DEVELOPMENT DOCUMENT

                  for

     EFFLUENT LIMITATIONS GUIDELINES

    NEW SOURCE PERFORMANCE STANDARDS

                   and

         PRETREATMENT STANDARDS

                 for the

    INORGANIC CHEMICALS MANUFACTURING
          POINT SOURCE CATEGORY
               (Phase II)

         William D. Ruckelshaus
              Administrator

            Edwin L. Johnson
                Director
Office of Water Regulations and Standards
         Jeffery Denit, Director
      Effluent Guidelines Division

            G. Edward Stigall
    Chief, Inorganic Chemicals Branch

         Dr. Thomas E. Fielding
                July 1984

      Effluent Guidelines Division
Office of Water Regulations and Standards
  U.S. Environmental Protection Agency
         Washington, D.C.  20460

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Section
                        TABLE OF CONTENTS
                                                            Page
          LIST OF FIGURES                                    xiv

          LIST OF TABLES                                    xvii

          ACKNOWLEDGEMENTS                                  xxiv

     1     SUMMARY AND CONCLUSIONS                              1

     2     RECOMMENDATIONS                                      4

     3     INTRODUCTION                                        16

          AUTHORITY                                           16

               The Federal Water Pollution Control
                    Act Amendments                            16
               Court Remand of Regulations                    19
               The Settlement Agreement                       19
               Phase II Inorganic Chemicals                   22

          GENERAL APPROACH AND METHODOLOGY                    22

               Industry Data Base Development and
                    Subcategorization Review                  23
               The Screening and Verification Sampling        23
               Engineering Evaluation                         23
               Treatment System Cost Estimates                24
               Treatability Studies                           24

          GENERAL CRITERIA FOR EFFLUENT LIMITATIONS           25

               BPT Effluent Limitations                       25
               BAT Effluent Limitations                       26
               BCT Effluent Limitations                       26
               New Source Performance Standards                27
               Pretreatment Standards for  Existing Sources    27
               Pretreatment Standards for  New Sources         28

     4     SUBCATEGORIZATION                                   30

               Basis for Subcategorization                    30

     5     SAMPLING PROGRAM                                    37

          SCOPE AND METHODOLOGY                               37
                               i

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Section
                         TABLE OF CONTENTS (Continued)
               Selecting Plants                               37
               Sampling Program                               38
               Analytical Methodology                         40
               Quality Assurance Provisions                   46

          SUMMARY OF ANALYTICAL RESULTS                       48

          PROCESS AND WASTEWATER TREATMENT INFORMA-
          TION DEVELOPMENT AND EVALUATION                     54

          INDUSTRY DATA BASE DESCRIPTION                      54

          PROCESS WASTEWATER SOURCES AND CURRENT TREATMENT
               PRACTICES                                      56

          ASSESSMENT OF TECHNOLOGY FOR ADVANCED TREATMENT
               AND CONTROL                                    62

               Introduction                                   62
               Hydroxide Precipitation                        63
               Ferrite Coprecipitation                        68
               Sulfide Precipitation                          68
               The Xanthate Process                           72
               Ion Exchange                                   74
               Reduction Processes                            76
               Oxidation Processes                            78
               Membrane Processes                             81
               Adsorption                                     85
               Fluoride Removal                               86
               Chlorine Removal                               87

          TREATABILITY ESTIMATES AND LONG-TERM DATA'
               ANALYSIS                                       93
                                                   j
               The Development of Treatability Estimates      93
               Final Analysis                                 94
               Selection of Toxic Metal Control Parameters   110
               The Use of Historical Pollutant Data'         113
               Assumptions Concerning Daily Pollutant
                    Level Measurement                        115
               Assumptions Concerning 30-Day Average
                    Pollutant Level Observation              122

          TREATMENT TECHNOLOGY APPLICATIONS FOR TOXIC
               POLLUTANT REMOVAL                  ' ?'         131
                               ii

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                         TABLE OF CONTENTS (Continued)


Section                                                     Page

               Selection of Pollutants to be Controlled      131
               Application of Advance Level Treatment
                    and Control Alternatives                 131
               Estimated Achievable Performance Character-
                    istics for Advanced Level Applications   133
               Pollution Control Parameters to be Regulated  134

     10   COST OF TREATMENT AND CONTROL SYSTEMS              138

          INTRODUCTION                                       138

          TREATMENT AND DISPOSAL RATIONALE                   138

          COST REFERENCES AND RATIONALE                      139

          CAPITAL COSTS                                      139

               Facilities         ,                           139
               Equipment/Installation                        140
               Engineering                                   142
               Contractor Overhead and Profit                143
               Contingency                                   143
               Land                                          143

          ANNUAL COSTS                                       143

               Operations and Maintenance                    160
               Amortization                                  161

          ACCURACY OF ESTIMATES                              162

          DESCRIPTION OF WASTEWATER TREATMENT TECHNOLOGIES   162

          MODEL PLANT TREATMENT COSTS                        165
             '£. - •         ,                      •   •
               General                                       165

          SAMPLE MODEL PLANT COST CALCULATION                166

               General                                       166
             £ Sample Calculation               .             167

          REFERENCES                                         170

     11    CADMIUM PIGMENTS AND SALTS INDUSTRY                171
                              iii

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                         TABLE OF CONTENTS (Continued)
Section
      12
INDUSTRIAL PROFILE    '

WATER USE AND KASTEWATER SOURCE CHARACTERISTICS

DESCRIPTION OF PLANTS VISITED AND SAMPLED

POLLUTION ABATEMENT OPTIONS

     Toxic Pollutants of Concern
     Existing Control and Treatment Practices
     Other Applicable Control and Treatment
          Technologies
     Process Modifications and Technology
          Transfer Options
     Best Management Practices
     Advanced Treatment Technology
     Selection of Appropriate Technology and
          Equipment                     ., .,
     Treatment Cost Estimates
          A.   Cadmium Pigments
          B.   Cadmium Salts
     Basis for Regulations
          Basis for BPT Effluent Limitations
          Basis for BCT Effluent Limitations
          Basis for BAT Effluent Limitations
          Basis for New Source Performance
               Standards
          Basis for Pretreatment Standards

REFERENCES

COBALT SALTS INDUSTRY

INDUSTRIAL PROFILE

WATER USE AND WASTEWATER SOURCE CHARACTERISTICS

DESCRIPTION OF PLANTS VISITED

POLLUTION ABATEMENT OPTIONS

     Toxic Pollutants of Concern
     Existing Control and Treatment Practices
     Other Applicable Control/Treatment
          Technologies
171

178

183

195

196
196

197

197
198
199

199
201
201
202
205
205
222
224

224
224

227

228

228

230

234

235

235
235

236

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                         TABLE OF CONTENTS (Continued)
Section
               Process Modifications and Technology
                    Transfer Options
               Best Management Practices
               Advanced Treatment Technology
               Selection of Appropriate Technology and
                    Equipment
               Treatment Cost Estimates
               Basis for Regulations
                    Basis for BPT Effluent Limitations
                    Basis for BCT Effluent Limitations
                    Basis for BAT Effluent Limiations
                    Basis for NSPS Effluent Limitations
                    Basis for Pretreatment Standards

          REFERENCES

     13   COPPER SALTS INDUSTRY

          INDUSTRIAL PROFILE

          WASTE USE AND WASTEWATER SOURCES

          DESCRIPTION OF PLANTS VISITED AND SAMPLED

          POLLUTION ABATEMENT OPTIONS
               Toxic Pollutants of Concern
               Existing Control and Treatment Practices
               Other Applicable Control and Treatment
                    Technologies
               Process Modifications and Technology
                    Transfer Options
               Best Management Practices
               Advanced Treatment Technology
               Selection of Appropriate Technology and
                    Equipment
               Treatment Cost Estimates
               Basis for Regulations
                    Basis for BPT Effluent Limitations
                    Basis for BCT Effluent Limitations
                    Basis for BAT Effluent Limitations
                    Basis for NSPS Effluent Limitations
                    Basis for Pretreatment Standards
236
236
237

237
238
240
240
245
245
246
246

249

250

250

259

263

271
271
271

272

272
273
273

273
275
279
279
284
284
289
289
          REFERENCES
292

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                         TABLE OF CONTENTS (Continued)
Section

     14
      15
NICKEL SALTS INDUSTRY

INDUSTRIAL PROFILE

WATER USE AND WASTEWATER SOURCES

DESCRIPTION OF PLANTS VISITED AND SAMPLED

POLLUTION ABATEMENT OPTIONS
     Toxic Pollutants of Concern
     Existing Wastewater Control and Treatment
          Practices
     Other Applicable Control and Treatment
          Technologies
     Process Modifications and Technology
          Transfer Options
     Best Management Practices
     Advanced Technology
     Selection of Appropriate Technology and
          Equipment
     Treatment Cost Estimates
     Basis for Regulations
          Basis for BPT Effluent Limitations
          Basis for BCT Effluent Limitations
          Basis for BAT Effluent Limitations
          Basis for NSPS Effluent Limitations
          Basis for Pretreatment Standards

REFERENCES

SODIUM CHLORATE INDUSTRY

INDUSTRIAL PROFILE

WATER USE AND WASTEWATER SOURCE CHARACTERISTICS

DESCRIPTION OF PLANTS VISITED AND SAMPLED

POLLUTION ABATEMENT OPTIONS
     Toxic Pollutants of Concern
     Existing Wastewater Control and Treatment
          Practices
     Other Applicable Control and Treatment
          Technologies
     Zero Discharge Option
293

293

298

301

308
308

308

310

310
311
312

312
314
318
318
323
323
328
328

330

331

331

335

338

351
351

352

353
354
                               vi

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                         TABLE OF CONTENTS (Continued)
Section
               Process Modifications and Technology
                    Transfer Options
               Best Management Practices
               Advanced Treatment Technology
               Selection of Appropriate Technology and
                    Equipment
               Treatment Cost Estimates
               Basis for Regulations                (
                    Basis for BPT Effluent Limitations
                    Basis for BCT Effluent Limitations
                    Basis for BAT Effluent Limitations
                    Basis for NSPS Effluent Limitations
                    Basis for Pretreatment Standards

          REFERENCES

     16   ZINC CHLORIDE INDUSTRY

          INDUSTRIAL PROFILE

          WATER USE AND WASTEWATER SOURCE CHARACTER-
             ..  ISTICS

          DESCRIPTION OF PLANTS VISITED AND SAMPLED

          POLLUTION ABATEMENT OPTIONS
               Toxic Pollutants of Concern
               Existing Wastewater Control and Treatment
                    Practices                    ;
               Other Applicable Control and Treatment
                    Technologies
               Process Modifications and Technology
                    Transfer Options
               Best Management Practices
               Advanced Treatment Technology
               Selection of Appropriate Technology and
                    Equipment
               Treatment Cost Estimates
               Basis for Regulations
                    Basis for BPT Effluent Limitations
                    Basis for BCT Effluent Limitations
                    Basis for BAT Effluent Limitations
                    Basis for NSPS Effluent Limitations
                    Basis for Pretreatment Standards
Page


 354
 355
 356

 356
 358
 359
 359
 366
 367
 370
 372

 375

 376

 376


 381

 381

 393
 393

 393

 393

 394
 394
 394

 395
 396
 399
 399
 403
 406
 409
 411
                                vii

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                         TABLE OF CONTENTS (Continued)
Section
          REFERENCES
Page

 413
     17   BAT REVISIONS

          BACKGROUND

          SODIUM CHLORIDE

               General
               Process Description
               Water Use and Wastewater Characteristics
               Review of Available Data
               Treatment Cost Estimates
               Basis for BCT Effluent Limitations

          CALCIUM CHLORIDE

               General
               Process Description
               Water Use and Wastewater Characteristics
               Recommendations

          SODIUM SULFITE

               General
               Process Description
               Water Use and Wastewater Characteristics
               Review of Available Data
               Treatment Cost Estimates
               Basis for BCT Effluent Limitations
               Basis for BAT Effluent Limitations
               Basis for NSPS Effluent Limitations ,
               Basis for Pretreatment Standards

          REFERENCES

     18   PRETREATMENT STANDARDS

          INTRODUCTION

               General
               Subcategories Surveyed
               Methods Employed
               Basis for PSES Exclusions
 414

 414

 415

 415
 415
 416
 416
 422
 429

 431

 431
 432
 432
 433

 434

 434
 435
 435
 436
 441
 441
 443
 444
 444

 446

 447

 447

 447
 447
 447
 448
                               vxn

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                         TABLE OF CONTENTS (Continued)
Section
     19
SURVEY RESULTS BY SUBCATEGORY

 1.   Borax
 2.   Bromine                           :
 3.   Calcium Carbide
 4.   Calcium Chloride                   , .
 5.   Chromic Acid
 6.   Fluorine
 7.   Hydrogen
 8.   Iodine
 9.   Lime
10.   Hydrated Line
11.   Potassium Chloride
12.   Potassium (Metal)
13.   Potassium Sulfate
14.   Sodium Bicarbonate
15.   Sodium Chloride
16.   Sodium Sulfite
17.   Stannic Oxide
18.   Zinc Sulfate
19.   Aluminum Sulfate
20.   Ferric Chloride
21.   Lead Monoxide
22.   Potassium Bichromate
23.   Sodium Fluoride

EXCLUSIONS

     Subcategories with no PSES in Effect
     Subcategories with PSES in Effect

PSNS             .' .    ,

REFERENCES

EXCLUDED SUBCATEGORIES

INTRODUCTION

     Subcategories Surveyed
     Methods Employed

EXCLUDED SUBCATEGORIES

 1.   Aluminum Chloride (Anhydrous)
448

449
449
449
449
449
449
449
450
450
450
450
450
450
450
451
451
451
452
452
452
453
453
454

454

454
456

456

458

459

459

459
459

463

463
                                IX

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                         TABLE OF CONTENTS (Continued)
Section
     34


     38
 2.   Aluminum Compounds
 3.   Aluminum Hydroxide
 4.   Aluminum Oxide
 5.   Alums
 6.   Ammonia Alum
 7.   Ammonia Compounds
 8.   Ammonium Molybdate
 9.   Ammonium Perchlorate
10.   Ammonium Thiosulfate
11.   Barium Compounds
12.   Barium Sulfate
13.   Barytes Pigments
14.   Beryllium Oxide
15.   Bleaching Powder
16.   Boron Compounds
17.   Borosilicate
18.   Brine Chemicals
19.   Calcium Compounds
20.   Calcium Hypochlorite
21.   Cerium Salts
22.   Chlorosulfonic Acid
23.   Chromium Oxide
24.   Chromium Sulfate
25.   Heavy Water
26.   Hydrated Alumina Silicate Powder
27.   Hydrogen Sulfide
28.   Hydrophosphites
29.   Indium Chloride
30.   Industrial Gases
31.   Inorganic Acids
32.   Iodides
33.   Iron Colors
36.   Iron Oxide(s) (Iron Oxide
          Pigments)
37.   Lead Arsenate
39.   Lead Dioxide (Red, Brown)
40.   Lead Silicate
41.   Lithium Compounds
42.   Magnesium Compounds
43.   Manganese Dioxide
44.   Mercury Chloride
45.   Mercury Oxides
46.   Nickel Ammonium Sulfate
47.   Nitrous Oxide
48.   Ochers
463
463
464
464
464
464
465
465
466
466
467
467
467
467
467
468
468
469
470
470
471
471
471
471
471
472
472
472
472
472
473
473

473
474
474
474
474
474
475
476
476
476
476
477

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                         TABLE OF CONTENTS (Continued)
Section
          49.  Oleum
          50.  Oxidation Catalysts made from
                    Porcelain
          51.  Perchloric Acid
          52.  Peroxides (Inorganic)
          53.  Potash Alum
          54.  Potash Magnesia
          55.  Potassium Aluminum Sulfate
          56.  Potassium Bromide
          57.  Potassium Carbonate
          58.  Potassium Chlorate
          59.  Potassium Compounds
          60.  Potassium Cyanide
          61.  Potassium Hypochlorate
          62.  Potassium Nitrate and Sulfate
          63.  Rare Earth Metal Salts
          64.  Reagent Grade Chemicals
          65.  Salts of Rare Earth Metals
          66.  Satin White Pigment
          67.  Siennas
          68.  Silica Amorphous
          69.  Silica Gel
          70.  Silver Bromide
          71.  Silver Carbonate
          72.  Silver Chloride
          73.  Silver Cyanide
          74.  Silver Iodide
          75.  Silver Nitrate
          76.  Silver Oxide
          77.  Soda Alum
          78.  Sodium Antimonate
          79.  Sodium Compounds
          80.  Sodium Cyanide
          81.  Sodium Hydrosulfite (Zinc
                    Process)
          82.  Sodium Silicofluoride
          83.  Stannic and Stannous Chloride
          84.  Strpntium Carbonate
          85.  Strontium Nitrate
          86.  Sulfides and Sulfites
          87.  Sulfocyanides (Thiocyanates)
          88.  Sulfur
          89.  Sulfur Chloride
          90.  Sulfur Hexafluoride
          91.  Thiocyanates
Page

 477

 477
 477
 477
 477
 477
 478
 478
 478
 478
 478
 479
 479
 479
 480
 480
 481
 481
 481
 481
 481
 481
 481
 481
 482
 482
 482
 482
 483
 483
 483
 484

 485
 485
 485
 485
 485
 486
 486
 486
 486
 487
 487
                               xi

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                         TABLE OF CONTENTS (Continued)
Section
          92.  Tin Compounds
          93.  Ultramarine Pigments
          94.  Umbers
          95.  White Lead Pigments
          96.  Whiting
          97.  Zinc Sulfide

          RADIOACTIVE MATERIALS

               General
               Radioactive Isotopes
               Radium Compounds
               Fissionable Materials
               Spent Nuclear Fuel
APPENDIX A
APPENDIX B
Analysis of Long-Term Effluent Monitoring
Data for the Inorganic Chemicals
Industry Phase II

Analysis of Long-Term Influent and Effluent
Monitoring Data for the Cadmium Pigments
and Salts Subcategory
488

488
489
489
489
490

 A-l
 B-1
                              XII

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                         LIST OF FIGURES
5-1.       Sample flow sheet for metals analysis.
7-1.       Theoretical solubilities of toxic metal hydrox-
          ides/oxides as a function of pH.
7-2.       Theoretical solubilities of toxic metal sulfides
          as a function of pH.
7-3.       Electrodialysis process.
8-1.       Cumulative distribution of daily concentrations
          of zinc (total) in treated effluent.
8-2.       Cumulative distribution of daily concentrations
          of TSS in treated effluent.
8-3.       Statistical distribution for daily pollution
          measurements.
8-4.       Cumulative distribution of monthly averages of
          cadmium in treated effluent.
8-5.       Cumulative distrubution of monthly averages of
          lead (total) concentrations in treated effluent.
8-6.       Statistical distributions for 30-day average
          pollution measurements.
10-1.     Land requirements for small and medium lagoons.
10-2.     Dike volumes of lagoons.
10-3.     Dike surface areas and circumferences of lagoons.
10-4.     Concrete pits and building costs.
10-5.     Holding/storage tank costs.
10-6.     Filter, thickener and clarifier costs.
10-7.     Chemical feed and neutralization system costs.
10-8.     Pump and chrome reduction system costs.
10-9.     Filter press costs.
 41

 65

 70
 82

119

120

121

125

126

127
145
146
147
148
149
150
152
153
154
                               xiii

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LIST OF FIGURES

10-10.
10-11 .
10-12.
10-13.
10-14.
11-1 .
11-2.
11-3.
11-4.
11-5.
11-6.
12-1 .
13-1.
13-2.
13-3.
13-4.

Alkaline precipitation, settling, pH adjustment,
sludge dewatering.
Granular media filtration.
Alkaline precipitation, settling, pH adjustment
(Batch Process).
Granular media filtration (Batch Process).
Chromium reduction, alkaline precipitation,
settling, final pH adjustment and sludge de-
watering.
Generalized process flow diagram for cadmium
salts.
Generalized process flow diagram for cadmium
pigments.
Process, wastewater treatment, and sampling
locations for plant F102.
Process, wastewater treatment, and sampling
locations for plant F134 (Pure Yellow).
Process, wastewater treatment, and sampling
locations for plant F134 (Lithopone Red).
Process, wastewater treatment, and sampling
locations for plant F134 (Lithopone Yellow).
Generalized process diagram for cobalt chloride,
sulfate or nitrate.
Generalized process flow diagram for copper
chloride.
Generalized process flow diagram for copper
carbonate.
Generalized process flow diagram for copper
nitrate.
Generalized process flow diagrams for copper
iodide.
Page
155
156
157
158
159
174
175
184
185
186
187
231
254
255
256
257
           XIV

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LIST OF FIGURES
13-5      Process and sampling locations for plant F130.
13-6.      Process, wastewater flow, and sampling locations
          for plant F127.
14-1.      Generalized process diagram for nickel
          carbonate.
14-2.      Generalized process flow diagram for nickel
          chloride, nitrate or fluoborate.
14-3.      Process and sampling locations for plant F1.13.
14-4.      Process, wastewater treatment, and sampling
          locations for plant F117.
14-5.      Process and sampling locations for plant Fl'07.
15-1.      Generalized process flow diagram for sodium
          chlorate.
15-2.      Process and sampling locations for plant
          F122.
15-3.      Process and sampling locations for plant
          F149.
15-4.      Process and sampling locations for plant
          F146.
15-5.      Process and sampling locations for plant
          F112.
16-1.      Generalized process flow diagram for zinc
          chloride.
16-2.      Process wastewater treatment and sampling
          locations for plant F120.
16-3.      Wastewater treatment process and sampling
          locations for plant F144.
17-1.      Surface condenser cost.
                                         264

                                         265

                                         296

                                         297
                                         303

                                         304
                                         305
                                         334

                                         342
                                         343
                                         344
                                         345
                                         378
                                         382
                                         383
                                         423
           xv

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                         LIST OF TABLES
2-1 .


2-2.


2-3.


2-4.


2-5.


2—6.


3-1.

5-1.

5-2.


5-3.


5-4.

6-1.


7-1.

7-2.

8-1.


8-2.


8-3.
Summary of regulations - best practicable
control technology currently available  (BPT).

Summary of regulations - best avctilable  tech-
nology economically achievable  (BAT).

Summary of regulations - pretreatment standards
for existing sources  (PSES).

Summary of regulations - new source performance
standards (NSPS).

Summary of regulations - pretreatment standards
for new sources  (PSNS).

Summary of regulations - best conventional
pollutant control technology (BCT).

List of toxic pollutants.

Analytical detection  limits for toxic metals.

Pollutant frequency based on sampling results
(raw and treated wastewater).

Priority organics detected by subcategory
(raw and treated wastewater; >  10 ug/1).

Occurrence of asbestiform fibers by plant.

308 questionnaire response data-
Data elements.

Solubility products of toxic metals.

Comparison of reverse osmosis concepts.

Wastewater treatment options and performance
data summary - antimony and arsenic removal.

Wastewater treatment options and performance
data summary - beryllium and cadmium removal.

Wastewater treatment options and performance
data summary - copper removal.
 5


 7


 9


10


12


14

21

44


49



51

52


57

64

83


95


96


97
                              xvi

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                    LIST OF TABLES (continued)
8-4.      Wastewater treatment options .and performance
          data summary - chromium III and chromium VI
          removal.

8-5.      Wastewater treatment options and performance
          data summary - lead removal.

8-6.      Wastewater treatment options and performance
          data summary - mercury II removal.

8-7.      Wastewater treatment options and performance
          data summary - nickel removal.

8-8.      Wastewater treatment options and performance
          data summary - silver removal.

8-9.      Wastewater treatment options and performance
          data summary - selenium and thallium removal.

8-10.     Wastewater treatment options and performance
          data summary - zinc removal.

8r-i 1 .     Achievable long-term averages for the applied
          technologies.
 98


 99


100


101


101


102


103


104
8-12.     Industrial wastewater treatment system per-
          formance - summary of effluent concentration
          data on toxic metals.

8-13.     Estimated achievable long-term average concen-
          trations for priority metals with treatment
          options.

8-14.     Theoretical solubilities of toxic metal
          hydroxides/oxides at various pH values.

9-1.      Listing of priority and non-conventional
          pollutants recommended for consideration by
          subcategory.

10-1.     Pipe size requirements and pipe costs.

11-1.     Subcategory profile data for cadmium pigments
          and salts.
106



111


112



132

144


172
                              xvn

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                    LIST OF TABLES (continued)
                                                            Page
11-2.      Water usage at cadmium salts facilities.            179
11-3.      Water usage at cadmium pigments facilities.         180
11-4.      Wastewater flow at cadmium salts facilities.       181
11-5.      Wastewater flow at cadmium pigments facilities.    182
11-6.      Pollutant concentrations and loads of the
          sampled waste streams for plant F102 cadmium
          pigments.                                          189
11-7.      Pollutant concentrations and loads of the
          sampled waste streams for plant Fl34 cadmium
          pigments.                                          190
11-8.      Toxic pollutant raw waste data - cadmium
          pigments.                                          193
11-9.      Toxic pollutant treated effluent data -
          cadmium pigments.                                  194
11-10.     Water effluent treatment costs model plant
          (cadmium pigments).                                203
11-11.     Water effluent treatment costs for model plant
          (cadmium salts).                                   204
11-12.     BPT effluent limitations for cadmium pigments.     220
11-13.     BPT effluent limitations for cadmium salts.         221
11-14.     BAT effluent limitations for cadmium pigments
          and salts subcategory.                             223
12-1.      Subcategory profile data for cobalt salts.         229
12-2.      Water usage at cobalt salts facilities.            232
12-3.      Wastewater flow at cobalt salts facilities.         233
12-4.      Water effluent treatment costs for model plant
          (cobalt salts).                                    239
12-5.      BPT effluent limitations for cobalt salts.         244
                               xviii

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                          LIST OF  TABLES  (continued)
                                                                  Page
      13-1.      Subcategory  profile  data  for  copper  salts.          251
      13-2.      Water  usage  at copper salts facilities.             260
      13-3.      Wastewater flow  at copper salts  facilities.         261
      13-4.     -Pollutant concentrations  and  loads for  sampled
                copper salts facilities.                            266
      13-5.      Toxic  pollutant  raw  wastewater data  for sampled
                copper salts facilities.                            270
      13-6.      Water  effluent treatment  costs for model plant
                (copper salts).                                     277
      13-7.      Water  effluent treatment  costs for model plant
                (copper carbonate).                          ,       278
      13-8.      BPT effluent limitations  for  copper salts.          285
      13-9.      BPT effluent limitations  for  copper carbonate.     286
      13-10.     BAT effluent limitations  for  copper salts.          287
      13-11.     BAT effluent limitations  for  copper carbonate.     288
      14-1.      Subcategory  profile  data  for  nickel salts.          294
      14-2.      Water  use at nickel  salts facilities.               299
      14-3.      Wastewater flow  at nickel salts  facilities.         300
      14-4.      Pollutant concentrations  and  loads for sampled
                nickel salts facilities.       .                     307
      14-5.      Toxic pollutant  raw waste data  for sampled nickel
                salts facilities.                                   309
      14-6.      Water effluent treatment  costs  for model plant
                (nickel salts).                                     315
      14-7.      Water effluent treatment  costs  for model plant
                (nickel carbonate).                                 316
      14-8.      BPT effluent limitations  for  nickel salts.          321
                                      xix
_

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                    LIST OF TABLES (continued)
14-9.
14-10.
14-11.
15-1 .
15-2.
15-2a.

15-3.
15-3a.
15-4.

15-5.

15-6.

15-7.
15-8.

15-9.

16-1 .
16-2.
16-3.
16-4.

16-5.
BPT effluent limitations for nickel carbonate.
BAT effluent limitations for nickel salts.
BAT effluent limitations for nickel carbonate.
Subcategory profile data for sodium chlorate.
Water usage at sodium chlorate facilities.
Page
 322
 326
 327
 332
 336
Raw materials, wastewater sources, type of product,
discharge status, and unit flows for sodium chlorate
plants                                             337
Wastewater flow at sodium chloride facilities.
Sodium chlorate model plant.
Pollutant concentrations and loads for sampled
sodium chlorate facilities.
Toxic pollutant raw wastewater data for
sampled sodium chlorate facilities.
Water effluent treatment costs for model plant.
(sodium chlorate).
BPT effluent limitations for sodium chlorate.
BAT effluent limitations for sodium chlorate
subcategory.
NSPS effluent limitations for sodium
chlorate subcategory
Subcategory profile data for zinc chloride.
Water usage at zinc chloride facilities.
Wastewater flow at zinc chloride facilities.
Pollutant concentrations and loads for sampled
zinc chloride facilities.
Results of Dual-Media Filtration Tests at
Plant F144
 339
 340

 347

 350

 360
 365

 369
 371

 377
 379
 380

 388
 389
                               XX.

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LIST OF TABLES (continued)

16-6.
16-7.
16-8.
16-9.
16-10.
16-11 .
17-1.
17-2.
. 17-3.
17-4.
1 7-5 .
17-6.
17-7.
18-1 .
19-1 .
19-2.

-~"'~-;.:-J* . .4 '". »';'•: •• •.--•>•: •-- -• *•
Toxic pollutant raw waste data for sampled
zinc chloride facilities.
Water effluent treatment costs for model plant.
(zinc chloride - large Plant).
Water effluent treatment costs for /model plant.
(zinc chloride - small Plant).
BPT effluent limitations for zinc chloride.
BAT effluent limitations for zinc chloride.
NSPS effluent limitations for zinc chloride.
Toxic metals dischared in barometric condenser
wastewater.
Chemical composition of crystal lizer, evaporator
and barometric condensate from plant F122.
Water effluent treatment costs for model plant.
(sodium chloride).
Toxic pollutant concentrations observed in
treatment effluent during verification sampling.
Comparison of sodium sulfite and sodium
bisulfite subcategories.
Water effluent treatment costs for model plant
(sodium sulfite).
BAT effluent limitations for sodium sulfite.
Summary of the discharge status of all PSES
subcategories .
Inorganic chemical subcategories surveyed.
Summary of toxic and non-conventional pollutant
for screening/verification sampling.
1 9-2a Ammonium Thiosulfate
19-2b Brine Chemicals
19-2c Calcium Hypochlorite
Page
392
397
398
404
408
410
419
421
424
437
439
440
442
455
460
data
491
491
492
493
          XXI

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          LIST OF TABLES (continued)
19-2d     Chlorosulfonic Acid
19-2e     Nitrous Oxide
19-2f     Iron Oxide Pigments
19-2g     Silica, Amorphous
19-2h     Silica Gel
19-2i     Tin Compounds
494
495
496
497
498
499
                    xxii

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                        ACKNOWLEDGEMENTS
The  technical  study  supporting  the  proposed  regulation  was
conducted by Frontier Technical Associates, inc., of Buffalo, New
York,  under  the  direction  of  Dr.  P.  Michael Terlecky, Vice
President and  Project  Manager.   Major  contributors  were  Mr.
Michael  A. Wilkenson, Mrs. Dolores M. Funke, Mr. David M. Harty,
Dr. V. Ray Frederick, Mr. Hans G. Reif, Mr.  Leo  C.  Ehrenreich,
and  Mr. W. Alan Bullerdiek.  Frontier Technical Associates was a
subcontractor to Environmental  Science  and  Engineering.  Inc.,
Gainesville,  Florida.   Mr.  John  Crane  and  Mr.  James Cowart
provided overall coordination of the  project  team.   The  early
data  collection  and sampling were performed under the direction
of the Jacobs Engineering Group, Inc.  Ms. Bonnie J. Parrott  and
Mr.  Dennis Merklin provided the bulk of the technical support in
the Phase II project leading to this document.

The   cooperation   and   assistance   of   numerous   individual
corporations  was  provided during the course of this study.  The
numerous company and plant personnel who  submitted  information,
cooperated  with plant visits, and otherwise provided information
and data are acknowledged and  thanked  for  their  patience  and
help.

Ms.  Susan Lepow and Mr. Joseph Freedman of the Office of General
Counsel  are   specially   acknowledged   for   their   extensive
contribution   to  the  drafting  of  the  regulations  and  this
development document.

Ms. Debra Maness, Ms. Josette Bailey, Mrs. Ellen Warhit, and  Mr.
Russ  Roegner  of  the Office of Analysis and Evaluation, and Ms.
Alexandra Tarnay, Monitoring and Data Support Division,  and  Mr.
Mahesh Podar and Mr. Fred Talcott, Office of Policy, Planning and
Evaluation are acknowledged for their assistance.
                              XXlll

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                            SECTION I

                     SUMMARY AND CONCLUSIONS
TOXIC POLLUTANTS
The  following  34  inorganic chemical products were screened for
the  purpose  of  establishing  wastewater  effluent  limitations
guidelines for existing sources, standards of performance for new
sources,  and pretreatment standards for new and existing sources
in this study:
          1.   Cadmium Pigments
          2.   Cadmium Chloride
          3.   Cadmium Nitrate
          4.   Cadmium Sulfate
          5.   Cobalt Chloride
          6.   Cobalt Nitrate
          7.   Cobalt Sulfate
          8.   Copper Carbonate
          9.   Copper Chloride
         10.   Copper Iodide
         11.   Copper Nitrate
         12.   Nickel Carbonate
         13.   Nickel Chloride
         14.   Nickel Fluoborate
         15.   Nickel Nitrate
         16.   Sodium Chlorate
         17.   Zinc Chloride
18.  Calcium Hypochlorite
19.  Bleaching Powders
20.  Brine Chemicals
21.  Potassium Bromide
22.  Ammonium Thiosulfate
23.  Chlorosulfonic Acid
24.  Iron Oxide, Yellow
25.  Iron Oxide, Black
26.  Iron Oxide, Magnetic
27.  Ochers
28.  Siennas
29.  Umbers
30.  Iron Colors
31.  Nitrous Oxide
32.  Silica Gel
33.  Silica Amorphous
34.  Tin Compounds
The  screening  studies  showed  that  only  the  plant   process
wastewaters  from  the first 17 subcategories contain significant
quantities of toxic metals at  treatable  levels.   (The  Calcium
Hypochlorite   (Bleaching   Powder)  subcategory  also  generates
treatable levels of toxic and nonconventional pollutants but that
industry is intimately associated with the chlor-alkali  industry
and  its  pollutants  are  controlled by effluent limitations and
standards for the chlor-alkali  subcategory.   See  Section  19).
Very  few  of  the organic toxic pollutants were found in process
waste streams and those that were identified were present at  low
level concentrations.

CONTROL AND TREATMENT TECHNOLOGY

A  considerable  amount  of  toxic pollutant removal is currently
achieved in the industry by the existing  control  and  treatment
practices.    Additional  removal  can  be  accomplished  by  the
application of  available  and  demonstrated  technologies  which
would  add  to or modify existing treatment systems.  Recovery of

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toxic metals for value or reuse in a process does not  appear  to
be  an  attractive  alternative  in  those  industries  where the
product  recovery  practices  now  in  effect  do   not   already
accomplish this.

The treatment of toxic metal-bearing waste streams results in the
production of sludges or residues which are potentially hazardous
and may require special means for handling and disposal under the
Resource Conservation and Recovery Act (RCRA) regulations.

COSTS OF ADDITIONAL IN-PLANT TREATMENT

The  estimated  incremental  costs  of applying the candidate BAT
treatment options represent a small proportion of the  investment
and  operating  and  maintenance  costs  already committed to the
existing BPT level treatment systems.  These costs, however, vary
widely from industry to industry  and  are  highly  dependent  on
site-specific factors.

SUBCATEGORIZATION

A  review  of  the product/process basis for subcategorization of
the inorganic chemical product subcategories designated for study
revealed that certain modifications may  be  appropriate  in  the
interest   of   developing   effective   regulations.    The   17
subcategories were reduced to six on the  basis  of  similar  raw
materials,    processes,   and   treatment   technologies.    Two
subdivisions were set  up  within  three  subcategories,  cadmium
pigments  and  salts,  copper  salts,,  and  nickel salts.  In the
cadmium pigments and  salts  subcategory,  two  subdivisions  are
promulgated,   (a)   cadmium  pigments  and  {b)  cadmium  salts.
Separate mass limitations are promulgated because of  significant
differences  in unit flows.  In the copper salts subcategory, two
subdivisions  are  promulgated,  including  (a)  copper  sulfate,
copper  chloride,  copper  iodide,  and  copper  nitrate; and (b)
copper carbonate.   Separate  mass  limitations  are  promulgated
because  of  significant differences in unit flows.  The existing
copper sulfate regulations are being replaced with a  new  copper
salts  subcategory  which  will include copper sulfate as well as
the  other  copper  salts.   Likewise,  in   the   nickel   salts
subcategory,   two   subdivisions  are  promulgated:  (a)  nickel
sulfate, nickel chloride, nickel nitrate, and nickel  fluoborate;
and   (b)   nickel  carbonate.   Separate  mass  limitations  are
promulgated because of significant  differences  in  unit  flows.
The existing nickel sulfate regulations are being replaced with a
new nickel salts subcategory which will include nickel sulfate as
well   as   the   other  nickel  salts.   In  the  zinc  chloride
subcategory, effluent limitations are based  upon  concentrations
rather than mass loadings because the product(s) produced exert a

-------
      significant   influence  on  the  unit flows,  the marketplace will
      determine the product at any  time, and because  there   is  a  very
      wide  difference  between  unit  flows- at  industry plants making
      different  forms  (liquid  or solid)  of   the  product.   Plants
      producing  solid  zinc chloride  also produce  liquid zinc  chloride
      using the same production equipment on different days.

      BAT REVISIONS

      In response to a petition from the Salt Institute, the study also
      included a reexamination of BAT  for the sodium  chloride  (solution
      brine-mining  process),  sodium  sulfite,   and  calcium   chloride
      subcategories.   Revisions  of   BAT are being promulgated for the
      sodium  chloride and sodium  sulfite  subcategories.    For sodium
      sulfite we also establish a  new BCT equal  to BPT, and a  new NSPS
      and PSNS equal to the new BAT.

      EXCLUDED SUBCATEGORIES

      After thorough study and review,  :04 subcategories  are   excluded
      primarly   because   the   toxic and  nonconventional pollutant
      discharges are insignificant  or  there are one or  no   discharging
      plants.   In  addition,  as noted above, the  calcium hypochlorite
      and bleaching powder  subcategories  (which  are  identical)  are
      excluded  because the calcium hypochlorite  effluent is controlled
      by the  technology on which chlor-alkali  limitations   are based.
      Development of regulations for the beryllium  oxide subcategory  is
      deferred  for coverage under the nonferrous  metals manufacturing
      point source  category (Phase  II), for which regulations   will   be
      promulgated   later, because beryllium oxide is  formed  only during
      the manufacturing of beryllium metal.
_

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                           SECTION II

                         RECOMMENDATIONS

On the basis of the toxic pollutant  screening  and  verification
results   and  the  evaluation  of  applicable  technologies  for
discharge control and treatment, it is recommended that  effluent
limitation  guidelines,  new  source  performance  standards  and
pretreatment  standards  for  new   and   existing   sources   be
promulgated   for   the   following   six   inorganic   chemicals
manufacturing subcategories:

               Cadmium Pigments and Salts
               Cobalt Salts
               Copper Salts
               Nickel Salts
               Sodium Chlorate
               Zinc Chloride

Table  2-1  summarizes  the  promulgated  regulations  for   Best
Practicable   Control   Technology   Currently  Available   (BPT).
Summaries of regulations for  Best  Available  Technology   (BAT),
Pretreatment  Standards  for  Existing Sources (PSES), New  Source
Performance  Standards  (NSPS),  Pretreament  Standards  for  New
Sources   (PSNS),   and   Best   Conventional  Pollutant  Control
Technology (BCT) are given in Tables 2-2, 2-3, 2-4, 2-5, and 2-6.

These tables also indicate that the cadmium pigments  and   salts,
copper   salts,   and  nickel  salts  subcategories  are  further
subdivided into two segments.

New BAT and BCT effluent limitations and PSNS and NSPS are  being
promulgated   for   the   sodium   sulfite   subcategory.   These
limitations are summarized in Tables 2-2, 2-4, 2-5, and 2-6.  The
Agency is revoking the existing BAT effluent limitations for  the
sodium  chloride (solution brine-mining process) and replacing it
with a BCT effluent limitation.

The Agency is excluding 104 subcategories and also excluding  two
subcategories  because  discharges  are  controlled  by  existing
regulations:   calcium   hypochlorite   and   bleaching   powder.
Beryllium   oxide  is  deferred  to  future  regulations  in  the
nonferrous metals  category  (Phase  II).   The  Agency  is  also
excluding  23 subcategories deferred from the inorganic chemicals
Phase I PSES regulation development from  further  national  PSES
regulation.   One  of  the 23 subcategories, hydrogen, is already
covered under existing limitations  for  the  petroleum  refining
category.

-------
                                   TABLE 2-1

          SUMMARY OF REGULATIONS - BEST PRACTICABLE CONTROL TECHNOLOGY
                           CURRENTLY AVAILABLE ;(BPT)
                                       Effluent Limitations
Subcategory
Parameter

Cadmium Pigments




Cadmium Salts



• „ .
Cobalt Salts




Copper Salts
(CuSO4/ CuC12,
GUI, cu(N03)2y:,


Copper Salts
(CuC03)



Nickel Salts
(NiSO.4, NiC12/
Ni(N03)2/
Nickel Salts
(NiC03)


TSS
Cadmium (T)
Selenium (T)
Zinc (T)
PH
TSS
Cadmium (T)
Selenium (T)
Zinc (T)
PH.
TSS
Cobalt (T)
Copper (T)
Nickel (T)
pH
TSS
Copper (T)
Nickel (T)
Selenium (T)
pH
TSS
Copper ( T )
Nickel (T)
Selenium (T)
pH
TSS
Nickel (T)
pH
TSS
Nickel (T)
pH
Max
30-day Avg
kg/kkg (or
1.57
0.026
0.037
0.0092
(1)
0.001
0.0000162
0.000023
0.0000058
m
0.0014
0.00012
0.000083
0.000083
(1)
0.023
0.0010
0.0020,
0.00050
(1)
1.4
0.064
0.12
0.031
(1)
0.032
0.002
(1)
5.6
0.36
(1)
24-hr
Max
lb/1000 Ib) of Product
2.59
0.078
0.11
0.017
(1)
0.0016
0.0000487
0.000070
0.0000104
m . .!'••
0.0023
0.00030
0.00027
0.00027
(1)
0.069
0.0030 ;
0.0060
0.0015
M) • :
4.2
0.19
0.37
0.093
m
0.096 ,
0.006
d) ,-.,,.-:
17
1.1
( 1 )
                    (1)  within the range 6.0 to 9.0

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                             TABLE 2-1 (Continued)

          SUMMARY OF REGULATIONS - BEST PRACTICABLE CONTROL TECHNOLOGY
                           CURRENTLY AVAILABLE (BPT)
Subcacegory
Parameter
                                       Effluent Limitations
                                       Max
                                   30-day Avg
                                  24-hr
                                   Max
                                  kg/kkg (or lb/1000 Ib) of Product
Sodiujr. Chlorate
Zinc Chloride
TSS
Antimony(T)
Chromium (T)
Chlorine
(Total
 Residual)
 pH
TSS
Arsenic (T)
Zinc (T)
Lead (T)
pH
 0.068
 0.0043
 0.0014
                                   0.0024
                                    (1)
                                          mg/l(ppm)
25
 1.0
 3.8
 0.6
  (2)
 0.12
 0.0086
 0.0027
                   0.0041
                    (1)
43
 3.0
11.4
 1.8
  (2)
                    (1) Within the range 6.0 to 9.0
                    (2) Within the range 6.0 to 10.0

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                                    TABLE 2.-2





            SUMMARY OF REGULATIONS  - BEST AVAILABLE TECHNOLOGY (BAT)
Subcategory
                                       Effluent  Limitations
Parameter

Cadmium Pigments
Cadmium Salts
Cobalt Salts
Copper Salts
(CuS04/ Cud 2,
Cul, Cu(N03)2)
Copper Salts
(CuC03)
Nickel Salts
(NiS04/ NiC12/
Ni(N03)2/
Ni(BF4)2)
Nickel Salts
(NiC03)
Sodium Chlorate

Zinc Chloride

Cadmium (T)
Selenium (T)
Zinc (T)
Cadmium (T)
Selenium (T)
Zinc (T)
Cobalt (T)
Copper ( T )
Nickel (T)
Copper (T)
Nickel (T.)
Selenium (T)
Copper (T)
Nickel (T)
Selenium (T)
Copper ( T )
Nickel (T)
Copper ( T )
Nickel (T)
Antimony
Chromium(T)
Chlorine
(Total
Residual )

Arsenic (T)
Zinc (T)
Lead (T)
Max
30- day Avg
kg/kkg (or lb/1000
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
0.00024
0.00024
0.042
0.042
0.0022
0.00086
0.0024
mg/l(ppm)
1.0
0.76
0.048
24-hr
Max
Ib) of Product
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
same as BPT
0.00074
0.00074
0.13
0.13
0.0043
0.0017
0.0041

3.0
2.3
0.18

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                             TABLE 2-2 (Continued)

            SUMMARY OF REGULATIONS - BEST AVAILABLE TECHNOLOGY (BAT)
                                       Effluent Limitations
Subcategory
Parameter
                                       Max
                                   30-day Avg
                                  24-hr
                                   Max
                                  kg/kkg (or lb/1000 Ib)  of Product
Sodium Chloride
(Solution Brine
Mining Process)

Sodium Sulfite
Chromium(T)
Zinc (T)
COD
               Reserved
0.00063
0.0015
1.7
0.0020
0.0051
3.4

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                                   TABLE 2-3
              SUMMARY OF REGULATIONS - PRETREATMENT STANDARDS FOR
                            EXISTING SOURCES  (PSES)
                                       Effluent Limitations
Subcategory
Parameter
Max
30-day Avg

Cadmium Pigments
Cadmium Salts
Cobalt Salts
Copper Salts
(CuSO4/ CuC12/
GUI, CU(N03)2)
Copper Salts
(CuC03)
Nickel Salts
(NiS04/ NiC12/
Ni(N03)2/
Nickel Salts
(NiC03)
Sodium Chlorate
Zinc Chloride

Cadmium (T)
Selenium (T)
Zinc (T)
Cadmium (T)
Selenium (T)
Zinc (T)
Cobalt (T)
Copper ( T )
Nickel (T)
Copper ( T )
Nickel (T)
Selenium (T)
Copper ( T )
Nickel (T)
, Selenium (T)
Copper ( T )
Nickel(T)
Copper ( T )
Nickel(T)
-
Arsenic (T)
Zinc (T)
Lead (T)
mg/1
0.28
0.40
0.10
0.28
0.40
0.10
1.4
1.0
1.0
1 .1
2.1
0.53
1.1
2.1
0.53
0.36
0.36
0.36
0.36
Reserved
1.0
0.76
0.048
kg/kkg
0.026
0.037
0.0092
0.0000162
0.000023
0.0000058
0.00012
0.000083
0.000083
0.0010
0.0020
0.00050
0.064
0.12
0.031
0.00024
0.00024
0.042
0.042


24-hr
Max
mg/1
0.84
1 .1
0.18
0.84
1.1
0.18
3.6
3.3
3.3
3.2
6.4
1.6.
3.2
6.4
1.6
1 .1
1 .1
1". 1
1 .1

3.0
2.3
0.18

kg/kkg
0.078
0.1 1
0.017
0.0000487
0.000070
0.0000104
0.00030
0.00027
0.00027
0.0030
0.0060
0.0015
0.19
0.37
0.093
0.00074
0.00074
0.13
0.13



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                                   TABLE 2-4




        SUMMARY OF REGULATIONS - NEW SOURCE PERFORMANCE STANDARDS (NSPS)




                                       Effluent Limitations
Subcategory
Parameter

Cadmium Pigments




Cadmium Salts




Cobalt Salts




Copper Salts
(CuSO<., Cud 2,
GUI, Cu(N03)2)


Copper Salts
(CuCO3)



Nickel Salts

(NiSO4/ NiC12/
Ni(N03)2,
Ni(BF4)2)
Nickel Salts

(NiC03)


TSS
Cadmium (T)
Selenium (T)
Zinc (T)
pH
TSS
Cadmium (T)
Selenium (T)
zinc (T)
PH
TSS
Cobalt (T)
Copper (T)
Nickel (T)
PH
TSS
Copper ( T )
Nickel (T)
Selenium (T)
PH
TSS
Copper ( T )
Nickel (T)
Selenium (T)
pH
TSS
Copper ( T )
Nickel (T)
pH

TSS
Copper ( T )
Nickel (T)
PH
Max
30-day Avq
kg/kkg ( or
1.57
0.026
0.037
0.0092
(1)
0.001
0.0000162
0.000023
0.0000058
(1)
0.0014
0.00012
0.000083
0.000083
(1)
0.023
0.0010
0.0020
0.00050
(1)
1 .4
0.064
0.12
0.031
(1)
0.032
0.00024
0.00024
(1)

5.6
0.042
0.042
(1)
24-hr
Max
lb/1000 Ib) of Product
2.59
0.078
0.1 1
0.017
(1)
0.0016
0.0000487
0.000070
0.0000104
(1)
0.0023
0.00030
0.00027
0.00027
(1)
0.069
0.0030
0.0060
0.0015
m
4.2
0.19
0.37
0.093
(1)
0.096
0.00074
0.00074
(U

17
0.13
0.13
(1)
                    (U  Within  the  range  6.0  to  9.0
                                       10

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                             TABLE 2-4  (Continued)

        SUMMARY OF REGULATIONS - NEW SOURCE PERFORMANCE STANDARDS (NSPS)

                                       Effluent Limitations
Subcategory
Parameter
                                       Max
                                   30-day Avg
                                  24-hr
                                   Max
                                  kg/kkg (or lb/1000 Ib)  of Product
Sodium Chlorate
Zinc Chloride
TSS
Antimony(T)
Chromium (T)
Chlorine
(Total  .
 Residual)
 PH
TSS
Arsenic (T)
Zinc (T)
Lead (T)
PH
 0.046
 0.0022
 0.00086
                                   0.0024
                                    (1)
                                         mg/1(ppm)
17
 1.0
 0.76
 0.048
  (2)
 0.076
 0.0043
 0.0017
                   0.0041
                    (1)
28
 3.0
 2.3
 0.18
  (2)
                                 kg/kkg (or lb/1000 Ib) of product
Sodium Sulfite
TSS
Chromium(T)
Zinc(T)
COD
pH
 0.016
 0.00063
 0.0015
 1.7
  (1)
 0.032
 0.0020
 0.0051
 3.4
  (1)
                    (1) Within the range 6.0 to 9.0
                    (2) Within the range 6.0 to 10.0
                                        11

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                                    TABLE 2-5

               SUMMARY  OF REGULATIONS  - PRETREATMENT  STANDARDS  FOR
                                NEW SOURCES  (PSNS)
Subcategory
Parameter
                                        Effluent  Limitations
                                        Max
                                    30-day Avq
                                  24-hr
                                   Max
                                   mg/1     kg/kkg
                                  mg/1
                            kg/kkg
Cadmium Pigments
Cadmium Salts
Cobalt Salts
Copper Salts
(CUS04, CuC12/
GUI, CU(N03)2)

Copper Salts
  (CuC03)
Nickel Salts
(NiS04, NiC12/
Ni(N03)2/
Ni(BF4)2)

Nickel Salts
  (NiC03)

Sodium Chlorate
Cadmium  (T)
Selenium  (T)
Zinc  (T)

Cadmium  (T)
Selenium  (T)
Zinc  (T)

Cobalt (T)
Copper (T)
Nickel (T)

Copper (T)
Nickel (T)
Selenium  (T)

Copper (T)
Nickel (T)
Selenium  (T)

Copper (T)
Nickel (T)
same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
same as PSES

same as PSES
same as PSES
Copper (T)
Nickel (T)
Chromium(T)
Antimony(T)
same as PSES
same as PSES
0.32 0.00086
0.8 0.0022
same as PSES
same as PSES
0.64 0.0017
1.6 0.0043
                                       12

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                                   TABLE 2-5

              SUMMARY OF REGULATIONS - PRETREATMENT STANDARDS FOR
                               NEW SOURCES (PSNS)
Subcategory
                                       Effluent Limitations
Parameter
Max
30-day Avq

Zinc Chloride Arsenic (T)
Zinc (T)
Lead (T)
Sodium Sulfite Chromium(T)
Zinc(T)
COD
mg/1
same
same
same
0.42
1.2
630
kg/kkg
as PSES
as PSES
as PSES
0.00063
0.0015
1.7
24-hr
Max
mg/1
same
same
same
1.3
3.4
1 260

kg/kkg
as PSES
as PSES
as PSES
0.0020
0.0051
3.4
                                       13

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                                   TABLE 2-6

          SUMMARY OF REGULATIONS - BEST CONVENTIONAL POLLUTANT CONTROL
                                TECHNOLOGY (BCT)
                                       Effluent Limitations
Subcategory
Parameter

Cadmium Pigments

Cadmium Salts

Cabalt Salts

Copper Salts
(CuS04/ CuC12/
GUI, CU(N03)2)
Copper Salts
(CuC03)
Nickel Salts
(NiSO4/ NiC12/
Ni(N03)2/
Ni(BF4)2)
Nickel Salts
(NiC03)
Sodium Chlorate

Zinc Chloride

Sodium Chloride
(Solution Brine-
Mining Process)
Sodium Sulfite


TSS
pH
TSS
pH
TSS
pH
TSS
PH

TSS
pH
TSS
pH


TSS
pH
TSS
PH
TSS
PH
TSS
PH

TSS
PH
Max
30-day Avg
kg/kkg (or lb/1000
same as BPT
(1)
same as BPT
(1)
same as BPT
(1)
same as BPT
(1)

same as BPT
(1)
same as BPT
(1)


same as BPT
(1)
same as BPT
(1)
same as BPT
(2)
reserved


same as BPT
(1)
24-hr
Max
Ib) of Product
same as BPT
(1)
same as BPT
(1)
same as BPT
(1)
same as BPT
(1)

same as BPT
(1)
same as BPT
(1)


same as BPT
(1)
same as BPT
m
same as BPT
(2)
reserved


same as BPT
(1)
                    (1)  Within the  range  6.0  to 9.0

                    (2)  Within the  range  6.0  to 10.0
                                       14

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The  Agency  is proposing PSNS of no discharge for 12 of those 23
subcategories;  the  other  11  of  those  23  subcategories  are
regulated by currently effective PSNS.
                                15

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                            SECTION 3

                          INTRODUCTION


                            AUTHORITY

The Federal Water Pollution Control Act Amendments

The  Federal  Water Pollution Control Act  (the Act) Amendments of
1972, 33 USC 1251 et seq., stated the national goal of  attaining
by  July  1,  1983,  a    water  quality  which  provides  for the
protection  and  propagation   of   fish   and   shellfish,   for
recreation  in  or  on  the  nation's  waters,  and  the  goal of
eliminating the discharge of pollutants into navigable waters  by
1985.

Purpose and Authority

The  Federal  Water  Pollution  Control  Act  Amendments  of 1972
established a comprehensive program to "restore and maintain  the
chemical,   physical,  and biological  integrity of the  Nation's
waters,"  Section 101(a).  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 ("BAT")...which will
result in reasonable further progress toward the national goal 'of
eliminating   the   discharge   of   all   pollutants"    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  dischargers to 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 dischargers to POTW (indirect dischargers).

Although Section 402(a)(l) of the 1972 Act authorized the setting
of requirements for direct dischargers on a  case-by-case  basis,
Congress  intended  that, for the most part, control requirements
would be based on regulations promulgated by the Administrator of
EPA.   Section 304(b) of the Act  required  the  Administrator  to
promulgate   regulations   providing   guidelines   for  effluent
limitations  setting  forth  the  degree  of  effluent  reduction
                               16

-------
attainable  through  the  application  of BPT and BAT.  Moreover,
Sections 304(c) and 306  of  the  Act  required  promulgation  of
regulations  for  NSPS,  and  Sections 304(f), 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  develop  a  list  of toxic pollutants and 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  put
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 BAT effluent
limitations guidelines, pretreatment standards,  and  new  source
performance standards for 65 "priority" pollutants and crasses of
pollutants  for  21  major  industries.   See  Natural  Resources
Defense Council, Inc.  v.   Train,  8  ERC  2120  (D.D.C.  1976),
modified 12 ERC 1833  (D.D.C.  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 of several of the  basic
elements  of the Settlement Agreement program for toxic pollution
control.  Sections 301(b)(2)(A) and 301(b)(2)(C) of the  Act  now
require  the  achievement by July 1, 1984 "of effluent limitations
requiring application of BAT for "toxic"  pollutants,   including
the  65  "priority"  pollutants and classes of  pollutants  which
Congress declared  "toxic"  under  Section  307(a)  of  the  Act.
Likewise, EPA's programs for new source performance standards and
pretreatment  standards  are  now  aimed   principally  at  toxic
pollutant controls.  Moreover, to strengthen the  toxics  control
program,  Section  304(e) of the Act authorizes the Administrator
to prescribe "best management practices"  ("BMPs") to prevent  the
release of toxic and hazardous pollutants from plant site runoff,
spillage  or  leaks, sludge or waste  disposal, and drainage from
raw material  storage  associated  with,  or  ancillary  to,  the
manufacturing or treatment process.

In keeping with its emphasis on toxic pollutants, the Clean Water
Act  of  1977  also  revises  the  control  program for non-toxic
pollutants.   Instead  of  BAT  for   "conventional"   pollutants
identified, under Section 304(a)(4) (including biochemical oxygen
demand, suspended solids, fecal coliform  and pH), the new Section
                                17

-------
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 a cost-reasonableness  test
for  attaining  a  reduction   in  effluents compared to  the costs
incurred  by  a   publicly   owned   treatment   works    (Section
304(b)(4)(B)).    This  is  determined  by  an  analysis of  the
reasonableness of the costs of attaining a reduction in  effluents
and the effluent pollutant reduction benefits  derived,   and  the
comparison  of the cost and level of reduction of such pollutants
from the discharge of publicly owned treatment works to  the  cost
and  level  of  reduction  of  such  pollutants  from  a class or
category of industrial sources.  For  non-toxic,  nonconventional
pollutants,   Sections   301(b)(2)(A)   and   (b)(2)(F)   require
achievement of BAT effluent limitations within three years  after
their  establishment  or by July 1, 1984, whichever is later, but
not later than July 1, 1987.

The  purpose  of  these  regulations  is  to   provide    effluent
limitations  guidelines  for  BPT, BAT, and BCT, and to  establish
NSPS, pretreatment standards for  existing  sources  (PSES),  and
pretreatment  standards  for  new  sources (PSNS), under Sections
301, 304, 306, 307, and 501 of the Clean Water Act.

The United States Environmental Protection  Agency  (the Agency)
was   entrusted   with   the  responsibility  to  carry   out  the
requirements of the Act, and initiated  an  intensive  effort  to
develop  the  necessary  regulatory means which would achieve the
stepwise reduction and elimination of pollutant discharges in all
major U.S. industries.  For the Inorganic Chemicals Manufacturing
Point Source Category, the Agency designed a comprehensive,  two-
stage  program  to  identify the control parameters and  establish
the technological basis for  regulations  development.     Stage  I
covered  22  Major Inorganic Chemical Products (1), and  the final
regulations for these industrial subcategories were published  in
the Federal Register on March 12, 1974.  The regulations included
specific   numerical   effluent   limitations  and  standards  of
performance for both existing and new  sources.     Zero-discharge
requirements  specified  for many of the subcategories were to be
applied either at the 1977 BPT step or later.  Stage  II  of  the
Agency's  effort  resulted  in  the  promulgation  of  BPT  based
effluent limitations for an additional group of 27  subcategories
referred  to as Significant Inorganic Chemical Products  (2).  The
interim final regulations were published on May 22, 1975.   Taken
together,  the  two  groups  of  regulations  cover  49  inorganic
chemical subcategories  many  of  which  include  more   than  one
specific  chemical  product.  Although some toxic pollutants were
covered in cases where a direct relationship to the  process  was
obvious (e.g.,  mercury and/or lead in the Chlor-Alkali  Industry),
                               18

-------
the  main  thrust  of  the  regulations  was  the  control of the
pollutant parameters which accounted, in terms of  quantity,  for
most of the pollution loading of navigable waters attributable to
the manufacture of inorganic chemicals.

Court Remand of_ Regulations

On  March  10,  1976,  the United States Court of Appeals for the
Fourth Circuit in £._!_._ duPont de Nemours &.  Co.  v.  Train,  541
F.2d   1018   (4th   Cir.  1976),  set  aside  and  remanded  for
reconsideration a number  of  general  definitions  and  specific
discharge  regulations  promulgated  in  1974.  These regulations
were all within Title 40, Parts  401  and  415  of  the  Code  of
Federal  Regulations  and  covered the chlor-alkali, hydrochloric
acid, hydrofluoric acid, nitric acid,  sodium  carbonate,  sodium
dichromate;  sodium  metal,  sodium  silicate, sulfuric acid, and
titanium dioxide subcategories.

     For the most part, the main target of the  remand  was  zero
discharge  regulations from which the  industry petitioners sought
relief on grounds of technological infeasibility.   During   1975,
the  Agency  funded  a special study of the remand  issues  (3) and
was prepared to propose amended regulations.

     Following the court remand of the stage  I final regulations,
the Agency revoked   the  stage  II   interim   final  and  proposed
regulations  published in May 1975,  for Aluminum Fluoride, Chrome
Pigments, Hydrogen Cyanide, and Sodium Silicofluoride.   In  this
instance,  the Agency's  intent was to  reconsider the specific BPT
effluent limitations established  for  these  industries   in the
light  of  information  made  available  on   process  differences
between plants and additional data on  the  actual   concentrations
and  treatability  of  the regulated discharge constituents.  The
information was presented to the Agency in the  form  of   various
documents prepared by members of the industries concerned  (4).

The Settlement Agreement

A consent  decree was issued as a result of  a suit filed  by four
environmental groups (Natural Resources Defense Council, Inc.  y.
Train,   8  ERC   2120  (D.D.C.  1976), modified 12 ERC  1833  (D.D.C.
1979).   The   consent decree  contained  a  Settlement  Agreement
wherein  the  Agency agreed to regulate 65 toxic pollutants  under
Sections 301, 304, 306,  and 307 of the Act in accordance with the
schedule and  provisions  stipulated.    The  original  list   of  65
chemicals  and   classes  of  chemicals attached to  the  Settlement
Agreement  was   redefined  to  cover  129  chemical  substances,
including   specific organic  compounds,  pesticides   and  their
metabolites,  polychlorinated biphenyls (PCB's), cyanide,  13  heavy
                                19

-------
metals  and  asbestos.   Table 3-1  lists  the   129   toxic   pollutants
 (sometimes    referred    to    in    the    literature   as   "priority
pollutants").

The  Settlement   Agreement   also  identified  21    point   source
categories   and   specified   the   scope of  application of effluent
limitations,  new  source  performance  standards,   and pretreatment
standards    within   each   category  in terms   of   the  Standard
Industrial  Classification  (SIC)  code numbers.   For  the   Inorganic
Chemicals    Manufacturing    Point   Source Category,   the  major
industries  included are:

            SIC 2812  - Alkalies  and  Chlorine
            SIC 2813  - Industrial Gases
            SIC 2816  - Inorganic Pigments
            SIC 2819  - Industrial Inorganic Chemicals,
                         Not Elsewhere Classified

Phase I of  the regulatory effort conducted in connection with the
Inorganic Chemicals Point   Source Category  covered* 60 of  177
subcategories previously identified  as belonging to the category.
The  Phase   I  regulations   were promulgated June 29, 1982  (47 FR
28260).   Phase   II  was  to have  covered  the  remaining   117
subcategories.    However,   after  review   of all of the inorganic
products listed in SIC codes 2812, 2813,   2816  and 2819,  seven
more  subcategories  were identified bringing the total  number of
subcategories examined in Phase   II  to 124.   These   additional
subcategories  were  identified   as  the   result of contacts with
chemical producers, a literature search, site visits by  EPA  and
contractor  personnel,  and telephone  communications.   Of the 124
subcategories, 107 were  excluded from further  study  for  the
following reasons (See Section 19 -  Excluded Subcategories):

     1.   The chemical is no longer  being  produced;
     2.   Only one plant was known to  be producing  the
          chemical;
     3.   Production quantities  were low (below 4.5 kkg/yr
          <<10,000 lb/yr));
     4.   No dischargers could be identified in the
          subcategory;
     5.   No toxic pollutants were found at significant
          treatable levels;
     6.   The subcategories  were already regulated  by existing
          guidelines; or
     7.   One subcategory will be covered  in a future
          rulemaking in another  category.

Phase II Inorganic Chemicals
                               20

-------

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 The  Agency identified 17 chemical products in Phase II  for which
 effluent limitations  guidelines  and  standards  are warranted.
 Engineering   and   sampling   visits   were   conducted   and  a
 comprehensive data gathering program was undertaken in  order   to
 complete   this   effort.    This  report  documents  the   Agency's
 findings with respect  to  the  list  of  17   chemical   products
 identified  in Table 3-2.

 TABLE 3-2.   CHEMICAL PRODUCTS COVERED UNDER THE PHASE II STUDY
           1.   Cadmium Pigments
           2.   Cadmium Chloride
           3.   Cadmium Nitrate
           4.   Cadmium Sulfate
           5.   Cobalt  Chloride
           6.   Cobalt  Nitrate
           7.   Cobalt  Sulfate
           8.   Copper  Carbonate
           9.   Copper  Chloride
10.   Copper Iodide
11.   Copper Nitrate
12.   Nickel Carbonate
13.   Nickel Chloride
14.   Nickel Fluoborate
15.   Nickel Nitrate
16.   Sodium Chlorate
17.   Zinc Chloride
On October  25,  1983,  the Agency proposed effluent  limitations and
standards   for  the   above subcategories (48 FR  49408) as well as
amended limitations and standards  for sodium chloride and  sodium
sulfite.    This  document  is a revised version  of the supporting
development document  for that proposal.

GENERAL APPROACH AND  METHODOLOGY

Initiating  and undertaking a comprehensive  study  of  the  toxic
pollutant   problem   in  the  Inorganic  Chemicals  Industry  was
preceded by an intensive evaluation by the Agency of the kinds of
data and supporting information that should  be  assembled  as  a
basis for the development of regulations.  All major decisions on
the  identity  of  pollutants  and  the establishment of effluent
limitations and standards of performance for each subcategory had
to be supportable by  documented evidence collected from operating
production  facilities.  Similarly, the necessary  information  on
production  rates,  processes,  raw  materials,  water use, waste
sources,  and  treatment  technologies  in  practice  had  to  be
acquired with sufficient detail and breadth of coverage to permit
an  analysis  of  the engineering and economic variables that are
characteristic of each  subcategory.    Toxic  pollutant  control
regulations  would  be based on the application of best available
technology  for treatment and reliable performance evaluations for
the removal of specific waste substances.
The following paragraphs briefly describe the major  study
and their results as they are presented in this report.
                  tasks
                               22

-------
Industry Data Base Development and Subcateqorization Review

Information  from  individual  manufacturers  and  previous study
documents were reviewed in detail and an evaluation  of  possible
subcategorization  was  performed.   A  review  of  the data base
acquired for this group of chemical products indicated that there
are 46 individual facilities  in  this  group  (many  plants  are
multiple  product  plants).   The  Agency  has  data submitted by
industry in response to requests for  information  under  Section
308  of  the  Act  (obtained during Phase I or II) or engineering
visit data on file for 44 of the 46  plants.   In  addition,  EPA
obtained  data  from State agencies, Regional offices, compliance
visits by the States, telephone contacts,  and  letter  requests.
During  screening  and  verification  sampling,  13  plants  were
sampled.  EPA  conducted  additional  engineering  visits  during
October  and  November  1982  to  twelve  plants   (three had been
visited previously  during  the  sampling  program).   Section   4
outlines the factors considered in subcategorization and presents
the  rationale  for  the proposed scheme of subcategorization for
the 17 chemical products  studied.   Final  subcategorization  is
identical to the proposed subcategorization of October 25,  1983.

The Screening and Verification Sampling Program

The  collection  of  detailed  analytical  data  on conventional,
nonconventional and toxic pollutant  concentrations   in  raw  and
treated   process   wastewater    streams   was   completed  in   a
comprehensive sampling  program.   The  sampling   and  analytical
methodology  is described  in Section 5.  The Phase I  study  showed
that organic priority pollutants  would  not  be  expected   to  be
significant  in this  industry group.  Therefore, the screening and
verification   sampling   program was  modified   to   reduce  the
frequency of  organic  sampling   for  Phase  II.    This  sampling
program   is  described in  detail  in Section  5.   In all,  13  of the
46 plants were sampled during  the sampling program.

Engineering  Evaluation

Section  6 describes  the procedures and  sources  used in developing
the  industry production and  wastewater  generation  characteristics
that  form the basis  of the model  plant  concept.   The   sources  of
detailed   process   and   waste  treatment   information  are  also
presented.   Section  7   contains  an   evaluation   of   treatment
technology   presently  applied  in  existing wastewater  treatment
systems  and advanced technologies that  may  be  recommended  for BAT
and  NSPS applications.    Section  8  provides   estimates  of   the
treatability of  selected toxic and nonconventional pollutants  to
be  applied  in   the  development   of    achievable   performance
characteristics    for   specific  technologies.    Section  8  also
                                23

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 presents  a discussion  of  the approach  taken  in  the  statistical
 analysis  of long-term  monitoring  data.   The statistically derived
 parameters,  including  variability factors for the 24-hour maximum
 and  maximum 30-day average limitations,  are presented in Appendix
 A.   Section 9  lays the groundwork for  the estimation of  pollutant
 removal   performances   for each subcategory.   The candidate toxic
 pollutants to  be  controlled in each  subcategory are  identified  on
 the   basis  of the screening  and  verification data   and the
 rationale  for the application of advanced level technologies  is
 presented.

 Treatment System  Cost  Estimates

 Section 10 presents the  general   approach  to  cost  estimating,
 discusses  the assumptions  made,   and   gives  the  detailed cost
 estimates for  alternative levels  of  treatment and control.   For
 each  subcategory,   the total estimated  installed cost of typical
 treatment systems  is developed on the basis of model plant design
 specifications.  Estimated incremental costs  are given  for  each
 of   the   advanced  level treatment alternatives.   Estimates of the
 sludge generated by treatment and the costs associated with their
 proper disposal in  compliance with anticipated RCRA   requirements
 are   included  (based upon evaluation of  EP toxicity  data).   Where
 available,  industry data  on sludge  volumes  and  characteristics
 were  utilized.   Disposal   costs were  estimated on the basis  of
 disposal  in  an off-site hazardous material  landfill  (except  where
 noted).

 Treatabilitv Studies

 Data was  collected  through  a treatability  study  in Phase I  (4)  to
 evaluate  the achievable   performance  of   various  treatment  and
 control   alternatives  and   to provide empirical  treatment  system
performance  information applicable to selected  inorganic  chemical
 subcategories.   The study,  completed in  July   1980,   specifically
 concentrated  on  those   subcategories   in  the  Phase  I  Inorganic
Chemicals  Industry  for which treatability   data   either   did  not
exist  or  was  deficient,  and   for  which  data were needed for
purposes of comparison with  proposed  effluent   limitations  for
 those  Phase I  subcategories.  Subcategories of  Phase  I  for which
treatability studies were conducted include:

     Nickel sulfate
     Hydrofluoric acid
     Copper sulfate
     Chlor-alkali  (diaphragm cells)
     Titanium dioxide (chloride process)
     Chrome pigments
     Sodium dichromate
                               24

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     Sodium bisulfite
     Sodium hydrosulfite

This treatability study is  relevant  to  Phase  II  because  the
chemical  manufacturing processes are similar, similar wastewater
treatment practices are employed, and similar wastewater  streams
have been encountered.

In  order  to evaluate the effectiveness of filtration technology
on zinc chloride process wastewaters, a  treatability  study  was
also  performed  at  a  zinc  chloride  manufacturing facility in
1984(5).  This study established the relationship  between  total
and  dissolved zinc as well as the effectiveness of the treatment
for removal of TSS, turbidity, total and dissolved zinc,  arsenic
and  lead.   The  results of this study are summarized in Section
16.

Where adequate data were unavailable for Phase  II,  treatability
study   results  for  similar  wastewater streams from Phase I and
other industries were taken  into  account  in  determination  of
achievable levels of performance.

GENERAL CRITERIA FOR EFFLUENT LIMTATIONS

BPT Effluent Limitations

The  factors   considered   in  defining  best  practicable  control
technology currently  available  (BPT)  include  the   total  cost  of
applying  such  technology  in relation  to  the effluent reductions
derived  from  such   application,   the  age   of    equipment    and
facilities   involved,   the  process   employed,  non-water  quality
environmental  impacts  (including energy requirements), and other
factors   the   Administrator    considers    appropriate   (Section
304(b)(l)(B».   In  general, the BPT technology   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.    BPT
focuses  on  end-of-pipe treatment  rather  than  process changes or
 internal   controls,   except  where   such   are   common   industry
practice.   The   cost/benefit   inquiry  for  BPT  is  a  limited
balancing,  committed to EPA's discretion,  which does not  require
 the Agency   to   quantify benefits  in monetary terms.   See,  e.g.,
American Iron  and Steel Institute v.  EPA,  526 F.2d 1027  (3rd Cir.
 1975).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 the cost and economic  impacts  of  the  required
                                25

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 pollution  control  level.    The  Act  does not require or permit
 consideration  of  water   quality   problems   attributable   to
 particular   point   sources  or  industries,  or  water  quality
 improvements in particular  water bodies.   Therefore,  EPA has  not
 considered  these  factors.    See Weyerhaeuser Co.  v.  Costle,  590
 F.2d 1011  (D.C.  Cir.   1978).	

 BAT  Effluent Limitations

 The  factors considered in   assessing  best  available  technology
 economically  achievable  (BAT)   include  the age of equipment  and
 facilities involved,  the process employed, process   changes,   and
 non-water   quality   environmental    impacts  (including  energy
 requirements),  (Section  304(b)(2)(B)).  At  a  minimum,   the  BAT
 technology  level  represents  the  best   economically achievable
 performance of  plants of various ages,  sizes, processes,  or other
 shared   characteristics.    As  with   BPT,   uniformly    inadequate
 performance  may  require   transfer  of   BAT  from  a  different
 subcategory or  category.  BAT  may  include  process   changes   or
 internal   controls,   even   when  these  technologies  are not common
 industry  practice.  The  statutory  assessment of  BAT   "considers"
 costs, but does  not require  a balancing of costs against  effluent
 reduction   benefits   (see   Weyerhaeuser  v.   Costle,   supra).   In
 developing  the   BAT   regulations,    however,   EPA   has   given
 substantial   weight   to  the reasonableness of  costs.   The Agency
 has  considered  the volume and nature of  discharges,   the  volume
 and  nature   of  discharges  expected  after  application  of  BAT,  the
 general environmental  effects of the pollutants,  and   the  costs
 and  economic  impacts  of  the required pollution control levels.
 Despite   this expanded  consideration  of  costs,  the    primary
 determinant  of BAT is  effluent reduction  capability.   As  a result
 of   the  Clean   Water  Act   of   1977,   33   USC   1251 et seq.,  the
 achievement  of BAT has become the  principal  national  means   of
 controlling  water  pollution  due  to toxic pollutants.

BCT  Effluent  Limitations

 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(b)(4) -  BOD, TSS,  fecal  coliform,  and pH.
Oil  and  grease  was  designated   by   the   Administrator    as
 'conventional"  on  July  30,  1979,  44 FR  44501.  BCT is  not  an
additional limitation,  but   replaces   BAT  for   the   control   of
conventional pollutants

Section  304(b)(4)(B). of the  Act requires  that BCT limitations  be
assessed in light of  a  two  part  "cost  reasonableness"  test,
                               26

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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).  However,
the cost test was remanded by the United States Court of  Appeals
for  the  Fourth  Circuit.   American Paper Institute v. EPA, 660
F.2d 954 (4th Cir. 1981).  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 had argued that   a
second  cost  test  was  not  required).   The  Agency proposed  a
revised BCT methodology October 29, 1982 (47 FR 49176).

New Source Performance Standards

The basis for  new  source  performance  standards   (NSPS)  under
Section  306  of  the  Act  is  the  best  available demonstrated
technology.  New plants have  the opportunity to design  the  best
and  most  efficient   inorganic chemicals  manufacturing processes
and wastewater treatment  technologies,  and  Congress  therefore
directed  EPA  to consider  the best demonstrated process  changes,
in-plant controls, and end-of-pipe  treatment  technologies  which
reduce pollution  to the maximum  extent  feasible.

Pretreatment Standards for  Existing Sources

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  POTWs.   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.   Pretreatment is  required  for
 toxic   pollutants  that  would pass through a POTW in amounts that
would violate  direct discharger effluent  limitations.    EPA  haj
 generally   determined that there is pass through of pollutants  if
 the  percent  of  pollutants  removed  by  a  well-operated  POTW
 achieving  secondary  treatment is less than the percent removed  by
 the  BAT  model treatment system.   The legislative history of the
 1977  Act   indicates  that  pretreatment  standards  are  to    be
 technology-based,  analogous to the best available technology for
 removal  of   toxic   polltuants.     The   general   pretreatment
                                27

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regulations  which served as the framework for these pretreatment
regulations can be found in 40 CFR Part 403, 46 FR  9409   (January
28, 1981); 47 FR 42688 and 47 FR 42698  (Sept.  28,  1982).

Pretreatment Standards for New Sources

Section 307(c) of the Act requires EPA to promulgate pretreatment
standards  for  new  sources  (PSNS)  at  the  same  time that it
promulgates NSPS.  New  indirect  dischargers,  like  new  direct
dischargers,   have  the  opportunity  to  incorporate  the  best
available demonstrated technologies  including  process  changes
in-plant controls, and end-of-pipe treatment technologies, and to
use  plant  site  selection  to  ensure adequate treatment system
installation.
                              28

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                            SECTION 3
                           REFERENCES
1 .



2.
3.
4.
5.
U.S.  Environmental  Protection
Products, Development Document.
Agency,   Major   Inorganic
EPA-440/l-74-007a, 1974.
U.S. Environmental Protection Agency,  Development  Document
for   Interim  Final  Effluent  Limitations  Guidelines., and
Proposed  New   Source   Performance   Standards   for   the
Significant Inorganic Products, EPA-440/1 -75-037, 1,975.  358
pp.

Calspan Corp.  Addendum to Development document for Effluent
Limitations Guidelines and New Source Performance Standards,
Major Inorganic  Products  Segment  of   Inorganic  Chemicals
Manufacturing    Point   source   Category,   Contract   No.
68-01-3281, 1978.

U.S. Environmental Protection Agency,  Development  Document
for  Final Effluent Limitations Guidelines and Standards for
the Inorganic Chemicals Manufacturing Point Source Category,
EPA 440/1-82/007, June 1982.

Harty, D.M., Funke, D.M., and  Terlecky,  P.M.,   "Dual-Media
Filtration  Treatability Test Results at Zinc Chloride  Plant
F144,"  Report   No.    FTA-84-E6-01,    Frontier   Technical
Associates, Buffalo, N.Y., May 1984.
                                29

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                             SECTION 4

                         SUBCATEGORIZATION
 Basis for Subcateqorization

 Factors Considered

 The   inorganic  chemicals  industry is very large and diversified
 and  has been segmented into  subcategories  for  the  purpose  of
 establishing    effluent    guidelines.     Factors   taken   into
 consideration for  subcategorization include:   raw materials  used,
 product produced,  manufacturing  process  employed,   geographical
 location,   size and  age of equipment  and facility involved,  non-
 water-quality aspects of waste characteristics,   water  pollution
 control  technology,   treatment  costs,   energy  requirements and
 solid waste disposal.   Following  is a  discussion  of  each  of   the
 general factors considered  for this industry.

 Raw  Materials

 Different  raw materials are used  to manufacture a wide variety of
 products,   and  vary    from  raw  brines  and ores to pure  reagent
 chemicals.   Some processes  use waste or  by-product  streams   from
 other plants or from  other  processes within the same plant.

 Because of   this  diversification,  raw material characteristics
 generally    do  not    constitute   a    logical    basis    for
 subcategorization.  Variations in  raw material quality  or purity
 are   not   normally  sufficient to   cause  a   great  difference in
 wastewater  treatment  needs,  except   in  the case   of  trace toxid
 materials which may occur in some sources but  not in  others.

 Dominant Product

 Subcategorization  by   chemical   name  of  the dominant  inorganic
 chemical  produced  involves  the  least   ambiguity   in  applying
 standards  to   a given  point source.   This  is  critical because of
 the   great   variety  of  product  mix,  manufacturing  processes,
 wastewater   constituents,   and other  factors at  existing  plants.
 Subcategorization by product becomes less useful  as  product   mix
 increases  in   complexity   because  multi-product  wastewater also
 becomes more complex  and   less   susceptible  to   simple   uniform
 treatment.

A  subcategory   established  on the basis of product manufactured
might have two  or more different processes but, in  the  majority
of  cases, the  characteristics of the wastewaters  are similar  and
                               30

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the same  treatment  technology  can  be  applied  for  different
process wastewaters.  If two or more dissimilar processes produce
wastewater   of   different •  quality,  and  different  treatment
technologies have to be used, then the subcategory may be further
classified or segmented.

Manufacturing Process

Typically, inorganic chemicals are manufactured  for  captive  or
merchant  use in four or more steps starting from raw material to
final product.  Two or more different products might use the same
process but  then  the  raw  materials  used,  process  sequence,
control,  recycle  potential,  handling, and quality control will
vary,   producing   wastes   of   different   quality.    Primary
subcategorization,  therefore,  by  process  is  unlikely  to  be
useful.  However, secondary subcategorization by process  may  be
necessary in some cases.

Geographical Location

Inorganic chemical plants exist in all parts of the United States
but   subcategorization   on   this   basis   is  not  appropriate.
Geographical location is important in analyzing  the  feasibility
of   various   treatment  alternatives.   Evaporation  ponds   are
functional only  in  areas  where  evaporation  exceeds  rainfall.
Ocean dumping and deep well disposal  are possible only in certain
areas,  and must  be  consistent with local, state and federal laws.
The  possibility  of  ground water contamination may preclude  the
use  of  unlined holding and settling ponds in many locations.

In the  northern  regions, climatic conditions may necessitate   the
inclusion  of special provisions to prevent  freezing of treatment
system   components,  particularly  biological  oxidation   units,
clarifiers,  ponds,  and  open  collection systems.  The  costs of
utilizing waste   heat   sources  from  the  process  or  providing
various types of thermal protection,  such as  insulation or burial
of   pipes  and   tanks   and   building  structural shelters, may  add
considerably  to  the capital  and  O&M   cost   associated  with  a
treatment technology.

Thus,   the   influence   of   geography,  climate, geology,  etc., is
reflected  in  wastewater  treatment modifications and  is  primarily
manifested   in   the cost  of  treatment.   This,  of  itself,  is  not  a
good basis for subcategorization.

Plant Size

Plant size and production capacity  were not  found  to   affect   the
characteristics   of the wastewater  produced.   Although  plant  size
                                31

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 can  affect  treatment cost,   this  variability  can  be  expressed
 graphically  or  mathematically  without  the  need  for  further
 segmentation  of the category.

 Plant  Age

 Plant  age can have an important bearing  on wastewater volume  and
 quality  and   is,   therefore,  a significant factor to consider in
 evaluating  the  applicability  of  treatment  technologies   and
 assessing   the  relative  costs of treatment for  plants  of widely
 differing   age  producing   the  same  or  similar  products.     A
 particular  problem  with   older  plants  is  that  their  present
 patterns of water use may have evolved over a long period  of time
 with little consideration for  the principles of   efficient  waste
 segregation,   collection,   and  treatment.    To a limited  degree,
 plant  modernization can correct or  at  least mitigate  some  of
 these  shortcomings  in  older  facilities,  however,  only  a small
 proportion  of the cost of   revamping  collection   systems   or  of
 converting  from  contact   to   noncontact   cooling systems can be
 offset by the resulting lower  cost  of  treatment.    In  general,
 older  plants,   even  after considerable  modernization, normally
 have a higher volume of wastewater flow  and higher waste loadings
 (although pollutant concentrations  may  be  lower  due  to  poor
 segregation  from noncontact sources)  in comparison to relatively
 new plants.   Pollution control  requirements could impose a severe
 treatment cost  penalty on   older  plants  due to  the  need  for
 backfitting  and replumbing of  outdated  collection systems.   Land
 availability  and land use restrictions are  also factors  which may
 translate into  higher treatment  costs  for  older facilities  which
 find   themselves  surrounded   by  highly developed industrial and
 residential areas.

 Unfortunately,  plant  age does   not   readily   lend  itself   to  an
 unambiguous   definition where  a  series of plant modifications has
 taken  place.  The  extent of modifications   also    varies   greatly
 among  plants within  the same product  industry.   For  those plants
 that have been  enlarged or  modified  from their  original   status,
plant  age  is not  unambiguously  calculable  and therefore is  not  a
 reasonable  basis for  subcategorization.

Non-Water-Quality  Characteristics

Airborne emissions  from  manufacturing   operations  can  be   kept
within  air  quality   control limits through  the  use of  cyclones,
wet scrubbers and  other methods.  The  nature  of the air pollution
 is related  to the product(s) manufactured and/or  the raw material
used.  Since both  of  these  elements   vary  widely  within   the
 inorganic    chemicals   industry,   there    is    no   logic    in
                               32

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subcategor i zat ion
characteristics.

Treatment Cost
on
the
basis
of
non-water-quality
From   a   technical   viewpoint,   subcategorization  by  common
technological requirements for treatment processes could  provide
a  logical  basis  for  selecting  one  or more unit processes to
accomplish the same treatment function, regardless of the  source
of  the  wastewater.   For  example, residuals of dissolved heavy
metals will respond to lime precipitation  and  sedimentation  at
high  pH  without  respect  to the specific origin of the metals.
This  "building  block"  concept  could  conceivably, result   in
selecting  various  combinations  of  unit  processes to meet the
treatment requirements.  However, if the treatment cost  must  be
expressed in terms of dollars per unit production, this method of
subcategorization  crosses  product  lines  and  interferes  with
comparison of treatment  costs  based  on  the  production  of  a
specific  chemical.   .Even  if  the  unit  operation  is commonly
applicable for treating wastewater flows of  different  products,
the  cost  of  treatment  will fluctuate because of variations in
wastewater quality, loading and flow rates, and subcategorization
on the basis of treatment cost is not recommended.

Energy Cost

Manufacturing  processes  in  the  Inorganic  Chemicals  Industry
typically   have   large   energy   requirements.   In  contrast,
wastewater treatment processes consume a small  fraction  of  the
total   energy  used.   There  appears  to  be  no  major  energy
requirements  for  wastewater  treatment  facilities,   therefore
subcategorization on the basis of energy cost is not justified.

Solid Waste                                              .

Not  all  inorganic manufacturing processes produce solid wastes.
Solid waste producers practice various disposal methods, such  as
on-site   landfills,  contract hauling to approved disposal sites,
or incineration.  Solid waste disposal becomes very site specific
and exhibits a wide range of  costs.   Because  of  the  lack  of
uniformity  within  the  industry,  solid  waste  generation  and
disposal   practices   are   not   a   satisfactory   basis   for
subcategorization.

General Conclusions

If effluent limitations are to be tied to effluent concentrations
or   units   of   production,   only   one   method   of  primary
subcategorization   is  broadly  applicable   to   the   inorganic
                                33

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ch'emicals  point  source category, namely subdivision by dominant
product.   Within  the  seventeen  chemicals  studied,   it   was
determined  that  wastewater  characteristics were more dependent
upon the cation (metal) involved than the anionic species.   Many
processes  within a group of compounds were found to be basically
similar and wastewater treatment processes expected  to  be ' used
would  be similar.  In fact, at many plants, many of the products
were produced utilizing batch processes  (e.g., copper  carbonate,
copper  sulfate,  and  copper nitrate may be produced at the same
plant at different times).  Wastewater treatment  process  design
at these plants focuses on treatment of  dissolved and particulate
metals,  TSS,  and pH.  These treatment  plants must be capable of
performance with a variety of wastewater streams.

From a cost standpoint, most plants in   the  Phase  II  chemicals
group  will not be impacted in the same  way as many large, single
product plants in Phase I because the  treatment  costs  incurred
can  be  allocated  to a large variety of products at the plants,
not just a single product  or  product   group.   Therefore  costs
expressed  in  this document may overstate the actual costs to be
incurred.

To  allow  a  workable  subcategorization  scheme,  the   factors
described    earlier    were   considered   and   the   following
subcategorization scheme is recommended:

I.   Cadmium Pigments and Salts

II.  Cobalt Salts

III. Copper Salts

IV.  Nickel Salts

V.   Sodium Chlorate

VI.  Zinc Chloride

It  is  recommended  that  separate  effluent   limitations   and
standards be promulgated for each of the six groups listed above.
This   subcategorization   allows   separate  limitations  to  be
established  within  groups  of  chemicals  whose  wastewater  is
basically similar, employ similar processes and raw materials and
would  be  expected  to  utilize  similar or identical wastewater
treatment within the subcategory.

Chemicals  Covered.   It  is  recommended,  therefore,  that  the
seventeen  chemicals  considered  in  Phase  II  be subdivided as
follows:
                               34

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I.   Cadmium Pigments and Salts

     A.   Cadmium Pigments
     B.   Cadmium Chloride
     C.   Cadmium Nitrate
     D.   Cadmium Sulfate

II.  Cobalt Salts

     A.   Cobalt Chloride
     B.   Cobalt Nitrate
     C.   Cobalt Sulfate

III. Copper Salts

     A.   Copper Carbonate
     B.   Copper Chloride
     C.   Copper Iodide
     D.   Copper Nitrate

The Copper Salts subcategory also includes Copper Sulfate.

IV.  Nickel Salts

     A.   Nickel Carbonate
     B.   Nickel Chloride
     C.   Nickel Fluoborate
     D.   Nickel Nitrate

The Nickel Salts subcategory also includes Nickel Sulfate.

V.   Sodium Chlorate

VI.  Zinc Chloride

EPA  is  replacing  two  subcategories  with   new   consolidated
subcategories.   Subpart  AJ  (Copper  Sulfate)  is  replaced  by
Subpart AJ (Copper Salts) which includes copper  sulfate,  copper
chloride,  copper  iodide,  copper nitrate, and copper carbonate.
Subpart AU (Nickel Sulfate) is replaced  by  Subpart  AU   (Nickel
Salts),  which  includes  nickel sulfate, nickel chloride, nickel
nitrate, nickel fluoborate, and nickel carbonate.
This subcategorization is used for the following reasons:
     a.
Many facilities produce copper sulfate  or  nickel
sulfate  as  well  as other copper or nickel salts
covered in these subparts.  The wastewater streams
are typically commingled  and  sent  to  a  common
wastewater treatment system.
                               35

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     b.
     c.
     d.
     e.
The production  processes  for  copper  or  nickel
sulfate . and  the  other  copper  or  nickel salts
covered in this subpart are very similar.

Wastewater flows and pollutant characteristics are
very similar for copper or nickel sulfate and  the
other copper or nickel salts.

Wastewater treatment  processes  which  have  been
determined to be effective in the copper or nickel
sulfate  industry  are  the  same as for the other
salts.

Levels of treatability are the same for copper  or
nickel  sulfate  and  the  other  copper or nickel
salts.
The exception to the above is  the  copper  or  nickel  carbonate
production  industry.   Copper  carbonate  is  a separate segment
within the Copper Salts subcategory and  nickel  carbonate  is  a
separate  segment within the Nickel Salts Subcategory because the
wastewater unit flows at copper carbonate  and  nickel  carbonate
facilities  are  substantially  greater  .than  at other copper or
nickel salts facilities covered in these subparts.

The  Agency  is  excluding  106  subcategories  from   regulation
primarily   because   the  discharges  from  all  plants  in  the
subcategory are insignificant.   The  Agency  is  also  deferring
regulation  of  one  subcategory for coverage under another, more
appropriate, point source category.  The Agency first  considered
consolidating  many  of  those subcategories by dominant metal to
develop new larger subcategories.  However, in  many  cases  this
consolidation  was  technically infeasible because the production
process, water use, raw material, and  expected  pollutants  were
too  dissimilar.  In the remaining cases, the combined discharges
from all  plants  in  the  consolidated  subcategories  are  also
insignificant  and  would  therefore  be  proposed for exclusion.
These  cases  are  noted  in  Section   19   infra.    Only   the
consolidations  of  the 17 subcategories just described above are
both technically feasible and result in  new  subcategories  with
significant   discharges.    The   Agency   would  have  proposed
exclusions for several of the nickel salts, copper salts,  cobalt
salts, and cadmium salts in the absence of this consolidation.
                               36

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                            SECTION 5

                        SAMPLING PROGRAM
SCOPE AND METHODOLOGY

The  specific   objective   of  the   sampling   program  was  to
establish  the  extent  of  the  required  regulation  of   toxic
pollutant discharges in the inorganic chemicals industry in terms
of  factual  information  derived  from the chemical analysis and
flow measurement of representative process raw wastewater streams
and  treated  effluents.   Prior  to  this  study,  most  of  the
information available on toxic pollutants has been concerned with
a  relatively  small  number  of known process-related substances
contaminating a variety of direct and  indirect  contact  process
waters  discharged from a production facility.  There had been no
previous requirement for a  comprehensive  survey  of  wastewater
chemistry addressing the possibility that a large number of other
potentially   toxic   substances  could  be  present,  albeit  at
extremely low concentrations.

The sampling program was designed to ascertain  the  presence  in
each subcategory of any of the 129 listed toxic pollutants at raw
waste concentrations or daily loadings which, if untreated, could
be  environmentally  significant.   The  program was based on the
sampling of one or more typical manufacturing operations in  each
subcategory  to  confirm  and  quantify  the  presence  of  toxic
pollutants.   (A goal was set for sampling of a sufficient number
of plants to account for at least 20 percent of  the  total  U.S.
plants, in each subcategory.)
A  detailed  description of the
the paragraphs below.
sampling program is presented in
Selecting Plants and Making Preliminary Contacts
In each subcategory, plants were selected
basis of the following general criteria:
          for  sampling  on  the
     A.   Minimal product mix and no organic product lines which
          could increase the potential for interprocess cross
          contamination of wastewater;

     B.   Presence of a physical-chemical treatment facility
          rather than a biological one, or no treatment system;

     C.   Manufacture of industrial grade products in volume,.
          rather than low volume reagent grade* products;
                               37

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     D.   Median production capacity within the subcategory;

     E.   Segregated wastewater streams to facilitate sampling;

     F.   Direct discharges rather than discharges to POTWs were
          usually preferred, since treatment for a direct
          discharge is usually more extensive;

     G.   Geographical clustering of selected plants to
          facilitate field logistics, but only to the extent that
          other factors are equal.

*Chemicals produced of high purity, generally with production
 rates of less than 4.5 kkg/yr {
-------
     for  the  13  toxic metal pollutants, cyanide and phenol, as
     well as  the  conventional  and  non-conventional  pollutant
     paramaters   associated  with  the  particular  subcategory.
     Where automatic compositing was not possible, grab   samples
     were  taken  at approximately 2-hr intervals during the same
     sampling period and composited manually.

     During one particular 24-hour composite period of the  three
     days,  samples  were  taken  and  analyzed for all 114 toxic
     organic pollutants and asbestos.  The non-volatile  organics
     were  taken  from  the  chosen  daily composite sample while
     volatile organics and asbestos  samples  were  collected  as
     grab samples or grab composite samples.

     Each sample was divided into several portions and preserved,
     as  required  for different types of analysis, in accordance
     with  the  procedure  established  by  EPA   (1)   for   the
     measurement of toxic pollutants.

     Volatile  organics were collected in teflon-sealed screw cap
     vials.  Eight 40 ml vials were filled at each sampling  site
     by  grab  sampling in pairs at approximately 2-hr intervals.
     The individual vials were cooled to 4°C and shipped  to  the
     laboratory  where  they  were  used to prepare composites in
     duplicate  just  prior  to  analysis.   Three  blank   vials
     prepared  and  sealed in the laboratory accompanied each set
     of samples during collection, shipment, and storage.

B.  Sample Shipping

     All samples, individually  labeled,  were  placed  in  large
     plastic  bags,  which  were  then  placed  in  a  waterproof
     insulated shipping container.  Enough ice  was  included  to
     maintain  a  temperature  of  approximately, four  degrees C
     during shipment to the laboratory.

     Containers were shipped by the best available route, usually
     air freight, usually arriving at the laboratory on the  same
     day,  but  occasionally taking overnight.  Upon receipt, all
     samples were immediately placed in  a  walk-in  refrigerator
     maintained at 4°C.

     In order to maintain the chain of custody and to maintain an
     account  of samples, sampling personnel kept logs of samples
     taken in ink in page-numbered, hard-bound books.   The  data
     recorded  included:   date, time, plant code, number, sample
     type,  and sampler.  This information was also  included  on
     the   label of individual samples.  Prior to their arrival at
     the laboratory, a list of samples shipped, including number,
                               39

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     type of samples, and analysis  to be performed, was  sent   to
     each department supervisor  to  alert him  of  incoming work.

     A  master  analytical  control  chart  was   maintained which
     included? date sample was received,  date  due,  number   and
     type of each sample, and the analysis required.

     At  the  time  of  analysis,   the  individual  samples  were
     distributed to the analytical  chemists  along  with  a  list
     which  included:  I.D.  number  of  sample,  type of sample,
     analysis required, date samples received, and due dates.

     All samples were kept in a  laboratory  refrigerator  at   4°C
     when  not  being handled by the analyst.  Upon completion of
     analysis, the  sample  was  checked  back  into  the  Sample
     Control Department and kept in an identified location in  the
     Sample  Control refrigerator.  A report of completed samples
     was then sent to the EPA Sample Control Center.

Analytical Methodology for Toxic Pollutants

The protocol for the analysis of toxic pollutants was established
in Sampling and Analysis Procedures for  Priority Pollutants   by
U.S.  Environmental  Protection  Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio, April 1977.  The Agency
subsequently proposed very similar methods  on  December 3,  1979
(44  FR  69464)  under  8304(h) of the Act.  We used the proposed
304(h) methods of analysis for toxic organic pollutants  and   the
promulgated   304(h)   methods  for  analysis  of  toxic  metals,
conventional and non-conventional pollutants (40  CFR 136).

The specified  analytical  methodologies  were  employed  without
modification  except  where  noted below in connection with toxic
metals analysis.

Implementation  of  the   methodology   and   quality   assurance
provisions  required the establishment of special sample handling
and control  procedures  specifically  suited  to  each  type  of
analysis.   These  procedures,  together with a discussion of  the
achievable detection  limits  for  each  parameter  or  group  of
similar parameters are presented in the following paragraphs.

A.  Trace Metal Analysis

     Figure  5-1  shows  a data flow diagram for metals analysis.
     Atomic absorption  methods  described  in  40  CFR  136  per
     Section  304(h) were used.   A set  procedure was followed  in
     the laboratory to generate the  analytical   values  and   the
     quality  control  data.    The  data  flow  diagram shows  the
                               40

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41

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actual sequence employed in the analytical program  and  the
following  notes,  which  are  keyed to the diagram, provide
additional information on the procedures:
1
Blanks —  two  for  each  set  of  analyses  digested.
Duplicates — one every seventh sample.

Quality Control at Operator Level  (Atomic Absorption):

     Blanks - These were run at the beginning  and  the
     end  of  every set analyzed for each metal.  Also,
     air blanks were run on furnace, or heated graphite
     atomizer, (HGA), after any  sample  with  a  large
     positive value.

     Standards  -  Three  different concentrations were
     run at the beginning and end of every set analyzed
     for each metal.  Standards  were  also  run  every
     tenth sample during the analysis of a set.

     Spikes  -  These  were  made  according to the EPA
     "Method of Standard Additions," by adding  such  a
     volume  of  standard  as  to  double  the apparent
     concentration of  metal  present  in  the  sample.
     Extrapolation    backwards    of   the   resultant
     absorbances allowed correction of  absorbance  for
     matrix effects.

     Duplicates  - For furnace analysis, the sample was
     run twice wherever a low but  positive  absorbance
     was  obtained.   In  addition, one sample in every
     seven was run in duplicate routinely.  The average
     of duplicate measurements was the taken value; the
     difference  between  duplicate  measurements   was
     noted   and   recorded   on  control  charts.   If
     reproducibility was  outside  the  limits  of  +33
     percent, the measurement was repeated.
3.
UTD   =   "Unable
interferences.
To   Determine"   due   to   matrix
4.   Criteria Employed in Spike Selection:

     a.   Samples were chosen to be spiked
          following criteria:
                                       based  upon  the
               All samples where  there  was  any  suspicion
               that   interference   or  matrix  effect  was
               present.
                          42

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                b.
     All   samples   containing
     concentration of analyte.
     In addition, at least  one
     seven.

The level of spike chosen was
following factors:
                                                        a    measurable

                                                      sample  in  every
controlled  by  the
                c.
     It should approximately double  the  apparent
     concentration.
-    If this results in an absorbance greater than
     that of  the  highest  standard,  the  spiked
     sample  is  suitably  diluted  with distilled
     water.

A reagent blank was run with each  set  of  spiked
samples prepared.
           During the sampling program*, the standard protocol followed
           for metals analysis was:

           1.   Ten of the  13  toxic  metals  were  determined  by  AA
                spectrophotometry  in  the furnace mode, namely Ag, Be,
                Cd, Cu, Cr, Ni, Pb, Tl, Sb and Zn.

           2.   If matrix interference were seen, samples  were  spiked
                and redetermined.

           3.   If  difficulties  due  to  excessively  high  detection
                limits  were found for the four elements Cd, Pb, Sb and
                Tl, the determination was repeated in the furnace  (HGA)
                mode for these four elements.

           4.   Selenium  and  arsenic  were  determined   by   hydride
                generation using sodium borohydride (NaBH4).

           5.   Mercury was  determined  by  the  standard  cold   vapor
                method.

      *During  the Phase I program, excessive interferences with metals
      analyses were encountered in some subcategories which were solved
      by changing the AA methods to the flame mode.  During  Phase II,
      the  flame  mode  was  used  as  the  first  step (because of the
      experience in Phase  I),  but  when  excessively  high  detection
      limits   were   found,   the  furnace  mode  was  used  to   allow
      determination with lower detection limits.

      Table 5-1 presents the analytical detection limits of the various
      methods for the 13 toxic metals.
                                     43
_

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      TABLE 5-1.  ANALYTICAL DETECTION LIMITS FOR TOXIC METALSd)
Method Detection Limit (ug/1) (2)
Element
Flame
Method
Furnace
Method (HGA)*
Gaseous
Hydride
Method
Cold
Vapor
Method
Antimony, Sb
Arsenic, As
Beryllium, Be
Cadmium, Cd
Copper, Cu
Chromium, Cr
Lead, Pb
Mercury, Hg
Nickel, Ni
Selenium, Se
Silver, Ag
Thallium, Tl
Zinc, Zn
200
5
5
20
50
100
0
0
1
1
1
.2
.1



 40

 10
100
  5
0.2
1
0.05
                                      0.2
*  Heated Graphite Atomizer
(1)   Assuming no matrix interferences requiring dilution of sample.
(2)   "Methods  for  Chemical  Analysis  of  Wastes  and  Water,"  USEPA
      Environmental  Monitoring   and  Support  Laboratory   office  of
      Research and Devlopment, Cincinnati, OH   (March 1979). This
      Manual has been revised periodically to incorporate slight changes
      in methods and to add  alternate methods.  Methods used in Phase  II
      are the same as have been used previously in Phase I, and the data
      are directly comparable.
                            44

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B.   Organic Compound Analysis

     The organic toxic pollutants were determined by the standard
     protocol (40 CFR 136 proposed December 3, 1979, 44 FR 69464)
     which   includes   sample   preparation,   extraction,   and
     analytical    methodologies    (Methods    624    and   625,
     "superscreened").  "Superscreening" is the term utilized  by
     the  Agency  to  denote  a  series  of procedures which were
     utilized for organic parameter analyses during Phase II.  In
     these procedures, one sample from each sampling episode (for
     each site) was split and analyzed in  duplicate  to  provide
     information   on   the  precision  of  the  method(s)  being
     employed.  At one site, for one day, replicate samples  were
     taken  for  recovery  information (may be same site at which
     precision  sample  was  obtained).   The  same  pattern  was
     followed  for  VOA  samples  for  quality  assurance/quality
     control.  During the Phase II program, organic analyses were
     performed at each sample site on one day (usually the second
     day).

     Extractions were carried out using methylene chloride in the
     case of the acid and base/neutral organic fractions and with
     hexane/methylene chloride to obtain the pesticide-containing
     fractions.  The acid and base/neutral fractions were reduced
     in  volume   and   analyzed   by   gas   chromatography-mass
     spectrometry   (GC/MS).  The  pesticides  were  analyzed  by
     electron  capture  gas  chromatography  followed  by   GC/MS
     confirmation  of  positive  results.  Volatile organics were
     analyzed by the purge and trap  method  of  introducing  the
     material into the GC/MS inlet system.

C.   Cyanide Analysis

     The standard methods for the wet chemical analysis of  total
     cyanide  and  cyanide  amenable  to chlorination (Cyanide A)
     were utilized (40 CFR 136).  Cyanide analysis is subject  to
     several sources of interference including:

     1.   Metals - The presence of Fe, Cd, Ca, Ni, Ag, and Zn may
          cause measurement errors on the low  side  due  to  the
          formation  of  stable complexes with cyanide.  The iron
          complexes may form  insoluble  precipitates  which  are
          particularly  difficult to break up both at the time of
          treatment  (alkaline  chlorination)  of   the   sampled
          wastewater   and   during  the  chemical  analysis  for
          cyanide.

     2.   Oxidizing agents - The  presence of  free  chlorine  in
          the  wastewater  sample  will destroy cyanide and cause
                               45

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     3.
measurement errors on the low side.  The  addition   of
ascorbic  acid  to  destroy  chlorine  at  the  time of
sampling is intended to mitigate this  problem.   Other
oxidizing  agents  such as peroxides and chromates  may
also react with cyanides over  a  period  of  time  and
cause low results.

Sulfides - Sulfide or bisulfide will interfere  in  the
analysis  of  cyanide by reacting with the colorimetric
reagents.
     The  presence  of  sulfur  dioxide  or  bisulfite    in    the
     wastewater  sample  should   have  no  appreciable  effect on
     cyanide results.  Detection  limits on the order of 1-4   vg/1
     can  be  achieved by the analytical method employed, but  the
     results have to be interpreted with regard to  the   possible
     interfering components of the sample.

D.   Asbestos Fiber Analysis

     The  analysis  of  selected  samples  for   asbestos  fiber
     (chrysotile)   was   conducted  by  the  recommended method
     utilizing transmission  electron  microscopy  with   selected
     area  electron  diffraction  as  described  by  Dr.  Charles
     Anderson (EPA, Athens, Georgia) at the  Analytical   Protocol
     Meeting in Denver (November  1977) (2).

E.   Conventional and Nonconventional Pollutants

     All techniques used for the  analysis  of  conventional   and
     nonconventional  pollutants  were  those  recommended by  the
     Agency.  The list of approved test procedures was  published
     in  the  Federal  Register on October 16, 1973 (38 FR 28758)
    . and amended December 1, 1976 (41 FR 52780) and may   be  also
     found in Title 40 of the Code of Federal Regulations (40  CFR
     136).

Quality Assurance Provisions

The  Agency and the contractor's analytical laboratories  maintain
consistently high standards for accuracy and quality control.  As
an in-house requirement, a minimum of ten percent of all  samples
are  routinely  run  in  duplicate.   Quantification  is  based on
standards which are prepared in  pure  water,  at  concentrations
such that all sample measurements are greater than the absorbance
of  the  lowest  standard,  and  less  than the absorbance of  the
highest  standard.    The   standards   are   also   checked   by
participation in the EPA Reference Sample Program that utilizes a
                               46

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double  blind  technique.
Research and Development.)
(EMSL,   Cincinnati,   Ohio,   Office of
Additionally, outside laboratories are  retained  for  checks  on
quality   by   analyzing  split  samples  and  running  submitted
standards.  Accuracy is also insured by analysis of a minimum  of
fifteen  percent  of  all  samples  with  spikes by the method of
standard  additions.   The  spikes  are  added  prior  to  sample
preparation  and  are  carried through the entire sample analysis
procedure.

The contractor's laboratories have  consistently  maintained  the
standards  for  laboratory certification which are imposed by the
State  of  California.   Certification  is  dependent  upon   the
accurate   performance  of  routine  analyses  on  check  samples
submitted by the State, as well as  on-site  inspections  by  the
State   of  California's  Sanitation  and  Radiation  Laboratory,
Department  of  Fish  and  Game,  and  the  U.  S.  Environmental
Protection Agency, NEIC, Denver, Colorado.

The quality assurance provisions outlined in the EPA Protocol for
GC/MS Analysis of Toxic Pollutants are rigorously adhered to with
one  added precaution, namely, the use of internal standards as a
means of  measuring  recovery.   Although  not  required  by  the
protocol for pesticide analysis, this technique is utilized as an
in-house  quality  control  requirement to ensure the accuracy of
results in this analysis.
The high sensitivity of instrumentation  used
chemical analysis dictates that contamination
any   possible   source   must  be  diligently
Accordingly, only glass sample containers with
were  used  and  these  were  subjected  to a
procedure prior to use, even though only  new
containers  were used.  All glassware used for
and analysis was subjected to a dual cleaning
                   in  trace  organic
                  of the samples from
                    guarded  against.
                   Teflon-lined  lids
                  three step cleaning
                   liners  and  glass
                   sample preparation
                  system.
The sample extraction and preparation rooms are dedicated  solely
to  toxic  pollutant  analysis,  and  have  their own ventilation
systems that are isolated from the other sample  preparation  and
receipt areas of the laboratories.

A documented system of existing practices, including calibrations
and  operational  checks  is  maintained to  assure uniformity of
performance  and  to  serve  as  a  basis   for   alteration   of
standardization  intervals.   A  chemist is assigned full time to
maintain  this  system,  assure  strict  record  formatting   and
controls,  and  to  direct  the  quality  control  program of the
laboratories.  The primary vehicle of this system is the  quality
                                47

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assurance  manual  containing  the  detailed  procedures  used in
sample preparation and analysis,-and the complete records of  all
quality control standards, blanks, spikes and duplicates.

SUMMARY OF ANALYTICAL RESULTS

There  are 46 plants producing the 17 chemical products listed in
the six proposed  subcategories.   Many  plants  produce  several
products  listed  under  the Phase II program as well as products
also covered under Phase  I  previously.   Thirteen  plants  were
visited  during  the  sampling program for this study.  One plant
was sampled twice.                                      .

The results obtained during the sampling program  are  summarized
in  Table  5-2  and  5-3.   These  tables  show the frequency and
distribution  of  the  pollutants  according  to  selected  plant
groupings,  concentration  ranges, and subcategories in which the
pollutants occur.

Pollutant frequencies  are  based  upon  the  highest  individual
pollutant  concentration  found  for each plant's raw and treated
wastewater during the sampling program.

The toxic pollutant asbestos has not been included in  either  of
the  tables  mentioned  above.  Asbestos concentrations for those
sites sampled for asbestos are reported in Table 5-4.  All values
are expressed as million fibers per liter (MFL) or mass per  unit
volume.

The treated effluent concentration of asbestiform fibers observed
in  this  industry group is considered to be low and close to the
limits of detection of the methods employed.
                               48

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TABLE 5-2.  POLLUTANT FREQUENCY BASED ON SAMPLING
      RESULTS (RAW AND TREATED WASTEWATER)*
                            Pollutant Occurrence Based on
                                 Concentration  (ug/1)

IB
3V
4V
6V
7V
10V
11V
12B
13V
14V
16V
18B
21A
23V
24A
27B
29V
30V
31A
32V
37B
39B
44V
45V
47V
48V
49V
51V
54B
56B
58A
59A
60A
62B
64A
65A
66B
67B
68B
Priority Organics Detected**
acenaphthene
acrylonitrile
benzene
carbon tetrachloride
chlorobenzene
1 , 2-dichloroethane
1 , 1 , 1-tr ichloroethane
hexachloroethane
1 , 1-dichloroethane
1 , 1 , 2- tr ichloroethane
chloroe thane
bis (2-chloroethyl) ether
2 , 4 , 6- tr ichlor ophenol
chloroform
2-chlor ophenol
1 , 4-dichlorobenzene
1 , 1-dichloroethylene
1 , 2-trans-dichloroethylene
2 , 4-dichlorophenol
1 , 2-dichloropropane
1 , 2-diphenylhydrazine
f luoranthene
methylene chloride
methyl chloride
bromoform
d ichlor obromome thane
trichlorofluoromethane
chlorodibromomethane
isophorone
nitrobenzene
4-ni tr ophenol
2, 4-dinitrophenol
4 , 6-dinitro-o-cresol
n-nitrosodiphenylamine
pentachlor ophenol
phenol
bis(2-ethylhexyl) phthalate
butyl benzyl phthalate
di-n-butyl phthalate
>50 >500
but but
<50 <500 <2500 < 2500
4 • ' -• . . ' •
2
••17 2
6 3
1 6
1 24
4
1
8
6
5
2
3
43 9 1 1
1
1
7
5
2
3
2
1
45 2 5
52 3
4 1
21
6 1
16
2
1
1
1
1
1
4
7
37 1
7
31
                     49

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TABLE  5-2  (continued)
                                    Pollutant Occurrence Based on
                                    	Concentration  (ug/1)
     Priority Organics Detected
<50
>50
but
<500
>500
 but
<2500
< 2500
69B di-n-octyl phthalate
70B diethyl phthalate
7 IB dimethyl phthalate
72B benzo (a) anthracene
76B chrysene
81B phenanthrene
85V tetrachloroethylene
86V toluene
87V trichloroethylene
88V vinyl chloride
89P aldrin
90P dieldrin
91P chlordane
92P 4,4' -DDT
93P 4,4' -DDE
94P 4,4' -ODD
95P a-endosulfan
96P $-endosulfan
97P endosulfan sulfate
98P endrin
100P heptachlor
101P heptachlor epoxide
102P a-BHC
103P B-BHC
104P Y-BHC
105P 6-BHC
14
17
2
4
5
1
12
18
7
5
9
10
1
2
9
10
3
4
3
4
8
3
27
4
14
30
*Blank spaces in this table denote concentration levels which did not
 occur in the wastewater samples analyzed.

**A - Acid fraction
  B = Base/Neutral fraction
  V - Volatile fraction
  P s Pesticide fraction
                            50

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           TABLE  5-3.  PRIORITY ORGANICS DETECTED  BY
      SUBCATEGORY (RAW AND TREATED WASTEWATER;  >_ 10  ug/1)
Priority Organics Detected
3V
4V
6V
10V
12B
16V
18B
21A
23V
31A
37B
44V
45V
47V
48V
49V
51V
54B
58A
59A
60A
64A
65A
66B
6 SB
69B
85V
86V
88V
103P
acrylonitrile
benzene
carbon tetrachloride
1 , 2-dichloroethane
hexachloroethane
chloroethane
bis (2-chloroethyl) ether
2 , 4 , 6-tr ichlorophenol
chloroform
2 , 4-d ichlorophenol
1 , 2-d ipheny Ihydr az i ne
methylene chloride
methyl chloride
bromoform
dichlorobromome thane
trichlorof luoromethane
chlorodibromome thane
isophorone
4-nitrophenol
2 , 4-dini trophenol
4f 6,-dinitro-o-cresol
pentachlorophenol
phenol
bis(2-ethylhexyl) phthalate
di-n-butyl phthalate
di-n-octyl phthalate
tetrachloroethylene
toluene
vinyl chloride
S-BHC
Subcategory
5
5
5, 6
5
5
5
1
3, 5
1, 3, 4, 5
5
3
1, 3, 4, 5, 6
5
3
3, 5
5
3
1
1
1
1
1
5
1. 3 .
1
5
3
3
5
3
Subcategory

1 = Cadmium Pigments and Salts
2 = Cobalt Salts
3 = Copper Salts
4 = Nickel Salts
5 = Sodium Chlorate
6 = Zinc Chloride
                            51

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           TABLE-5-4.  OCCURRENCE  OP ASBESTIPORM FIBERS  BY PLANT
Plant
P122
F102
F102
F107
F107
(Shaken)
F107
(Settled)
F134
F134
F134
F134
F117
F117
F117
Influent/
Effluent
E
I
E
Ed)
E
E
I
I
E
E
I
E(2)
E(2)
Total
Fibers
(MFL)
85
283
<7
1630
1100
840
186
7.2
<3
16.2
0.96
12
5.4
Chrysotile
Fibers
(MFL)
20
170
<7
15
890
252
<6
<1.2
<3
1.2
<0.12
<1.2
<0.3
Detection
Limit
(MFL)
0.8
56.7
7
15
12
12
*
6
1.2
3
0.6
0.12
1.2
0.3
Total
Calculated
: Mass
(Chrysotile
only) ug/1
0.3
4.51
	
0.3
5.4
2.7
	
	
	
0.017
	
—
	
  I = influent
  E = effluent
MFL = million fibers per liter
(1)  Untreated
(2)  Two different waste streams
                                 52

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                            SECTION 5
                           REFERENCES
1 .


2.
Sampling Screening Procedure for the Measurement of Priority
Pollutants, U.S. Environmental Protection Agency,, 1976, 6pp.

Anderson,  C.  H.  and  Long,  J.  M.   Interim  Method  for
Determining   Asbestos   in  Water.  EPA-600/4-80-005,  U.S.
Environmental Protection Agency, Athens, Ga.,  1980.
                                53

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                             SECTION 6

           PROCESS AND WASTEWATER TREATMENT INFORMATION
                    DEVELOPMENT AND EVALUATION
 INDUSTRY  DATA BASE DESCRIPTION

 Information  and data on  the   inorganic   chemicals   industry  were
 obtained   from  a   number  of  sources.     These sources  included
 literature reviews,  plant  visits,  telephone contacts,  lead   visit
 reports,   industry  responses  to   the   Agency's request  for data
 under  Section 308  of the Act  (the  "Section   308-Questionnaires"),
 visits by  EPA personnel,   self-monitoring  (NPDES)  reports and
 additional data supplied by industry  after publication  of  the
 proposed   regulation.    The   type  of material  gathered from these
 sources is discussed below.

 Literature Review

 A review  of  the literature was  conducted to identify and  collect
 information   related to manufacturing  processes,  raw materials,
 water  use, wastewater sources,  wastewater   treatment   technology,
 raw    waste    characteristics,   and   economic  data.    Relevant
 information  from reports, books, papers, conference presentations
 and periodicals were  identified   by  computer  search   and  are
 presented    in   the  reference  section  of  this   report.    This
 information  was incorporated  into   a  broad-based   assessment of
 process   and  technology practices  aimed   at selecting  the best
 available  treatment  technology  and  best  demonstrated   technology
 for  the   various   industry subcategories.   It also provided  the
 background required  for  evaluating  the proposed subcategorization
 of the chemical  products.

 Plant Visits

 During the screening and verification phase  of this project,  much
 information  was  gathered  from  individual  plants  relating  to
production  capacity, manufacturing processes, waste flows,  water
reuse, wastewater  treatment systems  and  performance,  and   best
management  practices  (BMP).    In October and November 1982, EPA
personnel  visited  12 plants to update and  clarify  some  of  the
 information  given  in the Section 308-Questionnaires.  Nine of the
twelve had not  been visited previously in this study.

Telephone  and Direct Contact

Numerous   contacts  were  made with knowledgeable persons in both
 industry and  government  to   gather  and  exchange   information
                               54

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concerning all phases of this study.
the text as personal communications.

308-Questionnaire Responses
These sources are cited in
The  basis  for  much  of the work in this study is the responses
from industrial inorganic chemical firms to the Section 308  data
requests.

Data  from all of the 46 plants were utilized by the project team
for the development of appropriate guidelines for  the  inorganic
chemicals   subcategory.    Industrial   firms,   through   their
compliance with  the  needs  of  the  Section  308-Questionnaire,
provided  a  valuable industry-wide data base used extensively in
this analysis.

Essential data elements from the questionnaires were used for the
purpose of creating a working data base  for  this  report.   The
types  of information obtained for the data base are presented in
Table 6-1.

These data provided the basis for the subcategory review  through
a   profile   of   each  industry.    After  compilation  of  the
questionnaire data, industry totals  for capacity and  production
(for  the  respondents)  were available.   In addition, derivative
quantities such as  percent  utilization,  effluent  per  ton  of
product,  and conversion to metric units were compiled.

Treatability Study

Beside   the  treatability  study  conducted  during  Phase   I,   a
treatability study was  conducted during  Phase   II  at  one   zinc
chloride facilityO).   The  purposes  of this  study  were  to
evaluate the effectiveness of granular media   filter  technology,
to establish  a  relationship between  total and  dissolved zinc in
the  treated   process   water  effluent,  and   to  determine   the
treatment levels  attained by filtration technology  for TSS,  total
zinc, total  lead,  and  total arsenic.   This study was conducted in
April 1984 and is described  in more  detail in  Section  16.

New Data

Public   comments   on   the  proposed  regulation were a  significant
source  of new  data.   Industry  commenters supplied   extensive new
 long-term data   on   treatment  efficiency  in  the cadmium pigments
and salts industry, providing  both  influent  and effluent data for
our evaluation.   In  addition,  one EPA Regional office  provided   a
 compliance   monitoring  and  inspection report  for  a zinc  chloride
                                55

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plant which  greatly  assisted  our  understanding  of   the  treatment
process and  efficiency  at  that  plant.

PROCESS WASTEWATER SOURCES AND  CURRENT  TREATMENT PRACTICES

Data Acquisition

The  information  presented  in  this section was  obtained  from  a
variety of published sources  and  the available  industry  responses
to the 308-Questionnaires   as  well  as  from   plant   visits   and
interviews   with  industry personnel conducted by the Agency  and
its  contractors  during   the  toxic  pollutant   screening    and
verification program.  The results of  visits and  interviews were
documented in field  notebooks  for  the  preparation   of  interim
plant visit  reports  and telephone communication records which  are
both part of the rulemaking record.

Plant  visits were particularly useful for obtaining the detailed
technical information necessary for creation of  the   data  base.
The   cooperative    attitude    displayed   by   industry  greatly
facilitated  the  acquisition  of  reliable  operating  data   and
meaningful sampling  results.

Evaluation of. Data

Each  of  the  various industrial subcategories in which sampling
was conducted was the  subject  of  an  extensive  evaluation  to
provide  the  technical  basis  for  selecting  candidate advanced
treatment  technologies  and  developing  the   related  base   and
incremental cost estimations.
                               56

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      TABLE 6-1 .   308 QUESTIONNAIRE RESPONSE DATA ELEMENTS

              INORGANIC CHEMICALS GUIDELINES STUDY
Datum Reference
                           Description
  Comments
Manufacturer
Product
Plant
Process
Effluent Treatment
                         Name
                         Location
                         EPA Region

                         Name
                         Subcategory

                         Number of other
                          Products

                         Capacity

                         Production
                         Age

                         Name
                         Volume of Process
                          Effluent
                         Volume of Noncontact
                          Effluent
Confidential
                                               Inorganic
                                                 Chemicals
Primarily
FY 1980
Operating Days
                         Type
                         Permit Number, or
                         POTW District
                         Major Pollutants
                         Long-term Treatment
                          Results

Costs                    Wastewater Treatment
                          Facilities and Equipment
                         Treatment Reagents
                         Energy
                         Solid and Hazardous
                          Waste Disposal

Individual  plant descriptions are presented later in this report
according to the following general format for each subcategory:

      General Process Description
        Description of process reactions and unit operations.
        Inventory of raw materials used.
        Typical process flow diagram.
                                57

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      Water  Use and Waste Source Inventory
         Description of individual  plants visited,  sampled
          and plant  information from other sources.
         Inventory of water uses for contact  and noncontact
          purposes.
         Inventory of raw process wastewater  sources  and
          identification of sampling points.
         Process wastewater quality and flow  data.
         Solid waste generation and disposal.

      Control and Treatment Practices
         Description of specific treatment technologies
          and operating facilities.
         Description of the total input to the  treatment system
          including  sources attributed  to other production
          operations and noncontact water -(e.g.,  cooling
          water).

      Evaluation of Production and Wastewater  Flow Data
         Tabular  summary of plant-specific data.
         Waste flows per unit of production (unit
         wastewater  flows)  with the range and average values.
         Solid waste quantities generated by  treatment.
         Treatment chemical requirements.

      Process Modifications and Technology Transfer Options

      Best Management  Practices (BMP)
         Plant area  operations  and  housekeeping.
         Runoff  control.
         Solid waste handling (e.g.,  fugitive dust and
          leachate control,  etc.).

Model Plant  and BPT Treatment  System Specification

The model  plant  concept   plays  a  central   role  in   both  the
development   of alternative treatment  system designs for  priority
pollutant removal and  for   estimating  the related internal  costs
of   such    treatment   in   each  subcategory.   In  order to  be
representative  of   a   subcategory,  each  set  of  model   plant
specifications was  composited  from a profile data summary derived
from the available  information  on production and wastewater flow.

Based  on typical wastewater flow and  production, the model plant
was used as  a starting  point for an  appropriately  designed  and
sized wastewater treatment  system.    Certain assumptions were made
regarding  the  possible process variations and the  specific raw
wastewater sources  incorporated  into each model.  In  most cases,
it was necessary to  assume  that  the  wastewater flow per   unit  of
                               58

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production  did  not vary over the particular range of production
capacities covered.  (There was little  variation  in  flow  from
plants  that  provided  reliable  data.)   Production  rates were
selected in most subcategories to represent a range in  sizes  of
plants   presently   in   operation.   Small  subcategories  were
represented by single mid-range production rates  for  the  model
plants,   Cost estimates were developed for each set of treatment
system design specifications.

Beginning with Section 11, the model plant and  treatment  system
descriptions   for   each   level  and  specifications  for  each
subcategory include the following information:

      1.   Production rates and mode of operation
      2.   Specific process type and wastewater  sources
      3.   Wastewater flow per unit of production
      4.   Solid waste generation and handling
      5.   Treatment reagent requirements

The model  plants  do   not   represent   exemplary  or  specific
existing  plants,  but  are   typical  plants  of adequate  design
derived  from  the  range   of  plants, treatment  facilities,  and
production characteristics found  in  the entire  subcategory.    For
the purpose of cost estimating, it  is necessary to  specify  cost
rationale,  define  a set   of  initial  assumptions,  and consider
the variability  of factors such  as  wastewater   flows,  pollutant
concentrations,  unit treatment process,  plant  age,  etc.   General
assumptions have been detailed  under Section  10 of  this   report
and   are   employed  as   the   basis  for  developing  baseline model
plant cost estimates presented  in the subsequent sections  dealing
with   individual   industries.   The use  of  model  plant   cost
estimates  to  assess the  economic  impact of  compliance  costs for
real  plants  is not always  accurate,  particularly with  respect  to
plants with  .wastewater   flows  varying  greatly   from  the model
plant. Accordingly, we have  used plant-specific data  to estimate
 compliance costs  for   the   cobalt  salts,  copper   salts,   nickel
 salts,  and   zinc   chloride   subcategories,  and the cadmium salts
 segment of the cadmium   pigments   and   salts  subcategory.   Most
 plants  in  those   subcategories   are   multi-product plants.   The
 plant-specific compliance cost  estimates  were used to assess   the
 economic  impact  of the  regulation.

 Dissolved Solids in. Wastewater  Effluent

 Many  wastewater  treatment plants discharge  final effluent into
 watercourses which feed  fresh water streams used as  sources  of
 water  supply by  downstream agencies or  industries.  Groundwater
 aquifers which underlie large portions of the country are  tapped
 to supply fresh water through wells serving public and industrial
                                59

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water  needs.    Saline    wastes   discharged   into streams or into
unlined  lagoons   can  significantly  alter   the  total   dissolved
solids content of the   fresh  water.   Although Federal regulations
seldom   limit the total  dissolved solids  or  the various  ions such
as   chloride,    sulfate,   bicarbonate,   and   nitrate,    these
constituents can be of  serious   concern to local  water users.

To  protect  the  mineral   quality  of ground and surface waters,
state  and  local water pollution  control   agencies   typically
establish  limits on the discharge of substances  which contribute
sodium,  potassium, hardness,  chloride, sulfate, or  conductivity,
which is a measure of total solids in solution.   This restriction
can  affect  the  chemicals chosen for wastewater treatment.  For
example, alkaline precipitation   can be  accomplished   by  using
lime,  which  forms  an   insoluble  calcium   sludge, or  by adding
caustic  soda, forming a  soluble  sodium salt.

In choosing an acid  for neutralization of alkaline  wastes,  it  is
important to weigh  the  overall    effects    of   chloride    (from
hydrochloric acid) and sulfate (from sulfuric acid), particularly
with respect to  irrigational  use  of  the receiving water.

Chemicals  used  in the model  plant processes  were selected on the
basis of best performance,  including  consideration  of   scaling
problems,  which   can  be  severe  when calcium and sulfate are at
saturation levels.  It may be  necessary to alter the  nature  of
chemicals used at  a specific plant,  in order  to  meet local water
quality requirements.
                               60

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                       SECTION 6

                      REFERENCES
Harty, D.M., Funke, D.M., and  Terlecky,  P.M.,  "Dual-Media
Filtration  Treatability Test Results at Zinc chloride Plant
F144,"  Frontier  Technical  Associates,  Inc.  Report   No.
FTA-84-E6-01,June 27, 1984.
                           61

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                             SECTION 7

    ASSESSMENT OF TECHNOLOGY FOR ADVANCED TREATMENT AND CONTROL


 INTRODUCTION

 In    the    inorganic    chemicals  industry,   pollution  abatement
 practices  vary and  a  wide range of treatment  technologies can  be
 found,  ranging  from  no  treatment to  the application of highly
 advanced technologies for the  removal of specific  pollutants.

 Until  the   NRDC  Settlement Agreement,   industry   attention   was
 primarily   directed  toward general pollution  problems including
 removal of  trace metals,  but not toward   treatment  of  over   TOO
 individual    specific  organic  compounds now   listed  as toxic
 pollutants.    Even    with   the   classical    (conventional    and
 nonconventional)    pollutants,    treatment  technology  had   been
 directed to removal down  to the part per million  level,   whereas
 now the  thrust is   toward part per billion level  requirements.
 For both   of  these   reasons,   higher  level  technologies    are
 sometimes   not  in  place  in the inorganic chemicals  industry,  and
 therefore it is necessary to examine technologies  that have   been
 applied  in  other  industries  or developed  at  the  laboratory or
 pilot-plant scale specifically for the  removal  of  these toxic
 substances  from industrial  wastewater, and determine whether  they
 can be adopted as viable  technological options.

 A   list    of   candidate  technologies   was  compiled  from   the
 literature,  in-house  expertise,   and  industry   contacts.   These
 were evaluated with respect  to:

     1.   Treatment effectiveness

     2.   Cost
     3.

     4.
Nonwater pollution environmental effects

Applications in the inorganic chemicals industry or on
other industrial wastes with similar wastewater
characteristics.
The  anticipation  that few of the organic toxic pollutants would
be found in inorganic chemical wastes in treatable concentrations
was justified by the results of the analytical programs  in  both
Phase  I  and  II.  As a result, the initial search for candidate
BAT technologies became limited to treatment technologies for the
thirteen metals.
                               62

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The  technologies  finally  adopted  were  not  new  or   untried
technologies  since it was found that most treatment requirements
could be met  by  taking  conventional  techniques—for  example,
chemical precipitation—and developing them to a higher degree of
engineering  and  design  sophistication, so that optimum removal
efficiencies could be achieved.

The following pages describe the theoretical basis for  treatment
systems   considered   for   application   in   this   group   of
subcategories.

HYDROXIDE PRECIPITATION

Hydroxide precipitation is the most widely  used  technology  for
removing trace metals from wastewaters, with lime or caustic soda
commonly  used  to  supply  the  hydroxide  ions.  Under suitable
conditions the metals form insoluble metal hydroxides  which  can
be separated from solution.

The  chemistry  of  the  process   is  not  simple,  and  must  be
understood for each  metal.    Many metals  are  amphoteric,  the
optimum  pH  for  precipitation varies,  and organic complexes can
interfere.  A simple form of the reaction may  be written as:

     M++ + 20H-  = M(OH)2                       •  (1)

     Metal  ion +• two hydroxyl  ions =   insoluble metal  hydroxide
 If  the pH   is   below  the
 soluble complexes form:
          +  OH- = M(OH)+
optimum  for  hydroxide  precipitation
                     (2)
      Metal  ion + hydroxyl ion  =  soluble metal complex

 Since  most metals have the capability of coordinating with other
 ions  or  molecules,   these  simple  equations  assume  that  the
 hydroxyl  ion  is  the  coordinated species.   However, if organic
 radicals are present,  they can form chelates and mask the typical
 precipitation reactions:
          + OH- + nR = M(R)n(OH)+
      Metal ion + hydroxyl ion
       + organic ions
                      (3)
       soluble metal
        chelate
 Such complexes may require unusual treatment to  hydrolyze  them,
 and  their  presence  often explains why some treatment practices
 yield relatively poor results.
                                63

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               TABLE 7-1.  SOLUBILITY PRODUCTS OF TOXIC METALS
       Metal
       Solubility Product Constant  (Kg_)
Metal Hydroxide            Metal Sulf ide
Antimony (III)
Arsenic
Beryllium
Cadmium
Chromium (III)
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium (I)
Zinc
1.6 X 1(
2.5 X 10
         22
        "14
         31
6.3 X l<
2.2 X 10-20
1.2 X ID'15 (1)
3.0 X 10-26 (1)
2.0 X 10
        '15
2.0 X 10
        r8 (D
1.2 X 10
        "17
3.6 X 10~29
                           8.5 X 10~45 {2)
                           3.4 X ID'28 (2)
                           2.0 X 10~49 (2)
                           1.4 X ID"24 (2)

                           1.6 X ID'49 (2>
                           5.0 X 10
                                   -21 (1)
                           1.2 X 10"28 (2)
NOTE:  References for above values are shown below.
(1)  Dean, J.A., Ed.f Lange's Handbook of Chemistry, 12th ed., McGraw-Hill
     Book Co., New York, 1979.
(2)  Vfeast, R.C., Ed., Handbook of Chemistry and Physics, 57th ed., CRC Press,
     Cleveland, Ohio, 1976.
                                 64

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Figure 7-1.  Theoretical solubilities of toxic metal hydroxides/oxides as a
             function of pH.:
     10
»	1	1	1	1
              4     5     6     7     8     9     10    11    12     13
NOTE:  Solubilities of metal hydroxides/oxides are from data by M. Pourbaix,
       Atlas of Electrochemical Equilibria in Aqueous Solutions/
       Pergamon Press, Oxford, 1966.
                               65

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Assuming the  absence  of  organic  complexing  agents,  the   treatment
levels attainable  by  hydroxide precipitation  can  be forecast  from
a  knowledge  of   the pH   of  the   system.   Figure 7-1  shows the
theoretical solubility of  those  toxic metals  which  form  insoluble
hydroxides,   while Table   7-1   shows   the    solubility    product
constants.    For   comparison,  the   values  for sulfides are  also
given in Table  7-1.

It is clear from the  range of optimum pH's  illustrated   that   for
wastewaters   containing  more than one metal,  no single optimum pH
exists, and problems  arise at the threshold of the  alkaline range
(circa pH  10) where some  metals have   least solubility,  while
others  are   at  the  point of redissolving  as an  anionic species.
For successful  application as a  wastewater  treatment  technology,
careful  control of pH must be practiced  if the best removals are
to be achieved.

In practice   the   solubility  of metallic  hydroxides,   and   the
tendency   for   fine insolubles to remain  in suspension,  may yield
effluents  which will  not   meet  
-------
The ability  to  separate  the  solids  from  the  wastewater  is
important.    Metallic  hydroxides  tend  to  be  gelatinous  and
separate poorly in gravity separators.  Finely  suspended  solids
tend  to  pass out with the effluent and increase the total metal
content.  Thus, improvements in precipitation  applications  have
been  directed  toward fine solids removal, and this is reflected
in the addition of various filtration  systems  and  the  use  of
flocculant aids as improved levels of treatment.

Soda  ash (sodium carbonate, Na2G03) is sometimes found to be the
reagent of choice particularly for lead removal.  Lead carbonate,
PbCO3, and lead hydroxide/carbonate,  2PbC03  .  Pb(OH)2,  (basic
carbonate)   are   formed  which  may  afford  improved  settling
properties for a particular waste.

Hydrated lime suspensions are more commonly used than soda ash or
caustic soda as  the  hydroxide  source  because  they  are  more
economical.   However,  if  there  is  sulfate ion present in the
waste water, gypsum will be formed;
     Ca(OH)2 + (SO4)— = CaS04 +

     Hydrated lime + sulfate ion
     hydroxyl ions
2OH-            (4)

 =  calcium sulfate  (gypsum)  +
This increases the sludge produced, may cause scaling problems  in
pipelines,  and  may clog a granular media filter.  Using caustic
soda is more expensive, but it generally eliminates  the  scaling
problem.   Total dissolved solids  in the form of sodium salts are
increased in the caustic soda treated wastewater.   Although  low
concentrations  of  sodium  are  not  regarded as polluting, high
levels can make drinking water  unpalatable,  limit  the  use   of
water  for  agriculture, and promote degradation of the structure
of arable soils.  Thus, where high total dissolved solids are   of
concern, lime would be the preferred neutralizing agent.

This   treatment   technology   is  widely   applied  in  treating
industrial wastewaters that contain metals.  Industries that  are
using  hydroxide  precipitation  to remove metals from wastewater
include:

               Inorganic Chemicals,
               Plating and Metal Finishing,
               Ore Mining and Dressing,
               Textiles,
               Iron and Steel,
               Non-Ferrous Metal Processing,
               Electronics,
               Copper Forming,
                                67

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           •    Coal Mining

 Better than 99 percent removal of trace metals have been reported
' in the  literature  with  final  concentrations  in  the  treated
 effluents ranging from sub ppm to low ppm (see Tables 8-1 through
 8-10).  The data also show that the concentrations and solubility
 products  are  the  determining  factors  in evaluating candidate
 technologies.  Therefore, it  is  appropriate  to  transfer  this
 technology  to  industries not currently using this technology if
 the wastewater contains metals.

 FERRITE COPRECIPITATION

 An interesting variation on the theme of hydroxide  precipitation
 is  a  process developed in Japan for the removal of heavy metals
 from  acidic  wastewater.   The   process,   known   as   ferrate
 coprecipitation,   has  the  potential  for producing a marketable
 residual by converting the metal ions in solution into > insoluble
 ferromagnetic   oxides   or   ferrites   which   can  be  removed
 magnetically or by filtration (1).   The treatment is  applied  by
 adding  a  ferrous  salt  to  the  metal-bearing wastewater,  then
 neutralizing  and  oxidizing  the  complex  heavy   metal-ferrous
 hydroxide  precipitate  by  aeration  to  form the stable ferrite
 coprecipitate.  Particle sizes  are  reported  to  be  relatively
 large   and   sludges   formed  can  be  safely  disposed  of  by
 landfilling.

 Although extensive performance data have not been developed,   the
 information   available   indicates   that   very   high  removal
 efficiencies can  be achieved for most of the common heavy metals,
 including mercury and hexavalent chromium.  The  method  has   not
 been  considered   here as an available technology due to the  lack
 of sufficient information on chemical dosage requirements,  energy
 requirements,  and performance  in  situations  similar  to those
 found in the inorganic chemicals industry.

 SULFIDE PRECIPITATION

 The basic principle of sulfide treatment technology is similar to
 that of hydroxide precipitation.   Sulfide is added to precipitate
 the  metals  as  metal  sulfides,   and  the precipitate formed is
 separated from the solution by gravity  settling  or  filtration.
 Sodium  sulfide  and  sodium  bisulfide  are  the  two  chemicals
 commonly used, with the choice between  these,  two  precipitation
 agents being strictly an economic consideration.

      Metal sulfides form according  to the following equation:

      M++ + Na2S = MS + 2Na+           "           (5)
                                68

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     Metal ion + sodium sulfide  =
                               insoluble metal sulfide
                                + sodium ions
In  order  to calculate the theoretical solubilities of the metal
sulfides as a function of pH, the equilibria  involved  in  solid
metal sulfide dissociation are taken into account:
MS  =
                 S~
                                            (6)
Metal sulfide = metal ion + sulfide ion and, depending on pH, the
sulfide  ion  can  react with hydrogen ions to form the bisulfide
ion and hydrogen sulfide.
     S— + H+
           HS-
                                            (7)
     Sulfide ion + hydrogen ion  =  bisulfide ion
HS
      H+ = HS
                                                 (8)
     Bisulfide ion + hydrogen ion  *  hydrogen sulfide

The concentration  of  metal  ion  in  solution  will  equal  the
concentration of sulfide ion, bisulfide ion and hydrogen sulfide.
Knowing  the metal sulfide solubility product (Table 7-1) and the
acid dissociation constants of hydrogen sulfide, Kj <= 9.1 x 10~8,
k2 = 1.1 x 10~12 (see Reference 2 in Table 7-1 ) the solubility of
the metal ion can be calculated as a function of the hydrogen ion
concentration and, therefore, as a function of pH.

     For a divalent metal ion the equation is:


(M++) =  [Ksp [1 + (H+)/(1.1 x 10-12)] + (H+)2/(l x 10-i»)]^

Using the above information, the theoretical solubilities of  the
toxic metal sulfides were calculated and are shown in Figure 7-2.

The major problem in applying sulfide precipitation techniques is
associated  with  the  toxicity  of sulfides.  This warrants both
care in application and post treatment systems to  remove  excess
sulfide.   Pretreatment  involves  raising  the  pH  of the waste
stream to minimize evolution of hydrogen sulfide gas.

A recently  developed  and  patented  process  to  eliminate  the
potential  hazard  of  excess  sulfide  in  the  effluent and the
formation of gaseous hydrogen sulfide uses ferrous sulfide as the
sulfide source (2).  The fresh ferrous  sulfide  is  prepared  by
adding  sodium  sulfide  to ferrous sulfate.  The ferrous sulfide
slurry formed is added  to  a  wastewater  to  supply  sufficient
                               69

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Figure 7-2.  Theoretical solubilities of toxic metal sulfides as a
             function of pH.
        10
 fl
 &

 I
H
                                                             13
                                      pH
                        70

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sulfide  ions  to  precipitate  metal  sulfides  which have lower
solubilities than ferrous sulfide.  Typical reactions are:
     FeS + Cu++ = CuS + Fe++
                                      (10)
     Ferrous sulfide
     iron ion
+ copper ion  =  insoluble copper sulfide  +
     FeS + Ni(OH)2 = Fe(OH)2 + NiS
                                      (11)
     Ferrous sulfide +
      nickel hydroxide
   =  ferrous hydroxide +
       insoluble nickel sulfide
A  detention  time  of  10-15  minutes is sufficient to allow the
reaction to go to completion (3).  Ferrous sulfide itself is also
a  relatively  insoluble  compound.    Thus   the  - sulfide   ion
concentration  is  limited  by the solubility of ferrous sulfide,
which amounts to about  0.02  mg/1,  and  the  inherent  problems
associated  with conventional sulfide precipitation are minimized
(4).

One other advantage of this process is that if chromium  (VI)  is
present, it will also be reduced at the pH of normal operation {8
to 9) and precipitate as the trivalent hydroxide (Cr III).

Treatment  systems for sulfide precipitation are similar to those
used for hydroxide precipitation.  A continuous treatment  scheme
generally  consists  of  a  pH  adjustment  tank and reagent feed
system, settling unit, ferrous  sulfide  addition  system,  flash
mixing  tank,  granular  media  filter,  and  sludge  storage and
disposal.

Before the addition of sodium sulfide or bisulfide the pH of  the
incoming wasteflow is adjusted to pH of 7-8 in the first reaction
tank  to  reduce  the  formation  of  hydrogen  sulfide gas.  The
chemicals are then added  to  the  flash  mixer  where  they  are
thoroughly mixed with the wastewater.

After   the   flash   mix,  the  precipitate  agglomerates  in  a
flocculating chamber either separate or integral to the  settling
unit,  and  is then settled.  The overflow from the settling unit
generally  passes  through  a   filter   to   remove   any   fine
precipitates.   Any  excess  sulfide must be removed before final
discharge.  This can be achieved either by aeration or  by  other
chemical oxidation techniques.

Sulfide   precipitation  is  being  practiced  in  the  inorganic
chemicals  industry,  mining  industry,  textile   industry,   and
nonferrous  metal  processing industry.  Most of the Chlor-Alkali
                               71

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industry is applying this technology to remove mercury
wastewater streams.
                 from  its
Literature  citations  on the efficiency of sulfide precipitation
(5, 6, 7) indicate that most results are in the  sub  ppm  range,
and that sulfide treatment is superior to hydroxide treatment for
the  removal  of several trace metals.  A recent report concluded
that, with no complexing agents  in the wastewater, the  following
effluent quality can be achieved  (7).

                      Metals Concentration
                     Cadmium
                     Copper
                     Zinc
                     Nickel
                     Chrom i urn  (tota1)
0.01  mg/1
0.01  mg/1
0.01  mg/1
0.05 mg/1
0.05 mg/1
     Adding  ferrous  sulfide  as  a  polishing  step  to  remove
residual metals appears to be a promising, economical technology.
However, there is no full-scale sulfide  treatment  system  as  a
polishing step operating in the inorganic chemicals industry, and
treatability  studies  conducted by the Agency on chrome pigments
wastewater and chlor-alkali (diaphragm cell) wastewater in  Phase
I  showed  that  sulfide  treatment as a polishing step following
hydroxide  precipitation  and   clarification   did   not   yield
significantly  increased  toxic  metal  removals.  Therefore, the
Agency  has  not  proposed  sulfide  treatment  as  an   advanced
treatment  technology  option for the Phase II inorganic chemical
subcategories.

One  cadmium  pigments  plant  is  using  ferrous   sulfide   and
filtration  treatment  as a scavenging process to recover cadmium
from its process wastewater for reuse.   The  effluent  from  the
scavenger  is discharged without further treatment.  Limited data
from that plant indicates that the treatment is not performing as
well in reducing cadmium discharge levels as lime, clarification,
and  filtration.   We  have  insufficient  information   on   the
operation  of  that plant to determine if the poor performance is
due to improper operation of the ferrous sulfide  and  filtration
treatment or if the poor performance results from other causes.

THE XANTHATE PROCESS

The use of xanthates for the removal of metals from waste streams
appears  to  be  a  new, promising technology for treating metal-
bearing wastewaters.  Xanthates contain functional groups capable
of forming insoluble complexes with metals,  and  the  sludge  so
formed can be separated by conventional means.
                               72

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Xanthates  can  be  generated  by mixing starch or cellulose with
carbon disulfide in a caustic medium.  Three types  of  xanthates
have  been proven in bench pilot scale studies to be effective in
removing cadmium, chromium (III), copper,  iron,  lead,  mercury,
nickel,  silver  and  zinc  from  industrial waste waters  (9-16).
These are:                    .                          ,     ,    "

          Soluble starch xanthate with a catlonic polymer,

          Insoluble starch xanthate, and

          Fibrous cellulose xanthate

     The general removal mechanism is as follows:

     2  ROCS(=S)Na  + M++ = ROCS(=S)j,M + 2Na+               (12)

     Xanthate + metal ion  =  insoluble metallic xanthate
                               + sodium ions

     where R = starch or cellulose

Unlike hydroxide precipitation, this process is  reported   to  be
effective  in  removing  metals  over a wide pH range of 3  to  11,
with an optimum range between 7 and 9.

Brass mill wastewaters,  lead  battery  effluent,  circuit  board
rinse   waters,   electroless   copper   plating   rinse  waters,
pyrophosphate electroplating rinse  waters,  and  copper  etching
rinse  waters were studied in a pilot plant with insoluble  starch
xanthate  as  the  complexing  agent  (16).   This  pilot   study
demonstrated  that the xanthates can either be added to a  reactor
to mix with the wastewaters or be  applied  as  a  precoat  on   a
pressure filter  (16).  Results of these pilot studies showed that
metals were reduced to below 50 *»g/l (ppb).               ,

Another  study   indicated  cellulose  xanthate is as effective as
starch xanthate  in removing trace metals.   The  following  table
summarizes  the  results  of  the study with a cellulose xanthate
dosage of 90 irig/1 and a contact time of 30 minutes (14,15):  '
          Metals
Concentration, mg/1

     Influent
Effluent
Cadmium
Chromium
Copper
Iron
1.35
0.30
1.6
3.1
0.027
0.022
0.06-0.14
0.08-0.36
                               73

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          Lead
          Nickel
          Zinc
3.9
2.4
1 .0
0.008-0.021
0.077
0.03-0.04
This study also concluded that cellulose xanthate  is superior  to
Starch  xanthate   in  terms  of  sludge settling characteristics,
filterability, and handling.

Xanthate may also be used as a complexing agent  to  prevent  the
formation  of  soluble  anions  from   insoluble  amphoteric metal
hydroxides.

The xanthate process is a  relatively  new  technology,  and  the
reagent compounds are not yet available in commercial quantities.
More  information  is  needed  on dosage rates in  continuous flow
operations.  Potentially the metals can be recovered by  leaching
the xanthate complex with nitric acid, but metal recovery has not
been demonstrated yet.  Sludge disposal problems may arise if the
sludge  complex is unstable and, if xanthates are  to be generated
on site, care will be needed in  handling  the  hazardous  carbon
bisulfide.   For these reasons, the xanthate process has not been
considered here as an available technology.

ION EXCHANGE

Ion exchange is a chemical reaction between the ions in  solution
and   the  ionic  sites  on  an  exchange  resin.   Many  natural
substances (e.g., soils, proteins,  and  zeolites)  exhibit  such
exchange  characteristics.   However,  synthetic   resins  are the
predominant ones used for ion  exchange  applications  in  modern
industrial  technology.   These  resins contain functional groups
that can react with the ions in  solution.   Depending  on  these
functional groups, the resins can be classified into:

          Strongly acidic cation exchanger,
          Weakly acidic cation exchanger.,
          Strongly basic anionic exchanger, and
          Weakly basic anionic exchanger.

Cation  exchangers  are  capable  of   exchanging   with cations in
solution.  Strongly acidic cation exchangers  contain  functional
groups  such  as  sulfonates,  (-SO3H  and  -SO3Na), while weakly
acidic exchangers have functional groups derived from  carboxylic
acids, (-COOH and -COONa).

Anionic  exchangers  are  used  to  exchange  with  the anions in
solution.  In general, strongly basic  exchangers  contain  amine
functional groups  (-R3NOH and R3NC1),  and weakly basic exchangers
contain ammonia functional groups (-NH3OH and -NH3C1).
                               74

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When  the  functional  groups  are  used  up in the reaction, the
resins can  usually  be  regenerated.   Cationic  resins  can  be
regenerated  by sodium chloride, hydrochloric acid, sulfuric acid
or sodium hydroxide.  Anionic resins are  regenerated  by  sodium
hydroxide, ammonium hydroxide, sodium carbonate, sodium chloride,
or hydrochloric acid.

The  exchanger  can  either  be  added to the wastewater in batch
operations or packed in a fixed bed or column.  Fixed bed  is  by
far  the  more  effective  and  hence  more  popular method.  The
operation  generally  follows  a   four-step   cycle:    exchange
(service), backwash, regeneration, and rinse.

During  the  exchange  step,  the  reaction  between  the ions in
solution and the ionic sites in the  resin  takes  place  as  the
wastewater  passes  down  the  bed.   The  reaction  is generally
regarded  as  a  result   of   electrostatic   attraction   (16).
Therefore, the size of the hydrated ion and the charge on the ion
are  the  determining  factors  for  the  exchange  reaction.   A
trivalent ion is attracted more  strongly  than  a  bivalent  ion
which  is  in turn attracted more strongly than a monovalent ion.
For ions with the  same  charge,  the  smaller  hydrated  ion  is
capable  of  moving  closer  to  the  exchange  site, and is thus
favored.

Many  synthetic  resins  contain  functional  groups   that   are
selective to certain metals. For example, a resin manufactured by
a  European company reacts preferentially with mercury (Hg++) and
mercuric  chloride  (HgCl+)  ions  according  to  the   following
equations:
     2RSH + Hg++ = RSHgSR + 2H+
     Resin + mercury ion  =
insoluble resin complex
 + hydrogen ions
     RSH + HgCl+ = RSHgCl + H+

     Resin + mercuric chloride ion  =
                              (13)
                              (14)
          insoluble resin complex
           + hydrogen ions
The  exchange  reaction  is  governed  by the Law of Mass Action.
During the reaction, the affinity of the resin for the  two  ions
is so great that essentially all the mercury or mercury chloride-
resin   complex  formation  equilibria  are  shifted  toward  the
formation of Hg++ and HgCl+ which are rapidly removed.  A  5  ppb
residual  mercury  concentration  in  the effluent is achieved by
this process (18).
                               75

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After all the exchangeable sites in the resin are  used  up,  the
bed is backwashed by passing clean water through to loosen up the
bed  and  to remove any fine particulates that are trapped inside
the bed.
After the backwash cycle the resins can be regenerated
appropriate regenerant.
RSHgCl + HC1  =  RSH + HgCl2

Insoluble resin complex
  + hydrochloric acid
                                                   with  the
                                                           (15)
                                 regenerated resin
                                  +  mercuric chloride
One  attractive  feature  of  the ion exchange process is that it
concentrates the  metals  in  the  regeneration  step,  and  thus
provides a potential for their recovery.  However, if recovery is
not  feasible,  this creates a secondary stream which needs to be
treated.

A recent study found that  sodium  alumino  silicates  (zeolites)
might  be a low-cost exchanger that can be discarded after a one-
time use (18).  This would eliminate the regeneration step.  On a
batch study with a five-minute contact time, cadmium and  mercury
were  removed to below 10 ppb.  Thermodynamic considerations show
this exchanger to have  a  high  affinity  for  cadmium,  copper,
mercury, nickel, silver, zinc, cesium, and barium.

Ion  exchange  is  a  proven  technology  that  can  reduce metal
concentrations to low levels.  However this  technology  is  used
only in limited industrial pollution abatement applications where
the  value  of  the materials recovered from the backwash offsets
the high cost associated with the process.  Ion exchange  is  not
used  in the Phase II industries.  Consequently, ion exchange has
not been recommended in this report for BAT technology.

REDUCTION PROCESSES

Many metals can exist in solution in  several  oxidation  states,
and it may be necessary to convert from a higher valence state to
a  lower  one  in  order to apply a given chemical reaction.  The
classic example is chromium which, as the trivalent chromic  ion,
will precipitate as the hydroxide in alkaline solution, while the
hexavalent chromate or dichromate ion will not.  The latter needs
to be reduced if precipitation is to occur.

Hexavalent  chromium  (e.g.,  Cr04=  and  Cr207=)  is  toxic  and
soluble.  The most efficient way of removing this  from  solution
is a two-step process of reduction followed by precipitation.
                               76

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Chromium  (III)  is much less toxic than chromium (VI), and forms
an insoluble hydroxide which can  be  removed  from  solution  by
settling and filtration.

A  number  of  chemicals  are used for the reduction of chromium.
Most common are sodium bisulfite,  sodium  metabisulfite,  sulfur
dioxide and ferrous salts.  The reduction is accomplished readily
at low pH with these reagents.  Typical reduction reactions are:
3S0
       Cr207— '+ 2H+ =
                                     3S04— + H20
(16)
     Sulfur dioxide + dichromate ion
     + hydrogen ion
3S03 — + Cr2O7 — + 8H+ =
     Sulfite ion + dichromate ion
     + hydrogen ion
                                 =  trivalerit chromium ion
                                     .+ sulfates and water
                                       3S04 — + 4H2O
                                                      (17)
                                 trivalent chromium ion
                                  + sulfates + water
6Fe++
        Cr2O7 — + 14H+ = 2
                                                  7H20
  (18)
     Ferrous ion + dichromate ion
      + hydrogen ion
                                 trivalent chromium ion
                                  + ferric ion + water
The  reduced  chromium  and the ferric ions produced in the third
equation will exist as the soluble sulfate at acid pH's.  If  the
pH  is  above  5,  the  reaction rate is drastically reduced, and
although dithionite will effect reduction at neutral pH's, it  is
very costly and its use may be contraindicated.

After  the reduction step, lime or caustic soda is added to raise
the pH to 8.5-9.0.  Trivalent chromium will be precipitated.
           + 30H- = Cr(OH)3
     Trivalent chromium ion
      + hydroxide ion
                                                      (19)
                        =  insoluble chromium hydroxide
The theoretical solubility limit of chromium hydroxide  is  above
0.02  mg/1  (4).  It  is reported that applying sulfur dioxide to a
pigment waste consistently reduces Cr  (VI) and Cr(T) to 0.5  mg/1
and 1.5 mg/1 respectively as 30-day averages (5, 6).  By applying
ferrous  sulfide  to a  plating  waste  with  an   initial Cr(VI)
concentration of 128 mg/1 and Cr(T) concentration of 153 mg/1, an
effluent quality of  less than 0.05  mg/1  of  either  species  is
achieved (8).

A one-step  precipitation reduction process using sodium bisulfide
was used in a sodium dichromate plant  to remove chromium from  its
                                77

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wastewater.   An  effluent  quality with  less  than  1 mg/1 Cr(VI),
and less than 5 mg/1 Cr(T) was reported  (20).

One other common reduction process is the application  of  sodium
borohydride   to   reduce   metals   in   waste streams.   Sodium
borohydride  is a mild but effective reducing agent  (20),  and   is
currently  used  in  one chlor-alkali plant to reduce the soluble
mercury ion  to metallic mercury which is  removed from solution  by
carbon adsorption:
             BH4
8 OH- = 4Hg + B (OH)4 + 4H20
(20)
     Mercury ion + borohydride  ion  =   insoluble mercury metal
      + hydroxyl ion                    + borate ion + water

A mercury level of 0.01 mg/1  in  the   final  effluent  has  been
reported (20).

Sodium  borohydride  is also reported to be effective in removing
silver, mercury, gold, lead,  and  cadmium  (5).   However,  this
technology  is  only  being applied in  limited cases, the cost of
the chemical being  the  major  drawback.   The  cost  of  sodium
borohydride was $19.00 per pound in 1983 (19).

OXIDATION PROCESSES

The  oxidation  of organic substances is generally carried out by
thermal processes such as wet oxidation and incineration,  or  by
biological  processes  such  as  the  activated  sludge  process,
trickling filters, biodiscs, and aerated lagoons.

Incineration  is  actually  a  combination   of   oxidation   and
pyrolysis.   Both  involve  chemical changes resulting from heat.
Oxidation involves actual reaction with oxygen,  while  pyrolysis
refers  to  rearrangement  or  breakdown  of  molecules  at  high
temperatures in the absence of oxygen.  There are five  types  of
incinerators  available  commercially.   These  are  rotary kiln,
multiple hearth, liquid injection, fluidized bed,  and  pyrolysis
(21).   A  minimum  temperature of 1000 degrees C and a residence
time of two seconds is required  for  the  reaction  to  proceed.
This  process  has  been  shown  to  be  successful  in  reducing
pesticides to harmless molecules (22).

Wet oxidation is a process in  which  an  aqueous  waste  can  be
oxidized  in the liquid phase in a closed,  high-temperature, high
pressure vessel.  This reduces some of the problems (such as  air
pollution  from  exhaust  gas),  inherent  in  incineration.  Wet
oxidation has been used for a variety of wastes including pulping
waste and acrylonitrile liquor (23).  A reduction  in  excess  of
                               78

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99.8  percent  of  some of the toxic pollutants has been reported
(24).

Thermal  oxidation  processes  are  not  expected  to  have  much
application  in  the inorganic chemicals industry, mainly because
of the high energy cost required and the  low  level  of  organic
contamination found in the wastes.

The  application  of  chemical  oxidation to industrial wastes is
well  established  for  cyanides,  sulfite,  ammonia,  and  other
harmful  species  in  dilute  waste streams (phenols, mercaptans,
polysulfides, etc.).  Common chemicals used as  oxidizing  agents
included  chlorine,  hypochlorite,  hydrogen  peroxide, potassium
permanganate, ozone, and chlorine dioxide.  Air  and  oxygen  are
also used.

The  most widely used chemical oxidation technology applicable to
the inorganic chemicals industry is  the  oxidation  of  cyanide.
The  oxidation  reaction between chlorine and cyanide is believed
to proceed in two steps as follows:

     CN- + C12 = CNC1 + Cl-                                 (21)

     Cyanide + chlorine  =  cyanogen chloride + chloride ion

     CNC1 + 20H- = CNO- + Cl- + H20                         (22)

     Cyanogen chloride  =  cyanate ion + chloride
      + hydroxyl ion        ion + water

The  formation  of  cyanogen  chloride   (CNC1)    is   essentially
instantaneous.  The second reaction, the formation of cyanate, is
accomplished  most rapidly and completely at a pH of  10 or  higher
(5,  25).  A detention time of 30 minutes to two hours is  usually
allowed.

The  cyanates  can be further decomposed into nitrogen and  carbon
dioxide by excess chlorination or acid hydrolysis:
2CNO- + 40H- + 3CL2 = 6C1~ + 2C02
N
                                               2H0
(23)
Cyanate + hydroxyl ion
 + chlorine

CNO- + 2H30+ = CO2 + NH<

Cyanate + hydronium ion
                              =   chloride  ion  +  carbon dioxide
                                  +  nitrogen + water
                                  HO
                  (24)
                                  carbon dioxide + ammonium ion
                                  + water
                                79

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The first reaction  can  be  accomplished  in  about  one  hour   if   the
pH  is  adjusted  to 8.0-8.5.  Acid  hydrolysis  usually  takes place
at pH 2-3 and care  must be taken  to avoid  the  liberation   of   the
toxic  cyanogen chloride as a gas.   Hydrolysis is  not  usually  the
chosen option.

Other common chemicals  used to  oxidize cyanide  include  sodium
hypochlorite,  ozone,   and hydrogen peroxide.  The reaction  for
sodium hypochlorite is  essentially  the  same  as for chlorine.   For
ozone and hydrogen   peroxide,  the   oxidation  step  proceeds  as
follows:

     03 + CN- = 02  + CNO-                                  (25)

     Ozone + cyanide  = oxygen + cyanate  ion

     H202 + CN- = CNO-  + H20                               (26)

     Hydrogen peroxide  + cyanide  =  cyanate ion + water

The  advantage  of  using  these two  oxidizing  reagents is  that no
dissolved solids are  added  to  the wastewater.    In  addition,
excess chlorine is  not  discharged.

A  patented  process  uses  hydrogen peroxide  and  formaldehyde to
decompose cyanide at about  120°F.    This   has  the  advantage  of
precipitating cadmium and  zinc simultaneously  (5).

Laboratory  studies  in  one  plant  currently  practicing alkaline
chlorination indicated  that  the  presence  of  ammonia   in  the
wastewater reduces  the  efficiency of cyanide removal.  It  is well
known  that  ammonia reacts with chlorine  or hypochlorous  acid to
form chloramines:
     NH
           HOC1 = NH,C1 + H,0
                                                           (27)
     Ammonia + hypochlorous acid = monochloramine + water, etc.

     NH2C1 + HOC1 = NHC12 + H20                            (28)

     NHC12 + HOC1 = NCI3 + H20                             (29)

                                              be  converted  into
If excess chlorine is added, chloramines can
nitrogen oxide(s):

     2NH3 + 4HOC1 = N20 + 4HC1 + 3H20
                                                           (30)
                               80

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This  equation  is  not  exact because the final form of nitrogen
oxide is believed to be a  mixture  of  nitrous  oxide,  nitrogen
dioxide and nitric oxide.                    •  ;

The  treatment  of  cyanide  by  chemical  oxidation is currently
practiced in the following industries:

     Inorganic Chemicals (Hydrogen Cyanide Production)

     Ore Mining and Dressing (Cyanidation Mills, Froth Flotation
     Mills)

     Plating

The free cyanide level after treatment  is  generally  below   0.1
mg/1  (5).   However,  cyanide  was  not  detected at significant
levels in the Phase II industries and therefore cyanide oxidation
was not further considered.

MEMBRANE PROCESSES

Membrane processes have emerged in the last decade as a promising
new technology for the treatment of saline water and  wastewater.
A membrane is a semi-permeable barrier which allows the transport
of  some  molecules (ions) and retains others.  The driving force
can either be electropotential differences   (electrodialysis)   or
pressure  difference   (reverse osmosis and ultrafiltration).   The
major application of these processes has been  the desalination of
brackish water and sea water.  More  recently,  these  have   also
found application in a number of industries, including:

     Mineral Mining (Extraction from brines)
     Electroplating
     Metal Finishing
     Printed Circuit Board Manufacturing
     Battery Manufacturing
     Pulp and Paper
     Food Processing

In  electrodialysis,   an  even  number  of   alternating anion and
cation selective membranes are  placed  between  two   electrodes.
When  current   is  applied the anions are attracted to the anode,
and cations are attracted to  the   cathode.    In  the   process  of
migration, the  cations pass through the cation-permeable  membrane
and  are  blocked by  the anion-permeable membrane.  Likewise,  the
anions pass through the  anion-permeable membrane and  are   blocked
by  the   cation  membrane.    This  results  in alternating  paths of
purified  water  and concentrated reject  (Figure 7-3).
                                81

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          I
          i
                   T
               PRODUCT
                WA2ER
               I
                   WASIE
Figure 7-3.  Electrodialysis process.
            82

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                                     *a«     w

                                     iH.     m
                        o     o
                        o     o
                        o     in
                        in     cs
                                        i    §
                                      o
                                        a
                                                    s
                                       83

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 The  electrodialysis  membranes  are  made  very  thin  and   are
 assembled  in stacks.  The flow path is the active portion of the
 cells.  Pretreatment to remove suspended materials is  absolutely
 essential.   Other  materials  in the waste feed that may lead to
 membrane fouling include high organic content,   calcium  sulfate,
 and  certain  complex  ions  such  as  ZnCl-  which can partially
 convert the anion membrane to the cation form,   with  significant
 loss in system performance (25).

 As  ionic concentration decreases,  the electroconductivity of the
 water also decreases, making it  less  efficient  to  remove  the
 remaining  salt.    Most operations  do not produce a product water
 of less than 500 mg/1 total dissolved solids.

 Reverse osmosis (RO)  and  ultrafiltration  (UF)   are  similar  in
 basic  concepts.    Both  are pressure-driven separation processes
 that employ high-flux semi-permeable  membranes   operating  under
 dynamic  flow  conditions  (26).   In contrast  to electrodialysis,
 these involve the transport of solvent,  not  solute,   across  the
 membrane.

 Osmosis  is  a process in which solvent  from a dilute solution is
 transported spontaneously across  a  semi-permeable membrane into a
 concentrated solution.   By applying enough pressure  to  overcome
 this  osmotic  pressure,   reverse  osmosis,   i.e.,  the passage of
 solvent from a concentrated solution to  a dilute solution through
 a  semi-permeable  membrane,  occurs.    The  operating  pressure  of
 reverse  osmosis   units  is  usually  between  350   and  600 psi.
 Ultrafiltration usually operates  at a much lower pressure  (5  to
 100   psi).    The   predominant  transport  mechanism  is selective
 sieving through  pores.    The  membrane   retains  high  molecular
 v.-eight   dissolved  solids such as synthetic  resins,  colloids,  and
 proteins.    The  upper   and  lower   molecular  weight  limit   is
 generally  defined as  500,000  and  500,  respectively.

 Membranes  are usually fabricated  in flat sheets  or  tubular  forms.
 The   most  common  material  is  cellulose acetate but  other  polymers
 such  as  polyamides   are   used.   There   are  four  basic  module
 designs:    plate-and-frame,   tubular,  spiral-wound,   and  hollow
 fiber.   Table 7-2  is  a  comparison  between  the   various  reverse
 osmosis  modules.   Membrane   processes  are effective in  removing
 (concentrating)   inorganic  and   organic   substances    from   a
 wastestream.    Usually  extensive  pretreatment   is   required   to
 reduce   the   suspended  solids  and  control   pH.     There   are
 uncertainties   about  operation   efficiency,  membrane  lifetime.
 re}ection specificity, and  other  factors.   If   recovery  is  not
 feasible,   the  concentrated reject  must  be disposed or  treated by
 other methods.  The high operating  and capital   costs   limit  the
widespread application of these technologies.  For these reasons,
                               84

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       the  membrane  processes  have  not  been considered as available
       technologies in the inorganic chemicals industry.

       ADSORPTION

       Adsorption is a  surface  phenomenon  in  which  a  substance  is
       accumulated  on  the surface of another substance.  Sorption of a
       soluts on a solid .surface is widely used in  pollution  abatement
       practices.   The  term  "adsorbate" refers to the substance being
       concentrated, and the term "adsorbent"  refers  to  the  material
       that provides the surface.

       Activated carbon is the prevalent adsorbent used.   Both inorganic
       and  organic  substances  are  known to be removed effectively by
       activated  carbon.   A  chlor-alkali  plant  is  currently  using
       activated carbon as a polishing step to remove mercury.

       Activated  carbon  is  made by charring basic substrates, such as
       wood, coke, coal, shell, husks, etc., at 600°C  in  a  controlled
       atmosphere,  where oxygen is kept low by adding carbon dioxide or
       steam.  This process  drives  out  volatiles,  leaving  a  porous
       carbon lattice in an "activated" state.

       Activated  carbon  can be obtained in powdered and granular form.
       Powdered carbon  is  about  50-70  microns  in  diameter,  and  90
       percent  should  pass through a 300-mesh screen.  Granular carbon
       is about 0.1-1 mm in diameter, and because of this is three times
       more expensive than powdered carbon.

       The application  involves  the passage of the wastewaters through  a
       contact bed.  When the bed is exhausted,  the  carbon  is  either
       regenerated  or  sent  to  landfill.    It is economical for large
       plants to regenerate the  carbon.  This  can  be   done  either  by
       thermal regeneration in a rotary kiln or multihearth incinerator,
       or  by  chemical  regeneration  by using oxidizing agents such as
       hydrogen peroxide or acids and bases.

       The application  of carbon adsorption has been mainly   in  organic
       waste  treatment.   Recently,  there  are  studies  indicating  the
       effectiveness  of carbon adsorption  in removing mercury,   cadmium,
       cyanide,   chromium,  lead, nickel,  zinc, arsenic, and  copper  (27,
       28).

       An  interesting development  in  carbon  technology is  its use  after
       the   wastewater   is   ozonated.    This  combination   (known  as
       Bacteriologically Activated  Carbon  or BAG) has  proved   effective
       in   treating  otherwise   biologically  inactive organic compounds.
       The  process involves chemical  modification of  the organics  by  the
       ozone.   Maintenance of  an aerobic  region on  the carbon  allows  a
                                       85
_

-------
 biologically  activated film to develop and the modified organics
 are further treated by a mixed process  of  biological  oxidation
 and  carbon  adsorption.  The system has the advantage of being a
 potential  add-on to existing BPT  systems,   and  should  be  cost
 effective   since  it  has  been  found that the carbon only needs
 regeneration at  infrequent intervals.

 No  industrial applications of this technology are known,  although
 research is under way (29).

 Bacteriologically Activated Carbon is  a very attractive potential
 BAT technology for the removal of organic toxic  pollutants  from
 waste  streams,    although   no   application  to  the  industry
 subcategories studied in Phase II was  found.

 FLUORIDE REMOVAL

 The conventional  method of treating fluoride-bearing wastes is  to
 precipitate the  fluoride as  calcium fluoride by the   addition  of
 lime.  The  reaction is:
     Ca(OH)2 + 2F- = CaF,  +  2OH-
                                            (31)
     Hydrated lime +  fluoride  ion  =  insoluble  calcium  fluoride
                                      + hydroxyl  ion

Using  this  process  alone,  it  is  difficult to remove  fluoride  to
below 8 mg/1 due to the solubility of calcium  fluoride  (5,   30).
Adding   alum  with   the  lime  generally  improves  the  removal
efficiency.  Fluoride ions are  removed as follows:
A1(OH)3 + F- = A1(OH)2 F + OH~

Aluminum hydroxide  =  aluminum monof luorohydroxide
 + fluoride ion         + hydroxyl ion, etc.  .

A1(OH)2F

A1(OH)F2
F- = A1(OH)F2 + OH~

F- = A1F3 + OH-
                                                            (32)





                                                            (33)

                                                            (34)
Complexed fluorides are also  adsorbed  to  some  extent  on  the
aluminum hydroxide surface and removed in the coagulation process
(30).   Large  amounts of alum (5000 mg/1) are required to reduce
the fluoride concentration to below 1 ppm.

Activated alumina has been shown  to  be  effective  in  removing
fluoride  and  arsenic  in  wastewater  (31)  and  fluoride  from
drinking water in municipal  water  treatment  practice  (32-35).
Typically,  the fluoride content of raw water can be reduced from
                               86

-------
about 8 to 1 ppm (35).  Application of activated alumina to  high
fluoride  industrial  wastes shows that a low ppm effluent can be
achieved  (36),  although  high  capital  and   operating   costs
generally limit the wide application of this process.

One  plant  produces  a variety of Phase I and Phase II chemicals
including nickel fluoborate.  Wastewater from  nickel  fluoborate
production  is  treated  together  with other fluoride-containing
wastewater streams in a conventional  fluoride  treatment  system
similar to that described above.

CHLORINE REMOVAL

The removal of residual chlorine  (in the form of hypochlorite) in
industrial wastewater is normally accomplished by the addition of
sulfur  dioxide  or   a  related  reducing  agent  such  as sodium
bisulfite or sodium metabisulf ite.  Typical reactions  are  shown
in Equations 35 and 36.
SO
           OC1-  + H20
H2SO4
                                Cl-
                                                            (35)
                                                            (36)
     Sulfur dioxide + hypochlorite ion  =  sulfuric acid
      + water                               + chloride ion

     Na2S03 + OC1- = Na2S04 + Cl~

     Sodium sulfite +    =  sodium sulfate +
      hypochlorite ion       chloride ion

Alternatively,  hydrogen peroxide, although relatively expensive,
may also be used for dechlorination according to Equation 37.

     H202 + OC1- = H20 + 02 + Cl-                          (37)

     Hydrogen peroxide + hypochlorite ion  =  water + oxygen +
                                               chloride ion

Chlorine  residuals   remaining   after   the   recovery   and/or
decomposition   steps  have  been  taken  would  be  amenable  to
treatment with reducing agents such as sulfur dioxide, bisulfite,
or hydrogen peroxide as described above.

CONCLUSION

This Section  has described the theoretical   basis  for  treatment
systems    considered  for  application   in   this   industry.    The
treatment  systems  selected  for   application    are   hydroxide
precipitation,  settling, and filtration, with chemical reduction
of hexavalent chromium and chlorine where   those   pollutants   are
                                87

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found  in  the  wastewater.   As  demonstrated by descriptions of
those technologies and the data presented  in  Section  8  below,
those  treatment  technologies  are  applicable to any wastewater
containing  those  pollutants.   Therefore,  when   an   industry
currently  discharges  those  pollutants  with  no  treatment  or
inadequate  treatment,  it  is  appropriate   to   transfer   the
technologies  and  estimate the effectiveness of the technologies
when applied to the new  industry  based  on  their  demonstrated
effectiveness in other industries.
                              88

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                            SECTION 7
                           REFERENCES
1 .
2.




3.




4.





5.



6.


7.




8.
 9.
 10.
Coleman, R.T., J.D. Colley, R.F. Klausmeiser,  D.A.  Malish,
N P.   Meserole,   W.C.  Micheletti,  and  K.  Schwitzgebel.
Treatment   Methods   for   Acidic   Wastewater   Containing
Potentially  Toxic Metal Compounds.  EPA Contract No. 68-02-
2608, U.S.  Environmental Protection Agency, 1978.  220 Pp.

Kraus, K.A.,  and  H.O.  Phillips.   Processes  for  Removal
and/or  Separation  of  Metals  from Solutions.  U.S. Patent
3,317,312, U.S.  Patent Office, May 2,  1967.  9 Pp.

Scott, M.C.   Heavy  Metals  Removal  at  Phillips  Plating.
WWEMA  Industrial  Pollution Conference, St.  Louis, Missouri,
1978.  16 Pp.

Scott  M.C.   SulfexT - A New Process Technology for  Removal
of   Heavy Metals from Waste Streams.  The 32nd Annual Purdue
Industrial Waste Conference, Lafayette, Indiana,   1977.    17
Pp.

Patterson, J.W.,   and  R.A.  Minear.    Wastewater  Treatment
Technology.   Illinois  Institute of Technology,  1973.

Patterson, J.W.  Wastewater Treatment Technology.  Ann  Arbor
Science  Publishers,  Inc.   Ann  Arbor, Michigan,  1975.

Schlauch,  R.M.,   and  A.C.  Epstein.   Treatment  of   Metal
Finishing Wastes  by Sulfide Precipitation.   EPA-600/2-75049,
U.S. Environmental Protection  Agency,  1977.   89  Pp.

Campbell,  H.J.,  Jr.,  N.C.   Scrivner,  K.   Batzar,   and   R.F.
White.     Evaluation  of   Chromium  Removal  from  a  Highly
Variable  Wastewater  Stream.    The   32nd   Annual    Purdue
 Industrial  Waste  Conference,  Lafayette,  Indiana,  1977. 38
 Pp.

 Wing, R.E.,  C.L.  Swanson,   W.M.  Doane,  and  C.R.  Russell.
 Heavy  Metal  Removal  with Starch Xanthate-Cationic Polymer
 Complex.  J. Water Pollution  Control   Federation,  46   (8):
 2043-2047, 1974.

 Wing, R.E.  Heavy Metal Removal from Wastewater with  Starch
 Xanthate.   In:   Proceedings  of  the  29th  Annual  Purdue
                                89

-------
      Industrial Waste Conference, Lafayette, Indiana, 1974.   Pp.
      348—356.

 11.   Wing, R.E.  Removal of Heavy Metals from Wastewater  with  a
      Starch  Xanthate-Cationic  Polymer Complex.  The 46th Annual
      Conference  of  the  Water  Pollution  Control   Federation,
      Cleveland, Ohio, 1973.  38 Pp.

      Wing, R.E.  Removal of Heavy  Metals  from  Wastewater  with
      Starch Xanthate.  Presented at the Traces of Heavy Metals in
      Water:   Removal  and  Monitoring Conference, Princeton, New
      Jersey,  1973.   Pp.  258-273.

      Swanson,  C.  L.,  R.  E.  Wing, W. M. Doane,  and C.  R.   Russell.
      Mercury  Removal  from  Waste  Water  with  Starch  Xanthate
      Cationic    Polymer    Complex.     Environmental   Science   &
      Technology 7(7) :614-619,  1973.

      Hanway,   J.E.,   Jr.,   R.G.   Mumford,   and  D.G.   Earth.     A
      Promising   New   Process   for   Removing  Heavy  Metals  from
      Wastewater.  Civil  Engineering-ASCE 47(10):78-79,  1976.

      Hanway, J.E.,  Jr.,  R.G. Mumford,  and P.N.  Mishra.   Treatment
      of  Industrial  Effluents for Heavy Metals  Removal  Using   the
      Cellulose Xanthate Process.   The 71st Annual Meeting of the
      ,me.olcan  institute  of  Chemical Engineers,   Miami,   Florida,
      1978.   21  Pp.

      Wing,  R.E.,  L.L.  Navickis,  B.K. Jasberg,  and  W.E.   Rayford.
      Removal   of  Heavy  Metals  from Industrial  Wastewaters Using
      Insoluble   Starch   Xanthate.      EPA-600/2-78-085,     U.S
      Environmental Protection Agency,  1978.   116 Pp.

17.   De Jong,  G.J., and  Ir. C.J.N.  Rekers.   The  Akzo  Process   for
      the   Removal  of  Mercury   from  Waste Water.   Journal  of
   .   Chromatography 102: 443-451, 1974.

18.   Van der Heem, P.  The  Removal  of  Traces of  Heavy Metals  from
      Drinking  Water and  Industrial  Effluent  with  Ion  Exchangers.
      The  Regional  American  Chemical Society Meeting,  1977.  16
      Pp.

19.   Chemical Marketing Reporter, February  7, 1983.
12.
13.
14.
15.
16.
20,
     Calspan  Corp.   Addendum to Development Document for Effluent
     Limitations  Guidelines  and New Source Performance Standards.
     Major  Inorganic  Products   Segment   of  Inorganic  Chemicals
     ,™V a?nUring   Point  Source  Category.   Contract No.  68-01-
     3281,  1978.
                               90

-------
21.   Slen,  T.T., M.  Chem,  and J. Lauber.  Incineration  of  Toxic
     Chemical Wastes.   Pollution Engineering 10(10):42, 1978.

22.   TRW  Systems  Group.    Recommended  Methods  of   Reduction/
     Neutralization,  Recovery  or  Disposal  of Hazardous Waste.
     NTIS PB-224589, 1973.

23.   Ellerbusch, F., and H.S. Skrovronek.  Oxidative Treatment of
     Industrial   Wastewater.    Industrial   Water   Engineering
     14(5):20-29, 1977.

24.   Knopp, P.V., and T.L. Randall.  Detoxification  of  Specific
     Organic  Substances  by  Wet  Oxidation.   The  51st  Annual
     Conference of Water Pollution Control Federation, 1978.

25.   Arthur D. Little, Inc.  Treatment  Technology Handbook.

26.   Schell, W.J.  Membrane Ultrafiltration for Water  Treatment.
     Envirogenics Systems Co.

27.   Vanderborght, B.M,,- and R.E.  Van  Grieken.   Enrichment  of
     Trace  Metals  in  Water   by Adsorption on Activated Carbon.
     Analytical Chemistry 49(2):311-316,  1977.

28.  Cheremisinoff, P.N., and F. Ellerbusch.   Carbon  Adsorption
     Handbook.   Ann  Arbor  Science  Publishers,  Inc., Ann  Arbor
     Michigan,  1978.

29.  Jacobs Engineering Group Inc.  Study of the  Application  of
     BAG to  Industrial Waste Water.  Office of Water Research  and
     Technology, U.S. Environmental Protection Agency,  1978.

30.  Otsubo,  K., S. Yamazaki, and Y.  Sakuraba.    Advanced   Water
     Treatment   for   Fluoride-Containing   Waste   Water.   Hitachi
     Hyoron  58(3):219-224,  1976.  Trans.  For Rockwell  Intl.

31.  Zabban,  W., and  H.W.   Jewett.   The   Treatment  of   Fluoride
     Wastes.     In:    Proceedings  of   the  22nd Annual   Purdue
     Industrial Waste Conference, Lafayette, Indiana,  1967.    Pp.
     706-716.

32.  Rubel,   F.,  Jr.,  and  R.D.   Woosley.    Removal   of  Excess
     Fluoride   from   Drinking   Water.    EPA-570/9-78-001.    U.S.
     Environmental  Protection Agency,  1978.   16  Pp.

33.  Wu, Y.C.    Activated  Alumina  Removes  Fluoride   Ions  From
     Water.   Water  and Sewage Works 125(6):76-82, 1978.
                                91

-------
34,
35
36,
Maier, F.J.  Partial Defluoridation of Water.  Public  Works
91(11), 1960.

Maier,  F.J.   New  Fluoride  Removal  Method  Cuts   Costs.
Engineering News-Record 148(24):40, 1952.

Kennedy, B.C., M.A. Kinder,  and  C.A.  Hammer.   Functional
Design  of  a Zero-Discharge Wastewater Treatment System for
the  National  Center  for  Toxicological   Research.    In:
Proceedings  of  the  31st  Annual  Purdue  Industrial Waste
Conference, Lafayette,  Indiana, 1976.   Pp. 823-830.
                              92

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                            SECTION 8

       TREATABILITY ESTIMATES AND LONG-TERM DATA ANALYSIS


•The Development of. Treatability Estimates

Preliminary Analysis

The review of  technological treatment  options  applicable   to   the
removal   of  toxic  pollutants has  led to  the  conclusion that  the
particular contaminants  found  in the raw process   wastewaters   of
the   subject   industries  can  be   effectively controlled by  the
proper   application   of   fairly   well-known    and   demonstrated
techniques.    In  order   to proceed from a general discussion  and
description of techniques to  a  detailed evaluation  for each
subcategory  of   the   levels   of  removal  that can be expected,  a
summary  is now presented of selected treatability  data for the 13
toxic metals.

The  treated wastewater concentrations   and removal  efficiencies
reported  in   the  literature  are  assumed to represent  the best
performance  characteristics   that  can be  obtained  under   the
specified operating   conditions.    The   treatment  technologies
considered can thus be assigned  a set  of optimum   conditions   and
best  performance  estimates   for removal  of  the  particular toxic
metals  that  are amenable to   treatment.   Taking   each  metal   in
turn,   Tables  8-1   through   8-10  give   the  initial  and final
concentrations,  the removal  efficiencies,  and the  pH  conditions
for   different  treatment  technologies.    The  best  performance
estimates for  metal removal  are  derived from  the   tabulated  data
and   are  utilized  in turn  as the  bases  for  making  estimates of
average achievable performance.  The sequence  of analytical  steps
 is:

      1.    Review and  analyze applicable performance data.

      2.    Estimate  best  performance  under   optimum   treatment
           conditions.

      3.    Estimate average achievable performance under  expected
           industrial  operating conditions.

 The  third  step  involves  the consideration of  treatment system
 variables under full-scale  operating  conditions  in  industrial
 situations  where  the design objective would be  the simultaneous
 removal  of   several   waste  load  constituents.    Each   industry
 designs  for maximum removal and/or recovery of the major process-
 related   wastewater   pollutants  and  utilizes  an  appropriate
                                93

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 technology which is both reliable  and  cost-effective.   Optimum
 treatment  conditions  for  the removal of a particular pollutant
 can  rarely  be  achieved  consistently  and  any  given  set  of
 conditions  will  be  somewhat less than optimum for most, if not
 all,  of  the  treatable  constituents.   In  any   well-operated
 production  facility,  the normal variations in production rates,
 raw material quality, the desired product mix in some cases,  and
 contact  water  use  requirements  may cause severe hydraulic and
 pollutant load input excursions which at best can be moderated by
 effective  equalization  in  the  treatment  system.    This   is
 considerably  less  of  a  problem in batch treatment than with a
 continuously operating system.  The  latter  requires  continuous
 feedback  monitoring  for pH control and chemical dosage in order
 to maintain the effluent quality within acceptable limits  for  a
 number of parameters.  Under continuous operating conditions, the
 long-term  averages  derived  from  the  actual  treated effluent
 monitoring data (NPDES,  etc.)   would  equate  to  what  has  been
 identified  in  Step  3   above as the estimated long-term average
 achievable  performance   using   the   same   general   treatment
 technology.

 The  estimated  ranges  of   average  achievable  performance  are
 presented in Table  8-11.   in formulating the  regulations,   these
 values  were used as long-term averages in  cases where there were
 insufficient data from sampling or long-term  monitoring  of  the
 actual industry discharges.

 Statistical   evaluation  of  long-term monitoring data is  described
 in  the subsections  which  follow,  and the results are presented in
 Appendix  A where various  derivative quantities  such  as  long-term
 averages  and standard deviations  are tabulated.

 Final  Analysis
          Publication of the proposed Phase  I  regulations on July
    »     (45 FR 49450> additional data on performance of the BPT
and BAT options for  several  subcategories  were  evaluated  and
eventually incorporated into the basis for the final regulations
The  sources  of additional data which are also applicable to the
subcategories considered here include the following;
A.
     Treatabilitv Study for the Inorganic Chemicals Manufacturina
      Source Category. EPA 440/1-80-103, July,  1980. - -
B.   Industry comments on the proposed Phase I regulations -  The
written comments received by EPA as well as comments given orally
fr   ?J?«bllc hearin9 on proposed pretreatment standards (October
15,  1980)  are part of the official public record of the Phase I
rulemakinc.  The comments are summarized and responses are  given
                               94

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TABLE 8-1.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            ANTIMONY AND ARSENIC REMOVAL
Treatment Technology
Antimony
Lime/Filter
Ferric chloride/Filter
Alum/Filter
Arsenic
Lime Softening
Sulf ide/Filter
Line (260 rog/1) /Filter
Lime (600 mg/1) /Filter
Ferric sulf ate
Ferric sulf ate
Lime/Ferric Chloride/
Filter
Activated alumina
(2 mg/1)
Activated carbon
(3 mg/1)
Ferric Chloride
Ferric Chloride
pH

11.5
6.2
6.4

•
6-7
10.0
11.5
5-7.5
6.0
10.3

6.8

3.1-3.6

-
—
Initial
Concen-
tration
(IKJ/D

0.6
0.5
0.6

0.2
-
5.0
5.0
0.05
5.0
3.0

0.4-10

0.4-10

0.3
0.6-0.9
Final
Concen-
tration
(mg/1)

0.4
0.2
0.2

0.03
0.05
1.0
1.4
0.005
0.5
0.05

<0.4

<4.0

0.05
<0.13
Removal References
(%)

28
65
62

85
- •
80
72
90
90
98

96-99+

63-97

98
'-

1
1
1

2,
2,
4
4
5
4
2,

6

6

2,
2,





3
3




3





3
3
                                95

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TABLE 8-2.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            BERYLLIUM AND CADMIUM REMOVAL
Treatment Technology pH
Beryllium
Line/Filter 11*5
Cadmium
Line (260 mg/1) /Filter 10.0
Line (600 mg/1) /Filter 11.5
Lime Softening 5-6.5
Lime/Sulf ide 8 . 5-11 . 3
Ferrous Sulfide (Sulfex) 8.5-9.0
Ferrite cx>precipita'tion/ neutral
Filter
Initial
Concen-
tration
(mg/l)

0.1
5.0
5.0
0.44-1.0
0.3-10
4.0
240
Final
Concen-
tration
(mg/1)

0.006
0.25
0.10
0.008
0.006
<0.01
0.008
Removal References
(%)

99.4 i
95 4
98 4
92-98 . 7
98+ 8
99+ 7,9,10
99+ 11
                               96

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TABLE 8-3.   WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
             COPPER REMOVAL
Treatment Technology
Lime/filter
Line (260 mg/1) /Filter
Lime (600 mg/1) /Filter
Ferric sulfate/Filter
Lime
Lime
Alum
Lime/Sulfide
Ferrous sulfide (Sulfex)
Ferrous sulfide (Sulfex)
Perrite Cc-Drecioitation/
pH
8.5-9.0
10.0
11.5
6.0
>8.5
9.5
6.5-7.0
5.0-6.5
8.5-9.0
8.5-9.0
t _
Initial
Concen-
tration
(mg/1)
3.2
5.0
5.0
5.0
10-20
3.0
3.0
50-130
3.2
4.0

Final
Concen-
tration
(mgA)
0.07
0.4
0.5
0.3
1-2
0.2
0.2
<0.5
0.02
0.01
0.01
Removal
(%)
98
92
91
95
90
93
93
-
99
99+
99+
References
7
4
4
4
2,3
12
,12
8
7
7,9,10
11
   Filter
                                  97

-------
TABLE 8-4.  WASTE HATER TREATMENT OPTIONS AMD PERFORMANCE DATA SOMVRY -
            CERCMUM III AND CHPCMItM VI RHOVM.

TiiMUiuit Technology
Qimuimi
Line (260 mg/1) /Filter
Line (600 mg/1) /Filter
BBductic*^
**-*«V^
Line Softening
Lima/Filter
T.i'ma
Line
Ferrite coprecipitation/
Filter
Ferric sulf ate
Ferric sulf ate/Filter
Chromium VI
Activated girixn
(pulverized, Pitts-
burgh type 1C)
Sane as above
Activated carbon
(granular)
Ferrite coprecipitation
Sulfur ^ «"nri Atk y^fi[\]r^-\nn
Bisulfite reduction
PH

10.0
11.5
7-8
7-8
10.6-11.3
7-9
9.5
9.5
	
6.5-9.3
— F.

3.0
2.0
, 6.0
	
	
_
Tivi-H»1
Concen-
tration
(ng/1)

5.0
5.0
140 (as
Cr VI)
1300 (as
Cr VI)
	
	
15
3.2
25
	
5.0

10
10
3
0.5
	
	
Final Removal References
Cancan- (%)
tration
(ng/1)

0.1 98 *'
0.1 98 4
1.0 — 2,- 3
0.06 Grin 	 2*3,13
0.15 98+ 14
0.05 — 15
0.1 	 12
<0.1 — 12
0.01 	 11
	 98+ 14
0.05 99 4

1.5 85 I6
0.4 96 16
0.05 98 4
not 	 '11
detectable
0.01-0.1 	 2, 3
0.05-1.0 — 2»3
                   98

-------
TABLE 8-5.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMXIARY -
            LEAD REMOVAL

Treatment Technology
Lime (260 mg/1)
Line/filter
Lime (260 mg/1) /Filter
Line (600 mg/1) /Filter
Ferrous sulfate/Filter
Sodium hydroxide (1 hour
settling)
Sodium hydroxide (24 hour
settling)
Sodium hydroxide/Filter
Sodium carbonate/Filter
Sodium carbonate/Filter
Sodium carbonate/Filter
Ferrous sulf ide (Sulfex)
Ferrite coprecipitation/
pH
10.0
8.5-9.0
10.0
11.5
6.0
5.5
7.0
10.5
10.1
6.4-8.7
9.0-9.5
8.5-9.0
.
Initial
Concen-
tration
(mg/1)
5.0
189
5.0
5.0
5.0
	
— —
1700
1260
10.2-70.0
5.0
189
480
Final
Concen-
tration
(mg/1)
0.25
0.1
0.075
0.10
0.075
1.6
0.04
0.60
0.60
0.2-3.6
0.01-0.03
0.1
0.01-0.05
Removal
(%)
95.0
99.9
98.5
98.0
98.5
___
—
99+
99+
82-99+
99+
99.9
99.9
References
4
11
4
4
4
3
3
17
17
3
2,3
7
11
  Filter
                                  99

-------
TABLE 8-6.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA. SUMMARY -
                           MERCURY II REMOVAL
Treatment Technology pH
Sulf ide
Sulfide 10.0
Sulfide/Filter 5.5
Sulfide/Filter 4.0
Sulfide/Filter 5.8-8.0
Ferrite ooprecipitation/
Filter
Activated Carbon
Activated Carbon/Alum
Activated Carbon
Initial
Concen-
tration
(mg/1)
0., 3-50.0
10.0
16.0
36.0
0.3-6.0
6.0-7.4
0.01-0.05
0.02-0.03
0.06-0.09
Final
Concen-
tration
(ng/1)
0.01-0.12
1.8
0.04
- 0.06
0.01-0.125
0.001-0.005
<0.0005
0.009
0.006
Removal
(%)
-
96.4
99
99.8
87-99.2
99.9
-
-
—
References
2,3
18
18
18
18
11
2,3
14
18
                             100

-------
TABLE 8-7.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            NICKEL REMOVAL

Treatment Technology
Lime 8
Lime (260 mg/1) /Filter
Lime (600 mg/1) /Filter
Caustic Soda/Filter
Ferrous sulfide (Sulfex) 8
Ferrite coprecipitation
PH
.5-9.0
10.0
11.5
11.0
.5-9.0
-
Initial
Concen-
tration
(mg/1)
75
5.0
5.0
-
75
1000
TABLE 8-8. WASTE WATER TREATMENT OPTIONS AND
SILVER REMOVAL
Final
Concen-
tration
(mg/1)
1.5
0.3
0.15
0.3
0.05
0.20
PERFORMANCE
Removal
(%)
98
94
97
-
99.9
99.9
References
8
4
4
17
7,10
11
DATA. SUMMARY -

Treatment Technology
Sodium hydroxide
Ferric sulfate (30 mg/1)
Lime Softening 9.
Chloride precipitation
(alkaline chlorination
in the presence of
cyanide)
Ferric chloride/Filter
Sulfide precipitation
PH
9.0
6-9
0-11.5

6.2
5-11
Initial
Concen-
tration
(mg/D
54
0.15
0.15
105-250
0.5
— •
Final
Concen-
tration
(mg/1)
15
0.03-0.04
0.01-0.03
1.0-3.5
0.04
—
Removal
(%)
72
72-83
80-93
97+
98.2
very hi<
References
19
14
14
2,3
1
3h 2,3
                               101

-------
TABLE 8-9.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            SELENIUM AND THALLIUM REMOVAL

Treatment Technology
Selenium
Ferric chloride/Filter
Ferric chloride/Filter
Alum/Filter
Ferric sulfate
Ferric sulfate
Lime/Filter
Line/Filter
Thallium
Lime/Filter
Ferric chloride/Filter
Alum/Filter
pH
6.2
6.2
6.4
5.5
7.0
11.5
11.5
11.5
6.2
6.4
Initial
Concen-
tration
(mg/1)
0.1
0.05
0.5[
0.10
0.10
0.5
0.06
0.5
0.6
0.6 .
Final
Concen-
tration
(mg/1)
0.03
0.01
0.26
0.02
0.03
0.3
0.04
0.2
0.4
0.4
Removal
(%)
75
80
48
82
75
35
38
60
30
31
References
1
1
1
20
20
1
1
1
1
1
                                102

-------
TABLE 8-10.  WASTE WATER TREATMENT OPTIONS 2ND PERFORMANCE DATA. SUMMARY -
              .      '           ZINC REMOVAL
Treatment Technology .
Lime/Filter
Lime (260 mg/1)
Lime (260 mg/1) /Filter
Lime (600 mg/1)
Lime (.600 mg/1) /Filter
Lime/Filter
Sodium hydroxide
Sulfide
Ferrous sulfide (Sulfex) •
Ferrite cqprecipitation
pH Initial
Concen-
tration
(mg/1)
8.5-9.0
10.0
10.0
11.5
11.5
-
9.0
-
8.5-9.0
—
3.6
5.0
5.0
5.0
5,0
16
33
42
3.6
18
Final
Concen-
tration
(mg/1)
0.25
0.85
0.80
0.35
1.2
0.02-0.23
1.0
1.2
0.02
0.02
Removal References
(%)
93
83
84
93
77
-
97
97
99+
99+
7
4
4
4
4
11
1.9
11
7,10
11
                              103

-------
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in  "Responses  to  Public Comments, Proposed Inorganic Chemicals
Manufacturing Effluent Guidelines and Standards," which is a part
of the Record for that rule.   Invidivual  comment  documents  or
letters  are  cited in this report where they are used as sources
of information.
C.   Treatability   Manual,    Volume   III,
Technologies
for
Control/Removal of Pollutants, EPA 600/8-80-042C, July, 1980.
Table  8-12  presents tabular summaries of the available industry
treatment performance data  for  most  of  the  priority  metals.
These  include  estimated long-term averages in cases where there
were sufficient data given  to  utilize  the  Maximum  Likelihood
Estimation  method  for  calculating  statistical  parameters  as
indicated in  the  footnotes.   Overall  arithmetic  medians  and
averages  are also given for metals where five or more individual
data sets were .available.

An industry long-term average  effluent  concentration  was  then
estimated  for  each  pollutant/treatment  option combination for
which sufficient data were available. Plants presently practicing
filtration  are   generally   those   with   higher   raw   waste
concentrations  of  metals  in  comparison  to  plants  which can
achieve adequate treatment without  filtration.   This  tends  to
reduce  the  observed differences in performance with and without
filtration and, therefore, understates the potential  benefit  of
adding  filtration  to  a  particular  lime/settling system.  The
estimated achievable long-term average concentrations,  as  shown
in  Table  8-13, generally fall within the estimated range of the
corresponding long-term averages in Table 8-11 which were derived
from literature  data.   Thus,  there  is  substantial  agreement
between  the  two  sets  of estimates and there is good reason to
conclude that the lower limits  of  the  treatability  ranges  in
Table  8-11  are  achievable long-term averages for the inorganic
chemicals industry.  The  metal  regulations  are  based  on  the
estimated achievable long-term average concentrations in Table 8-
13  in  cases  where  there  are  insufficient  industry-specific
performance data available.  The  numerical  limitation  in  each
case   was   obtained   by   multiplying  the  long-term  average
concentration  by  the  model  plant  unit  flow  rate   and   an
appropriate  variability  factor.   The  variability  factors are
selected to represent as accurately as possible the actual  full-
scale  treatment  system's  variability  under  normal  operating
conditions.

It is understood that in each subcategory plant treatment  system
conditions,   particularly   where   chemical   precipitation  is
involved, are usually optimized  for  the  removal  of  only  one
metal.   Other  metals may be removed incidentally under the same
                               109

-------
conditions   although   their   removal   efficiencies   may   not    be
optimal.     An    example    is   the    prevalent   use  of   sulfide
precipitation/filtration  technology for  the  removal   of   mercury.
The  precipitation  is normally  carried  out   under neutral  to
moderately-acid conditions   in   order  to  limit the amount   of
residual  sulfide  in   the   system and,  depending on specific raw
waste characteristics,  to obtain desirable solid properties  for
filtration.   Under  these  conditions, the incidental removals  of
other metals such as nickel  and  zinc are not  at their   maximum
efficiencies, but are  still  effective.

The  industry  performance data  summarized in Table  8-12  for many
of the toxic metal/treatment combinations   express   an   observed
incidental removal rather than an optimum removal.   This  provides
an  empirical  basis   for estimating practical control levels for
metals  under  off-optimum   pH   conditions   in   either    alkaline
precipitation or  sulfide  precipitation systems.

Selection of Toxic Metal  Control  Parameters

Control Parameters for  Hydroxide  Precipitation

Section 7 of this report  describes hydroxide precipitation as the
most  widely-used technology for removing  trace   metals  from
wastewater.  Out  of the thirteen  toxic metal pollutants,  two have
hydroxide/oxide solubilities independent of  the 1-14  pH  range
(selenium  and  thallium)  and   two  have minimum hydroxide/oxide
solubilities over a wide  pH  range (antimony  at pH  2-10.4  and
mercury  at  pH 4-12).   Arsenic is removable by precipitation with
lime (probably as calcium arsenate) in   the  presence of  excess
calcium  ion under  neutral  to alkaline conditions.  As  shown  in
Tables 8-1 and 8-9, removals of antimony and selenium can also  be
accomplished using  excess   lime.   The  mechanism   probably   is
similar  to  the  removal  of  arsenic, i.e., as the calcium salt  of
antimony and selenium.  The  remaining  eight  toxic   metals  have
minimum  hydroxide/oxide  solubilities only over  relatively narrow
pH ranges (see Figure  7-1).   Lead may also be effectively treated
with carbonate (soda ash, Na-,C03)  to form  insoluble basic  lead
carbonate precipitates.

It  is clear from the range  of optimum pH's illustrated in Figure
7-1 that no  single pH exists  which  can  effectively remove  all
eight  of  these  metals.  Because they rarely occur at treatable
levels and,  therefore,  rarely require removal, beryllium, silver,
mercury and  thallium can  be  eliminated from the  selection  of   an
optimum pH range  for each group.

Table  8-14  indicates that control of any metal  of Group A in the
8.5 - 9.5 pH range should control  the other members  of the group.
                              110

-------
TABLE 8-13.  ESTIMATED ACHIEVABLE LONG TEEM AVERAGE
             CONCENTRATIONS FOR PRIORITY METALS
             WITH TREATMENT OPTIONS
Toxic
Metal
Antimony
Arsenic
Beryllium
Cadmium
Qiromium
Copper
Lead
Mercury
Nickel ,
Selenium
Silver
Thallium
Zinc
(1) ID:
(2) «n.
Line/Clarification
(mg/1)
1D(«
ID
ND
0.10
0.32
0.40
0.15
ND
: 0.40
ND
ND
ND
0.80
Lime/Filtration
(mg/1)
ND<2>
ID
ND
3D
0.16
0.30
ID
ND
0.30
ND
ND
ND
0.20
Sulfide/Filtration
(rog/1)
ID
0.15
ND
ND
ND
0.20
0.10
0.034
ID
ND
ID
ND
0.12
Insufficient data for a reliable estimate
MCN /^a4-a aTT= T 1 aV\T A


                    111

-------
           TABLE 8-14.  THEORETICAL SOLUBILITIES OF TOXLC METAL
                       HYDROXIDES/OXIDES AT VARIOUS pH VALUES

PH
Metal
Group A
CZ+++
di1*
Pb"-
Zn"
Group B
ca"-
Ni"1"1"
8.5 9.5 10.5 11.5
Concentration

0.030(1) 0.20
0.00010 0. 000080 (1)
8.0 0.50(1)
0.60 0.070(1)
*
>10 1.0
1.0 0.010
(mg/1)

1.0 9.0
0.00050 0.0020
4.0 >10
0.50 3.0

0.010 0.0010(1)
0.0010(1) 0.010
(1)
    Lowest value
                              112

-------
Control of any metal of Group B in  the  10.5  -  11.5  pH  range
should control the other members of the group.  Control of metals
from  different  groups  will depend on the details of each case.
Possible approaches to controlling metals from  different  groups
might  involve the use of the intermediate 9.5 - 10.5 pH range or
the control of one  metal  in  one  group  when  the  theoretical
solubilities  of  the  metal or metals in the other group are low
throughout the 8.5 - 11.5 pH range.

Control Parameters for Sulfide Precipitation

Section 7 of  this  report  describes  sulfide  precipitation  as
potentially  superior  to  hydroxide treatment for the removal of
several toxic metals.  Sulfide precipitation has been applied  in
mercury  removal.  Figure 7-2 points out that mercury is the most
insoluble  of  the  priority  metal   sulfides   and   that   the
solubilities  of  the  metal sulfides are strongly dependent upon
pH. Operation of sulfide precipitation in the neutral or slightly
alkaline  range  should  result  in  acceptable  removal  of  all
priority  metal  sulfides  as  well  as minimizing the problem of
hydrogen sulfide evolution.  Soluble polysulfide formation can be
prevented by avoiding the very alkaline pH  range  and  by  close
control  of  excess  sulfide.   These  data  suggest that sulfide
precipitation might be used as a polishing treatment  to  enhance
metals  removal  to  very low concentrations  in other industries.
However, in  the  Phase  I  project,  we  conducted  treatability
studies    (Treatability   Study    for   the   Inorganic  Chemicals
Manufacturing Point  Source  Category,  EPA  440/1-80-103,  July,
1980)  to  determine  the effectiveness of sulfide treatment as  a
                      chlor-alkali(diaphragm  cell)  and   chrome
                        treatment.    Both   subcategories   have
                      to  those  encountered  in  the  Phase   II
                      treatability  study  showed  that  sulfide
treatment  is not significantly  more  effective  in  toxic  metal
pollutant  removal  than  lime  precipitation, clarification, and
filtration in the inorganic chemicals industry.   Hence,  we  did
not  propose  the use of sulfide treatment as a polishing step in
Phase  II   because   available  data shows  it  does  not  provide
significant  improvement  over  lime precipitation, clarification,
and filtration.

The Use of. Historical Pollutant Data

Determination  of   Effluent  Limitation  Guidelines  Based   Upon
Historical Performance

In cases  where  there  has  been long-term monitoring  of the
pollution  levels  in the effluent stream discharged by a plant, it
is possible  to   assess   in-plant   treatment   performance  through
polishing  step  for
pigments   wastewater
wastewaters  similar
industries.    That
                               113

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analysis  of  historical  data   that   has been  collected  for  this
purpose.   The  propriety  of  standards  constructed   from   data
collected   from   a   single  plant  performance  is,   of   course,
dependent on  the plant's current performance  in relation   to   the
performance of other  plants  in the manufacturing  subcategory.  As
economically    feasible     alternative    wastewater   treatment
technologies  become   available,  pollutant  discharge   guidelines
should be reviewed and revised to reflect these advances.

Statistical analysis  of historical monitoring data  is  required to
assess  a plant's  ability to discharge within set guidelines.  To
perform this  analysis certain assumptions must  be made regarding
the nature of applicable statistical or probabilistic  models,  the
constancy  of  the operation  of the  treatment facility,  and  the
quality of the monitoring methods.

The statistical analyses contained in  this  development  document
belong  to  either of  two  principal  types:  those   for  daily
observations of pollutant concentrations, and the others for   30-
day average pollutant levels.

Tables in Appendix A  provide a summary of traditional  descriptive
measures,   i.e.,   number   of   observations .(No),  mimima(Min),
arithmetic  average(Avg),  maxima(Max),   and   coefficient    of
variation(CV).     In addition,  a  descriptive  statistic,   the
variability factor, pertinent to the development  of   performance
standards  for  pollution monitoring,  is included.  These  tables,
prepared for both  daily  measurements  as  well  as   for  30-day
averages,  are statistical summaries derived from data offered by
industry in response  to Section  308-Questionnaires,  and  offered
in  comments  on   the proposed Phase I and Phase II re gulations.
Data in these tables  are  representative  of  currently  achieved
pollutant  discharge  performance  levels  in   the several plants
presented.
                                                            /
Formulation of variability factors to be used in determination of
effluent limitations  guidelines based upon historical  performance
was accomplished by employing standard statistical analysis  from
the  data  resulting  from long-term monitoring of effluent stream
discharges from plants in the  inorganic  chemical  manufacturing
subcategories.  In the following paragraphs are presented details
of the theory and  derivation of these statistical procedures,  and
of the resulting formulae which  relate  variability   factors  to
estimated  long-term  parameter  averages,   standard   deviations,
coefficients of  variation,   and  "Z-values"  computed  from  the
normal  probability  distribution.    These details are given both
for the analysis applying to daily maxima criterion and for  that
applying to 30-day averages.
                              114

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The term "variability factor" refers to the multiple of the long-
term  average which is used in formulating performance standards.
This factor allows for variation in pollution level  measurements
due  to  sampling  error,  measurement error, fluctuations in the
amount of the pollutant  in  raw  materials,  and  other  process
variations.

In  the recording of actual data, as reported by industrial point
sources in their responses to Section 308 Questionnaires, certain
data values were entered as "less than" detectability  limits,  in
these cases, the set of monitoring data has  been   censored   in
the  process of data recording since only the threshold value has
been retained  (i.e., if a pollutant concentration was  reported as
<0 050  mg/1,  the  value  of  0.050  mg/1  was  used).   In  the
statistical  analysis  of  monitoring  data, censored  values were
included with measured  values   in  the  sample.   This   practice
provides   a  reasonable  approach,  both for assessing industry  s
capability to  perform  and  environmental  concerns   for  valid
pollutant  limitations.

First,  since  censoring was done only for  "less  than"  bounds, any
bias from  their  inclusion would  cause a slight   increase   in  the
long-term   average,  moderately  affecting   (in  the  direction of
leniency toward   industry)   the  estimate   of   long-term   average
pollution  levels.

On  the other  hand,   the   use  of  censored values  combined  with
measured values  tends  to reduce  the  variability  slightly   (or  in
the  direction of less leniency  toward  industrial point sources).
For  illustration,  if  the  sample  consisted  solely   of  censored
values,   the   estimated  long-term   average  might   be  slightly
overstated.    Nevertheless,   the  point  source  should  have  no
difficulty  with  the  threshold  or  detectability   limit  as   a
performance guideline, since none  of the historical  data exceeded
 that limit.

 Statistical analysis of  influent   and  effluent  data  submitted
 during  the  comment  period  by  cadmium  pigments  producers is
 described in detail in Section 11  below.   Statistical analysis of
 data from a treatability study we conducted at  a  zinc  chloride
 manufacturing plant is described in detail in Section 16 below.

 Assumptions Concerning Daily Pollutant Level Measurement

 In  the  formulation and calculation of the following performance
 standards, individual sample  measurements  of  pollutant  levels
 were   assumed  to follow the lognormal distribution,  a well known
 and generally accepted  statistical  probability  model  used   in
 pollution  analyses.   Under  this  assumption  the logarithms of
                                115

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 these measurements follow a normal  probability  model.   It  was
 also  assumed  that  monitoring  at  a  given plant was conducted
 responsibly and in such a way that resulting measurements can  be
 considered  statistically  independent  and  amenable to standard
 statistical procedures.  A final assumption  was  that  treatment
 tacilities  and  monitoring techniques had remained substantially
 constant throughout the monitoring period.

 As an  indication  of  the  propriety  of  assuming  a  lognormal
 distribution for daily measurements,  the  plot of the cumulative
 distribution  of  logarithms of daily effluent concentration data
 on normal probability paper is illustrated in Figure 8-1.

 The linearity of the cumulative  plot  indicates  the  degree  to
 which   actual   monitoring   data  are  in  agreement  with  the
 theoretical lognormal model for their distribution.
 In addition,  Figure 8-2,  also demonstrates the
 lognormal  assumption for  daily data.
validity  of  the
 In   the  analysis  of  daily  data,   the  inherent variability of
 measured pollutant levels in the effluent stream  from  inorganic
 chemical   manufacturing   processes   must   be  incorporated  in
 calculating upper limits for daily  pollutant  discharge  levels
 Even  plants exercising good treatment  and control may experience
 some days when  atypically high levels of pollutants  are  present
 in  their treated  wastewater streams.  Such high variations may be
 due to a variety  of factors,  such as short-term maladjustments in
 treatment  facilities,   variation  in  flow  or  pollutant load,  or
 changes in the  influent stream.   To  allow for  this  variability
 performance  standards   must  necessarily be  set above the plant's
 long-term average  performance.    However,   effluent   limitations
 guidelines  must   be set at a level  low enough  to  ensure adequate
 control.   Establishing  effluent   guidelines   that   balance  these
 factors  means  that occasional,,   infrequent  instances  of  non-
 compliance are  statistically   predictable at  well-operated   and
 maintained  treatment  facilties.    Since pollutant  discharge is
 often  expressed in  terms of average  level, it  is   convenient   to
 describe   standards  of  performance and  allow  variability in terms
 of multiples  of  this   average.   Such   a  method  of   computing
 standards   as functions  of  multiples  of  average  level performance
 is explained below.   The ratio of the pollutant  standard level  to
 tne  estimated  long-term  average    is   commonly    called    the
 "variability factor".

This  factor  is  especially  useful  with lognormally distributed
pollutant  levels because  its value is independent  of  the  lonq-
term  average,  depending only upon the day-to-day variability of
the process  and  the  expected  number  of   excessive   discharge
                              116

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periods.   For  a  lognormal  population,  the variability factor
(P/A), the performance standard P, and the long-term  average  A,
are related by:

          In (P/A) = S'(Z - SV2)

          where
     A.   "In" represents the natural logarithm
          numerical quantity.
                                                 (base   e)   of   a
     B.
      C.
          S'   is   the  estimated   standard   deviation   of    the
          logarithms  of   pollutant   level measurements.    In the
          calculations which  follow,   S1  is  computed   by  the
          statistical procedure known as the "method of moments".
          The  "method of  moments"  is a commonly used method of
          estimating the  parameters  of a population  distribution
          from    computed    characteristics   of   the    sample
          distribution.  In this  case,  the mean and variance (the
          first two "moments") of the lognormal distribution were
          equated  to  the  mean   and  variance  of  the    sample
          distribution.   The  formula for the parameter, S1, was
          then derived (S1  is  the   standard  deviation   of  the
          logarithms).

          Z  is  a  factor  derived   from  the  standard    normal
          distribution.    Z   is   chosen  to  give  performance
          limitations which provide  a balance between appropriate
          consideration of day to day  variation  in  a  properly
          operating  plant  and  the  necessity  to ensure that a
          plant is functioning properly.

The value of Z used for  determining  performance  standards  for
daily  measurements  of  pollutant  concentration  is  chosen  as
Z=2.33.  This Z-value corresponds to the  99th percentile  of  the
lognormal  distribution  meaning  that  only  1  percent  of  the
pollutant observations taken from a plant with  proper  operation
of  treatment  facilities  would  be greater than the performance
standard, P.  Use of this percentile statistically  predicts  one
incident  of  non-compliance for every  100 samples for a plant in
normal operation.  Many plants in this  industry are  required  by
their  NPDES  Permits  to  self-monitor   once  per week.   At this
frequency, there will be  260 samples analyzed  over  the  5  year
life  of the permit.  The use of the 99th percentile to establish
daily maximum limitations statistically predicts  2 to  3  incidents
of non-compliance per pollutant  in 5 years.  This percentile  has
been  used   to  establish daily maximum limitations for  inorganic
chemicals manufacturing.
                               117
                       V

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 A.    Calculation of Variability Factors

 As  mentioned above, development of variability factors for  daily
 pollution  level  measurements  was  based on the assumption that
 these data,  (XI,X2,...Xn),  follow a lognormal distribution.   When
 this distribution is  not  a  precise  model,  lognormally  based
 procedures  tend to somewhat overestimate variability and produce
 liberal standards which act to the benefit of permittees.

 Following this assumption,  if Yi=ln(Xi),  where ln(Xi)  represents
 the natural  logarithm or log base e of the pollution measurement,
 then  the  Yi;  i=l,2,...,n are each normally distributed.   If A'
 and  S1   are  the  mean  and  standard   deviation   of   Y=ln(X)
 respectively,    then    the   probability  is  k  percent  that  an
 individual Y  will  not  exceed  A'+ZS',   where  Z  is  the   k-th
 percentile  of the standard normal distribution,  e.g.,  Z=2.33 is
 the 99th percentile of  the  standard  normal  distribution.    It
 follows  that   A'+ZS'   is  the  natural  logarithm  of  the   k~th
 percentile of  X  and that the probability  is k percent that X will
 not  exceed  a  performance   standard   P=exp(A'    +ZS1).     The
 variability  factor VF,  is obtained by dividing  P by A.   For the
 lognormal distribution,  the best measure  of central tendency,   or
 the expected value,  is A =  exp(A'+S'(S'/2)).   Hence,

 VF  =  P  = exp (A1  •»• ZS' )
       A   exp (A1  + S1  (S'/2))

    - exp [A1 + ZS1  -  (A1  +  S1  (S'/2))]

    = exp [ZS1  -  S'  (S'/2)]

    = exp [S1 (Z-SV2)]

      ln(VF)  =  ln(P/A)  =  S'(Z  - S'/2)

 To  estimate  the  VF for  a  particular  set of  monitoring data, where
 the   method  of  moments  is  used, S'  is  calculated as the square
 root  of   ln(1.0   +  (CV)2),   where   the  sample   coefficient   of
 variation,   (CV  =  S/X),  is  the ratio  of sample standard deviation
 to sample  average.  The performance  standard  is then  calculated
 by   multiplying  the  variability  factor,  VF,  by the long-term
 average, A.  In  these calculations,  the  sample average,  X,   is
 used  as  the  unbiased estimator of  A  (the  best  estimate of A)(22).
B.   Example Calculation of Variability  Factors
Data
From  Long-Term
Given  the  following  descriptive  statistics  for  a particular
parameter, as might be found for zinc (mg/l)in Appendix A:
                              118

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         Total  Zinc Concentration (mg/1)
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             NDBMAL DISTRIBUTION
              (MODEL DENSITY OF LOGARITHMS OF POLLUTION VALUES)
                                       ln(P) = A' + 2.33(S')
                                          Y  = Oji(X) = Logarithm  (mg/1)
        LOGNORMAL DISTRIBOTION
         (MODEL DENSITY OF
        POLLUTION VALUES)
                                                  X(mg/l)

                                          _ P (Performance Standard)
                      '-A (Long Term Arithmetic Average)
         SAMPLE DISTRIBUTION OF N MEASUREMENTS
            (LONG TERM MONITORING DATA)
       ^Min   f        M33^       XCmg/1)
               X (Sample Average)

  Note:  (a)   S1  is estimated as (S1)2 = [ln(l + CV2)J
              S2= Z (X-X)

              X= ZX/N

Figure 8-3.  Statistical distribution for daily pollution measurements.
                             121

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          No
Min
Avg
Max
CV
          442  0.014   0.224   4.4     1.26

Calculate the estimated standard deviation of logarithms

          (S')2 = In  (1.0 +  (1.26)2)  = 0.951
          S' = 0.975

Then:

          ln(P/A> = 0.975(2.33 - 0.975/2) = 1.796

          The variability factor VF  is,

          VF = P/A = exp(1.796) =6.03

          The performance standard P;

          P = A(VF) = A  (P/A) = (0.224)  (6.03) = 1.35

That  is,  using  the  descriptive   statistics  for  a  pollutant
presented  above and the statistical approach just described, the
daily maximum limitation established  for  that  pollutant  in  a
guideline would be 1.35 mg/1.

The  statistical distributions relevant  for the analysis of daily
data are shown in Figure 8-3.

The statistical interpretation of P, the performance standard, is
that one estimates that 99 percent (for  the selected Z=2.33 value
corresponding to the 99th  percentile)  of  the  daily  pollution
level  measurements will not exceed  P.  For large data sets, P is
roughly equivalent to an upper 99 percent confidence bound for an
individual daily measurement.

Assumptions Concerning 30-day Average Pollutant Level Observation

While individual pollution level measurements should  be  assumed
lognormally  distributed, that assumption is not appropriate when
analyzing 30-day averages.    These  averages  generally  are  not
distributed  as  lognormal  quantities.  However, for averages of
daily (lognormal)  measurements,  a  statistical  principle,  the
"Central  Limit Theorem", provides the basis for using the normal
probability model.  Therefore,  the  methods  used  in  computing
historical performance characteristics for 30-day averages differ
from  those  used  for  daily  samples.  In this case, the sample
                              122

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coefficient of  variation  is  the  primary  determinant  of  the
variability factor, and there is no need to resort to logarithmic
transformation.   Examples of the propriety of this assumption is
the cumulative distribution of 30-day averages shown  in  Figures
8-4  and  8-5.   A  straight line plot here on normal probability
paper indicates the validity of this model.

Under these conditions, the 30-day average values  (X1,  X2,
Xm),  for  m  months  behave  approximately as random data from a
normal distribution  with  mean  A  and  standard  deviation  S .
Therefore,  the probability is k percent that a monthly average X
will not exceed the performance standard P, where

          P = A +  Z(S")

          The variability factor iss

          VF  = P/A = 1.0 + Z(S"/A) and will be estimated by
VF = 1.0

Where:
                      Z(CV)
      1 .     i   is   a   factor   derived   from   the   standard   normal
distribution.    If  one   wishes  a  performance  standard based  upon
expecting  95  percent of  monthly  averages  to  be within guidelines,
then  Z=1.64 should be used.

      2.    CV  is the  estimated coefficient of variation of  the 30-
day averages  and is  computed by  Sx/X,  the ratio  of standard error
of sample  means to overall  or grand average  of monthly averages.

Calculation of Variability  Factors

A sample calculation of   30-day   average  variability  factor  is
shown below.   The descriptive statistical data is for lead (mg/1)
from  Appendix A:
           No
     Min
Avg
Max
                                        CV
           38   0.025 -  0.036   0.047   0.15

      VF « 1  + Z(CV) - 1.0 + 1.64(0.15) = 1.25

      P = A(VF) = (0.036X1.25)  = 0.045

 That  is,  the maximum 30-day average effluent limitation derived
 from the descriptive statistics above would  be  0.045  mg/1  for
 that pollutant.
                               123

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 Given  the  previous  descriptive  statistics  for  a  particular
 sample,  one obtains the performance standard  P,   by  multiplying
 the  mean  of  the  30-day  averages  in  the data set by VF.   An
 appropriate statistical interpretation is that,   for the selected
 value of Z=1.64 corresponding to the 95th percentile of a  normal
 distribution,  one estimates that 95 percent of the 30-day average
 pollution  level  measurements  will  not  exceed  P,  or in other
 words,  the statistics predict an average of 3 incidents  of  non-
 compliance  with the 30-day average per pollutant over the 5-year
 (60-month)  life of a permit at  a  well-operated   and  maintained
 treatment  facility.    This  is  essentially  the  same number  of
 predicted incidents of non-compliance as was predicted for  daily
 maximum   limitations derived using the 99th percentile confidence
 level (see above).   In Phase I,  the  95th  percentile  confidence
 level was  used  to  establish  the  30-day average limitations.
 Moreover,  in a number of  instances,  plants in Phase II also make
 Phase I  chemicals and treat the wastewater in the same treatment
 facility.

 In  developing  the statistical  derivatives for monthly  averages,
 in  many   cases,   a  full  30 days of daily average determinations
 were  not  available.   In the above example,   the   monthly  average
 is,  based   on   eight   data   points  taken  during the  month.  The
 standard  deviation  is then  derived from these "monthly"   averages
 assuming  a normal   distribution for the population of  averages.
 Permits are usually written on   the   basis  of  monthly   averages
 obtained  from   fewer  than 30  data  points per month.   The  use of
 such  monthly   averages results   in   a   higher  variability  than
 averages  based  on   30 data points per  month and,  hence,  a less
 stringent performance standard  than  would be  attained   using  30-
 day averages based  on 30 data points per  month.

 Figure  8-6  shows the relationship between  the normal  probability
model and frequency distribution  of  a set  of  30-day  averages.
                              124

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                          DISTRIBUTION

    (MODEL DENSITY OF 30-DAY AVERAGE POLLUTION
                                      X(mg/l)
                                — P (Performance Standard)
                    „ A (Long Term Average)
            SAMPLE DISTRIBUTION OF M MONTHLY AVERAGES
                   (LONG TERM MONITORING DATA)
           •Min
Max
X(mg/l)
                   - X (Average of 30-Day Averages)
          Note:   (a)  P/A = 1+1.64 (CV)

                       CJ = S^/X

                      (S^)2=(Z  (X-XV(M-1))

                     1=2:  X/M
Figxore 8-6.  Statistical distributions for 30-day average pollution measurements.
                              127

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                             SECTION  8

                             REFERENCES
10,
11
Hannah,  S.A.,  M.  Jelus,  and  J.M.  Cohen.   Removal  of Uncommon
Trace Metals by  Physical and Chemical   Treatment   Processes.
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Patterson,  J.W.,   and  R.A.   Minear.    Wastewater   Treatment
Technology.  Illinois  Institute  of  Technology,  1973.

Patterson,  J.W.,  and Wastewater  Treatment  Technology.    Ann
Arbor Science  Publishers,  Inc.   Ann Arbor,  Michigan,  1975.

Maruyama, T.,  S.A.  Hannah,   and J.M.   Cohen.   Removal   of
Uncommon Trace   Metals   by   Physical  and Chemical  Treatment
Processes.   Journal   Water   Pollution  Control    Federation
49(11):2297-2305,  1977.

Gulledge, H.H.,  and J.T.  O'Connor.  Removal of  Arsenic   (V)
from  Water by Adsorption on Aluminum  and Ferric Hydroxides.
Journal  American  Water  Works Association  65   (8):548-552,
1973.

Gupta, S., and K.Y. Chen.  Arsenic  Removal  by  Adsorption.
Journal  Water  Pollution  Control  Federation  50  (3):493, 1978.

Scott, M.C. Sulfex - A New Process  Technology for Removal  of
Heavy Metals from Waste  Streams.    The  32nd  Annual  Purdue
Industrial  Waste Conference, Lafayette, Indiana,  1977.   17
Pp.

Larsen,  H.P.,  J.K. Shou,  and L.W. Ross.   Chemical   Treatment
of  Metal-Bearing Mine   Drainage.   Journal Water  Pollution
Control  Federation.

Scott,  M.C. Heavy Metals  Removal  at Phillips Plating.  WWEMA
Industrial Pollution Conference,  St. Louis, Missouri,  1978.
16 Pp.

Schlauch,  R.M.,  and  A.C.   Epstein.    Treatment   of  Metal
Finishing Wastes  by Sulfide  Precipitation.  EPA-600/2-75049,
U.S. Environmental Protection Agency,  1977.  89 Pp.

Coleman, R.T.,  J.D. Colley,  R.F.  Klausmeiser, D.A.   Malish,
N.P.   Meserole,   W.C.   Micheletti,   and  K.  Schwitzgebel.
Treatment   Methods    for    Acidic   Wastewater   Containing
                              128

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12.


13.
14.
15.
16,
17
18
19,
20,
21
Potentially  Toxic Metal Compounds.  EPA Contract No. 68-02-
2608, U.S. Environmental Protection Agency, 1978.  220 Pp.

Nilsson, R.  Removal of  Metals  by  Chemical  Treatment  of
Municipal Wastewater.  Water Research 5:51-60, 1971.

Calspan Corp. Addendum to Development Document for  Effluent
Limitations Guidelines and New Source Performance Standards.
Major  Inorganic  Products  Segment  of  Inorganic Chemicals
Manufacturing   Point   Source   Category.    Contract   No.
68-01-3281, 1978.

Sorg,  T.J.,  O.T.  Love,  and  G.S.  Logsdon.   Manual   of
Treatment   Techniques   for  Meeting  the  Interim  Primary
Drinking   Water   Regulations.    EPA-600/8-77-005.    U.S.
Environmental Protection Agency, 1977.  73 Pp.

Colley, J.D., C.A. Muela, M.L.  Owen,  N.P.  Meserole,  J.B.
Riggs, and J.C. Terry.  Assessment of Technology for Control
of Toxic Effluents from the Electric Utility Industry.  EPA-
600/7-78-090.  U.S. Environmental Protection Agency, 1978.

Smithson, G.R., Jr.   An  Investigation  of  Techniques  for
Removal  of  Chromium from Electroplating Wastes.,  EPA 12010
EIE.  U.S. Environmental Protection Agency, 1971, 91 Pp.

Patterson, J.W., H.E.  Allen,  and  J.J.  Scala.   Carbonate
Precipitation  for  Heavy  Metals Pollutants.  Journal Water
Pollution Control Federation 49(12):2397-2410, 1977.

Sabadell, J.E.  Traces of  Heavy  Metals   in  Water  Removal
Processes    and    Monitoring.    EPA-902/9-74-001.    U.S.
Environmental Protection Agency, 1973.

Wing, R.E., C.L. Swanson,  W.M.  Doane,  and  C.R.   Russell.
Heavy   Metal  Removal  with Starch Xanthate-Cationic Polymer
Complex.   J.  Water  Pollution   Control   Federation,    46
 (8):2043-2047, 1974.

U.S. Environmental  Protection Agency.  Environmental Multi-
Media Assessment of  Selected  Industrial  Inorganic Chemicals.
EPA Contract No.  68-03-2403,  1977.

U.S. Environmental  Protection Agency,  Development   Document
for  Final  Effluent  Limitations   and  Standards   for   the
 Inorganic Chemicals Manufacturing  Point  Source Category,  EPA
Report  No.  440/1-82-007, June  1982.
                               129

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22.   Edmonson, B.C., "Letter to Jacobs  Engineering  Group  Inc.,
     detailing  statistical methodology developed for Phase I and
     II Inorganic Chemicals," March 15, 1983.
                             130

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                            SECTION 9

                TREATMENT TECHNOLOGY APPLICATIONS
                   FOR TOXIC POLLUTANT REMOVAL
Selection of Pollutants to be Controlled

In order to determine which toxic pollutants, if any, may require
effluent limitations, the pollutants observed in each subcategory
were evaluated with regard to their treatability on the basis  of
the   raw   waste   concentrations  found  during  screening  and
verification.  In an attempt to determine the need for regulation
the toxic metals were divided into two groups:

Group 1  - Those priority pollutants which appear at concentration
levels that are readily treatable using available technology.

Group 2 - Other treatable and/or potentially  treatable  priority
pollutants  observed  in  the  subcategory.   These include toxic
metals  which  exist  at   concentrations   rbelow   the   minimum
treatability  limit  and  above the minimum detection level.  The
Group 2 pollutants would be  controlled  by  the  same  treatment
technology used to control the Group 1 pollutants.

Table  9-1  presents the significant toxic pollutant metals found
in each group.  In general, those metals occurring in  the  first
group  are  of  prime concern and require regulation, while those
occurring in the second group are of somewhat  less  concern  and
are  not  expected  to require regulation.  Metals in Group 2 are
controlled by the technologies used  to  control  the  metals  in
Group  1, which are the dominant metals in the raw wastewater and
are directly related to the particular product, process involved,
or raw material.

Application of Advance Level Treatment and Control Alternatives

General Design Objectives

Beginning with Section 11 of this  document,  the  selection  and
application  of  toxic pollutant treatment and control technology
for model plant systems for each of the  regulated  subcategories
are described.  Several levels of treatment are indicated.  Level
1  represents  existing  treatment systems and the advanced level
(Level 2) is the selected technology for  step-wise  improvements
in  toxic  pollutant  removal  over  that achieved by the Level  1
system.   Flow diagrams show Level  1  components  as  a  starting
point for advanced level treatment additions and incremental cost
estimates.
                              131

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     TABLE 9-1.
Subcategory

Cadmium Pigments
 and Salts
Listing of priority and non-conventional pollutants
recommended for consideration by subcategory
         Group 1(1)

         Cadmium
         Selenium
         Zinc
Cobalt Salts
Copper Salts
Nickel Salts
Sodium Chlorate
Zinc Chloride
         Cobalt
         Copper
         Nickel

         Copper
         Nickel
         Nickel
         Copper
         Chromium (Total)
         Chlorine (Total
                   Res.)
        Arsenic
        Zinc
 Group 2(2)

 Antimony
 Arsenic
 Barium
 Chromium
 Copper
 Lead
 Nickel

 Lead
 Zinc
Antimony
Arsenic
Chromium
Lead
Zinc

Antimony
Cadmium
Chromium
Lead
Zinc

Antimony
Copper
Lead
Nickel
Zinc
Chromium  (VI)

Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
(1)   Group 1 - dominant raw waste pollutant's as  control  parameters for
     effluent limitations  or  guidance.

(2)   Group 2  - secondary  raw  waste pollutants  found less  frequently
     and  at  lower  concentrations.    These  pollutants   have  not  been
     selected  as   control parameters   but  are   expected  to  receive
     adequate  treatment   as  a  result   of  controlling   the  Group  1
     pollutants.
                            132

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For  both existing and new sources, the advanced level technology
options are selected as candidates for BAT with  toxic  pollutant
removal  as  the  primary objective.  Although the advanced level
systems chosen also give improved performance over  the  Level  1
systems  for  the  removal  of  conventional  and nonconventional
pollutants, this is regarded as a secondary design objective.

Pretreatment Technology

Since untreated heavy metal ions will  either  pass  through  the
treatment  provided  in  a  typical POTW, or will be precipitated
with the POTW solid residue, pretreatment  of  wastes  containing
significant  amounts  of heavy metals is necessary.  As a general
rule, alkaline precipitation, followed by settling and removal of
the solids will  suffice.   Normally  the  Level  1  or  2  model
treatment  processes  shown  in the following subsections will be
appropriate for pretreatment prior to discharge to a POTW.  Pass-
through would occur in the absence of pretreatment  when  BPT  or
BAT  treatment  would  reduce  toxic  metal  concentrations  by a
greater percent than is achieved by a POTW.

New Source Performance Standards

New Source Performance Standards are at least equal to  BAT.   In
cases where new plants have the opportunity to design systems for
better  toxic removal performance without expensive retrofitting,
EPA has used  the  higher  technology  systems  as  a  basis  for
regulation.

Estimated  Achievable  Performance  Characteristics  for Advanced
Level Applications

Advanced level control and treatment alternatives  for  reduction
of   pollutant   discharges   and  their  applicability  to  each
subcategory are presented in the sections dealing with individual
products.  With few exceptions, these alternatives were  selected
specifically for removal of priority pollutants and were designed
for end-of-pipe treatment.

Treatment   technologies   practiced  outside  the  industry  are
recommended when appropriate and, in most  cases,  apply  to  the
removal  of  toxic  pollutant  metals.   The  estimated long-term
average treatability levels (Section 8, Tables 8-11, 8-12, 8-13),
long-term data parameters, and  the  screening  and  verification
results   are  all  utilized  in  the  development  of  estimated
performance   characteristics   for   the   indicated   treatment
applications in each subcategory.

Advanced Level Removal of BPT Pollutants
                              133

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Performance  estimates  for  these  systems,  when possible, were
based on effluent quality achieved at plants currently practicing
these technologies.  However, in some cases, the advanced  levels
are not currently being practiced within the specific subcategory
of  concern,  and  performance information from other appropriate
sources is necessarily utilized.

When  established  wastewater  treatment   practices,   such   as
clarification  or  filtration,  form a part of advanced treatment
alternatives, the specified achievable effluent quality has  been
based  on  concentrations  accepted  as achievable through proper
design and control.  The  prime  example  of  this   is  suspended
solids redaction by filtration.

Advanced Level Removal of Toxic Pollutants

Performance  estimates for toxic pollutants were also based, when
possible,  on  effluent  quality  achieved  at  plants  currently
practicing  these  technologies.  However, in some subcategories,
toxic pollutant analyses are  not  conducted  unless  a  specific
pollutant  is  regulated and requires monitoring.  Where transfer
of technology is applied as a treatment alternative,  performance
estimates   for  toxic  pollutant  removals  were  based  on  the
demonstrated performances in other industries while  incorporating
allowances   for   specific   differences   in   process    waste
characteristics  and operating conditions.  Statistically derived
long-term monitoring data parameters were Described  in Section  8
and  are  compiled  in  tabular form in Appendix A.  The sampling
data are used to supplement the available long-term data  applied
to  each  subcategory.   A  judgment is made whether the sampling
data represent a well-performing  system  or  one  which  is  not
performing at its technological potential.  For a well-performing
system, the sampling data are regarded as representative of long-
term  averages  and  are compared with the estimated treatability
ranges from  Table  8-11,  as  well  as  the  long-term  averages
developed  from  long-term data.  In this manner, the performance
estimates for each pollutant, at each  treatment  level  for  the
subcategories,  are developed and presented in tabular summaries.
By starting with the estimated achievable long-term averages, the
specific variability factors derived for each pollutant are  used
to estimate the daily maximum values and 30-day average values.

Pollution Control Parameters to be Regulated
Conventional Pollutants

Wastewater   quality   parameters   which   are
conventional pollutants include the following:
identified   as
                              134

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     pH
     Total Suspended Solids (TSS)
     Biochemical Oxygen Demand, 5-Day (BOD-5)
     Fecal Coliform
     Oil and Grease

Only the first two parameters  (pH and TSS)  in  this  group  have
been   selected   for   regulation  in  the  Inorganic  Chemicals
Manufacturing Point Source  Category,  because  the  other  three
pollutants  are  not  found  at  treatable  levels  in  inorganic
chemical  process  wastewaters,  and  are  not  associated   with
inorganic chemical manufacturing.  For direct dischargers, the pH
range  of 6 to 9 (6-10 in the zinc chloride subcategory) has been
established as the general control  limitation.   For  continuous
monitoring  of  pH,  40 CFR 8401.17 allows pH excursions of up to
one hour per day.  The limitations on TSS are specified for  both
BPT  and  BCT-based  regulations,  the  former  being  largely  a
function of industry performance and  the  latter  stemming  from
treatability estimates with the appropriate technologies.

Nonconventional Pollutants

The  wastewater  quality parameters classified as nonconventional
pollutants include the nontoxic metals such as  aluminum,  boron,
barium, cobalt, and iron along with chemical oxygen demand (COD),
total   residual   chlorine,   fluoride,  ammonia,  nitrate,  and
"phenols," etc.  Of  these,  only  total  residual  chlorine  and
cobalt  were  considered  for  regulation  in  this  group of the
inorganic  chemicals  industry  because  they   were   the   only
nonconventional  pollutants detected at treatable levels.  Due to
its toxicity, chlorine would be controlled in direct  discharges,
but  would  be  excluded from control in pretreatment regulations
because influent to POTW's is often chlorinated.

Toxic Pollutants

The toxic pollutants found at significant levels during screening
and verification are listed by  subcategory  in  Table  9-1.   Of
these,  toxic  pollutant control parameters were selected largely
on the basis of treatability.  Since several toxic pollutants may
be controlled by a common treatment technology, it is possible to
select one or  more  control  parameters  which  will  act  as  a
surrogate   for   others   exhibiting   the   same   treatability
characteristics.  Treatment  system  operating  conditions  would
normally  be  optimized  for the removal of the specified control
parameters which would be monitored  on  a  regular  basis.   The
other toxic pollutants would be monitored much less frequently as
a periodic check of the effectiveness of surrogate control.
                              135

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The  following  toxic  metals and nonconventional pollutants have
been designated  as  control  parameters   in  this  point  source
category:

     Antimony
     Arsenic
     Cadmium
     Cobalt
     Chlorine (Total Residual)
     Chromium (Total)
     Copper
     Lead
     Nickel
     Selenium
     Zinc

The specific control parameters selected for each subcategory are
presented  in the tables entitled "Control Parameter Limitations"
in the sections  of  this  report  dealing  with  the  individual
industries.  Some general comments about them are given here.

The most common technology applied in  industry for the removal of
chromium  from  wastewaters involves a reduction step, whereby Cr
(VI) in solution is converted to the less  toxic  Cr  (III)  form
which  can  then  be  removed  by  alkaline  precipitation.   The
efficiency of this treatment depends   upon  the  presence  of  an
excess  reducing 'agent and pH control  to drive the reduction step
to completion.  When treated effluent  samples  are  collected  to
monitor   residual   Cr  (VI)  and  total  chromium  levels,  the
analytical results for Cr (VI) are  subject  to  several  factors
which  adversely  affect  the accuracy and reproducibility of the
diphenylcarbazide (DPC) colorometric method.  The problem is  not
so  much  one  of analytical interferences with the Cr (VI) - DPC
color development, but rather  the  actual  changes  in  Cr  (VI)
concentration   that  can  take  place  during  sampling,  sample
preservation and storage, and analysis.  The major cause of  such
changes  is  the  presence  of  an  excess  reducing agent in the
treated effluent.  This tends to give  false low readings  for  Cr
(VI) although in some cases the opposite may occur as a result of
sample   preservation   and   storage   under   acidic  oxidizing
conditions.

Thus, in view of the questionable reliability  of  the  presently
accepted Cr (VI) monitoring procedure, total chromium, Cr (T), is
recommended  as the control parameter  to be used in the inorganic
chemicals  industry.   The  adequacy  of  Cr  (T)  as  a  control
parameter  is  predicated on its effectiveness as a surrogate for
Cr (VI) control.  Since the concentration of  Cr  (T)  represents
the summation of all forms of chromium normally found in solution
                              136

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or  suspension  including  Cr (VI), the final concentration of Cr
(T) in a treated effluent is dependent on  the  effectiveness,  of
both the reduction and the alkaline precipitation steps.  In this
way,  the  use  of  Cr  (T) as the control parameter assures that
adequate removal of  Cr  (VI)  is  being  achieved  as  a  direct
consequence of the treatment technology required.
                              137

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                           SECTION 10

              COST OF TREATMENT AND CONTROL SYSTEMS
INTRODUCTION
The  costs,  cost factors, and costing methodology used to derive
the capital and annual costs of treatment and control systems are
documented in this section.   All  costs  are  expressed  in  3rd
quarter 1982 dollars.

The following categorization is used for presenting the costs:

     Capital Costs

     Facilities
     Equipment (including monitoring instrumentation)
     Installation
     Engineering
     Contractor Overhead & Profit
     Contingency
     Land

     Annual Costs

     Operations and Maintenance
     Operating Personnel
     Facility and Equipment Repair and Maintenance
     Materials
     Energy
     Residual Waste Disposal
     Monitoring, Analysis and Reporting
     Taxes and Insurance
     Amortization

TREATMENT AND DISPOSAL RATIONALE

The following assumptions are employed in the cost development:

     A.   Noncontact cooling water  generally  is  excluded  from
          treatment   (and  treatment  costs)  provided  that  no
          pollutants are introduced.

     B.   Water treatment,  cooling  tower  and  boiler  blowdown
          discharges are not considered process wastewater unless
          such flows contain significant amounts of pollutants.

     C.   Sanitary sewage flow is excluded.
                              138

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     D.
Sodium chorate plants are assumed to operate 350 days a
year, sodium chloride and  sodium  sulfite  plants  365
days  per year, and all other plants 250 days per year.
All plants are assumed to operate 24 hours per day.
     E.


     F.
Manufacturing plants are assumed to be
plants.
single  product
     G.
The  inorganic  chemical  industry   extensively   uses
in-plant   control   techniques   such   as  in-process
abatement   measures,   housekeeping   practices,   and
recycling  of  process  wastewaters to recover valuable
materials or use these materials as feed for other  by-
products.   Segregation  of  uncontaminated cooling and
other waters prior to treatment  and/or  disposal,  and
other  similar  measures  can  contribute to waste load
reduction.  The costs associated with these  activities
are not included in the cost estimates.

Excluded from the estimates are  any  costs  associated
with   environmental   permits,   reports  or  hearings
required by regulatory agencies.
COSTS REFERENCES AND RATIONALE

The  cost  information  developed  in  this   report   represents
engineering  estimates.   The basic cost information utilized was
obtained  from  a   variety   of   sources   including   building
construction   manuals  and  vendors  of  the  various  types  of
equipment utilized  in  the  prescribed  treatment  and  disposal
systems (References 1, 2, 3, 4, 5, and 6).

Selected facility and treatment system engineering cost estimates
were  validated  by  comparing  computed  costs with actual costs
incurred for the installation of such facilities and equipment by
contractors and vendors.

CAPITAL COSTS

Facilities

Lagoons/Settling Ponds.  The cost  of  constructing  lagoons  can
vary widely, depending on local topographic and soil conditions.

The  costs  and  required areas of lagoons and settling ponds are
developed as a function of volume  (capacity).  It is assumed that
lagoons and settling ponds are rectangular  in  shape,  with  the
bottom  length twice the bottom width.  The dikes are constructed
with a 2:1 slope and a 3m (10 ft.) top surface to  permit  sludge
                               139

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removal  by the clamshell method.  The interior area is excavated
to a depth sufficient to provide all the material needed for  the
construction  of  the  dikes.   The earth is assumed to be fairly
heavy and to contain stiff clay.
A  common,  transverse  dike  is
dewatering for sludge removal.
 provided  to  permit  alternate
The  cost-estimating relationship shown below is used to estimate
lagoon/settling pond costs.

     1.1 (($0.25 x total area) + ($5.15 x dike volume)
     +  ($0.45 x dike surface))

The 1.1 factor represents the  cost  of  the  common,  transverse
dike.  The cost factors are derived from References  1 and 2.  The
cost factor applied to the total area occupied by the impoundment
(measured  in  square  meters)  is for clearing with a bulldozer.
The cost factor associated with dike volume  (measured  in  cubic
meters)  includes  excavation  with  a  bulldozer, compaction and
grading.  The  cost  factor  associated  with  the  dike  surface
(measured in square meters) represents the cost of fine grading.

The  variables  required  for  the  use  of  the  cost-estimating
relationship can be obtained from Figures 10-1, 10-2, 10-3.
Lagoons are unlined, except where specified.
costs are noted below:
             Liner material  and
     Polyethylene (installed)

     Clay, 60 cm (2 ft) depth
     Clay on-site (installed)
     Clay off-site (installed)
  $6.50/m2 ($0.60/ft2)
$2.35/m2 ($0.20/ft2)
$7.80/m2 ($0.70/ft2)
Perimeter  fencing  (chain  link,  industrial)  is  provided  for
lagoons and sludge disposal sites at a cost of $8.80/linear meter
($2.65/ft) plus a sliding gate at $100.

Roads where necessary represent temporary (graded  and  graveled)
roads  4  m  (13  ft)  in  width.   The  cost is $11/linear meter
($3.30/ft).

Concrete  Pits.   Concrete  pits  are  frequently  used  for  the
temporary  storage  of wastewater.  Pit costs are shown in Figure
10-4a.  The walls and floors of the pits are constructed of 20 cm
(8 in) reinforced concrete.  The costs  are  based  on  $425  per
cubic  meter   ($327  per  cubic  yard)  of reinforced concrete in
place.
                              140

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Buildings.  Some equipment and  material  must  be  installed  or
stored  in  buildings.   The building costs shown in Figure 10-4b
represent the construction cost ($325 per square meter  ($30  per
square  foot))  of  warehouses and storage buildings.  These cost
estimates are based on Reference 2.

Piping.  Pipe size requirements as a function of flow and  piping
costs  (including  an  allowance for fittings) are shown in Table
10-1.  Pipe costs are shown separately only where the  wastewater
must  be  transported outside the plant area, e.g., to lagoons or
settling ponds.  Piping used for the interconnection of equipment
is included in the installation cost.

Equipment

Many of the described wastewater treatment  and  control  systems
consist  of  combinations of items such as chemical feed systems,
mixers, clarifiers, filters, tanks, pumps, etc.

Parametric costs of these equipment  items  related  to  relevant
variables  are  shown in Figures 10-5 to 10-9.  Surface condenser
costs for the sodium chloride subcategory are given in Section 17
- "BAT Revisions." The costs are bare  equipment  costs  obtained
from current catalogs, vendors and equipment manufacturers.

     Other equipment costs employed include the following:
     Hydrated Lime Storage and Feeder System
     Pebble Lime Storage and Feeder System
     Vacuum Filter (31 x 1')
     Vacuum Filter (31 x 3')

     Filter Cartridges

     Agitated Falling-Film Evaporator (316SS) 6 m2**
     Agitated Falling-Film Evaporator (316SS) 7 m2**
     Agitated Falling-Film Evaporator (316SS)
     Multiple Effect Evaporator 9.3 m2***
     Multiple Effect Evaporator 32.5 m2***
         $40,000*
         $60,000*
         $45,000
         $55,000

      $100 - 300

         $76,000
         $85,000
11  m2** $104,000
        $100,000
        $190,000
   *For large-scale use of lime.
  **Heat transfer area.
 ***Total heating surface.
                              141

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Duplicate   items   are  provided   for   critical   items  to  permit
continuous  operation during  equipment  shutdown  for scheduled  and
unscheduled maintenance.

It   is assumed  that monitoring equipment will be  installed at the
treated  effluent  discharge  point.    The    basic   monitoring
requirements  include the  following:

          1.    pH  measurement and recording
          2.    Flow measurement
          3.    Automatic  sampling

The  installed cost of this equipment is estimated to be $10,000.

Installation

Installation  costs  consist of  material  and   labor.  Material
included  piping,  concrete,  steel,   instruments,   electrical,
insulation, paint  and field  materials.  Labor includes direct and
indirect  costs for  equipment erection and installation.  These
costs are extremely site-specific.

The  factors shown  below provide representative  costs for types of
systems considered in this report.
1.  Installation materials
2.  Erection and installation labor
45% of bare equipment cost
35% of equipment and installation
 material cost
They are based on Reference 3.

Engineering

This includes the design  and  inspection  services  to  bring  a
project  from  a  concept  to an operating system.  Such services
broadly include laboratory and  pilot  plant  work  to  establish
design  parameters,  site surveys to fix elevations and formulate
plant layout,  foundation  and  groundwater  investigations,  and
operating    instructions;   in   addition   to   design   plans,
specifications and inspection during construction.  These  costs,
which   vary   with   job  conditions,  are  often  estimated  as
percentages of construction cost, with typical ranges as follows:
Preliminary survey and construction
surveying

Soils and groundwater investigation

Laboratory and pilot process work
                  1  to 2%

                  1  to 2%

                  2  to 4%
                              142

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Engineering design and specifications

Inspection and engineering support during
construction

Operation and maintenance manual
7 to 12%


2 to 3%

1 to 2%
I'rom these totals of 14 percent to 25 percent, a midvalue  of  20
percent  of  in-place  facility,  equipment,  and instrumentation
costs has been used in this study to  represent  the  engineering
and  design  costs  applied to model plant cost estimates.  These
costs include, in addition to the professional service hours, the
costs for expenses such  as  telephone,  reproductions,  computer
services, and travel.

Contractor Overhead and Profit

This  cost is estimated as 15 percent of the installed plant cost
(equipment, installation and engineering costs).

Contingency

This is an allowance of 10 percent applied to the  total  capital
cost,  excluding land, based on the status of engineering, design
and specifications, quality of prices used, and  the  anticipated
jobsite  conditions.   This  covers  design  development (but not
scope), errors and  omissions,  impact  of  late  deliveries  and
unusually   adverse   weather  conditions,  variations  in  labor
productivity   and   other   unforeseen    difficulties    during
construction.

The  cost  factors  employed for engineering, contractor overhead
and profit, and  contingency  correspond  to  those  employed  in
Reference 4.

Land

Lagoons/settling ponds and sludge disposal areas can entail large
land  requirements.   Land  costs  are  included  only where such
facilities are prescribed.    .    - .   •

The  availability  and  cost  of  land  can  vary  significantly,
depending on plant location.  For the purpose of this study, land
is valued at $30,000/hectare or $12,000/acre.

ANNUAL COSTS

Operations and Maintenance
                              143

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        TABLE 10-1.   PIPE SIZE REQUIREMENTS AND PIPE COSTS

Cubic
Meters
100
150
350
650
2,500
4,500
8,000
12,500
35,000
DAILY FLOW
Cubic
Meters/Min
0.07
0.10
0.24
0.45
1.74
3.13
5.56
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                           144

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                           152

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 Operating  Personnel.   Personnel  costs  are based  on an hourly  rate
 of    $25.00.     This    includes   fringe   benefits/  overhead   and
 supervision.   Personnel  are  assigned to   specific   activities  as
 required.

 Maintenance   and  Repair.    Cost of facility  and equipment  repair
 and maintenance  is estimated as  10 percent of the   total  capital
 cost,  excluding  land.

 Materials.  The  materials  employed in  the treatment processes and
 their  costs   are  shown below.   Unit  costs of the materials  were
 obtained   from  vendors  and  the Chemical  Marketing  Reporter.
 Representative  transportation  costs  were added to arrive  at the
 following  material costs.
     Soda, Caustic Liquid  (50%)
     Sulfuric Acid (100%)
     Lime, Hydrated
     Sodium Bisulfite
     Soda Ash
$375/metric ton
$ 60/metric ton
$ 65/metric ton
$720/metric ton
$130/metric ton
Energy.  Electricity costs are based on horsepower ratings,
computed as follows:

     Cy  - 1.1  (HP x .7457 x Hr x Ckw)/(E x P)

     where:

     Cy  = Annual cost
     1.1 * Allowance factor for miscellaneous energy use
     Hr  « Annual operating hours

     HP  = Total horsepower rating of motors (1 HP = 0.7457 kw)
     Ckw = Cost per kilowatt hour of electricity ($0.06)
       E = Efficiency factor (0.9)
       P = Power factor  (1.0)

This yields a cost of $328 per horsepower assuming operations are
conducted 24 hours per day, 250 days per year.   Adjustments  are
made   for   increased  operating  days  and  for  batch  process
operations.

The cost of steam, where employed in the  treatment  process,  is
estimated  to  cost $22 per 1000 kg at 689.5 kPa ($10 per 1000 Ib
at 100 psi).

Residual Waste Disposal.  Sludge disposal costs can  vary  widely
depending on the characteristics and bulk of the waste.  Off-site
hauling  and  disposal costs are estimated as $60 per cubic meter
                              160

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($46 per cubic yard) for deposit in a secure landfill  (permitted
for hazardous material) and $15 per cubic meter ($1*1.50 per cubic
yard)   for   deposit  in  a  sanitary  landfill.   The  cost  of
containerized (drummed) waste disposal in a  secure  landfill  is
$160  per  cubic meter ($123 per cubic yard).  This is based on a
cost of $20 for a 0.2 cubic meter (55 gallon) drum.

On-site waste disposal is based on land  valued  at  $30,000  per
hectare  ($12,000 per acre).  The work is assumed performed by an
outside contractor at a cost of $360 per day or $855 per week for
a 1.15 cubic meter (1% cubic yard) front end loader and $725  per
day  or  $2,525  per  week for a 1.15 cubic meter  (1% cubic yard)
bucket clamshell.

Monitoring, Analysis and Reporting.   The  manpower  requirements
covered  by  the annual labor and supervision costs include those
activities associated  with  the  operation  and  maintenance  of
monitoring  instruments,  recorders,  automatic samplers and flow
meters.  Additional costs for analytical laboratory services have
been estimated assuming that samples are analyzed once a week  at
the  point  of  discharge  and that an analytical cost of $20 per
constituent is incurred.  The determination of  six  constituents
is  assumed.   The addition of a nominal reporting cost yields an
annual cost of $8,000; this cost is applied  except  where  noted
otherwise.

Taxes  and  Insurance.   An  annual provision of 3 percent of the
total capital cost has been included for taxes and insurance.

Amortization

Annual depreciation and capital costs are computed as
follows:

                   n          n
     C =  (B(r).(l+r)  ) t <(l*r) -1)

     Where:            ;

      C = Annual Cost
      B =  Initial amount invested excluding  cost of land
      r = Annual interest rate  (assumed  10%)
      n = Useful life  in years

The multiplier for B  in the equation  is  often referred to as  the
capital   recovery  factor,  and is  0.1627 for the  assumed overall
useful life of   10  years.   No  residual  or  salvage  value   is
assumed.                            *                ,
                               161

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Batch  Processing of. Wastewater

The  quantity   of  wastewater  generated in the production of  the
inorganic  chemicals considered in  this  report varies widely from
as   little  as   0.07  m3   to  1,000 m3 per day.   Batch rather than
continuous wastewater  treatment is  used  for  the  small   flows.
Where  batch  processing is  employed,  it  is so indicated.

There   is  a trade-off in  batch processing between equipment size
and  the frequency with which  treatment  operations  are performed.

ACCURACY OF  ESTIMATES

Errors in  the cost estimates  can arise  from a number of  sources.
The  actual equipment costs are based largely on vendor quotations
and    thus   represent  current  prices.    The cost estimating
relationship used to derive settling pond construction costs   was
validated    by    comparing actual   costs  incurred  by  a local
contractor in the construction of  several  sized settling   ponds,
with   costs  for  similarly sized  impoundments,  as estimated with
the  cost estimating relationship.   The  cost difference was less
than 10  percent.

The  installation  material and labor constitute approximately 25
to 30  percent of the total  system  costs.   Since these costs   are
extremely site-specific, errors as  large as 50  to  100 percent  can
occur   in  selected instances.    It should be  noted that this
magnitude of error  would result in  a total  system   error   in   the
order  of ±25 percent.

The  largest  source  of   error in  this   report  arises from  the
simplifying  assumption  that the plants   producing   the chemicals
are  single  product plants.   In  fact,  most of  the chemicals  are
manufactured in  multi-product  plants and  may  be   produced  only
intermittently   during  the  year.   Specific plant  operation data
would  be needed  to  determine which  treatment modules  or fractions
of such module costs should be assigned  to  the  treatment costs of
specific chemicals.

In the absence   of   such   information,   it   is   not  possible  to
quantify  the  error  range  for  this   source   of  error.  It is
believed that the costs developed  in this   study   are. generally
somewhat  greater than  those that would  be  incurred by individual
plants which comprise the   industry  because the   costs  do   not
include  the economies  of scale  that result  when wastewaters from
several products  are treated in  a common treatment  system.    The
Economic Impact  Analysis does  take those economies  into account.

DESCRIPTION OF WASTEWATER TREATMENT  TECHNOLOGIES
                              162

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The   technologies  considered  for  the  treatment  of  effluent
wastewater streams of the model  plants  are  described  in  this
section.   Schematics of the treatment technologies are provided.
They form the bases for the model plant  capital  and  annualized
costs   presented  in  the  section  that  follows  (Model  Plant
Treatment Costs).

Alkaline   Precipitation,   Settling,   p_H   Adjustment,   Sludge
Dewatering

This  treatment system is shown in Figure 10-10.  A holding basin
sized to retain 4-6 hours of flow is provided  at  the  treatment
system  in-flow.   The  function  of  this  basin is to provide a
safeguard  in  the  event  of  treatment  system  shut-down   for
scheduled or unscheduled maintenance.

The initial treatment step is the addition of caustic soda.  This
is   followed   by  clarification/settling.   If  the  wastewater
characteristics are suitable, a tube settler may  be  substituted
for   a   clarifier.    It  has  the  advantage  of  lower  space
requirements and is generally less expensive  than  a  clarifier.
Provisions  for  backwashing  the  tubes  (if  clogged) should be
included.  Treated supernatant would be used to backwash the tube
settlers, and the backwash water should be returned to  the  head
of  the  plant  for  treatment.   The  sludge is removed from the
clarifier and directed to a filter press  for  dewatering.   Pits
are  provided  at  the  filter press for the temporary storage of
sludge and the resultant dewatered residual material.  The latter
is assumed to be periodically transported to a  secure  landfill.
The  pH  of  the  clarified  wastewater  stream is adjusted to an
acceptable  level  by  acid  addition  prior  to   discharge   if
necessary.

A monitoring system is installed at the discharge point.

Granular Media Filtration

Further  removal of metal hydroxide precipitates and other solids
from the wastewater can be achieved by sand filtration  as  shown
in  Figure  10-11.   A  granular  media filter generally provides
better removals of solids than is achieved with  a  filter  press
and  therefore  the costs used to estimate total system costs are
based on granular media filters.

Alkaline Precipitation, Settling, p_H Adjustment (Batch Process)

The treatment technology is essentially similar to that described
in the previous section.  It is shown in Figure 10-12.  The batch
process  is employed in plants  characterized  by  low  wastewater
                               163

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flow.   Again,   a   holding   basin   is  provided  at  the  head  of  the
treatment system.   The system  consists of  a  mixing/settling tank
to  which the reagents, NapH for alkaline  precipitation  and H2S04
for final pH adjustment prior  to discharge,  are added  manually.

In most cases, the  quantity  of sludge  formed is very   small;   too
small  to justify the addition of  a filter press.  A holding tank
is provided for  the temporary  storage  of the wot sludge  prior   to
its shipment to  a secure  landfill.

Granular Media Filtration (Batch Process)

This  technology is an add-on  to the above and  is  shown  in  Figure
10-13.  It consists of a  small sand  filter through  which  the
wastewater flows prior to discharge.

Hexavalent  Chromium Reduction, Alkaline Precipitation,  Settling,
Final pH Adjustment, and  Sludge Dewaterinq

This technology  is  shown  in  Figure  10-14.  A retention  pond   or
pit,  depending  on  the size  of wastewater  stream,  is installed  at
the head of the  treatment   system.    The  wastewater  stream   is
initially  treated  with  acid to   reduce  the pH  to  the level
required for chromium reduction (CrVI   to  CrIII).   This   scheme
would  be  utilized only in   the   sodium  chlorate subcategory.
Sodium  bisulfite   is  added  to  accomplish the  reduction   of
hexavalent  chromium.  Hydrated lime is then added to  precipitate
the chromium at  a pH of 8 to 9.  The wastewater is then  directed
to  a  clarifier.   The   sludge is  removed  and a  filter press  is
employed for  sludge  dewatering.    Pits   are  provided  for  the
temporary retention of the sludge and  the  "dry"  cake prior  to the
latter's  shipment  to  a hazardous  material  landfill.   The pH  of
the clarified wastewater  stream is  adjusted  to  an  acceptable
level by acid addition if necessary  prior  to discharge.

A monitoring system is installed at  the discharge point.

Chlorine  Destruction

This is achieved by the addition of  sodium bisulfite.  Given that
the  treatment   technology   described  above  {hexavalent chromium
reduction,   etc.)   is  in  place,  no  additional  equipment    is
required.    Chlorine  reduction is achieved  by  an  increase  in the
amount of sodium bisulfite used (see Figure  10-14).

Dual-Media Filtration

In cases of high flow systems,   dual-media  filters can  be used   to
increase  the  total filtration capacity.  In general, dual-media
                              164

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filters exhibit greater capacity than single media filters,  thus
increasing  the  length  of filter runs prior to backwashing.  In
extremely large systems this can mean  less  spare  capacity  and
less   maintenance  time.   However  for  the  purposes  of  this
analysis, there is not a significant difference in costs  due  to
these factors.

MODEL PLANT TREATMENT COSTS

General

On   the   basis   of  hypothetical  model  plant  specifications
(production, flow,  etc.),  the  capital  and  annual  costs  for
various wastewater treatment options have been estimated for each
of  the  six subcategories.  The rationale for selection of model
plants for each subcategory is presented in Sections  11  through
16.

Capital and annualized costs for model plant wastewater treatment
systems for each subcategory are presented in tabular form in the
specific  subcategory  sections  (Sections 11-16).  Specifically,
the costs are for the treatment systems described in Figures  10-
10  to  10-14  and  are  based  on  the  costs,  cost factors and
assumptions documented previously in this section.

As noted in  this  section,  facilities  include  items  such  as
buildings,  ponds  and concrete pits.  The buildings provided are
sufficiently large so that  space  is  available  for  additional
equipment  which  may  be  required for additional treatment.  In
most instances, equipment requirements for  additional  treatment
are  relatively small compared to those proposed for the basic or
initial wastewater treatment scheme.

Equipment costs shown in the cost  tables  include  the  cost  of
installation,  materials,  and  labor as well as instrumentation.
The remaining capital cost categories shown in these  tables  are
self-explanatory.

The annualized costs shown in the cost tables are presented under
three  major headings:  amortization, operations and maintenance,
and solid waste disposal.  The amortization cost is derived  from
the   capital  cost  less  the  cost  of  land.   Operations  and
maintenance  costs  include  the  following  costs:    personnel,
facility  and equipment repair and maintenance, reagents, energy,
taxes and insurance.

Solid wastes generated in the treatment processes are  considered
hazardous  and  are assumed to be disposed of in secure landfills
(permitted for hazardous wastes).
                               165

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In the Cadmium Pigments and Salts subcategory, two  model  plants
were  chosen,  one  representing the cadmium pigments segment and
the other representing the cadmium salts segment.  In each  case,
two treatment options were considered  (see Section 11).

In  the Cobalt Salts subcategory, only one model plant was chosen
because production is  relatively  low  and  a  small  amount  of
wastewater   is  generated  from  the  production  processes.  Two
treatment alternatives were considered (see Section 12).

Model plants used in the Copper Salts subcategory were based upon
copper  carbonate  production  and  upon   other   copper   salts
production   due   to   the   large   disparity   in   unit  flow
characteristics.  Two model plants were chosen, one  representing
each  segment,  and  the costs for two treatment alternatives for
each model plant were estimated in Section 13.

The Nickel Salts subcategory was also represented  by  two  model
plants  based  upon  large  differences in unit flow values.  One
model plant represents production of nickel carbonate, while  the
other  represents  production  of  the other nickel salts.  Model
plant costs, consisting of two treatment  alternatives  for  each
model plant, are presented in Section 14.

The  Sodium  Chlorate  subcategory  is  represented  by one model
plant.  Model plant costs  for  two  treatment  alternatives  are
presented in Section 15.

Two  model  plants  were  chosen  to  represent the .Zinc Chloride
subcategory.  Two treatment alternatives  were  costed  for  this
subcategory  (See Section 16).

Two  subcategories  were  considered  for.  BAT  revisions, sodium
chloride  and  sodium  sulfite.   Detailed  costs   for   various
alternatives are presented in Section 17 - "BAT Revisions."

SAMPLE MODEL PLANT COST CALCULATION

General

The  subsection  which  follows outlines the methodology which is
used  to  derive  the  estimated  costs  for  various  levels  of
technology  which  might  be  employed  typically in the Phase II
chemicals group.  The example given is for a hypothetical  plant,
but  a  number of Phase II plants producing a variety of products
would encounter a similar situation where wastewater  from  those
products are commingled for treatment.
                              166

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This  subsection  demonstrates  individual  system component cost
estimating procedures.  .If a particular design should  vary  from
the  system description given, it would be possible to follow the
procedures given for those system components which are  the  same
making   appropriate  substitutions  for  any  differences.   For
example, a company might use a fabricated steel tank for  holding
sludge  in  place  of  the  concrete  sludge  pit specified.  The
remainder  of  the  system  would  be  costed  according  to  the
methodology  shown  while  the  cost of the concrete pit would be
replaced by the cost of the steel tank.   Similarly,  if  a  lime
feed  system  were  chosen rather than a sodium hydroxide system,
the capital costs and reagent costs could be substituted  in  the
place of those given.

Sample Calculation

The  model  plant  considered  produces  4,800 kkg of metal salts
annually  and  discharges  300  m3  of  wastewater  daily.    Two
treatment  levels  are  considered.   Treatment is performed on a
continuous basis.  The plant is assumed to operate 24  hours  per
day, 350 days per year.
Level
1
Alkaline   precipitation,   clarification,   sludge
dewatering and p_H adjustment.

Two concrete pits are constructed at the  wastewater  intake  for
the temporary retention of wastewater.  A caustic solution  (NaOH,
50 percent solution) is added to the wastewater at a rate of 1.33
kg  per  cubic  meter  before  clarification.   Sludge  from  the
clarifier is dewatered in a filter press.  Two concrete pits  are
provided  for  the  temporary  storage of sludge and dried  filter
cake.   Approximately  0.22  cubic  meters  of  filter  cake  are
extracted  daily and periodically shipped to a hazardous material
landfill.   Final  pH  adjustment  of  the  wastewater  is   made
utilizing  sulfuric  acid  (H2SO4,  100  percent solution)  before
discharge.  Instrumentation includes a pH meter and  recorder,  a
flow  meter and an automatic sampler.  A building is provided for
housing the system components.
Capital Costs;

Facilities

  Concrete wastewater holding pits
     (2-25 m3)
  Concrete sludge pits  (2-3 m3)
  Building (55 m=)

Equipment
                                    Cost
                                        Source
                                $
                             7,000
                             1,600
                            18,000
(Fig.  10-4a)
(Fig.  10-4a)
(Fig.  10-4b)
                               167

-------
   NaOH feed system (300 mVday)  (1  HP)
   Clarifier (.300 mVday)  (6 HP)
   Filter press (0.5  m3)
   Neutralization system (300 ms/day)
     (2 HP)
   Installation (materials  and
     erection labor)
   Instrumentation
   Engineering (20%)
   Contractor overhead and  profit  (15%)
   Contingency (10%)
     Total Capital Costs
 7,000
42,000
18,000
(Fig.
(Fig.
(Fig.
 10-7)
 1 0-6)
 10-9)
  13,900   (Fig. 10-7)
  77,500
  10,000
  39,000
  35,100
  26,900
$296.000
  (P-
  (P-
  (P.
  (P.
 142)
 142)
 142)
 143)
  (p.  143)
Annual Costs;

Operating personnel  (3.25 Hrs./Day
  at  $25/Hr.)
Facility and equipment maintenance
  (10%)

Materials

  NaOH (50% solution) (140 kkg/year)
  H2S04 (100% solution)(5.25 kkg/year)

Energy (9 HP)
Monitoring and analysis
Taxes and insurance  (3%)
Residual waste (77 mVYr. at $60/m3)
Amortization
     Total Annual Cost
$28,400
29,600

52,500
300
4,100
8,000
8,900
4,600
48,200
$184,600
(P-
(P.
(P.


(P.
(P.
(P-
(P-
(p.

160)
160)
160)


160)
161 )
161 )
160)
161 )

Level 2;  Filtration

The wastewater flows through a sand filter before discharge.
Capital Costs;

Facilities

Equipment

  Sand filter (300 mVday)
  Installation (materials and erection
    labor)
  Engineering (20%)
  Cost
    Source
  None
 $15,800    (Fig.  10-6)
  15,100
  6,200
 (P.
 (P-
142)
142)
                              168

-------
  Contractor overhead and profit (1.5%)   .    5,600   (p. 143)
 Contingency (10%)                           4,300   (p. 143)
     Total Capital Cost                    $47,000 .

Annual Costs;

Operating personnel (0.5 Hrs/Day at
  $25/Hr)
Facility and equipment maintenance
.  (10%)                              ,        4,700   (p." 1.60);
Taxes and insurance (3%)                     1,400   (p. 161)
Residual waste (2 m3/yr at $60/m3)       ,      100   (p. 160)
Amortization                                 7,600   (p. 160)
    Total Annual Cost                      $18,200
$ 4,400   (p. "160)
                               169

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                           SECTION 10

                           REFERENCES
3.


4.





5.

6.
     "Development Document for BAT Effluent Limitations
     Guidelines and New Source Performance Standards for the Ore
     Mining ari3 Dressing Industry"/ prepared by Calspan ATC for
     USEPA Effluent Guidelines Division, September 1979.

     "Building Construction Cost Data, 1982," by Robert Snow,
     Means Company, Inc.
"Modern Cost-Engineering Techniques,
McGraw-Hill Book Company.
by Robert Popper,
"Development Document for Effluent Limitations Guidelines
and Standards for the Inorganic Chemicals Manufacturing
Point Source Category"
EPA 440/1-82/007, June 1982.

Vendor Quotations.

"Plant Design and Economics for Chemical Engineers", by M.S. Pet
and K. D. Timmerhaus, McGraw - Hill Book Co., Third Edition.
                              170

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                           SECTION 11

               CADMIUM PIGMENTS AND SALTS INDUSTRY
INDUSTRIAL PROFILE

General Description

Cadmium pigments are a family of  inorganic  compounds  primarily
used  as  colorants  in  a number of industries and applications.
These pigments have an important use in paints, where lead  based
paints  cannot be used due to the presence of hydrogen sulfide in
the environment.  When  hydrogen sulfide is  present,  it  causes
the  formation of lead sulfide, which darkens the paint.  Cadmium
pigments are resistant to the effects of H2S, high  temperatures,
and alkaline environments.  For these reasons, they are also used
in  ceramics  and  glass,  artists' colors, printing inks, paper,
soaps and vulcanized rubber.  Cadmium pigments vary  somewhat  in
their chemical makeup depending on the colors.  The various types
include  cadmium  red,  cadmium  yellow,  cadmium orange, cadmium
lithopone red and cadmium lithopone yellow.

Cadmium salt compounds have wide and  varied  uses  in  industry.
These  include  cadmium  chloride  which  is used in photographic
emulsions as a fog inhibitor,  copying  papers,  dyeing,  textile
printing,  as  an  ingredient  in  electroplating  baths and as a
catalyst.  Cadmium nitrate is used principally  by  manufacturers
of  nickel-cadmium  batteries and also as a catalyst and coloring
agent  in  glass.   Cadmium  sulfate  is  used  in   electrolytic
solutions  for  certain  electrical  elements and cells, and as a
starting material for cadmium pigments.

Cadmium sulfide is the most important cadmium compound.  It  also
occurs  naturally  combined  with  zinc ores.  By itself, cadmium
sulfide is used primarily as a yellow pigment.   It  is  used  in
paints,  ceramics,  glass,  soaps  and paper and is also combined
with other compounds to produce the cadmium  pigments  previously
mentioned.    Cadmium  sulfide,  when  containing  certain  trace
impurities, displays  a  very  strong  photoelectric  effect  and
luminescent  properties.  These properties have wide applications
across various industries.  The industry data profile is given in
Table 11-1.

There are 12  facilities  producing  cadmium  compounds  in  this
subcategory.  Five of the producers manufacture cadmium pigments;
however,  pigment production is always associated with production
of a precursor cadmium salt, predominately cadmium sulfate.   The
                               171

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           •TABLE 11-1.  SUBCATEGORY PROFILE DATA FOR
                    CADMIUM PIGMENTS  AND  SALTS
Number of Plants in Subcategory
12
Total Subcategory Production Rate

     Minimum
     Maximum
>4,000 kkg/yr

 NA
>1,000 kkg/yr
Total Subcategory Wastewater Discharge

     Minimum
     Maximum
>1,200 m3/day
450 m3/<3ay
Types of Wastewater Discharge

     Direct
     Indirect
     Zero
6
4
2
 NA  Not Available
                           172

-------
remaining  seven  producers  manufacture  cadmium  salts  with no
production of pigments.         .

Total  annual  production  of  cadmium  pigments  and  salts   is
estimated to be in excess of 4,000 metric tons per year and total.
daily  flow  is  estimated at greater than 1,200 cubic meters per
day for all plants (flow attributed to cadmium pigments and salts
production only).  In 1977  cadmium  sulfide  pigment  production
alone  accounted for approximately 1,950 metric tons according to
the Bureau of the Census (1981 data unavailable).

General Process Description and Raw Materials

Cadmium Salts

Cadmium salts are produced by dissolving cadmium or its oxide  in
acid  and  evaporating to dryness.  The starting material for all
cadmium compounds is metallic  cadmium.   For  special  purposes,
cadmium  can  be converted to cadmium oxide first.  Cadmium salts
are manufactured in batch modes usually for a certain  number  of
days per year, depending on market demand.

The general manufacturing process for each of the above compounds
is given below.

Cadmium  chloride,  cadmium  nitrate,  and  cadmium  sulfate  are
produced by dissolving cadmium  metal  or  cadmium  oxide  in  an
aqueous  solution  of  hydrochloric,  nitric,  or  sulfuric acids
respectively.  The resulting solution can be used as is,  but  is
usually  evaporated  to  dryness to recover the solid product(l).
The general reactions are:

     Cd + 2HC1 = CdClj, + H2

     Cd -i- 2HN03 = Cd(N03)2 + H2

     Cd + H2S04 = CdS04 + H2

In the production of cadmium pigments, the resulting solution  of
cadmium sulfate may be used as is.

Cadmium Pigments

The  basic  component  of  cadmium pigments is the yellow-colored
compound, cadmium sulfide, which is produced by the  reaction  of
the  purified cadmium sulfate solution with sodium sulfide in the
strike (reaction) tanks.  However, cadmium  pigments  are  batch-
produced  to  meet  product  specifications.   Depending upon the
shade of pigment desired, a variety of  other  materials  may  be
                               173

-------
 CADMIUM CHLORIDE
Cadmium Source
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 CADMIUM SULFIDE
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 H2S
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          FIGURE 11-1.  GENERALIZED PROCESS FLOW DIAGRAM FOR CADMIUM SALTS.
                               174

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-------
added or co-precipitated with cadmium sulfide in the strike tank.
Zinc  is  a common component of cadmium yellows.  Cadmium sulfide
and cadmium selenide are coprecipitated in the reaction  tank  to
form   cadmium  red.   Red  and  yelldw  lithopone  pigments  are
manufactured  by  co-precipitating  the  pigments   with   barium
sulfide.   Another  class  of  pigments  may  be  obtained by co-
precipitating mercury sulfide with cadmium sulfide.   The  normal
running  time  per  batch for cadmium pigment manufacturing is 1D
days from strike to dry product.  The number  of  operating  days
per  year  also depends on market demands.  More detailed process
descriptions and general reactions for the various pigment  types
are provided below.

Cadmium sulfide (cadmium yellow) is produced by the reaction of a
sulfide  source,  usually  sodium  sulfide,  with  a  solution of
cadmium  salt  forming  a   precipitate   of   cadmium   sulfide.
Generally,  cadmium  sulfate  is used as the cadmium salt source.
The general reaction is:

     CdS04 + Na2S = CdS + Na2S04

The production of  cadmium  pigments  is  more  complex  than  is
implied  by the above equation.  First, a soluble cadmium salt is
produced by digesting cadmium metal  in  sulfuric  acid.   Nitric
acid  is  often added to increase the reaction rate.  The general
reaction is:

     8Cd + 9H2S04 + 2HN03 = 8CdS04 + (NH4)2S04 + 6H20

The cadmium sulfate liquor is then purified in  successive  steps
by addition of reagents and by filtration to remove iron, nickel,
and copper impurities.

Cadmium Yellow (Pure)

This  pigment  is  produced  by  reacting cadmium sulfate, sodium
sulfide and zinc sulfate in the strike tanks.  This pigment is  a
co-precipitated  mix  of  cadmium sulfide and zinc sulfide, which
gives it the distinct yellow color.  The basic lemon yellow shade
is essentially all cadmium sulfide as  described  above  and  the
various   different  shades  of  yellow  depend  on  the  cadmium
sulfide/zinc sulfide mix.

The basic general reaction is:

CdS04 + 2Na2S + ZnS04 = CdS • ZnS + 2Na2S04

Cadmium Red (Pure)
                              176

-------
The basic pure red pigment is produced  by  reacting  a  prepared
solution  of cadmium sulfate with a prepared solution of selenium
metal in aqueous sodium sulfide together in the strike  tanks  to
form  a  cadmium  sulfoselenide  complex.   The amount of cadmium
sulfide in the pigment determines the shade of red desired.   The
basic reaction is:

CdS04 + Na2SxSe(l-x) = CdSxSe(l-x) + NazS04


(when x is always less than or equal to  1)

The  variable  subscript   indicates  the  complex  nature of this
compound.
                                               reds  and   cadmium
Cadmium Orange

This pigment is produced by blending  cadmium
yellows until the desired shade is produced.

Cadmium Lithopone Pigments

Both  the  red  and  yellow  cadmium  pigments can be produced as
lithopone pigments instead of pure.  The reactions and  processes
are  essentially  the same.  The difference is in the addition of
barium sulfide to the strike tanks where it is reacted,  and  co-
precipitated with the other chemicals previously mentioned.

The basic general reactions are, for red lithopone pigments:

CdS04 + BaSx + Se(l-x) = CdSxSeO-x) • BaS04  (when x <  1)

while the reaction for yellow lithopone pigments is:
CdS0
2BaS
                Zn
                         CdS • BaS04 • ZnS + BaS04
 Regardless   of   which   pigment   is  produced,   the  resulting
 precipitated pigments  are  decanted  or  filtered,   washed,  and
 dewatered  in  a filter.   The pigments are subsequently dried and
 calcined for uniform color.   Calcining  emissions  are  generally
 scrubbed  to  capture  pigment  dust  and  sulfur dioxide.  Final
 polishing steps vary  from  plant  to  plant,  but  the  calcined
 pigments   are   usually   quenched  in  water  for  washing  and
 filtration.  The pigment is again dried  before  blending  and/or
 packaging.   Generally  the  pigments are ground or crushed after
 drying.  A general process diagram for the cadmium salts is given
 in Figure 11-1  while  Figure  11-2  gives  the  general  process
 diagram for cadmium pigments.
                               177

-------
 WATER USE AND WASTEWATER SOURCE CHARACTERISTICS

 Water Use
 In   the  cadmium
 reaction medium.
 control  (scrubbers)
 areas.
salts  industry, water is used primarily as the
A small amount may be  used  in  air  pollution
    and  in  washdown  of equipment and process
 In  the  cadmium pigments industry,  water is used as  the  reaction
 medium   (in  the strike tanks)  and  to wash the pigments in several
 stages  of  production.   Water is also  used  for  maintenance  and
 cleaning  of  filters   and   process areas.   Water use varies from
 plant to plant for  other process   uses  such  as  air  pollution
 control  equipment.  These  flows are minor compared to the direct
 contact  process uses.

 Normally,  the  production of  pure  pigments  requires  a  longer
 washing  period to wash out  soluble impurities.   This results in  a
 larger water usage  for this part of the process.

 Table 11-2 is  a summary of  water usage at different cadmium salts
 plants   while   Table   11-3   summarizes  water  usage at different
 cadmium  pigment plants.

 Wastewater Sources

 Wastewater flows from  cadmium  salt production vary from plant  to
 plant    and  also   vary for  different  products.    In  general,
 wastewater   can emanate from  decanted,   filtered  or  purified
 reaction  media,  washdown   of  equipment and area,  air pollution
 control  devices and   various   other   indirect  process  sources.
 These  flows   are  minor compared  to  wastewater generated from
 pigment production.  Table  11-4  summarizes  wastewater flows  from
 several  cadmium salts  plants.

 At  cadmium  pigment   plants,   the different  pigment  products  are
 manufactured concurrently   on   separate  process   lines  and  the
 wastewaters  may be treated separately or  combined for treatment
 and then discharged.   Wastewater can originate  from decanting  or
 filtering  the   pigment  slurry  after   it  is precipitated  in  the
 strike vessels,  and from secondary filtration during  purification
 and finishing operations.   The major sources  of  wastewater  flow
 are  from  washing,  quenching and  rinsing  tho   pigments.   The
 quantity of wash and rinse  water may be greater for  some  pigments
 than for others.  A  third   source of   wastewater   includes   the
washing of the  filters  (primary and finishing)  to  remove  pigments
and  impurities, especially  when there  is a color  shade change in
 the production.  Other sources of  wastewater  flow,  which  can vary
                              178

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   TABLE  11-2.  WATER USAGE  AT CADMIUM SALTS FACILITIES(D


Flow
(m3/kkg)
Plant Designation •
Water Use
Noncontact Cooling
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
Noncontact Ancillary
TOTALS
F125(2)
0
0.183
0
0
0.0365
0
0 . 219
F117(3)
0
1.69
0
0
0
0
1.69
F117(4)
0
1.08
0
0
0
0
1.08
(1)   Values indicated only for those plants that reported
     separate and complete information.
(2)   Cadmium Nitrate.
(3)   Cadmium Sulfate (batch basis).
(4)   Cadmium Chloride (batch basis).


Source:  Section 308 Questionnaires and Plant Visit Reports
                          179

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   TABLE 11-3.  WATER USAGE AT CADMIUM PIGMENTS FACILITIES(D
Flow (m3/kkg)
Plant Designation (2)
Water Use
Noncontact Cooling
Direct process Contact
Indirect Process Contact
Maintenance
Air Pollution Scrubbers
Noncontact Ancillary
TOTALS
F102
0
71.2
42.2
1.6
1.07
0
116.1
F101
34
132
0
3
<0
0
170
.4
.4
--
.19
.067
.16
.2
F134
0
27
v o
0
0
0
29
.116
.9

.116
.35
.87
.35
F110
0
34.
0
1.
0
0
35.

65

07


7
(1)  Values indicated only for those plants that reported
     separate and complete information.
(2)  Values indicated were for all cadmium pigment production
     and include production of cadmium sulfate as starting
     material.

Source:  Section 308 Questionnaires and Plant visit Reports
                          180

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TABLE 11-4 *  WASTEWATER FLOW AT CADMIUM SALTS FACILITIESU)


Wastewater Source
Direct Process Contact
Indirect Process Contact
Maintenance
Air Pollution Scrubbers
TOTAL PROCESS
WASTEWATER DISCHARGED
Noncontact Cooling
Noncontact Ancillary
(1) Values indicated only
separate and complete
(2) Cadmium Nitrate.
(3) Cadmium Sulfate.
(4) Cadmium Chloride.
Flow
Plant
(m3/kkg)

Designation
F125(2) F117^.
0
0
0
0.036
0.036
0
0
0
0
0.085
0
0.085
0
0
for those plants that
information.
) Fiiy^J
0
0
0.054
0
0.054
0
0
reported
Source:   Section 308 Questionnaires and Plant Visit Reports
                          181

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  TABLE 11-5.  WASTEWATER FLOW AT CADMIUM PIGMENTS FACILITIES
                                      Flow (m3/kkg)

                                  Plant Designation(2)
Wastewater Source
Direct Process Contact
Indirect Process Contact
Maintenance
Air Pollution Scrubbers
TOTAL PROCESS
WASTEWATER DISCHARGED
Noncontact Cooling
Noncontact Ancillary
F102
71.2
42.2
1.60
1.07
116.1
0
1.6
F101
132.4
0
3.19
0
135.6
34.4
0.16
F134
25.5
0
0.12
NA
25.62
0
0.87
F110
34.65C3)
0
0
0
0
0
0
 NA   Flow volume not available.
      Values indicated only for those plants that reported
      complete information.
 (2)   Values indicated are for all cadmium pigments production
      and include production of cadmium sulfate as starting
      material.
 (3)   Discharge to on-site pond.
Source:   Section 308 Questionnaires and Plant Visit Reports
                          182

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from plant to plant, are maintenance and area washdowns  and  air
pollution  control  devices.   The  sources  of  wastewater  flow
applicable to typical cadmium pigment plants  are  shown  in  the
generalized  flow  diagram,  Figure 11-3.  The wastewater sources
are similar for all pigment products.  Table  11-5  presents  the
wastewater flow data summary for several cadmium pigment plants.

DESCRIPTION OF PLANTS VISITED AND SAMPLED

Eight   facilities  at  which  cadmium  pigments  and  salts  are,
manufactured were visited during the course of the program  (many
plants produce other Phase  II products).  Wastewater sampling was
conducted at two of these plants.

Sampled Plants

Plant F102 produces several cadmium pigments by the process shown
in  Figure 11-3, and described above.  The plant produces cadmium
reds, cadmium yellows and cadmium orange pigments.

Wastewater emanates from  a  number  of  sources  in  the  entire
process.   These consist of the reaction decants and direct rinse
waters to wash  out  salts,  filter  washes,  wet  scrubbers  and
maintenance  washdowns.  Once-through noncontact cooling water  is
also used for washing the   filters.   Excess  cooling  water  not
needed  to  wash the filters is discharged with the other process
wastewaters.

At the time of the sampling visit  in  1980  all  wastewater  was
collected  in  a sump, then was pumped to pigment plant treatment
system (for cadmium recovery) and then discharged  to  the  POTW.
Cadmium  treatment consisted of a 10,000-gallon equalization tank
where caustic soda was added to raise the pH.  A  polyelectrolyte
was  added  in a flash mix  chamber and then the wastewater flowed
to a tube settler.   The  overflow  from  the  tube  settler  was
discharged  to an in-plant  receiver, while the underflow was sent
through a filter press  for  dewatering.   The  filter  cake  was
collected  and  removed  for  cadmium  recovery.   At the time  of
sampling,  the  filtrate  was  combined  with  the  tube  settler
overflow and discharged to  a POTW without further treatment.

In   1982  the  wastewater   treatment  system  was  changed.   The
discharge from the cadmium  process treatment plant was commingled
with other wastewater generated at the  facility.   The  overflow
from  the  tube  settler  was  discharged  to the main wastewater
treatment facility, and the filtrate from the filter  press  sent
to   the beginning of the main wastewater treatment facility.  The
main wastewater treatment facility  treats  wastewater  from  the
cadmium pigments plant  (about 10 percent of the total flow) along
                               183

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 with  process  wastewater from all other parts of the plant.   The
 90   percent  of  the  wastewater  from  the  non-cadmium  pigment
 products and the filtrate from cadmium recovery filter press  were
 treated  with  caustic  and  then  clarified in a clarifier.   The
 effluent from the clarifier,  and the effluent  from  the  cadmium
 treatment  plant  were  then  filtered through a sand filter.   The
 filtrate was discharged  to  a  publicly  owned  treatment works
 (POTW),    and  the  backwash   recycled  to  the  clarifier.    The
 underflow from  the  clarifier  was  dewatered  and  disposed  as
 hazardous wastes and the water recycled for more treatment.

 In  1983  the treatment facility was again changed to eliminate the
 use of the cadmium recovery system.   All cadmium pigments  process
 wastewater  is now combined with the non-cadmium pigments  process
 wastewater  for  combined  treatment,   consisting  of  hexavalent
 chromium reduction in acidic  solution (the hexavalent chromium is
 from  non-cadmium  pigments wastewater)  followed by pH adjustment
 to  basic conditions,  clarification,  and filtration through a  sand
 filter.

 During the sampling period, only pure cadmium red  pigments   were
 being  produced.    Figure  11-3  shows wastewater sources from the
 various  processes  at  Plant   F102  and  the  sample  points,   in
 addition  to  the  cadmium  recovery  treatment  system, with its
 sample points.   Table 11-6  gives the pollutant concentrations and
 unit loadings  of  pollutants for  the  sampled streams.

 Plant  F134 produces both  red  and yellow cadmium pigments in   both
 the  pure  and lithopone  forms,  by the processes shown in  Figures
 11-4,  11-5 and 11-6,  which  are similar to  the  general   processes
 described previously.

 Process   wastewater and treatment for  each  color (red and  yellow)
 are similarly  segregated.   Process   wastewater  originates   from
 both   the  primary   filter  presses  (greencake)  and  the  finishing
 filter presses  during  loading/pressing  and   washing   operations.
 For the  cadmium lithopone pigments (red  and  yellow),  only  the  two
 filter   press   operations   generate  wastewater.   For   the  pure
 cadmium  pigments  an  additional washing  period   was   utilized   to
wash out  impurities, which  created an  additional  wastewater flow.

Ferrous   sulfide  is  added to  the  wastewater  in  a floor sump where
wastewater  is  collected, and  the  wastewater  is  then pumped  to  a
 large holding  tank.  The resulting precipitate/slurry material  is
pumped    to    a   final  scavenger  filter  press.   The  filtrate
represents  the  final effluent which  is discharged directly, while
the recovered  filtercake is sold  as  a  by-product.   A  continuous
turbidity  monitoring system permits wastewater  to be returned  to
treatment  if certain  turbidity   levels  are  exceeded.   Process
                              188

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wastewater   sources   and   treatment   system  along  with  the
corresponding sampling points for each pigment product are  shown
in Figures 11-4, 11-5 and 11-6.

Two  visits  to  plant  F134  resulted in separate wastewater and
treated effluent samples from the pure cadmium yellow pigment and
lithopone cadmium yellow pigment, as well as from  the  lithopone
cadmium red pigment operations.

.Table   11-7   presents   the   wastewater   flow  and  pollutant
concentrations for each type of pigment.

Other Plants Visited

Six plants producing cadmium pigments and/or salts  were  visited
during the program period, but not  sampled.  A description  of the
individual  products  and  treatment  facilities for those  plants
visited is given in the discussion  below.

Plant F101 manufactures cadmium sulfate  and cadmium pigments.   At
present there  is no wastewater treatment facility at  this  plant
for treatment  of process wastewater.  All process wastewaters are.
discharged  to a POTW.  Plant personnel  are investigating several
alternatives to reduce or  eliminate  the  discharge  of  process
water  pollutants.   One  alternative   is  the  use  of  soda ash
neutralization to treat the effluent from the  pigment  quenching
operation.  The neutralized effluent would be discharged, and the
cadmium carbonate precipitate would be  recovered and recycled.   A
second  alternative  consists of  recycling the quenching effluent
directly.  This second alternative  has  not been demonstrated, and
some  technical problems including safe  handling of   the  hydrogen
sulfide   gas   that  could  be  evolved   during  recycling,  may  be
difficult to solve.

Plant F128 manufactures   cadmium  sulfate,  cadmium  nitrate  and
cadmium pigments, as well as other  chemical products.  All  of the
cadmium   pigment  plant wastewater  except  that emanating from the
drying operations and  air scrubbers is  discharged  to an   in-plant
receiver.    The  wastewater   is   treated  with  alkali   and  then
filtered.  The filter  cake  is  either  sold  for  recovery of  cadmium
or disposed  of in a  chemical waste  landfill.   The   effluent  from
cadmium  treatment  joins the wastewater  from  the drying operations
and  air  scrubbers  in  a separate  in-plant  receiver.  The receiver
carries  the  wastewaters generated from   the   rest   of   the  plant
processes,    as  well   as  the  above-mentioned   treated  cadmium
wastewater,  to  the  main  wastewater   treatment   facility.   The
wastewater  is  neutralized  with lime,  settled  and filtered in a
dual-media filter  before  discharge  to surface waters.   The sludge
 from settling  is filtered in  a filter  press  and  the  filter  cake
                               191

-------
is  disposed of in a chemical landfill.  The filtrate is recycled
to  the  wastewater  treatment  facility,  as  is  the   backwash
wastewater  from  the  periodic  backwashing  of  the  dual-media
filter.

Plant FIT 7 manufactures cadmium sulfate and cadmium  chloride  as
well  as a variety of other metal salts.  Process wastewater from
cadmium salts production are treated separately.  These are  very
small  flows  consisting of leaks, spills and washups.  Treatment
consists of the addition of caustic (NaOH) to the collection sump
until the pH is around 10.  The sump is then pumped out through a
small filter press, and the filtrate is  discharged  directly  to
surface waters.  The residue is sent to solids disposal.

Plant  F107  manufactures  cadmium nitrate and a variety of other
metal salts.  There is no treatment facility at  this  plant  and
all wastewaters are discharged to a POTW.

Plant  F119  manufactures  cadmium nitrate and a variety of other
metal salts.  All process wastewater  from  production  of  metal
products   undergo   combined   treatment.    This   consists  of
neutralization tanks where pH is  adjusted  to  8.7  -  9.0  with
caustic.   The  neutralized waste is sent to a settling basin for
settling.  The settled wastewater is then sent  to  a  flash  mix
tank  where  flocculating  agents are added and then on to a tube
settler for additional solids removal.  The  overflow  discharges
to  a  municipal  treatment  plant  while the underflow goes to a
sludge holding tank where it then undergoes filtering in a filter
press and disposal  in  a  chemical  landfill.   Supernatant  and
filtrate  from  sludge  handling  is  recycled  to  the treatment
facility.

Plant F145 manufactures cadmium chloride and a variety  of  other
inorganic  and  organic  compounds.  All process wastewaters from
the entire plant  which  cannot  be  recycled  are  sent  to  the
combined  plant wastewater treatment facility.  Here the waste is
equalized, neutralized  with  lime  slurry  to  pH  9.5  -  10.2,
agitated,  and  settled  in  clarifiers.   The  overflow from the
clarifiers is sent to the organics removal portion  of  the  WWTF
where it receives biological treatment and is discharged directly
to  surface waters.  Sludge is dewatered and disposed of as solid
waste.

Toxic Pollutant Concentrations

Thirteen toxic pollutants were found at detectable concentrations
in the raw wastewater at the two  sampled  plants.   The  maximum
concentrations observed are given in the table below.
                              192

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  TABLE 11-8.   TOXIC POLLUTANT RAW WASTE DATA-CADMIUM PIGMENTS
        Average Daily Pollutant Concentrations and Loads
                              mg/1
kg/kkg
Plant Designation
Pollutant
Antimony
Cadmium
Thallium
Selenium
Zinc
Lead
Nickel
Copper
(PR
F102(
0.
0.
1040.
47.
0.
0.
29.
1.
25.
1.
0.
0.
0.
0.
0.
0.
1,
19
00874
0
8
14
00644
7
37
1
154
25
0115
18
00828
097
00446
(PY)
F134(2)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.54
.0566
.49
.0514
.064
.0067
.26
.00273
.20
.0210
.3
.0315
.15
.0157
.061
.00640
(LR)
F134(2)
0
0
6
0
0
0
2
0
0
0
0
0
0
0
0
0
.225
.00176
.76
.0530
.003
.00002
.0
.0157
.035
.00027
.081
.00063
.008
.00006
.026
.00020
(LY)
F134
0.
0.
11.
°-
0.
0.
0.
0.
2.
0.
0.
0.
0.
0.
0.
0.
(2)
24
00237
14
110
002
00002
005
00005
12
0209
072
0071
0072
00007
015
00015
Overall
Average
0.
0.
264.
12.
0.
0.
7.
0.
6.
0,
0.
0.
0.
0.
0.
0.
30
0174
6
0
052
00330
99
347
86
299
18
0127
086
00603
05
00280
(1)   Data from three 24-hour composite samples, averaged, from
     the  combined total raw waste sampling point.

(2)   Data from three days of composite samples collected from
     individual batches, flow proportioned from each raw waste
     stream for that particular day and then averaged over the
     three days.

(PR)  Pure Red Pigments.

(PY)  Pure Yellow Pigments.

(LR)  Lithopone Red pigments.

(LY)  Lithopone Yellow Pigments.
                           193

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       TABLE  11-9.   TOXIC  POLLUTANT TREATED EFFLUENT DATA
                         CADMIUM PIGMENTS
        Average  Daily  Pollutant  Concentrations  and Loads
                               mg/1
                               Plant  Designation
Pollutant
Antimony
Cadmium
Thallium
Selenium
Zinc
Lead
Nickel
Copper
F102(l)
0.21
0.00898
92.0
3.93
0.21
0.00898
0.19
0.00813
0.26
0.00111
0.18
0.0077
0.23
0.00984
0.29
0.0124
(?Y1
F134(2)
0.33
0.0407
0.106
0.0131
0.047
0.00580
0.11
0.0136
0.027
0.00333
0.115
0.0142
0.056
0.00691
0.027
0.00333
(LR)
F134(2)
0.2
0.00181
0.41
0.00371
0.001
0.00001
3.12
0.0282
<0.026
<0. 00024
<0.078
<0. 00071
0.0086
0.00008
0.016
0.00014
(LY)
F134(2)
0.1
0.00195
0.13
0.00254
0.001
0.00002
0.01
0.00020
0.069
0.00135
0.15
0.00293
0.014
0.00027
0.01
0.00020
Overall
Average
0.21
0.0134
23.2
0.987
0.065
0.00370
0.86
0.0125
<0.095
<0. 00151
<0.1.3
<0. 00640
0.077
0.00430
0.085
0.00327
(1)   Data from three 24-hour composite samples, averaged.
(2)   Data from composite samples collected from individual
     batches over three days and averaged.
(PR)  Pure Red Pigment.
(PY)  Pure Yellow Pigment.
(LR)  Lithopone Red pigment.
(LY)  Lithopone Yellow Pigment.
                          194

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     Pollutant

     Antimony
     Arsenic
     Cadmium
     Chromium
     Copper
     Lead
     Nickel
     Selenium
     Thallium
     Zinc
     Bis(2-chloroethyl) ether
     Bis (2-ethyhexyl) phthalate
     Chloroform
     Methylene chloride
Maximum Concentration
    Observed (ug/1)

          540
          190
    1,400,000
          400
          250
          530
          420
       81,000
          190
       62,000
           84
           24.4
           40.3
           14.8
Data  was  obtained  at Plants F102 (one type of cadmium pigment)
and  F134  (three  different  cadmium  pigments).   The   organic
compounds bis(2-ethylhexyl) phthalate and chloroform were present
in  high  concentrations  in  the  supply water at one plant.  In
addition, phthalates and methylene chloride are  generally  found
at  this  concentration  as a result of sample contamination from
the plasticizers in  tubing  and  laboratory  glassware  cleaning
procedures.

Section  5  of  this  report  describes  the  methodology  of the
sampling program.  In the cadmium pigments industry, nine days of
sampling were conducted at Plants F102 and F134.   This  involved
15  different  sampling  points  for  raw  and treated wastewater
streams.   The  evaluation  of  toxic  metals  content  of  these
process-related  wastewater  streams  was based on 507 analytical
data points.  Sampling for organic pollutants  generated  another
1,824 data points.

In  Table  11-8, the toxic pollutant raw wastewater data from the
sampling   program   are   presented   as   the   average   daily
concentrations  and  unit loadings found at the individual plants
and pigment processes.  The overall averages were calculated  and
shown  also  to  present  a  situation  as if a single plant were
making all four types of pigments  at  the  same  time  and  they
combined  the  wastes  into one raw wastewater stream which could
occur at  the  four  discharging  plants.   The  toxic  pollutant
concentrations  and  unit  loadings in the treated effluents from
the sampling program are presented in Table  11-9  for  the  four
pigment types sampled.

POLLUTION ABATEMENT OPTIONS
                              195

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Toxic Pollutants of Concern

The  toxic  pollutants  found  in  significant amounts are  the heavy
metal components of the raw materials and product, as well as the
impurities found in the raw materials.  The primary pollutant   is
cadmium, which  is present  throughout the process  train.  Selenium
and  zinc  are  the second most  abundant pollutants and  of course
depend on which pigment (red  or  yellow) is being  produced.  Since
all plants produce both pigments, both of these metals   would   be
present  in significant  amounts at all plants.

The  other  toxic  metals  of  concern found were lead,  antimony,
copper,  nickel  and thallium.  These are present in trace amounts
due  to  impurities in  the raw materials and subsequently removed
during processing of  the  cadmium  pigments.   The  presence   or
absence  of  these five trace metals at significant levels in the
wastewater may  depend mainly  on  the levels present as  impurities
in  the  materials  as  well  as  the degree of purification of the
materials to remove them.  The fact that these metals  are  found
in such  small concentrations  could present problems in monitoring
due  to  analytical variability.  For example, one plant  exhibited
higher concentrations of some of  these  metals   in  the treated
effluent than were found in the  raw wastewater.

All  the  process  contact  wastewater  generated in the cadmium
pigments  subcategory   contain   dissolved  cadmium  and   pigment
particulates.

Existing Control and Treatment Practices

A  description  of  the individual treatment facilities  for those
plants visited was given previously.  In addition, the   following
information was obtained for  the remaining plants.

Plant  F110  manufactures  the basic cadmium sulfide pigment.  The
process wastewater from this plant is sent to the plant  treatment
facility where  it  is   neutralized  with  lime  to  pH   12.   The
wastewater is then sent to a  lagoon for settling.  The solids are
dredged  to  the sides  of  the lagoon and there is no discharge of
wastewater from the lagoon.  The plant  is  located  in  an  arid
region of the country.

Plant  FT 25  manufactures  cadmium nitrate and other metal salts.
Wastewaters from the cadmium process are combined with the  other
product  process wastes and treated together.  Treatment consists
of equalization, sedimentation, pH adjustment with  NaOH,  and  a
series  of  lined  and  unlined  impoundments before discharge to
surface waters.
                              196

-------
Plant No. F123 produces  small  quanities  of  cadmium  chloride.
This  plant  discharges no wastewater.  All process wastewater is
incorporated in the product.

Plant F124 produces cadmium nitrate as well as other metal salts.
Treatment  of  wastewaters  for  the  entire  plant  consists  of
alkaline  precipitation,  clarification, filter press filtration,
multi-media filtration, pH adjustment and sedimentation in  ponds
before discharging directly to surface waters.

Other Applicable Control and Treatment Technologies

Cadmium  pigment  plants  commonly have a cadmium recovery system
which uses alkaline or ferrous sulfide precipitation followed  by
settling  and/or  filtration.  Effluent from the recovery systems
still  contains  considerable  amounts  of  cadmium  and  further
treatment  should be applied before discharge.  Further treatment
by lime precipitation and  clarification,  followed  by  sand  or
dual-media filtration would remove more residual cadmium.

Process Modifications and Technology Transfer Options

One  cadmium  pigment manufacturer employs a continuous turbidity
monitor  as  part  of  the  wastewater  treatment  system.    The
monitoring  device  is  located downstream of a cadmium scavenger
filter  press  and  upstream  of  the  final  treated  discharge.
Wastewater  not  meeting  turbidity  standards  is  automatically
pumped back to treatment and again sent through the filter press.
This  offers  the  advantage  of  reducing  the   variations   in
performance of treatment and aids in control of suspended solids.
Control of suspended solids at pigment facilities is essential to
reduction  of  effluent  concentrations of cadmium, selenium, and
zinc in the final discharge.     .

Several cadmium pigment producers practice segregation of process
wastewater from other products manufactured to enable recovery of
cadmium-containing   solids.     Typically,    cadmium-containing
wastewater streams are segregated for wastewater treatment/solids
recovery,  and  sludges  obtained  are sold for recovery of metal
values.   Treated  wastewater  is  then  either   discharged   or
commingled  with  other wastewater streams for further treatment.
In the case of POTW dischargers, much cadmium, selenium, and zinc
can be prevented from accumulating in POTW - generated sludges by
using wastewater stream segregation and recovery technology.

The  use  of  filter  aids  to  improve  filter  performance   is
commonplace   in  inorganic  chemicals  manufacturing  processes.
Transfer of this technology to wastewater treatment processes may
facilitate  decreasing   suspended   solids   concentrations   in
                              197

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wastewater  treatment  filtrates.   The  identification and use of
effective flocculants and other settling  aids  could  contribute
significantly   toward   enhancing   effluent   quality   in  this
subcategory.
An overall reduction in water use at "cadmium pigments
might be obtained by the following approaches:
     1
     2.
     3.
Recycle of filter washwater  during  pigment
process, where possible;
                                             facilities
          finishing
Use of noncontact cooling water for  make-up  water  in
the salt and pigment process (this would reduce overall
water use, but not pollutant discharges);
Limit excessive usage of washwater
wastewater, where possible;
and  other  process
     4.   Recycle of scrubber wastewater where possible.

As shown on Tables 11-3 and 11-5, the major water use by  far  at
cadmium  pigments  plants  is direct and indirect process contact
wastewater resulting from  cleaning  impurities  from  the  crude
pigments.   This  cleaning  is  necessary  to  produce a saleable
product, and the amount of water used for cleaning  depends  upon
the  product,  the  amount  of  impurity,  and the demands of the
customer.  Therefore, while the above suggestions may save  water
at  those  plants that can implement them, no specific technology
was identified which could be applied at all plants .and result in
a significant reduction in the amount of wastewater discharged to
treatment.

Best Management Practices

If contact is possible with leakage, spillage of raw materials or
product,  all  storm  water  and  plant  site  runoff  should  be
collected  and  directed  to  the plant treatment facility.  This
contamination can be minimized by indoor  storage  of  chemicals,
proper  air  pollution  control,  and development of an effective
spill prevention and control program.

All  other  contact  wastewater  including  leaks,  spills,   and
washdowns  should  be contained and treated because this practice
may enhance recovery of raw materials and product.

If solids from the wastewater treatment plant are  hazardous  and
disposed  or  stored  on-site,  provision must be made to control
leachates and permeates.  Leachates and permeates  which  contain
                              198

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toxic  pollutants  should be directed to the treatment system for
further treatment.

Advanced Treatment Technology

Cadmium pigments wastewater contains fugitive  pigment  particles
which  in  turn  contain  significant  concentrations of cadmium,
selenium and zinc.  Low concentrations of suspended  solids  must
be  achieved  to  ensure  reduction  of  these  toxic  metals  in
wastewater discharges.  Level 1 plus Level 2 technology  will  be
required  as  a minimum to achieve these low concentrations.  The
effectiveness of these technologies can be enhanced  by  addition
of  flocculating  agents prior to clarification and by the use of
sand or  multi-media  filtration  (as  opposed  to  filter  press
filtration)  for  Level  2.   To illustrate the above, plant FT 28
practices  cadmium  recovery  followed   by   further   treatment
consisting  of  pH adjustment, clarification, and sand filtration
to achieve an average cadmium concentration of 0.07 mg/1.

Selection of_ Appropriate Technology and Equipment

Technologies for Different Treatment Levels

A.   Level 1

Level   1   treatment   consists   of   alkaline   precipitation,
clarification . or  settling,  and  final  pH  adjustment  of  the
effluent if necessary.  Sludges  generated  are  dewatered  in  a
filter  press  or  collected and disposed of in a hazardous waste
landfill.  As part of the treatment system, a holding basin sized
to retain 4-6 hours of influent is provided as a safeguard in the
event of treatment system shutdown.  The treatment technology  is
illustrated in Figure 10-10.

The initial treatment step is the addition of caustic soda.  This
is   followed   by   clarification/settling  (if  the  wastewater
characteristics are suitable, a tube settler may  be  substituted
for  a  clarifier to conserve space).  Sludge is removed from the
clarifier and directed to a filter press  for  dewatering.   Pits
are  provided  at  the  filter press for the temporary storage of
sludge.  The sludge is periodically transported  to  a  hazardous
material landfill.  Filter press filtrate is returned to the head
of the treatment system.

The  pH  of  the  treated  wastewater  stream  is  adjusted to an
acceptable  level  by  acid  addition  prior  to   discharge   if
necessary.   A  monitoring  system  is installed at the discharge
point.  The objective of Level 1 technology is  to  remove  heavy
metals and suspended solids.
                               199

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Level  1  treatment was not selected as the basis for BPT because
it  provides  inadequate  removal  of  fine   suspended   cadmium
hydroxide  particles.   Currently,  only  three  facilities still
employ Level 1 treatment alone.
B.
Level 2
Level 2 treatment consists of granular media  filtration  of  the
Level  1  effluent  for  further  removal  of  cadmium  hydroxide
precipitates  and  other  solids  from  the   wastewater.    This
technology is portrayed in Figure 10-11.  In practice, when Level
2  technology  is  added to Level 1, final pH adjustment would be
reconfigured to occur after filtration  not  prior  to  it.   The
objective  of Level 2 treatment technology in this subcategory is
to achieve, at a reasonable cost, more effective removal of toxic
metals than provided by Level 1.  Filtration will  both  increase
treatment  system  solids  removal  and decrease the variation in
solids removal exhibited by typical clarifier performance.

Level 2 treatment was selected as the basis for  BPT  because  it
represents a typical and viable industry practice for the control
of suspended solids, cadmium, zinc and selenium.  Currently seven
of  twelve  plants in this subcategory have Level 2 or equivalent
treatment technology.  Four of the six  direct  dischargers  have
Level   2  treatment  already  installed.   Two  plants  have  no
discharge and would not incur additional costs.

Equipment for Different Treatment Levels

A.   Equipment functions

Conventional sludge dewatering by a  filter  press  is  used  for
sludge  removed  by  the  clarification/settling  system.  In the
cadmium pigments segment,  this  sludge  has  value  and  may  be
recovered.   The  sludge from the filter press is either disposed
of off-site in a hazardous material landfill or sent to  an  off-
site cadmium reclaiming/recovery operation.  If a tube settler is
used,  backwash  from  the  settler as well as from the granular-
media filters is returned to the  influent  holding  basin.   All
equipment is conventional and readily available.

B.   Chemical Handling

Caustic soda (50 percent  NaOH)  is  used  to  precipitate  heavy
metals  in  Level 1.  Sulfuric acid (concentrated) may be used to
reduce the pH of the wastewater prior to discharge.

C.   Solids Handling
                              200

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Treatment sludges for cadmium pigments generated by Level  1  are
dewatered  in a filter press.  The solids may be disposed of off-
site in a hazardous material landfill  or  sent  to  Tan  offrSite
cadmium  reclaiming/recovery  operation.  Level 2 filter backwash
may be  sent  to  the  head  of  the  plant  or,  if  the  solids
concentration  is  sufficiently high, may be sent directly to the
filter press.  Cadmium salts wastewater treatment sludges are not
dewatered since  the  low  volume  typically  produced  does  not
justify the use of a filter press.

Treatment Cost Estimates

In  the  cadmium pigments and salts subcategory, two model plants
were chosen, one representing the cadmium  pigments  segment  and
the  other representing the cadmium salts segment.  In each case,
two treatment options  were  considered.   Costs  for  two  model
plants  were  developed,because there are significant differences
between the production and amounts of wastewater  generated  even
though the wastewaters have similar chemical characteristics.

General                                                          *

Production  ranges  and wastewater flow characteristics have been
presented earlier in this section and are summarized in Table 11-
1.  There are six direct dischargers, four indirect  dischargers,
and two plants which achieve zero discharge.

A.   Cadmium Pigments

During development of the model plant characteristics, only  data
from  those  facilities  which  manufacture cadmium pigments were
considered.  However, since  pigment  production  is  universally
preceded  by manufacture of cadmium salts and since cadmium salts
manufacture generates small volumes of wastewater,  both  sources
of  wastewater  were  combined  for the purpose of defining model
plant characteristics.  In fact, most wastewater flow information
supplied by industry for pigment  plants  did  not  differentiate
between  wastewater  attributable  to  salts  production  and  to
pigments production at those plants.                             ,

The model plant production rate  of  711  metric  tons  per  year
represents  the  average  production  for all discharging, pigment
producers.  At proposal, the model plant unit flow of 92.4  cubic
meters/metric  ton (m3/kkg) was obtained by computing the average
unit flow for the three discharging facilities for which detailed
water use information was available  (see Table  11^-5).  Since zero
discharge facilities were not  included  in  the  computation,  the
average  unit  flow value is greater than if zero discharge  (zero
unit flow)  facilities were included.  Since  proposal,  flow  and
                               201

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production data for  the  fourth discharging plant  (F128)  have been
obtained  and  are shown in Table  11-5.  Averaging  the unit flows
for all four plants  results in   an  average   unit   flow   of  89.2
mVkkg,  which  is   an   insignificant  difference   of  only three
percent.  Flow measurements normally are  subject   to   an  error
greater than three percent.  Therefore,  the Agency  has decided to
continue  to  use  92.4  mVkkg as  the flow basis for establishing
the promulgated limitations, because the differences  in actual
discharges  and  cost  of treatment  would be  insignificant if the
lower flow (89.2 mVkkg)  were   used.    Needless  expenditure  of
resources   would  be  required  to  revise   that   number.   Most
discharging cadmium  pigment facilities operate on a 250   day  per
year  basis,  so the model plant was also assumed to operate on a
similar schedule.  The daily discharge volume (262  cubic meters)
was  derived  from   the  model plant  characteristics listed above.
These characteristics were used  as the basis  for  treatment  cost
estimates at all levels.

Material usage for all levels was  estimated as follows:

     Chemical  	Amount        Treatment Level
     NaOH (50% sol.)
     H.,S04  (100%)
 445 kg/day
52.4 kg/day
Total solid waste generated is estimated at 0.18 cubic meters/day
for  Level  1 and 0.018 cubic meters/day for Level 2.  The sludge
is assumed to be dewatered to 50% solids by volume.

Model Plant Treatment Costs.  On the basis  of  the  model  plant
specifications  and  design  concepts  presented  earlier  and in
Section 10, the estimated costs of treatment for one  model  with
two  levels  are  shown  in  Table 11-10.  The cost of Level 2 is
incremental to Level 1.

B.   Cadmium Salts

During development of the model plant characteristics, only those
facilities producing cadmium salts not destined for production of
cadmium pigments were considered salt producers.  The model plant
for the cadmium salts segment has a production rate of 1'69 metric
tons per year.  This figure was obtained by computing the average
production for discharging cadmium  salt  producers.   The  model
plant  operating  schedule  of 150 days per year was based on the
average  of  operating  days  reported   for   discharging   salt
producers.   The  unit  flow  value of 0.058 cubic meters/kkg was
obtained by computing the average unit flow for those  facilities
where wastewater flow information was available (see Table 11-4).
The  daily  discharge  volume (0.07 cubic meters) was obtained by
                              202

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    TABLE 11-10.  WATER EFFLUENT TREATMENT COSTS
                  FOR MODEL PLANT..
SUBCATEGORY:  Cadmium Pigments Subgroup
ANNUAL PRODUCTION: 	

DAILY FLOW: 	2.62

PLANT AGE:
                           711
               METRIC TONS
                  NA
	 CUBIC  METERS

 YEARS   PLANT LOCATION:
NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY
                                    COSTS ($1,000) TO ATTAIN  LEVEL
                                     23.0
Facilities
Installed Equipment
  (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Wastd; Disposal) 112.4
Residual Waste Disposal
168.6
38'.3
34.5
26.4
290.8
47.3
112.4
2.7
29.4
5.9
5.3
4.1
44.7
7.3
8.9
0.3
  Total Annual Cost
                                    162.4  16.5

                        b.  TREATMENT DESCRIPTION
LEVEL 1:   Alkaline precipitation,  clarification, sludge dewatering,
            pH adjustment
LEVEL 2:   Filtration
                            203

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    TABLE 11-11.  WATER EFFLUENT TREATMENT COSTS
                  FOR MODEL PLANT.
 SUBCATEGORY:  Cadmium Salts Subgroup
ANNUAL PRODUCTION: 	

DAILY FLOW: 	0.07

PLANT AGE:        NA
169
. METRIC TONS
 	 CUBIC METERS

 YEARS   PLANT LOCATION:
                  • NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS

                                    COSTS  ($1,000) TO ATTAIN  LEVEL
COST CATEGORY                       12345

Facilities
Installed Equipment
   (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital

Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Wast6 Disposal) 4.1
Residual Waste Disposal
1.9
0.4
0.3
0.3
2.9
0.5
4.1
0.1
0.2
Negl.
Negl.
Negl.
0.2
Negl.
0.1
Negl.
  Total Annual Cost
                        b.
          4.7    0.1

  TREATMENT DESCRIPTION
LEVEL 1:   Alkaline precipitation,  clarification,  pH adjustment

LEVEL 2:   Filtration
                             204

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multiplying daily production by the unit flow value.  These  data
were  used  as  the  basis  for  treatment  cost estimates at all
levels.

Material usage for both levels was estimated as follows:

     Chemical               Amount	Treatment Level
     NaOH  (50% sol.)
     H2S04  (100%)
                         0.12  kg/day
                         0.014 kg/day
Total  solid  waste  generated  is  estimated  at  0.0012   cubic
meters/day for Level 1 and 0.001 cubic meters per day as Level 2.
The sludge is assumed to contain 2% solids by volume.

Model  Plant  Treatment  Costs.   On  the  basis  of  model plant
specifications and  design  concepts  presented  earlier  and  in
Section   10,  the estimated costs of treatment for one model with
two levels are shown in Table  11-11.  The  cost  of  Level  2  is
incremental to Level 1.

Basis for Regulations

Basis for BPT Limitations

A.   Technology Basis

For BPT,  the Agency is proposing limitations based upon  alkaline
precipitation,  clarification,  dewatering  of  the  sludge  in  a
filter  press,  granular  media  filtration  of   the   clarifier
effluent,  followed  by  pH adjustment  (if necessary).  Currently
seven  of  the  twelve  plants  in  this  subcategory  have  this
technology  or  its  equivalent  installed.   Of  the  six direct
dischargers   in   this  subcategory,  four  have  this  technology
installed.   Two  additional   plants  have  no discharge and thus
would not be affected.
B.
Flow Basis
 For  the  cadmium pigments  segment,  a  unit  flow rate of  92.4  mVkkg
 was  selected as being  representative of   the  group.    This  flow
 rate  was   derived as  described above under model  plant treatment
 costs.

 For  the  cadmium salts  segment,  a unit flow of  0.058   mVkkg   was
 selected  as  being representative  of the group.   This flow  rate
 was  derived as described  above  under model plant treatment  costs.

 C.    Selection of Pollutants to be Regulated
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 The   selection  of  pollutants  for   which    specific   effluent
 limitations  are  being  established is based on an evaluation of
 the   raw  wastewater  data  from  screening    and   verification,
 consideration   of   the  raw  materials  used  in  the  process,
 literature data,   historical  discharge  monitoring  reports  and
 permit    applications,    and   the   treatability  of  the  toxic
 pollutants.

 Tables  8-1  through 8-14 summarize  the  achievable  concentrations
 of   toxic  metal   pollutants  from the literature using available
 technology options,  other industries,  and treatability  studies.
 Water  use and discharge data are  presented  earlier in Section 11
 together with  generalized  process  characteristics.    Pollutant
 concentrations of  raw wastewater streams and a summary of maximum
 concentrations  observed  of  toxic  pollutants  detected during
 screening and verification sampling at several  plants  are   also
 presented  earlier  in  this section.   Data from Appendix A on the
 performance of  in-place  industry  treatment  systems  was   also
 utilized in developing  the list of pollutants to be regulated.

 Based  upon   the occurrence of  treatable levels of specific  toxic
 metals,  cadmium,   lead,   selenium,   and  zinc  were  selected  as
 candidate  toxic  pollutants  for  BPT  regulations.    Antimony,
 arsenic,  chromium, copper,  mercury,  nickel,  silver,  and  thallium
 were  detected but  at  less than  treatable levels.

 Consideration  of  the   raw  wastewater  concentrations presented
 earlier,  industry  data,  and information in Section 8   related  to
 the   effectiveness of  hydroxide precipitation,  clarification and
 filtration  leads to the selection  of  cadmium,  selenium,  and   zinc
 as  toxic pollutants  to be regulated.   As discussed in Section  8,
 proper  control  of  zinc  concentrations  will also  achieve  control
 of lead,  so that lead was not selected  for regulation.

 D.    Statistical Analysis  of   Influent  and   Effluent  Data   for
 Cadmium  Pigments

 The   proposed  effluent   limitations   for  the   Cadmium  Pigments
 subcategory were based   upon  treatment  consisting  of   alkaline
precipitation,  clarification, and  granular media  filtration.  The
proposed  effluent limitations  for  cadmium and  zinc were  based on
 effluent  data  from Plant  F128.

 Industry  comments  on the  proposed  regulation suggested   that  the
 limitations  were  too  stringent   because  the   cadmium pigments
process wastewater at Plant Fl28, which produces  other   inorganic
chemical  products  and   combines   the  wastewater  for  treatment,
comprises only  three percent of  the total flow of  wastewater  to
treatment.  The industry  contended  that the cadmium levels in the
                              206

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raw  waste were diluted and consequently the effluent levels were
abnormally low.  Industry also commented that only  some  cadmium
pigments  contained  zinc  and  that  the zinc level in raw waste
would be higher when producing those pigments than  it  would  be
otherwise.   To address these issues, EPA utilized data submitted
during the comment period from Plant FT 28, which  submitted  both
influent  and  effluent  data,  and  Plant  F102, which submitted
effluent data with only a limited amount of influent data.

Analysis of Cadmium Data

Analytical Plan

     1.)  In order-to address  the  question  of  the  effect  of
          dilution,   a   correlation   analysis   was  performed
          comparing influent and  effluent  data  sets  at  Plant
          F128.  This analysis was performed to determine whether
          or   not   a  more  dilute  influent  stream  would  be
          associated with lower effluent  cadmium  concentrations
          provided the same treatment technology were applied.

     2.)  If a strong positive  correlation  were  found  by  the
          above  analysis  it  was determined that the Plant F128
          data would be screened to remove all  effluent  cadmium
          values  associated with low levels of influent cadmium.
          The screening level would be determined on the basis of
          the limited influent cadmium data available from  Plant
          F102.   In  this  way  it  was hoped that the resulting
          influent data set would be comparable to the  available
          Plant  F102  influent data set.  That is, the effect of
          the greater dilution at Plant F128 would be eliminated.
          The resulting Plant F128 influent  data  set  would  be
          compared  statistically  with  the  Plant F102 influent
          data set to determine whether the two  are  equivalent.
          If   no  correlation  were  found  (or  if  a  negative
          correlation were indicated), the commenter's contention
          would be judged to be unfounded and no change would  be
          made to the proposed limitations.

     3.)  If the influent data sets  were  comparable,  then  the
          screened  effluent  data  set  from Plant FT 28 would be
          analyzed to determine long-term average and variability
          factors using the methods described in Section 8.

     4.)  The Plant FT 02 effluent  cadmium  data  would  also  be
          analyzed  according to the methodology described below.
          However, the data would first  be  screened  to  remove
          data   associated  with  non-compliance  with  chromium
          pigments guidelines (see discussion below).
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     5.)  The screened effluent data sets  from  Plants   F128  and
          FT 02  would  be  compared  statistically  to   determine
          whether they are also comparable.  This analysis  would
          address  the  question  of  conflict  between   chromium
          removal and cadmium removal requirements.

Statistical Methods

Mann-Whitney U-test

The Mann-Whitney U-test, also known as the Wilcoxon  test,  is  a
nonparametric   method   for  testing  the hypothesis   that  two
populations of data are identical on the   basis  of  sample  data
sets  taken  from  these  populations.  This test is based upon a
rank ordering of the data and is independent of the shape of  the
data  distribution.   A  complete  discussion of this test can be
found in Reference 4.  The formulae used are:
U
                             + n, (nt +  1 ) - R,
                                   2
where nj and nz are the numbers of data in each sample set and R,
is the sum of the ranks in the first sample set.
    var (U) = n,ng(n1 +
                                               +1 )
                                       12

                        2 = U - E(U)
                             var(U)

where E(U) is the expected value of U and var  (U) is the variance
of U.  If |£| is greater  than  1.96  then  the  populations  are
judged to be different at the 5% significance  level.

Spearman's Rho

Spearman's  rank  order  correlation  is a method for determining
whether two paired data sets are related.  This analysis is based
upon a rank-ordering of the two  data  sets  and  the  subsequent
comparison  of  the  ranks  of the corresponding elements of each
set.  Rho, the correlation coefficient computed, can  range  from
-1   to   +1.    Values   close  to  -1  or  +1  indicate  strong
relationships,  while  values  close  to   zero   indicate   weak
relationships.   This  method,  since  it  is  based upon the rank
orders rather than the data themselves,  is  independent  of  the
shapes  of the data distributions.  A complete description of the
                              208

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computational procedure involved can be  found  in  Reference  5.
The formulae used are:

                         rho = 1 - 6 ED2
                                   N(N2 -1)

where  D is the difference between the ranks of a given data pair
and N is the number of data pairs.

The significance of the rho value calculated is determined on the
basis of a £-test.  That is,
                                 N
1
If |2| is greater than 1.96, then rho is significant at the  0.05
level. •

DATA ANALYSIS RESULTS

A  rank  order  correlation  was performed in order to assess the
relationship between influent and effluent cadmium concentrations
at  Plant  F128.   Data  used  omitted  only  those  data  having
discrepancies   in  reported  flows.   This  was  done  since  the
effluent cadmium'data were reported as loadings and thus required
conversions  dependent  on  the  flow  in  order  to  arrive   at
concentration values.  Eight data points were omitted due  to flow
reporting  discrepancies.   For  this analysis there remained 141
data pairs.  A  positive correlation coefficient (Spearman's  Rho)
of  0.65  was obtained having a Z value of 7.68.  The correlation
coefficient of  0.65  indicates a  level  of  relationship   between
influent and effluent cadmium concentrations which would occur by
chance  less  than   1  time  in  100,  given  the 141 data points
available.

The correlation coefficient of 0.65 suggests that  when  influent
cadmium   concentrations   are  higher,  the  resulting  effluent
concentrations  will  be higher given the  same  treatment   system.
This  result  might  be  extrapolated  to  suggest  that   if  two
facilites have  comparable treatment systems in place,  the plant
having  the  greater influent concentrations of cadmium would not
be expected to  achieve the same effluent level as its counterpart
with  the lower  influent concentrations.  This analysis  addresses
the   comment   questioning   the   use   of   long-term   average
concentrations  at a  plant whose influent cadmium concentration  is
diluted by other waste streams.   Since  there  is  apparently   a
relationship  between  influent  and  effluent  concentrations of
cadmium, the Plant   F128  data  were  screened  to  minimize  the
effluent of low influent cadmium concentrations on the calculated
long-term average.
                               209

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Many  of  the   influent   samples   at  Plant  F128 were  quite  low  in
total cadmium  content as  compared  with  the   Plant   F102   influent
data.   In order  to use the data submitted  by  F128  as a  predictor
of achievable  effluent  cadmium  concentrations,  the data were
screened  to   remove  all  data  points corresponding to influent
levels less  than 1.2  mg/1.   1.2   mg/1   was selected as  the
screening  level  since this was the lowest  influent total cadmium
concentration  reported in the data from Plant  F102, excluding the
first two days, which were judged  to  be non-representative  due  to
start-up conditions.

In addition to the differences at  the low ends of their   influent
cadmium  concentration ranges, the maximum  value reported by F128
was 19 mg/1 while the maximum value reported  by  F102   was 43.8
mg/1.   The  average influent concentration at F102 was   10 mg/1
while after screening the F128 data,  the   average  concentration
was  4  mg/1.   Therefore,  following the data screening, a Mann-
Whitney U-test was performed to determine   whether  the   influent
data  at  F102 were comparable to  the screened influent  data from
F128.  The result of this analysis was  that the two data sets are
equivalent at  the 5% level (Z = 1.22).   This  is  interpreted   to
mean  that  the  screened influent data at  Fl28 are comparable  to
the  influent   data  at  F102.   On   the basis  of  the earlier
correlation    analysis,  the  effluent   concentrations   would   be
expected to be similar if equivalent  treatment were practiced.

On the basis of the above results, and   the technical   judgement
that  F128  achieves  good  operational  control in  its wastewater
treatment system, the effluent data corresponding to  the screened
influent data  set were analyzed to determine a long-term average
and variability factors.  These results  are summarized below:

     F128 Screened Effluent Cadmium Data (All  data  excluded
     where influent total Cd<1.2 mg/1)
     Number of data points
     Mean
     Standard Deviation
     Range
     Variability Factor (24-hr, max.)
     Variability Factor (30-day avg.)
39
0.14 mg/1
0.14 mg/1
0.025 to 0.77 mg/1
5.09
1 .31
The   treatment  technology  upon  which  the  chromium  pigments
guidelines were established includes S02  reduction  of  Cr+6  to
Cr+3,  alkaline  precipitation  at about pH = 8.5, clarification,
and filtration.  For cadmium pigments, alkaline precipitation  is
recommended  at  about  pH  = 10.5, followed by clarification and
filtration.  Control of pH is critical in order to maintain total
chromium discharge levels within  the  effluent  guidelines.   pH
                              210

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control  is  equally critical for cadmium discharge limits, while
the two metals follow  different  solubility  trends  around  the
control point (about pH - 9-10).  Therefore screening was applied
to the data in order to avoid selecting a cadmium discharge level
which  in  effect  forces chromium non-compliance.  The FT 28 data
set contained only one data point which had an 'effluent  chromium
concentration  above  2.9  mg/1  (the  maximum  chromium effluent
limitation in the chromium pigments guideline).  This  value  was
3.0  mg/1  (i.e.  3% over the maximum limitation).  However, this
point  had  been  screened  out  due  to  low  influent   cadmium
concentration.

In  addition,  effluent  cadmium  data  from  FT 02  were analyzed
according to the methodology described in Section 8.   Data  were
first   screened   to  remove  all  data  corresponding  to  poor
treatment.

Fifty data points had been identified for exclusion by Plant F102
because of treatment system upset conditions.  Consequently these
data  were  not  included.   Further  screening  was  based  upon
concentrations  of  chromium  and  TSS,  which are subject to the
limitations for  the  chromium  pigments  subcategory.   Effluent
cadmium  data  were omitted which correspond to effluent chromium
concentrations  greater   than   2.9   mg/1   or   effluent   TSS
concentrations greater than 87 mg/1.  These screening levels were
selected  since  they  are  the  effluent  guideline  levels  for
chromium pigments currently in effect.  A long-term  average  and
variability factors were computed as summarized below:

F102   Screened  Effluent  Cadmium  Data   (All data excluded where
effluent Cr<2.9 mg/1 or effluent TSS<87 mgl)
Number of data points
Mean
Standard Deviation
Range
Variability Factor
Variability Factor
                            (24  hr.  max.)
                            (30-day  avg.)
130
0.20 mg/1
0.25 mg/1
0.02 to 1
5.87
1 .37
 A secondary  screening  was  performed on the FT 02  data in order  to
 eliminate   instances  of   low  chromium discharge with associated
 high  cadmium levels, which could indicate a pH  optimization  for
 chromium removal  which could cause high cadmium  discharges.   Four
 such  data  points  were  identified.
 The resulting summary statistics are as follows:

         Number of data points
         Mean
                                                                   29 mg/1
126
0.18 mg/1
                               211

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        Standard Deviation
        Range
        Variability Factor  (24-hr, max.)
        Variability Factor  (30-day avg.)
                    0.21  mg/1
                    0.02  to 1.29 mg/1
                    5.64
                    1 .35
These  statistics  suggest that even after screening the two data
sets,  F128  achieves  superior   effluent   cadmium   reduction.
However, a Mann-Whitney U-test was performed to determine whether
the  apparent differences between the screened effluent data sets
at the two plants were statistically significant.  The result  of
this   test  indicates  that  the  two  effluent  data  sets  are
equivalent at the 5% level,   (Z
1.91).    Thus,   the  apparent
differences are attributable to chance.

It  should be noted that the data provided by Plant F102  included
data from a considerable number  of  days  (50)  when  wastewater
treatment  plant  upsets  had  occurred.   These  data  had  been
identified as non-representative by  the  company  and  generally
were  characterized  by extremely high effluent concentrations of
one or more control parameter(s).
Summary and Conclusions

On the basis of the statistical  analyses
following conclusions can be drawn:
       described  above,   the
     1.   There  is  a  positive  correlation  between   influent
          cadmium     concentration    and    effluent    cadmium
          concentration at Plant FT 28.  This suggests that, while
          effluent cadmium concentrations are consistently low at
          this facility, this may be related  to  lower  influent
          concentrations  at this facility as compared with other
          cadmium pigments production facilities.

     2.   When the data  from  Fl28  are  screened  to  eliminate
          instances  of low influent cadmium concentrations (i.e.
          lower than F102, the only other plant  having  provided
          influent data) creating an influent data set comparable
          to that of F102, the long-term average effluent cadmium
          concentration is approximately 0.14 mg/1.

     3.   When the data  from  FT 02  are  screened  to  eliminate
          instances   of   poor  treatment  system  control,  the
          effluent data set is comparable  statistically  to  the
          screened  effluent data set from F128, yielding a long-
          term average cadmium concentration of 0.20 mg/1.

Recommendations
                              212

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In view of the high  effluent  cadmium  concentrations,  frequent
high  chromium  levels,  the  high  variability  in  cadmium  and
chromium effluent levels as well as  the  frequent  instances  of
very  poor  TSS control, it is apparent that the FT 02 facility is
in need of improved treatment system control.  Therefore the data
from this facility are  not  believed  to  represent  the  levels
achievable  by application of BAT/BPT treatment technology to the
cadmium pigments subcategory.  While the facility employs a  sand
filtration  unit,  there have been multiple  instances of effluent
TSS concentrations greater than TOO mg/1 (and frequently  in  the
500  to  1,000  mg/1   range).   Also  pH  control  is applied for
chromium  removal,   but   frequent   occurrences   of   chromium
concentrations  greater  than  5  and as high as 94.8 mg/1 in the
plant's  treated  effluent  suggest  that  the  control  of  this
treatment  process  is inadequate.   In view of these facts this
plant  is  not  used   as  a  basis  for  recommended  guidelines.
However,  the  results of  analysis  of  screened data from this
facility indicate that improved  filtration  unit  operation  and
improved  pH control will substantially  improve overall treatment
system performance,  producing  effluent  cadmium  concentrations
similar  to  those  obtained  at F128.   This improved performance
should not require  large  capital  expenditures,   since  the  BAT
treatment  system   unit operations  have already  been installed.
There  would  most  likely   be  need  for  smaller   expenditures
associated  with   improved   control  systems and  operating  and
maintenance  practices.   Costs  associated  with  the  necessary
control  systems  have  been  included  in  the EPA  cost  analysis both
for  capital and  annual costs.

On the other hand,  FT 28 exhibits relatively  consistent  effluent
quality.   No  data  from   this  facility  were  omitted   due   to
treatment  upset  conditions.   In  addition,  the   screening   process
employed  has  apparently  eliminated  the effect  of  dilution on  the
effluent quality.   Therefore,  we have  used  a long-term average  of
0.14 mg/1  for  guideline development.

Variability  factors,  however,  should be selected on   a  different
basis.    Since  both   data sets  have been truncated  either on  the
high end or  the  low end of their ranges, the natural  variability
of  the  data   sets  has   been  compressed,  and cannot be  used as
representative of wastewater treatment system performance  at  the
average  plant.    Variability factors of 2 and 6 were established
 for the subcategory on the basis of  unscreened  historical  data
 for  the  period  1/79-12/80 at plant F128.   These factors were 2
 for the 30-day average and 6 for the 24-hour maximum.   These data
 covered a period of time when EPA believes the plant to have been
 operating  normally   since  economic  conditions  were  generally
 normal.
                               213

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Using  these  factors  and the long-term average concentration of
0.14 mg/1 yields the following recommended standards:

     30-day average Cd concentration = 2 X 0.14 mg/1 =0.28 mg/1

     24-hr, maximum Cd concentration = 6 X 0.14 mg/1 = 0.84 mg/1

Variability factors calculated from the entire  Plant  F128  data
set  (i.e.,  1/3/79 through 12/21/83) were not used for guideline
development since this time period included  several  periods  of
atypically  low  production due to the economic conditions at the
time.  These periods are believed by EPA to affect the  long-term
variability.

Analysis of Zinc Data

Only  Plant F128 data were used because Plant F102 submitted only
five days of zinc effluent data.

Analytical Plan

     1.)   In order to address  the  question  of  the  effect  of
          dilution,    a   correlation   analysis   was  performed
          comparing influent and  effluent  data  sets  at  Plant
          F128.     This   analysis  was  performed  in  order  to
          determine whether or not a more dilute influent  stream
          would   be   associated   with   lower   effluent  zinc
          concentrations provided the same  treatment  technology
          were applied.

     2.)   If a strong  positive  correlation  was  found  it  was
          determined  that  the  F128  data  would be screened to
          remove all effluent zinc  values  associated  with  low
          levels  of influent zinc.   The screening level would be
          determined on  the  basis   of  an  examination  of  the
          influent  data base to  locate a break or other point in
          the data where it could be judged that  zinc-containing
          pigment   (cadmium  yellow)   production  was  evidently
          underway when the influent zinc concentration was above
          the selected  level.

     3.)   Long-term  average  and   variability  factors  would  be
          computed  according  to the   methodology  described in
          Section 8.

     4.)   If a weak  relationship  were shown between influent  and
          effluent zinc  concentrations,  the long-term average and
          variability   factors would  be calculated  for both the
          screened and  unscreened data  sets,   and  a   statistical
                              214

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          comparison  would  be  made  between  the  screened and
          unscreened effluent data sets to determine  whether  or
          not  any  apparent .differences  between  the  two were
          statistically significant. '

Statistical Methods

The statistical methods used were the same as described above for
analysis of the cadmium data.

Results

A rank-order correlation was performed in  order  to  assess  the
relationship   between   influent   and   effluent   total   zinc
concentrations.   Data  used  omitted  only  those  data   having
discrepancies  in  reported  flows.   This  was  done  since  -the
effluent zinc data were reported as loadings  and  thus  required
conversions   dependent  on  the  flow  in  order  to  arrive  at
concentration values.  Eight data points were omitted due to flow
reporting discrepancies.  For this analysis  there  remained  142
data  pairs.   Correlation  coefficients  range  from  -1  to +1.
Values close to -1 or  +1  indicate  strong  relationships  while
those  close  to zero indicate weak relationships.  This analysis
yielded a  correlation  coefficient  of  0.38   (Spearman's  Rho),
showing   a  weak,  but  statistically  significant  relationship
between influent and effluent zinc concentrations at this  plant.
Given  the number of data pairs available for the analysis  (142),
this degree of correlation would occur by chance  less  than  one
time in TOO.

This  result  was further supported by the subsequent analysis of
the effluent data set both with and without screening  to  remove
all  instances of low influent zinc concentrations.  Low influent
zinc concentrations were taken as  concentrations below 1.2  mg/1.
This  level  was  selected  on the basis of an  examination of the
F128 influent data.  There  is an apparent break in  the  data  at
the  1.2  mg/  level.    In  addition,  it  is   highly likely that
influent  concentrations  above  this  level  are   indicative  of
cadmium  yellow  pigment  production  (See the data  for Plant F134
above.)  Also, the  1.2 mg/1  concentration represents a  treatable
level  of   zinc   in  wastewater.    The table below  summarizes the
results of  these analyses:
                                    Screened  Data
            Unscreened Data
 Number  of  Observations

 Mean (mg/1)
46

.06
142

.05
                               215

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 Standard Deviation (mg/1)

 Range (mg/1)

'Coefficient of Variation

 Variability Factor (24-hr,  max.)

 Variability Factor (30-day  avg.)
      .035

0.005-0.20

      .58

     3.05

     1 . 17
      .028

0.005-0.20

      .56

     2.95

     1 .17
 In order to determine whether the  apparently  small  differences
 between  the  screened and unscreened data sets are statistically
 significant,  a Mann-Whitney U-test was performed.   The result  of
 this  analysis  was  that  the  two  data  sets  are judged to be
 different with a statistical significance at the 5%  level  (Z  =
 3.00).    That  is,   these  differences would occur by chance less
 than 5% of the time given the number of data available.

 From a treatability standpoint,  the means  of  the  screened  and
 unscreened data sets are very nearly the same as are the standard
 deviations,   while   the  ranges  of the data are identical and the
 coefficients  of variation and variability factors are nearly  the
 same.

 The  similarity of  these two data sets may be related to the fact
 that the influent concentrations of zinc reported are  considered
 to  be  relatively   low  and  the  treatment system appears to be
 consistently  reducing the zinc concentrations in the effluent  to
 levels  generally  recognized as  treatability  levels   in other
 industries.
Summary  and  Conclusions

On  the basis of  the  statistical   analyses
following  conclusions  can  be  drawn:
        described  above,   the
      1.)  There   is   a   weak,    but    statistically    significant
          relationship    between   influent    and  effluent   zinc
          concentrations at  Plant  F128.

      2.)  When the data  from this  plant  are  screened  to  eliminate
          instances   of   low  influent  zinc  concentrations   the
          resulting   data set  is different  from the unscreened
          data set with  statistical significance at the  5% level.


      3.)  Actual  numerical values  for  the  long-term   average   and
          variability factors  for  the  screened and unscreened
                              216

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          data  sets  are
          standpoint.
very   close   from
treatability
Recommendations
On  the  basis  of  these  results  the  long-term  average  zinc
concentration of 0.061 mg/1  to  establish  final  effluent  zinc
guidelines  for the cadmium pigments subcategory of the Inorganic
Chemicals Point Source Category.

However, we have used the variability  factors  of  1.67   (30-day
avg.)  and  3.00 (24-hr, max.) derived from effluent data  for the
period 1/79-12/80 rather than those calculated here, since it  is
believed  by  EPA that the period 1/3/79 through 12/21/83, during
which time these data were obtained, includes some atypically low
production periods due to economic factors.  These periods would
certainly influence the variability of the data.

E.   Basis of BPT Pollutant Limitations

Limitations are presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is  based   on  the
unit  flow  rate  of  92.4  mVkkg for cadmium pigments and 0.058
mVkkg for cadmium salts.

BPT  limitations,  which  apply   to   all   process   wastewater
discharged,  are  presented in Table 11-12  (Cadmium pigments) and
Table 11-13  (Cadmium  salts).

1.   Conventional Pollutants

     a.   pH

          The treated effluent  is to  be   controlled   within  the
          range  of  6.0 -  9.0.   This limitation  is  based  upon the
          data  presented   in  Appendix  B  of   the    Development
          Document   for  Proposed Effluent Guidelines  for Phase  I
          Inorganic  Chemicals  (Ref. 2) and the   JRB  study  (Ref.
          3)-

     b.   TSS

          The BPT  limitations  for TSS are  based  on  an  average  of
          long-term   TSS   monitoring  data from  Plants A  and K as
          presented  in  Appendix  A   of  the  Phase   I   Development
          Document   which   use  the same   Level  2   (filtration)
          technology to control  TSS that  is  promulgated  for   the
          cadmium  pigments and salts subcategory.
                               217

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          Data received from Plant FT 28 during the comment period
          shows  the  plant  is achieving the limitations derived
          below.  Therefore, we have not revised this section.  A
          long-term average of 9.3  mg/1  (the  average  of  both
          plants)  was  used to develop the discharge limitations
          for plants employing filtration.  Variability  factors,
          also  obtained from Plants A and K of 1.8 for a monthly
          average and  3.0  for  a  24  hour  maximum  were  used
          yielding  TSS  concentration  limits  of 17 mg/1 and 28
          mg/1 respectively.  Thus, utilizing these  values,  one
          obtains  TSS  mass limitations for the cadmium pigments
          segment of:

          30-day average;
          (17 mg/1) (92.4 mVkkg) (kg/10«mg) (1000 1/m3)
          = 1.57 kg/kkg

          24-hour maximum;
          (28 mg/1) (92.4 m3kg) (kg/10* mg) (1000 1/m3)
          = 2.59 kg/kkg

          Similarly, for the cadmium salts segment;

          30-day average;
          (17 mg/1) (0.058 mVkkg) (kg/10* mg) (1000 1/m3)
          = 0.001 kg/kkg

          24-hour maximum;
          (28 mg/1) (0.058 mVkkg) (kg/106 mg) (1000 1/m3)
          = 0.0016 kg/kkg

2.    Toxic Pollutants

     a.   Cadmium

          The BPT limitations for cadmium are based on  long-term
          monitoring  data from Plant F128 as described above and
          presented in Appendix  A.    In  addition  to  the  data
          described above, some data is available from Plant F134
          which  has  ferrous  sulfide plus filtration technology
          which is not the same as Level 2 and does  not  perform
          as  well.   Since  the plant F134 treatment system does
          not perform as well as Level 2 treatment, the data from
          Plant F134 were not used.   Variability factors  derived
          from the unscreened data at Plant F128 of 2.0 for a 30-
          day  average  and  6.0  for a 24-hour maximum were used
          yielding cadmium limitations  of  0.28  mg/1  and  0.84
          mg/1  respectively.    Thus utilizing these values,  mass
                              218

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limitations  for  the
obtained as follows:
                            cadmium  pigments   segment    are
     30-day  average;
     (0.28 mg/1)(92.4  mVkkg  )  (kg/10*  mg)  (1000  1/m3)
     =  0.026 kg/kkg

     24-hour maximum;              •
     (0.84 mg/l)(92.4  mVkkg)  (kg/10« mg)  (1000 l/m»)
     =  0.078 kg/kkg

     Similarly,  for  the cadmium salts segment:

     30-day  average;
     (.28 mg/l)(0.058  mVkkg)  (kg/10* mg)  (1000 1/m3)
      = 0.0000162 kg/kkg

     24-hour maximum;
     (.84 mg/1) (0.058  mVkkg)  (kg/10« mg)  (1000 1/m3)
     = 0.0000487 kg/kkg

b.   Selenium

     The  BPT  limitations  for  selenium  are  based   upon
     screening and verification sampling at Plant F102 since
     no plant with a well-operated treatment system could be
     found  with  long-term  effluent  monitoring  data  for
     selenium.  Plant F102 provided  long-term  data  during
     the comment period.  However, as discussed above, we do
     not  believe  it  is  operating  the  treatment  system
     optimally.   Since  cadmium  is  very  toxic,  we   are
     concerned  that adjustments to the proposed limitations
     for  selenium  could  upset  the  control  of  cadmium.
     Therefore,  we  did  not use the new effluent data from
     F102.  Screening and verification data from plant  F134
     were not used because it was not producing pure cadmium
     reds   and  had  a  low  selenium raw waste load.  Since
     there   is  insufficient   data   to   derive   reliable
     variability   factors  for  selenium,  the  variability
     factors of 2 for a 30-day average and 6 for  a  24-hour
     maximum  from  treatment system performance for cadmium
     from Plant F128 were used yielding selenium limitations
     of  0.4 and   1.2  mg/1  respectively.   Thus,  utilizing
     these   values,  mass  limitations  computed for cadmium
     pigments are as  follows:

     30-day average;
      (0.4 mg/1) (92.4  mVkkg)  (kg/10* mg)  (1000 1/m3)
     = 0.037  kg/kkg
                          219

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    TABLE 11-12.   BPT EFFLUENT LIMITATIONS FOR CADMIUM PIGMENTS
Conventional
Pollutants
TSS < * )
Toxic
Pollutants
Cadmium ( s >
Selenium(s)
Zinc
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    TABLE 11-13.  BPT EFFLUENT LIMITATIONS FOR CADMIUM SALTS
Conventional
Pollutants
Toxic
Pollutants

Cadmium<*>

Selenium<«>

Zinc<5>
Long-Term
Avq.(mg/l)
0.2<3>

0.061
VFR
                                         Cone.'Basis
                                            (mq/1)
                                        17
                                >        0.28

                           2/6(25        0.4

                           1.67/3.0<*>   0.10
                                                 24-hr.
                                                  max.

                                                 28
                                   0.84

                                   1.2

                                   0.18
                                           Effluent Limit
                                              (Kq/kkg)
                                           30-day
                                            avg.

                                           0.001
24-hr.
max.

0.0016
                             0.0000162  0.0000487

                             0.000023   0.000070

                             0.0000058  0.0000104
VFR - variable Factor Ratio (30-day avg./24-hr, max.)

(1)  Based upon long-term data at "Plants A and K (Phase I).
(2)  Based upon long-term data at Plant F128.
(3)  Based upon screen sampling at Plant F102.
(4)  Also applicable to NSPS and BCT.
(5)  Also applicable to BAT and NSPS.
                                       221

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          24-hour maximum;
          (1.2 mg/l)(92.4 mVkkg)  (kg/10« mg)  (1000  1/m')
          =0.11 kg/kkg

          Similarly, for cadmium salts:

          30-day average;
          (0.4 mg/l)(0.058 mVkkg)  (kg/10«)  .1000 l/m*)
          » 0.000023 kg/kkg

          24-hour maximum;
          (1.2 mg/l)(0.058 mVkkg  (kg/10« mg)  (1000  l/m*)
          « 0.000070 kg/kkg

     c.   Zinc

          The BPT Limitations for  zinc  are  based   on  long-term
          monitoring data from Plant F128 presented  in Appendix A
          and  as described above.  No other long-term monitoring
          data is available from any other  cadmium  pigments  or~
          cadmium salts plant.  Variability factors  developed for
          zinc  at  that plant were 1.67 for a 30-day average and
          3.0 for a 24-hour maximum which  yield  limitations  of
          0.10  mg/1 and 0.18 mg/1 respectively.  Utilizing these
          values,  mass  limitations  for  the  cadmium  pigments
          segment are obtained as  follows;

          30-day average;
          (0.1 mg/1) (92.4 mVkkg (kg/10* mg) (1000 l/m')
          - 0.0092 kg/kkg

          24-hour maximum;
          (0.18 mg/1) (92.4 mVkkg)  (kg/10« mg) (1000 1/m')
          = 0.017 kg/kkg

          Similarly, for the cadmium salts segment:

          30-day average;
          (0.1 mg/1) (0.058 mVkkg)  (kg/10« mg) (1000 l/m*)
          * 0.0000058 kg/kkg

          24-hour maximum;
          (0.18 mg/1) (0.058 mVkkg) (kg/10* mg) (1000
          » 0.0000104 kg/kkg

Basis for BCT Effluent Limitations
                              222

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   TABLE 11-14.  BAT EFFLUENT LIMITATIONS FOR CADMIUM PIGMENTS
                      AND SALTS SUBCATEGORY
a.    Cadmiurn Pigments (Flow basis 92.4 m3/kkg)
Concentration
(mq/1)
Toxic L.
Pollutants
Cadmium
Selenium
Zinc
b. Cadmium
Cadmium
Selenium
Zinc
T.A.
(mg/1)
0.14
0.2
0.061
•Salts (Flow
0.14
0.2
0.061
VFR
2/6
2/6
1 .67/3.0
basis 0.058
,2/6
2/6
1.67/3.0
30-day
avg.
0.28
0.4 .
0.10
mVkkg)
0.28
0.4
0.10
24-hr .
max.
0.84
1.2
0.18
0.84
1.2
0.18
Effluent
Limitations
30-day
avg .
0.026
0.037
0.0092
0.0000162
0.000023
0.0000058
24-hr.
max .
0.078
0.11
0.017
0.0000487
0,000070
0.0000104
L.T.A. = Long-term average achievable level.

VFR = Variability Factor Ratio,- ratio of the 30-day average
      variability factor to the 24-hour maximum variability
      factor.
                                       223

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 On   October  29,   1982,   EPA  proposed a revised BCT methodology.
 While  EPA is considering revising that proposed  methodology,   in
 this subcategory  no  additional technologies were identified which
 would   remove  significant  additional quantities of conventional
 pollutants.   Accordingly,  EPA has determined that BCT equals  BPT
 in   this   subcategory.    As a result,  BCT for TSS is equal  to  the
 BPT  limitations.

 Basis  for BAT Effluent Limitations

 Application of Advanced  Level Treatment

 For  BAT,   the Agency   is  promulgating  limitations  based   on
 treatment  consisting  of   Level  1  plus Level 2 (BPT)  technology.
 Toxic  pollutants  limited  by  the  proposed  BAT  regulation  are
 cadmium,   selenium,  and  zinc at the same concentration levels  and
 loadings  promulgated for BPT.   No  additional   technology   which
 would   remove  significant quantities  of additional  pollutants is
 known.

 A.   Technology Basis

 Alkaline  precipitation followed by clarification,  dewatering   of
 the  sludge   in  a   filter press,  and  filtration of  the clarifier
 effluent  followed by pH  adjustment (if necessary)  used for  BPT is
 the  same  as  for BAT.

 B.   Flow  Basis

 A unit wastewater flow rate of  92.4  mVkkg   of   cadmium pigments
 and  0.058  mVkkg  of  cadmium salts  has  been  selected  for BAT (same
 as BPT).

 C.   Selection  of Pollutants  to be Regulated

 Toxic Pollutants

 The  toxic  pollutants  cadmium,  selenium,   and   zinc   have been
 selected   at  the same concentration levels  and  loadings proposed
 for BPT.   Table   11-14   presents   the   BAT   limitations for   the
Cadmium Pigments  and Salts  Subcategory.

Basis for  NSPS  Effluent  Limitations

For  NSPS,  the   Agency  is promulgating  limitations equal  to BPT
because  no  additional  technology  that    removes    significant
quantities  of  additional  pollutants   is known.  The  pollutants
limited include pH, TSS,  cadmium,  selenium,  and   zinc   which  are
                              224

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listed in Table 11-12 (cadmium pigments) and Table llr-13  (cadmium
salts).                  .                ••-,.-.*' .'.<  • - -  *

Basis for Pretreatment Standards

The  Agency  is  promulgating PSES and PSNS that are equal  to BAT
limitations because, as shown below, BAT provides better  removal
of  cadmium,  selenium,  and  zinc  than  is  achieved  by  a well
operated POTW with secondary treatment  installed and,  therefore,
these  toxic  pollutants would pass through a POTW in the absence
of pretreatment.  Pollutants regulated under PSES  and  PSNS  are
cadmium, selenium, and zinc.

Using  the average raw waste data presented in Table 11-8 and the
long term average effluent  from  Table  11-12,  the  Agency  has
estimated the percent removals for cadmium, selenium, and zinc by
comparing  the  untreated  waste  concentrations  for those three
toxic metals  with  the  treated  waste  concentrations   for  the
selected  BAT  technology  for  those same three pollutants.  The
calculation is as follows;

          Cadmium;   Raw Waste = 265 mg/1
                     BAT       =0.14 mg/1

                 Percent Removal =  [ (265-0.14)-?(265) 1 (1 00)
                                 = 99.94%

          Selenium;  Raw Waste = 8 mg/1
                     BAT       =0.2 mg/1

                 Percent Removal =  [(8-0.2)t(8)J(100)
                                 = 97.5%

          Zinc;      Raw Waste =6.9 mg/1
                     BAT       = 0.061  mg/1

                 Percent Removal =  [(6.9-0.061)t(6.9)](100)
                                 = 99.1%

The percent removals are greater than the removals   achieved  for
cadmium   (38% removal) and  zinc  (65% removal)  by 25% of  the POTWs
in the  "50  cities study"  (Fate of Priority Pollutants  in  Publicly
Owned Treatment Works, Final Report, EPA 440/1-82/303,   September
1982).    Limited  information  showing  the removal of selenium  by
POTWs is  available  but the  removals  by  25% of  the POTWs   in  that
study   for  other  toxic metals ranged from  19%  to 66%.  We presume
that  selenium removals are  in that  range because selenium behaves
similarly to  other  toxic  metals.   Therefore,  since   the  BAT
technology   achieves  a  greater  percent  removal   of   cadmium,
                               225

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selenium, and zinc than is achieved by a well operated POTW  with
secondary  treatment, those three toxic metals would pass-through
the POTW in the absence of pretreatment.

Existing Sources

There are currently four indirect discharger cadmium pigments and
salts plants in the subcategory.  For Pretreatment Standards  for
Existing  Sources  (PSES), the Agency is promulgating limitations
based  on  BAT  described  above.   The  pollutants  limited  are
cadmium,  selenium, and zinc as presented in Table 11-12 (cadmium
pigments) and Table 11-13 (cadmium salts).

New Sources

For Pretreatment Standards for New Sources (PSNS), the Agency  is
setting  limitations  based on NSPS.  Since NSP'S is equal to BAT,
Table 11-12 (cadmium pigments) and Table  11-13  (cadmium  salts)
summarize  the  limitations  for  the  toxic  pollutants cadmium,
selenium, and zinc.
                              226

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                           SECTION  11

                           REFERENCES
1 .



2.
3.
4.

5.
Kirk and Othmer, Encyclopedia of Chemical  Technology,  Wiley-
Interscience, 3rd ed., Vol. 4, pp 397-411,  (1978).

U,S. Environmental Protection Agency,  "Development  Document
for  Effluent  Limitations  Guidelines and Standards for  the
Inorganic Chemicals Manufacturing  Point   Source  Category,"
EPA Report No. 440/1-79-007, June 1980.

JRB Associates,  Inc.,  "An  Assessment  of  pH  Control  of
Process  Waters  in  Selected  Plants,"  Draft Report  to  the
Office of  Water  Programs,  U.S.  Environmental  Protection
Agency, 1979.                                   .,.'„•'.

Freund, J. E., Mathematical Statistics. 1962, Prentice Hall.

Bruning, J. L. and Kintz, B. L., Computational  Handbook  of
Statistics, second edition/ 1977, Scott, Foreman and Co.  .•""
                              227

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                           SECTION 12

                      COBALT SALTS INDUSTRY
INDUSTRIAL PROFILE

General Description

The  cobalt  salts  considered  in  this  subcategory  are cobalt
chloride, cobalt nitrate, and  cobalt  sulfate.   Each  salt  has
specialized  applications, however many uses are common to two or
all three salts.  All three salts are  used  as  catalysts,  soil
additives,  and  in  the  manufacture of inks.  Two of the cobalt
salts have found uses in the manufacture of pigments and vitamins
and various applications in the ceramics industry.  The status of
cobalt as a strategic material combined with  recent  changes  in
the  world  market  may  tend  to limit the use of cobalt and its
salts in many applications.

Table 12-1 presents the  industry profile for cobalt salts.

There are ten facilities which manufacture cobalt  salts.   Total
annual production of cobalt salts is estimated to be in excess of
3,000  metric   tons  while  total  daily  flow is estimated to be
greater than 40 cubic meters per day (10,500 gpd).   In  general,
wastewater flow as a function of unit production  is very low.

General Process Description and Raw Materials

Cobalt  salts   are  produced by reacting cobalt metal with either
hydrochloric, sulfuric,  or nitric acid.  The   reactions  for  the
formation of the cobalt  salts under consideration are:

     Co  + 2HC1  = CoCl2 + H2

     Co  + H2S04 = CoS04  + H2

     Co  + 2HN03 = Co(N03>2 + H2

      (Nitrogen  oxides   may  also  be  produced   by decomposition
     reactions  of the nitric acid.)

The production  of a  cobalt salt  is a batch process  consisting  of
five   primary   steps.    These   five   steps   are   digestion,
purification,   concentration,   crystallization,   and   filtration.
Digestion    is  simply   the  dissolving  of   the  cobalt   in   the
appropriate  acid.  Once  the  cobalt  is  dissolved  a purification
step   using   chemical addition  and filtration may be necessary  to
                               228

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      TABLE  12-1.   SUBCATEGORY  PROFILE DATA FOR COBALT  SALTS
Number of Plants in Subcategory

     Total Subcategory Production Rate

          Minimum
          Maximum


     Total Subcategory Wastewater Discharge

          Minimum
          Maximum


     Types of Wastewater Discharge

          Direct
          Indirect
          Zero
10

>3,000 kkg/yr

<4.5 kkg/yr
Confidential


>40 m3/day

0
19 m3/day
5
3
2
                          229

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remove impurities found in the raw materials.  The  solution  may
then be concentrated by evaporation.  The solution is then cooled
causing  the  cobalt  salt  to  precipitate out of solution.  The
final step is the removal  of  the  precipitated  salt  from  the
solution   by   centrifugation,  filtration,  or  other  settling
process.   The  salt  is  then  dried  and  packaged,  while  the
supernatant  (or  mother liquor) is returned to the concentration
step.  Figure  12-1  presents  graphically  the  above  described
steps.

WATER USE AND WASTEWATER SOURCES

Water Use

Noncontact  cooling  water is used for cobalt salts production in
the reactor (digester) and  crystallizers,  and  constitutes  the
major  water  use.   Water is used in direct process contact as a
reaction component.  A portion of this water goes  into  the  dry
product  as  its  water  of  crystallization and the remainder is
evaporated.  Small amounts of  water  are  used  for  maintenance
purposes, washdowns, cleanups, etc., and several plants use water
in scrubbers for air pollution.  Table 12-2 presents a summary of
water usage for the one plant which provided reliable information
in  its  Section  308  questionnaire.  Data from other plants was
combined with wastewater flows from other products or  the  plant
provided  inconsistant  information.   None of the six plants the
Agency or its contractors visited was producing cobalt salts when
visited so more data could not be obtained.   However,  based  on
the  site  visit observations and the process chemistry, the data
from Plant F117 is  considered  reliable  and  representative  of
process   water   use  and  wastewater  flows  for  cobalt  salts
production.

Wastewater Sources

Noncontact Cooling Water

Noncontact cooling water is the main source of wastewater.   This
stream  is  usually  not  contaminated  and is not treated before
discharge.

Direct Process Contact

All  direct  process  contact   water   not   evaporated   during
concentration  steps  is  recycled  back  into  the  process.  In
addition, air pollution control water may be  recycled  into  the
process.   Finally  a  small  amount  of sludge is generated as a
result of removing process impurities.
                               230

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     a
     3
     T3
     O
     J-i
     P*

     A
                                               OS
                                               g
    o
    CJ
231

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    TABLE 12-2.   WATER USAGE  AT  COBALT  SALTS  FACILITIES(D


                          Flow  (m3/kkg of Cobalt Salts)

                         	Plant Designation	
WATER USE
F117(2)
                                                F117(3)
Noncontact
Cooling

Direct Process
Contact

Indirect Process
Contact

Maintenance

Air Pollution
Scrubbers

Noncontact
Ancillary
  TOTALS
 1.65
NA
NA
1.33
NA
NA
 1.65
1.33
NA   Flow volume not available.
	  No information.
(1)  Values indicated only for those plants that reported
     separate and complete information.
(2)  Cobalt Chloride.
(3)  Cobalt Sulfate.

Source:  Section 308 Questionnaires and Plant Visit Reports
                           232

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  TABLE 12-3.   WASTEWATER FLOW AT COBALT SALTS FACILITIES

WASTEWATER SOURCE
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
TOTAL PROCESS
WASTEWATER DISCHARED
Flow (m3/kkg of Cobalt Salts)
Plant Designation
F117(2) F117<3)
0 0
0 0
0.083 NA '' ,
0.083 0 , ,
Noncontact
Cooling

Noncontact
Ancillary
NA   Flow volume not available.
	  No information.
(1)  Values   indicated   only  for  those   plants
     separate and complete information.
(2)  Cobalt Chloride.
(3)  Cobalt Sulfate.
(4)  Wastewater recycled within plant.
that  reported
Source:   Section 308 Questionnaires and Plant Visit Reports
                          233

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Maintenance

Washdowns, cleanups, spills, and  pump  leaks  are  periodic  and
account for the remaining wastewater.

Table  12-3  presents  information  on  sources and quantities of
wastewater produced in the production of cobalt salts.

DESCRIPTION OF PLANTS VISITED

Six of  the  10  plants  producing  cobalt  salts  were  visited.
Unfortunately,  at the time of sampling none of these plants were
producing cobalt salts, so that it was  not  possible  to  sample
wastewater streams associated with cobalt salt production.

The  process  steps  used at each plant are very similar to those
described previously.

At Plant F119 cobalt chloride, cobalt nitrate, and cobalt sulfate
are produced in addition to many other inorganic compounds.   All
process  wastewater  from  production  of  metal  products is pH-
adjusted to 8.7 - 9.0 with caustic.  The  neutralized  wastewater
is  sent to a settling basin.  Flocculating agents are then added
and flow is directed to a  tube  settler  for  additional  solids
removal.  The overflow is discharged to a POTW, and the underflow
is  sent  to  a  sludge  holding  tank.  The supernatant from the
sludge holding tank is recycled to the  settling  basin  and  the
sludge  is filtered in a filter press.  The filtrate is sent back
for more treatment and the  filter  cake  is  disposed  of  in  a
chemical landfill.

Plant  F113  produces  cobalt  chloride  and cobalt sulfate.  All
process wastewater is discharged  to  a  POTW  without  treatment
except neutralization.

Plant  Fll7  produces  cobalt chloride, cobalt nitrate and cobalt
sulfate.  Separate treatment systems are provided  for  both  the
cobalt  chloride  and  cobalt  nitrate processes.  Each treatment
system consists of caustic addition  (to  pH  10)  and  filtration
before  discharge to a surface water.  The cobalt sulfate process
generates no wastewater.

Plant F107 produces cobalt nitrate as well as other metal  salts.
All process wastewater is discharged to a POTW without treatment.

Plant  Fl 18  produces  cobalt  nitrate along with other products.
The  plant  has  a  combined  wastewater  treatment  system  with
wastewater  from  all production processes going to the treatment
system.  The treatment system consists of equalization,  chemical
                               234

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addition,  precipitation,   sedimentation,  and  final  pH  adjustment
before discharge  to  surface waters.

Plant F145 produces  cobalt  chloride  and  cobalt nitrate   in   minor
quantities   in  addition  to  many  other  chemicals.  Wastewater from
all production  processes, both organic and inorganic are treated
in the plant  treatment system.   Treatment  processes  used are lime
precipitation,  clarification,   sludge  dewatering and  biological
treatment.

POLLUTION ABATEMENT  OPTIONS

Toxic Pollutants  of_  Concern

The toxic pollutants present in  cobalt salt  process wastewaters
depend  upon  the purity of- the  sources  and  the nature  of the raw
materials being used.  Toxic metals  which  are  known  to  be present
in the raw materials are copper, lead, nickel,  and zinc.  Most of
the impurities  will  be  removed  in  the  purification   step and
disposed  of  as a solid sludge.  There are no  raw wastewater data
because cobalt  salts were not being  produced during   sampling at
the  plants   visited.   However,  data  submitted by one facility
indicated that  4,000 mg/1 of cobalt  might  be expected  in  a raw
wastewater  stream.   Nickel and  copper  are  also expected  to be
present in wastewater streams at treatable levels  because   those
metals are present in the cobalt raw material.

Existing Control  and Treatment Practices

Wastewater treatment practices for plants  visited were  previously
described  above.    Provided below are the treatment  practices at
the four plants not  visited.

Plant Fl24. produces  cobalt  sulfate and cobalt  nitrate as well  as
other metal salts.   Treatment of wastewaters for the  entire  plant
consists  of  alkaline precipitation,  clarification,  filter  press
filtration,   multi-media    filtration,    pH    adjustment    and
sedimentation   in  ponds  before  discharging  directly  to surface
waters.

Plant F139 produces  cobalt  sulfate and cobalt  chloride  as well as
other metal salts.   Treatment of wastewaters for the  entire  plant
consists  of    equalization,   sedimentation,   filtration,   and
neutralization  before discharge to surface waters.

Plants F150 and F138 have no  discharge,  as all process  wastewater
is disposed of  by a  waste contractor.

Other Applicable Control/Treatment Technologies
                              235

-------
Neutralization,  clarification,  and filtration are practiced for
the treatment of cobalt salt process wastewaters at most  plants.
No demonstrated advanced level technology was identified for this
industry.

Process Modifications and Technology Transfer Options

In  general,  little  process  wastewater  is  generated  in this
subcategory.   Most  plants  minimize  the  volume   of   process
wastewater generated by:

     1.   Recycling all direct process contact water back into
          the process; and

     2.   Minimizing product changes by careful product
          scheduling and by increasing the number of reactors.

Caustic  soda  (rather than lime) may be advantageous when used as
an alkaline reagent in wastewater  treatment  for  the  following
reasons:
     1
Caustic soda reduces or eliminates the problem of scale
formation;
          Caustic  soda  exhibits  a  faster
          results in better pH control;

          Caustic  soda  treatment  results
          reduction in sludge volume; and
                                    reaction  time  and
                                   in   a   significant
     4.   The  sludge  contains
          precipitated   metal,
          recycled.

Best Management Practices
                       high   concentrations   of   the
                        which   may  be  reclaimed  and
The best technology available for the  treatment of air  pollution
scrubber   wastewater  from  cobalt  salts  production  is   total
recycle.   To   implement  this   technology,   recycle  piping and
pumping  are  needed.   At  one  plant,   this technology  is  being
implemented for three cobalt salt products  and most plants either
recycle the scrubber water or use it as   make up  water  in the
reactors.

If contact is possible with leakage, spillage of raw materials  or
product,  all   storm  water  and plant   site runoff   should   be
collected  and   directed  to  the  plant    wastewater   treatment
facility.   This contamination can be  minimized by indoor storage
of chemicals, and proper  air pollution control.
                               236

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 If solids from the wastewater treatment  plant  are  disposed  or
 stored  on-site,   provision must be .made to control leachates and
 permeates.    Leachates  and   permeates   which   contain   toxic
 pollutants  should be directed to the wastewater treatment system
 for further treatment.

 Advanced Treatment Technology

 No demonstrated advanced treatment technology has been identified
 for this subcategory.

 Selection of. Appropriate Technology and Equipment

 Technologies for  Different  Treatment Levels

 A.   Level  1

 Level    -l    treatment    consists   of   alkaline   precipitation.
 clarification  or  settling,  dewatering of  the sludge in  a filter
 press  followed  by pH adjustment  if necessary.   This technology is
 illustrated by  Figure  10-10.   A  holding basin sized to retain 4-6
 hours  of flow is  provided.

 The initial  treatment  step  is the addition  of caustic soda.   This
 is   followed by   clarification/settling   (if   the   wastewater
 characteristics   are   suitable,  a tube  settler may  be substituted
 for a  clarifier to save   space).    Sludge   is  removed from   the
 clarifier   and  directed to  a filter press for dewatering.   Pits
 are provided at the filter  press for the   temporary  storage  of
 sludge.   The sludge  is periodically  transported  to a hazardous
 material  landfill.  The  pH  of the treated   wastewater  stream  is
 adjusted to an   acceptable   level   by acid  addition prior to
 discharge if  necessary.  A  monitoring system is installed  at   the
 discharge   point.   The  objective  of   Level   1  technology is to
 remove heavy  metals and  suspended solids.
B.
Level 2
Level 2 treatment consists of  the  addition  of  granular  media
filtration  following  clarification  in  the  Level  1 treatment
system.  This technology is illustrated in Figure 10-11.  Level 2
technology has been selected as a  means  of  achieving  improved
removal  of  metal  hydroxide  precipitates  and  other suspended
solids.

Level 2 treatment was selected as the basis for  BPT  because  it
represents a typical and viable industry practice for the control
of  suspended  solids, cobalt, nickel and copper.  Currently four
of five direct discharge plants in this subcategory have Level  2
                              237

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or  equivalent  treatment technology.  Two additional plants have
no  discharge  from  this  process  and  thus  would  not   incur
additional costs.


Equipment for Different Treatment Levels

A.   Equipment Functions

Conventional sludge dewatering by a  filter  press  is  used  for
sludge  removed by the clarification/settling system.  The sludge
from the filter press is disposed  of  off-site  in  a  hazardous
material  landfill.  If a tube settler is used, backwash from the
settler is returned to the influent holding basin.  Likewise,  if
granular  media  filters  are used, backwash water is returned to
the  influent  holding  basin.   After  mixing  in  a  tank,  the
wastewater  is filtered prior to pH adjustment (if necessary) and
discharged.  All equipment is conventional and readily available.

B.   Chemical Handling

Caustic soda (50 percent  NaOH)  is  used  to  precipitate  heavy
metals  in  Level  1.  Sulfuric acid  (concentrated) may be used to
reduce the pH of the wastewater prior to discharge.

C.   Solids Handling

Treatment sludges  generated by Level 1 are dewatered in a  filter
press.   The  solids  may  be disposed of off-site in a hazardous
material   landfill   or   sent    to    an    off-site    cobalt
reclaiming/recovery  operation.   Level  2 filter backwash may be
sent to the head of the plant or, if the solids concentration  is
sufficiently high, may be sent directly to the filter press.

Treatment Cost Estimates

General

Production  ranges and wastewater flow characteristics have been
presented earlier  in this section and are summarized in Table 12-
2.   There  are    five   direct   dischargers,   three   indirect
dischargers, and two plants which have no discharge.

The  average  production  rate  for  the  five  plants  providing
separate and complete production data is 358 metric tons per year
with an average of 115 operating days per year.  Only  one  plant
provided  relieable  flow  data  but  that  flow data is believed
representative  of cobalt  salts  production  based  on  process
chemistry  and engineering visits to six plants by the Agency and
                               238

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      TABLE 12-4.   WATER EFFLUENT TREATMENT COSTS
                   FOR  MODEL  PLANT.
 SUBCATEGORY:  Cobalt Salts
 ANNUAL PRODUCTION: 	

 DAILY  FLOW:  	0.26

 PLANT  AGE:        NA
 358
METRIC TONS
      CUBIC METERS
YEARS   PLANT LOCATION:
                 NA
           a.  COST  OF TREATMENT  TO ATTAIN  SPECIFIED  LEVELS
 COST CATEGORY

 Facilities
 Installed Equipment
   (Including Instrumentation)
 Engineering
 Contractor Overhead and Profit
 Contingency
 Land

  Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 6.0
Residual Waste Disposal
         COSTS ($1,000) TO ATTAIN LEVEL

         1      23      4      5
6.6
1.3
1.2
0.9
10.0
1.6
6.0
1.0
0.4
0.1
0.1
0.1
0.7
0.1
0.2
Negl,
  Total Annual Cost
         8.6
  0.3
                        b.   TREATMENT DESCRIPTION
LEVEL 1:  Alkaline precipitation, clarification, pH adjustment
LEVEL 2:  Filtration
                            239

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its contractors.  Therefore, the model plant for the cobalt salts
subcategory has a production rate of 358 metric tons per year and
a daily flow of 0.26 cubic meters (0.083m3/kkg with 115 operating
days  assumed).   These  figures  were  used  as  the  basis  for
treatment cost estimates for both levels.
                                                              r
     Material usage for both levels was estimated as follows:

     Chemical                   Amount       Treatment Level
     NaOH (50 percent sol.)
     H2S04 (TOO percent)
                          3.3 kg/day
                          0.05 kg/day
Total  solid  waste  generated  is  estimated  below  (Level 2 is
incremental to level 1 ):
          Level

            1
            2
                         Solid Waste

                           0.024 mVday
                           0.00004 m3/day
Model Plant  Treatment  Costs.   Based  on  of  the  model  plant
specifications  and  design  concepts  presented  earlier  and in
Section 10, the estimated costs of treatment for one  model  with
two  levels  are  shown  in  Table  12-4.  The cost of level 2 is
incremental to Level 1.

Basis for Regulations

Basis for BPT Limitations

A.   Technology Basis

For BPT, the Agency is setting limitations  based  upon  alkaline
precipitation,    clarification,   granular   media   filtration,
dewatering of the  sludge  in  a  filter  press  followed  by  pH
adjustment  (if  necessary).   Of  the five direct dischargers in
this subcategory, four  of  five  have  this  technology  or  its
equivalent  installed.   Two  additional plants have no discharge
and thus would not be affected.
B.
Flow Basis
As described above under model plant  treatment  costs,  for  the
cobalt  salts  subcategory  0.083  mVkkg  was  selected as being
representative of the group.

C.   Selection of Pollutants to be Regulated
                              240

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 The   selection   of   pollutants   for    which   specific   effluent
 limitations   are being   established  is  based on an evaluation of
 the   wastewater   data    from    discharge    monitoring   reports,
 consideration   of    the   raw   materials  used  in   the  process,
 literature data, permit applications,  and  the treatability of  the
 toxic pollutants.

 Tables  8-1 through  8-14 summarize  the  achievable  concentrations
 of   toxic  metal  pollutants  from the literature using available
 technology options,  other  industries,  and   treatability  studies.
 Water  use and discharge  data are  presented earlier in Section 12
 together with generalized  process characteristics.    Data from
 Appendix  A   on  the performance  of  in-place industry treatment
 systems were  also utilized in developing the list  of   pollutants
 to be regulated.

 Copper  and nickel are commonly  found as  secondary constituents of
 many  cobalt  ores,  therefore   the  two  toxic   metals  would be
 expected to occur in raw materials used  in production   of  cobalt
 salts.  The copper and nickel impurities would be carried over in
 the   process  wastewater,  and   therefore   these two  metals were
 selected as candidate toxic  metals  for  BPT regulations.    The
 non-conventional   pollutant,    cobalt,  was  also  selected   for
 limitation.   Lead and  zinc  were  not   selected for   limitation
 because,  as  described in Sections 7 and 8,  control of  copper  and
 nickel will provide  adequate control of  lead and zinc.

 Consideration of industry  data  and   information  in   Section 8
 related   to   the   effectiveness  of   hydroxide  precipitation,
 clarification and filtration lead  to  the   selection  of   cobalt
 copper and nickel as pollutants  to be regulated.

 D.    Basis of BPT Pollutant Limitations

 Limitations are presented as both  concentrations  (mg/1) and loads
 (kg/kkg), and the relationship between the  two is   based   on   the
 unit  flow rate of 0.083mVkkg.
BPT   limitations,   which   apply   to  all
discharged, are presented in Table 12-5.

     1.    Conventional Pollutants
process  wastewater
          a.   pH

               The treated effluent is to  be  controlled  within
               the  range,of 6.0 - 9.0.   This limitation is based
               upon the data  presented  in  Appendix  B  of  the
               Development   Document   for   Proposed   Effluent
                              241

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     b.
Guidelines for Phase I Inorganic
1) and the JRB study (Ref. 2).

TSS
                                            Chemicals  (Ref.
          The BPT limitations for  TSS  are  based  upon  an
          average  of  long-term  data  from  Plants A and K
          (Phase I Development Document).   Both  plants  are
          using  dual-media  filtration  to  reduce  TSS and
          toxic metals which is the technology basis for the
          promulgated BPT for the cobalt salts  subcategory.
          Removal of suspended solids by a dual-media filter
          is a mechanical process independent of the type of
          solid.  Therefore, the TSS effluent quality should
          be  the same for cobalt salts plants as for plants
          A and K.  No long-term TSS data from cobalt  salts
          plants  using  dual-media filtration is available.
          A long-term average of 9.3 mg/1  (the  average  of
          both  plants)  was  used  to develop the discharge
          limitations  for  plants   employing   filtration.
          Variability  factors,  also obtained from Plants A
          and K, of 1.8 for a monthly average and 3.0 for  a
          24   hour   maximum  .were   used   yielding   TSS
          concentration limits  of  17  mg/1  and  28  mg/1,
          respectively.   Thus  utilizing  these values, one
          obtains TSS mass limitations for the cobalt  salts
          subcategory of:

          30-day average;

          (17 mg/1) (0.083mVkkg) (kg/1 0* mg)(1000 1/m')
          = 0.0014 kg/kkg

          24-hour maximum

          (28 mg/1 )(0.083mVkkg)(kg/10* mg)(1000 1/mM
          = 0.0023 kg/kkg

2.   Non-Conventional Pollutants

     a.   Cobalt

          The BPT Limitations for cobalt are based on  long-
          term  monitoring  data from Plant 124 presented in
          Appendix A.  The plant is  achieving  a  long-term
          average  concentration  of 0.97 mg/1.  Variability
          factors of 1.44 for a 30-day average and 3.75  for
          a   24-hour  maximum  were  used  yielding  cobalt
          limitations of  1.4  and  3.6  mg/1  respectively.
                         242

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r
                       Thus, utilizing these values, mass limitations may
                       be obtained as follows:

                       30-day average;

                       (1.4 mg/l)(0.083mVkkg)(kg/10* mg)(1000 1/m*)
                       = 0.00012 kg/kkg

                       24-hour maximum;

                       (3.6 mg/1 )(0.083mVkkg)( kg/10* mg)(1000 1/m3)
                       = 0.00030 kg/kkg

             3.   Toxic Pollutants

                  a.   Copper

                       Since there  is no  long-term  monitoring   data   for
                       copper from  any  cobalt  salts manufacturing  plants,
                       the  BPT   limitations   for  copper  are based on the
                       long-term monitoring   data   for  nickel   at Plant
                       F124.   Plant F124  manufactures  cobalt  salts and
                       nickel salts.  The BAT effluent  limitations   for
                       the   nickel  sulfate   subcategory, which  were
                       supported by our treatability study  for  the nickel
                       sulfate subcategory  (see  Section 14) show that the
                       copper and nickel  concentrations in  effluent  from
                       the   Level   2  treatment   system  are  the same in
                       nickel sulfate wastewater.    Since  the   treatment
                       system   is  the   same   for cobalt  salts  and nickel
                       salts, and at least  half  the existing  dischargers
                        in  the   cobalt  salts  subcategory  also manufacture
                        nickel  sulfate or other nickel salts and commingle
                        the  wastewater for treatment, it is reasonable  to
                        assume   that  the  copper concentration in treated
                        cobalt  salts wastewater is the same as the  nickel
                        concentration  in  that wastewater.   The long-term
                        average  nickel concentration in treated wastewater
                        at Plant  F124  is  0.69  mg/1,   with  variability
                        factors  of 1.52 for a 30-day average and 4.83 for
                                               Using  these  figures,   the
                                               concentrations  are  1.0 and
                                                Utilizing   these  figures,
                                                copper  are  calculated as
a  24-hour  maximum.
corresponding  copper
3.3 mg/1 respectively.
mass  limitations  for
follows;
                        30-day average;

                        (1.0 mg/1 )(0.083mVkkg)(kg/10* mg)(1000  1/m3)
                                        243

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             TABLE 12-5.   BPT EFFLUENT LIMITATIONS FOR COBALT SALTS
Conventional    Long-Term
Pollutants      Avg.(mg/1)
TSS1-0-'            9.3
  *

Non-Conventional
Pollutants
      .(4) '
Cobalt
Toxic
Pollutants

Copper^)
Nickel*-4)
0.97(2)
0.69(2)
                                  VFR
                               1.8/3.0
                             Cone.  Basis
                                (rog/1)
                            30-day   24-hr,
                             avg.     max.
                            17
1.44/3.75(2)  1.4
1.5,2/4.83(2)
1.52/4.83(2)
                      28
                                                     3.6
                                                    3.3
                                                    3.3
                              Effluent Limit
                                 (kg/kkg)
                              30-day  24-hr.
                               avg.     max.
                                                            0.0014   0.0023
                                            0.00012   0.0003
                                                            0.000083  0.00027
                                                            0.000083  0.00027
LTA * Long-term average  achievable  level.

VFR - Variability Factor Ratio (30-day avg./24-hr, max.)

(1) Basjid upon long-term data at  Plants A and K (Phase I)
(2) Based upon long-term data at  Plant  F124.
(3) Also applicable to NSPS and BCT.
(4) Also applicable to BAT and NSPS.
                            244

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r
                        = 0.000083 kg/kkg

                        24-hour maximum;

                        (3.3 mg/l)(0.083 mVkkg) (kg/10« mg)(1000 l/m»)
                        = 0.00027 kg/kkg
                   b.   Nickel

                        The BPT  limitations for nickel are  based  upon  a
                        long-term  average  of  0.69 mg/1 obtained from 26
                        months of  monitoring  at  Plant  F124   (657  data
                        points).   No  other   long-term monitoring data is
                        available  from   any   cobalt  salts  manufacturing
                        plant    with   a   Level   2   treatment   system.
                        Variability factors of 1.52 for a  30-day  average
                        and  4.83  for  a 24-hour maximum were used yielding
                        nickel    limitations   of   1.0   and    3.3   mg/1
                        respectively.     Utilizing   these   values,  mass
                        limitations for nickel may be obtained  as follows:

                        30-day average;

                         (1.0 mg/1) (0.083  mVkkg) (kg/1 0* mgMlOOO l/m»)
                        =  0.000083 kg/kkg

                         24-hour  maximum;

                         (3.3 mg/1) (0.083  mVkkg) (kg/10« mgMlOOO l/m»)
                         {- 0.00027 kg/kkg

          Basis for BCT Effluent  Limitations

          On October 29, 1982,  EPA proposed  a  revised  BCT  methodology.
          While  EPA  is  considering  revising that proposed methdology,  in
          this subcategory no additional  technologies  were identified which
          would remove significant additional  quantities   of  conventional
          pollutants.   Accordingly,  EPA has determined that BCT equals BPT
          in this subcategory.   As a  result, BCT for TSS is  equal  to  the
          BPT limitations.

          Basis for BAT Effluent Limitations

          Application of Advanced  Level Treatment

          For   BAT,  the  Agency  is  promulgating  limitations  based  on
          treatment consisting of  Level 1 plus  Level  2  (BPT)  technology
          because  we   identified  no  other  technology which would remove
          significant additional amounts of pollutants.  Pollutants limited
                                        245

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 by the BAT regulation are cobalt, copper and nickel at  the  same
 concentration levels and loadings proposed for BPT.

 A.   Technology Basis

 Alkaline precipitation, clarification, filtration, dewatering  of
 the  sludge  in  a  filter  press,  followed  by pH adjustment if
 necessary, is used for BAT which is the same technology used  for
 BPT.

 B.   Flow Basis

 A unit wastewater flow rate of 0.083mVkkg of  cobalt  salts  has
 been  selected for BAT (same as BPT).

 C.   Selection of Pollutants to be Regulated

      Toxic Pollutants

 The non-conventional  pollutant cobalt,  and toxic polutants copper
 and nickel have been  selected at the   same  concentration   levels
 and  loadings  promulgated   for BPT.   Table 12-5 presents  the BAT
 limitations for Cobalt  Salts Subcategory  (BAT=BPT).

 Basis for NSPS Effluent Limitations

 For NSPS,  the Agency  is promulgating   limitations  equal   to  BAT
 since  no  additional   technology which  would  remove  significant
 additional  amounts   of pollutants   has   been   identified.    The
 pollutants  limited are pH,  TSS,  cobalt,  copper,  and nickel.   The
 limitations are  presented in Table 12-5.

 Basis for Pretreatment  Standards

 The Agency is promulgating PSES and PSNS  that are equal   to  BAT
 limitations   because  BAT  provides   better  removal   of   cobalt
 copper, and nickel than  is achieved by a  well-operated POTW   with
 secondary   treatment and, therefore,  these toxic  pollutants would
 pass  through  a POTW in  the absence of  pretreatment.   Pollutants
 regulated  under  PSES and PSNS are cobalt, copper, and  nickel
The  Agency  has  no  screening  and  verification data to use to
estimate the  raw  waste  concentrations  for  the  cobalt  salts
subcategory.   One  company  reported one sample of a cobalt salt
raw wastewater contained 4000 mg/1 of cobalt but did not have any
data on any toxic metals in  the  cobalt  salt  wastewater.   The
cobalt  salts  are  produced from cobalt metal.  Commerical grade
                              246

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cobalt is, on average 99.5% pure, with the range from 99 to 99.9-s
pure cobalt.  The major impurities are copper  and  nickel,  with
smaller  amounts  of  silicon, manganese, iron, carbon, lead, and
zinc.  The amount of each depends upon the source of the ore from
which the cobalt was refined.  Since the  source  of  the  cobalt
cannot  be predicted for any cobalt salt manufacturing plant, and
may vary at any plant from time to time, the Agency  has   assumed
that  the  copper  and  nickel  are equally probable and together
account for about half the impurity in average  commerical  grade
cobalt.   That  is,  for  99.5%  pure cobalt,  0.25% is copper and
nickel  and the copper is assumed to be  0.125% and the nickel   is
0 125%  of  the  total  metal.  The primary source of the  process
wastewater at cobalt salts manufacturing plants is spillage.    We
assume that the spill contains cobalt and other impurities in the
same  ratio  as  found  in the purchased cobalt,  i.e., copper and
nickel are each about 0.125%  of  the concentration of  the   cobalt
in  the wastewater.  Therefore, for a cobalt concentration  of  4000
mg/1,  the  copper concentration would be 4000 x  .00125  =  5 mg/1,
and the nickel concentration  would also  be  5 mg/1.

In  the absence of  any other   raw waste  data  for  cobalt  salts
manufacturing  the Agency  has used these calculations  to estimate
the percent removals for cobalt,  copper, and  nickel  by   applying
the  selected  BAT  technology  to the  untreated  wastewater.   The
calculations for percent removals are as follows:

           Cobalt:    Raw waste =  4000 mg/1
                        BAT    =0.97 mg/1


           Percent  Removal  »  [(4000  -0.97)]  -r  (4000)]  (100)
                           »  99.98%

           Copper;    Raw waste = 5 mg/1
                          BAT  =0.69 mg/1

           Percent Removal  - [(5 - 0.6S) * (5)] (100)
                           =86.2%
           Nickel;


           Percent Removal
Raw waste = 5 mg/1
     BAT  =0.69 mg/1
      = [(5 - 0.69) -r (5)]  (100)
      =86.2%
 These estimated removals are greater than the  removals,  achieved
 for  copper  (58%) and nickel (19%) by 25% of the  POTWs  in the   50
 Cities" study  (Fate of  Priority  Pollutants ^in.  Publicly .Owned
 Treatment      Works,     Final    Report,    EPA     440/1-82/303,
                                247

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 September,  1982).   Limited  information   showing   the   removal   of
 cobalt   is  available but  the removals by 25%  of  the POTWs  in that
 study for other  toxic metals range  from  19% to 66%.    Presumably
 the  removals  for   cobalt   would be in  that  range because cobalt
 behaves  similarly to other  toxic metals.    Therefore,   since  BAT
 technology  achieves a greater  percent removal of cobalt,  copper,
 and nickel  than is  achieved  by  a  well  operated   POTW with
 secondary treatment,  those  three metals  would pass through a POTW
 in the absence of pretreatment.

 Existing Sources

 There  are  currently  three indirect   discharging  cobalt salts
 plants   in  the  subcategory.   For  Pretreatment  Standards  for
 Existing  Sources   (PSES),  the  Agency is promulgating  limitations
 based on BAT described  above.   The pollutants limited  are  cobalt,
 copper, and nickel  as presented in Table 12-5.

 New Sources

 For Pretreatment Standards  for  New Sources  (PSNS), the Agency   is
 setting  limitations  based  on  NSPS.  Since NSPS is equal  to BAT
 Table 12-5 summarizes the   limitations  for the  nonconventional
pollutant cobalt and  toxic pollutants copper and nickel.
                              248

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                      SECTION 12

                       REFERENCES
U.S. Environmental Protection Agency, "Development  Document
for  Effluent  Limitations  Guidelines and Standards for the
Inorganic Chemicals Manufacturing  Point  Source  Category,
EPA Report No. 440/1-79-007, June 1980.
JRB Associates,
Process  Waters
Office of  Water
Agency, 1979.
Inc.,   "An  Assessment  of  pH  Control  of
in  Selected  Plants,"  Draft Report to the
 Programs,  U.S.   Environmental  Protection
                          249

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                            SECTION  13

                       COPPER SALTS  INDUSTRY
 INDUSTRIAL PROFILE

 General Description
                  included in tnis subcategory are copper sulfate,
           ™       copper  carbonate,  copper nitrate, and copper
           These  compounds  are  produced  by  several  different
 A  process  description  and  discussion  of  the  copper sulfate
 industry can be found in the Phase I development document:

           Development   Document   for    Effluent    Limitations
           Guidelines  and  Standards  for the Inorganic Chemicals
           Manufacturing Point Source Category, EPA  440/1-82-007
           June 1982.                  .                          '

 Briefly,  copper sulfate is produced by reaction of copper, copper
 oxide,  or waste copper (such as spent plating bath) with sulfuric
Cu
                H2 S04 = CuS04
 The copper sulfate may be sold in solution as produced,  or mav be
 purified  and   crystallized  before  sale as the solid!   Detailed
 5^??«  ^formation and the results of screening and verification
 ?he?elo?ear%h£r°f "f ?d • ln ^he  Phase  J  development  document.
 Therefore,   the  following discussion will cover the other copper
 salts  included  in this subcategory.                         v,upp«t

 Most copper  chloride is marketed  as cuprous chloride (CuCl )     It
 is  used  as  a catalyst,  decolorizer,  and desulfurizing agent in
 the petroleum industry,  in the clenitration of cellulose,  and   fo?
 many   other  applications.    The  other form of copper chloride is
 3J?or?^hl°ride'  Produced  as   an   intermediate  in*  some  cuprUs
 chloride  processes.    Cupric   chloride   (CuCl2)   has   many
 appatlon? SUCh  P a catalyst in a  number of organic  oxidation
         / in Swe!;tenin9 petroleum oils,  a wood preservative,  and
    0      US?^'  .foth  cuprous  and cupric  chloride can be produced
 as  either a liquid  solution or  as dried crystals.

 Copper carbonate  (CuCO3) is produced  as   a  dry product  and   is
 normally  produced  for outside  sale.   It  is  used in pyrotechnics
paint and varnish pigments, ceramic frits,  in  the  elec?roplSting
                              250

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     TABLE 13-1.  SUBCATEGORY PROFILE DATA FOR COPPER SALTS
            (a)    COPPER  SALTS EXCLUSIVE OF COPPER SULFATE
Number of Plants in Subcategory

Total Subcategory Production Rate
          Minimum
          Maximum

Total Subcategory Wastewater Discharge
          Minimum
          Maximum
    15

>3000 kkg/yr
   <4.5 kkg/yr
  640 kkg/yr

~2000 m3/day
    0
 1060 m3/day
Types of Wastewater Discharge
          Direct
          Indirect
          Zero
    4
    5
    6
                            251

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 TABLE 13-1.
       00 '
SUBCATEGORY PROFILE DATA SUMMARY FOR COPPER SALTS
COPPER SULFATE^
 Total  Subcategory Capacity Rate
 Total  Subcategory Production Rate
 Number of  Plants  in  this  Subcategory
 308 Data on  File  for
           With  total capacity of
           With  total production of
           Representing capacity
           Representing production
           Plant production  range:
                  Minimum
                  Maximum
          Average production
          Median production
          Average capacity utilization
          Plant age  range:
                  Minimum
                  Maximum
          Waste water flow range:
                  Minimum
                  Maximum
          Volume per  unit product:
                  Minimum
                  Maximum
                            Indeterminate
                            27,300 kkg/year
                                16
                                10
                            38,850 kkg/year
                            21,420 kkg/year

                                78 percent

                                45 kkg/year
                             9,100 kkg/year
                             2,100 kkg/year
                               790 kkg/year •
                               *63 percent

                                3 years
                              •  52  years

                                0  cubic meters/day
                                45  cubic meters/day

                                0  cubic meter/kkg
                                23  cubic meter/kkg
(1)   Source:  page 632 of Draft development Document for Effluent
     Limitations  Guidelines  and Standards  for the Inorganic  Chemicals
     Manufacturing Point Source Category,  EPA 440/1-82/007;  June,1982
     Sources  of data  are Stanford Research Institute,  Directory of
     ChemicarProducers,  U.S.A.,  1977,  U.S.  Department of  Commerce,
     Current  Industrial  Reports,  December,  1977;  Energy and
     Environmental Analysis,  Inc.;  Draft Report,  "Preliminary
     Economic Assessment of  Effluent  Limitations  in the Inorganic
     Chemical Industry," June,  1978 and "Economic Analysis of  Proposec
     Revised  Effluent  Guidelines  and  Standards  for  the Inorganic
     Chemicals  Industry," March,  1980.
                         252

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industry as a source of copper, and agriculturally as a fungicide
for treating seed.

Copper  nitrate   (Cu(NO2)3)  can  be  sold in crystal or solution
form.  It is used in light-sensitive reproductive  papers,  as  a
ceramic  color,  as  a  mordant and oxidant in textile dyeing and
printing, in nickel-plating baths and aluminum  brighteners,  and
as a catalyst for numerous organic reactions.

Copper iodide  (Cul) is produced and sold in a powder form.  It is
used  as  a  catalyst  in  certain  organic reactions, as an ice-
nucleating chemical, and as  a  coating  in  cathode  ray   tubes.
Table  13-1  is   a  profile  data  summary  for  the copper salts
subcategory.

There are 15 facilities producing copper salts.   Six  facilities
have  no  discharge,   four  discharge directly and five discharge
indirectly.  Of the 15 producers of other copper salts,   six  are
known to produce  copper sulfate as well.

Total annual production in this subcategory  is estimated  to be in
excess of 3,000 metric tons, while total daily wastewater flow is
estimated  to  be approximately 2,000  cubic meters.   It  has been
found that copper carbonate   production  accounts   for   over  90
percent  of the wastewater  flow in this  subcategory.

General  Process Description and Raw Materials

The  four copper salts  exclusive of copper sulfate are  produced by
different processes, each  discussed separately below.

Copper  chloride  is produced  in two forms, cupric  chloride (CuCl2)
and   cuprous chloride  (CuCl).   Each product  involves the  reaction
of copper with chlorine,  and may  be produced in  solid  or  solution
form.   The  general reactions are:

      Cu +  1/2 C12 =  CuCl

      Cu +  C12 =  CuCl2

      CuCl2  + 3Cu  + C12 =  4 CuCl

 Copper chloride  (cuprous  or cupric)  is manufactured  in  a  solid
 form  by reacting chlorine and pure copper  in a molten bath.   The
 molten copper chloride is withdrawn  continuously  and  materials
 are  added  to maintain the desired material balance.   The molten
 copper chloride  is cast,  cooled,  and  if  desired,   ground  to  a
 powder.
                               253

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                                                      257

-------
 Copper   chloride  in  solution   form  is  manufactured by  reacting
 copper,  chlorine and hydrochloric  acid which  acts  as a solvent  in
 the  reaction.   The cuprous form  also requires cupric chloride   as
 a  starting  material.    The  resulting solution may be purified,
 filtered and then crystallized.  Various   forms  of   copper  feed
 material may be used,  such as pure copper,  copper  oxide and  spent
 plating   and etching solutions.  Figure 13-1  presents the general
 process  diagram for these processes.

 Copper carbonate is produced by  reacting  either copper sulfate  or
 copper nitrate  with sodium carbonate  in  water   to  precipitate
 copper carbonate.   The  general reactions  are:

     CuSO4 + Na2C03 = CuC03 + Na2SO4

     Cu(NO3)2 + Na2CO3  =  CuCO;i + 2NaN03

 The  product  is  decanted to remove  the  sodium sulfate or sodium
 nitrate  solution and washed  to   remove   impurities.   The  pure
 copper   carbonate  product is   then   milled,  dried  and packaged.
 Figure   13-2  presents  the  general   process  diagram for   the
 production of copper carbonate.

 Copper   nitrate  is produced  by   the reaction of pure copper  or
 copper oxide with  nitric  acid.  The general  reactions for  pure
 copper are:

     3Cu  + 8 HN03  =  3Cu(N03)2 + 2NO +  4H20
Cu + 4HNO3 = Cu(NO3)2 + 2H20
                                    2N0
The   resulting  solution  is  treated  and  filtered  to  remove
impurities.  The residue from filtration  is  disposed  of  as  a
solid waste.  The filtrate is treated in a boil tank to drive off
water  forming  a saturated copper nitrate solution which is then
cooled in a crystallizer to crystallize the product.  The  liquid
from crystallization is generally recycled.   The slurried product
is  recovered,  dried  and  packaged.   Figure  13-3 presents the
general diagram for the production of copper nitrate.
Copper iodide (Cul) is produced
reactions are:
                            by  two  methods.   The  general
CuS04 + 2KI - Cul

2Cu + I2 = 2CuI
                         K2S04 + 0.51,
The first process involves the precipitation of cuprous iodide by
reacting  a  copper  salt  (i.e.,  copper  sulfate) and potassium
                              258

-------
iodide.  A reducing agent may be used to prevent contamination of
the cuprous iodide by reacting with the  liberated  iodine.   The
cuprous  iodide  slurry  is  collected, washed in a filter press,
dried, ground, and packaged.  The second process requires  finely
divided  copper  metal and elemental iodine.  These are mixed and
fed into a furnace.  Molten cuprous iodide flows from the  bottom
into  a mold which is cooled by water.  Iodine vapor is collected
by a scrubber, settled  and  periodically  reused.   Figure  13-4
presents the general process diagrams for this product.

WATER USE AND WASTEWATER SOURCES

Water Use

The  major  use  of water in the production of copper chloride is
noncontact cooling water.  Direct contact process water  is  used
in  the  reaction  process  for  copper  chloride  solution.   In
addition,  water   is  also  used  for  air   pollution   control,
maintenance, washdowns, and noncontact ancillary uses.

The  major  water  use  in  the production of copper carbonate is
direct contact  process  water  used  to  wash  the  precipitated
product.    Indirect  process  water  is  also  used  along  with
noncorttact ancillary uses.

Noncontact cooling water used in the crystallizer  is  the  major
use  of  water in  the production of copper nitrate in solid form.
Water  is  also  used  for  air  pollution  control,  maintenance,
washdowns, and noncontact ancillary uses.

In  the  production  of copper iodide noncontact cooling water is
used  in the furnace process and direct contact water may be  used
for  product  washing in the solution process.  Water may also be
used  in air pollution control devices.

Table  13-2 presents a summary of available plant  data  on  water
use.

Wastewater Sources

Noncontact Cooling Water

Noncontact  cooling water is used to cool reaction vessels  in the
production of the  copper salts,  with  the  exception  of   copper
carbonate.    This  wastewater stream should not be contaminated by
process leaks, and therefore can be discharged without treatment.

Direct Process Contact Water
                               259

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Direct  process  contact water is used in the production of  copper
carbonate   and   may  be  used in the production of  copper iodide.
The   direct  contact  water   originates  from  product  washings,
decants of  sodium sulfate  and sodium nitrate,  and filtration  to
remove  impurities.   Solid wastes are disposed of at  a  landfill
while remaining solutions are usually discharged.

Noncontact  Ancillary

A  few  plants   that  manufacture copper nitrate use steam as the
heat  source  in  the  evaporators.    The  steam condensate    is
noncontact  ancillary wastewater.   This can be discharged without
treatment.

Indirect Process Contact

Washdown, pump  seal  leaks, and spills  are   sources  of  indirect
contact wastewater.    Depending  on the plant and  product, these
flows may or  may not be a major source of wastewater.   Wastewater
emanating from  this  source is either recycled or discharged.  For
most  copper salts,   including  copper  sulfate,   but  not  copper
carbonate,  the major source of  process wastewater is washdown,
pump  seal leaks, and spills.

Air Pollution Control

Wet scrubbers are frequently  used  to  control   the   discharge   of
fumes  from  reaction   tanks   and   evaporators  or  concentrators.
Slowdown from these  scrubbers may  be intermittent   or   continuous
process  wastewater.    Scrubber wastewater  generated  from  copper
nitrate production  is  frequently recycled as make-up  water  into
the   copper nitrate  reactor.   All  plants providing  information  on
air scrubber  wastewater recycle that wastewater  either  within the
scrubber system or as  make-up water  for  the  reactors.

Sludge

Solid waste can  be   generated  in  product   purification  by  the
filtration  step  in copper  salts manufacture.   The filtration step
is  usually only necessary when plants utilize impure  copper as a
raw material.    These filter sludges  contain  metallic   impurities
and   require  disposal  at  a  hazardous  waste  landfill.   No solid
waste is generated at  plants   that   produce   copper  chloride   in
liquid  form.   Plants  utilizing pure copper  feedstock are able  to
eliminate,  reduce or recycle  most  contact wastes.

The available data concerning wastewater  flows   at   copper  salts
facilities  is  summarized in Table  13-3.  Facilities F142, FIT  5,
and FT27 produce copper carbonate, while  the remaining  facilities
                              262

-------
listed in the table do not.   It  is  observed  that  the  copper
carbonate   facilities   produce   substantially   more   process
wastewater  than  do  other  copper   salts   facilities.    This
difference  is  attributable  to  the  greater quantities of wash
water required for removal of product impurities  in  the  copper
carbonate  production  process.   The  typical wastewater flow at
copper sulfate plants is 0.94 mVkkg, and results  from  indirect
contact  water  use  (See  the Phase I Development Document, page
649).

DESCRIPTION OF PLANTS VISITED AND SAMPLED

Plants Sampled

Plant F130 produces cuprous chloride  by  the  process  shown  in
Figure   13-5.   The  plant  produces  cuprous  chloride,  cupric
chloride and other inorganic compounds.  Cupric chloride is  used
almost   entirely   as   an  intermediate  for  cuprous  chloride
production.  The process used at this plant is  similar  to  that
described  previously  for the production of copper chloride from
spent plating  and  etching  solutions.   The  solutions  contain
dilute  cupric  chloride  and  copper  ammonium  chloride.   This
solution is then reacted with hydrochloric acid to  form  a  more
concentrated  cupric  chloride solution.  Equal amounts of cupric
chloride solution and copper  metal  are  reacted  together  with
water  and  hydrochloric  acid to produce the appropriate cuprous
chloride solution.

Wastewater originates from tank and  drum washdown, and pump  seal
leaks.   All washes from tank and loading areas are directed to  a
sump where it is collected  and  transferred  to  the  wastewater
holding  tank.   All  wastewater  and  sludge  collected  in   the
wastewater tank is recycled into the process.  Most of the  water
used  in the process is shipped with  the product solutions.  There
is   no  wastewater  treatment  facility,  consequently no treated
wastewater samples could be collected.

During the sampling episode the pump seals were not   leaking   and
water  was  forced  through  the seals in order to take  a sample.
Toxic pollutant concentrations and  loads  in Table  13-4 were taken
from tank  and drum  washes  and  not  from  the  collection  tank
because  the  tank  is only  periodically dumped and pollutants have
time to   settle.   Figure   13-5  shows  wastewater   sources   and
sampling locations at Plant F130.

Plant  F127   produces copper carbonate  (Figure  13-6)  as  well as  a
variety of other metal products  and  inorganic  chemicals.    The
process  used  at  this  plant   is   similar   to  that previously
described  for the  production of  copper   carbonate.    Nearly   all
                               263

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   FIGURE 13-5.  PROCESS AND SAMPLING LOCATIONS FOR PLANT F130.
                    264

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water  is  used  as direct contact water in dissolving, reacting,
and filter washing.  Noncontact cooling water is not used in  the
process.   A majority of the wastewater from the process consists
of reaction supernatant decants, filtrate, and filter wash water.
These wastewater streams are collected in a settling  tank  where
coarse  particulates are settled out and recovered.  The overflow
is sent to a thickener where additional copper is separated  from
the  wastewater.   The  settled  sludge  is  recycled back to the
process while the thickener  overflow  is  sent  to  the  central
treatment  system.  Floor washings, leaks and spills are directed
to another  thickener  for  copper  recovery,  and  the  overflow
discharged  to  the  central  treatment  system.   At the central
treatment system, copper carbonate wastewater is commingled  with
wastewater from inorganic and organic chemicals manufacture, then
subjected  to alkaline precipitation, aeration, and clarification
before discharge to surface waters.  Figure 13-6 shows wastewater
sources and sampling locations at Plant FT 27.  Since the  central
wastewater  treatment  system treats wastewater from a variety of
products, and therefore  may  not  be  representative  of  copper
carbonate  wastewater  only,  no  sampling  was  performed at the
central treatment system.  Table  13-4  presents  the  wastewater
loads and pollutant concentrations for the sampled streams.

Other Plant Visits

Nine  plants in the Copper Salts Subcategory were visited but not
sampled.  A description of the  individual  products,  wastewater
treatment,  and  discharge  status  for  those plants visited are
given below.

Plant F145 produces cupric chloride,  copper  nitrate  and  other
inorganic  and organic compounds.  The copper chloride process is
similar to  the  process  previously  described.   The  resulting
solution   is  purified,  filtered  to  remove  impurities,  then
crystallized.  The pure crystals are  collected,  dried,  ground,
and  sold.   The  residue from filtration  is disposed of as solid
waste.   Copper  nitrate  is  produced  similar  to  the  process
previously  described.   The majority of water used  is noncontact
cooling  water  with  minimal  usage  of  direct  contact  water.
Scrubber  wastes,  washings, filtrates, tank cleanouts, and leaks
or spills  which  cannot  be  recycled  are  sent  to  a  central
treatment   system  where  all  plant  wastewaters   are  treated.
Treatment   consists   of   equalization,    lime   precipitation,
clarification  and  sludge dewatering.  Overflow from  this system
is then treated by biological treatment  prior  to   discharge  to
surface waters.

Plant   FIT9  produces  copper  nitrate, copper  iodide, and copper
carbonate.   All  processes  are  similar   to   those  previously
                               267

-------
described.   Off-  gases  from   the copper  nitrate production  are
exhausted though a condenser  to  recover nitric  acid,  and  the off-
gases then are  incinerated  to   destroy  nitrogen  oxides  before
release  to  the  atmosphere.    Dust  from   the copper  iodide  and
copper carbonate grinding operations are collected in a baghouse,
and the recovered dust is disposed of  in   a chemical  landfill.
Process  wastewaters  from all products manufactured  are  directed
to a  central   treatment  system consisting of  pH  adjustment,
settling,  flocculation,  clarification,  and   sludge dewatering.
The clarifier overflow discharges to a municipal treatment  plant
while  the  underflow  is  dewatered  in  a filter   press  before
disposal in a chemical landfill.

Plant FIT 8 produces copper carbonate in addition  to  many  other
inorganic chemicals.  The manufacturing process is similar  to  the
previously  described  process,.   Wastewater from  all   chemical
processes are combined and  passed  through a   treatment  system
consisting  of  equalization,  alkaline precipitation,  settling  and
final pH adjustment before discharge to surface waters.

Plant FT 13 produces cuprous chloride and other   inorganic  salts.
The  manufacturing process is similar to the previously described
process for producing molten  cuprous chloride from  the  .reaction
of  copper  metal  and  chlorine.   All  contact  and  noncontact
wastewater is discharged to a POTW  without pretreatment  except
neutralization.

Plant  F142  manufactures  copper  carbonate.   The manufacturing
process is similar to the  previously  described  process.   Wash
waters  and filtrates are passed through settling tanks to  remove
sediments before discharge to a  POTW.

Plant F133 manufactures copper nitrate in solution form and other
inorganic products.  The manufacturing process  is similar to   the
previously   described  process.   The  only process wastewater
generated is derived from leaks  and spills.  This small volume of
wastewater is sent to a separate copper wastewater treatment unit
before being discharged to a central treatment  system where  all
facility  wastewater  is pretreated prior to discharge to a POTW.
The copper treatment system  consists  of   equalization,  caustic
addition   to   pH   8-9,  sulfide  addition,   and  filter  press
filtration.   The  filtrate  is   then  equalized in   the  central
treatment  facility, treated with ,caustic to pH 6-9,  and  filtered
for discharge.

Plant F120 produces copper nitrate and other inorganic  products.
Wastewater  from  scrubbers,  equipment  washdowns,   pump  seals,
maintenance and  various  other  product  process  are  combined,
treated  with   lime and lagooned.  The treated  wastewater is used
                              268

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to slurry the purification and  treatment  sludges  back  to  the
settling  ponds for temporary storage.  There was no discharge of
process wastewater streams when visited.  Since the  lagoons  are
unli'ned,  percolation  of some of the wastewater from the lagoons
into the subsoil could account for the fact that the plant had no
discharge when visited.

Plant F129 produces copper iodide by direct  reaction  of  copper
and  iodine.   This  plant  has no discharge as all wastewater is
recycled since the plant uses pure raw materials  only  and  does
not  need  a purification step.  Plants that did not use pure raw
materials would need a purification step and thus  would  have  a
discharge of process wastewater.

Summary of. Toxic Pollutant Data

Thirteen  toxic  metals  and  four  toxic  organics were found at
detectable concentrations in the total combined raw wastewater at
the two sampled plants.  The table  below  presents  the  maximum
daily  concentrations  observed for these pollutants found in the
total combined raw wastewater.   No   treated  wastewater  samples
were  collected  during the sampling  program at these facilities,
for the reasons given above, pages 263 and 267.
Pollutant

Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc

Bis(2-ethylhexyl)  phthalate
Tetrachloroethylene
Toluene
Methyl Chloride
Maximum Concentration
   Observed (ug/1)

     1,300
       270
         3
        20
       270
   560,000
    12,000
        32
       390
       140
       130
       180
     8,300

        23
        30  (28)*
        27  (29)*
        10*
 *preserved samples
                               269

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   TABLE 13-5.  TOXIC POLLUTANT  RAW WASTEWATER DATA FOR SAMPLED
                      COPPER SALTS FACILITIES
Average
Daily Pollutant Concentrations and Loads
mg/1

kg/kkg

Plant Designation
Pollutant
Antimony
Arsenic
Chromium
Copper
Lead
Nickel
Selenium
Silver
Thallium
Zinc
F130(l)
0.483
0.00047
0.100
0.00010
0.220
0.00021
351.333
0.342
5.717
0.00557
0.357
0.00035
<0.005
<0. 00001
0.055
0.00005
<0.104
<0. 00010
7.067
0.00688
F127 (2)
0.200
0.0105
0.103
0.00542
0.047
0.00248
107.000
5.63
0.148
0.00779
0.176
0.00927
0.069
0.00363
0.026
0.00137
0.041
0.00216
0.045
0.00237
Overall
Average
0.341
0.00550
0.102
0.00276
0.134
0.00135
229.167
2.99
2.947
0.00668
0.267
0.00481
<0.037
<0.0018
0.041
0.00071
<0.073
<0.0011
3.556
0.00463
(1)   Data from three daily grab samples,
(2)   Copper carbonate wastewater.
Cuprous chloride wastewater,
                          270

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Section 5  of  this  report  describes  the  methodology  of  the
sampling  program.   In  the Copper Salts Subcategory, a total of
six days of sampling were conducted at two plants.  Six different
wastewater streams were sampled and analyzed.  The evaluation  of
toxic  pollutants  in  these streams was based on 234 data points
for toxic metals and 678 data  points  for  toxic  organics.   In
Table  13-5,  toxic  metal  pollutant  raw  wastewater  data  are
presented as average daily concentrations and loads for  the  two
sampled plants.

POLLUTION ABATEMENT OPTIONS

Toxic Pollutants of_ Concern

The  major  toxic  pollutant  of  concern  in  the  Copper  Salts
Subcategory is copper.  Other toxic metals found  in  significant
concentrations in process wastewaters are probably related to the
purity  of the raw materials used.  Antimony, arsenic, and nickel
occurred  in process wastewaters from two of the   sampled  plants,
while  lead  and zinc were found at significant concentrations at
only one  plant.  No toxic  organics  were  found  in  significant
concentrations.   Antimony,  arsenic,  copper,  lead, nickel, and
zinc were also found at significant concentrations in  raw  waste
during  screening  and  verification sampling at  a copper sulfate
plant during Phase I  (see the Phase I Development Document).

When impure raw materials are used, toxic  metal  impurities  are
removed in the purification process through filtration or washing
of  the product.  These pollutants then occur in  wastewater or as
solid wastes.  Using pure raw materials,  which   are  not  always
available or economical, however, can often allow recycle of most,
or all of the process wastewater.

Existing  Control  and  Treatment Practices

Treatment and  control  practices  conducted at  plants that were
visited during this program were previously described.  Presented
below are brief descriptions  of  treatment  practices  at  other
plants producing  copper salts.

Plant  F115  produces   copper carbonate.  Process wastewaters  are
treated  in  a system using  alkaline precipitation, sedimentation,
and  final pH adjustment prior to discharge  to surface waters.

Plant  F108  manufactures   cuprous chloride  by  direct reaction of
copper and  chlorine.    No   process  wastewater   is   generated   or
discharged  from  this  process.
                               271

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Plant   F1.32  produces  copper  chloride  by  direct  reaction  of  copper
and  chlorine.   Process  wastewaters, which   consist   of   only   air
scrubber  blowdown  are  treated  in a system  using  sedimentation,
and  filtration.   These  treated  wastewaters  are   recycled .to   the
air  scrubber.

Plant   FIT 6  produces  copper iodide  by  direct  reaction  of  copper
and  iodine.  The  only source of process  wastewater  is   the   air
scrubber,  and  all   air   scrubber  water   is  recycled   with   no
blowdown.

Other Applicable  Control  and Treatment Technologies

Alkaline precipitation  and clarification will remove copper   and
most other  toxic  metals  found in  copper salts process wastes.
Filtration of the effluent  from  this  treatment   process  would
further   reduce   metals and  solids.   Three of  four  direct
dischargers  are  currently  using    this   technology    or   its
equivalent.

Process Modifications and Technology  Transfer Options
                                            i
One  of  the major  sources  of  process wastewater  in the subcategory
is   copper carbonate  washwater.  The  copper carbonate precipitate
which must be washed  results from  addition   of soda ash  to  a
copper  salt  solution, usually copper sulfate.  The washwater  is
of relatively  high   pH   (approximately  pH   8-9)   and   typically
contains  low  concentrations   of  most  toxic  metals.   Optimum
removal of copper occurs  at  a pH of 8.5  to 9.0, however,  elevated
concentrations of copper  may occur in  the wastewater in  suspended
form.  The application of  Level 2 technology  (sand  or multi-media
filtration) at this point  may produce  a  suitable quality  effluent
without application of Level 1.  Increased product  yield  (copper
carbonate)  would  result  from  the wastewater treatment  system  by
recovery of the copper carbonate from  the filter.

A reduction in the volume  of process contact  wastewater  generated
might be achieved by:

     1.   Recycling of scrubber water or use  of scrubber  water  as
          make-up for product solutions, where  possible;

     2.   Minimizing   product   changes   by   careful   product
          scheduling,   or,   for  multi-product  facilities,   by
          increasing  the number of reactors.  This  can result   in
          reducing  the  volume  of  washdown  water  required  by
          minimizing product changeover.
                              272

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As shown on Table  13-3,  all  four  plants  with  scrubbers  are
recycling the scrubber water.  Product scheduling is a management
perogative subject to customer demands.  Consequently, the Agency
has not identified any technology which would provide significant
reduction in water use in this industry.

Sludge  volumes may be reduced by the use of caustic soda instead
of lime.  This practice offers other advantages including reduced
scale formation and faster reaction times.

Best Management Practices

The best technology for the  treatment of scrubber wastewater from
copper salts production is recycle, where  technically  feasible.
Implementation of this technology requires installation of piping
and  pumping  as needed.  Scrubber liquors may be used as process
makeup.  All four plants with air  scrubbers  are  recycling  the
scrubber liquor.

If contact is possible with  leakage, spillage of raw materials or
product,  all  storm  water  and  plant  site  runoff  should  be
collected and directed to the  plant  treatment  facility.   This
contamination  can  be  minimized by indoor storage of chemicals,
proper air pollution  control, and elimination of spills.
All  other   contact  wastewater   including
washdowns should  be contained  and treated.
leaks,   spills,    and
 If  solids   from   the  wastewater  treatment  plant  are  disposed  or
 stored on-site, provision  should be made  to  control  leachates and
 permeates.   Leachates   and    permeates    which    contain   toxic
 pollutants  should  be directed  to the  treatment system  for further
 treatment.

 Advanced  Technology

 No  demonstrated   advanced  technology was   identified  for this
 subcategory.

 Selection of. Appropriate Technology and Equipment

 Technologies for Different Treatment  Levels

 A.    Level  1

 Level   1   treatment    consists   of  alkaline   precipitation,
 clarification   or   settling,  and  final   pH  adjustment  of  the
 effluent  if necessary.   Sludges  generated  are   dewatered  in   a
 filter  press.   As part of the treatment system,  a holding basin
                               273

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 sized to retain 4-6 hours of influent is provided as a
 in   the  event  of  treatment  system  shutdown.    The
 technology  is  illustrated in Figure 10-10.
safeguard
treatment
 The  initial  treatment step is  the addition of caustic soda.   This
 is   followed  by  clarification/settling   (if   the   wastewater
 characteristics   are  suitable,  a tube settler may be substituted
 for  a  clarifier  to conserve space).   Sludge is removed  from  the
 clarifier  and  directed   to a filter press for dewatering.   Pits
 are  provided at  the filter press for   the  temporary  storage  of
 sludge.    The sludge  is  periodically transported to a hazardous
 material landfill.   Filter press filtrate is returned to the head
 of the treatment system.

 The  pH of  the  treated wastewater   stream  is  adjusted  to  an
 acceptable   level    by acid   addition  prior  to  discharge  if
 necessary.   A monitoring system is installed  at  the  discharge
 point.   The  objective of Level 1 technology is to remove  heavy
 metals and suspended solids.

 B.   Level 2

 Level  2 treatment   consists of   granular  media  filtration  for
 further  removal of  metal  hydroxide precipitates and other solids
 from the wastewater.   This  technology is portrayed in Figure  10-
 11.    In   practice,   when  Level  2 technology is added to Level  1,
 final  pH  adjustment  would   be  reconfigured  to  occur   after
 filtration   not  prior to  it.   The objective of Level  2  treatment
 technology in  this  subcategory is to   achieve,   at  a  reasonable
 cost,  more   effective removal   of toxic metals than  provided  by
 Level  1.   Filtration will  both increase treatment  system solids
 removal and  decrease the variation in solids removal  exhibited  by
 typical    clarifier    performance.     Four   facilities   in   this
 subcategory  practice  filtration of  copper   salts   wastewater,
 including  three  of  four direct dischargers.

 Level  2  treatment   was selected as  the basis for BPT because  it
 represents a typical  and viable  industry practice for  the control
 of suspended solids,  copper and  nickel.   Three of the  four direct
 dischargers  have Level  2 treatment already installed.  One of the
 five   indirect  dischargers  also has   Level   2   installed.    In
 addition,  level  2   technology  was the basis  for the  promulgated
 copper sulfate BPT and  BAT  effluent   limitations.    Six  plants
 currently  do  not discharge copper salts  process wastewater, and
will not incur additional costs  for treatment.

As discussed under  "Process Modifications  and  Technology  Transfer
Options" in this Section,   copper  carbonate   wastewater  may  be
amenable  to  Level   2 treatment  without  first  practicing Level 1
                              274

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treatment.  The benefits to this approach would  include increased
recovery of copper carbonate product,  a  reduction  in  cost  of
treatment,  and  a  reduction   in  discharge  of  toxic metals to
receiving waters.

Equipment for Different Treatment Levels

A.   Equipment Functions                                      ,

Conventional sludge dewatering  by a  filter  press   is  used  for
sludge  generated  by  the  clarification/settling system.   In some
cases,  the sludge may  be amenable to copper  recovery.   However,
off-site  disposal in  compliance with RCRA Subtitle  C regulations
is generally assumed.   If  a tube settler  is  used instead of   a
clarifier,  backwash from  the settler is  returned to the influent
holding basin.  Solids resulting from  Level   2   filter  backwash
.would   be handled as discussed  in item C  (Solids Handling)  below.
All  equipment  is conventional and readily available.

B.   Chemical  Handling

Caustic soda  (50 percent   NaOH) is  used to  precipitate heavy
metals  in  Level   1.   At all  levels of  treatment,  sulfuric acid
 (concentrated) may be  used to   reduce   the  pH   of  the   treated
wastewater prior to  discharge.

C.   Solids Handling

Treatment  sludges  generated by  Level  1  are dewatered in  a   filter
press.    The   solids may  be disposed of  off-site or  processed  for
 copper  recovery.   Level 2  filter backwash may  be sent  to the head
 of  the  plant  or,  if   the   solids  concentration   is   sufficiently
 high, may  be  sent  directly to the  filter press.

 Treatment  Cost Estimates

 Based   upon   copper  salt  subcategory  profile characteristics,  two
 model plants  were  selected for  costing  of Level   1   and  Level  2
 treatment   systems.    The  overall   ranges  of  production   and
 wastewater flow have been discussed earlier  in this   section   and
 summarized  in  Table  13-1.    Since  copper carbonate production
 accounts  for   a  large  portion  (>90   percent)   of   the  process
 wastewater  generated  in the subcategory,  one set of model plant
 wastewater flow characteristics are based upon flow  attributable
 to  this product,  and a separate model  plant has been established
 for the other copper salts.
 Estimates of material usages for both  treatment
 copper salts segment are listed below:
levels  in  the
                               275

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      Chemical
  Amount
Level
      NaOH  (50 percent sol.)
      H2SO«.  (100 percent)
    3.0 kg/day
    0.08 kg/day
 Estimates   of   solid waste generated for both treatment, levels in
 the  copper  salts segment  are provided below:
     Waste  Source
Amount
     Level  1  sludge
     Level  2  sludge
  0.0176 mVday
  0.0018 mVday
Flow data  for  copper  salts  producers  is  presented  in  Table   13-3.
The flow for copper salts plants  exclusive  of  copper  carbonate  is
very   close   to   the  flow  from  copper   sulfate plants.   The
pollutants are the same, and  are  at similar levels.    Therefore,
the  Agency  has   combined  the copper salts subcategory with the
copper sulfate subcategory.   The  model plant for all  copper  salts
exclusive  of copper carbonate has an  annual production of  85.2
metric  tons   (the average of the plants reporting production  in
Phase II)  and   a   daily  wastewater  flow   of   0.8 cubic  meters
calculated from   the daily  production  and the unit  flow of 0.94
mVkkg (as found at copper  sulfate  plants)   with an  operating
schedule   of   102  days per  year.   These  characteristics were used
as the basis for treatment  cost estimates at all levels.

For the copper carbonate industry,  the unit flow is   the  average
flow  from all  three  plants reporting flow data.  The average
production rate and operating days for the  plants  reporting  these
data are used  for  the model plant.  Therefore,  the   model   plant
has  an  annual  production   of   155  metric   tons and a   daily
wastewater flow of 291 cubic   meters.    The unit  flow is  58.1
mVkkg  with   an   operating   schedule of 31 days per  year.   These
characteristics  were used   as   the  basis for   treatment  cost
estimates  at all levels.

Estimates  of  material  usages   for both treatment levels in the
copper carbonate subgroup are listed below:
Chemical

NaOH (50 percent sol.)
H2S04 (100 percent sol. )
 Amount

 87.3 kg/day
 29.1 kg/day
Level

1
1
Estimates of solid waste generated for both treatment
the copper carbonate subgroup are listed below:
                           levels   in
                              276

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     TA.BLE 13-6.  WATER EFFLUENT TREATMENT COSTS
                  FOR MODEL PLANT.
SUBCATEGORY:  Copper Salts Subgroup
ANNUAL PRODUCTION: 	

DAILY FLOW:          0.8

PLANT AGE:         NA
85.2
METRIC TONS
      CUBIC METERS
YEARS   PLANT LOCATION:
                  NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED. LEVELS

                                    COSTS ($1,000) TO ATTAIN  LEVEL
COST CATEGORY


Facilities
Installed Equipment
   (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital

Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Wast6 Disposal) 6.3
Residual Waste Disposal
1
0.7
6.6
1.5
1.3
1.0
11.1
1.8
6.3
0.7
2

0.4
0.1
0.1
0.1
0.7
0.1
0.2
0.1
  To ta1 Annual Co s t
         8.8
  0.4
                        b.   TREATMENT DESCRIPTION
LEVEL 1:  Alkaline precipitation, clarification, pH adjustment

LEVEL 2:  Filtration
                            277

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      TABLE 13-7.   WATER EFFLUENT TREATMENT COSTS
                   FOR MODEL  PLANT.
 SUBCATEGORY:   Copper  Carbonate Subgroup
 ANNUAL PRODUCTION:

 DAILY FLOW:  	

 PLANT AGE:
         155
               METRIC  TONS
  291
NA
	 CUBIC METERS

YEARS   PLANT  LOCATION:
                                                           NA
            a.   COST  OF TREATMENT  TO ATTAIN  SPECIFIED  LEVELS
 COST  CATEGORY

 Facilities
 Installed Equipment
   (Including Instrumentation)
 Engineering
 Contractor Overhead and Profit
 Contingency
 Land

  Total Invested Capital
                                    COSTS  ($1,000)  TO  ATTAIN LEVEL
                 1

                 25.4

                163.7
                 37.8
                 34.0
                 26.1


                287.0

                 46.7
Annual Capital Recovery
Annual Operating and Maintenance
 (Excluding Residual Waste Disposal) 78.3
Residual Waste Disposal              0.9
  Total Annual Cost
                31.3
                 6.3
                 5.6
                 4.3
                47.5

                 7.7

                 9.3
                 0.1
                       b.
                125.9    17.1

        TREATMENT  DESCRIPTION
LEVEL 1:   Alkaline  precipitation,  clarification,  sludge dewatering,
             !H adjustment
             tration
                            278

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Waste Source

Level 1  sludge
Level 2 sludge

Model Plant Treatment Costs
                             Amount

                             0.058 mVday
                             0.006 mVday
On  the  basis  of  the  model  plant  specifications  and design
concepts presented earlier and in Section 10, the estimated  cost
of  treatment  for  the model plant with two treatment levels are
shown  in  Tables  13-6  and  13-7.   The  cost  of  Level  2   is
incremental to Level 1 .

Basis for Regulations

Basis for BPT Limitations

A.   Technology Basis

For BPT, the Agency is setting limitations  based  upon   alkaline
precipitation,    clarification,   granular   media   filtration,
dewatering  of  the  sludge   in  a  filter  press  and   final   pH
adjustment  of  the  effluent (if necessary).   Three of the four
direct dischargers have Level 2  treatment.   One   of   the  five
indirect  dischargers  also   has  Level   2  installed.  All copper
sulfate plants have this technology or  its  equivalent  installed.
Six  plants  currently  do   not  discharge  copper   salts process
wastewater, and will not incur additional costs  for  treatment.
 B.
Flow Basis
 For the  copper  salts  segment  of  the Copper Salts  Subcategory,   a
 unit  flow  rate  of   0.94  mVkkg  was selected as representative.
 This flow rate  was derived  as described above under  model  plant
 treatment  costs.   The  unit  flow  is  the  same  as for copper
 sulfate.

 For the  copper  carbonate segment of the Copper Salts Subcategory,
 a unit flow of  58.1 mVkkg  was selected as  being  representative
 of  the   group.   This  flow  rate was derived as described above
 under model plant treatment costs.

 C.   Selection  of Pollutants to be Regulated

 The  selection   of pollutants  for   which   specific   effluent
 limitations  are  being  established is based on an evaluation of
 the raw  wastewater data from screening and verification  sampling
 in  Phase I and Phase II, consideration of the raw materials used
 in the process, literature data, historical discharge  monitoring
                               279

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 reports  and   discharge permit  applications,  and the treatability
 of  the toxic  pollutants.

 Tables 8-1  through  8-14 summarize  the   achievable  concentrations
 of   toxic  metal  pollutants  from the  literature using  available
 technology  options,   information   from  other   industries,    and
 treatability  studies.   Water  use and discharge  data are  presented
 earlier  in   this   section   together   with   generalized  process
 characteristics.    Pollutant  concentrations  of  raw wastewater
 streams and a summary  of  maximum concentrations observed of  toxic
 pollutants  detected during screening and  verification sampling at
 several  plants are also  presented earlier  in this section.   Data
 from Appendix A on  the performance of in-place  industry  treatment
 systems were  also utilized in developing  the  list  of pollutants
 to  be regulated.

 The  following parameters  were   selected  initially as  candidate
 toxic pollutants for BPT  regulations:   copper,  nickel,   lead  and
 zinc.    These pollutants were  observed  at  least  once during
 screening and verification sampling at  concentrations considered
 treatable.    A number of  other   priority pollutant metals were
 detected during screening and  verification  sampling,   however,
 concentrations were   generally  less than 0.3  mg/1.   Arsenic and
 selenium were also   considered   as  toxic   pollutants    to   be
 regulated.

 During  Phase I, significant  concentrations of  arsenic were  found
 at  a  copper sulfate facility  during screening   and   verification
 sampling.   However,   arsenic  was  not  selected  as a  regulated
 pollutant in  Phase  I,   because  it  will  be  controlled   by  the
 technology    selected   for  control  of  the  other   toxic  metal
 pollutants.    For the same reason,  arsenic was also  rejected  as  a
 regulated pollutant in Phase  II.

 Selenium was  also found during Phase I screening  and  verification
 sampling in  a treated effluent.   However, selenium  was  not  found
 in  the  raw wastewater.  The  maximum  concentration   of   selenium
 found   in  a  combined  raw wastewater influent to  treatment during
 Phase  II  screening  and verification sampling  was  0.14 mg/1.

 Consideration  of  the   raw  wastewater  concentrations  presented
 earlier   in   this   section,  wastewater information obtained  from
 industry and  from Phase I, and information presented  in Section 8
 on  the  effectiveness of hydroxide  precipitation,  clarification,
 and  filtration suggested a reduction in the  number of parameters
 to  be regulated.  Copper, nickel, and selenium were   selected  as
 the  toxic  pollutants  to be regulated.   Since selenium was  found
 in  Phase  I in treated  effluent but not the  raw   waste,   selenium
was  selected  for  regulation  in Phase I, along with copper and
                              280

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nickel, to assure that excessive amounts
discharged after treatment.
                     of  selenium  were  not
Control of the regulated parameters, copper, nickel and selenium,
will  provide  adequate  control  for  arsenic,  lead  and  zinc;
therefore no limitations are set for these three parameters.

D.   Basis of BPT Pollutant Limitations

Limitations are presented as both concentrations (mg/1) and loads
(kg/kkg), and the relationship between the two is  based  on  the
unit  flow  rates of 0.94 m3/kkg for copper salts and 58.1 m3 for
copper carbonate.  BPT limitations, which apply  to  all  process
wastewater discharged, are presented in Table  13-8 and 13-9.

     1.   Conventional Pollutants

          a.   pH

               The treated effluent is to be controlled within
               the range of 6.0 - 9.0.  This limitation is based
               upon the data presented in Appendix B of the
               Development Document for Proposed Effluent
               Guidelines for Phase I Inorganic Chemicals  (Ref.
               1) and the JRB study (Ref. 2).

          b.   TSS

               The BPT limitations  for TSS  are  based  upon  the
               limitations  promulgated  for   the  copper  sulfate
               industry in Phase  I.  The long-term average of   20
               mg/1  was  used  to  develop  discharge limitations.
               Variability factors  of 1.2 for  a  monthly   average
               and  approximately   3.6 for  a 24-hour maximum were
               used yielding TSS  concentration limitations of   24
               mg/1  and  73  mg/1  respectively.  Thus, utilizing
               these values, one  obtains TSS mass limitations for
               the Copper Salts subcategory of:
                1
Copper Salts Segment
                30-day average;

                (24  mg/1) (0.94 mVkkg) (kg/10*  mg)(1000  1/m3)
                =  0.023 kg/kkg

                24-hour maximum;

                (73  mg/l)(0.94 mVkkg) (kg/106  mg) (1000  1/m3)
                               281

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          = 0.069 kg/kkg
          2.   Copper Carbonate Segment
          30-day average;
          (24 mg/1) (58.1 mVkkg) (kg/1 0« mg)(1000 1/m3)
          -1.4 kg/kkg
          24-hour maximum;
          (73 mg/1) (58.1 m^/kkg) (kg/10* mg)(1000 1/m*)
          =    4.2 kg/kkg
2.    Toxic Pollutants
     a.    Copper
          The BPT limitations for copper are  based  on  the
          limitations  promulgated  in  Phase  I  for copper
          sulfate manufacture.  During Phase I, a  long-term
          average  concentration  of  0.89  mg/1  copper was
          derived, and estimated variability factors of  1.2
          and  3.6  were  used to compute the 30-day average
          and 24-hour maximum values of  1.1  and  3.2  mg/1
          respectively.
          Utilizing  these  values,  mass limitations for the
          Copper  Salts  Subcategory  may  be  obtained   as
          follows:
          1.   Copper Salts Segment
          30-day average;
          (1.1  mg/1) (0.94 mVkkg) (kg/106 ing) (1000 1/m,)
          = 0.0010 kg/kkg
          24-hour maximum;
          (3.2  mg/1) (115 mVkkgX kg/10* mg)(1000 1/m3)
          = 0.0030 kg/kkg
          2.   Copper Carbonate Segment
          30-day average;
          (1.1  mg/1) (58.1 rn3/kkg) (kg/10« mg)(1000 1/m3)
          = 0.064 kg/kkg
                         282

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24-hour maximum;

(3.2 mg/1)(58.T mVkkgf(kg/1 0«mg) (1000 1/m*)
=0.19 kg/kkg

Nickel

The  DPT  limitations  for nickel are based on the
limitations promulgated  in  Phase  I  for  copper
sulfate  manufacture.   In  Phase  I,  a long-term
average  concentration  of  1.8  mg/1  nickel  was
derived,  and estimated variability factors of 1.2
and 3.6 were used to compute  the  30-day  average
and  24-hour  maximum  values  of 2.1 and 6.4 mg/1
respectively.

The mass limitations  for  nickel  in  the  Copper
Salts Subcategory were derived as follows:

1.   Copper Salts Segment

30-day average;

(2.1 mg/1) (0.94 mVkkg) (kg/10« mg)(1000 1/m')
= 0.0020 kg/kkg

24-hour maximum;
(6.4 mg/1) (0.94 m^/kkg) (kg/1 0* mgMTOOO
= 0.0060 kg/kkg

2.   Copper Carbonate Segment

30-day average;

(2.1 mg/1) (58.1 mVkkg) (kg/10* mgMlOOO
     0.12 kg/kkg

24-hour maximum
(6.4 mg/1) (58.1 mVkkg) (kg/1 0« rag)' (1000 l/m» )
=0.37 kg/kkg

Selenium

The BPT limitations for selenium are based on  the
limitations  promulgated  in  Phase  I  for  copper
sulfate manufacture.  During Phase I7 a  long-term
average  concentration  of  0.44 mg/1 selenium was
               283

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               derived, and estimated variability factors of   1.2
               and  3.6  were  used to compute the  30-day average
               and 24-hour maximum values of  0.53   and   1.6  mg/1
               respectively.

               Utilizing  these  values, mass limitations for  the
               Copper  Salts  Subcategory  may  be  obtained   as
               follows:

               1.   Copper Salts Segment

               30-day average;

               (0.53 mg/1) (0.94 mVkkg) (kg/1 0« mg)(1000  1/m3)
               * 0.00050 kg/kkg

               24-hour maximum;

               (1.6 mg/1) (0.94 mVkkg) (kg/10«) (1000 1/m')
               = 0.0015 kg/kkg

               2.   Copper Carbonate Segment

               30-day average

               (0.53 mg/1) (58.1 mVkkg) (kg/10« mg)(1000  1/m')
               « 0.031 kg/kkg

               .24-hour maximlm

               (1.6 mg/1) (58.1 mVkkg) (kg/10« mg)(1000 1/m')
               = 0.093 kg/kkg

Basis for BCT Effluent Limitations

On  October  29,  1982,  EPA  proposed a revised BCT methodology.
While EPA is considering revising that  proposed  methdology,  in
this subcategory no additional technologies were identified which
would  remove  significant  additional quantities of conventional
pollutants.  Accordingly, EPA has determined that BCT equals  BPT
in  this  subcategory.   As a result, BCT for TSS is equal to the
BPT limitations.

Basis for BAT Effluent Limitations

Application of Advanced Level Treatment

For  BAT,  the  Agency  is  promulgating  limitations  based   on
treatment   consisting   of  Level  2  (BPT)  technology.   Toxic
                              284

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      TABLE 13-8.    BPT EFFLUENT LIMITATIONS FOR COPPER SALTS
Coventional
Pollutants
Long-Term
Avg.(mg/1)
                20
VFR
   CD
               1.2/3.6
Cone. Basis*- ' Effluent Limit
    (mg/1)        Ckg/kkg)
30-day  Z4-hr. 30-day  24-hr.
avg.    max.    avg.   max.
            24
                                                     73
               0.023 '  0.069
Toxic
Pollutants
Copper^3)
Nickel^35
SeleniumC3J
0.89
1.8
0.44
1.2/3.6
1.2/3.6
1.2/3.6
                                              1.1      3.2   0,0010   0.0030

                                              2.1      6.4   0.0020   0.0060

                                              0.53     1.6   0.00050  0.0015
VFR  - Variability Factor  Ratio
 (1)  Based  upon limitations promulgated for the copper sulfate sub'
     category in Phase I.
 (2)  Also applicable to NSPS and BCT.
 (3)  Also applicable to BAT and NSPS.
                            285

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       TABLE 13-9.   BPT EFFLUENT LIMITATIONS FOR COPPER  CARBONATE
 Conventional   Long-Term*-1-*
 Pollutants     AvgTCmg/l")
TSS(3)


Toxic
Pollutants
       f 21
Copper*- J

Nickel^

Selenium^- '
20
                VFR
1.2/3.6
             Cone. Basis'- ^  Effluent Limit
            	 Cmg/1)	       Ckg/kkgl
            30-day  24-hr.   30-day  24-hr.'
                     max.     avg.    max.
                           24
73
1.4
                                                   4.2
0.89
1.8
0.44
1.2/3.6
1.2/3.6
1.2/3.6
1.1
2.1
0.53
3.2
6.4
1.6
0.064
0.12
0.031
0.19
0.37
0.093
VFR - Variability Factor  Ratio

(1)  Based upon limitations promulgated for the copper sulfate sub-
     category in Phase  I.

(2)  Also applicable to BAT 'and NSPS.

(3)  Also applicable to NSPS and BCT.
                           286

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     TABLE  13-10.    BAT  EFFLUENT  LIMITATIONS FOR COPPER SALTS
Cone. Basis
   (mg/1)
                                                           Effluent Limit
                                                              Tke/kkg")
                                                                         (1
Toxic
Pollutants
Copper
Nickel
Selenium
Long - Term ^ J
Avg. (mg/1)
0.
1.
0.
89
8
44
VFR^
1.
1.
1.
2/3.
2/3.
2/3.
6
6
6
30- day
avg.
1.
2.
0.
1
1
53
24 -hr.
max.
3.2
6.4
1.6
30-day
avg.
0.
0.
0.
0010
0020
00050
24-hr;
max.
0.0030
0.0060
0.0015
VFR - Variability Factor Ratio
     Based upon  limitations  promulgated for the  copper sulfate sub-
     category  in Phase  I.
                            287

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        TABLE 13-11.   BAT EFFLUENT LIMITATIONS FOR COPPER CARBONATE
Toxic
Pollutants
Long-Term
Avg.Cmg/1)
VFR
   CD
Cone.  Basis
   Cmg/1)
30-day24-hr,
 avg.     max.
Effluent Limit|
   (kg/kkg)
30-day  24-hr.|
 avg.    max.
Copper
Nickel
Selenium
0.89
1.8
0.44
1.2/3.6
1.2/3.6
1.2/3.6
1-1
2.1
0.53
3.2
6.4
1.6
0.064
0.12
0.031
0.19
0.37
0.093
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated  for  the  copper sulfate  sub-
     category in Phase  I.
                              288

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pollutants limited by the BAT regulation are copper,  nickel  and
selenium   at   the   same   concentration  levels  and  loadings
established for BPT.'  No  other  technology  which  would  remove
significant additional amounts of pollutants is known.

A.   Technology Basis

Alkaline precipitation followed by clarification and  filtration,
dewatering  of  the  sludge  in  a  filter  press,  followed by pH
adjustment (if necessary) form the selected BAT .technology  basis
(same as BPT). "                    ,                . ,

B.   Flow Basis

Unit wastewater flow rates of 0.94 m3/kkg  of  copper  salts  and
58.1  mVkkg of copper carbonate have been selected for BAT  (same
as BPT).

C.   Selection of Pollutants to be Regulated

     Toxic Pollutants

The toxic pollutants  copper,  nickel,   and  selenium  have   been
selected  at  the same concentration  levels and  loadings proposed
for BPT.  Tables  13-10 and 13-11 present the BAT  limitations  for
the Copper Salts  Subcategory.

Basis for NSPS Effluent  Limitations

For  NSPS,  the   Agency   is promulgating limitations equal to BAT
since no additional technology  which   would   remove   significant
additional  amounts  of   pollutants   is  known.    The  pollutants
limited include pH, TSS,  copper, nickel, and selenium  which  • are
listed  in Table 13-8 and 13-9.

Basis for Pretreatment Standards

The  Agency   is   promulgating PSES and  PSNS  that are  equal to BAT
limitations because BAT  provides better removal  of copper, nickel
and selenium  than is   achieved  by   a  well  operated   POTW   with
secondary   treatment   installed  and  therefore   these pollutants
would pass  through  the POTW  in the absence of  pretreatment.   The
promulgated  PSES  and  PSNS  for copper sulfate  are also based  on
the BAT technology.  Pollutants regulated under  PSES  and PSNS are
copper, nickel, and  selenium.

Using  the summary data presented  in  Tables 13-5  and 13-8,  and the
data  from Phase  I,  the Agency has  estimated  the   percent  removal
for    copper    and   nickel   by  comparing  the   untreated  waste
                               289

-------
 concentrations for those two toxic metals with the treated  waste
 concentrations for the selected BAT technology for those same two
 pollutants.    The  untreated waste concentrations presented below
 are an average of the concentrations  found  for  copper  sulfate
 during Phase I and for those copper salts plants sampled in Phase
 II.    This is a reasonable approach since many plants make copper
 sulfate and  other copper salts and combine the wastewater streams
 for treatment.  The  calculation  of  the  percent  removals  for
 copper and nickel is as follows:
           Copper:    Raw Waste •>
                          BAT  =

           Percent  Removal     =
          Nickel:
Raw Waste
     BAT
          PercentRemoval
1175 mg/1
0.89 mg/1

[(1175 -
99.9%

51.2 mg/1
1 .8 mg/1
            [(51.2 - 1.8)
            96.5%
                     0.89) t (1175)] (100)
              t (51.2)]  (100)
The  percent  removals are greater  than  the  removals  achieved  for
copper  (58%) and  nickel  (19%)  by  25% of   the  POTWs   in   the   "50
Cities"  study   (Fate  of  Priority Pollutants  in Publicly Owned
Treatment  Works,   Final  Report,   EPA   440/1-827303^  SepteinberT
1982).   Therefore,  since  the BAT technology achieves  a greater
percent removal of  copper  and nickel   than  is  achieved by a
well-operated  POTW with  secondary  treatment,  those  two toxic
metals would pass through a POTW  in the  absence of pretreatment.

Selenium has also been selected for regulation under  PSES for  the
reasons previously  given for its  selection for regulation under
BAT.

Existing Sources

There are currently five indirect discharging  copper  salts plants
in  the subcategory.  There is also one  indirect discharge copper
?«i  \e Plant-  For Pretreatment Standards for  Existing   Sources
(PSES),  the  Agency  is  promulgating   limitations   based on  BAT
described above.  The pollutants  limited are copper,  nickel,   and
selenium as presented in Table 13-8 and  13-9.


New Sources

For  Pretreatment Standards for New Sources  (PSNS),  the Agency is
setting limitations based on NSPS.  Since NSPS is equal   to  BAT,
                              290

-------
Tables  13-8  and  13-9  summarize  the limitations for the toxic
pollutants copper, nickel, and selenium.
                              291

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                      SECTION 13

                      REFERENCES
U.S. Environmental Protection Agency, "Development  Document
for  Effluent  Limitations  Guidelines and Standards for the
Inorganic Chemicals Manufacturing  Point  Source  Category,"
EPA Report No. 440/1-79-007, June 1980.

JRB Associates,  Inc.,  "An  Assessment  of  pH  Control  of
Process  Waters  in  Selected  Plants,"  Draft Report to the
Office of  Water  Programs,  U.S.  Environmental  Protection
Agency, 1979.
                         292

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                           SECTION 14

                      NICKEL SALTS INDUSTRY
INDUSTRY PROFILE

General Description

The  nickel  salts  covered  under  this  subcategory  are nickel
sulfate, nickel carbonate, nickel chloride, nickel  nitrate,  and
nickel  fluoborate.   A process description and discussion of the
nickel sulfate industry can be found in the Phase  I  Development
Document:   Development   Document   for   Effluent   Limitations
Guidelines   and   Standards   for   the   Inorganic    Chemicals
Manufacturing  Point  Source  Category,  EPA  440/1-82/007, June,
1982.

Briefly, nickel sulfate is produced by reaction of nickel, nickel
oxide or waste nickel (such as spent plating bath) with  sulfuric
acid:
Ni
                  NiS04
The nickel sulfate may be sold in solution as produced, or may be
purified  and  crystallized  before  sale as the solid.  Detailed
process information and the results of screening and verification
sampling are  provided  in  the  Phase  I  Development  Document.
Therefore,  the  following discussion will cover the other nickel
salts covered in this subcategory.

These salts, produced for both captive use and merchant  markets,
are primarily used in electroplating and catalysts.  The chloride
salt  is  most widely used in electroplating, while the carbonate
and fluoborate  salts  are  used  to  a  lesser  extent.   Nickel
carbonate, is produced from other nickel salts, particularly from
nickel sulfate.  Upon reduction with hydrogen,  nickel  carbonate
yields  a  finely  divided  nickel  with good catalytic activity.
Nickel nitrate is used in nickel plating, preparation  of  .nickel
catalysts,  and  in  manufacture of brown ceramic colors.  Tables
1 (a) and l(b) are profile data summaries  for  the  nickel  salts
subcategory .

There  are  12  known facilities manufacturing nickel salts.  Two
plants have no process wastewater  discharge,  while  six  plants
discharge directly and four discharge indirectly.

Total  annual  production  of  nickel salts is estimated to be in
excess of 5,000 metric tons per year  and  total  daily  flow  is
                              293

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TABLE 14-1.   SUBCATEGORY PROFILE DATA FOR NICKEL SALTS
      (a)     NICKEL SALTS EXCLUSIVE OF NICKEL SULFATE
Number of Plants in Subcategory
   12
Total Subcategory Production Rate
         Minimum (3 plants)
         Maximum
>5000   kkg/yr
   <4.5" kkg/yr
 1550   kkg/yr
Total Subcategory Wastewater Discharge
         Minimum
         Maximum
  600 nT/day
    0
  195 m3/day
Types of Wastewater Discharge
         Direct
         Indirect
         Zero
    6
    4
    2

                       294

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TABLE 14-1.
       (b)
SUBCATEGORY PROFILE DATA
NICKEL SULFATE*-1)
SUMMARY FOR NICKEL SALTS
Total Subcategory, Capacity Rate
                               (2)
                                 (2)
Total Subcategory Production Rate
Number of Plants in this Subcategory1- -1
308 Data on File for
          With total capacity of
          With total production of
          Representing capacity
          Representing production
          Plant production range:
                Minimum
                Maximum
          Average production
          Medium production
          Average capacity utilization
          Plant age range:
                Minimum
                Maximum
          Waste water flow range
                Minimum
                Maximum
          Volume per unit product:
                Minimum
                Maximum
                           Indeterminant
                               6,350 kkg/year
                                  11
                                   6
                              17,700 kkg/year
                              12,650 kkg/year
                                 1 NA
                                  NA'
                                  NA
                                  45 kkg/year
                               5,900 kkg/year
                               2,100 kkg/year
                               1,600 kkg/year
                                  71.5
                              »

                                   3
                                  48
                                   1.5 cubic meters/day
                                  17.0 cubic meters/day

                                   0.42 cubic meters/kkg
                                   0.72 cubic meters/kkg
 (1) Source: page 674 of Draft Development Document for Effluent
    Limitations Guidelines and Standards for the  Inorganic Chemicals
    Manufacturing Point Source Category, EPA 440/1-82/007; June  1982.
 (2) "Economic Analysis of Proposed Revised Effluent Guidelines and
    Standards for the Inorganic Chemicals Industry," March,  1980.
 (3) Sources of data are Stanford Research Institute, Directory of
    Chemical Producers, U.S.A., 1977.
 NA  Not Available
                         295

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estimated at greater than 600 cubic meters per day for all plants
combined.   Based  upon available data, it is estimated that over
90 percent of the wastewater flow in the  category  is  generated
from nickel carbonate production alone.

General Process Descriptions and Raw Materials

Nickel  carbonate  is  produced by reacting any of several nickel
salts with sodium carbonate (soda ash).  The general reaction is:

          NiS04 + Na2C03 = NiC03 + Na2S04

Two different types of raw  materials  may  be  used  to  produce
nickel  carbonate:  pure nickel salts or impure materials such as
spent plating solutions.  When pure salts are used, the resultant
nickel carbonate  precipitate  is  filtered,  dried,  ground  and
packaged.   When  impure  sources  of  nickel  are  used  as  raw
materials, additional rinsing of the precipitate is necessary  to
remove  impurities.   Figure 14-1 presents a general process flow
diagram for the manufacture of nickel carbonate.

Other nickel salts, nickel chloride, nickel nitrate,  and  nickel
fluoborate,  are  produced  by  reaction of pure nickel or nickel
oxides with hydrochloric acid, nitric acid,  or  fluoboric  acid.
The general reactions for nickel oxide are:

          NiO + 2HC1 - NiCl2 + H2O

          NiO + 2HN03 = Ni(N03)2 + H2O

          NiO + 2HBF4 = Ni(BF4)2 + H2O

The  resulting  solutions  are  filtered  to  remove  impurities,
crystallized and centrifuged.  The pure crystals are then  dried,
ground   and   packaged.   The  products  may  also  be  sold  as
concentrated solutions.  Figure 14-2 presents a  general  process
diagram  for  the  manufacture of nickel chloride, nickel nitrate
and nickel fluoborate.

WATER USE AND WASTEWATER SOURCES

Water Use

Noncontact cooling water used in the reactors  and  crystallizers
constitutes  one  of  the  major  water uses in the production of
nickel salts.  Water is also used in direct process contact as  a
reaction  component  and  for  washing  precipitated products.  A
portion of the reaction water occurs in the  product  concentrate
or  in  the dry product as its water of hydration, but much of it
                              298

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-------
is evaporated to the atmosphere.  Small amounts of water are used
for  maintenance  purposes,  and  several  plants  use  water  in
scrubbers  for  dust  or  fume  control.   Table  14-2 presents a
summary of available plant data on water use.

Wastewater Sources

Noncontact Cooling Water

Noncontact cooling is one of  the  major  sources  of  discharged
water.   This  stream  is  usually  not  contaminated  and is not
treated before discharge.

Direct Process Contact

Plants which use impure  nickel  raw  materials  generate  filter
sludges  or  wash  wastes which must be treated before discharge.
Filter  sludges  and  decants  from  processes  using  pure   raw
materials  are  often  recycled  back  to the process.  In nickel
carbonate production,  direct  contact  process  wastewater  from
washing  impurities from the nickel carbonate is the major source
of process wastewater.

Maintenance

Equipment  and  area  cleaning  wastes,  and   indirect   contact
wastewater  such  as  spills  and sump leaks are periodic streams
that account for a small amount of wastewater  generated  by  the
production  of  nickel  salts.   For most nickel salts, including
nickel sulfate but not including nickel carbonate,  this  is  the
major source of process wastewater.

Air Pollution Control

Wet  scrubbers  are  frequently  used to control the discharge of
fumes from  reaction  tanks  and  evaporators  or  concentrators.
Slowdown from these scrubbers may be intermittent or continuous.

The  available  data  concerning wastewater flows at nickel salts
facilities is summarized in Table 14-3.  It is observed that  the
nickel  carbonate  processes  produce  substantially more process
wastewater than do other nickel salts processes.  This difference
is attributable to the greater quantities of wash water  required
for  removal  of  product  impurities  in  the  nickel  carbonate
production process.

DESCRIPTIONS OF PLANTS VISITED AND SAMPLED
                              301

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Six plants producing nickel salts were visited during this study.
In addition, wastewater sampling was conducted at three of  these
plants.  This section presents summary descriptions of facilities
visited and sampled during this program.

Plants Sampled

Plant  FIT 3  produces  nickel  carbonate, nickel chloride, nickel
nitrate and other inorganic salts.  During  the  sampling  visit,
only   the   nickel  carbonate  process  was  operating.   Nickel
carbonate is produced on  a  batch  basis  by  reacting  a  spent
plating  solution with soda ash.  After reaction, the precipitate
is rinsed to remove impurities, then  dried  and  packaged.   The
decanted  rinse  water  passes  through  two filter presses.  The
filter cake is recovered and returned  to  the  process  and  the
filtrate  is  discharged.   Other  sources  of wastewater include
washdown, pump seal leaks, and spills.  All wastewater from  this
plant  is discharged to a POTW without pretreatment.  Figure 14-3
is a diagram of the process showing sampling points.  Table  14-4
presents data on the major pollutant concentrations and loads for
the sampled streams.

Plant  F117  produces  nickel  carbonate, nickel chloride, nickel
nitrate, nickel fluoborate, and a variety of other  metal  salts.
During  the  plant  visit,  only the nickel carbonate process was
sampled.  Nickel carbonate is produced by reacting nickel sulfate
with soda ash.  The resultant slurry is passed through  a  vacuum
filter.    The  filter  cake  is  washed  with  water  to  remove
impurities, then dried, milled and packaged.   The  washwater   is
treated  in  a nickel recovery system which uses caustic addition
to pH  10, sand filtration, with final pH adjustment with sulfuric
acid   addition  before  discharge  to  surface  waters.    Solids
captured  in  the  sand  filter  are  subjected  to  filter press
filtration for nickel recovery.   Fluoride-containing  wastewater
from   nickel  fluoborate  production, when  it occurs, is combined
with   other   process   wastewater   for   treatment   by   lime
neutralization,  flocculant addition, clarification, and final  pH
                            is  a  diagram  of  the  process  and
                            sampling points.  Table 14-4 presents
                             concentrations  and  loads  for  the
adjustment.   Figure  14-4
treatment  system  showing
data on the major pollutant
sampled streams.
Plant  F107 produces  nickel  carbonate,  nickel  nitrate and  several
other  inorganic salts.  Both nickel  carbonate  and  nickel   nitrate
processes  were  operating   during   the  sampling   visit.  Nickel
carbonate  is produced by  a proprietary  batch   process.   Washdown
wastes,    spills   and  filter  backwash  from   this process   are
collected  in a trench with   other  process  wastewaters  and   are
discharged to  a   POTW  without  treatment.    Nickel  nitrate is
                               302

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 produced  at  this plant by a process  similar  to  that  described
 previously.    Figure  14-5  is  a  diagram  of  the two processes
 showing sampling points.   Table 14-4 presents data on  the  major
 pollutant concentrations  and loads for the sampled streams.

 Other  Plants Visited

 Plant  FT 45 produces  nickel carbonate,  nickel chloride,  anc. nickel
 nitrate salts in addition to many other chemicals.   Manufacturing
 processes for  the   nickel salts are similar to those previously
 described.   Scrubber wastes,  washings,  filtrates,  tank cleanouts,
 and  leaks or spills  which  cannot  be  recycled   are  sent  to  a
 central treatment system  where all plant wastewaters are treated.
 Treatment   consists   of   equalization,    lime   precipitation,
 clarification and sludge  dewatering.   Overflow from  this  system
 is then treated  by biological  treatment prior to discharge.

 Plant  F119   produces  nickel   carbonate  and nickel   nitrate in
 addition  to  numerous other inorganic salts.    Processes  for  the
 nickel  salts are  similar  to those  previously described.  Off-
 gases  from   the  nitrate  production   are  exhausted   through  a
 condenser to recover  nitric  acid,   and  the   gases   are  then
 incinerated  to destroy  nitrogen  oxides  before   release  to  the
 atmosphere.    Process  wastewaters from all  products manufactured
 are directed to  a central   treatment   system consisting of   pH
 adjustment,   settling,  flocculation,   clarification,   and sludge
 dewatering.   The clarifier  overflow  is  discharged  to a  POTW.

 Plant FIT  8 produces   nickel   carbonate   and   nickel  chloride   in
 addition  to  many other  inorganic compounds.  Wastewater streams
 from all  chemical processes  are combined  and passed   through  a
 treatment     system     consisting    of    equalization,    alkaline
precipitation,   clarification   and  final  pH adjustment before
discharge.

Plants  FIT 3,  FIT 7,  F145, and F118 also  produce nickel  sulfate.
The nickel sulfate process wastewaters  are  combined  with   other
nickel process wastewaters  for  treatment  and  discharge.

Summary of. Toxic  Pollutant Data

Nine  toxic metals were found at detectable  concentrations in  the
total raw wastewater  at the  three  sampled   plants.    The   table
below  presents   the  maximum   daily  concentrations observed  for
these pollutants  found  in the total process raw wastewater:
                              306

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Pollutant

Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
Maximum Concentration
    Observed (uq/1)

         1,545
         1,513
           170
           877
   >   .     170
     1,513,000
            82
           300
           698
Section 5  of  this  report  describes  the  methodology  of  the
sampling  program.   In  the Nickel Salts Subcategory, a total of
nine days of sampling were  conducted  at  these  plants.   Seven
different  process  wastewater streams were sampled and analyzed.
The evaluation of toxic pollutants in these streams was based  on
260  data  points  for toxic metals and 791 data points for toxic
organics.  In Table 14-5, toxic  pollutant  raw  waste  data  are
presented as average daily concentrations and loads for the three
sampled plants.

POLLUTION ABATEMENT OPTIONS

Toxic Pollutants of Concern

The  toxic  pollutants of concern in the Nickel Salts Subcategory
are nickel and copper.  Other toxic metals found  in  significant
concentrations  in  process wastewaters are related to the purity
of the raw materials used.  Antimony  and  thallium  occurred  in
process  wastewater  at concentrations greater than 100 ug/1 from
two of the sampled plants, while cadmium and zinc were  found  at
significant  concentrations at only one. plant.  No toxic organics
were  found  in  significant  concentrations.   Nickel,   copper,
antimony,  cadmium, and zinc we?re also found in untreated process
wastewater during the Phase I screening and verification sampling
at three nickel sulfate plants.

When impure raw materials are used, toxic metal  impurities  will
be  removed  in  the  purification  process through filtration or
washing of the product.   These  pollutants  can  then  occur  in
wastewater  or solid wastes.   Using pure raw materials, which are
not always available or  economical,   however,  can  often  allow
recycle of the process water.

Existing Wastewater Control and Treatment Practices
                              308

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  TABLE  14-5,
TOXIC POLLUTANT RAW WASTE DATA FOR SAMPLED
   NICKEL SALTS FACILITIES
      Average Daily Pollutant Concentrations and Loads
                            mg/1
                           kg/kkg
                            Plant Designation
Pollutant
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium
Zinc
F113
0.673
0.0477
<0.010
<0.0007
0.073
0.0052
0.025
0.00177
0.007
0.0005
16.6
1.18
0.029
0.0021
0.118
0.00837
0.037 ,
0.00262
F117
0.057
0.014
0.013
0.0033
0.025
0.0063
0.024
0.0061
0.060
0.0152
41.0
10.4
0.008
0.002
0.217
0.0549
0.023
0.0058
,107 (D
<0.531
<0.850
0.047
0.460
<0.003
540.3
<0.001
<0.003
0.387
Overall
Average
<0.420
0.0309
<0.291
<0.002
0.048
0.00575
0.170
0.00394
<6.023
0.00785
199.3
5.79
<0.013
0.0021
o!o316
0.149
0.00421
	  Insufficient information.
(1)  Flow-proportioned averages from two nickel product
     wastewater streams.
                     309

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 Treatment   and   control   practices   at   plants   that  were visited
 during  this program  were previously  described.    Presented  below
 are   brief   descriptions  of   treatment  practices at  other plants
 producing nickel  salts.

 Plant F125  produces  nickel nitrate and   several   other   inorganic
 compounds.   Wastewater streams  from all processes are  treated  in
 a  system consisting of  equalization, pH adjustment with  caustic,
 and sedimentation in a series  of lined and   unlined  impoundments
 prior to discharge.

 Plant  F106 produces nickel   chloride   and nickel fluoborate  in
 addition to other inorganic compounds.   Discharge is  to   a  POTW
 after  pretreatment   with  lime  precipitation   and clarification
 technology.

 Plant F139  produces  nickel carbonate, nickel chloride,  and nickel
 nitrate salts   in   addition   to  other   inorganic    compounds.
 Treatment   for  all   process wastewater  consists of equalization,
 sedimentation, neutralization  and filter press   filtration  prior
 to discharge.

 Plant F124  produces  nickel nitrate in addition to other inorganic
 salts.   Treatment   of   process  wastewater   consists of  alkaline
 precipitation, clarification,  filtration and final  pH   adjustment
 prior to discharge.

 Plant  FT 04  produces nickel   chloride  and  nickel  fluoborate and
 other inorganic chemicals.  All  products are sold as produced   in
 liquid  solution  and therefore no  wastewater is generated and
 there is no  discharge.

 Plant F138 produces  nickel  fluoborate in small   quantities   along
 with  a  large variety  of  other  inorganic  chemicals.  No wastewater
 is    generated    from the small  volume production  of   nickel
 fluoborate and therefore  there  is no discharge.

 Other Applicable  Control  and Treatment Technologies

Alkaline precipitation and clarification will remove  nickel  and
most  other  toxic  metals  found in nickel  salts process wastes.
 Several  plants   are  currently   using   this  technology.   Other
applicable technologies would  include filtration  of the clarified
effluent for further  solids and  metals removal.

Process Modifications and  Technology Transfer Options

One of the major  sources of process wastewater in the subcategory
 is  nickel carbonate  washwater.  The product which  must be washed
                              310

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results from addition of soda ash  to  a  nickel  salt  solution,
usually  nickel  sulfate.  The washwater is of relatively high pH
(approximately pH 8-10) and typically contains low concentrations
of most toxic metals.  Nickel concentrations may be  elevated  in
the  rinse water, however.  Optimum removal of nickel occurs at a
pH of 10.2.  The application of sand or multimedia filtration  at
this  point  could  produce  a  suitable quality effluent at some
facilities without other  treatment.    Increased  product  yield
(nickel  carbonate)  would result from this technique by recovery
of nickel carbonate from the filter  backwash.   Plants  with  no
current treatment may wish to study this possibility.

A reduction in the volume of process contact wastewater generated
might be achieved by:

     1.   Recycling all direct process contact wastewater or  use
          scrubber  water as make-up for product solutions> where
     :     possible;

     2.   Minimizing   product   changes   by   careful   product
          scheduling  and  by  increasing the number of reactors.
          This can result in  reducing  the  volume  of  washdown
          water required by minimizing product changeover.

As  shown  in  Tables  14-2  and  14-3, both plants with scrubber
wastewater have minimized the discharge  of  process  wastewater.
Plant  FT 13  recycles over 90% of its scrubber water, while Plant
F125 has eliminated  all  other  sources  of  process  wastewater
discharges  except  the  scrubber water.  Product scheduling is a
management perogative suject to customer demand.  The agency  has
not  identified  any additional technology which could be applied
to significantly reduce the volume of  wastewater  discharges  in
this subcategory.

Best Management Practices

The best technology for the treatment of scrubber wastewater from
nickel  salts  production is recycle, where technically feasible.
Implementation of this technology requires installation of piping
and pumping as needed.  Scrubber liquors may be usable as process
makeup.

If contact is possible with leakage, spillage of raw materials or
product,  all  storm  water  and  plant  site  runoff  should  be
collected  and  directed  to  the plant treatment facility.  This
contamination can be minimized by indoor  storage  of  chemicals,
proper air pollution control and elimination of spills.
                               311

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All   other  contact  wastewater  including
washdowns should be contained and treated.
leaks,   spills,   and
If solids from the wastewater treatment  plant  are  disposed  or
stored on-site, provision should be made to control leachates and
permeates.    Leachates   and   permeates   which  contain  toxic
pollutants should be directed to the treatment system for further
treatment.

Plant Fl17, which  produces  a  variety  of  inorganic  chemicals
(including all four Phase II nickel salts), practices segregation
and  commingling . of  various  wastewater  streams depending upon
chemical characteristics.   Some  wastewater,  particularly  that
originating  from nickel carbonate and nickel sulfate production,
is combined and treated in the same wastewater treatment facility
and the treatment sludge  is  recovered  to  reclaim  its  nickel
whereas  other  streams  like  the  nickel  nitrate wastewater is
commingled  with  cobalt  nitrate   wastewater   for   treatment.
Segregation  of  wastewater  may  at some facilities enable lower
concentrations of toxic  metals  to  be  attained  or  may  allow
increased  product  yield  by  recovery of product from treatment
sludges.

Advanced Technology

For  facilities  using  impure  raw  materials  such  as  plating
solutions, etc., significant concentrations of a variety of toxic
metals  may  be  present in wastewater, particularly in dissolved
form.  Careful control of pH to  reduce  the  solubility  of  the
metals  followed by clarification and filtration may be necessary
for optimum treatment.

Selection of_ Appropriate Technology and Equipment

Technologies for Different Treatment Levels

A.   Level 1

Level   1    treatment   consists   of   alkaline   precipitation,
clarification  or  settling,  and  final  pH  adjustment  of  the
effluent if necessary.  Sludges  generated  are  dewatered  in  a
filter  press.   As part of the treatment system, a holding basin
sized to retain 4-6 hours of influent is provided as a  safeguard
in  the  event  of  treatment  system  shutdown.   The  treatment
technology is illustrated in Figure 10-10.

The initial treatment step is the addition of caustic soda.   This
is  followed  by  clarification/settling   (if   the   wastewater
characteristics  are  suitable,  a tube settler may be substituted
                              312

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for a clarifier to conserve space),, Sludge is removed  from  the
clarifier  and  directed  to a filter press for dewatering.  Pits
are provided at the filter press for  the  temporary  storage  of
sludge.   The  sludge  is periodically transported to a hazardous
material landfill.  Filter press filtrate is returned to the head
of the treatment system.

The pH of  the  treated  wastewater  stream  is  adjusted  to  an
acceptable   level   by  acid  addition  prior  to  discharge  if
necessary.  A monitoring system is  installed  at  the  discharge
point.   The  objective  of Level 1 technology is to remove heavy
metals and suspended solids.
B.
Level 2
Level 2 treatment  consists  of  granular  media  filtration  for
further  removal of metal hydroxide precipitates and other solids
from the wastewater.  This technology is portrayed in Figure  10-
11.   In  practice,  when Level 2 technology is added to Level 1,
final pH adjustment would occur after filtration not prior to it.
The objective of Level 2 treatment technology in this subcategory
is to achieve, at a reasonable cost, more  effective  removal  of
toxic  metals  than  provided  by  Level 1.  Filtration will both
increase  treatment  system  solids  removal  and  decrease   the
variation  in  solids  removal  exhibited  by  typical  clarifier
performance.  Four facilities in this subcategory have Level 2 or
its equivalent, including four of  the  six  direct  dischargers.
Level  2  technology  was the basis for the promulgated BPT, BCT,
and BAT effluent limitations and NSPS, PSES,  and  PSNS  for  the
nickel sulfate subcategory.

As discussed under "Process Modifications  and Technology Transfer
Options"  in  this  section,  nickel  carbonate wastewater may be
amenable to Level 2 treatment without first  practicing  Level   1
treatment.  The benefits to this approach  would include increased
recovery of nickel carbonate product and a reduction in treatment
costs.

Equipment for Different Treatment Levels

A.   Equipment Functions

Conventional sludge dewatering by a  filter  press  is  used  for
sludge  generated  by the clarification/settling system.   In some
cases, the sludge may be amenable to  nickel  recovery,  however,
off-site  disposal  in a hazardous material landfill is generally
assumed.  If a tube settler  is  used   instead . of  a  clarifier,
backwash  from  the  settler  is returned  to the influent  holding
basin.  Solids resulting from Level 2 filter  backwash  would  be
                               313

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 handled   as   discussed   in   item  C (Solids  Handling)  below.   All
 equipment is  conventional and  readily available.

 B.   Chemical Handling

 Caustic  soda  (50 percent NaOH)   is  used  to   precipitate  heavy
 metals   in Level   1.    At  all  levels of treatment,  sulfuric acid
 (concentrated) may  be used  to  reduce the   pH  of   the   wastewater
 prior to discharge.

 C.   Solids Handling

 Treatment sludges generated by  Level 1  are dewatered in a   filter
 press.    The   solids  may   be  disposed of  off-site in  a hazardous
 material  landfill or processed   for  nickel  recovery.   Level   2
 filter   backwash  may be sent  to the head  of the plant or,  if  the
 solids concentration is  sufficiently high, may be   sent directly
 to the filter press.

 Treatment Cost Estimates

 Based  upon   Nickel Salt Subcategory profile characteristics,  two
 model plants  were selected  for  costing of .Level  1   and Level   2
 treatment  systems.     The overall  ranges  of   production   and
 wastewater flow have been discussed earlier  in this  section   and
 summarized  in  Table  14-1.    Since  nickel carbonate production
 accounts  for   a  large   portion   (>90  percent)  of  the  process
 wastewater  generated  in the subcategory, one set of  model plant
 wastewater flow characteristics  are based  upon flow  attributable
 to  this  product,  and  a second model  plant has been  established
 for the other nickel salts.

 Flow data for nickel salts  producers is presented  in   Table  14-3,
 The flow  for  nickel salts plants exclusive of  nickel carbonate is
 very  close to the flow  from nickel  sulfate  plants (See the Phase
 I Development Document).  The pollutants are the same,  and are at
 similar levels.  Therefore, the  Agency  has   combined   the  nickel
 salts subcategory with the  nickel sulfate subcategory.

 The  model  plant  for   all  nickel   salts   exclusive   of  nickel
 carbonate has an  annual  production  of  429  metric   tons   (the
 average   of   the  plants  reporting  production  in  Phase II) and a
daily wastewater flow of 1.67 cubic  meters   calculated   from  the
daily  production  and   the unit  flow of 0.68 mVkkg (as found at
nickel sulfate plants)  with an operating schedule  of 175 days per
year.  These  characteristics were used  as the basis for  treatment
 cost estimates at all levels.
                              314

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     TABLE 14-6.  WATER EFFLUENT TREATMENT COSTS
                  FOR MODEL PLANT.
SUBCATEGORY:  Nickel Salts  Subgroup
ANNUAL PRODUCTION:

DAILY FLOW: 	

PLANT AGE:
        429
              METRIC TONS
   1.67
      CUBIC METERS
NA
YEARS   PLANT LOCATION:
                                        NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS

                                    COSTS  ($1,000) TO ATTAIN  LEVEL
COST CATEGORY

Facilities
Installed Equipment
   (Including Instrumentation)
Engineering
Contractor Overhead and Profit •
Contingency
Land

   Total Invested Capital

Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal) 7.4
Residual Waste Disposal
I
1.1
12.2
2.7
2.4
1.8
20.2
3.3
7.4
0.5
2

0.4
0.1
0.1
0.1
0.7
0.1
0.2
Negl.
  Total Annual Cost
                11.2
                0.3
                         b.  TREATMENT DESCRIPTION
 LEVEL  1:   Alkaline  precipitation,  clarification,  pH adjustment

 LEVEL  2:   Filtration
                            315

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      TABLE 14-7.   WATER EFFLUENT TREATMENT COSTS
                   FOR MODEL PLANT.
 SUBGATEGORY:   Nickel  Carbonate  Subgroup
 ANNUAL PRODUCTION:  	

 DAILY  FLOW:	94.8

 PLANT  AGE:
         142
              METRIC TONS
              CUBIC METERS
NA
YEARS   PLANT LOCATION:
                                                           NA
            a.   COST  OF TREATMENT  TO ATTAIN  SPECIFIED  LEVELS
 COST CATEGORY


 Facilities
 Installed Equipment
   (Including Instrumentation)
 Engineering
 Contractor Overhead and Profit
 Contingency
 Land

  Total Invested Capital
                                    COSTS  ($1,000)  TO  ATTAIN LEVEL
                 1

                 11.7

                122.9
                 26.9
                 24.2
                 18.6


                204.3

                 33.2
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste-; Disposal) 55.8
Residual Waste Disposal              o!s
  Total Annual Cost
                22.5
                 4.5
                 4.1
                 3.1
               34.2

                5.6

                7.5
               Negl.
                        b.
                 90.3    13.1

         TREATMENT DESCRIPTION
LEVEL 1:  Alkaline precipitation, clarification, sludge dewatering,
            pH adjustment
LEVEL 2:  Filtration
                            316

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For the nickel carbonate industry, the  average  production  rate
and  operating  days for the plants reporting these data are used
for the model plant.  Therefore, the model plant  has  an  annual
production of 142 metric tons and a daily wastewater flow of 94.8
cubic  meters.   The  unit  flow  is 120 m3/kkg with an operating
schedule of 179 days per year.  These characteristics  were  used
as the basis for treatment costs at all levels.  The unit flow is
the average (to two significant figures) of Plants F113 and F117.
Plant  F107 was not included because nickel carbonate is produced
for captive used and the additional cleaning water  use  at  F113
and  F117  is  not  done  at Plant'Fl07.  Plant F145 was not used
because the plant uses pure raw materials to  produce  a  reagent
grade  product, and it also does not have the additional cleaning
steps necessary at the average plant.
Estimates of material usages for both treatment
nickel salts segment are listed below:
     Chemical
     NaOH
     H2S04
(50 percent sol.)
 (100 percent)
Amount

 2.34 kg/day
 0.17 kg/day
                                       levels  for  the
                                             Level
Level 1
Level 1
Estimates of solid waste generated for all treatment
levels for the nickel salts segment are provided below:
     Waste Source

     Level 1 sludge
     Level 2 sludge
                         Amount

                         0.012 mVday
                         0.001 mVday
Estimates of material  usage  for  all  three  treatment  levels  in  the
nickel  carbonate  segment  are listed  below:
      Chemical

      NaOH (50  percent  sol.)

      H2SO4 (100  percent)
                         Amount

                         53.0 kg/day

                          9.8 kg/day
 Estimates of  solid waste generated for  all  treatment  levels  are
 provided belows                                                 ,
      Waste Source

      Level 1  sludge

      Level 2  sludge
                         Amount

                         0.019 mVday

                         0.0019 mVday
                               317

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Model Plant --Treatment  Costs

On the basis of model  plant specifications   and   design   concepts
presented  earlier  and   in  Section   10,   the estimated  costs'of
treatment  for  two model plants  with   two   treatment   levels  are
shown  in  Tables   14-6   and  14-7.    The   cost   of  Level  2   is
incremental to Level 1.

Basis for  Regulations

Basis for  BPT  Limitations ;

A.   Technology Basis

For BPT, the Agency is setting  limitations   based upon   alkaline
precipitation,  clarification,  dewatering   of  the  sludge  in a
filter press,  filtration, and final pH adjustment of the  effluent
(if necessary).  Four  of  the six direct dischargers have  Level  2
treatment  installed.   Two plants currently have no discharge of
nickel salts process wastewater, and will   not  incur  additional
costs  for  treatment.    Level  2 was the technology basis for the
promulgated effluent limitations guidelines  and standards for the
nickel sulfate subcategory.

B.   Flow Basis

For the nickel salts segment of the Nickel  Salts  Subcategory,  a
unit   flow    rate   of   0.68   mVkkg  was selected  as  being
representative of the group.    This  flow   rate   was  derived  as
described above under model plant treatment  costs.

For the nickel carbonate  segment of the Nickel Salts Subcategory,
a unit flow of 120 m3/kkg was selected as being representative of
the  group.    This flow rate was derived as  described above under
model plant treatment costs.

C.   Selection of Pollutants to be Regulated

The  selection  of  pollutants  for   which   specific    effluent
limitations  are  being   established is based on  an evaluation of
the raw wastewater data from screening and verification sampling,
consideration  of  the  raw  materials  used  in   the    process,
literature  data,  historical  discharge  monitoring  reports and
discharge permit applications,  and the treatability of the  toxic
pollutants.

Tables  8-1  through 8-14 summarize the achievable concentrations
of toxic metal pollutants from  the  literature   using  available
technology   options,   information  from  other   industries,  and
                              318

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treatability studies.  Water use and discharge data are presented
earlier  in  this  section  together  with  generalized   process
characteristics.   Pollutant  concentrations  of  raw  wastewater
streams and a summary of maximum concentrations observed of toxic
pollutants detected during sampling at several  plants  are  also
presented  earlier  in this section.  Data from Appendix A on,the
performance of in-place  industry  treatment  systems  were  also
utilized in developing the list of pollutants to be regulated.
                                                                i
The  following  parameters  were  selected initially as candidate
toxic pollutants for BPT regulations!  cadmium, copper, chromium,
nickel, and zinc.  These pollutants were observed at  least  once
during  screening  and  verification  sampling  at concentrations
considered treatable in  raw  wastewater.   However  all  of  the
toxics   except  for  nickel  were  observed  at  relatively  low
concentrations in nickel  carbonate  wastewater.   One  facility,
which  was  sampled  for nickel nitrate wastewater, accounted for
numerous observations of significant concentrations  of  cadmium,
copper,  chromium  and zinc.  Nickel concentrations were found at
treatable levels at all facilities sampled.  A  number  of  other
priority pollutant metals were detected during sampling, however,
concentrations were generally less than 0.3 mg/1.

Consideration  of  the  raw  wastewater  concentrations presented
earlier in this section,  wastewater  information  obtained   from
industry  in both Phase I and Phase  II, and information presented
in  Section  8  related  to  the   effectiveness   of   hydroxide
precipitation,  clarification,  and  filtration  in  reducing the
amounts of all toxic metals discharged suggested a  reduction  in
the number of parameters to be regulated.  Copper and nickel  were
finally  selected  as  the  toxic  pollutants  to  be  regulated.
Cadmium, chromium, and zinc may occur in  some  cases  at  nickel
salts  facilities  (probably  associated  with  some raw material
use).  However, their occurrence does not appear to be consistent
enough to warrant adoption as control parameters  for  the  whole
subcategory.    In  addition,  the technology necessary to control
copper and nickel will also result  in the control of other  toxic
metals.

D.   Basis of BPT Pollutant Limitations

Limitations are presented as both concentrations  (mg/1) and loads
 (kg/kkg), and the relationship between the  two  is  based  on  the
unit   flow  rates  of 0.68 m3 for nickel salts and  120 mVkkg for
nickel carbonate.  BPT  limitations  which  apply  to  all  process
wasteswater discharged, are presented  in Tables  14-8 and  14-9..
      1
Conventional Pollutants
                               319

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     a.   pH

          The treated effluent  is  to  be   controlled  within
          the  range of 6.0 - 9.0.  This  limitation is  based
          upon the data  presented in  Appendix  B  of  the
          Development   Document   for    Proposed   Effluent
          Guidelines for Phase  I Inorganic Chemicals and  the
          JRB study.

     b.   TSS

          The BPT limitations for  TSS are based upon the  BPT
          limitations promulgated  in  Phase   I  for  nickel
          sulfate  manufacture.    The  long-term  average of
          39.2  mg/1   was   used   to   develop   discharge
          limitations.   Variability  -factors  of  1.2  for a
          monthly average and 3.6  for a 24-hour maximum were
          used yielding TSS concentration limitations of  47
          mg/1  and  141 mg/1 respectively.  Thus, utilizing
          these values, one obtains TSS mass limitations  for
          the Nickel Salts Subcategory of:

          1.   Nickel Salts Segment

          30-day average;

          (47 mg/1) (0.68 mmVkkg) (kg/1 0« mg)(1000 l/m*)
          • 0.032 kg/kkg

          24-hour maximum;

          (141 mg/1) (0.68 mVkkg) (kg/10« mg)(1000 l/m»)
          » 0.096 kg/kkg

          2.   Nickel Carbonate Segment

          30-day average

          (47 mg/1) (120 mVkkg)  (kg/1 0«) (1000 1/n*)
          = 5.6 kg/kkg

          24-hour maximum

          (141 mg/1) (120 mVkkg) (kg/10«  mg)(1000 1/m3)
          * 17 kg/kkg

2.    Toxic Pollutants
     a.
Nickel
                         320

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         TABLE 14-8.   BPT EFFLUENT LIMITATIONS FOR NICKEL SALTS
Conventional    Long-Term
Pollutants	    Avg.Cmg/D
                         CD
             VFR
                CD
           Cone.  Basis^ Effluent Limit
              Cmg/p	Ckg/kkg)
           30-day  24-hr. '30-day  24-hr.
            avg.     max.   avg.    max.
TSS

Toxic
Pollutants

Nickel
39.2
 2.5
1.2/3.6     47     141    0.032   0.096
1.2/3.6      3.0     9.0  0.002   0.006
VFR - Variability Factor Ratio


(1)  Based upon limitations promulgated  for  the nickel  sulfate  sub-
     category in Phase I.
                           321

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       TABLE 14-9.   BPT EFFLUENT. LIMITATIONS  FOR NICKEL CARBONATE
Coventional     Long-Term
Pollutants
                          ^  •*
                                VFR
             Cone. Basis*• •* Effluent Limit
                  (mg/1)	Ckg/kkg)
             30-day  24-hr. 30-day  24-hr.
              avg.    max.   avg.    max.
TSS

Toxic
Pollutants

Nickel
                   39.2
                    2.5
1.2/3.6
1.2/3.6
47
141
3.0
               5.6
                                     17
          9.0   0.36
                 1.1
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated for the nickel  sulfate  sub-
     category in Phase I.
                             322

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               The BPT limitations for nickel are  based  on  the
               BPT  limitations promulgated in Phase I for nickel
               sulfate manufacture.   Concentration limitations of
               3.0 mg/1 (on a monthly basis) and 9.0 mg/1  (on  a
               daily   basis)   were   obtained  by  use  of  the
               variability factors of J. 2 for a  monthly  average
               and 3.6 for daily maximum computations.  Utilizing
               these  values,  mass  limitations  for  the Nickel
               Salts Subcategory may be obtained as follows:

               1 .    Nickel Salts Segment

               30-day average;

               (3.0 mg/1) (0.68 mVkkg) (kg/1 0« mg)(1000 1/m3)
               = 0.002 kg/kkg

               24-hour maximum;

               (9.0 mg/1) (0.68 mVkkg) (kg/10« mgXlOQO 1/m3)
               = 0.006 kg/kkg

               2.    Nickel Carbonate Segment                ,

               3 0-day average

               (3.0 mg/1) (120 mVkkg) (kg/1 0* rag)(1000 1/m3)
               =0.36 kg/kkg

               24-hour maximum

               (9.0 mg/l)(120 mVkkg) (kg/10« mg)(1000 1/m3)
               =1.1 kg/kkg

Basis for BCT Effluent Limitations

On October 29, 1982, EPA  proposed  a  revised  BCT  methodology.
While  EPA  is  considering revising that proposed methdology, in
this subcategory no additional technologies were identified which
would remove significant additional  quantities  of  conventional
pollutants.   Accordingly, EPA has determined that BCT equals BPT
in this subcategory.  As a result, BCT for TSS is  equal  to  the
BPT limitations.

Basis for BAT Effluent Limitations

Application of Advanced Level Treatment
                              323

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For   BAT,  the  Agency   is  promulgating   limitations  based  on
treatment consisting of Level 2 technology   Csame  technology  as
BPT)  because  we have identified no other  technology which would
remove  significant  additional  amounts  of  pollutants.   Toxic
pollutants  limited by the proposed BAT regulation are copper and
nickel.
A.   Technology Basis

Granular media filtration  (Level 2) added to
selected as the basis of BAT  (same as BPT).

B.   Flow Basis
Level  1   has  been
Unit wastewater flow rates of 0.68 mVkkg of nickel salts and 120
mVkkg for nickel carbonate has been selected for  BAT   (same  as
for BPT).

C.   Selection of Pollutants to be Regulated

     Toxic Pollutants                    ;

The toxic pollutants copper and nickel have been selected for BAT
limitation.  Tables 14-10 and 14-11 present the  BAT  limitations
for the Nickel Salts Subcategory.

D.   Basis of Pollutant Limitations

As  in  BPT,  the  BAT  limitations   are   presented    as   both
concentrations  (mg/1)  and  loadings  (kg/kkg).   Loadings  were
derived from the calculated concentrations using the model  plant
flow  rates  of  0.68  mVkkg for nickel salts and 120 m3/kkg for
nickel carbonate.

The BPT effluent limitations for the nickel  sulfate  subcategory
were  promulgated  May 22,  1975  (40  FR 22402).  These effluent
limitations were based on  Level  2  technology,  but  there  was
limited  data  available  to  estimate  the  performance  of  the
technology.  Since 1975, long-term treatment  system  performance
data  from  nickel  sulfate  manufacturing  plants (including one
plant manufacturing another Phase II nickel product and  treating
the  combined  nickel sulfate and Phase II nickel product process
wastewater in the same Level 2 wastewater treatment  system)  and
the  agency's  treatability  study  (Treatabilitv Studies for the
Inorganic Chemicals  Manufacturing  Point  Source  Category,  EPA
440/1-80/103,  July 1980)shows  that  the  Level  2  technology
performs much better than anticipated in 1975.   The  promulgated
BAT  effluent  limitations  for  nickel sulfate are based on this
better performance.  Since the same technology is used  at  Phase
                              324

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II   nickel  salts  plants  to  treat  nickel  salts  wastewaters
(including nickel sulfate wastewater in several cases), and since
the same pollutants are found at similar levels for nickel  salts
products,,  the  BAT  limitations for the nickel salts subcategory
are based on the demonstrated achievable performance of the Level
2 technology.

     Toxic Pollutants

     a.   Copper

          The BAT limitations for copper are  based  on  the  BAT
          limitations  promulgated in Phase I for nickel sulfate.
          The long-term average value for copper was 0.3 mg/1 and
          variability factors used were 1.2 for a 30-day  average
          and  3.6  for  a  24-hour  maximum.   The concentration
          values that are derived using  these  values  are  0.36
          mg/1   (30-day  average) and 1.1 mg/1  (24-hour maximum).
          Mass limitations are computed as follows:

          1.   Nickel Salts Segment
          30-day average;

          (0.36 mg/1) (0.68 mVkkg) (kg/1 0« mg)  (1000  1/m3)
           = 0.00024  kg/kkg

          24-hour maximum;

          (1.1 mg/l)(0.68 mVkkg) (kg/10«mg)( 1000  1/m*)
          = 0.00074 kg/kkg

          2.   Nickel Carbonate Segment

          30-day average

          (0.36 mg/l)(120 mVkkg) (kb/10* mg)(1000  1/m*)
          = 0.042 kg/kkg

          24-hour maximum

          (1.1 mg/1) (120 mVkkg)(kg/10« mg) (1 000 1/m*)
          • » 0.13 kg/kkg

      b.   Nickel
                               325

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        TABLE  14-10.    BAT EFFLUENT LIMITATIONS FOR NICKEL SALTS
Toxic
Pollutants
                 Long - Term
                 Avg. Cmg/1)
                          CD
VFR
   CD
          Cone. Basis
               Cmg/1)
                                                           Effluent Limit
                                                              .(kg/kkg)
30-day  24-hr.  30-day  24-hr.
 avg.     max.   avg.     max.
Copper
*i
Nickel
0.3
0.3
1.2/3.6
1.2/3.6
0.36
0.36
1.1
1.1
0.00024 0.00074
0.00024 0.00074
VFR - Variability Factor Ratio


(1)  Based upon limitations promulgated for the nickel sulfate  sub-
     category in Phase I.
                            326

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     TABLE 14-11.   BAT EFFLUENT LIMITATIONS FOR NICKEL CARBONATE
Toxic
Pollutants
Copper
Nickel
Long-Term d)
Avg.(mg/l)
0.3
0.3
Cone. Basis '
(mg/1)
m 30-day
VFR1- J avg.
1.2/3,6 0.36
1.2/3.6 0.36
max. .
1.1
1.1
Effluent Limit
(kg/kkg)
30-day
avg.
0.042
0.042
24-hr.
max.
0.13
0.13
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated for the nickel sulfate sub-
     category in Phase I.
                              327

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          The BAT  limitations  for  nickel  are  based  upon   the   BAT
          limitations  promulgated in  Phase I  for nickel  sulfate.
          The long-term  average  value  for nickel was  0.3  mg/1  and
          the variability  factors  used were   1.2   for  a  30-day
          average   and    3.6    for    a    24-hour   maximum.    The
          concentrations that  are  derived using these values   are
          0.36  mg/1 and 1.1 mg/1  respectively.  Mass limitations
          are computed as  follows:

          1•   Nickel Salts Segment

          30-day average;

          (0.36 mg/1) (0.68 mVkkg) (kg/1 0* mg)(1000  1/m3)
          = 0.00024 kg/kkg

          24-hour  maximum;

          (1.1 mg/1) (0.68 mVkkg) (kg/1 0«  mg)(1000 l/m3)
          = 0.00074 kg/kkg

          2.   Nickel Carbonate  Segment

          30-day average

          (0.36 mg/1) (120 mVkkg) (kg/1 0«  ing) (1000 l/m*)
          » 0.042  kg/kkg

          24-hour  maximum

          (1.1 mg/1) (1 20 mVkkg) (kg/1 0« mg)( 1000 1/m')
          =0.13 kg/kkg

Basis for NSPS Effluent  Limitations

For NSPS, the Agency is  promulgating   limitations   equal  to  BAT
since  no  additional  technology  which  would remove significant
additional amounts of pollutants is known to  the   Administrator.
The  pollutants  limited include pH,  TSS, copper and nickel, and
the limitations are presented  in Tables 14-10 and 14-11.

Basis for Pretreatment Standards

The Agency is promulgating PSES and PSNS  that are   equal  to  BAT
limitations  because  BAT  provides  better removal of copper and
nickel than is achieved  by a well operated  POTW  with  secondary
treatment  installed and, therefore, these toxic pollutants would
pass through a POTW in the absence of  pretreatment.   Pollutants
regulated under PSES and PSNS  are copper  and nickel.
                              328

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Using  the summary data presented in Tabl.es 14-5, 14-10, and from
Phase I, the Agency has estimated the percent removals of  copper
and  nickel  by  comparing the untreated waste concentrations for
those two toxic metals with the treated waste concentrations  for
the  selected  BAT technology for those same two pollutants.  The
untreated waste concentrations are the average of the  raw  waste
concentrations  found  for  nickel sulfate in Phase I and the raw
waste concentrations found at nickel salts plants  in  Phase  II.
This  approach  is  reasonable because many plants produce nickel
sulfate and other nickel salts and treat the combined wastewaters
from those products in the same wastewater treatment system.  The
calculation of the percent removals is as follows:
          Copper;
Raw Waste
     BAT
          Percent Removal
 27 mg/1
 0.3 mg/1

= [(27 - 0.3)  7  (27)](100)
 98.8%
          Nickel:
Raw Waste
     BAT
          Percent Removal
 343 mg/1
 0.3 mg/1

= [(343 -  0.3)
 99.9%
                          t (343)] (100)
The percent removals are greater than the removals  achieved  for
copper  (58%)  and  nickel  (19%)  by 25% of the POTWs in the "50
Cities" study, (Fate of Priority  Pollutants  in  Publicly  Owned
Treatment  Works,  Final  Report,  EPA  440/1-82/303,  September,
1982).  Therefore, since the BAT technology  achieves  a  greater
percent  removal  of copper and nickel than is achieved by a well
operated POTW with secondary treatment, those  two  toxic  metals
would pass through a POTW in the absence of pretreatment.

Existing Sources

There are currently four indirect dischargers in the nickel salts
subcategory.   For  Pretreatment  Standards  for Existing Sources
(PSES), the Agency  is  promulgating  limitations  based  on  BAT
described  above.   The  pollutants  to be limited are copper and
nickel as presented in Tables 14-10 and 14-11.

New Sources

For Pretreatment Standards for New Sources (PSNS), the Agency  is
setting  limitations  based on NSPS.  Since NSPS is equal to BAT,
Tables 14-10 and 14-11 summarize the limitations  for  the  toxic
pollutants copper and nickel.
                              329

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                      SECTION 14

                      REFERENCES
U.S. Environmental Protection Agency, "Development Document
for Effluent Limitations Guidelines and Standards for the
Inorganic Chemicals Manufacturing Point Source Category,"
EPA Report No. 440/1-79-007, June 1980.

JRB Associates, Inc., "An Assessment of pH Control of
Process Waters in Selected Plants," Draft Report to the
Office of Water Programs, U.S. Environmental Protection
Agency, 1979.
                         330

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                           SECTION 15

                    SODIUM CHLORATE INDUSTRY
INDUSTRIAL PROFILE

General Description

Most  of  the sodium chlorate produced (approximately 82 percent)
is marketed for use in the conversion to chlorine dioxide  bleach
in  the pulp and paper industry.  Sodium chlorate is also used as
a chemical intermediate in the production of other chlorates  and
of  perchlorates  (7  percent).  Agricultural uses (4 percent) of
sodium chlorate are as an herbicide, as a  defoliant  for  cotton
and  as  a  dessicant  in soybean harvesting.  Sodium chlorate is
used to a lesser extent in the processing of ore (5 percent), the
preparation of certain dyes and the processing of textiles, furs,
and the manufacture of pyrotechnics.  Industry profile  data  are
provided in Table 15-1.

Facilities  producing  sodium chlorate are usually located at the
same site as other facilities such as  pulp  mills,  chlor-alkali
plants,  and large chemical manufacturing complexes.  None of the
other  Phase  II  inorganic  chemicals  are  produced  at  sodium
chlorate  facilities.  Seven of the 13 sodium chlorate plants are
located  at  the  same   site   as   chlor-alkali   manufacturing
facilities.

There  are  13  known facilities producing sodium chlorate.  Nine
facilities are direct dischargers while four  facilities  achieve
zero   discharge   of  process  water.   There  are  no  indirect
dischargers in this subcategory.

The total annual production of sodium chlorate is estimated to be
between 250,000 and 300,000 metric tons.   In 1981 sodium chlorate
production was estimated to be about 274,000 metric tons  by  the
Bureau of the Census.

Total   daily   discharge  from  sodium  chlorate  production  is
estimated at greater than 17,000 cubic  meters  (four  facilities
achieve zero discharge).

General Process Description and Raw Materials

Sodium  chlorate  is  produced  by  the  electrolysis  of  sodium
chloride solution (brine) in diaphragmless electrochemical cells.
In older plants, cells with graphite anodes are  used  while  the
newer  plants are using titanium anodes.   Steel cathodes are used
                              331

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           TABLE 15-1.  SUBCATEGORY PROFILE DATA FOR
                        SODIUM CHLORATE
Number of Plants in Subcategory
     13
Total Subcategory Production Rate
     Minimum
     Maximum
250,000-300,000 kkg/yr
  2,300 kkg/yr
 54,000 kkg/yr
Total Subcategory Wastewater Discharge >17,000 m3/day
     Minimum                                 0 m3/day
     Maximum                             8,180 m3/day
Types of Wastewater Discharge
     Direct
     Indirect
     Zero
      9
      0
      4
                          332

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uniformly across  the  industry.
follows:

          NaCl + 3H20 = NaC103 +
                                   The  overall  reaction  is  as
                                 3H
The  brine  for  the  electrolysis  may  be obtained from natural
brines, or rock salt (NaCl) or pure  salt  may  be  dissolved  -in
water  to  produce  a brine.  The brine is then purified by using
sodium  carbonate  (Na2C03)  and  sodium  hydroxide    (NaOH)   to
precipitate  calcium  carbonate  and magnesium hydroxide (1 ).  At
some facilities, barium chloride (BaCl2) is also added to  remove
sulfate.   The  total  concentration  of  calcium  plus magnesium
should be less than 10 mg/1 to prevent  fouling  of  the  cathode
(1).   The  brine is; filtered to remove the calcium and magnesium
precipitates prior tp introduction into the cell (1).  Sufficient
hydrochloric acid is added to maintain the pH of the -cell  liquor
at   approximately   6.5.   At  a  higher  pH,  oxygen  evolution
increases.  At a lower pH, chlorine evolution increases, and both
effects are undesirable (1).  Noncontact cooling water is used to
maintain the temperature of the electrolytic cells  between  55°C
and 90°C, depending upon the process technology used (V).

Sodium  dichromate  is  added to the electrolytic cells to form a
layer of hydrated chromium oxide on the cathode  to  prevent  the
following undesirable reactions (1):

     CIO- + H20 + 2e- » Cl- + 2 OH~

     C103- + 3 H20 + 6e- = Cl~ + 6 OH~

The  dichromate  also  acts as a buffer to maintain the pH of the
cell at  a  near  optimum  value  by  the  following  equilibrium
reaction ( 1 ) ;
     Cr207 —
                H20
2 CrO«. -- + 2H+
The  sodium  dichromate  also  acts  to reduce corrosion of steel
surfaces and inhibit the reduction of chlorate  and  hypochlorite
(1).  The cell concentration of sodium dichromate ranges from 900
to  5,000  mg/1 and approximately 0.5 to 5 kg (1 to 10 Ib/ton) of
sodium dichromate are consumed per metric ton of  product  (1,2).
Sodium  dichromate  is added to the electrolytic cells regardless
of the type of anode used (graphite or titanium).

Hydrogen and chlorine gas  are  evolved  in  the  manufacture  of
sodium  chlorate.   The  chlorine  gas  is  often scrubbed with a
sodium  hydroxide  solution  to  remove  hydrochloric  acid   and
chlorine   gas  (1).   The  hydrogen  gas  is  either  vented  or
recovered.
                              333

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                                      04
                                      at
334

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After electrolysis,  the  sodium  chlorate  liquor  is  fed  into
"dehypo"     tanks     to     destroy    residual    hypochlorite
(dehypochlorination) (1).  The hypochlorite  is  destroyed  by  a
combination  of  heat (live steam) and chemical reduction (sodium
formate, urea, or sodium  sulfite).   Barium  chloride  often  is
added  to  precipitate  the chromate as barium chromate (2).  The
liquor is then filtered.  The filtered liquor may be sold as  is,
or,  if  the customer prefers solid sodium chlorate, the filtered
liquor is concentrated in an evaporator  for  crystallization  of
the  product.   Soda ash is added to control the pH of the liquor
in  the  evaporator.   In  the  evaporator,   the   solution   is
concentrated  to  precipitate  sodium  chloride.   The vapors are
condensed and may become a source of  wastewater  depending  upon
the  type  of  condenser  used.   The  liquor is then filtered or
allowed to settle to remove sodium  chloride  from  the  product.
The sodium chloride is returned to the salt dissolver for reuse.

The  liquor  is cooled to produce sodium chlorate crystals in the
crystallizer.  The crystals are centrifuged and dried to  produce
solid   sodium   chlorate.   The  centrate  is  recycled  to  the
evaporator for reuse.

The product  is either marketed as  a  solid  or  as  a  solution.
Figure  15-1  shows  a  general  process  flow  diagram  for  the
manufacture  of sodium chlorate.

WATER USE AND WASTEWATER SOURCE CHARACTERISTICS

Water Use

Noncontact cooling water is the single largest use  of  water  in
the production of sodium chlorate.  In addition, water is used in
direct  process contact as a reaction medium with a portion going
into the dry product as its  water  of  crystallization.   Plants
producing  solution-grade sodium chlorate incorporate much of the
direct contact process water as the solution water  in the product
shipped.   Small  amounts  of  water  are  used  for  maintenance
purposes, washdowns, cleanups, filtration, backwashing, etc., and
the  majority  of  plants use water in wet scrubbers.  Water uses
for plants producing sodium chlorate are summarized from industry
responses to the Agency's request for information   under  section
308  of  the Act  and  engineering  visit reports  in Table 15-2.
Table   15-2(a)  shows  the  relationships  between  type  of  raw
materials,   type  of product, water 'use, and discharge status for
11  of  the   13  plants  in  the   industry.     (Little   detailed
information   is  available  for  the other two plants, as one was
being rebuilt, and the other did not have data.  Both plants  are
associated with paper mills).
                               335

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 Wastewater 'Sources

 Table  15-3 summarizes flow volumes from wastewater streams in the
 sodium chlorate industry.   Noncontact cooling water which is used
 to maintain  the temperature of the electrolytic cells  is the main
 source  of  wastewater.   This stream is frequently comingled with
 process wastewater and  may  or  may  not   be  treated  prior  to
 discharge.    One  source of process water  stems from purification
 of the brine fed to the  electrolytic cells.   Purification of this
 brine  is accomplished by the addition of caustic  soda  and  soda
 ash  to  precipitate metal impurities.   This  purification process
 results in wastewater produced  with  the sludge  (precipitated
 metal   hydroxides).    The  purified brine  is  then  electrolyzed in
 the  cells.   The  cell liquor  from  the  electrolytic  cells  is
 filtered  and  the  filter  backwash  may   be a source of process
 wastewater.   The filtered cell liquor following chlorination  and
 electrolysis  is  partially  evaporated to effect  crystallization
 and  the  resulting  slurry  is  filtered.    The  mother   liquor
 resulting from  the  crystallization  step is either  recycled to
 brine    purification  or    to   the   evaporator    for   further-
 concentration.     An  additional   source  of   process   wastewater
 includes brine  and caustic  discharged   by air scrubbers  which
 remove HC1 and  C12 from  cell  off-gases.  Other process wastewater
 is   generated  from  cell   washdown,   filter   bag  wash,  leaks and
 spills.   This liquor and the  scrubber water may be recycled  or
 discharged,   generally  with   neutralization  and sedimentation as
 the  only treatment.   Barometric condenser  water is a major source
 of process wastewater at one   plant.    Table   15-3(a)   shows  the
 derivation    of    the   model   plant  for the sodium  chlorate
 subcategory.

 DESCRIPTION  OF  PLANTS VISITED AND SAMPLED

 Six  of  the 13 plants which produce sodium  chlorate  were  visited
 during  the study program.   Of  these,  four  plants were  sampled for
 toxic   and   conventional   pollutants.    All   four   sampled plants
 (F122,  F149,  F146  and F112) produce sodium chlorate  (NaC103)   by
 the  electrolysis  of brine similar to the  process  shown  in Figure
 I O~" I  •

 Plants  Sampled

At Plant  F122, rock  salt is dissolved in recycled  water  from  the
 barometric condenser  and river  water  to make  up the  brine  for  the
process.   The  brine  is purified  to  remove calcium  carbonate  and
 calcium sulfate, passed  through a  sand filter   and   then   further
 treated   to   inhibit  corrosion.  The  feed  solution then  undergoes
 chlorination and electrolysis at the  cells and  the cell  liquor  is
                              338

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evaporated to  produce  sodium  chlorate  crystals.
product is sold as solid sodium chlorate.
Almost  all
River  water  is  also  used  as  make-up  for the cooling water.
Slowdown from the cooling tower collects  in  the  cooling  water
supply sump and is discharged.  The cooling water is treated with
a  corrosion  inhibitor.  All of the barometric condensate in the
process area is recycled to the  salt  dissolving  pit.   Contact
wastewater  from  spills,  washdown,  roof  and  floor  drains is
collected in the sumps.  Part of this sump liquor is recycled and
the rest is discharged.  Wastewater from the chlorate process  in
excess  of  that  recycled  is  discharged  to an on-site lagoon.
Effluents from other product processes also flow into the  lagoon
from  where  they  are  discharged to surface water.  Figure 15-2
presents the sodium chlorate process and sampling points at Plant
FT 22.

Sodium chloride from another on-site process is used in preparing
the brine solution  used  in  Plant  149.   The  brine  is  first
prepared  and  treated,  then   is  fed to the electrolytic cells,
after which the solution undergoes treatment and filtration.  The
liquid product is partly  marketed  and  partly  used  captively.
Brine  purification  wastes  are  attributed to the other on-site
process, hence, no brine purification wastes are assigned to  the
sodium chlorate process at this plant.

Sources   of   process   wastewater  include  brine  and  caustic
discharged by the air scrubbers, equipment leaks and spills, pump
seal leaks, and equipment washdown.  Equipment washdown  includes
general  area washdown plus scheduled maintenance of the chlorate
electrolytic cells and  cleaning  of  the  product  filter.   The
process   wastewater  consists  of  the  equipment  washdown  and
maintenance wastewater plus the small  portion  of  the  scrubber
wastewater  and  product filter backwash that cannot be recycled.
All  process  wastewater  is  combined   with   other   inorganic
industrial   wastewater   sources,  and  undergoes  equalization,
neutralization and sedimentation before  being  discharged  to   a
river.   The process steps and wastewater sampling points at Plant
F149 are shown in Figure  15-3.

Plant  F146  uses  purified   brine  obtained from another on-site
operation.  The brine  undergoes further  treatment and   filtration
to   remove   impurities.   Chlorine  is added  to  the  brine prior  to
electrolysis for pH control  in  the  cell.   Sodium   dichromate   is
also  added  to  the   brine.    The  cell   liquor  produced during
electrolysis is resaturated with sodium  chloride,   treated  with
urea  to remove  hypochlorites, and  filtered  to produce a sodium
chlorate solution.
                               341

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 The contact wastewater sources  consist  of  a  strong  and  weak
 liquor.    The  strong  liquor results from drainage from the cell
 pad sump and is recycled internally  to  the  brine  purification
 resaturator.   The weak liquor consists of overflow from the brine
 purification  filter,  and  drainage  from  the overflow filtrate
 receiver and clarified water, and is recycled to the brine  pond.
 Hence, most brine purification wastes are attributed to the other
 on-site  process,  and little to sodium chlorate production at this
 plant.    Noncontact  cooling  water (treated for corrosion and pH
 control) is recycled to a cooling tower,  and tower  blowdown  may
 be  discharged  either  manually  or automatically to a rainwater
 sump.  Plant  effluent consists primarily  of pump  seal  and  tank
 seal water  but   also  contains the overflow from the strong and
 weak liquor sumps,  rainwater and blowdown from the cooling tower.
 The effluent  is discharged to another plant downstream  from  the
 chlorate  process  and undergoes neutralization and sedimentation
 before discharge   into  the  river.    Figure  15-4  presents  the
 wastewater sampling points and process steps at Plant F146.

 Plant  FT 12  obtains  salt  from  an off-site source.   A brine is
 produced,  treated with sodium carbonate and caustic,  and filtered
 before being  fed  to the electrolytic cells.    The  solution   then
 undergoes   dehypochlorination  and  resaturation.    The  product
 solution also undergoes final adjustment   with  water  and  brine
 before   being  marketed  either  as solid sodium chlorate or as a
 sodium   chlorate   solution.    The  filter  residue   from   brine
 purification   is   dried  to  80-90 percent solids and disposed as
 solid waste.   There is no wastewater from the brine  purification
 process  at  this  plant.    The plant  does not filter the product
 solution and  has  no product filter backwash  water.

 Noncontact  cooling  water  blowdown is the  only  wastewater stream
 generated   at  the   facility  and  is  discharged to a  river.   The
 cooling  water is  treated  for corrosion control  and  also undergoes
 chlorination  with C12  gas and pH  adjustment  with   H2S04 before
 final  discharge.    All   water  from  the process   area sumps  is
 recycled to the salt feed tanks.   Figure  15-5  shows  the  process
 steps and sampling  points at Plant FT 12.
Table  15-4  shows  the  wastewater  stream
concentrations for the four sampled plants.

Other Plants Visited
flow  and  pollutant
The production of sodium chlorate at Plant F103 begins  with  the
dissolution  of rock salt in water and treatment of the resulting
brine to remove impurities.  The solution is adjusted for pH  and
electrolyzed.    Caustic  and  urea  are  then  added  to  reduce
hypochlorite concentrations, the pH is adjusted  and  the  liquor
                              346

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filtered.   The  filtrate  is  evaporated and the hot solution is
filtered and cooled to precipitate sodium chlorate crystals which
are recovered by centrifuge.

Wastewater discharge consists  primarily  of  noncontact  cooling
water   which   is  not  treated  prior  to  discharge.   Process
wastewater from the spray condensers (less than four  percent  of
total) may also be discharged; however, most of the condensate is
recycled  along  with  most  other  process contact wastewater as
makeup water in the salt dissolvers.  The air scrubber  discharge
is  not  recycled  to  the  process  but  is  commingled with the
noncontact cooling water.  Some of the product filter backwash is
recycled and some is discharged.   Undissolved  solids  from  the
brine  purification  process  are  commingled with the noncontact
cooling water and discharged.

Plant FT 47 combines rock salt with sodium chlorate mother   liquor
which is then purified and filtered.  The filtrate is sent  to the
electrolytic  cells.  The electrolyzed brine is treated with urea
and caustic, filtered  and  crystallized.   The  sodium  chlorate
crystals are dried, packaged and shipped.

As  mentioned  above, the mother liquor following .crystallization
is recycled to the  beginning  of  the  process.  ! The  remaining
process  wastewater,  including  filter cake from filters and air
scrubber wastewater is treated along with wastewater from another
inorganic chemical product.  Pollutants in  the  wastewater from
the  other  inorganic chemical product effect hexavalent chromium
and total residual chlorine removal.  Treatment consists  of  two
stage  neutralization  followed by settling prior to discharge to
surface water.

Summary of_ Toxic  Pollutant  Data

Ten toxic metals  were found  in significant concentrations  in  the
raw  wastewater   streams  at  the four sampled plants.  Chromium,
antimony, copper  and  lead appeared  in  the highest concentrations.
A number of metals  (e.g. arsenic, silver, thallium) were found at
very  low concentrations  in  three of  the four plants,   with  Plant
FT 49  containing  the maximum  observed  concentration for these and
several  of the other metals.  Toxic  organics were  found   at  all
sampled  plants   with  the  exception of Plant F112  (cooling water
only).   Chloroform was the  only organic found  in  common   at  the
three remaining plants.  Maximum observed concentrations  in total
combined raw  wastewater   streams   of  the  sampled   plants  are
summarized below.
                               349

-------
TABLE 15-5.  TOXIC POLLUTANT RAW WASTEWATER DATA FOR SAMPLED
                 SODIUM CHLORATE FACILITIES

Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Thallium
Zinc
Average
F149
1.933
0.00052
0.210
0.00006
<0.010
<:0. 000003
17.000
0.00455
1.227
0.00033
1.033
0.00028
0.0057
0.000002
0.640
0.00017
0.357
0.0001
0.577
0.00015
0.540
0.00014
Daily Pollutant Concentrations and Loads
mg/1

F146
<0.106
<0. 00083
<0.005
<0. 00004
<0.010
<0. 00008
0.246
0.00193
0.090
0.00071
0.022
0.00017
<0.002
<0. 00002
0.039
0.00031
<0.001
<0. 00001
<0.068
<0. 00053
0.140
0.0011
kg/kkg
F122
0.459
0.121
<0.0027
<0. 00071
<0.0043
<0. 00113
1.300
0.342
0.021
0.00553
<0.0041
<0. 00108
0.145
0.0382
0.149
0.0392
0.013
0.00342
<0.031
<0. 00816
0.012
0.00316

F112(D
0.333
0.00084
<0.004
<0. 00001
<0.023
<0. 00006
0.239
0.00060
0.357
0.00090
0.215
0.00054
<0.008
<0. 00002
<0.117
<0. 00030
0.001
0.000003
<0.150
<0. 00038
0.613
0.00155

Avg. (2)
<0.833
<0.0408
<0.073
<0. 00027
<0.0081
<0. 00040
6.182
0.116
0.446
0.00219
<0.353
<0. 00051
<0.051
<0.0127
0.276
0.0132
<0.124
<0. 00118
<0.225
<0. 00295
0.231
0.00147
1. Cooling Tower Slowdown only.
2. Includes only those plants with process wastewater samples.
  does not include Plant F112.
                       350

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     Pollutant
Maximum Concentration Observed
             (ug/1)
Antimony
Arsenic
Chromium
Copper
Lead
Mercury
Nickel
Silver
Thallium
Zinc
2,000
610
20,000
2,300
1,300
220
690
500
1,100
1,100
     Benzene
     Chloroform
     1,2-Dichloroethane
     Dichlorobromoethane
     Chlorodibromoethane
     Carbon Tetrachloride
     Methyl Chloride
     Methylene Chloride
     Trichlorofluoromethane
                 83
                220
              4,710
                 95
                 27
                 19
                183
                 12
                 27
Section  5  of  this  report  describes  the   sampling   program
methodology.   In  the  sodium  chlorate industry, twelve days of
sampling were conducted.  Twenty-one  streams  were  sampled  and
analyzed.   The evaluation of toxic metal pollutants was based on
778  analytical  data  points  while  toxic  organics  evaluation
consisted  of  2,280 analytical data points.  Table 15-5 presents
the  toxic  pollutant  raw  waste  data  as  the  average   daily
concentrations  found  in  the  combined  raw  wastewater  at the
individual  plants.   The  overall  averages  for   the   various
pollutants are also included.

POLLUTION ABATEMENT OPTIONS

Toxic Pollutants of_ Concern

Toxic  metals  found  in  high  concentrations in the wastewaters
during sampling include chromium, lead  and  antimony.   Chromium
results  from  the  addition  of  sodium  dichromate  to  inhibit
corrosion and to reduce the formation of hypochlorite ion.  Other
metals detected in the wastewaters may be contained  in  the  raw
material  feed (brines or rock salt) which,  in some cases, may be
obtained from other product process  wastewater  streams.   These
impurities  may be released to sodium chlorate wastewater streams
                               351

-------
 during  purification processes.   The  extensive use of  recycling  in
 this  industry  tends  to  build   up   the  concentration  of   toxic
 pollutants   in  the  mother  liquor   and  in  purges,   leaks and
 washdowns.

 While nine  toxic organics were  found above 10 ug/1   in  the raw
 wastewater   streams,   only one  pollutant,  1,2-Dichloroethane, was
 found at  significantly higher concentrations.   This pollutant was
 present in  all wastewater streams sampled at one   facility.   Its
 source  is   considered  to  be   the   river water  which is used  to
 dissolve  the feed salt.   The 1,2-Dichloroethane concentration   in
 the   sampled river water was 13,700  ug/1 as opposed to 4,710 ug/1
 found  in  the  total   raw  waste  of  the  plant.     Since   the
 1,2-Dichloroethane  was found at only one plant and is related  to
 its presence in the intake water at  that  plant,   the   Agency   is
 excluding  that  pollutant  under  Paragraph  8(a)  (iii)  of the
 Settlement  Agreement.

 During  a  visit to one  sodium chlorate facility,   plant  personnel
 indicated  that  chlorinated organics are generated by the use  of
 graphite  anodes;  however,  they  also  indicated that they had   no
 data  to  demonstrate  which chlorinated organics  are generated  or
 the amount  generated.

 Existing  Wastewater Control and  Treatment  Practices

 Control and treatment   technologies   at  the  plants   which  were
 visited   and  sampled   were  discussed   previously.    Control and
 treatment practices at   the remaining  sodium  chlorate  plants
 (F141,  F114,   F131,   Fill,   F136,   F105  andF135) are  discussed
 briefly below.

 Plant F141  does not discharge any process  wastewater.   Two   lined
 evaporation ponds  allow  for solar  evaporation and total recycle
 of the process  wastewater  streams.   The plant  is   located  in   an
 arid  region  of   the   country.   Approximately  15,000  mVday  of
 noncontact  cooling  water  is discharged  to   surface  water  during
 the  summer months only.    The  plant uses  pure  salt as the raw
material  and has  minimal   brine  purification  wastewater.    The
product is  sold as  solid sodium  chlorate.

Process wastewater  streams  in Plant  FIT4 are  recycled  and blended
with  a brine solution obtained  from  an adjacent plant.   In  1980,
the plant was  in  the process  of  installing  a  liquid ring hydrogen
compressor  which  would allow  reuse of the  gas as a  boiler   fuel.
Seal  water  from  the   installed  compressor   would   be the only
process wastewater  discharged from the  plant.   Brine purification
wastes are  attributed to the  adjacent plant  which  provides  the
purified brine.   The product  is sold  as  the solution only.
                              352

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Plant  FT 31  does  not discharge any wastewater streams to either
surface waters or treatment facilities.  Noncontact•cooling water
is discharged to  ah  in-plant  holding  pond  for  use  in  dust
control.   The  plant  uses a pure salt as the raw material, with
minimal brine purification wastes.  The plant does not  have  air
scrubbers, and produces only solution grade sodium chlorate.  The
product is not .filtered before shipment.

Plant  Fill  discharges  all wastewater streams to surface water.
The largest source  of  wastewater  flow  is  noricpntact  cooling
water.   Sources  of  process  contact  wastewater  include brine
purification and product filter backwashes, chlorate  trench  and
cell  flush  streams,  barometric  condensate,  and water used to
purify hydrogen from  cell  off-gases.   No   information  on  any
wastewater  treatment, including  in-plant treatment, is available
but limited effluent data indicate  that  chlorine  and  chromium
levels   in the discharge are low.  The plant  uses an impure brine
as raw material.  Most of .the product  is  sold  as  solid  sodium
chlorate.

At  Plant F136, the source of raw material is purified brine from
an adjacent chlor-alkali plant.   Most wastewater is recycled, but
excess air scrubber wastewater, washwater  (cell wash and tank car
wash)  and  pump  seal  water  is  combined   with   chlor-alkali
wastewater  and noncontact cooling water before pH  adjustment and
discharge.

At Plant F105, wastewater streams consisting  of  equipment  wash
water  and  cooling water are combined with pulp mill wastewater,
clarified and aerated.  The final effluent is discharged directly
to surface water.
Plant  F135   combines  wastewater  streams   from   sodium   chlorate
production   with pulp mill  effluent.   No information  is  available
on wastewater  treatment  technologies  at this   plant.   The   final
effluent  is  discharged to surface water.

Other  Applicable Control/Treatment  Technologies            ,

The  existing treatment technology in  the sodium  chlorate industry
consists  of  pH   adjustment   and   sedimentation as the  result of
combination  with wastewater streams from   other   products.    Many
facilities   combine process   wastewater   with  large volumes of
noncontact cooling water for  discharge.  Of the  plants  which  do
discharge,   only   one  case  is known where treatment effects the
removal of toxic metals  and chlorine.  Over half of the  plants in
the  industry also  practice  either complete or extensive  recycling
of process wastewater.   Other  identified   control   or  treatment
technologies   which   might   be  applicable  include hexavalent
                               353

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chromium   reduction,
reduction.
dual-media   filtration,   and   chlorine
The Zero Discharge Option

The  amount of process wastewater  that  can  be  recycled  and reused
in the process depends   critically on   the source  of  the  raw
material   (whether natural brines, purified brines, rock  salt, or
purified salt) and on the type of  product   sold   (whether  solid
sodium chlorate or in water solution).   Plants using rock salt or
purified   salt  can  recycle much  of  the process water, including
barometric condenser water, to dissolve the salt;  .plants  using
brines  cannot recycle much water  for this  purpose.  Plants using
purified brine or purified salt generate minimal amounts  of brine
purification process  wastewater   whereas   plants  using  natural
brines  or rock  salt must purify the  brine before electrolysis,
thus generating a significant amount  of wastewater.  Plants  that
produce  a considerable portion of product as the water  solution
eliminate  a significant  amount of  water that would  otherwise  be
process  wastewater  with the product shipped.  All four  existing
plants that have achieved zero discharge use a purified  salt  as
raw material and three of the four ship a considerable  portion of
the  product  in solution (the one plant of these four  that ships
primarily  solid sodium chlorate is located  in  an arid   region  of
the  country  and  recycles  process  water  through an evaporation
pond).

One other  zero discharge plant is  also  located in an arid region.
A third plant uses a very pure salt from an adjacent   plant  and
generates  no brine purification wastewater,  which allows  complete
recycle  of  the  remaining process wastewater.  The fourth plant
evaporates the water from the  residue   from  brine  purification
(there  is  little water generated from purification of the brine
from a purified salt anyhow), and  does   not filter  its  product
solution,  thus  eliminating that  source of wastewater  also.  The
customers  for  the  fourth  plant  apparently do  not   require
filtration  of  the  product  solution.   Since  the  four plants
achieve zero discharge through special  circumstances  (access  to
an  economic  source  of  purified  salt, customer preference for
solution grade product,  and/or location in  an  arid region of  the
country),  the  zero discharge option is not technically  feasible
for the average plant.

Process Modifications and Technology  Transfer  Options

Process modifications  which  have  been implemented   at  sodium
chlorate  plants  which  reduce  the  amount  of process wastewater
discharged include the following:
                              354

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     1.
     2.
Recycle of scrubber wastewater within the
improve reagent utilization.
scrubber  to
     3.
Use of sodium hydroxide as the alkali in the  scrubbers
so  that  the  water is amenable to reuse in the plant.
Calcium-based  alkalies  reduce   the   efficiency   of
electrodes by forming a coating on the electrode

Use of noncontact evaporators and crystallizers in  the
production  of solid sodium chlorate.  Noncontact water
would thus be used which would  reduce  the  amount  of
process   contact  water.   Plants  practicing  contact
cooling  through  the  use  of  barometric   condensers
generate   large   amounts   of  slightly  contaminated
wastewater.  Two plants use the contact  cooling  water
to dissolve the raw salt to make the brine.
     4,
Operations using rock salt use the recycled
in dissolving the salt..
  wastewater
     5.   Use of a coated titanium anode instead  of  a  graphite
          electrode.    Graphite   electrodes  may  contain  lead
          dioxide and are  also  consumed  more  rapidly  in  the
          process.  The elimination of a source of lead,  reduced
          generation  of  solid waste (graphite), and elimination
          of a source of chlorinated  organics  can  be  obtained
          using  coated  titanium  anodes.   However, the primary
          reason  many  manufacturers  are  switching  to  coated
          titanium anodes is increased electrical efficiency.

No  other process modifications or technology options which would
reduce the amount of wastewater discharged were identified.


Best Management Practices

Recycle  of  some  wastewater  streams  is  already   extensively
practiced  in this industry.  Collection and recycle of pump seal
water and spills is employed at several facilities.  Rain  water,
to  the  extent  possible, should be diverted around salt storage
pads and other contact areas.  The use of high  purity  brine  or
salt  can  minimize  pretreatment  of  the salt and generation of
wastewater; however, the purity of the salt used  is  usually  an
economic  decision.   In combination with recycle the use of high
purity salt may enable the attainment of zero discharge.

The use of chromate and its concentration in the cell  should  be
reduced  to  the  lowest  concentration  feasible for cell use to
                              355

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reduce the cost of production and reduce  the cost of  wastewater
treatment.

Advanced Treatment Technology

In  some  case,  additional  treatment  may be required, to reduce
chromium and antimony to lower concentrations.  Level 2 treatment
technology may be needed to accomplish adequate removal.

Selection of Appropriate Technology and Equipment

Technologies for Different Treatment Levels

A.   Level 1

Level 1 treatment consists of hexavalent  chromium  and  chlorine
reduction,  alkaline  precipitation,  settling, pH adjustment and
sludge dewatering.  This technology is illustrated in Figure  10-
16.   A  holding basin for equalization sized to retain 4-6 hours
of flow is •. provided.

The pH of wastewater leaving the holding basin must be reduced by
the addition of concentrated sulfuric acid to a pH range of 2  to
3.   This  pH  is  necessary  to  reduce  hexavalent  chromium to
trivalent chromium.  A reducing agent such as sodium bisulfite is
then  added   to   the   wastewater   (sulfur   dioxide,   sodium
metabisulfite,  or  ferrous  iron  are alternative reagents which
could also be used to reduce hexavalent chromium).  Hydrated lime
is  then  added  to  the  wastewater  to  elevate   the   pH   to
approximately  8.5  to  produce  a chromium (trivalent) hydroxide
precipitate.  The chromium hydroxide and other solids are allowed
to settle in a clarifier.  The overflow  from  the  clarifier  is
aerated  and  neutralized  (if  necessary)  before  discharge.  A
monitoring system is  installed  at  the  discharge  point.   The
reducing agent, sodium bisulfite, is also effective as a means of
total residual chlorine reduction.

Sludge  collected  in the clarifier is directed to a filter press
for dewatering.  Pits are provided at the filter  press  for  the
temporary   storage   of  sludge.   The  sludge  is  periodically
transported off-site  to  a  hazardous  material  landfill.   The
objective  of  Level  1 is to reduce the chlorine residual and to
reduce hexavalent chromium to trivalent  chromium,  and  then  to
precipitate  chromium, antimony, other heavy metals and suspended
solids.

Level 1 treatment was selected as the basis  of  BPT  because  it
represents   a  viable  industry  practice  for  the  control  of
hexavalent and total chromium, antimony, total residual chlorine,
                              356

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and  suspended  solids.   No  other  technologies   will   obtain
significant removals of these pollutants.  Currently, one of nine
direct  dischargers  in  the  sodium  chlorate  industry  has the
technology or its equivalent installed.  Four facilities  achieve
zero  discharge and thus would not be affected.  In addition, two
of the direct dischargers direct their wastewater to a  paper  or
pulp  mill  for  use  or treatment.  The effluent reduction to be
achieved by Level 1 technology justifies the cost Involved.
B.
Level 2
Level 2 treatment consists of granular media filtration  for  the
additional  removal  of  suspended solids containing-precipitated
chromium hydroxide and antimony from the effluent.  Sludges  from
brine  purification  and chromium hydroxide precipitates would be
removed  by  filtration.   Dual-media  filtration  is   preferred
because   it  overcomes  the  limitations  on  loadings  normally
encountered  with  sand  filters  due  to  the  high  flow  rates
encountered  in  this  subcategory.   Level 2 was selected as BAT
because it provides significant additional  removal  of  antimony
and chromium.

Equipment for Different Treatment Levels

A.   Equipment functions

A conventional type clarifier is used  to  remove  the  suspended
solids.   A  plate  and  frame  filter  press  is used for sludge
dewatering and the filtrate from the filter is  returned  to  the
lime  mixing  tank.   Level 2 requires the addition of a granular
media filter, typically anthracite and sand, to handle  a  higher
loading.  All equipment is conventional and readily available.

B.   Chemical Handling

Concentrated sulfuric  acid  is  added  to  lower  the  pH  using
conventional   acid  handling  equipment.   Sodium  bisulfite  is
manually added to a chemical feed system  which  is  fed  into  a
mixing  reaction  tank.  A conventional hydrated lime storage and
feed system is used to proportionally add the  proper  amount  of
lime.

C.   Solids Handling

Treatment sludges produced by Levels 1 and 2 are  directed  to  a
sludge  holding  basin  from which it is fed to the filter press.
The solids produced by the filter are assumed to be dewatered  to
50  percent  solids  by  volume  and  disposed  of in an off-site
                              357

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hazardous materials landfill.   The  sludge  was  assumed  to  be
hazardous because of its high metal content.

Treatment Cost Estimates

In  the  sodium  chlorate  industry, costs were developed for one
model plant representing the average production  and  flow.   The
Agency  in  developing  the  proposed regulations considered data
from all plants in the subcategory.  The Agency  used  flow  data
from the seven dischargers which provided sufficient flow data in
developing  the  model  plant unit flow (See Table 15-3(a).  (Two
dischargers did not provide flow data; those plants are pulp  and
paper  mills  using  the  typical production process and would be
expected to produce solution  grade  product  for  internal  use.
Therefore,  the  flow  from  those  two  plants is believed to be
within the range of flows observed at other  plants).   The  unit
flow does not include barometric condenser wastewater because one
of  the  three  plants  using  barometric  condensers  completely
recycles  the  barometric  condenser  wastewater  and  a   second
recycles  most  of  it.   The  barometric condenser wastewater is
considered process wastewater, and the proposed limitations would
include  pollutants  discharged  with  the  barometric  condenser
wastewater.   The  barometric  condenser  wastewater  is  high in
volume but low in  pollutant  concentrations,  and  those  plants
where   the   barometric   condenser   wastewater  is  discharged
separately from the rest of the process wastewater should have no
difficulty in achieving the proposed limitations since  treatment
of  the low volume concentrated wastewaters should be sufficient.
However, plants that mix  barometric  condenser  wastewater  with
other  process  wastewater before discharge will be at a distinct
disadvantage because the resulting wastestream will  be  high  in
volume (thus increasing treatment plant size and costs) and lower
in  concentration  of pollutants (thus reducing the efficiency of
the treatment).  In developing the proposed limitations and model
plant, the Agency  assumed  that  plants  that  mixed  barometric
condenser   wastewater   with   other  process  wastewater  could
economically separate  the  other  process  wastewater  from  the
barometric  condenser  wastewater  for treatment.  However, since
the costs for such a separation are  highly  site  specific,  the
Agency  has been unable to quantify those costs, and they are not
included  in  the  treatment  system  costs.   At  proposal,   we
requested  comment  and data on this issue.  However, no comments
or data were provided.   Therefore,  the  Agency  concludes  that
separation  of  barometric  condenser  water  from  other process
wastewater can  be  economically  accomplished.   Therefore,  the
Agency is promulgating the regulations as proposed.

General
                              358

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Production  ranges  and wastewater flow characteristics have been
presented earlier in this section and are summarized in Table 15-
1.   There are nine  direct  dischargers  and  four  plants  which
achieve  zero discharge.  No plants in this subcategory discharge
to a POTW.

A.    Sodium Chlorate

The model  plant  for  the  sodium  chlorate  subcategory  has  a
production  rate  of 32,000 metric tons per year and a daily flow
rate of 237 cubic meters per day.  These figures were used as the
basis for the treatment  cost  estimates  at  both  levels.   See
Figure 15-3(a).

Material  usage for both levels is estimated as follows:

     Chemical                  Amount      Treatment Level
H2S04 (100 percent)
NaOH ( 50 percent sol . )
Sodium Bisulfite
59.25 kg/day
152.6 kg/day
33.2 kg/day
1
1
1
Total  solid  waste  generated  is  estimated at 0.021 m3/day for
Level 1 and an additional 0.002 m3/day for Level 2.

Model Plant Treatment Costs.  On the basis  of  the  model  plant
specifications  and  design  concepts  presented  earlier  and in
Section 10, the estimated costs of treatment for one  model  with
two  levels  are  shown  in  Table  15-6.  The cost of Level 2 is
incremental to Level 1 .

Basis for Regulations                         .

Basis for BPT Limitations    •

A.   Technology Basis    -                                     ,

For BPT, the Agency is setting limitations based upon  hexavalent
chromium reduction, chlorine destruction, alkaline precipitation,
clarification,  final  pH  adjustment  (if  necessary) and sludge
dewatering (Level 1).  Of the nine  direct  dischargers  in  this
subcategory,  one  facility  has BPT or  its equivalent installed.
One additional facility may  achieve  the  BPT  levels  based  on
limited  effluent  data.   Two direct dischargers discharge their
effluent to a  paper  or  pulp  mill.    The  majority  of  direct
dischargers  currently  provide  less  than  Level 1 treatment of
process  wastewater.   Four  additional   plants   achieve   zero
discharge and thus would not be affected.
                              359

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     TABLE 15-6..  WATER EFFLUENT TREATMENT COSTS
                  FOR MODEL PLANT.
 SUBCATEGORY:  Sodium Chlorate
ANNUAL PRODUCTION:

DAILY FLOW: 	

PLANT AGE:
       52.000
               METRIC  TONS
  237
NA
	 CUBIC  METERS

YEARS   PLANT  LOCATION:
NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS,
COST CATEGORY

Facilities
Installed Equipment
   (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Wast6 Disposal) 109.0
Residual Waste Disposal
                                    COSTS  ($1,000) TO ATTAIN  LEVEL
                  21.2
191.1
42.5
38.2
29.3
322.3
52.4
109.0
0.4
27.4
5. 5
4.9
3.8
41.6
6.8
9.8
Negl.
  Total Annual Cost
                 161.8  16.6

      b. TREATMENT  DESCRIPTION
 LEVEL 1:  Hexavalent chromium' reducti9n, chlorine reduction, alkaline
            precipitation, clarification, sludge dewatering, r>H adjustment!
 LEVEL 2:  Filtration                                                      '
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B.   Flow Basis

For the sodium chlorate subcategory, a  unit  flow  rate  of  2.7
mVkkg  was  selected as being representative of the group.  This
flow was derived as shown on  Table  15-3{a).   Accordingly,  the
model  plant  has  a  daily  flow  of  237 cubic meters, based on
production of 32,000 kkg per year  and  365  operating  days  per
year.

C.   Selection of Pollutants to be Regulated

The  selection  of  pollutants  for   which   specific   effluent
limitations  are  being  established is based on an evaluation of
the  raw  wastewater  data  from  screening   and   verification,
consideration   of   the  raw  materials  used  in  the  process,
literature data,  historical  discharge  monitoring  reports  and
permit   applications,   and   the   treatability  of  the  toxic
pollutants.

Tables 8-1 through 8-14 summarize the  achievable  concentrations
of  toxic  metal  pollutants  from the literature using available
technology options, other industries, and  treatability  studies.
Water  use and discharge data are presented earlier in Section 15
together with  generalized  process  characteristics.   Pollutant
concentrations of raw wastewater streams and a summary of maximum
concentrations  observed  of  toxic  pollutants  detected  during
screening and verification sampling at several  plants  are  also
presented  earlier  in this section.  Data from Appendix A on the
performance of  in-place  industry  treatment  systems  was  also
utilized in developing the list of pollutants to be regulated.

Based  upon  the occurrence of treatable levels of specific toxic
metals, antimony and chromium were selected  as  candidate  toxic
pollutants  for BPT regulation.  Chromium is added to the process
at sodium chlorate plants.  Antimony was detected  in  cell  room
wastes  and  scrubber  discharges  at  all  four  plants sampled.
Copper, lead, thallium and zinc were detected but  at  less  than
treatable  levels.   Because  the wastewater streams that contain
hexavalent chromium  also  contain  chlorine,  and  because  both
hexavalent  chromium  and chlorine will be reduced simultaneously
by the sodium bisulfite, the Agency has  also  selected  chlorine
for regulation at the BPT level.

Consideration  of  the raw wastewater characteristics, widespread
industry use,  and  information  in  Section  8  related  to  the
effectiveness  of  hexavalent  chromium  and  chlorine reduction,
alkaline precipitation, and settling  led  to  the  selection  of
antimony and chromium as the toxic pollutants to be regulated.
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D.   Basis of BPT Pollutant Limitations

Limitations are presented as both concentrations  (mg/1) and loads
(kg/kkg), and the relationship between the two is based on a unit
flow rate of 2.7 mVkkg.
BPT  limitations,  which  apply   to   all
discharged, are presented in Table  15-8.
process   wastewater
     1.   Conventional Pollutants

          a.   pH

               The treated effluent  is to be controlled within
               the range of 6.0 - 9.0.  This limitation is based
               upon the data presented in Appendix B of the
               Development Document  for Proposed Effluent
               Guidelines for Phase  I Inorganic Chemicals  (Ref.
               3) and the JRB study  (Ref. 4).

          b.   TSS

               Three  Phase  II  plants   (FT 25,  FIT 5  and  F140)
               considered  to  be  efficiently  operating   their
               wastewater treatment  facilities provided long-term
               Level 1 treatment system performance data for TSS.
               TSS data from Plant F144 were not used because the
               wastewater  is  passed  through a limestone bed  in
               the first  stage  of  the  plant's  neutralization
               system.   This would  reduce  the TSS loading to the
               clarifier giving lower TSS results  than  expected
               for  the average inorganic chemicals plant.  Since
               no other data from well-operated Level 1 treatment
               systems was available, and since the clarification
               provided at plants F125, FIT 5  and  F140  for  TSS
               removal would be similar to  that necessary  for TSS
               removal   at   sodium chlorate  plants,  the  BPT
               limitations for TSS are based upon  a  summary   of
               long-term  data  from Plants F125, F115 and FT 40.
               The long-term average of  13  mg/1  was  used   to
               develop    discharge   limitations.    Variability
               factors of 1.9 for a  monthly average and 3.3 for a
               24   hour   maximum   were   used   yielding   TSS
               concentration  limits of  25  mg/1  and  43 mg/1,
               respectively.   The   monthly average  variability
               factor  was  obtained from the variability  factors
               from  all  three  plants   with   long-term   data
               employing  Level 1 type treatment.  Since the data
               from all three plants was  not  in  a  form  which
                               362

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          could be used to develop daily maximum variability
          factors,  the  daily maximum variability factor of
          3.0 for filters was  adjusted  upward  by  10%  to
          account  for  the  higher  variability experienced
          with clarification only.   Thus,  utilizing  these
          values,  one  obtains TSS mass limitations for the
          sodium chlorate subcategory of:

          30-day average;

          (25 mg/l)(2.7 mVkkg) (kg/1 0* rag)(1000,1/m*)
          =0.068 kg/kkg

          24-hour maximum;                   .

          (43 mg/l)(2.7 m*/kkg)(kg/10« mg)(1000 l/m*)
          - 0.12 kg/kkg

2.   Toxic Pollutants

     a.    Chromium (Total)

          Since there is no long-term performance  data  for
          this    subcategory,    the    long-term   average
          concentration for chromium is based on  industrial
          wastewater  system performance data found in Table
          8-12   and   the   promulgated   total    chromium
          limitations for the sodium dichromate subcategory,
          which  uses  a similar wastewater treatment system
          for  chromium  control.   The  variability  factor
          ratio  is  based  on  those  used  for  the Sodium
          Dichromate  subcategory.   The  long-term  average
          used  was  0.25  mg/1.   Variability factors of 2.0
          for the 30-day average and  4.0  for  the  24-hour
          maximum  from  the  Sodium  Dichromate subcategory
          were used, yielding chromium  limitations  of  0.5
          mg/1  and  1.0  mg/1 respectively.  Thus utilizing
          these values,  mass  limitations  for  the  sodium
          chlorate subcategory may be obtained as follows;

          30-day average;

          (0.5 mg/1) (2.7 mVkkg) (kg/10« mgMlOOO 1/m*)
          =0.0014 kg/kkg

          24-hour maximum;

          (1.0 mg/1) (2.7 mVkkg) (kg/10« mg)(1000 l/m*)
          = 0.0027 kg/kkg
                         363

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     b.    Antimony (total)

          Since there is no  long-term  average  performance
          data  for  this  industry,  the  long-term average
          concentration for antimony is based on  industrial
          wastewater treatment system performance data found
          in  Table  8-11.   The  lowest reported achievable
          concentration   for   antimony   with    a    lime
          precipitation  and clarification system (0.8 mg/1)
          was  used  as  the   long   term   average.    The
          variability  factors of 2.0 for 30-day average and
          4.0 for the 24-hour maximum used for chromium were
          used  for  antimony,  yielding  antimony  effluent
          concentrations   of   1.6   mg/1   and   3.2  mg/1
          respectively.   Utilizing   these   values,   mass
          limitations for antimony are obtained as follows:

          30-day average;

          (1.6 mg/1) (2. 7 mVkkg)(kg/1 0«mg)( 1000 l/m»)
          = 0.0043 kg/kkg

          24-hour maximum;

          (3.2 mg/1)(2.7 mVkkg)(kg/10«mg)(1000 l/m»)
          = 0.0086 kg/kkg

3.    Non-conventional Pollutants

     a.    Chlorine (Total Residual)

          Since there is no long-term performance  data  for
          this  industry,  the  BPT limitations for chlorine
          are based on the  long-term  monitoring  data  for
          chlorine  in  the  chlor-alkali  subcategory which
          uses a similar wastewater treatment technology for
          chlorine control.  (See the  Phase  I  Development
          Document,  Appendix  A, Plant A).  The variability
          factors are based  on  that  same  facility.   The
          plant  is  achieving  a  long-term  average  total
          residual chlorine concentration of 0.64 mg/1.  The
          variability factors for this longterm average  are
          1.4 for the 30-day average and 2.3 for the 24-hour
          maximum.  These variability factors yield effluent
          limitations  of 0.9 mg/1 and 1.5 mg/1, for the 30-
          day average and 24-hour maximum respectively.  The
          mass  limitations  for  chlorine  in  the   sodium
          chlorate subcategory are as follows;
                         364

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          TABLE 15-7.  BPT EFFLUENT LIMITATIONS FOR SODIUM CHLORATE
Conventional
pollutants
TSS

Toxic
Pollutants

Antimony
 (Total)
                Long-Term
                Avg. (mg/1)
               13 v
                0.8*
   VFR
1.9/3.3C1)
2/4
   (2)
 Cone.  Basis
    (mg/1)
30-day  24-hr,
 avg.     max.
                                            2.5-
 1.6
        43
       Effluent Limit
          (kg/kkg)
       30-day  24-hr.
        avg.    max.
                                                            0.068    0.12
3.2    0.0043  0.0086
Chromium
 (Total)        0.25(2)

Non-Conventional
Pollutants
Chlorine
 (Total
  Residual)     0.64
                    (3)
                              2/4(2)
                              1.4/2.3
              0.5
              0.9
         1.0    0.0014  0.0027
         1.5   ' 0.0024  0.0041
LTA = Long-term average achievable level.

VFR - Variability Factor Ratio

(1) Based upon long-term data at Plants  F115,  F125  and F140.
C2) LTA used as basis for promulgated  limitations for  Sodium  Dichromate
    Subcategory - Phase I.
(3) LTA and limitations based upon promulgated total residual chlorine
    limitations for Chlor-Alkali subcategory - Phase I -  Chlor-Alkali
    Mercury Cell Subcategory.

*From Table 8-11.

See Phase I Inorganic Chemicals Development  Document;  EPA 440/1-82-007.
                             365

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               30-day average;

               (0.9 mg/l)(2.7 mVkkg) (kg/10* mg)(1000 l/m»)
               = 0.0024 kg/kkg

               24-hour maximum;

               (1.5 mg/1)(2.7 mVkkg) (kg/10* mg)(1000 l/m»>
               = 0.0041 kg/kkg

Basis for BCT Effluent Limitations

On  October  29,  1982, EPA proposed a new and revised methodology
for determination of BCT for conventional  pollutants.   In  this
subcategory,  only two conventional pollutants have been selected
for limitation, pH and total suspended solids (TSS).   Two  tests
are  required  according  to the revised methodology, a POTW test
and an industry  cost-effectiveness  test.   Under  the  proposed
methodology,  the POTW test is passed if the incremental cost per
pound of conventional pollutant removed in going from BPT to  BCT
is  less than $0.46 per pound in 1981 dollars.  The industry test
is passed if the same incremental cost per pound is less than 143
percent  of  the  incremental  cost  per  pound  associated  with
achieving BPT.

The methodology for the first BCT cost test is as follows:

(1)  Calculate the amount of additional TSS removed by the
     BCT technology.

     (a)  BPT long-term average     =  13   mg/1
          Level 2 long-term average* =  9.3 mg/1
          Difference                   3.7 mg/1

*(See Sections 11 and 12 for derivation)

     (b)  Annual  flow for model plant:
          (2.7 m3/kkg) (32,000 kkg/yr)  = 86,400 mVyr

     (c)  Total annual additional TSS removed for model plants

          (3.7 mg/1) (86,400 mVyr) (kg/10*mg) (1 000 1/m*)
          = 320 kg/yr
          = 705 Ibs/yr

(2)  Calculate incremental cost, in dollars per pound of TSS
     removed, for the model plant.

     (a)  Incremental annualized cost of Level 2 technology,
                              366

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          from Table 15-6: $16,660 per year.

     (b)  Divide annualized cost by annual TSS removal:
          ($16,600 per year) t (705 Lbs per year) = $23.56 per
          pound of TSS removed.

This   is  far  above  the  $0.46  per  pound  bench  mark  cost.
Therefore, the candidate BCT technology failed the first BCT cost
test and there is no need to apply the second BCT cost test.

On October 29, 1982, EPA  proposed  a  revised  BCT  methodology.
While  EPA  is  considering  revising  that  methodology, we have
determined that in this subcategory no technology beyond BPT will
pass the proposed BCT cost test or any other BCT  test  that  the
Agency  is  likely to adopt.  Accordingly, in this subcategory we
are setting BCT equal to BPT.  As a result, BCT for TSS is  equal
to  the  BPT  limitations.   However,  the  Agency  will  need to
reconsider the BCT limitations for this subcategory  when  a  new
BCT cost test is promulgated.

Basis for BAT Effluent Limitations

Application of Advanced Level Treatment

Utilizing  the  cost  estimates  in  this  report, the Agency has
analyzed the cost of the base level system (BPT =  Level  1)  and
the  advanced  level  option  for  toxic  pollutant removal.  The
economic impacts on the Sodium  Chlorate  Subcategory  have  been
evaluated   in   detail  and  taken  into
determination of the BAT regulations.
                                      consideration  in  the
For  BAT,  the  Agency  is  promulgating  limitations  based   on
treatment  consisting  of  Level  1  plus  Level 2.  Level 2 adds
granular media filtration of the Level  1  effluent.   The  toxic
pollutants limited by the promulgated BAT regulation are antimony
and  chromium.  The non-conventional pollutant to be regulated is
total residual chlorine.

A.   Technology Basis

The overflow from the clarifier is filtered in a  granular  media
filter  to remove additional antimony and chromium from the waste
stream.  The  backwash  from  the  filters  is  returned  to  the
clarifier or if the solids concentration is sufficiently high the
backwash  is  directed  to  the filter press for dewatering.  The
filter will not remove additional amounts of chlorine.
B.
Flow Basis
                              367

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A unit flow rate of 2.7 mVkkg of sodium chlorate wastewater  has
been selected for BAT (same as BPT).

C.   Selection of Pollutants to be Regulated

     Toxic Pollutants

Antimony and chromium have been selected as the toxic  pollutants
for  control  under BAT, as both pollutants have been detected at
sodium chlorate plants at significant, treatable  concentrations.
Table  15-9  presents the BAT limitations for the Sodium Chlorate
Subcategory.

          a.   Chromium

               Since  there  is  no  long-term  treatment  system
               performance  data for this industry, the estimated
               achievable long-term average concentration of 0.16
               mg/1 for chromium from Table 8-13 is used for  the
               long-term average.  The variability factors of 2.0
               for  the  30-day  average  and 4.0 for the 24-hour
               maximum used for chromium at  the  BPT  level  are
               used  for BAT, yielding effluent concentrations of
               0.32 mg/1 and 0.64 mg/1, respectively.   The  mass
               limitations  for  chromium  in the sodium chlorate
               subcategory are calculated as follows:

               30-day average;

               (0.32 mg/1) (2. 7 mVkkg) (kg/1 0« rag)(1000 1/m')
               = 0.00086 kg/kkg

               24-hour maximum;

               (0.64 mg/1)(2.7 m'/kkg)(kg/10«)(1000 l/m*)
               - 0.0017 kg/kkg

          b.   Antimony

               Since  there  is  no  long-term  treatment  system
               performance  data for this industry, the estimated
               achievable  long-term  average  concentration   is
               taken  from  industry  performance  data  in Table
               8-11.     The    lowest    reported     achievable
               concentration  of  0.4 mg/1 for antimony utilizing
               lime addition plus  filtration  is  taken  as  the
               long-term average.  The variability factors of 2.0
               for  30-day  average  and  4.0 for 24-hour maximum
               used for chromium are used for antimony,  yielding
                              368

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    TABLE 15-8.  BAT EFFLUENT LIMITATIONS FOR  SODIUM CHLORATE SUBCATEGORY
Toxic
Pollutants

Antimony (T)
Long-Term
Avg.(rng/1)

0,4*
   VFR
2/4
   (2)
 Cone. Basis
    (mg/1)
30-day  24-hr.
 avg.     max.
0.80
1.6
                                                            Effluent Limit
                                                               (kg/kkq)
                30-day
                 avg.
               24-hr.
                max.
                0.0022   0.0043
Chromium (T)
              2/4(2)
             0.32
        0.64
       0...00086 0.0017
Non-Conventional
Pollutants	

Chorine
  (Total
  Residual)     0.64
    (3)
              1.4/2.3
        (3)
             0.9
        1.5
       0.0024  0.0041
LTA = Long-term average achievable  level.

VFR - Variability Factor Ratio;  ratio  of  the  30-day average variability
      factor to the 24-hour maximum variability factor.
 (1) From Table  8-13.
 (2) Phase  I  Inorganic  Chemicals  Development Document;  EPA 440/1-82/007,
    variability factors  for  Sodium Dichromate.
 (3) See Table 15-7.

 *From Table  8-11.
                             369

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                effluent   antimony   concentrations  of  0.8  mg/1  and
                1.6  mg/1  respectively.   The mass  limitations   are
                calculated as  follows:

                30-day  average;

                (0.80 mg/1) (2. 7  mVkkg) (kg/1 0«) (1 000 l/m»)
                =  0.0022  kg/kkg

                24-hour maximum;

                (1.6 mg/1) (2, 7 mVkkg) (kg/1 0* rag) (1000 ' l/m»)
                =  0.0043  kg/kkg

     Non-Conventional  Pollutants

Total  residual   chlorine has been  selected for  control under  BAT
but is  not  reduced   by  Level  2  technology.    Therefore,   the
concentrations  and loading  promulgated  for BAT  are  the same as
for BPT for this  parameter.

Basis for NSPS Effluent  Limitations

For NSPS, the Agency is  promulgating  limitations based on the  BAT
technology since  no technology  which  would  remove  significant
additional  amounts of   pollutants   is  known.    The  pollutants
limited include pH, TSS,  antimony,  chromium (total), and chlorine
(total residual).

The limitations for antimony and chromium  are the  same  as  BAT.
See  pages  368 and 370  for the development of these limitations.
The limitations for pH and total residual  chloride are  the  same
as  for  BPT.  See  pages  362 and 364 for the development of those
limitations.  The TSS  limitations are based on filtration and  are
developed as follows:

     Since no long-term monitoring data for TSS  is available from
     any sodium chlorate plant with Level  2 treatment,  the  NSPS
     limitations for TSS are based on an average of long-term  TSS
     monitoring data from Plants A and K as presented in Appendix
     A  of  the  Phase I Development Document which uses the same
     Level 2 (filtration)  technology  to  control  TSS  that  is
     promulgated  for  the  sodium chlorate subcategory.  A long-
     term average of 9.3 mg/1 (the average of  both  plants)  was
     used   to  develop  the  discharge  limitations  for  plants
     employing filtration.  Variability  factors,  also  obtained
     from  Plants  A  and K,  of 1.8 for a monthly average and  3.0
     for a 24-hour maximum were used yielding  TSS  concentration
     limits of 17 mg/1 and 28 mg/1 respectively.
                              370

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   TABLE  15-9.  NSPS EFFLUENT LIMITATIONS FOR  SODIUM CHLORATE
[Conventional    Long-Term
 Pollutants      Avq.(mg/1)
 TSS             9.3

 Toxic
 Pollutants

 Antimony(T)     0.4*

 Chromium(T)     0.16<3>

 Nonconventional
 Pollutants
Chlorine
 (Total
 Residual)
                0.64<«>
                             VFR
                            2/4 < 2 )
1.4/2.3 c3
                                         Cone. Basis
                                             (mq/1)
                                        30-day
                                         avq.

                                        17
                                         0.80

                                         0.32
0.9
                      24-hr,
                       max.

                      28
                       1.6

                       0.64
1.5
                                                          Effluent Limit
                                                             (kq/kkq)
                 30-day
                  avg.

                 0.046
                 0.0022

                 0.00086
                                                           0.0024
                   24-hr.
                   max.

                   0.076
                   0.0043

                   0.0017
0.0041
|LTA -  Long-term average achievable level.

IVFR -  Variability  Factor Ratio;  ratio of  the 30-day average variability
       factor  to the 24-hour  maximum variability factor.

 (1) Based upon long-term data  at Plants  A and K. (Phase  I).
 (2) Phase I  Inorganic Chemicals Development Document; EPA 440/1-82/007,
     variability factors for Sodium Dichromate.
 (3) FRom Table 8-13.
 (4) See Table 15-7.
I*  From Table  8-11.
                               371

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 Thus,   utilizing  these  values, one obtains TSS mass limitations
 for the sodium chlorate subcategory of:

      30-day averages;

      (17 mg/l)(2.7 mVkkg) (kg/1 0* mg)(1000 1/rn*)
      = 0.046 kg/kkg

      24-hour maximum;

      (28 mg/l)(2.7 mVkkg) (kg/1 0« mg)(1000 l/m*)
      - 0.076 kg/kkg

 The NSPS limitations are found in Table 15-9.

 Basis  for Pretreatment  Standards

 Pretreatment is  necessary because it provides  better  removal   of
 antimony  and chromium  than  is achievable by a well  operated POTW
 with secondary treatment installed,  and  thereby  prevents  pass-
 through    that  would    occur  in  a   POTW in  the  absence   of
 pretreatment.

 Using  the summary  data  presented in  Tables  15-5  and   15-8,   the
 Agency  has   estimated   the  percent  removals  for  antimony  and
 chromium by  comparing the treated waste   concentration   for  the
 selected  BAT technology for  those   two  toxic metals  with  the
 average   untreated  waste concentrations  for  those  same    two
 pollutants.   The calculation is  as follows:

           Antimony;  Raw Waste  *  0.83 mg/1
                     BAT       =0.4  mg/1

           Percent  Removal -  [(0.833  -  0.4)  -r (0.8)]  (100)
                          = 52%

           Chromium  (Total); Raw  Waste  =6.2 mg/1
                            BAT        =0.16 mg/1

           Percent Removal = [(6.2  -  0.16)/(6.2)]  (100)
                          = 97%

The  percent  removal   for  total  chromium  is   greater than the
removals achieved by 25% of the  POTWs  in the   "50  Cities"  study
 (Fate  2i  Priority Pollutants in  Publicly Owned  Treatment Works,
Final Report,  EPA  440/1-82/303,  September";T9827:	There—is
limited  data available on the removal of antimony by a POTW, but
removals for other toxic metals range from  19% to 66% for 25%  of
the  POTWs  in  that study.   Therefore, the Agency believes it is
                              372

-------
prudent to assume that antimony could pass through a POTW.  Since
both chromium and antimony pass through a well operated POTW with
secondary treatment, pretreatment is necessary.

Using the summary data presented in Tables  15-5  and  15-7,  the
Agency  has  also estimated the percent removals for antimony and
total chromium by comparing the treated waste  concentration  for
the  selected  BPT technology for those two toxic metals with the
treated waste concentrations for the selected BAT technology  for
those same two pollutants.  The calculation is as follows:

          Antimony; BPT =0.8 mg/1
                    BAT =0.4 mg/1

          Percent Removal = [(0.8 - 0.4) ? (0.8)] (TOO)
                          = 50%       .

          Chromium  (Total) BPT =0.25 mg/1
                           BAT = 0.16 mg/1

          Percent Removal = [(0.25 - 0.16) -r  (0.25)3 (100)
                          = 36%

The  percent  removals  for  total  chromium  are  less  than the
removals achieved by 25% of the POTWs in the  "50  Cities"  study
for  chromium (65%).  However, a portion of the total chromium is
hexavalent chromium, which is removed poorly  by a POTW.   Federal
Guidelines:  State  and  Local Pretreatment Standards, Volume II,
EPA 430/9-16-017b, January, 1977,  page  6-51,  states  that  the
average  hexavalent  chromium  removal for plants with biological
treatment  (i.e.,  secondary  treatment)  is   18%.    Hexavalent
chromium  could  interfere  with the operation of the POTW, or be
incorporated into the sludge and thus interfere with  the   POTW's
chosen  sludge  disposal  method.   Information  from  the  chrome
pigments industry and the sodium  dichromate  industry  indicates
that  filtration does remove some additional  hexavalent chromium.
Accordingly, since additional hexavalent chromium is  removed  by
filtration, since the removal of hexavalent chromium by a POTW is
small,  and since hexavalent chromium is highly toxic, the  Agency
believes it  is  prudent  to  regulate  the   discharge  of  total
chromium,  which  includes  hexavalent  chromium in discharges to
POTW from sodium chlorate plants  with  pretreatment  limitations
based on the application of BAT technology.

There   is  only very limited data on the removal of antimony by  a
POTW available.  The removals achieved by 25% of the POTWs  in the
"50 Cities" study for other toxic metals range from 19%  to 66%.
The  removal  of  antimony  by  a  POTW  could  be less than 50%.
Therefore, the Agency believes it  is  prudent  to  regulate  the
                               373

-------
discharge  of  antimony  to  POTW in the sodium chlorate industry
with pretreatment limitations based on BAT technology.

Existing Sources

Since there are no indirect dischargers in this subcategory,  the
Agency  is excluding this subcategory from categorical PSES under
the provisions of paragraph 8(b) of the Settlement Agreement.

New Sources

The Agency is promulgating PSNS that are equal  to  NSPS  because
these standards provide for the removal of antimony and chromium,
which  would  likely  pass  through  a  well  operated  POTW with
secondary treatment in the absence of  pretreatment.   Pollutants
regulated  under PSNS are antimony and chromium.  Chlorine is not
regulated under PSNS because POTW influent is often chlorinated.
                              374

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                           SECTION 15

                           REFERENCES
1.    Coleman,  John E., '"Electrolytic Production of Sodium
     Chlorate," American Institute of Chemical Engineers
     Symposium Series 1981, vol. 77 (204), pp. 244-263.

2.    Shreve, R. Norris and Brink, Joseph A. Jr., "Chemical
     Process Industries," McGraw-Hill, 1977.

3.    U.S. Environmental Protection Agency, "Development Document
     for proposed Effluent Limitations Guidelines and Standards
     for the Inorganic Chemicals Manufacturing Point Source
     Category," EPA Report No. 440/1-79-007, June 1980.

4.    JRB Associates, Inc., "An Assessment of pH Control of
     Process Waters in Selected Plants," Draft Report to the
     Office of Water Programs, U.S. Environmental Protection
     Agency, 1979.
                               375

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                            SECTION 16

                      ZINC CHLORIDE INDUSTRY
 INDUSTRIAL PROFILE

 General Description

 Zinc chloride is manufactured primarily for market  use  although
 some  zinc  chloride  is  used  in the captive production of zinc
 ammonium chloride.   Zinc chloride is used as an ingredient in dry
 cell batteries;  oil well completion fluids; tinning;   galvanizing
 and  soldering fluxes;  and for the preservation and flameproof ing
 of  wood.   It is  also used as a deodorant,  and in disinfecting and
 embalming  fluids.    In  chemical  manufacturing,   zinc  chloride
 serves  as  a catalyst  and as a dehydrating and condensing agent.
 Further, uses include the manufacture of  parchment  paper,   dyes,
 activated  carbon  and  durable press fabrics and the printing and
 dyeing of textiles.   The industry data profile  is  presented  in
 Table 16-1 .

 There  are  seven  known producers of zinc chloride of  which five
 plants  discharge  wastewater  directly,   while   two   discharge
 indirectly.

 Production in this  subcategory is more than 25,000 tons per  year,
 while total  daily flow  is in excess of 1,500 cubic meters.

 General  Process  Description and Raw Materials

 Zinc   chloride   is   produced   by  reacting  zinc  metal   with
 hydrochloric acid and concentrating the zinc chloride solution  by
 evaporation.   The general  reaction is:
Zn
               2HC1 = ZnCl,  + H
Various forms of zinc feed material  are  used,  from  pure  zinc
metal   to   galvanizer   skimmings.    The   latter  may  contain
galvanizing fluxes, iron oxide, cadmium and  lead in  addition  to
the  zinc  metal.   Galvanizing  wastes  may  require milling and
further  processing  prior  to   use   in    the   zinc   chloride
manufacturing  process.   A zinc chloride solution is produced by
the dissolution of the zinc feed  with  hydrochloric  acid.   The
solution  is  generally  purified  by chemical addition to remove
metal salts, then filtered  and  concentrated.   The  product  is
either  marketed as a solution or further concentrated to yield a
solid product.  One facility utilizes a zinc  chloride-containing
process  wastewater containing organic chemicals from an adjacent
                              376

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           TABLE 16-1.  SUBCATEGORY PROFILE DATA FOR
                         ZINC CHLORIDE
Number of Plants in Subcategory

Total Subcategory Production Rate
     Minimum
     Maximum .
>25,000 kkg/yr
    <4.5 kkg/yr
 Confidential
Total Subcategory Wastewater Discharge    >1500 m3/<3ay
     Minimum                                 26 m3/day
     Maximum                                719 m3/day
Types of Wastewater Discharge
     Direct
     Indirect
     Zero
      5
      2
      0
                          377

-------
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       378

-------
     TABLE  16-2.  WATER USAGE AT  ZINC CHLORIDE  FACILITIES

WATER USE
Noncontact
Cooling
Direct Process
Contact ,
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
Noncontact
Ancillary
TOTALS
Flow (n\3/kkg
Plant
of Zinc
Designat
F125 F140 F120
0 0
0 1.6
4.94 13.65
NA 0.03
NA , 0
NA 0.32
4.94 , 15.6
0
0.03
0.69
0.05
1.38
0.10
2.25
Chloride)
ion
F144
0
5.67
7.56
0.05
0
NA
13.3


F143
5.7
0
1.6
0.4
3.3



3

2
2
3
1.39
12.
5
NA   Flow volume not available.


1.   Values indicated only for those plants that reported
     separate and complete information.

Source:  Section 308 Questionnaires and Plant Visit Reports
                           379

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      TABLE 16-3.  WASTEWATER AT ZINC CHLORIDE FACILITIESU)
Flow (m3/kkg of Zinc Chloride)
WASTEWATER SOURCE
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
TOTALS
Noncontact
Cooling
Noncontact
Ancillary
Storm Water

F125

0

4.94
NA

NA
4.94

0

NA
NA
Plant Designation
F140 F120 F144

1.6 0 1.89

13.65 0.69(2) 7.56
0 NA(2) 0.05

0 1.24(2) o
15.3 1.93 9.5

00 0

0.032 0.01 NA
NA ^ 7.14 0.53

F143

0

1.62
0.42

3.33
5.37

5.73

1.39
2.67
NA Flow volume not available.
1. Values indicated only for those plants that
separate and complete information.
2. Wastewater recycled within plant.
3. Storiwater un
iknown but
not zero.
repor tec

Source:  Section 308 Questionnaires and Plant Visit Reports
                          380

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facility as a raw material for  zinc  chloride  production.   The
organic  chemicals  are  removed  from that wastewater before the
zinc chloride solution is processed.  Figure 16-1 shows a general
process flow diagram for the manufacture of zinc chloride.

WATER USE AND WASTEWATER SOURCE CHARACTERIZATION

Water Use

Water is used primarily for air pollution control, in  barometric
condensers,  equipment washdowns, pump seal maintenance, and as a
reaction medium for the hydrochloric acid.  Table 16-2 summarizes
plant water use in the subcategory as  determined  from  industry
responses  to  the Agency's request for information under S308 of
the Act and engineering visit reports.

Wastewater Sources

Generally, condensate from the evaporators  used  to  concentrate
the  zinc chloride product solution and blowdown from the cooling
of the barometric condenser water constitute the major wastewater
streams.  These streams are combined  with  wastewater  from  air
pollution scrubbers, equipment washdowns, pump seal leaks and, in
some  cases, other product processes and treated before discharge
or recycle.  Table 16-3 identifies the various wastewater streams
and related daily flows for  those  zinc  chloride  plants  which
supplied  complete  data.  Storm water can contribute significant
additional water  flow  to  the  treatment  facility  at  several
plants.

DESCRIPTION OF PLANTS VISITED AND SAMPLED

Five  plants   (F118,  F120,  F140,  F144 and F145) producing zinc
chloride were visited during  the  course  of  the  program.   In
addition,  wastewater  sampling  was conducted at Plants F120 and
F144.  One of these plants, plant F120, no longer  produces  zinc
chloride  and  is  therefore  not  counted as one of the existing
seven plants.

Plants Sampled

Plant F120 produced zinc  chloride and a number of other  inorganic
products, but has since discontinued  zinc  chloride  production.
At  the  time  of  sampling,  the  plant produced a zinc  chloride
solution by  the  reaction  of   zinc-containing  waste  materials
 (galvanizer  skimmings)   with  hydrochloric acid.  A wet  scrubber
used to minimize hydrochloric acid  emissions generated   a   dilute
acid  waste.   Solids  from   the batch reactor  were hauled to an
approved  landfill site.   The  zinc  chloride  solution   was then
                               381

-------
                             -a
                            c c
                                      S O
382

-------
             ZnCl-, Other Product Process Wastewater
                           #2
                           #3
                       Limestone
                       Neutralization
                       Clarifier
                           (Underflow)
          (Centrate)
                       Centrifuge
                       Solids
                                                        -Supply .Water
                                                  #1
                                               Stormwater, Process Upsets
                                              -Other Product Process Wastewater
                                              Storm Water
                                                Reservoir
                                               -Caustic Addition
                                          #4
Discharge
                                                             Sampling Points
FIGURE 16-3.  WASTEWATER TREATMENT PROCESS AND SAMPLING LOCATIONS FOR PLANT F144.
                              383

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separated  from  unreacted  materials, and  purified  by chemical
additives to remove iron and manganese salts.   The  precipitated
salts  were  filtered  and a solution grade product was marketed.
The filter residue was slurried to the in-plant treatment system.
An   additional   wet   scrubber   stream   resulted   from   the
purification/evaporation stage.

Wastewater  from  scrubbers, equipment washdowns, pump seal leaks
and various other product processes were combined,  treated  with
lime and lagooned.  The treated wastewater was used to slurry the
purification and treatment sludges back to the settling ponds for
temporary  storage.   At the time of sampling, there had been  no
discharge of process wastewater streams in one and a half  years.
Since  the  lagoons  are  unlined,  percolation  of  part  of the
wastewater into the subsoil could account for the fact that there
has been no discharge.

Solid waste generated from rotary vacuum filtration of the  crude
product  and  from  filtration  of  the  crude after treatment to
remove impurities is slurried with  the  recycled  wastewater  as
described  above  and  treated  with  lime  to pH 10.  Solids are
allowed to settle,  and  the  supernatant  is  air  stripped  for
ammonia removal prior to recycle or discharge (optional).

Three  streams at Plant F120 were identified for sampling.  These
streams included the wet  scrubber  discharge,  caustic  scrubber
discharge,   and   raw  water  used  for  make-up.   Figure  16-2
illustrates  a  process  flow  diagram  and  associated  sampling
locations at Plant F120.

Plant  F144  produces  zinc  chloride  from  the reaction of zinc
crudes with hydrochloric acid.   The  zinc  crudes  contain  zinc
metal, galvanizing fluxes, iron oxide, cadmium and lead.

The  process  involves the milling and classifying of the crudes,
dissolution in hydrochloric acid, and concentration, purification
and filtration steps considered proprietary.  The product may  be
sold as a solution or as a solid product.

Wastewater  sources  from the zinc chloride process include purge
from   the   barometric   condenser,   condensate   from    steam
concentrators,  washout  waters  and accidental leaks and spills.
Solid residues with entrained liquid  are  sent  to  a  landfill.
Process  wastewater  from the zinc chloride operation is combined
with other process wastewaters and fed to  a  pair  of  dolomitic
limestone  neutralizers where the pH is raised to a range of 5-6.
Caustic is then added  to  adjust  the  pH  to  8.8-8.9  and  the
wastewater  is sent through a clarifier before discharge.  Sludge
from the clarifier is sent to a centrifuge.  Solids are collected
                              384

-------
and the centrate is recycled to the  beginning  of  the  process.
Plant  FT44  also  has a large wastewater impoundment facility to
contain excess runoff during storms, process  upsets,  and  other
wastewater  flows  during preventive maintenance at the treatment
facility.  The water in the holding pond  is  discharged  through
the treatment plant when process wastewater flows are reduced.

Streams  sampled  at  Plant FT 44 included the intake water, plant
raw  wastewater  (which  contained  the  zinc  chloride   process
wastewater),  combined  plant  raw wastewater with raw wastewater
from  other  products  produced  at  the  facility,  and  treated
clarifier  effluent.   Figure  16-3'. ^ presents  a schematic of the
wastewater treatment process and the sampling points.

Table 16-4 presents flow  data,  total  suspended  solids  (TSS),
zinc,  arsenic,  lead and antimony concentrations for the sampled
wastewater streams.

Treatability Study Conducted at Zinc Chloride Plant F144

Treatability experiments were conducted in  April  1984  at  zinc
chloride  Plant  FT 44  to  develop  additional information on the
application  of  filtration  technology  in  the  zinc   chloride
subcategory.   (See  the contractor's report entitled "Dual-Media
Filtration Test Results at Zinc Chloride Plant F144", which is  a
part  of  the  record  for this rulemaking.)  A pilot-scale dual-
media filtration system (Level 2) was tested on-site over a three
day  period.   Filtration  was  evaluated   as   an   end-of-pipe
technology.   The  wastewater at Plant F144 is subject to Level 1
technology in the existing treatment plant, and the effluent from
that treatment was  used  as  the  influent  to  the  pilot-scale
treatment system.

The  filter media used during the tests at Plant FT44 were silica
sand and anthracite coal, which are typical media  normally  used
in dual-media filters.  A schematic of the pilot-scale filtration
system   is  shown  in  Figure 16-4.  The tests were run for eight
hours per day over a three day period, which  nine  influent  and
effluent  samples  collected  in each eight hour period, one each
hour.  All tests ran the full eight-hours because no breakthrough
of the filters occurred.  The three different hydraulic  loadings
tested  were  4.5  gpm/ft2,  7.3  gpm/ft2, and 10.2 gpm/ft2.  The
three  flow  rates  were  tested  to  better   characterize   the
filtration  efficiencies,  and  determine  if  higher  flow  rate
filters, which are cheaper than low rate filters,  would  provide
adequate removals of zinc.

The  test  was designed to determine the efficiency of filtration
in removing TSS  and  total  zinc  from  effluent  from  Level  1
                              385

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treatment.   Plant   FT44  is achieving excellent removals of  lead,
consequently   lead   in the  wastewater  was  monitored  only  to
determine if the  lead  levels were abnormally high during the test
period.    The   less   sensitive   304(h)  method   (flame  atomic
absorption) was believed  to be adequate for this purpose,  rather
than  the  heated graphite  atomizer  method.   Arsenic was also
monitored to gather  additional data,  although  limited  data  at
Plant  FT 44  suggested that  arsenic levels would  be very low in
treated effluent.  Dissolved zinc was monitored because the  plant
has  historically monitored  dissolved  zinc.    Turbidity   was
monitored  on-site   as a rapid  check  on  breakthrough  of the
filters.  We also monitored pH, and collected  a  sample  of the
solids collected  on  the filter for  analysis of total zinc content
as  a  quality control   check  for the  analysis  of zinc in the
wastewater, because  the calculated  amount of zinc   removed   (from
comparing influent and effluent total zinc analyses) should  equal
the  amount  of   zinc  collected  by the filter.  In summary, the
pollutant parameters monitored in influent and  effluent  samples
were  TSS, total  zinc, dissolved zinc, total lead,  total arsenic,
pH, and turditity.

The results of the tests  for TSS and  total  zinc   are  shown  in
Table  16-5.   These  data  demonstrate  that  the  filter is very
efficient in removing  TSS  and  total  zinc,  with  average TSS
removal  of  about   95  percent and average total zinc removal of
about 90 percent.    The   minimum  total  zinc  removal  was  80.7
percent.  No break through of the filter, which would be shown by
high levels of TSS,  was observed.

As  expected   from   historical data, the lead discharges are well
controlled by  the Level 1 treatment system at this plant, and all
values were less  than  0.1 mg/1, the typical detection  limit for
the  flame  atomic   absorption  method used.  The heated graphite
atomizer, the  more sensitive 304(h) method, could have been  used
to provide lower  detection limits,  although, as noted above, lead
analyses during this test were used only to determine if the lead
levels  were   significantly higher  than the historic values.  All
arsenic values were  reported as less than 0.003 mg/1 using 304(h)
methods which  indicates that, during the three days of the   test,
arsenic levels were  quite low.

Plant  F144  split several samples with us and has provided  their
results to us.   These  results are shown in  Table   16-5A.    These
results  are   similar  to our results although the plant took less
than half as many samples and consequently their  data  could  be
misinterpreted.   For  example, the  last samples analyzed by  Plant
F144 on days 1  and 2 of the test show higher levels of total zinc
than the previous samples for,those days,  which  might  indicate
breakthrough.   However, our later samples show the total zinc and
                              386

-------
TSS  levels decreased; Plant F144 shows no analytical results for
those later samples.

Plant F144 lead analyses were more sensitive than  our  analyses.
Their  data shows that lead is removed efficiently by the filter,
even when the lead in the influent to the filter is less than 0.1
mg/1.  Plant F144 data also shows arsenic at  measurable  levels.
We  do not know the reason for the difference between our results
for arsenic and the Plant F144 results, but  both  sets  of  data
show arsenic levels much less than 0.5 mg/1.

Other Plants Visited

Plant  F118 combines zinc metal with hydrochloric acid to yield a
zinc chloride solution.  The solution is diluted  with  water  to
the desired concentration for sale.  Wastewater generated in this
process  consists  of spills and maintenance washdowns.  The zinc
chloride wastewater is combined with wastewaters from  all  other
products    and   treated   with   alkaline   precipitation   and
clarification before discharge to a receiving stream.

Plant F140 receives process wastewater from an adjacent  facility
as  a  raw material for zinc chloride production.  The wastewater
contains zinc chloride along  with  other  metal  impurities  and
organic wastes.  The process water is treated to remove organics.
Metal  impurities  are  then  removed by pH adjustment using zinc
carbonate, and filtration.  The process water may be strengthened
first  by  addition  of  zinc  and  hydrochloric  acid  and  then
purified.   The  solution  is then concentrated by evaporation to
the desired strength.

All  wastewater  streams  (blowdown  resulting  from  cooling  of
barometric condenser water, precipitation run-off, leaks, spills,
and  pump  seal water) are collected and pumped to a holding tank
where the pH is raised to about 7.  The neutralized wastewater is
allow to settle before discharge  to  a  river  and  the  settled
sludge is recycled to the production process.

Plant FT 45 produces a variety of inorganic and organic chemicals.
Zinc  chloride  is produced by combining zinc metal or zinc oxide
with hydrochloric acid.  All zinc chloride wastewater,  including
scrubber water and any process water which cannot be recycled, is
sent  to  the  wastewater  treatment facility which receives both
organic  and  inorganic  streams  from   all   plant   production
processes.   The  wastewater  is  equalized,  subjected  to  lime
precipitation at pH 9.5-10.2, agitated and clarified.  The sludge
from the clarifiers is dewatered and  disposed  as  solid  waste.
The  overflow  from  the clarifiers receives biological treatment
before being discharged directly to a receiving stream.
                              387

-------








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Table 1.6-5. Results of the Environmental Protection Agency's  Dual-Media
            Filtration Tests at Plant FT 44  (all  values  mg/1).
                    TSS Results



Influent Effluent
Day 1 (4.
1*
2
3
4
5
6
7
8
9
Average
Day 2 (7.
1*
2
3
4
5
6
7
8
9
Average
Day 3(10
1*
2
3
4
5
6
7
8
9
Average
5 gpm/ft*)
7.60
8.15
7.63
8.07
7.48'
6.44
5.70
5.63
5.19
6.88
3 gpm/ft3)
12.00
11 .78
11.56
1 1 .56
10.96
9.48
8.89
9.70
10.59
10.72
.2 gpm/ft2)
7.63
7.33
7.63
7.33
7.85
9.11
11 .86
9.63
10.00
8.71

0.30
0.52
0.74
0.44
0.15
0.30
0.30
0.15
0.44
0.37

0.37
0.44
0.37
0.52
0.15
0.67
1.11
0.81
0.96
0.60

0.07
0.30
0.30
0.52
0.15
0.37
0.44
0.52
0.96
0.40
TSS
Removal (%)

96.1
93.6
90.3
94.5
98.0
95.3
94.7
97.3
91 .5
94.6

96.9
96.3
96.8
95.5
98.6
92.9
87.5
91 .6
90.9
94. 1

99.1
95.9
96.1
92.9
98. 1
95.9
96.3
94.6
90.4
95.5
Zinc Results

Influent
4.53
4.62
4.60
4.48
4.12
4.02
3.57
3.44
3.31
4.08
7,38
8.19
7.26
7.38
7.11
6.33
6.54
7.11
7.44
7.19
4.36
4.33
4.24
4.27
4.27
4.91
4.82
5.02
5.37
4.62

Effluent
0.27
0.20
0.34
0.64
0.69
0.75
0.69
0.41
0.52
0.50
0.45
0.50
0.58
0.54
0.59
0.65
0.69
0.76
1.18
0.66
0.41
0.30
0.42
0.45
0.47
0.46
0.42
0.41
0.46
0.42
Total Zinc
Removal (%)
94.0
95.7
92.6
85.7
83.3
81.3
80.7
88. 1
84.3
87.3
93.9
93.9
92.0
92.7
91 .7
89.7
89.4
89.3
84. 1
90.7
90.6
93. 1
90.1
89.5
89.0
90.6
91 .3
91 .8
91 .4
90.8
*Initial Value.  Samples taken every hour during the test.
                              389

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Table 16-5A  Plant F144 Results for Split Samples of Dual-Media
             Filtration Tests
                    TSS Results
                                          Zinc Results

Day 1 (4
1
2
3
4
5
6
7
8
9
Average
Day 2 (7
1
2
3
4
5
6
7
8
9
Average
Day 3 (1
1
2
3
4
5
6
7
8
9
TSS
Influent Effluent Removal (%)
.5 gpm/ft2)
No samples taken









.3 gpm/ft2)
No samples taken









0.2 gpm/ft2)
7.2 1.0 86.1
_ _ _
_ _ _
6.8 1.6 76.5
7.2 1.0 86.1
8.6 0.8 90.7
10.0 0.8 92.0
10.4 1.0 90.4
— - -
Influent

5.2
-
5.1
-
4.3
_
-
-
-.
4787

9.3
-
8.3
-
-
7.0
-
-
-
"872

4.7
-
-
3.0
4.4
5.1
5.1
5.2
-
Effluent

0.73
-
0.88
-
1 .38
_ -' •'' "
-
-
-
0.99

1 .5
—
1 .2
-
-
3.4
-
-
-
2.03

0.8 '
-
-
0.8
0.9
0.9
0.7
0.7
-
Total Zinc
Removal (%)

86.0
• -
82.7
-
67.9
-
-
-
-
78.9*

83.9
-
85.5
-
-
51 .4
-
-
-
73.6*

82.9
-
-
73.3
79.5
82.3
86.2
86.5
-
Average
8.37
1.03
87.0
4.58
0.8
81 .8*
*Averages may not agree with influent/effluent averages because of
 rounding.
                               390

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Summary of Toxic Pollutant Data
Eleven toxic metals were found at  detectable  concentrations  in
the  raw wastewater at the two sampled plants.  Two toxic organic
pollutants were found in untreated  wastewater  at  concentration
levels  greater  than  0.010  mg/1 -(10  ug/1).    One  of  these,
methylene chloride, was found in high concentrations in  the  raw
wastewater  of'  Plant  F144.   There  is  no known source for the
methylene  chloride  at  the  plant  and  its  presence  in   the
wastewater was not be confirmed by resampling.  The most probable
explanation  is contamination of sampling equipment or containers
or an erroneous laboratory determination.
The maximum concentrations observed in the raw wastewater at
two sampled plants are presented below:
                               the
Pollutant
Maximum Concentration Observed*
           (ug/1)
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Selenium
Silver
Thallium
Zinc

Chloroform
Methylene Chloride
            1 ,869
           14,170
               95
              640
              350
            2,100
            1 ,205
                6
              165
              485
          490,000

              521
          430,000
*Maximum daily observed concentrations for antimony, arsenic,
cadmium, copper, lead, nickel, silver, and thallium were obtained
from daily flow-proportioned averages for the two wastewater
streams at Plant F120.

Section  5  of  this  report  describes  the , methodology  of the
sampling program.  In the zinc chloride industry, a total of  six
days  of  sampling  were conducted at Plants F120 and F144.  Five
wastewater streams were sampled and analyzed.  The evaluation  of
toxic  metal  pollutants  in; these  streams  was  based  on  195
analytical data points.  In Table 16-5, the toxic  pollutant  raw
                              391

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TABLE 16-6.  TOXIC POLLUTANT RAW WASTE DATA FOR  SAMPLED
                ZINC  CHLORIDE FACILITIES
Average Daily Pollutant Concentrations and Loads
mg/1

kg/kkg

Plant Designation
Pollutant
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Thallium*
Zinc
F120
1.435
0.00396
5.605
0.0155
0.069
0.00019
0.146
0.00040
0.279
0.00077
1.834
0.00506
1.049
0.00289
0.14*2
0.00039^
0.325
0.00090
111.724
0.308
F144
0.045
0.00104
<0.006
0.00014
0.032
0.00074
0.520
0.0121
0.067
0.00155
0.107
0.00248
0.017
0.00039
<0.001
0.00002
<0.100
0.00232
184.700
4.29
Overall
Average
0 .74
O.*00250
<2.81
0.00782
0.05
0.00047
0.333
0.00625
0.173
0.00116
0.854
0.00377
0.533
0.00164
<0.071
0.00021
<0.213
0.00161
148.200
2.3
                      392

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waste  data  are  presented  as  the average daily concentrations
found at the sampled plants.

POLLUTION ABATEMENT OPTIONS

Toxic Pollutants of Concern

The principal pollutant of concern  is  zinc.   Other  pollutants
found  in  significant  concentrations in the process wastewaters
are probably related to the purity of the  zinc  metal  and  acid
sources.   The toxic metals arsenic, antimony, lead, chromium and
nickel found during screening and  verification  sampling  likely
originate as constituents of the galvanizer skimmings used as the
raw  zinc  material.  Highest concentrations of these metals were
found primarily in the scrubber  wastewater  streams  from  Plant
F120.   The  scrubber step preceeds the heavy metals removal step
noted in several other plant  processes.   Therefore,  such  high
levels  of the above-mentioned heavy metals would not be expected
unless a facility's operations included scrubbing of  the  Zn/HCl
reactor gases.

Existing Wastewater Control and Treatment Practices

Treatment practices at the visited plants were presented earlier.
Available  information on treatment practices at other plants are
presented below.

Plant F125 produces other inorganic salts  in  addition  to  zinc
chloride.   Wastewater  from all processes is treated in a system
consisting of  equalization,  pH  adjustment  with  caustic,  and
sedimentation  in  a  series  of  lined  and unlined impoundments
before discharge to a receiving stream.  Solid wastes are  hauled
to a chemical landfill.

Plant  F143  produces zinc chloride using zinc oxide, zinc powder
and brass  skimmings  as  raw  materials.   Wastewater  from  the
process is neutralized before discharge to a POTW.

Plant  F126  produces  zinc  chloride  in  small quantities.  The
company reported that no process wastewater was  discharged  from
the process.

Other Applicable Control/Treatment Technologies

Although   some   plants  only  neutralize  their  wastes  before
discharge, the primary method of wastewater treatment in the zinc
chloride  industry  is   precipitation   and   clarification   or
sedimentation  of process wastes.  Another technology which would
                              393

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be applicable to this industry is filtration for
and toxic metal removal.
further  solids
Process Modifications and Technology Transfer Options

A reduction in the volume of .process contact wastewater generated
might  be  achieved  by  recycling  all  direct  process  contact
wastewater  where  possible.   For  example,  several  facilities
employ  recycle  of  scrubber  water  with only a small volume of
blowdown necessary.  Condensate from  product  concentration  and
crystallization  appears  to: be  another  wastewater source with
potential for recycle.  The principle difference  between  plants
with  high  water  use  and  those with low water use is that the
latter use pure  raw  materials  and  sell  solution  grade  zinc
chloride only.  This is an economic decision not a technology per
se.  One existing zinc chloride manufacturer reported that it has
no discharge of process wastewater from the very small quantities
of zinc chloride produced at its plant.

Sludge  volumes may be reduced by the use of caustic soda instead
of lime for wastewater treatment.   This  practice  offers  other
advantages  including reduced scale formation and faster reaction
times.

Best Management Practices

If contact is possible with leakage, spillage of  raw  materials,
or  product,  all  storm  water  and  plant  site  runoff must be
collected and directed to the  plant  treatment  facility.   This
contamination can be minimized by indoor storage of chemicals and
proper air pollution control.

If  solids  from  the  wastewater treatment plant are disposed or
stored on-site, provision must be made to control  leachates  and
permeates.    Leachates   and   permeates   which  contain  toxic
pollutants should be directed to the treatment system for further
treatment.

Advanced Treatment Technology

Zinc-containing residues such  as  galvanizing  wastes  and  zinc
dusts   are  often  used  as  raw  materials  for  zinc  chloride
production.  These materials contain a variety of toxic and  non-
toxic  metals  such  as  lead, zinc, cadmium, iron and manganese.
The manufacturing process removes much of these metals  from  the
zinc  chloride  product  in  the  form  of  filter  cake.   Other
constituents can  be  transmitted  to  the  wastewater.   Further
reduction  of  metals  would  require treatment by granular media
filtration.
                               394

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One facility producing zinc chloride from an  organic  wastewater
stream  generated  at a nearby chemical manufacturing complex may
require treatment technology in addition to the levels considered
here.  The" water is treated to remove organics  as  part  of  the
manufacturing  process, but no data is available on the amount of
toxic organics in the wastewater.  Elevated COD and the  presence
of  toxic  organics would be pollutants which could occur at this
facility.  The presence of these additional  pollutants  are  not
expected  to  affect  the  effectiveness  of treatment for metals
removals, as a similar  situation  occurs  at  Plant  F145  which
provides effective treatment for removal of metals.

Selection of Appropriate Technology and Equipment

Technologies for Different Treatment Levels

A.   Level 1

Level   1   treatment   consists   of   alkaline   precipitation,
clarification  or  settling,  and  dewatering  of the sludge in a
filter press.  This technology is illustrated in Figure 10-10.  A
holding basin sized to retain 4-6 hours of flow is provided.

The initial treatment step is the addition  of  lime  or  caustic
soda.    This  is  followed  by  clarification/settling  (if  the
wastewater characteristics are suitable, a tube  settler  may  be
substituted  for  a  clarifier to save space).  Sludge is removed
from the clarifier and directed to a filter press for dewatering.
Pits are provided at the filter press for the  temporary  storage
of sludge.  The sludge is periodically transported to a hazardous
material  landfill.   A  monitoring  system  is  installed at the
discharge point.  The objective  of  Level  1  technology  is  to
remove heavy metals and suspended solids.

Level  1  treatment  was selected as the basis for BPT because it
represents a typical and viable industry practice for the control
of suspended solids, arsenic, lead and zinc.  All of  the  direct
dischargers   have   Level  1  treatment  or  equivalent  already
installed.
B.
Level 2
Level 2 treatment consists of  the  addition  of  granular  media
filtration  following  clarification  in  the  Level  1 treatment
system.  The granular media filtration technology is  illustrated
in Figure 10-11.  Level 2 technology has been selected as a means
of achieving improved removal of metal hydroxide precipitates and
other  suspended solids because our treatability study shows that
this technology gives excellant results when transferred to  this
                              395

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industry.    Currently  no  plants  in  this  subcategory  employ
granular media filtration for wastewater treatment.but plant F145
is achieving the limitations.

Equipment for Different Treatment Levels

A.   Equipment Functions

Conventional sludge dewatering by a  filter  press  is  used  for
sludge  removed by the clarification/settling system.  The sludge
from the filter press is disposed  of  off-site  in  a  hazardous
material  landfill.  If a tube settler is used, backwash from the
settler is returned to the influent holding basin.  Likewise,  if
granular  media  filters  are used, backwash water is returned to
the influent holding basin.  All equipment  is  conventional  and
readily available.

B.   Chemical Handling

Caustic soda (50 percent  NaOH)  is  used  to  precipitate  heavy
metals  in  Level  1 at most plants.  However, lime precipitation
may be used at large plants due  to  the  quantity  and  cost  of
alkaline reagent required.  Precipitation of zinc is best at a pH
of  about  9,  and  occasional pH discharges above 9 could occur.
For this reason,  and  recognizing  that  regulations  for  other
industries  allow pH range up to 10, the pH limitations have been
revised in the final rules from the proposed levels  of  6-9  and
are  now  6-10.   Therefore,  readjustment  of  pH  will  not  be
necessary.

C.   Solids Handling

Treatment sludges generated by Level 1 are dewatered in a  filter
press.   The  solids would be disposed of off-site in a hazardous
material landfill.  Level 2 filter backwash may be  sent  to  the
head of the plant or, if the solids concentration is sufficiently
high, may be sent directly to the filter press.

Treatment Cost Estimates

As  stated  earlier  in  this  section,  there  are  seven  known
producers of zinc chloride, five of which are direct  dischargers
of wastewater.  The average wastewater generation in the industry
was  thought  to  be  10.5  mVkkg, but this included some plants
using pure zinc or zinc oxide and selling solution grade  product
only.   The  zinc  chloride  model  plant  used  for the proposed
regulations has a unit flow of 13.5 m3/kkg.  However, recent data
indicate that unit flow may vary considerably depending upon  the
product  produced  (liquid or solid).  Because this is determined
                              396

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     TABLE 16-7.  WATER EFFLUENT TREATMENT COSTS
                  FOR MODEL PLANT.
SUBCATEGORY:
               Zinc Chloride
ANNUAL PRODUCTION:  26.000

DAILY FLOW:  3.785	

PUNT AGE:      NA
                                         METRIC  TONS
                           	 CUBIC METERS  (1,000,0.00 GPD)

                           YEARS   PLANT  LOCATION:      NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY

Facilities
Installed Equipment
  (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital
                                    COSTS  ($1,000) TO ATTAIN LEVEL
                                     1

                                  152.9

                                  703.0
                                  171.2
                                  15.4.1
                                  118.1
                                    3.6

                                1,302.9

Annual Capital Recovery           211.4
Annual Operating and Maintenance  300.8
(Excluding Residual Waste Disposal)
Residual Waste Disposal            31.7
  Total Annual Cost
                                  543.9
105.1
 21.0
 18.9
 18.5
159.5

 26.0
 44.5

  0.9

 71.4
                            TREATMENT DESCRIPTION
LEVEL 1:  Alkaline precipitation, clarification, sludge  dewatering

LEVEL 2:  Filtration
                              397

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      TABLE  16-8.   WATER  EFFLUENT  TREATMENT COSTS
                   FOR MODEL PLANT.
 SUBCATEGORY:   Zinc  Chloride
ANNUAL PRODUCTION:   5.700
DAILY FLOW:    260	
PLANT' AGE:      NA
                METRIC  TONS
  	 CUBIC METERS

  YEARS   PLANT  LOCATION:
              MA
           a.  COST OF TREATMENT TO ATTAIN  SPECIFIED  LEVELS
COST CATEGORY

Facilities
Installed Equipment
   (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital
           COSTS  ($1,000)  TO ATTAIN LEVEI

           1       2      3       45

           21.6
          142.7
           32.9
           29.6
           22.7
          249.5

           40.6
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Wast6 Disposal) 95.6
Residual Waste Disposal              2.1
44.0
 8.8
 7.9
 6.1
66.8

10.9

18,0
 0.1
  Total Annual Cost
          138.3  29.0

b. TREATMENT DESCRIPTION
LEVEL 1:   Alkaline  precipitation,  clarification,  sludge  de.watering

LEVEL 2:   Filtration
                            398

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by the market  and  cannot  be  predicted,  we  are  promulgating
guidelines  and  standards on a concentration basis only. : Permit
writers may convert the concentration-based limit to a mass-based
limit based on the flow at individual plants.

Costs for two model plants were developed  because  of  the  wide
variation  of  plant  sizes  in  this  subcategory.   The  annual
productior. rates  used  were  26,000  kkg  and  5,700  kkg.   The
wastewater   flows   used   were  3,785  m3/day  and  260  m3/day
respectively.  Costs for the smaller plant were developed on  the
basis  of  the  same  wastewater characteristics as for the large
plant to represent many plants which produce  smaller  quantities
of  the  chemical.   Chemical  usage  and  sludge production were
proportioned based upon flow but the small plant was  assumed  to
use  caustic  soda while the large plant was assumed to use lime.
Lime is cheaper but  produces  considerably  more  sludge,  which
cannot economically be reclaimed for zinc.  Caustic produces less
sludge  and,  when  pure  zinc  is used (as is often the case for
small plants), the sludge can be recovered for reclamation of the
zinc.
Chemical reagent usage for wastewater treatment at the two
plants are estimated as follows:
                                       model
     Ca(OH)
          Large Plant

       400 kg/day
Small Plant

 88 kg/day (1 )
     Total solid waste generated is estimated as follows (Level 2
listings are incremental amounts):
     Level
      (1)
      (2)
Solid Waste
    Large Plant

    0.39 m3/day
    0.011 mVday
     Small Plant

     0.086 mVday
     0.0024 mVday
Model  Plant  Treatment  Costs.   On  the  basis  of  model plant
specifications and  design  concepts  presented  earlier  and  in
Section  10, the estimated costs of treatment for two models with
two levels are shown in Tables 16-7 and 16-8.  The cost of  Level
2 is incremental to Level 1.

Basis for Regulations

Basis for BPT Limitations

A.   Technology Basis
                              399

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For BPT, the Agency is setting limitations  based  upon  alkaline
precipitation  and clarification, and dewatering of the sludge in
a  filter  press.   Of  the  five  direct  dischargers  in   this
subcategory, all have this technology or equivalent installed.

B.   Flow Basis

The limitations have been  developed  on  a  concentration  basis
only.

C.   Selection of Pollutants to be Regulated

The  selection  of  pollutants  for   which   specific   effluent
limitations  are  being  established is based on an evaluation of
the  raw  wastewater  data  from  screening   and   verification,
consideration   of   the  raw  materials  used  in  the  process,
literature data,  historical  discharge  monitoring  reports  and
permit   applications,   and   the   treatability  of  the  toxic
pollutants.

Tables 8-1 through 8-14 summarize the  achievable  concentrations
of  toxic  metal  pollutants  from the literature using available
technology options, data from other industries, and  treatability
studies.   Water  use and discharge data are presented earlier in
this section together with generalized  process  characteristics.
Pollutant  concentrations of raw wastewater streams and a summary
of maximum concentrations observed of toxic  pollutants  detected
during  screening and verification sampling at several plants are
also presented earlier in this section.  Data from Appendix A  on
the  performance  of in-place industry treatment systems was also
utilized in developing the list of pollutants to be regulated.

Based upon the occurrence of treatable levels of  specific  toxic
metals,  arsenic, lead, and zinc were selected as candidate toxic
pollutants for BPT  regulations.   Antimony,  cadmium,  chromium,
copper,  nickel, selenium, silver, and thallium were detected but
at less than treatable levels.

Consideration of  the  raw  wastewater  concentrations  presented
earlier,  industry  data, and information in Section 8 related to
the effectiveness of hydroxide precipitation,  and  clarification
leads  to  the  selection  of  arsenic,  lead,  and zinc as toxic
pollutants to be regulated.

D.   Basis of BPT Pollutant Limitations

Limitations are presented on a concentration (mg/1) basis only.
                              400

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BPT  limitations,  which  apply   to   all
discharged, are presented in Table 16-9.

     1.   Conventional Pollutants

          a.   pH
process   wastewater
               The treated effluent is to  be  controlled  within
               the  range  of 6.0 - 10.  This limitation is based
               upon the data  presented  in  Appendix  B  of  the
               Development   Document   for   Proposed   Effluent
               Guidelines for Phase I Inorganic  Chemicals  (Ref.
               1)  and  the  JRB study (Ref. 2).  Zinc removal  is
               best at a pH of about 9,  and  the, effluent   from
               treatment  could  be  above 9 occasionally, unless
               additional effluent pH control is provided.  For a
               large plant, the costs  for  compliance  with  the
               effluent pH of 6-9 would be $110,000  capital costs
               and  over  $20,000  annualized  costs.  Because  no
               significant environmental impact is expected   from
               effluent   at  a  pH  of  10,  and  because  other
               industries allow effluent pH at a  pH of  10,   we
               believe a pH of up to 10 should be allowed for the
               zinc chloride subcategory.

               TSS                   i                    . . ".
               Three  Phase   II  plants   (F125,   Fll5   and   F140)
               considered    to   be   efficently   operating   their
               wastewater  treatment  facilities provided long-term
               Level  1  treatment system  performance  data for TSS.
               TSS data from Plant F144  were  not  used  because the
               wastewater  is passed  through a limestone bed  in
               the  first  stage  of  the plant's neutralization
               .system.   This would reduce the TSS loading to  the
               clarifier  giving  lower  TSS results  than expected
               for the  average  inorganic chemicals plant.   Since
               no other data from well-operated Level  1 treatment
               systems  was available,  and since the  clarification
               provided at   Plants   F125,  Fll5  and F140 for TSS
               removal  would be similar  to that necessary for TSS
               removal  at  zinc  chloride  plants  (Plants  F125  and
               FT 40   are    zinc   chloride   plants),   the  BPT
               limitations for  TSS are based  upon the  average  of
               long-term  averages calculated from data collected
               at Plants F125,  F115  and F140.   The  long-term
               average   of  13  mg/1  was  used  to develop discharge
               limitations.   Variability factors   of  1.9  for  a
                               401

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          monthly average and 3.3 for a 24-hour maximum were
          used  yielding TSS concentration limitations of 25
          mg/1 and 43 mg/1 respectively.  (See  Section  15,
          BPT Limitations, for derivation of the variability
          factors.)
2.    Toxic Pollutants

     a.   Arsenic
          Since  there  is  no  long-term  treatment  system
          performance   data   for  arsenic  from  any  zinc
          chloride manufacturing plant, the BPT  limitations
          for  arsenic are based on estimated maximum 30-day
          averages achievable with Level 1   treatment  taken
          from  Table 8-11, and variability factors computed
          from long-term data for dissolved  zinc  at  Plant
          F144  presented  in  Appendix A.   Using a value of
          0.5  mg/1  as  a  long-term  average,  2.0  as   a
          variability     factor    for    30-day    average
          computations, and 6.0 as a variability factor  for
          24-hour    maximum   computations,   concentration
          limitations of 1.0 mg/1 (30-day avarage)  and  3.0
          mg/1 (24-hour maximum) are obtained.

          Lead

          Long-term performance data for lead  is  available
          for Plants F140 and FT 44.   The data for Plant F144
          show  very  low effluent lead levels, and the data
          are  considered  to  be   typical   of   Level   2
          performance   for   lead   in  the  zinc  chloride
          subcategory  rather  than  Level   1    performance.
          Consequently,  we  did not use Plant  F144 data for
          lead limitations for BPT,  although we did use that
          data for lead limitations for BAT.  Plant F140 has
          an in-plant lead removal system which is not  part
          of  Level  1   treatment  and is not typical of the
          industry.  Therefore,  we also did  not  use  Plant
          F140  data  for lead limitations  for  BPT.  Because
          there are no long-term performance data  for  lead
          from  any  other  zinc chloride plant with Level 1
          treatment, the BPT limitations for lead are  based
          on estimated 30-day averages achievable with Level
          1  treatment taken from Table 8-11, and variability
          factors for dissolved zinc computed from long-term
          data at Plant F144 presented in Appendix A.  Using
          a   value  of 0.3  mg/1  as(a long-term  average,   2.0
          as  a  variability  factor  for   30-day   average
                         402

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               computations,   and 6.0 as a variability factor for
               24-hour maximum computations,  concentration limits
               of 0.6 mg/1  (30-day  average)  and  1.8  (24-hour
               maximum) are obtained.

          c.    Zinc

               The BPT limitations for zinc are  based  on  long-
               term  monitoring data from Plant F140 presented in
               Appendix A.  The plant has  a  Level  1  treatment
               system.    The  plant  is  achieving  a  long-term
               average concentration for zinc of 1.9 mg/1.   Data
               from  Plant  FITS were not used because Plant FIT8
               is a multiproduct plant where  process  wastewater
               from   all   products   is   combined  for  common
               treatment,   and   the   zinc   chloride   process
               wastewater  comprises  only  five  percent  of the
               total  flow  to   treatment,   consequently,   the
               effluent  total  zinc  levels  are  lower than the
               levels achievable at a plant which  produces  zinc
               chloride only.  Data from Plant F144 were not used
               for  estimating  the  long-term  average for total
               zinc  because  all  of  that  long-term  data   is
               dissolved zinc.  Variability factors for dissolved
               zinc  developed  at  Plant  F144, and presented in
               Appendix A, were used because the data from Plants
               F140 and FIT 8 were not in a  form  that  could  be
               used  to  develop variability factors and there is
               no other data available.  These are 2.0 for a  30-
               day  average  and 6.0 for a 24-hour maximum.  From
               these values,  limitations  of  3.8  mg/1,  30-day
               average  and  11.4  mg/1,  24-hour  maximum,  were
               derived.  Use of variability factors derived  from
               long-term TSS data at Plant F144 for total zinc is
               not  appropriate because the TSS would account for
               the precipitated  zinc  hydroxide  only,  not  the
               dissolved  zinc.   Total  zinc  is  the sum of the
               precipitated and dissolved zinc.

Basis for BCT Effluent Limitations

On October 29, 1982, EPA proposed a new and  revised  methodology
for  determination  of  BCT for conventional pollutants.  In this
subcategory, only two  conventional pollutants have been  selected
for  limitation,  pH and total suspended solids (TSS).  Two tests
are required according to the revised methodology,  a  POTW  test
and an industry  cost effectiveness test.  The POTW test is passed
if  the  incremental   cost  per  pound  of conventional pollutant
removed in going from  BPT to BCT is  less than $0.46 per pound   in
                              403

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     TABLE 16-9.    BPT EFFLUENT LIMITATIONS FOR ZINC CHLORIDE
Coventional
Pollutants

pH

TSS

Toxic
Pollutants

Arsenic

Zinc

Lead
                 Long-Term
                 Avg.Cmg/1}
                  13.0
                     CD
                   1.9
  VFR
1.9/3.3
        CD
2/6^)

2/6 C3)
Cone. Basis
,	Cmg/1 j
Sunday 24-hr.
 Avg.   max.

 6-10*  6-10*

25     43
 1.0

 3.8

 0.6
 3.0

11.4

 1.8
VFR - Variability Factor Ratio
 * pH  units
(1)  Based upon long-term data at Plants F115,  F125  and F140,
(2)  Based upon Table 8-11.
(3)  Based upon long-term data at Plant F144.
(4)  Based upon long-term data at Plant F140.
                            404

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1981   dollars.  Under the proposed methodology, the industry test
is passed if this same incremental cost per pound  is  less  than
143  percent  of  the  incremental cost per pound associated with
achieving BPT.

The methodology for the first BCT cost test is as follows:

(1)  Calculate the amount of additional TSS removed by the BCT
     technology.

     (a)  BPT long-term average       = 13 mg/1
          Level 2 long-term average * = 9.3 mg/1
          *(See Sections 11 and 12 for derivation)

          Difference                =3.7 mg/1

     (b)  Annual flow for model plant:

          <260 mVday)(250 day/yr) = 65,000 mVyr "Small"
          (3785 mVday)(365 day/yr) = 1,381,525 mVyr "Large"

     (c)  Total annual additional TSS removed for model plant:

          Small Plant:

          (3.7 mg/1) (65, 000 mVyr) (kg/1 0* mgHlOOO 1/m* )
          = 241 kg/yr
          » 530 lbs/yr

          Large Plant:

          (3.7 mg/1) (1,381,525 mVyr) (kg/1 0«mg) (1000 1/m3)
          =5112 kg/yr
          - 11269 lbs/yr

(2)  Calculate the incremental cost,  in dollars per pound of TSS
removed, for  the model plant.

     (a)  Incremental annualized  cost for Level 2 technology, from
          Tables 16-6 and  16-7:

          $29,000 "Small", and $71,400 "Large"

     (b)  Divide annualized  cost  by annual additional TSS.removals:

          ($29,000 per yr) t  (530 lbs/yr) « $54.72 per Ib of TSS
                                removed for small model plant.

          ($71,400 per year)  t (11269  lbs/yr)  = $6.34 per Ib of TSS
                               405

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                                               removed for the large
                                               model plant.

The costs for both model plants are far above the $0.46 per pound
bench mark cost.  Therefore, the candidate BCT technology  failed
the  first BCT cost test there is no need to apply the second BCT
cost test.

On October 29, 1982, EPA  proposed  a  revised  BCT  methodology.
While  EPA  is  considering  revising  that  methodology, we have
determined that in this subcategory no technology beyond BPT will
pass the proposed BCT cost test or any other BCT  test  that  the
Agency  is  likely to adopt.  Accordingly, in this subcategory we
are setting BCT equal to BPT.  As a result, BCT for TSS is  equal
to  the  BPT  limitations.   However,  the  Agency  will  need to
reconsider the BCT limitations for this subcategory  when  a  new
BCT cost test is promulgated.

Basis for BAT Effluent Limitations

Application of Advanced Level Treatment

Utilizing  the  cost  estimates  in  this  report, the Agency has
analyzed the cost of the base level systems (BPT - Level  1)  and
an  additional advanced level option for toxic pollutant removal.
The economic impacts on the Zinc Chloride Subcategory  have  been
evaluated   in   detail  and  taken  into  consideration  in  the
determination of the BAT regulations.

For  BAT,  the  Agency  is  promulgating  limitations  based   on
treatment  consisting  of Level 1 plus Level 2 technology.  Toxic
pollutants limited by the promulgated BAT regulation are arsenic,
lead, and zinc.

A.   Technology Basis

Alkaline precipitation followed by clarification,  dewatering  of
the  sludge  in  a  filter press, and filtration of the clarifier
effluent form the selected BAT technology basis.

B.   Flow Basis

The limitations have been  developed  on  a  concentration  basis
only.

C.   Selection of Pollutants to be Regulated

     Toxic Pollutants
                              406

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The toxic pollutants arsenic, lead, and zinc have  been  selected
for BAT limitation.  Table 16-10 presents the BAT limitations for
the Zinc Chloride Subcategory.

D.   Basis of BAT Pollutant Limitations

As in BPT, the BAT limitations are  presented  as  concentrations
(mg/1).

     Toxic Pollutants

     a.   Arsenic

          Because there  is  no  long-term  monitoring  data  for
          arsenic,  the  BAT limitations for arsenic are based on
          estimated long-term averages achievable  with  Level  2
          treatment   taken  from  Table  8-11,  and  variability
          factors computed from long-term data for dissolved zinc
          at Plant F144 presented  in Appendix A for  the  reasons
          given  below  for  zinc.  Using a value of 0.5 mg/1 as a
          long-term average, 2.0 as a variability factor for  30-
          day  average  concentrations,  and 6.0 as a variability
          factor for 24- hour maximum computations, concentration
          limits of 1.0 mg/1  (30-day average) and 3.0  mg/1   (24-
          hour maximum) are  obtained.

     b.   Lead

          The BAT  limitations for  lead  are  based  on  long-term
          data  from Plant F144.   These data indicate a long-term
          average  effluent   lead   concentration  of  0.038  mg/1.
          Variability factors at Plant F144 were used.  These are
          1.25  for  a  30-day  average  and  4.8  for  a  24-hour
          maximum.  From these  values, limitations of 0.048 mg/1,
          30-day average, and 0.18 mg/1,   24-hour  maximum  were
          derived.

     c.   Zinc

          The BAT  limitations for  zinc are  based upon removals  of
          greater   than  80% of   total  zinc  present  from   the
          effluent of a BPT-type treatment  system  as demonstrated
          by a  treatability  study  of  filtration  at Plant F144.   A
           long-term average effluent zinc concentration  of  0.38
          mg/1  represents  80% removal of total  zinc  from the   BPT
           long   term  average  value  of   1.9  mg/1.    Filtration
           technology   is   applicable  for    removal   of    solids
           including precipitated   metal   hydroxides such  as  zinc
           hydroxide but  has  little effect  on  removing  dissolved
                               407

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    TABLE 16-10.  BAT EFFLUENT LIMITATIONS FOR ZINC CHLORIDE
                                               Cone Basis
                                                 (ma/1)
TOXIC
Pollutants
Arsenic
Zinc
Lead
Long-Term
Avg. (mq/1)
0.5CD
0.38<2>
0.038<3>
VFR
2/6C3)
2/6C3)
1 .25/4.79C3)
30-day
avq.
1.0
0.76
0.048
24-hr .
max.
3.0
2.28
0. 18
VFR - Variability Factor Ratio

(1)  Based upon Table 8-11.
(2)  Based upon 80 percent removal demonstrated by Plant F144
     treatability study.
(3)  Based upon long term data at Plant F144.
                              408

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          metals.    The  total zinc discharged from the filter is
          the sum of the dissolved  zinc  and  precipitated . zinc
          that   passes   through   the   filter.    Because  our
          treatability study demonstrated that filtration is very
          effective in removing precipitated zinc, the total zinc
          discharged   consists   mostly   of   dissolved   zinc.
          Therefore,  use  of  dissolved  zinc, data  to estimate
          variability factors is appropriate in  the  absence  of
          any  long-term  data  from  a  zinc chloride plant with
          Level 2 technology.  Variability factors developed  for
          dissolved zinc at Plant F144, and presented in Appendix
          A,  were  used.  These are 2.0 for a 30-day average and
          6.0  for  a  24-hour  maximum.   From   these   values,
          limitations  of  0.76,  30-day  average,  and 2.3 mg/1,
          24-hour maximum, are obtained";

Basis for NSPS Effluent Limitations

For NSPS, the Agency is promulgating limitations based on the BAT
technology  since  no   additional   technology   which   removes
significant  additional  quantities  of pollutants is known.  The
pollutants limited include pH, TSS, arsenic, lead, and zinc.  The
NSPS effluent limitations are listed in Table  16-11.

The limitations for arsenic,  lead, and zinc are  the same  as  for
BAT.   See  the  BAT  section  above   (pages 407 and 409) for the
development of those limitations.  The pH limitations are  within
the  range 6-10, as described above for BPT  (pages 401-403).  The
TSS limitations are based on  filtration  and  are  developed  as
follows:

     Since no long-term monitoring data for TSS  is available from
     any  zinc  chloride  plant  with Level 2  treatment, the NSPS
     limitations for TSS are  based on an average of long-term TSS
     monitoring data from Plants A and K as presented  in Appendix
     A of the Phase I Development Document which uses  the  same
     Level  2   (filtration)   technology  to  control  TSS that is
     promulgated for the zinc chloride subcategory.  A  long-term
     average of 9.3 mg/1  (the average of both  plants) was used to
     develop  the   discharge  limitations  for  plants  employing
     filtration.  Variability factors, also obtained from   Plants
     A   and K, of  1.8 for a monthly average and  3.0 for a 24 hour
     maximum were used yielding  TSS concentration   limits   of  17
     mg/1 and 28 mg/1 respectively.

     The treatability study  (pages 385-387   above) showed  higher
     TSS removals  than are required by the  NSPS.  However, the
     treatability  study'was  only a three day test,  which must  be
     considered   less reliable  than long-term  data  from operating
                               409

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    TABLE 16-11.  NSPS EFFLUENT LIMITATIONS FOR ZINC CHLORIDE
Conventional
Pollutants

TSS

Toxic
Pollutants

Arsenic

Zinc

Lead
Long-Term
Avg.(mg/1)
0.5C2)

0.38C3)


0.038<0
   VFR
              1.2/3.0
2/6 <
                                               Cone Basis
                                                 (mq/1)
30-day
 avg.

17
24-hr,
 max.

28
 1.0       3.0

 0.76      2.28

 0.048     0.18
VFR - Variability Factor Ratio

(1)  See Text
(2)  Based upon Table 8-11
(3)  Based upon 80 percent removal demonstrated by Plant F144
     treatability study
(4)  Based upon long term data at Plant F144
                               410

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     facilities.   Therefore,  the  treatability  study  was  not
     relied upon to establish TSS limitations for NSPS.

Basis for Pretreatment Standards

Existing Sources

     The  Agency  is  promulgating  PSES equal to BAT  limitations
because BAT provides better removal of arsenic,  lead,  and  zinc
than is achieved by a POTW and, therefore, these toxic pollutants
would  pass  through  a  POTW  in  the  absence  of pretreatment.
Pollutants regulated under PSES  are  arsenic,  lead,  and  zinc.
Table 16-9 contains these limitations.

Using  the  summary  data presented in Tables 16-6 and 16-10, the
Agency has estimated that percent removals for arsenic, lead, and
zinc by comparing the untreated waste  concentrations  for  those
three   metals  with  the  concentrations  of  those   same  three
pollutants in effluent from the  selected  BAT  technology.   The
calculations are as follows:

     Arsenic;  Raw Waste = 2.8 mg/1
                    BAT   =0.5 mg/1

     Percent Removal = [(2.8 - 0.5) t  (2.8)1(100)
                     « 82%
     Lead:
Raw Waste =0.86 mg/1
    BAT = 0.038 mg/1
     Percent Removal  =  [(0.86 -  0.038)7(0.86)](100)
                      =  96%
     Zinc:
Raw Waste = 150 mg/1
    BAT   =0.38 mg/1
     Percent Removal  =  [(150  -  0.38)/(150)]  (100)
                      =  99.75%

The percent removals  are  greater  than  the  removals  for  lead  (48%)
and  zinc   (65%)   achieved by 25% of the POTWs in the  "50  Cities"
study  (Fate of_ Priority Pollutants .in   Publicly Owned   Treatment
Works,  Final   Report,  EPA 440/1-82/303, September  ,  1982).   Only
limited data  is available on  removal of arsenic by  POTWs,  but the
removals for  other toxic  metals by 25% of  the POTWs in  that  study
ranged from 19% to 65%.   We assume  that   the  POTW removals  of
arsenic  are   in  that range.  Therefore, since the  BAT  technology
achieves a  greater percent removal of   arsenic,  lead,   and   zinc
than   is   achieved  by  a well   operated  POTW with   secondary
                               411

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treatment, those  three  toxic metals would pass-through
in the absence of pretreatment.
                                    the  POTW
Using  the  summary  data presented  in Tables  16-9 and  16-10, the
Agency has also estimated the percent removals for lead and  zinc
by  comparing  the  concentrations   of  those  two toxic metals  in
effluent from BAT treatment with the concentrations of  the  same
two  pollutants  in  effluent  from  BPT  treatment.   Since  the
concentrations  of  arsenic  are  the  same  from  BPT  and   BAT
technology,    the    Agency   compared   the   untreated   waste
concentrations for arsenic with the  effluent   concentration  from
BAT treatment for that metal.  The calculations are as follows!

     Arsenic;  Raw Waste = 2.8 mg/1
                    BAT =0.5 mg/1

     Percent Removal = [(2.8 - 0.5)  t (2.8)](100)
                     = 82%
     Lead:
BPT
BAT
     Percent Removal
   [(0.3
   87%
  =0.3 mg/1
  = 0.035 mg/1

 - 0.038) t (0.3)]  (100)
     Zinc:
BPT
BAT
     Percent Removal =  [(19
                     =  80%
  =1.9 mg/1
  = 0.38 mg/1

- 0.38) ^ (1.9)[(100)
The percent removals are greater than the removals for lead (48%)
and  zinc  (65%)  achieved by 25% of the POTWs in the "50 Cities"
Study.

Only limited data is available on the  removal  of  arsenic,  but
removals  achieved  by  25%;of the POTW's in that study for other
toxic metals ranged from 19% to 66%.  We  assume  that  the  POTW
arsenic  removals  are  in  that range.  Therefore, since the BAT
technology achieves a greater percent removal of  arsenic,  lead,
and  zinc than is achieved by a well operated POTW with secondary
treatment, those three toxic metals would pass-through  the  POTW
in the absence of pretreatment.

New Sources

     The  Agency  is  promulgating  PSNS  equal to NSPS for toxic
pollutants.  The pollutants limited include  arsenic,  lead,  and
zinc and are listed in Table 16-9.
                              412

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                      SECTION 16 REFERENCES
1.    U.S.  Environmental Protection Agency,  "Development Document
     for Effluent Limitations Guidelines and Standards for the
     Inorganic Chemicals Manufacturing Point Source Category,"
     EPA Report No.  440/1-79-007, June 1980.

2.    JRB Associates, Inc.,  "An Assessment of pH Control of
     Process Waters in Selected Plants," Draft Report to the
     Office of Water Programs, U.S. Environmental Protection
     Agency, 1979.
                               413

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                            SECTION 17

                           BAT REVISIONS
 BACKGROUND
 The   effluent limitations guidelines and standards for the sodium
 chloride (solution brine-mining process),  calcium  chloride,   and
 sodium   sulfite  suboategories were promulgated on March 12,  1974
 and   are  still  in  effect.    These  guidelines  set   numerical
 discharge  limitations   for  BPT and established BAT limitations,
 NSPS, and PSNS of no  discharge of process  wastewater  pollutants.
 PSES  were reserved for  each  subcategory.   The  technology used as
 a  basis  for the BAT limitations,  NSPS and   PSNS  for  the  sodium
 chloride  (solution  brine-mining  process)   and calcium chloride
 subcategories was  the   use  of  surface  condensers  instead  of
 barometric  condensers.    For the sodium sulfite subcategory,  the
 technology basis was  evaporation of the  treated wastewater.

 Each  of  these subcategories was excluded  from   further   national
 BAT   regulation  development   under  the  provisions of  Paragraph
 8(a)(i)  of the Settlement Agreement  in  the  Phase  I   Inorganic
 Chemicals  BAT  regulation (47 FR 28260,  June  29,  1982),  because
 there  was  an  existing   zero  discharge  BAT.    Each   of these
 subcategories  was  included   in  the Phase II Inorganic  Chemicals
 regulation  development   study  to  consider  appropriate  PSES,
 because   PSES  for  these  subcategories were not  included in  the
 March 1974 promulgation  (see  Section 18).

 On May 19,  1981,  the  Salt  Institute  petitioned  the Agency   to
 review   the  BAT  limitations  for  the  sodium  chloride  (solution
 brine-mining  process) subcategory  because  the   industry   believed
 the  costs  of  compliance with  the zero  discharge requirements,
 including the adverse effect  on production efficiency that would
 result   from  the use of surface condensers rather  than barometric
 condensers, were not  justified by  the  effluent  reductions  to   be
 achieved.

After receiving  the petition  from  the  sodium chloride industry  to
reconsider  the   BAT  guidelines   for  sodium chloride, the Agency
extended  its  study to include the   calcium chloride  and  sodium
sulfite   subcategories  because  they  are also  subject  to a zero
discharge  of  process water  requirement for BAT but  are allowed  a
discharge  under  BPT.

EPA  is   amending existing BAT  limitations for facilities  engaged
 in production  of  sodium chloride  (solution brine-mining  process)
 and  sodium   sulfite.   No  changes  are promulgated for the  calcium
                              414

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chloride subcategory.  The remainder of this section  sets  forth
the background, rationale for the amendments, and recommendations
concerning each subcategory.

SODIUM CHLORIDE (Solution Brine-Mining Process)

General

In   early  1984,  the  sodium  chloride  (solution  brine-mining
process) subcategory included 18 plants (1), none  of  which  are
indirect  dischargers.   The  annual  production was estimated at
about 3,175,000 metric tons (3,500,000 short tons)  per  year  in
1981  (3.36  million  metric  tons in 1979).  The estimated daily
discharge is 15,503 mVday  (4.1  million  gallons  per  day)  of
barometric  condensate  wastewater.1  The  plants  are located in
inland rural areas where the annual precipitation is too high  to
permit  solar  evaporation of the water from the brine to be used
to recover the sodium chloride product.  Fourteen of the existing
eighteen  plants  operating  in  early   1984   discharge   their
wastewater  (barametric  condenser  water)  directly.  Two of the
eighteen plants achieve zero discharge by reinjection  (both  also
use  cooling  ponds)«,   Two plants employ cooling towers with one
achieving  zero  discharge,  and  the  second   only   discharges
infrequently  during  cooling  tower  blowdown.  Hence, there are
fifteen dischargers  in the subcategory.  It should be  noted  that
the  1974  rulemaking  considered only the handling of condensate
alone rather than total flow of  condensate  plus  cooling  water
(see note below).

Process Description

In  the production of sodium chloride by the solution brine-mining
process,  underground  salt  deposits  are mined by pumping water
into the salt  deposit where the  water  dissolves  the salt  and
forms a concentrated solution or brine.  The brine is  then pumped
back  to  the  surface  where   it is chemically treated to remove
impurities and then  evaporated  to  recover   the  sodium  chloride
(table  salt).  The chemical treatment  varies from plant to plant,
but a  typical  process  will  first  aerate  the brine to remove
dissolved hydrogen sulfide  and  oxidize any  iron salts  present  to
the ferric  state.   The brine is then treated with soda ash and
 JThis amount  represents only  the   actual   amount  of   condensate
 before  mixture  with   contact  cooling  water  in the barometric
 condenser.  The actual  total amount of discharged  process  water
 (condensate plus cooling water)  is estimated to be 925,000 mVday
 (244 MGD).
                               415

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caustic  soda  to  convert  most  of  the  calcium,  magnesium,  iron,  and
other metal impurities   present   to   insoluble   precipitates   (as
hydroxides  or   carbonates)   which   are  removed  by  clarification.
The brine is  then  evaporated  using   multiple-effect  evaporators.
As  the  water is  removed,  the salt  crystals  form and are  removed
as a slurry.  The  solids are  screened to   remove   lumps,   washed
with  fresh   brine  to remove calcium sulfate crystals {which  are
returned to the  evaporator),  filtered, dried, and screened.

Water Use and Wastewater Characteristics

The process wastewater discharged consists  essentially   of   the
barometric  condenser  water  used   to  condense the  steam   and
maintain a vacuum  in the multiple-effect   evaporators.    As   the
water  bubbles,  boils,   and  evaporates,   some  salt  crystals  are
carried  over  in  the  escaping  vapor   (become  entrained)  and   are
mixed  with   the  barometric  condenser  water   and  subsequently
discharged.   Any impurities,  such as toxic  pollutants,  that   may
be  present   in  the evaporating solution,  could  also   become
entrained and contaminate the barometric   condenser   wastewater.
The  order  of   concentration of contaminants in the wastewater,
from highest  to  lowest,  will  be  the  same as the  order of  their
concentrations   in  the   evaporating solution.   The residue after
evaporation is the product  sold.  Accordingly,   the  most   likely
contaminant in the barometric condenser  wastewater  is the  product
itself.

The  technology  used  as  a  model   for the zero discharge  BAT
promulgated in 1974  assumed replacement  of  barometric  condensers
by  surface   condensers   (e.g.,   shell and  tube  condensers).   The
surface  condensers would prevent  contact of the  condensed  vapor
and entrained solids with the cooling  water which is  subsequently
discharged,   and consequently reduce the volume  of  the condensate
to a level that  allows the  recycle   of   the  complete wastewater
stream as make-up  water  for the process  (e.g., pumped back to  the
mine  for  solution  mining)  thereby  eliminating  the  need  to
discharge process  water.  Presently,   the   barometric  condensers
currently  installed bring   large   amounts  of  cooling water in
contact  with  condensate  from  the  last  evaporator, and even though
current  data  demonstrates  that  entrainment  of   process  water
pollutants  is low,  this stream  is considered to be process water
by definition.   In  response to  the   petition from the  Salt
Institute,  we   have reexamined  the installed cost and pollutant
reduction associated with the use  of  surface   condensers  using
information that was not available in  1974.

Review of Available  Data
                              416

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Most of the data available have been previously published'by EPA,
and all of it was acquired during the course of studies conducted
to  assist  in  developing  effluent guidelines for the Inorganic
Chemicals  industry.   Data  specific 'to  the  sodium    chloride
(solution  brine-mining  process)  industry  are contained in the
"Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the  Major  Inorganics   Products
segment  of  the  Inorganic  Chemicals Manufacturing Point Source
Category," EPA-440/1-74-007a (March, 1974) (2). , Additional  data
have been collected and developed during the Phase I and  Phase II
studies   which   directly   bear   on  the  issue  of  pollutant
entrainment.   These  data  include  the   analytical   data   on
barometric  condenser  discharge  water  from two sodium  chloride
facilities as well as several plants from other industries.

In the  sodium  chloride   (solution  brine-mining)  manufacturing
process,  the  source  of  the wastewater is barometric condenser
wastewater.  Accordingly,  we  also  reviewed  data  for  similar
processes in other inorganic chemicals industries.  Relevant data
are  available  for  the   chlor-alkali  (diaphragm  cell), sodium
thiosulfate, sodium chlorate, and ammonium bromide subcategories.
The chlor-alkali  (diaphragm  cell)  data  are  contained  in'--'the
"Development  Document  for  Effluent Limitations Guidelines/ New
Source Performance Standards, and Pretreatment Standards  for  the
Inorganic  Chemicals  .Manufacturing  Point  Source  Category" EPA
440/1-82/007  (July,  1982)  (3).   The  data  for   the   sodium
thiosulfate  and  ammonium bromide  subcategories  includes both
screening  and  verification  data  acquired   in   1978    (sodium
thiosulfate)  and   1980   (ammonium bromide) and data submitted to
EPA in 1976 and 1980, respectively, in response to  our   requests
for  data  under  Section  308 of  the Act.  The  data for the sodium
chlorate subcategory  were developed  under   Phase  II   and ; are
summarized  elsewhere  in this  document  (Section  15 and  Appendix
A).  The 1974 data  included results of analyses for  only a  few
metals; the more  recent data included results  of analyses for all
toxic  metal  and  toxic   organic  pollutants.  In all cases, the
products are being  recovered from  solution  by  evaporating  the
water   and   condensing   the  escaping   steam using  barometric
condensers.  Also,  in all cases, the existence of  toxic  organic
pollutants   is  highly  unlikely because  organic substances are
neither used  in the production process nor  likely  contaminants of
the raw materials.   In any event, no toxic organic pollutants are
likely to be added  to  wastewater   as  the  result  of  the  NaCl
process because the process raw  material  is salt  (formed  millions
of  years ago) and  no organic chemicals are added  in the  process.
Essentially  then, we have a purely  inorganic process  in the  case
of  sodium chloride  produced  in the  manner described previously.
                               417

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 The   data  acquired  in  1973  for  barometric  condenser water from
 sodium  chloride production are presented in the  following  table
 (from  Table  22,   page  143   of   the  1974 Development Document,
 Reference 2):

Stream
Intake
Effluent
Concentration (mg/1)
TSS
0
0
PH
8.
8.

0
1
Ca
1
1

28
47
Cl

1
SO.
65
20
i- Fe
13,
37

0
0
These data  show  that  the  barometric  condenser  discharge   contains
some   net   addition   of   calcium,   sulfate,   and   chloride,   but
essentially  no   iron.    The  sodium  chloride  addition   to   the
discharge   averages   2 pounds  per  ton of product  or  0.1  percent
(page 141 of the 1974  Development Document,  Reference 2).    The
calcium  and sulfate  carried over are from the  small  amount  left
after purification of  the brine.  The  absence  of any net  increase
in iron  (Fe)  indicates that no  toxic  metals  are  carried   over
either,  because the   iron  is  present  in the treated  brine at
higher concentrations  than any of the  toxic metals.  Treatment of
the brine to remove iron  by precipitation  as  the  hydroxide  or
carbonate will also reduce the amount  of toxic metals  as  has  been
demonstrated  throughout  the  inorganic  chemicals  and other
industries.   Precipitation of toxic  metals  (and   iron)   as   the
metal  hydroxide is the  technology  basis for  the promulgated BPT
limitations  for  most   of the  subcategories  of   the Inorganic
Chemicals    Manufacturing industry.   This  treatment generally
reduces toxic metal concentrations to  less than  1   milligram   per
liter  and   iron concentrations  to  less  than 10 ppm  (see the
Development  Document   for the  Inorganic   Chemicals   Effluent
Guidelines   and  Standards,  EPA 440/1-82/007, July, 1982, Tables
14-17, 14-18, 14-33b,  14-34, and 14-37,  Reference  3).    Because
the  toxic   metal,  iron,  sodium  and  calcium  compounds in the
purified brine do not  evaporate with the boiling water, the   only
way   these   substances   can  enter  the  barometric condenser
wastewater  is by entrainment.  The most likely   substance  to  be
entrained   is  the substance present in the purified brine in the
greatest amount, which  is  the sodium chloride product.  Of  toxic
metals and  iron, the most  likely pollutant to be entrained is the
iron  since  the treated  brine contains more iron than any of the
toxic metals.  The data above show that  the  discharge   contains
less  than   60   ppm  chloride  (a measure of the amount of sodium
chloride entrained) and no net addition of  iron.   Treatment   of
the  brine  produces  a  product that  is 99.8 percent  pure sodium
chloride, and the data above indicate that much  of  the impurities
are calcium and  sodium sulfates and calcium chloride.
                              418

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           TABLE 17-1.  TOXIC METAL DISCHARGES IN BAROMETRIC
                         CONDENSER WASTEWATER

                           Concentration  (ug/1(ppb))
Plant
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
A
<20
<10
:<15
<2
<50
<50
<10
18
<50
<10
<15
<20
30
B
<20
<10
<15
<25
<50
<50

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The conclusion to be drawn from the data described above  is  that
the  barometric  condenser  water  discharged  from plants in the
solution brine-mining process for sodium chloride production does
not contain toxic metals at significant levels.

The toxic metal discharges in barometric condenser wastewater for
the  chlor-alkali   (diaphragm   cell),   (Plants   A-E),   sodium
thiosulfate   (Plant   F),   and   ammonium   bromide   (Plant  G)
subcategories are shown in Table 17-1.

As shown in Table 17-1, none of the toxic metals are  present  at
significant  levels  and  most  metals  are  below the  detectable
level.  In contrast, the maximum concentrations of  toxic  metals
in  the solutions being evaporated were as follows (samples taken
at the same time as those in Table 17-1):
Plant
  Cu
     Concentration (ug/1  (ppb))
  Cr	  Pb        Ni         Zn
  A
B,C,D
  E
  F
  G
1,700
  600
  530

  140
1,900

  940
  260
2,000
  160
  260

  220
22,000
1,600
  500
  240
  550
  650
The sampling data above strongly support the conclusions that the
toxic metals are left behind in  the  evaporating  solution,  and
that discharges of barometric condenser wastewater do not contain
significant levels of toxic ^metals.

Additional  relevant  data are available from an ammonium bromide
plant, with a total of 18 months of monitoring data  for  ammonia
concentrations  in  the  condenser discharge as well as three-day
screening and  verification  sampling  results.   The  long  term
average  ammonia  discharge  is  1.4 mg/1 ammonia, with a maximum
ammonia concentration of 5.6 mg/1.   This  shows  practically  no
carry-over  (entrainment)  of  the  ammonium  bromide  salt.  The
average  screening  and  verification  results  for  ammonia  and
bromide are as follows (in mg/1):
     Ammonia
         3.2 mg/1
              Bromide
                   6.0 mg/1
In  this  case, the ammonium bromide is the product, and would be
expected to be found at higher concentrations in  the  wastewater
than  any other pollutant.  The fact that the ammonia and bromide
are at very low levels shows that there is very little  carryover
of  the product, and hence negligible amounts of toxic pollutants
would be expected in barometric condenser wastewater.
                              420

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 TABLE -17-2.
CHEMICAL COMPOSITION OF BAROMETRIC CONDENSATE
FROM PLANT F122 (ALL VALUES ARE AVERAGE OF
THREE DAILY MEASUREMENTS).
Pollutant
    Sb
    As
    Be
    Cd
    Cr
    Cu
    Pb
    Hg
    Ni
    Se
    Ag
    Tl
    Zn
              Barometric
              Condensate

               <0.007
               <0.002
               <0.0002
               <0.0037
                0.22*
                0.022
               <0.0016
               <0.0013
                2.87**
               <0.007
                0.00027
               <0.003
               <0.0025
 *Added to the process as sodium dichromate,
**Evaporators are made of a nickel alloy.
                           421

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Another example which  is relevant is one from the sodium chlorate
subcategory at Plant F122.  This plant was described in detail in
Section 15.  Table 17-2 presents data on the toxic metal  content
of  the  barometric condenser water at Plant F122.  Each entry is
an average of three daily values obtained  during  screening  and
verification sampling.

These data confirm that the metals concentrations attributable to
comparable  portions   of  the  process  are extremely low levels.
Chromium present in these streams is explained by the addition of
sodium dichromate  in  the  process  used  for  sodium  chlorate.
Nickel  is  present  because  stainless  steel  is  used  in  the
evaporators.

Our conclusion from  this  data  review  is  that  discharges  of
barometric   condenser   wastewater  from  production  of  sodium
chloride by the solution  brine-mining  process  do  not  contain
significant levels of  toxic pollutants.

This  conclusion is confirmed by analytical data submitted by two
sodium chloride (solution brine-mining  process)  plants  to  the
permitting  authorities  as  part  of  the applications for NPDES
permits for those  plants.   That  data  shows  all  toxic  metal
pollutants  are  below significant levels, and most are below the
detection limit.

Treatment Cost Estimates

In order to determine  the  potential  costs  of  installation  of
surface  condensers  in the sodium chloride subcategory (solution
brine-mining process), a model plant was chosen and the costs  of
installation  of surface condensers were estimated based upon its
characteristics.

The hypothetical model plant chosen produces 1088.4  metric  tons
per day (1200 short tons) of purified sodium chloride.   This size
model  plant was chosen because it is similar to that used in the
1974  Development  Document.   Therefore  costs  and  flows   are
comparable.   Average  daily  process water flow (condensate plus
contact cooling water  in the barometric condenser) at this  plant
is  taken as 45,420 mVday (12 MGD) of which 757 mVday (0.2 MGD)
is condensate from the last evaporation  stage.   In  this  case,
there  is  a  60-fold  dilution  of  the  final condensate before
discharge.
The following assumptions were utilized in
estimates presented in Table 17-3.
developing  the  cost
                              422

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100
           200      300  400  500 600   800  1000
                Surface Area in Square Meters          —

Figure 17.1.   SURFACE CONDENSER COST (SOURCE:  REFERENCED)
                    423

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      TABLE 17-3.  WATER EFFLUENT TREATMENT COSTS AND RESULTING
                  WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY:   Sodium Chloride
ANNUAL PRODUCTION:       597.266	 METRIC TONS  (438,000  short tons)

DAILY FLOW:       45,420	 CUBIC METERS (total flow);  757 n  condens;

                           YEARS   PLANT LOCATION:        N/A  	
  PLANT AGE:
N/A
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY


Facilities
Installed Equipment
   (Including Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital

Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste: Disposal)
Residual Waste Disposal
                                      COSTS ($1,000)  TO ATTAIN LEVEL

                                                    23       4
1A
30.0
172.3
40.5
36.4
27.9
IB
150.0
861.3
202.3
182.6
139.6
                                     307.1  1,535.2
                                      SO". 0
                                      58.2
                        249.8
                        245.2
  Total Annual Cost                108.2  495.0

               b.  RESULTING WASTE-LOAD CHARACTERISTICS

            Avg. Cone.
                                                Long-Term Avg.
                                             Concentration (mg/1)
                                           After Treatment To Level
Pollutant     Untreated(mg/1)          1A     IB      2       3       4
  TSS
                  27
                                     0
                        C.  TREATMENT DESCRIPTION



LEVEL 1A:  Surface condenser'- loss of 10% capacity during summer months

LEVEL IB:  Surface condenser - no loss of capacity
                            424

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The  surface  condenser  would  replace  the  existing barometric
condenser.  The costs developed here do not take into account the
dismantling of the barometric condenser, the  possible  reuse  of
equipment  or  parts, or any salvage value.  No estimate of costs
associated  with  loss  of   production   occurring   while   the
installation  of  the  surface  condensers is proceeding has been
utilized in preparation of these estimates.

Costs are shown for two systems.,  The Level 1A condenser  is  the
smaller  of  the two.  Its use will result in a potential loss of
production during the summer months when the temperature  of  the
incoming  cooling water is assumed to be about 25°C (77°F).  This
loss of capacity is  approximately  10  percent.2  The  Level  IB
condenser   is  sized  such  that  there  would  be  no  loss  in
productivity during such a period.  In both cases, the amount  of
condensate to be handled was assumed to be the same.
In  both  cases,
condensers.

     Facilities

     Building

     Equipment
a  building  is provided for the housing of the
     Level 1A
       85 m2
     Surface Condenser
          (cold steel)   920 m2
          (See Figure 17-1)
Level IB
5 - 85 m2
                    5 - 920 m2
     Operating Personnel 2 m.h./day     5 m.h./day

Level IB condensers are 5 times the size of the level 1A condensers.

Since the available information indicates that the model plant is
a  typical  plant  for  the  industry,  it  is   estimated   that
replacement  of  barometric condensers with surface condensers at
all 15 dischargers would  require  a  total  capital  and  annual
investment as follows (1982 dollars):
2If the temperature of the incoming cooling water is greater than
25°C (77°F), a greater loss of capacity would result.
                              425

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     Total Capital Costs
     Total Annual Costs
Level 1A

$4,606,500
$1,623,000
Level IB*

$23,028,000
$ 7,425,000
*    Sized for no loss of capacity during summer months

The  level  1A costs do not include the costs associated with the
loss of 10% of the production capacity.  Because  available  data
lead  to  the conclusion that the barometric condenser wastewater
in  this  subcategory  does  not  contain  toxic  pollutants   at
significant  levels,  the Agency does not believe these costs are
justified.  Therefore, we are withdrawing the currently effective
BAT regulation for this subcategory.

We are also excluding the subcategory from further  national  BAT
and  PSES  regulation  development because based on the available
data it is concluded that the wastewater does not  contain  toxic
or  nonconventional  pollutants at significant levels and because
there are no indirect dischargers in this subcategory.

New Source Performance Standards

We proposed to retain the zero discharge regulation for  NSPS  on
the  basis that noncontact condensers were not significantly more
expensive for a new plant to  install  than  contact  condensers.
However,-  industry  comments estimated that noncontact condensers
cost about three times as much as contact  condensers.   We  have
reanalyzed   the  condenser  costs.   We  also  identified  three
existing  plants  which  achieve  zero  discharge  with   contact
condensers  and  recycle  of  the  cooling  water through cooling
towers or cooling ponds.  We estimated the  additional  cost  for
new  plants  to  use  cooling towers or cooling ponds and contact
condensers.  The new  cost  estimates  were  developed  as  given
below.

The  design  and  sizing  of  facilities  and equipment for these
wastewater treatment options are very sensitive to local climatic
and  operating  conditions.   The  costs  presented   below   are
estimates  based  on the postulated assumptions.  The accuracy of
these estimates is thought to be ± 25% for the set of assumptions
stated here.  Actual costs incurred at any one plant  could  vary
significantly from the values presented depending especially upon
climatic conditions and land costs.

Cooling Pond

Costs  of  cooling  ponds by which zero discharge is achieved are
based on the following assumptions:
                              426

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          Daily Flow

          Avg. Daily Temp.

          Rel. Humidity

          Solar Radiation Input

          Equilibrium Temp.

          Receiving Temp.

          Returning Temp.
                               45,420 m3 (12 MGD)

                               20°C (68°F)

                               50%

                               315 Watts/m2 (100 BTU/hr/ft2)

                               27°C (80 F)*

                               30°C (86°F)*

                               28°C (83°F)*
*Assumed conditions are probably representative of conditions in
 Michigan.
This yields approximately a 5 hectare (12.3 acre)  cooling  pond.
The costs presented below are for a somewhat larger 8 hectare (20
acre) cooling pond.  In addition, included in the costs are 400 m
(1300  ft)  of piping and pumps to return the cooled water to the
plant.

With respect to land costs, a cost of $12,000/acre  was  assumed.
However,  land  costs may actually be closer to $1,000-2,000/acre
in some rural areas.  In addition, costs presented below assume a
20 acre  area.   A  12.3  acre  area  may  be  adequate  in  most
instances.  Tables 1 and 2 are summaries of capital and operating
costs for the cooling pond option.
Table  1.
Option.
       Capital  and  Annual  Costs for the Cooling Pond NSPS


Capital Costs
     Facilities

          Cooling Pond
          Piping

     Equipment

          Pumps

     Installation
     Engineering
     Contractor OH&P
     Contingency
                                     $109,600
                                       55,100
                                       44,800

                                       42,900
                                       50,500
                                       45,400
                                       34,800
                              427

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     Land
 240,000* (may vary from
          $12,300-240,000)
                             Total
$623,100
($395,400  to
 $623,100)
     Annual Costs

     Operations and Maintenance
          Operating Personnel
          Facility & Equipment
            Maintenance
          Materials

     Energy
     Monitoring and Analysis
     Taxes and Insurance
     Residual Waste
     Amortization
                              Total
$ 18,300

  38,300


  47,900
    **
  18,700

  62,300
$185,500
*See text
**Zero discharge system
Cooling Tower

The cooling tower costs are based on the following assumptions:

          Daily Flow                     45,420 m* (12 MGD)

          Wet Bulb Temp.                 25°C (78°F)

          Receiving Temp.                30°C (86°F)

          Returning Temp.                28°C (83°F)

          Fan Horsepower                 120 HP

Additionally included in the costs are a holding pond  sized  for
six  hours  retention  of  wastewater,  150  meters of piping and
pumps.  Tables 3 and 4 are summaries of the  capital  and  annual
costs associated with this option.


Table 2.  Capital and Annual Costs for the Cooling Tower NSPS
          Option.
                              428

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          Capital Costs
          Facilities
               Holding Pond
               Piping

          Equipment
               Cooling Tower
               Pumps

          Installation
          Engineering
          Contractor OH&P
          Contingency
          Land
                              Total
   22,800
   20,700
 187,500
  44,800

 222,400
  99,600
  74,700
  57,300
  27,000
$657,200
          Annual Costs
          Operations and Maintenance
               Operating Personnel
               Facility and Equipment
                 Maintenance
               Materials (Water Trmt. Chem.)

          Energy
          Monitoring and Analysis
          Taxes and Insurance
          Residual Waste
          Amortization
                                  Total
$
  27,400
  63,000

   7,000

 105,400

  19,700

 102,500
$325,000
The  economic impact analysis shows that the zero discharge NSPS,
whether  achieved  using   noncontact   condensers   or   contact
condensers  with  recycle  of  cooling water, is not a barrier to
entry.  The economic impact analysis included the assumption that
industry's figures were correct.  Since there is  no  barrier  to
entry, there is no need to change the currently effective NSPS or
PSNS for this subcategory.

Basis for BCT Effluent Limitations

On  October  29,  1982 EPA proposed a new and revised methodology
for determination of  BCT  for  conventional  pollutants  (47  FR
49176).   The methodology has been described in detail in several
                              429

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preceding sections of this document (see, for example, Section 16
- "Basis for BCT Effluent Limitations").

Two  candidate  BCT  technologies  have  been  tested   in   this
subcategory,  namely,  the  use of surface condensers in place of
barometric  condensers  to  eliminate  the  discharge  of   total
suspended  solids  (TSS),  and  the  use of filters to reduce the
discharge of TSS (TSS is the only conventional pollutant  in  the
wastewater}.

A.   Option 1 - Surface Condensers

The use of surface condensers at the  15  discharging  plants  is
estimated  to  be  capable  of  removing approximately 450,000 kg
(992,000 Ib) of TSS annually at a cost  of  $1,623,000  (for  the
Level  1A,  or  smaller  condenser).   The  annual  cost  for the
industry using the larger condenser  with  no  loss  of  capacity
would  be  $7,425,000.  Therefore, the computation of TSS removed
would be as follows:

     (BPT limitation) (ann. production) - TSS removed/yr.

     (0.17 kg/kkg) (2,645,833 kkg/yr) - 449,792 kg/yr

     For the surface condenser option as BCT:

                     =  $3.61/kg (1 kg « 2.2 Ibs.)

                         $1.64/lb. TSS removed (1982)
$1,623,000/yr
449,792 kg/yr
As  a  result  of  the  above  computation,  the  candidate   BCT
technology  failed  the BCT - POTW cost test.  Since the Level  1A
option failed the BCT cost test,  inclusion of costs due  to  loss
of  production and production capacity, or applying the BCT cost-
test to the more expensive Level  IB  would  also  fail  the  test
because  the  amount  of  TSS removed would not change with these
more expensive options.  Use of cooling ponds or  cooling  towers
are  also  more  expensive  than  the Level 1A option  (See above,
NSPS), and would also fail the proposed BCT cost test.

B.   Option 2 - Granular Media Filtration

The use of granular media filtration at the 15 discharging plants
is estimated to be capable of removing 240,000 kg   (525,000  Ib.)
of  additional  TSS   (over BPT) annually at a cost of  $3,750,000.
The TSS removals were estimated,  by  assuming  the  filter  would
remove 50% of the TSS.  This removal is better than that normally
expected  from a filter, and tends to minimize the cost per pound
                               430

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of TSS removed.  The cost of the filter has been estimated  using
the cost tables in Chapter 10.

    (Additional TSS removed) (Ann. prod.) = Add. TSS removed/yr.
     (0.09 kg/kkg) (2,645,833 kkg/yr) = 240,000 kg/yr.
     For the granular media filtration option as BCT:

                         $15.63/kg (1 kg = 2.2 Ibs.)

                         $7.10/lb. TSS removed (1982)
$3,750-,000/yr
240,000 kg/yr
     As  a  result  of  the above computations, the candidate BCT
technology failed the BCT-POTW test ($0.43 per pound (1982)).

All  technologies  to  control   conventional   pollutants   more
stringent  than  BPT failed the proposed BCT cost test.  However,
EPA is considering revising that proposed methodology.   In  this
subcategory,  it  is  not  clear that all technologies to control
conventional pollutants more stringent  than  BPT  would  fail  a
revised  BCT  cost  test.   Therefore,  the  Agency  is deferring
establishing a BCT for the sodium chloride (solution brine-mining
process) subcategory.

CALCIUM CHLORIDE (Brine Extraction Process)

General

The  calcium  chloride  subcategory   (brine  extraction  process)
includes  seven  plants,  none of which are indirect dischargers.
Three of these facilities are known to achieve zero discharge  by
reinjection  of  the brine, and none of  the seven have a process
water discharge.  Four plants are  located  in  desert  areas  of
California,  and  three  are  located in Michigan.  All seven use
natural brines as raw material.  The annual  production  capacity
of  calcium  chloride from all processes is 1,047,585 metric tons
(1,155,00 short tons) per year(5).   The  U.S.  Bureau  of  Mines
reported  actual total production of 735,700 metric tons (811,135
short tons) in 1980, however, 526,978 metric tons (581,012  short
tons) or 71.6 percent were produced from natural sources (brines)
(6).

The  uses  of  calcium  chloride  are principally for deicing (30
percent),  dust  control  (25  percent),  industrial   uses   (20
percent),  oil recovery (10 percent), concrete set-accelerator (5
percent), tire  ballasting  (3  percent),  and  miscellaneous  (7
percent) (6).
                              431

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Calcium  chloride is usually sold either as solid flake or pellet
averaging 75 percent CaC12, or as a .concentrated liquid averaging
about 40 percent CaCl2 (6).  The average value in 1980 for solid,
natural calcium chloride was $92.09 per metric  ton   ($83.53  per
short  ton), whereas a recent selling price was listed as $145.50
per metric ton ($132.00/short ton) in  1983  (Chemical  Marketing
Reporter, 5/6/83).

As  a  consequence  of  the  petition  from the Salt  Institute to
review the sodium chloride subcategory, EPA decided to review the
calcium  chloride  subcategory  as  well  because  the  currently
effective zero discharge BAT effluent limitations for the calcium
chloride  subcategory  are  based upon the same technology as the
currently  effective  zero  discharge  BAT  effluent  limitations
promulgated  for  the sodium chloride subcategory (replacement of
barometric condensers with surface condensers) and because  there
are similarities in the processes.

Process Description

The calcium chloride is extracted from impure natural brines.  In
the  manufacturing  of calcium chloride from brine, the salts are
solution mined and the resulting .brines are first concentrated to
remove sodium chloride by precipitation.   Bromides  and  iodides
are  separated from the brines before sodium chloride recovery is
performed.  The brine is then purified by the addition  of  other
materials  to precipitate sodium, potassium, and magnesium salts.
The purified calcium is  flaked  and  calcined  to  a  dry  solid
product.  Extensive recycling of partially purified brine is used
to recover most of the sodium chloride values.
     A typical concentration of the brine is (2):
          CaC12
          MgCl2
          NaCI
          KC1
19.3%
 3. 1%
 4.9%
 1 .4%
Bromides
Other Minerals
Water
 0.25%
 0.5%
70.8%
Water Use and Wastewater Characteristics
In  1974,  one  plant  was  visited  and used as the basis of BPT
limitations.  At this plant,  process  wastewater  resulted  from
process blowdown and from several partial evaporation steps.  The
effluent  from  this  plant  contained  approximately 2,860 cubic
meters/day (0.755 MGD) of washdown and washout water.

At this plant, the wastewater  from  all  chemical  manufacturing
processes  located at the site was treated in an activated sludge
treatment plant to remove organic substances, and then passed  to
                              432

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a  settling  basin  to  remove suspended matter.  The pH was then
adjusted and the -water passed to a second pond to further  settle
suspended  matter,  and  finally  discharged.  In 1974, the plant
planned on making a  change  in  the  evaporators  to  reduce  or
eliminate  calcium  chloride  discharges  and  eliminate ammonia.
More recycling of spent brines was also planned.

During a follow-up study in 1976, considerable changes  had  been
made  in  the  usage  of  water  at  this  plant.   Average total
wastewater discharge (including  noncontact  cooling  water)  was
reduced  from  31,600  cubic meters per day  (8.35 MGD) in 1974 to
11,550 cubic meters per ,day (3.05 MGD) in 1976.  Currently (1983)
the discharge consists solely of  noncontact  cooling  water.   A
surface  condenser  was  installed to eliminate discharges from a
barometric condenser.  The condensate from the surface  condenser
is  now  recycled  and  is  estimated at approximately 1458 cubic
meters per day (385,000 gpd).  Approximately 955 mVday  (252,000
gpd) of concentrated brine is returned to the formation.

In late 1982 and early 1983, a survey of all seven plants in this
subcategory  was  conducted  to determine the discharge status of
all seven plants.  The results of this survey and  data  gathered
previously are listed below:
     Plants
Zero Discharge3
Indirect Discharge4
This survey was conducted by consulting the  1982 SRI Directory of
Chemical  Producers   (7),  by  telephone contact with each of the
plants, review of the  1974 Development Document and the  Phase   I
rulemaking record and  a previous contractor's report  (8),

There are no known dischargers in this industry.


Recommendat i ons

BAT,  NSPS,  PSNS  Effluent  Limitations.    Based  upon the survey
conducted, there are  no known dischargers   in  this  subcategory.
All seven facilities  already are achieving  the BAT limitations of
 3Includes  three  plants  known   to   be   zero   discharge   and   three
 others   located   in  inland, arid  areas;  these  facilities  reinject
 waste brine  because  of  a  scarcity of  process water  available.
 4A11 plants  confirmed that  they were  not indirect dischargers   or
 were located in  rural areas with  no POTW.
                               433

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no  discharge  of  process wastewater pollutants.  Therefore, the
Agency is not proposing any changes in  the  currently  effective
BAT effluent limitation.

Similarly, since new sources can be designed for this requirement
and  avoid  any retrofit, and the costs of surface condensers are
similar to barometric condensers, there is  no  reason  to  amend
NSPS or PSNS.

PSES   Effluent   Limitations.    Since  there  are  no  indirect
dischargers in this subcategory, the Agency proposes  to  exclude
the subcategory from any development of PSES.
                                                are  no  existing
BCT   Effluent   Limitations.     Since    there
dischargers, there  is no need  for a BCT.

SODIUM SULFITE

General

The  major  inorganic  chemical   process   for   sodium   sulfite
manufacture  consists essentially of reacting sulfur dioxide with
soda ash.  Another  source  is as a by-product from the  production
of  phenol  or  its derivatives   through  the reaction of sodium
benzene sulfonate with sodium  hydroxide.  The latter  process   is
an   organic  chemical  process   and  is  not  included   in  this
subcategory.

There are three sodium sulfite plants which utilize the soda  ash
    sulfur  dioxide reaction  process.   The  annual  production
capacity of sodium  sulfite by  this process  is  estimated  to   be
approximately  69,840  metric  tons  (77,000  short tons) with  an
estimated total average daily  discharge  of  416.4  cubic  meters
(110,000  gpd).   There  are   two direct dischargers and a single
indirect discharger, which discharges  an  average  of  70  cubic
meters  per  day  (18,500 gpd).   This stream consists of slightly
contaminated washdown water only.

At the time of promulgation of the  sodium  sulfite  regulations,
there  were  seven  plants in  the subcategory with a total annual
production capacity of 181,000 metric tons (200,000  short  tons)
per  year and a total average  daily discharge of 568 cubic meters
(0.15 MGD).  However, as stated above, there are now  only  three
plants  included  in  the  sodium sulfite  subcategory,  with  a
substantial decrease in capacity.

After receiving the petition from the Salt  Institute  to  review
the  sodium  chloride  subcategory, EPA decided to reconsider the
BAT for the sodium  sulfite subcategory (soda ash -sulfur  dioxide
                              434

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process).   BAT  for  this  subcategory  requires no discharge of
"process  wastewater  pollutants"   except   for   excess ..  water
discharged  from  wastewater impoundments designed to contain the
25-year - 24-hour  storm.   BPT,  however,  allows  a  continuous
discharge.

Process Description

In  the  soda ash-sulfur dioxide reaction process, sulfur dioxide
gas is passed into a  solution  of  sodium  carbonate  until  the
product   is   acidic.   At  this  point  the  solution  consists
primilarly of sodium  bisulfite  which  is  converted  to  sodium
sulfite  by  the  further addition of soda ash and heat until all
the carbon dioxide is released.

The crude sulfite formed from this reaction is purified, filtered
to remove insolubles from the purification  steps,  crystallized,
dried and shipped.

Water Use and Wastewater Characteristics

The   process   water  generated  in  this  subcategory  consists
primarily of evaporator/crystallizer condensate, condensed  dryer
vapor,  filter washwater, and process cleanout water.  Wastewater
volumes are generally low, and  for  the  three  plants  in  this
subcategory are as follows:
Plant    Capacity*

  A     27,210 kkg



  B     33,560 kkg
  C      9,070 kkg
        69,840 kkg/yr
Direct/Indirect

     Direct
     Direct

     Indirect
           Treatment

           pH adjust,
              oxidation,
             filtration
330.0 m3   pH adjust, oxidation,
             settling
 70.0 m3   None  .
416.4 mVday
Treatment technologies  in use by the direct dischargers are equal
to or better than those used in the sodium bisulfite subcategory.

Typical flows used for  development of the BPT  limitations were as
follows:
     Process condensate
     Dryer ejector and
       filter wash
           mVkkg
          0.17
          0.29 - 0.63
                              435

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The   limitations  were  based  upon  the  wastewater stream  from  the
dryer ejector  and filter wash  operations  at  the high  end  of   the
range {0.63 mVkkg).

Data  available for the three  remaining plants utilizing  the soda
ash - sulfur dioxide reaction  process yield  an average unit  flow
of 2.2 m3 kkg** (581 gal/ton)  for all wastewater discharged.

BPT  for  this subcategory  is  oxidation of the sulfite to sulfate
(usually by aeration) and filtration of the  wastewater to remove
suspended solids.  BPT effluent  limitations  in effect are:
         Parameter

        pH
        TSS
        COD
Limitations
(30 day average)

   6-9
   0.016 kg/kkg
   1 .7 kg/kkg
(24-hr Maximum)
0.032 kg/kkg
3.4 kg/kkg
*Reference 7
**Range:  0.22 mVkkg to 3.6 mVkkg

The  treatment  technology used as a basis for the zero discharge
BAT limitations, NSPS, and PSNS was evaporation  of  the  treated
process   wastewater.    This   technology  was  believed  to  be
economically achievable based on 1971 fuel costs and the sale  of
the  residue (sodium sulfate) from the evaporation.  Those plants
located in  areas  of  the  country  where  evaporation  exceeded
precipitation could use solar evaporation to achieve no discharge
of  process  wastewater  pollutants.   However,  for  plants that
cannot use solar evaporation, the cost  of  fuel  has  quadrupled
since  1971,  whereas  the  selling  price  of sodium sulfate has
increased only slightly.

Review of Available Data

Data specific to the sodium sulfite industry are contained in the
1974 Development Document (Reference 2), and we  also  have  data
from  sodium  sulfite  plants  submitted  to  EPA  in  1976-77 in
response to our request for data under Section 308 of the Act.

The data specific to sodium sulfite contain  limited  information
about the amount of toxic pollutants in the wastewater.  However,
the  sodium  sulfite  production  process  is very similar to the
production  process  for  sodium  bisulfite  (compare  the   1974
Development  Document,  pp.   154-8,  with  the  1982  Development
Document,  page 711).   The  major  differences  are  that  sodium
                              436

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   TABLE 17-4.  TOXIC POLLUTANT CONCENTRATIONS OBSERVED IN
       TREATMENT EFFLUENT DURING VERIFICATION SAMPLING
Pollutant
Arsenic
Copper
Zinc
Cadmium
Chromium
Lead
Mercury
Nickel
Antimony
Thallium
Silver
Concentration (mg/1)
Plant         Plant
 #987          #586
  ND
0.27
0.010
  ND
0.11
0.15
  ND
  ND
  ND
  ND
  ND
 ND
 ND
 ND
 ND
 ND
 ND
0.010
0.050
0.020
 ND
 ND
ND - Not Detected
                      437

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sulfite  is collected  from  the reaction mixture  at  a higher pH and
that  purification  of  the sodium  sulfite, at least at one plant,
includes the addition of small amounts of  copper.

Since the raw materials are  the   same  for  sodium  sulfite  and
sodium  bisulfite,  and since the unit flows are  nearly  the same
(2.2  mVkkg  for  sodium  sulfite  and  1.5  mVkkg  for sodium
bisulfite),  we  estimated the total  torcic pollutant load for the
sodium  sulfite  industry  based   on  the  observed  total  toxic
pollutant  loads found  at  sodium bisulfite plants, with allowance
for a slightly higher flow for sodium sulfite and  for the use  of
copper  during  purification  of   sodium   sulfite  (these factors
increased estimated raw waste  loads above  those  observed  at
sodium  bisulfite plants).  We also considered  the fact that both
direct discharge plants reported in their  responses to  our  1976
request for data that the  plants have treatment systems identical
to  those used in the sodium bisulfite industry.   Those treatment
systems do control discharges of toxic metals and  chemical oxygen
demand (COD).  In addition, sodium sulfite and  sodium  bisulfite
wastewaters  are  commingled  for   treatment  in common treatment
plants at both of those facilities.

Table 17-4 summarizes  the toxic   pollutant  concentration  data
observed  in  treated  effluent during verification sampling from
the two sodium bisulfite plants visited  during Phase  I.   Both
plants  employ  hydroxide  precipitation,  aeration, and settling.
All  toxic  metal  levels  are  below detection   levels  or  are
marginally  treatable  by  the technologies examined elsewhere in
this document for metal  salts  production.   All  concentrations
listed   in  the  table are  below  the   proposed BPT   and  BAT
limitations for the same parameters listed in Sections 11 through
16.

Comparison of Sodium  Sulfite and Sodium Bisulfite  Subcategories

The discussion above  points out the similarity  between the Sodium
Sulfite and Sodium Bisulfite Subcategories.  Our review   of  both
subcategories  has shown that the  processes and raw materials for
the two chemicals are the  same.  In the case  of   sodium  sulfite
the  process  is taken  further to  completion.   Examination of the
wastewater flows shows  that the unit  flows for  the two  processes
were  nearly  identical  (1.5  mVkkg  vs.   2.2  mVkkg), and the
wastewater  treatment   technology   in  use  at  the  plants   was
identical.    In  addition,   both   of  the  direct discharge sodium
sulfite plants also produce sodium  bisulfite and the  wastewaters
are  commingled  in   a  common treatment system.   Table 17-5 is a
summary and comparison of  the two  subcategories pointing  out  the
similarities between  them.
                              438

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            TABLE 17-5.   Comparison of Sodium Sulfite
               and Sodium Bisulfite Subcategories
Plants
Unit Flow
Process
Raw Materials
Treatment Tech.
  In Place
BAT
Sodium Sulfite
3
2.2 mVkkg
Soda Ash - S02
NaC03, S02
OH Pptn., Aeration,
Filt. or Settling
Zero Discharge <*>
Sodium Bisulfite
7
1 .5 mVkkg
Soda Ash - SO 2
NaC03, S02
OH Pptn., Aeration
Settling
Discharge subject
to 40 CFR 415.542
 (1)  Eliminated by the final rule.
                              439

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         TABLE  17-6.!WATER EFFLUENT TREATMENT COSTS AND RESULTING
                     WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
   SUBCATEGORY:    Sodium Sulfite
   ANNUAL PRODUCTION;A-27,210;B-53,560 ; C-9 .  METRIC TONS
                       070
   DAILY FLOW:  A-16.4;B-350;C-70     CUBIC METERS
   PLANT AGE:
      N/A
YEARS   PLANT LOCATION:   DE, VA.  CA
              a.   COST  OF TREATMENT  TO ATTAIN  SPECIFIED LEVELS
   COST  CATEGORY

   Facilities
   Installed Equipment
     (Including Instrumentation)
   Engineering
   Contractor Overhead and Profit
   Contingency
   Land

    Total Invested Capital

  Annual Capital Recovery
  Annual Operating and Maintenance
   (Excluding Residual Wast6 Disposal)
  Residual Waste Disposal

    Total Annual Cost
                        COSTS  ($1,000)  TO  ATTAIN LEVEL 1
                        Plant A   Plant B   Plant C
                        $152.6    $1,012.8  $373.8
                          30.5       202.6    74.8
                          27.5       182.3    67.3
                          21.1       139.8    51.6
                        $231.7    $1,537.5  $567.5
                         •37.7
                         180.4

                          32.9

                        $251..0
                      250.2
                    1,622.2
               92.3
              399.7
                      674.5    144.5

                   $2,546.9   $636.5
Parameter

   TSS
   COD
   TDS
                 b.   RESULTING WASTE-LOAD CHARACTERISTICS

              Avg.  Cone.
   BPT
               Effluent  Loading kg/kkg
             After Treatment  To  Level
               B     C
0.016 kg/kkg
1.7 kg/kkg
70,000-90,000 mg/1
          0
          0
          0
0
0
0
0
0
0
                         c.   TREATMENT DESCRIPTION
   PLANT A:  Evaporation -  Agitated Falling-Film Evaporator (to dryness)
   PLANT B:  Evaporation -  Multiple Effect Evaporator plus Agitated Falling-
                           Film Evaporator
   PLANT C:  Evaporation -  Multiple Effect Evaporator plus Agitated Falling
                           Film Evaporator
                             440

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Treatment Cost Estimates

Based upon last quarter 1982 costs, treatment cost estimates were
prepared  for  the  three  existing  plants.  The only technology
considered was evaporation because the  existing  BAT  was  based
upon  this  technology.   Table  17-6  summarizes  the  cost data
developed.

Based upon these estimates,  installation  of  the  existing  BAT
technology  at  all  three  plants  would  require  the following
investment:
     Total Capital Costs
     Total Annual Costs
$1,916,200
$2,817,100s
Based on these costs,  our  Economic   Impact  Analysis  for  this
subcategory  predicts  at   least  two  plant  closures and severe
impacts for the other plant assuming the one  indirect  discharger
had to comply with the currently effective BAT.  Considering that
the  existing  data base indicates  low levels of toxic pollutants
in treated effluent, we conclude that  the costs  associated  with
the  existing BAT are not reasonable and that no discharge is not
economically  achievable.   Therefore,  we  are  withdrawing  the
existing  BAT  and  establishing  a new BAT  for toxic pollutants
equal to BAT for sodium  bisulfite.    Further  justification  for
this  proposal  is  provided   by the similarity  in processes,
materials, treatment systems  and  wastewater  flow   for   the
subcategories.   The limitations for TSS and  COD would remain the
same based upon the same BPT  technology.
                                raw
                                two
Basis  for BCT  Effluent  Limitations

On  October  29,  1982  EPA proposed a  new  and  revised  methodology
for determination  of   BCT  for conventional   pollutants (47  FR
49176).  The methodology has been described in  detail  in  several
preceding sections.   (See for example, Section  16 -"Basis for BCT
Effluent Limitations").

Only  one   candidate BCT  technology  has  been  tested  in this
subcategory namely,  the  use  of evaporation  to  eliminate all
wastewater   and  contained  TSS, total dissolved solids, COD and
metals.   TSS   is  the   only  conventional   pollutant   in  the
wastewater.   Filtration was not tested as a candidate technology
 sAnnual costs include energy costs which are very  high
 BAT technology (evaporation).
                            for   the
                               441

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 TABLE 17-7.    BAT  AND  BCT EFFLUENT LIMITATIONS FOR SODIUM SULFITE
Conventional^- ^
Pollutants

PH
TSS
                                       Effluent Limitations
30-day avg.

    (1)
0.016(2)
24-hour max.
0.032
      (2)
Non-Conventional
Pollutants	

COD
1.7(2)
 3.4(2)
Toxic Pollutants

Chromium  (T)
Zinc (T)
0.00063(3)
0.0015 O)
 0.0020(3)
 0.0051(3)
(1)   Within the range 6.0 to 9.0^
(2)   Based upon BPT promulgated for Sodium Sulfite Subcategory
     (40 CFR Sec.  415.202).
(3)   Based upon BAT promulgated for Sodium Bisulfite Subcategory
     C40 CFR Sec.  415.542).
(4)   BCT only.
                          442

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because  the  BPT   limitations   were   based   upon   hydroxide
precipitation, aeration, and filtration.

The  amount  of  TSS  removed  by the candidate technology may be
calculated from the BPT limitations and production  capacity  for
the subcategory:

(0.016 kg/kkg) (69,840 kkg/yr) = 1,117.4 kg/yr (2,458.4 Ibs.)
Therefore:
     $2,817,100/yr
      1,117.4 kg/yr
$2,512.12/kg TSS removed -t 2.2 Ib/kg

=  $1,141.87/lb TSS removed (1982)
On  October  29,   1982,  EPA  proposed  a revised BCT methdology.
While EPA  is considering revising that  proposed  methdology,  we
have determined that  in this subcategory no technology  beyond BPT
will  pass  the proposed BCT cost test or any other BCT test that
the Agency is  likely  to adopt.  Accordingly, EPA  has   determined
that  BCT  equals  BPT  in  this  subcategory.  Therefore,  EPA is
promulgating BCT equal to BPT.

Basis for  BAT  Effluent Limitations

Since BPT  is already  in effect  for  this subcategory,  the   Agency
evaluated  its effectiveness for removal of toxic metals  as well
as the  effectiveness  of similar BPT and BAT  systems  which form
the  basis of limitations for the sodium bisulfite  subcategory.
In addition, the costs were reevaluated for the  technology used
as  the basis for  the  1974 BAT effluent  limitations.   Using  the
data presented earlier and these cost estimates for   evaporation,
it  was concluded  that  the   BAT   effluent   limitation  of zero
discharge  for  this subcategory  should be withdrawn.

In  its  place,  the  Agency  is promulgating effluent limitations  for
toxic metal  and non-conventional pollutants based  upon  the   BPT
technology.  Additional  parameters, chromium and zinc,  are added,
and   these  limitations  are based  upon the limitations  already in
effect  for the sodium bisulfite subcategory.6
 •Although one facility  adds  small  amounts  of  copper  in  the
 process,  this  parameter  will  be effectively controlled by the
 technology upon which the limitations for the other  toxic  metal
 parameters are based.
                               443

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 Table  17-7  summarizes  the  limitations  promulgated  for  this
 subcategory.

 Since  the  evaporation technology is not economically achievable
 and  since  the  raw  materials,  processes  employed,  treatment
 systems,  unit  flows,  and  toxic  pollutant  concentrations are
 similar,  we  are  basing  the  promulgated . limits   for   toxic
 pollutants  on the existing BAT for sodium bisulfite.  We are not
 changing the limitations established for COD  under  BPT  because
 the BAT limitations are based upon the BPT technology.

 Basis for NSPS Effluent Limitations

 Since  the evaporation technology is not economically achievable,
 a no discharge limitation would be a barrier to entry.  For NSPS,
 the Agency is promulgating limitations equal to BAT  since  there
 is  no  other  technology  known  which  would remove significant
 additional  amounts  of  pollutants.    For  TSS  and   COD,   the
 limitations  are  the  same as BPT since the technology basis for
 BAT is the same as for BPT.

 Basis for Pretreatment Standards

 Pretreatment is necessary because it  provides better  removal  of
 chromium,   zinc,   and  COD  than is achievable by a well  operated
 POTW with secondary treatment  installed,   and  thereby  prevents
 pass-through  that  would  occur  in   a  POTW  in  the absence of
 pretreatment.

 The Agency does not have raw waste load data for  sodium   sulfite
 manufacturing   but  does  have  such   data  for  sodium bisulfite
 manufacturing.   Because of the similarities in the processes  and
 wastewater  sources,  the sodium bisulfite  raw waste load  data for
 COD,  chromium,  and zinc have been used as   the  raw  waste  loads
 expected  from  sodium sulfite manufacturing.   These concentrations
 are   compared   to   the   treated  effluent  long-term   average
.concentrations for the selected BAT technology for sodium sulfite
 to estimate the percent removals for   COD,   chromium,   and  zinc.
 The calculations  are as follows:
               COD;


                  Percent  Removal
Raw Waste *>
BAT
1960 ppm
 550 ppm
    = [<1960-550)t(1960)J{100)
    - 71.9%
               Chromium:
Raw Waste = 1.95 ppm
BAT       =0.22 ppm
                              444

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                 Percent Removal = [ (1 . 95-0. 22)'t( 1 . 95) ] (1 00)
                                 =88.7%
              Zinc:
Raw Waste = 1.81 ppm
BAT       =0.52 ppm
                 Percent Removal = [(1.81-0.52)^(1.81)](100)
                                 » '71 .3%       ;

The  percent removals of chromium, zinc, and COD are greater than
the removals for  chromium  (65%),  zinc  (65%),  and  COD  (72%)
achieved  by  25% of the POTWs in the "50 Cities" study (see Fate
of Priority Pollutants in Publicly Owned Treatment  Works,  Final
Report,  Volume I, EPA-440/1-82-303,  September 1982).  Therefore,
chromium, zinc, and COD would pass through a POTW in the  absence
of pretreatment.

Existing Sources

There  is  one  indirect  discharger  in  this  subcategory which
discharges 70 cubic meters per day (18,500 gpd) to a POTW.  Total
toxic metal  pollutant  loading  for  this  single  facility  are
estimated  to  be  0.053  kg/day  (0.12 Ib/day).  This estimate  is
based on the COD data provided by the  Plant.   That  data  shows
that the average COD discharge is less than the' long-term average
COD  used  to  develop  the  COD effluent limitations.  Since the
toxic metals are in the wastewater with the COD, the toxic metals
are also estimated to be low in concentration and about equal   to
their  long-term average concentrations.  On the basis of flow and
low  toxic  pollutant  loading, we are excluding this subcategory
from further PSES development under  Paragraph  8(b)(ii)  of  the
EPA-NRDC Settlement Agreement.


New Sources

The  Agency  is  promulgating PSNS that are equal to NSPS because
these  standards provide for the removal of  toxic metals which may
pass through a well operated POTW with secondary treatment  in the
absence of pretreatment.  The pollutants regulated under PSNS are
chromium,  zinc,  and  COD.   Table  17-6   summarizes   the   PSNS
limitations for chromium, zinc, and COD.
                               445

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                           SECTION  17

                           REFERENCES
2.
3.



4.



5.


6.


7.


8.



9.
U.S. Bureau of Mines,  "Directory of Companies Producing Salt
in the United States   -   1981,"  Mineral   Industry  Surveys,
prepared in the Division  of  Industrial Materials.

U.S. Environmental Protection Agency, "Development  Document
for   Effluent   Limitations   Guidelines   and  New  Source
Performance  Standards  for  the  Major  Inorganic  Products
segment  of  the  Inorganic  Chemicals  Manufacturing  Point
Source Category," EPA-440/l-74-007a, March  1974.

U.S. Environmental Protection Agency, "Development  Document
for   the   Inorganic   Chemicals  Effluent  Guidelines  and
Standards," EPA 440/1-82-007, July, 1982.

Peters,  M.S.  and  Timmerhaus,  K.D.,  "Plant  Design   and
Economics for Chemical Engineers," Third edition, McGrawHill
Book Co., 1980.

Chemical Marketing Reporter,  "Chemical  Profile  -  Calcium
Chloride," December 25, 1978.

U.S. Bureau of Mines,  "Minerals Yearbook -  1980,"  Vol.  I,
Meals and Minerals.
Stanford  Research
Producers - 1982".
Institute,    "Directory   of   Chemical
"Supplement for Pretreatment to the Development Document for
the   Inorganic   Chemicals   Manufacturing   Point   Source
Category," EPA 440/1-77/087.

Terlecky, P.M. and Harty  D.M., "Status of Group II Chemical
Subcategories  of  the  Inorganic  Chemicals   Manufacturing
Industry of (Phase II)," Frontier Technical Associates, Inc.
Report No. FTA-82-E-2/03 Revised January 14, 1983.
                              446

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                           SECTION 18

                     PRETREATMENT STANDARDS
                   FOR DEFERRED SUBCATEGORIES
INTRODUCTION

General

As part of Phase II, EPA considered pretreatment standards for 23
additional  subcategories of the Inorganic Chemicals Point Source
Category.  For 18 of  these  subcategories,  PSES  had  not  been
promulgated.   Therefore, for these 18 subcategories, the purpose
of this review was to determine which subcategories might require
development of PSES.  For the remaining five  subcategories,  the
purpose   of   the  review  was  to  determine  whether  existing
pretreatment standards were adequate.

Pretreatment Standards for  New  Sources   (PSNS)  requiring  zero
discharge   are   currently   in   effect  for  10  of  those  23
subcategories.  Of the remaining 13 subcategories, one is covered
under the Petroleum Refining Point  Source  Category  (Hydrogen).
Each  of  the  12  subcategories not covered by PSNS is currently
subject to a zero discharge BPT requirement.

Subcateqor i es Surveyed
     The 23 subcategories surveyed are as follows:
 1 .
 2.
 3.
 4.
 5.
 6.
 7.
 8.
 9.
 10.
 11 .
 12.
Borax
Bromine
Calcium Carbide**
Calcium Chloride**
Chromic Acid
Fluorine
Hydrogen***
Iodine
Calcium Oxide**
Calcium Hydroxide
Potassium Chloride
Potassium (metal)**
13.   Potassium Sulfate**
14.   Sodium Bicarbonate**
15.   Sodium Chloride**
16.   Sodium Sulfite**
17.   Stannic Oxide
18.   Zinc Sulfate
19.   Aluminum Sulfate*,**
20.   Ferric Chloride*
21.   Lead Monoxide*
22.   Potassium Dichromate*,**
23.   Sodium Fluoride*
   *Subcategories with existing PSES.
 **Subcategories with existing PSNS.
***Subcategory  covered by Petroleum Refining  Category.

Methods Employed
                               447

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An accurate and up-to-date  list of all  companies  and plants  which
manufacture the products  in the 23 subcategories  was   developed.
Sources  utilized   in   compiling  that list  included: the  Stanford
Research Institute's "Directory of Chemical  Producers  - 1982"  (1)
the OPD Chemical  Buyers  Directory   (2),   the  Salt   Institute's
membership   list,  the  U.S.  Bureau   of   Mines  (3),   the  Lime
Association, the Thomas Register, in-house  files  at EPA  and  the
contractor,  and  a  previous  EPA survey.   All plants  identified
from the above sources  were contacted to determine  which plants
and  facilities  in  each  subcategory  were  indirect dischargers.
Some  of  the  plants   initially  identified were   subsequently
determined  to  be  distributors  or  repackagers and  were  not
producing the chemical.

The several sources listed  above  identified 304 plants in  22
subcategories (all except the Hydrogen  subcategory).   Information
on  302 of those plants was provided through telephone  or written
contacts with the plants, by  Regional  and  State  NPDES permit
authorities,  and  from  local  POTW authorities.  The  two plants
which could not be contacted are  located in  remote,  rural   areas
where   there  are  no  POTW's.   For   the   hydrogen  subcategory
(refinery by-product),  there are  137 plants  listed in addition to
those above.  However,  any  discharges to  POTW's  are   controlled
under   existing   PSES  and  PSNS  for  the Petroleum  Refining
Subcategory (40 CFR Part  419).

Basis for PSES Exclusions

Paragraph 8(a)(i) of  the   Settlement  Agreement  authorizes  the
Administrator to exclude  from regulation industrial categories or
subcategories  for  which equal or more stringent limitations are
already provided by existing effluent limitations  and  standards
(in  this case,  the Hydrogen Subcategory).   Paragraph 8(b) of the
Settlement Agreement authorizes the Administrator to exclude from
regulation under the pretreatment standard a subcategory  if   (i)
95  percent  or  more   of   all  point  sources in the subcategory
introduce into POTWs only pollutants  which  are  susceptible  to
treatment  by  the  POTW  and which do not interfere with, do not
pass  through,   or  are  not  otherwise  incompatible   with  such
treatment   works;   or  (ii)  the  toxicity  and  amount  of  the
incompatible pollutants introduced by  such  point  sources  into
POTWs  is  so  insignificant  as  not  to  justify  developing  a
pretreatment regulation.

SURVEY RESULTS BY SUBCATEGORY

This  section  summarizes   the  results  obtained  for    the   23
subcategories  surveyed.    Subcategories  1   through  18  have no
                              448

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current PSES proposed or promulgated.   For  the  remaining  five
subcategories (19-23), "PSES have been promulgated.

Subcategories 1-18

1.    Borax

There are four known producers of borax (sodium  tetraborate)  by
the  mining  process  or  trona  process.   There are no indirect
dischargers  in  this  subcategory  because  all  facilities  use
evaporation ponds for process wastewater.
2.
Bromine
     There are eight known producers  of  bromine  by  the  brine
mining  process  and by the Trona process.  There are no indirect
dischargers.

3.   Calcium Carbide                      	

     There are three known  producers  of  calcium  carbide  from
uncovered  furnaces.   There  are no indirect dischargers in this
subcategory.  Calcium carbide from covered furnaces is  .regulated
under the Ferroalloys Category at 40 CFR 424.40 and 424.50.
4.
Calcium Chloride
There are seven known producers of calcium chloride by the  brine
extraction  process.  There are no direct or indirect dischargers
in this subcategory.                                       •

5.   Chromic Acid

There are two known producers of chromic acid in facilities which
also manufacture sodium dichromate (see 40 CFR  415.350).   There
are no indirect dischargers in this subcategory.
6.
Fluorine
There  are  two  known  producers  of  fluorine  by  the   liquid
hydrofluoric  acid  electrolysis  process.  There are no indirect
dischargers in this subcategory.

7.   Hydrogen

There are approximately 137 plants producing hydrogen  as  a  by-
product  of the petroleum refining process.  Wastewater from this
                              449

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 subcategory  is  subject  to  effluent  limitations  for  the
 Refining Point  Source Category  (40  CFR  419).
                                                   Petroleum
 8.
Iodine
There are  three  known  producers  of   iodine   but   only   one  plant
discharges  to   a   POTW.   That one plant  discharges  approximately
200 gpd  to a POTW.

9.   Calcium Oxide  (Lime)

There are  50 known  facilities  producing  calcium oxide   (lime).
There  are  no   indirect   dischargers.    One  plant  could not  be
contacted  but is located  in  a remote,  rural  area  far from  a POTW.

10.  Calcium Hydroxide (Hydrated Lime)

There are  37 known  producers of  hydrated  lime.   One  of  these
discharges  to a POTW,  and two discharge  directly.   A total of  33
•facilities  achieve zero  discharge   because   they   are  dry
operations,   by  recycle,  and by  impoundment  and evaporation.  The
discharge  status of one facility is  unknown,  but  it  is  located  in
a remote,  rural  area  far  from  a   POTW.    The   single indirect
discharger  discharges only 200 gallons/day (10  gpm for 20 min.)
to a POTW.

11.  Potassium Chloride

There are  eight  known  producers  of  potassium chloride   by the
Trona  process   and by  the mining  process (40 CFR 415.500)  at
present.   There  are no indirect  dischargers  in this  subcategory.

12.  Potassium (Metal)

There is one known  producer  in this  subcategory   which  does not
discharge   process   wastewater from  potassium metal  manufacturing
to a POTW.

13.  Potassium Sulfate

There are  six known producers of potassium sulfate none of  which
discharge  to POTWs.                                    ,

14.  Sodium Bicarbonate

There are  four known plants  producing  sodium bicarbonate.    Three
plants   do  not  discharge  process  wastewater   while  one plant
commingles wastewater  from  sodium   bicarbonate   production with
                               450

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other
POTW.
process  wastewater,  treats  it  and then discharges to a
With regard to the  single  indirect  discharger,  the  following
monitoring  information  was  obtained  from  the POTW concerning
toxic metal concentrations in the discharge to the POTW from  the
plant (for a period 13 months){from Reference 6):
                            Parameter
                  Average Concentration (mg/1)
  Cd
    Cr
Cu
               Pb
Hq
Ni
Ni
<0.017
   0.018  0.051  <0.029  <0.0011  0.026  0.076
Toxic metals in the discharge are present at concentrations which
are low and near detection levels.

15.  Sodium Chloride

Sodium chloride is produced by both the solution brine-mining and
solar evaporation processes.  The results of the survey of plants
employing both processes are included here.
     a.
     b.
   Solution Brine Mining.  There are 18 known producers of
   sodium chloride by the solution brine  mining  process.
   None of these plants discharge to POTWs.
                                  There
                               are   39   known
Solar  Evaporation  Process.
producers  of  sodium chloride by the solar evaporation
process.  There are no indirect dischargers.
Both processes (a and b) are employed at some facilities.

16.  Sodium Sulfite                              ,

There are three known producers of  sodium  sulfite  by  reacting
sulfur  dioxide  with  sodium carbonate (soda ash).  Two of these
discharge  wastewater  directly  while  one  facility  discharges
washdown  water  only  to a POTW (70 cubic meters per day (18,500
gpd)).  On the basis of the information and analysis presented in
Section  17  of  this  report,  the  Agency  is  excluding   this
subcategory from PSES.

17.  Stannic Oxide

There is one known producer of stannic oxide.  This facility uses
a dry thermal process which involves the reaction  of  tin  metal
                              451

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with  air  or  oxygen.  No wastewater is produced and there is no
discharge.
18.  Zinc Sulfate

There are 12 known producers of  zinc  sulfate.   There  are  two
indirect dischargers.  One of these discharges an average of 4000
gpd  to  the  POTW.  Flows are less than 1 percent of plant flow.
The zinc sulfate process discharge at the second plant amounts to
less than 350 gpd, which is less than 1 percent  of  total  plant
discharge to the POTW.

Subcateqories 1 9-23

This group of five categories represents chemicals for which PSES
are  already  in  effect.   The  purpose  of  this  review was to
determine if the current regulatons are adequate for  control  of
toxic pollutants.

19.  Aluminum Sulfate

There are 70 known producers of aluminum sulfate at present.   Of
these,  only  two  discharge indirectly.  One of these two plants
discharges less than 1000 gallons per year to the POTW, while the
discharge to a POTW from the second is  in  compliance  with  the
currently effective PSES.
     PSES
follows:
In  Effect.    Current  PSES in this subcategory are as
        Parameter

          Zinc (Total)
               PSES (30-day avg./24-hr,   max.)

                            2.5/5.0 mg/1
Since these concentrations are similar to those  promulgated  for
other subcategories in Phase I, the existing PSES are believed to
be adequate.

20.  Ferric Chloride

There are eight known producers of ferric  chloride  from  pickle
liquor.   Only one plant in this subcategory currently discharges
indirectly while four achieve zero discharge.

     in Effect.  Current PSES in this subcategory are as follows:

              Parameter       PSES (30-day avq./24-hr, max.)
              Cr (Total)
              Cr (VI)
                           1.0/3.0 mg/1
                           0.09/0.25 mg/1
                              452

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              Cu  (Total)
              Ni  (Total)
              Zn  (Total)
0.5/1.0 mg/1
1.0/2.0 mg/1
2.5/5.0 mg/1
These concentrations are similar to those promulgated  for  other
subcategories  in  Phase  I.   Therefore,  the  existing PSES are
believed to be adequate.

21.  Lead Monoxide

There are nine known producers of lead monoxide in the U.S. There
are no direct or indirect dischargers of  process  wastewater  in
this subcategory.  Lead monoxide is produced by a dry process and
produces no wastewater.

PSES Ir\ Effect.  Current PSES in this subcategory are as follows:

                Parameter         PSES (30-day avq./24-hr, max.)

                Pb (Total)                 1.0/2.0 mg/1

These  concentrations  are similar to those promulgated for other
subcategories in Phase  I.   Therefore,  the  existing  PSES  are
believed to be adequate.

22.  Potassium Bichromate

There is one plant in this subcategory.  The  plant  achieves  no
discharge by total recycle of process wastewater.

PSES in Effect.  Current PSES in this subcategory are as follows:

                Parameter          PSES (30^-dav avq./24-hr, max. )
                Cr (VI)
                Cr (Total)
    0.090/0.25 mg/1
    1.0/3.0 mg/1
These  concentrations  are similar to those promulgated for other
subcategories in  Phase  I.   Therefore,  the  existng  PSES  are
believed to be adequate.
                              453

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 23.   Sodium Fluoride

 There are four  known producers  of which  two discharge indirectly.

 PSES  in Effect.   Current PSES  in this  subcategory are as follows:

              Parameter      PSES (30-day avq./24-hr,  max.)
              Fluoride
   25/50 mg/1
 One plant is known to produce less than 1000 pounds per  year  of
 sodium  fluoride,   which  would  generate  an insignificant flow.
'Control of fluoride,  as  required  by  the  PSES,   involves  lime
 precipitation   and  clarification.    This  technology  not  only
 removes fluoride from the wastewater but also effects the removal
 of  any  toxic  metal   pollutants  that  may  be  present  in  the
 untreated  wastewater.  Therefore, the existing PSES are believed
 to  be adequate.

 EXCLUSIONS

 The Agency is excluding the  twelve  subcategories  listed  below
 from national PSES regulation development under Paragraph 8 b(ii)
 of   the  Settlement  Agreement  because  there  are  no  indirect
 dischargers in the subcategory:

                      No Indirect Dischargers
           Borax
           Bromine
           Calcium Carbide
           Calcium Chloride
           Chromic Acid
           Fluorine
Calcium Oxide (Lime)
Potassium Chloride
Potassium Metal
Potassium Sulfate
Sodium Chloride
Stannic Oxide
 The Agency is excluding the  following  subcategories  from  PSES
 development  under  Paragraph  8 (b)(ii) because the discharge to
 POTW from the one indirect discharger in each subcategory  is  so
 insignificant  due  to  low  flow  or  low  quantities  of  toxic
 pollutants:

                    One Indirect Discharger

                          Iodine
                          Hydrated Lime
                          Sodium Bicarbonate
                          Sodium Sulfite (See also Section 17)
                               454

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               TABLE 18-1.
SUMMARY OF THE DISCHARGE STATUS OF ALL
PSES SUBCATEGORIES
                                                        Discharge  Method
Plants
4
8
3
7
2
2
*(137)
3
50
37
8
1
6
4
22
39
3
1
12
70
8
9
1
4
Other**
4
8
3
7
2
2
*
2
49
35
8
1
6
3
22
39
2
1
10
68
7
9
1
2
Indirect
0
0
0
0
0
0
*
1
0
1
0
0
0
1
0 '
0
1
0
2(2)
2
1
0
0
2
Unknown
0
0
0
0
0
0
*
0
id)
Id)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
 1.   Borax
 2.   Bromine
 3.   Calcium Carbide
 4.   Calcium Chloride
 5.   Chromic Acid
 6.   Fluorine
 7.   Hydrogen
 8.   Iodine
 9.   Lime
10.   Hydrated Lime
11.   Potassium Chloride
12.   Potassium (Metal)
13.   Potassium Sulfate
14.   Sodium Bicarbonate
15.   Sodium Chloride (brine)
      Sodium Chloride (evap.)
16.   Sodium Sulfite
17.   Stannic Oxide
18.   Zinc Sulfate
19.   Aluminum Sulfate(3)
20.   Ferric Chloride(3)
21.   Lead Monoxide(3)
22.   Potassium Bichromate
23.   Sodium Fluoride(3)
 *Covered by petroleum refining guidelines
**Zerof direct, but not POTW
(1)  One plant unable to be contacted, thought to be zero or direct.
(2)  Flow at both plants is low, and less than 1% of plant flow to POTW.
(3)  PSES currently in effect.

                                455

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The  zinc  sulfate  subcategory  has  two  indirect  dischargers.
However,  the  total  flow of both plants is very low  (15.9 cubic
meters per day (4200 gallons per day)) and in each case  is  less
than  1  percent  of the plant total daily flow to the POTW.  The
Agency is excluding this subcategory from  categorical  PSES  for
zinc sulfate under Paragraph 8 b(ii).

The  Hydrogen (By-product from Petroleum Refining) subcategory is
included under the promulgated PSES for  the  Petroleum  Refining
Point Source Category.

Subcategories with PSES In Effect

Information was developed during the survey to show that the PSES
in  effect  are adequate, therefore, no change is promulgated for
the PSES following five subcategories:

     Aluminium Sulfate
     Ferric Chloride
     Lead Monoxide
     Potassium Bichromate
     Sodium Fluoride
PSNS

The 12 subcategories for which no PSNS are  currently
are:
                              in  effect
     Borax
     Bromine
     Chromic Acid
     Fluorine
     Iodine
     Calcium Hydroxide
Potassium Chloride
Stannic Oxide
Zinc Sulfate
Ferric Chloride
Lead Monoxide
Sodium Fluoride
Each  of  the  above subcategories is currently subject to a zero
discharge requirement under BPT.  Therefore, a PSNS equal to  BPT
would  not  be  a  barrier  to  entry  since  existing plants are
required  to  achieve  zero  discharge  of   process   wastewater
pollutants and meet that requirement.

The  Agency  is promulgating PSNS for each subcategory based upon
the currently effective BPT, which for each subcategory  requires
zero discharge of process wastewater pollutants.

There  are  also  no  New Source Performance Standards (NSPS) for
these 12 subcategories.  However, none are needed since,  in  the
absence  of  an  NSPS,  a  new  plant is subject to the currently
                              456

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effective BPT effluent limitations of
wastewater pollutants.
zero discharge  of  process
                               457

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                           SECTION 18

                           REFERENCES
1.   SRI International,  1982  Directory  of  Chemical  Producers
     United States of America, SRI Menlo Park, California.

2.   Chemical  Marketing  Reporter,  1983  OPD  Chemical   Buyers
     Directory,  70th  ed.,  Schnell  Publishing  Co.,  New  York
     (1982).

3.   U.S. Bureau of Mines, "Directory of Companies Producing Salt
     in  the  United  States  -  1981,"  Division  of  Industrial
     Minerals, Mineral Industry Surveys, 10 p.

4.   Calspan  Corporation,  Addendum  B-l  (Background  Data)  to
     "Supplement  for  Pretreatment  to Development Documents for
     the   Inorganic   Chemicals   Manufacturing   Point   Source
     Category,"  Calspan  Report  No. ND-5782-M-85, 17 March 1977
     (Survey conducted in 1976).

5.   Terlecky, P.M. and Harty, D.M., "Status of Group II Chemical
     Subcategories  of  the  Inorganic  Chemicals   Manufacturing
     Industry  -  Phase  II," Frontier Technical Associates, Inc.
     Report No. FTA-82-E2/03, January 14, 1983.

6.   Terlecky, P.M., Personal Communication,  Letter  to  Dr.  T.
     Fielding,  (USEPA,  May 17, 1983 (A summary of data supplied
     by the New York DEC, Region 2).
                              458

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                           SECTION  19
                     EXCLUDED SUBCATEGORIES
INTRODUCTION
The Inorganic Chemicals Manufacturing Point Source  Category  has
been  divided into 184 subcategories for regulatory purposes.  On
June  29,  1982  the  Agency  promulgated  effluent   limitations
guidelines  and  standards  for or excluded from regulation 60 of
those subcategories (the Phase I guidelines).  The Agency is  now
promulgating effluent limitations guidelines and standards for 17
additional  subcategories  (the Phase II guidelines).  The Agency
is excluding 106 of the remaining 107 subcategories from national
regulation  development.   One  subcategory   is   deferred   for
regulation under another, more appropriate guideline.

The  determinations  in  this  section  complete  the examination
required  by  the   Settlement   Agreement   of   all   remaining
subcategories  covering  the  chemical  products listed under SIC
Codes 2812, 2813, 2816, and  2819.   The  methods  used,  sources
examined,  a summary of the determinations, and the rationale for
the proposed exclusions are provided in this section.


Subcategories Surveyed

The 107 subcategories surveyed are listed in Table 19-1.

Methods Employed

An accurate and up-to-date list of all companies and plants which
manufactured the products  in  the  subcategories  was  compiled.
Sources  utilized  include:  The  Stanford  Research  Institute's
"Directory of Chemical Producers - 1982", (2)  The  OPD  Chemical
Buyers  Directory (3), the Thomas Register, in-house files at EPA
and the contractor and previous surveys for EPA.  The purpose  of
this  survey  was  to  identify  which plants and facilities were
producing  the  individual  chemicals,  and  to   determine   the
discharge  status of the plants in each subcategory.   Some of the
plants  identified  from  the  above  sources  were  subsequently
determined  to  be  distributors  or  repackagers,   and  were not
producing the chemical.

Information  was  obtained  through   telephone   contacts   with
knowledgeable  personnel  at  269 plants.  Additional information
was gathered  from  69  of  those  269  plants  through  industry
responses  to  EPA's  requests  for information under S308 of the
Act.  Engineering visits were made to 16 of the plants,  and 14 of
                              459

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    Table 19-1.  Inorganic Chemical Subcategories Surveyed
 1.     Aluminum Chloride
 2.     Aluminum Compounds
 3.     Aluminum Hydroxide (Hydrated Alumina)
 4.     Aluminum Oxide (Alumina)
 5.     Alums (also 6, 55, 77)
 6.     Ammonia Alum (also 5)
 7.     Ammonia Compounds
 8.     Ammonia Molybdate
 9.     Ammonia Perchlorate
10.     Ammonia Thiosulfate
11.     Barium Compounds
12.     Barium Sulfate
13.     Barytes Pigments
14.     Beryllium Oxide
15.     Bleaching Powder (Calcium Hypochlorite, No.  20)
16.     Boron Compounds (not produced at mines)
17.     Borosilicate
18.     Brine Chemicals
19.     Calcium Compounds (Inorganic)
20.     Calcium Hypochlorite (Bleaching Powder, No.  15)
21.     Cerium Salts
22.     Chlorosulfonic Acid
23.     Chrome Oxide  (Chrome Pigments)
24.     Chromium Sulfate
25.     Deuterium Oxide (Heavy Water)
26.     Hydrated Alumina Silicate Powder
27.     Hydrogen Sulfide
28.     Hydrophosphites
29.     Indium Chloride
30.     Industrial Gases
31.     Inorganic Acids (except nitric and phosphoric acid)
32.     Iodides
33.     Iron Colors
34.     Iron Oxide  (Black) (Iron Oxide Pigments)
35.     Iron Oxide  (Magnetic)   (Iron Oxide Pigments)
36.     Iron Oxide  (Yellow) (Iron Oxide Pigments)
37.     Lead Arsenate
38.     Lead Dioxide, Brown
39.     Lead Dioxide, Red
40.     Lead Silicate
41.     Lithium Compounds
42.     Magnesium Compounds, Inorganic
43.     Manganese Dioxide  (Powdered Synthetic)
44.     Mercury Chloride
45.     Mercury Oxide
46.     Nickel Ammonium Sulfate
47.     Nitrous Oxide
48.     Ochers  (Iron Oxide Pigments, No. 34-36)
49.     Oleum  (Sulfuric Acid)
50.     Oxidation Catalyst made from Porcelain
                          460

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Tatole 19-1.  (continued)
 51.    Pechloric Acid
 52.    Peroxides (Inorganic)
 53.    Potash Alum (Potassium Aluminum Sulfate, also 5)
 54.    Potash Magnesia
 55.    Potassium Aluminum Sulfate (also 5, 53)
 56.    Potassium Bromide
 57.    Potassium Carbonate
 58.    Potassium Chlorate
 59.    Potassium Compounds, Inorganic
 60.    Potassium Cyanide
 61.    Potassium Hypochlorate
 62.    Potassium Nitrate and Sulfate
 63.    Rare Earth Metal Salts (Salts of Rare Earth Metals, No.
        65)
 64.    Reagent Grade Chemicals
 65.    Salts of Rare Earth Metals (Rare Earth Metal Salts, No.
        63)
 66.    Satin White Pigment
 67.    Siennas (Iron Oxide Pigments, No. 34-36)
 68.    Silica, Amorphous
 69.    Silica Gel
 70.    Silver Bromide
 71.    Silver Carbonate
 72.    Silver Chloride
 73.    Silver Cyanide
 74.    Silver Iodide
 75.    Silver Nitrate
 76.    Silver Oxide
 77.    Soda Alum (also 5)
 78.    Sodium Antimonate
 79.    Sodium Compounds, Inorganic
 80.    Sodium Cyanide
 81.    Sodium Hydrosulfite  (Zinc Process)
 82.    Sodium Silicofluoride
 83.    Stannic and Stannous Chloride
 84.    Strontium Carbonate
 85.    Stronium Nitrate
 86.    Sulfide and Sulfites
 87.    Sulfocyanides (Thiocyanates also 91)
 88.    Sulfur
 89.    Sulfur Chloride
 90.    Sulfur Hexafluoride
 91.    Thiocyanates  (also 87)
 92.    Tin Compounds
 93.    Ultramarine Pigments
 94.    Umbers (Iron Oxide Pigments, No. 34-36)
 95.    White Lead Pigment
 96.    Whiting (Calcium Carbonate)
 97.    Zinc Sulfide
                           461

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Table 19-1.   (continued)
Radioactive Materials;

 98.    Cobalt 60
 99.    Fissionable Materials
100.    Isotopes, Radioactive  (also 98)
101.    Luminous Compounds  (Radium) (also 105, 106)
102.    Nuclear Cores, Inorganic  (also 103)
103.    Nuclear Fuel Reactor Cores, Inorganic  (also 102)
104.    Nuclear Fuel Scrap Reprocessing
105.    Radium Chloride  (also 101, 106)
106.    Radium Luminous Compounds  (also 101, 105)
107.    Uranium Slugs, Radioactive
                           462

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the 16 were sampled.  Supplemental information  was  provided  by
NPDES permit authorities and by POTW authorities.  The exclusions
and other actions described in this section are based on the data
acquired by the Agency through this survey.    .

EXCLUDED SUBCATEGORIES

Miscellaneous Inorganic Chemicals

1.    Aluminum Chloride (Anhydrous).   There  are  currently  five
     plants   in  this  subcategory.   Two  plants  achieve  zero
     discharge while two plants are direct dischargers and  there
     is  one  indirect  discharger.   The  two direct discharging
     plants discharge a total of less than 37.9 cubic meters  per
     day  (<10,000  gpd)  of  wastewater.   Because  of  this low
     volume, the Agency does not expect  significant  amounts  of
     toxic  or  nonconventional  pollutants  to be discharged and
     therefore is excluding the subcategory under the  provisions
     of  Paragraph  8  (a)(iv) because the amount and toxicity of
     each  pollutant  does  not   justify   developing   national
     regulations.    PSES   are  currently  in  effect  for  this
     subcategory.
     Aluminum  Compounds.    Specific
     addressed elsewhere are:
aluminum   compounds   not
     a.   Aluminum Nitrate - Three plants, low production {<4.5
                             kkg/yr (<10,000 Ib/yr each)).

     b.   Aluminum Silicate - There is one plant which has no
                              discharge.

The  Agency  is  excluding  the  above chemicals under Paragraphs
8{a)(iv) and 8(b) of the Settlement Agreement because (1) the low
production results in low flow and thus loading; and (2) there is
no discharge of process wastewater  from  the  plant  making  the
chemical.

3.   Aluminum Hydroxide (Hydrated Alumina).  The promulgated  BPT
     and  BAT limitations, NSPS and PSNS for hydrated alumina are
     contained in 40 CFR 421.10 (Subpart  A  -  Bauxite  Refining
     Subcategory  of  the  Nonferrous  Metals Manufacturing Point
     Source Category).   Under  the  provisions  of  Paragraph  8
     (a)(i),  this  subcategory  is  excluded  from  any  further
     regulation development under the inorganic  chemicals  point
     source  category  because  the wastewater from the plants in
     the subcategory is controlled by other effluent  limitations
     guidelines and standards.
                              463

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4.    Aluminum  Oxide  (Alumina).    BPT,  BAT,  NSPS,   and   PSNS
     limitations , and  standards  have  been  promulgated (40 CFR
     421.10 Subpart A  -  Bauxite  Refining  Subcategory  of  the
     Nonferrous  Metals  Manufacturing  Point  Source  Category).
     Under the provisions of Paragraph 8 (a)(i), this subcategory
     is excluded from any further regulation development as  part
     of   the  inorganic  chemicals  manufacturing  point  source
     category because the  wastewater  from  the  plants  in , the
     subcategory  is  controlled  by  other  effluent limitations
     guidelines and standards.  The current effluent  limitations
     would continue to apply.

5*    "Alums".  This subcategory represents the  consolidation  of
     four  subcategories  as  originally  listed  in  Table 19-1:
     ammonia alum  (No.  6),  potash  alum  (No.,  53),  potassium
     aluminum  sulfate  (No.  55),  and  soda alum  (No. 77).  The
     subcategories were consolidated because  production  methods
     and  probable pollutants are expected to be the same.  There
     is only one producer of alums and that one  plant  does  not
     discharge process wastewater.

     Therefore  the  Agency  is  excluding this subcategory under
     Paragraphs 8 (a)(iv) and 8{b)(ii) because there are no known
     dischargers.

6.    Ammonia Alum.  (See subcategory No. 5 above)
7.    Ammonia  Compounds.
Specific   ammonium   compounds   not
     addressed elsewhere are:

     a.   Ammonium Bisulfite - There are  three  plants  in  this
          subcategory.   Two  plants achieve zero discharge.  The
          remaining plant discharges  about  10,000  gallons  per
          year  to a POTW.  The Agency is excluding this chemical
          from national BAT regulation under  Paragraph  8(a)(iv)
          of  the  Settlement Agreement.  In addition, the single
          indirect discharger is excluded from  categorical  PSES
          under  Paragraph  8(b)(ii)  because the low flow is too
          insignificant to justify a national regulation.

     b.   Ammonium Bichromate - There is only one plant  in  this
          subcategory.  This  plant,  a  direct  discharger, also
          produces sodium dichromate and combines the  wastewater
          for treatment and discharge.  This chemical is excluded
          from national BAT and PSES regulation development under
          Paragraphs  8(a)  (iv)  and  8(b)(ii) of the Settlement
          Agreement based upon the fact that there  is  only  one
          plant and there are no indirect dischargers.
                              464

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     c.    Ammonium Fluoride— There is only one  plant  producing
          this   chemical  in  quantity.    This  plant  does  not
          discharge process wastewater.   Two other plants produce
          a  very  pure  product  (reagent  grade)  in  very  low
          quantities (<4.5 kkg/yr).  Both of these plants achieve
          zero  discharge.   This  chemical  is  excluded because
          there  are  no  dischargers  (Paragraphs  8(a)(iv)  and
          8(b)(ii)).

     d.    Ammonium Fluoborate - There is only one plant producing
          this chemical and that plant does not discharge process
          wastewater.   This chemical is excluded under Paragraphs
          8(a)(iv)  and  8(b)(i)  of  the  Settlement   Agreement
          because there are no dischargers.

     e.    Ammonium Sulfide - There are two plants producing  this
          chemical,  but the product is produced in solution form
          only and no effluent is produced because all water used
          is incorporated into the  product.   This  chemical  is
          excluded  under Paragraphs 8(a)(iv) and 8(b)(ii) of the
          Settlement Agreement because there is no  discharge  of
          process wastewater.

     f.    Ammonium Tungstate - There  are  two  plants  producing
          this  chemical  each  employing  a different production
          process.  One of the facilities disposes of  wastewater
          in  an  evaporation  pond  and achieves zero discharge.
          Therefore, there is only one discharging facility which
          is a direct discharger.

          This chemical product is excluded based upon Paragraphs
          8(a)(iv)  and  8(b)(ii)  of  the  Settlement  Agreement
          because there is only one discharger.

8.   Ammonium Molybdate.  There are  two  plants  producing  this
     chemical.   One  plant  has  no  discharge, while the second
     plants produces a reagent grade  product  in  small  amounts
     (<4.5  kkg/yr  (<5 tons/yr)).  This chemical is produced only
     intermittently.  All plant wastewater is commingled with all
     other product wastewaters and treated in a treatment  system
     equivalent to BAT technology prior to discharge.  The Agency
     is   excluding  this  subcategory  Paragraphs  8(a)(iv)  and
     8(b)(ii) of the Settlement Agreement because there  is  only
     one discharger.

9.   Ammonia Perchlorate.  There are two  plants  producing  this
     chemical   and   neither   discharges   to  surface  waters.
     Therefore, the Agency is excluding  this  subcategory  under
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     Paragraphs  8(a)(iv)  and  8(b)(ii)  because  there  are  no
     dischargers.

10.   Ammonia Thiosulfate.  The total toxic metal  discharge  from
     all  10  plants  in the subcategory based upon screening and
     verification sampling is less than 0.27 kg/day (0.6 Ib/day).
     Relevant data are presented in Table 19-2a.  Five of the ten
     plants achieve zero discharge.  No toxic organic  pollutants
     were   detected   at   treatable  levels  at  these  plants.
     Therefore, the Agency is excluding  this  subcategory  under
     Paragraph 8(a)(iii), 8(a)(iv) and 8(b)(ii) of the Settlement
     Agreement.

11.   Barium Compounds.   Inorganic barium compounds  are  produced
     at   a  limited  number  of  sites.   Barium  compounds  not
     addressed elsewhere are:

     a,b. Barium Chloride, Barium Peroxide -  All  production  of
          these  chemicals occurs at three plants which also make
          barium  carbonate.   All  three  plants  use  the  same
          wastewater  treatment  system  for all barium chemicals
          produced.  The combined wastewater was sampled in Phase
          I and no  toxic  pollutants  were  found  at  treatable
          levels  during  screening  and verification sampling at
          one plant.

     c.   Barium Sulfide - This chemical is produced  exclusively
          as  an  intermediate  in the overall process for barium
          carbonate.  Barium carbonate was excluded under Phase I
          because no toxic pollutants  were  found  at  treatable
          levels  during  screening  and verification sampling at
          one plant.

     d.   Barium Hydroxide - This chemical is  produced  at  four
          plants.  The large producer achieves no discharge by an
          evaporation  pond  while the other three plants produce
          reagent grade chemicals with very low production.   One
          of  these  plants  is  known to achieve zero discharge.
          The total discharge from  the  other  two  plants  (one
          direct,  one  indirect  discharger)  is estimated to be
          about 10,000 gallons per year.

     e.   Barium Nitrate -  There  are  five  producers  of  this
          chemical.  The only bulk producer achieves no discharge
          by  use  of an evaporation pond.  The other four plants
          produce  reagent  grade   chemicals   with   very   low
          production.   One  of  these plants is known to achieve
          zero discharge.  The other three plants (two direct and
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          one indirect)  are estimated to  discharge
          less than 10,000 gallons per year.
    a  total  of
     f.    Barium Perchlorate - There  are  two  plants  producing
          this  chemical.    One  achieves no discharge by recycle
          while the second discharges to a POTW.   Production  at
          the  second plant is less than 2.3 kkg/yr (5000 Ib/yr).
          Because of the very low production, discharges of toxic
          pollutants would be insignificant.

          The Agency is  excluding  all  of  the  above  chemical
          products  under Paragraphs 8{a)(iv) and 8(b)(ii) of the
          Settlement Agreement (low loading because of low flow).

12,13.          Barium  Sulfate,  Barytes   Pigments.    In   each
          subcategory  there is only one plant which produces the
          chemical in bulk, and two other plants that  have  very
          low  production  rates.   None  of  the small producers
          discharges process wastewater.  The Agency is excluding
          each subcategory under Paragraphs 8(a)(iv) and 8(b)(ii)
          because  there  is  only   one   discharger   in   each
          subcategory.    The  Agency  considered  combining  the
          subcategories because the products are very similar but
          the production processes, raw materials,  and  expected
          pollutants  are significantly different for each plant.
          Hence combining the subcategories was  not  technically
          feasible.

14.   Beryllium Oxide.  This compound is produced at one  site  as
     part  of  the  production  process  for  beryllium  metal or
     beryllium-copper alloys.  This subcategory is  deferred  for
     coverage  under  limitations and standards to be established
     for the Non-Ferrous Metals Category (40 CFR  Part  421).   A
     new study of this category by EPA is currently underway.

15.   Bleaching Powder (also Calcium Hypochlorite, No.  20).   See
     Subcategory No. 20.  Note that sodium perborate is sometimes
     also  referred  to as bleaching powder.  Sodium perborate is
     addressed under Sodium Compounds (Subcategory No. 79).
16.   Boron Compounds (Not produced at  Mines).
     compounds not addressed elsewhere are:
Inorganic  boron
     a.   Boron Trifluoride - Two plants produce this chemical on
          a specialty basis with very low production.  Generally,
          this chemical would be produced two or three times  per
          year  in small batches.  Little flow is expected beside
          process cleanup,  leaks,  and  spills.   Any  wastewater
          produced  is  treated in the plant treatment system for
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b.
c.
a.
e.
f.
other chemical  production.   Both  plants  are  direct
dischargers  with  a  total  discharge  estimated to be
5,000 gallons per year.

Boron Trichloride - One plant  produces  this  chemical
and   utilizes   an  evaporation  pond  to  achieve  no
discharge of process wastewater.

Boron Hydrides - There is only qne plant producing this
chemical on a specialty basis wfth very low production.

Boron Nitride - There are three p\lants  producing  this
chemical at present.  All three discharge to a POTW but
flows are low (two plants discharge less than 3.8 cubic
meters  per day each (<1000 gpd).  The third plant flow
is unknown but is expected to be similar (and  low)  to
the  other  producers  because process technologies are
known  to  be  similar.   Hence,  the  total  flow   is
estimated to be about 3,000 gallons per day.

Sodium Borohydride - The production of this chemical is
a non-aqueous process  with  no  discharge  of  process
wastewater.    There    are    two   plants   currently
manufacturing  this   chemical   but   there   are   no
dischargers.
                                                    two
                                                     No
          Lithium Metaborate - This chemical is produced  at
          plants  on  a  specialty basis with low production.
          priority pollutants are known to  be  involved  in  its
          production.   One  plant  achieves  zero  discharge  of
          process wastewater.  The other plant  is  estimated  to
          discharge  less than 2,000 gallons per year directly to
          surface waters.

          All of  the  above  chemicals  are  produced  in  small
          quantities  at  few plants with little or no wastewater
          flow.  The Agency is excluding this  subcategory  under
          Paragraphs  8(a)(iv)  and 8(b)(ii) (low production, low
          flow and loading).

17.   Borosilicate.  This chemical is no longer produced  in  this
     country.  Therefore the Agency is excluding this subcategory
     from   further  regulatory  consideration  under  Paragraphs
     8(a)(iv) and 8(b)(ii).

18.   Brine Chemicals.  Brine refers  to  strong  salt  solutions.
     This  subcategory  has  been  interpreted  to mean chemicals
     produced from brine.  Most  of  these  chemicals  have  been
     considered   separately   (e.g.,  calcium  chloride,   sodium
                         468

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     chloride).    Four  salts  which  have  not  been  considered
     separately   are  sodium,  calcium,   potassium  and  ammonium
     bromide.                                           .

     There  are   five  plants  producing  these  four   products.
     However,    only  two  plants  (direct  dischargers)   have  a
     discharge of process wastewater.   Screening and verification
     sampling at one of those two plants show that  no  toxic  or
     nonconventional  pollutants  were found at treatable levels.
     Relevant data are presented in  Table  19-2b.   Most  plants
     return spent  brines  to  their  source without addition of
     toxic ..materials,  because  the  process  is  primarily   an
     extractive  one.

     The  Agency  is  excluding this subcategory under Paragraphs
     8{a)(iii),   8(a)(iv)  and  8(b)ii)   because  no   toxic   or
     nonconventional   pollutants   were  detected  at  treatable
     levels.
19.   Calcium Compounds (Inorganic).
     not addressed elsewhere are:
Inorganic calcium  compounds
          Calcium lodate - There are four plants  producing  this
          chemical  but  only one is a bulk producer.   This plant
          does  not- discharge  process  wastewater   from   this
          product.   The  other  three  produce  a  reagent grade
          product in very low quantities and  one  of   the  three
          small  plants  does not discharge.  The two  dischargers
          (one  direct  and  one  indirect)  are   estimated   to
          discharge a total of less than 5,000 gallons per year.

          Calcium Nitrate - This chemical is produced  only  as  a
          reagent  grade  material  at three locations, therefore
          production quantities are low  with  little   wastewater
          generated.   Only  one of those three plants discharges
          process wastewater.  Since the raw materials  are  lime
          or  calcium  carbonate  and nitric acid, chemical grade
          raw materials would  be  used  producing  little  toxic
          pollutants.

          Calcium Stannate - There  are  three  plants  producing
          this chemical with only two dischargers, one direct and
          one   indirect.    The   two   plants  produce  limited
          quantities of the chemical as a specialty product  and
          the total discharge from both plants is estimated to be
          less than 10,000 gallons per year.

          Calcium Tungstate - There are two plants producing this
          chemical but  only  one  discharger  (indirect).   That
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          plant  produces  the  chemical  on a specialty basis in
          small quantities.  No priority pollutants are  involved
          in its production.  The total discharge is estimated to
          be less than 5,000 gallons per year.

     All of the above chemical products are produced primarily by
     plants which supply reagent or specialty chemicals and hence
     produce in small quantities only.  There are only two plants
     (each  producing  a  separate chemical) which produce any of
     the chemicals in bulk quantities.  Therefore, the Agency  is
     excluding  this  subcategory  under  Paragraphs 8(a)(iv) and
     8(b)(ii) (few plants, low production, low flow and loading).

20.  Calcium Hypochlorite (Bleaching  Powder).   There  are  four
     producers, one of which is a paper mill, and the other three
     are chlor-alkali plants.

     Screening  and  verification  sampling at the paper mill (an
     indirect  discharger)  showed  no  toxic   pollutants   were
     discharged at treatable levels.  Relevant data are presented
     in  Table  19-2c  (Plant  A).   Total  Residual  Chlorine is
     discharged at treatable  levels,  but  the  Agency  has  not
     regulated  discharges  of  total  residual chlorine to POTWs
     because POTW influent is often chlorinated.  This segment of
     •the subcategory is excluded under Paragraph 8(b)(ii).

     The remaining three plants mix calcium hypochlorite  process
     wastewater with chlor-alkali plant wastewater for treatment.
     EPA  proposed  to  amend  the  applicability  section in the
     effluent limitations guidelines for chlor-alkali  plants  to
     include  effluent  from  the  calcium  hypochlorite process.
     Based upon plants sampled in 1979  and   1981,  and  effluent
     data  provided  by  those  plants, plants that combine these
     process wastewaters are meeting all existing guidelines  and
     standards   for  chlor-alkali  plants.   Relevant  data  are
     presented in Table 19-2c (Plant B).

We continue to believe that existing  plants  that  produce  both
calcium  hypochlorite  and  chlor-alkali  can  meet  the effluent
limitations  and  standards  for  the  chlor-alkali  subcategory.
However,   we  believe  that  because  the  calcium  hypochlorite
effluent is controlled by the  technology  on  which  the  chlor-
alkali  limitations  are based, it is more appropriate to exclude
the calcium hypochlorite from national  regulation,  pursuant  to
paragraph 8(a)(i) of the Settlement Agreement.

21.  Cerium Salts.  There  are  two  plants   currently  producing
     cerium  ("eerie")  salts as separate products.  Other plants
     may produce small amounts of cerium salts  with  other  rare
                              470

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     earth  metals (see Subcategory No. 63).  One of these plants
     is a direct discharger which produces eerie salts from  rare
     earth  hydroxides  imported  from  France  (7).   The second
     plant,  an indirect discharger, obtains rare earth oxides and
     treats them with various acids to produce the salts.  Little
     effluent is produced by this process (about 40  gallons  per
     day).  Consideration was given to combining this subcategory
     with  rare  earth metal salts> but this was rejected because
     the processes employed in this subcategory are substantially
     different as are the raw materials used.

     Since there are only one direct and one indirect discharger,
     and since the indirect discharger has such a low  flow,  the
     Agency is excluding this subcategory from further regulation
     development  under  Paragraph  8(a)(iv) and 8 (:b>(ii) of the
     Settlement Agreement.

22.   Chlorosulfonic Acid.  No toxic pollutants were  detected  at
     treatable  levels during screening and verification sampling
     at one plant of the three plants  producing  this  chemical.
     Effluent wastewater discharged at this plant was the same as"
     influent  water  quality.   Relevant  data  are presented in
     Table  19-2d.   This  subcategory  is  excluded  under   the
     provisions  of  Paragraphs  8(a)(iii),  8(a)(iv)  and  8(b),
     because toxic pollutants  were  not  detected  at  treatable
     levels during screening and verification sampling, hence the
     toxic pollutant discharges were too insignificant to justify
     developing a national regulation.

23.   Chromium  Oxide  (a  Chrome  Pigment).   Chromium  oxide  is
     defined  as  a  chrome pigment in the promulgated guidelines
     for the Chrome Pigments subcategory.  The  promulgated  BPT,
     BAT,  and  BCT  limitations and NSPS, PSES, and PSNS for the
     Chrome  Pigments  Subcategory  are  at   40   CFR   415.340.
     Therefore,  the  Agency  is  excluding this subcategory from
     further  consideration  (Paragraph  8{a)(i)).   The  current
     effluent limitations would continue to apply.

24.   Chromium Sulfate.  There is only one  plant  producing  this
     chemical, therefore the Agency is excluding this subcategory
     under Paragraphs 8(a)(iv) and 8(b)(ii).

25.   Heavy Water (Deuterium Oxide)..  There are  no  producers  of
     deuterium  oxide (heavy water) in the U.S. today.  Therefore
     the Agency is excluding this  subcategory  under  Paragraphs
     8(a)(iv) and 8(b)(ii).

26.   Hydrated  Alumina  Silicate  Powder.   There  is  one  plant
     currently  producing  this  chemical,  and this plant has no
                              471

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27
28
29,
30,
31
     discharge of process wastewater.  Therefore, the  Agency  is
     excluding  this  subcategory  under  Paragraphs 8(a)(iv) and
Hydrogen Sulfide.  There are four plants producing  hydrogen
sulfide  essentially  as  a by-product.  Three of the plants
are petroleum refineries and one  is  an  organic  chemicals
plant.   Wastewater  for the three plants producing hydrogen
sulfide at  petroleum  refineries  is  subject  to  effluent
limitations for the Petroleum Refining Point Source Category
(40  CFR Part 419).  These limitations are applicable to all
discharges from any facility producing petroleum products by
the  use  of   topping,   catalytic   reforming,   cracking,
petrochemical operations, and lube oil manufacturing whether
or  not  the  facility  includes  any process in addition to
those  listed  above.   There  is  only  one  other   plant.
Therefore,  the  Agency  is  excluding this subcategory from
national regulation  development  under  Paragraph  8(a)(i),
8(a)(iv), and 8(b>.

Hydrophosphites.  This chemical is  no  longer  produced  in
this  country.   Therefore,  the  Agency  is  excluding this
subcategory under the provisions of Paragraphs 8(a)(iv)  and
8(b)(ii) because there are no known producers.

Indium Chloride.  There are three plants in this subcategory
but only one has a  discharge.   All  plants  produce  small
quantities  as a specialty product.  The Agency is excluding
this subcategory  under  Paragraphs  8(a)(iv)  and  8(b)(ii)
because there is only one discharger.
Industrial Gases.  Specific industrial gases  not  addressed
elsewhere  are  the  "rare"  or  "inert"  gases  produced in
conjunction with oxygen and nitrogen  from  liquefaction  of
air (e.g., neon and argon).  In Phase I, oxygen and nitrogen
were  excluded  under  Paragraph 8(a)(iv) because the amount
and toxicity of each pollutant observed  in samples collected
from plants in the subcategory did  not  justify  developing
national  regulations (see the Phase I Development Document,
p.  806).  Since the inert gases are produced simultaneously
with oxygen and nitrogen from the same liquid air,  and  the
wastewaters  were included in the samples collected in Phase
I, the Agency is excluding these  products  also  under  the
provisions of Paragraph 8(a)(iv) and 8(b)(ii).

Inorganic Acids (except nitric and  phosphoric  acid).   The
only common inorganic acids not addressed elsewhere are:
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          Hydrobromic Acid - There is  no  discharge  of
          wastewater from production of this chemical.
process
     b.    Hydriodic Acid -  There  is  no  discharge  of  process
          wastewater from production of this chemical.

          Since  there  is  no process wastewater discharged from
          this subcategory, the Agency is excluding it under  the
          provisions of Paragraphs 8(a)(iv) and 8(b)(ii).

32.   Iodides.   Specific iodides not addressed elsewhere are:

     a.    Calcium Iodide - There is only one plant producing this
          chemical and that plant has  no  discharge  of  process
          wastewater from calcium iodide production.

     b.    Lithium Iodide - There are two  plants  producing  this
          chemical, but neither has a discharge of lithium iodide
          process wastewater.

     c.    Sodium Iodide - There are  two  plants  producing  this
          chemical  in  bulk  form, but only one has a discharge.
          That plant discharges an  estimated  1000  gallons  per
          year directly to a receiving stream.

          Since there is only one discharger, with a discharge of
          only   1000  gallons  per  year,  this  subcategory  is
          excluded under the provisions  of  Paragraphs  8(a)(iv)
          and 8(b)(i i).

33.   Iron Colors.  Iron colors can be broadly subdivided into two
     groups:  those colors based upon various  iron  oxides  (see
     No. 34-36 below), and those colors, generally blue, based on
     iron cyanide complexes.  The products based upon iron oxides
     are   considered   below   under  iron  oxides   (iron  oxide
     pigments).  There is only one plant   (a  direct  discharger)
     producing   iron  cyanide-based  pigments.   The  Agency  is
     excluding this subcategory  under  Paragraphs  8(a)(iv)  and
     8{b)(ii) because there is only one plant.

34,  35,  36, 48, 67, and 94.  Iron Qxide(s) (Iron Oxide Pigments).
     These  subcategories include the Iron Oxides (Black, Yellow,
     Red, and Magnetic)  and  the  Ochers,  Siennas,  and  Umbers
     Subcategories.   Four  plants, one direct and three indirect
     dischargers, produce iron oxide  pigments  by  an   inorganic
     chemical  process.   One  other  plant  produces  iron oxide
     pigments by an organic chemical process.   Most  iron  oxide
     pigments  producers  use  a  mechanical   (grinding) process.
     Based upon screening and verification sampling at two of the
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     four  inorganic  chemical  plants,  there   are   no   toxic
     pollutants  at treatable levels discharged from any of these
     four plants.  Relevant data are presented  in  Table  19-2f.
     All  three indirect dischargers are required by the POTWs to
     control the nonconventional pollutant iron.  All four plants
     (including the direct discharger)  use  the  same  treatment
     technology  to  control the discharge of iron, and, based on
     long-term data from the direct discharger,  that  technology
     is  the technology the Agency would have chosen as the basis
     for BAT and PSES.  Since the three indirect dischargers  are
     already required to control the discharge of iron using that
     technology,  and  since there is only one direct discharger,
     the  Agency  is  excluding  these  six  subcategories  under
     Paragraphs 8(a)(iv) and 8(b).

37.  Lead Arsenate.  This chemical is no longer produced in  this
     country  and  is unlikely to be produced in the future.  The
     Agency  is  excluding  this  subcategory  under   Paragraphs
     8(a)(iv) and 8(b)(ii) of the Settlement Agreement.

38,39.     Lead  Dioxide  (Red)  and  Lead  Dioxide  (Brown).   No
     process  wastewater  is  discharged from any plant producing
     these products.  Therefore, the Agency  is  excluding  these
     two subcategories under Paragraphs 8(a)(iv) and 8(b)(ii) (no
     discharging plants).

40.  Lead  Silicate.   See  "White  Lead  Pigments,"  subcategory
     number 95.

41.  Lithium Compounds.   Specific lithium compounds not addressed
     elsewhere are:
     a.
     b.
     Lithium Chloride - There are  three
     discharge process wastewater.
plants,  but  none
     Lithium Fluoride - There are two plants, but the  total
     production  is  estimated  to  be  less than 4 tons per
     year.  The wastewater discharge flow from such a  small
     production is insignificant.

The   chemicals  in  this  subcategory  are  excluded  under
Paragraphs 8(a)(iv) and 8(b) because the discharge of  toxic
pollutants is insignificant.
42.  Magnesium   Compounds   (Inorganic).
     compounds not addressed elsewhere are:
                                        Specific   magnesium
     a.   Magnesium Chloride - There are eight  plants  employing
          two  different processes to obtain this chemical.  Four
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43.
    plants derive magnesium chloride  from  natural  brines
    and return the spent brinek to their source.  The other
    four   plants   produce   the  product  from  magnesium
    hydroxide and hydrochloric  acid  by  a  process  which
    generates   no   wastewater.    Hence   there   are  no
    dischargers.

    Magnesium Fluoride - This  chemical  is  produced  from
    hydrofluoric   acid   and   magnesium  hydroxide  on  a
    specialty basis at two plants.  The total production is
    less than ten  tons  per  year,  which  results  in  an
    insignificant discharge.

    Magnesium Nitrate - There  are  five  plants  producing
    this  chemical,  however,  the two large plants have no
    discharge of process wastewater from this product.  The
    other  three  plants   (one  direct  and  two    indirect
    dischargers)  produce  specialty or reagent grades only
    in  small quantities.  The total flow is estimated to be
    less than 20,000 gallons per  year..

    Magnesium Silicate - There are only two plants, and one
    has no discharge.

    Magnesium Sulfate - There   are  five  plants   producing
    this chemical, but none  of  the plants have  a  discharge.

    Magnesium Carbonate -  There  are   four  plants  (three
    direct   and one  indirect) producing magnesium carbonate
    but each uses  a, different   raw   material   source   and
    production   process   (ore,   by   chemical  process,  from
    ocean  brine,  and solution mining).   Since   each  plant
    uses   an entirely  different  process  and  raw material
    source,  the identity  and quantity  of  pollutants  would
    be different   for  each process.   Hence,  this chemical
    would  require different   subcategories   each  with   one
    plant.    The  one  indirect  discharger is  estimated to
    discharge  less than  5,000 gallons  per year   because  of
     its very low production  rate.

The Agency  is   excluding this  subcategory  under Paragraphs
8(a)(iv) and 8(b).   For  magnesium carbonate,  two of the four
plants are producing small quantities,  while all four of the
plants produces by a different process.

Magnesium Dioxide (Powdered  Synthetic).    There  are  eight
plants  in this subcategory but seven plants do  not discharge
process wastewater from this product.   Therefore, the Agency
    d.
    e.
     f.
                              475

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      is   excluding this  subcategory under Paragraphs 8(a)(iv)  and
      8(b)(ii),  because there is only one discharging plant.

 44.   Mercury  Chloride.   There is only one  plant   producing   this
      chemical.    The  plant   is  an  indirect   discharger and is
      required 'by  the  POTW to  control  its discharge   using   an
      advanced  level   technology.     That technology   involves
      additional treatment beyond that used as  the  basis   for   the
      chlor-alkali   BAT   limitations and therefore  toxic  pollutant
      discharges to the POTW  are  expected  to   be   insignificant.
      Therefore,   the  Agency  is excluding this subcategory under
      Paragraphs 8(a)(iv)  and 8(b).

 45.   Mercury  Oxides.  There  is  only  one  plant   producing  this
      chemical.    That plant  is  the  same plant  that produces
      mercury  chloride (product No.  44  above)   and  combines   the
      wastewaters   from   both  products  for treatment.    For  the
      reasons  presented for excluding mercury chloride, the Agency
      is excluding   this   chemical   subcategory  under  Paragraphs
      8(a)(iv) and  8(b).

 46.   Nickel Ammonium  Sulfate.   There  are  two  plants   producing
      this  chemical.   One has no  discharge of  process wastewater
      from  this  product.    The second   produces    reagent    and
      specialty  grade  chemicals  along   with   hundreds   of other
      chemicals in  small quantities.   All  combined  wastewater   is
      treated  in   an  advanced  level   treatment   system prior  to
     discharge.  Monitoring  data confirms  the   absence   of  toxic
     pollutants  at   treatable  levels  at  this  plant.  Therefore,
     the Agency is excluding  this  subcategory  under  Paragraphs
      8(a)(iv) and  8(b)(ii).

47.  Nitrous Oxide.  There are  six plants   in   this  subcategory,
     all  of  which  are  indirect   dischargers.   Total  process
     wastewater discharge  at   all   six  plants  is  only  30,000
     gallons per day.   Screening and verification  sampling of all
     the  process wastewater sources at two plants showed that no
     toxic  or  nonconventional  pollutants  are   discharged   at
     treatable  levels  in process wastewater from plants in this
     subcategory.   The screening and verification  sampling of the
     final effluent at both plants detected ammonia at  excessive
     levels,   but  at   very  low levels in all  process wastewater
     sources contributing to that final effluent.   Relevant  data
     are  presented  in   Table  19-2e.  At one plant, the water in
     the discharge trench was so low that the trench  had  to  be
     dammed  to  raise  the  water  level  so  samples  could  be
     obtained.  The dam  was constructed of ceramic  clay  wrapped
     in  an  old burlap  sack  found at the plant.  This could  have
     introduced pollutants  into  the  sample  causing  the  high
                              476

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     values  found.    The ammonia could not be process related at
     that plant  because  all  process  wastewater  sources  were
     sampled  and  no  ammonia  was  found at treatable levels in
     those sources.   At the  second  plant,  the  source  of  the
     ammonia  is  believed  to  be fugitive ammonium nitrate dust
     (the raw material for  nitrous  oxide  production).   Proper
     control  of  dust  emissions  to  the air could correct this
     problem.  The Agency is  excluding  this  subcategory  under
     Paragraphs 8(a)(iv) and 8 b(ii).

48.  Qchers (Iron Oxide  Pigments).   See  Iron  Oxide  Pigments,
     Subcategories No. 34, 35 and 36.
49
50.
51
52,
 53.


 54
Oleum (Sulfuric Acid).   Oleum is  sulfuric  acid.   Sulfuric
acid  has been excluded from further national BAT regulation
in Phase  I  because  no  toxic  pollutants  were  found  at
treatable  levels during screening sampling (see the Phase I
Development Document, pages 830, 832).

Oxidation Catalysts  Made  from  Porcelain.   There  are  no
plants  producing  this  material in the U.S.  The Agency is
excluding this subcategory  under  Paragraphs  8(a)(iv)  and
Perchloric Acid.  There is only  one  plant  which  produces
this  chemical.   The  Agency  is excluding this subcategory
under Paragraphs 8(a)(iv) and 8(b)(li).
Peroxides  (Inorganic).
elsewhere  are:
                         Specific  peroxides  not  addressed
                                            one  plant  producing
                                            Therefore there  is no
     Sodium Peroxide - There  is  only
     this  chemical by a dry  process.
     discharge of process wastewater.

     Potassium Peroxide - There  are  no  producers
     chemical in the United States today.
                                                          of   this
 The  Agency   is  excluding  this  subcategory  under  Paragraphs
 8(a)(iv)  and   8(b)(ii)   because   there   are   no discharging
 facilities.

 Potash  Alum.   This  subcategory has  been  addressed  under   the
 "Alums" Subcategory,  No.  5.
 Potash   Magnesia.
	  	    There  are  two  plants  producing  this
chemical from ore.  These plants are located in an arid area
and  dispose  of all aqueous wastewater in evaporation ponds
with no discharge.
                               477

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55.



56.


57.
58,
59,
 The  Agency  is  excluding  this   subcategory  under  Paragraphs
 8(a')(iv)  and 8(b)(ii)  of the  Settlement  Agreement.

 Potassium Aluminum  Sulfate.   This  chemical  is  "potash   alum"
 which   has  been  addressed under  the  "Alums"  subcategory,  No.
 J *

 Potassium Bromide.   This subcategory   has  been   addressed
 under the "Brine Chemicals" subcategory,  No. 18.

 Potassium Carbonate.   This chemical  is produced  at  only  one
 plant,  a direct discharger.   The  chemical process  generates
 little  wastewater which  results  from the  infrequent washdown
 of the  reactor.   Most  of  that  wastewater  is   recovered  and
 recycled,   but   some   is  discharged.  The discharge averages
 less than 10,000  gallons  per day.

 The Agency  is excluding  this   subcategory  under  Paragraphs
 8(a)(iv)  and  8{b)(ii)   because there is only one  plant  and
 the discharge is  insignificant.

 Potassium Chlorate - There is  only one  producer,   a  direct
discharger.    The Agency  is excluding this subcategory  under
Paragraphs  8(a)(iv)  and 8(b)(ii).
Potassium   Compounds   (Inorganic).
compounds not addressed elsewhere are:
                                             Specific   potassium
          Potassium Fluoride - There are  three  plants  in  this
          subcategory,  but  only  two  dischargers,  both direct
          dischargers.  One plant produces less than  4.5  kkg/yr
          (<10,000  Ib/yr) of the product and all wastewater from
          hundreds  of  chemicals  produced  at  that   site   is
          commingled in the plants' advanced wastewater treatment
          system.     The   remaining   plant   has   intermittent
          production and generates less than  0.38  cubic  meters
          per  day  (<100 gpd) of process wastewater when producing
          the   chemical.  The total discharge from both plants is
          estimated to be less than 5,000 gallons per year.

          Potassium Bicarbonate - This chemical is produced on  a
          specialty  basis  (i.e.,  low production quantities) at
          two  locations.  Each plant (one direct and one indirect
          discharger)  makes numerous other reagent and  specialty
          chemicals with all wastewater handled in a common plant
          treatment  system.   The total discharge from potassium
          bicarbonate production from both plants is estimated to
          be less  than 10,000 gallons per year.
                              478

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     c.    Potassium Thiocyanate - There is  one  plant  producing
          this  chemical  in quantity while two other plants have
          very low production rates.  The process is  essentially
          dry and there are ho dischargers.

     d.    Potassium Silicofluoride - There is one plant producing
          this chemical but no process wastewater  is  discharged
          from this product.

     e.    Potassium Silicate - No toxic  pollutants  attributable
          to  potassium  silicate production were detected during
          screening  and  verification  at  one  plant  of  three
          producing  the  chemical.   The process is identical to
          the process used to produce sodium silicate except  for
          the  substitution  of  potassium  hydroxide  for sodium
          hydroxide when the  potassium  salt  is  made.   Sodium
          silicate  was  excluded  in  Phase  I  because no toxic
          pollutants  were  detected  at  treatable   levels   in
          untreated wastewater at the one plant sampled.

     The  Agency  is excluding all of the above chemical products
     in this subcategory under Paragraph 8(a)(iv) and 8(b)(ii) of
     the Settlement Agreement because of low production resulting
     in little or no discharge and thus insignificant  discharges
     of toxic and nonconventional pollutants.

60.  Potassium Cyanide.  There are only two plants producing this
     chemical at present.  One achieves zero discharge  by  total
     recycle,  and the second plant discharges process wastewater
     to a POTW after treating for  cyanide  removal  by  alkaline
     chlorination.

     The  Agency  is  excluding this subcategory under Paragraphs
     8(a){iv) and 8(b), because the one discharger is required by
     the POTW  to  utilize  advanced  treatment  for  pretreating
     wastewater before discharge to the POTW.

61.  Potassium Hypochlorate.  This chemical is no longer produced
     in  the  United  States.   The  Agency  is  excluding   this
     subcategory  under the provisions of Paragraphs 8(a)(iv) and
     8(b)(ii).

62.  Potassium  Nitrate  and  Sulfate.   The  potassium   sulfate
     subcategory  was excluded in Phase I BAT development because
     the promulgated  BPT  and  BAT  for  the  potassium  sulfate
     subcategory  required  that  plants  achieve no discharge of
     process  wastewater  pollutants.   There  is  one  potassium
     nitrate   plant   in  the  U.S.   This  plant  is  a  direct
     discharger.
                              479

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     Because equal or more stringent  effluent  limitations  have
     been  promulgated  for  potassium sulfate manufacturing, and
     because there is only one potassium  nitrate  producer,  the
     Agency  is  excluding  the  potassium  nitrate  and  sulfate
     subcategory from further regulation  development  under  the
     provisions   of   Paragraphs   8(a)(i),  and  8(a)(iv),  and
63.  Rare Earth Metals Salts.  There are five known producers  of
     rare  earth  metal  salts in the U.S. (Cerium or eerie salts
     are discussed above in Subcategory No. 21).   Three  of  the
     five  plants achieve zero discharge, and there is one direct
     discharger and one indirect discharger  in  the  subcategory
     (7).   The  direct discharger produces less than 4.5 kkg per
     year (<10,000  Ib/yr)  and  combines  wastewater  from  many
     chemical  products  together  for  treatment.   The indirect
     discharger produces rare  earth  metal  salts  from  an  ore
     concentrate  which  contains  thorium,  which is an entirely
     different process.  That plant is required by  the  POTW  to
     control  its  discharge  to  the  POTW.   Thorium and related
     materials that may be in  the  wastewater  are  source,  by-
     product,  or  special  nuclear  material, as these terms are
     defined at 10 CFR 820.3(a),  (3), (15), and (16).   As  such,
     the  wastewater discharges of these materials are controlled
     by the Nuclear Regulatory  Commission.   The  Supreme  Court
     decided,  in  Train v. Colorado PIRG, 426 U.S.I  (1976), that
     these materials, at least when regulated by the NRC, are not
     "pollutants" under the Clean Water Act.

     Accordingly, the Agency is excluding this  subcategory  from
     further regulatory development under Paragraphs 8(a)(iv) and
     8(b).

64.  Reagent Grade Chemicals.   Reagent  grade  chemicals  are  a
     particular  grade or quality (purity) of chemical.  The term
     can apply to any  chemical.    All  the  individual  chemical
     products    included    within   the   inorganic   chemicals
     manufacturing point source category could be produced  as  a
     reagent   grade   chemical.    All  of  the  regulations  and
     exclusions  promulgated  in  Phase  I,  and   all   of   the
     regulations  and exclusions promulgated in Phase II included
     the production of each product  (within  a  subcategory)  in
     reagent  grade  quality  as  well  as  other  (lower purity)
     grades.    Hence,  each  reagent  grade  chemical  has   been
     addressed separately as the individual chemical.   Therefore,
     the   Agency   is   excluding  this  subcategory  under  the
     provisions of  Paragraph  8(a)(i)  (for  chemicals  included
     under  regulated  subcategories) and 8(a)(iv) (for chemicals
     included under subcategories that have been excluded).
                              480

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65.
66,
68
69
70
71..
     Salts of Rare Earth Metals.
     to No. 63 above.
This subcategory  is  identical
     Satin White Pigment.   This chemical product is  produced  at
     only  one  plant.   Therefore  the  Agency is excluding this
     subcategory under,Paragraphs 8(a)(iv) and 8(b)(ii).
67.  Siennas.  (See Iron Oxide Pigments, No. 34-36).
     Silica,  Amorphous .    There  are   seven   plants   in   the
     subcategory.   Screening  and verification sampling at three
     of the seven plants found no toxic pollutants  at  treatable
     levels  at  any  of  the  three  plants.   Relevant data are
     presented  in  Table  19-2g  (Plants  A,  B  and  C) .   This
     subcategory is excluded under Paragraphs 8(a)(iii)/ 8(a)(iv)
     and 8(b)(ii) ( low loading) .

     Silica Gel.  There are three  plants  in  this  subcategory.
     Screening  and  verification sampling at one of these plants
     found  no  treatable  levels  of  toxic  or  nonconventional
     pollutants  in  effluent from that plant.  Relevant data are
     presented in Table  19-2h.   This  subcategory  is  excluded
     under Paragraphs 8(a)(iii), 8(a)(iv), and 8(b)(ii).

     Silver Bromide.  This chemical is  produced  in  -very  small
     quantities  for  research  or other highly specialized uses.
     There is only one discharger in this subcategory.  That  one
     plant  discharges to a POTW.  Minimal wastewater is expected
     from  such  small  production  volumes  and  no  significant
     pollutant  loads  are anticipated.  Therefore, the Agency  is
     excluding this subcategory  under  Paragraphs  8(a)(i'v)  and
     8(b).

     Silver Carbonate.  This chemical  is produced in  very  small
     quantities  for  research  or other highly specialized uses.
     There  is only one discharger in this subcategory.  That  one
     plant  discharges to a POTW.  Minimal wastewater is expected
     from  such  small  production  volumes  and  no  significant
     pollutant  loads  are anticipated.  Therefore, the Agency  is
     excluding this subcategory  under  Paragraphs  8(a)(lv)  and
 72.  Silver Chloride.   This  chemical  is  produced   in   very   small
     quantities   for   research   or  other highly specialized  uses.
     There is only  one discharger  in  this subcategory.   That  one
     plant  discharges to  a  POTW.   Minimal wastewater  is expected
     from  such   small  production  volumes  and   no   significant
     pollutant   loads   are anticipated.   Therefore, the Agency is
                               481

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     excluding this subcategory
     8(b).
under  Paragraphs  8(a)(iv)  and
73.  Silver Cyanide.  There are two plants which manufacture this
     chemical.  Both plants discharge to  a  POTW.   One  plant's
     discharge  is  less than 1.9 cubic meters per day  (<500 gpd)
     and  treats  the  discharge  with  an  advanced    wastewater
     treatment  system for silver recovery and to comply with the
     POTW's pretreatment requirements.  The second  plant  treats
     all  process wastewater with a two stage ion-exchange system
     for  silver  recovery,  and  to  comply  with   the   POTW's
     pretreatment  requirements.   Since  both plants must comply
     with the POTW's pretreatment  requirements,  and   since  the
     value  of  the  recovered  silver offsets most or  all of the
     cost of the treatment syterns, the  plants  are  unlikely  to
     cease  operating  the  treatment  systems.   Therefore,  the
     Agency  is  excluding  the  subcategory   under    Paragraphs
     8(a)(iv) and 8(b).

74.  Silver Iodide.  This chemical  is  produced  in  very  small
     quantities  for  research  or other highly specialized uses.
     There is only one discharger in this subcategory.  That  one
     plant  discharges to a POTW.  Minimal wastewater is expected
     from  such  small  production  volumes  and  no  significant
     pollutant  loads  are anticipated.  Therefore, the Agency is
     excluding this subcategory  under  Paragraphs  8(a)(iv)  and
     8(b).

75.  Silver Nitrate.  There are three plants in this subcategory.
     Screening and verification sampling at the largest of  these
     plants  found  no  toxic  or  nonconventional  pollutants at
     treatable  levels  in  the  treated  wastewater  from   this
     process.   The  wastewater  discharged  at that plant was in
     compliance with existing BPT effluent limitations.  PSES has
     also been promulgated for this subcategory.  40 CFR  415.530
     lists the applicable discharge limitations and standards for
     the silver nitrate subcategory.

     The  Agency  is  excluding  this  subcategory  from  further
     regulatory development under Paragraph 8(a)(iv) and 8(b).

76.  Silver Oxide.  There are currently two plants producing this
     chemical.  One  is  a  direct  discharger,  and  one  is  an
     indirect discharger.  The indirect discharger treats process
     wastewater   in  a  two-stage  ion  exchange  system  before
     discharge to a POTW.  The direct  discharger  produces  only
     research  quantities of silver oxide (only 2 kg (4.4 lb.) in
     1981).  All wastewater from this  process  and  other  plant
     process  water  is  treated  in  a  lime  precipitation-alum
                              482

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     coagulation   treatment   system   before  discharge.
     wastewater volume  discharged  is  negligible.
                                                          Process
     The   Agency   is   excluding  this  subdategory  under Paragraphs
     8(a)(iv)  and 8(b).

     Note:    The   Agency  considered   combining  all  the  silver
     product  subcategories  (No.'s  70  to  76)   into  a  silver
     compounds subcategory.   However,  silver nitrate  is  soluble
     in   water whereas   the other six products are insoluble,  so
     that  the production  process,   raw   materials,   expected
     pollutants  and   unit  flows are significantly different for
     silver  nitrate   production  compared  to the   other   six
     products. Therefore, the combined subcategory would have to
     have   two  segments,  which  does  not  appear  to  provide
     significant   regulatory  simplification.   The  Agency  also
     considered combining six products (No.'s 70, 71, 72, 73, 74,
     and   76)   into  one subcategory.   There are  six plants which
     manufacture  one  or  more of  those products,  but  only  three
     (one  direct  and  two  indirect)  dischargers.   The direct
     discharger produces only a  few pounds  of silver  compounds
     each  year,   and  consequently generates minimal wastewater.
     That minimal wastewater is  treated with  an   advanced  level
     treatment technology for silver recovery.  The two indirect
     dischargers  use  advanced level treatment systems for  silver
     recovery  and  to  comply with the pretreatment requirements
     established  by the POTWs.  Accordingly, the  Agency  has  not
     combined  the  silver  products into a new silver comppounds
     subcategory, because that new subcategory would  also  have
     been excluded under Paragraph's 8(a)(iv) and 8(b).

77.   Soda Alum.  This subcategory has been  addressed  under  the
   '  "Alums" Subcategory, No. 5.

78.   Sodium Antimonate.   This product is generated  at  only  two
     sites  by a  process releasing no wastewater.  Therefore, the
     Agency is excluding this subcategory from national  effluent
     limitations    development   under  Paragraphs  8(a)(iv)  and
79.  Sodium Compounds (Inorganic).
     addressed elsewhere are:
                                    Specific sodium compounds not
     a.   Sodium Molybdate - There are two plants producing  this
          chemical.   One  has  no  discharge,  while  the second
          produces  research   quantities   and   is   a   direct
          discharger.   The  total  flow  from the process at the
          second facility is estimated to  be  less  than  10,000
          gallons per year.  The second facility produces a large
                              483

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f.
          number  of  different  chemicals  of  many  types on an
          intermittent basis.  All plant  process  wastewater  is
          treated in an advanced treatment system.

          Sodium  Perborate  -  There  is  one  plant,  a  direct
          discharger, producing this chemical.

          Sodium  Perchlorate  -  There  are  only   two   plants
          producing this chemical and neither has a discharge.

          Sodium Stannate - Three plants (two direct  dischargers
          and one indirect discharger) produce this chemical on a
          specialty   basis  along  with  many  other  chemicals.
          Production quantities at each plant are very low.   The
          total  flow  from  all  three plants is estimated to be
          less than 10,000 gallons per year.

          Sodium Thiocyanate - There are three  plants  producing
          this  chemical but none of the plants discharge process
          wastewater.

          Sodium Tungstate - There are two plants producing  this
          chemical,   but  one  plant  achieves  no  discharge  of
          process wastewater.   The  remaining  plant  discharges
          less  than  1.9  cubic  meters  per  day  (<500 gpd) of
          process wastewater from this product.

     The Agency is excluding the above  chemical  products  under
     Paragraphs  8(a)(iv)  and  8(b)(ii)  because  the  volume of
     wastewater discharged is insignificant.

80.  Sodium  Cyanide.   There  are  two  plants  producing   this
     chemical  in  the  U.S.  today.   One  plant  achieves8 zero
     discharge  while  the  second   plant   discharges   process
     wastewater  together  with  other  process water through the
     plant  treatment  system  and  then  to  a  POTW.   Alkaline
     chlorination is used at this plant to destroy cyanide before
     discharge.   The discharge is treated in compliance with the
     POTW's pretreatment requirements, consequently the plant  is
     unlikely to cease operating the treatment system.

     The  Agency  is  excluding this su.bcategory under Paragraphs
     8(a)(iv) and 8(b).

     This plant is also the only potassium cyanide producer  with
     a  discharge.   Therefore,  the  Agency  did not combine the
     potassium cyanide and sodium  cyanide  subcategories,  since
     there is only one discharger.
                         484

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81 .
82
83,
84,
85.
Sodium Hvdrosulfite (Zinc  Process).    There  is  one  plant
producing  this  chemical  by  the zinc process.  This plant
achieves  no  discharge  of  process  wastewater  from  this
product.   Therefore,   .this  subcategory  is  excluded under
Paragraph 8(a)(iv).

Sodium Silicofluoride.  This chemical is produced as  a  by-
product  of  wet  process  phosphoric acid production at six
fertilizer plants and by one plant which  does  not  produce
wet process phosphoric acid.  At phosphate fertilizer plants
there  is  no  discharge  of  process  wastewater  from  the
production of sodium silicofluoride.   The  one  plant  which
does  not  produce  sodium silicofluoride as a by-product of
wet process phosphoric  acid  production  uses  a  different
production  process  to  manufacture  sodium silicofluoride.
Thus there is only one discharger in this subcategory.
     Therefore, the Agency is excluding
     Paragraphs 8(a)(iv) and 8(b)(ii).
                                    this  subcategory  under
Stannic and Stannous Chloride.  There are three plants which
produce tin chlorides, but only two have a discharge.   Both
are  direct  dischargers.   Both plants produce the products
intermittantly at low production rates.  The total discharge
is estimated  to  be  less  than  5,000  gallons  per  year.
Therefore,  no significant pollutant loads are expected from
these sources, and the Agency is excluding this  subcategory
under Paragraphs 8(a)(iv) and 8(b)(ii).

Strontium Carbonate.  There are five  plants  which  produce
strontium  carbonate  but only three plants have a discharge
of  process  wastewater  (two  direct  dischargers  and  one
indirect  discharger).   Ail  three dischargers also produce
barium carbonate  and  combine  the  wastewaters  from  both
products  for  treatment  and  discharge.   One of the three
plants was sampled in Phase I and no toxic  pollutants  were
detected.    Therefore,   the   Agency   is  excluding  this
subcategory under the Paragraphs 8(a)(iv) and 8(b)(ii).

Strontium Nitrate.  There are  four  plants  producing  this
chemical.   One  of  the  producers achieves no discharge of
process wastewater.  One of  the  two  indirect  dischargers
discharges  to  a  POTW  but  the flow is low (less than 0.4
cubic  meters  per  day  (<100  gpd).   The  other  indirect
discharger  produces the chemical in small quantities and is
estimated to discharge less than 5,000 gallons per  year  to
POTW.  The remaining plant is a direct discharger which also
produces the chemical in small quantities, with an estimated
discharge of about 5,000 gallons per year.
                              485

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     The  Agency  is  excluding this subcategory under Paragraphs
     8(a)(iv) and 8(b)(ii).

86.  Sulfide and Sulfites.  All specific  sulfides  and  sulfites
     are  addressed  elsewhere under the metal sulfide or sulfite
     such as sodium hydrosulfite, sodium sulfite, barium sulfide,
     sodium hydrosulfide.  Regulations have been promulgated  for
     sodium  sulfite;  sodium  hydrosulfite,  barium sulfide, and
     sodium  hydrosulfide  have  been  excluded.   Therefore  the
     Agency   is  excluding  this  subcategory  under  Paragraphs
     8(a)(i), 8(a)(iv) and 8{b)(ii).

87.  Sulfocyanides   (Thiocyanates).    All   sulfocyanides    or
     thiocyanates   are  addressed  elsewhere  (such  as  No.  59
     (Potassium Thiocyanate) or No. 79(e) (Sodium  Thiocyahate)).
     There   are   no  dischargers.   Therefore,  the  Agency  is
     excluding the sulfocyanides (thiocyanates) subcategory under
     Paragraphs 8(a)(iv) and 8(b)(ii).

88.  Sulfur (Recovered or Refined Including  Sour  Natural  Gas).
     This  chemical  is produced (a) at petroleum refineries from
     crude petroleum, and (b) as part of the process of  removing
     hydrogen  sulfide  from  sour natural gas.  The national BAT
     regulations for the Petroleum Refining Industry address  the
     total   wastewater   discharge  from  petroleum  refineries,
     including any wastewater  from  sulfur  production  (40  CFR
     419).   Accordingly, the Agency is excluding this segment of
     the Sulfur subcategory under Paragraph 8(a)(i) because it is
     regulated under another industrial category.   There  is  no
     wastewater discharge from the production of sulfur from sour
     natural  gas,  and  therefore  the  Agency is excluding this
     segment under Paragraph 8(a)(iv) and 8(b)(ii).

89.  Sulfur Chloride.  Specific sulfur chlorides considered were:

     a.   Sulfur Monochloride - There are three plants, but  only
          one has a discharge.

     b.   Sulfur Dichloride - There are two plants, but only  one
          has a discharge.

     c.   Thionyl Chloride - There are two plants, but  only  one
          has a discharge.

     d.   Sulfuryl Chloride - There are only two plants, but only
          one has a discharge.

     The one discharger produces all four chemicals.   Therefore,
     the  Agency is excluding this subcategory under Paragraphs 8
                              486

-------
     (a)(iv) and 8(b)(ii) because there is only one discharger in
     the subcategory.

90.   Sulfur  Hexafluoride.   There  are  two   plants   in   this
     subcategory,   one a direct discharger and the other does not
     discharge from this process.  The direct discharger has only
     a small volume of process wastewater (1.5 cubic  meters  per
     day (<400 gpd)).

     The  Agency  is  excluding this subcategory under Paragraphs
     8(a)(iv) and 8(b)(ii) because there is only  one  discharger
     in the subcategory.

91.   Thiocyanates.  (See Subcategory No. 59 (c), 79 (f) and 87).

92.   Tin, Compounds.  Most tin compounds not  addressed  elsewhere
     are  produced,  if  at  all, only infrequently as low volume
     special order or research products.  The only  tin  compound
     not addressed elsewhere which is produced in quantity is tin
     fluoborate.  There are four plants producing tin fluoborate.
     However,  only one plant has a discharge of  19 cubic meters
     per  year  (5000  gallons  per  year).   This  flow  is  too
     insignificant  to  justify  developing a national regulation
     and therefore the Agency is excluding this subcategory under
     Paragraphs   8(a)(iv).   and   8(b)(ii).     Screening    and
     verification  sampling  data  for  the  one  discharger  are
     presented in Table 19-21.-.

93.   Ultramarine Pigments.  These substances are not produced  in
     the  U.S.  at  present.   Therefore, the Agency is excluding
     this subcategory under Paragraphs 8(a)(iv) and 8(b)(ii).

94.   Umbers.  This subcategory  has  been  addressed  under  Iron
     Oxides - see subcategory No. 34.

95.   White Lead Pigments.  The white  lead  pigments  subcategory
     includes  the  production  of  lead carbonate, lead silicate
     (subcategory No. 40), and lead  sulfate.    There  are  three
     plants  producing  any  of these products, one of which is a
     direct  discharger  and   the   other   two   are   indirect
     dischargers.    Both indirect dischargers are required by the
     POTWs to treat the wastewater before discharge to the POTWs.
     One plant must comply with the POTW's limitation for lead of
     0.5  mg/1  (long-term  average).   The  second   plant   has
     installed  lime precipitation, clarification, and filtration
     technology to comply  with  the  other  POTW's  pretreatment
     requirements.   That technology is the technology the Agency
     believes it would have used as the basis for  any  PSES  (or
     BAT)  regulations.   Since  the  plants  are required by the
                              487

-------
     POTWs  to  pretreat,  the  plants  are  unlikely  to   cease
     operating  the  treatment technologies.  Accordingly, a PSES
     is not needed.  Since there is only one  direct  discharger,
     and  both indirect dischargers must comply with pretreatment
     requirements imposed by the POTWs, the Agency  is  excluding
     the  white  lead  pigments  and  lead silicate subcategories
     under Paragraphs 8{a)(iv) and 8(b).

96.  Whiting (Calcium Carbonate).  Whiting is  another  name  for
     Calcium  Carbonate.   The  promulgated  guidelines  for  the
     Calcium  Carbonate  Subcategory  are  at  40  CFR   415.300.
     Calcium carbonate has been excluded from futher national BAT
     regulation   development   in   Phase  I  because  no  toxic
     pollutants were found at treatable levels  during  screening
     sampling.  (See the Phase I Development Document, pg. 793.).
     Therefore,  the  Agency  is  excluding this subcategory from
     further national regulation development under the provisions
     of Paragraphs 8(a)(iv) and 8(b)(ii).

97.  Zinc Sulfide,  There are two plants in this subcategory, one
     of which has no discharge.  The single discharger makes many
     specialty  chemicals  in  small  quantities  primarily   for
     captive  consumption.  The discharge of zinc sulfide process
     wastewater is less than 500 gallons per day.  The Agency  is
     excluding  this  subcategory  under  Paragraphs 8(a)(iv) and
     8(b)(ii) because there is only one discharging plant in  the
     subcategory.

Radioactive Materials

General.    Ten  of  the  subcategories  in  Phase  II involve the
production of products which are radioactive.  For convenience in
the regulatory review, these ten subcategories have been  grouped
together.  Those ten subcategories are:
98.  Cobalt 60


99.  Fissionable Materials

TOO. Isotopes, Radioactive

101. Luminous Compounds (Radium)


102. Nuclear Cores, Inorganic

103. Nuclear Fuel Reactor Cores,
       Inorganic
104.  Nuclear Fuel  Scrap
       Reprocessing

105.  Radium Chloride

106.  Radium Luminous Compounds

107.  Uranium Slugs,
       Radioactive
                              488

-------
In  many  cases two or more of the ten subcategories refer to the
same or similar products.  To facilitate the Agency's review, the
similar subcategories were addressed together, as follows:

     (a)  Cobalt 60 and isotopes, radioactive, since cobalt 60 is
          a radioactive'isotope.

     (b)  Luminous  compounds  (radium),  radium  chloride,   and
          radium    luminous    compounds,    since   all   three
          subcategories involve radium.

     (c)  Fissionable  materials,  nuclear   cores   (inorganic),
          nuclear  fuel  reactor  cores  (inorganic), and uranium
          slugs (radioactive), since all four subcategories refer
          to the production of the fissionable uranium slugs used
          in nuclear reactors.
     (d)  Nuclear fuel scrap reprocessing.

The  rationale  for  the  Agency's  actions  for
subcategories is presented below.
each  group  of
A.   Cobalt 60 and other radioactive  isotopes  are  produced  in
     nuclear  reactors by inserting the non-radioactive precurser
     (such as a  non-radioactive  isotope  of  cobalt)  into  the
     reactor,  where  it is bombarded by neutrons released in the
     reactor.  The  cobalt  60  (or  other  radioactive  isotope)
     produced  is  removed from the reactor and used as produced.
     There is no water used in producing the radioactive isotopes
     and no wastewater is generated  or  discharged.   Therefore,
     the   Agency  is  excluding  the  cobalt  60  and  isotopes,
     radioactive subcategories from  regulation  under  Paragraph
     8(a)(iv) because there are no dischargers.

B.   No radium chloride or radium  luminous  compounds  (luminous
     compounds, radium) are produced in this country nor have any
     been  produced  for  over  25  years.   Hence, the Agency is
     excluding the radium chloride,  radium  luminous  compounds,
     and luminous compounds, radium subcategories from regulation
     under Paragraph 8(a)(iv) because there are no producers.

C.   Fissionable materials production involves the production  of
     the  uranium  or  uranium  oxide  slugs  used as the fuel in
     nuclear reactors.  The fuel is loaded into  the  reactor  in
     rods.   Since,  strictly  speaking,  the  nuclear core is an
     assembly of fuel rods, moderators, and supporting  elements,
     and  the  assembling  of the core is a construction process,
     the Agency has interpreted the  nuclear  cores  (inorganic),
     and  nuclear fuel reactor cores (inorganic) subcategories to
                              489

-------
D.
mean the production of the fissionable uranium slugs used in
the core fuel rods, as that is the only chemical process.

Fissionable materials (nuclear cores, nuclear  fuel  reactor
cores,  uranium  slugs)  production  is  conducted  in  this
country only under license issued by the Nuclear  Regulatory
Commission  (NRC).   The license controls all aspects of the
production of  fissionable  materials  including  wastewater
discharges.   Any  materials  in  the  wastewater are source
material, by-product material, or special nuclear  material,
as these terms are defined in the Atomic Energy Act of 1954,
as  amended.  The Supreme Court decided in Train v. Colorado
PIRG, 426 U.S.I. (1976) that these materials, at least  when
regulated  by  the NRC, are not "pollutants" under the Clean
Water Act.

Spent nuclear fuel may  be  reprocessed  to  recover  useful
fissionable  materials that may remain in the spent fuel or,
in the case of plutonium 239, have been produced during  the
"burn"  cycle.   All  facilities  engaged  in  this  process
operate under licenses issued  by  the  NRC.   The  licenses
control   all   aspects   of   the  reprocessing,  including
wastewater discharges.  Any materials in the wastewater  are
source  material,  by-product  material,  or special nuclear
material, as these terms are defined in  the  Atomic  Energy
Act  of  1954,  as  amended.   The Supreme Court decided, in
Train  v.  Colorado  PIRG,  426  U.S.I.  (1976)  that  these
                       when
     materials,  at  least  when  regulated
     "pollutants" under the Clean Water Act.
by  the NRC, are not
                              490

-------
Table 19-2. SUMMARY OF TOXIC AND NON-CONVENTIONAL POLLUTANT DATA
            FOR SCREENING/VERFICATION SAMPLING (Table 19-2a, AMMONIUM
            THIOSULFATE).

SUBCATEGORY: 10 - Ammonium Thiosulfate
Pollutant

   Sb
   As
 .  Be
   Cd
   Cr
   Cu
   Pb
   Hg
   Ni
   SI
   Ag
   Tl
   Zn
   Ethyl benzene
   Tolune
   2,4 Dinitrophenol
   4,6 Dinitro-o-cresol
   Bis (2-ethylhexyl)phthalate
   Thiosulfate
                                Plant A*

                                 0. 88
                                 0.004
                                 0.008
                                 0. 084
                                 0.153
                                 2.0
                                 3.6
                                 0.006
                                 0.38
                                 0.018
                                 0.002
                                 0.121
                                 1.3
                                  7300
                                 0.019
                                 0.021
                                 0.351
                                 0.054
                                 0.033
                                23,000
Concentration (mg/1)

         Plant B

           0.32
           0
           0
           0.016**
           0.071
           0.01
           0.44
           0
           0
           0
           0
           0.13
           0
           Not Analyzed
 * Samples may have been contaminated by contact with sealing compound
   on new floor.  Total flow averaged 150 gallons per day.

** Two samples only.  Analysis for cadmium in third sample erroneous, as
   analysis of the blank for that sample showed high cadmium result.
                                491

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
            FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 b.,  BRINE CHEMICALS)

SUBCATEGORY: 18 - Brine Chemicals

                        Concentration (mg/1)
Pollutant

  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  Ni
  Se
  Ag
  n
  Zn
Plant A

 0.003
 0.0002
 0.0002
 0.057
 0.091
 0.13
 0.079
 0.0003
 0.052
 0.014
 0.055
 0.008
 0.55
Flow averaged 700 gallons per day.
                                492

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA FOR
            SCREENING/VERIFICATION SAMPLING (Table 19-2 £, CALCIUM HYPOCHLORITE)
SUBCATEGORY:  20 - Calcium Hypochlorite

Pollutant                     Plant A

   Sb                            0.1
   As                            0.004
   Be                            0.001
   Cd                            0.006
   Cr                            0.039
   Cu                            0.041
   Pb                            0.14
   Hg                            0.002
   Ni                            0.015
   Se                            0.004
   Ag                            0.0003
   Tl                            0.002
   Zn                            0.085.
   Chloroform                    0.090
   Methylene Chloride            0.014
   Dichlorobromomethane          0.025
   Chlorodibromomethane          0.041
Plant B

  4.1
  0.002
  0.011
  0.15
  0.11
  0.17
  0.27
  0.01
  0.6
  0.007
  0.014
  1.1
  0.37
  0.17
  1.1
  ND
  0.0007
                                 493

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA FOR .
            SCREENING/VERIFICATION SAMPLING .(Table 19-2 d^ CHLOROSULFONIC ACID),

Subcategory: 22 - Chlorosulfonic Acid

                                Concentration (mg/1)

Pollutant                        Plant A
  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  Ni
  Se
  Ag
  Tl
  Zn
  Chloroform
  Methylene Chloride
  Di-n-octyl phthalate
0.067
0.017
0.0011
0.0
0.0036
0.0
0.0
0.0
0.022
0.0
0.0
0.01
0.0067
0.017
0.014
0.011
                                494

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
            FOR SCREENING/VERIFICATION SAMPLING (TABLE 19-2 
-------
Table 19-2. SUMMARY OF TOXIC AND  NONCONVENTIONAL  POLLUTANT  DATA  FOR
            SCREENING/VERIFICATION SAMPLING  (Table  19-2 f_,  IRON  OXIDE  PIGMENTS),

SUBCATEGORY: 34.35.36.48,67.94  -  Iron Oxide  Pigments
Pol 1utant

  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  N1
  Se
  Ag
  Tl
  Zn
  Fe
  Methyl ene Chloride
                                Concentration  (mg/1)
Plant A*
0.55
0.005
0.005
0.036
0.22
0.12
0.39
0.001
0.74
0.015
0.008
0.14
0.65
83
Not Analyzed
Plant B
0.13
0.002
0.002
0.002
0.038
0.018
0.13
0.003
0.21
0.009
0.044
0.084
0.015
Not Analyzed
0.015
Plant C**
 0.02
 0.045
 0.04
 0.04
 9.3
 * Treatment system not functioning optimally.  Effluent not in compliance with
   POTW's requirements.

** Long-term treatment system performance data.
                                496

-------
TABLE 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
            FOR SCREENING/VERFICATION SAMPLING (Table 19-2 _g_, SILICA, AMORPHOUS),
SUBCATEGORY: 68 - Silica,
Pollutant
Sb
As
Be
Cd
Cr
Cu
Pb
Hg
Ni
Se
Ag
Tl
Zn
Chloroform
Methyl ene Chloride
Methyl Chloride
Di chl orobromomethane
2,4 Dinitrophenol
Di-n-octyl phthalate
1,1,1 - Trichloroethane
Amorphous
Plant. A*
0.008
0.009
0.0005
0.011
0.09
0.018
0.01
0.002
0.17
0.007
0.007
0.003
0.16
0.192
0.065
0.548
0.015
0.064
0.012
ND
                                                Plant B

                                                 0.075
                                                 0.025
                                                 0.002
                                                 0.011
                                                 0.017
                                                 0.011
                                                 0.10
                                                 0.003
                                                 0.037
                                                 0.046
                                                 0.0012
                                                 0.006
                                                 0.086
                                                 ND
                                                 ND
                                                 ND
                                                 ND
                                                 ND
                                                 ND
                                                 ND
Plant C

 0.12
 0.0025
 0.005
 0.016
 0.015
 0.013
 0.20
 0.001
 0.12
 0.015
 0.01
 0.007
 0.031
 ND
 0.026
 ND
 0.028
 ND
 ND
 0.086
* Toxic organic pollutants from organic chemical  process at same site.
                                 497

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
            FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 h^ SILICA GEL),

SUBCATEGORY: 69 - Silica Gel
Pol1utant

  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  Ni
  Se
  Ag
  Tl
  Zn
  Chloroform
  Methylene Chloride
Concentration (mg/1)

        Plant A

         0.067
         0.023
         0.002
         0.005
         0.024
         0.024
         0.030
         0.0
         0.038
         0.35
         0.015
         0.12
         0.048
         0.040
         0.015
                                498

-------
TABLE 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
            FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 1, TIN COMPOUNDS),

SUBCATEGORY: 92 - Tin Compounds (Tin Fluoborate)

                            Concentration (mg/1)

Pollutant                  Plant A
  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  N1
  Se
  Ag
  n
  Zn
  Phenol
  Butyl Benzyl
Phthalate
0.008
0.016
0.005
0.006
0.007
0.17
0.12
0.0005
0.22
0.005
0.0004
0.045
0.12
0.045
0.043
                                 499

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                           SECTION 19

                           REFERENCES
10,
Office  of  Management  and  Budget,   "Standard    Industrial
Classification  Manual,"  U.S.  Government  Printing Office,
1972.

SRI International,  1982  Directory  of_ Chemical   Producers,
United States of America, Stanford Research Institute, Menlo
Park, California.

Chemical Marketing  Reporter, OPD Chemical  Buyers  Directory
-1983.

Calspan  Corporation,  Addendum  B-l   (Background  Data)  to
"Supplement  for  Pretreatment  to Development Documents for
the   Inorganic   Chemicals   Manufacturing   Point   Source
Category,"  Calspan Report  No. ND-5782-M-85, 17  March 1977
(Survey conducted in 1976).

Terlecky, P.M., and Frederick, V.R., "Status of the Excluded
Subcategories  of   the  Inorganic  Chemicals  "Manufacturing
Industry  -  Phase  II," Frontier Technical Associates, Inc.
Report No. FTA-82-E2/02, February 7, 1983.

Terlecky, P.M., Harty, D.M., and Bullerdiek,  W.A.,  "Status
of  the Radioactive Materials Subcategories of the Inorganic
Chemicals  Manufacturing  Industry  -  Phase  II,"  Frontier
Technical Associates, Inc. Report No.  FTA-82-E2/01, February
9, 1983.

Terlecky, P.M. and  Frederick,  V.R.,   "Discharge  Status  of
Rare   Earth   Metal   Salts   and   White   Lead   Pigments
Subcategories,"   Memorandum   from    Frontier    Technical
Associates to Dr. Thomas Fielding, USEPA, 11 January 1983.

Personal Communication:  William Kirk, U.S. Bureau of Mines,
Washington,  D.C.   to   D.M.   Harty,   Frontier   Technical
Associates, Inc., November 30, 1982.

U.S. Bureau of Mines, Minerals Yearbook, vol. 1  (Metals  and
Minerals), "Minor Metals" (1978-79).

U.S. Bureau of Mines, Minerals Yearbook, vol. 1  (Metals  and
Minerals), "Minor Metals" (1977).
                              500

-------
11
12
13
14
15
16,
17
18
19
20
21
22
U.S. Bureau of Mines,  Minerals  Yearbook,  vol.  1  (Metals  and
Minerals),  "Minor  Metals"  (1976).

U.S. Bureau of Mines,  Minerals  Yearbook,  vol.  1  (Metals  and
Minerals),  "Minor  Metals"  (1975).

U.S. Bureau of Mines,  Minerals  Yearbook,  vol.  1  (Metals  and
Minerals),  "Minor  Metals"  (1974).

U.S. Bureau of Mines,  Minerals  Yearbook,  vol.  1  (Metals  and
Minerals),  "Minor  Metals"  (1973)..

Personal    Communications     R.     Call is,     EPA    Eastern
Environmental  Radiation  Facility,   Montgomery,   AL to D.M.
Harty,  Frontier  Technical  Associates,   Inc.,  December  1,
 1982.

Personal  Communication:   Mr. Dan  Kaufman,   Radium  Chemical
Co., Woodside, NY  to D.M.  Harty,  FTA, December 2, 1982.

Stinson,   S.C.,    "Supply   Problems   Cloud   Outlook   for
Radioisotopes,"  Chemical and Engineering News, May 31, 1982.

Personal    Communication:     George   Mayberry,    Automation
 Industries, Phoenixville,  PA to D.M. Harty, FTA,  December 6,
 1982.

 Personal  Communication:   Marvin Turkanis, Neutron  Products,
 Inc.,  Dickerson, MD to D.M.  Harty, FTA,  December 7, 1982.

.Personal  Communication:   Bob McNally, Technical  Operations,
 Inc.,  Boston,  MA to D.M. Harty, FTA, December 7,  1982.
 Personal Communication:  X-ray Industries,  Detroit,  MI
 D.M.  Harty, FTA,  December 7, 1982.
                                                               to
 U.S.  Bureau of Mines, Mineral Facts and Problems,  "Depleted
 Uranium"  by  William  S.  Kirk, BUMINES Bull. 671, 1980, p.
 997-1003.
                               501

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-------
                  Appendix A

Analysis of Long-Term Effluent Monitoring Data
                   Phase II
                        A-i

-------
                      TABLE OF CONTENTS
Section

CADMIUM PIGMENTS AND SALTS
   Plant F101
   Plant F102
   Plant F110
   Plant F117
   Plant F119
   Plant F124
   Plant F125
   Plant F128
   Plant F134

COBALT SALTS
   Plant F117
   Plant F118
   Plant F119
   Plant F124
   Plant F139

COPPER SALTS
   Plant E115
   Plant F118
   Plant F119
   Plant F127
   Plant F133

NICKEL SALTS
   Plant F117
   Plant F118
   Plant F119
   Plant F124
   Plant F125
   Plant F139

SODIUM CHLORATE
   Plant F103
   Plant F147
   Plant F149

ZINC CHLORIDE
   Plant F118
   Plant F125
   Plant F140
   Plant F144
A-12
A-13
A-14
A-17
A-19
A-20

A-21
A-22
A-23
A-26
A-28
A-29

A-33
A-34
A-36
A-39
A-41
A-42
A-43

A-44
A-45
A-49
A-SI

A-52
A-53
A-56
A-5 7
A-58
                             A-

-------
Treatment Technology Abbreviations Used:
Eq         =  Equalization
Neut       =  Neutralization
Neut (2)   =  Two stage neutralization, if used in sequence
FL(m)      =  Filtration with multi-media
FL(s)      =  Filtration with sand filter
FL(p)      =  Filtration with filter press
FLCu)      =  Filtration-method unknown
CL         =  Clarifier
S          =  Sulfide addition
Sd         -  Sedimentation  (basin, pond, lagoon)
RCL        =  Recycle
pH         =  pH adjustment
Floe       =  Flocculant  addition
Act.
  Sludge   =  Biological  activated  sludge
AR         =  Aeration
Cr-Red    =  Hexavalent  chromium reduction
Pep        =  Alkaline  precipitation
                            A- iii

-------

-------
CADMIUM PIGMENTS AND SALTS
            A-l

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