. Although aluminum is very reactive, it forms a
protective oxide film on the surface which prevents corrosion
under many conditions. In contact with other metals in presence
of moisture the protective film is destroyed and voluminous white
corrosion products form. Strong acids and strong alkali also
break down the protective film.
There is increasing evidence that dissolved aluminum has
substantial adverse effects on human health. Aluminum has been
implicated by several studies in the development of Alzheimer's
disease (progressive senile dementia). This disease is
associated with the formation of tangled bunches of nerve fibers
or "neurofibrillary tangles" (NFT). Autopsy studies have shown
that aluminum is present in 90 percent of the nuclei of NFT
neurons. It is present in less than 6 percent of the nuclei of
normal neurons. This trend is also apparent in the cytoplasm of
NFT neurons, although less prominent than in the nuclei: aluminum
was found in 29.4 percent of the cytoplasms of NFT neurons and
11.1 percent of the cytoplasms of normal neurons.
Brains of individuals suffering from several other neurological
diseases have also displayed elevated concentrations of aluminum.
These diseases include Huntington's disease, Parkinsons' disease,
progressive supranuclear palsy, acoustic neuroma, and Guamanian
amyotrophic lateral sclerosis (ALS).
These increased concentrations of aluminum may be a result of the
development of the disease, rather than a contributing cause;
however, this possibility seems less likely in light of several
456
-------
recent studies correlating high concentrations of aluminum in the
environment to a high incidence of several of these neurological
disorders.- These and other studies are discussed in greater
detail in the report "Aluminum: An Environmental and Health
Effects Assessment," cited as a reference in this document.
Although much work remains to be done on this subject, the Agency
believes that the evidence points to a much broader neurotoxic
role for aluminum than had previously been assumed.
In addition, mildly alkaline conditions can cause precipitation
of aluminum as the hydroxide. When aluminum hydroxide
precipitates in waterways or bodies of water, it can blanket the
bottom, having an adverse effect on the benthos and on aquatic
plant life rooted on the bottom. Aluminum hydroxide, like many
precipitates, can also impair the gill action of fish when
present in large amounts.
Alum, an aluminum salt with the chemical formula A12(S04)3»14 H20
is used as a coagulant in municipal and industrial wastewater
treatment. This form is different from dissolved aluminum and
aluminum hydroxide, which are both harmful pollutants. The
amount of dissolved aluminum in finished water does not generally
depend upon the amount of alum used as a coagulant, unless a
large excess is used. The alum is contained in the treatment
sludge; very little passes through into the effluent.
Similarly, the amount of aluminum hydroxide in finished water
does not depend on the amount of alum used in coagulation, but
rather on the pH and the concentration of dissolved aluminum.
Therefore, the use of alum as a coagulant does not result in
large amounts of either aluminum or aluminum hydroxide in
finished water. There are no data available on the POTW removal
efficiency for the pollutant aluminum.
Ammonia. Ammonia (chemical formula NH3) is a nonconventional
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 -33QC). 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)
457
-------
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 destructively 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 un-ionized 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.
Cobalt. Cobalt is a nonconventional 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
458
-------
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
carcinogenicity 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 nonconventional polluant. It is an abundant
metal found at many places in the earth's crust. The most common
iron ore is hematite (Fe2O3) from which iron is obtained by
reduction with carbon. Other forms of commercial ores are
magnetite (Fe3O4) and taconite (FeSiO). Pure iron is not often
found in commercial use, but it is usually alloyed with other
metals and minerals. The most common of these is carbon.
Iron is the basic element in the production of steel. Iron with
carbon is used for casting of major parts of machines and it can
be machined, cast, formed, and welded. Ferrous iron is used in
paints, while powdered iron can be sintered and used in powder
metallurgy. Iron compounds are also used to precipitate other
metals and undesirable minerals from industrial wastewater
streams.
Corrosion products of iron in water cause staining of porcelain
fixtures, and ferric iron combines with tannin to produce a dark
violet color. The presence of excessive iron in water
discourages cows from drinking and thus reduces milk production.
High concentrations of ferric and ferrous ions in water kill most
fish introduced to the solution within a few hours. The killing
action is attributed to coatings of iron hydroxide precipitates
on the gills. Iron oxidizing bacteria are dependent on iron in
water for growth. These bacteria form slimes that can affect the
459
-------
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 irdn in domestic water supplies based on aesthetic and
organoleptic properties of iron in water.
High concentrations of iron do not pass through a POTW into the
effluent. In some POTW iron salts are added to coagulate
precipitates and suspended sediments into a sludge. In an EPA
study of POTW the concentration of iron in the effluent of 22
biological POTW meeting secondary treatment performance levels
ranged from 0.048 to 0.569 mg/1 with a median value of 0.25 mg/1.
This represented removals of 76 to 97 percent with a median of 87
percent removal.
Iron in sewage sludge spread on land used for agricultural
purposes is not expcected to have a detrimental effect on crops
grown on the land.
Manganese. Manganese is a nonconventional pollutant. It is a
gray-white metal resembling iron, but more brittle. The pure
metal does not occur in nature, but must be produced by reduction
of the oxide with sodium, magnesium, or aluminum, or by
electrolysis. The principal ores are pyrolusite (Mn02) and
psilomelane (a complex mixture of MnO2 and oxides of potassium,
barium and other alkali and alkaline earth metals). The largest
percentage of manganese used in the U.S. is in ferro-manganese
alloys. A small amount goes into dry batteries and chemicals.
Manganese is not often present in natural surface waters because
its hydroxides and carbonates are only sparingly soluble.
Manganese is undesirable in domestic water supplies because it
causes unpleasant tastes, deposits on food during cooking, stains
and discolors laundry and plumbing fixtures, and fosters the
growth of some microorganisms in reservoirs, filters, and
distribution systems.
i
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
460
-------
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 lethargy and
edema, was traced to manganese in the drinking water in a village
near Tokyo. Three persons died,as a result of poisoning by well
water contaminated by manganese derived from dry-cell batteries
buried nearby. Excess manganese in the drinking water is also
believed to be the cause of a rare disease endemic in
Northeastern China.
No data were found regarding the behavior of manganese in POTW.
However, one source reports that typical mineral pickup from
domestic water use results in an increase in manganese
concentration of 0.2 to 0.4 mg/1 in a municipal sewage system.
Therefore, it is expected that interference in POTW, if it
occurs, would not be noted until manganese concentrations
exceeded 0.4 mg/1.
Phenols(Total). "Total Phenols" is a nonconventional pollutant
parameter. Total phenols is the result of analysis using the 4-
AAP (4-aminoantipyrene) method. This analytical procedure
measures the color development of reaction products between 4-AAP
and some phenols. The results are reported as phenol. Thus
"total phenol" is not total phenols because many phenols (notably
nitrophenols) do not react. Also, since each reacting phenol
contributes to the color development to a different degree, and
each phenol has a molecular weight different from others and from
phenol itself, analyses of several mixtures containing the same
total concentration in mg/1 of several phenols will give
different numbers depending on the proportions in the particular
mixture.
Despite these limitations of the analytical method, total phenols
is a useful parameter when the mix of phenols is relatively
constant and an inexpensive monitoring method is desired. In any
given plant or even in an industry subcategory, monitoring of
"total phenols" provides an indication of the concentration of
this group of priority pollutants as well as those phenols not
selected as priority pollutants. A further advantage is that the
method is widely used in water quality determinations.
In an EPA survey of 103 POTW the concentration of "total phenols"
ranged from 0.0001 mg/1 to 0.176 mg/1 in the influent, with a
median concentration of 0.016 mg/1. Analysis of effluents from
22 of these same POTW which had biological treatment meeting
secondary treatment performance levels showed "total phenols"
concentrations ranging from 0 mg/1 to 0.203 mg/1 with a median of
0.007. Removals were 64 to 100 percent with a median of 78
percent.
461
-------
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.
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: nonemulsifiable 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, PCB, PAH, and almost any
462
-------
other organic pollutant in the oil and grease make
characterization of this parameter almost impossible. However,
all of these other organics add to the objectionable nature of
the oil and grease.
Levels of oil and grease which are toxic to aquatic organisms
vary greatly, depending on the type and the species
susceptibility. However, it has been reported that crude oil in
concentrations as low as 0.3 mg/1 is extremely toxic to fresh-
water fish. It has been recommended that public water supply
sources be essentially free from oil and grease.
Oil and grease in quantities of 100 1/sq km show up as a sheen on
the surface of a body of water. The presence of oil slicks
decreases the aesthetic value of a waterway.
Oil and grease is compatible with a POTW activated sludge process
in limited quantity. Howeve'r, 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.
Suspended solids in water interfere with many industrial
processes and cause foaming in boilers and incrustations 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
463
-------
things, including blanketing the stream or lake bed and thereby
destroying the living spaces for those benthic organisms that
would otherwise occupy the habitat. When of an organic nature,
solids use a portion or all of the dissolved oxygen available in
the area. Organic materials also serve as a food source for
sludgeworms and associated organisms.
Disregarding any toxic effect attributable to substances leached
out by water, suspended solids may kill fish and shellfish by
causing abrasive injuries and by clogging the gills and
respiratory passages of various aquatic fauna. Indirectly,
suspended solids are inimical to aquatic life because they screen
out light, and they promote and maintain the development of
noxious conditions through oxygen depletion. This results in the
killing of fish and fish food organisms. Suspended solids also
reduce the recreational value of the water.
Total suspended solids is a' traditional pollutant which is
compatible with a well-run POTW. This pollutant with the
excepti6n 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
I-OTW effluent, TSS may be considered a toxic waste hazard.
pH. Although not a specific pollutant, pH is related to the
acidity or alkalinity of a wastewater stream. It is not,
however, a measure of either. The term pH is used to describe
the hydrogen ion concentration (or activity) present in a given
solution. Values for pH range from 0 to 14, and these numbers
are the negative logarithms of the hydrogen ion concentrations.
A pH of 7 indicates neutrality. Solutions with a pH above 7 are
alkaline, while those solutions with a pH below 7 are acidic.
The relationship of pH and acidity and alkalinity is not
necessarily linear or direct. Knowledge of the water pH is
useful in determining necessary measures for corroison control,
sanitation, and disinfection. Its value is also necessary in the
treatment of industrial wastewaters to determine amounts of
chemicals required to remove pollutants and to measure their
effectiveness. Removal of pollutants, especially dissolved
solids is affected by the pH of the wastewater.
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
464
-------
increases, and it is advantageous to keep the pH close to 7.0.
This is significant for providng safe drinking water.
Extremes of pH or rapid pH changes can exert stress conditions or
kill aquatic life outright. Even moderate changes from
acceptable criteria limits of pH are deleterious to some species.
The relative toxicity to aquatic life of many materials is
increased by changes in the water pH. For example,
metallocyanide complexes can increase a thousand-fold in toxicity
with a drop of 1.5 pH units.
Because of the universal nature of pH and its effect on water
quality and treatment, it is selected as a pollutant parameter
for many industry categories. A neutral pH range (approximately
6-9) is generally desired because either extreme beyond this
range has a deleterious effect on receiving waters or the
pollutant nature of other wastewater constituents.
Pretreatment for regulation of pH is covered by the "General
Pretreatment Regulations for Exisiting and New Sources of
Pollution," 40 CFR 403.5. This section prohibits the discharge
to a POTW of "pollutants which will cause corrosive structural
damage to the POTW but in no case discharges with pH lower than
5.0 unless the works is specially designed to accommodate such
discharges."
SPECIFIC POLLUTANTS CONSIDERED FOR REGULATION
For all subcategories, 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 Subcategory
Pollutant Parameters Selected for Regulation. Based on
verification sampling results of the manufacturing elements and
wastewater sources listed in Figure V-2 (Page 392), 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
465
-------
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 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.
466
-------
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.
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 cadmium 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, from both direct and
indirect discharges in 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
467
-------
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 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 Subcateqory
Parameters Selected For Specific Regulation. Based on the
results of verification sampling and analysis of the
manufacturing elements and wastewater sources listed in Figure V-
8 (page 399), and a careful review of calcium subcategory raw
materials, four pollutant parameters were selected to be
considered for specific regulation. These are asbestos,
chromium, TSS and pH. They were observed at significant levels
in raw wastewater produced in this subcategory, and are amenable
to control by identified wastewater treatment and control
practices.
Asbestos appeared in one of two process wastewater samples
analyzed in this subcategory and is known to be used as a raw
material in the heat paper production process element.
Therefore, it is considered for specific regulation.
468
-------
Chromium appeared in both of the process wastewater samples
analyzed for verification. It is also used as a raw material in
the heat paper production process element. Chromium is removed
by treatment to levels less than those observed in raw wastewater
samples. Therefore, chromium is considered for specific
regulation.
Suspended solids appeared in both of the process wastewater
samples analyzed for verification. Measured concentrations were
up to 715 mg/1. Some of the TSS is comprised of asbestos and
barium chromate. Because this conventional pollutant contains
quantities of priority pollutants, TSS requires consideration for
regulation in both direct and indirect discharges from this sub-
category.
The pH of wastewater streams resulting from the manufacture of
calcium anode batteries was observed to range from 2.9 to 6.2.
Acidic wastewater results from the use of acidic solutions in
heat paper manufacture. Since deleterious environmental effects
may result from pH values outside the range of 6.0 - 9.0.
regulation of this parameter in calcium subcategory effluents is
clearly required. Further, pH must be controlled for effective
removal of chromium present in these effluents.
Parameters Not Selected For Specific Regulation. Fourteen
pollutant parameters - 1,1,2-trichloroethane, chloroform,
methylene chloride, bis(2-ethylhexyl) phthalate, cadmium,tcopper,
lead, nickel, silver, zinc, cobalt, iron, manganese, and oil and
grease - were included in verification analyses but were dropped
from consideration for regulation in this subcategory after
consideration of measured concentration levels and manufacturing
materials and processes.
1,1,2-trichloroethane appeared in 1 of 2 verification samples in
this subcategory. The maximum concentration observed was 0.013
mg/1, which is below the level considered achievable by available
treatment methods. Therefore, 1,1,2-trichloroethane is not
considered for specific regulation in this subcategory.
Chloroform appeared in both wastewater samples analyzed in this
subcategory. It is not a specific raw material or part of any
process in the subcategory. The highest concentration observed
was 0.038 mg/1. Specific treatment methods are not expected to
reduce chloroform below the levels observed in raw wastewater.
Therefore, chloroform is not considered for specific regulation
in this subcategory.
Methylene chloride appeared in 1 of 2 wastewater samples analyzed
in this subcategory. The maximum concentration observed was
0.038 mg/1, which is below the level generally achieved by
469
-------
available treatment methods. Therefore, methylene chloride is
not considered for specific regulation in this subcategory.
Bis (2-ethylhexyl) phthalate appeared in 1 of 2 wastewater
samples analyzed in this subcategory. The maximum measured
concentration was 0.024 mg/1. This ester is widely used as a
plasticizer which would result in its presence in plant piping
and equipment. Its presence is therefore not related to a
specific process source. Therefore, although the measured
concentrations may exceed levels attainable by specific
treatment, specific regulation of bis (2-ethylhexyl) phthalate is
not considered.
Cadmium appeared in 1 of 2 wastewater samples analyzed in this
subcategory. The highest measured concentration is 0.002 mg/1
which is below the level which can be achieved by specific
treatment. Therefore, cadmium is not considered for specific
regulation in this subcategory.
Copper appeared at measurable levels in both samples analyzed in
the calcium subcategory. The maximum concentration found was
0.150 mg/1. This concentration is lower than concentrations
achieved by specific treatment for this metal. Therefore," copper
is not considered for specific regulation.
Lead appeared in 1 of 2 wastewater samples from this subcategory.
It occurred at a maximum concentration of 0.044 mg/1. Since
lower concentrations are not achieved in treatment, specific
regulation of lead in calcium subcategory wastewater effluents is
not considered.
Nickel appeared in 1 of 2 wastewater samples analyzed in this
subcategory. The highest measured concentration was 0.067 mg/1
which is lower than concentrations achieved in specific treatment
for this parameter. Therefore, nickel is not considered for
specific regulation in this subcategory.
Silver appeared in 1 of 2 wastewater samples analyzed in the cal-
cium subcategory. It is not used in the process and was measured
at a maximum concentration of only 0.012 mg/1. Since this is
below the concentration attained in treatment for this parameter,
specific regulation for silver is not considered.
Zinc appeared in both wastewater samples from the calcium sub-
category. The highest concentration measured was 0.110 mg/1.
This is lower than concentrations generally achieved in specific
treatment for this parameter. Therefore, zinc is not considered
for specific regulation in this subcategory.
470
-------
Cobalt appeared in one wastewater sample in this subcategory but
occurred at a maximum concentration of only 0.006 mg/1. This is
below the concentations of this pollutant achievable by specific
treatment. Therefore, specific regulation of cobalt is not
considered.
Iron appeared in both wastewater samples from the calcium
subcategory. The highest measured concentration was 0.52 mg/1
which is lower than the concentrations achieved in specific
treatment for this parameter. Therefore, iron is not considered
for specific regulation in this subcategory.
Oil and grease did not appear in wastewater samples from this
subcategory. Therefore, specific regulation of this parameter is
not considered.
Leclanche Subcategory
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-10 (page 401), 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 in 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
471
-------
be removed by specific treatment methods. Therefore, it is
considered for specific regulation.
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
wastewater 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
472
-------
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.
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
473
-------
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 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. The detection is
considered unique because antimony is not used or introduced in
the raw materials of the battery manufacturing process in this
subcategory. 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. Based on the
results of sampling and analysis of the manufacturing elements
and wastewater sources listed in Figure V-12 (Page 403), and a
careful examination of raw materials, nine pollutant parameters
were selected for consideration for specific regulation. These
parameters are asbestos, chromium, lead, zinc, cobalt, iron,
manganese, TSS, and pH. These pollutants were found in process
wastewater from this subcategory at concentrations which are
amenable to control by specific treatment methods.
Asbestos appeared in 2 of 4 raw waste streams from this
subcategory which were characterized by sampling. The highest
measured concentration was 630 million fibers per liter.
Asbestos in process waste streams from the subcategory results
primarily from its use in heat paper manufacture. Therefore,
asbestos is considered for specific regulations.
474
-------
Chromium appeared in all four sampled waste streams in the
subcategory. The highest concentration observed was 120 mg/1.
This concentration results from the use of barium chromate in
heat paper manufacture. Other process waste streams contain less
than 0.02 mg/1 of total chromium. Since chromium is known to be
a process raw material in the subcategory, and it is found in
process wastewater at treatable concentrations, it is considered
for specific regulation.
Lead appeared in 2 of 4 sampled wastewater'streams in this
subcategory at concentrations of up to 4.94 mg/1. This
concentration was observed in the wastewater from iron disulfide
cathode manufacture. Other process waste streams contained less
than 0.05 mg/1 of lead. The highest concentrations of lead
observed in sampling exceed the concentrations which may be
achieved by treatment. Therefore, lead is considered for
specific regulation.
Zinc appeared in all of the process wastewater streams from this
subcategory which were characterized by sampling. The maximum
observed concentration was 0.473 mg/1. This concentration
exceeds levels which can be achieved by treatment. Therefore
zinc is considered for specific regulation.
Cobalt appeared in 2 of 4 raw wastewater streams from the lithium
subcategory. The highest measured concentration is 0.176 mg/1.
Since the observed concentration is above levels which are
achieved in treatment, cobalt is considered for specific
regulation.
Iron appeared in all wastewater streams in this subcategory. It
was measured at a maximum concentration of 54.9 mg/1. The
measured concentrations are substantially higher than those
achieved in treatment. Therefore iron is considered for specific
regulation in this subcategory.
Manganese appeared in all wastewater streams in the lithium
subcategory, with a maximum concentration of 1.60 mg/1.
Manganese concentrations in all other process waste streams are
less than 0.04 mg/1. Specific treatment for the removal of
manganese can achieve concentrations substantially below 1.6
mg/1. Therefore manganese is considered for specific regulation.
Suspended solids appeared in all of the process waste streams
characterized by sampling in this subcategory. The maximum
concentration was 715 mg/1. Suspended solids in process
wastewater in this subcategory contain asbestos, barium chromate,
and metal hydroxides. Specific treatment methods remove TSS
below the levels which were measured in all wastewater samples.
475
-------
Therefore specific regulation of TSS in wastewater effluents from
the lithium subcategory is considered.
The pH of 4 raw wastewater samples in the lithium subcategory
ranged from 2.9 to 6.2. Acidic pH values result from the use of
acidic solutions in heat paper manufacture and from the iron
disulfide cathode manufacturing process. Deleterious
environmental effects may result from wastewater pH values
outside the range of 6.0-9.0. Further, pH must be controlled for
effective removal of other pollutants from these process waste
streams. Therefore, pH is considered for specific regulation.
Parameters Not Selected For Regulation. Ten pollutant parameters
which were evaluated in verification analysis were dropped from
further consideration for regulation in the lithium subcategory.
These parameters were found to be present in process wastewaters
infrequently, or at concentrations below those usually achieved
by specific treatment methods. Pollutants dropped from
consideration are: 1,1,2-trichloroethane, chloroform, methylene
chloride, bis(2-ethylhexyl)phthalate, cadmium, copper, nickel,
silver, lithium, and oil and grease.
1/1,2-trichloroethane appeared in 2 of 4 samples analyzed in this
subcategory. The maximum concentration observed was 0.013 mg/1.
Available specific treatment methods are not expected to reduce
1/1/2-trichloroethane present in wastewater below this
concentration. Therefore, it is not considered for specific
regulation in this subcategory.
Chloroform concentrations appeared in all of the wastewater
streams analyzed in this subcategory. In two of these samples,
however/ it was present below the analytical quantifiable limit.
The maximum reported concentration was 0.038 mg/1. This
concentration is lower than those generally achieved by available
specific treatment methods. Therefore, chloroform is not
considered for specific regulation in the lithium subcategory.
Methylene chloride appeared in only 2 of 4 raw wastewater streams
in this subcategory. The highest measured concentration was
0.016 mg/1. 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.
Bis(2-ethylhexyl)phthalate appeared in 2 of 4 raw wastewater
streams in this subcategory. The maximum concentration observed
was 0.024 mg/1. This pollutant is not a raw material or process
chemical in this battery manufacturing subcategory and is found
widely distributed in industrial environments as a result of its
476
-------
use as a plasticizer. Therefore, bis(2-ethylhexyl)phthalate is
not considered for specific regulation in this subcategory.
Cadmium appeared in 2 of 4 sampled wastewater streams in the
lithium subcategory. The highest measured concentration was
0.025 mg/1. This concentration is below levels achievable by
available specific treatment methods. Therefore, cadmium is not
considered for specific regulation.
Copper appeared in all four wastewater streams characterized by
sampling in this subcategory. The maximum measured concentration
was 0.15 mg/1. Since this concentration is below the levels
achieved by available specific treatment methods, copper is not
considered for specific regulation in the lithium subcategory.
Nickel appeared in 3 of 4 wastewater streams in the lithium
subcategory. The maximum concentration observed was 0.235 mg/1.
Available specific treatment methods are not expected to achieve
lower concentrations. Therefore, nickel is not considered for
specific regulation in this subcategory.
Silver appeared in 2 of 4 sampled wastewater streams in the
lithium subcategory. The highest measured concentration was
0.006 mg/1. This is lower than effluent concentrations achieved
by available specific treatment methods. Therefore silver is not
considered for specific regulation in this subcategory.
Lithium appeared in 1 of 4 sampled wastewater streams in this
subcategory. The measured concentration in that sample (from
lithium scrap disposal) was 0.59 mg/1. Available specific
treatment methods will not reduce lithium present in wastewater
below this level. Therefore, lithium is not selected for spe-
cific regulation in this subcategory.
Oil and grease appeared in only 1 of 4 wastewater streams in the
lithium subcategory. The measured concentration in that stream
was only 1 mg/1. This is lower than concentrations achieved by
available specific treatment methods. Therefore, oil and grease
is not considered for specific regulation.
Magnesium Subcategory
Parameters Selected For Specific Regulation. Based on the
results of all sampling and analysis of the manufacturing
elements and wastewater sources listed in Figure V-14 (Page 405),
and a careful review of magnesium subcategory raw materials,
seven pollutant parameters were selected to be considered for
specific regulation. These are asbestos, chromium, lead, silver,
TSS, COD and pH. They were observed at significant levels in raw
477
-------
wasterwater produced in this subcategory, and are amenable to
control by identified wastewater treatment and control practices.
Asbestos appeared in all process wastewater samples analyzed in
this subcategory. For the heat paper production process element
asbestos is used as a raw material. For the silver chloride
process elements, the presence of asbestos is attributable to
plant influent and not to the processes. Asbestos is therefore
considered for specific regulation.
Chromium appeared in two process wastewater samples analyzed for
verification for heat paper production, and also in one raw
wastewater sample for the silver chloride electrolytically
oxidized cathode waste stream. Chromium is removed by treatment
to levels less than those observed in raw wastewater samples.
Therefore, chromium is considered for regulation.
Lead appeared in 2 of 5 process wastewater samples considered in
this subcategory. The maximum concentration of 0.170 mg/1 can be
reduced by specific treatment. Therefore, lead is considered for
regulation.
Silver appeared in all but one process wastewater sample
considered in this subcategory. Two samples from the silver
chloride process were at concentrations that could be treated,
and also silver is a raw material for this process. Therefore,
silver is considered for specific regulation.
Suspended solids appeared in all process wastewater samples
considered. Measured concentrations were up to 715 mg/1, which
was from heat paper production. Some of the TSS is comprised of
asbestos and barium chromate. Because this conventional
pollutant contains quantities of priority pollutants, TSS
requires consideration for regulation in both direct and indirect
discharges from this subcategory.
COD was analyzed only for samples taken in the silver chloride
surface reduced cathode process element. This was done because
phenolic compounds are used in the process and because of the
limitations of 4AAP total phenol analysis. COD appeared at 140
mg/1 for the total process, but was as high as 4100 mg/1 in the
developer solution. Therefore, COD is considered for specific
regulation in this subcategory.
The pH of wastewater streams in this subcategory was observed to
range from 1.0 to 10.6. Since deleterious environmental effects
may result from pH values outside the range of 6.0 to 9.0,
regulation of this parameter is required.
478
-------
Parameters Not Selected For Specific Regulation. Sixteen
pollutant parameters - 1,1,2-trichloroethane, chloroform,
methylene chloride, dichlorobromomethane, bis(2-ethylhexyl)
phthalate, di-n-octyl phthalate, toluene, cadmium, copper,
mercury, nickel, zinc, cobalt, iron, manganese, and oil and
grease - are not considered for regulation. They were included
in verification analyses for heat paper production or detected in
the silver chloride analyses, but were dropped after
consideration of measured concentration levels and manufacturing
materials and processes.
1,1,2-trichloroethane appeared in 1 of 5 samples considered in
this subcategory. The concentration of 0.013 mg/1, is below the
level considered achievable by available treatment methods.
Therefore, the pollutant is not considered for specific
regulation in this subcategory.
Chloroform appeared in all wastewater samples considered in this
subcategory. The maximum concentration observed was 0.155 mg/1.
Since both influent water samples paired with the process waste-
water samples contained higher concentrations than the process
water, the pollutant is not attributable to the process and is
not considered for regulation.
Methylene chloride appeared in 2 of 5 samples considered in this
subcategory. The maximum concentration observed was 0.038 mg/1,
which is below the level generally achieved by available treat-
ment methods. Therefore, methylene chloride is not considered
for specific regulation in this subcategory.
Dichlorobromomethane appeared in 1 of 3 wastewater samples
considered in this subcategory. The concentration observed was
0.026 mg/1, which is below the level generally achieved by
available treatment methods. Therefore, this pollutant is not
considered for specific regulation in this subcategory.
Bis(2-ethylhexyl) phthalate appeared in 2 of 5 wastewater samples
considered in this subcategory. The maximum concentration was
0.024 mg/1. This ester is widely used as a plasticizer which
would result in its presence in plant piping and equipment, and
its presence cannot be related to a specific process source in
this battery manufacturing subcategory. Therefore, although the
measured concentration may exceed the level attainable by
specific treatment, regulation of bis-(2-ethylhexyl) phthalate is
not considered.
Di-n-octyl phthalate appeared in 1 of 3 wastewater samples
considered in this subcategory. The concentration observed,
0.051 mg/1, is treatable, however, the pollutant cannot be
related to a specific process source in this battery
479
-------
manufacturing subcategory and also does not have ambient water
criteria concentrations proposed. Therefore, regulation of di-n-
ocytl phthalate is not considered.
Cadmium appeared in 1 of 5 wastewater samples considered in this
subcategory. The measured concentration was 0.002 mg/1, which is
below the level which can be achieved by specific treatment.
Therefore, cadmium is not considered for specific regulation in
this subcategory.
Copper appeared in all process wastewater samples considered in
this subcategory. The maximum concentration was 0.150 mg/1.
This concentration is lower than concentrations achieved by
specific treatment for the metal. Therefore, copper is not
considered for specific regulation.
Mercury appeared in one process wastewater sample considered in
this subcategory. Since the concentration observed is below
specific treatment methods and since it is not known to result
from the process, this pollutant is not considered for specific
regulation.
Nickel appeared in 2 of 5 process wastewater samples considered
in this subcategory. The highest measured concentration was
0.067 mg/1 which is lower than concentrations achieved in
specific treatment for this parameter. Therefore, nickel is not
considered for specific regulation in this subcategory.
Zinc appeared in all process wastewater samples considered in
this subcategory. The maximum concentration was 0.130 mg/1.
This is lower than concentrations generally achieved in specific
treatment for this parameter. Therefore zinc is not considered
for specific regulation in this subcategory.
Cobalt appeared in 1 of 5 wastewater samples considered in the
magnesium subcategory. The concentration was 0.006 mg/1 which is
below the concentrations achievable by treatment. Therefore,
specific regulation is not considered.
Iron appeared in 4 of 5 wastewater samples considered in this
subcategory. The maximum concentration was 0.56 mg/1 which is
lower than concentrations generally achieved by treatment for
this parameter. Therefore, iron is not considered for regulation
in this subcategory.
Oil and grease did not appear in quantifiable concentrations for
any samples considered in this subcategory. Therefore,
regulation is not considered.
480
-------
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-16 (Page 407), 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 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 the nickel impregnated cathode waste streams,
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.
481
-------
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 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.
482
-------
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 the concentrations are greater than the
concentration 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.
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 waste-
water 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.
483
-------
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, 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.
484
-------
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, ethylbenzene is not considered
for specific regulation in this subcategory.
Methylene chloride concentrations appeared in 18 of 67 raw waste-
water 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.
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
naphthalene 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)
485
-------
phthalate is not considered for specific regulation in this
subcategory.
Diethyl phthalate concentrations appeared in 14 of 37 raw waste-
water 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.
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
Table VI-1, (page 488) presents the selection of priority
pollutant parameters considered for regulation for each
subcategory. The selection is based on all sampling results.
The "Not Detected" notation includes pollutants which were not
detected and not selected during screening analysis of total
486
-------
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. "Small Unique Sources" for both screening and
verification includes those pollutants which were present only in
small amounts and includes those samples which were detected at
higher concentrations in the influent or effluent than in the raw
process wastewater, were detected at only one plant, or were
detected and could not be attributed to this point source
category. "Not Treatable" means that concentrations were lower
than the level achievable with the specific treatment methods
considered in Section VII. The "Regulation" notation includes
those pollutants which are considered for regulation. Table VI-2
(page 493) summarizes the selection of nonconventional and
conventional pollutant parameters for consideration for specific
regulation by each subcategory.
487
-------
TRBLE VI-1
PRIORITY FOLLOTANT DISPOSITION
BATTER* MANUFACTURING
Subcategory
00
00
j?ollutarvt
1 Acenapthene
2 Acrelein
3 Acrylonitrile
1 Benzene
5 Benzidine
6 carbon tetrachloride
(tetrachloromethane)
7 Chlorobenzene
8 1,2,1-trichlorobenzene
9 Hexachlorobenzene
10 1,2-dichloroethane
11 1,1,1-t richloroethane
12 Hexachloroethane
13 1,1-dichloroethane
14 1,1,2-trichloroethane
15 1,1,2,2-tetrachloroethane
16 chlcroethane
17 Bis (chloromethyl) ether
18 Bis (2-chloroethyl)ether
19 2-chloroethyl vinyl
ether (irixed)
20 2-chloronaphthalene
21 2,1,6-trichlorophenol
22 Parachlorometa cresol
23 chloroform(trichloromethane)
21 2-chlorophenol
25 1,2-dic hlorobenzene
26 1,3-dichlorobenzene
Cadmium Calcium
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
ND
ND
Leclanche
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SO
ND
ND
ND
Lithium
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
NT
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
ND
ND
Magnesium Zinc
ND
N0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
ND
ND
ND
ND
ND
ND
ND
SO
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
NT
ND
Nf
NQ
ND
ND
ND
ND
ND
ND
NQ
ND
SU
NQ
ND
ND
I1GEND:
ND = NOT DETECTED
NQ * NOT QUANTIFIABLE
SU = SMALL, UNIQUE SOURCES
NT = NOT TBEATABLE
REG = REGULATION CONSIDERED
-------
TABL1
-1
PRIORITY POLLUTANT DISPOSITION
BATTER* MANUFACTURING
gubcategory
-o
OD
fcllutant
27 1,4-dichlorobenzene
28 3,3-dichlorobenzidine
29 1,1-dichloroethylene
30 1,2-trans-dichloroethylene
31 2,4-dichlorophenol
32 1»2-dichloropropane
33 1,2-dichloropropylene
{1,2-dichloropropene)
34 2,4-dimethylphenol
35 2,4-dinitrotoluene
36 2,6-dinitrotoluene
37 1,2-diphenylhydrazine
3 8 Ithylfcenzene
39 Fluoranthene
40 4~chlorophenyl phenyl ether
11 4-bromophenyl phenyl ether
42 Bis (2-chloroisopropyl)ether
43 Bis (2-chloroethoxyl)methane
44 Methylene chloride
(dichloromethane)
45 Methyl chloride
(ehloromethane)
46 Methyl bromide
(bromomethane)
47 Bromofortn
(tribromomethane)
48 Dichlorobromomethane
49 irichlcrofluoromethane
50 Dichlorodifluoromethane
51 Chlorodibromomethane
52 Hexachlorobutadiene
53 Hexachlorocyclopentadiene
54 laophorone
55 Naphthalene
56 Nitrobenzene
Cadmium Calcium
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
BD
ND
ND
ND
ND
ND
NQ
ND
ND
ND
NQ
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
NT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Leclanche
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
NQ
ND
ND
NQ
ND
ND
ND
ND
ND
Lithium
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Magnesium Zinc
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
ND
ND
" ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
NT
ND
ND
ND
NT
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NT
ND
-------
fABLE VI-1
PRIORITY POLLOTANE DISPOSITION
BATTERJf MANUFACTURING
Sttbcategory
•p-
VD
O
jgollutant
57 2-nitrophenol
58 1-nitrophenol
59 2,4-dinitrophenol
60 i»,6-dinitro-o-c£esol
61 N-nitrosodimethylamine
62 N-nitrosodiphenylamine
63 N-nitrosodi-n-propylamine
64 Pentachlorophenol
6 5 Phenol
66 Bis(2-etbylhexyl) 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
(benzo(a)anthracene)
7 3 Benzo (a)pyrene
(3,4-benzopyrene)
74 3,4-Benzofluoranthene
(benzo(b)fluoranthene)
75 11,12-benzofluoranthene
(benzo (b)fluoranthene
76 Chrysene
77 Acenaphthylene
78 Anthracene
79 1,12-benzoperylene
(benzo(ghi)perylene)
80 Fluorene
81 Phenanthrene
82 1,2,5,6-d ibenz anthracene
dibenzo (,h)anthracene
83 Indeno(1,2,3-cd) pyrene
(2,3-o-phenylene pyrene)
84 Pyrene
85 letrachloroethylene
Cadmium Calcium
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
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
NQ
ND-
SU
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Leclanche
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
NQ
NQ
NQ
NT
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Lithium
ND
ND
ND
ND
ND
ND
ND
NQ
ND
SO
NQ
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Magnesium Zinc
ND
ND
ND
ND
ND
ND
ND
NQ
ND
SO
ND
NQ
SO
ND
ND
ND
ND
ND
ND
ND
ND
ND
SO
SO
SO
NQ
NQ
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
ND
NQ
NQ
ND
ND
NQ
NQ
-------
TABLE VI-1
PRIORITY POLLUTANT DISPOSITION
BATTER* MANUFACTURING
Subcateggry
Pollutant
Cadmium Calcium
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
10 4
105
106
107
108
109
110
111
112
113
111
115
116
117
118
119
120
121
loluene
Irichloroethylene
Vinyl chloride
(chloroethylene)
Aldzin
Dieldrin
Chlordane (technical
mixture and metabolites)
4,4-DDl
4,4-DDI (p,p-DDX)
4,4-DDD (p,p-TDE)
Alpha-endosulfan
Beta-endosulfan
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
(BHC hexachlorohexane)
Alpha-BHC
Beta-BBC
Gamma-BBC (lindane)
Delta-BHC (PCB-poly-
cblorinated biphenyls)
PCB-1232 (Arochlor 1242)
(Arochlor 1254)
(Arochlor 1221)
(Arochlor 1232)
(Arochlor 12*8)
{Arochlor 1260)
(Arochlor 1016)
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
loxaphene
Antimony
Arsenic
Asbestos
Beryllium
Cadirium
Chrcmium
Copper
Cyanide
SU
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SU
NQ
RES
REG
SU
REG
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
REG
NQ
NT
REG
NT
ND
Leclanche
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SU
REG
ND
NQ
REG
REG
REG
SU
Lithium
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
REG
NQ
NT
REG
NT
NT
Magnesium Zinc
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
NQ
RES
NQ
NT
REG
NT
•ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
TO
ND
ND
NQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NQ
REG
ND
NQ
REG
REG
REG
REG
-------
TABLE VI-1
PRIORI!* POLLUTANT DISPOSITION
BATTER* MANUFACTURING
jcllutant
122 Lead
123 Mercury
124 Nickel
125 Selenium
126 Silver
127 lhallium
128 Zinc
129 2,3,7,8-tetraehlorodi-
benzo-p-dioxin
Cadmium Calcium
RIG
REG
REG
ND
Reg -
ND
REG
ND
NT
NQ
NT
NQ
NT
NQ
NT
ND
Subcategory
Leclanche Lithium
RIG
REG
REG
REG
NQ
ND
REG
ND
REG
NQ
NT
NQ
NT
NQ
REG
ND
Magnesium zinc
REG
NT
NT
NQ
REG
NQ
NT
REG
REG
REG
REG
REG
ND
REG
ND
ND
1 For all subcategory elements except silver cathodes and related processes
-------
Muirinum
Cobalt
Iron
Manganese
Oil B Grease
1SS
pH
COD
TABLE VI-2
Other Pollutants Considered for Regulation
Subcategory
Cadmium Calcium Leclanche Lithimn Kggn_esium Zinc
X
X
X X
X X
X
X
X XX
X X
XX X
XX XX
XX XX
X
-------
494
-------
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. These
treatment technologies are widely used in many industrial
categories, and data and information to support their
effectiveness has been drawn from a similarly wide range of
sources and data bases.
END-OF-PIPE TREATMENT TECHNOLOGIES
Individual recovery and treatment technologies are described
which are used or are suitable for use in treating wastewater
discharges from battery manufacturing plants. Each description
includes a functional description and discussion of application
and performance, advantages and limitations, operational factors
(reliability, maintainability., solid waste aspects), and
demonstration status. The treatment processes described include
both technologies presently demonstrated within the battery
manufacturing category, and technologies demonstrated in
treatment of similar wastes in other industries.
Battery manufacturing wastewaters characteristically may be acid
or alkaline; may contain substantial levels of dissolved or
particulate metals including cadmium, chromium, lead, mercury,
nickel, silver, zinc and manganese; contain only small or trace
amounts of toxic organics; and are generally free from strong
chelating agents. The toxic inorganic pollutants constitute the
most significant wastewater pollutants in this category.
In general, these pollutants are removed by chemical
precipitation and sedimentation or filtration. Most of them may
be effectively removed by precipitation of metal hydroxides or
carbonates utilizing the reaction with lime, sodium hydroxide, or
sodium carbonate. For some, improved removals are provided by
the use of sodium sulfide or ferrous sulfide to precipitate the
pollutants as sulfide compounds with very low solubilities.
Discussion of end-of-pipe treatment technologies is divided into
three parts: the major technologies; the effectiveness of major
technologies; and minor end-of-pipe technologies.
495
-------
MAJOR TECHNOLOGIES
In Sections IX, X, XI, and XII the rationale for selecting
treatment systems is discussed. The individual technologies used
in the system are described here. The major end-of-pipe
technologies for treating battery manufacturing wastewaters are:
(1) chemical reduction of chromium, (2) chemical precipitation,
(3) cyanide precipitation, (4) granular bed filtration, (5)
pressure filtration, (6) settling, and (7) skimming. In
practice, precipitation of metals and settling of the resulting
precipitates is often a unified two-step operation. Suspended
solids originally present in raw wastewaters are not appreciably
affected by the precipitation operation and are removed with the
precipitated metals in the settling operations. Settling
operations can be evaluated independently of hydroxide or other
chemical precipitation operations, but hydroxide and other
chemical precipitation operations can only be evaluated in
combination with a solids removal operation.
1 . Chemical Reduction of_ Chromium
Description of. the Process. Reduction is a chemical reaction in
which electrons are transferred to the chemical being reduced
from the chemical initiating the transfer (the reducing agent).
Sulfur dioxide, sodium bisulfite, sodium metabisulfite, and
ferrous sulfate form strong reducing agents in aqueous solution
and are often used in industrial waste treatment facilities for
the reduction of hexavalent chromium to the trivalent form. The
reduction allows removal of chromium from solution in conjunction
with other metallic salts by alkaline precipitation. Hexavalent
chromium is not precipitated as the hydroxide.
Gaseous sulfur dioxide is a widely used reducing agent and
provides a good example of the chemical reduction process.
Reduction using other reagents is chemically similar. The
reactions involved may be illustrated as follows:
3 S02 + 3 H20 > 3 H2SO3
3 H2S03 + 2H2Cr04 > Cr2(S04)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
496
-------
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 VII-4 (Page 616)
shows a continuous chromium reduction system.
Application and Performance. Chromium reduction is used in
battery manufacturing for treating chromium containing cell wash
solutions and heat paper production wastewater. Chromium
reduction is most usually required to treat electroplating and
metal surfacing rinse waters, but may also be required in battery
manufacturing plants. A study of an operational waste treatment
facility chemically reducing hexavalent 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.
Advantages and Limitations. The major advantage of chemical
reduction to reduce hexavalent chromium is that it is a fully
proven technology based on many years of experience. Operation
at ambient conditions results in minimal energy consumption, and
the process, especially when using sulfur dioxide, is well suited
to automatic control. Furthermore, the equipment is readily
obtainable from many suppliers, and operation is straightforward.
One limitation of chemical reduction of hexavalent chromium is
that for high concentrations of chromium, the cost of treatment
chemicals may be prohibitive. When this situation occurs, other
treatment techniques are likely to be more economical. Chemical
interference by oxidizing agents is possible in the treatment of
mixed wastes, and the treatment itself may introduce pollutants
if not properly controlled. Storage and handling of sulfur
dioxide is somewhat hazardous.
Operational Factors. Reliability: Maintenance consists of
periodic removal of sludge, the frequency of removal depends on
the input concentrations of detrimental constituents.
Solid Waste Aspects:. Pretreatment to eliminate substances which
will interfere with the process may often be necessary. This
process produces trivalent chromium which can be controlled by
further treatment. However, small amounts of sludge may be
collected as the result of minor shifts in the solubility of the
contaminants. This sludge can be processed by the main sludge
treatment equipment.
497
-------
Demonstration Status. The reduction of chromium waste by sulfur
dioxide or sodium bisulfite is a classic process and is used by
numerous plants which have hexavalent chromium compounds in
wastewaters from operations such as electroplating conversion
coating and noncontact cooling.
2. Chemical Precipitation
Dissolved toxic metal ions and certain anions may be chemically
precipitated for removal by physical means such as sedimentation,
filtration, or centrifugation. Several reagents are commonly
used to effect this precipitation:
1) Alkaline compounds such as lime or sodium hydroxide may be
used to precipitate many toxic metal ions as metal
hydroxides. Lime also may precipitate phosphates as
insoluble calcium phosphate, fluorides as calcium fluoride,
and arsenic as calcium arsinate.
2) Both "soluble" sulfides such as hydrogen sulfide or sodium
sulfide and "insoluble" sulfides such as ferrous sulfide may
be used to precipitate many heavy metal ions as metal
sulfides.
3) Ferrous sulfate, zinc sulfate or both (as is required) may
be used to precipitate cyanide as a ferro or zinc
ferricyanide complex.
4) Carbonate precipitates may be used to remove metals either
by direct precipitation using a carbonate reagent such as
calcium carbonate or by converting hydroxides into
carbonates using carbon dioxide.
These treatment chemicals may be added to a flash mixer or rapid
mix tank, to a presettling tank, or directly to a clarifier or
other settling device. Because metal hydroxides tend to be col-
loidal in nature, coagulating agents may also be added to faci-
litate settling. After the solids have been removed, final pH
adjustment may be required to reduce the high pH created by the
alkaline treatment chemicals.
Chemical precipitation as a mechanism for removing metals from
wastewater is a complex process of at least two steps - pre-
cipitation of the unwanted metals and removal of the precipitate.
Some very small amount of metal will remain dissolved in the
wastewater after complete precipitation. The amount of residual
dissolved metal depends on the treatment chemicals used and
related factors. The effectiveness of this method of removing
any specific metal depends on the fraction of the specific metal
in the raw waste (and hence in the precipitate) and the
498
-------
effectiveness of suspended solids removal. In specific
instances, a sacnticai ion sucn as iron or aluminum may be added
to aid in the removal of toxic metals by co-precipitation process
and reduce t-.h^ fraction of a specific metal in the precipitate.
Application and Performance. Chemical precipitation is used in
battery manufacturing for precipitation of dissolved metals. It
can be used to remove metal ions such as antimony, arsenic,
beryllium, cadmium, chromium, copper, lead, mercury, zinc,
aluminum, cobalt, iron, manganese, molybdenum, and tin. The
process is also applicable to any substance that can be
transformed into an insoluble form such as fluorides, phosphates,
soaps, sulfides and others. Because it is simple and effective,
chemical precipitation is extensively used for industrial waste
treatment.
The performance of chemical precipitation depends on several
variables. The more important factors affecting precipitation
effectiveness are:
1. Maintenance of an appropriate (usually alkaline) pH
throughout the precipitation reaction and subsequent
settling;
2. Addition of a sufficient excess of treatment ions to
drive the precipitation reaction to completion;
3. Addition of an adequate supply of sacrifical ions (such
as iron or aluminum) to ensure precipitation and
removal of specific target ions; and
4. Effective removal of precipitated solids (see
appropriate solids removal technologies).
Control of pH. Irrespective of the solids removal technology
employed, proper control of pH is absolutely essential for
favorable performance of precipitation-sedimentation
technologies. This is clearly illustrated by solubility curves
for selected metals hydroxides and sulfides shown in Figure VII-1
(page 613), and by plotting effluent zinc concentrations against
pH as shown in Figure VII-3 (page 615). Figure VII-3 was
obtained from Development Document for the Proposed Effluent
Limitations Guidelines and New Source Performance Standards for
the Zinc Segment of Nonferrous Metals Manufacturing Point Source
Category, U.S. E.P.A., EPA 440/1-74/033, November, 1974. Figure
VII-3 was plotted from the sampling data from several facilities
with metal finishing operations. It is partially illustrated by
data obtained from 3 consecutive days of sampling at one metal
processing plant (47432) as displayed in Table VII-1 (page 592).
499
-------
Flow through this system is approximately 49,263 1/hr (13,000
gal/hr).
This treatment system uses lime precipitation (pH adjustment)
followed by coagulant addition and sedimentation. Samples were
taken before (in) and after (out) the treatment system. The best
treatment for removal of copper and zinc was achieved on day one,
when the pH was maintained at a satisfactory level. The poorest
treatment was found on the second day, when the pH slipped to an
unacceptably low level; intermediate values were achieved on the
third day, when pH values were less than desirable but in between
those for the first and second days.
Sodium hydroxide is used by one facility (plant 439) for pH
adjustment and chemical precipitation, followed by settling
(sedimentation and a polishing lagoon) of precipitated solids.
Samples were taken prior to caustic addition and following the
polishing lagoon. Flow through the system is approximately
22,700 1/hr (6,000 gal/hr). These data displayed in Table VII-2
(page 592) indicate that the system was operated efficiently.
Effluent pH was controlled within the range of 8.6 to 9.3, and,
while raw waste loadings were not unusually high, most toxic
metals were removed to very low concentrations.
Lime and sodium hydroxide (combined) are sometimes used to
precipitate metals. Data developed from plant 40063, a facility
with a metal bearing wastewater, exemplify efficient operation of
a chemical precipitation and settling system. Table VII-3 (page
593) 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
19,000 1/hr (5,000 gal/hr).
At this plant, effluent TSS levels were below 15 mg/1 on each
day, despite average raw waste TSS concentrations of over 3500
mg/1. Effluent pH was maintained at approximately 8, lime
addition was sufficient to precipitate the dissolved metal ions,
and the flocculant addition and clarifier retention served to
remove effectively the precipitated solids.
Sulfide precipitation is sometimes used to precipitate metals
resulting in improved metals removals. Most metal sulfides are
less soluble than hydroxides, and the precipitates are frequently
more dependably removed from water. Solubilities for selected
metal hydroxide, carbonate and sulfide precipitates are shown in
Table VII-4 (page 593). (Source: Lange's Handbook of Chemistry).
Sulfide precipitation is particularly effective in removing
specific metals such as silver and mercury. Sampling data from
500
-------
three industrial plants using sulfide precipitation appear in
Table VII-5 (page 594). In all cases except iron, effluent
concentrations are below 0.1 mg/1 and in many cases below 0.01
mg/1 for the three plants studied.
Sampling data from several chlorine-caustic manufacturing plants
using sulfide precipitation demonstrate effluent mercury
concentrations varying between 0.009 and 0.03 mg/1. As shown in
Figure VII-1, the solubilities of PbS and Ag2S are lower at
alkaline pH levels than either the corresponding hydroxides or
other sulfide compounds. This implies that removal performance
for lead and silver sulfides should be comparable to or better
than that for the metal hydroxides. Bench scale tests on several
types of metal finishing and manufacturing wastewater indicate
that metals removal to levels of less than 0.05 mg/1 and in some
cases less than 0.01 mg/1 are common in systems using sulfide
precipitation followed by clarification. Some of the bench scale
data, particularly in the case of lead, do not support such low
effluent concentrations. However, lead is consistently removed
to very low levels (less than 0.02 mg/1) in systems using
hydroxide and carbonate precipitation and sedimentation.
Of particular interest is the ability of sulfide to precipitate
hexavalent chromium (Cr+6) without prior reduction to the tri-
valent state as is required in the hydroxide process. When
ferrous sulfide is used as the precipitant, iron and sulfide act
as reducing agents for the hexavalent chromium according to the
reaction:
Cr03+ FeS + 3H20 > Fe(OH)3 + Cr(OH)3 + S
The sludge produced in this reaction consists mainly of ferric
hydroxides, chromic hydroxides, and various metallic sulfides.
Some excess hydroxyl ions are generated in this process, possibly
requiring a downward re-adjustment of pH.
Based on the available data, Table VI1-6 (page 595) shows the
minimum reliably attainable effluent concentrations for sulfide
precipitation-sedimentation systems. These values are used to
calculate performance predictions of sulfide precipitation-
sedimentation systems.
Carbonate precipitation is sometimes used to precipitate metals,
especially where precipitated metals values are to be recovered.
The solubility of most metal carbonates is intermediate between
hydroxide and sulfide solubilities; in addition, carbonates form
easily filtered precipitates.
Carbonate ions appear to be particularly useful in precipitating
lead and antimony. Sodium carbonate has been observed being
501
-------
added at treatment to improve lead precipitation and removal in
some industrial plants. The lead hydroxide and lead carbonate
solubility curves displayed in Figure VII-2 (page 614) ("Heavy
Metals Removal," by Kenneth Lanovette, Chemical
Engineering/Deskbook Issue, October 17, 1977) explain this
phenomenon.
Co-precipitation With Iron - The presence of substantial
quantites of iron in metal bearing wastewaters before treatment
has been shown to improve the removal of toxic metals. In some
cases this iron is an integral part of the industrial wastewater;
in other cases iron is deliberately added as a pre or first step
of treatment. The iron functions to improve toxic metal removal
by three mechanisms: the iron co-precipitates with toxic metals
forming a stable precipitate which desolubilizes the toxic metal/
the iron improves the settleability of the precipitate; and the
large amount of iron reduces the fraction of toxic metal in the
precipitate. Co-precipitation with iron has been practiced for
many years incidentally when iron was a substantial consitutent
of raw wastewater and intentionally when iron salts were added as
a coagulant aid. Aluminum or mixed iron-aluminum salt also have
been used. The addition of iron for co-precipitation to aid in
toxic metals removal is considered a routine part of
state-of-the-art lime and settle technology which should be
implemented as required to achieve optimal removal of toxic
metals.
Co-precipitation using large amounts of ferrous iron salts is
known as ferrite co-precipitation because magnetic iron oxide or
ferrite is formed. The addition of ferrous salts (sulfate) is
followed by alkali precipitation and air oxidation. The
resultant precipitate is easily removed by filtration and may be
removed magnetically. Data illustrating the performance of
ferrite co-precipitation is shown in Table VII-7 (page 596).
Advantages and Limitations. Chemical precipitation has proved to
be an effective technique for removing many pollutants from
industrial wastewater. It operates at ambient conditions and is
well suited to automatic control. The use of chemical
precipitation may be limited because of interference by chelating
agents, because of possible chemical interference with mixed
wastewaters and treatment chemicals, or because of the
potentially hazardous situation involved with the storage and
handling of those chemicals. Battery manufacturing wastewaters
do not normally contain chelating agents or complex pollutant
matrix formations which would interfere with or limit the use of
chemical precipitation. Lime is usually added as a slurry when
used in hydroxide precipitation. The slurry must be kept well
mixed and the addition lines periodically checked to prevent
blocking of the lines, which may result from a buildup of solids.
502
-------
Also, lime precipitation usually makes recovery of the
precipitated metals difficult, because of the heterogeneous
nature of most lime sludges.
The major advantage of the sulfide precipitation process is that
the extremely low solubility of most metal sulfides promotes very
high metal removal efficiencies; the sulfide process also has the
ability to remove chromates and dichromates without preliminary
reduction of the chromium to its trivalent state. In addition,
sulfide can precipitate metals complexed with most complexing
agents. The process demands care, however, in maintaining the pH
of the solution at approximately 10 in order to restrict the gen-
eration of toxic hydrogen sulfide gas. For this reason,
ventilation of the treatment tanks may be a necessary precaution
in most installations. The use of insoluble sulfides reduces the
problem of hydrogen sulfide evolution. As with hydroxide
precipitation, excess sulfide ion must be present to drive the
precipitation reaction to completion. Since the sulfide ion
itself is toxic, sulfide addition must be carefully controlled to
maximize heavy metals precipitation with a minimum of excess
sulfide to avoid the necessity of 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 to hydroxide
precipitants, and disposal of metallic sulfide sludges may pose
problems. An essential element in effective sulfide
precipitation is the removal of precipitated solids from the
wastewater and proper disposal in an appropriate site. Sulfide
precipitation will also generate a higher volume of sludge than
hydroxide precipitation, resulting in higher disposal and
dewatering costs. This is especially true when ferrous sulfide
is used as the precipitant.
Sulfide precipitation may be used as a polishing treatment after
hydroxide precipitation-sedimentation. This treatment
configuration may provide the better treatment effectiveness of
sulfide precipitation while minimizing the variability caused by
changes in raw waste and reducing the amount of sulfide
precipitant required.
Operational Factors. Reliability: Alkaline chemical
precipitation is highly reliable, although proper monitoring and
control are required. Sulfide precipitation systems provide
similar reliability.
Maintainability: The major maintenance needs involve periodic
upkeep of monitoring equipment, automatic feeding equipment,
mixing equipment, and other hardware. Removal of accumulated
503
-------
sludge is necessary for efficient operation of precipitation-
sedimentation systems.
Solid Waste Aspects: Solids which precipitate out are removed in
a subsequent treatment step. Ultimately, these solids require
proper disposal.
Demonstration Status. Chemical precipitation of metal hydroxides
is a classic waste treatment technology used by most industrial
waste treatment systems. Chemical precipitation of metals in the
carbonate form alone has been found to be feasible and is
commercially used to permit metals recovery and water reuse.
Full scale commercial sulfide precipitation units are in
operation at numerous installations, including several plants in
the battery manufacturing category. As noted earlier,
sedimentation to remove precipitates is discussed separately.
Use in Battery Manufacturing Plants. Chemical precipitation is
used at 81 battery manufacturing plants. The quality of
treatment provided, however, is variable. A review of collected
data and on-site observations reveals that control of system
parameters is often poor. Where precipitates are removed by
clarification, retention times are likely to be short and
cleaning and maintenance questionable. Similarly, pH control is
frequently inadequate. As a result of these factors, effluent
performance at battery plants nominally practicing the same
wastewater treatment is observed to vary widely.
3. Cyanide Precipitation
Cyanide precipitation, although a method for treating cyanide in
wastewaters, does not destroy cyanide. The cyanide is retained
in the sludge that is formed. Reports indicate that during
exposure to sunlight, the cyanide complexes can break down and
form free cyanide. For this reason, the sludge from this
treatment method must be disposed of carefully.
Cyanide may be precipitated and settled out of wastewaters by the
addition of zinc sulfate or ferrous sulfate. In the presence of
iron, cyanide will form extremely stable cyanide complexes. The
addition of zinc sulfate or ferrous sulfate forms zinc
ferrocyanide or ferro and ferricyanide complexes.
Adequate removal of the precipitated cyanide requires that the pH
must be kept at 9.0 and an appropriate retention time be
maintained. A study has shown that the formation of the complex
is very dependent on pH. At a pH of either 8 or 10, the residual
cyanide concentration measured is twice that of the same reaction
carried out at a pH of 9. Removal efficiencies also depend
heavily on the retention time allowed. The formation of the
504
-------
complexes takes place rather slowly. Depending upon the excess
amount of zinc sulfate or ferrous sulfate added, at least a 30
minute retention time should be allowed for the formation of the
cyanide complex before continuing on to the clarification stage.
One experiment with an initial concentration of 10 mg/1 of
cyanide showed that (98 percent) of the cyanide was complexed ten
minutes after the addition of ferrous sulfate at twice the
theoretical amount necessary. Interference from other metal
ions, such as cadmium, might result in the need for longer
retention times.
Table VII-8 (page 596) presents cyanide precipitation data from
three coil coating plants. A fourth plant was visited for the
purpose of observing plant testing of the cyanide precipitation
system. Specific data from this facility are not included
because: (1) the pH was usually well below the optimum level of
9.0; (2) the historical treatment data were not obtained using
the standard cyanide analysis procedure; and (3) matched input-
output data were not made available by the plant. Scanning the
available data indicates that the raw waste CN level was in the
range of 25.0; the pH 7.5; and treated CN level was from 0.1 to
0.2.
The concentrations are those of the stream entering and leaving
the treatment system. Plant 1057 allowed a 27-minute retention
time for the formation of the complex. The retention time for
the other plants is not known., The data suggest that over a wide
range of cyanide concentration in the raw waste, the
concentration of cyanide can be reduced in the effluent stream to
under 0.15 mg/1.
Application and Performance. Cyanide precipitation can be used
when cyanide destruction is not feasible because of the presence
of cyanide complexes which are difficult to destroy. Effluent
concentrations of cyanide well below 0.15 mg/1 are possible.
Advantages and Limitations. Cyanide precipitation is an
inexpensive method of treating cyanide. Problems may occur when
metal ions interfere with the formation of the complexes.
4. Granular Bed Filtration
Filtration occurs in nature as the surface ground waters are
cleansed by sand. Silica sand, anthracite coal, and garnet are
common filter media used in water treatment plants. These are
usually supported by gravel. The media may be used singly or in
combination. The multimedia filters may be arranged to maintain
relatively distinct layers by virtue of balancing the forces of
gravity, flow, and buoyancy on the individual particles. This is
505
-------
accomplished by selecting appropriate filter flow rates (gpm/sq-
ft), media grain size, and density.
Granular bed filters may be classified in terms of filtration
rate, filter media, flow pattern, or method of pressurization.
Traditional rate classifications are slow sand, rapid sand, and
high rate mixed media. In the slow sand filter, flux or
hydraulic loading is- relatively low, and removal of collected
solids to clean the filter is therefore relatively infrequent.
The filter is often cleaned by scraping off the inlet face (top)
of the sand bed. In the higher rate filters, cleaning is
frequent and is accomplished by a periodic backwash, opposite to
the direction of normal flow.
A filter may use a single medium such as sand or diatomaceous
earth, but dual and mixed (multiple) media filters allow higher
flow rates and efficiencies. The dual media filter usually
consists of a fine bed of sand under a coarser bed of anthracite
coal. The coarse coal removes most of the influent solids, while
the fine sand performs a polishing function. At the end of the
backwash, the fine sand settles to the bottom because it is
denser than the coal, and the filter is ready for normal
operation. The mixed media filter operates on the same
principle, with the finer, denser media at the bottom and the
coarser, less dense media at the top. The usual arrangement is
garnet at the bottom (outlet end) of the bed, sand in the middle,
and anthracite coal at the top. Some mixing of these layers
occurs and is, in fact, desirable.
The flow pattern is usually top-to-bottom, but other patterns are
sometimes used. Upflow filters are sometimes used, and in a
horizontal filter the flow is horizontal. In a biflow filter,
the influent enters both the top and the bottom and exits
laterally. The advantage of an upflow filter is that with an
upflow backwash, the particles of a single filter medium are
distributed and maintained in the desired coarse-to-fine (bottom-
to-top) arrangement. The disadvantage is that the bed tends to
become fluidized, which ruins filtration efficiency. The biflow
design is an attempt to overcome this problem.
The classic granular bed filter operates by gravity flow;
however, pressure filters are fairly widely used. They permit
higher solids loadings before cleaning and are.advantageous when
the filter effluent must be pressurized for further downstream
treatment. In addition, pressure filter systems are often less
costly for low to moderate flow rates.
Figure VII-14 (page 626) 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
506
-------
that permits gravity upflow of the backwash, with the stored
filtrate serving as backwash. Addition of the indicated
coagulant and polyelectrolyte usually results in a substantial
improvement in filter performance.
Auxilliary filter cleaning is sometimes employed in the upper few
inches of filter beds. This is conventionally referred to as
surface wash and is' accomplished by water jets just below the
surface of the expanded bed during the backwash cycle. These
jets enhance the scouring action in the bed by increasing the
agitation.
An important feature for successful filtration and backwashing is
the underdrain. This is the support structure for the bed. The
underdrain provides an area for collection of the filtered water
without clogging from either the filtered solids or the media
grains. In addition, the underdrain prevents loss of the media
with the water, and during the backwash cycle it provides even
flow distribution over the bed. Failure to dissipate the
velocity head during the filter or backwash cycle will result in
bed upset and the need for major repairs.
Several standard approaches are employed for filter underdrains.
The simplest one consists of a parallel porous pipe imbedded
under a layer of coarse gravel and manifolded to a header pipe
for effluent removal. Other approaches to the underdrain system
are known as the Leopold and Wheeler filter bottoms. Both of
these incorporate false concrete bottoms with specific porosity
configurations to provide drainage and velocity head dissipation.
Filter system operation may be manual or automatic. The filter
backwash cycle may be on a timed basis, a pressure drop basis
with a terminal value which triggers backwash, or a solids carry-
over basis from turbidity monitoring of the outlet stream. All
of these schemes have been used successfully.
Application and Performance. Wastewater treatment plants often
use granular bed filters for polishing after clarification,
sedimentation, or other similar operations. Granular bed
filtration thus has potential application to nearly all
industrial plants. Chemical additives which enhance the upstream
treatment equipment may or may not be compatible with or enhance
the filtration process. Normal operating flow rates for various
types of filters are:
Slow Sand 2.04 - 5.30 1/sq m-hr
Rapid Sand 40.74 - 51.48 1/sq m-hr
High Rate Mixed Media 81.48 - 122.22 1/sq m-hr
507
-------
Suspended solids are commonly removed from wastewater streams by
filtering through a deep 0.3-0.9 m (1-3 feet) granular filter
bed. The porous bed formed by the granular media can be designed
to remove practically all suspended particles. Even colloidal
suspensions (roughly 1 to 100 microns) are adsorbed on the
surface of the media grains as they pass in close proximity in
the narrow bed passages.
Properly operated filters following some pretreatment to reduce
suspended solids below 200 mg/1 should produce water with less
than 10 mg/1 TSS. For example, multimedia filters produced the
effluent qualities shown in Table VII-9 (page 621).
Advantages and Limitations. The principal advantages of granular
bed filtration are its comparatively (to other filters) low
initial and operating costs, reduced land requirements over other
methods to achieve the same level of solids removal, and
elimination of chemical additions to the discharge stream.
However, the filter may require pretreatment if the solids level
is high (over 100 mg/1). Operator training must be somewhat
extensive due to the controls and periodic backwashing involved,
and backwash must be stored and dewatered for economical
disposal.
Operational Factors. Reliability: The recent improvements in
filtertechnology 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.
508
-------
Demonstration Status. Deep bed filters are in common use in
municipal treatment plants. Their use in polishing industrial
clarifier effluent is increasing, and the technology is proven
and conventional. Granular bed filtration is used in several
battery manufacturing plants. As noted previously, however,
little data is available characterizing the effectiveness of
filters presently in use within the industry.
5. Pressure Filtration
Pressure filtration works by pumping the liquid through a filter
material which is impenetrable to the solid phase. The positive
pressure exerted by the feed pumps or other mechanical means
provides the pressure differential which is the principal driving
force. Figure VII-15 (page 627) represents the operation of one
type of pressure filter.
A typical pressure filtration unit consists of a number of plates
or trays which are held rigidly in a frame to ensure alignment
and which are pressed together between a fixed end and a
traveling end. On the surface of each plate, a filter made of
cloth or synthetic fiber is mounted. The feed stream is pumped
into the unit and passes through holes in the trays along the
length of the press until the cavities or chambers between the
trays are completely filled. The solids are then entrapped, and
a cake begins to form on the surface of the filter material. The
water passes through the fibers, and the solids are retained.
At the bottom of the trays are drainage ports. The filtrate is
collected and discharged to a common drain. As the filter medium
becomes coated with sludge, the flow of filtrate through the
filter drops sharply, indicating that the capacity of the filter
has been exhausted. The unit must then be cleaned of the sludge.
After the cleaning or replacement of the filter media, the unit
is again ready for operation.
Application and Performance. Pressure filtration is used in
battery manufacturing for sludge dewatering and also for direct
removal of . precipitated and other suspended solids from
wastewater. Because dewatering is such a common operation in
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.
509
-------
Advantages and Limitations. The pressures which may be applied
to a sludge for removal of water by filter presses that are
currently available range from 5 to 13 atmospheres. As a result,
pressure filtration may reduce the amount of chemical
pretreatment required for sludge dewatering. Sludge retained in
the form of the filter cake has a higher percentage of solids
than that from centrifuge or vacuum filter. Thus, it can be
easily accommodated by materials handling systems.
As a primary solids removal technique, pressure filtration
requires less space than clarification and is well suited to
streams with high solids loadings. The sludge produced may be
disposed without further dewatering, but the amount of sludge is
increased by the use of filter precoat materials (usually
diatomaceous earth). Also, cloth pressure filters often do not
achieve as high a degree of effluent clarification as clarifiers
or granular media filters.
Two disadvantages associated with pressure filtration in the past
have been the short life of the filter cloths and lack of
automation. New synthetic fibers have largely offset the first
of these problems. Also, units with automatic feeding and
pressing cycles are now available.
For larger operations, the relatively high space requirements, as
compared to those of a centrifuge, could be prohibitive in some
situations.
Operational Factors. Reliability: With proper pretreatment,
design, and control, pressure filtration is a highly dependable
system.
Maintainability: Maintenance consists of periodic cleaning or
replacement of the filter media, drainage grids, drainage piping,
filter pans, and other parts of the system. If the removal of
the sludge cake is not automated, additional time is required for
this operation.
Solid Waste Aspects: Because it is generally drier than other
types of sludges, the filter sludge cake can be handled with
relative ease. The accumulated sludge may be disposed by any of
the accepted procedures depending on its chemical composition.
The levels of toxic metals present in sludge from treating
battery wastewater necessitate proper disposal.
Demonstration Status. Pressure filtration is a commonly used
technology in a great many commercial applications. Pressure
filtration is used in six battery manufacturing plants.
510
-------
6. ' Settling
Settling is a process which removes solid particles from a liquid
matrix by gravitational force. This is done by reducing the
velocity of the feed stream in a large volume tank or lagoon so
that gravitational settling can occur. Figure VII-16 (page 628)
shows two typical settling devices.
Settling is often preceded by chemical precipitation which
converts dissolved pollutants to solid form and by coagulation
which enhances settling by coagulating suspended precipitates
into larger, faster settling particles.
If no chemical pretreatment is used, the wastewater is fed into a
tank or lagoon where it loses velocity and the suspended solids
are allowed to settle out. Long retention times are generally
required. Accumulated sludge can be collected either
periodically or continuously and either manually or mechanically.
Simple settling, however, may require excessively large
catchments, and long retention times (days as compared with
hours) to achieve high removal efficiencies. Because of this,
addition of settling aids such as alum or polymeric flocculants
is often economically attractive.
In practice, chemical precipitation often precedes settling, and
inorganic coagulants or polyelectrolytic flocculants are usually
added as well. Common coagulants include sodium sulfate, sodium
aluminate, ferrous or ferric sulfate, and ferric chloride.
Organic polyelectrolytes vary in structure, but all usually form
larger floe particles than coagulants used alone.
Following this pretreatment, the wastewater can be fed into a
holding tank or lagoon for settling, but is more often piped into
a clarifier for the same purpose. A clarifier reduces space
requirements, reduces retention time, and increases solids
removal efficiency. Conventional clarifiers generally consist of
a circular or rectangular tank with a mechanical sludge
collecting device or with a sloping funnel-shaped bottom designed
for sludge collection. In advanced settling devices, inclined
plates, slanted tubes, or a lamellar network may be included
within the clarifier tank in order to increase the effective
settling area, increasing capacity. A fraction of the sludge
stream is often recirculated to the inlet, promoting formation of
a denser sludge.
Settling is based on the ability of gravity (Newton's Law) to
cause small particles to fall or settle (Stokes1 Law) through the
fluid they are suspended in. Presuming that the factors
affecting chemical precipitation are controlled to achieve a
readily settleable precipitate, the principal factors controlling
51 1
-------
settling are the particle characteristics and the upflow rate of
the suspending fluid. When the effective settling area is great
enough to allow settling, any increase in the effective settling
area will produce no increase in solids removal.
Therefore, if a plant has installed equipment that provides the
appropriate overflow rate, the precipitated metals in the
effluent can be effectively removed. The number of settling
devices operated in series or in parallel by a facility is not
important with regard to suspended solids removal, but rather
that the settling devices provide sufficient effective settling
area.
Another important facet of sedimentation theory is that
diminishing removal of suspended solids is achieved for a unit
increase in the effective settling area. Generally, it has been
found that suspended solids removal performance varies with the
effective up-flow rate. Qualitatively the performance increases
asymptotically to a maximum level beyond which a decrease in up-
flow rate provides incrementally insignificant increases in
removal. This maximum level is dictated by particle size
distribution, density characteristic of the particles and the
water matrix, chemicals used for precipitation and pH at which
precipitation occurs.
Application and Performance. Settling or clarification is 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
512
-------
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 VII-10 (page 597) indicate suspended
solids removal efficiencies in settling systems. The mean
effluent TSS concentration obtained by the plants shown in Table
VII-10 is 10.1 mg/1. Influent concentrations averaged 838 mg/1.
The maximum effluent TSS value reported is 23 mg/1. These plants
all use alkaline pH adjustment to precipitate metal hydroxides,
and most add a coagulant or flocculant prior to settling.
Advantages and Limitations. The major advantage of simple
settling is its simplicity as demonstrated by the gravitational
settling of solid particulate waste in a holding tank or lagoon.
The major problem with simple settling is the long retention time
necessary to achieve complete settling, especially if the
specific gravity of the suspended matter is close to that of
water. Some materials cannot be practically removed by simple
settling alone.
Settling performed in a clarifier is effective in removing slow-
settling suspended matter in a shorter time and in less space
than a simple settling system. Also, effluent quality is often
better from a clarifier. The cost of installing and maintaining
a clarifier, however, is substantially greater than the costs
associated with simple settling.
Inclined 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.
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
513
-------
shock loadings, as from storm water runoff, but proper system
design will prevent this.
Maintainability: When clarifiers or other advanced settling
devices are used, the associated system utilized for chemical
pretreatment and sludge dragout must be maintained on a regular
basis. Routine maintenance of mechanical parts is also
necessary. Lagoons require little maintenance other than
periodic sludge removal.
Demonstration Status. Settling represents the typical method of
solids removal and is employed extensively in industrial waste
treatment. The advanced clarifiers are just beginning to appear
in significant numbers in commercial applications. Sedimentation
or clarification is used in many battery manufacturing plants as
shown below.
Settling Device No. Plants
Settling Tanks 55
Clarifier 13
Tube or Plate Settler 1
Lagoon 10
Settling is used both as part of end-of-pipe treatment and within
the plant to allow recovery of process solutions and raw
materials. As examples, settling tanks are commonly used on
pasting waste streams in lead acid battery manufacture to allow
recovery of process water and paste solids, and settling sump
tanks are used to recover nickel and cadmium in nickel cadmium
battery manufacture.
7. Skimming
Pollutants with a specific gravity less than water will often
float unassisted to the surface of the wastewater. Skimming
removes these floating wastes. Skimming normally takes place in
a tank designed to allow the floating debris to rise and remain
on the surface, while the liquid flows to an outlet located below
the floating layer. Skimming devices are therefore suited to the
removal of non-emulsified oils from raw waste streams. Common
skimming mechanisms include the rotating drum type, which picks
up oil from the surface of the water as it rotates. A doctor
blade scrapes oil from the drum and collects it in a trough for
disposal or reuse. The water portion is allowed to flow under
the rotating drum. Occasionally, an underflow baffle is
installed after the drum; this has the advantage of retaining any
floating oil which escapes the drum skimmer. The belt type
skimmer is pulled vertically through the water, collecting oil
which is scraped off from the surface and collected in a drum.
514
-------
Gravity separators, such as the API type, utilize overflow and
underflow baffles to skim a floating oil layer from the surface
of the wastewater. An overflow-underflow baffle allows a small
amount of wastewater (the oil portion) to-flow over into a trough
for disposition or reuse while the majority of the water flows
underneath the baffle. This is followed by an overflow baffle,
which is set at a height relative to the first baffle such that
only the oil bearing portion will flow over the first baffle
during normal plant operation. A diffusion device, such as a
vertical slot baffle, aids in creating a uniform flow through the
system and in increasing oil removal efficiency.
Application and Performance. Oil skimming is used in battery
manufacture to remove free oil used as a preservative or forming
lubricant for various metal battery parts. Another source of oil
is lubricants for drive mechanisms and other machinery contacted
by process water. Skimming is applicable to any waste stream
containing pollutants which float to the surface. It is commonly
used to remove free oil, grease, and soaps. Skimming is often
used in conjunction with air flotation or clarification in order
to increase its effectiveness.
The removal efficiency of a skimmer is partly a function of the
retention time of the water in the.tank. Larger, more buoyant
particles require less retention time than smaller particles.
Thus, the efficiency also depends on the composition of the waste
stream. The retention time required to allow phase separation
and subsequent skimming varies from 1 to 15 minutes, depending on
the wastewater characteristics.
API or other gravity-type separators tend to be more suitable for
use where the amount of surface oil flowing through the system is
consistently significant. Drum and belt type skimmers are
applicable to waste streams which evidence smaller amounts of
floating oil and where surges of floating oil are not a problem.
Using an API separator system in conjunction with a drum type
skimmer would be a very effective method of removing floating
contaminants from nonemuls.ified oily waste streams. Sampling
data shown in Table VII-11 (page 598) illustrate the capabilities
of the technology with both extremely high and moderate oil
influent levels.
These data are intended to be illustrative of the very high level
of oil and grease removals attainable in a simple two-step oil
removal system. Based on the performance of installations in a
variety of manufacturing plants and permit requirements that are
consistently achieved, it is determined that effluent oil levels
may be reliably reduced below 10 mg/1 with moderate influent
concentrations. Very high concentrations of oil such as the 22
515
-------
percent shown above may require two step treatment to achieve
this level.
Skimming which removes oil may also be used to remove base levels
of organics. Plant sampling data show that many organic
compounds tend to be removed in standard wastewater treatment
equipment. Oil separation not only removes oil but also organics
that are more soluble in oil than in water. Clarification
removes organic solids directly and probably removes dissolved
organics by adsorption on inorganic solids.
The source of these organic pollutants is not always known with
certainty, although in metal forming operations they seem to
derive mainly from various process lubricants. They are also
sometimes present in the plant water supply, as additives to
proprietary formulations of cleaners, or as the result of
leaching from plastic lines and other materials.
High molecular weight organics in particular are much more
soluble in organic solvents than in water. Thus they are much
more concentrated in the oil phase that is skimmed than in the
wastewater. The ratio of solubilities of a compound in oil and
water phases is called the partition coefficient. The logarithm
of the partition coefficients for selected polynuclear aromatic
hydrocarbon (PAH) and other toxic organic compounds in octanol
and water are shown in Table VI1-12 (page 599).
A review of priority organic compounds commonly found in metal
forming operation waste streams indicated that incidental removal
of these compounds often occurs as a result of oil removal or
clarification processes. When all organics analyses from visited
plants are considered, removal of organic compounds by other
waste treatment technologies appears to be marginal in many
cases. However, when only raw waste concentrations of 0.05 mg/1
or greater are considered, incidental organics removal becomes
much more apparent. Lower values, those less than 0.05 mg/1, are
much more subject to analytical variation, while higher values
indicate a significant presence of a given compound. When these
factors are taken into account, analysis data indicate that most
clarification and oil removal treatment systems remove
significant amounts of the toxic organic compounds present in the
raw waste. The API oil-water separation system performed notably
in this regard, as shown in Table VII-13 (page 600).
Data from five plant days demonstrate removal of organics by the
combined oil skimming and settling operations performed on coil
coating wastewaters. Days were chosen where treatment system
influent and effluent analyses provided paired data points for
oil and grease and the organics present. All organics found at
quantifiable levels on those days were included. Further, only
516
-------
those days were chosen where oil and grease raw wastewater
concentrations exceeded 10 rr.g/1 and where there was reduction in
oil and grease going through the treatment system. All plant
sampling days which met the above criteria are included below.
The conclusion is that when oil and grease are removed, organics
also are removed.
Percent Removal
Plant-Day Oil & Grease Organics
1054-3
13029-2
13029-3
38053-1
38053-2
Mean 96.9 84.2
The unit operation most applicable to removal of trace priority
organics is adsorption, and chemical oxidation is another
possibility. Biological degradation is not generally applicable
because the organics are not present in sufficient concentration
to sustain a biomass and because most of the organics are
resistant to biodegradation.
Advantages and Limitations. Skimming as a pretreatment is
effective in removing naturally floating waste material. It also
improves the performance of subsequent downstream treatments.
Many pollutants, particularly dispersed or emulsified oil, will
not float "naturally" but require additional treatments. There-
fore, skimming alone may not remove all the pollutants capable of
being removed by air flotation or other more sophisticated
technologies.
Operational Factors. Reliability: Because of its simplicity,
skimming is a very reliable technique.
Maintainability: The skimming mechanism requires periodic
lubrication, adjustment, and replacement of worn parts.
Solid Waste Aspects: The collected layer of debris must be
disposed of by contractor removal, landfill, or incineration.
Because relatively large quantities of water are present in the
collected wastes, incineration is not always a viable disposal
method.
Demonstration Status. Skimming is a common operation utilized
extensively by industrial waste treatment systems. Oil skimming
is used in seven battery manufacturing plants.
517
-------
MAJOR TECHNOLOGY EFFECTIVENESS
The performance of individual treatment technologies was
presented above. Performance of operating systems is discussed
here. Two different systems are considered: L&S (hydroxide
precipitation and sedimentation or lime and settle) and LS&F
(hydroxide precipitation, sedimentation, and filtration or lime,
settle, and filter). Subsequently, an analysis of effectiveness
of such systems is made to develop one-day maximum, and ten-day
and thirty-day average concentration levels to be used in
regulating pollutants. Evaluation of the L&S and the LS&F
systems is carried out on the assumption that chemical reduction
of chromium, cyanide precipitation, and oil removal are installed
and operating properly where appropriate.
L&S Performance — Combined Metals Data Base
A data base known as the "combined metals data base" (CMDB) was
used to determine treatment effectiveness of lime and settle
treatment for certain pollutants. The CMDB was developed over
several years and has been used in a number of regulations.
During the development of coil coating and other categorical
effluent limitations and standards, chemical analysis data were
collected of raw wastewater (treatment influent) and treated
wastewater (treatment effluent) from 55 plants (126 data days)
sampled by EPA (or its contractor) using EPA sampling and
chemical analysis protocols. These data are the initial data
base for determining the effectiveness of L&S technology in
treating nine pollutants. Each of the plants in the initial data
base belongs to at least one of the following industry
categories: aluminum forming, battery manufacturing, coil coating
(including canmaking), copper forming, electroplating and
porcelain enameling. All of the plants employ pH adjustment and
hydroxide precipitation using lime or caustic, followed by
Stokes1 law settling (tank, lagoon or clarifier) for solids
removal. An analysis of this data was presented in the
development documents for the proposed regulations for coil
coating and porcelain enameling (January 1981). Prior to
analyzing the data, some values were deleted from the data base.
These deletions were made to ensure that the data reflect
properly operated treatment systems. The following criteria were
used in making these deletions:
- Plants where malfunctioning processes or treatment
systems at the time of sampling were identified.
- Data days where pH was less than 7.0 for extended
periods of time or TSS was greater than 50 mg/1 (these
are prima facie indications of poor operation).
518
-------
In response to the coil coating and porcelain enameling
proposals, some commenters claimed that it was inappropriate to
use data from some categories for regulation of other categories.
In response to these comments, the Agency reanalyzed the data.
An analysis of variance was applied to the data for the 126 days
of sampling to test the hypothesis of homogeneous plant mean raw
and treated effluent levels across categories by pollutant. This
analysis is described in the report "A Statistical Analysis of
the Combined Metals Industries Effluent Data" which is in the
administrative record supporting this rulemaking. Homogeneity is
the absence of statistically discernable differences among the
categories, while heterogeneity is the opposite, i.e., the
presence of statistically discernable differences. The main
conclusion drawn from the analysis of variance is that, with the
exception of electroplating, the categories included in the data
base are generally homogeneous with regard to mean pollutant
concentrations in both raw and treated effluent. That is, when
data from electroplating facilities are included in the analysis,
the hypothesis of homogeneity across categories is rejected.
When the electroplating data are removed from the analysis the
conclusion changes substantially and the hypothesis of
homogeneity across categories is not rejected. On the basis of
this analysis, the electroplating data were removed from the data
base used to determine limitations for the final coil coating and
porcelain enameling regulations and proposed regulations for
copper forming, aluminum forming, battery manufacturing,
nonferrous metals (Phase I), and canmaking.
The statistical analysis provides support for the technical
engineering judgment that electroplating wastewaters are
sufficiently different fro'm the wastewaters of other industrial
categories in the data base to warrant removal of electroplating
data from the data base used to determine treatment
effectiveness.
For the purpose of determining treatment effectiveness,
additional data were deleted from the data base. These deletions
were made, almost exclusively, in cases where effluent data
points were associated with low influent values. This was done
in two steps. First, effluent values measured on the same day as
influent values that were less than or equal to 0.1 mg/1 were
deleted. Second, the remaining data were screened for cases in
which all influent values at a plant were low although slightly
above the 0.1 mg/1 value. These data were deleted not as
individual data points but as plant clusters of data that were
consistently low and thus not relevent to assessing treatment. A
few data points were also deleted where malfunctions not
previously identified were recognized. The data basic to the
CMDB are displayed graphically in Figures VII-4 to 12 (pages 616-
624). The ranges of raw waste concentrations for battery
519
-------
manufacturing are also shown in these figures. These levels of
metals concentrations in the raw waste are within the range of
raw waste concentrations in metals bearing industrial wastewater.
After all deletions, 148 data points from 19 plants remained.
These data were used to determine the concentration basis of
limitations derived from the CMDB used for the proposed battery
manufacturing regulation.
The CMDB was reviewed following its use in a number of proposed
regulations (including battery manufacturing). Comments pointed
out a few errors in the data, and the Agency's review identified
a few transcription errors and some data points that were
appropriate for inclusion in the data that had not been used
previously because of errors in data record identification
numbers. Documents in the record of this rulemaking identify all
the changes, the reasons for the changes, and the effect of these
changes on the data base. Other comments on the CMDB asserted
that the data base was too small and that the statistical methods
used were overly complex. Responses to specific comments are
provided in a document included in the record of this rulemaking.
The Agency believes that the data base is adequate to determine
effluent concentrations achievable with lime and settle
treatment. The statistical methods employed in the analysis are
well known and appropriate statistical references are provided in
the documents in the record that describe the analysis.
The revised data base was reexamined for homogeneity. The
earlier conclusions were unchanged. The categories show good
overall homogeneity with respect to concentrations of the nine
pollutants in both raw and treated wastewaters with the exception
of electroplating.
The same procedures used in developing proposed limitations from
the combined metals data base were then used on the revised data
base. That is, certain effluent data associated with low
influent values were deleted, and then the remaining data were
fit to a lognormal distribution to determine limitations values.
The deletion of data was done in two steps. First, effluent
values measured on the same day as influent values that were less
than or equal to 0.1 mg/1 were deleted. Second, the remaining
data were screened for cases in which all influent values at a
plant were low although slightly above the 0.1 mg/1 value. These
data were deleted not as individual data points but as plant
clusters of data that were consistently low and thus not relevant
to assessing treatment.
The revised combined metals data base used for this final
regulation consists of 162 data points from 18 plants in the same
industrial categories used at proposal. The changes that were
520
-------
made since proposal resulted in slight upward revisions of the
concentration bases for the limitations and standards for zinc
and nickel. The limitations for iron decrease slightly. The
other limitations were unchanged. A comparison of Table VII-21
in the final development document with Table VII-20 in the
proposal development document will show the exact magnitude of
the changes.
One-day Effluent Values
The same procedures used to determine the concentration basis of
the limitations for lime and settle treatment from the CMDB at
proposal were used in the revised CMDB for the final limitations.
The basic assumption underlying the determination of treatment
effectiveness is that the data for a particular pollutant are
lognormally distributed by plant. The lognormal has been found
to provide a satisfactory fit to plant effluent data in a number
of effluent guidelines categories and there was no evidence that
the lognormal was not suitable in the case of the CMDB. Thus, we
assumed measurements of each pollutant from a particular plant,
denoted by X, were assumed followed a lognormal distribution with
log mean n and log variance
-------
plant log variances or average plant variability for the
pollutant.
The one day effluent values were determined as follows:
Let Xij = the jth observation on a particular pollutant at
plant i where
i = 1, ..., I
j = 1, ..., Ji
I = total number of plants
Ji = number of observations at plant i.
Then yij = In Xij
where In means the natural logarithm.
Then "y = log mean over -all plants
where
n = totai number of observations
and
where
V(y) = pooled log variance
- 1)
Si2 = log
plant i
yi - log mean at plant i.
Thus, "y and V(y) are the log mean and log variance, respectively,
of the lognormal distribution used to determine the treatment
effectiveness. The estimated mean and 99th percentile of this
522
-------
distribution form thp basis for the lona term average and daily
maximum effluent limitations, respectively. The estimates are
mean =^(X) = exp(y) * n (0.5 V(y))
99th percentile = H.99 = exp [y + 2.33V/V(y) ]
where * (.) is a Bessel function and exp is e, the base of the
natural logarithms (See Aitchison, J. and J.A.C. Brown, The
Lognormal Distribution, Cambridge University Press, 1963). In
cases where zeros were present in the data, a generalized form of
the lognormal, known as the delta distribution was used (See
Aitchison and Brown, op. cit., Chapter 9).
For certain pollutants, this approach was modified slightly to
ensure that well operated lime and settle plants in all CMDB
categories would achieve the pollutant concentration values
calculated from the CMDB. For instance, after excluding the
electroplating data and other data that did not reflect pollutant
removal or proper treatment, the effluent copper data from the
copper forming plants were statistically significantly greater
than the copper data from the other plants. This indicated that
copper forming plants might have difficulty achieving an effluent
concentration value calculated from copper data from all CMDB
categories. Thus, copper effluent values shown in Table VII-14
(page 600) are based only on the copper effluent data from the
copper forming plants. That is, the log mean for copper is the
mean of the logs of all copper values from the copper forming
plants only and the log variance is the pooled log variance of
the copper forming plant data only. A similar situation occurred
in the case of lead. That is, after excluding the electroplating
data, the effluent lead data from battery manufacturing were
significantly greater than the other categories. This indicated
that battery manufacturing plants might have difficulty achieving
a lead concentration calculated from all the CMDB categories.
The lead values proposed were therefore based on the battery
manufacturing lead data only. Comments, on the proposed battery
manufacturing regulation objected to this procedure and asserted
that the lead concentration values were too low. Following
proposal, the Agency obtained additional lead effluent data from
a battery manufacturing facility with well operated lime and
settle treatment. These data were combined with the proposal
lead data and analyzed to determine the final treatment
effectiveness concentrations. The mean lead concentration is
unchanged at 0.12 mg/1 but the final one-day maximum and monthly
10-day average maximum increased to 0.42 and 0.20 mg/1,
respectively. A complete discussion of the lead data and
analysis is contained in a memorandum in the record of this
rulemaking.
523
-------
In the case of cadmium, after excluding the electroplating data
and data that did not reflect removal or proper treatment, there
were insufficient data to estimate the log variance for cadmium.
The variance used to determine the values shown in Table VI1-14
for cadmium was estimated by pooling the within plant variances
for all the other metals. Thus, the cadmium variability is the
average of the plant variability averaged over all the other
metals. The log mean for cadmium is the mean of the logs of the
cadmium observations only. A complete discussion of the data and
calculations for all the metals is contained in the
administrative record for this rulemaking.
Average Effluent Values
Average effluent values that form the basis for the monthly
limitations were developed in a manner consistent with the method
used to develop one-day treatment effectiveness in that the
lognormal distribution used for the one-day effluent values was
also used as the basis for the average values. That is, we
assume a number of consecutive measurements are drawn from the
distribution of daily measurements. The average of ten
measurements taken during a month was used as the basis for the
monthly average limitations. The approach used for the 10
measurements values was employed previously in regulations for
other categories and was proposed for the battery manufacturing
category. That is, the distribution of the average of 10 samples
from a lognormal was approximated by another lognormal
distribution. Although the approximation is not precise
theoretically, there is empirical evidence based on effluent data
from a number of categories that the lognormal is an adequate
approximation for the distribution of small samples. In the
course of previous work the approximation was verified in a
computer simulation study (see "Development Document for Existing
Sources Pretreatment Standards for the Electroplating Point
Source Category", EPA 440/1-79/003, U.S. Environmental Protection
Agency, Washington, D.C., August 1979). We also note that the
average values were developed assuming independence of the
observations although no particular sampling scheme was assumed.
Ten-Sample Average:
The formulas for the 10-sample limitations were derived on the
basis of simple relationships between the mean and variance of
the distributions of the daily pollutant measurements and the
average of 10 measurements. We assume the daily concentration
measurements for a particular pollutant, denoted by X, follow a
lognormal distribution with_log mean and log variance denoted by
// and
-------
mean of X10 = E(X10) = E(X)
variance of ~X10 = V(X10) = V(X) -r 10.
Where E(X) and V(X) are the mean and variance of X, respectively,
defined above. We then assume that )C10 follows a lognormal
distribution with log jnean »10 and log standard deviation *2.
The mean and variance of X10 are then
EU10) - exp (n 10 + 0.5 *210)
V(X10) = exp (2 „ 10 + «r210) [exp( *210)-1]
Now, v 10 and and a2 obtained for the
underlying lognormal distribution. The 10 sample limitation
value was determined by the estimate of the approximate 99th
percentile of the distribution of the 10 sample average given by
xfo (.99) « exp (7IO + 2.33*0,0).
where ^ J0 and ^ 10 are the estimates of ,10 and e10,
respectively.
Thirty-Sample Average
Monthly average values based on the average of 30 daily
measurements were also calculated. These are included because
monthly limitations based on 30 samples have been used in the
past and for comparison with the 10-sample values. The average
values based on 30 measurements are determined on the basis of a
statistical result known as the Central Limit Theorem. This
Theorem states that, under general and nonrestrictive
assumptions, the distribution of a sum of a number of random
variables, say n, is approximated by the normal distribution.
The approximation improves as the number of variables, n,
increases. The Theorem is quite general in that no particular
distributional form is assumed for the distribution of the
individual variables. In most applications (as in approximating
the distribution of 30-day averages) the Theorem is used to
approximate the distribution of the average of n observations of
a random variable. The result makes it possible to compute
approximate probability statements about the average in a wide
range of cases. For instance, it is possible to compute a value
below which a specified percentage (e.g., 99 percent) of the
averages of n observations are likely to fall. Most textbooks
525
-------
state that 25 or 30 observations are sufficient for the
approximation to be valid. In applying the Theorem to the
distribution of the 30-day average effluent values, we
approximate the distribution of the average of 30 observations
drawn from the distribution of daily measurements and use the
estimated 99th percentile of this distribution.
Thirty-Sample Average Calculation
The formulas for the 30-sample average were based on an
application of the Central Limit Theorem. According to the
Theorem, the average of 30 observations drawn ^rom the
distribution of daily measurements, denoted by ^30/ _is
approximately normally distributed. The mean and variance of X30
are:
mean of ~X30 .=. E(~X30)_= E(X)
variance of X30 = V(X30) = V(X) -t 30.
The 30-sample average value was determined by the estimate of the
approximate 99th percentile of the distribution of the 30-sample
average given by
X-3>J,{.99) = E(X) = 2.33YV(X) t 30
where ^
E(X) « exp(y) fn(0.5V(y))
and V?X) - exp(2y) I *n(2V(y)) - *r
The formulas for E?X) and V?X) .are estimates of E(X) and V(X),
respectively, given in Aitchison, J. and J.A.C. Brown, The
Loqnormal Distribution, Cambridge University Press, 1963, page
45.
Application
In response to the proposed coil coating and porcelain enameling
regulations, the Agency received comments pointing out that
permits usually required less than 30 samples to be taken during
a month while the monthly average used as the basis for permits
and pretreatment requirements usually is based on the average of
30 samples.
In applying the treatment effectiveness values to regulations we
have considered the comments, examined the sampling frequency
required by many permits and considered the change in values of
averages depending on the number of consecutive sampling days in
the averages. The most common frequency of sampling requiredf in
526
-------
permits is about ten samples per month or slightly greater than
twice weekly. The 99th percentiles of the distribution of
averages of ten consecutive sampling days are not substantially
different from the 99th percentile of the distribution's 30-day
average. (Compared to the one-day maximum, the ten-day average
is about 80 percent of the difference between one- and 30-day
values). Hence the ten-day average provides a reasonable basis
for a monthly average limitation and is typical of the sampling
frequency required by existing permits.
The monthly average limitation is to be achieved in all permits
and pretreatment standards regardless of the number of samples
required to be analyzed and averaged by the permit or the
pretreatment authority.
Additional Pollutants
Ten additional pollutant parameters were evaluated to determine
the performance of lime and settle treatment systems in removing
them from industrial wastewater. Performance data for these
parameters is not a part of the CMDB so other data available to
the Agency from other categories has been used to determine the
long term average performance of lime and settle technology for
each pollutant. These data indicate that the concentrations
shown in Table VII-15 (page 601) are reliably attainable with
hydroxide precipitation and settling. Treatment effectiveness
values were calculated by multiplying the mean performance from
Table VII-15 (page 601) by the appropriate variability factor.
(The variability factor is the ratio of the value of concern to
the mean). The pooled variability factors are: one-day maximum -
4.100; ten-day average - 1.821; and 30-day average - 1.618 these
one-, ten-, and thirty-day values are tabulated in Table VII-21
(page 606).
In establishing which data were suitable for use in Table VII-14
two factors were heavily weighed; (1) the nature of the
wastewater; and (2) the range of pollutants or pollutant matrix
in the raw wastewater. These data have been selected from
processes that generate dissolved metals in the wastewater and
which are generally free from complex ing agents. The pollutant
matrix was evaluated by comparing the concentrations of
pollutants found in the raw wastewaters with the range of
pollutants in the raw wastewaters of the combined metals dat^a
set. These data are displayed in Tables VII-16 (page 601) ana
VII-17 (page 602) and indicate that there is sufficient
similarity in the raw wastes to logically assume transferability
of the treated pollutant concentrations to the combined metals
data base. Battery manufacturing wastewaters also were compared
to the wastewaters from plants in categories from which treatment
effectiveness values were calculated. The available data on
527
-------
these added pollutants do not allow homogeneity analysis as was
performed on the combined metals data base. The data source for
each added pollutant is discussed separately.
Antimony (Sb) - The achievable performance for antimony is based
on data from a battery and secondary lead plant. Both EPA
sampling data and recent permit data (1978-1982) confirm the
achievability of 0.7 mg/1 in the battery manufacturing wastewater
matrix included in the combined data set.
Arsenic (As) - The achievable performance of 0.5 mg/1 for arsenic
is based on permit data from two nonferrous metals manufacturing
plants. The untreated wastewater matrix shown in Table VII-17
(page 602) is comparable with the combined data set matrix.
Beryllium (Be) - The treatability of beryllium is transferred
from the nonferrous metals manufacturing industry. The 0.3 mg/1
performance is achieved at a beryllium plant with the comparable
untreated wastewater matrix shown in Table VII-17.
Mercury (Hg) - The 0.06 mg/1 treatability of mercury is based on
data from four battery plants. The untreated wastewater matrix
at these plants was considered in the combined metals data set.
Selenium (Se) - The 0.30 mg/1 treatability of selenium is based
on recent permit data from one of the nonferrous metals
manufacturing plants also used for antimony performance. The
untreated wastewater matrix for this plant is shown in Table
VII-17.
Silver - The treatability of silver is based on a 0.1 mg/1
treatability estimate from the inorganic chemicals industry.
Additional data supporting a treatability as stringent or more
stringent than 0.1 mg/1 is also available from seven nonferrous
metals manufacturing plants. The untreated wastewater matrix for
these plants is comparable and summarized in Table VII-17.
Thallium (Tl) - The 0.50 mg/1 treatability for thallium is
transferred from the inorganic chemicals industry. Although no
untreated wastewater data are available to verify comparability
with the combined metals data set plants, no other sources of
data for thallium treatability could be identified.
Aluminum (Al) - The 2.24 mg/1 treatability of aluminum is based
on the mean performance of three aluminum forming plants and one
coil coating plant. These plants are from categories included in
the combined metals data set, assuring untreated wastewater
matrix comparability.
528
-------
Cobalt (Co) - The 0.05 mg/1 treatability is based on nearly
complete removal of cobalt at a porcelain enameling plant with a
mean untreated wastewater cobalt concentration of 4.31 mg/1. In
this case, the analytical detection using aspiration techniques
for this pollutant is used as the basis of the treatability.
Porcelain enameling was considered in the combined metals data
base, assuring untreated wastewater matrix comparability.
Fluoride (F) - The 14.5 mg/1 treatability of fluoride is based on
the mean performance (216 samples) of an electronics
manufacturing plant. The untreated wastewater matrix for this
plant shown in Table VI1-17 is comparable to the combined metals
data set. The fluoride level in the electronics wastewater (760
mg/1) is significantly greater than the fluoride level in raw
battery manufacturing wastewater leading to the conclusion that
the battery manufacturing wastewater should be no more difficult
to treat for fluoride removal than the electronics wastewater.
The fluoride level in the CMDB - electroplating data ranges from
1.29 to 70.0 mg/1 while the fluoride level in the battery
manufacturing wastewater was lower ranging from 0.44 to 3.05 mg/1
and leading to the conclusion that the battery manufacturing
wastewater should be no more difficult to treat to remove
fluoride than electroplating wastewater.
Phosphorus (P) - The 4.08 mg/1 treatability of phosphorus is
based on the mean of 44 samples including 19 samples from the
Combined Metals Data Base and 25 samples from the electroplating
data base. Inclusion of electroplating data with the combined
metals data was considered appropriate, since the removal
mechanism for phosphorus is a precipitation reaction with calcium
rather than hydroxide.
LS&F Performance
Tables VII-18 and VII-19 (pages 603 and 604) show long term data
from two plants which have well operated precipitation-settling
treatment followed by filtration. The wastewaters from both
plants contain pollutants from metals processing and finishing
operations (multi-category). Both plants reduce hexavalent
chromium before neutralizing and precipitating metals with lime.
A clarifier is used to remove much of the solids load and a
filter is used to "polish" or complete removal of suspended
solids. Plant A uses a pressure filter, while Plant B uses a
rapid sand filter.
Raw wastewater data was collected only occasionally at each
facility , and the raw wastewater data is presented as an
indication of the nature of the wastewater treated. Data from
plant A was received as a statistical summary and is presented as
received. Raw laboratory data was collected at plant B and
529
-------
reviewed for spurious points and discrepancies. The method of
treating the data base is discussed below under lime, settle, and
filter treatment effectiveness.
Table VII-20 (page 605) shows long-term data for zinc and cadmium
removal at Plant C, a primary zinc smelter, which operates a LS&F
system. This data represents about 4 months (103 data days)
taken immediately before the smelter was closed. It has been
arranged similarily to Plants A and B for comparison and use.
These data are presented to demonstrate the performance of
precipitation-settling-filtration (LS&F) technology under actual
operating conditions and over a long period of time.
It should be noted that the iron content of the raw wastewater of
plants A and B is high while that for Plant C is low. This
results, for plants A and B, in co-precipitation of toxic metals
with iron. Precipitation using high-calcium lime for pH control
yields the results shown above. Plant operating personnel
indicate that this chemical treatment combination (sometimes with
polymer assisted coagulation) generally produces better and more
consistent metals removal than other combinations of sacrificial
metal ions and alkalis.
The LS&F performance data presented here are based on systems
that provide polishing filtration after effective L&S treatment.
We have previously shown that L&S treatment is equally applicable
to wastewaters from the five categories because of the
homogeneity of its raw and treated wastewaters, and other
factors. Because of the similarity of the wastewaters after L&S
treatment, the Agency believes these wastewaters are equally
amenable to treatment using polishing filters added to the L&S
treatment system. The Agency concludes that LS&F data based on
porcelain enameling and nonferrous smelting and refining is
directly applicable to the aluminum forming, copper forming,
battery manufacturing, coil coating, and metal molding and
casting categories, and the canmaking subcategory as well as it
is to porcelain enameling and nonferrous melting and refining.
Analysis of Treatment System Effectiveness
Data are presented in Table VII-14 showing the mean, one-day, 10-
day, and 30-day values for nine pollutants examined in the L&S
combined metals data base. The pooled variability factor for
seven metal pollutants (excluding cadmium because of the small
number of data points) was determined and is used to estimate
one-day, 10-day and 30-day values. (The variability factor is
the ratio of the value of concern to the mean: the pooled
variability factors are: one-day maximum - 4.100; ten-day average
- 1.821; and 30-day average - 1.618.) For values not calculated
530
-------
from the CMDB as previously discussed, the mean value for
pollutants shown in Table VII-15 were multiplied by the
variability factors to derive the value to obtain the one-, ten-
and 30-day values. These are tabulated in Table VI1-21.
The treatment effectiveness for sulfide precipitation and
filtration has been calculated similarly. Long term average
values shown in Table VI1-6 (page 595) have been multiplied by
the appropriate variability factor to estimate one-day maximum,
and ten-day and 30-day average values. Variability factors
developed in the combined metals data base were used because the
raw wastewaters are identical and the treatment methods are
similar as both use chemical precipitation and solids removal to
control metals.
LS&F technology data are presented in Tables VI1-18 and VII-19.
These data represent two operating plants (A and B) in which the
technology has been installed and operated for some years. Plant
A data was received as a statistical summary and is presented
without change. Plant B data was received as raw laboratory
analysis data. Discussions with plant personnel indicated that
operating experiments and changes in materials and reagents and
occasional operating errors had occurred during the data
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 (from a total of about 1300) were eliminated by this method.
Another approach was also used as a check on the above method of
eliminating certain high values. The minimum values of raw
wastewater concentrations from Plant B for the same four
pollutants were compared to the total set of values for the
corresponding pollutants. Any day on which the treated
wastewater pollutant concentration exceeded the minimum value
selected from raw wastewater concentrations for that pollutant
was discarded. Forty-five days of data were eliminated by that
procedure. Forty-three days of data in common were eliminated by
either procedures. Since common engineering practice (mean plus
3 sigma) and logic (treated wastewater concentrations should be
less than raw wastewater concentrations) seem to coincide, the
data base with the 51 spurious data days eliminated is the basis
for all further analysis. Range, mean plus standard deviation
and mean plus two standard deviations are shown in Tables VI1-18
and VII-19 for Cr, Cu, Ni, Zn and Fe.
531
-------
The Plant B data was separated into 1979, 1978, and total data
base (six years) segments. With the statistical analysis from
Plant A for 1978 and 1979 this in effect created five data sets
in which there is some overlap between the individual years and
total data sets from Plant B. By comparing these five parts it
is apparent that they are quite similar and all appear to be from
the same family of numbers. The largest mean found among the
five data sets for each pollutant was selected as the long term
mean for LS&F technology and is used as the LS&F mean in Table
VII-21.
Plant C data was used as a basis for cadmium removal performance
and as a check on the zinc values derived from Plants A and B.
The cadmium data is displayed in Table VII-20 (page 605) and is
incorporated into Table VII-21 for LS&F. The zinc data was
analyzed for compliance with the 1-day and 30-day values in Table
VII-21; no zinc value of the 103 data points exceeded the 1-day
zinc value of 1.02 mg/1. The 103 data points were separated into
blocks of 30 points and averaged. Each of the 3 full 30-day
averages was less than the Table VII-21 value of 0.31 mg/1.
Additionally the Plant C raw wastewater pollutant concentrations
(Table VII-20) are well within the range of raw wastewater
concentrations of the combined metals data base (Table VI1-16),
further supporting the conclusion that Plant C wastewater data is
compatible with similar data from Plants A and B.
Concentration values for regulatory use are displayed in Table
VII-21. Mean one-day, ten-day and 30-day values for L&S for nine
pollutants were taken from Table VII-14; the remaining L&S values
were developed using the mean values in Table VI1-15 and the mean
variability factors discussed above.
LS&F mean values for Cd, Cr, Ni, Zn and Fe are derived from
plants A, B, and C as discussed above. One-, ten- and thirty-day
values are derived by applying the variability factor developed
from the pooled data base for the specific pollutant to the mean
for that pollutant. Other LS&F values are calculated using the
long term average or mean and the appropriate variability
factors.
Copper levels achieved at Plants A and B may be lower than
generally achievable because of the high iron content and low
copper content of the raw wastewaters. Therefore, the mean
concentration value from plants A and B achieved is not used; the
LS&F mean for copper is derived from the L&S technology.
L&S cyanide mean levels shown in Table VI1-8 are ratioed to one-
day, ten-day and 30-day values using mean variability factors.
LS&F mean cyanide is calculated by applying the ratios of
removals L&S and LS&F as discussed previously for LS&F metals
532
-------
limitations. The cyanide performance was arrived at by using the
average metal variability factors. The treatment method used
here is cyanide precipitation. Because cyanide precipitation is
limited by the same physical processes as the metal
precipitation, it is expected that the variabilities will be
similar. Therefore, the average of the metal variability factors
has been used as a basis for calculating the cyanide one-day,
ten-day and thirty-day average treatment effectiveness values.
The filter performance for removing TSS as shown in Table VI1-9
(page 597) yields a mean effluent concentration of 2.61 mg/1 and
calculates to a 10-day average of 4.33, 30-day average of 3.36
mg/1; a one-day maximum of 8.88. These calculated values more
than amply support the classic thirty-day and one-day values of
10 mg/1 and 15 mg/1, respectively, which are used for LS&F.
Although iron concentrations were decreased in some LS&F
operations, some facilities using that treatment introduce iron
compounds to aid settling. Therefore, the one-day, ten-day and
30-day values for iron at LS&F were held at the L&S level so as
to not unduly penalize the operations which use the relatively
less objectionable iron compounds to enhance removals of toxic
metals.
The removal of additional fluoride by adding polishing filtration
is suspect because lime and settle treatment removes calcium
fluoride to a level near its solubility. The one available data
point appears to question the ability of filters to achieve high
removals of additional fluoride. The fluoride levels
demonstrated for L&S are used as the treatment effectiveness for
LS&F.
MINOR TECHNOLOGIES
Several other treatment technologies were considered for possible
application in this category. These technologies are presented
here.
8. Carbon Adsorption
The use of activated carbon to remove dissolved organics from
water and wastewater is a long demonstrated technology. It is
one of the most efficient organic removal processes available.
This sorption process is reversible, allowing activated carbon to
be regenerated for reuse by the application of heat and steam or
solvent. Activated carbon has also proved to be an effective
adsorbent for many toxic metals, including mercury. Regeneration
of carbon which has adsorbed significant metals, however, may be
difficult.
533
-------
The term activated carbon applies to any amorphous form of carbon
that has been specially treated to give high adsorption
capacities. Typical raw materials include coal, wood, coconut
shells, petroleum base residues, and char from sewage sludge
pyrolysis. A carefully controlled process of dehydration,
carbonization, and oxidation yields a product which is called
activated carbon. This material has a high capacity for
adsorption due primarily to the large surface area available for
adsorption, 500 to 1500 m2/sq m resulting from a large number of
internal pores. Pore sizes generally range from 10 to TOO
angstroms in radius.
Activated carbon removes contaminants from water by the process
of adsorption, or the attraction and accumulation of one
substance on the surface of another. Activated carbon
preferentially adsorbs organic compounds 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 VII-17 (page 629). Powdered carbon is less
expensive per unit weight and may have slightly higher adsorption
capacity, but it is more difficult to handle and to regenerate.
Application and Performance. Carbon adsorption is used to remove
mercury from wastewaters. The removal rate is influenced by the
mercury level in the influent to the adsorption unit. In Table
VI1-24 (page 609), removal levels found at three manufacturing
facilities are listed.
In the aggregate these data indicate that very low effluent
levels could be attained from any raw waste by use of multiple
adsorption stages. This is characteristic of adsorption
processes.
534
-------
Isotherm tests have indicated that activated carbon is very
effective in adsorbing 65 percent of the organic priority
pollutants and is reasonably effective for another 22 percent.
Specifically, for the organics of particular interest, activated
carbon was very effective in removing 2,4-dimethylphenol,
fluoranthene, isophorone, naphthalene, all phthalates, and
phenanthrene. It was reasonably effective on 1,1,1-
trichloroethane, 1,1-dichloroethane, phenol, and toluene. Table
VII-22 (page 607) summarizes the treatment effectiveness for most
of the organic priority pollutants by activated carbon as
compiled by EPA. Table VI1-23 (page 608) 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 use exceeds
about 1,000 Ib/day. Carbon cannot remove low molecular weight or
highly soluble organics. It also has a low tolerance for
suspended solids, which must be removed to at least 50 mg/1 in
the influent water.
Operational Factors. Reliability: This system should be very
reliable with upstream protection and proper operation and
maintenance procedures.
Maintainability: This system requires periodic regeneration or
replacement of spent carbon and is dependent upon raw waste load
and process efficiency.
Solid Waste Aspects: Solid waste from this process is
contaminated activated carbon that- requires disposal. Carbon
undergoes regeneration, reduces the solid waste problem by
reducing the frequency of carbon replacement.
Demonstration Status. Carbon adsorption systems have been
demonstrated to be practical and economical in reducing COD, BOD,
and related parameters in secondary municipal and industrial
wastewaters; in removing toxic or refractory organics from
isolated industrial wastewaters; in removing and recovering
certain organics from wastewaters; and in removing and some times
535
-------
recovering selected inorganic chemicals from aqueous wastes.
Carbon adsorption is a viable and economic process for organic
waste streams containing up to 1 to 5 percent of refractory or
toxic organics. Its applicability for removal of inorganics such
as metals has also been demonstrated.
9. Centrifugation
Centrifugation is the application of centrifugal force to
separate solids and liquids in a liquid-solid mixture or to
effect concentration of the solids. The application of
centrifugal force is effective because of the density
differential normally found between the insoluble solids and the
liquid in which they are contained. As a waste treatment
procedure, centrifugation is applied to dewatering of sludges.
One type of centrifuge is shown in Figure VII-18 (page 630).
There are three common types of centrifuges; disc, basket, and
conveyor. All three operate by removing solids under the
influence of centrifugal force. The fundamental difference among
the three types is the method by which solids are collected in
and discharged from the bowl.
In the disc centrifuge, the sludge feed is distributed between
narrow channels that are present as spaces between stacked
conical discs. Suspended particles are collected and discharged
continuously through small orifices in the bowl wall. The
clarified effluent is discharged through an overflow weir.
A second (type of centrifuge which is useful in dewatering sludges
is the basket centrifuge. In this type of centrifuge, sludge
feed is introduced at the bottom of the basket, and solids
collect at the bowl wall while clarified effluent overflows the
lip ring at the top. Since the basket centrifuge does not have
provision for continuous discharge of collected cake, operation
requires interruption of the feed for cake discharge for a minute
or two in a 10 to 30 minute overa.ll cycle.
The third type of centrifuge commonly used in sludge dewatering
is the conveyor type. Sludge is fed through a stationary feed
pipe into a rotating bowl in which the solids are settled out
against the bowl wall by centrifugal force. From the bowl wall,
the solids are moved by a screw to the end of the machine, at
which point they are discharged. The liquid effluent is
discharged through ports after passing the length of the bowl
under centrifugal force.
536
-------
Application And Performance. 'Virtually all industrial waste
treatment systems producing sludge can use centrifugation to
dewater it. Centrifugation is currently being used by a wide
range of industrial concerns.
The performance of sludge dewatering by centrifugation depends on
the feed rate, the rotational velocity of the drum, and the
sludge composition and concentration. Assuming proper design and
operation, the solids content of the sludge can be increased to
20 to 35 percent.
Advantages And Limitations. Sludge dewatering centrifuges have
minimal space requirements and show a high degree of effluent
clarification. The operation is simple, clean, and relatively
inexpensive. The area required for a centrifuge system
installation is less than that required for a filter system or
sludge drying bed of equal capacity, and the initial cost is
lower.
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, nonsettling 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.
537
-------
Demonstration Status. Centrifugation is currently used in a
great many commercial applications to dewater sludge. Work is
underway to improve the efficiency, increase the capacity, and
lower the costs associated with centrifugation.
10. Coalescing
The basic principle of coalescence involves the preferential
wetting of a coalescing medium by oil droplets which accumulate
on the medium and then rise to the surface of the solution as
they combine to form larger particles. The most important
requirements for coalescing media are wettability for oil and
large surface area. Monofilament line is sometimes used as a
coalescing medium.
Coalescing stages may be integrated with a wide variety of
gravity oil separation devices, and some systems may incorporate
several coalescing stages. In general, a preliminary oil
skimming step is desirable to avoid overloading the coalescer.
One commercially marketed system for oily waste treatment
combines coalescing with inclined plate separation and
filtration.' In this system, the oily wastes flow into an
inclined plate settler. This unit consists of a stack of
inclined baffle plates in a cylindrical container with an oil
collection chamber at the top. The oil droplets rise and impinge
upon the undersides of the plates. They then migrate upward to a
guide rib which directs the oil to the oil collection chamber,
from which oil is discharged for reuse or disposal.
The oily water continues on through another cylinder containing
replaceable filter cartridges, which remove suspended particles
from the waste. From there the wastewater enters a final
cylinder in which the coalescing material is housed. As the oily
water passes through the many small, irregular, continuous
passages in the coalescing material, the oil droplets coalesce
and rise to an oil collection chamber.
Application and Performance. Coalescing is used to treat oily
wastes which do not separate readily in simple gravity systems.
The three-stage system described above has achieved effluent
concentrations of 10 to 15 mg/1 oil and grease from raw waste
concentrations of 1000 mg/1 or more.
Advantages and Limitations. Coalescing allows removal of oil
droplets too finely dispersed for conventional gravity
separation-skimming technology. It also can significantly reduce
the residence times (and therefore separator volumes) required to
achieve separation of oil from some wastes. Because of its
simplicity, coalescing provides generally high reliability and
538
-------
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.
Maintainability: Maintenance requirements are generally limited
to replacement of the coalescing medium on an infrequent basis.
Solid Waste Aspects: No appreciable solid waste is generated by
this process.
Demonstration Status. Coalescing has been fully demonstrated in
industries generating oily wastewater, although none are
currently in use at any battery manufacturing facilities.
11 . Cyanide Oxidation by_ Chlorine
Cyanide oxidation using chlorine is widely used in industrial
waste treatment to oxidize cyanide. Chlorine can be utilized in
either the elemental or hypochlorite forms. This classic
procedure can be illustrated by the following two step chemical
reaction:
1. C12 + NaCN + 2NaOH > NaCNO + 2NaCl + H20
2. 3C12 + 6NaOH + 2NaCNO > 2NaHCO3 + 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 VII-
19 (page 631).
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
539
-------
metered to the reaction tank as required to maintain the ORP in
the range of 350 to 400 millivolts, and 50 percent aqueous
caustic soda is added to maintain a pH range of 9.5 to 10. In
the second reaction tank, conditions are maintained to oxidize
cyanate to carbon dioxide and nitrogen. The desirable ORP and pH
for this reaction are 600 millivolts and a pH of 8.. 0. Each of
the reaction tanks is equipped with a propeller agitator designed
to provide approximately one turnover per minute. Treatment by
the batch process is accomplished by using two tanks, one for
collection of water over a specified time period, and one for the
treatment of an accumulated batch. If dumps of concentrated
wastes are frequent, another tank may be required to equalize the
flow to the treatment tank. When the holding tank is full, the
liquid is transferred to the reaction tank for treatment. After
treatment, the supernatant is discharged and the sludges are
collected for removal and ultimate disposal.
Application and Performance. The oxidation of cyanide waste by
chlorine is a classic process and is found in most industrial
plants using cyanide. This process is capable of achieving
effluent levels that are nondetectable. The process is
potentially applicable to battery facilities where cyanide is a
component in cell wash formulations.
Advantages and Limitations. Some advantages of chlorine
oxidation for handling process effluents are operation at ambient
temperature, suitability for automatic control, and low cost.
Disadvantages include the need for careful pH control, possible
chemical interference in the treatment of mixed wastes, and the
potential hazard of storing and handling chlorine gas.
Operational Factors. Reliability: Chlorine oxidation is highly
reliable with proper monitoring and control and proper
pretreatment to control interfering substances.
Maintainability: Maintenance consists of periodic removal of
sludge and recalibration of instruments.
Solid Waste Aspects: There is no solid waste problem associated
with chlorine oxidation.
Demonstration Status. The oxidation of cyanide wastes by
chlorine is a widely used process in plants using cyanide in
cleaning and metal processing baths. Alkaline chlorination is
also used for cyanide treatment in a number of inorganic chemical
facilities producing hydroganic acid and various metal cyanides.
540
-------
12. Cyanide Oxidation By Ozone
Ozone is a highly reactive oxidizing agent which is approximately
ten times more soluble than oxygen on a weight basis in water.
Ozone may be produced by several methods, but the silent
electrical discharge method is predominant in the field. The
silent electrical discharge process produces ozone by passing
oxygen or air between electrodes separated by an insulating
material. A complete ozonation system is represented in Figure
VII-20 (page 632).
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- + Oj,
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.
541
-------
Maintainability: Maintenance consists of periodic removal of
sludge, and periodic renewal of filters and de«?ir^?»tor«? r°r".nre^
for the input of clean dry air; filter life is a function of
input concentrations of detrimental constituents.
Solid Waste Aspects: Pretreatment to eliminate substances" which
will interfere with the process may be necessary. Dewatering of
sludge generated in the ozone oxidation process or in an "in
line" process may be desirable prior to disposal.
13. Cyanide Oxidation By Ozone With UV Radiation
One of the modifications of the ozonation process is the
simultaneous application of ultraviolet light and ozone for the
treatment of wastewater, including treatment of halogenated
organics. The combined action of these two forms produces
reactions by photolysis, photosensitization, hydroxylation,
oxygenation, and oxidation. The process is unique because
several reactions and reaction species are active simultaneously.
Ozonation is facilitated by ultraviolet absorption because both
the ozone and the reactant molecules are raised to a higher
energy state so that they react more rapidly. In addition, free
radicals for use in the reaction are readily hydrolyzed by the
water present. The energy and reaction intermediates created by
the introduction of both ultraviolet and ozone greatly reduce the
amount of ozone required compared with a system using ozone
alone. Figure VI1-21 (page 633) 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. i
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.
542
-------
14. Cyanide Oxidation By Hydrogen Peroxide
Hydrogen peroxide oxidation removes both cyanide and metals in
cyanide containing wastewaters. In this process, cyanide bearing
waters are heated to 49 to 54°C (120 to 130°F) and.the pH is
adjusted to 10.5 to 11.8. Formalin (37 percent formaldehyde) is
added while the tank is vigorously agitated. After 2 to 5
minutes, a proprietary peroxygen compound (41 percent hydrogen
peroxide with a catalyst and additives) is added. After an hour
of mixing, the reaction is complete. The cyanide is 'converted to
cyanate, and the metals are precipitated as oxides or hydroxides.
The metals are then removed from solution by either settling or
filtration.
The main equipment required for this process is two holding tanks
equipped with heaters and air spargers or mechanical stirrers.
These tanks may be used in a batch or continuous fashion, with
one tank being used for treatment while the other is being
filled. A settling tank or a filter is needed to concentrate the
precipitate.
Application and Performance; The hydrogen peroxide oxidation
process is applicable to cyanide-bearing wastewaters, especially
those containing metal-cyanide complexes. In terms of waste
reduction performance, this process can reduce total cyanide to
less than 0.1 mg/1 and the zinc or cadmium to less than 1.0 mg/1.
Advantages and Limitations. Chemical costs are similar to those
for alkaline chlorination using chlorine and lower than those for
treatment with hypochlorite. All free cyanide reacts and is
completely oxidized to the less toxic cyanate state. In
addition, the metals precipitate and settle quickly, and they may
be recoverable in many instances. However, the process requires
energy expenditures to heat the wastewater prior to treatment.
Demonstration Status. This treatment process was introduced in
1971 and is used in several facilities. No battery manufacturing
plants use oxidation by hydrogen peroxide.
15. Evaporation
Evaporation is a concentration process. Water is evaporated from
a solution, increasing the concentration of solute in the
remaining solution. If the resulting water vapor is condensed
back to liquid water, the evaporation-condensation process is
called distillation. However, to be consistent with industry
terminology, evaporation is used in this report to describe both
processes. Both atmospheric and vacuum evaporation are commonly
used in industry today. Specific evaporation techniques are
shown in Figure VII-22 (page 634) and discussed below.
543
-------
Atmospheric evaporation could be accomplished simply by boiling
the liquid. However, to aid evaporation, heated liquid is
sprayed on an evaporation surface, and air is blown over the
surface and subsequently released to the atmosphere. Thus,
evaporation occurs by humidification of the air stream, similar
to a drying process. Equipment for carrying out atmospheric
evaporation is quite similar for most applications. The major
element is generally a packed column with an accumulator bottom.
Accumulated wastewater is pumped from the base of the column,
through a heat exchanger, and back into the top of the column,
where it is sprayed into the packing. At the same time, air
drawn upward through the packing by a fan is heated as it
contacts the hot liquid. The liquid partially vaporizes and
humidifies the air stream. The fan then blows the hot, humid air
to the outside atmosphere. A scrubber is often unnecessary
because the packed column itself acts as a scrubber.
Another form of atmospheric evaporator also works on the air
humidification principle, but the evaporated water is recovered
for reuse by condensation. These air humidification techniques
operate well below the boiling point of water and can utilize
waste process heat to supply the energy required.
In 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 may be either single or double effect.
In double effect evaporation, two evaporators are used, and the
water vapor from the first evaporator (which may be heated by
steam) is used to supply heat to the second evaporator. As it
supplies heat, the water vapor from the first evaporator
condenses. Approximately equal quantities of wastewater are
evaporated in each unit; thus, the double effect system
evaporates twice the amount of water that a single effect system
does, at nearly the same cost in energy but with added capital
cost and complexity. The double effect technique is
thermodynamically possible because the second evaporator is
maintained at lower pressure (higher vacuum) and, therefore,
lower evaporation temperature. Vacuum evaporation equipment may
be classified as submerged tube or climbing film evaporation
units.
Another means of increasing energy efficiency is vapor
recompression evaporation, which enables heat to be transferred
from the condensing water vapor to the evaporating wastewater.
Water vapor generated from incoming wastewaters flows to a vapor
compressor. The compressed steam than travels through the
wastewater via an enclosed tube or coil in which it condenses as
heat is transferred to the surrounding solution. In this way,
544
-------
the compressed vapor serves as a heating medium. After
condensation, this distillate is drawn off continuously as the
clean water stream. The heat contained in the compressed vapor
is used to heat the wastewater, and energy costs for system
operation are reduced.
In the most commonly used submerged tube evaporator, the heating
and condensing coil are contained in a single vessel to reduce
capital cost. The vacuum in the vessel is maintained by an
eductor-type pump, which creates the required vacuum by the flow
of the condenser cooling water through a venturi. Wastewater
accumulates in the bottom of the vessel, and it is evaporated by
means of submerged steam coils. The resulting water vapor
condenses as it contacts the condensing coils in the top of the
vessel. The condensate then drips off the condensing coils into
a collection trough that carries it out of the vessel.
Concentrate is removed from the bottom of the vessel.
The major elements of the climbing film evaporator are the
evaporator, separator, condenser, and vacuum pump. Wastewater is
"drawn" into the system by the vacuum so that a constant liquid
level is maintained in the separator. Liquid enters the steam-
jacketed evaporator tubes, and part of it evaporates so that a
mixture of vapor and liquid enters the separator. The design of
the separator is such that the liquid is continuously circulated
from the separator to the evaporator. The vapor entering the
separator flows out through a mesh entrainment separator to the
condenser, where it is condensed as it flows down through the
condenser tubes. The condensate, along with any entrained air,
is pumped out of the bottom of the condenser by a liquid ring
vacuum pump. The liquid seal provided by the condensate keeps
the vacuum in the system from being broken.
Application and Performance. Both atmospheric and vacuum
evaporation are used in many industrial plants, mainly for the
concentration and recovery of process solutions. Many of these
evaporators also recover water for rinsing. Evaporation has also
been applied to recovery of phosphate metal cleaning solutions.
In theory, evaporation should yield a concentrate and a deionized
condensate. Actually, carry-over has resulted in condensate
metal concentrations as high as 10 mg/1, although the usual level
is less than 3 mg/1, pure enough for most final rinses. The
condensate may also contain organic brighteners and antifoaming
agents. These can be removed with an activated carbon bed, if
necessary. Samples from one plant showed 1,900 mg/1 zinc in the
feed, 4,570 mg/1 in the concentrate, and 0.4 mg/1 in the
condensate. Another plant had 416 mg/1 copper in the feed and
21,800 mg/1 in the concentrate. Chromium analysis for that plant
indicated 5,060 mg/1 in the feed and 27,500 mg/1 in the
545
-------
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. Capital costs for vapor compression
evaporators are substantially higher than for other types of
evaporation equipment. However, the energy costs associated with
the operation of a vapor compression evaporator are significantly
lower than costs of other evaproator types. For some
applications, pretreatment may be required to remove solids or
bacteria which tend to cause fouling in the condenser or
evaporator. The buildup of scale on the evaporator surfaces
reduces the heat transfer efficiency and may present a
maintenance problem or increase operating cost. However, it has
been demonstrated that fouling of the heat transfer surfaces can
be avoided or minimized for certain dissolved solids by
maintaining a seed slurry which provides preferential sites for
precipitate deposition. In addition, low temperature differences
in the evaporator will eliminate nucleate boiling and
supersaturation effects. Steam distillable impurities in the
process stream are carried over with the product water and must
be handled by pre- or posttreatment.
Operational Factors. Reliability: Proper maintenance will
ensure a high degree of reliability for the system. Without such
attention, rapid fouling or deterioration of vacuum seals may
occur, especially when corrosive liquids are handled.
Maintainability: Operating parameters can be automatically
controlled. Pretreatment may be required, as well as periodic
cleaning of the system. Regular replacement of seals, especially
in a corrosive environment, may be necessary.
Solid Waste Aspects: With only a few exceptions, the process
does not generate appreciable quantities of solid waste.
546
-------
Demonstration Status. Evaporation is a fully developed,
commercially available wastewater treatment system. It is used
extensively to recover plating chemicals in the electroplating
industry, and a pilot scale unit has been used in connection with
phosphating of aluminum. Proven performance in silver recovery
indicates that evaporation could be a useful treatment operation
for the photographic industry, as well as for metal finishing.
Vapor compression evaporation has been practically demonstrated
in a number of industries, including chemical manufacturing, food
processing, pulp and paper, and metal working. One battery plant
has recently reported showing the use of evaporation.
16. Flotation
Flotation is the process of causing particles such as metal
hydroxides or oil to float to the surface of a tank where they
can be concentrated and removed. This is accomplished by
releasing gas bubbles which attach to the so-lid particles,
increasing their buoyancy and causing them to float. In
principle, this process is the opposite of sedimentation. Figure
VII-23 (page 635) shows one type of flotation system.
Flotation is used primarily in the treatment of wastewater
streams that carry heavy loads of finely divided suspended solids
or oil. Solids having a specific gravity only slightly greater
than 1.0, which would require abnormally long sedimentation
times, may be removed in much less time by flotation. Dissolved
air flotation is of greatest interest in removing oil from water
and is less effective in removing heavier precipitates.
This process may be performed in several ways: foam, dispersed
air, dissolved air, gravity, and vacuum flotation are the most
commonly used techniques. Chemical additives are often used to
enhance the performance of the flotation process.
The principal difference among types of flotation is the method
of generating the minute gas bubbles (usually air) in a
suspension of water and small particles. Chemicals may be used
to improve the efficiency with any of the basic methods. The
following paragraphs describe the different flotation techniques
and the method of bubble generation for each process.
Froth Flotation - Froth flotation is based on differences in the
physiochemical properties in various particles. Wettability and
surface properties affect the particles' ability to attach
themselves to gas bubbles in an aqueous medium. In froth
flotation, air is blown through the solution containing flotation
reagents. The particles with water repellant surfaces stick to
air bubbles as they rise and are brought to the surface. A
mineralized froth layer, with mineral particles attached to air
547
-------
bubbles, is formed. Particles of other minerals which are
readily wetted by water do not stick to air bubbles and remain in
suspension.
Dispersed Air Flotation - In dispersed air flotation, gas bubbles
are generated by introducing the air by means of mechanical
agitation with impellers or by forcing air through porous media.
Dispersed air flotatioYi • 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
wastewater with air either directly in an aeration tank, or by
permitting air to enter on the suction of a wastewater pump. A
partial vacuum is applied, which causes the dissolved air to come
out of solution as minute bubbles. The bubbles attach to solid
particles and rise to the surface to form a scum blanket, which
is normally removed by a skimming mechanism. Grit and other
heavy solids that settle to the bottom are generally raked to a
central sludge pump for removal. A typical vacuum flotation unit
consists of a covered cylindrical tank in which a partial vacuum
is maintained. The tank is equipped with scum and sludge removal
mechanisms. The floating material is continuously swept to the
tank periphery, automatically discharged into a scum trough, and
removed from the unit by a pump also under partial vacuum.
Auxiliary equipment includes an aeration tank for saturating the
wastewater with air, a tank with a short retention time for
removal of large bubbles, vacuum pumps, and sludge pumps.
Application and Performance. The primary variables for flotation
design are pressure, feed solids concentration, and retention
period. The suspended solids in the effluent decrease, and the
concentration of solids in the float increases with increasing
retention period. When the flotation process is used primarily
for clarification, a retention period of 20 to 30 minutes usually
is adequate for separation and concentration.
548
-------
Advantages and Limitations. Some advantages of the flotation
process are the high levels of solids separation achieved in many
applications, the relatively low energy requirements, and the
adaptability to meet the treatment requirements of different
waste types. Limitations of flotation are that it often requires
addition of chemicals to enhance process performance and that it
generates large quantities of solid waste.
Operational Factors. Reliability: Flotation systems normally
are very reliable with proper maintenance of the sludge collector
mechanism and the motors and pumps used for aeration.
Maintainability: Routine maintenance is required on the pumps
and motors. The sludge collector mechanism is subject to
possible corrosion or breakage and may require periodic
replacement.
Solid Waste Aspects: Chemicals are commonly used to aid the
flotation process by creating a surface or a structure that can
easily adsorb or entrap air bubbles. Inorganic chemicals, such
as the aluminum and ferric salts, and activated silica, can bind
the particulate matter together and create a structure that can
entrap air bubbles. Various organic chemicals can change the
nature of either the air-liquid interface or the solid-liquid
interface, or both. These compounds usually collect on the
interface to bring about the desired changes. The added
chemicals plus the particles in solution combine to form a large
volume of sludge which must be further treated or properly
disposed.
Demonstration Status. Flotation is a fully developed process and
is readily available for the treatment of a wide variety of
industrial waste streams. Flotation separation has been used in
two battery manufacturing plants as a part of precipitation
systems for metals removal.
17. Gravity Sludge Thickening
In the gravity thickening process, dilute sludge is fed from a
primary settling tank or clarifier to a thickening tank where
rakes stir the sludge gently to density it and to push it to a
central collection well. The supernatant is returned to the
primary settling tank. The thickened sludge that collects on the
bottom of the tank is pumped to dewatering equipment or hauled
away. Figure VI1-24 (page 636) shows the construction of a
gravity thickener.
549
-------
Application and Performance. Thickeners are generally used in
facilities where the sludge is to be further dewatered by a
compact mechanical device such as a vacuum filter or centrifuge.
Doubling the solids content in the thickener substantially
reduces capital and operating cost of the subsequent dewatering
device and also reduces cost for hauling. The process is
potentially applicable to almost any industrial plant.
Organic sludges from sedimentation units of one to two percent
solids concentration can usually be gravity thickened to six to
ten percent; chemical sludges can be thickened to four to six
percent.
Advantages and Limitations. The principal advantage of a 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.
Demonstrat i on 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.
550
-------
18. Insoluble Starch Xanthate
Insoluble starch xanthate is essentially an ion exchange medium
used to remove dissolved heavy metals from wastewater. The water
may then either be reused (recovery application) or discharged
(end-of-pipe application). In a commercial electroplating oper-
ation, starch xanthate is coated on a filter medium. Rinse water
containing dragged out heavy metals is circulated through the
filters and then reused for rinsing. The starch-heavy metal
complex is disposed of and replaced periodically. Laboratory
tests indicate that recovery of metals from the complex is
feasible, with regeneration of the starch xanthate. Besides
electroplating, starch xanthate is potentially applicable to any
other industrial plants where dilute metal wastewater streams are
generated. Its present use is limited to one electroplating
plant.
19. Ion Exchange
Ion exchange is a process in which ions, held by electrostatic
forces to charged functional groups on the surface of the ion
exchange resin, are exchanged for ions of similar charge from the
solution in which the resin is immersed. This is classified as a
sorption process because the exchange occurs on the surface of
the resin, and the exchanging ion must undergo a phase transfer
from solution phase to solid phase. Thus, ionic contaminants in
a waste stream can be exchanged for the harmless ions of the
resin.
Although the precise technique may vary slightly according to the
application involved, a generalized process description follows.
The wastewater stream being treated passes through a filter to
remove any solids, then flows through a cation exchanger which
contains the ion exchange resin. Here, metallic impurities such
as copper, iron, and trivalent chromium are retained. The stream
then passes through the anion exchanger and its associated resin.
Hexavalent chromium, for example, is retained in this stage. If
one pass does not reduce the contaminant levels sufficiently, the
stream may then enter another series of exchangers. Many ion
exchange systems are equipped with more than one set of
exchangers for this reason.
The other major portion of the ion exchange process concerns the
regeneration of the resin, which now holds those impurities
retained from the waste stream. An ion exchange unit with in-
place regeneration is shown in Figure VII-25 (page 637). 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,
551
-------
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 alternating cycles with the ion removal process.
A regeneration frequency of twice an hour is typical. This
very short cycle time permits operation with a very small
quantity of resin and with fairly concentrated solutions,
resulting in a very compact system. Again, this process
varies according to application, but the regeneration cycle
generally begins with caustic being pumped through the anion
exchanger, carrying out hexavalent chromium, for example, as
sodium dichromate. The sodium dichromate stream then passes
through a cation exchanger, converting the sodium dichromate
to chromic acid. After concentration by evaporation or
other means, the chromic acid can be returned to the process
line. Meanwhile, the cation exchanger is regenerated with
sulfuric acid, resulting in a waste acid stream containing
the metallic impurities removed earlier. Flushing the
exchangers with water completes the cycle. Thus, the
wastewater is purified and, in this example, chromic acid is
recovered. The ion exchangers, with newly regenerated
resin, then enter the ion removal cycle again.
Application and Performance. The list of pollutants for which
the ion exchange system has proved effective includes aluminum,
arsenic, cadmium, chromium (hexavalent and trivalent), copper,
cyanide, gold, iron, lead, manganese, nickel, selenium, silver,
tin, zinc, and more. Thus, it can be applied to a wide variety
of industrial concerns. Because of the heavy concentrations of
metals in their wastewater/ the metal finishing industries uti-
lize ion exchange in several ways. As an end-of-pipe treatment,
ion exchange is certainly feasible, but its greatest value.is in
recovery applications. It is commonly used as an integrated
treatment to recover rinse water and process chemicals. Some
552
-------
electroplating facilities use ion exchange to concentrate and
purify plating baths. Also, many industrial concerns, including
a number of battery manufacturing plants, use ion exchange to
reduce salt concentrations in incoming water sources.
Ion exchange is highly efficient at recovering metal bearing
solutions. Recovery of chromium, nickel, phosphate solution, and
sulfuric acid from anodizing is commercial. A chromic acid
recovery efficiency of 99.5 percent has been demonstrated.
Typical data for purification of rinse water have been reported
and are displayed in Table VII-25 (page 609). 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.
Advantages and Limitations. Ion exchange is a versatile
technology applicable to a great many situations. This
flexibility, along with its compact nature and performance, makes
ion exchange a very effective method of wastewater treatment.
However, the resins in these systems can prove to be a limiting
factor. The thermal limits of the anion resins, generally in the
vicinity of 60°C, could prevent its use in certain situations.
Similarly, nitric acid, chromic acid, and hydrogen peroxide can
all damage the resins, as will iron, manganese, and copper when
present with sufficient concentrations of dissolved oxygen.
Removal of a particular trace contaminant may be uneconomical
because of the presence of other ionic species that are preferen-
tially removed. The regeneration of the resins presents its own
problems. The cost of the regenerative chemicals can be high.
In addition, the waste streams originating from the regeneration
process are extremely high in pollutant concentrations, although
low in volume. These must be further processed for proper
disposal.
Operational Factors. Reliability: With the exception of
occasional clogging or fouling of the resins, ion exchange has
proved to be a highly dependable technology.
Maintainability: Only the normal maintenance of pumps, valves,
piping and other hardware used in the regeneration process is
required.
Solid Waste Aspects: Few, if any, solids accumulate within the
ion exchangers, and those which do appear are removed by the re-
generation process. Proper prior treatment and planning can eli-
minate solid buildup problems altogether. The brine resulting
from regeneration of the ion exchange resin must usually be
treated to remove metals before discharge. This can generate
solid waste.
553
-------
Demonstration Status. All of the applications mentioned in this
document are available for commercial use, and industry sources
estimate the number of units currently in the field at well over
120. The research and development in ion exchange is focusing on
improving the quality and efficiency of the resins, rather than
new applications. Work is also being done on a continuous
regeneration process whereby the resins are contained on a fluid-
transfusible belt. The belt passes through a compartmentalized
tank with ion exchange, washing, and regeneration sections. The
resins are therefore continually used and regenerated. No such
system, however, has been reported beyond the pilot stage.
Ion exchange is used for nickel recovery at one battery plant,
for silver and water recovery at another, and for trace nickel
and cadmium removal at a third.
20. Membrane Filtration
Membrane filtration is a treatment system for removing
precipitated metals from a wastewater stream. It must therefore
be preceded by those treatment techniques which will properly
prepare the wastewater for solids removal. Typically, a membrane
filtration unit is preceded by pH adjustment or sulfide addition
for precipitation of the metals. These steps are followed by the
addition of a proprietary chemical reagent which causes the
precipitate to be nongelatinous, easily dewatered, and highly
stable. The resulting mixture of pretreated wastewater and
reagent is continuously recirculated through a filter module and
back into a recirculation tank. The filter module contains
tubular membranes. While the reagent-metal hydroxide precipitate
mixture flows through the inside of the tubes, the water and any
dissolved salts permeate the membrane. When the recirculating
slurry reaches a concentration of 10 to 15 percent solids, it is
pumped out of the system as sludge.
Application and Performance. Membrane filtration appears to be
applicable to any wastewater or process water containing metal
ions which can be precipitated using hydroxide, sulfide or
carbonate precipitation. It could function as the primary
treatment system, but also might find application as a polishing
treatment (after precipitation and settling) to ensure continued
compliance with metals limitations. Membrane filtration systems
are being used in a number of industrial applications,
particularly in the metal finishing area. They have also been
used for toxic metals removal in the metal fabrication industry
and the paper industry.
The permeate is claimed by one manufacturer to contain less than
the effluent concentrations shown in Table VII-26 (page 610)
regardless of the influent concentrations. These claims have
554
-------
been largely substantiated by the analysis of water samples at
various plants in various industries.
In the performance predictions for this technology, pollutant
concentrations are reduced to the levels shown in Table VII-26
unless lower levels are present in the influent stream.
Advantages and Limitations. A major advantage of the membrane
filtration system is that installations can use most of the
conventional end-of-pipe systems that may already be in place.
Removal efficiencies are claimed to be excellent, even with
sudden variation of pollutant input rates; however, the
effectiveness of the membrane filtration system can be limited by
clogging of the filters. Because pH changes in the waste stream
greatly intensify clogging problems, the pH must be carefully
monitored and controlled. Clogging can force the shutdown of the
system and may interfere with production. In addition, the
relatively high capital cost of this system may limit its use.
Operational Factors. Reliability: Membrane filtration has been
shown to be a very reliable system, provided that the pH is
strictly controlled. Improper pH can result in the clogging of
the membrane. Also, surges in the flow rate of the waste stream
must be controlled in order to prevent solids from passing
through the filter and into the effluent.
Maintainability: The membrane filters must be regularly
monitored, and cleaned or replaced as necessary. Depending on
the composition of the waste stream and its flow rate, frequent
cleaning of the filters may be required. Flushing with
hydrochloric acid for 6 to 24 hours will usually suffice. In
addition, the routine maintenance of pumps, .valves, and other
plumbing is required.
Solid Waste Aspects: When the recirculating reagent-precipitate
slurry reaches 10 to 15 percent solids, it is pumped out of the
system. It can then be disposed of directly or it can undergo a
dewatering process. Because this sludge contains toxic metals,
it requires proper disposal.
Demonstration Status. There are more than 25 membrane filtration
systems presently in use on metal finishing and similar
wastewaters. Bench scale and pilot studies are being run in an
attempt to expand the list of pollutants for which this system is
known to be effective. Although there are no data on the use of
membrane filtration in battery manufacturing plants, the concept
has been successfully demonstrated using battery plant
wastewater. A unit has been installed at one battery
manufacturing plant based on these tests.
555
-------
21. Peat Adsorption
Peat moss is a complex natural organic material containing lignin
and cellulose as major constituents. These constituents,
particularly lignin, bear polar functional groups, such as
alcohols, aldehydes, ketones, acids, phenolic hydroxides, and
ethers, that can be involved in chemical bonding. Because of the
polar nature of the material, its adsorption of dissolved solids
such as transition metals and polar organic molecules is quite
high. These properties have led to the use of peat as an agent
for the purification of industrial wastewater.
Peat adsorption is a "polishing" process which can achieve very
low effluent concentrations for several pollutants. If the
concentrations of pollutants are above 10 mg/1, then peat
adsorption must be preceded by pH adjustment for metals
precipitation and subsequent clarification. Pretreatment is also
required for chromium wastes using ferric chloride and sodium
sulfide. The wastewater is then pumped into a large metal
chamber called a kier which contains a layer of peat through
which the waste stream passes. The water flows to a second kier
for further adsorption. The wastewater is then ready for
discharge. This system may be automated or manually operated.
Application and Performance. Peat adsorption can be used in
battery manufacturing for removal of residual dissolved metals
from clarifier effluent. Peat moss may be used to treat
wastewaters containing heavy metals such as mercury, cadmium,
zinc, copper, iron, nickel, chromium, and lead, as well as
organic matter such as oil, detergents, and dyes. Peat
adsorption is currently used commercially at a textile plant, a
newsprint facility, and a metal reclamation operation.
Table VII-27 (page 610) contains performance figures obtained
from pilot plant studies. Peat adsorption was preceded by pH
adjustment for precipitation and by clarification.
In addition, pilot plant studies have shown that chelated metal
wastes, as well as the chelating agents themselves, are removed
by contact with peat moss.
Advantages and Limitations. The major advantages of the system
include its ability to yield low pollutant concentrations, its
broad scope in terms of the pollutants eliminated, and its
capacity to accept wide variations of waste water composition.
Limitations include the cost of purchasing, storing, and
disposing of the peat moss; the necessity for regular replacement
of the peat may lead to high operation and maintenance costs.
556
-------
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.
Maintainability: The peat moss used in this process soon
exhausts its capacity to adsorb pollutants. At that time, the
kiers must be opened, the peat removed, and fresh peat placed
inside. Although this procedure is easily and quickly
accomplished, it must be done at regular intervals, or the
system's efficiency drops drastically.
Solid Waste Aspects: After removal from the kier, the spent peat
must be eliminated. If incineration is used, precautions should
be taken to insure that those pollutants removed from the water
are not released again in the combustion process. Presence of
sulfides in the spent peat, for example, will give rise to sulfur
dioxide in the fumes from burning. The presence of significant
quantities of toxic heavy metals in battery manufacturing
wastewater will in general preclude incineration of peat used in
treating these wastes.
Demonstration Status. Only three facilities currently use
commercial adsorption systems in the United States - a textile
manufacturer, a newsprint facility, and a metal reclamation firm.
No data have been reported showing the use of peat adsorption in
battery manufacturing plants.
22. Reverse Osmosis
The process of osmosis involves the passage of a liquid through a
semipermeable membrane from a dilute to a more concentrated
solution. Reverse osmosis (RO) is an operation in which pressure
is applied to the more concentrated solution, forcing the per-
meate to diffuse through the membrane and into the more dilute
solution. This filtering action produces a concentrate and a
permeate on opposite sides of the membrane. The concentrate can
then be further treated or returned to the original operation for
continued use, while the permeate water can be recycled for use
as clean water. Figure VI1-26 (page 638) depicts a reverse
osmosis system.
As illustrated in Figure VII-27, (page 639), 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.
557
-------
The tubular membrane module uses a porous tube with a cellulose
acetate membrane lining. A common tubular module consists of a
length of 2.5 cm (1 inch) diameter tube wound on a supporting
spool and encased in a plastic shroud. Feed water is driven into
the tube under pressures varying from 40 to 55 atm (600-800 psi).
The permeate passes through the walls of the tube and is
collected in a manifold while the concentrate is drained off at
the end of the tube. A less widely used tubular RO module uses a
straight tube contained in a housing, under the same operating
conditions.
Spiral-wound membranes consist of a porous backing sandwiched
between two cellulose acetate membrane sheets and bonded along
three edges. The fourth edge of the composite sheet is attached
to a large permeate collector tube. A spacer screen is then
placed on top of the membrane sandwich, and the entire stack is
rolled around the centrally located tubular permeate collector.
The rolled up package is inserted into a pipe able to withstand
the high operating pressures employed in this process, up to 55
atm (800 psi) with the-spiral-wound module. When the system is
operating, the pressurized product water permeates the membrane
and flows through the backing material to the central collector
tube. The concentrate is drained off at the end of the container
pipe and can be reprocessed or sent to further treatment facili-
ties.
The hollow fiber membrane configuration is made up of a bundle of
polyamide fibers of approximately 0.0075 cm (0.003 in.) OD and
0.0043 cm (0.0017 in.) ID. A commonly used hollow fiber module
contains several hundred thousand of the fibers placed in a long
tube, wrapped around a flow screen, and rolled into a spiral.
The fibers are bent in a U-shape and their ends are supported by
an epoxy bond. The hollow fiber unit is operated under 27 atm
(400 psi), the feed water being dispersed from the center of the
module through a porous distributor tube. Permeate flows through
the membrane to the hollow interiors of the fibers and is
collected at the ends of the fibers.
The hollow fiber and spiral-wound modules have a distinct advan-
tage over the tubular system in that they are able to load a very
large membrane surface area into a relatively small volume.
However, these two membrane types are much more susceptible to
fouling than the tubular system, which has a larger flow channel.
This characteristic also makes the tubular membrane much easier
to clean and regenerate than either the spiral-wound or hollow
fiber modules. One manufacturer claims that their helical
tubular module can be physically wiped clean by passing a soft
porous polyurethane plug under pressure through the module.
558
-------
Application and Performance. In a number of metal processing
plants, the overflow from the first rinse in a countercurrent
setup is directed to a reverse osmosis unit, where it is
separated into two streams. The concentrated stream contains
dragged out chemicals and is returned to the bath to replace the
loss of solution caused by evaporation and dragout. The .dilute
stream (the permeate) is routed to the last rinse tank to provide
water for the rinsing operation. The rinse flows from the last
tank to the first tank, and the cycle is complete.
The closed-loop system described above may be supplemented by the
addition of a vacuum evaporator after the RO unit in order to
further reduce the volume of reverse osmosis concentrate. The
evaporated vapor can be condensed and returned to the last rinse
tank or sent on for further treatment.
The largest application has been for the recovery of nickel solu-
tions. It has been shown that 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
559
-------
has caused failures, and fouling of membranes by feed waters with
high levels of suspended solids can be a problem. A final limi-
tation is inability to treat or achieve high concentration with
some solutions. Some concentrated solutions may have initial os-
motic pressures which are so high that they either exceed avail-
able operating pressures or are uneconomical to treat.
Operational Factors. Reliability: Very good reliability is
achieved so long as the proper precautions are taken to minimize
the chances of fouling or degrading the membrane. Sufficient
testing of the waste stream prior to application of an RO system
will provide the information needed to insure a successful
application.
Maintainability: Membrane life is estimated to range from six
months to three years, depending on the use of the system.
Downtime for flushing or cleaning is on the order of two hours as
often as once each week; a substantial portion of maintenance
time must be spent on cleaning any prefilters installed ahead of
the reverse osmosis unit.
Solid Waste Aspects: In a closed loop system utilizing RO there
is a constant recycle of concentrate and a minimal amount of
solid waste. Prefiltration eliminates many solids before they
reach the module and helps keep the buildup to a minimum. These
solids require proper disposal.
Demonstration Status. There are presently at least one hundred
reverse osmosis wastewater applications in a variety of
industries. In addition to these, there are 30 to 40 units being
used to provide pure process water for several industries.
Despite the many types and configurations of membranes, only the
spiral-wound cellulose acetate membrane has had widespread suc-
cess in commercial applications. Reverse osmosis is used at one
battery plant to treat process wastewater for reuse as boiler
feedwater.
23. Sludge Bed Drying
As a waste treatment procedure, sludge bed drying is employed to
reduce the water content of a variety of sludges to the point
where they are amenable to mechanical collection and removal to
landfill. These beds usually consist of 15 to 45 cm (6 to 18
in.) of sand over a 30 cm (12 in.) deep gravel drain system made
up of 3 to 6 mm (1/8 to 1/4 in.) graded gravel overlying drain
tiles. Figure VII-28 (page 640) 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
560
-------
200 ft) long. The partitions may be earth embankments, but more
often are made of planks and supporting grooved posts.
To apply liquid sludge to the sand bed, a closed conduit or a
pressure pipeline with valved outlets at each sand bed section is
often employed. Another method of application is by means of an
open channel with appropriately placed side openings which are
controlled by slide gates. With either type of delivery system,
a concrete splash slab should be provided to receive the falling
sludge and prevent erosion of the sand surface.
Where it is necessary to dewater sludge continuously throughout
the year regardless of the weather, sludge beds may be covered
with a fiberglass reinforced plastic or other roof. Covered
drying beds permit a greater volume of sludge drying per year in
most climates because of the protection afforded from rain or
snow and because of more efficient control of temperature.
Depending on the climate, a combination of open and enclosed beds
will provide maximum utilization of the sludge bed drying
facilities.
Application and Performance. Sludge drying beds are a means of
dewatering sludge from clarifiers and thickeners. They are
widely used both in municipal and industrial treatment
facilities.
Dewatering of sludge on sand beds occurs by two mechanisms:
filtration of water through the bed and evaporation of water as a
result of radiation and convection. Filtration is generally
complete in one to two days and may result in solids
concentrations as . high as 15 to 20 percent. The rate of
filtration depends on the drainability of the sludge.
The rate of air drying of sludge is related to temperature,
relative humidity, and air velocity. Evaporation will proceed at
a constant rate to a critical moisture content, then at a falling
rate to an equilibrium moisture content. The average evaporation
rate for a sludge is about 75 percent of that from a free water
surface.
Advantages and Limitations. The main advantage of sludge drying
beds over other types of sludge dewatering is the relatively low
cost of construction, operation, and maintenance.
Its disadvantages are the large area of land required and long
drying times that depend, to a great extent, on climate and
weather.
561
-------
Operational Factors. Reliability: Reliability is high with
favorable climactic conditions, proper bed design and care to
avoid excessive or unequal sludge application. If climatic
conditions in a given area are not favorable for adequate drying,
a cover may be necessary.
Maintainability: Maintenance consists basically of periodic
removal of the dried sludge. Sand removed from the drying bed
with the sludge must be replaced and the sand layer resurfaced.
The resurfacing of sludge beds is the major expense item in
sludge bed maintenance, but there are other areas which may
require attention. Underdrains occasionally become clogged and
have to be cleaned. Valves or sludge gates that control the flow
of sludge to the beds must be kept watertight. Provision for
drainage of lines in winter should be provided to prevent damage
from freezing. The partitions between beds should be tight so
that sludge will not flow from one compartment to another. The
outer walls or banks around the beds should also be watertight.
Solid Waste Aspects: The full sludge drying bed must either be
abandoned or the collected solids must be removed to a landfill.
These solids contain whatever metals or other materials were
settled in the clarifier. Metals will be present as hydroxides,
oxides, sulfides, or other salts. They have the potential for
leaching and contaminating ground water, whatever the location of
the semidried solids. Thus the abandoned bed or landfill should
include provision for runoff control and leachate monitoring.
Demonstration Status. Sludge beds have been in common use in
both municipal and industrial facilities for many years.
However, protection of ground water from contamination is not
always adequate.
24. Ultrafiltration
Ultrafiltration (UF) is a process which uses semipermeable
polymeric membranes to separate emulsified or colloidal materials
suspended in a liquid phase by pressurizing the liquid so that it
permeates the membrane. The membrane of an ultrafilter forms a
molecular screen which retains molecular particles based on their
differences in size, shape, and chemical structure. The membrane
permits passage of solvents and lower molecular weight molecules.
At present, an ultrafilter is capable of removing materials with
molecular weights in the range of 1,000 to 100,000 and particles
of comparable or larger sizes.
In an Ultrafiltration process, the feed solution is pumped
through a tubular membrane unit. Water and some low molecular
weight materials pass through the membrane under the applied
562
-------
pressure of 2 to 8 atm (10 to 100 psig). Emulsified oil droplets
and suspended particles are retained, concentrated, and removed
continuously. In contrast to ordinary filtration, retained
materials are washed off the membrane filter rather than held by
it. Figure VII-29 (page 641) represents the ultrafiltration
process.
Application and Performance. Ultrafiltration has potential
application to battery manufacturing for separation of oils and
residual solids from a variety of waste streams. In treating
battery manufacturing wastewater, its greatest applicability
would be as a polishing treatment to remove residual precipitated
metals after chemical precipitation and clarification.
Successful commercial use, however, has been primarily for
separation of emulsified oils from wastewater. Over one hundred
such units now operate in the United States, treating emulsified
oils from a variety of industrial processes. Capacities of
currently operating units range from a few hundred gallons a week
to 50,000 gallons per day. Concentration of oily emulsions to 60
percent oil or more is possible. Oil concentrates of 40 percent
or more are generally suitable for incineration, and the permeate
can be treated further and in some cases recycled back to the
process. In this way, it is possible to eliminate contractor
removal costs for oil from some oily waste streams.
The test data in Table VII-28 (page 611) indicate ultrafiltration
performance (note that UF is not intended to remove dissolved
solids):
The removal percentages shown are typical, but they can be
influenced by pH and other conditions.
The permeate or effluent from the ultrafiltration unit is
normally of a quality that can be reused in industrial
applications or discharged directly. The concentrate from the
ultrafiltration unit can be disposed of as any oily or solid
waste.
Advantages and Limitations. Ultrafiltration is sometimes an
attractive alternative to chemical treatment because of lower
capital equipment, installation, and operating costs, very high
oil and suspended solids removal, and little required
pretreatment. It places a positive barrier between pollutants
and effluent which reduces the possibility of extensive pollutant
discharge due to operator error or upset in settling and skimming
systems. Alkaline values in alkaline cleaning solutions can be
recovered and reused in process.
A limitation of ultrafiltration for treatment of process
effluents is its narrow temperature range (18° to 30°C) for
563
-------
satisfactory operation. Membrane life decreases with higher
temperatures, but flux increases at elevated temperatures.
Therefore, surface area requirements are a function of
temperature and become a tradeoff between initial costs and
replacement costs for the membrane. In addition, ultrafiltration
cannot handle certain solutions. Strong oxidizing agents,
solvents, and other organic compounds can dissolve the membrane.
Fouling is sometimes a problem, although the high velocity of the
wastewater normally creates enough turbulence to keep fouling at
a minimum. Large solids particles can sometimes puncture the
membrane and must be removed by gravity settling or filtration
prior to the ultrafiltration unit.
Operational Factors. Reliability: The reliability of an
ultrafiltration system is dependent on the proper filtration,
settling or other treatment of incoming waste streams to prevent
damage to the membrane. Careful pilot studies should be done in
each instance to determine necessary pretreatment steps and the
exact membrane type to be used.
Maintainability: A limited amount of regular maintenance is
quired for the pumping system. In addition, membranes must be
periodically changed. Maintenance associated with membrane plug-
ging can be reduced by selection of a membrane with optimum phy-
sical characteristics and sufficient velocity of the waste
stream. It is occasionally necessary to pass a detergent
solution through the system to remove an oil and grease film
which accumulates on the membrane. With proper maintenance,
membrane life can be greater than twelve months.
Solid Waste Aspects: Ultrafiltration is used primarily to
recover solids and liquids. It therefore eliminates solid waste
problems when the solids (e.g., paint solids) can be recycled to
the process. Otherwise, the stream containing solids must be
treated by end-of-pipe equipment. In the most probable
applications within the battery manufacturing category, the
ultrafilter would remove hydroxides or sulfides of metals which
have recovery value.
Demonstration Status. The ultrafiltration process is well
developed and commercially available for treatment of wastewater
or recovery of certain high molecular weight liquid and solid
contaminants.
25. Vacuum Filtration
In wastewater treatment plants, sludge dewatering by vacuum
filtration generally uses cylindrical drum filters. These drums
have a filter medium which may be cloth made of natural or
synthetic fibers or a wire-mesh fabric. The drum is suspended
564
-------
above and dips into a vat of sludge. As the drum rotates slowly,
part of its circumference is subject to an internal vacuum that
draws sludge to the filter medium. Water is drawn through the
porous filter cake to a discharge port, and the dewatered sludge,
loosened by compressed air, is scraped from the filter mesh.
Because the dewatering of sludge on vacuum filters is relativley
expensive per kilogram of water removed, the liquid sludge is
frequently thickened prior to processing. A vacuum filter is
shown in Figure VII-30 (page 642).
Application and Performance. Vacuum filters are frequently used
both in municipal treatment plants and in a wide variety of
industries. They are most commonly used in larger facilities,
which may have a thickener to double the solids content of
clarifier sludge before vacuum filtering.
The function of vacuum filtration is to reduce the water content
of sludge, so that the solids content increases from about 5
percent to about 30 percent.
Advantages and Limitations. Although the initial cost and area
requirement of the vacuum filtration system are higher than those
of a centrifuge, the operating cost is lower, and no special
provisions for sound and vibration protection need be made. The
dewatered sludge from this process is in the form of a moist cake
and can be conveniently handled.
Operational Factors. Reliability: Vacuum filter systems have
proven reliable at many industrial and municipal treatment
facilities. At present, the largest municipal installation is at
the West Southwest wastewater treatment plant of Chicago,
Illinois, where 96 large filters were installed in 1925,
functioned approximately 25 years, and then were replaced with
larger units. Original vacuum filters at Minneapolis-St. Paul,
Minnesota, now have over 28 years of continuous service, and
Chicago has some units with similar or greater service life.
Maintainability: Maintenance consists of the cleaning or
replacement of the filter media, drainage grids, drainage piping,
filter pans, and other parts o'f 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.
565
-------
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.
26. Permanganate Oxidation
Permanganate oxidation is a chemical reaction by which wastewater
pollutants can be oxidized. When the reaction is carried to
completion, the byproducts of the oxidation are not
environmentally harmful. A large number of pollutants can be
practically oxidized by permanganate, including cyanides,
hydrogen sulfide, and phenol. In addition, the chemical oxygen
demand (COD), and many odors in wastewaters and sludges can be
significantly reduced by permanganate oxidation carried to its
end point. Potassium permanganate can be added to wastewater in
either dry or slurry form. The oxidation occurs optimally in the
8 to 9 pH range. As an example of the permanganate oxidation
process, the following chemical equation shows the oxidation of
phenol by potassium permanganate:
3 C6HS(OH) + 28KMnO4 + SH^ > 18 CO2 + 28KOH + 28 MnO2.
One of the byproducts of this oxidation is manganese dioxide
(MnO2), which occurs as a relatively stable hydrous colloid
usually having a negative charge. These properties, in addition
to its large surface area, enable manganese dioxide to act as a
sorbent for metal cation, thus enhancing their removal from the
wastewater.
Application and Performance. Commercial use of permanganate
oxidation has been primarily for the control of phenol and waste
odors. Several municipal waste treatment facilities report that
initial hydrogen sulfide concentrations (causing serious odor
problems) as high as 100 mg/1 have been reduced to zero through
the application of potassium permanganate. A variety of
industries (including metal finishers and agricultural chemical
manufacturers) have used permanganate oxidation to totally
destroy phenol in their wastewaters.
Advantages and Limitations. Permangana'te oxidation has several
advantages as a wastewater treatment technique. Handling and
storage are facilitated by its non-toxic and non-corrosive
nature. Performance has been proved in a number of municipal and
industrial applications. The tendency of the manganese dioxide
566
-------
by-product to act as a coagulant aid is a distinct advantage over
other types of chemical treatment.
The cost of permanganate oxidation treatment can be limiting
where very large dosages are required to oxidize wastewater
pollutants. In addition, care must be taken in storage to
prevent exposure to intense heat, acids, or reducing agents;
exposure could create a fire hazard or cause explosions. Of
greatest concern is the environmental hazard which the use of
manganese chemicals in treatment could cause. Care must be taken
to remove the manganese from treated water before discharge.
Operational Factors. Reliability: Maintenance consists of
periodic sludge removal and cleaning of pump feed lines.
Frequency of maintenance is' dependent on wastewater
characteristics.
Solid Waste Aspects: Sludge is generated by the process where
the manganese dioxide byproduct tends to act as a coagulant aid.
The sludge from permanganate oxidation can be collected and
handled by standard sludge treatment and processing equipment.
No battery manufacturing facilities are known to use permanganate
oxidation for wastewater treatment at this time.
Demonstration Status. The oxidation of wastewater pollutants by
potassium permanganate is a proven treatment process in several
types of industries. It has been shown effective in treating a
wide variety of pollutants in both municipal and industrial
wastes.
IN-PROCESS POLLUTION CONTROL TECHNIQUES
In general, the most cost-effective pollution reduction tech-
niques available to any industry are those which prevent
completely the entry of pollutants into process wastewater or
reduce the volume of wastewater requiring treatment. These "in-
process" controls can increase treatment effectiveness by
reducing the volume of wastewater to treatment as more
concentrated waste streams from which 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 in
reduced water consumption, in decreased waste treatment costs and
in decreased consumption or recovery of process materials.
Process water use in battery manufacturing provides many
opportunities for in-process control and, as Table VI1-30 (page
642) shows, some in-process control measures have been
implemented by many battery manufacturing facilities. The wide
range of in-process water use and wastewater discharge exhibited
567
-------
by battery manufacturing plants (as shown in the data presented
in Section V) reflects the present variability of in-process
control at these facilities.
Many in-process pollution control techniques are of general
significance, although specific applications of these techniques
vary among different battery manufacturing subcategories. Some
of the available in-process control techniques apply only to
specific processing steps.
Generally Applicable In-Process Control Techniques
Techniques which may be applied to reduce pollutant discharges
from most battery manufacturing subcategories include wastewater
segregation, water recycle and reuse, water use reduction, pro-
cess modification, and plant maintenance and good housekeeping.
Effective in-process control at most plants will entail a
combination of several techniques. Frequently, the practice of
one in-process control technique is required for the successful
implementation of another. For example, wastewater segregation
is frequently a prerequisite for the extensive practice of
wastewater recycle or reuse.
Wastewater Segregation - The segregation of wastewater streams is
a key element in cost-effective pollution control. Separation of
noncontact cooling water from process wastewater prevents
dilution of the process wastes and maintains the character of the
non-contact stream for subsequent reuse or discharge. Similarly,
the segregation of process wastewater streams differing
significantly in their chemical characteristics can reduce
treatment costs and increase effectiveness. Segregation of
specific process wastewater streams is common at battery
manufacturing plants.
Mixing process wastewater with noncontact cooling water increases
the total volume of process wastewater. This has an adverse
effect on both treatment performance and cost. The resultant
waste stream is usually too contaminated for continued reuse in
noncontact cooling, and must be treated before discharge. The
increased volume of wastewater increases the size and cost of
treatment facilities and lowers the mass removal effectiveness.
Thus a plant which segregates noncontact cooling water and other
nonprocess waters from process wastewater will almost always
achieve a lower mass discharge of pollutants while substantially
reducing treatment costs.
Battery manufacturing plants 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.
568
-------
Wastewater from a specific process 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 bear-
ing high pollutant loads often allows further process use of the
dilute streams. Sometimes the lightly polluted streams may be
cycled to the process from which they were discharged; other
wastewater streams may be suitable for use in another process
with only minimal treatment; and in selected cases dilute process
wastewater streams are suitable for incorporation into the
product.
Segregation of wastewater streams may lower the cost of separate
treatment of the wastewater stream. For example, wastewater
streams containing high levels of suspended solids may be treated
in separate inexpensive settling systems rather than more
expensive lime and settle treatment. Often the clarified
wastewater is suitable for further process use and both pollutant
loads and the wastewater volume requiring further treatment are
reduced.
Segregation and separate treatment of selected wastewater streams
may yield an additional economic benefit to the plant by allowing
increased recovery of process materials. The solids borne by
wastewater from a specific process operation are primarily
composed of materials used in that operation. These sludges
resulting from separate settling of these streams may be
reclaimed for use in the process with little or no processing or
recovered for reprocessing. 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 a particularly effective technique for the re-
duction of both pollutant discharges and treatment costs. The
term "recycle" is used to designate the return of process
wastewater usually after some treatment to the process or
processes from which it originated, while "reuse" refers to the
use of wastewater from one process in another. Both recycle and
reuse of process wastewater are presently practiced at battery
manufacturing plants 'although recycle is more extensively used.
The most frequently recycled waste streams include air pollution
control scrubber discharges, and wastewater from equipment and
area cleaning. Numerous other process wastewater streams from
battery manufacturing activities may also be recycled or reused.
Common points of wastewater recycle in present practice include
air pollution control scrubbers, equipment and area washdown
water, some product rinsing operations and contact cooling.
569
-------
Both recycle and reuse are frequently possible without extensive
treatment of the wastewater; process pollutants present in the
waste 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 expense and comp-
lications because the required treatment is often minimal and the
water for recycle is immediately available. As an example for
electrode manufacture, pasting area washdown water can be
collected in the immediate area of pasting, settled and the
supernatant reused for the next washdown of the pasting area.
The rate of water used in wet air scrubbers is determined by the
requirement for adequate contact with the air being scrubbed and
not by the mass of pollutants to be removed. As a result,
wastewater streams from once-through scrubbers are character-
istically very dilute and high in volume. These streams can
usually be recycled extensively without treatment with no
deleterious effect on scrubber performance. Limited treatment
such as neutralization where acid fumes are scrubbed can signifi-
cantly increase the practical recycle rate.
Water used in washing process equipment and production floor
areas frequently serves primarily to remove solid materials and
is often treated by settling and recycled. This practice is
especially prevalent at lead subcategory plants but is observed
in other subcategories as well. In some instances the settled
solids as well as the clarified wastewater are returned for use
in the process. The extent of recycle of these waste streams may
be very high, and in many cases no wastewater is discharged from
the recycle loop.
Water used in product rinsing is also recirculated in some cases,
especially from battery rinse operations. This practice is ulti-
mately limited by the concentrations of materials rinsed off the
product in the rinsewater. Wastewater from contact cooling oper-
ations also may contain low concentrations of pollutants which do
not interfere with the recycle of these streams. In some cases,
570
-------
recycle of contact cooling water with no treatment is observed
while in others, provisions for heat removal in cooling towers or
closed heat exchangers is required. Where contact cooling water
becomes heavily contaminated with acid, neutralization may be
required to minimize corrosion.
Water used in vacuum pump seals and ejectors commonly becomes
contaminated with process pollutants. The levels of contaminants
in these high volume waste streams are 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 provisions for neutralization or removal of heat.
The extent of recycle possible in most process water uses is
ultimately limited by increasing concentrations of dissolved
solids in the water. The buildup of dissolved salts generally
.necessitates some small discharge or "blowdown" from the process
to treatment. In those cases, where the rate of addition of
dissolved salts is balanced by removal of dissolved solids in
water entrained in settled solids, complete recycle with no
discharge can be achieved. In other instances, the contaminants
which build up in the recycle loop may be compatible with another
process operation, and the "blowdown" may be used in another
process. One example of this condition is observed in lead
subcategory scrubbers, battery rinse, and contact cooling wastes
which become increasingly laden with sulfuric acid and lead
during recycle. Small volumes bled from these recycle loops may
be used in diluting concentrated acid to prepare battery
electrolyte as observed at some existing facilities.
Water Use Reduction - The volume of wastewater discharge from a
plant or specific process operation may be reduced by simply
eliminating excess flow and unnecessary water use. Often this
may be accomplished with no change in the manufacturing process
or equipment and without any capital expenditure. A comparison
of the volumes of process water used in and discharged from
equivalent process operations at different battery manufacturing
plants or on different days at the same plant indicates
substantial opportunities for water use reductions. Additional
reductions in process water use and discharge may be achieved by
modifications to process techniques and equipment.
Many production units in battery manufacturing plants were
observed to operate intermittently or at highly variable pro-
duction rates. The practice of shutting off process water flow
during periods when the unit is not operating and of adjusting
flow rates during periods of low production can prevent much
unnecessary water use. Water may be shut off and controlled
manually or through automatically controlled valves. Manual
adjustments involving the human factor have been found to be
571
-------
somewhat unreliable in practice; production personnel often fail
to turn off manual valves when production units are shut down and
tend to increase water flow rates to maximum levels "to insure
good operation" regardless of production activity. Automatic
shut off valves may be used to turn off water flows when
production units are inactive. Automatic adjustment of flow
rates according to production levels requires more sophisticated
control systems incorporating production rate sensors.
Observations and flow measurements at visited battery manufactur-
ing plants indicate that automatic flow controls are rarely
employed. Manual control of process water use is generally
observed in process rinse operations, and little or no adjustment
of these flows to production level was practiced. The present
situation is exemplified by a rinse operation at one plant where
the daily average production normalized discharge flow rate was
observed to vary from 90 to 1200 I/kg over a three-day span.
Thus, significant reductions in pollutant discharges can be
achieved by the application of flow control in this category at
essentially no cost. (A net savings may be realized from the
reduced cost of water and sewage charges.) Additional flow
reductions may be achieved by the implementation of more
effective water use in some process operations.
Rinsing is a common operation in the manufacture of batteries and
a major source of wastewater discharge at most plants. Efficient
rinsing requires the removal of the greatest possible mass of
material in the smallest possible volume of water. It is
achieved by ensuring that the material removed is distributed
uniformly through the rinse water. (The high porosity of many of
the electrode structures makes the achievement of uniform mixing
difficult, necessitating longer product residence times and high
mixing rates in rinses.) Rinsing efficiency is also increased by
the use of multi-stage and countercurrent cascade rinses. Multi-
stage rinses reduce the total rinse water requirements by
allowing the removal of much of the contaminant in a more
concentrated rinse with only the final stage rinse diluted to the
levels required for final product cleanliness. In a
countercurrent cascade rinse, dilute wastewater from each rinse
stage is reused in the preceding rinse stage and all of the
contaminants are discharged in a single concentrated waste
stream. The technical aspects of countercurrent cascade rinsing
are detailed later in this section.
Equipment and area cleanup practices observed at battery manu-
facturing plants vary widely. While some plants employ
completely dry cleanup techniques, many others use water with
varying degrees of efficiency. The practice of "hosing down"
equipment and production areas generally represents a very in-
efficient use of water, especially when hoses are left running
572
-------
during periods when they are not used. Alternative techniques
which use water more efficiently include vacuum pick-up floor
wash machines and bucket and sponge or bucket and mop techniques
as observed at some plants.
A major factor contributing in many cases, to the need for
battery washing is electrolyte spillage on the battery case
during filling. This spillage and subsequent battery washing
requirements are maximized when batteries are filled by immersion
or by "overfill and withdraw" techniques. Water use in battery
washing may be significantly reduced by the use of filling
techniques and equipment which add the correct amount of
electrolyte to the battery without overfilling and which minimize
drips and spills on the battery case. These electrolyte addition
techniques and the production of finished batteries with little
or no battery washing are observed at numerous plants in the
category.
Additional reduction in process water use and wastewater dis-
charge may be achieved by the substitution of dry air pollution
control devices such as baghouses for wet scrubbers where the
emissions requiring control are amenable to these techniques.
Countercurrent Cascade Rinsing and Multistage Rinsing
Of the many schemes discussed above for reduction of water use in
a battery production plant, countercurrent cascade rinsing is
most likely to result in the greatest reduction of water
consumption and use.
Countercurrent cascade rinses are employed 'at many plants in the
battery manufacturing category. In most cases/ however/ these
techniques are not combined with effective flow control, and the
wastewater discharge volumes from the countercurrent cascade
rinses are as large as or larger than corresponding single stage
rinse flows at other plants. Three instances of countercurrent
cascade rinsing with reasonable levels of flow control are noted
to illustrate the benefits achievable by this technique within
the battery manufacturing category.
Two lead subcategory plants use two-stage countercurrent cascade
rinses to rinse electrodes after open-case formation. These
rinses discharge 3.3 and 3.6 I/kg. At 28 other plants, single
stage rinses are used after open-case formation with an average
discharge of 20.9 I/kg. Thus, the use of two-stage
countercurrent cascade rinsing in this application is seen to
reduce rinse wastewater flow by a factor of 6.05 (83% flow
reduction). Still further reductions would result from better
operation of these rinse installations or from the use of
additional countercurrent cascade rinse stages.
573
-------
One cadmium subcategory plant has recently implemented a five-
stage countercurrent rinse after electrode impregnation. This
change has reduced the rinse discharge from 150,000 to 12,000
gal/day. In addition, the countercurrent rinse discharge is
sufficiently concentrated to be sold for its caustic (NaOH)
content. The flow rates before and after implementation of the
cascade rinse indicate a 12.5 fold reduction in wastewater flow
by this technique. Since a substantial increase in production
also occurred, the actual flow reduction attributable to counter-
current rinsing must have been greater. These results illustrate
the flow reductions which may be achieved by countercurrent
rinsing. The transfer of this performance to other process
elements and subcategories requires the consideration of rinsing
factors which may differ.
Rinse water requirements and the benefits of countercurrent
cascade rinsing may be influenced by the volume of drag-out
solution carried into each rinse stage by the electrode or
material being rinsed, by the number of rinse stages used, by the
initial concentrations of impurities being removed, and by the
final product cleanliness required. The influence of these
factors is expressed in the rinsing equation which may be stated
simply as:
Vr
Co
Cf
(1/n)
X VD
Vr is the flow through each rinse stage.
Co is the concentration of the contaminant(s) in
the initial process bath
Cf is the concentration of the contaminant(s) in
the final rinse to give acceptable product
cleanliness
n is the number of rinse stages employed,
and
VD is the flow of drag-out carried into each
rinse stage
For a multistage rinse, the total volume of rinse wastewater is
equal to n times Vr while for a countercurrent rinse, Vr is the
total volume of wastewater discharge. Multistage rinsing uses
two or more stages of rinsing each of which is supplied with
fresh water and discharges to sewer or treatment.
574
-------
Drag-out is solution which remains in the pores and on the
surface of electrodes or materials being rinsed when they are
removed from process baths or rinses. In battery manufacturing,
drag-out volumes may be quite high because of the high porosity
and surface areas of electrodes. Based on porosity and surface
characteristics, it is estimated that the drag-out volume will be
approximately 20 percent of the apparent electrode volume
(including pores). Because of the highly porous nature of many
electrodes, perfect mixing in each rinse generally is not
achieved, and deviation from ideal rinsing is anticipated.
The application of the rinsing equation with these considerations
to the lead subcategory example cited above provides a basis for
the transfer of countercurrent rinse performance to other
subcategories and process elements. Based on the specific
gravities of component materials and approximately 20 percent
porosity, the apparent specific gravity of lead electrodes may be
estimated as 7.0; the volume of drag-out per unit weight of lead
is therefore:
VD = 0.2 = 0.029 I/kg.
7.0
Based on the average single stage rinse flow, the rinse
ratio (equal to Co/Cf) is:
« Vr » 20.9 = 720
YD 0.029
The calculated flow for a two stage countercurrent rinse
providing equivalent product cleaning is then given by
Vr « Co (i/n) x Vd - 720 °.* x 0.029 «= 0.78 I/kg.
Cf
This calculated flow yields a rinse ratio of 26.8 and is 4.4
times (26.8 t- 6.05) lower than the observed countercurrent rinse
flow reflecting the extent to which ideal mixing is not achieved
in the rinses. One of these two plants was visited for sampling
and was observed to employ no mixing or agitation in the rinse
tanks. Therefore, performance significantly closer to the ideal
should be attainable simply by adding agitation to the rinse
tanks.
A corresponding comparison between theoretical and actual
countercurrent rinse performance cannot be made for the cadmium
subcategory plant because of uncertainties in production level,
number of impregnation and rinse cycles performed on each
electrode, and electrode pore volume during the early stages of
575
-------
impregnation (a process which fills electrode pores with active
material to achieve the final electrode porosity).
To transfer countercurrent rinse results to other process ele-
ments, allowance must be made for the fact that required rinse
ratios may be substantially different in order to provide
adequate contaminant removal from some electrodes. To encompass
all process element requirements, an extreme case is considered
in which contaminants initially present at 10 percent (100,000
mg/1) in a process bath must be reduced to a nearly immeasurable
1.0 mg/kg (one part per million) in the final rinsed electrode.
The 20 percent drag-out found appropriate for lead electrodes is
also applicable to other electrode types and materials rinsed,
since all have high porosity and surface area requirements in
order to sustain high current densities. The specific gravities
of most electrode materials are lower than those of lead and its
salts. Consequently, lower electrode densities are expected. An
estimated specific gravity of 4.5 is used for purposes of this
calculation. Also, the active materials used as the basis of
production normalizing parameters make up only approximately 45
percent of the total electrode weight in most cases.
On the basis of these figures, it may be calculated that the
volume of drag-out amounts to:
VD = 0.2 = 0.044 I/kg of electrode
4.5
or
VD = 0.2 x 1 = 0.1 I/kg of pnp
The concentration of pollutant in the final rinse may be
calculated as 10 mg/1 based on the factors postulated and
calculated above. The rinse ratio (Co/Cf) is 10,000.
Using these rinsing parameters, theoretical rinse flow require-
ments may be calculated for single stage rinses and for a variety
of multi-stage and countercurrent rinses. Both ideal flows and
flows increased by the 4.4 factor found in the lead subcategory
are shown for countercurrent rinses.
576
-------
Number of Required Rinse Water per Mass of Product (pnp)
Rinse (I/kg)
Stages Multistage Countercurrent
Ideal Ideal Adjusted Rinse
Ratio
1 1000 1000
2 20 10 44.0 22.7
3 6.6 2.2 9.68 103.3
4 4.0 1.0 4.4 227.3
5 3.2 0.63 2.77 361.
7 2.6 0.37 1.63 613.
10 2.5 0.25 1.1 909.
Single stage rinse flow requirements calculated for these
conditions are somewhat higher than those presently observed in
the battery manufacturing category. The highest reported rinse
flow is approximately 2000 I/kg, and most are substantially less
than 1000 I/kg. This indicates that the cleanliness level has
been conservatively estimated.
In general, these calculations confirm that extreme conditions
have been chosen for the calculations and that the lead
subcategory data have been transferred to rinsing requirements
more severe in terms of drag-out and cleanliness than any
presently encountered in practice. Therefore, countercurrent
rinse discharge flows lower than those calculated should be
attainable in all process elements in the category.
In later sections of this document it is necessary to calculate
the wastewater generation when countercurrent cascade rinsing is
substituted for single stage rinsing. A rinse ratio of 6.6 is
used later for this calculation. It is based on the 6.05 rinse
ratio found in existing lead subcategory plants with an allowance
of 10 percent added for increased efficiency obtained by improved
agitation. As shown above, a rinse ratio of 22 would be expected
from a two stage system and much higher ratios are obtained by
using additional stages.
Process Modification - There'are numerous process alternatives
for the manufacture of batteries in most of the battery manu-
facturing 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 sub-
categories and are discussed in subsequent sections. In general,
process modifications considered deal with changes in electrolyte
addition techniques as discussed previously and changes in elec-
577
-------
trode 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 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 observed to be important in eliminating
unnecessary spil-ls and leaks and in reducing contamination of
noncontact cooling water. Examples of the impact of faulty
maintenance were observed in the contamination of noncontact
cooling water in a leaking ball mill cooling jacket at one lead
subcategory facility and in the use of excess water in hosing
down a malfunctioning 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 toxic
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 collected 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.
578
-------
Reduction in spillage in bulk handling by provision for
dust control and for rapid dry cleanup of spilled
materials.
Cadmium Subcategory
Cadmium subcategory manufacturing processes involve 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 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 sub-
category because all process waste streams are amenable to
treatment by the same technologies. The segregation of non-
contact cooling and heating water from process wastewater is es-
sential 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 or
filtering 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
579
-------
from scrubbing impregnated electrodes or electrode stock, and
process solutions used in material deposition and electrode
formation. Recycle of these waste streams is presently practiced
and is observed to yield 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 scrubber systems were as low as 1.1
1/hr, while the nonrecirculated 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 wet
scrubbing operation. Since the primary contaminants in this
waste stream are suspended solids, a very high degree of recycle
after settling is practical. Recycle of this waste stream
following settling to remove suspended solids is practiced at one
plant with wastewater discharged 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 plant which does not recycle electrode scrubbing
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
resultant 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.
580
-------
Water Use Control and Reduction - Large volumes of process water
are used in rinsing at cadmium subcategory plants. On site
observations at several plants and analysis of flow rate informa-
tion from other sites indicate that effective control of water
use in these operations is not achieved, and that substantial re-
ductions from present discharge rates may be attained by institu-
ting effective water use control. The lack of effective water
use control in these operations is demonstrated by the wide range
of flow rates among plants and on different days at the same
plant. 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, although the production rate was
about 50 percent less than that reported. The wastewater
discharge per unit of production was approximately three 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 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 shutoffs which will close water supply valves when the
process line is not running and adjustment of rinse flow rates
when production rates vary.
Further reductions may be achieved by application of multistage
countercurrent rinse techniques. While multistage 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 at different plants 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
plants 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
581
-------
addition equipment is reported by only a few plants. Other
plants 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
cleanup is a viable option in this subcategory since most of the
materials requiring removal from production floor areas are dry
solids. Seven active plants in the subcategory reported no pro-
cess wastewater from washing floors and apparently employ dry
floor cleaning techniques. Only two plants in the subcategory
reported wastewater discharge from floor cleaning.
Process Modification - Numerous manufacturing processes for the
production 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
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%.
582
-------
Calcium Subcateqory
Process water use in this subcategory is very limited. Con-
sequently, the opportunities for in-process controls
significantly reducing water use or wastewater discharge are
correspondingly limited. Wastewater generated from heat
generation component manufacture, cell testing and scrap disposal
can be eliminated.
The manufacture of thermal heat paper produces solids and
wastewater from the pasting equipment cleanup which is similar to
pasting in the lead subcategory. As is practiced at numerous
plants in the lead subcategory the solids can be recycled back to
the process and wastewater can be used for past make-up water.
This is feasible because wastes generated contain constiuents
used in the paste. Water used for cell testing can also be
treated when necessary and reused. 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.
Leclanche Subcateqory
Process water use and wastewater discharge in this subcategory
are limited. Many plants presently report no discharge of
process wastewater, and most others discharge only limited
volumes of wastewater from one or two sources. Almost all of the
existing discharges can 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 wastes. Only . one or two battery
manufacturing 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
583
-------
the specific recycle and reuse techniques differ, waste streams
from both paste preparation and application and from other
equipment cleanup 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 buildup 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. For foliar batteries reuse is restricted
because of cell failure which can result from small quantities of
contaminants in this particular cell design. 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 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 drag-out of water on the cells and conveyors. Discharge
from each of these process sources may be reduced or eliminated
by recycle and reuse of the water.
584
-------
The paste processing steps in making mercury containing seperator
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
cleanup 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 subcategoty.
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.
For foliar battery production water use is excessive and can be
controlled with various flow control practices and limited
recycle of wastewater. The present flow of 0.132 I/kg can be
reduced to half of its present flow using these in-process
techniques discussed above.
Water is used in a washing machine at one plant 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.
585
-------
A majority of manufacturers reported no wastewater discharged
from floor wash procedures, and it is concluded that dry
maintenance techniques 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 usage 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 substi-
tution 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 Housekeeping - Dry cleanup 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 Subcategory
Process water use and wastewater discharges in the lithium
subcategory are limited. The cell anode material reacts
vigorously with water, necessitating the use of nonaqueous
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.
586
-------
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 different 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 Subcategory
Manufacturing processes 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. Consequently a variety of techni-
ques 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 noncontact
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 waste streams. The segregation of the organic laden waste
streams from waste streams bearing predominantly toxic metals and
587
-------
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 than wastewater treatment 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 are present at particularly
high concentrations in wastewater streams from some active
material and cathode preparation operations. The segregation of
these waste streams may allow recovery of the silver for use on
site or its 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.
Segregation, and separate treatment of these streams can reduce
the total mass 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 some degree of treatment
before being recycled.
The opportunity for wastewater recycle and reuse in this
subcategory is in general minimal because plants in this
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 plants, 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
588
-------
vessels, this electrolyte can be returned for addition to cells
eliminating this source of highly concentrated wastes.
At most plants, it was observed that cell washing removed small
amounts of contaminants from most cells and that water use was
governed by the need to ensure adequate contact of the wash solu-
tion and rinse wate£ -with the complete cell surface. At two
plants, wastewater discharges from these operations are presently
reduced by the practice of recycling the cell wash and rinse
wastewater and discharging from the recycle system only
occasionally, generally once each day. Cell wash operations in
which this recycle is practiced result in 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, and 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 use
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 where1 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
589
-------
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 or countercurrent
rinses.
Other techniques which reduce process flows include the re-
placement of wet processes with processes that do not use water.
For example, 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 sub-
category although not specifically identified by most plants.
Only a few plants discharge significant volumes of floor wash
water because of such practices as hosing down floor areas.
Material recovery may also significantly reduce pollutant load-
ings. Zinc cell manufacturerers practice material recovery for
silver and mercury in either process wastewater or reject cells.
Process Modification - Manufacturing processes in this sub-
category are widely varied and correspond 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 which is subsequently drained off and
discharged; "gelled" amalgamation in which 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 zinc and mercury 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
590
-------
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.
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.
Another process modification involves forming electrodes in the
battery case. This eliminates the post-formation rinsing step,
thereby reducing water usage and pollutant loadings. One plant
presently uses this procedure.
Plant Maintenance and Good Housekeeping - As in subcategories
previously discussed, 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.
591
-------
TABLE VII-1
pH CONTROL EFFECT ON METALS REMOVAL
Day 1 Day 2 Day 3
In Out In Out In Out
pH Range
TSS
Copper
Zinc
2.4-3.4
39
312
250
8.5-8.7
8
0.22
0.31
1.0-3.0
16
120
32.5
5.0-6.0
19
5.12
25.0
2.0-5.0
16
107
43.8
6,5-8.1
7
0.66
0.66
TABLE VI 1-2
EFFECTIVENESS
pH Range
(mg/1)
Cc
Cu
Fe
Pb
Mn
Ni
Zn
TSS
Day 1
In
2.1-2.9
0.097
0.063
9.24
1.0
0.11
0.077
.054
1
OF SODIUM
Out
9.0-9.3
0.0
0.018
0.76
0.11
0.06
0.011
0.0
3
HYDROXIDE
Day
In
2.0-2.4
0.057
0.078
15.5
1 .36
0.12
0.036
0.12
FOR METALS
2
Out
8.7-9.1
0.005
0.014
0.92
0. 13
0.044
0.009
0.0
1 1
REMOVAL
Day
In
2.0-2.4
0.068
0.053
9.41
1.45
0.11
0.069
0.19
3
Out
8.6-9.1
0.005
0.019
0.95
0.11
0.044
0.01 1
0.037
11
592
-------
TABLE VII-3
EFFECTIVENESS OF LIME AND SODIUM HYDROXIDE FOR METALS REMOVAL
Day 1
Day 2
Day 3
pH Range
(mg/1)
Al
Co
Cu
Fe
Mn
Ni
Se
Ti
Zn
In
9.2-9.6
37.3
3.92
0.65
137
175
6.86
28.6
143
18.5
Out
8.3-9.8
0.35
0.0
0.003
0.49
0.12
0.0
0.0
0.0
0.027
In
9.2
38. 1
4.65
0.63
110
205
5.84
30.2
125
16.2
Out
7.6-8.1
0.35
0.0
0.003
0.57
0.012
0.0
0.0
0.0
0. 044
In
9.6
29.9
4.37
0.72
208
245
5.63
27.4
115
17.0
Out
7.8-8.2
0.35
0.0
0.003
0.58
0. 12
0.0
0.0
0.0
0.01
TSS
4390
3595
13
2805
13
TABLE VI1-4
THEORETICAL SOLUBILITIES OF HYDROXIDES AND SULFIDES
OF SELECTED METALS IN PURE WATER
Metal
Cadmium (Cd++)
Chromium (Cr+++)
Cobalt
Copper (Cu •«"«•)
Iron (Fe**)
Lead (Pb++)
Manganese {Mn++)
Mercury (Hg++)
Nickel (Ni++)
Silver (Ag+)
Tin (Sn++)
Zinc (Zn++)
AsHydroxide
2.3 x 10-s
8.4 x 10--*
2.2 x 10-i
2.2 x 10-2
8.9 x 10-*
2.1
1 .2
3.9 x 10—»
6.9 x 10~3
13.3
1.1 x 10-*
1 .1
Solubility of metal ion, mg/1
As Carbonate
1.0 x 10-*
7.0 x 10-3
3.9 x 10-2
1.9 x 10-»
2.1 x 10-1
7.0 x 10-*
As Sulfide
6.7 x 1Q~*°
No precipitate
1.0 x 10-8
5.8 x 10~*8
3.4 x ID-5
3.8 x 10-»
2.1 x 10~3
9.0 x 10-20
6.9 x 10-8
7.4 x 10~12
3.8 x 10-8
2.3 x 10~7
593
-------
TABLE VII-5
SAMPLING DATA FROM SULFIDE
PRECIPITATION-SEDIMENTATION SYSTEMS
Treatment
Lime, FeS, Poly-
electrolyte,
Settle, Filter
Lime, FeS, Poly-
electrolyte,
Settle, Filter
NaOH, Ferric
Chloride, NazS
Clarify (1 stage)
pH
(mg/1
Cr+6
Cr
Cu
Fe
Ni
Zn
These
In
5.0-6,
25.
32.
0.
39.
6
3
52
5
.8
<0
<0
0
<0
data were obtained
Summary Report^
Metal Finishing
Out
8-9
.014
.04
.10
.07
from
Control
Industry
In
7
0
2
108
0
33
three
.7
.022
.4
.68
.9
<0
<0
0
<0
0
Out
7.38
.020
.1
.6
.1
.01
In
11
18
0
0
.45
.35
.029
.060
Out
<.005
<.005
0.003
0.009
sources:
and Treatment
: Sulf
ide
Technology
Precipitation,
for
USEPA,
the
EPA
No. 625/8/80-003, 1979.
Indus.tria 1 Fin i sh ing, Vol. 35, No. 11, November, 1979.
Electroplating sampling data from plant 27045.
594
-------
TABLE VI1-6
SULFIDE PRECIPITATION-SEDIMENTATION PERFORMANCE
Parameter
Cd
Cr
Cu
Pb
Hg
Ni
Ag
Zn
(T)
Treated Effluent
(mg/1)
0.01
O.D5
0.05
0.01
0.03
0.05
0.05
0.01
Table VI1-6 is based on two reports:
Summary Report, Control and Treatment Technology for the
Metal Finishing Industry; Sulfide Precipitation, USEPA, EPA
No. 625/8/80-003, 1979.
Addendum to Development Document for Effluent Limitations
Guidelines and New Source Performance Standards, Major
Inorganic Products Segment of Inorganics Point Source
Category, USEPA., EPA Contract No. EPA-68-01-3281 (Task 7),
June, 1978.
595
-------
Table VII-7
FERRITE CO-PRECIPITATION PERFORMANCE
Metal Influent(mg/l) Effluent(mg/1)
Mercury 7.4 0.001
Cadmium 240 0.008
Copper 10 0.010
Zinc 18 0.016
Chromium 10 <0.010
Manganese 12 0.007
Nickel 1,000 0.200
Iron 600 0.06
Bismuth 240 0.100
Lead 475 0.010
NOTE: These data are from:
Sources and Treatment of Wastewater in the Nonferrous
Metals Industry, USEPA, EPA No. 600/2-80-074, 1980.
TABLE VII-8
CONCENTRATION OF TOTAL CYANIDE
Plant
1057
33056
12052
Mean
Method
FeS04
FeSO*
ZnS04
(mg/1)
In
2.57
2.42
3.28
0.14
0.16
0.46
0. 12
Out
0.024
0.015
0.032
0.09
0.09
0. 14
0.06
0.07
596
-------
Plant ID |
06097
13924
18538
30172
36048
mean
Table VII-9
MULTIMEDIA FILTER PERFORMANCE
TSS Effluent Concentration, mq/1
0.
1 .
3.
1 .
1 .
2.
2.
o,
8,
o,
0
4,
1,
61
0.
2.
2.
7.
2.
o,
2,
o,
o,
6,
0.
5.
5.
1 .
1 .
5
6, 4.0, 4.0, 3.0, 2.
6, 3.6, 2.4, 3.4
0
5
2, 2.8
TABLE VII-10
PERFORMANCE OF SELECTED SETTLING SYSTEMS
PLANT ID
01057
09025
11058
12075
19019
33617
40063
44062
46050
SETTLING
DEVICE
Lagoon
Clarifier &
Settling
Ponds
Clarifier
Settling
Pond
Settling
Tank
Clarifier &
Lagoon
Clarifier
Clarifier
Settling
Tank
SUSPENDED SOLIDS CONCENTRATION (mg/1)
Day 1
In
54
1100
451
284
170
-
4390
182
295
Out
6
9
17
6
1
-
9
13
10
Day
In
56
1900
—
242
50
1662
3595
118
42
2
Out
6
12
—
10
1
16
12
14
10
Day 3
In
50
1620
-
502
-
1298
2805
174
153
Out
5
5
-
14
-
4
13
23
8
597
-------
Table VII-11
SKIMMING PERFORMANCE
Oil & Grease
mg/l
Plant Skimmer Type In Out
06058 API 224,669 17.9
06058 Belt 19.4 8.3
598
-------
TABLE VII-12
SELECTED PARITION COEFFICIENTS
Log Octanol/Water
Priority Pollutant Partition Coefficient
1
1 1
13
15
18
23
29
39
44
64
66
67
68
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
Acenaphthene
1 t 1 , 1 -Trichloroethane
1 , 1-Dichloroethane
1,1,2, 2-Tetrachloroethane
Bis( 2-chloroethyl )ether
Chloroform
1 , 1-Dichloroethylene
Fluoranthene
Methylene chloride
Pentachlorophenol
Bis( 2-ethylhexyl )
phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Benzo ( a ) anthracene
Benzo { a ) py rene
3,4-benzof luoranthene
Benzo ( k ) f 1 uor anthene
Chrysene
Acenaphthylene
Anthracene
Benzo (ghi >perylene
Fluorene
Phenanthrene
Dibenzo ( a, h ) anthracene
I ndeno ( 1 , 2 , 3 , cd ) pyr ene
Pyrene
Tetrachloroethylene
Toluene
4.33
2.17
1 .79
2.56
1 .58
1 .97
1 .48
5.33
1 .25
5.01
8.73
5.80
5.20
5.61
6.04
6.37
6.84
5.61
4.07
4.45
7.23
4, 18
4.46
5.97
7.66
5.32
2.88
2.69
599
-------
TABLE VII-13
TRACE ORGANIC REMOVAL BY SKIMMING
API PLUS BELT SKIMMERS
(From Plant 06058)
Eff.
mg/1
Oil & Grease 225,000 14.6
Chloroform 0.023 0.007
Methylene Chloride 0.013 0.012
Naphthalene 2.31 0.004
N-nitrosodiphenylamine 59.0 0.182
Bis-2-ethylhexyl phthalate 11.0 0.027
Diethyl phthalate
Butylbenzyl phthalate 0.005 0.002
Di-n-octyl phthalate 0.019 0.002
Anthracene - phenanthrene 16.4 0.014
Toluene 0.02 0.012
Table VII-14
COMBINED METALS DATA EFFLUENT VALUES (mg/1)
One Day 10 Day Avg. 30 Day Avg,
Mean Max. Max. Max.
Cd 0.079 0.34 0.15 0.13
Cr 0.084 0.44 0.18 0.12
Cu 0.58 1.90 1.00 0.73
Pb 0.12 0.42 0.20 0.16
Ni 0.74 1.92 1.27 1.00
In 0.33 1.46 0.61 0.45
Fe 0.41 1.20 0.61 0.50
Mn 0.16 0.68 0.29 0.21
TSS 12.0 41.0 19.5 15.5
600
-------
TABLE VI1-15
L&S PERFORMANCE
Pollutant Average Performance (mg/I)
Sb 0.7
As 0.51
Be 0.30
Hg 0.06
Se 0.30
Ag 0.10
Tl 0.50
Al 2.24
Co 0.05
F 14.5
TABLE VI1-16
COMBINED METALS DATA SET - UNTREATED WASTEWATER
Pollutant Min. Cone (mq/1) Max. Cone, (mq/1)
Cd <0.1 3.83
Cr <0.1 116
Cu <0.1 108
Pb <0.1 29.2
Ni <0.1 27.5
Zn <0.1 337.
Fe <0.1 263
Mn <0.1 5.98
TSS 4.6 4390
601
-------
TABLE VII-17
MAXIMUM POLLUTANT LEVEL IN UNTREATED WASTEWATER
ADDITIONAL POLLUTANTS
(mg/1)
Pollutant As & Se Be Aq F Sb
Sb - - 8.5
As 4.2 - 0.024
Be - 10.24
Cd <0.1 - <0.1 <0.1 0.83
Cr
Cu
Pb
Ni
Ag
Zn
F
Fe
O&G
TSS
0.18
33.2
6.5
—
—
3.62
_
—
16.9
352
8.60
1 .24
0.35
^,
-
0. 12
_
646
_
796
0.23
110.5
1 1 .4
100
4.7
1512
_
—
16
587.8
22.8
2.2
5.35
0.69
-
<0.1
760
—
2.8
5.6
—
0.41
76.0
_
-
0.53
_
—
_
134
602
-------
TABLE VII-18
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant A
Parameters
No Pts.
For 1979-Treated Wastewater
Range mg/1
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
Pe
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
0.06 ±0.10
0.016 ±0.010
0.20 ±0.14
0.23 ±0.34
0.49 +0.18
Mean + 2
std. dev,
0.10
0.03
0.48
0.35
0.26
0.04
0.48
0.91
0.85
603
-------
TABLE VII-19
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant B
Parameters
No Pts.
Range mq/1
Mean +_
std. dev.
Mean + 2
std. dev.
For 1979-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
TSS
175
176
175
175
174
2
0.
0.
0.
0.
0.
1 .
0
0
01
01
01
00
_ o
- 0
1
- 0
- 2
- 1
.40
.22
.49
.66
.40
.00
0.
0.
0.
0.
0.
068
024
219
054
303
+ 0.
+ 0.
+ 0.
+ 0.
+ 0.
075
021
234
064
398
0
0
0
0
1
.22
.07
.69
.18
.10
For 1 978-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
Total 1974-1
Cr
Cu
Ni
zn
Fe
Raw Waste
Cr
Cu
Ni
Zn
Fe
TSS
144
143
143
131
144
979-Treated
1288
1290
1287
1273
1287
3
3
3
2
3
2 1
0.
0.
0.
0.
0.
0
0
0
0
0
- 0
- 0
_ 1
- 0
- 1
.70
.23
.03
.24
.76
0.
0.
0.
0.
0.
059
017
147
037
200
+ 0.
i-O.
+ 0.
+0.
+ 0.
088
020
142
034
223
0
0
0
0
0
.24
.06
.43
.11
.47
Wastewater
0.
0.
0.
0.
0.
2.
0.
1 .
2.
3.
77
0
0
0
0
0
80
09
61
35
13
- 0
- 0
-1
- 0
- 3
_ 9
- 0
_ 4
— "2
-35
-466
.56
.23
.88
.66
.15
.15
.27
.89
.39
.9
„
0.
0.
0.
0.
0.
5.
0.
3.
22.
038
Oil
184
035
402
90
17
33
4
+0.
+ 0.
+ 0.
+ 0.
+0.
055
016
211
045
509
0
0
0
0
1
.15
.04
.60
.13
.42
604
-------
TABLE VI1-20
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
Plant C
For Treated Wastewater
Parameters No Pts.
For Treated Wastewater
Range mq/1
Mean ±
std. dev.
Cd
Zn
TSS
PH
103
103
103
103
For Untreated Wastewater
Cd
Zn
Fe
TSS
PH
103
103
3
103
103
0.010 - 0.500 0.049 ±0.049
0.039 - 0.899 0.290 ±0.131
0.100 - 5.00 1.244 ±1.043
7.1 - 7.9 9.2*
0.039 - 2.319 0.542 +0.381
0.949 -29.8
0.107 - 0.46
0.80 -19.6
6.8 - 8.2
* pH value is median of 103 values.
11.009 ±6.933
0.255
5.616 +2.896
7.6*
Mean + 2
std. dev,
0.147
0.552
3.33
1 .304
24.956
11.408
605
-------
TABLE VII-21
SUMMARY OF TREATMENT EFFECTIVENESS (ng/1)
Pollutant
Parameter
114
115
117
118
119
120
121
122
123
124
125
126
127
128
Sb
As
Be
Cd
Cr
Cu
CN
Pb
Hg
Ni
Se
Ag
Tl
In
Al
Co
F
Fe
Mn
P
O&G
TSS
Mean
0.70
0.51
0.30
0.079
0.084
0.58
0.07
0.12
0.06
0.74
0.30
0.10
0.50
0.33
2.24
0,05
14.5
0.41
0.16
4.08
12.0
L & S
Technology
System
One
Day
Max.
2.87
2.09
1.23
0.34
0.44
1.90
0.29
0.42
0.25
1.92
1.23
0.41
2.05
1.46
6.43
0.21
59.5
1.20
0.68
16.7
20.0
41.0
Ten
Day
1.28
0.86
0.51
0.15
0.18
1.00
0.12
0.20
0.10
1.27
0.55
0.17
0.84
0.61
3.20
0.09
26.4
0,61
0.29
6.83
12.0
19.5
Thirty
Day
Avg.
1.14
0.83
0.49
0.13
0.12
0.73
0.11
0.16
0.10
1.00
0.49
0.16
0.81
0.45
2.52
0.08
23.5
0,50
0.21
6.60
10.0
15.5
Mean
0.47
0.34
0.20
0.049
0.07
0.39
0.047
0.08
0.036
0.22
0.20
0.07
0.34
0.23
1.49
0.034
0.28
0.14
2.72
2.6
LS&F
Technology
System
One
Day
Max.
1.93
1.39
0.82
0.20
0.37
1.28
0.20
0.28
0.15
0.55
0.82
0.29
1.40
1.02
6.11
0.14
59.5
1.20
0.30
11.2
10.0
15.0
Ten
Day
*m±
0.86
0.57
0.34
0.08
0.15
0.61
0.08
0.13
0.06
0.37
0.37
0.12
0.57
0.42
2.71
0.07
26.4
0.61
0.23
4.6
10.0
12.0
Thirty
Day
Avg.
0.76
0.55
0.32
0.08
0.10
0.49
0.08
0.11
0.06
0.29
0.33
0.10
0.55
0.31
2.41
0.06
23.5
0.50
0.19
4.4
10.0
10.0
Sulfide
Precipitation
Filtration
One
Day
Mean Max.
0. 01 0. 04
0.08 0.21
0.05 0.21
0.01 0.04
0.03 0.13
0.05 0.21
0.05 0.21
0.01 0.04
Ten
Day
Avg.
0.018
0.091
0.091
0.018
0.0555
0.091
0.091
0.018
Thirty
Day
Avg.
0.016
0.081
0.081
0.016
0.049
0.081
0.081
0.016
-------
Priority Pollutant
1 .
2 .
3.
4.
5 .
6.
7.
9.
9.
10.
11.
12 .
13.
14.
15.
16.
17.
IB.
19.
20.
21.
22.
23.
24.
25.
26 .
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38 »
39.
40.
41.
42.
43 .
44.
45.
46.
47.
48.
acenaphthane
acrolein
acrylonitrila
banzena
banzldine
carbon tatrachlorida
( tetraehloroawthane )
chlorobancen*
1,2,3-trichlorobanzene
haxachlorobencena
1,2-diehloroathana
1,1,1-triehloroathana
haxachloroethana
1,1-dichloroathana
1,1,2-trichloroathana
1,1, 2, 2-e«trachlor ethane
chloroathana
bia(chloroawthyl) ether
bla(2-chloroethyl) ether
2-chloroethyl vinyl ether
2-chloroaaphthalena
2,4,6-trichlorophanol
parachloroMta creeol
chloroform (trichloroaethane)
2-ehloroph«nol
1,2-dichlorobancan*
1,3 -dichlorobenxen*
1,4-dichlorobencan*
3,3'-dichlorobenzidine
1,1-dichloroathylene
1,2-trana-dichloroethylene
2,4-dlchlorophaaol
1,2-dichloropropane
1,2-dichloropropylen*
( 1 , 3-dichloropropen* )
2,4-diaethylphanol
2,4-dinitrotoln«n«
2,6-dinitro«oluan«
l/2-diphan7lhydr«*ins
«thylb«nc«n«
fluoranthana
4-chloroph«nyl phcnyl «th«r
4-bronoph«nyl phrayl «th«r
bi«(2-chloroi«opropyl)«th«r
bis ( 2 -chloroathoxy ) aathan*
nathylcn* chlorid*
( dichlorooMthan* )
aathyl chlorid* ( dtloroaathan* )
Mthyl broavid* (broaoawthan*)
broBefoxB (tribroaoMtbana)
dichlorobroanaathan*
TABU! VII-22
TREATABXLITY RATING OF PRIORITY POLLUTANTS
. OTH.IZING CARBON ADSORPTION
*Keaaval *Raaoval
Rating Priority Pollutant Rating
H 49. trichlorofluoromathane M
L 50. dichlorodifluoromathana L
L 51. chlorodibroooaathana M
N 52. hexachlorobutadiena 8
a 53. haxachlorocyclopantadiana H
M 54. iaophoron* H
55. naphthalene H
a 56. nitrobenzene a
a 57. 2-nitrophanol H
B 58. 4-nitrophenol 8
M 59. 2,4-dinitrophenol a
M 60. 4,6-dinitro-o-craaol 8
H 61. N-nitroaodiaethylanin* K
M 62. H-nitroaodiphenylaain* 8
K 63. N-nitroaodi-n-propylaain* M
H 64. pantachlorophenol a
L 65. phenol K
66. bia(2-ethylhejcyl)phthalata H
M 67. butyl benzyl phthalate a
It 68. di-n-butyl phthalate 8
69. dl-n-octyl phthalate H
H 70. diathyl phthalata 8
a 71. diaethyl phthalata H
H 72. 1,2-bancanthracena 8
L (banco(a)anthracana)
8 73. benzo(a)pyren* (3,4-banro- 8
8 pyrene)
B 74. 3,4-benzofluoranthan* H
a (benco(b)fluoranthen*)
8 75. 11,12-bencofluoranthen* 8
L , (benzo(lc)fluoranthene)
L 76. chryaen* 8
H 77. acenaphthylene H
H 78. anthracene H
N 79. 1,12-benzoperylena (benzo H
(gfai)-parylene)
H 80. fluorene H
H 81. phenanthrane H
8 82. 1,2,3,6-dibenza nthracena H
8 (dibanzo(a,h) anthracene)
N 83. indeno (1,2,3-cd) pyrene H
H (2/3-o-phenylene pyrene)
H 84. pyrene
a 85. tetrachloroethylene M
K 86. toluene M
N 87. trichloroethylena L
L 88. vinyl chloride L
(chloroethylane)
L 106. PCB-1242 (Aroclor 1242) B
L 107. PCB-1254 (Aroclor 1254) H
8 108. PC8-1221 (Aroclor 1221) K
N 109. PCB-1332 (Aroclor 1232) B
110. PCB-1248 (Aroclor 1248) B
111. PCB-1260 (Aroclor 1260) H
112. PCB-1016 (Aroclor 1016) H
•Note Explanation of Ramoval Ratinga
Cataqory H (high raaoval)
adaorba at lavala i 100 auj/g carbon at Cf - 10 mg/1
adaorba at lavala > 100 119/9 carbon at C, < 1.0 09/1
Cataqory M (aodarata reaoval)
adaorba at lavala i100 mo/9 carbon at c « 10 mg/1
adaorba at lavala i 100 mg/g cxrbon a.c C.< 1.0 mg/1
Cataqory L (low removal)
adaorba at lavala < 100 09/9 carbon at C. • 10 mg/1
adaorba at lavala < 10 019/9 carbon at S < 1.0 mg/1
C. * final concentrations of priority pollutant at equilibrium
607
-------
TABLE VII - 23
CLASSES OF ORGANIC COMPOUNDS ADSORBED ON CARBON
Organic Chemical Class
Aromatic Hydrocarbons
Polynuclear Aromatics
Chlorinated Arcmatics
Phenolics
Chlorinated Phenolics
*High Molecular Weight Aliphatic and
Branch Chain hydrocarbons
Chlorinated Aliphatic hydrocarbons
*High Molecular Weight Aliphatic
Acids and Aromatic Acids
*High Molecular Weight Aliphatic
Amines and Aromatic Amines
*High Molecular Weight Ketones,
Esters, Ethers and Alcohols
Surfactants
Soluble Organic Dyes
Examples of Chemical Class
benzene, toluene, xylene
naphthalene, anthracene
biphenyls
chlorobenzene, polychlorinated
biphenyls, aldrin, endrin,
toxaphene, DDT
phenol, cresol, resorcenol
and polyphenyls
trichlorophenol, pentachloro-
phenol
gasoline, kerosine
carbon tetrachloride,
perchloroethylene
tar acids, benzole acid
aniline, toluene diamine
hydroquinone, polyethylene
glycol
alkyl benzene sulfonates
methylene blue, indigo carmine
* High Molecular Weight includes compounds in the broad range of from
4 to 20 carbon atoms
608
-------
Plant
A
B
C
Table VII-24
ACTIVATED CARBON PERFORMANCE (MERCURY)
Mercury levels - mg/1
In
28,0
0.36
0.008
Table VII-25
ION EXCHANGE PERFORMANCE
Parameter
All Values mg/1
Al
Cd
Cr+3
Cr+6
Cu
CN
Au
Fe
Pb
Mn
Ni
Ag
SO4
Sn
Zn
Plant
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
A
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
Plant
Prior To
Purifi-
cation
_
—
—
_
43.0
3.40
2.30
, -
1 .70
_
1 .60
9.10
210.00
1.10
-
B
After
Purifi-
cation
—
-
—
,_
0.10
0.09
0.10
—
0.01
_
0.01
0.01
2.00
0.10
—
609
-------
Table VII-26
MEMBRANE FILTRATION SYSTEM EFFLUENT
Specific Manufacturers Plant 19066 Plant 31022 Predicted
Metal Guarantee In Out In Out Performan
Al
Cr, (+6)
Cr (T) 0.03 4.13 0.018 98.4 0.057 0.05
Cu 0.1 18.8 0.043 8.00 0.222 0.20
Manufacturers
Guarantee
0.5
0.02
0.03
0. 1
0.1
0.05
0.02
0.1
0.1
— _
Plant 19066
IH Out
___
0.46
4. 13
18.8
288
0.652
<0.005
9.56
2.09
632
___
0.01
0.018
0.043
0.3
0.01
<0.005
0.017
0.046
0.1
Plant
jtn
___
5.25
98.4
8.00
21 . 1
0.288
<0.005
194
5.00
13.0
31022
Out
*__.«_
<0.005
0.057
0.222
0.263
0.01
<0.005
0.352
0.051
8.0
Fe 0.1 288 0.3 21.1 0.263 0.30
Pb 0.05 0.652 0.01 0.288 0.01 0.05
CN 0.02 <0.005 <0.005 <0.005 <0.005 0.02
Ni 0.1 9.56 0.017 194 0.352 0.40
Zn 0.1 2.09 0.046 5.00 0.051 0.10
TSS —- 632 0.1 13.0 8.0 1.0
Table VI1-27
PEAT ADSORPTION PERFORMANCE
Pollutant Iri 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
610
-------
Table VII-28
ULTRAFILTR&TION PERFORMANCE
Parameter Feed (rog/1). Permeate (mg/lj
Oil (freon extractable) 7230 4
COD 8920 148
TSS 1380 13
Total Solids 2900 296
611
-------
V1I-29
PROCESS casmoL TEOWOWGIES IN USE AT MMRY MAMFACTIRE HANTS
USE REDUCTION
HWEESS MODIFICATION
CCMBINED MOIOT- FORMATION
TREATED ERY AIR SIME CRY BATTERY OORIACT IN CfeSE
EQUIJMEWT WASTE POUWTKW O31WIIR- PIAQUE WASH COOLING (EXCEPT CRY
EHV WASH & PAS1E PROCESS SCRIBBER EIAQUE STREAMS CORIROL ClHRim SCWB ELMl- EUMI- 1MD SUB- GWATION MATERIAL
IDI FORMMTIOH SOmTIOH RINSES WSIE SCRUBBING W-SBQCSSS TECHNOLOGY RINSE TEOffiHQjIE IM10N NATION CATEQORY gg)CESS RECOVERY
Cadmium SiAcategory
X
X
X
X
X
NJ
Calcium Subcategory
Leclanche Subcategory
X
X
Lithium Subcategpry
Magnesium SubcaCegory
X
X
X
X
X
X
X
X
X
X
Zinc Subcategory
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
10'
10
,0
-3
w to-4
Q
U
o «o*5
«0
w
0
o »o-«
o
U
U
to
•10
to
•II
10
-12
10
-t3
(ON)
Cd(OH)2 -
Pbs
23
9 tO II 12 19
FIGURE VU -1. COMPARATIVE SOLUBILITIES OF METAL HYDROXIDES
AND SULFIDE AS A FUNCTION OF pH
613
-------
0.40
SODA ASH AND
CAUSTIC SODA
•.0
10.S
FIGURE VII - 2. LEAD SOLUBILITY IN THREE ALKALIES
614
-------
Ul
9
IT
o
o
<«
j
K
H
Z
U
u
z
o
u
u
z
f-
z
u
3
J
b.
U
O
<
0
rf
o
O
O
o
0
0 0
o
r\O f
0 <
r, Ofi «
0 °
_ft
8
Oft ^ X
< 3 6 ~ 7 ~ 8 "9
o
Q_
O
10 11 12
MINIMUM EFFLUENT pH
FIGURE VII - 3. EFFLUENT ZINC CONCENTRATION VS. MINIMUM EFFLUENT pH
-------
0.1
_O
"^
2
i
o
CJ
1
H
I °'01
•a
10
CJ
0.001
22 Values
OffGi
0© ©(
©00©
*
ri
&»
iph
)
3 ©
K
©(
©(
K3
)S
tm\
<•
fl
£
©
s> ©
3ttt
©
(•
try
©
Ca
te
10
^
r!
^aw Waste
VlllU
d
«
«
*-
3
©
©G
IVilUB
Ofi
:G
'«;
c
)h
i
'D
%
*
0.01
Data points with a raw waste concentration
less than 0.1 mg/l were not included in
treatment effectiveness calculations.
0.1
1.0
Cadmium Raw Waste Concentration (mg/l)
10 100
(Number of observations = 2)
FIGURE VII-4
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
CADMIUM
-------
1
34 Values
OffG
®©
raph
©0©
Sfi
6
S>
0
—
© <•
Batt
©
<£>
ery
Ca
te
JO
ry
Raw Waste
Value
©C
!S
N
Os
^J
o>
c in
Q 1 .1*
*«3
u
e
e
O
«•*
c
at
3
3=
111
•o
s
H
1 "
o
l_
£
0
nni
(
©
<
}
^~
f.
\
w
s
/;
©
©
<
>
•
0.1
1.0 10
Chromium Raw Waste Concentration (mg/l)
100
1000
(Number of observations = 25)
FIGURE VII-5
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
CHROMIUM
-------
21 values
OffGi
0© ©
'»ph
)
3
•>
9 G
6
©i
oan
ery
©
Ui
©
lie
JO
n
M
n aw waste
vatoi
«
^
CT>
_-»
00
on
Copper Treated Effluent Concen
1.0
0.1
0.01
0
*
A
^%
V"1
©
©
©
G
,
D
(i
C
i
i
^
)
Si
1 1.0 10 100 1000
Copper Raw Waste Concentration (mg/l)
FIGURE VII-6
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
(Number of observations = 18)
-------
Lead Treatment Effluent Concentration (mg/l)
o
s £ p
p - - -
20 Values
OffG
e «
»
raph
b
3©
0®
® ®
©
.
Batl
i
ogv
ery
h
Ci
ite
jor
_fi L
01 0.1
/ Raw Waste
3 ®
i) ©
0 ft
^^
iValu
BS
<
0
)
"
1.0 10 101
Lead Raw Waste Concentration (mg/l)
(Number of observations = 22)
FIGURE VII-7
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
i Fan
-------
E ss-
2 «=
«5 a
o
c
c o
ii
•a =
03 ^
to
O
< ii
x ®
0.1
0.01
22 Values
OffG
0©
&
ffi
raph
I
©
36
•^
•Xi
©
©
)
©
Batti
©
©
sryC
S
6
'ate
'
>
p
©
ry
R
at
(
H
>
«
•
Waste Vali
©
i
©
© © <
B®
ies(N
•>
)
icke
©
1)
e
i i i i i
t:
:our
>ffgi
XV
rapl
ah
i
je.
<
) ©
Ij
X
X
©
X
1
X
X
%
*y
0.1
1.0 10
© Nickel Raw Waste Concentration (mg/l)
x Aluminum Raw Waste Concentration (mg/l)
100
(Number of observations = 12)
(Number of observations = 11)
1000
FIGURE VII-8
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
NICKEL AND ALUMINUM
-------
1 1.0
o
e
o
a>
£
Ui
u
N
7 Values
Off Graph
0 ©I
® © q e
k
%
©
/a
3
®l
§5)
I
1
•)
•
t
'l .
(
(.
<•
) €
!>
fl
Batl
©
9
ery
W
C
©
s)
ItC
9
9'
(
iry
>
Raw Wasti
©
•©© ©
^®
©
©
Q
/^
5 Valu
(
6
(
®
BS
©(
) ©
©
©
1
)
)
<•
5)
(
(
i>
)
!>
' 1 Value ' '
C
©©
Iff
Gr
ap
h
«
N
^
0.1
0.01
0.1
1.0
10
Zinc Raw Waste Concentration (mg/l)
100
1000
(Number of observations = 28)
FIGURE Vll-9
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
-------
N>
J 1.0
a
1
o
o
_
9=
Ul
1
a>
0.1
0.01
1VlJU8
" OffGi
iph
(
) <
)
Battery
©I
0j©
Cttegc
9S
r
f
•
flaw Waste Value
©.
¥> 1®
s
3
k *i
h >
0
®,, ,..
©0
©
D®
(
)
'
©
©
w
<
j
£i
fe)
©
s)
•
•>
®
©
«\
©
(
©
m
0.1
1.0
10
Iron Raw Waste Concentration (mg/l)
100 1000
(Number of observations = 28)
FIGURE VII-10
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
IRON
-------
17 Values
Off Graph
N
D>
7 0.1
e
%
+*
e
u
S
w
a
*:
01
•a
£
S
t-
i 0.01
m
o>
c
a
0.001
©
«
1
9®
Av
^
5
ft
p)
rfi
®
i
«'
(!
)
} n
Batt
ery Gate
u
6
gory Raw Wastf
1 ll®0®
! Values
^t
©
©
>
0.1
1.0 10
Manganese Raw Waste Concentration (mg/l)
100 1000
(Number of observations =10)
FIGURE VII-11
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
-------
E 100
a>
u
c
a
U
a>
3
N>
10
CO
1.0
I*
te
5>
(
(
(
°{
<•
> (
)
<
)
)
J
•>
(
)
>
(
, ©^
©
©
©
©
Bitt
3*
©
ft
c
ery
0
1
(•)
)
(C
^J
Ci
©
>e
?G
•w
©
©
^
te*
i)<
JQ
|
)
ry
1
)
J
•
RiwWwte
•3n
'9© S
§
\y
® ©
9.
1
a\
Vitu
©
5 6
K
3
€
<
<
3
S>
©(
^
)
©
)
<
)!
e
© ©
&
©
©
@, ... .
A
©
©
©
\
^
5>
4
«y
1.0
10
100
TSS Raw Waste Concentration (mg/l)
1000
10,000
(Number of observation = 45)
FIGURE VII-12
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
TSS
-------
SULFURIC SULFUR
ACID DIOXIDE
LIME OR CAUSTIC
PH CONTROLLERI
to
RAW WASTE
(HEXAVALJENT CHROMIUM)
CO
ORPCONTROLLER
(TRIVALENT CHROMIUM)
REACTION TANK
PRECIPITATION TANK
pH CONTROLLER
-^- TO CLARIFIER
(CHROMIUM
HYDROXIDE)
FIGURE VII-13. HEXAVALENT CHROMIUM REDUCTION WITH SULFUR DIOXIDE
-------
INFLUENT
EFFLUENT
WATER
LEVEL
STORED
BACKWASH
WATER
THREE WAY VALVE
COMPARTMENT V MI£'.A.
HI U U UUU
0 COLLECTION CHAMBER
DRAIN
FIGURE VII-14. GRANULAR BED FILTRATION
626
-------
PERFORATED
BACKING PLATE.
FABRIC
FILTER MEDIUM^
SOLID
RECTANGULAR
END PLATE •—
4^_
Ml
pi
£•**—*
^X
f
f
f
{
\ <
'•• J
T
\ 111
:'• :%;K;:£
•$
Si'
X,
**•
tf
s
/
/
/
^
•y
—
1MB
^— •
,*^«
,«—
;:<•:
11
||
:•:
fck-'
M ^
MM y
• '' '
iMIj
M
::
: ?:
?Sw
>-':•:•:-!
11
*«
;"/.'
';•••
si
i
i.l
• ?i$
^X
^
S
S
J
\\
II
1 \
i
\
A
\
1 1
\
v
L 1
V'
^
:£;§
iili
l||i
^-^
ii
.'.!**• •' '
Wi
!iS
^*i, .-**
<:;*x'.:*::-.'
^:::>: ::v>:
\
s
:>|f
-;-*'
^ ?!t
'T
S •*•
X "**
^ ;X
X ;-;.':
X /;'•:
ii
\
Sll§i
^N
— N
— •>
— -s
— %,
— X
J$:¥:j
Hi
\s
\.
1
<
\
>
\
i
^
\
Iili
/
^
••• - INLET
SLUDGE
^FABRIC
S^ FILTER MEDIUM
..ENTRAPPED SOLJDS
^
fj PLATES AND FRAMES ARE
PRESSED TOGETHER DURING
••>: FILTRATION CYCLE
i\
^RECTANGULAR
METAL PLATE
FIGURE Vli-15. PRESSURE FILTRATION
627
-------
SEDIMENTATION BASIN
INLET ZONE
INLET LIQUID
BAFFLES TO MAINTAIN
QUIESCENT CONDITIONS
OUTLET ZONE
""-••l^, * * SETTLING PARTl^Lf
" * » *"****-»*• TRAJECTORY . «
. * * ' * * *^*"*--l. "• ••!••.['•
te&<&4*&^^
OUTLET LIQUID
BELT-TYPE SOLIDS COLLECTION
MECHANISM
SETTLED PARTICLES COLLECTED
AND PERIODICALLY REMOVED
CIRCULAR CLARIFIER
INLET LIQUID
CIRCULAR BAFFLE
SETTLING ZONE.
^J^r~r
INLET ZONE
"•".* V •*• * • •". * ** * */'** * *."
V*.*.^**«*» • • *• .'4* {* UQUID f
~WM*$$mJiMr-
ANNULAR OVERFLOW WEIR
OUTLET LIQUID
REVOLVING COLLECTION
MECHANISM
•SETTLING PARTICLES
SETTLED PARTICLES
COLLECTED AND PERIODICALLY
REMOVED
SLUDGE DRAWOFF
FIGURE VII-16. REPRESENTATIVE TYPES OF SEDIMENTATION
628
-------
FLANGE
WASTE WATER
WASH WATER
BACKWASH
SURFACE WASH
MANIFOLD
INFLUENT
DISTRIBUTOR
BACKWASH
REPLACEMENT CARBON
CARBON REMOVAL PORT
TREATED WATER
SUPPORT PLATE
FIGURE VII - 17. ACTIVATED CARBON ADSORPTION COLUMN
629
-------
CONVEYOR DRIVE
r—BOWL DRIVE
DRYING _
'ZONE
LIQUID
OUTLET
[ i
SLUDGE
INLET
JVAJ\J\J\J\J\JI
CYCLOGEAR
SLUDGE
DISCHARGE
BOWL
REGULATING
RING
IMPELLER
FIGURE VII - 18. CENTRIFUGATION
630
-------
RAW WASTE
CAUSTIC
SODA
PM
CONTROLLER
CO
_r<
V
ORP CONTROLLERS
\
WATER
CONTAINING
CYANATE
CHLORINE-
CIRCULATING
PUMP
d
REACTION TANK
CHLORINATOR
CAUSTIC
SODA
CO
CONTROLLER
t
TREATED
WASTE
REACTION TANK
FIGURE VII-19. TREATMENT OF CYANIDE WASTE BY ALKALINE CHLORINATION
-------
CONTROLS
OZONE
GENERATOR
DRY AIR
D
J JL
OZONE
REACTION
TANK
RAW WASTE-
TREATED
WASTE
X
FIGURE \f\l - 20. TYPICAL OZONE PLANT FOR WASTE TREATMENT
632
-------
MIXER I
FIf
ST
SE
ST
Tl
WASTEWATER
FEED TANK
1 '
V,
t
1/1
tST §
AGE j
>
3
H
SOND |
AGE '3
>
3
H
•I1RD §
•AGE 3
un 5
rHD
kPUMP
TREATED WATEF
c:
II
c
1 I
II
r __ EXHAUST
a
i
C
a
1 1
i
L
i
=3
i i
j
1 '
1
C
i
GAS
— — TEMPERATURE
— — CONTROL
— PH MONITORING
— TEMPERATURE
-— - CONTROL-
— — PH MONITORING
— — TEMPERATURE
— — CONTROL
— PH MONITORING
OZONE
OZONE
GENERATOR
FIGURE VII-21. UV/OZONATION
633
-------
EXHAUST
WATER VAPOR
PACKED TOWER
EVAPORATOR
WASTEWATER
HEAT
EXCHANGER
TEAM
STEAM
COMPENSATE
CONCENTRATE
PUMP
ATMOSPHERIC EVAPORATOR
VACUUM LINE
CONDENSATC
WASTEWATER
CONCENTRATE
1 VACUUM
PUMP
STEAM
COOLING
WATER
STEAM
CONDENSER
EVAPORATOR-
STEAM-
STEAM
CONDENSATE
VAPOR-LIQUID
MIXTURE
.SEPARATOR
WASTEWATER •
WATER VAPOR
v///.
LIQUID
RETURN
WASTE
WATER-
FEED
STEAM
CONDENSATE
SUBMERGED TUBE EVAPORATOR
COOLING
WATER
CONDENSATE
VACUUM PUMP
— «•• CONCENTRATE
CLIMBING FILM EVAPORATOR
VAPOR
HOT VAPOR
STEAM
CONDENSATE
CONCENTRATE
CONDEN-
SATE
COOLING
WATER
CONDENSATE
VACUUM PUMP
•- EXHAUST
ACCUMULATOR
CONDENSATE
FOR REUSE
CONCENTRATE FOR REUSE
DOUBLE-EFFECT EVAPORATOR
FIGURE VII - 22. TYPES OF EVAPORATION EQUIPMENT
-------
OILY WATER
INFLUENT
WATER
DISCHARGE
OVERFLOW
SHUTOFF
VALVE
AIR IN
BACK PRESS
VALVE
TO SLUDGE
TANK "*
EXCESS
AIR OUT
LEVEL
CONTROLLER
FIGURE VH-23. DISSOLVED AIR FLOTATION
635
-------
CONDUIT
TO MOTOR
INFLUENT —m
CONDUIT TO
OVERLOAD
ALARM
COUNTERFLOW
INFLUENT WELL
DRIVE UNIT
OVERLOAD ALARM
EFFLUENT WEIR
DIRECTION OF ROTATION
EFFLUENT. PIPE
EFFLUENT CHANNEL
PLAN
TURNTABLE
BASE'
HANDRAIL
L
INFLUENT *
WEIR
STILTS
CENTER SCRAPER
SQUEEGEE
SLUDGE PIPE
FIGURE VII-24. GRAVITY THICKENING
636
-------
WASTE WATER CONTAINING
DISSOLVED METALS OR •
OTHER IONS
/T
_REOENERANT
"SOLUTION
-DIVERTER VALVE
-DISTRIBUTOR
-SUPPORT
REGENERANT TO REUSE,
TREATMENT, OR DISPOSAL
-DIVERTER VALVE
METAL-FREE WATER
FOR REUSE OR DISCHARGE
FIGURE VII - 25. ION EXCHANGE WITH REGENERATION
637
-------
MACROMOLECULES
AND SOLIDS
MEMBRANE
490 PSli
WATER
PERMEATE (WATER)
MEMBRANE CROSS SECTfON,
IN TUBULAR, HOLLOW F7BEH,
OR SPIRAL-WOUND CONFIGURATION
FEED-
. o
O*O
'O O
0 • o •
DO. O
O SALTS OR SOLIDS
• WATER MOLECULES
CONCENTRATE
(SALTS)
FIGURE VII-26. SIMPLIFIED REVERSE OSMOSIS SCHEMATIC
638
-------
PERMEATE
TUBE
ADHESIVE BOUND
SPIRAL. MODULE
CONCENTRATE
FUOW
BACKINS MATERIAL
MESH SPACER
•MEMBRANE
SPIRAL MEMBRANE MODULE
POROUS SUPPORT TUBE
WITH MEMBRANE
.'.* BRACKISH
WATER
FEED FLOW
PRODUCT WATER
PERMEATE FLOW
PRODUCT WATER
o«."«
BRINE
CONCENTRATE
FLOW
TUBULAR REVERSE OSMOSIS MODULE
SNAP
RING
"O" RING
SEAL
OPEN ENDS
OF FIBERS
,_ EPOXY
TUBE SHEET
POROUS
BACK-UP DISC
SNAP
RING
CONCENTRATE
OUTLET
END PLATE
POROUS FEED
DISTRIBUTOR TUBE
PERMEATE
END PLATE
HOLLOW FIBER MODULE
FIGURE VII - 27. REVERSE OSMOSIS MEMBRANE CONFIGURATIONS
639
-------
c
\
f f.
1 ^—> ^
IT
II
] U C
Ij
1
I
1
1
1 1'
II
8-IN. VITRIFI
o
:
E:
J U U 1.
1
1
j | r
1
1
1
|l
!
i
ii
n
JL_
"? f~ ~y"
3 PIPE LAID-^^
WITH PLASTIC JOINTS
3 ii 'l
n
n
n
n
] |l C
ii
^-SPLASH BOX
\ !! r~
:
ii [I
i
n
i
i
i
i
i
n ^
B
' U U i.
V
Q jj
< '.
i u r
|in
u olj
- zl|
H a!|'
> ll
zM| C
•511
_J^_
— — — -wa =«- — — -
(I
1 C
1
1
1
1
ll 1
ll (
f U -U H
ir
i
? [
1 I!
i
Ii
) II f
ll
- ^
"""if
|l
'
I •
• i
H [
6-IN. FLANGED | |
S^\SHeAR GATE
\ 11
H
II
ll
B
___4jq-_|— __ __4jLt.______,aH — _. M,|
8-IN. Cl PIPE
PLAN
6-IN. FINE SAND
3-IN. COARSE SAND
3-IN. FINE GRAVEL
3-IN. MEDIUM GRAVEL
3 TO 6 IN. COARSE GRAVEL
>—
J
2-IN. PLANK
WALK
PIPE COLUMN FOR
GLASS-OVER
3-IN. MEDIUM GRAVEL
6-IN. UNDERORAIN LAID-
WITH OPEN JOINTS
SECTION A-A
FIGURE VII-28. SLUDGE DRYING BED
640
-------
ULTRAFILTRATION
P » 10-90 Ml
MEMBRANE
WATER SALTS
-MEMBRANE
PERMEATE
FEED
• o •
• • • o .. .
o • •
CONCENTRATE
. . . t , , • ,
1 • I • • • I • • • I •
O OIL PARTICLES
• DISSOLVED SALTS AND LOW-MOLECULAR-WEIGHT ORGANICS
FIGURE VII - 29. SIMPLIFIED ULTRAFILTRATION FLOW SCHEMATIC
641
-------
FABRIC OR WIRE
FILTER MEDIA
STRETCHED OVER
REVOLVING DRUM
DIRECTION OF ROTATION
ROLLER
SOLIDS SCRAPED
OFF FILTER MEDIA
LIQUID
THROUGH
MEDIA BY
MEANS
VACUUM
SOLIDS COLLECTION
HOPPER
INLET LIQUID
TO BE
FILTERED
-TROUGH
FILTERED LIQUID
FIGURE VII - 30. VACUUM FILTRATION
642
-------
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 this document of the battery
manufacturing category. The cost estimates provide the basis for
the determination of the probable economic impact of regulation
at different pollutant discharge levels on these subcategories.
These costs are also among the factors required to be considered
in developing effluent limitations for BPT and BAT. In addition,
this section addresses other factors which must be considered in
developing effluent limitations including nonwater quality
environmental impacts of wastewater treatment and control
alternatives including air pollution, noise pollution, solid
wastes, and energy requirements.
To arrive at the cost estimates 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. 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.
643
-------
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.
This section discusses cost breakdown and adjustment factors as
well as other aspects of the cost estimation process.
Cost Estimation Input Data
The waste treatment system descriptions input to the cost
estimation program include both a specification of the waste
treatment components included and a definition of their
sequences. 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, the 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.
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 encompass a number of widely varying waste
streams which are present to varying degrees at different plants.
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 plant.
The process by which these raw wastes were defined is explained
in Sections IX and X.
The final input data set corresponds to the flow rates reported
by each plant in the category which were input to the computer to
provide cost estimates for use in economic impact analysis.
644
-------
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 700). In the computation,
raw waste characteristics and flow rates 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 701) 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 mix tank and 4 hour retention with 610
1/hr/m2 (159 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 poly-
electrolyte 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 character-
istics are then used with performance algorithms for the
645
-------
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
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
dependent upon discharge flows produced by plants in the
category. The use of in-process technology to achieve flow
reduction is cost effective because savings result from buying
less water, recovering metals in the solids, and selling
concentrated process solutions. These savings are not evaluated
in the computer program. Reliance on the computer estimation
procedure without attention to in-process technologies results in
646
-------
an overstatement of the cost required to achieve various levels
of environmental improvement.
For the subcategories sufficient data were available from plant
visits and dcp to estimate costs of treatment which include
plant-specific in-process controls. .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 approp-
riate to individual plants. Flows resulting from in-plant
technology were then used as input to the computer.
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 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 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
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.
Dollar Base - A dollar base of January 1978 was used for all
costs.
647
-------
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 nonsupervisory 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 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.
648
-------
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 plant. 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 w, which was assumed to be
ten years. The annual cost of capital is 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 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:
administration and laboratory facilities
garage and shop facilities
line segregation
yardwork
land
engineering
legal, fiscal, and administrative
interest during construction
649
-------
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 EPA Water Compliance Division.
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.
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.
650
-------
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 VIII-4 (page 680) lists the technologies which are
incorporated in the wastewater treatment and control options
offered for the battery manufacturing subcategories included in
this document and for which cost estimates have been developed.
These treatment technologies have been selected from among the
larger set of available alternatives discussed in Section VII on
the basis of an evaluation of raw waste characteristics, 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
capital (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.
651
-------
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 cost item).
Depreciation - Depreciation is an allowance, based on tax
regulations, for the recovery of fixed capital from an in-
vestment 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 dis-
cussed 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. 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 energy requirements are a factor considered when
developing effluent limitations, and energy is important to
the nation's economy and natural resources.
Lime Precipitation and Settling (L&S)
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. Because of their interrelationships and integration in
common equipment in some plants, 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.
652
-------
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-16 (page 715).
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 plants 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 61, 1/hr/m2 (15 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 VIII-3 (page 702). 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 settling, 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 are included. The capital cost for the batch
system (not including the sludge pump costs) is shown in Figure
VIII-4 (page 703). To complete the capital cost estimation for
batch treatment, a fixed $3,202 cost is included for sludge pumps
as discussed above.
653
-------
Operation £ Maintenance Costs - The operation and maintenance
costs for the chemical precipitation and settling routine
include:
1) Cost of chemicals added (lime, alum, and polyelectrolyte)
2) Labor (operation and maintenance)
3) Energy
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, or settling, unit. The methods used in
determining the lime requirements are shown in Table VIII-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 VIII-5 (page 704) 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 (Ib. 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. 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.
654
-------
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
$0.033/kilowatt-hour of required electricity
Sulfide Precipitation and Settling
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 settling 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 settling are identical to those for lime
precipitation and settling as shown in Figures VIII-3 and VIII-4.
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 settling.
Operation and Maintenance Costs - Costs estimated for the
operation and maintenance of a sulfide precipitation and settling
system are also identical to those for lime precipitation and
settling 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 stoichiometric
requirements. Sulfide costs are based on the addition of ferrous
sulfate and sodium bisulfide (NaHS) (on a 2:1 ratio by weight) to
form a 10 percent excess of ferrous sulfide over stoichiometric
requirements for precipitation. Reagent additions are calculated
as shown in Table VIII-6 (page 682). Addition of alum and
polyelectrolyte is identical to that shown for lime precipitation
and settling as are labor (in Figure VII-5) and energy rates.
The following rates are used in determining operating and
maintenance costs for this technology.
655
-------
$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
$0.033/kilowatt-hour of electricity
Mixed 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 settling processes, mixed media filtration provides improved
removal of .precipitates and thereby improved removal of the
original dissolved pollutants.
Investment Cost - The size of the mixed media filtration unit is
based on 20 percent excess flow capacity and a hydraulic loading
of 0.5 ftz/gpm. The capital cost, presented in Figure VIII-6
(page 705) 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 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.
Investment Cost - Based on manufacturer's data, a factor of
$52.60 per 1 gph flow rate to the membrane filter is used to
estimate capital cost. Capital cost includes installation.
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.
656
-------
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
Chromium, Total
Copper
Acidity
Iron, DIS
Zinc
Cadmium
Cobalt
Manganese
Aluminum
Sodium Hydroxide Per Pollutant (Ib/day)
(GPH) x Pollutant Concentration (mg/1)
ENERGY
ANaOH
0.000508
0.000279
0.000175
0.000474
0.000268
0.000158
0.000301
•0.000322
0.000076
= ANaOH x Flow Rate
The energy required is as follows:
mixers operating 34 minutes per
two 1/2 horsepower
operational hour
two one horsepower
operational hour
one 20 horsepower
operational hour
pumps operating 37 minutes per
pump operating 45 minutes per
Given the above requirements, operation and maintenance
costs are calculated based on the following:
$6.00 per man-hour +10 percent indirect labor charge
$0.11 per pound of sodium hydroxide required
$0.033 per kilowatt-hour of energy required
657
-------
Calculated costs in the battery category as a function of flow
rate for membrane filtration are presented in Figure VIII-7 (page
706).
Reverse Osmosis (RO)
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 pollu-
tants. 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.
Investment Cost - Data from several manufacturers of RO equipment
is summarized in the cost curve shown in Figure VIII-8 (page
707). The cost shown includes 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 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 VII1-9 (page
708). 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 709).
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
The power requirements for reverse osmosis unit is shown in
Figure VIII-11 (page 710). This requirement is assumed to be
658
-------
constant over the operating hours of the system being estimated.
The energy cost is determined using a charge of $0.033 per kilo-
watt-hour.
Ion Exchange
This technology achieves the concentration of inorganic
pollutants in wastewater by exchanging ions on the surface of the
ion exchange resin with ions of similar charge from the waste
stream in which the resin is immersed. The contaminants in the
waste stream are exchanged for harmless ions of the resin. The
water is then suitable for reuse in most manufacturing process
operations. A number of different resins are available which are
optimized for different wastewater characteristics.
Investment cost, and operation and maintenance cost are
comparable to those discussed above under "Reverse Osmosis." The
costs are summarized in the cost curve shown in Figure VII1-8.
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.
Investment 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 Ib/ft2-hr). The curves of cost versus
flow rate at TSS concentrations of 3 percent and 5 percent are
shown in Figure VIII-12 (page 711). The capital cost obtained
from this curve includes installation costs.
Operation and Maintenance Cost - Contributions to operation and
maintenance costs include:
LABOR
The vacuum filtration labor costs may be determined for off-site
sludge disposal or for on-site sludge disposal. The required
operating hours per year varies with both flow rate and the total
suspended solids concentration in the influent stream. Figure
VIII-13 (page 712) shows the variance of operating hours with
flow rate and TSS concentration. Maintenance labor for either
sludge disposal mode is fixed at 24 man-hours per year.
MATERIALS
The cost of materials and supplies needed for operation and
maintenance includes belts, oil, grease, seals, and chemicals
659
-------
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
713) .
ENERGY
Electrical costs needed to supply power for pumps and controls is
presented in Figure VIII-15 (page 714). As the required
horsepower of 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
in-process 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.
Investment 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 concrete and steel tanks
sized for 20 percent excess capacity are shown as functions of
volume in Figure VIII-16 (page 715).
Operation and 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 VII1-17 (page 716).
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
VIII-18 (page 717). 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.
660
-------
pH Adjustment (Neutralization)
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 feed-
back control.
Investment Costs - Figure VIII-19 (page 718) 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 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 - Contributions to operation and
maintenance costs include:
LABOR
The annual manhour requirement is presented as a function of flow
rate in Figure VIII-20 (page 719). 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 is 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 VII1-7
(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 0.8 kilowatts per horsepower
and $0.33 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
661
-------
off-site disposal. System cost estimates 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 treatment component and may be selected in place
of on-site treatment on a least-cost basis.
Investment 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 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 TOO 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 Haulage Cost
>.05 mg/1 CN- $0.45/gallon
>.l mg/1 Cr+« $0.20/gallon
Oil & grease > TSS $0.12/gallon
All others $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 Ib per day.
662
-------
Investment Costs - Capital investment costs estimated for carbon
adsorption systems applied to battery manufacturing wastewater
are provided in Figure VII1-21 (page 720) 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 adsorption.
The high cost of removing a small amount of a given priority
pollutant results from the requirement that the system be sized
and operated to remove all organics present which are more easily
removed than the species of interest. Removal efficiencies
depend upon the type of carbon used, and a mixture of carbon
types may be cost beneficial. In regenerative systems removal
efficiencies achieved by regenerated carbon are vastly different
from fresh carbon. 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 VIII-21 (page
720). 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.
Investment Costs - Cost estimates include all required equipment
for performing this treatment technology including reagent feed,
equipment 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.
663
-------
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 20
percent excess capacity factor. 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
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 pre-
sented in Figure VIII-22 (page 721).
Operation and Maintenance - Costs for operating and maintaining
chromium reduction systems are determined as follows:
Labor
The labor requirements are plotted in Figure VIII-23 (page 722).
Maintenance of the batch system is assumed negligible and so it
is not shown.
Chemical Addition
664
-------
For the continuous system, sulfur dioxide is added according to
the following:
(Ib S02/day) = (15.43) (flow to unit-MGD) (Cr + * 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+« mg/1)
Energy
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
$0.033/kilowatt hour of required electricity
Vapor Recompression Evaporation
Vapor recompression evaporation is used to increase energy
efficiency by allowing heat to be transferred from the condensing
water vapor to the evaporating wastewater. The heat contained in
the compressed vapor is used to heat the wastewater, and energy
costs for system operation are reduced.
Costs for this treatment component related to flow are displayed
in Figure VIII-24 (page 723).
In-Process Treatment and Control Components
A wide variety of in process controls has been identified for
application to battery manufacturing wastewaters, and many of
these require in process treatment or changes in manufacturing
plants and capital equipment for which additional costs must be
estimated. For most of these in-process controls, especially
recirculation and reuse of specific process streams, the required
equipment and resultant costs are identical to end-of-pipe
components discussed above. The recirculation of amalgamation
area wash water requires the removal of mercury for which costs
are estimated based on the sulfide precipitation and settling
system previously discussed. Other area wash water costs are
based on the holding tank costs associated with sizing
665
-------
assumptions discussed for each treatment technology sequence
within each subcategory.
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 to VIII-20
(pages 684-696). Three levels of cost are provided for each
technology representative of median, 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.
BPT or_ PSES Option 0_ System Cost Estimates
Cadmium Subcategory - The option 0 treatment system for this sub-
category, shown in Figure IX-1 (page 810), consists of oil
skimming (if necessary) lime precipitation and settling 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.
Data from dcp and plant visits were evaluated to determine the
existing in-process treatment technologies for wastewater
conservation, and the actual and achievable loading levels.
These technologies include recycle or reuse of process solutions,
segregation of noncontact cooling water from process wastewater
and control of electrolyte drips and spills. The in-process
costs reflect additional controls required for water use
reduction at high flow plants.
Calcium Subcategory - The option 0 treatment system, shown in
Figure IX-2 (page 811), 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 chromium,
and then merged with the second wastewater stream from cell
testing. The combined stream is treated with lime to precipitate
dissolved metals. The precipitate is removed, and the water is
neutralized in the sedimentation tank before being discharged.
The sludge from sedimentation is filtered, and the filtrate is
666
-------
recycled to the lime precipitation tank. Contract hauling of the
solid wastes from the treatment is more economical than on-site
disposal for the low flows encountered in the calcium
subcategory.
Leclanche Subcategory - Option 0 for this subcategory achieves
zero discharge of process wastewater pollutants by the
application of in-process control techniques, for all processes
except foliar battery miscellaneous wash discharges. No costs
are incurred in most plants in the subcategory because no process
wastewater is presently produced. Cost estimates for the
remaining plants 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 lime or
sulfide (ferrous sulfide) precipitation prior to recycle, and
equipment wash wastewater is treated in settling tanks. For the
foliar battery plants cost estimates are for holding tanks,
pumps, piping and lime, settle and filter wastewater treatment
facilities needed to achieve some flow reduction and final
treatment of miscellaneous wash waters. The treatment system is
illustrated in Figure IX-3 (page 812). In some cases in the
subcategory, where the reported volume of process wastewater was
small, estimated costs reflect contract removal of the wastes
rather than treatment and recycle.
Lithium Subcateqory - The option 0 treatment for this
subcategory, as shown in Figure IX-4 (page 813), includes
grouping of wastes into three streams. Stream A resulting from
heat paper production is settled to remove asbestos, barium
chromate and zirconium powder suspension. Hexavalent chromium in
this stream is then reduced to the trivalent state. Metals are
precipitated by lime addition, and the precipitate along with the
solid particulates are removed in a clarifier. The resulting
sludge is dewatered by vacuum filtration, and the filtrate is
recycled to the lime precipitation tank.
Treatment for Stream B resulting from all cathode and ancillary
operations except heat paper production and air scrubber
wastewaters includes precipitation with lime or acid addition,
and settling.
The process wastewater from Stream C, air scrubbers, is first
aerated to oxidize sulfur, and then treated with lime to
precipitate metals. The precipitates along with solid
particulates are removed by settling. Contract hauling of all
wastes from this subcategory is used when there are low flows and
hauling is less costly than treatment.
667
-------
Magnesium Subcategory - The option 0 treatment for this
subcategory presented in Figure IX-5 (page 814) includes grouping
wastes into three streams. Wastewater from heat paper production
(Stream A) is settled in a tank to remove asbestos, barium
chromate and zirconium, and then treated for the reduction of
hexavalent chromium to the trivalent state. The final treatment
includes precipitation of chromium and any other metals by lime
addition, settling of the precipitate along with suspended solids'
and vacuum filtration of the sludge following settling. The
filtrate is recycled to the chemical precipitation tank.
For Stream B, wastewater from silver chloride cathode production
and spent process solution are first oxidized by means of
potassium permanganate to reduce the COD level. This stream is
then treated along with the wastewater from cell testing, and
floor and equipment wash for precipitation of heavy metals (by
means of lime or acid addition), followed by settling and vacuum
filtration of the sludge. The filtrate is recycled to the
chemical precipitation tank.
The process wastewater from Stream C, air scrubbers, is first
treated by lime for precipitation of metals, and then settling of
the precipitate and solid particulates. Solids are dewatered by
means of a vacuum filter. The filtrate is recycled to the
precipitation tank. Contract hauling of the solid wastes from
this treatment is usually more economical than on-site disposal
for the low flows encountered in the magnesium subcategory.
Zinc Subcategory. The option 0 wastewater treatment and control
system for this subcategory, as shown in Figure IX-6 (page 815),
includes skimming for the removal of oil and grease, lime or acid
addition for the precipitation of metals, sedimentation of the
precipitate along with solid particulates, and vacuum filtration
of the sludge. The filtrate is recycled to the chemical
precipitation treatment tank. In the draft development document
distributed for comment in 1980, this option included sulfide
precipitation and filtration. This option was changed to L&S
technology because of the difficulty and expense of retrofitting
existing plants so that sulfide precipitation may be used safely,
and the fact .that filters are less costly with flow reduction,
evaluated as a BAT (PSES) option.
In-process control technologies included at option 0 for this
subcategory include the following: reuse of process solutions,
segregation of noncontact cooling water, segregation of organic-
bearing cell cleaning wastewater, control of electrolyte drips
and spills, elimination of chromates in cell washing, and flow
controls for rinse waters.
668
-------
BAT (PSES) Treatment System Cost Estimates - Existing Sources
The following discussion of cost estimates for treatment options
is based on data from existing sources. Rationale for the
selection of the BAT options are discussed in Section X and the
PSES options are discussed in Section XII.
Cadmium Subcateqory - Costs were estimated for three options of
treatment and control considered appropriate for BAT and PSES.
Option 1
As shown in Figure X-l (page 908), end-of-pipe treatment for
option 1 is the same as the option 0 treatment with the addition
of a number of in-process control techniques to limit the volume
of process wastewater and pollutant loads to treatment. The in-
process control technology recommended for option 1, in addition
to that listed for option 0, include: recycle or reuse of pasted
and pressed powder anode wastewater, use of dry methods to clean
floors and equipment, control of rinse flow rates, recirculation
of wastewater from air scrubber, dry cleaning of impregnated
electrodes, reduction of the cell wash water use, countercurrent
rinse of silver and cadmium powder, and countercurrent rinse for
sintered and electrodeposited 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 plants on a competitive basis with wet brushing
techniques. Estimates include costs for the segregation of two
scrubber discharge streams. 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.
Option 2
As shown in Figure X-2 (page 909), end-of-pipe treatment provided
for cadmium subcategory wastes at option 2 is identical to that
provided at option 1, except that the effluent from settling is
filtered in option 2 and that the backwash from polishing filter
is recycled to the precipitation tank. In-process control
669
-------
techniques for option 2 are identical to those recommended for
option 1.
Option 3
End-of-pipe treatment for option 3 includes concentration of
process wastewater using reverse osmosis prior to chemical
precipitation, settling and filtration for final treatment.
Permeate from the reverse osmosis unit is reused in the process.
As shown in Figure X-3 (page 910), before reverse osmosis,
wastewater is skimmed to remove oil and grease, treated with lime
or acid to form metal precipitates, and then filtered to remove
precipitates and solids. Initial precipitation and filtration
steps protect the permeators. Sludge is dewatered in a vacuum
filter. In-process control techniques at option 3 include
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 option 2.
Option 4
As shown in Figure X-4 (page 911), option 4 end-of-pipe treatment
includes oil skimming, chemical precipitation, settling,
filtration, and ion exchange (or reverse osmosis) prior to vapor
recompression evaporation of the ion exchange regenerant (or
reverse osmosis brine). The sludge from settling is dewatered by
vacuum filtration, and the filtrate is recycled to the chemical
precipitation tank. Distillate or permeate from the evaporation
unit is returned to the production process for reuse. In-process
control technologies include all those discussed for options 2
and 3 as well as the elimination of discharge from the
impregnation rinse.
Calcium Subcategory - Costs were estimated for two options of
treatment and control considered appropriate for BAT and PSES.
Option 1
At option 1, end-of-pipe treatment is identical to that provided
for option 0 with the addition of a mixed-media filter prior to
discharge. This filter is intended to act as a 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 912).
Option 2
This level of treatment is similar to option 1 except that the
waste stream from heat paper production is recycled back to the
670
-------
process. A schematic of the system is provided in Figure X-6
(page 913).
Leclanche Subcateqory - Only one option is considered for BAT
(PSES) for this subcategory. This option is identical to BPT
(PSES) option 0 and achieves zero discharge of process wastewater
pollutants by the application of in-process control technology
for all processes except foliar battery miscellaneous wash
discharges. For foliar batteries the option is identical to BPT
and includes flow reduction and lime, settle and filter end-of-
pipe treatment.
Lithium Subcategory - Costs were estimated for three options of
treatment and control presented for evaluation as BAT and PSES.
Option 1
This level of treatment is similar to that prescribed for option
0 except that the wastewaters from Streams A and B are passed
through a polishing filter after settling. Stream C is unchanged
from option 0. The schematic for this system is provided in
Figure X-7 (page 914). The filter backwash is returned to waste
treatment.
Option 2
As shown in Figure X-8 (page 915) option 2 treatment is identical
to option 1 treatment except that Stream A wastewater is treated
in a settling tank for the removal of solids, and then recycled
to the process.
Option 3
At this level of treatment and control shown in Figure X-9 (page
916), treatment identical to option 2 is provided, except that
Stream C process wastewater originating from air scrubbers is
filtered following aeration, precipitation and settling.
Magnesium Subcategory - Costs were estimated for three options of
treatment and control presented for evaluation as BAT and PSES.
Option 1
This level of treatment is similar to that prescribed for option
0 except that the effluent originating from Stream A is filtered
following precipitation and settling. The backwash from the
filter is recycled to the chemical precipitation tank. The
schematic for this system is provided in Figure X-10 (page 917).
The additional recommended in-process technology includes
671
-------
countercurrent cascade rinsing for silver chloride cathodes in
Stream B.
Option 2
Option 2 treatment is identical to option 1 except that Stream A
wastewater is treated in a settling tank for the removal of
solids, and then recycled to the process and sedimentation
discharge in option 1 treatment of Stream B is filtered. No in-
process control technology is recommended. Stream C treatment is
unchanged. The schematic for this system is in Figure X-l1 (page
918).
Option 3
Option 3 is identical to option 2 treatment except that on Stream
B a carbon adsorption unit is used instead of the oxidizer in
option 2 treatment of the silver chloride cathode production
wastewater and spent process solution, and sedimentation effluent
in option 2 treatment of Stream C wastewaters is filtered before
discharge. A schematic of option 3 is shown in Figure X-l2 (page
919).
Zinc Subcategory - Costs were estimated for three options of
treatment and control presented for evaluation as BAT and PSES.
Option 1
This level of treatment and control combines end-of-pipe
treatment as specified for option 0 with additional in-process
control techniques to reduce wastewater flow rates and pollutant
loads discharged to treatment. Additional in-process controls
include countercurrent cascade rinsing of amalgamated zinc
powder, formed zinc electrodes, electrodeposited silver powder,
formed silver oxide electrodes, silver peroxide, impregnated
nickel cathodes, and silver ' etching grids; as well as
recirculation of amalgamation area floor wash water, elimination
of electrolyte preparation spills, and dry cleanup or wash water
reuse for floor and equipment. The schematic for the system is
shown in Figure X-13 (page 920).
Cost estimates include provision of eight tanks, associated pumps
and piping to provide retention of rinse waters from wet amal-
gamation 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 lime or ferrous
sulfide and are discussed under lime or sulfide precipitation and
settling. Cost estimates are also provided for countercurrent
672
-------
rinses as described in the general discussion of that technology.
No costs are estimated Ion dry cleanup of general plant floor
areas.
Option 2
Option 2 is identical to option 1 except that the settled
effluent from option 2 is treated by filtration. A schematic of
option 2 is shown in Figure X-14 (page 921). No additional in-
process control techniques beyond those listed for option 1 are
recommended.
Option 3
Option 3 is identical to option 2, except chemical precipitation
is performed by sulfide addition rather than lime addition, and
membrane filtration is used instead of mixed media polishing
filtration. Additional in-process controls include elimination
of wastewater from gelled amalgam. Costs for gelled amalgam
equipment wash- are estimated based on provision of pumps and
piping as discussed for line segregation costs. A schematic for
option 3 is provided in Figure X-15 (page 922).
Option 4
End-of-pipe treatment for option 4 includes concentration of
process wastewaters using reverse osmosis prior to sulfide
precipitation, settling and filtration. Permeate from the
reverse osmosis is reused in the process. As shown in Figure X-
16 (page 923), prior to reverse osmosis, wastewater is skimmed to
remove oil and grease, treated with lime to form precipitates,
and then filtered to remove precipitates and solids. Additional
recommended in-process technology includes amalgamation by dry
processes which eliminates all wastewater from amalgamation.
NSPS (PSNS) Treatment System Cost Estimates - New Source
The suggested treatment options and estimated costs for new
sources are identical to the treatment options for existing
sources. Each option is discussed above. Rationale for the
selection of new source options is discussed in Sections XI and
XII. Cost estimates overstate the actual costs a new source
would incur because new sources will be able to plan and
implement both in-process modifications arid end-of-pipe treatment
without any retrofitting costs. Additionally, new sources will
be able to plan and implement more cost saving systems such as
resource recovery of metal and process solutions.
673
-------
Use of Cost Estimation Results
The costing methodology and recommended treatment system options
were used primarily to estimate compliance costs for the
implementation of treatment in the category. Costs for each
plant were calculated for what additional equipment would be
needed at an existing site for the treatment options. Contract
hauling costs were estimated for plants when hauling would be
less costly than installing treatment. In this category actual
costing is plant specific and is dependent upon what processes a
plant is using. The results of estimating compliance costs for
the category are tabulated in Table X-56 (page 907). Plants
which were known to be closed were eliminated from summation.
The cost results were also used for the economic impact analysis
(See "Economic Impact Analysis of Proposed Effluent Standards and
Limitations for the Battery Manufacturing Industry"). For this
analysis cost estimates were broken down for each facility
(location for producing final battery products, i.e., alkaline
manganese, silver oxide-zinc) and cost results were expressed in
dollars per pound of battery produced.
Finally, this section can be used to estimate costs for
alternatives to the options presented by using the component
graphs for investment and annual costs based on varying flows.
NONWATER QUALITY ENVIRONMENTAL ASPECTS
Nonwater quality environmental aspects including an evaluation of
energy requirements of all of the wastewater treatment
technologies described in Section VII are summarized in Tables
VIII-20 and VIII-21 (pages 696 and 697). These general 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
VIII-20 and sludge and solids handling processes on Table VIII-
21.
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. Table VIII-22 (page 698)
summarizes the battery manufacturing category and subcategory
energy costs which would result at existing plants with the
implementation of the different technology options.
Energy requirements are generally low, although evaporation can
be an exception if no waste heat is available at the plant.
674
-------
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.
Nonwater Quality Environmental Aspects
It is important to consider the impact of each treatment process
on water scarcity and air, noise and radiation, and solid waste
pollution of the environment to preclude the development of a
more adverse environmental impact.
Consumptive Water Loss - Where evaporative cooling mechanisms are
used, water loss may result and contribute to water scarcity
problems, a concern primarily in arid and semi-arid regions.
This regulation does not require substantial evaporative cooling
and recycling which would cause a significant consumptive water
loss.
Air - 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. Implementation of sulfide
technology at existing plants is costly because of the additional
retrofitting a plant would have to do to create a safe working
environment. Due to their high content of volatile heavy metals,
(eg. cadmium and .mercury) sludges from battery manufacturing
wastewater treatment are not amenable to incineration except in
retorts for metals recovery.
Noise and Radiation - None of the wastewater treatment processes
causes objectionable noise levels and none of the treatment
processes has any potential for radioactive radiation hazards.
Solid Waste - Costs for treatment sludge handling were included
in the computer cost program and are included in the compliance
cost summary. In addition, the cost impact that wastewater
treatment will have on the battery manufacturing category in
terms of satisfying RCRA hazardous waste disposal criteria was
analyzed for the lime and settle technology. Only plants which
have mercury containing treatment sludges or sulfide treatment
sludges were considered as hazardous under RCRA. The RCRA costs
for disposing of hazardous wastewater treatment sludges are
presented by subcategory, in Table VIII-23 (page 699). Only
675
-------
indirect dischargers are shown because no hazardous waste
disposal costs would be incurred by direct dischargers. Many
existing plants recover the metals from the sludges. The costs
for indirect dischargers can be summarized as follows:
o Only seven plants (all in the Leclanche and zinc
subcategories) of the 69 plants in the battery
manufacturing subcategories which are included in this
document would incur RCRA costs because of the disposal
of hazardous sludges from wastewater treatment.
o The annual cost for disposal of hazardous sludges from,
wastewater treatment •for these seven plants is
estimated at $34,000.
Lime precipitation and settling produces a sludge with a high
solids content, consisting of calcium salts, which in some
instances has a potential economic benefit. The recovery
potential for the principal toxic metals(s) contained in the
wastewater treatment sludge from lime precipitation was also
considered. Recovery of nickel and cadmium from the cadmium
subcategory sludge has a potential economic benefit. In fact,
most cadmium subcategory plants already reclaim wastewater
treatment sludges.
The RCRA related costs presented are based on an analysis of lime
and settle treatment costs and wastewater loadings provided in
this document, on-site disposal costs developed in an EPA report
and contact with hazardous waste disposal tranporters and
operators. This analysis is in the public record for this
category. These costs were developed using the following four-
steps process: (1) the total amount of wastes for each battery
manufacturing plant and the total subcategory were determined;
(2) the waste constituents were then evaluated according to RCRA
criteria to determine whether they would be characterized as
hazardous; (3) the amount of waste characterized as hazardous was
then used to determine whether off-site or on-site disposal was
the preferred alternative based on disposal site cost curves; and
(4) the disposal cost was calculated on a dollar-per-pound of
battery produced basis and presented as the incremental cost
resulting from hazardous sludge disposal.
676
-------
TABLE VIII-1
COST PROGRAM POLLUTANT PARAMETERS
Parameter, Units
Flow, MOD
pH, pH units
Turbidity, Jackson Units
Temperature, degree C
Dissolved Oxygen, mg/1
Residual Chlorine, mg/1
Acidity, mg/1 CaCO3
Alkalinity, mg/1 CaCO3
Ammonia, mg/1
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, rag/1
Total Volatile Solids, mg/1
Parameter, Units
Oil, Grease, mg/1
Hardness, mg/1
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 VIII-2
TREATMENT TECHNOLOGY SUBROUTINES
Spray/Fog Rinse
Countercurrent Rinse
Vacuum Filtration
Gravity Thickening
Sludge Drying Beds
Holding Tanks
Centri fugation
Equalization
Contractor Removal
Revr rse 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 (Diatomaceous Earth)
Ion Exchange - w/Plant Regeneration
Ion Exchange - Service Regeneration
Flash Evaporation
Climbing Film Evaporation
Atmospheric Evaporation
Cyclic Ion Exchange
Post 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
Mixed-media Filter
Sump
Cooling Tower
Ozonation
Activated Sludge
Coalescing Oil Separator
Non Contact Cooling Basin
Raw Wastewater Pumping
Preliminary Treatment
Preliminary Sedimentation
Aerator - Final Settler
Chlorination
Flotation Thickening
Multiple Hearth Incineration
Aerobic Digestion
Lime Precipitation (metals)
678
-------
TABLE VIII-3
WAST1WAT1R SAMPLING FREQUENCY
Wastewater Discharge
(litersperday) 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 VII1-4
WASTE-TREATMENT TECHNOLOGIES FOR BATTERY MANUFACTORING CATEGORY
Hydroxide Precipitation and settling; Batch Treatment
Hydroxide Precipitation and Settling, Continuous Treatment
Sulfide Precipitation and Settling; Batch Treatment
Sulfide Precipitation and Settling; Continuous Treatment
Mixed-media Filtration
Membrane Filtration
Reverse osmosis
Ion Exchange
Vacuum Filtration
Holding and Settling Tanks
pH Adjustment (Neutralization)
Contract Removal
Aeration
Carbon Adsorption
Chrome Reduction
Vapor Recompression Evaporator
680
-------
TABLE VII1-5
LIME ADDITIONS FOR LIME PRECIPITATION
Lime Addition
Stream Parameter kg/kg (Ib/lb)
Acidity (as CaCOj) 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
Ferrous Sulfide Requirement
kg/kg (ib/lb)
Cadmium
Calcium
Chromium (Hexavalent)
Chromium (Trivalent)
Cobalt
Copper
Lead
Mercury
Nickel
Silver
Tin
Zinc
0.86
2.41
1.86
2.28
1.64
1.52
0.47
0.24
1.65
0.45
0.81
1.48
Sodium Bisulfide Requirement
Ferrous Sulfate Requirement
Lime Requirement
= 0.65 x Ferrous Sulfide Requirement
= 1,5 x Ferrous Sulfide Requirement
= 0.49 x FeS04(lb) + 3.96 x NaHS(lb)
+ 2.19 x Ib of Dissolved Iron
682
-------
TABLE VIII-7
NEUTRALIZATION CHEMICALS REQUIRED
a
Chemical Condition _ o
Lime pH less than 6.5 .00014
Sulfuric Acid pH greater than 8.5 .00016
(Chemical demand, Ib/day) = Ao x Flow Rate (GPH) x Acidity
(Alkalinity, mgCa.CO3/l)
683
-------
TABLE VIII-8
WATER TREATMENT COMPONENT COSTS
Process:
least cost:
HYDROXIDE PRECIPITATION AND SETTLING
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
BATCH
4
8
18090
1134
1809
2706
0.001
BATCH
23890
101000
54630
3428
5463
4491
17.72
CONTINUOUS
56780
360000
72620
4557
7262
8815
61.29
$ 8650
$ 13400
$ 20700
684
-------
TABLE VIII-9
WATER TREATMENT COMPONENT COSTS
Process:
Least cost:
SULFIDE PRECIPITATION AND SETTLING
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy Costs
Total annual costs:
BATCH
4
8
3722
234
372
824
0.031
BATCH
95
600
6101
383
610
2488
2.33
BATCH
6529
13800
31060
1949
3106
3351
107
$ 1430
$ 3484
$ 8513
685
-------
TABLE VIII-10
WATER TREATMENT COMPONENT COSTS
Process:
least cost:
SULF3DE PRECIPITATION AND SETTLING
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
CONTINUOUS
5677
24000
26820
1683
2682
6615
4.88
CONTINUOUS
10740
45400
32300
2027
3230
9780
8.84
CONTINUOUS
19240
122000
39030
2449
3903
20331
23.36
$ 10980
$ 15050
$ 26710
686
-------
TABLE VIII-11
WATER TREATMENT COMPONENT COSTS
Process:
Least cost;
MIXED-MEDIA FILTRATION
System flow rates 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Biergy costs
Total annual costs:
OONTINOOOS
4
8
261
16
26
6065
284
CONTINUOUS
5195
10980
21470
1347
2147
6065
284
CONTINUOUS
17348
110000
44800
2811
4480 '
6065
284
$ 6391
$ 9843
$ 13640
687
-------
TABLE VIII-12
WATER TREATMENT COMPONENT COSTS
Process:
Least cost:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
MEMBRANE FILTRATION
CONTINUOUS CONTINUOUS
26
380
112
2412
367
5280
CONTINUOUS
1223
7755
16970
23
331
37
527
3128
3300
1650
2610
1065
1697
3406
2694
$ 4838
$ 6769
$ 8862
688
-------
TABIE VIII-13
WATER TREATMENT COMPONENT COSTS
Process:
least cost:
REVERSE OSMOSIS
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs.
Total annual costs:
CONTINUOUS
4
.8
2707
170
270
419
75
CONTINUOUS
182
768
15080
946
1508
799
335
CONTINUOUS
16180
102600
145100
9102
14510
40080
5895
$ 934
$ 3587
$ 69580
689
-------
TABLE VIII-14
WATER TREATMENT COMPONENT COSTS
Process:
Least cost:
VACUUM FILTRATION
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
CONTINUOUS
25
106
25220
1582
2522
3990
CONTINUOUS CONTINUOUS
168
326
210
1377
25220
25220
1582
1582
2522
2522
5179
5940
$ 8094
$ 9283
$ 10040
690
-------
TABLE VIII-15
WATER TREATMENT COMPONENT COSTS
Process:
least cost:
HOLDING AND SETTLING TANKS
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
CONTINUOUS
700
44
70
50
CONTINUOUS
151
640
1180
74
118
CONTINUOUS
3406
7200
3592
225
359
107
75
$ 164
$ 300
$ 660
691
-------
TABLE VIII-16
WATER TREATMENT COMPONENT COSTS
Process:
least cost:
pH ADJUSTMENT (NEUTRALIZATION)
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
CONTINUOUS
4
8
106
7
11
11
0.008
CONTINUOUS
261
552
891
56
89
120 .
0.536
CONTINUOUS
5267
33400
4144
260
414
1190
34
$ 29
$ 266
$ 1898
692
-------
TABIE VIII-17
WATER TREATMENT COMPONENT COSTS
Process:
Least cost:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs
Total annual costs:
AERATION
CONTINUOUS
53
223
800
50
80
0
101
CONTINUOUS
466
984
1191
75
119
0
52
$ 231
$ 245
$
693
-------
TABLE VIII-18
WATER TREATMENT COMPONENT COSTS
Process:
Least cost:
System flow rate: 1/hr
gal/day
Investment:
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Energy costs '
Total annual costs:
CARBON ADSORPTION
45
192
14630
918
1463
491
0.88
$ 2873
466
984
26180
1643
2618
1767
4.49
$ 6033
$
694
-------
TABLE VIII-19
WATER TREATMENT COMPONENT COSTS
Process:
least cost:
CHROME REDUCTION
System flow rate:
Investment:
1/hr
gal/day
Annual costs:
Capital costs
Depreciation
Operating & Maintenance
costs (excluding energy)
Biergy costs
Total annual costs:
BATCH
26
56
7853
423
785
7
108
BATCH
61
128
8355
524
835
16
103
BATCH
3406
7200
19970
1253
1997
891
103
$ 1393
$ 1479
$ 4244
695
-------
KKVGZR gjUHr ASPO35 OP WSU5KIER TFOOBff
CTi
VO
CTi
Tgirajj
Chemical Induction
rjariflmrlcn
Flotaticn
ChpnrfcTil Qddnfion hy
Chlorine
Oxidation by Ozone
Chendcal Py**rH p^ t^^ rF1
Deep Bed
Ion Btchange
Adsorption
Evapuiatlon
Reverse Osmosis
DltrafUtration
Meoixatie Flltzatlcn
fflMtjIjlM JKJtrHf^il
ChromluB ItedUctdcn
ELucLuxiiaalcal
Chranliin %aener8tijm
Dcror racanssNES
Itouer
Mi
1000 liters
1.0
0.01-.3
0.1-3.2
1.0
0.3
0.5-5.0
1.02
0.1-3.2
0.10
0.5
0.1
3.0
1.25-3.0
1.25-3.0
0.2-0.8
2.0
Ftel
—
—
—
—
—
—
2.5*
—
—
—
BrergyUse
Mixing
SDdjmer Drive
Sludge Cbllector
Drive
l^rrt i^i1^j_nn
ftup/ Cbcptcssor/
S3dm
Mixing
Mixing
Ozone Generation
£3jooculBfcion
Paddles, Mboers
glmVjp CbllectoBr
Drive
Head, Bsc5cwBsh
Pups
Pups
Pups, Evaporate
During Regeneration
EVri^n i^ ALc Hnl ^1
High Pressure Puop
Hic/h Pressure Pup
High Pressure Pup
Rectifier, Pup
Jtegsreratian, Pup
KKKER QOUUCK TtfKX
Mr Pollution
Iqpoct
Vans
None
Hone
None
None
None
None
None, Passible
H S Brolution
None
None
None
Ifcne
None
None
Ifcne
None
Ifcne
Naifle Pollution
Inpact
Ifcne
None
None
None
None
None
None
None
None
Hat
CbjecHmnnle
None
None
Not
Cbjecticnable
Not
Objectionable
Not
Objectionable
None
None
Solid Vfeste
None
O-A KJd iu Au3u
OcnosntXEtted
Ifcne
Ifcne
Ocnoentxated
Oonosntxsted
Gbnccntxated
None
None/VJasbe
Carbon
DsHBtered
Dilute
Ocnoentarate
DUvite
O^fiosnteste
Dilute
Ocnocntxate
None
Solid Hate
QixMitA^Mrn
* Dry Solids
5-50 (oil)
1-10
3-5
—
1-10
1-3
Variable
NA
40
50-100
1-40
1-40
1-40
1-3
"
* 10 HTO/UJOO liters
-------
TOBEE VHI-21
NOWHIER QORIJnY ftSKCTS CF StBDGE flND SCUDS HANDLING
PROCESS
Sludge Thickening
Pressure Filtration
Sand Bed Drying
Vacuum Filter
Centrifugation
landfill
Lagocning
ENERGY l*yjiM=MENR3
ftjwer
kwh
ton dry solids
29-930
21
—
16.7-66.8
0.2-98.5
—
™*~
Fuel
kwh
ton dry solids
—
—
35
—
—
20-980
36
Ehergy Use
Skinner, Sludge
Rake Drive
High Pressure
Puops
Removal Equipment
Vacwm Punp,
Rotation
Rotation
Haul, landfill
1-10 Mile Trip
Removal Equipment
IOWKIER Quamy Mpacr
Mr Pollution
Dtpact
None
None
None
None
None
None
None
Noise Pollution
Inpact
None
None
None
Not
Ohjectionable
Not
Objectionable
None
None
Solid Waste
Concentrated
Dewatered
Devcttered
Dewatered
Dewatered
DsHatered
Deuatered
Solid Waste
JT106nLX.clCU.Hi
% Dry Solids
4-27
25-50
15-40
20-40
15-50
R/ft
>5
D
•J
-------
vm-22
BATTERY CATEGORY ENERGY COSTS AND REQUIREMENTS
BPT/PSES-O BPT/PSES-O BAT-l/PSES-1 BAT-l/PSES-1 BRT-2/PSES-2 BAT-2/PSES-2 BAT-3/PSES-3 BAT-3/PSES-3 BAT-4/PSES-4 BAT-4/PSES-4
COSTS REQUIREMENTS COSTS REQUIREMENTS COSTS REQUIREMENTS COSTS REQUIREMENTS COSTS REQUIREMENTS
(t) (kwh) (*) (kwh) ($) (kwh) ($) (kwh) ($) (kwh)
VO
Cadmium Subcategory
Direct
Indirect
Total
Calcium Subcategory
Direct
Indirect
Total
Leclanche Subcategory
Direct
Indirect
Total
Lithium Subcategory
Direct
Indirect
Total
Magnesium Subcategory
Direct
Indirect
Total
Zinc
Direct
Indirect
Total
Category
Direct
Indirect
Total
46.3
1,998.7
2,045.0
316.0
316.0
—
2,584.0
2,584.0
100.0
372.0
472.0
202.0
383.0
585.0
655.0
3,705.0
4,360.0
8,465.8
61,808.7
70,274.5
1,403.0
60,566.7
61,969.7
—
9,575.8
9,575.8
— — -
78,303.0
78,303.0
3,030.3
11,272.7
14,303.0
6,724.2
11,606.1
17,727.3
19,848.5
112,272.7
132,121.2
257,142.4
1,872,990.9
2,129,530.3
596.0
1,644.0
2,240.0
— —
884.0
884.0
100.0
656.0
756.0
486.0
951.0
1,437.0
871.0
4,347.0
5,218.0
6,342.0
32,248.3
38,590.3
18,060.6
49,818.2
67,878.8
— —
26,787.9
2F i
-------
SUBCATEGQRY
Cadmium
Calcium
Leclanche
Lithium
Magnesium
Zinc
TABLE VIII- 23
INDIRECT DISCHARGERS - L & S TREATMENT
WASTEWATER TREATMENT SLUDGE RCRA
DISPOSAL COSTS
TOTAL ANNUAL COST
PSES-0
0
0
14,450
0
0
PSES
0
0
14,450
0
0
$/lb of BATTERY
PSES-0 PSES
2,400
2,700
0
0
0.00011
0
0
0.00006
0
0
0.00011
0
0
0.00007
699
-------
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
COSTS
B) ADD SUBSIDIARY COSTS
C) ADJUST TO DESIRED
DOLLAR BASE
OUTPUT
A) STREAM DESCRIPTIONS -
COMPLETE SYSTEM
B) INDIVIDUAL PROCESS SIZE
AND COSTS
C) OVERALL SYSTEM INVESTMENT
AND ANNUAL COSTS
FIGURE VIII -1
SIMPLIFIED LOGIC DIAGRAM
SYSTEM COST ESTIMATION PROGRAM
700
-------
MAW WAITK
(FLOW. TSS, LKAO,
ZINC. ACIDITY)
CHEMICAL
ADDITION
.J£
CMCMICAL
SCOIMKNTATION
ILUOOC
BtCYCL*
SLUOOK
ICONTMACTOIt
MKMOVKO)
FIGURE VIII - 2. SIMPLE WASTE TREATMENT SYSTEM
701
-------
10*
z
I
VI
cc
_1
_1
o
10J
IN
10
100
103
FLOW RATE (1/HR)
FIGURE VIII-3
PREDICTED PRECIPITATION AND SETTLING COSTS
CONTINUOUS
10"
10s
O DENOTES FLOW LIMITS OBSEI VED FOR
THIS TREATMENT FOR THE Lf AD
SUBCATEGORY
-------
I
in
cc
FLOW RATE (1/HR)
FIGURE VIII-4
PREDICTED COSTS FOR PRECIPITATION AND SETTLING
BATCH
O DENOTES FLOW LIMIT (^0) OBSERVED FOR
THIS TREATMENT IN THE BATTERY
INDUSTRY (NON-LEAD SUBCATEGORY).
INDIVIDUAL PLANTS MAY DIFFER BECAUSE
OF VARIATION IN OPERATING HOURS.
ALL COMPUTER SELECTED TREATMENT WAS
BATCH.
-------
50
100
110 200 250
FLOW RATE(1/HR )
300
350
400
FIGURE VIII-5
CHEMICAL PRECIPITATION AND SETTLING COSTS
704
-------
-J
:>
/I
ta
cc
u>
o
u
FLOW RATE (1/HR)
FIGURE VIII-6
PREDICTED COSTS OF MIXED MEDIA FILTRATION
ID3
O DENOTES FLOW LIMIT ( *0) OBSERVED FOR THIS
TREATMENT IN THE BATTERY INDUSTRY.
INDIVIDUAL PLANTS MAY DIFFER BECAUSE OF
VARIATION IN OPERATING HOURS.
-------
I
tn
EC
in
O
u
I
tn
ee
00
O
100
10
100
FLOW RATE (1/HR)
104
O DENOTES FLOW LIMITS FOR THIS TREATMENT
IN THE BATTERY CATEGORY.
FIGURE VIII-7
MEMBRANE FILTRATION COSTS
-------
I
ta
s
a
o
3.785
37.85
378.5
3785
37850
378500
FLOW RATE (1/HR)
FIGURE VIII-8
REVERSE OSMOSIS OR ION EXCHANGE INVESTMENT COSTS
-------
o
00
oc
UJ
in
DC
111
DC
DC
DC
3.785
37.85
378.5 3785
FLOW RATE (1/HR)
37850
378500
FIGURE VIII-9
REVERSE OSMOSIS OR ION EXCHANGE LABOR REQUIREMENTS
-------
10°
o
VO
3.785
37.85
378.5 3785
FLOW RATE (1/HR)
37850
378500
FIGURE VIII-10
REVERSE OSMOSIS OR ION EXCHANGE MATERIAL COSTS
-------
a.
a
in
cc
a:
ul
3.785
37.85
378.5
3785
37850
378500
FLOW RATE (1/HR)
FIGURE VIII-11
REVERSE OSMOSIS OR ION EXCHANGE POWER REQUIREMENTS
-------
TOTAL SUSPENDED SOLIDS 50.000 mg/1
TOTAL SUSPENDED SOLIDS 30.000 mg/1
3.785
37.85
378.5
3786
37850
378500
FLOW RATE (1/HR)
FIGURE VIII-12
VACUUM FILTRATION INVESTMENT COSTS
-------
10a
N)
TOTAL SUSPENDED SOLIDS 50.000 mg/l
TOTAL SUSPENDED SOLIDS 30.000 mg/l
37.85
378.5
378S
378SO
378SOO
FLOW RATE (t/HR)
FIGURE VIII-13
VACUUM FILTRATION LABOR REQUIREMENTS
-------
U)
TOTAL SUSPENDED SOLIDS 50.000 mg/l
TOTAL SUSPENDED SOLIDS 30.000 mo/l
103
3.785
3785
FLOW RATE (1/HR)
378SO
378500
FIGURE VIII-14
VACUUM FILTRATION MATERIAL COSTS
-------
I
C/l
ce
u
_l
<
E
u
TOTAL SUSPENDED SOLIDS 50,000 ra§/l
TOTAL SUSPENDED SOLIDS 30.000 mg/l
3.7(5
37.85
378.5 3785
FLOW RATE (1/HR)
37850
378500
FIGURE Vill-15
VACUUM FILTRATION ELECTRICAL COSTS
-------
120
1200
12000
120000
1200000
VOLUME (LITERS)
COST = 41.93 x VOLUME (LITERS) °'5344
RETENTION TIME -12 HOURS
FIGURE VIII-16
HOLDING TANK INVESTMENT COSTS
-------
I
v>
K
CO
o
o
2
o
Ul
100
1680
16.800 168.000
VOLUME (LITERS)
FIGURE VIII-17
HOLDING TANK ELECTRICAL COSTS
1.680.000
16,800,000
RETENTION TIME = 7 DAYS
-------
£ 10*
ui
GC
a
Ul
K
3.78S
37.85
378.6 378S
FLOW RATE (1/HR)
37850
378500
FIGURE VIII-18
HOLDING TANK LABOR REQUIREMENTS
-------
00
I
to
fe
o
u
10"
103
FLOW RATE (1/HR)
FIGURE VIII-19
NEUTRALIZATION INVESTMENT COSTS
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.
-------
3.785
37.85
378.5
3785
37860
378500
FLOW RATE (1/HR)
FIGURE VIII-20
NEUTRALIZATION LABOR REQUIREMENTS
-------
I
M
oe
CO
o
u
N>
o
100
FLOW RATE (1/HR)
1000
FIGURE VIII-21
CARBON ADSORPTION COSTS
-------
3.785
37.85
378.5 3785
FLOW RATE (1/HR)
37850
378500
FIGURE VIII-22
CHEMICAL REDUCTION OF CHROMIUM
-------
BATCH (OPERATION)
CONTINUOUS (OPERATION)
CONTINUOUS
(MAINTENANCE)
MINIMUM CONTINUOUS PROCESS MAINTENANCE
3.785
37.85
378.5 3785
FLOW RATE (1/HR)
FIGURE VIII-23
ANNUAL LABOR FOR CHEMICAL REDUCTION OF CHROMIUM
37850
378500
BATCH MAINTENANCE EQUALS 0 HOURS
-------
IxlO4
1000
WASTE F LOW (gph)
10000
FIGURE VIII-24
COSTS FOR VAPOR RECOMPRESSION EVAPORATION
. 723
-------
724
-------
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through application of the best practicable control technology
currently available (BPT), Section 301(b)(1)(A), for each
subcategory within the battery manufacturing category. BPT
reflects the performance of existing treatment and control
practices at battery manufacturing plants of various sizes, ages,
and various 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
the application of technology in relation to the effluent
reduction benefits from such application, the age of equipment
and facilities involved, the processes employed, nonwater quality
environmental impacts (including energy requirements), and other
factors considered appropriate by the Administrator. In general,
the BPT technology level represents the average of the best
existing practices at plants of various ages, sizes, processes or
other common characteristics. Where existing practice is
universally inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology must be supported by a conclusion that the technology
is transferrable and by a reasonable prediction that the
technology will be capable of achieving the prescribed effluent
limits. See Tanner's Council of America v. Train, 540 F.2d 1188
(4th Cir. 1976). BPT focuses on end-of-pipe treatment rather
than process changes or internal controls, except where such
practices are common throughout the category or subcategory.
TECHNICAL APPROACH TO BPT
The entire battery manufacturing category was examined to
identify the processes used, wastewater generated, and treatment
practices employed in battery manufacturing operations. After
preliminary subcategorization and collection of additional
information using both dcp forms and specific plant sampling and
analysis, the total information about the category was evaluated.
On the basis of this evaluation, the subcategorization was
revised as described in Section IV to reflect the anode
materials, since specific anode metals can be combined with many
cathode materials, and the electrolytes used in battery
manufacturing. Each subcategory was further subdivided into
discrete manufacturing process elements as shown in Table IV-1
(page 154). These process elements are the basis for defining
production normalized flows and pollutant raw waste
725
-------
concentrations. All information was then evaluated to determine
an appropriate BPT. Specific factors considered for BPT are:
• Each subcategory encompasses several manufacturing
elements each of which may or may not generate process
wastewater. These elements are divided into, groups for
anode manufacture, cathode manufacture, and ancillary
(or all other) operations considered to be part of
battery manufacturing. A plant usually is active in
one or more anode process elements, one or more cathode
process elements, and in one or more ancillary
operations. Process elements within the subcategory
are combined in a variety of ways at battery
manufacturing plants.
• Wastewater streams from different elements within each
subcategory usually share similar pollutant
characteristics, have similar treatment requirements
and are often treated in combined systems.
• The most significant pollutants present in battery
process wastewater are generally different in each
subcategory. Combined treatment or discharge of
wastewater from different subcategories occurs quite
infrequently.
• Most wastewater streams generated in this category are
characterized by high levels of toxic metals.
• Treatment practices vary extensively in the category
and also within the subcategories. Observed category
practices include: chemical precipitation of metals as
hydroxides, carbonates, and sulfides; amalgamation;
sedimentation; filtration; ion exchange; and carbon
adsorption.
Other factors which must be considered for establishing effluent
limitations based on BPT have already been addressed by this
document. The age of equipment and plants involved and the
processes employed are taken into account and discussed in
Section IV. Nonwater quality impacts and energy requirements are
discussed in Section VIII.
In making technical assessments of data, processes and treatment
technology both indirect 'and direct dischargers have been
considered as a single group. An examination of plants and
processes did not indicate any process or product differences
based on wastewater destination. This has also been followed in
describing applicable technology options with initial description
made for direct dischargers, and indirect discharger applications
726
-------
largely described by reference to the direct discharge
descriptions. Hence, treatment technologies for BPT (and BAT)
are described in substantial detail for all subcategories even
though there may be no direct discharge plants in that
subcategory.
For each subcategory included in this document, a specific
approach was followed for the development of BPT mass
limitations. To account for production and flow variability from
plant to plant, a unit of production or production normalizing
parameter (pnp) was determined for each element which could then
be related to the flow from the element to determine a production
normalized flow. Selection of the pnp for each process element
is discussed in Section IV and summarized in Table IV-1 (page
154). Each process element within the subcategory was then
analyzed, (1) to determine whether or not operations included in
the element generated wastewater, (2) to determine specific flow
rates generated, and (3) to determine the specific production
normalized flows (mean, median) for each process element. This
analysis is discussed in general and summarized for each
subcategory in Section V.
Normalized flows were analyzed to determine which flow was to be
used as part of the basis for BPT mass limitations. The selected
flow (sometimes referred to as a BPT regulatory flow or, BPT
flow) reflects the water use controls which are common practices
within the subcategory based upon dcp and plant visit data.
Significant differences between the mean and median reflect a
data set which has skewed or biased a wide range of points. When
one data point (for a small data set) or several data points (for
a large uniform data set) have an abnormally high flow (improper
water control) or unusually low flow (extensive in-process
control or process variation), the average or mean may not
represent category practice. In cases where there was evidence
that data was atypical, use of the median value was considered as
a means of minimizing the impact of one point (on a small data
base) or several points (on the larger data base). In general,
the mean or average production normalized flow is used as a part
of the basis for BPT mass limitations. In those cases where the
median rather than mean normalized flow was used as the BPT flow,
specific rationale for its use is presented in the subcategory
discussion. Factors considered in using the median values
include: numerical variations between the mean and median,
absolute size of mean and median value within a process element,
relative importance of the size of an element to the total
subcategory, and an analysis of specific atypical numbers.
The general assumption was made that all wastewaters generated
within a subcategory were combined for treatment in a single or
common treatment system for that subcategory even though flow and
727
-------
sometimes pollutant characteristics of process wastewater streams
varied within the subcategory. Since treatment systems
considered at BPT were primarily for metals and suspended solids
removalt and existing plants usually had one common treatment
system in place, a common treatment system for each subcategory
is reasonable. Both treatment in place at battery plants and
treatment in other categories having similar wastewaters were
evaluated. The BPT treatment systems considered require chemical
precipitation, and settling. These treatment systems when
properly operated and maintained, can reduce various pollutant
concentrations to specific levels for each pollutant parameter.
Derivation of these concentrations achievable by specific
treatment systems are discussed in Section VII and summarized in
Table VII-21 (page 606).
The overall effectiveness of end-of-pipe treatment for the
removal of wastewater pollutants is improved by the application
of water flow controls within the process to limit the volume of
wastewater requiring treatment. The controls or in-process
technologies recommended at BPT include only those measures which
are commonly practiced within the category or subcategory and
which reduce flows to meet the production normalized flow for
each process element.
For the development of effluent limitations, mass loadings were
calculated for each process element within each subcategory.
This calculation was made on an element by element basis
primarily because plants in this category are active in various
process elements, process element production varies within the
plants, and pollutants generated and flow rates can vary for each
process element. The mass loadings (milligrams of pollutant per
kilogram of production unit - mg/kg) were calculated by
multiplying the BPT normalized flow (I/kg) by the concentration
achievable using the BPT treatment system (mg/1) for each
pollutant parameter considered for regulation at BPT. The BPT
normalized flow is based on the average of all applicable data
rather than the average of the best plants. This was done to
provide a measure of operating safety for BPT treatment
operations.
The following method is used to calculate compliance with the BPT
limitation. The allowable mass discharge for each process
element is determined by multiplying the allowable mass discharge
limitation (mg/kg) for that process element by its level of
production (in kg of production normalizing parameter). The
allowable mass discharge for a plant is then calculated by
summing the individual mass discharge allowances of the process
elements performed at the plant. The actual mass discharge of
the plant is calculated by multiplying the effluent concentration
of the regulated pollutant parameters by the total plant effluent
728
-------
flow. The actual mass discharge can then be compared against the
allowable mass discharge.
Reasonableness of the limitations was determined in several ways.
The approach generally used to determine reasonableness was to
evaluate the treatment effectiveness numbers for lime and settle
systems (already discussed in Section VII) and the reported
discharge flows for each plant as compared with the flow the
plant would need to comply with the BPT mass limitations. BPT
treatment effectiveness numbers were determined to be reasonable
based upon engineering and statistical analysis, as discussed in
Section VII. When operating hours and plant processes varied
throughout the year, the annual flow, as opposed to hourly flow,
was used as the rate for comparison. The actual annual flow for
each plant was then compared with the calculated annual flow
necessary for BPT compliance. BPT flows were considered
reasonable if most of the plants in the subcategory were meeting
their BPT flow.
SELECTION OF POLLUTANT PARAMETERS FOR REGULATION
The pollutant parameters selected for regulation in each sub-
category were selected because of their frequent presence at
treatable concentrations in wastewaters from the process
elements. In general, pollutant parameters selected are
primarily metals and suspended solids. No organic pollutants
(except for cyanide) are considered for BPT regulation in this
category. pH is selected as a treatment control parameter. As
discussed in Section VII, the importance of pH control for metals
removal cannot be overemphasized. Even small excursions away
from the optimum pH range (in most cases 8.8 - 9.3) can result in
less than optimum functioning of the system. To accommodate this
operating pH range (8.8 - 9.3) without requiring a final pH
adjustment the effluent pH range is shifted from the commonly
required 6.0 - 9.0 to 7.5 to 10.0.
CADMIUM SUBCATEGORY
The cadmium subcategory includes the manufacture of cadmium anode
batteries such as nickel-cadmium, silver-cadmium, and mercury-
cadmium batteries. Of these, nickel-cadmium batteries account
for almost all of the production in the subcategory. Sixteen
process elements identified in Table IV-1 (page 154) are
manufacturing activities included within this subcategory.
Thirteen of these process elements, as shown in Figure V-2 (page
392), generate a wastewater discharge; the other three do not.
Normalized flows and production normalizing parameters for these
elements are summarized in Table V-10 (page 274).
729
-------
Model Treatment Technology
BPT end-of-pipe treatment for this subcategory is illustrated in
Figure IX-1 (page 810). The treatment system consists of oil
skimming, pH adjustment (chemical precipitation) followed by
settling. Lime, sodium hydroxide, or acid is used to adjust the
pH to a level that promotes 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. Proper pH control will
enhance the settling of both metal precipitates and suspended
solids. Treatment system performance for some wastewater streams
in this subcategory may be significantly improved by the addition
of iron salts as an aid in the removal of toxic metals,
particularly nickel. This technology, sometimes called iron co-
precipitation, is described in Section VII. Where required for
acceptable effluent this technique is included in BPT. An
effective settling device for use in the BPT system is a
clarifier; however, similar results can be achieved using other
settling devices or by filtration. In some cases, provisions of
an oil skimmer may also be required to achieve acceptable
effluent quality.
The lime and settle technology set forth as BPT for this
subcategory was selected primarily because the treatment system
components are generally used in the subcategory. Process
wastewaters from the cadmium subcategory are predominantly
alkaline, and seven presently operating plants reported settling
treatment (see Table V-29 page 293). Four of these plants also
reported subsequent filtration. On-site observations, however,
indicated that the settling was often inadequate and that
filtration was used as a primary solids removal device, rather
than as polishing filtration where it is most effective.
Consequently alkaline precipitation and settling without
polishing filtration corresponds more closely to the actual
present practice in the cadmium subcategory.
BPT water flow controls do not require any significant
modification of the manufacturing process or process equipment
for their implementation. The in-process technologies practiced
in the subcategory and recommended at BPT include:
• Recycle or reuse of process solutions (already
practiced by 6 plants).
• Segregation of noncontact cooling water from process
water (necessary for effective treatment).
• Control of electrolyte drips and spills (observed at
various plants visited).
730
-------
Table IX-1 (page 758) presents the normalized discharge flows
which form part of the basis for mass discharge limitations for
each process element. These normalized flows are equal to the
mean normalized flows presented in Table V-10 and represent the
average level of water use presently achieved by plants active in
each process element. They therefore correspond to internal
controls which are common industry practice.
Pollutant characteristics of process wastewater from the process
elements in this subcategory are essentially similar because all
contain toxic metals especially cadmium and nickel. The raw
wastewater characteristics from nine process elements are
presented in Tables V-ll through V-26 (pages 275-290) and Tables
V-113 and V-ll4 (pages 379-380). The remaining four process
elements (cell washing, electrolyte preparation, cadmium
hydroxide production, and nickel hydroxide production) were not
characterized by sampling. Based on raw materials used and the
nature of these process operations, their process wastewaters are
expected to be similar to those resulting from other process
elements. Cell washing wastewaters are not expected to contain
high concentrations of pollutants other than the ones already
considered for regulation. Flows from electrolyte preparation
are minimal (normalized mean flow of 0.08 I/kg) and are not
expected to contain unusually high concentrations of any toxic
pollutants. Any contaminants in the wastewater from this process
element would likely be similar to others found within the
subcategory. Process wastewaters from cadmium hydroxide
production and nickel hydroxide production are expected to be
similar to process wastewaters from cadmium impregnation and
nickel impregnation, respectively, because of the similarity in
raw materials involved, the chemical reactions occurring, and the
nature of the water use.
Specific manufacturing process elements at each plant will affect
the overall pollutant characteristics of the combined process
wastewater flowing to one end-of-pipe treatment system. Some
loss in pollutant removal effectiveness may result where waste
streams containing specific pollutants at treatable levels are
combined with other streams in which these same pollutants are
absent or present at very low concentrations. Although process
wastewater streams with different raw waste concentrations will
be combined for end-of-pipe treatment, the treatment
effectiveness concentrations can be achieved with the recommended
treatment technologies as discussed in Section VIII.
Total subcategory raw waste characteristics are needed to
evaluate the pollutant removals which would be achieved by
implementing the recommended treatment technologies. Total raw
waste characteristics from sampled plants alone do not represent
the total subcategory. To present raw waste for the total
731
-------
subcategory the following methodology was used. For pollutants
in each process element the mean raw waste concentration (from
sampling data in Section V) was multiplied by the total
wastewater flow for the process. The annual mass of pollutants
generated by each process was summed and divided by the total
subcategory flow to obtain the subcategory raw waste
concentrations. The results of these calculations are shown in
Table X-2 (page 851).
Selection of Pollutant Parameters for Regulation
All process element raw wastewater samples and calculated total
raw waste concentrations were evaluated to determine which
pollutants should be considered for regulation. Tables VI-1 and
VI-2 (pages 488 and 493) summarize this analysis and list the
pollutants that should be considered. Pollutant parameters which
were found frequently or at high concentrations in process
element waste streams in this subcategory, and are regulated at
BPT are cadmium, nickel, silver, zinc, cobalt, oil and grease,
and TSS. Silver is regulated for the process elements associated
with silver cathode production only. pH is also selected for
regulation as a control parameter. Other pollutants which
appeared at lower concentrations and were considered, but not
selected for regulation at BPT, are expected to be incidentally
removed by the application of BPT technology. With the
application of lime and settle technology, combined with oil
skimming when necessary, the concentration of regulated
pollutants should be reduced to the concentration levels
presented in Table VII-21 (page 606).
Effluent Limitations .
Pollutant mass discharge limitations based on BPT are determined
by multiplying the process element BPT flows summarized in Table
IX-1 by the achievable effluent concentration levels for lime and
settle technology from Table VII-21 For process elements relating
to silver cathodes, waste streams will generally need to be
treated separately to comply with the BPT mass limitations for
the silver processes because the silver limitation cannot be
achieved when these wastewaters are combined with other process
wastewaters. Separate treatment is presently practiced by plants
within the subcategory who recover and reuse the silver. The
results of this computation for all process elements and
regulated pollutants in the cadmium subcategory are summarized in
Tables IX-2 to IX-15 (page 759-772). To alleviate some of the
monitoring burden, several process elements which occur at most
plants and have the same pnp are combined in one regulatory
table. Table IX-11 (page 768) is the combined table for Tables
IX-7 to IX-10. These limitation tables list all the pollutants
732
-------
which were considered for regulation and those regulated are
indicated by "*".
Reasonableness of the Limitations
The mass discharge limitations are reasonable based on the
demonstrated ability of the selected BPT to achieve the effluent
concentrations presented. As discussed in Section VII, the
effluent concentrations shown are, in fact, achieved by many
plants with wastewater characteristics similar to those from the
cadmium subcategory by the application of lime and settle
technology with a reasonable degree of control over treatment
system operating parameters.
To confirm the reasonableness of these limitations for this
subcategory, the Agency compared them to actual performance at
cadmium subcategory plants. Since plants presently discharge
wastewaters from various process elements and BPT is projected on
a single end-of-pipe treatment from multiple process elements,
this comparison must be made on the basis of the total plant
rather than a process element. This was accomplished by
calculating total process wastewater discharge flow rates for
each plant in the subcategory based on available production
information and the normalized process element flows shown in
Table IX-1. These calculated effluent flow rates were then
compared to flow rates actually reported or measured. Effluent
concentrations were also compared to those attainable by lime and
settle technology as presented in Table VI1-21. Finally total
plant mass discharges were compared to BPT limitations for plants
which, on the basis of effluent flows and concentrations/ were
potentially meeting BPT mass discharge limitations.
As a first step in this comparison, cadmium subcategory process
wastewater flow rates from each plant were compared to the flow
rates upon which mass limitations for the plant would be based.
In order to minimize the effects of irregular operating schedules
for some process operations, this comparison was made on the
basis of annual flows. To calculate actual annual process
wastewater discharge flows, the discharge flow rate (1/hr) from
each process element at the plant was multiplied by the hours of
production activity reported for the process element. The
resultant process element annual discharge flows were summed to
determine the total plant discharge flow. In some cases, the
only available data were combined flow rates for several process
elements as reported in dcp; these combined flow rates were then
multiplied by plant production hours to determine the total
contribution from these process elements to the plant's annual
process wastewater discharge. Production information from each
plant was used to determine an annual calculated BPT flow for
comparison to the actual values. The total annual production (in
733
-------
terms of pnp) for each process element was determined and
multiplied by the normalized flow shown for that process element
in Table IX-1 to determine the BPT flow for the process element
at the plant. Flows for each process element were summed to
obtain a total plant BPT flow. Table IX-16 (page 773) presents a
comparison of these values.
Nine of thirteen cadmium subcategory plants in the data base (6
of 10 currently active plants) were found to produce annual
process wastewater volumes equal to or lower than those upon
which BPT pollutant mass discharge limitations would be based.
Two other plants produced process wastewater discharges only one
percent larger than those used in calculating BPT mass discharge
limitations. This analysis supports the thesis that the flow
basis for BPT mass discharge limitations is reasonable and
reflects techniques widely practiced in the subcategory.
Most plants have BPT equivalent or more sophisticated treatment
systems in place, but few plants in the cadmium subcategory
presently apply BPT effectively. ' Two plants which produce
wastewater and discharge treat cadmium subcategory process
wastewater and achieve effluent concentrations equivalent to
those used to determine mass discharge limitations for BPT
technology. Three plants which treat wastewater and discharge
can readily comply with the BPT technology by some upgrading and
by properly operating their treatment systems. Two additional
plants comply with this technology by process selection and are
not generating a wastewater discharge. Treatment performance at
the three remaining active cadmium subcategory plants could not
be evaluated because of the limited amount of data submitted,
however all three of these plants have the BPT equivalent or
better technology in place.
On-site observations (discussed in Section V) have shown that
existing systems- in the subcategory are inadequately maintained
and operated. Consequently, it is necessary to base BPT mass
discharge limitations on the transfer of demonstrated technology
performance from other industrial categories. The limitations
based on this transfer are reasonable based on the general
attainment of the flow levels used as the basis for BPT within
the cadmium subcategory and on the basis of effluent
concentrations achieved at many industrial plants treating
similar process wastewater streams containing primarily metals,
oil and grease, and TSS.
Pollutant Removals and Costs
In the establishment of BPT, the cost of application of
technology must be considered in relation to the effluent
reduction benefit from such application. The quantity of
734
-------
pollutants removed by BPT and the total costs of application of
BPT were determined by consideration of wastewater flow rates and
treatment costs for each plant in the cadmium subcategory.
Pollutant reduction quantities are shown in Table X-4 (page 854)
for the total subcategory and Table X-5 (page 855) for direct
dischargers. Treatment costs (1978 dollars) are shown in Table
X-56 (page 906). The capital cost of BPT as an increment above
the cost of in place treatment is estimated to be $390,562 for
the cadmium subcategory ($60,472 for direct dischargers only).
Annual cost of BPT for the subcategory is estimated to be $98,690
($23,065 for direct dischargers -only). The quantity of
pollutants removed by the lime and settle system for this
subcategory is estimated to be 474,910 kg/yr (341,700 for direct
dischargers) including 193,500 kg/yr of toxic pollutants (139,200
for direct dischargers only). The pollutant reduction benefit is
worth the dollar cost of required BPT.
CALCIUM SUBCATEGORY
Currently there are no direct discharging plants in this
subcategory and therefore no BPT (or BAT) will be established.
This discussion of the BPT technology option is presented here
for consistency and completeness and will form the basis for new
source discussions in Section XI, and pretreatment discussions in
Section XII.
This subcategory encompasses the manufacture of calcium anode
batteries, such as thermal batteries, which are used primarily
for military applications. Three plants presently manufacture
this type of battery and the total production volume is limited.
Eight process elements identified in Table IV-1 (page 154) are
manufacturing activities included within this subcategory. Since
the cell anode material, calcium, reacts vigorously with water,
water use and discharge in this subcategory is limited. Only two
of the process elements, as shown in Figure V-8 (page 399),
generate a wastewater discharge; the other six do not.
Normalized flows for these elements are summarized in Table V-33
(page 297).
Model Treatment Technology
The end-of-pipe treatment technology for the calcium subcategory
was selected after a review of the manufacturing processes
involved and the wastewaters generated. This review showed that
the construction of calcium anode cells generates two distinct
wastewater streams which differ in their initial treatment
requirements. The first step in treatment technology for the
calcium subcategory is the segregation of the two waste streams
for separate treatment. A schematic diagram of the end-of-pipe
treatment.system selected to treat these wastewaters is presented
735
-------
in Figure IX-2 (page 811). The chromium-bearing 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 hexavalent chromium in the waste stream to the
trivalent form which may be effectively removed by precipitation
as the hydroxide.
Following pretreatment of the heat paper production waste stream,
the wastewater is combined with wastewater from cell leak
testing. The combined stream is treated with lime and then
clarified by settling. The sludge which accumulates during
settling must be removed to ensure continued effective operation
of the settling device. A vacuum filter is included in the lime
and settle treatment system to reduce the water content of the
sludge and minimize the quantity of material requiring disposal.
The resulting filtrate is returned for further treatment and the
sludge disposed in a secure landfill.
The chromium reduction and lime and settle technology set forth
for heat paper production in this subcategory has been
transferred from other categories with chromium wastes, because
treatment in this subcategory is universally inadequate or
lacking. Chromium-containing heat paper production wastewaters
are not treated at one plant, and are only pH adjusted and
settled at another. (See Table V-36, page 300). Hence, transfer
of technology from another category is necessary and reasonable.
Chromium reduction followed by lime and settle technology is a
widely used treatment system of proven effectiveness on
essentialy similar wastewaters. No in-process technologies are
recommended at the BPT treatment level since no in-process
control is practiced within the subcategory.
Table IX-17 (page 774) presents the normalized discharge flows
which form part of the basis for mass discharge limitations for
each process element. For heat paper production and cell testing
associated with thermal battery production, data were combined
from the calcium, lithium and magnesium subcategories since
manufacturing processes and wastewaters generated from these
elements are identical. The normalized flow used for mass
limitations is equal to the median flow for heat paper
manufacture because one plant (which was not visited, but
contacted twice) had a normalized flow more than fifty times
(more recently reduced to thirty times) greater than the flows
achieved by other plants for this process element. In this case,
the median flow is believed to more accurately represent what is
common practice for this process element and is used as the basis
for mass limitations for the heat paper production and cell
testing elements.
736
-------
Pollutant characteristics of the process wastewater from heat
paper production (Table V-34, page 298} in the three
subcategories are essentially similar and can include asbestos,
chromium and iron. No sampling data are available on the cell
testing waste stream because testing which is done intermittently
was not being done at the time of sampling. As cell testing
exposes water to the same materials as are inside the cell, all
testing water is assumed to be the same as heat paper wastewater.
The volume of water generated by this process is minimal in
comparison to heat paper production (about 0.2 percent) and has a
negligible contribution to the overall raw wastewater
characteristics of the calcium subcategory. Total raw wastewater
characteristics calculated from process element raw waste
characteristics and total wastewater flow from each process
element are shown in Table X-18 (page 868).
Selection of Pollutants
For the purpose of selecting pollutant parameters for limitations
with lime and settle technology the raw wastewaters were examined
for pollutants found frequently at treatable concentrations.
Only chromium and TSS were noted at levels great enough for
effluent limitations. Chromium appears in high concentrations
due to the use of barium chromates in the manufacture of heat
paper. TSS is selected because of its high concentrations in
heat paper manufacture .wastewater. Proper pH control is also
specified to ensure the efficient performance of the lime and
settle treatment.
Effluent Limitations
The effluent concentrations of the pollutants considered for
regulation attainable through the use of lime and settle
technology are listed in Table VII-21 (page 606). When these
concentrations are combined with the BPT technology flows from
each process element as shown in Table IX-17, the mass of
pollutant allowed to be discharged per unit of production
normalizing parameter can be calculated. Table IX-18 (page 775)
shows the effluent limitations derived from this calculation, and
is presented as guidance for state or local pollution control
agencies because effluent limitations for the discharges from
this subcategory are not established for national regulation at
BPT.
LECLANCHE SUBCATEGORY
Currently, there are no direct discharging plants in this sub-
category and therefore no BPT (or BAT) will be established. This
discussion is presented here for consistency and completeness and
737
-------
will form the basis for new source discussions in Section XI and
pretreatment discussions in Section XII.
The Leclanche subcategory includes the manufacture of the zinc
anode, acid electrolyte batteries such as the conventional
carbon-zinc Leclanche cell or "dry cell" (cylindrical,
rectangular, and flat), silver chloride-zinc cells, carbon-zinc
air cells, and foliar batteries. Ten process elements identified
in Table IV-1 (page 154) are manufacturing activities included
within the Leclanche subcategory. Five of these process
elements, as shown in Figure V-10 (page 401), generate a
wastewater discharge; the other five do not. Normalized flows
for these elements are summarized in Table V-39 (page 303).
Model Treatment Technology
Treatment technology for this subcategory for all battery types
except foliar is .the implementation of in-process treatment and
controls to eliminate process wastewater discharge. For foliar
batteries the model treatment technology is in-process recycle
and lime, settle and filter end-of-pipe treatment. Information
collected to characterize manufacturing practices, wastewater
sources, and present treatment and control practices was
carefully reviewed to define treatment options. Table V-50 (page
314) summarizes present treatment practices which indicate that
zero discharge is presently common practice within the
subcategory.
The elimination of most wastewater discharges does not require
significant modification of the manufacturing process or process
equipment. In-process technologies practiced in the subcategory
and recommended for zero discharge include:
• Wastewater recycle and reuse
• Water use control
• Good housekeeping
• Process modifications for some waste streams
For wastewater recycle and reuse, wastewater sources which are
encountered in this subcategory can be segregated into two
groups: those that are related to mercury use and those that are
related to other metals use (manganese and zinc). Paste
separators, both cooked and uncooked, pasted paper separators,
and equipment and utensils which are used to mix or transport
mercury-containing materials are included in the mercury use
group. The other group includes paste separators and equipment
and utensils which are not related to mercury use. Segregation
738
-------
of streams in the mercury use group is important for effective
treatment as well as wastewater recycle and reuse. Since
wastewater would contain only the constituents used in ti'iese
processes (primarily mercury) recycle is practical. When all
process wastewaters are combined, the contaminants from other
processes, primarily zinc and manganese, prevent recycle. All
waste streams in this subcategory can be recycled and reused,
whether with or without treatment, as deemed necessary by the
individual plant. This in-process technology is presently
implemented at plants within the subcategory.
Water use within plants can be controlled and good housekeeping
techniques can be practiced to substantially reduce the amount of
water used. Water use can be eliminated by using dry cleanup
procedures or by minimizing spills and keeping production areas
clean. These techniques are presently practiced, especially for
equipment and floor cleaning processes.
Mechanical and production practices vary from plant to plant, and
in some instances within the subcategory, wastewater is
discharged from equipment and area cleanup. If all other
in-process techniques cannot be implemented at a plant, another
alternative is to consider implementation for process
modifications. The final alternative is to implement all
available in-process practices and contract haul the wastes to a
secure landfill or sell for metals reclamation.
Wastewater characteristics of Leclanche subcategory process
elements are similar in that they contain metals (primarily
mercury and zinc), oil and grease, and TSS. These
characteristics are presented for all process elements in Tables
V-40 to V-43 (pages 304 - 307) and Tables V-45 to V-48 (pages 308
- 311).
Total subcategory raw waste characteristics are needed to
evaluate the pollutant removals which would be achieved by
implementing the recommended treatment technology. To present
raw waste for the subcategory, the mean raw waste concentration
for each process from the sampling data in Section V was
multiplied by the wastewater flow for the process. The annual
mass of pollutants generated by each process was summed and
divided by the total subcategory flow to obtain the subcategory
raw waste calculations. Although not specifically sampled,
foliar battery miscellaneous wash raw wastewater characteristics
are similar to the average for the subcategory. Raw waste
characteristics for the subcategory are in Table X-20 (page 870).
All process element raw wastewater samples and plant data were
evaluated to determine which pollutants should be considered for
regulation. Tables VI-1 and VI-2 (pages 488 and 493) summarize
739
-------
this analysis and list the pollutants that should be considered.
Pollutant parameters found frequently or at high concentrations,
in process element waste streams in this subcategory include
mercury, zinc, manganese, oil and grease, and TSS. These
parameters along, with pH, should be regulated for the Leclanche
subcategory wastewaters.
Other pollutants which appeared at lower concentrations and were
considered, but not recommended or selected for regulation should
be incidentally removed by the application of lime, settle and
filter (LS&F) technology. With the application of the LS&F
technology, the concentration of pollutants should be reduced to
the concentration levels presented in Table VI1-21 (page 606)
No discharge was selected for most plants primarily because 12 of
the 19 existing plants are presently achieving no discharge.
Most of these plants achieve zero discharge by employing
manufacturing processes, operating practices, and maintenance
procedures which do not result in the generation of process
wastewater. The remaining plants which presently discharge
wastewater, except for the foliar battery plants, could
accomplish zero discharge by using in-process treatment and
technology practices. Plants with foliar battery production can
recycle and reuse some process wastewater and use their existing
treatment equipment to achieve LS&F technology effectiveness for
the water that is discharged.
At plants where paste is prepared and applied to cells containing
paste separators or to paper for use as cell separator material,
equipment is periodically washed down with water as part of
normal maintenance. Wastewater from equipment cleaning usually
contains the paste constituents, including ammonium chloride,
zinc and mercury. This, water is retained and reused in
subsequent paste equipment washing. The build-up of contaminants
in the wash water is controlled by using a portion of the wash
stream in paste preparation. Of the six plants supplying data
for paste preparation, three plants which use mercury in the. mix
have reported no process wastewater discharge. One plant has
recently discontinued this process, but before changing processes
was practicing segregation, recycle and reuse. The second plant
is presently practicing segregation, recycle and reuse, and the
third plant does not generate any process wastewater since its
equipment is not washed. The other three plants do not practice
recycle or reuse. Two of these plants use less than 10 gallons a
day of process water and do not have mercury in their paste
processes. The third plant presently uses mercury and discharges
water from paste equipment washing.
Water is used at one plant in the cooked paste separator process
element, to supply heat for setting paste separators. As a
740
-------
result of contact with machinery used to convey the cells and
occasional spillage from cells, this water becomes contaminated
with oil and grease, paste constituents (zinc, ammonium chloride
and mercury) and manganese dioxide particulates. These
contaminants 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 can be eliminated by recycle and reuse of the water.
Water drawdown from the paste setting tanks during breaks in
production serves to prevent overcooking of the paste separators
in cells left in the tanks during these periods. Discharge
resulting from the tank drawdown and from emptying tanks for
maintenance can be eliminated without loss of productivity by
providing a tank to hold the drawdown water during the break.
The water can later be pumped back into the process tanks. These
practices will eliminate the wastewater discharge and the energy
requirement for heating water used in the paste setting tanks.
Dragout from paste setting tanks which is presently treated and
discharged can be collected and returned to the process tank for
recycle. This practice will eliminate wastewater discharge and
reduce the amounts of oil and grease (from the process machinery)
in wastewater from the paste setting process.
Process wastewater generated by cooking to "set" the paste
separator may be eliminated entirely by substitution of a low
temperature setting paste. This is presently practiced by one
plant. Alternatively, paper separators can be used in accordance
with prevailing practice at other Leclanche subcategory plants.
Water used for equipment and floor cleaning in assembly as well
as electrolyte preparation areas was reported at seven Leclanche
subcategory plants. One plant which was recycling equipment
cleaning water has discontinued production. The six remaining
plants presently do not practice any substantial in-process
technologies to completely eliminate wastewater discharge. Water
use and subsequent discharge can be substantially reduced by the
implementation of water use controls or eliminated by the
substitution of dry equipment cleanup procedures. Eight plants
which were visited, presently employ some dry equipment and floor
cleaning techniques. The assumption is made that other plants
not visited and reporting zero discharge of process wastewater
are also practicing dry equipment and floor cleaning techniques.
One plant which was visited and is presently discharging
substantial volumes of equipment cleaning water, claimed that
zero discharge could be achieved through in-process controls,
treatment and recycle. Where the quality of the water is
essential for final product performance, wastewater can be
segregated, treated and reused. Existing treatment at the four
741
-------
plants which treat and discharge wastewater can be used for this
purpose. In the unlikely event that all process water cannot be
reused after in-process technologies are implemented, resulting
wastewaters can be contractor hauled to an approved landfill or
sold for metals reclamation if appropriate.
As shown in the above discussion, zero discharge for almost all
of the processes in the Leclanche subcategory is reasonable.
This level of control is presently achieved by 12 plants and is
viable for the remaining seven plants, except for foliar battery
production which was reevaluated after proposal.
Comments on the proposal were received which stated that a
separate subcategory was needed for foliar batteries and that a
discharge was necessary. Separate subcategorization of foliar
batteries was rejected because the battery chemistry is classic
Leclanche chemistry. However, the nature of the manufacturing
process and the sensitivity of the thin layers of active
materials in the battery to minute particles of impurities make
the reuse of wastewater in the product undesirable. Therefore, a
flow allowance was established for foliar battery miscellaneous
wash based on data presented in Section V. The in-process
technology for reduction of wastewater volume is wastewater
segregation, water reuse and improved tool cleaning processes.
Application of these technologies will reduce wastewater
discharge to one-half of the present discharge level or 0.066
I/kg of cells produced.
The effluent concentrations of the pollutants considered for
regulation attainable through the use of this technology are
listed in Table VII-21 (page 606). These concentrations are
multiplied by the production normalized discharge flow to obtain
the mass limitations listed in Table IX-19 (page 776). These
limitations for foliar batteries are presented as guidance only,
since there are no direct discharging plants in this subcategory.
Pollutant reduction benefits are listed in Table X-20 (page 870).
LITHIUM SUBCATEGORY
Currently, the discharge by direct dischargers of process waste-
water from this subcategory is small (less than 4 million 1/yr)
and the quantity of toxic pollutants is also small (less than 220
kg/yr). Because of the small quantities, the Agency has elected
not to establish national BPT (and BAT) limitations for this
subcategory. Applicable technologies, and potential limitations
are set forth as guidance should a state or local pollution
control agency desire to establish such limitations. Detailed
discussions on technology presented here will form the basis for
new source discussions in Section XI and XII.
742
-------
The lithium subcategory includes the manufacture of lithium anode
batteries, including thermal batteries and other high cost, low
volume special purpose batteries, such as those used in heart
pacemakers, lanterns, watches, and for military applications.
Fifteen process elements identified in Table IV-I (page 154) are
manufacturing activities included within this subcategory. Since
the cell anode material, lithium, reacts vigorously with water,
water use and discharge in this subcategory is limited. Eight of
these process elements, as shown in Figure V-12 (page 403),
generate a wastewater discharge; the other seven do not.
Normalized flows for these elements are summarized in Table V-53
(page 317).
Model Treatment Technology
End-of-pipe treatment for this subcategory is illustrated in
Figure IX-4 (page 813). Since no lithium subcategory plants
presently have adequate treatment systems in place (See Table V-
57, page 321), treatment technology is transferred from other
similar industrial categories. Three separate treatment systems
are shown to account for the processes and waste streams
currently encountered. Lithium cell manufacturers do not use
processes at any one plant which produce waste streams for all
three treatment systems.
The first treatment system is for plants producing lithium anode
thermal batteries and generating process wastewater from heat
paper production only. This waste stream is treated separately
because of the chromium and large quantities of suspended solids
present in the raw waste stream, as is discussed in the calcium
subcategory on page 736.
The second treatment system is for plants generating process
wastewater from lead iodide cathode production, iron disulfide
cathode production, cell testing, lithium scrap disposal, and
floor and equipment wash. Treatment includes chemical
precipitation with lime and settling. A clarifier can be used as
a settling device. This treatment system is identical to the
first except for the chromium reduction steps. Settled solids
are treated identically as the first treatment system, by
dewatering in a vacuum filtration unit. As .an alternative, for
the plants with heat paper production and one or more of the
second system process elements, wastewaters can be combined
following chromium pretreatment; however, additional pollutant
parameters would be regulated.
The third treatment system is for plants generating process
wastewater from air scrubbers located in various production
areas, such as sulfur dioxide preparation, thionyl chloride
preparation, electrolyte preparation, battery filling, and
743
-------
assembly areas. Initially these wastewaters are aerated to
reduce the oxygen demand, then neutralized since thionyl chloride
and sulfur dioxide streams form hydrochloric and sulfuric acid,
respectively. The neutralized waste stream is settled prior to
discharge because of the formation of precipitates and suspended
solids. Settled solids are removed and contractor hauled to a
secure landfill. These solids are not expected to be hazardous.
BPT water flow controls do not require any significant
modification of the manufacturing process or process equipment
for their implementation. There are no in-process technologies
recommended at BPT.
Table IX-20 (page 777) presents the normalized discharge flows
which form part of the basis for mass discharge limitations for
each process element. These normalized flows are equal to the
mean normalized flows presented in Table V-53 (page 317) (except
for heat paper production which was discussed under the calcium
subcategroy) and represent the average level of water use
presently achieved by plants active in each process element.
These flows correspond to internal controls which are common
industry practices.
Pollutant characteristics of process wastewater from the process
elements in this subcategory are related to the three separate
treatment systems. Heat paper production wastewaters, which were
described under the calcium subcategory and characterized in
Table V-34 (page 298), contain treatable levels of chromium as
well as TSS. This element was separated for,separate treatment
because of the presence of chromium in the wastewater.
The lead iodide cathode production, iron disulfide cathode
production, lithium scrap disposal, cell testing and floor and
equipment wash process elements contain pollutants such as iron,
lead and TSS. These pollutants can be treated by chemical
precipitation and settling technology, which is the second
treatment system. The iron disulfide cathode production element
was sampled since it was expected to contain the most pollutants
and comprised a large percentage of the wastes streams considered
for this treatment system. The raw waste characteristics are
shown in Table V-54 (page 318). The lithium scrap disposal area
was also sampled and characteristics are summarized in Table V-56
(page 320). The second largest contributing waste stream, the
lead iodide cathode production element was not sampled, but one
plant reported that it contained lead. The wastewater was
contractor hauled. For the lead iodide, cell testing and floor
and equipment wash process elements, no pollutants in addition to
those detected in the iron disulfide stream are expected to be
present in the wastewaters.
744
-------
The cell wash wastewater stream which was characterized by plant
supplied data, contains high levels of COD. This is expected
since acetonitrile, used as a raw material, contains cyanide.
Because the flow from this process is low (less than 55 gallons
per week) and the waste stream contains organics, this waste
stream is contractor hauled for disposal and zero discharge is
promulgated.
The wastewater from the air scrubbers process element, which are
treated by the third treatment system, are expected to be acidic
and contain some suspended solids. These streams were not
sampled, however by evaluating raw materials and plant data, the
conclusions reached concerning the raw waste characteristics are
reasonable.
Specific manufacturing process elements at each plant will affect
the pollutant characteristics and the treatment system used.
Total subcategory raw waste characteristics and total wastewater
flow from each process element are summarized in Table X-23 (page
873) .
All process element raw wastewater samples and plant data were
evaluated to determine which pollutants should be considered for
regulation. Tables VI-1 and VI-2 (pages 488 and 493) summarize
this analysis and list the pollutants that should be considered.
Pollutant parameters found frequently, or at high concentrations,
in process element waste streams in this subcategory include
chromium, lead, iron, and TSS. These parameters, along with pH,
should be regulated as appropriate for the process elements
included in the separate treatment systems. Chromium, TSS and pH
should be regulated when only heat paper production wastewater is
treated. When cathode and all ancillary operations except
scrubber wastewater are treated, chromium, lead, iron, TSS and pH
should be regulated. Air scrubber wastewater is segregated from
other process wastewater and treated for TSS and pH only.
Other pollutants which appeared at lower concentrations and were
considered, but not recommended or selected for regulation should
be incidentally removed by the application of lime and settle
technology. With the application of chromium reduction and
chemical precipitation and settling technology, the concentration
of regulated pollutants should be reduced to the concentration
levels presented in Table VII-21 (page 606). Pollutant mass
discharge limitations based on lime and settle technology are
determined by multiplying the process element normalized flows,
summarized in Table IX-20, by the achievable effluent
concentration levels for lime and settle technology. One
limitation is presented for floor and equipment wash, cell
testing, and lithium scrap disposal because of the small amounts
of wastewater generated. The results of this computation for all
745
-------
process plptnent-.s and s<=>1 <=>ri-<=>r? pollutants for specific process
elements in the lithium subcategory are summarized in Table IX-21
to IX-25 (pages 778-782). These tables are presented as guidance
for state or local pollution control agencies agencies because
effluent limitations for the discharges from this subcategory are
not established for national regulation at BPT.
The pollutant mass discharge limitations are reasonable based on
the demonstrated ability of the selected BPT technologies to
achieve the effluent concentrations presented. As discussed in
Section VII, the effluent concentrations shown are achieved by
many plants with wastewater characteristics (metals, TSS) similar
to those from the lithium subcategory by the application of lime
and settle technology with a reasonable degree of control over
treatment system operating parameters.
To determine the reasonableness of these mass limitations, the
Agency examined the available effluent data, the treatment
systems in place, and the processes conducted at each plant in
the subcategory. As discussed in the calcium subcategory, no
plants have lime and settle treatment in place for the heat paper
production process element. Therefore, for the one lithium
subcategory plant active in this process element, reasonableness
is based upon the proven effectiveness of lime and settle
technology in other industrial categories with similar wastewater
characteristics. Of the two plants active in the lead iodide
cathode production, iron disulfide cathode production, cell
washing, cell testing, floor and equipment wash, and lithium
scrap disposal process elements, one plant does not have a
complete, effective treatment system in place for all of these
elements, and the other contractor hauls their wastes. The first
plant does not pH adjust and settle all process element streams,
and the second only settles the wastewater before contractor
removal. Two plants, active in the air scrubber element, treat
process wastewaters by pH adjustment only. This treatment alone
is not considered to represent the selected treatment technology,
since pH adjustment causes precipitates to form in the wastewater
which should be settled before discharge. The reasonableness of
this technology is again based on proven effectiveness in other
industrial categories with similar wastewater characteristics.
The data collected indicates that plants active in the
subcategory do not have adequate treatment in place. Therefore,
treatment technology is transferred from other industrial
categories which treat wastewaters containing such pollutants as
chromium, lead, iron and TSS.
If the application of lime and settle technology at a specific
plant does not result in sufficiently low effluent concentrations
to meet mass discharge regulations, there are alternative
746
-------
technologies available, such as sulfide precipitation, carbonate
precipitation and ferrite co-pt.ee j.pii,ct LI on \wit.h hydroxide
precipitation) which may achieve lower effluent concentrations
than hydroxide precipitation. A more simple way of meeting the
discharge limitations would be to reduce the discharge flow
either through process modification or in-process flow controls.
Alternatively, plants with significantly small volumes of
wastewater (less than 50 gallons per week) can consider
contractor removal to a secure, approved landfill.
MAGNESIUM SUBCATEGORY
Currently, the discharge by direct dischargers of process waste-
water from this subcategory is small (less than 4 million 1/yr)
and the quantity of toxic pollutants is also small (less than 220
kg/yr). Because of the small quantities, the Agency has elected
not to establish national BPT (and BAT) limitations for this
subcategory. Applicable technologies, and potential limitations
are set forth as guidance should a state or local pollution
control agency desire to establish such limitations. Detailed
discussions on technology presented here will form the basis for
new source discussion in Section XI and pretreatment discussions
in Section XII.
The magnesium subcategory includes the manufacture of magnesium
anode batteries, such as magnesium carbon batteries, and reserve
and thermal batteries, which are activated by electrolyte
addition or by initiation of a chemical reaction to raise the
cell temperature to operating levels. Of these, magnesium carbon
batteries account for 85 percent of the production in the
subcategory. Sixteen process elements identified in Table IV-I
(page 154) are manufacturing activities included within this
subcategory. Seven of these process elements, as shown in Figure
V-14 (page 405), generate a wastewater discharge; the other nine
do not. Normalized flows for these elements are summarized in
Table V-59 (page 323).
Model Treatment Technology
End-of-pipe treatment for this subcategory is illustrated in
Figure IX-5 (page 814). Since no plants in the subcategory are
effectively treating the wastewater (See Table V-62, page 626),
technology is transferred from other industrial categories with
similar pollutants. Three separate treatment systems are shown
to account for the processes and waste streams currently combined
and encountered in the subcategory at present. Magnesium cell
manufacturers at any one plant do not conduct manufacturing
processes which produce aid of the identified wastewater streams
for all three treatment systems.
747
-------
The first treatment system is for wastewaters from the silver
chloride cathode processes in which silver or silver chloride is
treated in process solutions. The batch dumps of the solutions
are bled into the rinsewaters from the operations and sent to
treatment. In order to reduce the oxygen demand of the organic
laden wastes, the wastewater is pretreated with potassium
permanganate. When this oxidation process is complete, the water
is subjected to chemical precipitation with lime or acid and
settling. As in the second system, settled solids are removed
and dewatered in a vacuum filtration unit. For plants with
silver chloride production and cell testing, or floor and
equipment washing process elements, wastewaters are combined
following permanganate pretreatment. For plants with only cell
testing or floor and equipment wash, pretreatment is not
necessary.
The second treatment system is for plants producing magnesium
anode thermal batteries and generating process wastewater from
heat paper production. The system is identical to the system
discussed and described in the calcium subcategory on page 736.
The third treatment system is for plants generating process
wastewater from air scrubbers. Treatment includes chemical
precipitation with lime or acid, and settling to remove metals
and suspended solids. A clarifier can be used as a settling
device. Settled solids are removed and dewatered in a vacuum
filtration unit. Solids are removed for disposal, and the
filtrate is recycled back to the chemical precipitation tank.
For plants with heat paper production and air scrubbers, the
wastewater streams are segregated.
BPT water flow controls do not require any significant
modification of the manufacturing process or process equipment
for their implementation. In-process flow control is recommended
for the silver chloride cathodes surface reduced process element.
On-site visits indicated that rinse water was left flowing
continuously in two tanks regardless of whether the process used
two rinses or not. Consequently, twice the amount of water was
used than was necessary and fifty percent of the observed flow is
believed to represent the average process flow.
Table IX-26 (page 783) presents the normalized discharge flows
which form part of the basis for pollutant mass discharge
limitations for each process element. These normalized flows are
equal to the mean normalized flows presented in Table V-59
(except for heat paper production, which was discussed under the
calcium subcategory and the silver chloride cathode surface
reduced process discussed above) and represent the average level
of water use presently achieved by plants active in each process
748
-------
element. These flows correspond to internal controls which are
common industry practice.
Pollutant characteristics of process wastewater from the process
elements in this subcategory are related to the three separate
treatment systems. Heat paper wastewaters and treatment
characteristics were discussed in the calcium subcategory. Air
scrubber wastewater is expected to only contain treatable levels
of TSS. The cell testing and floor and equipment wash process
elements should contain pollutants such as metals and TSS which
can be treated by chemical precipitation and settling technology.
These process elements were not characterized by sampling.
However, by evaluating raw materials and plant data, no
pollutants, other than those detected in other waste streams
sampled in this subcategory, are expected to be present. The
characteristics for the silver chloride cathode processes are
presented in Table V-6 (page 261), and Table V-60 (page 324).
These elements were separated for pretreatment because of the
presence of COD in the wastewaters.
Specific manufacturing process elements at each plant will affect
the pollutant characteristics and the treatment system used.
Total subcategory raw waste characteristics and total wastewater
flow from all process elements are summarized in Table X-29
(page 879). '
All process element raw wastewater samples and plant data were
evaluated to determine which pollutants should be considered for
regulation. Table VI-1 and VI-2 (pages 154 and 155) summarize
this analysis and list the pollutants that should be considered.
Pollutant parameters which were found at high concentrations in
process element waste streams from this subcategory and should be
regulated include chromium, lead, silver, iron, COD, and TSS.
These parameters, along with pH, are considered for regulation.
Specific pollutants considered depend on processes practiced at
each plant. Other pollutants which appeared at lower
concentrations and were considered, but not selected for
regulation should be incidentally removed by the application of
the selected treatment technology. With the application of
chromium reduction, oxidation, chemical precipitation and
settling technology, the concentration of the selected pollutants
should be reduced to the concentration levels presented in Table
VII-21 (page 606). Mass discharge limitations based on the
discussed lime and settle treatment are determined by multiplying
the process element normalized flows summarized in Table IX-26 ,
with the achievable effluent concentration levels for lime and
settle technology from Table VII-21. The results of this
computation for all process elements and considered pollutants
and pollutant parameters in the magnesium subcategory are
summarized in Tables IX-27 to IX-32 (pages 784-789). These
749
-------
tables are presented as guidance for state or local pollution
control agencies because effluent limitations for the discharges
from this subcategory are not established for national regulation
at BPT.
As discussed in Section VII, the effluent concentrations shown
are achieved by many plants with wastewater characteristics
(metals, TSS) similar to those from the magnesium subcategory, by
the application of lime and settle technology with a reasonable
degree of control over treatment system operating parameters.
To determine the reasonableness of these mass limitations, the
Agency examined the processes conducted, the available effluent
data, and the treatment systems in place at each plant in the
suBcategory. As discussed in the calcium subcategory, no plants
have BPT in place for the heat paper production process element.
Therefore, for the one magnesium subcategory plant active in this
process element, reasonableness is based upon the proven
effectiveness of BPT technology in other industrial categories
with similar wastewater characteristics. For the silver chloride
cathode production wastewater streams, no plant has BPT in place.
Neither the one plant that produces silver chloride cathodes nor
the other that is capable of producing them oxidizes the solution
waste stream prior to treatment. Therefore, reasonableness is
based on the proven effectiveness of the BPT technology in other
industrial categories with similar (high COD, metals and TSS)
wastewater characteristics. Air scrubber wastewater is generated
at a plant which does not treat the process wastewater. Cell
testing is also generated at a plant which does not treat process
wastewateer;however, the plant does have a BPT system in place
which can be used for treatment. Reasonableness for these
technologies is based on the proven effectiveness of the
technologies in other industrial categories with similar
wastewater characteristics. All but one plant, which reported a
discharge from floor and equipment wash, have a treatment system
in place, but do not treat the wastewater. Proven effectiveness
for the technology is transferred from other industrial
categories.
Although the effluent limitations are based on the application of
chemical precipitation and settling technology, there are
alternative technologies available, such as sulfide
precipitation, carbonate precipitation and ferrite co-
precipitation (with hydroxide precipitation), which may achieve
lower effluent concentrations than lime precipitation. A simpler
way of meeting the mass limitations would be to reduce the
discharge flow either through process modification or in-process
flow controls. Alternatively, plants with significantly small
volumes of wastewater (less than 50 gallons per week) can
consider contractor removal to a secure, approved landfill.
750
-------
ZINC SUBCATEGORY
The zinc subcategory includes the manufacture of a variety of
zinc anode batteries such as alkaline manganese, silver
oxide-zinc, mercury-zinc, carbon zinc-air depolarized, and
nickel-zinc. Twenty-five process elements identified in Table
IV-I (page 154) are manufacturing activities included within this
subcategory. Sixteen of these elements, as shown in Figure V-16
(page 407), generate a wastewater discharge, the other nine do
not. Normalized flows for these elements are summarized in Table
V-64 (page 329).
Model Treatment Technology
BPT end-of-pipe treatment for the zinc subcategory, as shown in
Figure IX-6 (page 815) consists of chemical precipitation and
sedimentation. Wastewaters are skimmed for oil and grease
removal and have hexavalent chromium reduced as necessary.
Sludges are dewatered in a vacuum filter. This system was
selected following a review of data submitted by plants in the
subcategory, observations at plants which were visited,
analytical results, and industry comments on the draft
development document circulated in September, 1980. As shown in
Table V-118 (page 384), plants in the subcategory reported
various treatment systems in place, ranging from pH adjustment
only, to innovative carbon adsorption and ion exchange systems.
Observations at plants indicated, however, that these treatment
systems were either rudimentary, improperly operated, or
installed during or after data collection activities before
performance could be evaluated completely. Most plants can, at
present, comply with the limitations based on this technology
with little or no treatment system modification. Treatment
effectiveness, however, is transferred from other industrial
categories with similar wastewater (toxic metals, TSS, oil and
grease) because of inadequate treatment system control and
operation.
Sulfide precipitation, sedimentation and filtration was initially
selected for BPT as being the average technology already in
place. Also, zinc subcategory wastewaters contain metals,
particularly mercury. Mercury is less soluble as a sulfide than
as a hydroxide. Consequently, lower concentrations of mercury
could be achieved by using sulfide rather than hydroxide
precipitation. The system was not selected primarily because (1)
sulfide precipitation may produce a toxic and reactive sludge
which would cause significant difficulties with disposal and (2)
lime precipitation is a more widely applied technology at the
present time, and that its effectiveness has consequently been
more thoroughly demonstrated in industrial wastewater treatment.
751
-------
In addition to end-of-pipe technology for the removal of
wastewater pollutants, BPT includes the application of controls
vr-ilhin the process to limit tfie 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 upon which BPT limitations are based include:
• Recycle or reuse of process solutions used for material
deposition, electrode formation, and cell washing
(already practiced by 4 plants)
• Segregation of noncontact cooling and heating water
from process wastewater streams (necessary for
effective treatment)
• Control of electrolyte drips and spills (observed at
various plants visited)
• Segregation of organic-bearing cell cleaning wastewater
(at various plants visited, these wastewaters were
segregated and contractor hauled)
• Elimination of chromate cell cleaning wastewater
(common industry practice as reported and observed is
the use of nonchromium cell cleaning solutions)
• Control of process water use in rinsing to correspond
to production requirements (already practiced by 5
plants).
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 cascade rinses, are presently
practiced at plants in this subcategory.
Table IX-33 (page 790) presents the normalized discharge flows
which form part of the basis for mass discharge limitations for
each process element. These flows are in most cases equal to the
mean normalized flows presented in Table V-64 and represent the
average level of water use presently achieved by plants active in
each process element. Specific discussion follows when the
median rather than mean was used as the BPT flow. All flows
correspond to internal controls which are common industry
practice.
752
-------
Pollutant characteristics of process wastewater from tne process
elements in this subcategory are essentially similar because they
contain toxic metals especially mercury, and also nickel, silver
and zinc. Raw wastewater characteristics for all sixteen process
elements are presented in Tables V-18 to V-21 (pages 282 - 285),
and in Tables V-66 to V-117 (pages 332 - 383). Specific
manufacturing process elements at each plant will affect the
overall pollutant characteristics of the combined process
wastewater flowing to one end-of-pipe treatment system. Some
loss in pollutant removal effectiveness will result where waste
streams containing specific pollutants at treatable levels are
combined with others in which these same pollutants are absent or
present at very low concentrations. Although process wastewater
streams with different raw waste concentrations will be combined
for end-of-pipe treatment, the treatment effectiveness
concentrations can be achieved with the recommended treatment
technologies as discussed in Section VII.
Total subcategory raw waste characteristcs are needed to evaluate
the pollutant removals which would be achieved by implementing
the recommended treatment technologies. Total raw waste
characteristics from sampled plants alone do not represent the
total subcategory. To present raw waste from the total
subcategory the following methodology was used. For pollutants
in each process element the mean raw waste concentration (from
sampling data in Section V) was multiplied by the total
wastewater flow for the process. The annual mass of pollutants
generated by each process was summed and divided by the total
subcategory flow to obtain the subcategory raw waste
concentrations. The results of these calculations are shown in
Table X-36 (page 885). For the total subcategory mercury raw
waste concentration all total raw wastewater sampling data from
both screening and verification was used to obtain an average
concentration and loading. This was done because one-fourth of
the mercury values from individual samples and combined process
element streams were not obtained and reported from the lab as
analytical interference.
Selection o_f_ Pollutants for Regulation
All process element raw wastewater samples and calculated total
raw waste concentrations were evaluated to determine which
pollutants should be considered for regulation. Tables VI-1 and
VI-2 (pages 488 and 493) summarize this analysis and lists the
pollutants that should be considered. Pollutant parameters which
were found frequently or at high concentrations in process
element waste streams in this subcategory include chromium,
mercury, nickel, silver, zinc, cyanide, manganese, oil and
grease, and TSS. Nickel is regulated only for the nickel
impregnated cathode and cell wash process elements. Cyanide is
753
-------
regulated only for the cell wash process element. Chromium,
mercury, nickel, silver, zinc, manganese, oil and grease, and
TSS, are selected for regulation at BPT. pH is regulated as a
control parameter. Other pollutants which appeared at lower
concentrations and were considered, but not selected for
regulation at BPT, should be incidentally removed by the
application of BPT technology.
Effluent Limitations
With the application of lime and settle technology, combined with
oil skimming and chromium reduction when necessary, the
concentration of regulated pollutants should be reduced to the
concentration levels presented in Table VII-21 (page 606).
Pollutant mass discharge limitations based on BPT are determined
by multiplying the process element BPT flows summarized in Table
IX-33, with the achievable effluent concentration levels for lime
and settle technology from Table VII-21. The results of this
computation for all process elements and regulated pollutants in
the zinc subcategory are summarized in Tables IX-34 to IX-50
(pages 791-807). To alleviate some of the monitoring burden,
several process elements which occur at most plants and have the
same pnp are combined in one regulatory table. Table IX-48 (page
805) is the combined table for Tables IX-42 to IX-43 and Tables
IX-45 to IX-47. These limitation tables list all the pollutants
which were considered for regulation and those regulated are *'d.
Reasonableness of the Limitations
These mass discharge limitations are substantiated by the
demonstrated ability of the selected BPT to achieve the effluent
concentrations presented. As discussed in Section VII, the
effluent concentrations shown are in fact achieved by plants with
wastewater characteristics (toxic metals, oil and grease, TSS)
similar to those from the zinc subcategory by the application of
lime and settle technology. Long-term, self-monitoring data have
demonstrated the feasibility of maintaining these levels reliably
over extended periods of time with a reasonable degree of control
over treatment system operating parameters. At least half of all
plants active in each process element presently produce
production normalized process wastewater volumes equal to or less
than the volume upon which pollutant discharge limitations are
based.
To confirm the reasonableness of these limitations, the Agency
compared them with actual results at zinc subcategory plants.
Since plants presently discharge wastewaters from various battery
process elements, and BPT is a single end-of-pipe treatment, this
comparison is best made on a total plant rather than a process
element basis. This was accomplished by calculating total
754
-------
wastewater discharge flow rates for each plant in the subcategory
based on available production information and the normalized
process element flows shown in Table IX-33. These flow rates
were then compared to calculated effluent flow rates actually
reported or measured. Effluent concentrations were also compared
with those attainable by lime and settle technology as presented
in Table VII-21. Finally, total plant mass discharges were.
compared to BPT limitations for plants which, on the basis of
effluent flow rates and concentrations, were potentially meeting
BPT mass discharge limitations.
Zinc subcategory process wastewater flow from each plant was
compared with the calculated flow upon which pollutant discharge
limitations for the plant would be based. In order to minimize
the effects of irregular operating schedules for some process
operations, this comparison was made on the basis of annual
flows. To calculate the actual annual process wastewater
discharge flows, the discharge flow rate (1/hr) from each process
element was multiplied by the hours of production activity in the
process element, and the resultant process element annual
discharge flows were summed to determine the plant total. In
some cases, process element flow rates were not available, and
reported total process wastewater flows or estimated flows for
specific process elements were used. Production information from
each plant was used to determine a calculated BPT flow for
comparison to the actual values. The total annual production (in
terms of pnp) for each process element was determined and
multiplied by the normalized flow shown for the process element
in Table IX-33 to determine this BPT flow for the process element
at the plant. Flows for each process element were summed to
obtain a total plant BPT flow. Table IX-51 (page 808) presents a
comparision of the actual and BPT calculated flows for each zinc
subcategory plant.
As shown in Table IX-51 eight of sixteen zinc subcategory plants
were found to produce process wastewater discharge equal to or
less than those upon which BPT pollutant discharge limitations
would be based. In addition, five of the remaining eight plants
had flows less than two times the BPT flow. The achievement of
BPT flows in present practice at the plants in the subcategory
confirms the thesis that the flow basis for BPT limitations is
reasonable and reflects control techniques widely practiced in
the subcategory at the present time.
Treatment reported to be applied to zinc subcategory process
wastewaters and summarized in Table V-119 (page 385) shows that
present treatment practice in the subcategory is highly diverse.
Many of the technologies practiced (e.g., amalgamation and carbon
adsorption) are aimed specifically at the removal of mercury.
Effluent data and on-site observations at plants in the zinc
755
-------
subcategory (discussed in Section V) reveal that most of the
technologi.es employed are not effectively applied for the
reduction of pollutant discharges. In some cases, such as
amalgamation, this is due to the inherent limitations of the
technologies employed. In other cases, such as sulfide
precipitation, failure to achieve effective pollutant removal
results from specific design, operation, and maintenance factors
at the plants employing the technologies. Despite these adverse
factors and observations, plants in this subcategory can comply
with the limitations achieved by lime and settle, the selected
BPT technology.
Present treatment and control practices in the zinc subcategory
are not only diverse, but are uniformly inadequate either in
their design or in their operation and maintenance (See Section V
discussion). Consequently, a treatment technology is selected
which can be related uniformly to the subcategory. The simplest
treatment system technology (lime and settle), and its
demonstrated effectiveness, is transferred from other industrial
categories with similar waste characteristics (toxic metals, oil
and grease, and TSS). By re-evaluating all the flow and effluent
data collected based on the selected BPT equivalent technology
flows and lime and settle treatment effectiveness, eight plants
in the subcategory meet the flows and can readily comply with the
mass limitations with some or no treatment modification to their
existing treatment systems. Of these eight plants, two plants
comply by having no process wastewater flows; one plant can
comply by segregating nonprocess wastewater streams; four plants
can comply by providing adequate maintenance (adequate solids
removal) and control (pH monitoring) of existing waste treatment
facilities; and the eighth plant can comply by upgrading design
and properly maintaining the existing waste treatment system.
The remaining eight plants, in addition to evaluating existing
treatment, would have to improve control of process wastewater
flow rates by implementing flow normalization to comply with BPT
mass limitations.
If the application of BPT.technology at specific plants does not
result in effluent concentrations sufficiently low to meet mass
discharge limitations, there are other available treatment alter-
natives, such as sulfide precipitation, carbonate precipitation
and ferrite co-precipitation, especially for mercury removal (see
Section VII, page 495) which could achieve lower effluent
concentrations than hydroxide .precipitation. Another way of
meeting the mass discharge limits is to reduce the discharge flow
either through process modification, in-process controls or reuse
of water.
Pollutant Removals and Costs
756
-------
In the establishment of BPT, the cost of application of
technology must be considered in relation to the pollutant
reduction benefits from such application. The quantity of
pollutants removed by BPT treatment are displayed in Table X-38
(page 889) and for direct dischargers in Table X-39 (page 890).
Total treatment costs are displayed in Table X-56 (page 907).
The capital cost of BPT treatment as an increment above the cost
of in place treatment equipment is estimated to be $308,768
($50294 for direct dischargers) for the zinc subcategory. Annual
cost of lime and settle technology for the zinc subcategory is
estimated to be $102,462 ($13219 for direct dischargers). The
quantity of pollutants removed by the BPT system for this
subcategory is estimated to be 9,887 kg/yr (2,274 for direct
dischargers) including 5,572 kg/yr (1,282 for direct dischargers)
of toxic metals. The pollutant reduction benefit is worth the
dollar cost of required BPT.
APPLICATION OF REGULATION IN PERMITS
The purpose of these limitations (and standards) is to form a
uniform national basis for regulating wastewater effluent from
the battery manufacturing category. For direct dischargers, the
regulations are implemented through NPDES permits. Because of
the many elements found in battery manufacturing and the apparent
complexity of the regulation, an example of applying these
limitations to determine the allowable discharge from battery
manufacturing is included.
Example. Plant Y manufactures nickel cadmium batteries using
pressed powder anodes and nickel impregnated cathodes. The plant
operates for 250 days during the year. The plant uses 55,800 kg
cadmium/yr in anode manufacture; 61,300 kg nickel/yr in cathode
manufacture; and produces 404,000 kg/yr of finished cells.
Table IX-52 (page 809) illustrates the calculation of the
allowable daily discharge of cadmium.
757
-------
TABLE IX-1
FLOW BASIS FOR BPT MASS DISCHARGE
LIMITATIONS - CADMIUM SUBCATEGOR!
Process Element
Anodes
00
Pasted 6 Pressed Powder
Electrodeposited
Impregnated
Cathodes
nickel Electrodeposited
Nickel Impregnated
Ancillary __Operations
Cell Wash
Electrolyte Preparation
Floor and Equipment Wash
Employee Wash
Cadmium Powder Production
Silver Powder Production
Cadmium Hydroxide Production
Nickel Hydroxide Production
BPT
Flow
(I/kg)
2.7
697.0
998.0
569.0
16HO.O
4.93
0.08
12.0
1.5
65.7
21.2
0.9
110.0
Mean Normalized
Discharge Flow
(I/kg)
2.7
697.0
998.0
569.0
1610.0
4.93
0.08
12.0
1.5
65.7
21.2
0.9
110.0
-------
TABLE IX-2
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Pasted and Pressed Powder Anodes
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of
cadmium
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*0il and Grease
*TSS
*pH
0.92
1.19
0.78
1.13
0.68
5. 18
1 .VI
3.94
0.57
54.0
111.0
Within the range of 7.5 -
0.41
0.49
0. 32
0.54
0.27
3.43
0.46
1 .65
0.24
32.4
52.65
10.0 at all times
*Regulated Pollutant
759
-------
TABLE IX-3
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 237.0 104.6
Chromium 306.7 125.5
Cyanide 202.1 83.6
Lead 292.7 139.4
Mercury 174.3 69.7
*Nickel 1338.2 885.2
Silver 285.8 118.5
*Zinc 1017.6 425.2
*Cobalt 146.4' 62.7
*Oil and Grease 13940.0 8364.0
*TSS 28577.0 13592.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
760
-------
TABLE IX-4
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Impregnated Anodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*Oil and Grease
*TSS
*pH Within
339.3
439. 1
289.4
419.2
249.5
1916.2
409.2
1457. 1
209.6
19960.0
40918.0
the range of
149.7
179.6
119.8
199.6
99.8
1267.5
169.7
608.8
89.8
11976.0
19461 .0
7.5 - 10.0 at all times
*Regulated Pollutant*
761
-------
TABLE IX-5
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Nickel Electrodeposited Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium 193.5 85.4
Chromium 250.4 102.4
Cyanide 165.0 68.3
Lead 239.0 113.8
Mercury 142.3 56.9
*Nickel 1092.5 722.6
Silver 233.3 96.7
*Zinc 830.7 347.1
*Cobalt 119.5 51.2
*0il and Grease 11380.0 6828.0
*TSS 23329.0 11095.5
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant *
762
-------
TABLE IX-6
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Nickel Impregnated Cathodes
Pollutant
Pollutant
Procterty
or
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*0il and grease
*TSS
*pH Within
557.6
721 .6
475.6
688.8
410.0
3148.8
672.4
2394.4
344.4
32800.0
67240.0
the range of 7.5 -
246.0
295.2
196.8
328.0
164.0
2082.8
278.8
1000.4
147.6
19680.0
31980.0
10.0 at all times
*Regulated Pollutant
763
-------
TABLE IX-7
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 1 .68 0.74
Chromium 2.17 0.89
Cyanide 1.43 0.59
Lead 2.07 0.99
Mercury 1.23 0.49
*Nickel 9.47 6.26
Silver 2.02 0.84
*Zinc 7.20 3.01
*Cobalt 1.04 0.44
*Oil and Grease 98.6 59.2
*TSS 202.1 96.1
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
764
-------
TABLE IX-8
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Electrolyte Preparation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.027 0.012
Chromium 0.035 0.014
Cyanide 0.023 0.009
Lead , 0.033 0.016
Mercury 0.020 0.008
*Nickel 0.153 0.101
Silver 0.032 0.013
*Zinc 0.116 0.048
*Cobalt 0.016 0.007
*Oil and Grease 1.60 0.960
*TSS 3.28 1.56
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
765
-------
TABLE IX-9
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Floor and Equipment Wash
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cell produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*Oil and Grease
*TSS
4
5
3
5
3
08
,28
,48
,04
,00
23.1
4.92
17.5
2.52
240.0
492.0
1 ,
2,
1 ,
2,
1 ,
80
16
44
40
20
15.2
2,
7
1 ,
04
32
08
*pH
Within the range of 7.5 -
144.0
234.0
10.0 at all times
*Regulated Pollutant
766
-------
TABLE IX-10
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.510 0.225
Chromium 0.660 0.270
Cyanide 0.435 0.180
Lead 0.630 0.300
Mercury 0.375 0.150
*Nickel 2.88 1.91
Silver 0.615 0.255
*Zinc 2.19 0.915
*Cobalt 0.315 0.135
*Oil and Grease 30.0 18.0
*TSS 61.5 29 3
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
767
-------
TABLE IX-11
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 6.29 2.77
Chromium 8.14 3.33
Cyanide 5.37 2.22
Lead 7.77 3.70
Mercury 4.63 1.85
*Nickel 35.54 23.50
Silver 7.59 3.15
*Zinc 27.02 11.29
*Cobalt 3.89 1.66
*Oil and Grease 370.20 222.12
*TSS 758.91 360.94
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
768
-------
TABLE IX-12
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Cadmium Powder Production
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - 16/1,000,000.16 of cadmium powder produced
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*0il and
*TSS
*pH
22,
28.
19,
27,
16,
126,
26
95,
13,
34
91
05
59
43
14
94
92
80
Grease
1314.0
2693.0
9
11
7
13
6
83
11
40
5
788
1281
86
83
88
14
57
44
17
08
91
4
2
Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
769
-------
TABLE IX-13
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
*Cadmium 7.21 3.18
Chromium 9.33 3.82
Cyanide 6.15 2.54
Lead 8.91 4.24
Mercury 5.30 2.12
*Nickel 40.70 26.92
*Silver 8.69 3.61
*Zinc 30.95 12.93
*Cobalt 4.45 1.91
*0il and Grease 424.0 254.4
*TSS 869.2 413.4
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
770
-------
TABLE IX-14
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Cadmium Hydroxide Production
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*0il and Grease
*TSS
0.31
0.40
0.26
0.38
0.23
1 .73
0.37
1 .31
0.19
18.0
36.9
0,
0.
0,
0,
0.
1,
0,
0,
0,
10,
17.
14
16
1 1
18
09
14
15
55
08
8
6
Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
771
-------
TABLE IX-15
CADMIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Nickel Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
*Cadmium 37.4 16.5
Chromium 48.4 19.8
Cyanide 31.9 13.2
Lead '46.2 22.0
Mercury 27.,5 11.0
*Nickel 211.2 139.7
Silver 45.1 18.7
*Zinc 160.6 67.1
*Cobalt 23.1 . 9.9
*0il and Grease 2200.0 1320.0
*TSS . 4510.0 2145.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
772
-------
TABLE IX-16
COMPARISON OF ACTUAL TO BPT ANNUAL PLOW
AT CADMIUM SOBCAT1GORY PLANTS
Plant ID Actual flow BPT Annual Flow
i10*l (1/yr) (10*1
A 0.17 0.909 V
B 3.0 1.14
C 156.0 153.0
D 13,5 102.0 1/
E 48.1 189.0
F 321.0 315.0
G 0.0 0.188
H 10.5 10.6
I 50.5 59.0
J 0.0 <. 00005
K 1.72 1.34
L 22.1 39.9
M 0.0 2/
]/ No longer active in the cadmium subcategory
2/ since actual flow rate was zero, and plant is now closed, the
calculation of BPT annual flow is insignificant.
-------
TABLE IX-17
FLOW BASIS FOR BPT MASS
DISCHARGE LIMITATIONS - CALCIUM SUBCATEGORY
Process Element
Mcillar¥_ggeratiQn3
Heat Paper Production
BPT Flow
24.1
Mean Normalized
Discharge Flow
(I/kg)
115.4
Cell Testing
0.014
0.014
-------
TABLE IX-18
CALCIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Heat Paper Production and Cell Testing
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of reactants
English Units - lb/1,000,000 Ib .of reactants
Chromium 10.61 4.34
TSS 988.7 470.2
pH Within the range of 7.-5 - 10.0 at all times
775
-------
TABLE IX-19
LECLANCHE SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Foliar Battery Miscellaneous Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.092 0.038
Cadmium 0.013 0.005
Chromium 0.024 0.010
Copper 0.084 0.040
Lead 0.018 0.009
Mercury 0.010 0.004
Nickel 0.036 0.024
Selenium 0.054 0.024
Zinc 0.067 0.030
Manganese 0.019 0.015
Oil and Grease 0.66 0.66
TSS 0.99 0.79
pH Within the range of 7.5 - 10.0 at all times
776
-------
TABLE IX-20
FLOW BASIS FOR BPT MASS DISCHARGE
LIMITATIONS - LITHIUM SUBCATEGORY
Process Element
BPT FLOW
(1/kq)
Mean Normalized
Discharge Flow
(I/kg)
Cathodes
Iron Disulfide
lead Iodide
7.54
63.08
7.54
63.08
Ancillary Operation
Heat Paper Production
Lithium Scrap Disposal
Cell Testing
Cell wash
Air Scrubbers
Floor and Eguipment Wash
24.1 1/
* ~
0.014 I/
0.0
10.59
0.094 2/
115.4
*
0.014
0.929
10.59
0.094
* Cannot be calculated at present time.
J/ Same as for calcium subcategory
2/ Same as for magnesium subcategory
-------
TABLE IX-21
LITHIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Iron Bisulfide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib iron disulfide
Chromium 3.32 1 .36
Lead 3.17 1.51
Zinc 11.01 4.60
Cobalt 1.58 0.68
Iron 9.05 4.60
TSS 309.1 147.0
pH Within the range of 7.5 - 10.0 at all times
778
-------
TABLE IX-22
LITHIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Lead Iodide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
Chromium 27.8 11.4
Lead 26.5 12.6
Zinc 92.1 38.5
Cobalt 13.3 5.68
Iron 75.7 38.5
TSS 2586.3 1230.1
pH Within the range of 7.5 - 10.0 at all times
779
-------
TABLE IX-23
LITHIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Heat Paper Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of reactants
English Units - lb/1,000,000 Ib of reactants
Chromium 10.6 4.34
Lead 10.1 4.82
Zinc 35.2 14.7
Cobalt 5.06 2.17
Iron 28.9 14.7
TSS 988.1 470.0
pH Within the range of 7.5 - 10.0 at all times
780
-------
TABLE IX-24
LITHIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.047 0.019
Lead 0.045 0.021
Zinc 0.16 0.065
Cobalt 0.022 0.009
Iron 0.13 0.065
TSS 4.43 2.11
pH Within the range of 7.5 - 10.0 at all times
781
-------
TABLE IX-25
LITHIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Air Scrubbers
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 4.66 1.91
Lead 4.45 2.12
Zinc 15.46 6.46
Cobalt 2.22 0.95
Iron 12.71 6.46
TSS 434.2 206.5
pH Within the range of 7.5 - 10.0 at all times
782
-------
TABLE IX-26
FLOWS BASIS FOR BPT MASS
DISCHARGE LIMITATIONS - MAGNESIUM SUBCATEGORY
oo
LO
Process Element
Cathodes,
Silver Chloride-Chemically
Reduced
Silver Chloride-Electrolytic
Oxidation
Ancillary_OperatiQns_
Air Scrubbers
Cell Testing
Flcor and Equipment Wash
Heat Paper Production
Mean Normalized
Discharge (I/kg)
4915.0
145.0
206.5
52.6
0.094
115.4
BPT Flow
(I/kg)
2458.0
145.0
206.5
52.6
0.094
24.1 1/
Same as for calcium subcategory
-------
TABLE IX-27
MAGNESIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Chloride Cathodes - Chemically Reduced
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 1081.5 442.4
Lead 1032.4 491.6
Nickel 4719.4 3121.7
Silver 1007.8 417.9
Iron 2949.6 1499.4
TSS 100700.0 47931.0
COD 122900.0 59975.0
pH Within the range of 7.5 - 10.0 at all times
784
-------
TABLE IX-28
MAGNESIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Chloride Cathodes - Electrolytic
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum
monthly
for
average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 63.8
Lead 60.9
Nickel 278.4
Silver 59.5
Iron 174.0
TSS 5945.0
COD 7250.0
pH Within the range of 7.5
26.1
29.0
184.2
24.7
88.5
2828.0
3538.0
10.0 at all times
785
-------
TABLE IX-29
MAGNESIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Floor and Equipment Wash
Pollutant or
Pollutant Maximum 'for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.041 0,016
Lead 0.039 0.018
Nickel 0.180 0.119
Silver -0.038 0.015
Iron 0.112 0.057
TSS 3.85 1.83
pH Within the range of 7.5 - 10.0 at all times
786
-------
TABLE IX-30
MAFNESIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Cell Testing
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 23.2 9.47
Lead 22.1 10.5
Nickel 101.0 66.8
Silver 21.6 8.94
Iron 63.1 32.1
TSS 2157.0 1026.0
pH Within the range of 7.5 - 10.0 at all times
787
-------
TABLE IX-31
. MAGNESIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Heat Paper Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of reactants
English Units - lb/1,000,000 Ib of reactants
Chromium 10.6 4.34
Lead 10.1 4.82
Nickel 46.3 30.6
Silver 9.88 4.10
Iron 29.9 14.7
TSS 988.1 470.0
pH Within the range of 7.5 - 10.0 at all times
788
-------
TABLE IX-32
MAGNESIUM SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Air Scrubbers
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 90.9 37.2
Lead 86.7 41.3
Nickel 396.5 262.3
Silver 84.7 35.1
Iron 247.8 126.0
TSS 8467.0 4027.0
pH Within the range of 7.5 - 10.0 at all times
789
-------
TABLE IX-33
FLOWS BASIS FOR EPT
MASS DISCHARGE LIMITATIONS - ZINC SOBCATEGORY
vo
o
Process Element
Anodes
Zinc Powder-Wet Amalgamated
Zinc Powder-Gelled
Amalgam
Zinc Oxide Powder-Pasted
or Pressed, Reduced
(Zinc Oxide, Formed)
Zinc Electrodeposited
Cathodes
Silver Powder Pressed and
Electrolytically Oxi-
dized (Silver Powder,
Fornred)
Silver Oxide Powder-Thermal-
mally Reduced or Sin-
tered, Electrolytically
formed (Silver Oxide
Powder, Formed)
Silver Peroxide Powder
Nickel Impregnated
Ancillary Operations
Cell Hash
Electrolyte Preparation
Silver Etch
Mandatory Employee Hash
Reject Cell Handling
Floor and Equipment Hash
Silver Peroxide Production
Silver Powder Production
BPT
Flew (I/kg)
3.8
0.68
143.0
3190.0
196.0
131.0
31.4
1640.0
1.13
0.12
49.1
0.27
0.01
7.23
52.2
21.2
Mean Normalized
Flow (I/kg)
3.8
0.68
143.0
3190.0
196.0
131.0
31.4
1640.0
1.13
0.12
49.1
0.27
0.01
7.23
52.2
21.2
-------
TABLE IX-34
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Wet Amalgamated Powder Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 10.9 4.86
Cadmium 1.29 0.57
*Chromium 1.67 0.68
Copper 7.22 3.80
Lead 1.60 0.76
*Mercury 0.95 0.38
Nickel 7.30 4.83
Selenium 4.67 2.09
*Silver 1.56 0.65
*Zinc 5.55 2.32
Aluminum 24.4 12.2
Iron 4.56 2.32
*Manganese 2.58 1.10
*0il and Grease 76.0 45.6
*TSS 155.8 74.1
*pH Within the range 7.5 - 10.0 at all times
*Regulated Pollutant
791
-------
TABLE IX-35
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Gelled Amalgam Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 1.95 0.87
Cadmium 0.23 0.10
*Chromium 0.30 0.12
Copper 1.29 0.68
Lead 0.29 0.14
*Mercury 0.17 0.07
Nickel 1.31 0.86
Selenium 0.84 0.37
*Silver 0.28 0.12
*Zinc 0.99 0.42
Aluminum 4.37 2.18
Iron 0.82 0.42
*Manganese 0.46 0.20
*Oil and Grease 13.6 8.16
*TSS 27.9 13.26
*pH Within the range of 7.5 - 10.0 at all times
*Regula"ted Pollutant
792
-------
TABLE IX-36
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Zinc Oxide Anodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 410.4 183.1
Cadmium 48.6 21.5
*Chromium 62.9 25.7
Copper 271.7 143.0
Lead 60.1 28.6
*Mercury 35.8 14.3
Nickel 274.6 181.6
Selenium 175.9 78.7
*Silver 58.7 24.3
*Zinc 208.8 87.2
Aluminum 919.5 457.6
Iron 171.6 87.2
*Manganese 208.8 87.2
*0il and Grease 2860.0 1716.0
*TSS 5863.0 2789.0
*pH Within the range 7.5 - 10.0 at all times
*Regulated Pollutant
793
-------
TABLE IX-37
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Electrodeposited Anodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
*pH Within
the
9155
1085
1404
6061
1340
798
6125
3924
1308
4657
20510
3828
2169
63800
130700
range
0
0
0
0
0
0
0
0
0
0
0
0
0
0
00
of 7
5 -
4083
478
574
3190
638
319
4051
1755
543
1946
10208
1946
925
38280
62210
10.0 at
0
5
0
0
0
0
0
0
0
0
0
0
0
0
0
all
times
*Regulated Pollutant
794
-------
TABLE IX-38
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Powder Cathodes,Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 562.5 250.9
Cadmium 66.7 29.4
*Chromium 86.2 35.3
Copper 372.4 196.0
Lead 82.3 39.2
*Mercury 49.0 19.6
Nickel 376.3 248.9
Selenium 241.1 107.8
*Silver 80.4 33.3
*Zinc 286.2 119.6
Aluminum 1260.0 627.2
Iron 235.2' 119.6
*Manganese 133.3 56.8
*Oil and Grease 3920.0 . 2350.0
*TSS 8036.0 3822.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
795
-------
TABLE IX-39
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Oxide Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 376.0 167.7
Cadmium 44.6 19.7
*Chromium 57.7 23.6
Copper 248.9 131.0
Lead 55.0 26.2
*Mercury 32.8 13.1
Nickel 251.5 166.4
Selenium 161.1 72.1
*Silver 53.7 22.3
*Zinc 191.3 79.9
Aluminum 842.3 419.2
Iron 157.2 79.9
*Manganese 89.1 38.0
*Oil and Grease 2620.0 1570.0
*TSS 5370.0 2554.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
796
-------
TABLE IX-40
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Peroxide Cathodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
90.1
10.7
13.8
59.7
13.2
7.85
60.3
38.6
12.9
45.8
202.0
37,
21 ,
628.0
1287.0
7
4
40,
4,
5,
31 ,
6,
3,
39.
17,
5,
19.
101 ,
19,
9,
377.
612,
2
71
65
4
28
14
9
3
34
2
0
2
1 1
0
0
"pH
Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
797
-------
TABLE IX-41
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Nickel Impregnated Cathodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
*pH Within the
4707.0
557.6
721 .6
3116.0
688.8
410.0
3149.0
2017.0
672.4
2394.4
10545.0
1968.0
1115.2
32800.0
- 67240.0
range of 7.5
2099.0
246.0
295.2
1640.0
328.0
164.0
2083.0
902.0
279.0
1000.4
5248.0
1001.0
475.6
19680.0
31980.0
10.0 at all times
*Regulated Pollutant
798
-------
TABLE IX-42
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,0.00,000 Ib of cells produced
Arsenic 3.24 1.45
Cadmium 0.38 0.17
*Chromium 0.50 0.20
Copper 2.15 1.13
*Cyanide 0.33 0.14
Lead 0.48 0.23
*Mercury 0.28 0.11
*Nickel 2.17 1.44
Selenium 1.39 0.62
*Silver 0.46 0.19
*Zinc 1.65 0.69
Aluminum 7.27 3.62
Iron 1.36 0.69
*Manganese 0.77 0.33
*0il and Grease 22.6 13.6
*TSS 46.3 22.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
799
-------
TABLE IX-43
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Electrolyte Preparation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - rag/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.344 0.153
Cadmium 0.040 0.018
*Chromium 0.052 0.021
Copper 0.228 0.120
*Cyanide 0.035 0.015
Lead 0.050 0.024
*Mercury 0.030 0.012
*Nickel 0.230 0.152
Selenium 0.147 0.066
*Silver 0.049 0.020
*Zinc 0.175 0.073
Aluminum 0.771 0.384
Iron 0.144 0.073
*Manganese 0.081 0.034
*Oil and Grease 2.40 1.44
*TSS 4.92 2.34
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
800
-------
TABLE IX-44
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Etch
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
141 ,
16,
21 .
93,
20,
12,
94
60,
20
71 ,
315
58
33
982
2013
Within the range of 7.5 -
62.9
7.37
8.84
49. 1
9.82
4.91
62.4
27.0
8.35
30.0
157. 1
30.0
14.3
589.2
957.5
10.0 at all times
*Regulated Pollutant
801
-------
TABLE IX-45
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic 0.774 0.345
Cadmium 0.091 0.040
*Chromium 0.118 0.048
Copper 0.513 0.270
*Cyanide 0.078 0.033
Lead 0.113 0.054
*Mercury 0.067 0.027
*Nickel 0.518 0.342
Selenium 0.332 0.148
*Silver 0.110 0.045
*Zinc 0.394 0.164
Aluminum 1.74 0.864
Iron 0.324 0.164
*Manganese 0.183 0.078
*0il and Grease 5.40 3s24
*TSS 11.1 5.27
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
802
-------
TABLE IX-46
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Reject Cell Handling
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic 0.028 0.012
Cadmium 0.003 0.001
*Chromium 0.004 0.001
Copper 0.019 0.010
*Cyanide 0.003 0.001
Lead 0.004 0.002
*Mercury 0.002 0.001
*Nickel 0.019 0.012
Selenium 0.012 0.005
*Silver 0.004 0.001
*Zinc 0.014 0.006
Aluminum 0.064 0.032
Iron 0.012 0.006
*Manganese 0.006 0.002
*0il and Grease 0.200 0.120
*TSS 0.416 0.195
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
803
-------
TABLE IX-47
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 20.8 9.26
Cadmium 2.46 1.09
*Chromium 3.18 1.30
Copper 13.7 7.23
*Cyanide 2.10 0.87
Lead 3.04 1.45
*Mercury 1.81 0.72
*Nickel 13.9 9.18
Selenium 8.89 3.98
*Silver 2.96 1.23
*Zinc 10.6 4.41
Aluminum 46.5 23.1
Iron 8.68 4.41
*Manganese 4.92 2.10
*0il and Grease 145.0 86.8
*TSS 297.0 141.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
804
-------
TABLE IX-48
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic
Cadmium
*Chromium
Copper
*Cyanide
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil. and Grease
*TSS
25,
2,
3
16,
2,
3,
2,
16,
10,
3,
12,
56,
10,
5.
175,
14
98
85
65
54
68
19
82
78
59
79
33
51
96
20
359.16
11 .
1 .
1 .
8.
1.
1 .
0,
11 .
4.
1 .
5.
28,
5.
2,
105,
170,
21
32
58
76
05
75
88
12
82
49
34
03
34
54
12
82
Within the limits of 7.5 - 10.0 at all times
*Regulated Pollutant
805
-------
TABLE IX-49
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Peroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Arsenic 150.0 66.8
Cadminum 17.8 7.83
*Chromium 23.0 9.40
Copper 99.2 52.2
Lead 21.9 10.5
*Mercury 13.1 5.22
Nickel 100.0 66.3
Selenium 64.2 28.7
*Silver 21.4 8.88
*Zinc 76.2 31.8
Aluminum 336.0 167.1
Iron 62.7 31.9
*Manganese 35.5 15.1
*0il and Grease 1044.0 627.0
*TSS 2140.0 1018.0
*pH Within the range of 7,5 - 10.0 at all times
*Regulated Pollutant
806
-------
TABLE IX-50
ZINC SUBCATEGORY
BPT EFFLUENT LIMITATIONS
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly .average,
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver
powder produced
Arsenic 60.85 27.14
Cadmium 7.21 3.18
*Chromium 9.33 3.82
Copper 40.28 21.20
Lead 8.91 4.24
*Mercury 5.30 2.12
Nickel 40.71 26.93
Selenium 26.08 11 .66
*Silver 8.69 3.61
*Zinc 30.95 12.93
Aluminum 136.3 67.84
Iron 25.44 12.93
*Manganese 14.42 6.15
*Oil and Grease 424.0 254.4
*TSS 869.0 413.4
*pH Within the range 7.5 - 10.0 at all times
*Regulated Pollutant
807
-------
TABLE IX-51
COMPARISON OF ACTUAL TO BPT ANNUM. FLOW
Al ZINC SUBCATEGORY PLANTS
Plant ID Actual Flow BPT Annual Flow
(1/yrl (10*1 (1/yr) (10*1
A 1.69 0.826
B 32.5 3.21
C 0.787 0.530
D 39.4 2.94
E 10.6 6.77
F 2.22 12.6
G 15.3 0.181
oo H 0.266 1.81
g I 0.0 0.0
J 0.0032 0.0151
K 10.1 21.0
L 2.70 2.17
M 0.0 0.0
N 1.71 2.71
0 1.11 1.96
P 1.72 3.67
-------
TABLE IX-52
SAMPLE DERIVATION OF THE BPT 1-DAY CADMIUM LIMITATION FOR PLANT Y
Process Elements
PNP
PNP
kg/yr
Avg. PNP
(kg/day)
1-Day Limits
(mg/kg)l/
Cadmium Mass
Discharge(mg/day).!/
oo
o
1. Pasted & Pressed
Povrfer Anode
Wgt. of
Cadmium Used
55800
2. Nickel Iirpregnated Wgt. of 61300
Cathode Nickel Applied
3, Electrolyte
Preparation
4. Floor Equipment
Wash
Wgt. of Cells 404000
Produced
223
245
1616
0.864
524.8
5.923
193
128576
9572
Total Plant Y Discharge (1-Day Value for Cadmium):
138341 ing/day
{0.3 Ib/day)
I/ I/kg values used from Table IX-1 multiplied by lime and settle treatment
concentrations (mg/l) from Table ¥11-20.
2/ Average PNP multiplied by the 1-day limits in Table IX-2, Table IX~6 , and BC-10A.
-------
UME OR ACID
ADDITION
ALL PROCESS
WASTEWATER
DISCHARGE
CHEMICAL
PRECIPITATION
<=£>
REMOVAL OF
OIL AND GREASE
SLUDGE TO
RECLAIM OR
DISPOSAL
SLUDGE
DEWATERING
00
o
RECOMMENDED IN-PROCESS TECHNOLOGY:
RECYCLE OR REUSE OF PROCESS SOLUTIONS
SEGREGATION OF NON-CONTACT COOLING WATER FROM PROCESS WATER
CONTROL ELECTROLYTE DRIPS AND SPILLS
FIGURE IX-1. CADMIUM SUBCATEGORY BPT TREATMENT
-------
CELL TESTING
WASTEWATER
HEAT PAPER
PRODUCTION
WASTEWATER
CHEMICAL
ADDITION
SETTLING
LIME
ADDITION
SLUDGE
CHEMICAL
PRECIPITATION
SEDIMENTATION
DISCHARGE
FILTRATE
SLUDGE
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
FIGURE IX-2. CALCIUM SUBCATEGORY BPT TREATMENT
-------
BACKWASH
FOLIAR BATTERY
MISCELLANEOUS WASH
WASTEWATER
/ / /
3V
SKIMMING
00
NO
1
REMOVAL OF
OIL AND GREASE
LIME OR ACID
ADDITION
CHEMICAL
PRECIPITATION
06
SEDIMENTATION
DISCHARGE
SLUDGE
FILTRATE
SLUDGE TO
RECLAIM OR
DISPOSAL
SLUDGE
DEWATERING
OTHER WASTEWATERS:
RECYCLE AND REUSE EITHER WITHIN THE PROCESS
OR FOLLOWING CHEMICAL PRECIPITATION AND
SETTLING END-OF-PIPE TREATMENT.
FIGURE IX-3. L.ECLANCHE SUBCATEGORY BPT TREATMENT
-------
STREAM A
CHEMICAL
ADDITION
HEAT PAPER
LIME
ADDITION
WASTEWATER
SETTLING
«•-
^-A^V^X^-A.
CHROMIUM
REDUCTION
SLUDGE
/
CHEMICAL
PRECIPITATION
«&>
SEDIMENTATION
DISCHARGE
SLUDGE
FILTRATE
ALTERNATE
STREAM B
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
LIME OR ACID
ADDITION
00
PROCESS
WASTEWATERS FROM:
IRON DISULF1DE CATHODE
LEAD IODIDE CATHODE
CELL TESTING
LITHIUM SCRAP DISPOSAL
FLOOR AND EQUIPMENT WASH
STREAM C
PROCESS WASTEWATERS
FROM AIR SCRUBBERS
AIR!
1
5H
LIME
ADDITION
h>*>t>LCA^V**>
CHEMICAL
PRECIPITATION
<=£=>
•*-
SEDIMENTATION
L*"*t**c£
FILTRATE
SLUDGE
^(
-DISCHARGE
AERATION
(O O O O O
Ift Q q Q y
CHEMICAL
PRECIPITATION
<=»&>
SLUDGE
DEWATEHING
SLUDGE TO
DISPOSAL
- DISCHARGE
SLUDGE TO DISPOSAL
FIGURE IX-4. LITHIUM SUBCATEGORY BPT TREATMENT
-------
CO
CHEMICAL
MEAT PAPER
PRODUCTION
WASTEWATER
SLUDGE TO
BISPOSAL
SLUDGE
DEWATGRING
STREAM B
SILVER CHLORIDE
CATHODE PRODUCTION
WASTEWATER
SPENT PROCESS SOLUTION
RECOMMENDED IN-PROCESS
TECHNOLOGY: RINSE WATER
HOLDING
TANK
BLi
:ED
KMno4
S_A-A^A^CA_A-A.
OXIDATION
<=4
CELL TESTING
FLOOR AND EQUrPMENT WASH
LIME OR ACID
ADDITION
-A^AW^LA^^.
CHEMICAL
PRECIPITATION
SEDIMENTATION
DISCHARGE
»_
SLUDGE
FILTRATE
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
STREAM C
LIME
ADDITION
PROCESS WASTEWATERS FROM:
AIR SCRUBBERS
1
I /
-A^A^*>^CA_A«^
CHEMICAL
PRECIPITATION
cafe,
FILTRATE
•AwAMA^*^A-'V^*w'^
SEDIMENTATION
SLUDGE
S(
^-DISCHARGE
SLUDGE TO
DISPOSAL
FIGURE 1X-5. MAGNESIUM SUBCATEGORY BPT TREATMENT
-------
LIME OR ACID
ADDITION
ALL PROCESS WASTEWATER
SEDIMENTATION
DISCHARGE
REMOVAL OF
OIL AND GREASE
FILTRATE
SLUDGE
•*\l 1
00
SLUDGE TO
RECLAIM OR
DISPOSAL
SLUDGE
DEWATERING
RECOMMENDED
IN-PROCESS TECHNOLOGY:
REUSE OF PROCESS SOLUTIONS
SEGREGATION OF NON-CONTACT COOLING WATER
SEGREGATION OF ORGANIC-BEARING CELL CLEANING WASTEWATER
CONTROL ELECTROLYTE DRIPS AND SPILLS
ELIMINATE CHROMATES IN CELL WASHING
FLOW CONTROLS FOR RINSE WATERS
FIGURE IX-6. ZINC SUBCATEGORY BPT TREATMENT
-------
vo
00
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
The effluent limitations presented in this section apply to
existing direct dischargers. A direct discharger is a site which
discharges or may discharge pollutants into waters of the United
States. These effluent limitations which were to be achieved by
July 1, 1984, are based on the best available control and
treatment employed by a specific point source within the
industrial category or subcategory, or by another industry where
it is readily transferrable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently employed for BPT, as well as improvements in reagent
control, process control, and treatment technology optimization.
The factors considered in assessing the best available technology
economically achievable (BAT) include the age of equipment and
plants involved, the processes employed, process changes, non-
water quality environmental impacts (including energy
requirements), and the costs of application of such technology
(Section 304 (b) (2) (B)). In general, the BAT technology level
represents, at a minimum, the best existing economically
achievable performance of plants of various ages, sizes,
processes or other shared characteristics. As with BPT, in those
subcategories where existing performance is universally
inadequate, BAT may be transferred from a different subcategory
or category. BAT may include process changes or internal
controls, even when not common industry practice. This level of
technology also considers those plants processes and control and
treatment technologies which at pilot plant and other levels have
demonstrated both technological performance and economic
viability at a level sufficient to justify investigation.
TECHNICAL APPROACH TO BAT
In pursuing effluent limitations for the battery manufacturing
category, the Agency desired to review a wide range of BAT
technology options. To accomplish this, the Agency elected to
develop significant technology options which might be applied to
battery manufacturing wastewater as BAT. These options were to
consider the range of technologies which were available and
applicable to the battery manufacturing subcategories, and to
suggest technology trains which would reduce the discharge of
toxic pollutants remaining after application of BPT. The
statuatory assessment of BAT considers costs, but does not
require a balancing of costs against effluent reduction benefits
[see Weyerhaeuser v. Costle, 11 ERC 2149 (D.C. Cir. 1978)].
817
-------
In a draft development document that was given limited
circulation in September, 1980 to battery manufacturers and
others who requested to receive a copy, a number of alternative
BAT systems were described for each subcategory. Comments from
this limited, but technically knowledgeable audience were used,
together with further review and analysis of available data, in
refining these alternatives and in making the selection of a
specific BAT option for each subcategory. Some options
originally presented in the draft development document were
eliminated from consideration, and others were modified on the
basis of comments received and other reevaluation prior to the
final selection of BAT options.
At proposal, generally favorable comments were received on the
subcategories included in this volume of the development
document. The Leclanche subcategory was reevaluated after
receiving comments on foliar battery production.
As discussed in Section IX treatment technology options are
described in detail for all subcategories even though there may
be no direct discharge plants in that subcategory. In general,
three levels of treatment technologies, or options, were
evaluated for each subcategory. The technology options
considered build on BPT (also referred to as option 0, as
described in Section IX), generally providing improved in-process
control to reduce or eliminate wastewater and improved end-of-
pipe treatment to reduce the pollutant concentration in treated
wastewaters. For one subcategory, the selected technology option
provides for no discharge of process wastewater pollutants from
all process elements. Other subcategory selected 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. The wastewater treatment technology options
considered vary among subcategories. This variation stems from
differences in wastewater flow and process characteristics. As a
general case - with variations already noted in each subcategory
- BPT (option 0) relied upon lime and settle technology applied
to the average flow from each manufacturing process element. The
BAT options build upon this base using greater wastewater flow
reduction gained from in-process controls; lime, settle and
filter technology to reduce effluent concentrations of
pollutants; augmented filtration; and increased recycle to
achieve lower discharge levels of toxic and other pollutants.
Waste segregation and separate treatment are also considered
where recycle can be substantially improved or where separate
treatment has other obvious environmental benefits.
818
-------
REGULATED POLLUTANT PARAMETERS
The toxic pollutants listed in Tables VI-1 and VI-2 (pages 488
and 493) for regulatory consideration were used to select the
specific pollutants regulated in each subcategory. The selection
of toxic pollutants for regulation was based primarily upon the
presence of the pollutant at high concentrations throughout a
subcategory and secondly on the pollutant concentrations in
specific process elements. Other pollutants, not specifically
regulated, would also be controlled by the removal of the
selected pollutants. The overall costs for monitoring and
analysis would therefore be reduced. Nonconventional pollutants
are regulated as appropriate when found at treatable
concentrations. Conventional pollutants (pH, TSS and O&G) are
not regulated under BAT, except where one might be used as a
indicator, but are generally considered under BCT. In the
limitation tables all the pollutants which were considered for
regulation are listed and those selected for regulation are *'d.
CADMIUM SUBCATEGORY
EPA has considered four technology options for the cadmium
subcategory. The first three build upon BPT (option 0) and
represent incremental improvements in pollutant discharge
reduction from the lime and settle technology level. The fourth,
based on a system recently implemented at one cadmium subcategory
plant, provides no discharge of process wastewater pollutants.
BAT Options Summary
Option 0 for this subcategory (Figure IX-1, Page 810) consists of
the following technology:
a) In-process technology:
- recycle or reuse of process solutions
segregation of noncontact cooling water
control of electrolyte drips and spills
b) End-of-pipe treatment:
oil skimming
chemical precipitation
sedimentation
sludge dewatering
Option 1 (Figure X-l, page 908) includes all aspects of option 0
and builds on it by adding the following:
a) In-process technology:
recycle or reuse pasted and pressed powder anode
wastewater
use dry methods to clean floors and equipment
819
-------
- control rinse flow rates
- recirculate water in air scrubbers
- dry clean impregnated electrodes
- ' reduce cell wash water use
- apply countercurrent rinse to silver powder
and cadmium powder
- apply countercurrent rinse for sintered and
electrodeposited anodes and cathodes
b) End-of-pipe treatment remains unchanged from option 0.
Option 2 (Figure X-2, page 909) builds on and includes all
of the technology and treatment of option 1:
• a) In-process technology is identical to option 1.
b) End-of-pipe treatment in addition to option 1:
- polishing filtration (mixed media)
Option 3 (Figure X-3, page 910) is based on further
improvement in both in-process control and end-of-pipe treatment.
a) In-process technology:
- continue all option 1 in-process technology
- reduce rework of cadmium powder
b) End-of-pipe treatment:
- oil skimming
- chemical precipitation
- filtration
- reverse osmosis (alternate, ion exchange) with
recycle of permeate
- chemical precipitation of brine
- sedimentation
polishing filtration (mixed media)
- sludge dewatering
Option 4 (Figure X-4, page 911) builds on option 3 by improving
the treatment of brine or regenerate to achieve no discharge of
process wastewater pollutant:
a) In-process technology:
- continue all in-process technology from option 3
- eliminate impregnation rinse discharge by
recovering used caustic.
b) End-of-pipe treatment:
oil skimming
- chemical precipitation
- sedimentation
- filtration
- sludge dewatering
- reverse osmosis (alternate, ion exchange) with
recycle of permeate
820
-------
evaporation with recycle of distillate
centrifugation of concentrate liquor solids
landfill dry solids.
Option 1
Option 1 builds on BPT by modifying processes to reduce the
amount of wastewater which is generated and must be treated. The
in-process technology and its application to specific process
elements to achieve the wastewater flow reductions for option 1
are discussed individually.
Countercurrent rinsing is applied for the removal of soluble
contaminants from metal powders and from sintered and
electrodeposited electrodes. Countercurrent cascade rinsing is
most frequently considered as a technique to more efficiently use
rinse water in metal finishing. It is equally effective in many
battery manufacturing operations. Almost any level of rinsing
efficiency can be obtained by providing enough countercurrent
cascading steps. In practice, more than ten cascade steps are
only rarely seen; two to three are usually adequate.
Industrywide, the lowest water use in rinsing sintered plaques is
achieved at one plant using three-stage countercurrent cascade
rinsing; another achieved a water use reduction of more than an
order of magnitude after instituting six-stage countercurrent
rinsing. A water reduction ratio of 6.6 is used as a
conservative estimate of the benefit of countercurrent cascade
rinsing. This can generally be achieved with two or three rinse
stages. A theoretical discussion of countercurrent rinsing is
included in Section VII.
Controlling rinse flow rates can substantially reduce excess and
unnecessary water use. Technology (actually techniques) includes
limited or controlled rinse flow, water shut off when not
actually being used, proper sizing of rinse tanks to parts being
rinsed, and other common sense types of water control.
Pasted and pressed powder anodes generate a small amount of
wastewater from tool cleaning, floor washing and related
activities. This- small volume of wastes can be introduced into
the product paste mix after gravity filtering through a paper
filter to remove suspended solids. This practice for dealing
with small amounts of tool cleaning and related wastes is
commonly practiced throughout many battery manufacturing
subcategories and is the basis for achieving zero discharge of
wastewater pollutants as is required at BAT.
Electrodeposited anodes and electrodeposited cathodes are
extensively rinsed and cleaned. Controlling reuse water flow
rates to correspond to production rather than allowing excessive
821
-------
flows at low or no production will reduce the mean water use to
"232 I/kg for the anodes and 218 I/kg for the cathodes. Applying
countercurrent cascade rinsing at a conservative water use
reduction will further reduce the water generation by a factor of
6.6 reducing the wastewater generation to 35.15 I/kg for the
anodes and 33.0 I/kg for the cathodes.
Impregnated anodes and impregnated cathodes are extensively
rinsed and cleaned, and also require extensive air scrubbing of
the process area vent gases. Both anode and cathode manufacture
have similar manufacturing and water use requirements. When data
from both electrodes at BPT is combined and averaged/ the
normalized flow is 1320 I/kg, Recirculating water to air
scrubbers is a widely used mechanism to reduce the amount of
water used. Varying degrees of recirculation are frequently
used. In-stream treatment to remove unwanted materials often
allows air scrubbers to be operated without discharging process
wastewaters. Using dry cleaning techniques, recirculating
scrubber water, and applying countercurrent cascade rinsing
reduces the wastewater from these two process elements to 200
I/kg.
Dry floor and equipment cleaning methods can be used to clean
process area floors and equipment. Floor and equipment cleaning
methods have been observed to vary from water flushing using high
pressure hoses and large quantities of water to dry vacuuming in
which no water is used. Even when wet floor and equipment
cleaning methods are used, the wastewater can be treated and
reused, thereby achieving zero discharge of wastewater
pollutants. Applying these techniques will eliminate the
generation of floor and equipment wastewater.
Cell wash water reduction can be achieved by using recirculated
washing solution and countercurrent cascade rinsing of cells. A
conservative water reduction rate of 6.6 is used to reduce
wastewater flow to 0.75 I/kg.
Cadmium powder production requires adherence to quality control
procedures and also requires substantial washing of the powder to
remove impurities. Where observed, quality control was
inadequate and water flow control was nonexistent. This
production process can be made more efficient by providing
adequate quality control, by controlling rinse flows, and by
applying • countercurrent cascade rinsing. Applying these
techniques will reduce the wastewater flow to 6.57 I/kg.
Silver powder, cadmium hydroxide and nickel hydroxide production
require substantial washing to remove impurities. This washing
process can be made more water efficient by applying
countercurrent cascade rinsing. If a conservative water
822
-------
reduction of 6.6 is used the wastewater flows for these elements
become 3.21 I/kg, 0.14 I/kg and 16.5 I/kg, respectively.
Reduction in wastewater generation achieved using these
in-process technologies are detailed for this and other options
in Table X-l (page 850).
Option 2_
Option 2 builds on option 1 and includes all of the in-process
technologies and end-of-pipe treatment used in option 1. In
addition, a polishing filter of the mixed media type is added to
reduce the discharge of toxic metals and incidentally to reduce
the discharge of suspended solids.
Option 3_
Option 3 generally builds on option 2 with substantial changes in
the end-of-pipe treatment. Additional in-process technology is
suggested for cadmium powder production to reduce wastewater
generation. By using more precise process controls, the amount
of off-specification powder produced will be reduced and the
reprocessing or rework which is necessary to recover the
off-specification powder and the attendent generation of
wastewater will also be reduced. Based on sampling and plant
visit information from one plant, this will reduce the wastewater
flow from cadmium powder production by a factor of 2 from option
1 .
End-of-pipe treatment is restructured by using reverse osmosis
(or alternatively ion exchange) to recover 85 percent of the
wastewater for reuse in the process. Brine (or regenerant) is
treated using lime, settle and filtration technology before
discharge. Figure X-3 (page 910) details this technology train
ind the technology performance is detailed in Section VII.
Option £
Option 4 builds on option 3 by replacing the brine or regenerant
treatment system with vapor recompression evaporation and
crystalized solids centrifugation. This combination of
technologies provides for zero discharge of process wastewater
and allows the wastewater pollutants to be disposed as solid
waste.
To reduce the hydraulic load on, this treatment system (and to
provide some economic return) it is suggested that impregnation
caustic be recovered and sold or concentrated for reuse in the
process. One major producer has converted to this option 4
823
-------
technology and is achieving zero discharge of process wastewater
pollutants.
These options are relatively similar to options depicted in the
draft development document. The principal changes are: (1)
sulfide precipitation to remove toxic metals has been deleted;
(2) flow reduction is considered mainly in option 1; (3) a
polishing filter is applied as part of option 2; (4) reverse
osmosis has been included as an alternative to ion exchange in
option 4; and (5) the option 4 diagram has been simplified to
show only major treatment steps.
BAT Option Selection
The four BAT options were carefully evaluated, and the technical
merits and disadvantages of each were compared. All of the BAT
options are considered to be technologically suitable for cost
and performance comparison. All of the options are compatible
with the operating requirements of cadmium anode battery
manufacturing operations. No comments were received indicating a
need to revise the in-process controls applicable to any option.
Therefore, selection is based on pollutant removals and economic
factors.
The Agency developed quantitative estimates of the total cost and
pollutant removal benefits of each technology option. These
estimates are based on all available data for each plant in the
subcategory. As a first step, an estimate of total raw
wastewater pollutant loads and wastewater flows from each
manufacturing process element was developed from data presented
in Section V. This forms the basis for estimating the mean raw
waste used to calculate the pollutant reduction benefits and is
shown in Table X-2, (page 851). All plants and process elements
in the subcategory are taken into account in this calculation.
Total kg/yr for each pollutant within each process element were
summed and divided by the total subcategory flow to obtain a
total subcategory mean raw waste concentration. Table X-3 (page
853) displays the pollutant concentrations - both mg/1 and mg/kg
of total subcategory anode weight for the raw waste and after
applying each treatment option. Effluent flow after application
of each treatment option was estimated based on wastewater
reduction achieved by the option. The mass of pollutant
discharged after each treatment option was calculated by using
the appropriate mean effluent concentrations for each pollutant
shown in Table VII-21 and multiplying them by the treatment-
option annualized flow. The mass of pollutants discharged after
application of treatment was subtracted from the total
subcategory raw waste to determine the mass of pollutants removed
824
-------
by each level of control and treatment. The results of these
calculations for the total s.ubcategory are shown in Table X-4
(page 854), to display the pollutant reduction of each technology
option. Results for direct dischargers only, based on reported
flow and production data are shown in Table X-5 (page 855).
An estimate of total annual compliance costs of each technology
option for the cadmium subcategory was also prepared and is
displayed in Table X-56 (page 907). BAT compliance estimates
were developed by estimating costs for each existing direct
discharge plant in the subcategory based on reported production
and wastewater flows, and summing individual plant costs for each
level of treatment and control. Since, the cost estimates for
option 4 do not include credits for recovered process materials
(cadmium, nickel, and caustic), it is likely that the true costs
for this option will be lower than shown. An economic impact
analysis based on estimated costs for each treatment and control
option at each plant in the subcategory indicates that there are
no potential plant closures projected for any option for direct
dischargers.
Option 1_ is the selected BAT option because limitations are
achievable using technologies and practices that are currently in
use at plants in the subcategory. Also, the result of
implementing this technology is a significant reduction of toxic
pollutant discharges. For this option flow is reduced to 102.3
million 1/yr for the subcategory and to 73.6 million 1/yr for
direct dischargers. The annual toxic pollutant removal is
194,149 kg/yr for the subcategory and 139,693 kg/yr for the
direct dischargers. For plants to comply direcly with this
option, the estimated compliance capital cost is $441,000 for the
subcategory ($123,000 for direct dischargers), and annual cost is
$147,000 for the subcategory ($38,000 for direct dischargers).
Option 2_ was rejected because the technology yields small
incremental pollutant removals when compared with option 1. For
this option flow is the same as for option 1, but , the annual
toxic pollutant removal is 194,204 kg/yr for the subcategory and
139,733 kg/yr for the direct dischargers. For plants to comply
directly with this option, the estimated compliance capital cost
is $563,000 for the subcategory ($147,000 for direct
dischargers), and annual cost is $189,000 for the subcategory
($49,000 for direct dischargers).
Options 3_ and 4_ were rejected because the technology yields small
incremental pollutant removals when compared with option 2. The
BAT limitations will remove approximately 99.81 percent of
current toxic pollutant discharges. Given the results achieved
by the technologies used as a basis for the promulgated
limitations, further treatment would result only in de minimis,
825
-------
insignificant reductions in annual national discharges.
Accordingly, EPA has determined that the total amount of each
pollutant in the remaining discharges after compliance with BAT
does not justify establishment of a national requirement based on
additional end-of-pipe technology.
Regulated Pollutant Parameters
In selecting pollutant parameters for BAT regulation for the
cadmium subcategory, all pollutants considered for regulation in
Section VI for the subcategory (Table VI-1, page 488) were
evaluated. The choice of pollutants selected for regulation was
dependent upon the toxicity of the pollutants, their use within
the subcategory, and their presence in the raw waste streams at
treatable concentrations. The pollutants do not have to appear
in every process element or necessarily at high concentrations in
the total raw waste streams of the plants which were sampled.
Since plants in the cadmium subcategory have a variety of
different combinations of process elements, the appearance of a
particular pollutant at significant concentrations in a single
process element is sufficient reason for selection.
Pollutant parameters regulated at BAT for this subcategory are
cadmium, nickel, silver, zinc and cobalt. As discussed in
Section IX, silver is regulated for the silver cathode and
associated process elements only. Other pollutants which
appeared at lower concentrations and were considered, but not
selected for regulation at BAT, are expected to be adequately
removed by the application of the selected technology.
The conventional pollutant parameters, oil and grease, total
suspended solids and pH are not regulated under BAT, but are
considered under BCT.
BAT Effluent Limitations
The effluent concentrations attainable through the effectiveness
of BAT technology is displayed in Table VI1-21 under L&S
technology. The BAT mass discharge limitations are calculated by
multiplying these concentrations by the applicable BAT flow
listed in Table X-l (page 850). These limitations are expressed
in terms of mg of pollutant per kg of production normalizing
parameter for each process element and are presented in Tables
X-6 to X-l7 (pages 856-867). To alleviate some of the monitoring
burden, several process elements which occur at most plants and
have the same pnp are combined in one table. Table X-l3 (page
863) is the combined table for Tables X-10 to X-l2. By
multiplying these limitations by the actual production within a
process element, the allowable mass discharge for that process
element can be calculated. The allowable pollutant discharge for
826
-------
the different process elements can be summed to determine the
total allowable mass discharge for the plant.
The reasonableness of these BAT limitations is based upon two
premises - the demonstrated ability to achieve the flow levels,
and the proven ability of the lime and settle technology to
achieve the designated effluent concentrations. The flows used
as a basis to calculate BAT mass discharge limitations are based
upon demonstrated performance at cadmium subcategory plants. By
process substitution or in-process controls, cadmium battery
manufacturing plants can meet the option 1 flow levels.
The effluent concentrations which are used to calculate BAT mass
discharge limitations are based upon the demonstrated performance
L&S technology upon waste streams from other industries which
have wastewater characteristics similar to those of waste streams
in the cadmium subcategory. The details of this performance are
documented in Section VII of this document. There are other
treatment alternatives available for implementation at existing
plants such as sulfide precipitation or iron co-precipitation
which are reported to achieve even lower effluent concentrations
than those achieved by L&S technology.
CALCIUM SUBCATEGORY
There are no direct dischargers in the calcium subcategory and
therefore no BAT regulation is promulgated at this time.
However, technology options were analyzed for treating the raw
wastewater streams in the subcategory and are discussed here for
use in Section XI and XII for pretreatment and new source
standards.
Two technology options beyond option 0 were considered for the
calcium subcategory. The first provided improved end-of-pipe
treatment technology by implementing lime, settle and filter
technology. The second included segregation, treatment, and
recycle of the major process waste stream (from heat paper
production) produced in the subcategory and total reuse or
recycle of treated wastewater using the same end-of-pipe system
specified for option 1. No significant in-process control
technologies were identified for inclusion in these options.
Technology Options Summary
Option 0 for this subcategory (Figure IX-2, page 812) consists of
the following technology:
a) In-process technology
- No water use reduction technology identified
b) End-of-pipe treatment
827
-------
Settling
- Chromium reduction
- Chemical precipitation
- Sedimentation
Sludge dewatering
Option 1 (Figure X-5, page 912) includes all aspects of option 0
and builds on it by adding additional end-of-pipe treatment.
a) In-process technology is identical to option 0.
b) End-of-pipe treatment:
- All option 0 end-of-pipe treatment
- Polishing filtration (mixed media)
Option 2 (Figure X-6, page 913) provides end-of-pipe treat-
ment for two separated wastewater streams, allowing recycle and
reuse of wastewater.
a) End-of-pipe treatment for heat paper production
wastewater includes:
Settling
- Holding tank
- Recycle to process
b) End-of-pipe treatment for cell testing wastewater
includes:
Chemical precipitation
- Sedimentation
- Polishing filtration
- Sludge dewatering
- Recycle treated water to process
The calcium subcategory technology options are unchanged from the
options set forth in a draft development document. There were no
comments on this part of the draft development document.
Option J_
The option 1 treatment system for the calcium subcategory is
shown in Figure X-5 (page 912). Two distinct process wastewater
streams are treated. Prior to combination in the chemical
precipitation system, wastewater from heat paper production is
passed through a settling tank where the suspended material is
allowed to settle. The settled sludge is removed periodically
and disposed. Effluent from the settling device is treated
chemically to reduce hexavalent chromium to the trivalent state
prior to chemical precipitation and clarification. After
chromium reduction, it may be combined with the wastewater from
cell leak testing to remove dissolved metals using chemical
828
-------
precipitation (with lime) followed by clarification and
filtration.
Settled solids are removed from the clarifier and dewatered in a
vacuum filter. Filter cake is disposed as a solid waste. The
filtrate from the vacuum filter is returned to the treatment
system for further treatment.
To further reduce the discharge of metals and suspended solids in
the effluent, the waste stream is passed through a multimedia
filter. 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.
Option 2_
The option 2 treatment begins with segregation of heat paper and
cell testing wastewater. Treatment of the cell test wastewater
is identical to option 1 treatment, except that following treat-
ment the wastewater is recycled or reused, with makeup water
added as required. For the heat paper wastewater stream 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.
Option Selection
In selecting an option for the calcium subcategory, the Agency
compared the pollutant reduction benefits of applying each
technology option. This comparison is presented in Table X-19,
(page 869) which shows the pollutant removal performance for each
of the treatment options. Costs for the options at existing
plants (all indirect dischargers) are displayed in Table X-56
(page 907). The performance shown is based on the effluent
concentrations achievable by the technology being used (as
discussed in Section VII and shown in Table X-18 (page 868)), and
the normalized discharge flows from each process element. The
raw waste is based on wastewater characteristics shown in Section
V (from sampled streams) and on the total flow for the heat paper
process element. Pollutant removals are for indirect dischargers
only.
Option 2 achieves greater pollutant removal than option 1 and
achieves zero discharge of process wastewater pollutants. Since
829
-------
option 2 eliminates the need for chromium reduction and chemical
precipitation on the heat paper waste stream, it reduces the
consumption of chemicals and the generation of toxic sludges
requiring disposal, making this option the least costly for the
removal of hexavalent chromium. Option 2 is technically
achievable since the role of water in heat paper production is as
a solids carrier. This water can therefore be recycled without
adversely affecting the production process. Similarly, the use
of cell testing water does not preclude recycle of this treated
effluent.
Pollutant Parameters Selected for Effluent Limitations
Because the selected treatment system achieves zero discharge of
process wastewater, no specific pollutants have been selected for
limitation. The limitation for the calcium subcategory is no
discharge of process wastewater pollutants.
LECLANCHE SUBCATEGORY
There are no direct dischargers in the Leclanche subcategory, and
therefore no BAT regulation is recommended at this time.
However, technology options were analyzed for treating the raw
waste streams in the subcategory.
Technology Summary
The technology considered and selected for this subcategory is
identical to option 0 which is presented in Figure IX-3 (page
812). This technology option consists of recycle and reuse for
all plants which generate wastewater and lime, settle and filter
technology for foliar battery producing plants.
Table X-20 (page 870) shows the pollutant reduction benefits of
this option. The corresponding compliance costs are displayed in
Table X-56 (page 907).
Pollutant Parameters Selected for Effluent Limitations
Pollutant parameters selected for limitation for this subcategory
are those selected and discussed for BPT in Section IX, except
that the conventional pollutants would be considered under BCT.
Effluent Limitations
The effluent concentrations attainable through the application of
the recommended technology are displayed in Table VII-21. The
mass discharge limitation can be calculated by multiplying the
concentration by the foliar battery miscellaneous wash flow
(0.066 I/kg of cells produced). These limitations are expressed
830
-------
in terms of mg of pollutant per kilogram of cells produced and
are displayed in Table X-21 {page 871). This table is presented
as guidance for state or local pollution control agencies because
a national regulation is not established at BAT.
LITHIUM SUBCATEGORY
As discussed in Section IX for the lithium subcategory, no BAT
regulation is recommended at this time. However, technology
options were analyzed for treating the raw waste streams in the
subcategory and are discussed here for use in Sections XI and
XII. Plants in the lithium subcategory generate three distinct
wastewaters: wastewater Stream A is generated by heat paper
production; wastewater Stream B is generated by the manufacture
of iron disulfide cathodes, lead iodide cathodes, cell testing,
lithium scrap disposal, floor and equipment wash, and cleanup;
and wastewater Stream C is generated by air scrubbers on various
plant operations. As discussed in Section IX, these wastewater
streams are most usually generated and treated separately.
Three alternative levels of treatment and control technology
beyond option 0 were considered for technology options for this
subcategory. Each of these options builds upon option 0, and
provides different treatment for one or more of the wastewater
streams generated in this subcategory. All three options
incorporate improvements in end-of-pipe treatment or recycle of
treated wastewater. In-process controls providing substantial
reductions in process wastewater volumes or pollutant loads have
not been identified.
Technology Options Summary
Because there are three wastwater streams the technology options
will be outlined for each wastewater stream. Technology options
for waste Stream A are identical to heat paper in the calcium
subcategory.
Option 0 for this subcategory {Figure IX-4, page 813) consists of
the following technology.
A. Wastewater Stream A
a) In-process technology:
None identified
b) End-of-pipe treatment:
Settling
- Chromium reduction
Chemical precipitation
Sedimentation
Sludge dewatering
B. Wastewater Stream B
831
-------
a) In-process technology:
None identified
b) End-of-pipe treatment:
Chemical precipitation
- Sedimentation
Sludge dewatering
C. Wastewater Stream C
a) In-process technology:
None identified
b) End-of-pipe treatment:
Aeration
Chemical precipitation
- Sedimentation
Option 1 (Figure X-7, page 914) for this subcategory
builds upon BPT.
A. Wastewater Stream A
a) In-process technology is identical to BPT.
b) End-of-pipe treatment:
All BPT end-of-pipe treatment
- Polishing filtration (mixed media)
B. Wastewater Stream B
a) In-process technology is unchanged from BPT.
b) End-of-pipe treatment is changed by adding:
Polishing filtration
C. Wastewater Stream C treatment is unchanged from BPT.
Option 2 (Figure X-8, Page 915) includes the following changes.
A. Wastewater Stream A
a) In-process technology is identical to BPT.
b) End-of-pipe treatment for heat paper production
wastewater includes:
Settling
Holding tank
Recycle to process
B. Wastewater Streams B and C treatment is unchanged from option 1
Option 3 (Figure X-9, Page 916) builds upon option 2.
A. Wastewater Streams A and B treatment is unchanged
from Option 2.
B. Wastewater Stream C treatment is upgraded by adding
polishing filtration.
Option 1
The Option 1 treatment system for the lithium subcategory, shown
in Figure X-7, consists of three distinct treatment systems, each
832
-------
of which is directly associated with one of three major
wastewater streams generated by this subcategory. These
wastewater streams result from: A) heat paper production; B) iron
disulfide cathode and lead iodide cathode manufacture, lithium
scrap disposal, cell testing, and floor and equipment wash; and
C) air scrubber blowdown.
Wastewater Stream A, 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 may be combined with the wastewater associated with wastewater
stream B prior to further treatment.
The combined wastewaters from wastewater Streams A and B are
treated to remove dissolved metals using chemical precipitation
(with lime) followed by settling in a clarifier. The settled
solids are removed from the clarifier, and dewatered in a vacuum
filter. The sludge filter cake is disposed on a contract haul
basis, along with any oil and grease removed by the skimming
mechanism on the clarifier. The filtrate from the vacuum filter
is sent 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
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 sent back to the
treatment system.
Wastewater Stream C is initially aerated to decrease the oxygen
demand. In the process, sulfuric acid is formed from the
sulfurous acid originally present. Subsequently, the low pH
wastewater is neutralized and settled prior to discharge. Lime
used to neutralize the waste stream may precipitate calcium
sulfate and calcium chloride. 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.
Option "l_
The option 2 treatment for the heat paper wastewater stream
consists of settling after which the clarified effluent is
discharged to a holding tank. This wastewater stream is recycled
833
-------
with makeup water added to the system as required. Solids are
recovered or contractor hauled.
Because of the recycle of the treated heat paper wastewater to
the process, further treatment will not be required to remove
hexavalent chromium from solution.
Stream B is identical to the system described for this wastewater
stream in option 1.
The option 2 treatment system for Stream C is identical to the
system described in option 1.
Option 3_
The option 3 treatment system for Streams A and B is identical to
the system described in option 2. A polishing filter is added to
remove additional solids from the air scrubber blowdown water.
Option Selection
These three treatment and control options were studied carefully
and the technical merits and disadvantages of each were compared.
In the selection of a technology option from among these
alternatives, the Agency considered pollutant reduction benefits,
costs, and the status of demonstration of each technical
alternative. Tables X-23 and X-24 (pages 873 and 874) provide a
quantitative comparison of polluant reduction benefits of the
different options and compliance costs are displayed in Table X-
56. In this subcategory, contract hauling is the least costly
method for compliance at existing plants.
Because there are three distinct wastewater streams in this
subcategory, it is necessary to consider and evaluate each of
them separately in determining the most appropriate technology
option for treatment and control of pollutants. The wastewater
generated by heat paper manufacture is identical to the heat
paper manufacturing operation discussed in detail in the calcium
subcategory. Employing the same logic as detailed in the calcium
subcategory is appropriate to arrive at the same conclusion about
treatment options for this operation. The technically preferred
option for this segment of the subcategory is option 2. This
option results in the maximum reduction in the discharge of toxic
pollutants.
Technology options 1-3 contain only one change from option 0 for
wastewater Stream B which contains wastewaters from iron
disulfide or lead iodide cathodes, cell testing, lithium scrap
disposal, and floor and equipment wash. This improved technology
is the addition of a polishing filter after sedimentation to
834
-------
improve removal of toxic metals and suspended solids. The
operability of lime, settle and filter technology is detailed in
Section VII. For this segment of the subcategory the technically
preferred option is option 1.
Option 3 adds a filter to improve removal of TSS from the
wastewater for Stream C. Since this wastewater stream is
believed to be essentially free from toxic metals, the filter
would only remove TSS. It is therefore not the technically
preferred option, and the selected technology for this segment of
the subcategory is lime and settle technology.
Pollutant Parameters Selected for Effluent Limitations
Pollutant parameters selected for limitation for this subcategory
are those selected and discussed in Section IX, except that the
conventional pollutants would be considered under BCT.
Effluent Limitations
Effluent concentrations from Table VI1-21 for L&S technology are
multiplied by the normalized process element flows shown in Table
X-22 to determine the pollutant mass discharge limitations shown
in Tables X-25 to X-27 (pages 876-877). These tables are
presented as guidance for state or local pollution control
agencies because effluent limitations for the discharges from
this subcategory are not established for national regulation at
BAT. The heat paper manufacturing process element is not shown
in the tables because the limitations would be at no discharge of
process wastewater pollutants. The air scrubber process elements
are not shown in the tables because no toxic pollutants would
need to be limited. The discharge limitation for any battery
manufacturing plant may be determined by summing the mass
discharge allowances for all of the applicable manufacturing
process elements.
MAGNESIUM SUBCATEGORY
As discussed in Section IX for the magnesium subcategory, there
is no BAT regulation at this time. However, technology options
were analyzed for treating the raw waste streams in the
subcategory and are discussed here for use in Section XI and XII.
The magnesium subcategory generates three distinct wastewaters:
wastewater Stream A is generated by heat paper production;
wastewater Stream B is generated by the manufacture of silver
chloride cathodes, cell testing, and floor and equipment wash;
and wastewater Stream C is generated by air scrubbers on various
plant operations. As discussed in Section IX, these wastewater
streams are usually generated and treated separately.
835
-------
Three alternative levels of treatment and control technology were
considered beyond option 0 for this subcategory. Each of these
options builds upon option 0 and, provides different treatment
for one or more of the wastewater streams generated in this
subcategory. All three options incorporate improvements in end-
of-pipe treatment or recycle of treated wastewater. Except for
one process element, in-process controls providing substantial
reductions in process wastewater volumes or pollutant loads have
not been identified.
Technology Options Summary
Because there are three distinct wastewater streams the
technology options will be outlined for each wastewater stream.
Options for waste Stream A are identical to heat paper production
options in the calcium subcategory.
Option 0 for this subcategory (Figure IX-5, page 814) consists of
the following technology.
A. Wastewater Stream A
a) In-process technology:
- None identified
b) End-of-pipe treatment:
Settling
- Chromium reduction
- Chemical precipitation
- Sedimentation
- Sludge dewatering
B. Wastewater Stream B
a) In-process technology:
- Rinse water flow control
b) End-of-pipe treatment:
- Chemical precipitation
- Sedimentation
- Sludge dewatering
C. Wastewater Stream C
a) In-process technology:
- None identified
b) End-of-pipe treatment:
- Chemical precipitation
- Sedimentation
Option 1 (Figure X-10, page 917) for this subcategory
builds upon option 0.
A. Wastewater Stream A
a) In-process technology:
- None identified
b) End-of-pipe treatment:
836
-------
All option 0 end-of-pipe treatment
Polishing filtration (mixed media)
B. Wastewater Stream B
a) In-process technology:
- Countercurrent cascade rinse
b) End-of-pipe treatment is identical to option 0
C. Wastewater Stream C treatment is identical to option 0
Option 2 (Figure X-ll, page 918)
A. Wastewater Stream A
a) In-process technology:
None identified
b) End-of-pipe treatment:
Settling
Holding tank
Recycle to process
B. Wastewater Stream B
a) In-process technology is unchanged from option 1.
b) End-of-pipe treatment:
All option 0 end-of-pipe treatment
Polishing filtration (mixedmedia)
C. Wastewater Stream C treatment is unchanged from option 0.
Option 3 (Figure X-12, page 919).
A. Wastewater Stream A treatment is unchanged
from option 2.
B. Wastewater Stream B treatment is upgraded by adding
carbon adsorption to remove organics.
C. Wastewater Stream C
a) In-process technology:
None identified
b) End-of-pipe treatment:
All option 0 end-of-pipe treatment
Polishing filtration (mixed media)
Option j_
The option 1 treatment system for the magnesium subcategory,
shown in Figure X-10, consists of three distinct treatment
systems, each of which is directly associated with one of three
major wastewater streams generated by this subcategory. These
wastewater streams result from: A) heat paper production; B)
silver chloride cathode manufacture, cell testing, and floor and
equipment cleaning; and C) air scrubbers.
Wastewater Stream A, from heat paper production, is passed
through a clarifier or settling tank where the suspended material
837
-------
is allowed to settl.e. The settled sludge is removed periodically
for disposal as solid waste. The effluent from the initial
settling is treated by chemical reduction to reduce hexavalent
chromium to the trivalent state. The wastewater is then treated
to remove dissolved metals using chemical precipitation (with
lime) followed by settling in a clarifier. 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. The liquid filtrate from the vacuum filter
is sent 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 mixed
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 sent back to the treatment system.
Wastewater stream B, from silver chloride cathode production,
cell testing and floor and equipment wash, is reduced in volume
by using three-stage countercurrent cascade rinsing of chemically
reduced silver cathodes. Because the cathode material is smooth
surfaced a high efficiency will be achieved and a rinse reduction
factor of 30 is reasonable for this material. End-of-pipe
treatment is the same as BPT.
Option 2 treatment for the heat paper wastewater stream, consists
of settling after which the clarified effluent is discharged to a
holding tank. From the tank all of the wastewater is recycled,
with makeup water added to the system as required. This is
discussed in detail in the calcium subcategory. Because of the
recycle of the treated heat paper wastewater back to the process
operation, the option 2 treatment equipment will not be required
to remove hexavalent chromium from solution.
The option 2 treatment for silver chloride cathode production,
cell testing, and floor and equipment wash wastewaters is the
same as option 1 with the addition of a mixed media polishing
filter to further reduce pollutant discharge.
The option 2 treatment system for Stream C is similar to the
system described in option 1 with the addition of a mixed media
polishing filter to remove additional amounts of solids.
The option 3 treatment system is very similar to the system
previously described for option 2 treatment. It differs only in
that carbon adsorption is included for the silver chloride
cathode wastewater to further reduce organic pollutant (COD)
discharges.
838
-------
Option Selection
These three treatment and control options were studied carefully
and the technical merits and disadvantages of each were compared.
In the selection of a technology option from among these
alternatives, the Agency considered pollutant reduction benefits,
costs, and the status of demonstration of each technical
alternative. Tables X-29 and X-30 (pages 879 and 880) provide a
quantitative comparison of pollutant reduction benefits of the
different technology options. The corresponding compliance costs
are displayed in Table X-56. These tables present the pollutant
removal which would occur if all of the existing plants in the
magnesium subcategory used a particular treatment system, and
shows the combined costs to all existing plants of using that
treatment.
Because there are three distinct wastewater streams in this
subcategory, it is necessary to consider and evaluate each of
them separately in determining the most appropriate technology
option for treatment and control of pollutants. The wastewater
generated by heat paper production is identical to the heat paper
production operation discussed in detail in the calcium
subcategory. It is appropriate, employing the same logic as
detailed in the calcium subcategory, to arrive at the same
conclusion about treatment options for this operation. The
technically preferred option for this segment of the subcategory
is option 2. This option results in the maximum reduction in the
discharge of pollutants at the least cost of any option
considered for this wastewater stream.
The three options displayed for the treatment of silver chloride
cathode, cell testing, and floor and equipment wash wastewaters
are not practiced at any manufacturing plant in this subcategory.
Since only minimal treatment is now provided to these
wastewaters, it is necessary to transfer any technology for use
in this segment. The first option employs water flow reduction,
transferring countercurrent cascade rinsing from other sub-
categories. The basis for the use of countercurrent cascade
rinsing is set forth in substantial detail in Section VII. A
high level of rinsing efficiency is projected because of the
compact, smooth nature of the surface being rinsed. This results
in a thirtyfold reduction in wastewater discharge from the
chemically reduced cathode production and a proportionate
reduction in pollutant discharge.
The^, second option adds polishing filtration to the lime and
settle end-of-pipe treatment employed at BPT to remove additional
pollutants. This technology is widely used and is described in
detail in Section VII.
839
-------
The third option requires the use of carbon adsorption to remove
COD. COD is known to contain phenol-like compounds which are not
detected by the analytical procedures used. The applicability of
the carbon adsorption technology is not well demonstrated on this
particular wastewater, and therefore this option is not selected.
The technically preferred option is option 2 based on the removal
of pollutants and the proven effectiveness of the technology
employed.
Wastewater Stream C, from air scrubbers, is not known to be
treated effectively in any of the plants in this subcategory. No
in-process technology is known which can be employed to
substantially reduce the wastewater flow and the quantity of
pollutants carried by that wastewater. The only technology
applied above option 0 is the addition of a polishing filter.
This occurs at option 3, however, since no toxics are removed by
this option, option 0 is selected as the technically preferred
option.
Pollutant Parameters Selected for Effluent Limitations
Pollutant parameters selected for limitation for this subcategory
are those selected and discussed for BPT in Section IX, except
that the conventional pollutants would be considered under BCT.
Effluent Limitations
The effluent concentrations attainable through the application of
the recommended technology are displayed in Table VI1-21. The
mass discharge limitation for each process element can be
calculated by multiplying these concentrations by the applicable
BAT flow listed in Table X-28 (page 878). These limitations are
expressed in terms of mg of pollutant per kg of production
normalizing parameter and are displayed in Tables X-31 to X-34
(pages 882-883). These tables are presented as guidance for
state or local pollution control agencies because effluent
limitations for the discharges from this subcategory are not
established for national regulation at BAT. By multiplying these
limitation numbers by the actual production in a process element
(kg of production normalizing parameter), the allowable mass
discharge for that process element can be calculated in mg. The
allowable masses for the different process elements can be summed
to determine the total allowable mass discharge for a plant.
•
Of the eight plants which are reported active in the magnesium
subcategory, five reported no wastewater discharge from the
magnesium subcategory, thereby meeting all levels of discharge
limitation. None of the three plants which reported wastewater
840
-------
discharge had the complete treatment technology system, although
one plant had some components of the BAT system.
ZINC SUBCATEGORY
Four technology options are presented to display the most
appropriate technology options. All four options build upon BPT
(option 0) and provide reduced pollutant discharge by reducing
wastewater volumes through the application of in-process control
techniques. In addition, three of the options provide augmented
end-of-pipe treatment.
BAT Options Summary
Option O for this subcategory (Figure IX-6, page 815) consists of
the following:
a) In-process technology
- Reuse of process solutions
- Elimination of the use of chromates in cell washing
- Segregation of noncontact cooling water
- Segregation of organic bearing cell cleaning wastewater
- Control electrolyte drips and spills
- Control flow of rinse waters
b) End-of-pipe treatment
- Oil skimming
Lime or acid precipitation
- Sedimentation
- Sludge dewatering
BAT Option 1 (Figure X-13, page 920) builds on option O by adding
the following:
a) In-process technology
- Countercurrent rinse amalgamated zinc powder
- Recirculate amalgamation area floor wash water
- Countercurrent rinse of formed zinc electrodes
- Countercurrent rinse of electrodeposited silver powder
- Countercurrent rinse of formed silver oxide electrodes
- Reduce flow and Countercurrent rinse silver peroxide
- Flow controls and Countercurrent rinse for im-
pregnated nickel cathodes
- Countercurrent rinse or rinse recycle for cell washing
- Countercurrent rinse after etching silver grids
- Dry cleanup or wash water reuse for floor and
equipment
b) End-of-pipe treatment is unchanged from BPT.
BAT Option 2 (Figure X-14, page 921) builds on BAT Option 1.
841
-------
a) In-process technology is unchanged from BAT Option 1.
b) End-of-pipe treatment continues BAT Option 1 and adds:
- Polishing filtration (mixed media)
BAT Option 3 (Figure X-15, page 922) follows BAT Option 2.
a) In-process technology
- All in-process technology employed at Option 2
- Eliminate wastewater from gelled amalgam
b) End-of-pipe treatment
Oil skimming
- Sulfide precipitation
- Sedimentation
- Filtration (membrane)
Sludge dewatering
BAT Option 4 (Figure X-16, page 923) provides reduced flow,
improved end-of-pipe treatment, and recycle.
a) In-process technology
- All in-process technology used in Option 3
- Eliminate amalgamation wastewater
b) End-of-pipe treatment
- Oil skimming
- Lime or acid precipitation
- Filtration
- Reverse osmosis with recycle of permeate
- Sulfide precipitation of brine
- Sedimentation of precipated brine
Filtration (membrane)
- Sludge dewatering
Option ]_
Option 1 adds in-process control technology to the end-of-pipe
treatment provided at BPT. This in-process technology
substantially reduces the quantity of wastewater which must be
treated before release. Normalized flows for the several
elements of this subcategory are listed in Table X-35, (page
884). Specific flow reductions for each of the manufacturing
process elements are discussed in detail.
Wet Amalgamated Zinc Powder Anode. Water is discharged as a
result of rinsing the amalgamated zinc powder and of area floor
washing. Area floor washing contributes 0.25 I/kg of the 3.8
I/kg BPT flow for this process element. Floor area wash water
may be eliminated by reusing treated amalgam rinse water or by
treatment and reuse of the floor wash water. By replacing the
typical zinc powder series rinsing systems with countercurrent
rinsing, the 3.55 I/kg can be reduced by a factor of 6.6 to 0.55
842
-------
I/kg. The effluent flow of 0.55 I/kg is used for setting BAT
effluent limitations for this process element.
Gelled Amalgam Zinc Powder Anode. Water discharged is a result
of equipment and process area floor washing. Water used in
washing amalgamation area floors becomes contaminated with
mercury as well as suspended solids. Recycle of this water for
continued use in floor washing is possible if the mercury and
other contaminants are removed by treatment prior to removal of
suspended solids. In order to control the dissolved solids
content in the recirculation water, a small bleedoff or blowdown
of wastewater may be necessary. This blowdown is established at
a nominal level of 10 percent of the BPT flow for this element.
Zinc Oxide Formed Anode. Wastewater is generated in the
post-formation rinse operation. The implementation of
countercurrent rinsing for this operation will reduce the amount
of wastewater discharged. Since existing practice does not
provide examples of this flow reduction technique, attainable
flow reductions for this process element are based upon the
calculated flow rate requirement for the three-stage
countercurrent rinse presented in Section VII. Applying a
conservative rinse reduction ratio of 6.6 to the BPT flow of 143
I/kg, the BAT flow for this element becomes 21.67 I/kg.
Electrodeposited Zinc Anode. Wastewater results from post-
electrodeposition and post-amalgamation rinsing operations. The
application of countercurrent rinses will reduce the flow of
wastewater from these rinsing operations after electrodeposition
in a similar fashion to the flow reduction for the zinc oxide
formed anode process element. Post-amalgamation rinsing is
eliminated by proper control of amalgamation solution
concentration. Hence, the BPT flow of 3,190 I/kg is halved by
eliminating one rinsing step and further reduced by a factor of
6.6 by using three-stage countercurrent rinsing. The BAT flow
for this process element is 241.7 I/kg.
Silver Powder Formed Cathode. This process element is similar to
the two previously described process elements in that wastewater
is generated as a result of rinsing operations. The flow
reduction attained through the application of countercurrent
rinses is also similar. Since this process element has only one
rinsing operation (post-formation) the BAT flow is the BPT flow
(196 I/kg) reduced by a factor of 6.6, or 29.70 I/kg.
Silver Oxide Powder Formed Cathodes. The water produced by this
process element also results from rinsing operations. The
attainable effluent flow reduction through the application of
countercurrent rinses is the same as the three previously
843
-------
described process elements. The BAT flow is the BPT flow (131
I/kg) reduced by a factor of 6.6, or 19.85 I/kg.
Silver Peroxide Powder Cathode. The production of silver
peroxide powder cathodes generates wastewater through spent bath
dumps and rinses. The BAT is determined by applying
countercurrent rinsing to the BPT flow of 31.4 I/kg to reduce the
water use by a factor of 6.6 to 4.76 I/kg.
Nickel Impregnated Cathode. The production of nickel impregnated
cathodes and the flow reductions possible through the application
of BAT technology were previously described under the cadmium
subcategory. The BAT flow allowed for this process element is
200 I/kg as developed and discussed under the cadmium
subcategory.
Cell Wash. Reduced wastewater discharge from cell washing can be
achieved through recycling of cell rinse water or by
countercurrent cell rinsing. The BAT flow for the cell wash
process element is determined by applying countercurrent rinsing
to the BPT flow of 1.13 I/kg to reduce the water use by a factor
of 6.6, to 0.17 I/kg.
Electrolyte Preparation. Wastewater is generated from spills
occurring while preparing electrolyte solutions and filling
cells. The BAT flow is determined to be the median or zero I/kg
because it is already achieved by half of the existing plants by
proper design and operation of filling equipment and reuse of
drips and spills.
Silver Etch. Wastewater results from rinsing etched silver foil.
The countercurrent rinse flow rate calculations presented in
Section VII were used as the basis for determining attainable
discharge flow rates from rinsing after silver foil etching
operations. A rinsing efficiency factor of 6.6 is estimated and
flow is reduced from 49.1 I/kg at BPT. The result of these
calculations is a BAT flow basis of 7.44 I/kg for the silver etch
process element.
Floor and Equipment Wash. Wastewater is generated from washing
floors and production equipment. The wastewater discharge from
floor wash (0.13 I/kg) remains unchanged from BPT. The BPT flow
from equipment wash, 7.1 I/kg can be reduced by treatment and
reuse with a blowdown at a nominal level of 10 percent of the BPT
flow. With these in-process controls the BAT flow for floor and
equipment wash is 0.84 I/kg.
Silver Peroxide Production. The production of silver peroxide is
similar to silver powder production in that water is generated by
rinsing operations and the rinse flows can be reduced by the
844
-------
implementation of countercurrent rinsing. The attainable flow
reductions for this process element are calculated in the same
manner as silver powder production, using a conservative rinse
flow reduction factor of 6.6. The BPT flow of 52.2 I/kg is
reduced to a BAT flow of 7.91 I/kg.
Silver Powder Production. Silver powder production generates
wastewater as a result of rinses relating to this operation. The
application of countercurrent rinsing in this operation will
reduce the present rinse water flow of 21.2 I/kg. Since no
examples of countercurrent rinsing on this operation exist,
estimates of flow reductions are made based upon the calculated
flow rate requirement for a three-stage countercurrent rinse
presented in Section VII. When loose powders are rinsed, good
rinse water contact and mixing can be achieved. Consequently, a
lower factor for rinsing efficiency could be considered/ however,
the conservative 6.6 factor is used to establish a BAT flow of
3.21 I/kg.
Option 2_
BAT option 2 builds on option 1 by including all of the
in-process technology used to reduce wastewater flow and improves
end-of-pipe treatment by adding a polishing filter.
Option 3^
BAT option 3 provides some reduction in wastewater flow by
eliminating wastewater from gelled amalgam production.
End-of-pipe treatment is improved by using sulfide as the
precipitation agent before settling and filtering the wastewater.
The reduced solubility of the sulfide precipitate provides a
basis of improved performance.
Option 4_
BAT option 4 substantially revises the end-of-pipe treatment to
allow reuse of the wastewater. This is accomplished by adding
reverse osmosis after filtration and recycling the permeate.
Brine from reverse osmosis is treated using sulfide to remove
metal pollutants before discharge.
BAT Option Selection
Three technology options were originally developed and presented
in the draft development document for consideration as BAT for
the zinc subcategory. These options have been restructured into
four options to better display the application of a full range of
technologies to this subcategory. These options are somewhat
modified from options outlined in the draft development document.
845
-------
Most of the wastewater generation control has been concentrated
in the first option while the second option adds filtration to
improve effectiveness. The third and fourth options continue to
depend on sulfide precipitation for pollutant removal.
The Agency developed quantitative estimates of the total cost and
pollutant removal benefits of each BAT option. These estimates
are based on all available data for each plant in the
subcategory. As a first step, an estimate of total raw
wastewater pollutant loads and wastewater flows from each
manufacturing process element was developed from data presented
in Section V. This forms the basis for estimating the mean raw
waste used to calculate the pollutant reduction benefits and is
shown in Table X-36, (page 885). All plants and process elements
in the subcategory are taken into account in this calculation.
Total kg/yr for each pollutant within each process element were
summed and divided by the total subcategory flow to obtain a
total subcategory mean raw waste concentration. Table X-37 (page
888) displays the pollutant concentrations - both mg/1 and mg/kg
of the total subcategory anode weight for raw waste and after
applying each treatment option. Effluent flow after application
of each treatment option was estimated based on wastewater
reduction achieved by the option. The mass of pollutant
discharged after each treatment option was calculated by using
the appropriate mean effluent concentrations shown in Table
VII-21 and multiplying them by the treatment option annualized
flow. The mass of pollutants discharged after application of
treatment was subtracted from the total subcategory raw waste to
determine the mass of pollutants removed by each level of control
and treatment. The results of these calculations for the total
subcategory are shown in Table X-38 (page 889) to display the
pollutant reduction of each technology option. Results for
direct dischargers only, based on reported flow and production
data are shown in Table X-39 (page 890).
An estimate of total annual compliance costs of BPT and of each
BAT option for the zinc subcategory was also prepared and is
displayed in Table X-56 (page 907). These estimates were
developed by estimating costs for each existing direct discharge
plant in the subcategory based on reported production and
wastewater flows, and summing individual plant costs for each
level of treatment and control. The costs for technology options
2 and 3 are listed as being equal. The costs of the two options
are estimated to be very close (within 10%) with option 2
slightly less expensive because of lower filter costs. An
economic impact analysis based on estimated costs for each
treatment and control option at each plant in the subcategory
indicates that there are no potential plant closures projected
for any options for direct dischargers.
846
-------
Option J_ is the selected BAT option because limitations are
achievable using technologies and practices that are currently in
use at plants in the subcategory. Also, the result of
implementing this technology is a significant reduction of toxic
pollutant discharges. For this option flow is reduced to 8.11
million 1/yr for the subcategory and to 1.87 million 1/yr for
direct dischargers. The annual toxic pollutant removal is 5701
kg/yr for the subcategory and 1311 kg/yr for direct dischargers.
For plants to comply directly with this option, the estimated
compliance capital cost is $437,000 for the subcategory ($90,000
for direct dischargers), and annual cost is $123,000 for the
subcategory ($24,000 for direct dischargers).
Options 2_t_ 3_ and 4_ were rejected because the technology yields
small incremental pollutant removals when compared with option 1.
The BAT limitations will remove approximately 99.81 percent of
current toxic pollutant discharges. Given the results achieved
by the technologies used as a basis for the promulgated
limitations, further treatment would result only in de minimis,
insignificant reductions in annual national discharges.
Accordingly, EPA has determined that the total amount of each
pollutant in the remaining discharges after compliance with BAT
does not justify establishing a national requirement based on
additional end-of-pipe technology.
Pollutant Parameters for Regulation
In selecting pollutant parameters for BAT regulation for the zinc
subcategory, all pollutants considered for regulation in Section
VI for the subcategory (Table Vl-1, page 488) were evaluated.
The choice of pollutants for regulation was dependent upon the
toxicity of the pollutants, their use within the subcategory, and
their presence in the raw waste streams at treatable
concentrations. The pollutants do not have to appear in every
process element or necessarily at high concentrations in the
total raw waste streams of the plants which were sampled. Since
plants in the zinc subcategory have a variety of different
combinations of process elements, the appearance of a particular
pollutant at significant concentrations in a single process
element is sufficient reason for selection.
Pollutant parameters regulated at BAT for this subcategory are
chromium, cyanide, mercury, nickel, silver, zinc and manganese.
As discussed in Section IX, nickel is regulated for the nickel
impregnated cathode and cell wash elements only, and cyanide is
regulated for the cell wash element only. Other pollutants which
appeared at lower concentrations and were considered, but not
selected for regulation at BAT, are expected to be adequately
removed by the application of the selected technology.
847
-------
The conventional pollutant parameters, oil and grease, total
suspended solids and pH are not regulated under BAT, but are
considered under BCT.
BAT Effluent Limitations
The effluent concentrations attainable through the application of
BAT technology are displayed in Table VI1-21 under L&S
technology. The BAT mass discharge limitations for the different
process elements are calculated by multiplying these
concentrations by the applicable BAT-1 flow listed in Table X-35.
These BAT limitations (shown in Tables X-40 to 55, pages 891 to
906) are expressed in terms of mg of pollutant per kg of
production normalizing parameter. To alleviate some of the
monitoring burden, several process elements which occur at most
plants and have the same pnp are combined in one regulatory
table. Table X-53 (page 904) is the combined table for Tables X-
48, 50, 51, and 52. By multiplying these limitation numbers by
the production per unit time (e.g. kg/day) within a process
element, the allowable mass discharge for that process element
can be calculated in mg per unit of time. The allowable masses
for the different process elements can be summed to determine the
total allowable mass discharge for the plant.
No plant in this subcategory presently employs the selected tech-
nology in its entirety, although most plants employ some of the
identified in-process and end-of-pipe technologies. Performance
at these facilities may be compared to that attainable at BAT
both in terms of the volume of wastewater produced and the
concentrations of pollutants present in the treated effluent, as
well as the mass of pollutants discharged.
The volumes of wastewater presently discharged from each plant in
the zinc subcategory have been compared to the flows attainable
by implementation of the selected BAT technology option. The
present discharge flows are derived from the best available data
including dcp, on-site measurements and data collection, and
supplementary contacts. The attainable flows were calculated
from individual plant production information and the individual
process operation flows shown in Table X-35. Three of the 17
plants in the subcategory for which data are available achieve no
discharge of process wastewater pollutants. Two additional
plants have indicated substantial discharge flow reductions and
plans for achieving zero discharge operation. Five plants in the
data base have effluent flows only slightly above (about twice or
less) the BAT technology option flow. Since 10 plants of 17 now
meet or are close to the BAT flow it may be concluded that this
part of the basis for BAT effluent limitations is reasonable and
attainable.
848
-------
As previously discussed in Section IX, present treatment practice
in the subcategory was found to be uniformly ineffective, both .as
a result of the treatment technologies employed and of the manner
in which the existing systems were operated. While one plant
employs end-of-pipe treatment nominally equivalent to BAT, the
system is not operated to provide effective removal of process
wastewater pollutants. However, based on the information
presented in Section VII and on careful examination of the
processes and wastewaters in this subcategory, the BAT
limitations are attainable by application of the selected
technology.
849
-------
TABLE X-l
oo
Ul
o
Process Elements Median
Anodes
Pasted & Pressed Powder 1.0
Electrodeposited 697.
Impregnated 998,
Cathodes
Nickel Electrodeposited 569.
Nickel Impregnated 1720.
Ancillary Operations
Cell Wash
Electrolyte Preparation
Floor and Equipment Wash
Employee Wash
Cadmium Powder Production
Silver Powder Production
Cadmium Hydroxide
Production 0.9
Nickel Hydroxide
Production 110.0
PROCESS ELEMENT FLOW SUMMARY
CADMIUM SUBCATEGORY
Plow (I/kg)
Mean
2.7
697.
998.
569.
1640.
BPT
(PSES 0)
2.7
697.
998.
569,
1640,
BAT 1
(PSES 1)
0.0
35.15
200.0
33.0
200.0
BAT 2
(PSES 2)
0.0
35.15
200.0
33.0
200.0
0.9
110.0
0.9
110.0
0.14
16.5
0.14
16.5
BAT 3
(PSES 3)
0.0
5.27
30.0
4.95
30.0
0.021
2.47
BAT 4
(PSES 4
0.0
0.0
0.0
0.0
0.0
3.33
0.08
2.4
1.5
5.7
1.2
4.93
0.08
12.0
1.5
65.7
21.2
4.93
0.08
12.0
1.5
65.7
21.2
0.75
0.08
0.0
1.5
6.57
3.21
0.75
0.08
0.0
1.5
6.57
3.21
0.112
0.012
0.0
0.225
0.493
0.482
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
-------
TOHLE X-2
PKX2SS HBffiNT WRSEWKIER SttMMDf
CNMICM
ANODES
Pasted & Pressed
Powder Electrodeposited
mg/1 kg/yr mg/1 hg/yr
Flow 3/yr (106) 0.948
Pollutants
118 Cachdttn 267.0 253.1
119 Chromium 0.004 0.004
121 Cyanide 3.184 3.018
122 Lead 0.023 0.022
123 Mercury 0.0 0.0
124 Nickel 18.930 17.95
126 Silver NA NA
178 Zinc 0.41 0.389
Cobalt 0.0 0.0
Oil & Grease 822»0 779.0
TSS 1038.0 984.0
80.9
94.6 7653.0
0.0 0.0
0.022 1.780
0.0 0.0
0.001 0.081
0.071 5.74
NA NA
0.006 0.485
0.0 0.0
5.23 423.0
126.7 10250.0
DIM UlTU-LJJL-ll _TLj1
f£2£.C9^1 K« UOU
ag/i kg/yr
179.623
31.7 5693.0
0.14 25.14
0.04 7.18
0.0 0.0
0.02 3.59
2.25 404.1
NA NA
0.04 7.18
0.08 14.37
2.5 449.0
204.0 36647.0
OUHJLES
Nickel Nickel
ELectrodeposited apregnated
wg/i kg/yr m^^l kg/yr
0.680
0.050 0.034
0.002 0.001
0.031 0.021
0.0 0.0
0.016 0.011
3.1B 1.262
NA NA
0.0 0.0
0.101 0.069
1.667 1.134
1.667 1.134
274.2
12.98 3559.0
0.061 16.73
0.054 14.81
0.003 0.823
0.004 1.097
117.3 32164.0
NA NA
0.198 54.3
0.663 181.8
6.80 1865.0
539.0 147794.0
MJCHMHf CEERSITCNS
Electrolyte
Cell Vfesh Preparation
rag/1* kg/yr rag/1* kg/yr
4.71
37.2 175.2
0.073 0.344
0.045 0.212
0.006 0.028
0.006 0.028
56.4 256.6
0.024 0.113
211.0 994.0
0.410 1.931
6.42 30.24
330.0 1554.0
0.0371
37.2 1.376
0.073 0.003
0.045 0.002
0.006 0.000
0.006 0.000
56.4 2.087
0.024 0.001
211.0 7.81
0.410 0.015
6.42 0.238
330.0 12.21
NA - Not analyzed (treated as zero in calculations) •
* Based on flow weighted mean concentrations fran sampled process elements.
-------
TOBI2X-2
HROCESS HH4NP WRSIHKIER StM*K3f
CMMUM SUBCHMXEV
Floor and Caamun Bowder Salver rowaer Cadatum Hyaraxiae Nickel Ryarad.de
Equipment Hash BqployeeWssh Production Production Production Production
mg/1 kg/yr mg/1 kg/yr mg/1 kg/yr nrj/1 kg/yr mg/1** kg/yr mg/1*** kg^yr
Flow Vyr (106) 7.781
Pollutants
118 CaAdun 29.2 227.2
119 Ctoondun 0.081 0.630
121 Cyanide NA ^BV
122 Lead 0.0 0.0
123 Mercury 0.0 0.0
124 Nickel 9.08 70.6
126 Silver NR NR
128 Zinc 12.9 100.4
Cobalt 5.04 39.21
Oil S Grease MR MR
TSS NR NR
0.068
0.069 0.005
0.0 0.0
0.022 0.001
0.0 0.0
0.0 0.0
0.130 0.009
MR NR
0.160 0.011
0.0 0.0
167.0 11.36
197.3 13.42
27.00
177.3 4787.0
0.004 0.108
0.026 0.702
0.0 0.0
0.008 0.216
0.062 1.674
MR MR
4272 115314
0.0 0.0
4.37 117.9
17.47 471.7
0.80
0.002 0.002
0.933 0.746
NR MR
0.147 O.llfi
0.003 0.002
0.877 0.702
16.67 13.34
0.333 0.266
0.900 0.720
MR MA
21.0 16.8
1.6
63.3 101.3
0.19 0.304
0.06 0.096
0.0 0.0
0.001 0.002
3.300 5.28
NR MR
0.060 0.096
0.110 0.176
2.700 4.320
354.1 567.0
170.0
12.98 2207.0
0.061 10.37
0.054 9.18
0.003 0.510
0.004 0.680
117.3 19941.0
NR MR
0.198 33.66
0.663 112.7 '
6.80 1156.0
539.0 91630.0
•iUlRJj a.lH A IT-UJMt
RRHHRSIE
jcg/1 kgfyr
748.35
32.96 24665.62
0.073 54.63
0.049 36.67
0.002 1.50
0.008 5.99
70.7 52908.35
0.018 13.47
155.8 116592.93
0.469 350.98
6.47 4841.82
387.7 290135.30
00
Ul
N>
NR - Not analyzed (treated as zero in calculations).
~ l^sfld on flow weighted moan ommdUiLtaLioi£ £i.un sanplod process elements.
** - Based on mean raw waste concentrations fran lapregnatfid Anode Manufacture.
***- Based on mean raw waste concentrations from Nickel Bqaregnated Cathode Manufacture.
-------
00
Ln
00
TABLE X-3
SW*RRY OF TREATMENT EFFECTIVENESS
CAEMIUM SUBCATEGORY
PARAMETER
FLOW (I/kg)*
118 CACMIUM
119 CHROMIUM
121 CfflNIDE
122 LEAD
123 MERCURY
124 NICKEL
126 SILVER
128 ZINC
COBALT
RAW WASTE
mg/1
1303
32. 960
0.073
0.049
0.002
0.008
70.700
0.018
155.800
0.469
OIL & GREASE 6.470
TSS 387.700
rag/kg
.740
42971.270
95.173
63.883
2.607
10.430
92174.418
23.467
203122.692
611.454
8435.198
505459.998
BPT
mg/i
(PSES 0)
ing/Kg
1303.740
0.079
0.073
0.049
0.002
0.008
0.570
0.018
0.300
0.070
6.470
12.000
102.995
95.173
63.883
2.607
10.430
743.132
23.467
391.122
91.262
8435.198
15644.880
BAT 1
rag/1
178.
0.079
0.080
0.070
0.015
0.059
0.570
0.100
0.300
0.070
10.000
12.000
(PSES 1)
mg/kg
220
14.079
14.258
12.475
2.607
10.430
101.585
17.822
53.466
12.475
1782.200
2138.640
BAT 2
mg/1
178
0.049
0.070
0.047
0.015
0.036
0.220
0.070
0.230
0.050
10.000
2.600
(PSES 2)
rag/kg
.220
8.733
12.475
8.376
2.607
6.416
39.208
12.475
40.991
8.911
1782.200
463.372
BAT
mg/1
0.049
0.070
0.047
0.080
0.036
0.220
0.070
0.230
0.050
10.000
2.600
3 (PSES 3)
mg/kg
26.410
1.294
1.849
1.241
2.113
0.951
5.810
1.849
6.074
1.321
264.100
68.666
BAT
W3/1
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
4 (PSES 4)
•ng/kg
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
* Normalized flow based on total subcategory cadmium anode weight.
-------
00
Ut
TRBLE X-4
REDUCTION BENEFITS OF OCNTBX SYSTEMS
CMMIUM SUBCHTEGOW - TOTRL
PARAMETER
FLOW 1/yr (106)
118 QUMIUM
119 CHHCKItM
121 CTWUDE
122 LEAD
123 MEICORy
124 fflCKEL
126 SOTER
128 ZINC
CDBRLT
OIL E. GREASE
TSS
TOXIC METALS
casvsjncHALs
TOTAL POULa.
RAW HASTE
Kg/yr
748.35
24665.62
54.63
36.67
1.50
5.99
52908.35
13.47
116592.93
350.98
4841.82
290135.29
194242.49
294977.11
489607.25
BST 6 PSES 0
Renoved
kg/yr
24606.50
0.00
0.00
0.00
0.00
52481.79
0.00
116368.42
298.60
0.00
281155,09
193456.71
281155.09
474910.40
Discharged
kg/yr
748.35
59.12
54.63
36.67
1.50
5.99
426.56
13.47
224.51
52.38
4841,82
8980.20
785.78
13822.02
14696.85
BKT1
Reaoved
kg/yr
24657.54
46.45
29.51
0.00
0.00
52850.04
3.24
116562.24
343,82
3818.82
288907.69
194119.51
292726.51
487219.35
& PSES 1
Discharged
kg/yr
102.30
8.08
8.18
7.16
1.50
5.99
58.31
10.23
30.69
7.16
1023.00
1227.60
122.98
2250.60
2387.90
BAT 2 & PSES 2
kg/yr
24660.61
47.47
31.86
0.00
2.31
52885.84
6.31
116569,40
345.86
3818.82
289869.31
194171.94
293688.13
488237.79
Discharged
102.30
5.01
7.16
4.81
1.50
3.68
22.51
7.16
23.53
5,12
1023.00
265.90
70,55
1288.98
1369.46
BAT 3 6 PSES 3
Removed Discharged
kg/yr kg/yr
24664.88
53.57
35.%
0.29
5.44
52905.01
12.41
116589.44
350.22
4690.22
290095.87
194231.04
294786.09
489403.31
15.16
0.74
1.06
0,71
1.21
0.55
3.34
1.06
3.49
0.76
151.60
39.42
11.45
191.02
203.94
BAT 4 S
Removed
kg/yr
- 24665.62
54.63
36.67
1.50
5.99
52908.35
13.47
116592.93
350.98
4841.82
290135.29
194242.49
294977.11
489607.25
PSES 4
Disd*. rged
to yr
C 00
( 00
( 00
C 00
C 00
( 00
(• 00
c.oo
C) 00
11.00
0.00
0.00
0.00
o.oo
(5.00
SLUDGE GEN
4470633.08
4546037.03
4552391.04
4559114.87
4560299.05
-------
TABU: x-5
POLUJTANT REDUCTION BENEFITS OP CONTROL SYSTEMS
CADMIUM SUBCATEGORY - DIRECT DISCHARGERS
J\-
ft
PARAMETER
FLOW 1/yr (106)
118 CADMIUM
119 CHROMIUM
121 CYANIDE
122 LEAD
123 MERCURY
124 NICKEL
126 SILVER
128 ZINC
COBALT
OIL & GREASE
TSS
TOXIC METALS
COSVEOTIONALS
TOTAL POLLU.
RAW HASTE
kg/yr
538.45
17747.32
39.31
26.38
1.08
4.31
38068.42
9.69
83890.51
252.54
' 3483.77
208757.06
139760.64
212240.83
352280.39
Removed
kg/yr
17704.78
0.00
0.00
0.00
0.00
37761.50
0.00
83728.97
214.85
0.00
202295.66
139195.25
202295.66
341705.76
BPT
Discharged
kg/yr
538.45
42.54
39.31
26.38
1.08
4.31
306.92
9.69
161.54
37.69
3483.77
6461.40
565.39
9945.17
10574.63
BAT
Removed
kg/yr
17741.51
33.43
21.23
0.00
0.00
38026.46
2.33
83868.43
247.39
2747.67
207873.74
139672.16
210621.41
350562.19
1
Discharged
kg/yr
73.61
5.81
5.88
5.15
1.08
4.31
41.96
7.36
22.08
5.15
736.10
883.32
88.48
1619.42
1718.20
Removed
kg/yr
17743.72
34.16
22.92
0.00
1.66
38052.22
4.54
83873.58
248.85
2747.67
208565.67
139709.88
211313.34
351294.99
BAT 2
Discharged
kg/yr
73.61
3.60
5.15
3.46
1.08
2.65
16.20
5.15
16.93
3.69
7.36.10
191.39
50.76
927.49
985.40
BAT
Renewed
kg/yr
17746.79
38.55
25.87
0.21
3.91
38066.02
8.93
83888.00
251.99
3374.67
208728.69
139752.41
212103.36
352133.63
3
Discharged
kg/yr
10.91
0.53
0.76
0.51
0.87
0.40
2.40
0.76
2.51
0.55
109.10
28.37
8.23
137.47
146.76
Removed
kg/yr
17747.32
39.31
26.38
1.08
4.31
38068.42
9.69
83890.51
252.54
3483.77
208757.06
139760.64
212240.83
352280.39
BAT 4
Discharged
kg/yr
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
SLUDGE GEN
3216693.20
3270947.21
3275519.04
3280357.34
3281209.35
-------
TABLE X-6
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 11.95 5.27
Chromium 15.47 6.33
Cyanide 10.19 4.22
Lead 14.76 7.03
Mercury 8.79 3.52
*Nickel 67.49 44.64
Silver 14.41 5.98
*Zinc 51.32 21.44
*Cobalt 7.38 3.16
*Regulated Pollutant
856
-------
TABLE X-7
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Impregnated Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 68.0 30.0
Chromium 88.0 36.0
Cyanide 58.0 24.0
Lead 84.0 40.0
Mercury 50.0 20.0
*Nickel 384.0 254.0
Silver 82.0 34.0
*Zinc 292.0 122.0
*Cobalt 42.0 18.0
*Regulated Pollutant
857
-------
TABLE X-8
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Nickel Electrodeposited Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium - 11.22 4.95
Chromium 14.52 5.94
Cyanide 9.57 3.96
Lead 13.86 6.60
Mercury 8.25 3.30
*Nickel 63.36 41.91
Silver 13.53 5.61
*Zinc 48.18 20.13
*Cobalt 6.93 2.97
*Regulated Pollutant
858
-------
TABLE X-9
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Nickel Impregnated Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium 68.0 30.0
Chromium 88.0 36.0
Cyanide 58.0 24.0
Lead 84.0 40.0
Mercury 50.0 20.0
*Nickel 384.0 254.0
Silver 82.0 34.0
*Zinc 292.0 122.0
*Cobalt 42.0 18.0
*Regulated Pollutant
859
-------
TABLE X-10
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.26 0.11
Chromium 0.33 0.14
Cyanide 0.22 0.090
Lead 0.32 0.15
Mercury 0.19 0.075
*Nickel 1.44 0.95
Silver 0.31 0.13
*Zinc 1.10 0.46
*Cobalt 0.16 0.067
*Regulated Pollutant
860
-------
TABLE X-11
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Electrolyte Preparation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.027 0.012
Chromium 0.035 0.014
Cyanide 0.023 0.009
Lead 0.033 0.016
Mercury 0.020 0.008
*Nickel 0.153 0.101
Silver 0.032 0.013
*Zinc 0.116 0.048
*Cobalt 0.016 0.007
*Regulated Pollutant
861
-------
TABLE X-12
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.51 0.23
Chromium 0.66 0.27
Cyanide 0.44 0.18
Lead 0.63 0.30
Mercury 0.38 0.15
*Nickel 2.88 1.91
Silver 0.62 0.26
*Zinc 2.19 0.92
*Cobalt 0.32 0.14
*Regulated Pollutant
862
-------
TABLE X-13
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.79 0.35
Chromium 1.03 0.42
Cyanide 0.68 0.28
Lead 0.98 0.47
Mercury 0.58 0.23
*Nickel 4.47 2.96
Silver 0.96 0.40
*Zinc 3.40 1.42
*Cobalt 0.49 0.21
*Regulated Pollutant
863
-------
TABLE X-14
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Cadmium Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
*Cadmium 2.23 0.99
Chromium 2.89 1.18
Cyanide 1.91 0.79
Lead 2.76 1.31
Mercury 1.64 0.66
*Nickel 12.61 8.34
Silver 2.69 1.12
*Zinc 9.59 4.01
*Cobalt 1.38 0.59
*Regulated Pollutant
864
-------
TABLE X-15
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
*Cadmium 1.09 0.48
Chromium 1.41 0.58
Cyanide 0.93 0.39
Lead 1.35 0.64
Mercury 0.80 0.32
*Nickel 6.16 4.08
*Silver 1.32 0.55
*Zinc 4.69 1.96
*Cobalt 0.67 0.29
*Regulated Pollutant
865
-------
TABLE X-16
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Cadmium Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
*Cadmium 0.05 0.02
Chromium 0.061 0.025
Cyanide 0.040 0.016
Lead 0.058 0.028
Mercury 0.035 0.014
*Nickel 0.27 0.18
Silver 0.057 0.023
*Zinc 0.20 0.09
*Cobalt 0.03 0.01
*Regulated Pollutant
866
-------
TABLE X-17
CADMIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Nickel Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
*Cadmium 5.61 2.48
Chromium 7.26 2.97
Cyanide 4.79 1.98
Lead 6.93 3.30
Mercury 4.13 1.65
*Nickel 31.68 20.96
Silver 6.77 2.81
*Zinc 24.09 10.07
*Cobalt 3.47 1.49
*Regulated Pollutant
867
-------
TABIJEX-18
SUMMARY OF TREATMENT EFFECTIVENESS
CALCIUM SUBCKFEGORY
PARAMETER RAW WASTE
rog/1
rag/kg
FLOW (I/kg)* 24.110
116 ASBESTOS!/ sis.ooo 7594.650
119 CHROMIUM 61.000 1470.710
TSS 368.000 8872.480
BPT (PSES 0)
mgTkg
BAT 1 (PSES 1)
BAT 2
10.352
0.080
12.000
mg/kg mg/1
2)
rag/kg
24.110
24.110
0.000
249.587
1.929
289.320
2.243
0.070
2.600
54.079
1.688
62.686
0.000
0.000
0.000
0,000
0.000
0,000
00
o
00
* Normalized flew based can total weiglit of reactants for "heat paper production.
"L/ Asbestos is in millions of fibers per liter and millions of fibers per kg.
-------
TABLE X-19
POLLUTANT REDUCTION BENEFITS OF coNrraaL SYSTEMS
OUJCIUM SUBCATEGORY - TOTAL
PARAMETER
RAW WASTE
oo
*9/yr
FLOW 1/yr (106)*
116 ASBESTOSi/
119 CHROMIUM
TSS
TOXIC METALS
OONVENTICNALS
TOTAL POLLU.
0.13
40.95
7.93
47.84
7.93
47.84
55.77
BPT
Removed
kg/yr
39.60
7.92
46.28
7.92
46.28
54.20
& PSES 0
Discharged
kg/yr
0.13
1.35
0.01
1.56
0.01
1.56
1.57
BAT 1
Removed
kg/yr
40.66
7.92
47.50
7.92
47.50
55.42
& PSES 1
Discharged
kg/yr „
0.13
0.29
0.01
0.34
0.01
0.34
0.35
BAT 2 & PSES 2
SLUDGE GEN
317.73
323.83
Removed
kg/yr
40.95
7.93
47.84
7.93
47.84
55.77
325.64
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.00
0.00
0.00
* 100% of the total flow is for indirect dischargers.
I/ Asbestos is in trillions of fibers per year; not included in total.
-------
TABLE X-20
POLLUTANT REDUCTION BENEFITS OF CONTROL OPTIONS
LECLANCHE SUBCATEGORY
RAW WASTE
BPT & BAT (PSES)
oo
"-J
o
Flow 1/yr (10^)
I/kg*
POLLUTANTS
115 Arsenic
118 Cadmium
119 Chromium.
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Oil and Grease
TSS
Toxic Metals
Convent ionals
All Pollutants
mg/1
0.090
0.053
0.409
0.466
0.101
13.40
1.212
0.086
317.5
69.3
115.0
*2,536
16.71 0.200
0.758 0.009
Removed Discharged
mg/kg kg/yr kg/yr kg/yr
0.068 1 .503 1 .435
0.040 0.881 0.871
0.310 6.84 6.826
• 0.353 7.78 7.702
0.076 1.684 1.668
10.16 223.9 223.893
0.919 20.25 20.206
0.065 1 .435 1 .395
240.7 5,305.4 5,305.35
52.5 1,158.0 1,157.97 "
87.2 1,921.7 1,919.70
1 ,922 42,376.5 42,375.98
5,569.7 5,569.35
44,298.2 44,295.7
51,025.9 51,023.0
0.068
0.010
0.014
0.078
0.016
0.007
0.044
0.040
0.046
0.028
2.00
0.520
0.323
2.52
2.87
Sludge Generated
288,555.0
formalized flow based on total subeategory zinc anode weight.
-------
TABLE X-21
LECLANCHE SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Foliar Battery Miscellaneous Wash
Pollutant or
Pollutant Maximum for Maximum for
Property ; any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.092 0.038
Cadmium 0.013 0.005
Chromium 0.024 0.010
Copper 0.084 0.040
Lead 0.018 0.009
Mercury 0.010 0.004
Nickel 0.036 0.024
Selenium 0.054 0.024
Zinc 0.067 0.030
Manganese 0.019 0.015
Oil and Grease 0.66 0.66
TSS 0.99 0.79
pH Within the range of 7.5 - 10.0 at all times
871
-------
00
TABLE X-22
PROCESS ELEMENT FLOW StMftTOT
LITHIUM SUBCATEGOM
Flow (I/kg)
Process Element Median Mean BPT (PSES) BAT (PSES)
Cathodes
Lead Iodide
Iron Disulfide
Ancillary Operations
Heat Paper Production
Lithium Scrap Disposal
Cell Testing
Cell Wash
Mr Scrubbers
Floor & Equipment Wash
63.08
7.54
24.1
nil.
0.014
0.929
10.59
0.094
63.08
7.54
115.4
nil.
0.014
0.929
10.59
0.094
63.08
7.54
24.1
—
0.014
0.0
10.59
0.094
63.08
7.54
0.0
. —
0.014
0.0
10.59
0.094
-------
TABLE X-23
SUMMARY OF TREATMENT EFFECTIVHNESS
LITHIUM SUBCATEGOKY
oc
—I
LO
PARAMEPER
RAW WASTE
mg/1
mg/kg
BPT (PSES 0)
mg/1
mg/kg
BAT 1 (PSES 1)
mg/1
mg/kg
BAT 2 (PSES 2)
mg/1
mg/kg
BAT 3 (PSKS 3)
mg/1
mg/kg
HEAT PAPER PRODUCTION
FLOW (I/kg)*
116 ASBESTOS!/
119 CHROMIUM
122 LEAD
128 ZINC
COLBALT
IRON
TSS
24.
315.000
61.000
368.000
110
7594.650
1470.710
8872.480
10.352
0.080
0.120
0.300
0.070
0.410
12.000
24.110
249
1
2
7
1
9
289
.587
.929
.893
.233
.688
.'885
.320
2.243
0.070
0.080
0.230
0.050
0.280
2.600
24.110
54.079
1.688
1.929
5.545
1.206
6.751
62.686
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
CATHODE AND ANCILLARY OPERATIONS
FLOW (I/kg)**
116 ASBESTOS!/
119 CHROMIUM
122 LEAD
128 ZINC
COBALT
IRON
COD
TSS
0.
6.440
0.781
4.880
0.464
0.175
54.153
1424.242
43.279
575
3.703
0.449
2.806
0.267
0.101
31.138
818.939
24.885
6.440
0.080
0.120
0.300
0.070
0.410
10.000
12.000
0.575
3
0
0
0
0
0
5
6
.703
.046
.069
.173
.040
.236
.750
.900
2.24
0.070
0.080
0.230
0.050
0.280
10.000
2.600
0.575
1.290
0.040
0.046
0.132
0.029
0.161
5.750
1.495
0.
2.243
0.070
0.080
0.230
0.050
0.280
10.000
2.600
575
1.290
0.040
0.046
0.132
0.029
0.161
5.750
1.495
2.243
0.070
0.080
0.230
0.050
0.280
10.000
2.600
Q.57r>
1.290
0.040
0.046
0.132
0.029
0.161
5.750
1.495
AIR SCRUBBER WASTEWATERS
FLOW (I/kg)**
TSS
10
1208.750
.590
12800.663
12.000
10.590
127
.080
12.000
10.590
127.080
10
12.000
.590
127.080
2.600
10.590
27.534
* Normalized flew based on total weight of reactants.
!/ Asbestos is millions of fibers per liter and millions of fibers per kilogram.
** Normalized flow based on process element(s) battery weight.
-------
oc
•-g
•P-
PARAMETER RAW VBSTE
kg/yr
HEAT PAPER PRODUCTION
HXW 1/yr (10s) 0.04
116 ASBESTOS!/ 12. eo
119 CHROMIUM 2.44
122 LEAD
128 ZINC
COBALT
IRON
TSS 14.72
CATHODE AND ANCILLARY OPERATIONS
FLOW 1/yr (106) 0.21
116 ASBESTOSl/ 1.35
119 CHROMIUM 0.16
122 LEAD 1.02
128 ZINC 0.10
COBALT 0.04
IRON 11.37
CCO 299.09
TSS 9.09
AIR SCRUBBER WASTEWATERS
BPT &
Removed
kg/yr
12.19
2.44
(-0.005)
(-0.010)
(-0.002)
(-0.014)
14.24
0.00
0.14
0.995
0.050
0.032
11.294
296.99
6.57
PSES 0
Discharged
kg/yr
0.04
0.41
0.00
0.005
0.010
0.002
0.014
0.48
0.21
1.35
0.02
0.025
0.050
0.008
0.076
2.10
2.52
TMLEX-24
REDUCTION BENEFITS OF OONTHOt SYSTEMS
LITHIUM SUKATBSOKif
BAT 1 & PSES 1
Believed
kg/yr
12.51
2.44
(-0.003)
(-0.008)
(-0.002)
(-0.010)
14.62
0.88
0.15
1.003
0.058
0.032
11.320
296.99
8.54
Fl£W 1/yr (106) 0.11 0.11
TSS 132.96 131.64 1.32 131.64
I/ Aslaestos is trillions of fibers per year? not included in totals.
Discharged
kg/yr
0.04
0.09
0.00
0.003
0.008
0.002
0.010
0.10
0.21
0.11
1.32
BAT 2 & PSES 2
Renewed
kg/yr
12.60
2.44
14.72
0.47
0.01
0.017
0.042
0.008
0.050
2.10
0.55
0.88
0.15
1.00
0.05
0.03
11.31
296.99
8.54
131.64
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.21
0.47
0.01
0.02
0.05
0.01
0.06
2.10
0.55
0.11
1.32
BAT 3 6 PSES 3
Removed
kg/yr
12.60
2.44
14.72
0.88
0.15
1.00
0.05
0,03
11.31
296.99
8.54
132.67
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.21
0.47
0.01
0.02
0.05
0.01
0.06
2.10
0.55
0.11
0.29
-------
00
-vl
TABLE X-24
POLUJFftOT REDUCTION BENEFITS OF COTTRQL SYSTEMS
LITHIUM SUBCATBGOKSf
PARAMETER RAW VftSTE
kg/yr
BPT & PSES 0
Removed
Discharged
kg/yr
LITHIUM SUBCATBGORy SIMMS' 2/
FLOW 1/yr (106)
116 ASBESTOS I/
119 CHROMIUM
122 LEAD
128 ZINC
COBALT
IRON
COD
TSS
TOXIC METALS
CDNVEHTIONALS
TOTAL POLLU,
0.36
13.95
2.60
1.02
0.10
0.04
11.37
299.09
156.77
3.72
156.77
470.99
12.19
2.58
0.99
0.04
0.03
11.28
296.99
152.45
3.61
152.45
464.36
0.36
1.76
0.02
0.03
0.06
0.01
0.09
2.10
4.32
0.11
4.32
6.63
BAT 1 & PSES 1 __
Removed Discharged Removed
SLUDGE GEN
922.02
13.39
2.59
1.00
0.05
0.03
11.31
296.9?
154.80
3.64
154.80
466.77
934.41
0.36
0.56
0.01
0.02
0.05
0.01
0.06
2.10
1.97
0.08
1.97
4.22
BftT 2 & PSiS 2
13.48
2.59
1.00
0.05
0.03
11.31
296.99
154.90
3.64
154.90
466.87
934.91
Discharged
kg/yr
0.32
0.47
0.01
0.02
0.05
0.01
0.06
2.10
1.87
0.08
1.87
4.12
BAT 3 S PSES 3
Removed
kg/yr
Discharged
13.48
2.59
1.00
0.05
0.03
11.31
296.99
155.93
3.64
155.93
467.90
940.06
0.32
0,47
0.01
0.02
0.05
0.01
0.06
2.10
0.84
0.08
0.84
3.09
I/ Asbestos is trillions of fibers per year? not includes! in totals.
2/ For direct dischargers only multiply totals by 0.01.
For indirect dischargers only multiply totals by 0.99.
-------
TABLE X-25
LITHIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Lead Iodide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
Chromium
Lead
Zinc
Cobalt
Iron
27.8
26.5
92. 1
13.3
75.7
1 1 .4
12.6
38.5
5.68
38.5
TABLE X-26
LITHIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Iron Bisulfide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib of iron disulfide
Chromium 3.32 1 .36
Lead 3.17 1.51
Zinc 11.0 4.60
Cobalt 1.58 0.68
Iron 9.05 4.60
876
-------
TABLE X-27
LITHIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.047 0.019
Lead 0.045 0.021
Zinc 0.157 0.065 '
Cobalt 0.022 0.009
Iron 0.129 0.065
877
-------
TABLE X-28
PSQCESS ELEMENT FLOW
SUBCATEGOKf
oc
•vj
QC
Process Element
Median
Flow (I/kg)
Mean BPT (PSES) BAT (PSES)
Cathodes
Silver Chloride
(Chemically Reduced)
Silver Chloride
(Electrolytic)
Ancillary Operations
Heat Paper Production
Cell Testing
Floor & Equipment Wash
Mr Scrubbers
4915.
145.
24.1
52.6
0.094
206.5
4915*
145.
115.4
52.6
0.094
206.5
2458.
145.
24.1
52.6
0.094
206.5
81.9
145.
0.0
• 52.6
0.094
206.5
-------
00
PARAMETER
RAWTOSTE
BIT 0)
TABLE X-29
OF TREAaMOfT
MAC3SES1UM SUBCATBSORSf
BAT 1 (PSES 1)
BftT 2 (PSES 2)
BAT 3 (PSES 3}
mg/i
mg/kg
mg/1
mg/kg
mg/1
rag/kg
mg/1
ing/kg
mg/1
tug/kg
HEAT PAPER PRODUCTION
FLOW (I/kg)*
116 ASBESTOS i/
119 CHROMIUM
TSS
24.
315.000
61.000
368.000
110
7594.650
1470.710
8872.480
24
10.352
0.080
12.000
.110
249.587
1.929
289.320
2.243
0.070
2.600
24.110
54
1
S2
.079
.688
.686
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo
0.000
0.000
0.000
CELL TESTING AND FLOOR AND BQUIPMSOT WASH
FLOW (I/kg)*
122 LEAD
124 NICKEL
126 SILVER
IROH
TSS
SILVER CHLORIDE
FLOW (I/kg)*
122 LEAD
124 NICKEL
126 SILVER
IRON
COD
TSS
AIR SCRUBBERS
FLOW (I/kg)*
TSS
52.
1.220
0.110
14.600
1.947
828.000
700
64.294
5.797
769.420
102.607
43635.600
52
0.120
0.110
0.100
0.410
12.000
.700
6.324
5.797
5.270
21.607
632.400
0.120
0.110
0.100
0.410
12.000
52.700
6
5
5
21
632
.324
.797
.270^
.607
.400
0.080
0.110
0.070
0.280
2.600
52.700
4.216
5.797
3.689
14.756
137.020
0.080
0.110
0.070
0.280
2.600
52.700
4.216
5.797
3.689
14.756
137.020
CATHODE PRODUCTION
844.
0.051
0.051
0.248
0.560
140.000
0.705
206.
1208.750
000
43.044
43.044
209.312
472.640
118160.000
595.020
500
249606.875
483
0.089
0.089
0.100
0.410
10.000
1.230
.900
43.044
43.044
48.390
198.399
4839.000
595.020
0.120
0.317
0.100
0.410
10.000
4.382
206.500
12.000
2478.000
12.000
135.800
16
43
13
55
1358
595
206.500
2478
.296
.044
.580
.678
.000
.020
.000
0.080
0.220
0.070
0.280
10.000
2.600
12.000
135.800
.10.864
29.876
9.506
38.024
1358.000
353.080
206.500
2478.000
0.080
0.220
0.070
0.280
10.000
2-600
2.600
135.800
10.864
29.876
9.506
38.024
1358.000
353.080
206.500
536.900
* Normalized flew based on weight of process element(s) production normalizing parameters.
I/ Asbestos is millions of fibers per liter and millions of fibers per kilogram.
-------
00
00
c
PARAMETER
Rsw WASTE
kg/yr
; BET & PSES 0
Removed
kg/yr
Disdiarged
Bfill S 5SES 1
Removed
kg/yr
Discharged
kf/yr
HEAT PAPER PRODUCTION
H/3W 1/yr (106)
116 ASBESTOS ll
119 CHBOMIUM
TSS
CSLb TESTING M!D Fl
FLO! 1/yr Cl06)
122 ISM) 0.
124 NICKEL
126 SILVER
IKON
TSS
2.60
819.00
' 158.60
956.80
QOR ABD EC
0.11
13
0.01
1.61
0.21
91.08
792.08
158.39
925.60
wsMsm mm
0.12
0.00
1.60
0.16
89.76
2.60
26.92
0.21
31.20
0.11
0:01 o.
0.01
0.01
0.05
1.32
813.17
158.42
950.04
12
0.00
1.60
0.16
89.76
2.60
5.83
0.18
6.76
0.11
0.01
0.01
0.01
0.05
1.32
SILVER CHDDRIDE CATHODE PRODUCTION
FI£W 1/yr (1Q6)
122 LEAD
124 NICKEL
126 STIVER
IRDH
COD
TSS
AIR SCWBBERS
FWW 1/yr ClO6)
TSS
0.75
0.04
0.04
0.19
0.42
105.00
0.53
0.45
543.94
0.00
0.00
0.15
0.24
100.70
0.00
538.54
0.43
0.04
0.04
0.04
0.18
4.30
0.53
0.45
5.40
0.03
0.00
0.18
0.37
103.80
0.00
538.54
0,12
0.01
0,04
0.01
0.05
1.20
0.53
0.45
5.40
•TABUS X-30
PCtWBOT REEOCJTION BENEFITS OF COOTBX SYSTEMS
WSG8BSMM SUBCWTBGOW
BAT 2 SPSES 2
Removed
819.00
158.60
956.80
0.12
0.00
1.60
0.18
90.79
0.03
0.01
0.18
0.39
103.80
0.22
538.54
Discharged
kg/yr
0.01
0.00
0.00
0.00
0.00
0.11
0.12
0.01
0.03
0.01
0.03
1.20
0.31
0.45
5.40
SKC 3 S, ESES 3
Removed
kg/yr
Discharged
kg/yr
819.00
158.60
956.80
0.03
0.01
0.18
0.39
103.80
0.22
542.77
0.00
0.00
0.00
0.00
0.11
0.01
0.01
0.03
0.29
0.12
0.00
1.60
0.18
90.79
0.01
0.01
0.01
0.03
0.29
0.12
0.01
0.03
0.01
0.03
1.20
0.31
0.45
1.17
\f Asbestos is trillions of fibers per yearj not included in totals.
-------
00
00
PARAMETER
RAW WASTE
fcg/yr
BPT
Removed
kg/yr
& PSES 0
Discharged
kg/yr
BAT
Removed
Kg/yr
1 & PSES 1
Discharged
Kg/yr
MAGNESIUM SUBCA.TB30KY SMftlff 2/
FLOW 1/yr (106)
116 ASBESTOS I/
119 CHROMIUM
122 LEAD
124 NICKEL
126 SILVER
IRON
ODD
TSS
TOKtC METALS
CONVEOTIONALS
TOTAL POIJJJ.
3.91
819.00
158.60
0.17
0.05
1.80
0.63
105,00
1592.35
160.62
1592.35
1858.60
792.08
158.39
0.12
O.'OO
1.75
0.40
100.70
1553.90
160.26
1553.90
1815.26
3.59
26.92
0.21
0.05
0.05
0.05
0.23
4.30
38.45
0.36
38.45
43.34
813.17
158.42
0.15
0.00
1.78
0,53
103.80
1578.34
160.35
1578.34
1843.02
3.28
5.83
0.18
0.02
0.05
0.02
0.10
1.20
14.01
0.27
14.01
15.58
TABLE X-30
REDUCTION BENEFITS OP OOHTBOL SYSTEMS
MAGNESIUM SUBCATEGORY
BAT 2 & PSES 2
SLUDGE GEM
9514.35
9638.83
I/ Asbestos is trillions of fibers per year; not included in totals.
2/ For direct dischargers only multiply totals by 0.05.
Bbr indirect dischargers only multiply totals by 0.95.
Removed
819.00
158.60
0.15
0.01
1.78
0.57
103.80
1586.35
160.54
1586.35
1851.26
9681.63
Discharged
kg/yr
0.68
0.00
0.00
0.02
0.04
0.02
0.06
1.20
6.00
0.08
6.00
7.34
BAT 3 S PSES 3
Removed
kg/yr
Discharged
kg/yr
819.00
158.60
0.15
0.01
1.78
0.57
103.80
1590.58
160.54
1590.58
2674.49
13797.78
0.68
0.68
0.00
0.02
0.04
0.02
0.06
1.20
1.77
0.08
1.77
3.11
-------
TABLE X-31
MAGNESIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Chloride Cathodes - Chemically Reduced
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium
Lead
Nickel
Silver
Iron
COD
36.04
34.40
157.3
33.58
98.28
122900.0
14.74
16.38
104.0
13.92
49.96
59975.0
TABLE X-32
MAGNESIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Chloride Cathodes - Electrolytic
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 63.8 26.1
Lead 60.9 29.0
Nickel 278.4 184.2
Silver 59.5 24.7
Iron 174.0 88.5
COD 7250.0 3538.0
882
-------
TABLE X-33
MAGNESIUM SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Cell Testing
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium
Lead
Nickel
Silver
Iron
23.2
22.1
101 .0
21 .6
63. 1
9.47
10.5
66.8
8.94
32.1
TABLE X-34
MAGNESIUM SUBCATEGORYv
BAT EFFLUENT LIMITATIONS
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.041 0.016
Lead 0.039 0.018
Nickel 0.180 0.119
Silver 0.038 0.015
Iron 0.112 0.057
883
-------
TABLE X-35
oo
00
Process Element
Anodes
Zinc Powder-Wet Amalgated
Zinc Powder-Gelled Amalgam
Zinc Oxide Powder-Pasted or
Pressed, Reduced
Zinc Electrodeposited
Cathodes
Silver Powder Pressed and
Electrolytically Oxidized
Silver Oxide Powder - Thermally
Reduced or Sintered/
Electrolytically Formed
Silver Peroxide Powder
Nickel Impregnated
Ancillary Operations
Cell Wash
Electrolyte Preparation
Silver Etch
Mandatory Employee Wash
Reject Cell Handing
Floor & Equipment Wash
Silver Peroxide Production
PROCESS ELEMENT PLOW SUMMARY
ZINC SUBCATEGORY
Flow (I/kg)
Median
2.2
0.68
117.
3190.
Mean
3.8
0.68
143.
3190.
BPT
3.8
0.68
143.
3190.
BAT 1&2
(PSES1&2)
0.55
0.068
21.67
241.7
BAT 3
(PSES 3)
0.55
0.0
21.67
241.7
BAT 4
(PSES 4)
0.0
0.0
3.251
36.26
196.
196.
196.
29.70
29.70
4.45
131.
12.8
1720.
0.34
0.0
49.1
0.27
0.002
7.23
52.2
131.
31.4
1640.
1.13
0.12
49.1
0.27
0.01
7.23
52.2
131.
31.4
1640.
1.13
0.12
49.1
0.27
0.01
7.23
52.2
19.85
4.76
200.0
0.17
0.0
7.44
0.27
0.01
0.84
7.91
19.85
4.76
200.0
0.17
0.0
7.44
0.27
0.01
0.84
7.91
2.978
0.714
30.0
0.026
0.0
1.116
0.041
0.002
0.126
1.187
-------
TAHZ X-36
MflNUFACTSRING ELBBir WSTEWKEER SttfftRY
ZHC SUBCAIEOCR*
ANODES
Zinc Powder
Wet Amalgamated
mg/1
Zinc Powder
Gelled Amalgamated
mg/1 kg/yr
Zinc Qd.de Powder
Pressed & Reduced
mg/1 kg/yr
Zinc
Electrodeposited
mg/1 kg/yr
Flow Vyr (106) 5.60
Pollutants
115 Arsenic 0.050 0.280
118 Cadmium 0.001 0.006
119 Chronium 0.068 0.381
120 Copper 0.014 0.078
121 Cyanide 0.005 0.028
122 Lead 0.0 0.0
123 Mercury 0.453 2.537
124 Nickel 0.0 0.0
125 Selenium 0.0 0.0
126 Silver 0.009 0.050
128 Zinc 301.8 1690.
Aluminum 0.0 0.0
Iron NA NA
Manganese 0.043 0.241
Oil & Grease 9.2 51.5
1SS 12.00 67.2
0.475
0.512 0.243
0.058 0.028
0.025 0.012
0.344 0.163
0.002 0.001
0.017 0.008
0.595 0.283
0.006 0.003
0.063 0.030
0.004 0.002
488.1 231.8
3.13 1.487
0.522 0.248
1.774 0.843
14.60 6.94
282.6 134.2
4.86
0.047 0.228
0.044 0.214
0.021 0.102
0.303 1.473
NA NA
0.073 0.355
0.069 0.335
0.018 0.087
0.0 0.0
0.098 0.476
46.3 225.0
0.160 0.778
NA NA
0.004 0.019
NA NA
57.0 277.0
15.60
0.0 0.0
0.0 0.0
0.012 0.187
0.013 0.203
0.007 0.109
0.015 0.234
14.71 229.5
0.003 0.047
0.0 0.0
0.175 2.730
12.26 191.3
0.0 0.0
NA NA
0.0 0.0
4.233 66.0
7.83 122.1
7.90
0.022 0.174
0.043 0.340
2.323 18.35
2.010 15.88
NA NA
0.342 2.702
0.034 0.269
0.188 1.485
0.0 0.0
1.904 15.04
64.7 511.
0.888 7.02
NA NA
0.016 0.126
NA NA
143.8 1136.
0.065
0.0 0.0
0.0 0.0
0.009 O.OOL
0.001 0.000
0.003 0.000
0.0 0.0
0.017 O.OOL
0.0 0.0
0.0 0.0
8.50 0.561
0.014 0.00.1
0.175 0.01.1
NA NA
0.0 0.0
10.65 0.703
3.55 0.234
CKMEES
Silver Powder
Electro, acidized
mg/1 kg/yr
Silver Oxide Povder
Electro. Fanned
mg/1
c
c
-------
TAHE X-36
ELEHHT WSHSWER
ZDC
OOHOCES
SilverBeaCTd.de
Bowder
rog/1
Impregnated
Nickel
mg/1 kg/yr
OSSffiDONS
Cell Hash
rag/l kg/yr
Electrolyte
Erqaratdoi
mg/1 kg/yr
Silver Etch
mg/1 kg/yr
Beject Cell
Handling
mg/1 kg/yr
Plow 3/yr (106) 0.230
Pollutants
115 Arsenic 0.0 0.0
US Cadndun 2.905 0.668
119 Chroaiun 0.119 0.027
120 Cqa>er 0.003 0.001
121 Cyanide 0.007 0.002
122 Lead 0.0 0.0
123 Mercury 0.007 0.002
124 Nickel 0.002 0.001
125 Selenium 0.0 0.0
126 Silver 43.40 9.98
128 Zinc 0.136 0.031
Mminum 0.890 0.205
Iron NR NA
Manganese 0.0 0.0
Oil & Grease 16.0 3.680
TSS 459.5 105.7
*
NA
12.98 —
0.061 —
NA
0.054 —
0.003 —
0.004
117.3
NA
NA
0.198
NA
NA
NA
6.80
539.0
19.11
0.007 0.134
0.047 0.898
77.1 1473.
0.254 4.854
2.208 42.19
0.015 0.287
1,019 19.47
4.967 94,9
0.015 0.287
0.203 3.879
9.99 190.9
0.028 0.535
NA NA
15.89 303.6
72.2 1380
40.3 770
1.26
i i
0.0 0.0
0.0 0.0
0.0 0.0
NA NA
0.0 0.0
0.040 0.050
0.220 0.277
i i
0.790 0.995
19.20 24.19
0.0 0.0
NA NA
0.0 0.0
m NA
70.0 88.2
0.003
0.0 0.0
0.040 '0.000
0.009 0.000
0.088 0.000
0.010 0.000
0.047 0.000
0.009 0.000
0.0 0.0
0.0 0.0
36.30 0.109
1.060 0.003
0.65 0.002
NA NA
0.013 0.000
0.0 0.0
7.0 0.021
0.022
0.147 0.003
0.006 0.000
0.030 0.001
1.539 0.034
0.055 0.001
0.100 0.002
4.710 0.104
0.207 0.005
NA NA
0.898 0.020
396.8 8.73
106.0 2.332
0.565 0.012
0.159 0.003
12.76 0.281
857 18.85
CO
00
* Negligable Blow.
i Invalid Analysis.
-------
TABLE X-36
MANUFACIWING EUMNT WSEEHAIER
znc SJBCA3B3CSY
GH5RAHCNS
Equipment Wash
mg/1
Floor Wash
mg/1 kg/yr
Btplovee
Wash
mg/1 kg/yr
Silver Powder
Production
mg/1 kg/yr
Silver Perod.de
Powder
mg/1 kg/yr
Flew Vyr (106) 1.180
Pollutants
115 arsenic 0.049 0.058
118 Cadmium 0.062 0.073
119 ChromLvm 0.006 0.007
120 Copper 0.024 0.028
121 Cyanide NA NA
122 Lead 0.002 0.002
123 Marcury V 0.194 0.229
124 Nickel 0.072 0.085
125 Selenium 0.030 0.035
126 Silver 0.336 0.3%
128 Zinc 2.971 3.506
Aluminum 0.041 0.048
Iron NA NA
Manganese 0.028 0.033
Oil & Grease NA NA
OSS 82.4 97.2
0.240
0.0 0.0
0..040 0.010
0.350 0.084
0.230 0.055
NA NA
4.130 0.991
I I
0.380 0.091
0.0 0.0
49.50 11.88
600 144.0
5.83 1.399
NA NA
0.340 0.082
NA NA
2800 672
2.610
0.0 0.0
0.0 0.0
0.0 0.0
0.022 0.057
0.0 0.0
0.0 0.0
0.0 0.0
0.0 0.0
NA NA
0.0 0.0
0.113 0.347
NA NA
NA NA
0.228 0.595
17.43 45.49
90.8 237.0
0.800
0.0 0.0
0.002 0.002
0.933 0.746
6.41 5.13
NA NA
0.147 0.118
0.003 0.002
0.877 0.702
0.0 0.0
16.67 13.34
0.333 0.266
5.29 4.232
NA NA
0.096 0.077
NA NA
21.00 16.80
0.365
5.91 2.157
0.0 0.0
0.09 0.033
0.0 0.0
NA NA
0.0 0.0
0.037 0.014
0.0 0.0
4.800 1.752
0.770 0.281
0.075 0.027
0.0 0.0
NA NA
0.0 0.0
NA NA
31.0 11.32
60.31
0.054 3.26
0.037 2.23
24.76 1493.28
0.464 27.98
0.702 42.34
0.078 4.70
12.71 766.54
1.620 97.70
0.035 2.11
0.991 59.77
53.4 3220.55
0.299 18.03
0.004 0.24
5.07 305.77
25.78 1554.79
62.26 3754.90
TOffiL
RBW WASTE
mg/1
00
00
I Analytical Interference.
I/ See discussion of Analytical Interference in Section DC.
-------
TABLE X-37
SUWMOf OF TREOMENT EEfBCHTVENESS
znc
00
oo
00
PARAMETER
FIOW (I/kg)*
115 ARSENIC
US CAEKTOM
119 CHKMIUM
120 COPPER
121 CfflNIDE
122 LEAD
123 MEBCUHy
124 NICKEL
125 SELENIUM
126 SIWER
128 ZINC
ALUMINUM
IROH
MANGANESE
OIL & GFEftSE
SAMVBBtE
nig/1
0.054
0.037
24.760
0.464
0,702
0.078
12.710
1.620
0.035
0.991
53.400
0.299
0.004
5.070
25,780
rag/Kg
16.550
0.894
0.612
409.778
7.679
11.618
1.291
210.351
26.811
0.579
16.401
883.770
4.948
0.066
83.909
426.659
BPT
mg/i
0.054
0.037
0.080
0..464
0.070
0.078
0.060
0.570
0.010
0.100
0.300
0.299
0.004
0.210
10.000
(PSES 0)
«ng/kg
16.550
0.894
0.612
1.324
7.679
1.159
1.291
0.993
9.434
0.166
1.655
4.965
4.948
0.066
3.476
165.500
BAT
ng/1
0.401
0.079
0.080
0.580
0.070
0.120
0.060
0.570
0.010
0.100
0.300
1.110
0.030
0.210
10.000
1 (PSES 1)
rag/kg
2.226
0.893
0.176
0.178
1.291
0.156
0.267
0.134
1.269
0.022
0.223
0.668
2.471
0.066
0.467
22.260
BAT
fflg/1
0.340
0.049
0.070
0.390
0.047
0.080
0.036
0.220
0.007
0.070
0.230
0.740
0.030
0.140
10.000
2 (PSES 2}
rag/kg
2.226
0.757
0.109
0.156
0.868
0.105
0.178
0.080
0.490
0.016
0.156
0.512
1.647
0.066
0.312
22.260
BAT
"3/1
0.340
0.010
0.050
0.050
0.047
0.010
0.034
0.050
0.007
0.050
0.010
0.740
0.031
0.140
10.000
3 (PSES 3)
mjfkg
2.097
0.713
0.021
0.105
0.105
0.099
0.021
0.071
0.105
0,015
0.105
0.021
1.552
0.066
0.294
20.970
BAT 4 (PSES
ng/1
0.283
0.340
0.010
0,050
0,050
0.047
0.010
0.034
0.050
0.007
0.050
0.010
0.740
0.233
0.140
10.000
4)
"3/Kg
0.096
0.003
0.014
0.014
0.013
0.003
0.010
0.014
0.002
0.014
0.003
0.209
0.066
0.040
2.830
TSS 62,260 1030.403 12.000 198.600 12.000
* Normalized flow based on total subeategory zinc anode weight.
26.712
2.600
5.788
2.600
5.452
2.600
0.736
-------
PARAMETER
RAW WASTE
kg/yr
TABLE X-38
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
ZINC SUBCATB30RY - TOTAL
BPT & PSES 0
Removed
kg/yr
Discharged
kg/yr
BAT 1 & PSES 1
Removed
kg/yr
BAT 2 & PSES 2
Discharged
kg/yr
Removed
kg/yr
Discharged
kg/yr
EAT 3 & PSES 3
Removed
kg/yr
Discharged
kg/yr
BAT 4 & PSES 4
Removed
kg/yr
kg/yr
FLOW 1/yr (106) 60.31
60.31
8.11
8.11
7.64
1.03
00
00
VO
115 ARSENIC
118 CADMIUM
119 CHROMIUM
120 COPPER .
121 CYANIDE
122 LEAD
123 MERCURY
124 NICKEL
125 SELENIUM
126 SILVER
128 ZDC
ALUMINUM
IRON
MANGANESE
OIL & GREASE
3.26
2.23
1493.28
27.98
42.34
4.70
766.54
97.70
2.11
59.77
3220.55
18.03
0.24
305.77
1554.79
0.00
0.00
1488.46
0.00
38.12
0.00
762.92
63.32
1.51
53.74
3202.46
0.00
0.00
293.10
951.69
3.26
2.23
4.82
27.98
4.22
4.70
3.62
34.38
0.60
6.03
18.09
18.03
0.24
12.67
603.10
0.00
1.59
1492.63
23.28
41.77
3.73
766.05
93.08
2.03
58.96
3218.12
9.03
0.00
304.07
1473.69
3.26
0.64
0.65
4.70
0.57
0.97
0.49
4.62
0.08
0.81
2.43
9.00
0.24
1.70
81.10
0.50
1.83
1492.71
24.82
41.96
4.05
766.25
95.92
2.05
59.20
3218.68
12.03
0.00
304.63
1473.69
2.76
0.40
0.57
3.16
0.38
0.65
0.29
1.78
0.06
0.57
1.87
6.00
0.24
1.14
81.10
0.66
2.15
1492.90
27.60
41.98
4.62
766.28
97.32
2.06
59.39
3220.47
12.38
0.00
304.70
1478.39
2. '60
0.08
0.38
0.38
0.36
0.08
0.26
0.38
0.05
0.38
0.08
5.65
0.24
1.07
76.40
2.91
2.22
1493.23
27.93
42.29
4.69
766.50
97.65
2.10
59.72
3220.54
17.27
0.00
305.63
1544.49
0.35
0.01
0.05
0.05
0.05
0.01
0.04
0.05
0.01
0.05
0.01
0.76
0.24
0.14
10.30
TSS
TOXIC METALS
CONVEOTIONALS
TOTAL POLLU.
3754.90
5678.12
5309.69
11354.19
3031.18
5572.41
3982.87
9886.50
723.72 -3657.58
105.71
1326.82
1467.69
5659.47
5131.27
11145.61
97.32
18.65
178.42
208.58
3733.81
5666.01
5207.50
11232.13
21.09
12.11
102.19
122.06
3735.04
5673.45
5213.43
11245.94
19.86
4.67
96.26
108.25
3752.22
5677.49
5296.71
11339.39
2.68
0.63
12.98
14.80
SLUDGE GEN
77122.08
85026.60
85644.34
85789.68
86415.27
-------
00
VO
o
TABLE X-39
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
ZINC SUBCATEGORY - DIRECT DISCHARGERS
PARAMETER
FLOW 1/yr (106)
115 ARSENIC
118 CADMIUM
119 CHROMIUM
120 COPPER
121 CYANIDE
122 LEAD
123 MERCURY
124 NICKEL
125 SELENIUM
126 SILVER
128 ZINC
ALUMINUM
IRON
MANGANESE
OIL & GREASE
TSS
TOXIC METALS
CONVEOTIONALS
TOTAL POLLU.
RAW WASTE
kg/yr
13.87
0.75
0.51
343.42
6.44
9.74
1.08
176.29
22.47
0.49
13.75
740.66
4.15
0.06
70.32
357.57
863.55
1305.86
1221.12
2611.25
Removed
kg/yr
0.00
0.00
342.31
0.00
8.77
0.00
175.46
14.56
0.35
12,36
736.50
0.00
0.00
67.41
218.87
697.11
1281.54
915.98
2273.70
BPT
Discharged
kg/yr
13.87
0.75
0.51
1.11
6.44
0.97
1.08
0.83
7.91
0.14
1.39
4.16
4.15
0.06
2.91
138.70
166.44
24.32
305.14
337.55
Removed
kg/yr
0.00
0.36
343.27
5.36
9.61
0.86
176.18
21.40
0.47
13.56
740.10
2.07
0.00
69.93
338.87
841.11
1301.56
1179.98
2563.15
BAT 1
Discharged
kg/yr
1.87
0.75
0.15
0.15
1.08
0.13
0.22
0.11
1.07
0.02
0.19
0.56
2.08
0.06
0.39
18.70
22.44
4.30
41.14
48.10
Removed
kg/yr
0.11
0.42
343.29
5.71
9.65
0.93
176.22
22.06
0.48
13.62
740.23
2.77
0.00
70.06
338.87
858.69
1303.07
1197.56
2583.11
BAT 2
Discharged
kg/yr
1.87
0.64
0.09
0.13
0.73
0.09
0.15
0.07
0.41
0.01
0.13
0.43
1.38
0.06
0.26
18.70
4.86
2.79
23.56
28.14
BAT 3
Removed
kg/yr
0.15
0.49
343.33
6.35
9.66
1.06
176.23
22.38
0.48
13.66
740.64
2.85
0.00
70.07
339.97
858.97
1304.77
1198.94
2586.29
Discharged
kg/yr
1.76
0.60
0.02
0.09
0.09
0.08
0.02
0.06
0.09
0.01
0.09
0.02
1.30
0.06
0.25
17.60
4.58
1.09
22.18
24.96
BAT 4
Removed
kg/yr
0.67
0.51
343.41
6.43
9.73
1.08
176.28
22.46
0.49
13.74
740.66
3.97
0.00
70.29
355.17
862.93
1305.73
1218.10
2607.82
Discharged
kg/yr
0.24
0.08
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.00
0.01
0.00
0.18
0.06
0.03
2.40
0.62
0.13
3.02
3.43
SLUDGE GEN
17736.59
19553.59
19696.31
19729.74
19873.97
-------
TABLE X-40
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Wet Amalgamated Powder Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 1.58 0.71
Cadmium 0.19 0.082
*Chromium 0.24 0.099
Copper 1.05 0.55
Lead 0.23 0.11
*Mercury 0.14 0.055
Nickel 1.06 0.70
Selenium 0.68 0.30
*Silver 0.23 0.093
*Zinc 0.80 0.34
Aluminum 3.54 1.76
Iron 0.66 0.34
*Manganese 0.37 0.16
*Regulated Pollutant
891
-------
TABLE X-41
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Gelled Amalgam Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 0.20 0.087
Cadmium 0.023 0.010
*Chromium 0.030 0.012
Copper 0.13 0.068
Lead 0.028 0.013
*Mercury 0.017 0.007
Nickel 0.13 0.086
Selenium 0.083 0.037
*Silver 0.028 0.012
*Zinc 0.099 0.042
Aluminum 0.44 0.22
Iron 0.081 0.041
*Manganese 0.046 0.020
*Regulated Pollutant
892
-------
TABLE X-42
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Zinc Oxide Anodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 62.19 27.74
Cadmium 7.37 3.25
*Chromium 9.53 3.90
Copper 41.17 21.67
Lead 9.10 4.34
*Mercury 5.42 2.17
Nickel 41.61 27.52
Selenium 26.66 11.92
*Silver 8.89 3.68
*Zinc 31.64 13.22
Aluminum 139.3 69.35
Iron 26.00 13.22
*Manganese 14.74 6.28
*Regulated Pollutant
893
-------
TABLE X-43
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
616.19
73.00
94.47
407.93
90.18
53.68
412.23
264.08
88.03
313.46
1380.52
257.64
146.00
274.82
32.21
38.65
214.70
42.94
21 .47
272.67
118.09
36.50
130.97
687.04
130.97
62.26
*Regulated Pollutant
894
-------
TABLE X-44
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 85.24 38.02
Cadmium 10.10 4.46
*Chromium 13.07 5.35
Copper 56.43 29.70
Lead 12.48 5.94
*Mercury 7.43 2.97
Nickel 57.03 37.72
Selenium 36.53 16.34
*Silver 12.18 5.05
*Zinc 43.36 18.12
Aluminum 190.97 95.04
Iron 35.64 18.12
*Manganese 20.20 8.61
*Regulated Pollutant
895
-------
TABLE X-45
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Oxide Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
56.97
6.75
8.73
37.72
8.34
4.96
38.1 1
24.42
8. 14
28.98
127.64
23.82
13.50
25.41
2.98
3.57
19.85
3.97
1 .99
25.21
10.92
3.37
12.11
63.52
12.11
5.76
*Regulated Pollutant
896
-------
TABLE X-46
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Peroxide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 13.66 6.09
Cadmium 1.62 0.72
*Chromium 2.09 0.87
Copper 9.05 4.76
Lead 2.00 0.95
*Mercury 1.19 0.48
Nickel 9.14 6.05
Selenium 5.86 2.62
*Silver 1.95 0.81
*Zinc 6.95 2.90
i Aluminum 30.61 15.23
Iron 5.71 2.90
*Manganese .3.24 1.38
*Regulated Pollutant
897
-------
TABLE X-47
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Nickel Impregnated Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - ing/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
574.0
68.0
88.0
380.0
84.0
50.0
384.0
246.0
82.0
292.0
1286.0
240.0
136.0
256.0
30.0
36.0
200.0
40.0
20.0
254.0
110.0
34.0
122.0
640.0
122.0
58.0
*Regulated Pollutant
898
-------
TABLE X-48
ZINC SUBCATEGORV
BAT EFFLUENT LIMITATIONS
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.49 0.22
Cadmium 0.057 0.025
*Chromium 0.074 0.030
Copper 0.32 0.17
*Cyanide 0.049 0.021
Lead 0.071 0.034
*Mercury 0.042 0.017
*Nickel 0.33 0.22
Selenium 0.21 0.093
*Silver 0.069 0.028
*Zinc 0.25 0.10
Aluminum 1.09 0.55
Iron 0.21 0.11
*Manganese 0.12 0.049
*Regulated Pollutant
899
-------
TABLE X-49
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Etch
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
21 .35
2.53
3.27
14.14
3.13
1 .86
14.29
9.15
3.05
10.86
47.84
8.93
5.06
9.52
1.12
1 .34
7.44
1 .49
0.74
9.45
4.09
1 .26
4.54
23.81
4.54
2.16
*Regulated Pollutant
900
-------
TABLE X-50
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.78 0.35
Cadmium 0.091 0.040
*Chromium 0.12 0.048
Copper 0.51 0.27
*Cyanide 0.078 0.033
Lead 0.11 0.054
*Mercury 0.067 0.027
*Nickel 0.52 0.34
Selenium 0.33 0.15
*Silver 0.11 0.045
*Zinc 0.40 0.17
Aluminum 1.74 0.87
Iron 0.33 0.17
*Manganese 0.18 0.078
*Regulated Pollutant
901
-------
TABLE X-51
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Reject Cell Handling
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.028 0.012
Cadmium 0.003 0.001
*Chromium 0.004 0.001
Copper 0.019 0.010
*Cyanide 0.003 0.001
Lead 0.004 0.002
*Mercury 0.002 0.001
*Nickel 0.019 0.012
Selenium 0.012 0.005
*Silver 0.004 0.001
*Zinc 0.014 0.006
Aluminum 0.064 0.032
Iron 0.012 0.006
*Manganese 0.006 0.002
*Regulated Pollutant
902
-------
TABLE X-52
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 2.41 1.08
Cadmium 0.29 0.13
*Chromium 0.37 0.15
Copper 1.60 0.84
*Cyanide 0.24 0.10
Lead 0.35 0.17
*Mercury 0.21 0.084
*Nickel 1.61 1.07
Selenium 1.03 0.46
*Silver. 0.35 0.14
*Zinc 1.23 0.51
Aluminum 5.40 2.69
Iron 1.01 0.51
*Manganese 0.57 0.24
*Regulated Pollutant
903
-------
TABLE X-53
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 3.70 1.65
Cadmium 0,44 0.19
*Chromium 0.57 0.23
Copper 2.45 1.29
*Cyanide 0.38 0.16
Lead 0.54 0.26
*Mercury 0.32 0.13
*Nickel 2.48 1.64
Selenium 1.59 0.71
*Silver 0.53 0.22
*Zinc 1.88 0.79
Aluminum 8.30 4.13
Iron 1.55 0.79
*Manganese 0.88 0.37
*Regulated Pollutant
904
-------
TABLE X-54
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Peroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver peroxide produced
Arsenic 22.70 10.13
Cadmium 2.69 1.19
*Chromium 3.48 1.42
Copper 15.03 7.91
Lead 3.32 1.58
*Mercury 1.98 0.79
Nickel 15.19 10.05
Selenium 9.73 4.35
*Silver 3.24 1.34
*Zinc 11.55 4.83
Aluminum 50.86 25.31
Iron 9.49 4.83
*Manganese 5.38 2.29
*Regulated Pollutant
905
-------
TABLE X-55
ZINC SUBCATEGORY
BAT EFFLUENT LIMITATIONS
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Arsenic 9.21 4.11
Cadmium 1.09 0.48
*Chromium 1.41 0.58
Copper 6.10 3.21
Lead 1.35 0.64
*Mercury 0.80 0.32
Nickel 6.16 4.08
Selenium 3.95 1.77
*Silver 1.32 0.55
*Zinc 4.69 1.96
Aluminum 20.64 10.27
Iron 3.85 1.96
*Manganese 2.18 0.93
*Regulated Pollutant
906
-------
TABLE X-56
BATTERY CATEGORY COSTS
O
Subcategory
BPT (PSES 0)
Capital Annual
Cost S Cost $
BftT 1 (PSES 1)
Capital Annual
Cost S Cost $
122762.
318290.
441052.
0.
0.
37576.
109185.
146761.
9554.
9554,
BAT 2 (PSES 2)
Capital Annual
Cost $ Cost $
146732.
416245,
562977.
4412.
4412.
48575.
140330.
188905.
3322,
3322.
BAT 3 (PSES 3)
Capital Annual
Cost § Cost $
181070. 65933
622480. 183368
803550. 249301
Cadmium
Direct Dischargers 60472. 23065.
Indirect Dischargers 330090. 75625.
Subcategory Total 390562. 98690.
Calcium
Direct Dischargers
Indirect Dischargers 23434. 7338.
Subcategory Total2 23434. 7338.
Leclanche
Direct Dischargers
Indirect Dischargers 42845. 21603.
Subcategory Total3 42845. 21603.
Lithium
Direct Dischargers 0. 494.
Indirect Dischargers 0. 6080.
Subcategory Total 2 0. 6574.
Magnesium
Direct Dischargers 20908. 8134.
Indirect Dischargers 28272. 14571.
Subcategory Total3 49180. 22705.
Zinc
Direct Dischargers 50294. 18219.
Indirect Dischargers* 258474. 88243.
Subcategory Total 308768. 102462.
^Reflect contract hauling costs when less than treatment costs. Costs are in 1978 dollars.
^Regulation proposed for new sources only.
^Regulation proposed for existing pretreatment and new sources only.
0.
0.
0.
0.
37371.
37371,
90013.
346662.
436675.
494.
6080.
6574.
14230.
22407.
36637,
23918.
100197.
123415.
0.
0.
0.
0.
37371.
37371.
102156.
405624.
507780.
494,
6080.
6574.
14230.
20236.
34466.
38187.
159308.
197495.
0.
0.
0.
0.
73784.
73784,
102156.
405624.
507780.
494
6080
6574
14230
27846
42076
38187
159308
197495
BAT 4 (PSES 4)
Capital Annual
Cost $ Cost $
624290. 133643.
1501581. 490754.
2125871. 624397.
109028. 55191.
547387. 252265.
656415. 307456.
Compliance cost for the selected PSES technology are $28,000 capitol and $12,000 annual.
-------
UME OR ACID
ADDITION
ALL PROCESS WASTEWATER
AFTER IN-PROCESS FLOW
REDUCTIONS
OIL
SKIMMING
REMOVAL OF
OIL AND GREASE
sC
C
00
ADDITIONAL RECOMMENDED IN-PROCESS TECHNOLOGY:
CHEMICAL
PRECIPITATION
SEDIMENTATION
•DISCHARGE
SLUDGE
FILTRATE
SLUDGE TO
RECLAIM OR
DISPOSAL
SLUDGE
DEWATERING
lg&S&£&:.
RECYCLE OR REUSE FOR PASTED AND PRESSED POWDER ANODE WASTEWATER
USE DRY METHODS TO CLEAN FLOORS AND EQUIPMENT
CONTROL RINSE FLOW RATES
RECIRCULATE WASTEWATER FROM AIR SCRUBBER
DRY CLEAN IMPREGNATED ELECTRODES
REDUCE CELL WASH WATER USE
COUNTERCUR.RENT RINSE SILVER AND CADMIUM POWDER
COUNTERCURRENT RINSE FOR SINTERED AND ELECTRODEPOSITED
ANODES AND CATHODES
FIGURE X-l. CADMIUM SUBCATEGORY BAT OPTION 1 TREATMENT
-------
BACKWASH
-. X / 4
ALL PROCESS WASTEWATER 7 / X !
OIL
SKIMMING
1
REMOVAL OF
OIL AND GREASE
LIME OR ACID
ADDITION
-*- -*• *- •* *• •*• •*- S<*A*~A^»*^***A~/>*, •r*pA'~'V"-\»"f**(r-ar> DISCHARGE
^^^ J"^^*^ f~^ -^^^ «^^M "V"^'"^^'"*^'''* '**'*"*'" ^M
CHEMICAL SEDIMENTATION $ POLISHING (|
1 PRECIPITATION ^FILTRATIONsj
SLUDGE
/^ ^\ ^O SLUDGE TO
1 ^ f /^ iWOji RECLAIM OR
FILTRATE \\ Iff I DISPOSAL
SLUDGE vs-rv^i •«>•]
FIGURE X-2. CADMIUM SUBCATEGORY BAT OPTION 2 TREATMENT
-------
BACKWASH
ALL PROCESS
WASTEWATERS
AFTER IN-PROCESS
FLOW REDUCTION
REMOVAL OF
OIL AND GREASE
LIME OR ACID
ADDITION
RETURN TO
SLUDGE
DEWATERiNG
DISCHARGE
ADDITIONAL, RECOMMENDED IN-PROCESS TECHNOLOGY: REDUCE CADMIUM POWDER REWORK
FIGURE X-3. CADMIUM SUBCATEGORY BAT OPTION 3 TREATMENT
-------
RETURNED
TO PROCESS
DISTILLATE
ALL PROCESS
BRINE OR REGENERANT
REMOVAL OF
OIL AND GREASE
ION EXCHANGE OR
REVERSE OSMOSIS
VAPOR
RECOMPRESSION
EVAPORATOR
(VRE)
LIQUOR ..BRINE
CENTRIFUGE
DRY SOLIDS TO
DISPOSAL.
DEWATERING
ADDITIONAL RECOMMENDED IN-PROCESS CONTROL TECHNOLOGY: ELIMINATION OF IMPREGNATION RINSE DISCHARGE
FIGURE X-4. CADMIUM SUBCATEGORY BAT OPTION 4 TREATMENT
-------
BACKWASH
CELL TESTING
WASTEWATER
CHEMICAL
ADDITION
HEAT PAPER
PRODUCTION
WASTEWATER
».
_yWWV»VjA_
SETTUNG
SLUDGE
LIME
ADDITION
s-A^A^ALOO»w^
CHEMICAL
PRECIPITATION
«£»
SEDIMENTATION
SLUDGE
POLISHING <{
DISCHARGE
»•
FILTRATE
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
FIGURE X-5. CALCIUM SUBCATEGORY BAT OPTION t TREATMENT
-------
RETURN TO
PROCESS
BACKWASH
CELL TESTING
WASTEWATER
VO
CO
RETURN TO
p
HEAT PAPER
PRODUCTION
WASTEWATER
ROC ESS
SETTLING
L^^J
HOLDING
TANK
LIME
ADDITION
CHEMICAL
PRECIPITATION
SEDIMENTATION
SLUDGE
V POLISHING
JJFILTRATION;
.«J*«.*«.*- >;.•''.»•'%.£.• •.w».»*~.*»i
FILTRATE
SLUDGE TO
DISPOSAL
SLUDGE TO
RECOVERY OR
DISPOSAL
FIGURE X-6. CALCIUM SUBCATEGORY BAT OPTION 2 TREATMENT
-------
BACKWASH
STREAM A
STREAM B
HEAT PAPER
PRODUCTION
WASTEWATER *^*-^^A
SETTLK
SL
CHEMICAL
ADDITION /Xj
.AW ,A^*-*_A^-^
*" CHROMIUM
REDUCTION
3?g cse>
UDGE
i
T
i
iC~
'I
I
1
LIME
ADDITION
L>wAw*J/CA^AJ _ |*«s>»-*w*.
*" CHEMICAL *" SEDIMEr
PRECIPITATION
s
FILTRATE
•****•
.TAT.ON I POL.SHIf
SFILTRATI
i-
-------
STREAM A
R
f>
HEAT PAPER
PRODUCTION
WASTEWATER
ETURN TO
ROC ESS
SETTLING
HOLDING
TANK
VO
MM!
Ul
STREAM B
SOLIDS TO
RECOVERY OR
DISPOSAL
PROCESS
WASTEWATERS FROM.-
IRON D1SULF1DE CATHODE
LEAD IODIDE CATHODE
CELL TESTING
LITHIUM SCRAP DISPOSAL
FLOOR AND EQUIPMENT WASH
STREAM C
BACKWASH
LIME OR ACID
ADDITION
it>V>t>^CA~*^
CHEMICAL
PRECIPITATION
<=£>
SEDIMENTATION
SLUDGE
y POLISHING §
gFILTRATION'i
•DISCHARGE
FILTRATE
LIME
ADDITION
SLUDGE TO
DISPOSAL
PROCESS WASTEWATERS
FROM AIR SCRUBBERS
AIR*
t
'
-A^A^V>^>«w
AERATION
0 O O O O
o n o o o
uJ&L
*-*^AyOw»w>.
CHEMICAL
PRECIPITATION
CD£>
SEDIMENTATION
SLUDGE
DEWATERING
DISCHARGE
SLUDGE TO DISPOSAL
FIGURE X-8. LITHIUM SUBCATEGORY BAT OPTION 2 TREATMENT
-------
STREAM A
p
HEAT PAPER
PRODUCTION
WASTEWATER"
ROCESS
SETTLING
HOLDING
TANK
STREAM B
SOLIDS TO
RECOVERY OR
DISPOSAL
PROCESS
WASTEWATERS FROM:
IRON DISULFIDE CATHODE
LEAD IODIDE CATHODE
CELL TESTING
LITHIUM SCRAP DISPOSAL
FLOOR AND EQUIPMENT WASH
BACKWASH
LIME OR ACID
ADDITION
«-**A>L6»*>Ws
CHEMICAL
PRECIPITATION
SEDIMENTATION
SLUDGE
•* POLISHING !'
-DISCHARGE
FILTRATE
SLUDGE T0
DISPOSAL
BACKWASH
~*^ ( '
V V
STREAM C
PROCESS WASTEWATERS
FROM AIR SCRUBBERS
AERATION
O O O O O
O O O O p
i i -„„„,„_
1
LIME
ADDITION
wA^V^Ldo^A
CHEMICAL
PRECIPITATION
<=>£3
SEDIMENTATION
y POLISHING «{
gFILTRATION^
•DISCHARGE
SLUDGE TO DISPOSAL
FIGURE X-9. LITHIUM SUBCATEGORY BAT OPTION 3 TREATMENT
-------
BACKWASH
STREAM A
HEAT PAPER
PRODUCTION
WASTEWATER
STREAM B
SILVER CHLORIDE
CATHODE PRODUCTION
WASTEWATER
SPENT PROCESS SOLUTION
KMnO4
RINSE
ADDITIONAL. RECOMMENDED
IN-PROCESS TECHNOLOGY:
COUNTEHCURRENTCASCADE
RINSE
^Nk/s^A^vj
EDI HOLDING
LIME OR ACID
ADDITION
CELL. TESTIMS
FLOOR AND EQUIPMENT WASH
SLUDGE TO
DISPOSAL
OEWATERING
STREAM C
PROCESS WASTEWATERS FROM:
AIR SCRUBBERS
DISCHARGE
SLUDGETO
DISPOSAL
FIGURE X-10. MAGNESIUM SUBCATEGORY BAT OPTION I TREATMENT
-------
STREAM A
R
P
HEAT PAPER
PRODUCTION
WASTEWATER
ETURN TO _jf.
ROCESS
SETTLING
S?iS#«#SS&*
,A-A-
^-a^^A.
SEDIME!"
"•WimU;
FILTRATE
-Arf^wS.
4TATION
SLUDGE
S(
• DISCHARGE
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
FIGURE X-11. MAGNESIUM SUBCATEGORY BAT OPTION 2 TREATMENT
-------
STREAM A
p
HEAT PAPER
PRODUCTION
WASTEWATER
ROCESS
SETTLING
msmtmz®
*
HOLDING
TANK
D
D
SOLIDS TO
STREAMS RECOVERY OR
DISPOSAL
SILVER CHLORIDE RINSE
CATHODE PRODUCTION 1
WASTEWATER 1
SPENT PROCESS SOLUTION ^A^S-«^
HOLDING BLEED
gj CARBON &
^.-ADSORPTIONS
i§m!w$*$&m$
BACKWASH
LIME OR ACID
ADDITION
, |£> _ c ,
b A JL JL*jf JL JL A U^^V^^W^^wJ [4*7 *"-*jr*Vi '.lt-Y.fc"''>j;rft, DISCHARGE
k^V^V^V^W^SV^V 1XV^WV^V^S^V^W^| XC£f6tf\$ea£:&St wia^r, «•«»..
CHEMICAL SEDIMENTATION K POLISHING f;
PRECIPITATION 1 1 |FILTRATIONx
SLUDGE
^~*n ( ^ M^ * SLUDGE TO
\V 1 // I DISPOSAL
CELL TESTING \^L^/
FLOOR AND EQUIPMENT WASH SLUDGE L^,««,,J
BACKWASH
STREAM C
PROCESS WASTEWATERS FROM:
AIR SCRUBBERS
LIME
ADDITION
>t>i»t>Luk*>0>.
CHEMICAL
PRECIPITATION
SEDIMENTATION
SLUDGE
•* POLISHING
SFILTRATIONi
-DISCHARGE
FILTRATE
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
FIGURE X-12. MAGNESIUM SUBCATEGORY BAT OPTION 3 TREATMENT
-------
ALL PROCESS WASTEWATER
AFTER IN-PROCESS FLOW
REDUCTION
S3
O
LIME OR ACID
ADDITION
EN
OIL.
SKIMMING
REMOVAL OF
OIL AND GREASE
CHEMICAL.
PRECIPITATION
<=&>
SEDIMENTATION
SLUDGE
DISCHARGE
»
FILTRATE
SLUDGE TO
DISPOSAL
SLUDGE
DEWATERING
ADDITIONAL RECOMMENDED
IN-PROCESS TECHNOLOGY:
COUNTERCURRENT RINSE AMALGAMATED ZINC POWDER
RECIRCULATE AMALGAMATION AREA FLOOR WASH WATER
COUNTERCURRENT RINSE OF FORMED ZINC ELECTRODES
COUNTERCURRENT RINSE OF ELECTRODEPOSITED SILVER-POWDER
COUNTERCURRENT RINSE OF FORMED SILVER OXIDE ELECTRODES
REDUCE FLOW AND COUNTERCURRENT RINSE SILVER PEROXIDE
FLOW CONTROLS AND COUNTERCURRENT RINSE FOR IMPREGNATED NICKEL CATHODES
COUNTERCURRENT RINSE OR RINSE RECYCLE FOR CELL WASHING
ELIMINATE ELECTROLYTE PREPARATION SPILLS
COUNTERCURRENT RINSE AFTER ETCHING SILVER GRIDS
DRY CLEANUP OR WASH WATER REUSE FOR FLOOR AND EQUIPMENT
FIGURE X-13. ZINC SUBCATEGORY BAT OPTION t TREATMENT
-------
BACKWASH
ALL PROCESS WASTEWATER
AFTER IN-PROCESS FLOW
REDUCTION
v£>
LIME OR ACID
ADDITION
^ *>V_/^LUOK-A.
CHEMICAL
PRECIPITATION
REMOVAL OF
OIL AND GREASE
•* POLISHING <{
jgFILTRATION'jj
FILTRATE
^l 1
SLUDGE
DEWATERING
•DISCHARGE
SLUDGE TO
DISPOSAL
ADDITIONAL IN-PROCESS TECHNOLOGY: NONE
FIGURE X-14. ZINC SUBCATEGORY BAT OPTION 2 TREATMENT
-------
SULFIDE
ADDITION
ALL PROCESS WASTEWATER
AFTER IN-PROCESS FLOW
REDUCTION
VO
N5
N5
REMOVAL OF
OIL AND GREASE
SLUDGE
DEWATERING
ADDITIONAL IN-PROCESS TECHNOLOGY: ELIMINATE WASTEWATER FROM GELLED AMALGAM
FIGURE X-15. ZINC SUBCATEGORY BAT OPTION 3 TREATMENT
-------
ALL. PROCESS
WASTEWATERS
AFTER IN-PROCESS
FLOW REDUCTION
LIME OR ACID
ADDITION
RETURN TO
PROCESS
PERMEATE
VO
**-*• *-4- *• J »,
OIL I
DISCHARGE
1
REMOVAL OF
OIL AND GREASE
SLUDGE
DEWATEHING
ADDITIONAL RECOMMENDED IN-PROCESS TECHNOLOGY: AMALGAMATION BY DRY PROCESSES
FIGURE X-16. ZINC SUBCATEGORY BAT OPTION 4 TREATMENT
-------
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the .Clean Water Act is the best available
demonstrated control technology (BDT).
This section presents effluent characteristics attainable by new
sources through the applcation of the best available demonstrated
control technology (BDT), processes, operating methods, or other
alternatives including, where practicable, a standard permitting
no discharge of pollutants. Three levels of technology are
discussed; cost, performance and environmental benefits are
presented; and the rationale for selecting one of the levels is
outlined. The selection of pollutant parameters for specific
regulations is discussed and discharge limitations for the
regulated pollutants are presented for each subcategory.
TECHNICAL APPROACH TO NSPS
As a general approach for the category, three or four levels of
BDT technology options were evaluated for each subcategory. The
levels evaluated are generally identical to the BAT technology
options. These options and the detailed discussion and
evaluation carried out in conjuntion with Section X will be
incorporated here by specific reference rather than duplicate
previous explanation and discussion.
CADMIUM SUBCATEGORY
The four options considered for BDT in the cadmium subcategory
are identical with the four options considered at BAT. These
options are described in summary form and in detail on pages
819-824. Schematics of the treatment systems are displayed on
pages 908-911.
As discussed in the BAT options selection discussions on pages
824-826, the second treatment option includes process flow
control followed by lime, settle and filter end-of-pipe
treatment. This option was selected for NSPS because it provides
additional removal of toxic pollutants but will not pose a
barrier to entry into the subcategory for new plants. The NSPS
limitations will remove approximately 99.96 percent of toxic
pollutants from the raw waste generated by a new plant. Given
the results achieved by the technologies used as a basis for the
promulgated limitations, further treatment would result only in
deminimis, insignificant reductions in annual national
discharges. Accordingly, EPA has determined that the total
925
-------
amount of each pollutant in the remaining discharges after
compliance with NSPS does not justify establishing a national
requirement based on additional end-of-pipe technology.
Although EPA is not basing the final regulations directly on the
additional technologies provided in options 3 and 4, their
availability, effectiveness and af^fordability provides
significant support for EPA's conclusion that the promulgated
effluent limitations are both technologically and economically
achievable.
New Source Performance Standards
The new source performance standards for the cadmium subcategory
are set forth in Tables XI-1 to XI-12 (pages 931-942). Table XI-
8 (page 938) is the combined table for Tables XI-5 to XI-7 (pages
935-937). These tables list standards for all the pollutants
considered for regulation and all pollutants regulated are *'d.
CALCIUM SUBCATEGORY
The options considered as BDT for the calcium subcategory are
identical with the two options considered in Section X. These
options are described in summary form and detail on pages 827-829
and schematics of the processes are displayed on pages 912-913.
As discussed in substantial detail in the options selection
discussions on pages 829 to 830, the second option, which
includes process flow control, settling and complete recycle of
process water results in no discharge of pollutants. This option
was selected as the preferred technology option because the
treatment costs associated with the removal of hexavalent.
chromium are eliminated by the implementation of recycle and
reuse. One plant already achieves no discharge of wastewater
pollutants. Therefore, this option is selected as the technology
option basic to the new source performance standards for this
subcategory. As discussed in the EIA, no entry impacts are
projected with the selection of this option.
New Source Performance Standards
The new source performance standard for the calcium subcategory
is no discharge of process wastewater pollutants.
LECLANCHE SUBCATEGORY
The technology selected for existing plants in this subcategory
(except foliar batteries) is no discharge of process wastewater
pollutants. Twelve existing plants already achieve no discharge
926
-------
of pollutants. This level of performance is continued for new
sources and the new source standard for the Leclanche subcategory
is no discharge of process wastewater pollutants. The discharge
allowance for foliar batteries is the same as discussed under BPT
page 742. No additional technology is identified to further
reduce water use and LS&F end-of-pipe treatment is required.
New Source Performance Standards
The new source performance standards for the foliar battery
miscellaneous wash element of the Leclanche subcategory are set
forth in Table XI-13 (page 943). This table lists standards for
all the pollutants considered for regulation and those pollutants
regulated are *'d.
LITHIUM SUBCATEGORY
The options considered for BDT in the lithium subcategory are
identical with the three options considered in Section X. These
options are described in summary form and detail on pages 831-834
and schematics of the processes are displayed on pages 914-916.
As discussed in the technology options selection discussions
(pages 834-835), the second option, provides the greatest level
of toxic pollutant removal and is therefore selected as the basis
for new source performance standards for the lithium subcategory.
Two existing plants in the subcategory achieve no discharge of
pollutants by choice of manufacturing processes. Many
alternatives can be considered when constructing new plants. As
discussed in the EIA, no entry impacts are projected with the
selection of this option.
New Source Performance Standards
New source performance standards for the lithium subcategory are
based on recycle and reuse technology for heat paper production,
LS&F technology for the cathode process elements, and L&S
technology for the air scrubber element. These standards are set
forth in Tables XI-14 to XI-17 (pages 944 to 947). These tables
list standards for all the pollutants considered for regulation
and those pollutants regulated are *'d. Flows used as the basis
for new source standards are displayed under BAT (PSES) in Table
X-22 (page 872). Effluent concentrations achievable by the
applications of the new source technology are displayed in Table
VII-21. Pollutants regulated by the new source standards are:
chromium, lead, iron, TSS, and pH for the cathode process
elements, and the combined stream which includes floor and
equipment wash, cell testing and lithium scrap disposal
wastewater, TSS and pH were regulated for the air scrubber
process element. The effluent standard for the heat paper
927
-------
element and cell wash element is no discharge of process
wastewater pollutants.
MAGNESIUM SUBCATEGORY
The options considered for BDT in the magnesium subcategory are
identical with the three options considered in Section X. These
options are described in summary form and in detail on pages 836-
838 and schematics of processes are displayed on pages 917-919.
As discussed in the technology options selection discussion
section (pages 839-840) the second option, provides the greatest
levels of toxic pollutant removal, and is therefore selected as
the basis for new source performance standards for the magnesium
subcategory. Four of the eight existing plants in the
subcategory achieve no discharge by choice of manufacturing
processes. Many alternatives can be considered when constructing
a new plant. As discussed in the EIA, no entry impacts are
projected with the selection of this option.
New Source Performance Standards
New source performance standards for the magnesium subcategory
are based on recycle and reuse technology for heat paper
production, L&S technology for the air scrubber process elements,
and LS&F technology for all other waste streams. These standards
are set forth in Tables XI-18 to XI-22 (pages 948-952). These
tables list standards for all the pollutants considered for
regulation and those pollutants regulated are *'d. Flows used as
the basis for new source standards are displayed under BAT (PSES)
in Table X-28 (page 878). Effluent concentrations achievable by
the application of the new source technology are displayed in
Table VII-21. Pollutants regulated by the new source standards
are: lead, silver, iron, COD, TSS, and pH. The effluent standard
for the heat paper production element is no discharge of process
wastewater pollutants.
ZINC SUBCATEGORY
The technology options considered as possible BDT for the zinc
subcategory are similar to the options considered at BAT. These
options are discussed in outline form and in detail on pages 841-
845 and are depicted schematically on pages 920-923. These
options were evaluated for their applicability, cost, and
pollution reduction benefits. Option 1 was selected as the
preferred technology option for BAT. In making a selection of
BAT, it was pointed out in the discussion that operational and
applicability problems with sulfide as a precipitant and
retrofitting costs at existing plants were taken into-account and
heavily weighted in the decision to not select a sulfide based
928
-------
treatment option. Additionally, the high cost of disposing of a
toxic reactive sludge was weighed in the decision. The
considerations, which were basic to the BAT selection, do not
apply in a new plant. The handling, application and control of
the use of sulfide precipitation, as well as adequate ventilation
and other necessary precautions, can be readily and inexpensively
built into a new plant. Also, retrofitting costs do not apply to
new plants. Similarly, the point of siting for a new plant can
be adjusted over a wide geographic area to provide an opportunity
for convenient and inexpensive disposal of toxic sludges. Hence,
the major technology objections to options 3 and 4 are overcome
by the inherrent advantages of a new plant.
The promulgated NSPS is based on the sulfide, settle, and filter
end-of-pipe treatment of option 3, plus additional in-process
technology (shown in Figure X-16, page 923) which is to eliminate
wastewater from gelled amalgam and wet amalgamated anode
production. Option 3 is selected as the preferred technology
option because it improves pollutant removal above option 1 (BAT)
and option 2, and the technology is demonstrated. Also, as
discussed in the EIA no entry impacts are projected with the
selection of this option.
As shown in Table X-38, option 3 removes about 75 percent of the
toxic pollutants remaining after the application of option 1
treatment, and 61 percent of the toxic pollutants remaining after
option 2 making option 3 the more desirable option from the
standpoint of pollutant reduction benefits. Sulfide
precipitation is applied in some • segments of battery
manufacturing and other industrial segments such as nonferrous
metals refining. Compliance costs associated with this option at
existing plants are shown in Table X-56 (page 907). These costs
overstate what would actually be incurred at a new plant because
some retrofitting costs are included. To reduce compliance
costs, new plants can also decide on whether to use processes
which do not generate wastewater or implement end-of-pipe
treatment to comply with the standards.
New Source Performance Standards
New source performance standards for this subcategory are based
on the wastewater flow reductions achieved by improved control
and recycle, and the pollutant concentrations achievable by
sulfide precipitation, settle and filter end-of-pipe treatment.
Some (13) process element streams are treated at new sources.
Flows used as the basis for new source standards are displayed
under BAT-1 and 2 (PSES-1 and 2) in Table X-35 (page 884), for
all elements except zinc powder-wet amalgamated and zinc
powder-gelled amalgam. No discharge allowance is provided for
these elements under NSPS. Effluent concentrations achievable by
929
-------
the application of new source technology are displayed in Table
VII-21.
The pollutants to be regulated are chromium, mercury, silver,
zinc, manganese, oil and grease, TSS, and pH, Nickel is to be
regulated for the nickel impregnated cathode and cell wash
elements only. Cyanide is to be regulated for cell wash only.
These are the same pollutants regulated at BAT with the addition
of oil and grease, TSS, and pH.
Tables XI-23 to XI-36 (pages 953-966) display the new source
performance standards for each element in the zinc subcategory.
To alleviate some of the monitoring burden, several process
elements which occur at most plants and have the same pnp are
combined in one regulatory table. Table XI-34 (page 964) is the
combined table for Tables XI-29, 31, 32 and 33. These tables
list standards for all pollutants considered for regulation and
those pollutants regulated are *'d.
930
-------
TABLE XI-1
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Electrodeposited Anodes
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*0il and Grease
*TSS
7.03
13.01
7.03
9.84
5.27
19.33
10. 19
35.85
4.92
351 .5
527.3
2
5
2
4
2
13
4
14
2
351
421
81
27
81
57
,11
01
22
.76
.46
5
,8
"pH
Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
931
-------
TABLE XI-2
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Impregnated Anodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*0il and Grease
*TSS
*pH Within the
40.0
74.0
40.0
56.0
30.0
110.0
58.0
204.0
28.0
2000.0
3000.0
range of 7.5 -
16.0
30.0
16.0
26.0
12.0
74.0
24.0
84.0
14.0
2000.0
2400.0
10.0 at all times
*Regulated Pollutant
932
-------
TABLE XI-3
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Nickel Electrodeposited Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium 6.60 2.64
Chromium 12.21 4.95
Cyanide 6.60 2.64
Lead 9.24 4.29
Mercury 4.95 1.98
*Nickel 18.15 12.21
Silver 9.57 3.96
*Zinc 33.66 13.86
*Cobalt 4.62 2.31
*Oil and Grease 330.0 330.0
*TSS 495.0 396.0
*pH Withifi the range of 7.5 - 10.0 at all times
*Regulated Pollutant
933
-------
TABLE XI-4
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Nickel Impegnated Cathodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*Oil and Grease
*TSS
*pH Within the
40.0
74.0
40.0
56.0
30.0
1 10.0
58.0
204.0
28.0
2000.0
3000.0
range of 7.5 -
16.0
30.0
16.0
26.0
12.0
74.0
24.0
84.0
14.0
2000.0
2400.0
10.0 at all times
*Regulated Pollutant
934
-------
TABLE XI-5
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Cell Wash
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.15
Chromium 0.28
Cyanide 0.15
Lead 0.21
Mercury 0.11
*Nickel 0.41
Silver 0.22
*Zinc 0.77
*Cobalt 0.11
*0il and Grease 7.50
*TSS 11.3
*pH Within the range of 7.5
0.06
0. 1 1
0.06
0.097
0.045
0.28
0.09
0.32
0.052
50
00
7,
9,
- 10.0 at all times
*Regulated Pollutant
935
-------
TABLE XI-6
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Electrolyte Preparation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.016 0.006
Chromium 0.029 0.012
Cyanide 0.016 0.006
Lead 0.022 0.010
Mercury 0.012 0.004
*Nickel 0.044 0.029
Silver 0.023 0.009
*Zinc 0.081 0.033
*Cobalt 0.011 0.005
*0il and Grease 0.80 0.80
*TSS 1.20 0.96
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
936
-------
TABLE XI-7
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Employee Wash
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*Oil and Grease
*TSS 22.5
*pH Within the range of 7.5
0.30
0.56
0.30
0.42
0.23
0.83
0.44
1 .53
0.21
15.0
0,
0,
0,
0,
0,
0.
0,
0,
0,
15,
18,
12
23
12
20
090
56
18
63
1 1
0
0
- 10.0 at all times
*Regulated Pollutant
937
-------
TABLE XI-8
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.47 0.19
Chromium 0.86 0.35
Cyanide 0.47 0.19
Lead 0.65 0.30
Mercury 0.35 0.14
*Nickel 1.28 0.86
Silver 0.68 0.28
*Zinc 2.38 0.98
*Cobalt 0.33 0.16
*0il and Grease 23.3 23.3
*TSS 35.0 28.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
938
-------
TABLE XI-9
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Cadmium Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
*Cadmium 1.31 0.53
Chromium 2.43 0.99
Cyanide 1.32 0.53
Lead 1.84 0.86
Mercury 0.99 0.40
*Nickel 3.61 2.43
Silver 1.91 0.79
*Zinc 6.70 2.76
*Cobalt 0.92 0.46
*0il and Grease 65.70 65.70
*TSS 98.55 78.84
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
939
-------
TABLE XI-10
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
*Cadmium 0.64 0.26
Chromium 1.19 0.48
Cyanide 0.64 0.26
Lead 0.90 0.42
Mercury 0.48 0.19
*Nickel 1.77 1.19
*Silver 0.93 0.39
*Zinc 3.27 1.35
*Cobalt 0.45 0.22
*Oil and Grease 32.10 32.10
*TSS 48.15 38.52
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
940
-------
TABLE XI-11
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Cadmium Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
*Cadmium 0.028 0.011
Chromium 0.051 0.021
Cyanide 0.028 0.011
Lead 0.039 0.018
Mercury 0.021 0.008
*Nickel 0.077 0.051
Silver 0.040 0.016
*Zinc 0.142 0.058
*Cobalt 0.019 0.009
*Oil and Grease 1.40 1.40
*TSS 2.10 1.68
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
941
-------
TABLE XI-12
CADMIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Nickel Hydroxide Production
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
*Oil and Grease
*TSS
3,
6
3,
30
1 1
30
4.62
2.48
9.08
4.79
16.83
2.31
165.0
247.5
1 ,
2,
1 ,
2.
0,
6,
1 ,
6.
1 ,
165,
198,
32
48
32
15
99
1 1
98
93
16
0
0
Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
942
-------
TABLE XI-13
LECLANCHE SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Foliar Battery Miscellaneous Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 lb of cells produced
Arsenic 0.092 0.038
Cadmium 0.013 0.005
Chromium 0.024 0.010
Copper 0.084 0.040
Lead 0.018 0.009
*Mercury 0.010 0.004
Nickel 0.036 0.024
Selenium 0.054 0.024
*Zinc 0.067 0.030
*Manganese 0.019 0.015
*0il and Grease 0.66 0.66
*TSS 0.99 0.79
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
943
-------
TABLE XI-14
LITHIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Lead Iodide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
*Chromium 23.34 9.46
*Lead 17.66 8.20
Zinc 64.34 26.49
Cobalt 75.70 38.48
*Iron 75.70 38.48
*TSS 946.2 756.96
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
944
-------
TABLE XI-15
LITHIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Iron Disulfide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib of iron disulfide
*Chromium 2.79 1.13
*Lead . 2.11 0.98
Zinc 7.69 3.17
Cobalt 1.06 0.53
*Iron 9.05 4.60
*TSS 113.1 90.5
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
945
-------
TABLE XI-16
LITHIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant , Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Chromium 0.039 0.016
*Lead 0.030 0.014
Zinc 0.110 0.045
Cobalt 0.015 0.007
*Iron 0.129 0.066
*TSS 1.62 1.30
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
946
-------
TABLE XI-17
LITHIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Air Scrubbers
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 4.66 1.91
Lead 4.45 2.12
Zinc 15.46 6.46
Cobalt 2.22 0.95
Iron 12.71 6.46
*TSS 434.0 207.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
947
-------
TABLE XI-18
MAGNESIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Chloride Cathodes - Chemically Reduced
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 30.30 12.29
*Lead 22.93 10.65
Nickel 45.05 30.30
*Silver 23.75 9.83
*Iron 98.28 49.96
*TSS 1228.5 982.8
*COD 4095.0 1999.0
*pH Wi,thin the range of 7.5 - 10.0 at all times
*Regulated Pollutant
948
-------
TABLE XI-19
MAGNESIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Chloride Cathodes - Electrolytic
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 53.7 21 .8
*Lead 40.6 18.9
Nickel 79.8 53.7
*Silver 42.1 17.4
*Iron 174.0 88.5
*TSS 2175.0 1740.0
*COD 7250.0 3540.0
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
949
-------
TABLE XI-20
MAGNESIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Cell Testing
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium
*Lead
Nickel
*Silver
*Iron
*TSS
*COD
*pH Within
*Regulated Pol
19.5
14.7
28.9
15.3
63. 1
789.0
2630.0
the range of 7.5 -
lutant
7.89
6.84
19.5
6.31
32.1
631 .2
1290.0
10.0 at all times
950
-------
TABLE XI-21
MAGNESIUM SUBCATEGORY -
NEW SOURCE PERFORMANCE STANDARDS
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.034 0.014
*Lead 0.026 0.012
Nickel 0.051 0.034
*Silver 0.027 0.011
*Iron 0.112 0.057
*TSS 1.41 1.13
*COD 4.70 2.30
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
951
-------
TABLE XI-22
MAGNESIUM SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Air Scrubbers
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium
Lead
Nickel
Silver
Iron
*TSS
*pH Within the range
90.9
86.7
396.5
84.7
247.8
8467.0
Of 7.5 -
37.2
41 .3
262.3
35. 1
126.0
4030.0
10.0 at all times
*Regulated Pollutant
952
-------
TABLE XI-23
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Zinc Oxide Anodes, Formed
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
*pH Within the
41 .82
0.87
4.55
4.55
0.87
2.82
4.55
17.77
4.55
0.87
132.4
26.01
6.50
216.7
325.0
range of 7.5 -
18.64
0.39
1 .97
1 .97
0.39
1 .19
1 .97
8.02
1 .97
0.39
58.73
13.22
4.98
216.7
260.0
10.0 at all times
*Regulated Pollutant
953
-------
TABLE XI-24
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Arsenic 414.37 184.64
Cadmium 8.59 3.87
*Chromium 45.09 19.54
Copper 45.09 19.54
Lead 8.59 3.87
*Mercury 27.91 11.81
Nickel 45.09 19.54
Selenium 8.59 3.87
*Silver 45.09 19.54
*Zinc 8.59 3.86
Aluminum 1311.82 581.84
Iron 257.64 130.97
*Manganese 64.41 49.38
*Oil and Grease 2147.00 2147.00
*TSS 3220.50 2576.40
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
954
-------
TABLE XI-25
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 57.32 25.54
Cadmium 1.19 0.54
*Chromium 6.24 2.70
Copper 6.24 2.70
Lead 1.19 0.54
*Mercury 3.86 1.63
Nickel 6.24 2.70
Selenium 24.35 10.99
*Silver 6.24 2.70
*Zinc 1.19 0.53
Aluminum 181.47 80.49
Iron 35.64 18.12
*Manganese 8.91 6.83
*Oil and Grease 297.00 297.00
*TSS 445.5 356.40
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
955
-------
TABLE XI-26
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Oxide Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 38.3 17.1
Cadmium 0.79 0.36 .
*Chromium 4.17 1.81
Copper 4.17 1.81
Lead 0.79 0.36
*Mercury 2.58 1.09
Nickel 4.17 1.81
Selenium 16.3 7.35
*Silver 4.17 1.81
*Zinc 0.79 0.36
Aluminum 121.3 53.8
Iron 23.8 12.1
*Manganese 5.96 4.57
*0il and Grease 198.5 198.5
*TSS 297.8 238.2
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
956
-------
TABLE XI-27
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Peroxide Cathodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*0il and Grease
*TSS
*pH Within the
9. 19
0. 19
1 .00
1 .00
0. 19
0.62
1 .00
3.90
1 .00
0. 19
29. 1
5.71
1 .43
47.6
71 .4
range of 7.5 -
4.09
0.09
0.43
0.43
0.09
0.26
0.43
.1 .76
0.43
0.09
12.9
2.90
1 .09
47.6
57.1
10.0 at all times
*Regulated Pollutant
957
-------
TABLE XI-28
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Nickel Impregnated Cathodes
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
*pH Within the
386.0
8.0
42.0
42.0
8.0
26.0
42.0
164.0
42.0
8.0
1222.0
240.0
60.0
2000.0
3000.0
range of 7.5 -
172.0
3.6
18.2
18.2
3.6
11 .0
18.2
74.0
18.2
3.6
542.0
122.0
46.0
2000.0
2400.0
10.0 at all times
*Regulated Pollutant
958
-------
TABLE XI-29
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.33 0.15
Cadmium 0.006 ,0.003
*Chromium 0.035 0.015
Copper 0.035 0.015
*Cyanide 0.025 0.010
Lead 0.006 0.003
*Mercury 0.022 - 0.009
*Nickel 0.035 0.015
Selenium 0.14 0.062
*Silver 0.035 0.015
*Zinc 0.006 0.003
Aluminum 1.04 0.46
Iron 0.21 0.10
*Manganese 0.051 0.039
*Oil and Grease 1.70 1.70
*TSS . 2.55 2.04
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
959
-------
TABLE XI-30
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Etch
Pollutant
Pollutant
Property
or
Maximum for
any one day
Maximum for
monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic
Cadmium
* Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*2inc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
*pH Within the
14.36
0.30
1 .56
1 .56
0.30
0.97
1 .56
6.10
1 .56
0.30
45.46
8.93
2.23
74.40
111 .60
range of 7.5 -
6.40
0.13
0.68
0.68
0.13
0.41
0.68
2.75
0.68
0.13
20.16
4.54
1 .71
74.40
89.28
10.0 at all times
*Regulated Pollutant
960
-------
TABLE XI-31
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.52 0.23
Cadmium 0.010 0.004
*Chromium 0.056 0.024
Copper 0.056 0.024
*Cyanide 0.039 0.016
Lead 0.010 0.004
*Mercury 0.035 0.014
*Nickel 0.056 0.024
Selenium 0.22 0.099
*Silver 0.056 0.024
*Zinc 0.010 0.004
Aluminum 1.65 0.73
Iron 0.33 0.16
*Manganese 0.081 0.062
*Oil and Grease 2.70 2.70
*TSS 4.05 -3.21
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
961
-------
TABLE XI-32
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Reject Cell Handling
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum
monthly
for
average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic
Cadmium
*Chromium
Copper
*Cyanide
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*Oil and Grease
*TSS
0.019
0.0004
0.002
0.002
0.0015
0.0004
0.001
0.002
0.008
0.002
0.0004
0.061
0.012
0.003
0.10
0. 15
008
00018
00091
00091
0006
00018
00055
00091
003
00091
00018
027
006
002
10
12
"pH
Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
962
-------
TABLE XI-33
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic
Cadmium
*Chromium
Copper
*Cyanide
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
*0il and Grease
*TSS
*pH Within the
1 .62
0.033
0. 18
0.18
0.12
0.033
0.1 1
0.18
0.69
0.18
0.033
5.13
1 .01
0.25
8.40
12.6
range of 7.5 -
0.72
0.015
0.076
0.076
0.051
0.015
0.046
0.076
0.31
0.076
0.015
2.28
0.51
0.19
8.40
10. 1
10.0 at all times
*Regulated Pollutant
963
-------
TABLE XI-34
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 2.49 1.11
Cadmium 0.051 0.023
*Chromium 0.27 0.12
Copper 0.27 0.12
*Cyanide 0.039 0.016
Lead 0.051 0.023
*Mercury 0.17 0.07
*Nickel 0.27 0.12
Selenium 1.06 0.48
*Silver 0.27 0.12
*Zinc 0.05 0.02
Alumium 7.88 3.50
Iron 1.55 0.79
*Manganese 0.39 0.30
*0il and Grease 12.90 12.90
*TSS 19.35 15.48
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
964
-------
TABLE XI-35
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Peroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produce
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Arsenic 15.27 6.80
Cadmium 0.32 0.14
*Chromium 1.66 0.72
Copper 1.66 0.72
Lead 0.32 0.14
*Mercury 1.03 0.44
Nickel 1.66 0.72
Selenium 6.49 2.93
*Silver 1.66 0.72
*Zinc 0.32 0.14
Aluminum 48.33 21.44
Iron 9.49 4.83
*Manganese 2.37 1.82
*Oil and Grease 79.10 79.10
*TSS 118.65 94.92
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
965
-------
TABLE XI-36
ZINC SUBCATEGORY
NEW SOURCE PERFORMANCE STANDARDS
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Arsenic 6.20 2.76
Cadmium 0.13 0.057
*Chromium 0.67 0.29
Copper 0.67 0.29
Lead 0.13 0.057
*Mercury 0.42 0.18
Nickel 0.67 0.29
Selenium 2.63 1.19
*Silver 0.67 0.29
*Zinc 0.13 0.06
Aluminum 19.61 8.70
Iron 3.85 1.96
*Manganese 0.96 0.74
*0il and Grease 32.10 32.10
*TSS 48.15 38.52
*pH Within the range of 7.5 - 10.0 at all times
*Regulated Pollutant
966
-------
SECTION XII
PRETREATMENT
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of Publicly
Owned Treatment Works (POTW). The Clean Water Act of 1977 adds a
new dimension by requiring pretreatment for pollutants, such as
toxic metals, that limit POTW sludge management alternatives,
including the beneficial use of sludges on agricultural lands.
The legislative history of the 1977 Act indicates that
pretreatment standards are to be technology-based, and analogous
to the best available technology for removal of toxic pollutants.
(Conference Report 95-830 at 87; reprinted in Comm. on
Environment and Public Works, 95th Cong., 2d Session, A
Legislative History of the Clean Water Act of 1977, Vol. 3 at
272).
The general pretreatment regulations can be found at 40 CFR Part
403. See 43 FR 27736 June 26, 1978, 46 FR 9404 January 28, 1981,
and 47 FR 4518 February 1, 1982. These regulations describe the
Agency's overall policy for establishing and enforcing
pretreatment standards for new and existing users of a POTW and
delineate the responsibilities and deadlines applicable to each
part of this effort. In addition, 40 CFR Part 403, Section
403.5(b), outlines prohibited discharges which apply to all users
of a POTW.
Section 307(c) of the Act requires EPA to promulgate pretreatment
standards for new sources (PSNS) at the same time that it promul-
gates NSPS. New indirect dischargers, like new direct
dischargers, have the opportunity to incorporate the best
available demonstrated technologies including process changes,
in-plant controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation.
This section describes the control technology for pretreatment of
process wastewaters from existing sources and new sources. The
concentrations and mass discharge limitations of regulated
pollutants for existing and new sources, based on the described
control technology, are indicated by the data presented in
Sections V and VII.
967
-------
DISCHARGE OF WASTEWATERS TO A POTW
Most plants in the battery manufacturing category currently
discharge to a POTW. Pretreatment standards are established to
ensure removal of pollutants discharged by such plants which
interfere with, pass through, or are otherwise incompatible with
a POTW. A determination of which pollutants may pass through or
be incompatible with POTW operations, and thus be subject to
pretreatment standards, depends on the level of treatment
employed by the POTW. In general, more pollutants will pass
through a POTW employing primary treatment (usually physical
separation by settling) than one which has installed secondary
treatment (settling plus biological treatment).
Most POTW consist of primary or secondary treatment systems which
are designed to treat domestic wastes. Many of the pollutants
contained in battery manufacturing wastes are not biodegradable
and are, therefore, ineffectively treated by such systems.
Furthermore, these wastes have been known to pass through or
interfere with the normal operations of these systems. Problems
associated with the uncontrolled release of pollutant parameters
identified in battery process wastewaters to POTW were discussed
in Section VI. The discussion covered pass through,
interference, and sludge useability.
The Agency based the selection of pretreatment standards for the
battery category on the minimization of pass through of toxic
pollutants at POTW. For each subcategory, the Agency compared
the removal rates for each toxic pollutant limited by the
pretreatment options to the removal rate for that pollutant at a
well operated POTW. The POTW removal rate were determined
through a study conducted by the Agency at over 40 POTW and a
statistical analysis of the data. (See Fate of Priority
Pollutants In Publicly Owned Treatment Works, EPA 440/1-80-301,
October, 1980; and Determining National Removal Credits for
Selected Pollutants for Publicly Owned Treatment Works, EPA
440/82-008, September, 1982). The POTW removal rates are
presented below:
Toxic Pollutant POTW Removal Rate
Cadmium 38%
Chromium 65%
Copper 58%
Cyanide 52%
Lead 48%
Nickel 19%
Silver 66%
Zinc 65%
968
•o
-------
The study did not analyze national POTW removals for mercury.
The range of removal indicated by the data ranged from 19 to 66
percent. However, as discussed in Section VI mercury has
inhibiting effects upon activated sludge from POTW at levels of
0.1 mg/1 and loss of COD removal efficiency of 59 percent is
reported with 10.0 mg/1 of mercury. Therefore, unless treated at
the source, mercury is likely to cause POTW interference. The
model treatment technologies chosen as the basis for PSES and
PSNS will achieve removals of greater than 99.9 percent for toxic
metals as is demonstrated by the pollutant reduction benefits
shown in subcategory tables in this section.
The pretreatment options selected provide for significantly more
removal of toxic pollutants than would occur if battery
wastewaters were discharged untreated to the POTW. Thus,
pretreatment standards will control the discharge of toxic
pollutants to the POTW and prevent pass through.
TECHNICAL APPROACH TO PRETREATMENT
As a general approach for the category, three or four options
were developed for consideration as the basis for PSES and three
or four for PSNS. These options generally provide for the
removal of metals by chemical precipitation and removal of
suspended solids by sedimentation or filtration. In addition,
they generally provide for the reduction or control of 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 metals which
pass through POTW, pretreatment requirements for these streams do
not differ significantly from treatment requirements for direct
discharge. Consequently the options presented for PSES and PSNS
are identical to treatment and control options presented for BAT
and NSPS, respectively. These options generally combine both in-
plant technology and wastewater treatment to reduce the mass of
pollutants (especially 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. A major factor in all of the technology
options considered is reduced pollutant discharge achieved
through wastewater flow reductions. Mass based (rather than
concentration based) limitations and standards are necessary to
ensure the pollutant removals required by this regulation.
969
-------
IDENTIFICATION OF PRETREATMENT OPTIONS
Option 0 for pretreatment standards for existing sources (PSES)
and pretreatment standards for new sources (PSNS) are identical
to BPT (option 0) for all subcategories as described in Section
IX. PSES and PSNS options 1-4 for each subcategory are identical
to BAT options 1-4 respectively. End-of-pipe treatment systems
for each of these options are depicted in Sections IX or X as
appropriate. Selected 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
be 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. Compliance cost data for all options is displayed in Table
X-56 (page 907).
CADMIUM SUBCATEGORY
PSES options 0-4 are identical to BPT and BAT options 1-4 as
discussed on page 730 to 732 for BPT and pages 819 to 824 for
BAT. Pollutant removals and cost discussions in this section are
stated for existing indirect discharges only. Pollutant removals
for this subcategory are displayed in Table XII-1 (page 978).
Pretreatment Option Selection
Option ]_ is the selected PSES option because standards are
achievable using technologies and practices that are currently in
use at plants in the subcategory. Also the result of
implementing this technology is a significant reduction of toxic
pollutant discharges to POTW which would otherwise pass through.
For this option flow is reduced to 28.7 million 1/yr. The annual
toxic pollutant removal is 54,456 kg/yr. For plants to comply
directly with this option, the estimated compliance capital cost
is $318/000 and annual cost is $109,000.
Option 0_ is rejected because significant amounts of cadmium,
nickel and zinc would pass through POTW and not be controlled.
Also, the use of cadmium usually prevents POTW from using their
sludges for land application. For this option flow is 210
million 1/yr and annual toxic pollutant removal is 54,261 kg/yr.
For plants to comply directly with this option, the estimated
compliance capital cost is $330,000 and annual cost is $76,000.
Options 2j_ 3_^ and 4. are rejected because, as discussed in Section
X the technology yields small incremental removals when compared
with option 1. The PSES will remove approximately 99.93 percent
970
-------
of the estimated raw waste generation for toxic pollutants.
Given the results achieved by the technologies used as a basis
for the promulgated limitations, further treatment would result
only in deminimis, insignificant reductions in annual national
discharges. Accordingly, EPA has determined that the total
amount of each pollutant in the remaining discharges after
compliance with PSES does not justify establishing a national
requirement based on additional end-of-pipe technology.
Although EPA is not basing the final regulations directly on
these additional technologies, their availability, effectiveness
and affordability provides significant support for EPA's
conclusion that the promulgated pretreatment standards are both
technologically and economically achievable.
Pollutant Parameters for Regulation
Pollutant parameters selected for pretreatment regulation in this
subcategory are cadmium, nickel, silver, zinc and cobalt. As
discussed in Section X, these pollutants were selected for their
toxicity, use within the subcategory and treatability. For the
pretreatment standards, POTW treatment and pass through (for
cadmium, nickel, silver, and zinc) was also considered.
Conventional pollutants are not specifically regulated because
POTW are specifically designed to treat the conventional
pollutants.
Pretreatment Effluent Standards
Effluent standards for existing pretreatment sources are
identical to the BAT limitations as discussed in Section X.
These standards are expressed in terms of mg of pollutant per kg
of production normalizing parameter for each process element.
PSES are presented in Tables XI1-2 to XI1-13 (pages 979-990). To
alleviate some of the monitoring burden, several process elements
which occur at most plants and have the same pnp are combined in
one regulatory table. Table XII-9 is the combined table for
Tables XI1-6 to XI1-8. These standard tables list all the
pollutants which were considered for regulation, and those
regulated are *'d.
PSNS are identical to NSPS discussed in Section XI, and are
displayed in Tables XII-14 to XII-25 (pages 991-1002).
CALCIUM SUBCATEGORY
The options considered for pretreatment are identical to option 0
discussed in Section IX (pages 735-737) and the two options
discussed in Section X (pages 827-829).
971
-------
Pretreatment Selection
Currently, the discharge by indirect dischargers of process
wastewater from this subcategory is small (less than 4,000,000
1/yr) and the quantity of toxic pollutants is also small (less
than 50 kg/yr). Because of the small quantities, the Agency has
elected not to establish national PSES for this subcategory.
Applicable technologies, and potential standards (in this case no
discharge) are set forth as guidance should a state or local
pollution control agency desire to establish such standards.
Pollutant removals for each option are shown in Table XI1-26
(page 1003). The option promulgated for new sources is
equivalent to the one selected for NSPS, as discussed on page
926. This option results in no discharge of pollutants. As
discussed in the EIA, no entry impacts are projected with the
selection of this option, and as discussed in Section XI one
existing plant already achieves no discharge.
Pretreatment Effluent Standards
PSNS for the calcium subcategory is no discharge of process
wastewater pollutants.
LECLANCHE SUBCATEGORY
The option considered for pretreatment is identical to option 0
discussed in Section IX (pages 738-742). Pollutant removals for
this subcategory are displayed in Table XII-27 (page 1004).
Pretreatment Option Selection
Option 0 is the selected PSES option because standards are
achievable using technologies and practices that are currently in
use at plants in the subcategory. Also the result of
implementing this technology is a significant reduction of
pollutant discharges (particularly mercury) which would otherwise
pass through. For this option flow is reduced to 0.2 million
1/yr. The annual toxic pollutant removal is 5569 kg/yr. For
plants to comply with this option, the estimated compliance
capital cost is $43,000 and annual cost is $22,000.
Pollutant Parameters for Regulation
Pollutant parameters selected for pretreatment regulation in this
subcategory are mercury, zinc, and manganese. As discussed in
Section IX, these pollutants were selected for their toxicity,
use within the subcategory and treatability. For the
pretreatment standards, POTW treatment and pass through (for
mercury and zinc) was also considered. Conventional pollutants
972
-------
are not specifically regulated because POTW are specifically
designed to treat the conventional pollutants.
Pretreatment Effluent Standards
The effluent standards for existing pretreatment sources involved
in foliar battery production are identical to the BPT limitations
discussed in Section IX. These standards are expressed in terms
of mg of pollutant per kg of cell produced. PSES are presented
in Table XII-28 (page 1005). This table lists all the pollutants
which were considered for regulation, and those regulated are
*'d.
PSNS are identical to PSES and are displayed in Table XI1-29
(page 1006).
LITHIUM SUBCATEGORY
The options considered for pretreatment are identical to option 0
discussed in Section IX (pages 743-747) and the three options
discussed in Section X (pages 831-834).
Pretreatment Selection
Currently, the discharge by indirect dischargers of process
wastewater from this subcategory is small (less than 4,000,000
1/yr) and the quantity of toxic pollutants is also small (less
than 50 kg/yr). Because of the small quantities, the Agency has
elected not to establish national PSES standards for this
subcategory. Applicable technologies, and potential standards
are set forth as guidance should a state or local polution
control agency desire to establish such standards.
Pollutant reduction benefits for the technology options are shown
in Table XI1-30 (page 1007). The option promulgated for new
sources option 2, is equivalent to the one selected for NSPS, as
discussed on page 927. This option allows no discharge from heat
paper production and allows treated wastewater discharge from
other subcategory processes which provides the greatest level of
toxic pollutant removal. As discussed in the EIA, no entry
impacts are projected with the selection of this option. Also,
two existing plants in the subcategory achieve no discharge of
pollutants by choice of manufacturing processes. Many
alternatives can be considered when constructing a new plant.
Pollutant Parameters for Regulation
For pretreatment, chromium and lead are selected for regulation
in this subcategory. As discussed in Section X these pollutants
were selected for their toxicity, use within the subcategory and
973
-------
treatability. For the pretreatment standards POTW treatment,
incompatability and pass through of chromium and lead were also
considered. In this subcategory asbestos is used as a raw
material and would be controlled by regulating TSS. Because POTW
are designed for treatment of conventional pollutants and
adequately control TSS and thus asbestos, a specific standard for
TSS is not promulgated. Also, POTW may use iron as a coagulant
in the treatment process and iron is not promulgated for
regulation.
Pretreatment Effluent Standards
Effluent standards for existing pretreatment sources are
identical to the limitations presented in Section X. These
standards are expressed in terms of mg of pollutant per kg of
production normalizing parameter for each process element.
Recommended standards for existing sources are displayed in
Tables XII-31 to XII-33 (pages 1009-1011). These standard tables
are presented as guidance should a state or local pollution
control agency desire to establish such standards.
PSNS are identical to NSPS presented in Section XI with one
exception; air scrubbers are used as a basis for regulation at
NSPS and not PSNS to control TSS and thus, asbestos. Standards
are displayed in Tables XII-34 to XII-36 (pages 1012-1014).
These standard tables list all the pollutants which were
considered for regulation, and regulated pollutants are *'d.
MAGNESIUM SUBCATEGORY
The options considered for pretreatment are identical to option 0
discussed in Section IX (pages 747-750) and the three options
discussed in Section X (pages 835-838). Pollutant removals for
this subcategory are displayed in Table XII-37 (page 1015).
Compliance costs for existing plants are displayed in Table X-56
for each technology option.
Pretreatment Selection
Option 0_ is the selected PSES option for all process wastewater
streams except heat paper production, and option 2 is promulgated
as the selected option for heat paper production because the
standards are achievable at existing plants and the result of
implementing the promulgated PSES is a significant reduction in
the toxic pollutant discharges which would otherwise pass through
POTW. For the final PSES, discharge flow is reduced to 1 million
1/yr and the annual toxic pollutant removal is 160 kg/yr. For
plants to comply directly with this option, the estimated
compliance capital cost is $28,000 and the annual cost is $15,000
974
-------
for existing plants, which is the least costly alternative for
indirect dischargers in this subcategory.
All other options were rejected for existing sources because the
toxic pollutant removals are about equal and the compliance costs
for the options are higher than for the selected PSES. For
option 0, estimated compliance capital costs are $28,000 and
annual costs are $15,000.
For option 1 estimated compliance capital cost is $37,000 and
annual cost is $22,000. For option 2 estimated compliance
capital cost is $37,000 and annual cost is $20,000. For option 3
estimated compliance capital cost is $74,000 and annual cost is
$28,000.
For new sources as discussed in Section XI, option 2 is selected
because it provides for the greatest level of toxic pollutant
removal. As discussed in the EIA, no entry impacts are projected
with the selection of this option. Also, four existing plants in
the subcategory achieve no discharge by choice of manufacturing
processes. Many alternatives can be considered when constructing
a new plant.
Pollutant Parameters for Regulation
For pretreatment lead and silver are selected for regulation in
this subcategory. As discussed in Section X these pollutants
were selected for their toxicity, use within the subcategory and
treatability. For the pretreatment standards POTW treatment,
incompatability and pass through of these pollutants were also
considered. In this subcategory asbestos is used as a raw
material and would be controlled by regulating TSS. Because POTW
are designed for treatment of conventional pollutants and
adequately control TSS, and thus asbestos, a specific standard
for TSS^is not promulgated. Also, iron and COD are not regulated
because POTW may use iron as a coagulant in the treatment process
and POTW are designed to treat oxygen demand.
Pretreatment Effluent Standards
PSES are identical to the limitations presented in Section X.
These standards are expressed in terms of mg of pollutant per kg
of production normalizing parameter for each process element.
Standards for existing sources are presented in Tables XI1-38 to
XII-41 (pages 1017-1020). These standard tables list all the
pollutants which were considered for regulation, and those
regulated are indicated by "*".
975
-------
PSNS are identical to NSPS presented in Section XI with one
exception; air scrubbers are promulgated for regulation at NSPS
and not PSNS to control TSS and thus asbestos. Standards are
displayed in Tables XII-42 to XII-45 (pages 1021-1024).
ZINC SUBCATEGORY
PSES options 0-4 are identical to BPT and BAT options 1-4 as
discussed on pages 751 to 753 for BPT and pages 841 to 845 for
BAT. Pollutant removals and cost discussions are stated for
existing indirect discharges only. Pollutant removals for this
subcategory are displayed in Table XII-46 (page 1025).
Pretreatment Option Selection
Option 1_ is promulgated as the selected PSES option because
standards are achievable using technologies and practices that
are currently in use at plants in the subcategory. Also, the
result of implementing this technology is a signficant reduction
of toxic pollutants to POTW which would otherwise pass through.
For this option flow is reduced to 6.25 million,1/yr. The annual
toxic pollutant removal is 4,390 kg/yr. For plants to directly
comply with this option the estimated compliance capital cost is
$347,000 and annual cost is $100,000.
Option jO is rejected because significant amounts of toxic metals
would pass through POTW and not be controlled. Also, the use of
mercury in this subcategory usually prevents the POTW from using
their sludges for land use purposes. For this option flow is 46
million 1/yr and annual toxic pollutant removal is 4,320 kg/yr.
For plants to comply directly with this option, the estimated
compliance capital cost is $258,000 and annual cost is $88,000.
Options 2, 3, and 4_ are rejected because, as discussed in Section
X the technologies yield small incremental removals when compared
to option 1. The PSES will remove approximately 99.81 percent of
current toxic pollutant discharges. Given the results achieved
by the technologies used as a basis for the promulgated
limitations, further treatment would result only in de minimis,
insignificant reductions in annual national discharges.
Accordingly, EPA has determined that the total amount of each
pollutant in the remaining discharges after compliance with PSES
does not justify establishing a national requirement based on
additional end-of-pipe technology.
Although EPA is not basing the final regulations directly on
these additional technologies, their availability, effectiveness
and affordability provides significant support for EPA's
conclusion that the promulgated pretreatment standards are both
technologically and economically achievable.
976
-------
Pollutant Parameters for Regulation
Pollutant parameters selected for pretreatment regulation in this
subcategory are chromium, mercury, silver, zinc and manganese.
As discussed in Section X these pollutants were selected for
their toxicity, use within the subcategory, and treatability.
For the pretreatment standards POTW treatment, incompatability,
and pass through (for chromium, mercury, silver and zinc) were
also considered. Conventional pollutants are not specifically
regulated because POTW are specifically designed to treat
conventional pollutants.
Effluent Standards
Effluent standards for existing pretreatment sources are
identical to the BAT limitations discussed in Section X. These
standards are expressed in terms of mg of pollutant per kg of
production normalizing parameter for each process element. PSES
are displayed in Tables XII-47 to XII-62 (pages 1026-1041). To
alleviate some of .the monitoring burden, several process elements
which occur at most plants and have the same pnp are combined in
one regulatory table. Table XII-60 is the combined table for
tables XII-55, 57, 58, and 59. These standard tables list all
the pollutants which were considered for regulation, and those
regulated are *'d.
PSNS are identical to NSPS discussed in Section XI. Standards
are displayed in Tables XII-63 to XII-76 (pages 1042-1055).
Table XII-74 is the combined table for tables XII-69, 71, 72, and
73.
977
-------
TABLE XCI-1
POLLUTANT REDUCTION BENEFITS OP CONTROL SYSTEMS
CAEMIUM SU8CATEGORY - INDIRECT DISCHARGERS
PARAMETER
FLOW 1/yr (106)
118 CADMIUM
119 CHRCMIUM
121 CYANIDE
122 LEAD
123 MERCURY
124 NICKEL
126 SILVER
~ 128 ZINC
00 COBAUT
OIL & GREASE
TSS
TCKCC METALS
CONVEOTICNALS
TOTAL POLLU.
RAW WASTE
kg/yr
209.90
6918.30
15.32
10.29
0.42
1.68
14839.93
3.78
32702.42
98.44
1358.05
81378.23
54481.85
82736.28
137326.86
PSES 0
Removed
kg/yr
6901.72
0.00
0.00
0.00
0.00
14720.29
0.00
32639.45
83.75
0.00
78859.43
54261.46
78859.43
133204.64
Discharged
kg/yr
209.90
16.58
15.32
10.29
0.42
1.68
119.64
3.78
62.97
14.69
1358.05
2518.80
220.39
3876.85
4122.22
PSES 1
Removed
kg/yr
6916.03
13.02
8.28
0.00
0.00
14823.58
0.91
32693.81
96.43
1071.15
81033.95
54447.35
82105.10
136657.16
Di scharged
kg/yr
28.69
2.27
2.30
2.01
0.42
1.68
16.35
2.87
8.61
2.01
286.90
344.28
34.50
631.18
669.70
PSES 2
Removed
kg/yr
6916.89
13.31
8.94
0.00
0.65
14833.62
1.77
32695.82
97.01
1071.15
81303.64
54462.06
82374.79
136942.80
Discharged
kg/yr
28.69
1.41
2.01
1.35
0.42
1.03
6.31
2.01
6.60
1.43
286.90
74.59
19.79
361.49
384.06
PSES 3
Removed
kg/yr
6918.09
15.02
10.09
0.08
1.53
14838.99
3.48
32701.44
98.23
1315.55
81367.18
54478.63
82682.73
137269.68
PSES 4
Discharged Removed Discharged
kg/yr kg/yr kg/yr
4.25
0.21
0.30
0.20
0.34
0.15
0.94
0.30
0.98
0.21
42.50
11.05
3.22
53.55
57.18
6918.30
15.32
10.29
0.42
1.68
14839.93
3.78
32702.42
98.44
1358.05
81378.23
54481.85
82736.28
137326.86
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
SLUD3E GEN
1253939.88
1275089.82
1276872.00
1278757.53
1279089.70
-------
TABLE XI1-2
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Unifcs - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 11.95 5.27
Chromium 15.47 6.33
Cyanide 10.19 4.22
^Lead 14.76 7.03
Mercury 8.79 3.52
*Nickel 67.49 44.64
Silver 14.41 5.98
*Zinc 51.32 21.44
*Cobalt 7.38 3.16
*Regulated Pollutant
979
-------
TABLE XI1-3
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Impregnated Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 68.0 30.0
Chromium 88.0 36.0
Cyanide 58.0 24.0
Lead 84.0 40.0
Mercury 50.0 20.0
*Nickel 384.0 254.0
Silver 82.0 34.0
*Zinc 292.0 122.0
*Cobalt 42.0 18.0
*Regulated Pollutant
980
-------
TABLE XI1-4
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Nickel Electrodeposited Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium 11.22 4.95
Chromium 14.52 5.94
Cyanide 9.57 3.96
Lead 13.86 6.60
Mercury 8.25 3.30
*Nickel 63.36 41.91
Silver 13.53 5.61
*Zinc 48.18 20.13
*Cobalt 6.93 2.97
*Regulated Pollutant
981
-------
TABLE XI1-5
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Nickel Impregnated Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 lb of nickel applied
*Cadmium 68.0 30.0
Chromium 88.0 36,0
Cyanide 58.0 24.0
Lead 84.0 40.0
Mercury 50.0 20.0
*Nickel 384.0 254.0
Silver 82.0 34.0
*Zinc 292.0 122.0
*Cobalt 42.0 18.0
*Regulated Pollutant
982
-------
TABLE XI1-6
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium ' 0.26 0.11
Chromium 0.33 0.14
Cyanide 0.22 0.090
Lead 0.32 0.15
Mercury 0.19 0.075
*Nickel 1.44 0.95
Silver 0.31 0.13
*Zinc 1.10 0.46
*Cobalt 0.16 ' 0.067
*Regulated Pollutant
983
-------
TABLE XII-7
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Electrolyte Preparation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.027 0.012
Chromium 0.035 0.014
Cyanide 0.023 0.009
Lead 0.033 0.016
Mercury 0.020 0.008
*Nickel 0.153 0.101
Silver 0.032 0.013
*Zinc 0.116 0.048
*Cobalt 0.016 0.007
*Regulated Pollutant
984
-------
TABLE XI1-8
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.51 0.23
Chromium 0.66 0.27
Cyanide 0.44 0.18
Lead 0.63 0.30
Mercury 0.38 0.15
*Nickel 2.88 1.91
Silver 0.62 0.26
*Zinc 2.19 0.92
*Cobalt 0.32 0.14
*Regulated Pollutant
985
-------
TABLE XI1-9
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.79 0.35
Chromium 1.03 0.42
Cyanide 0.68 0.28
Lead 0.98 0.47
Mercury 0.58 0.23
*Nickel 4.47 2.96
Silver 0.96 0.40
*Zinc 3.40 1.42
*Cobalt 0.49 0.21
*Regulated Pollutant
986
-------
TABLE XII-10
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Cadmium Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 Ib of cadmium powder produced
*Cadmium 2.23 0.99
Chromium 2.89 1.18
Cyanide 1.91 0.79
Lead 2.76 1.31
Mercury 1.64 0.66
*Nickel 12.61 8.34
Silver 2.69 1.12
*Zinc 9.59 4.01
*Cobalt 1.38 0.59
*Regulated Pollutant
987
-------
TABLE XII-11
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
*Cadmium 1.09 0.48
Chromium 1.41 0.58
Cyanide 0.93 0.39
Lead 1.35 0.64
Mercury 0.80 0.32
*Nickel 6.16 4.08
*Silver 1.32 0.55
*Zinc 4.69 1.96
*Cobalt 0.67 0.29
*Regulated Pollutant
988
-------
TABLE XII-12
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Cadmium Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric .Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
*Cadmium 0.05 0.02
Chromium 0.061 0.025
Cyanide 0.040 0.016
Lead 0.058 0.028
Mercury 0.035 0.014
*Nickel 0.27 . 0.18
Silver 0.057 0.023
*Zinc 0.20 0.09
*Cobalt 0.03 0.01
*Regulated Pollutant
989
-------
TABLE XII-13
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Nickel Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
*Cadmium 5.61 2.48
Chromium 7.26 2.97
Cyanide 4.79 1.98
Lead 6.93 3.30
Mercury 4.13 1.65
*Nickel 31.68 20.96
Silver 6.77 2.81
*Zinc 24.09 10.07
*Cobalt 3.47 1.49
*Regulated Pollutant
990
-------
TABLE XI1-14
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 7.03 2.81
Chromium 13.01 5.27
Cyanide 7.03 2.81
Lead 9.84 4.57
Mercury 5.27 2.11
*Nickel 19.33 13.01
Silver 10.19 4.22
*Zinc 35.85 14.76
*Cobalt 4.92 2.46
*Regulated Pollutant
991
-------
TABLE XI1-15
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Impregnated Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium
English Units - lb/1,000,000 Ib of cadmium
*Cadmium 40.0 16.0
Chromium 74.0 30.0
Cyanide 40.0 16.0
Lead 56.0 26.0
Mercury 30.0 12.0
*Nickel 110.0 74.0
Silver 58.0 24.0
*Zinc 204.0 84.0
*Cobalt 28.0 14.0
*Regulated Pollutant
992
-------
TABLE XI1-16
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Nickel Electrodeposited Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium 6.60 2.64
Chromium 12.21 4.95
Cyanide 6.60 2.64
Lead 9.24 4.29
Mercury 4.95 1.98
*Nickel 18.15 12.21
Silver 9.57 3.96
*Zinc 33.66 13.86
*Cobalt 4.62 2.31
*Regulated Pollutant
993
-------
TABLE XI1-17
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Nickel Impegnated Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
*Cadmium 40.0 16.0
Chromium 74.0 30.0
Cyanide 40.0 16.0
Lead 56.0 26.0
Mercury 30.0 12.0
*Nickel 110.0 74.0
Silver 58.0 24.0
*Zinc 204.0 84.0
*Cobalt 28.0 14.0
*Regulated Pollutant
994
-------
TABLE XI1-18
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.15 0.06
Chromium 0.28 0.11
Cyanide 0.15 0.06
Lead 0.21 0.097
Mercury 0.11 0.045
*Nickel 0.41 0,28
Silver 0.22 0.09
*Zinc 0.77 0.32
*Cobalt 0.11 0.052
*Regulated Pollutant
995
-------
TABLE XI1-19
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Electrolyte Preparation
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.016 0.006
Chromium ,0.029 0.012
Cyanide 0.016 0.006
Lead 0.022 0.010
Mercury 0.012 0.004
*Nickel 0.044 0.029
Silver 0.023 0.009
*Zinc 0.081 0.033
*Cobalt 0.011 0.005
*Regulated Pollutant
996
-------
TABLE XI1-20
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.30 0.12
Chromium 0.56 0.23
Cyanide 0.30 0.12
Lead 0.42 0.20
Mercury 0.23 0.090
*Nickel 0.83 0.56
Silver 0.44 0.18
*Zinc 1.53 0.63
*Cobalt 0.21 0.11
*Regulated Pollutant
997
-------
TABLE XI1-21
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Cadmium 0.47 0.19
Chromium 0.86 0.35
Cyanide 0.47 0.19
Lead 0.65 0.30
Mercury 0.35 0.14
*Nickel 1.28 0.86
Silver 0.68 0.28
*2inc 2.38 0.98
*Cobalt 0.33 0.16
*Regulated Pollutant
998
-------
TABLE XI1-22
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Cadmium Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium powder produced
English Units - lb/1,000,000 lb of cadmium powder produced
*Cadmium
Chromium
Cyanide
Lead
Mercury
*Nickel
Silver
*Zinc
*Cobalt
1 .31
2.43
1 .32
1 .84
0.99
3.61
1 .91
6.70
0.92
0.53
0.99
0.53
0.86
0.40
2.43
0.79
2.76
0.46
*Regulated Pollutant
999
-------
TABLE XI1-23
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
*Cadmium 0.64 0.26
Chromium 1.19 0.48
Cyanide 0.64 0.26
Lead 0.90 0.42
Mercury 0.48 0.19
*Nickel 1.77 1.19
*Silver 0.93 0.39
*Zinc 3.27 1.35
*Cobalt 0.45 0.22
*Regulated Pollutant
1000
-------
TABLE XII-24
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Cadmium Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cadmium used
English Units - lb/1,000,000 Ib of cadmium used
*Cadmium 0.028 0.011
Chromium 0.051 ' 0.021
Cyanide 0.028 0.011
Lead 0.039 0.018
Mercury . 0.021 0.008
*Nickel 0.077 0.051
Silver 0.040 0.016
*Zinc 0.142 0.058
*Cobalt 0.019 0.009
*Regulated Pollutant
1001
-------
TABLE XI1-25
CADMIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Nickel Hydroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel used
English Units - lb/1,000,000 Ib of nickel used
*Cadmium 3.30 1.32
Chromium 6.11 2.48
Cyanide 3.30 1.32
Lead 4.62 2.15
Mercury 2.48 • 0.99
*Nickel 9.08 6.11
Silver 4.79 1.98
*Zinc 16.83 6.93
*Cobalt 2.31 1.16
*Regulated Pollutant
1002
-------
TABLE XII-26
POLLUTAffl1 REDUCTION ^JSEFITS OP OOWTBOL SYSTEMS
CALCIUM SUBC&TBGOFY - TOTAL
o
o
u>
PARAMETER
FLOW 1/yr (106)*
116 ASBSSTOSi/
119 CHRCMIUM
TSS
TOXIC METALS
COaVENTIONALS
TOTAL POLLU.
RAW WASTE
kg/yr
0.13
40.95
7.93
47.84
7.93
47.84
55.77
BPT
Removed
kg/yr
39.60
7.92
46.28
7.92
46.28
54.20
& PSES 0
Discharged
kg/yr
0.13
1.35
0.01
1.56
0.01
1.56
1.57
BAT 1
Removed
kg/yr
40.66
7.92
47.50
7.92
47.50
55.42
& PSES 1
Discharged
kg/yr
0.13
0,29
0.01
0.34
0.01
0.34
0.35
BAT 2 & PSES 2
SLUDGE GM
317.73
323.83
Reaoved
kg/yr
40.95
7.93
47,84
7.93
47.84
55.77
325.64
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.00
0.00
0.00
* 100% of the total flow is for indirect dischargers.
I/ Asbestos is in trillions of fibers per year; not included in total.
-------
XEL-27
POLLUTANT REDUCTION BENEFITS OF CONTROL OPTIONS
LECUNCHE SUBCATEGORY
RAW WASTE
BPT & BAT (PSES)
o
o
Flow 1/yr (10&)
I/kg*
POLLUTANTS
115 Arsenic
118 Cadmium
119 Chromium
120 Copper
122 Lead
123 Mercury
124 Nickel
125 Selenium
128 Zinc
Manganese
Oil and Grease
TSS
mg/1
0.090
0.053
0.409
0.466
0.101
13.40
1.212
0.086
317.5
69,3
115.0
2,536
0.758
mg/kg
0.068
0.040
0.310
0.353
0.076
10.16
0.919
0.065
240.7
52.5
87.2
1,922
16.71
kg/yr
1.503
0.881
6.84
7.78
1.684
223.9
20.25
1.435
5,305.4
1,158.0
1 ,921 .7
42,376.5
Removed
kg/yr
1.435
0.871
6.826
7.702
1.668
223.893
20.206
1.395
5,305.35
1,157.97
1,919.70
42,375.98
0.200
0.009
Discharged
kg/yr
0.068
0.010
0.014
0.078
0.016
0.007
0.044
0.040
0.046
0.028
2.00
0.520
Toxic Metals
Conventionals
All Pollutants
Sludge Generated
5,569.7 5,569.35
44,298.2 44,295.7
51,025.9 51,023.0
288,555.0
0.323
2.52
2.87
*Normalized flow based on total subcategory zinc anode weight.
-------
TABLE XII-28
LECLANCHE SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Foliar Battery Miscellaneous Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic
Cadmium
Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Zinc
*Manganese
0.092
0.013
0.024
0.084
0.018
0.010
0.036
0.054
0.067
0.019
0.038
0.005
0.010
0.040
0.009
0.004
0.024
0.024
0.030
0.015
*Regulated Pollutant
1005
-------
TABLE XI1-29
LECLANCHE SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Foliar Battery Miscellaneous Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.092 0.038
Cadmium 0.013 0.005
Chromium 0.024 0.010
Copper 0.084 0.040
Lead 0.018 0.009
*Mercury 0.010 0.004
Nickel 0.036 0.024
Selenium 0.054 0.024
*Zinc 0.067 0.030
*Manganese 0.019 0.015
*Regulated Pollutant
1006
-------
TABLE X1I-30
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LITHIUM SUBCATEGORY
O
O
PARAMETER RAW WASTE
kg/yr
HEAT PAPER PRODUCTION
FLOW 1/yr (106) 0.04
116 ASBESTOSi/ 12.60
119 CHROMIUM 2.44
122 LEAD
128 ZINC
COBALT
IRON
TSS 14.72
CATHODE AND ANCILLARY OPERATIONS
FLOW 1/yr (106) 0.21
116 ASBESTOS!/ 1.35
119 CHROMIUM 0.16
122 LEAD 1.02
128 ZINC 0.10
COBALT 0.04
IRON 11.37
COD 299.09
TSS 9.09
AIR SCRUBBER WASTEWATERS
BPT &
Removed
kg/yr
12.19
2.44
(-0.005)
(-0.010)
(-0.002)
(-0.014)
14.24
0.00
0.14
0.995
0.050
0.032
11.294
296.99
6.57
PSES 0
Discharged
kg/yr
0.04
0.41
0.00
0.005
0.010
0.002
0.014
0.48
0.21
1.35
0.02
0.025
0.050
0.008
0.076
2.10
2.52
BAT 1 & PSES 1
Removed
kg/yr
12.51
2.44
(-0.003)
(-0.008)
(-0.002)
(-0.010)
14.62
0.88
0.15
1.003
0.058
0.032
11.320
296.99
8.54
FLOW 1/yr (106) 0.11 0.11
TSS 132.96 131.64 1.32 131.64
I/ Asbestos is trillions of fibers per year; not included in totals.
Discharged
kg/yr
0.04
0.09
0.00
0.003
0.008
0.002
0.010
0.10
0.21
0.47
0.01
0.017
0.042
0.008
0.050
2.10
0.55
0.11
1.32
BAT 2 & PSES 2
Removed
kg/yr
12.60
2.44
14.72
0.88
0.15
1.00
0.05
0.03
11.31
296.99
8.54
131.64
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.21
0.47
0.01
0.02
0.05
0.01
0.06
2.10
0.55
0.11
1.32
BAT 3 & PSES 3
Removed
kg/yr
12.60
2.44
14.72
0.88
0.15
1.00
0.05
0.03
11.31
296.99
8.54
132.67
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.21
0.47
0.01
0.02
0.05
0.01
0.06
2.10
0.55
0.11
0.29
-------
O
o
oo
TABLE XI1-30
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
LITHIUM SUBCATEGORY:
PARAMETER RAW WASTE
kg/yr
BPT
Renoved
kg/yr
& PSES 0
Discharged
kg/yr
LITHIUM SUBCATB30RV SUMMARY 7J
FLOW 1/yr (106)
116 ASBESTOS If
119 CHROMIUM
122 LEAD
128 ZINC
COBALT
IRON
COD
TSS
TOXIC METALS
CONVEOTICNALS
TOTAL POLLU.
0.36
13.95
2.60
1.02
0.10
0.04
11.37
299.09
156.77
3.72
156.77
470.99
12.19
2.58
0.99
0.04
0.03
11.28
296.99
152.45
3.61
152.45
464.36
0.36
1.76
0.02
0.03
0.06
0.01
0.09
2.10
4.32
0.11
4.32
6.63
BAT 1 & PSES 1
Removed
SLUDGE GES
922.02
13.39
2.59
1.00
0.05
0.03
11.31
296.99
154.80
3.64
154.80
466.77
934.41
Discharged
kg/yr
0.36
0.56
0.01
0.02
0.05
0.01
0.06
2.10
1.97
0.08
1.97
4.22
BKf 2 S PSES 2
Removed
kg/yr
13.48
2.59
1.00
0.05
0.03
11.31
2%.99
154.90
3.64
154.90
466.87
934.91
Discharged
kg/yr
0.32
0.47
0.01
0.02
0.05
0.01
0.06
2.10
1.87
0.08
1.87
4.12
BftI 3 S PSES 3
Removed
kg/yr
Discharged
kg/yr
13.48
2.59
1.00
0.05
0.03
11.31
296.99
155.93
3.64
155.93
467.90
940.06
0.32
0.47
0.01
0.02
0.05
0.01
0.06
2.10
0.84
0.08
0.84
3.09
I/ Asbestos is trillions of fibers per year; not included in totals.
2/ For direct dischargers only multiply totals by O.ul.
For indirect dischargers only multiply totals by 0.99.
-------
TABLE XII-31
LITHIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Lead Iodide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
Chromium 27.8 11.4
Lead 26.5 12.6
Zinc 92.1 38.5
Cobalt 13.3 5.68
Iron 75.7 38.5
1009
-------
TABLE XI1-32
LITHIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Iron Disulfide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib of iron disulfide
Chromium 3.32 1.36
Lead 3.17 1.51
Zinc 11.0 4.60
Cobalt 1.58 0.68
Iron 9.05 4.60
1010
-------
TABLE XI1-33
LITHIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.047 0.019
Lead 0.045 0.021
Zinc 0.157 0.065
Cobalt 0.022 0.009
Iron 0.129 0.065
1011
-------
TABLE XI1-34
LITHIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Lead Iodide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of lead
English Units - lb/1,000,000 Ib of lead
*Chromium 23.34 9.46
*Lead 17.66 8.20
Zinc 64.34 26.49
Cobalt 75.70 38.48
Iron 75.70 38.48
*Regulated Pollutant
1012
-------
TABLE XI1-35
LITHIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Iron Disulfide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of iron disulfide
English Units - lb/1,000,000 Ib of iron disulfide
*Chromium 2.79 1.13
*Lead 2.11 0.98
Zinc 7.69 3.17
Cobalt 1.06 0.53
Iron 9.05 4.60
*Regulated Pollutant
1013
-------
TABLE XII-36
LITHIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
*Chromium 0.039 0.016
*Lead 0.030 0.014
Zinc 0.110 0.045
Cobalt 0.015 0.007
Iron 0.129 0.066
*Regulated Pollutant
1014
-------
TABLE HI-37
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
MAGNESIUM SUBCATBGORY
PARAMETER
RAW
O
Ui
BPT & PSES 0
Renewed Disdharged
BAT 1 & PSES 1
Removed
kg/yr
HEAT PAPER PRODUCTION
FLOW 1/yr (106) 2.60
116 ASBESTOS I/ 819.00
119 CHROMIUM 158.60
TSS 956.80
792,08
158.39
925.60
2.60
26.92
0.21
31.20
813.1?
158.42
950.04
CELL TESTING AND FLOOR AND EQUIPMENT WASH
FLOW 1/yr
122 LEAD
124 NICKEL
126 SILVER
IRON
TSS
(106) 0.11
0.13
0.01
1.61
0.21
91.08
0.12
0.00
1.60
0.16
89.76
0.11
0.01
0.01
0.01
0.05
1.32
0.12
0.00
1.60
0.16
89.76
SILVER CHLORIDE CATHODE PRODUCTION
FLOW 1/yr (106) 0.75
0.43
122 LEAD
124 NICKEL
126 SILVER
IRON
COD
TSS
AIR SCRUBBERS
FLOW 1/yr (106)
TSS
0.04
0.04
0.19
0.42
105.00
0.53
0.00
0.00
0.15
0.24
100.70
0.00
0.04
0104
0.04
0.18
4.30
0.53
0.03
0.00
0.18
0.37
103.80
0.00
0.45
543.94
538.54
0.45
5.40
Discharged
kg/yr
0.01
538.54
2.60
5.83
0.18
6.76
0.11
0.01
0.01
0.05
1.32
0.12
0.01
0.04
0.01
0.05
1.20
0.53
0.45
5.40
BAT 2
Renewed
kg/yr
819.00
158.60
956.80
0.12
0.00
1.60
0.18
90.79
0.03
0.01
0.18
0.39
103.80
0.22
538.54
& PSES 2
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.11
0.01
0.01
0.01
0.03
0.29
0.12
0.01
0.03
0.01
0.03
1.20
0.31
0.45
5.40
BAT 3
Removed
kg/yr
819.00
158.60
956.80
0.12
0.00
1.60
0.18
90.79
0.03
0.01
0.18
0.39
103.80
0.22
542.77
& PSES 3
Discharged
kg/yr
0.00
0.00
0.00
0.00
0.11
0.01
0.01
0.01
0.03
0.29
0.12
0.01
0.03
0.01
0.03
1.20
0.31
0.45
1.17
I/ Asbestos is trillions of fibers per year? not included in totals.
-------
TABLE XI1-37
POLLOTftNT RH3UCTION BENEFITS OF CQOTRQL SYSFHIS
MAGNESIUM SUBCA.TB30RY.
BAT2 & PSES 2
PARAt^TER
RftW SffiSTE
kg/yr
BPT
Removed
kg/yr
& PSES 0
Discharged
kg/yr
BAT 1
Removed
kg/yr
S PSES 1
Discharged
kg/yr
MAGNESIUM SUBCATBGOKir SUMWQT 2J
FLOW 1/yr (106)
116 ASBESTOS I/
119 CHKCMIUM
122 LEAD
124 NI«SL
126 SILVER
IRON
COD
TSS
TOXIC METALS
CONVEOTICNALS
TOTAL POLLU.
3.91
819.00
158.60
0.17
0.05
1.80
0.63
105.00
1592.35
160.62
1592.35
1858.60
792.08
158.39
0.12
0.00
1.75
0.40
100.70
1553.90
160.26
1553.90
1815.26
3.59
26.92
0.21
0.05
0.05
0.05
0.23
4.30
38.45
0.36
38.45
43.34
813.17
158.42
0.15
0.00
1.78
0.53
103.80
1578.34
160.35
1578.34
1843.02
3.28
5.83
0.18
0.02
0.05
0.02
0.10
1.20
14.01
0.27
14.01
15.58
SLUDGE GEN
9514.35
9638.83
I/ Asbestos is trillions of fibers per year; not included in totals.
2} for: direct dischargers only multiply totals by 0.05.
For indirect dischargers only multiply totals by 0.95-
_
Renewed
kg/yr
819.00
158.60
0.15
0.01
1.78
0.57
103.80
1586.35
160.54
158S.35
1851.26
9681.63
Discharged
kg/yr
0.68
o.oo
0.00
0.02
0.04
0.02
0.06
20
.00
0.08
6.00
7.34
& PStS 3
Renewed
kg/yr
Diselwrgerf
kg/yr
819.00
158.60
0.15
0.01
1.78
0.57
103.80
1590.58
160.54
.1590.58
2674.49
13797.78
0.68
0.68
0.00
0.02
0.04
0.02
0.06
1.20
1.77
0.08
1.77
3.11
-------
TABLE XI1-38
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Chloride Cathodes - Chemically Reduced
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 36.04 14.74
*Lead 34.40 16.38
Nickel 157.3 104.0
*Silver 33.58 13.92
Iron 98.28 49.96
COD 122900.0 59975.0
*Regulated Pollutant
1017
-------
TABLE XI1-39
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Chloride Cathodes - Electrolytic
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 63.8 26.1
*Lead 60.9 29.0
Nickel 278.4 184.2
*Silver 59.5 24.7
Iron 174.0 88.5
COD 7250.0 3538.0
*Regulated Pollutant
1018
-------
TABLE XII-40
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Cell Testing
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 23.2 9.47
*Lead 22.1 10.5
Nickel 101.0 66.8
*Silver 21.6 8.94
Iron 63.1 32.1
*Regulated Pollutant
1019
-------
TABLE XI1-41
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.041 0.016
*Lead 0.039 0.018
Nickel 0.180 0.119
*Silver 0.038 0.015
Iron 0.112 0.057
*Regulated Pollutant
1020
-------
TABLE XI1-42
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Chloride Cathodes - Chemically Reduced
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 30.30 12.29
*Lead 22.93 10.65
Nickel 45.05 30.30
*Silver 23.75 9.83
Iron 98.28 49.96
COD 4095.0 1999.0
*Regulated Pollutant
1021
-------
TABLE XI1-43
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Chloride Cathodes - Electrolytic
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Chromium 53.7 21.8
*Lead 40.6 18.9
Nickel 79.8 53.7
*Silver 42.1 17.4
Iron 174.0 88.5
COD 7250.0 3540.0
*Regulated Pollutant
1022
-------
TABLE XI1-44
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Cell Testing
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 19.5 7.89
*Lead 14.7 6.84
Nickel 28.9 19.5
*Silver 15.3 6.31
Iron 63.1 32.1
COD 2630.0 1290.0
*Regulated Pollutant
1023
-------
TABLE XI1-45
MAGNESIUM SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Chromium 0.034 0.014
*Lead 0.026 0.012
Nickel 0.051 0.034
*Silver 0.027 0.011
Iron 0.112 0.057
COD 4.70 2.30
*Regulated Pollutant
1024
-------
TABLE XII-46
POLLUTANT REDUCTION BENEFITS OF CONTROL SYSTEMS
ZINC SUBCATEGORY - INDIRECT DISCHARGERS
O
N>
t_n
PARAMETER RAW WASTE
FLOW 1/yr (106)
115 ARSENIC
118 CACMIUM
119 CHROMIUM
120 COPPER
121 CYANIDE
122 LEAD
123 MERCURY
124 NICKEL
125 SELENIUM
126 SILVER
128 ZINC
ALUMINUM
IRON
MANGANESE
OIL & GREASE
TSS
TOXIC METALS
CONVEOTIONALS
TOTAL POLLU.
kg/yr
46.44
2.51
1.72
1149.86
21.54
32.60
3.62
590.25
75.23
1.62
46.02
2479.89
13.88
0.18
235.45
1197.22
2891.35
4372.26
4088.57
8742.94
PSES O
Removed
kg/yr
0.00
0.00
1146.15
0.00
29.35
0.00
587.46
48.76
1.16
41.38
2465.96
0.00
0.00
225.69
732.82
2334.07
4290.87
3066.89
7612.80
PSES 1
Discharged Removed
kg/yr kg/yr
46.44
2.51
1.72
3.71
21.54
3.25
3.62
2.79
26.47
0.46
4.64
13.93
13.88
0.18
9.76
464.40
557.28
81.39
1021.68
1130.14
0.00
1.23
1149.36
17.92
32.16
2.87
589.87
71.68
1.56
45.40
2478.02
6.96
0.00
234.14
1134.82
2816.47
4357.91
3951.29
8582.46
Discharged
kg/yr
6.24
2.51
0.49
0.50
3.62
0.44
0.75
0.38
3.55
0.06
0.62
1.87
6.92
0.18
1.31
62.40
74.88
14.35
137.28
160.48
PSES 2
Removed Discharged
kg/yr kg/yr
0.39
1.41
1149.42
19.11
32.31
3.12
590.03
73.86
1.57
45.58
2478.45
9.26
0.00
234.57
1134.82
2875.12
4362.94
4009.94
8649.02
6.24
2.12
0.31
0.44
2.43
0.29
0.50
0.22
1.37
0.05
0.44
1.44
4.62
0.18
0.88
62.40
16.23
9.32
78.63
99.92
PSES 3
Removed
kg/yr
Discharged
kg/yr
0.51
1.66
1149.57
21.25
32.32
3.56
590.05
74.94
1.58
45.73
2479.83
9.53
0.00
234.63
1138.42
2876.06
4368.68
4014.49
8659.65
5.88
2.00
0.06
0.29
0.29
0.28
0.06
0.20
0.29
0.04
0.29
0.06
4.35
0.18
0.82
58.80
15.28
3.58
74.08
83.29
PSES 4
Removed
kg/yr
2.24
1.71
1149.82
21.50
32.56
3.61
590.22
75.19
1.61
45.98
2479.88
13.30
0.00
235.34
1189.32
2889.29
4371.76
4078.61
8731.57
Discharged
kg/yr
0.79
0.27
0.01
0.04
0.04
0.04
0.01
0.03
0.04
0.01
0.04
0.01
0.58
0.19
0.11
7.90
2.06
0.50
9.96
11.37
SLUDGE GEN
59385.49
65473.01
65948.03
66059.94
66541.30
-------
TABLE XI1-47
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Wet Amalgamated Powder Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 1.58 0.71
Cadmium 0.19 0.082
*Chromium 0.24 0.099
Copper 1.05 0.55
Lead 0.23 0.11
*Mercury 0.14 0.055
Nickel 1.06 0.70
Selenium 0.68 0.30
*Silver 0.23 0.093
*Zinc 0.80 0.34
Aluminum 3.54 . 1.76
Iron 0.66 0.34
*Manganese 0.37 0.16
*Regulated Pollutant
1026
-------
TABLE XI1-48
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Gelled Amalgam Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic 0.20 0.087
Cadmium 0.023 0.010
*Chromium 0.030 0.012
Copper 0.13 0.068
Lead 0.028 0.013
*Mercury 0.017 0.007
Nickel 0.13 0.086
Selenium 0.083 0.037
*Silver 0.028 0.012
*Zinc 0.099 0.042
Aluminum 0.44 0.22
Iron 0.081 0.041
*Manganese 0.046 0.020
*Regulated Pollutant
1027
-------
TABLE XI1-49
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Zinc Oxide Anodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
62. 19
7.37
9.53
41.17
9. 10
5.42
41 .61
26.66
8.89
31 .64
139.3
26.00
14.74
27.74
3.25
3.90
21 .67
4.34
2. 17
27.52
1 1 .92
3.68
13.22
69.35
13.22
6.28
*Regulated Pollutant
1028
-------
TABLE XI1-50
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Arsenic 616.19 274.82
Cadmium 73.00 32.21
*Chromium 94.47 38.65
Copper 407.93 214.70
Lead 90.18 42.94
*Mercury 53.68 21.47
Nickel 412.23 272.67
Selenium 264.08 118.09
*Silver 88.03 36.50
*Zinc 313.46 130.97
Aluminum 1380.52 687.04
Iron 257.64 130.97
*Manganese 146.00 62.26
*Regulated Pollutant
1029
-------
TABLE XI1-51
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - rag/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
85.24
10.10
13.07
56.43
12.48
7.43
57.03
36.53
12.18
43.36
190.97
35.64
20.20
38.02
4.46
5.35
29.70
5.94
2.97
37.72
16.34
5.05
18.12
95.04
18.12
8.61
*Regulated Pollutant
1030
-------
TABLE XI1-52
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Oxide Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 56.97 25.41
Cadmium 6.75 2.98
*Chromium 8.73 3.57
Copper 37.72 19.85
Lead 8.34 3.97
*Mercury 4.96 1.99
Nickel 38.11 25.21
Selenium 24.42 10.92
*Silver 8.14 3.37
*Zinc 28.98 12.11
Aluminum 127.64 63.52
Iron 23.82 12.11
*Manganese 13.50 5.76
*Regulated Pollutant
1031
-------
TABLE XI1-53
ZINC SUBCATEGQRY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Peroxide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 13.66 6.09
Cadmium 1.62 0.72
*Chromium 2.09 0.87
Copper 9.05 4.76
Lead 2.00 0.95
*Mercury 1.19 0.48
Nickel 9.14 6.05
Selenium 5.86 2.62
*Silver 1.95 0.81
*Zinc 6.95 2.90
Aluminum 30.61 15.23
Iron 5.71 2.90
*Manganese 3.24 1.38
*Regulated Pollutant
1032
-------
TABLE XI1-54
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Nickel Impregnated Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Arsenic
Cadmium
*Chromium
Copper
Lead *
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
574.0
68.0
88.0
380.0
84.0
50.0
384.0
246.0
82.0
292.0
1286.0
240.0
136.0
256.0
30.0
36.0
200.0
40.0
20.0
254.0
110.0
34.0
122.0
640.0
122.0
58.0
*Regulated Pollutant
1033
-------
TABLE XI1-55
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.49 0.22
Cadmium 0.057 0.025
*Chromium 0.074 0.030
Copper 0.32 0.17
*Cyanide 0.049 0.021
Lead 0.071 0.034
*Mercury 0.042 0.017
*Nickel 0.33 0.22
Selenium 0.21 0.093
*Silver 0.069 0.028
*Zinc 0.25 0.10
Aluminum 1.09 0.55
Iron 0.21 0.11
*Manganese 0.12 0.049
*Regulated Pollutant
1034
-------
TABLE XI1-56
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Etch
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic 21.35 9.52
Cadmium 2.53 1.12
*Chromium 3.27 1.34
Copper 14.14 7.44
Lead 3.13 1.49
*Mercury 1.86 0.74
Nickel 14.29 9.45
Selenium 9.15 4.09
*Silver 3.05 1.26
*Zinc 10.86 4.54
Aluminum 47.84 23.81
Iron 8.93 4.54
*Manganese 5.06 2.16
*Regulated Pollutant
1035
-------
TABLE XI1-57
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.78 0.35
Cadmium 0.091 0.040
*Chromium 0.12 0.048
Copper 0.51 0.27
*Cyanide 0.078 0.033
Lead 0.11 0.054
*Mercury 0.067 0.027
*Nickel 0.52 0.34
Selenium 0.33 0.15
*Silver 0.11 0.045
*Zinc 0.40 0.17
Aluminum 1.74 0.87
Iron 0.33 0.17
*Manganese 0.18 0.078
*Regulated Pollutant
1036
-------
TABLE XI1-58
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Reject Cell Handling
Pollutant or
Pollutant Maximum for Maximum for
Property \ any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.028 0.012
Cadmium 0.003 0.001
*Chromium 0.004 0.001
Copper 0.019 0.010
*Cyanide 0.003 0.001
Lead 0.004 0.002
*Mercury 0.002 0.001
*Nickel 0.019 0.012
Selenium 0.012 0.005
*Silver 0.004 0.001
*Zinc 0.014 0.006
Aluminum 0.064 0.032
Iron 0.012 0.006
*Manganese 0.006 0.002
*Regulated Pollutant
1037
-------
TABLE XI1-59
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 2.41 1.08
Cadmium 0.29 0.13
*Chromium 0.37 0.15
Copper 1.60 0.84
*Cyanide 0.24 0.10
Lead 0.35 0.17
*Mercury 0.21 0.084
*Nickel 1.61 1.07
Selenium 1.03 0.46
*Silver 0.35 0.14
*Zinc 1.23 0.51
Aluminum 5.40 2.69
Iron 1.01 0.51
*Manganese 0.57 0.24
*Regulated Pollutant
1038
-------
TABLE XI1-60
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic
Cadmium
*Chromium
Copper
*Cyanide
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
3.70
0.44
0.57
2.45
0.38
0.54
0.32
2.48
1 .59
0.53
1 .88
8.30
1 .55
0.88
1 .65
0. 19
0.23
1 .29
0.16
0.26
0.13
1 .64
0.71
0.22
0.79
4. 13
0.79
0.37
*Regulated Pollutant
1039
-------
TABLE XI1-61
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Peroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver peroxide produced
Arsenic 22.70 10.13
Cadmium 2.69 1.19
*Chromium 3.48 1.42
Copper 15.03 7.91
Lead 3.32 1.58
*Mercury 1.98 0.79
Nickel 15.19 10.05
Selenium 9.73 4.35
*Silver 3.24 1.34
*Zinc 11.55 4.83
Aluminum 50.86 25.31
Iron 9.49 4.83
*Manganese 5.38 2.29
*Regulated Pollutant
1040
-------
TABLE XI1-62
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR EXISTING SOURCES
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Arsenic 9.21 4.11
Cadmium 1.09 0.48
*Chromium 1.41 0.58
Copper 6.10 3.21
Lead 1.35 0.64
*Mercury 0.80 0.32
Nickel 6.16 4.08
Selenium 3.95 1.77
*Silver 1.32 0.55
*Zinc 4.69 1.96
Aluminum 20.64 10.27
Iron 3.85 1.96
*Manganese 2.18 0.93
*Regulated Pollutant
1041
-------
TABLE XI1-63
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Zinc Oxide Anodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc
English Units - lb/1,000,000 Ib of zinc
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
41 .82
0.87
4.55
4.55
0.87
2.82
4.55
17.77
4.55
0.87
132.4
26.01
6.50
18.64
0.39
1 .97
1 .97
0.39
1 .19
1 .97
8.02
1 .97
0.39
58.73
13.22
4.98
*Regulated Pollutant
1042
-------
TABLE XII-64
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Electrodeposited Anodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of zinc deposited
English Units - lb/1,000,000 Ib of zinc deposited
Arsenic
Cadmium
*Chromium
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
414.37
8.59
45.09
45.09
8.59
27.91
45.09
8.59
45.09
8.59
131 1 .82
257.64
64.41
184.64
3.87
19.54
19.54
3.87
11.81
19.54
3.87
19.54
3.86
581 .84
130.97
49.38
*Regulated Pollutant
1043
-------
TABLE XI1-65
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic
Cadmium
*Chromiu7n
Copper
Lead
*Mercury
Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
57.32
1.19
6.24
6.24
1.19
3.86
6.24
24.35
6.24
1.19
181 .47
35.64
8.91
25.54
0.54
2.70
2.70
0.54
1 .63
2.70
10.99
2.70
0.53
80.49
18.12
6.83
*Regulated Pollutant
1044
-------
TABLE XI1-66
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Oxide Powder Cathodes, Formed
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 38.3 17.1
Cadmium 0.79 0.36
*Chromium 4.17 1.81
Copper 4.17 1.81
Lead 0.79 0.36
*Mercury 2.58 1.09
Nickel 4.17 1.81
Selenium 16.3 7.35
*Silver 4.17 1.81
*Zinc 0.79 0.36
Aluminum 121.3 53.8
Iron 23.8 12.1
*Manganese 5.96 4.57
*Regulated Pollutant '
1045
-------
TABLE XI1-67
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Peroxide Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver applied
English Units - lb/1,000,000 Ib of silver applied
Arsenic 9.19 4.09
Cadmium 0.19 0.09
*Chromium 1.00 0.43
Copper 1.00 0.43
Lead 0.19 0.09
*Mercury 0.62 0.26
Nickel 1.00 0.43
Selenium 3.90 1 .76
*Silver 1.00 0.43
*Zinc 0.19 0.09
Aluminum 29.1 12.9
Iron 5.71 2.90
*Manganese 1.43 1.09
*Regulated Pollutant
1046
-------
TABLE XI1-68
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Nickel Impregnated Cathodes
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of nickel applied
English Units - lb/1,000,000 Ib of nickel applied
Arsenic 386.0 172.0
Cadmium 8.0 3.6
*Chromium 42.0 18.2
Copper 42.0 18.2
Lead 8.0 3.6
*Mercury 26.0 11.0
*Nickel 42.0 18.2
Selenium 164.0 74.0
*Silver 42.0 18.2
*Zinc 8.0 3.6
Aluminum 1222.0 542.0
Iron 240.0 122.0
*Manganese 60.0 46.0
*Regulated Pollutant
1047
-------
TABLE XI1-69
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Cell Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.33 0.15
Cadmium 0.006 0.003
*Chromium 0.035 0.015
Copper 0.035 0.015
*Cyanide 0.025 0.010
Lead 0.006 0.003
*Mercury 0.022 0.009
*Nickel 0.035 0.015
Selenium 0.14 0.062
*Silver 0.035 0.015
*Zinc 0.006 0.003
Aluminum 1.04 0.46
Iron 0.21 0.10
*Manganese 0.051 0.039
*Regulated Pollutant
1048
-------
TABLE XII-70
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Etch
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver processed
English Units - lb/1,000,000 Ib of silver processed
Arsenic 14.36 6.40
Cadmium 0.30 0.13
*Chromium 1.56 0.68
Copper 1.56 0.68
Lead 0.30 0.13
*Mercury 0.97 0.41
Nickel 1.56 0.68
Selenium 6.10 2.75
*Silver 1.56 0.68
*Zinc 0.30 0.13
Aluminum 45.46 20.16
Iron 8.93 4.54
*Manganese 2.23 1.71
*Regulated Pollutant
1049
-------
TABLE XI1-71
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Employee Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 0.52 0.23
Cadmium 0.010 0.004
*Chromium 0.056 0.024
Copper 0.056 0.024
*Cyanide 0.039 0.016
Lead 0.010 0.004
*Mercury 0.035 0.014
*Nickel 0.056 0.024
Selenium 0.22 0.099
*Silver 0.056 0.024
*Zinc 0.010 0.004
Aluminum 1.65 0.73
Iron 0.33 0.16
*Manganese 0.081 0.062
*Regulated Pollutant
1050
-------
TABLE XI1-72
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Reject Cell Handling
Pollutant or
Pollutant
Property
Maximum for
any one day
Maximum for
monthly average
Metric Units -
English Units
mg/kg of cells produced
- lb/1,000,000 Ib of cells produced
Arsenic
Cadmium
*Chromium
Copper
*Cyanide
Lead
*Mercury
*Nickel
Selenium
*Silver
*Zinc
Aluminum
Iron
*Manganese
0.019
0.0004
0.002
0.002
0.0015
0.0004
0.001
0.002
0.008
0.002
0.0004
0.061
0.012
0.003
0.008
0.00018
0.00091
0.00091
0.0006
0.00018
0.00055
0.00091
0.003
0.00091
0.00018
0.027
0.006
0.002
*Regulated Pollutant
1051
-------
TABLE XI1-73
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Floor and Equipment Wash
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 1.62 0.72
Cadmium 0.033 0.015
*Chromium 0.18 0.076
Copper 0.18 0.076
*Cyanide 0.12 0.051
Lead 0.033 0.015
*Mercury 0.11 0.046
*Nickel 0.18 0.076
Selenium 0.69 0.31
*Silver 0.18 0.076
*Zinc 0.033 0.015
Aluminum 5.13 2.28
Iron 1.01 . 0.51
*Manganese 0.25 0.19
*Regulated Pollutant
1052
-------
TABLE XI1-74
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Miscellaneous Wastewater Streams
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of cells produced
English Units - lb/1,000,000 Ib of cells produced
Arsenic 2.49 1.11
Cadmium 0.051 0.023
*Chromium 0.27 0.12
Copper 0.27 0.12
*Cyanide 0.039 0.016
Lead 0.051 0.023
*Mercury 0.17 0.07
*Nickel 0.27 0.12
Selenium 1.06 0.48
*Silver 0.27 0.12
*Zinc 0.05 0.02
Alumium 7.88 3.50
Iron 1.55 0.79
*Manganese 0.39 0.30
*Regulated Pollutant
1053
-------
TABLE XI1-75
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Peroxide Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver in silver peroxide produced
English Units - lb/1,000,000 Ib of silver in silver
peroxide produced
Arsenic 15.27 6.80
Cadmium 0.32 0.14
*Chromium 1.66 0.72
Copper 1.66 0.72
Lead 0.32 0.14
*Mercury 1.03 0.44
Nickel 1.66 0.72
Selenium 6.49 2.93
*Silver 1.66 0.72
*Zinc 0.32 0.14
Aluminum 48.33 21.44
Iron 9.49 4.83
*Manganese 2.37 1.82
*Regulated Pollutant
1054
-------
TABLE XI1-76
ZINC SUBCATEGORY
PRETREATMENT STANDARDS FOR NEW SOURCES
Silver Powder Production
Pollutant or
Pollutant Maximum for Maximum for
Property any one day monthly average
Metric Units - mg/kg of silver powder produced
English Units - lb/1,000,000 Ib of silver powder produced
Arsenic 6.20 2.76
Cadmium 0.13 0.057
*Chromium 0.67 0.29
Copper 0.67 0.29
Lead 0.13 0.057
*Mercury 0.42 0.18
Nickel 0.67 0.29
Selenium 2.63 1.19
*Silver 0.67 0.29
*Zinc 0.13 0.06
Aluminum 19.61 8.70
Iron 3.85 1.96
*Manganese 0.96 0.74
*Regulated Pollutant
1055
-------
-------
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
The 1977 amendments added section 301(b)(2)(E) to the Act,
establishing "best conventional pollutant control technology"
(BCT) for discharges of conventional pollutants from existing
industrial point sources. Conventional pollutants are those
defined in section 304(a)(4) [biological oxygen-demanding
pollutants (BOD5), (TSS), fecal coliform and pH], and any
additional pollutants defined by the Administrator as
"conventional" [oil and grease (O&G), 44 FR 44501,July 30, 1979].
BCT is not an additional limitation but replaces BAT for the
control of conventional pollutants. In addition to other factors
specified in Section 304(b)(4)(B), the Act requires that BCT
limitations be assessed in light of a two part
"cost-reasonableness" test (American Paper Institute v. EPA, 660
F.2d 954 (4th Cir. 1981)). The first test compares the cost for
private industry to reduce its conventional pollutants with the
costs to publicly owned treatment works for similar levels of
reduction in their discharge of these pollutants. The second
test examines the cost-effectiveness of additional industrial
treatment beyond BPT. EPA must find that limitations are
"reasonable" under both tests before establishing them as BCT.
In no case may BCT be less stringent than BPT.
EPA published its methodology for carrying out the BCT analysis
on August 29, 1979 (44 FR 50732). In the case mentioned above,
the Court of appeals ordered EPA to correct data errors
underlying EPA's calculation of the first test, and to apply the
second cost test. (EPA argued that a second cost was not
required.) On October 29, 1982, the Agency proposed a revised
BCT methodology. EPA is deferring proposal of BCT limitations
for the battery manufacturing category until the proposed
methodology is made final.
1057
-------
-------
SECTION XIV
ACKNOWLEGEMENTS
This document has been prepared by the staff of the Effluent
Guidelines Division with the assistance from technical
contractors, other EPA offices and other persons outside of EPA.
This Section is intended to acknowledge the contribution of the
persons who have contributed to the development of this report.
The initial effort on this project was carried out by Hamilton
Standard Division of United Technologies, under Contract Nos. 68-
01-4668 and 68-01-5827. They performed data collection, data
compilation, field sampling and analysis, and initial wastewater
treatment costing, and made the initial drafts for this project.
Hamilton Standard's effort was managed by Daniel J. Lizdas,
Walter Drake, and Robert W. Blaser. Edward Hodgson directed the
engineering activities and field sampling operations were under
the direction of Richard Kearns.
Assistance with the assembling of the proposed document was done
under Contract 68-01-6469 by Versar Inc. Versar's effort on the
proposed document was managed by Lee McCandless and Jerome
Strauss. Efforts done by Whitescarver Associates, a Versar
subcontractor, were managed by John P. Whitescarver. Lawrence
Davies directed the project activities of the support staff at
Versar Inc. and made contributions to the report. Contributions
to the report were made by Robert W. Hardy of Whitescarver
Associates, and Pamela Hillis, Jean Moore, Gayle Riley and other
technical and support staff at Versar.
In preparation of this final document, the Agency performed the
technical effort and John Collins of Radian Corp., a
subcontractor to Versar, assisted with the assembly of the
document. Thomas Wall of JFA, a subcontractor to Versar, and
Anna Wojciechowski of Versar provided assistance in assembly of
the administrative record.
Dov Weitman, Ellen Siegler and Mark Greenwood of the Office of
General Counsel provided legal advise to the project. Ellen
Warhit, Debra Maness, Mary Ives, Allen Leduc, Emily Hartnell, and
William Webster were economic project officers; Henry Kahn,
Barnes Johnson, and Richard Kotz provided statistical analysis;
Alexandra Tarney and Eleanor Zimmerman provided environmental
evaluations.
Word processing was provided by Pearl Smith, Glenda Nesby, and
Carol Swann.
1059
-------
Technical direction and supervision of the project was provided
by Ernst P. Hall, P.E., Chief, Metals and Machinery Branch. The
technical project officer was Mary L. Belefski. V. Ramona Wilson
provided assistance in assembly of the document. Acknowledgement
is given to Robert W. Hardy, formerly of the Environmental
Protection Agency for his technical contributions to this
document.
Finally appreciation is expressed to the many battery
manufacturing companies who provided detailed information and
explanations of the many and varied battery manufacturing
processes and individuals who contributed comments and data for
the formulation of this document.
1060
-------
SECTION XV
BIBLIOGRAPHY
"Antimony" Final Water Quality Criteria, FBI 17319, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
"Arsenic" Final Water Quality Criteria, FBI 17327, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
"Batteries find a niche on the circuit board." Machine Design, L.
Teschler (editor), p. 75-79 (May 10, 1979).
"A big breakthrough in batteries...almost."
Mechanix Illustrated, p. 50-51, 115 (March 1978).
Bellack, Ervin, "Arsenic Removal from Potable Water," Journal
American Water Works Association, July, 1971.
Bhattacharyya, 0., Jumawan, Jr., A.B. and Grieves, R.B.,
"Separation of Toxic Heavy Metals by Sulfide Precipitation,"
Separation Science and Technology, 14(5), 1979, pp. 441-452.
Brown, H.G., Hensley, C.P., McKinney, G.L. and Robinson, J.L.,
"Efficiency of Heavy Metals Removal in Municipal Sewage Treatment
Plants, "Environmental Letters, 5 (2), 1973, pp. 103-114.
"Cadmium" Final Water Quality Criteria, PB117368, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980.
Chamberlin, N.S. and Snyder, Jr., H.B., "Technology of Treating
Plating Waste," 1Oth Industrial Waste Conference.
Chen, K.Y., Young, C.S., Jan, T.K. and Rohatgi, N., "Trace Metals
in .Wastewater Effluent," Journal of Water Pollution Control
Federation, Vol. 46, No. 12, December, 1974, pp. 2663-2675.
"Chlorinated Ethanes" Final Water Quality Criteria, PB117400, and
Standards (45 FR 79318-79379, Nobember 28, 1980).
"Chloroform" Final Water Quality Criteria, PB117442, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
1061
-------
"Chromium" Final Water Quality Criteria, PB117467, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Collins, D.H. Power Sources 3. New Castel upon Tyne: Oriel
Press, 1971.
The Condensed Chemical Dictionary. Van Nostrand Reinhold Co.,
Ninth Edition, 1977.
"Control technology for the metal finishing industry - sulfide
precipitation." Centec Corporation, Reston, VA., Prepared for
U.S. Environmental Protection Agency, Contract No. 68-03-2672
Work Directive 14, September, 1979.
"Copper" Final Water Quality Criteria, PB 117475, Criteria and
Standards Division Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Curry, Nolan A., "Philogophy and Methodology of Metallic Waste
Treatment," 27th Industrial Waste Conference.
"Cyanide" Final Water Quality Criteria, PB117483, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Dean, J. Lange's Handbook of Chemistry. McGraw Hill, 1973.
Davis, III, James A., and Jacknow, Joel, "Heavy Metals in
Wastewater in Three Urban Areas", Journal of Water Pollution
Control Federation, September, 1975, pp. 2292-2297.
"Development document for interim final and proposed effluent
limitations guidelines and new source performance standards for
the ore mining and dressing point source category." U.S.
Environmental Protection Agency, EPA 440/1-75/061-c, October,
1975.
"Development document for proposed effluent limitations guide-
lines and new source performance standards for the battery
manufacturing point source category." U.S. Environmental
Protection Agency, 40 CFR 461, 1977.
"Development document for proposed existing source pretreatment
standards for the electroplating point source category." U.S.
Environmental Protection Agency, EPA 440/1-78/085, February 1978.
"Dichloroethylenes" Final Water Quality Criteria, PB117525,
Criteria and Standards Division, Office of Water Regulations and
Standards (45 FR 79318-79379, November 28,1980).
1062
-------
"Draft development document for effluent limitations guidelines
and new source performance standards for the miscellaneous
nonferrous metals segment of the nonferrous metals manufacturing
point source category." U.S. Environmental Protection Agency,
EPA 440/1-76/067, March 1977.
Electrochemical Power Sources: Primary and Secondary Batteries,
Edited by M. Barak, Peter Peregrimus Ltd. 1980.
Encyclopedia of Chemical Technology. Interscience, Second
Edition, 1963.
Encyclopedia of Chemical Technology. John Wiley & Sons, Third
Edition, 1978.
"Ethylbenzene" Final Water Quality Criteria, PB117590, Criteria
and Standards Division, Office of Water Regulations and Standards
(45 FR 79318-79379, November 28, 1980).
"Everready" Battery Applications and Engineering Data. Union
Carbide Corporation, 1971.
Falk, S.U., and A.J. Salkind. Alkaline Storage Batteries. John
Wiley & Sons Inc., 1969.
Flynn, G. "Slowly but surely...batteries move up the power
ladder." Product Engineering, p. 81-84 (September 1978).
"General Electric Company." Communication from Environmental
Industry Council to Effluent Limitations Guidelines Division,
U.S. Environmental Protection Agency, April 1980.
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.
Graham, R.W. Primary Batteries - Recent Advances. Noyes Data
Corporation, Park Ridge, NJ, Chemical Technology Review No. 105,
Energy Technology Review No. 25, 1978.
Graham, R.W. Secondary Batteries - Recent Advances. Noyes Data
Corporation, Park Ridge, NJ, Chemical Technology Review No. 106,
Energy Technology Review No. 26, 1978.
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.
1063
-------
"Halomethanes" Final Water Quality Criteria, PB117624, Criteria
and Standards Division, Office of Water Regulations and Standards
(45 FR 79318-79379, November 28, 1980).
Handbook of Analytical Chemistry. L. Meites (editor), McGraw
Hill, no date provided.
Handbook of Chemistry and Physics. R.C. Weast (editor), Chemical
Rubber Company, Cleveland, OH, 50th Edition, 1969.
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.
Heise, G.W., and Cahoon, N.C. The Primary Battery. John Wiley &
Sons, 1971.
Howes, R., and R. Kent. Hazardous Chemicals Handling and
Disposal. Noyes Data Corporation, 1970.
"Inside the C&D Battery." C&D Batteries Division, Plymouth
Meeting, PA., no date provided.
"Insulation keeps lithium/metal sulfide battery over 400C."
Society of Automotive Engineers, Inc., p. 67-70 (June 1979).
"An Investigation of Techniques for Removal of Cyanide from
Electroplating Wastes," Battelle Columbus Laboratories,
Industrial Pollution Control Section, November, 1971.
"Ionic equilibrium as applied to qualitative analysis." Hogness
& Johnson, Holt, Rinehart & Winston Co., 1954, complete citation
not available.
Intersociety of Energy Conversion Engineering Converence,
Proceedings of the 7th Annual Conference, 1972.
Intersociety of Energy Conversion Engineering Conference,
Proceedings of the 9th Annual Conference, 1974.
Intersociety of Energy Conversion Engineering Conference,
Proceedings of the 10th Annual Conference, 1975.
Jasinski, R. High Energy Batteries. Plenum Press, 1967.
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. 537-556.
1064
-------
Jones, H. R. Environmental Control in the Organic and Petro-
chemical Industries. Noyes Data Corp., 1971.
•*r
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. 2653-2663.
Kopp, J. F., and R. C. Kroner. "Trace metals in waters of the
United States - a five year summary of trace metals in rivers and
lakes of the United States (October 1, 1962 - September 30,
1967)." U.S. Department of the Interior, Cincinnati, OH, no date
provided.
Langer, B. S. "Contractor's engineering report for the develop-
ment of effluent limitations guidelines for the pharmaceutical
industry (BATEA, NSPS, BCT, BMP, Pretreatment)." Burns and Roe
Industrial Services Corp., Paramus, NJ, Prepared for U.S.
Environmental Protection Agency, October 1979.
Lanouette, K. H. "Heavy metals removal." Chemical Engineering/
Deskbook Issue, 84(22);73-80 (October 17, 1977).
"Lead" Final Water Quality Criteria, PB117681, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Lonouette, Kenneth H., "Heavy Metals Removal," Chemical
Engineering, October 17, pp. 73-80.
Martin, L. Storage Batteries and Rechargeable Cell Technology
Noyes Data Corporation, Park Ridge, NJ, Chemical Technology
Review No. 37, 1974.
"Mercury" Final Water Quality Criteria, PB117699, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Mezey, Eugene J. "Characterization of priority pollutants from a
secondary lead-acid battery manufacturing facility." U.S.
Environmental Protection Agency, EPA-600/2-79-039, January 1979.
Mohler, J. B. "The rinsing equation." Metal Finishing, p. 64
(February 1978).
"More power to you." C&D batteries Division, Plymouth Meeting,
PA, no date provided.
1065
-------
Mowat, Anne, "Measurement of Metal Toxicity by Biochemical Oxygen
Demand," Journal of Water Pollution Control Federation, Vol. 48,
No. 5, May, 1976, pp. 853-866.
Mytelka, Alan I., Czachor, Joseph S., Guggino William B. and
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.
"Naphthalene" Final Water Quality Criteria, PB117707, Criteria
and Standards Division, Office of Water Regulations and Standards
(45 FR 79318-79379, November 28, 1980).
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.
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.
"New batteries." Recovery Engineering News - Recycling and
Reprocessing of Resources. L. Delpino (editor), ICON/ Information
Concepts, Inc., Philadelphia, PA, 4(1) January 1979.
"Nickel" Final Water Quality Criteria, PB117715, Criteria and
Standards Division, Office of Water Regulations and Standards. (45
FR 79318-79379, November 28, 1980).
Oliver, Barry G. and Cosgrove, Ernest G., "The Efficiency of
Heavy Metal Removal by a Conventional Activated Sludge Treatment
Plant," Water Research, Vol. 8, 1974, pp. 869-874.
"Organic electrolyte batteries." In: Intersociety of Energy
Conversion Engineering Conference (IECEC) Proceedings. 7th
Edition, p. 71-74 (1972).
Patterson, J. W. Wastewater Treatment Technology. Ann Arbor
Science Publishers, 1975.
Patterson, James W., "Carbonate Precipitation Treatment for
Cadmium and Lead," presented at WWEMA Industrial Pollutant
conference, April 13, 1978.
Patterson, J. W., H. E. Allen, and J. J. Scala. "Carbonate pre-
cipitation for heavy metals pollutants." Journal of Water
Pollution Control Federation, p. 2397-2410 (December 1977).
1066
-------
Patterson, James W. and Minear, Roger A., "Wastewater Treatment
Technology," 2nd edition (State of Illinois, Institute for
Environmental Quality) January, 1973.
Peck, K., and J. C. Gorton. "Industrial waste and pretreatment
in the Buffalo municipal system." U.S. Environmental Protection
Agency, 1977.
"Pentachlorophenol" Final Water Quality Criteria PB117764,
Criteria and Standards Division, Office of Water regulations and
Standards (45 FR 79318-79379, November 28, 1980).
"Phenol" Final Water Quality Criteria, PB117772, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
"Phthalate Esters" Final Water Quality Criteria, PB117780,
Criteria and Standards Division, Office of Water Regulations and
Standards (45 FR 79318-79379, November 28, 1980).
Poison, C.J. and Tattergall, R.N., "Clinical Toxicology," (J.B.
Lipincott Company), 1976.
"Polynuclear Aromatic Hydrocarbons" Final Water Quality Criteria,
PB117806, Criteria and Standards Division, Office of Water
Regulations and Standards (45 FR 79318-79379, November 28, 1980).
Power Sources Conference, Proceedings of_ the 1.4th Annual Meeting,
1960.
Power Sources Conference, Proceedings of the 16th, 17th and 18th
Annual Meetings, 1962-1964.
Power Sources Conference, Proceedings of the 20th through 27th
Annual Meetings, 1966-1970, 1972, 1974, and 1976.
"Pretreatment of industrial wastes." Seminar Handout, U.S.
Environmental Protection Agency, 1978.
"Redox battery promising to store energy cheaply." Machine
Design p. 6, no date available.
Remirez, R. "Battery development revs up."
Chemical Engineering, p. 49-51 (August 27, 1979).
"Removal of priority pollutants by PACT* at the Chambers Works."
Letter communication from R. E. Funer, DuPont Nemours & Company
to R. Schaffer, U.S. Environmental Protection Agency, January 24,
1979.
1067
-------
Roberts, R. "Review of DOE battery and electrochemical
technology program." U.S. Department of Energy, ET-78-C-01-3295,
September 1979.
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.
Rohrer, Kenneth L., "Chemical Precipitants for Lead Bearing
Wastewaters," Industrial Water Engineering, June/July, 1975.
Santo, J., J. Duncan, et al. "Removal of heavy metals from
battery manufacturing wastewaters by Hydroperm cross - flow
microfiltration." U.S. Environmental Protection Agency,
Presented at the Second Annual Conference on Advanced Pollution
Control for the Metal Finishing Industry, Kissimmee, FL, February
5-7, 1979.
Sax, N. I. Industrial Pollution. Van Nostrand Reinhold Co.,
1974.
Sax, N. I. Dangerous Properties of Industrial Materials. Van
Nostrand Reinhold Co., 1975.
Schroder, Henry A. and Mitchener, Marian, "Toxic Effects of Trace
Elements on the Reproduction of Mice and Rats," Archives of
Environmental Health, Vol. 23, August, 1971, pp. 102-106.
Scott, Murray C., "Sulfex11 - A new Process Technology for Removal
of Heavy Metals from Waste Streams," presented at 1977 Purdue
Industrial Waste Conference, May 10, VI , and 12, 1977.
Scott, Murray C., "Treatment of Plating Effluent by Sulfide
Process," Products Finishing, August, 1978.
Schlauch, R. M., and A. C. Epstein. "Treatment of metal
finishing wastes by sulfide precipitation." U.S. Environmental
Protection Agency, EPA 600/2-77-049, February 1977.
"Selenium" Final Water Quality Criteria, PB117814, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
Shapira, N. I., H. Liu, et al. "The demonstration of a crossflow
microfiltration system for the removal of toxic heavy metals from
battery manufacturing wastewater effluents." U.S. Environmental
Protection Agency, Presented at Division of Environmental
Chemistry 179th National Meeting, American Chemical Society,
Houston, TX, March 23-28, 1980.
1068
-------
"Silver" Final Water Quality Criteria, FBI 17822, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
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.
"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).
Stover, R.C., Sommers, L.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.
"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).
"Tetrachloroethylene" Final Water Quality Criteria, PB117830,
Criteria and Standards Division, Office of Water Regulations and
Standards (45 FR 79318-79379, November 28, 1980).
"Toluene" Final Water Quality criteria, PB117855, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
"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.
"Trichloroethylene" Final Water Quality criteria, PB117871,
Criteria and Standards Division, Office of Water Regulations and
Standards (45 FR 79318-79379, November 28, 1980).
1069
-------
Unit Operations for Treatment of Hazardous Industrial Wastewater.
D. J. Denyo (editor), 1978.
Vaccari, J. A. Product Engineering, p. 48-49 (January 1979).
Venugopal, B. and Luckey, T.D., "Metal Toxicity in Mammals .2,"
(Plenum Press, New York, N.Y.), 1978.
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.
"Zinc" Final Water Quality Criteria, PB117897, Criteria and
Standards Division, Office of Water Regulations and Standards (45
FR 79318-79379, November 28, 1980).
"1977 census of manufacturers - primary batteries, dry and wet
(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-1(p), April 1979.
1070
-------
SECTION XVI
GLOSSARY
Active Material - Electrode material that reacts chemically to
produce electrical energy when a cell discharges. Also, such
material in its original composition, as applied to make an
electrode.
Air Scrubbing - A method of removing air impurities such as dust
or fume by contact with sprayed water or an aqueous chemical
solution.
Alkalinity - (1) The extent to which an aqueous solution contains
more hydroxyl ions than hydrogen ions. (2) The capacity of water
to neutralize acids, a property imparted by the water's content
of carbonates, bicarbonates, hydroxides, and occasionally
borates, silicates and phosphates.
Amalgamation - (1) Alloying a zinc anode with mercury to prevent
internal corrosion and resultant gassing in a cell. (2)
Treatment of wastewater by passing it through a bed of metal
particles to alloy and thereby remove mercury from the water.
Anode - The electrode by which electrons leave a cell. The
negative electrode in a cell during discharge.
Attrition Mill - A ball mill in which pig lead is ground to a
powder and oxidized to make the active material (a mixture of
lead and lead oxide called leady oxide) in lead acid batteries.
Backwashing - The process of cleaning a filter or ion exchange
column by a reverse flow of water.
Baffles - Deflector vanes, guides, grids, gratings, or similar
devices constructed or placed in flowing water or wastewater to
(1) effect a more uniform distribution of velocities or (2)
divert, guide, or agitate the liquids.
Bag House - The large chamber for holding bag filters used to
filter gas streams from a furnace such as in manufacture of lead
oxide.
Ball Mill - A reactor in which pig lead is ground to a powder and
oxidized to make the active material (a mixture of lead and lead
oxide called leady oxide) for lead acid batteries.
Barton Pot - A reactor vessel, used in the Barton process, into
which molten lead is fed and vigorously agitated to form fine
1071
-------
lead droplets in the presence of air. The resulting mixture of
unoxidized lead and lead oxides (leady oxide) comprises an active
material in lead acid batteries.
Batch Treatment - A waste treatment method where wastewater is
collected over a period of time and then treated before
discharge, often in the same vessel in which it is collected.
Battery - A device that transforms chemical energy into
electrical energy. This term usually applies to two or more
cells connected in series, parallel or a combination of both.
Common usage has blurred the distinction between the terms "cell"
and "battery" and frequently the term battery is applied to any
finished entity sold as a single unit, whether it contains one
cell, as do most flashlight batteries, or several cells, as do
automotive batteries.
Bobbin - An assembly of the positive current collector and
cathode material, usually molded into a cylinder.
Buffer - Any of certain combinations of chemicals used to
stabilize the pH values or alkalinities of solutions.
Burn - Connection of terminals, posts, or connectors in a lead
acid battery by welding.
Button Cell - A tiny, circular battery, any of several types,
made for a watch or for other microelectronic applications.
Can - The outer case of a cylindrical cell.
Carcinogen - A substance that causes cancer.
Casting - The process by which grids for lead acid batteries are
made by pouring molten lead into molds and allowing
solidification.
Cathode - The electrode by which electrons enter a cell. The
positive electrode in a cell during discharge.
Cathodic Polarization - Electrical connection of a nickel
electrode plaque to promote deposition of active nickel material.
Caustic - (1) An alkaline battery electrolyte, sodium or
potassium hydroxide. (2) Sodium hydroxide, used to precipitate
heavy metals from wastewater.
Cell - The basic building block of a battery. It is an
electrochemical device consisting of an anode and a cathode in a
common electrolyte kept apart with a separator. This assembly
1072
-------
may be used in its own container as a single cell battery or be
combined and interconnected with other cells in a container to
form a multicelled battery.
Central Treatment Facility - Treatment plant which co-treats
process wastewaters from more than one manufacturing operation or
co-treats process wastewaters with noncontact cooling water, or
with nonprocess wastewaters (e.g., utility blowdown,
miscellaneous runoff, etc).
Centrifugation - Use of a centrifuge to remove water in the
manufacture of active material or in the treatment of wastewater
sludge.
Charge - The conversion of electrical energy into chemical energy
within a cell-battery. This restoration of active electronic
materials is done by forcing a current through the cell-battery
in the opposite direction to that during discharge. See
"Formation."
Chemical Coagulation - The destablization and initial aggregation
of colloidal and finely divided suspended matter by the action of
a floe-forming chemical.
Chemical Oxygen Demand (COD) - (1 ) A test based on the fact that
organic compounds, with few exceptions, can be oxidized to carbon
dioxide and water by the action of strong oxidizing agents under
acid conditions. Organic matter is converted to carbon dioxide
and water regardless of the biological assimilability of the
substances. One of the chief limitations is its inability to
differentiate between biologically oxidizable and biologically
inert organic matter. The major advantage of this test is the
short time required for evaluation (2 hrs). (2) The amount of
oxygen required for the chemical oxidization of organics in a
liquid.
Chemical Precipitation - The use of an alkaline chemical to
remove dissolved heavy metals from wastewater.
Chemical Treatment - Treating contaminated water by chemical
means.
Clarifier - A unit which provides settling and removal of solids
from wastewater.
CMC - Sodium carboxymethyl cellulose; an organic liquid used as a
binder in electrode formulations.
1073
-------
Colloids - A finely divided dispersion of one material called the
"Dispersed phase" (solid) in another material which is called the
"dispersion medium" (liquid).
Compatible Pollutant - An industrial pollutant that is
successfully treated by a secondary municipal treatment system.
Composite Wastewater Sample - A combination of individual samples
of water or wastewater taken at selected intervals and mixed in
proportion to flow or time to minimize the effect of stream
variability.
Concentration, Hydrogen Ion - The weight of hydrogen ions in
grams per liter of solution. Commonly expressed as the pH value
that represents the logarithm of the reciprocal of the hydrogen
ion concentration.
Contamination - A general term signifying the introduction into
water of microorganisms, chemicals, wastes or sewage which
renders the water unfit for its intended use.
Contractor Removal - The disposal of oils, spent solutions,
wastewaters, or sludge by means of an approved scavenger service.
Cooling Tower - A device used to remove heat from cooling water
used in the manufacturing processes before returning the water
for recycle or reuse.
Countercurrent Rinsing - A method of rinsing or washing 'using a
segmented tank system in which water flows from one tank segment
to the next counter to the direction of movement of the material
being washed.
Current Collector - The grid portion of the electrode which
conducts the current to the terminal.
Cyclone Separator - A funnel-shaped device for removing particles
from air or other fluids by centrifugal means.
Decantation - A method for mechanical dewatering of a wet solid
by pouring off the liquid without disturbing the underlying
sediment or precipitate.
Demineralization - The removal from water of mineral contaminants
usually present in ionized form. The methods used include ion-
exchange techniques, flash distillation or reverse osmosis.
Depolarizer - A term often used to denote the cathode active
material.
1074
-------
Dewatering - Any process whereby water is removed from sludge.
Discharge - Release of electric power from a battery.
Discharge of_ Pollutant(s) - The addition of any pollutant to
waters of the U.S. from any point source.
Dissolved Oxygen (DO) - The oxygen dissolved in sewage, water, or
other liquid, usually expressed in milligrams per liter.
Dissolved Solids - Theoretically the anhydrous residues of the
dissolved constituents in water. Actually the term is defined by
the method used in determination. In water and wastewater
treatment, the Standard Methods tests are used.
Dry Charge Process - A process for the manufacture of lead acid
storage batteries in which the plates are charged by electrolysis
in sulfuric acid, rinsed, and drained or dried prior to shipment
of the battery. Charging of the plates usually occurs in
separate containers before assembly of the battery but may be
accomplished in the battery case. Batteries produced by the dry-
charge process are shipped without acid electrolyte.
Drying Beds - Areas for dewatering of sludge by evaporation and
seepage.
Effluent - Industrial wastewater discharged to a sanitary sewer,
stream, or other disposal point outside the plant property.
Electrode - The positive (cathode) or negative (anode) element in
a cell or battery, that enables it to provide electric power.
Electrodeposition - Electrochemical deposition of an active
material from solution onto an electrode grid or plaque.
Electroforming - See (1) Electrodeposition, and (2) Formation.
Electroimpregnation - See Cathodic Polarization.
Electrolyte - The liquid or material that permits conduction of
ions between cell electrodes.
Electrolytic Precipitation - Generally refers to making powdered
active material by electrodeposition and physical removal; e.g.,
silver powder from silver bars.
Electroplating - (1) Electrodeposition of a metal or alloy from a
suitable electrolyte solution; the article to be plated is
connected as the cathode in the electrolyte solution; direct
current is introduced through the anode which consists of the
1075
-------
metal to be deposited. (2) The Electroplating Point Source
Category.
Element - A combination of negative and positive plates and
separators to make a cell in a lead-acid storage battery.
End-of-Pipe Treatment - The reduction or removal of pollutants by
treatment just prior to actual discharge to a point outside an
industrial plant.
Equalization - The collection of waste streams from different
sources, which vary in pH, chemical constituents, and flow rates
in a common container. The effluent stream from this
equalization tank has a fairly constant flow and pH level, and
will contain a homogeneous chemical mixture. This tank helps to
prevent an unnecessary shock to the waste treatment system.
Evaporation Ponds - A pond, usually lined, for disposal of
wastewater by evaporation; effective only in areas of low
rainfall.
Filter, Rapid Sand - A filter for the purification of water where
water which has been previously treated, usually by coagulation
and sedimentation, is passed through a filtering medium
consisting of a layer of sand or prepared anthracite coal or
other suitable material, usually from 24 to 30 inches thick and
resting on a supporting bed of gravel or a porous medium such as
carborundum. The filtrate is removed by a drain system. The
filter is cleaned periodically by reversing the flow of the water
upward through the filtering medium. Sometimes supplemented by
mechanical or air agitation during backwashing to remove
impurities that are lodged in the sand.
Filter, Trickling - A filter consisting of an artificial bed of
coarse material, such as broken stone, clinkers, slats, or
plastic media over which wastewater is distributed and applied in
drops, films, or spray, from troughs, drippers, moving
distributors or fixed nozzles and through which it trickles to
the under-drain, oxidizing organic materials by means of
microorganisms attached to the filter media.
Filter, Vacuum - A filter consisting of a rotating cylindrical
drum mounted on a horizontal axis, covered with a filter cloth
partially submerged in a liquid. A vacuum is maintained under
the cloth for the larger part of a revolution to extract
moisture. Solids collected on the surface of the filter cloth
are continuously scraped off.
Filtrate - Liquid that has passed through a filter.
1076
-------
Filtration - Removal of solid particles from liquid or particles
from air or gas stream through a permeable membrane or deep bed.
The filter types include: gravity, pressure, microstraining,
ultrafiltration, reverse osmosis (hyperfiltration).
Float Gauge - A device for measuring the elevation of a liquid
surface, the actuating element of which is a buoyant float that
rests on the liquid surface and rises or falls with it. The
elevation of the surface is measured by a chain or tape attached
to the float.
Floe - A very fine, fluffy mass formed by the aggregation of fine
suspended particles.
Flocculator - An apparatus designed for the formation of floe in
water or sewage.
Flocculation - In water and wastewater treatment, the
agglomeration of colloidal and finely divided suspended matter
after coagulation by addition of chemicals and gentle stirring by
either mechanical or hydraulic means.
Flock - Natural or synthetic fiber added to lead-acid battery
paste as a stiffening agent.
Flow Proportioned Sample - See "Composite Wastewater Sample."
Formation - An electrochemical process which converts the battery
electrode material into the desired chemical condition. For
example, in a silver-zinc battery the silver applied to the
cathode is converted to silver oxide and the zinc oxide applied
to the anode is converted to elemental zinc. "Formation" is
generally used interchangeably with "charging," although it may
involve a repeated charge-discharge cycle.
Gelled Electrolyte - Electrolyte which may or may not be mixed
with electrode material, that has been gelled with a chemical
agent to immobilize it.
GPP - Gallons per day.
r
Grab Sample - A single sample of wastewater taken without a set
time or at a set flow.
Grease - In wastewater, a group of substances including fats,
waxes, free fatty acids, calcium and magnesium soaps, mineral
oil, and certain other nonfatty materials.
Grease Skimmer - A device for removing grease or scum from the
surface of wastewater in a tank.
1077
-------
Grid - The support for the active materials and a means to
conduct current from the active materials to the cell terminals;
usually a metal screen, expanded metal mesh, or a perforated
metal plate.
Hardness - A characteristic of water, imparted by salts of
calcium, magnesium, and iron such as bicarbonates, carbonates,
sulfates, chlorides, and nitrates that cause curdling of soap,
deposition of scale in boilers, damage in some industrial
processes, and sometimes objectionable taste. It may be
determined by a standard laboratory procedure or computed from
the amounts of calcium and magnesium as well as iron, aluminum,
manganese, barium, strontium, and zinc, and is expressed as
equivalent calcium carbonate.
Heavy Metals - A general name given to the ions of metallic
elements such as copper, zinc, chromium, and nickel. They are
normally removed from wastewater by forming an insoluble
precipitate (usually a metallic hydroxide).
Holding Tank - A tank for accumulating wastewater prior to
treatment.
Hydrazine Treatment - Application of a reducing agent to form a
conductive metal film on a silver oxide cathode.
Hydroquinone - A developing agent used to form a conductive metal
film on a silver oxide cathode.
Impregnation - Method of making an electrode by precipitating
active material on a sintered nickel plaque.
In-Process Control Technology - The regulation and conservation
of chemicals and rinse water throughout the operations as opposed
to end-of-pipe treatment.
Industrial Wastes - The liquid wastes from industrial processes
as distinct from domestic or sanitary wastes.
Influent - Water or other liquid, either raw or partly treated,
flowing into a treatment step or plant.
Ion Exchange - Wastewater treatment by contact with a resin that
exchanges harmless ions (e.g. sodium) for toxic inorganic ions
(e.g. mercury), which the resin adsorbs.
Jacket - The outer cover of a dry cell battery, usually a paper-
,plastic laminate.
1078
-------
Kjeldahl Nitrogen - A method of determining the ammonia and
organically bound nitrogen in the -3 valence state but does not
determine nitrite, azides, nitro, nitroso, oximes or nitrate
nitrogen.
Lagoon - A man-made pond or lake for holding wastewater for the
removal of suspended solids. Lagoons are also used as retention
ponds after chemical clarification to polish the effluent and to
safeguard against upsets in the clarifier; for stabilization of
organic matter by biological oxidation; for storage or sludge;
and for cooling of water.
Landfill - Land area used for controlled burial of solid wastes,
sludges, ashes, industrial wastes, construction wastes, or
demonition wastes. Solid wastes are garbage, refuse, and other
discarded material including solid, liquid, semisolid, or
contained gaseous material resulting from industrial, .commercial,
mining, and agricultural operations, and from community
activities.
Leaching - The solubilizing of pollutants by the action of a
percolating liquid, such as water, seeping through a landfill,
which potentially contaminates ground water.
Leady Oxide - Active material used for manufacture of lead-acid
battery plates consisting of a mixture of lead oxides and finely
divided elemental lead.
Lime - Any of a family of chemicals consisting essentially of
calcium hydroxide made from limestone (calcite) which is composed
almost wholly of calcium carbonates or a mixture of calcium and
magnesium carbonates.
Limiting Orifice - A device that limits flow by constriction to a
relatively small area. A constant flow can be obtained over a
wide range of upstream pressures.
Make-Up Water - Net amount of water used by any process or
process step, not including recycled water.
Mass - The active material used in a pocket plate cell, for
example "nickel mass."
Milligrams Per Liter (mg/1) - This is a weight per volume
concentration designation used in water and waste analysis.
Mixed Media Filtration - A depth filter which uses two or more
filter materials of differing specific gravities selected so as
to produce a filter uniformly graded from coarse to fine.
1079
-------
national Pollutant Discharge Elimination System (NPDES) - This
federal mechanism for regulating point source discharge by means
of permits.
Neutralization - Chemical addition of either acid or base to a
solution to adjust the pH to approximately 7.
Non-Contact Cooling Water - Water used for cooling which does not
come into direct contact with any raw material, intermediate
product, waste product or finished product.
Outfall - The point or location where wastewater discharge from a
sewer, drain, or conduit.
Oxidation - 1. Chemical addition of oxygen atom(s) to a chemical
compound; 2. In general any chemical reaction in which an element
or ion is raised to a more positive valence state; 3. The process
at a battery anode during discharge.
Parshall Flume - A calibrated device developed by Parshall for
measuring the flow of liquid in an open conduit. It consists
essentially of a contracting length, a throat, and an expanding
length. At the throat is a sill over which the flow passes as
critical depth. The upper and lower heads are each measured at a
definite distance from the sill. The lower head cannot be
measured unless the sill is submerged more than about 67 percent.
Paste - Powdered active material mixed with a liquid to form a
paste to facilitate application to a grid to make an electrode.
Pasting Machine - An automatic machine for applying lead oxide
paste in the manufacture of lead-acid batteries.
pH - The reciprocal of the logarithm of the hydrogen ion
concentration. The concentration is the weight of hydrogen 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 higher than 7, a solution is alkaline.
pH Adjustment - A means of treating wastewater by chemical
addition; usually the addition of lime to precipitate heavy metal
pollutants.
Plaque - A porous body of sintered metal on a metal grid used as
a current collector and holder of electrode active materials,
especially for nickel-cadmium batteries.
Plate - A positive or negative electrode used in a battery,
generally consisting of active material deposited on or in a
current-collecting support.
1080
-------
Pocket Plate - A type of battery construction where the electrode
is a perforated metal envelope containing the active material.
Point Source - Any discernible, confined and discrete conveyance,
including but not limited to any pipe, ditch, channel, tunnel,
conduit, well, discrete fissure, container, rolling stock,
concentrated animal feeding operation, or vessel or other
floating craft, from which pollutants are or may be discharged.
Pollutant Parameters - Those constituents of wastewater
determined to be detrimental to the public health or the
environment and, therefore, requiring control.
Polyelectrolytes - Materials used as a coagulant or a coagulant
aid in water and wastewater treatment. They are synthetic or
natural polymers containing ionic constituents. They may be
cationic, anionic, or nonionic.
Post - A battery terminal, especially on a lead-acid battery.
Precipitation - Process of separation of a dissolved substance
from a solution or suspension by chemical or physical change,
usually as an insoluble solid.
Pressed Powder - A method of making an electrode by pressing
powdered active material into a metal grid.
Pressure Filtration - The process of solid-liquid phase
separation effected by forcing the more permeable liquid phase
through a mesh which is impenetrable to the solid phase.
Pretreatment - Any wastewater treatment process used to partially
reduce pollution load before the wastewater is introduced into a
main sewer system or delivered to a municipal treatment plant.
Primary Battery - A battery which must usually be replaced after
one discharge; i.e., the battery cannot be recharged.
Primary Settling - The first settling unit for the removal of
settleable solids through which wastewater is passed in a
treatment works.
*
Primary Treatment - A process to remove substantially all
floating and settleable solids in wastewater and partially reduce
the concentration of suspended solids.
Priority Pollutant - Any one of the 129 specific pollutants
established by the EPA from the 65 pollutants and classes of
pollutants as outlined in the Consent Decree of June 8, 1976.
1081
-------
Process Wastewater - Any water which, during manufacturing or
processing, comes into direct contact with or results from the
production or use of any raw materials, intermediate product,
finished product, by product, or waste product.
Raw Water - Plant intake water prior to any treatment or use.
Recycled Water - Process wastewater or treatment facility
effluent which is recirculated to the same process.
Reduction - 1. A chemical process in which the positive valence
of species is decreased. 2. Wastewater treatment to (a) convert
hexavalent chromium to the trivalent form, or (b) reduce and
precipitate mercury ions.
Reserve Cell - A class of cells which are designated as
"reserve", because they are supplied to the user in a non-
activated state. Typical of this class of cell is the carbon-
zinc air reserve cell, which is produced with all the components
in a dry or non-activated state, and is activated with water when
it is ready to be used.
Retention Time - The time allowed for solids to collect in a
settling tank. Theoretically retention time is equal to the
volume of the tank divided by the flow rate. The actual
retention time is determined by the purpose of the tank. Also
the design residence time in a tank or reaction vessel which
allows a chemical reaction to go to completion, such as the
reduction of hexavalent chromium or the destruction of cyanide.
Reused Water - Process wastewater or treatment facility effluent
which is further used in a different manufacturing process. For
example, the reuse of process wash water as non-contact cooling
water.
Reverse Osmosis (Hyperf i1tration) - A treatment or recovery
process in which polluted water is put under a pressure greater
than the osmotic pressure to drive water across the membrane
while leaving behind the dissolved salts as a concentrate.
Reversible Reaction - A chemical reaction capable of proceeding
in either direction depending upon the conditions.
Rinse - Removal of foreign materials from the surface of an
object by flow or impingement of a liquid (usually water) on the
surface. In the battery industry, "rinse" may be used
interchangeably with 'wash".
Ruben - Developer of the mercury-zinc battery; also refers to the
mercUry-zinc battery.
1082
-------
Sand Filtration - A process of filtering wastewater through sand.
The waste water is trickled over the bed of sand, which retains
suspended solids. The clean water flows out through drains in
the bottom of the bed. The solids accumulating at the surface
must be removed from the bed periodically.
Sanitary Sewer - A sewer that carries liquid and water carried
wastes to a municipal treatment plant.
Sanitary Water - Wastewater from toilets, sinks, and showers.
Scrubber - General term used in reference to an air pollution
control device that uses a water spray.
Sealed Cell - A battery cell which can operate in a sealed
condition during both charge and discharge.
Secondary Cell - An electrochemical cell or battery system that
can be recharged; a storage battery.
Secondary Wastewater Treatment - The treatment of wastewater by
biological methods after primary treatment by sedimentation.
Sedimentation - The gravity induced deposition of suspended
matter carried by water, wastwater, or other liquids, by gravity.
It is usually accomplished by reducing the velocity of the
suspended material. Also called settling.
Separator - A porous material, in a battery system, used to keep
plates of opposite polarity separated, yet allowing conduction of
ions through the electrolyte.
Service Water - Raw water which has been treated preparatory to
its use in a process of operation; i.e., make-up water.
Settling Ponds - A large shallow body of water into which
industrial wastewaters are discharged. Suspended solids settle
from the wastewaters due to the long retention time of the water
in the pond.
Settleable Solids (1) That matter in wastewater which will not
stay in suspension during a preselected settling period, such as
one hour, but settles to the bottom. (2) In the Imhoff cone
test, the volume of matter that settles to the bottom of the cone
in one hour.
Sewer - A pipe or conduit, generally closed, but normally not
flowing full or carrying sewage and other waste liquids.
1083
-------
SIC - Standard Industrial Classification - Defines industries in
accordance with the composition and structure of the economy and
covers the entire field of economic activity.
Silver Etch - Application of nitric acid to silver foil to
prepare it as a support for active material.
Sinter - Heating a metal powder such as nickel to an elevated
temperature below its melting point which causes it to
agglomerate and adhere to the supporting grid.
Sintered-plate Electrode - The electrode formed by sintering
metallic powders to form a porous structure, which serves as a
current collector, and on which the active electrode material is
deposited.
Skimming Tank - A tank so designed that floating matter will rise
and remain on the surface of the wastewater until removed, while
the liquid discharges continuously under certain wall or scum
boards.
Sludge - A suspension, slurry, or solids matter produced in a
waste treatment process.
Sludge Conditioning - A process employed to prepare sludge for
final disposal. Can be thickening, digesting, heat treatment
etc.
Sludge Disposal - The final disposal of solid wastes.
Sludge Thickening - The increase in solids concentration of
sludge in a sedimentation or digestion tank or thickener.
Solvent - A liquid capable of dissolving or dispersing one or
more other substances.
Spills - A chemical or material spill is an unintentional
discharge of more than 10 percent of daily usage of a regularly
used substance. In the case of a rarely used (one per year or
less) chemical or substance, a spill is that amount that would
result in 10% added loading to the normal air, water or solid
waste loadings measured as the closest equivalent pollutant.
Sponge - A highly porous metal powder.
Stabilization Lagoon - A shallow pond for storage of wastewater
before discharge. Such lagoons may serve only to detain and
equalize wastewater composition before regulated discharge to a
stream, but often they are used for biological oxidation.
1084
-------
Stabilization Pond - A type of oxidation pond in which biological
oxidation of organic matter is effected by natural or
artificially accelerated transfer of oxygen to the water from
air.
Storage Battery - A battery that can store chemical energy with
the potential to change to electricity. This conversion of
chemical energy to electricity can be reversed thus allowing the
battery to be recharged.
Strap - A metal conductor connecting individual cells to form a
battery.
Sump - A pit or tank which receives and temporarily stores
drainage or wastewater at the lowest point of circulating or
drainage system.
Suspended Solid - (1) Solids that are in suspension in water,
wastewater, or other liquids, and which are largely removable by
laboratory filtering. (2) The quantity of material removed from
wastewater in a laboratory test, as prescribed in "Standard
Methods for the Examination of Water and Wastewater" and referred
to as non-filterable residue.
Surface Waters - Any visible stream or body of water.
Terminal - The part of a battery to which an external circuit is
connected.
Thickener - A device wherein the solids in slurries or
suspensions are increased by gravity settling and mechanical
separation of the phases, or by flotation and mechanical
separation of the phases.
Total Cyanide - The total content of cyanide including simple
and/or complex ions. In analytical terminology, total cyanide is
the sum of cyanide amenable to chlorination and that which is not
amenable to chlorination according to standard analytical
methods.
Total Solids - The total amount of solids in wastewater including
both dissolved and suspended solids.
Toxicity - The ability of a substance to cause injury to an
organism through chemical activity.
Treatment Efficiency - Usually refers to the percentage reduction
of a specific pollutant or group of pollutants by a specific
wastewater treatment step or treatment plant.
1085
-------
Treatment Facility Effluent - Treated process wastewater.
Turbidity - (1) A condition in water or wastewater caused by the
presence of suspended matter, resulting in the scattering and
absorption of light rays. (2) A measure of fine suspended matter
in liquids. (3) An analytical quantity usually reported in
arbitrary turbidity units determined by measurements of light
diffraction.
Vacuum Filtration - See Filter, Vacuum.
Vented Cell - A type of battery cell which has a vent that allows
the escape of gas and the addition of water.
Wash - Application of water, an aqueous solution, or an organic
solvent to a battery part to remove contaminating substances.
Water Balance - An accounting of all water entering and leaving a
unit process or operation in either a liquid or vapor form or via
raw material, intermediate product, finished product, by-product,
waste product, or via process leaks, so that the difference in
flow between all entering and leaving streams is zero.
Weir - A device that has a crest and some containment of known
geometric shape, such as a V, trapezoid, or rectangle and is used
to measure flow of liquid. The liquid surface is exposed to the
atmosphere. Flow is related to upstream height or water above
the crest, to position of crest with respect to downstream water
surface, and to geometry of the weir opening.
Wet Charge Process - A process for the manufacture of lead acid
storage batteries in which the plates are formed by electrolysis
in sulfuric acid. The plate forming process is usually done with
the plates inside the assembled battery case but may be done with
the plates in open tanks. In the case of large industrial wet
lead acid batteries, problems in formation associated with
inhomogeneities in the large plates are alleviated by open tank
formation. Wet charge process batteries are shipped with acid
electrolyte inside the battery casing.
Wet Shelf Life - The period of time that a secondary battery can
stand in the charged condition before total degradation.
Wet Scrubber - A unit in which dust and fumes are removed from an
air or gas stream to a liquid. Gas-liquid contact is promoted by
jets, sprays, bubble chambers, etc.
Data Base 518
1086
-------
METRIC UNITS
CONVERSION TABLE
o
oc
MULTIPLY (ENGLISH UNITS)
ENGLISH UNIT ABBREVIATION
acre ac
acre - feet ac ft
British Thermal Unit BTU
British Thermal Unit/
pound BTU/lb
cubic feet/minute cfra
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpra
horsepower hp
inches in
inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square inch
(gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
by
CONVERSION
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
TO OBTAIN (METRIC UNITS)
ABBREVIATION METRIC UNIT
ha hectares
cu m cubic meters
kg cal kilogram - calories
kg cal/kg kilogram calories/
kilogram
cu m/min cubic meters/minute
cu m/min cubic meters/minute
cu m cubic meters
1 liters
cu cm cubic centimeter
°C degree Centigrade
m meters
1 liters
I/sec liters/second
kw killowatts
cm centimeters
atm atmospheres
kg kilograms
cu m/day cubic meters/day
km kilometer
atm atmospheres (absolute)
sq m square meters
sq cm square centimeters
kkg metric ton (1000
kilogram)
m meter
*Actual conversion, not a multiplier.
------- |