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

             Steven Schatzow
                Director
Office of Water Regulations and Standards
         Jeffery Denit, Director
      Effluent Guidelines Division

            G. Edward Stigall
    Chief, Inorganic Chemicals Branch

           Dr. Thomas Fielding
             September 1983

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

-------
                        TABLE OF CONTENTS
Section
Page
          LIST OF FIGURES                                     xiv

          LIST OF TABLES                                     xvii

          ACKNOWLEDGEMENTS                                   xxiv

     1    SUMMARY AND CONCLUSIONS                               1

     2    RECOMMENDATIONS                                       4

     3    INTRODUCTION                                         15

          AUTHORITY                                            15

               The Federal Water PollutionControl
                    Act Amendments                             15
               Court Remand of Regulations                     18
               The Settlement Agreement                        18
               Phase II Inorganic Chemicals                    21

          GENERAL APPROACH AND METHODOLOGY                     21

               Industry Data Base Development and
                    Subcategorization Review                   21
               The Screening and Verification Sampling         22
               Engineering Evaluation                          22
               Treatment System Cost Estimates   •              23
               Treatability Study                              23

          GENERAL CRITERIA FOR EFFLUENT LIMITATIONS            24

               BPT Effluent Limitations                        24
               BAT Effluent Limitations                        24
               BCT Effluent Limitations                        25
               New Source Performance Standards                26
               Pretreatment Standards for Existing Sources     26
               Pretreatment Standards for New Sources          26

     4    SUBCATEGORIZATION                                    29

               Basis for Subcategorization                     29

     5    SAMPLING PROGRAM                                     36

          SCOPE AND METHODOLOGY                                36
                                     ii Ail, i, a, n iniSr	!,!', I'll,• iiiim,!.Hi1,,,,S:i,iM!,h .m,;,!,'

-------
                         TABLE OF CONTENTS (Continued)
Section
               Selecting Plants
               Sampling Program
               Analytical Methodology
               Quality Assurance Provisions

          SUMMARY OF ANALYTICAL RESULTS

          PROCESS AND WASTEWATER TREATMENT INFORMA-
          TION DEVELOPMENT AND EVALUATION

          INDUSTRY DATA BASE  DESCRIPTION

          PROCESS WASTEWATER  SOURCES  AND CURRENT  TREATMENT
               PRACTICES

          ASSESSMENT OF TECHNOLOGY FOR  ADVANCED TREATMENT
               AND CONTROL

               Introduction
               Hydroxide Precipitation
               Ferrite  Coprecipitation
               Sulfide  Precipitation
               The Xanthate Process
               Ion Exchange
               Reduction Processes
               Oxidation Processes
               Membrane  Processes
               Adsorption
               Fluoride Removal
               Chlorine Removal

         TREATABILITY ESTIMATES AND LONG-TERM DATA
              ANALYSIS

              The Development of Treatability Estimates
              Final Analysis
              Selection of Toxic Metal  Control Parameters
              The Use of Historical  Pollutant Data
              Assumptions Concerning Daily Pollutant
                   Level Measurement
              Assumptions Concerning 30-Day Average
                   Pollutant  Level Observation

         TREATMENT TECHNOLOGY APPLICATIONS FOR TOXIC
              POLLUTANT REMOVAL
  36
  37
  39
  45

  47
  53

  53


  54


  60

  60
  61
  66
  66
  70
  72
  74
  76
  79
  82
  84
  84


  90

  90
  91
107
110

112

119


128
                              iii

-------
                         TABLE OF CONTENTS (Continued)
Section
     10
     Selection of Pollutants to be Controlled
     Application of Advance Level Treatment
          and Control Alternatives
     Estimated Achievable Performance Character-
          istics for Advanced Level Applications
     Pollution Control Parameters to be Regulated

COST OF TREATMENT AND CONTROL SYSTEMS

INTRODUCTION

TREATMENT AND DISPOSAL RATIONALE

COST REFERENCES AND RATIONALE

CAPITAL COSTS

     Facilities
     Equipment/Installation
     Engineering
     Contractor Overhead and Profit
     Contingency
     Land

ANNUAL COSTS

     Operations and Maintenance
     Amortization

ACCURACY OF ESTIMATES

DESCRIPTION OF WASTEWATER  TREATMENT TECHNOLOGIES

MODEL PLANT TREATMENT COSTS

     General

SAMPLE MODEL  PLANT COST  CALCULATION

     General
     Sample Calculation

REFERENCES

CADMIUM  PIGMENTS AND SALTS INDUSTRY
Page

 128

 128

 130
 131

 135

 135

 135

 136

 136

 136
 138
 139
 140
 140
 140

 140

 156
 157

 158

 158

 161

 161

 162

 162
 163

 166

  167
                                IV

-------
                         TABLE OF CONTENTS (Continued)
Section
    12
 INDUSTRIAL PROFILE

 WATER USE AND WASTEWATER 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
Page

 167

 174

 179

 191

 191
 192

 193

 193
 194
 195

 195
 197
 197
 198
 201
 201
 207
 207

 209
 209

 212

213

213

215

219

220

220
220

221

-------
                         TABLE OF CONTENTS (Continued)
Section
     13
     Process Modifications and Technology
          Transfer Options                         221
     Best Management Practices                     221
     Advanced Treatment Technology                 222
     Selection of Appropriate Technology and
          Equipment                                222
     Treatment Cost Estimates                      223
     Basis for Regulations                         225
          Basis for BPT Effluent Limitations       225
          Basis for BCT Effluent Limitations       230
          Basis for BAT Effluent Limiations        230
          Basis for NSPS Effluent Limitations      231
          Basis for Pretreatment Standards         231

REFERENCES                                         234

COPPER SALTS INDUSTRY                              235

INDUSTRIAL PROFILE                                 235

WASTE USE AND WASTEWATER SOURCES                   244

DESCRIPTION OF PLANTS VISITED AND SAMPLED          248

POLLUTION ABATEMENT OPTIONS                        256
     Toxic Pollutants of Concern                   256
     Existing Control and Treatment Practices      256
     Other Applicable Control and Treatment
          Technologies                             257
     Process Modifications and Technology
          Transfer Options                         257
     Best Management Practices                     258
     Advanced Treatment Technology                 258
     Selection of Appropriate Technology and
          Equipment                                258
     Treatment Cost Estimates                      260
     Basis for Regulations                         264
          Basis for BPT Effluent Limitations       264
          Basis for BCT Effluent Limitations       269
          Basis for BAT Effluent Limitations       269
          Basis for NSPS Effluent Limitations      274
          Basis for Pretreatment Standards         274

REFERENCES                                         276
                               VI

-------
                         TABLE OF CONTENTS (Continued)
Section
     14   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

    15   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
Page

 277

 277

 282

 285

 292
 292

 292

 294

 294
 295
 296

 296
 298
 302
 302
 307
 307
 312
 312

 314

 315

 315

 319

 322

 335
 335

 336

 337
 338
                              vii

-------
                         TABLE OF CONTENTS (Continued)
Section
               Process Modifications and Technology
                    Transfer Options                         338
               Best Management Practices                     339
               Advanced Treatment Technology                 340
               Selection of Appropriate Technology and
                    Equipment                                340
               Treatment Cost Estimates                      342
               Basis for Regulations                         343
                    Basis for BPT Effluent Limitations       343
                    Basis for BCT Effluent Limitations       348
                    Basis for BAT Effluent Limitations       351
                    Basis for NSPS Effluent Limitations      354
                    Basis for Pretreatment Standards         354

          REFERENCES                                         357

     16   ZINC CHLORIDE INDUSTRY                             358

          INDUSTRIAL PROFILE                                 358

          WATER USE AND WASTEWATER SOURCE CHARACTER-
               ISTICS                                        363

          DESCRIPTION OF PLANTS VISITED AND SAMPLED          363

        •  POLLUTION ABATEMENT OPTIONS                        371
               Toxic Pollutants of Concern                   371
               Existing Wastewater Control and Treatment
                    Practices                                371
               Other Applicable Control and Treatment
                    Technologies                             371
               Process Modifications and Technology
                    Transfer Options                         372
               Best Management Practices                     372
               Advanced Treatment Technology                 372
               Selection of Appropriate Technology and
                    Equipment                                373
               Treatment Cost Estimates                      374
               Basis for Regulations                         377
                    Basis for BPT Effluent Limitations       377
                    Basis for BCT Effluent Limitations       381
                    Basis for BAT Effluent Limitations       384
                    Basis for NSPS Effluent Limitations      386
                    Basis for Pretreatment Standards         386
                              viii

-------
                         TABLE OF CONTENTS (Continued)
Section
          REFERENCES
Page

 390
     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
               Recommendat ions

          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
 391

 391

 392

 392
 392
 393
 393
 399
 403

 404

 404
 405
 405
 407

 407

 407
 408
 408
 410
 412
 415
 415
 417
 417

 420

 421

 421

 421
 421
 422
 422
                               ix

-------
                         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 Dichromate
 23.  Sodium Fluoride

 PROPOSED EXCLUSIONS

      Subcategories with  no PSES in Effect
      Subcategories with  PSES  in Effect

 PROPOSED PSNS

 REFERENCES

 EXCLUDED SUBCATEGORIES

 INTRODUCTION

     Subcategories Surveyed
     Methods Employed

EXCLUDED SUBCATEGORIES

 1.  Aluminum Chloride (Anhydrous)
  422

  423
  423
  423
  423
  423
  423
  423
  424
  424
  424
  424
  424
  424
  424
  425
  425
 425
 426
 426
 426
 427
 427
 427

 428

 428
 430

 430

 431

 432

 432

 432
 432

436

436

-------
                         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 Coumpounds
 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
 2 8.   Hydrophosph i tes
 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
 436
 436
 437
 437
 437
 437
 438
 439
 439
 439
 440
 440
 440
 440
 440
 441
 442
 442
 443
 443
 444
 444
 444
 444
 444
 445
 445
 445
 445
 445
 446
 446

 446
 447
 447
 447
 447
447
448
449
449
449
449
450
                              xi

-------
                         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.   Strontium Carbonate
          85.   Strontium Nitrate
          86.   Sulfides  and Sulfites
          87.   Sulfocyanides  (Thiocyanates)
          88.   Sulfur
          89.   Sulfur  Chloride
          90.   Sulfur  Hexafluoride
          91.   Thiocyanates
 450

 450
 450
 450
 450
 450
 451
 451
 451
 451
 451
 452
 452
 452
 453
 453
 454
 454
 454
 454
 454
 454
 454
 454
 455
 455
 455
 455

 456
 456
458
458
458
458
458
459
459
459
459
460
460
                              XII

-------
                         TABLE OF CONTENTS  (Continued)
Section
APPENDIX A
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

     Analysis of Long-Term Effluent Monitoring
     Data for the Inorganic Chemicals
     Industry Phase II
460
460
460
460
461
461

461

461
462
462
463
463

 A-l
                              xiii

-------
                          LIST OF  FICURES
 5-1 .
 7-1 .

 7-2.

 7-3.
 8-1.

 8-2.

 8-3.

 8-4.

 8-5.

 8-6.

 10-1.
 10-2.
 10-3.
 10-4.
 10-5.
 10-6.
 10-7.
 10-8.
10-9.
 Sample  flow sheet for metals analysis.
 Theoretical solubilities of toxic metal hydrox-
 ides/oxides as a function of pH.
 Theoretical solubilities of toxic metal sulfides
 as a function of pH.
 Electrodialysis process.
 Cumulative distribution of daily concentrations
 of zinc (total) in treated effluent.
 Cumulative distribution of daily concentrations
 of TSS in treated effluent.
 Statistical distribution for daily pollution
 measurements.
 Cumulative distribution of monthly averages of
 cadmium in treated  effluent.
 Cumulative distrubution of monthly averages of
 lead  (total)  concentrations  in  treated effluent.
 Statistical  distrubutions  for 30-day average
 pollution  measurements.
 Land  requirements for small and medium lagoons.
 Dike .volumes of lagoons.
 Dike surface areas and circumferences  of lagoons.
 Concrete pits and building costs.
 Holding/storage tank costs.
 Filter, thickener and clarifier  costs.
 Chemical feed and neutralization system costs.
 Pump and chrome reduction system costs.
Filter press costs.
Page
  40

  63

  68
  80

 116

 117

 118

 122

 123

 124
 142
 143
144
145
146
147
148
149
150
                               xiv

-------
                     LIST QF 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.
          PreciPitation, settling, pH adjustment
 (Batch Process).


 Granular media filtration (Batch Process).


 Chromium reduction,  alkaline precipitation
 settling,  final pH adjustment arid 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
 151


 152



 153


 154





 155



 170



 171



 180



 181



 182



 183



 216



 239



 240



241



242
                               xv

-------
                    LIST OF FIGURES

                                                            Page

13.5      Process and sampling locations for plant F130.     249

13-6.     Process, wastewater flow, and sampling locations
          for plant F127.                                    250

14-1.     Generalized process diagram for nickel
          carbonate.                                         280

14-2.     Generalized process flow diagram for nickel
          chloride, nitrate or fluoborate.                   281

14-3.     Process and sampling locations for plant F113.     287

14-4.     Process, wastewater treatment, and sampling
          locations for plant F117.                          288

14-5.     Process and sampling locations for plant F107.     289

15-1.     Generalized process flow diagram for sodium
          chlorate.                                          318

15-2.     Process and sampling locations for plant
          F122.                                              326

15-3.     Process and sampling locations for plant
          F149.                                              327

15-4.     Process and sampling locations for plant
          F146.                                              328

15-5.     Process and sampling locations for plant
          F112.                                              329

16-1.     Generalized process flow diagram for zinc
          chloride.                                          360

16-2.     Process wastewater treatment and sampling
          locations for plant F120.                          364

16-3.     Wastewater treatment process and sampling
          locations for plant F144.                          365

17-1.     Surface condenser cost.                             400
                               xvi

-------
                          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  available 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 treat 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.
Page

   5

   7

   9

  10

  12

  13
  20
  43

  48

  50
  51

  56
  62
  61
  92

  93

  94
                              xvii

-------
                     LIST OF TABLES (continued)
 8-4.




 8-5.



 8-6.



 8-7.



 8-8.



 8-9.



 8-10.



 8-11.
 Wastewater treatment options and performance
 data summary - chromium III and chromium VI
 removal.

 Wastewater treatment options and performance
 data summary - lead removal.

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

 Wastewater treatment options and performance
 data summary - nickel removal.

 Wastewater treatment options and performance
 data summary - silver removal.

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

 Wastewater treatment options and performance
 data summary - zinc removal.

 Achievable long-term averages for the applied
 technologies.
  95



  96



  97



  98



  98



  99



100



101
8-12. '




8-13.




8-14.



9-1.




10-1.

11-1 .
 Industrial wastewater  treatment system per-
 formance - summary of  effluent concentration
 data on toxic metals.

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

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

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

Pipe size requirements and pipe costs.

Subcategory profile data for cadmium pigments
and salts.
103




108



109




129

141



168
                              xviii

-------
                    LIST OF TABLES (continued)

                                                            Page

11-2.      Water usage at cadmium salts facilities.            175

11-3.      Water usage at cadmium pigments facilities.         176

11-4.      Wastewater flow at cadmium salts facilities.        177

11-5.      Wastewater flow at cadmium pigments facilities.     178

11-6.      Pollutant concentrations and loads of the
          sampled waste streams for plant F102 cadmium
          pigments.                      .                    185

11-7.      Pollutant concentrations and loads of the
          sampled waste streams for plant F134 cadmium
          pigments.                                          186

11-8.      Toxic pollutant raw waste data - cadmium
          pigments.                                          189

11-9.      Toxic pollutant treated effluent data -
          cadmium pigments.                                  190

11-10.     Water effluent treatment costs and resulting
          waste-load characteristics for model plant
          (cadmium pigments).                                199

11-11.     Water effluent treatment costs and resulting
          waste-load characteristics for model plant
          (cadmium salts).                                   200

11-12.     BPT effluent limitations for cadmium pigments.      205

11-13.     BPT effluent limitations for cadmium salts.         206

11-14.     BAT effluent limitations for cadmium pigments
          and salts subcategory.                             208

12-1.      Subcategory profile data for cobalt salts.         214

12-2.      Water usage at cobalt salts facilities.            217

12-3.      Wastewater flow at cobalts salts facilities.        218

12-4.      Water effluent treatment costs and resulting
          waste-load characteristics for model plant
          (cobalt salts).                                    224
                               xix

-------
                      LIST  OF  TABLES  (continued)
 12-5.
 13-1.
 13-2.
 13-3.
 13-4.

 13-5.

 13-6.

 13-7.

 13-8.
 13-9.
 13-10.
 13-11.
 14-1.
 14-2.
 14-3.
 14-4.

14-5.

14-6.
  BPT  effluent  limitations  for cobalt  salts.
  Subcategory profile  data  for copper  salts.
  Water usage at  copper salts  facilities.
  Wastewater flow at copper salts  facilities.
  Pollutant concentrations and loads for sampled
  copper salts facilities.               »«ui,piea
  Toxic pollutant raw wastewater data for sampled
  copper salts facilities.                sampiea
 Water effluent  treatment costs and resulting
 waste-load characteristics for model plant
  (copper salts) .
 Water effluent treatment costs and resulting
 waste-load characteristics for model plant
  (copper carbonate).
 BPT effluent  limitations for copper salts.
 BPT effluent  limitations for copper carbonate.
 BAT effluent  limitations for copper salts.
 BAT effluent  limitations for copper carbonate.
 Subcategory profile data for nickel salts.
 Water use at nickel salts  facilities.
 Wastewater flow  at nickel salts facilities.
 Pollutant concentrations and  loads for sampled
 nickel salts facilities.
salts facilities""
                               f°r sampled nickel
Water effluent treatment costs and resultina
waste-load characteristics for model plant
(nickel salts).
 Page
  229
  236
  245
  246

  251

 255

 262

 263
 270
 271
 272
 273
 278
 283
 284

 291

293

299
                               xx

-------
                    LIST OF TABLES (continued)
14-7.

14-8.
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.

16-1 .
16-2.
16-3.
16-4.
                                                  Page
Water effluent treatment costs and resulting
waste-load characteristics for model plant
(nickel carbonate).                                300
BPT effluent limitations for nickel salts.         305
BPT effluent limitations for nickel carbonate.     306
BAT effluent limitations for nickel salts.         310
BAT effluent limitations for nic.kel carbonate.     311
Subcategory profile data for sodium chlorate.      316
Water usage at sodium chlorate facilities.         320
Raw materials, wastewater sources, type of product,
discharge status, and unit flows for sodium chlorate
plants                                             321
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 and resulting
waste-load characteristics for model plant.
(sodium chlorate).
BPT effluent limitations for sodium chlorate.
BAT 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
323
324

331

334

344
349

353
359
361
362
                               xxi

-------
                     LIST OF TABLES (continued)
 16-5.

 16-6.

 16-7.

 16-8.
 16-9.
 17-1.

 17-2.

 17-3.

 17-4.

 17-5.

 17-6.

 17-7.
 18-1.

19-1.
19-2.
 zinc chloride facilities.
 Toxic pollutant raw waste data for sampled
 zinc chloride facilities.
 Water effluent treatment costs and resulting
 waste-load characteristics for model plant.
 (zinc chloride - large Plant).
 Water effluent treatment costs and resulting
 waste-load characteristics for model plant.
 (zinc chloride - small Plant).
 BPT effluent limitations for zinc chloride.
 BAT effluent limitations for zinc chloride.
 Toxic metals dischared in barometric condenser
 wastewater.
 Chemical  composition of crystallizer,  evaporator
 and barometric condensate from plant F122.
 Water effluent treatment costs and resulting
 waste-load characteristics  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 and  resulting
 water-load characteristics  for model plant
 (sodium sulfite).
 BAT effluent limitations  for  sodium sulfite.
 Summary of the discharge  status of all PSES
 subcategories.
 Inorganic  chemical subcategories surveyed.
Page
 368

 370

 375

 376
 382
 387

 396

 398

 401

 4T1

 413

 414
 416

429
433
Summary of toxic and non-conventional pollutant data
for screening/verification sampling.               464
                              xxii

-------
          LIST OF TABLES (continued)
19-2a     Ammonium Thiosulfate
19-2b     Brine Chemicals
19-2c     Calcium Hypochlorite
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
464
465
466
467
468
469
470
471
472
                   XXlll

-------
                        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 Biillerdiek.   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.

Mr.  Steven  Schatzow,  Director,  Office of  Water  Regulations  and
Standards, is greatly  acknowledged for  his contributions to  the
project.

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 and Mr. Russ  Roegner of the Office   of  Analysis
and  Evaluation,  and   Ms.  Alexandra Tarnay,  Monitoring and Data
Support Division, and Mr. Fred Talcott, Office   of  Planning   and
Evaluation are acknowledged for  their assistance.
                              XXIV

-------
                             SECTION I
                      SUMMARY AND CONCLUSIONS
 TOXIC POLLUTANTS

           1.    Cadmium Pigments    18.
           2.    Cadmium Chloride    19.
           3.    Cadmium Nitrate     20.
           4.    Cadmium Sulfate     21.
           5.    Cobalt Chloride     22.
           6.    Cobalt Nitrate      23.
           7.    Cobalt Sulfate      24.
           8.    Copper Carnonate    25.
           9.    Copper Chloride     26.
          10.    Copper Iodide        27.
          11.    Copper Nitrate      28.
          12.    Nickel Carbonate    29.
          13.    Nickel Chloride     30.
          14.    Nickel Fluoborate    31!
          15.    Nickel Nitrate      32.
          16.    Sodium Chlorate     33.
          17.    Zinc Chloride        34.
Calcium Hypochlorite
Bleaching Powders
Brine Chemicals
Potassium Bromide
Ammonium Thiosulfate
Chlorosulfonic Acid
Iron Oxide, Yellow
Iron Oxide, Black
Iron Oxide, Magnetic
Ochers
Siennas
Umbers
Iron Colors
Nitrous Oxide
Silica Gel
Silica Amorphous
Tin Compounds
CONTROL AND TREATMENT TECHNOLOGY


-------
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 relatively 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
proposed,   (a)  cadmium pigments and (b)  cadmium salts.  Separate
mass-limitations are proposed because of significant  differences
in unit flows. " In  the  copper salts subcategory,  two  subdivisions
are  proposed,  including  (a)   copper   sulfate,  copper chloride,
copper  iodide, and  copper  nitrate;   and (b)  coppet  carbonate.
Separate  mass  limitations are  proposed  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  proposed:   (a)   nickel   sulfate,    nickel
chloride,  nickel   nitrate, and  nickel  fluoborate;  and  (b)  nickel
carbonate.  Separate  mass limitations  are   proposed  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.

BAT REVISIONS

-------
                a Potion  from  the Salt  Institute,  the study  also
b        -n-eeXaminat^°n °f BAT for  the  sodium  chloride  (solution
brine- mining process),  sodium sulfite,  and   calcium  chloride
subcategories    Revisions  of   BAT  are being propped  for the
sodium chloride and sodium sulfite subcategories.

EXCLUDED SUBCATEGORIES
               StUdy a?d r?view' 104 subcategories  are  "proposed
              H Pearly  because  the  toxic and nonconventional
          dlschars are insignificant or there  are  one  or  no

metals  manufacturing point source categoryU?Phase II) "fSr^hJrh
regulations will be promulgated later, because beryllium oxide is
formed only during the manufacturing of beryllium metal

-------
                           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   proposed   regulations   for   Best
Practicable   Control   Technology   Currently  Available   (BPT).
Summaries of proposed 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 would be further
subdivided into two segments.

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

The  Agency  is  proposing to exclude 104 subcategories and defer
three subcategories to existing or  future  regulations:  calcium
hypochlorite,  bleaching powder, and beryllium oxide.  The  Agency
is also proposing to exclude  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)
Subcategory
Parameter
                                       Effluent Limitations

Cadmium Pigments




Cadmium Salts




Cobalt Salts




Copper Salts
(CuS04, CuCl2,
Cul, Cu(N03)2)


Copper Salts
(CuC03)



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
Nickel (T)
PH

TSS
Nickel (T)
PH
Max
30-day Avg
kg/kkg (or lb/1
1 .57
0.014
0.037
0.0062
(1)
0.001
0.0000087
0.000023
D.,0000039
CD
0.0014
0.00012
0.000083
0.000083
(1)
0.023
0.0010
0.0020
0.00050
(D
1 -4
0,064
0.12
0,031

-------
                             TABLE 2-1 (Continued)

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

Sodium Chlorate






Zinc Chloride





TSS
Antimony(T)
Chromium (T)
Chlorine
(Total
Residual)
PH
TSS
Arsenic (T)
Zinc (T)
Lead (T)
pH
Max
30-day Avq
kg/kkg (or lb/1000
0.068
0.0043
0.0014


0.0024
(1)
0.34
0.014
0.026
0.0081
(1)
24-hr
Max
Ib) of Product
0.12
0.0086
0.0027


0.0041
(1)
0.58
0.041
0.076
0.024
(1)
                    (1)  Within the range 6.0 to 9.0

-------
                                     TABLE 2T.2.
                            1 '.''*, 7- - •'.   - • . «• _  •*. •.i"*^ •

             SUMMARY pp REGULATIONS - J^ESTAVAILABLE,:TEGHIJQLQGY; (BAT)
 Subcategory
 Cadmium Pigments



 Cadmium Salts



 Cobalt Salts
 Copper  Salts
 (CuS04,  CuCl2,
 Cul,  Cu(N03)2)

 Copper  Salts
   (CuC03)
Nickel Salts
(NiS04, NiClz/
Ni(NO,)2,
Ni(BF4)2)

Nickel Salts
  (NiC03)

Sodium Chlorate
 Parameter
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)
                                        Effluent  Limitations
                                     .                   24-hr        "
                                     30-dav Avq 	Max
                                   kg/kkg.-Hor lb/1000  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

 0.00024
 0.00024
0.042
0.042

0.0022
0.00086
0.0024

0.014
0.0061
0.00060
 same as BPT
 same as £PT
 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

0.041
0.018
0.0023

-------
                             TABLE 2-2  (Continued)

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

Sodium Sulfide
Chromium(T)
Zinc (T)
COD
               Reserved
0.00063
0.0015
1 .7
0.0020
0.0051
3.4

-------
                                   TABLE 2-3

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

Cadmium Pigments
Cadmium Salts
Cobalt Salts
Copper Salts
(CuS04, CuCl2,
Cul, Cu(N03)2)
Copper Salts
(CuC03)
Nickel Salts
(NiS04/ 'NiCl2,
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)
-
Arsenic (T)
Zinc (T)
Lead (T)
mg/1
0.15
0.40
0.067
0.15
0.40
0.067
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 .1
0.45
0.044
kg/kkg
0.014
0.037
0.0062
0.0000087
0.000023
0.0000039
0.00012
0.000083
0.000083
0.0010
0.0020
0.00050
0.064
0.12
0.031
0.00024
0.00024
0.00024
0.00024

0.014
0.0061
0.00060
24-hr
Max
mg/1
0.47
l .1
0.12
0.47
1 .1
0.12
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
1 .35
0.17

kg/kkg
0.043
0. 11
0.011
0.000027
0.000070
0.0000070
0.00030
0.00027
0.00027
0.0030
0.0060
0.0015
0.19
0.37
0.093
0.00074
0.00074
0.00074
0.00074

0.041
0.018
0.0023
                                  9

-------
        SUMMARY OF REGULATIONS -
Subcategory
Parameter
               TABLE 2-4



             NEW SOURCE PERFORMANCE STANDARDS (NSPS)



                   Effluent Limitations

Cadmium Pigments




Cadmium Salts




Cobalt Salts




Copper Salts
(CuS04, CuCl2,
Cul, Cu(N03)2)


Copper Salts
(CuC03)



Nickel Salts

(NiS04, NiClz,
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 lb/1
1.57
0.014
0.037
0.0062
(1)
0.001
0.0000087
0.000023
0.0000039
(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
000 Ib) of Product
2.. 59
0.043
0.11
0.011
(1)
0.0016
0.000027
0.000070
0.0000070
(1)
0.0023
0.00030
0.00027
0.00027
(1)
0.069
0.0030
0.0060
0.0015
(1)
4.2
0.19
0.37
0.093
(1)
0.096
0.00074
0.00074
(1)

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

-------
Subcategory
                             TABLE 2-4 (Continued)



        SUMMARY OF REGULATIONS - NEW SOURCE PERFORMANCE STANDARDS (NSPS)



                                       Effluent Limitations
Parameter
Max 24-hr
30-dav Avq Max

Sodium Chlorate






Zinc Chloride




Sodium Sulfite


'


TSS
Antimony (T)
Chromium (T)
Chlorine
(Total
Residual)
PH
TSS
Arsenic (T)
Zinc (T)
Lead (T)
pH
TSS
Chromium(T)
Zinc(T)
COD
PH
kg/kkg (or
0.068
0.0022
0.00086


0.0024
(1)
0.34
0.014
0.0061
o.oobeo
(1)
0.016
0.00063
0.0015
1 .7
(1)
ib/1000 Ib) of Product
0.12
0.0043
0.0017


0.0041
(1)
0.58
0.041
0.018
0.0023
(1)
0.. 032
0.0020
0.0051
3.4
(1)
                    (1)  Within the range 6.0 to 9.0
                                  11

-------
                                   TABLE 2-5

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

Cadmium Pigments
Cadmium Salts
Cobalt Salts
Copper Salts
(CuS04, CuC12,
Cul, Cu(NC3)2)
Copper Salts
(CuC03)
Nickel Salts
(NiS04, NiCl2,
Ni(N03)2/
Ni(BF4)2)
Nickel Salts
(NiC03)
Sodium Chlorate
Zinc Chloride
Sodium Sulfite

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)
Chromium(T)
Antimony (T)
Arsenic (T)
Zinc (T)
Lead (T)
Chromium(T)
Zinc(T)
COD
Max
30-day Avg
mg/1 kg/kkg
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
0.32 0.00086
0.8 0.0022
same as PSES
same as PSES
same as PSES
0.42 0.00063
1.2 0.0015
630 1.7
24-hr
Max
mg/1 kg/kkg
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
0.64 0.0017
1.6 0.0043
same as PSES
same as PSES
same as PSES
1.3 0.0020
3.4 0.0051
1260 3.4
                                 12

-------
                                   TABLE 2-6

          SUMMARY OF REGULATIONS - BEST CONVENTIONAL POLLUTANT CONTROL
                                TECHNOLOGY (BCT)
Subcategory
Parameter
                                       Effluent Limitations
Max
30-dav Avg
24-hr
Max
kg/kkg (or- lb/1000 Ib) of
Cadmium Pigments

Cadmium Salts

Cabalt Salts

Copper Salts
(CuS04, CuCl2,
Cul, Cu(N03)2)
Copper Salts

-------
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.
                               14

-------
                            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)(l)(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
                               15

-------
 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 out
 his functions" under the Act.

 The EPA was unable to promulgate many of these regulations by the
 dates  contained in the Act.   In 1976,  EPA was  sued  by  several
 environmental  groups,   and  in settlement of this lawsuit EPA and
 the plaintiffs  executed a  "Settlement Agreement"   which   was
 approved  by the Court.   This  Agreement required EPA to develop a
 program and adhere to a schedule for  promulgating  BAT  effluent
 limitations  guidelines,   pretreatment  standards,  and new source
 performance standards for 65 "priority" pollutants and classes 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
                               16

-------
       f?>(  }  rec?uires  achievement by July  1, 1984, of "effluent

   imitations requiring the application of  the  best  conventional

 pollutant control technology"  ("BCT").  The  factors considered in


 ?o?eKta?n'SCT f°r/n *ndustry in<^e a cost^SSSnSblSSS^eS
 for attaining a reduction in  effluents  compared  to  the  costJ

           *ft   a   Purely   owned   treatment wo?ks  (SecMon


    s     e^  s of^l
                          B?SJ?i,uT "and-^i

                 BAJ ef£luent limitations within three years after


                     " %*?* ''  1984'  WhtCheVSr lS  ^>   &



 •fhe . . Purpose of these proposed regulations is to provide effluent
 2:

                    r-












         f°»3? Sl«n"i?«nt Inorganic Chemical UoducS (!)!°  Jh!
          JSal Fe9ulati°ns were published on May 22, 1975   Taken
            K  JW°  ?roups  of  regulations  coJer  49  inorgSni?




obvious (e.g., mercury and/or lead in the Chlor-Alkal i Industry??

                               17

-------
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.  v.
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
                               18

-------
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 subcategory was already regulated by existing
          guidelines;
     7.   Two subcategories are being included under
          existing guidelines by amendment; or
     8.   One subcategory will be covered in a future
          rulemaking in another category.
                               19

-------
S"
gg
 s
                         20

-------
 Phase  II  Inorganic  Chemicals

 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.
11.
12.
13.
14.
15.
16.
17.
Copper
Copper
Nickel
Nickel
Nickel
Nickel
Sodium
Zinc C!
  Iodide
  Nitrate
  Carbonate
  Chloride
  Fluoborate
  Nitrate
  Chlorate
Chloride
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  tasks
and their results as they are presented in this report.

Industry Data Base Development and Subcategorization Review
                               21

-------
  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
           ?v^  ? ?r°V?  °f  Chemical  products indicated that there
          divxduaj facilities   in   this  group  (many plants  are
          -product  Plants).    The  Agency  has  datJ submitted by
  industry in response  to  requests for  information  under Section
  J?®4i.°L ^he  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   wer4
  sampled.  EPA   conducted  additional   engineering  visits  durind
  S^?f!S  and  November   1982   to  twelve  plants  (three had  been
  n,,?^nf0P^V1?USJy  durin?J the  sampling  program).   Section  4
  outlines the factors  considered in subcategorization  and presents
  J5  i£a £°nale,  forJ  the Pr°P°sed scheme of subcategorization for
  the 17 chemical products studied.

 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
 £2?£3hfnsive  sampling  program.    The  sampling  and analytical
 methodology is described in Section 5.  The Phase I  study  showed
 3t™^?2K?1? P£-°r-ty,  P°llutants  *ould  not be expected to be
 «i2?J-   S"      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  thS
 46 plants were sampled during the sampling program.

 Engineering Evaluation

 Section  6 describes the procedures  and sources used  in developing
 f£^-in^Stry4.1;r0uUC*10Vn?  wastewater generation characteristic^
 S ? ,1 2rm  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
 JJ^ wlnand advanced technologies that may be recommended for BAT
 ?™i-^f^apPJ1Ca?10^   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
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
                               22

-------
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 Study

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
     Sodium bisulfite
     Sodium hydrosulfite
                               23

-------
 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.

 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
 !«?£??? v,fc^e   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
 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
                               24

-------
 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,
 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
                               25

-------
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).   That
methodology  was used to evaluate BCT limitations in the Phase II
study.

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  has
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
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
                                26

-------
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.
                               27

-------
                            SECTION 3
                           REFERENCES
1.


2.
3.
4.
U.S.  Environmental  Protection  Agency,   Major    Inorganic
Products, Development Document.  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, 1975.  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.
                               28

-------
                             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  toxic
 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
                               29

-------
 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
 lunctional  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.
 Tne 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,
 Ci*?l  .  rs' P°nds/  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
                               30

-------
 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.    The  present  and  forthcoming  requirements  for
 pollution control may 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
                               31

-------
 subcategorization
 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
                               32

-------
                                  namely s^division  by  dominant
    ™«^ «-       *.      seventeen  chemicals  studied,   it  was
 determined that wastewater characteristics  were  more  deoendent
                  (metal) inv°lved than the antonic secies* "££
                  f gr°Up °f comP°unds were found to be  basically
 would    ?2-iWa8te?atfr  treatment processes expected to  be used
 were  DrJnr^; • , — faC£'/£ 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
           1di"erent times)'   Wastewater treatment process de!™!
         o,liantSJfocuses on treatment of dissolved and particulate
 npr     TSS/  ??? PH'   These treatn.ent plants must be  capable  of
 performance with a variety of wastewater streams.

 From  a  cost  standpoint,   most plants in the Phase II c
 group will not be impacted in the same way as many !arge

 can be .if^L J"  P?3Se '  because the treatment costs ' incur e
        a   f    ^ fc? a larie variety of products  at  the  plants,
           in  i-S-"9^   Profuct  or Product group.   Therefore costs
 incurred          document may overstate the actual costs  to  be
    ^       a  w
-------
 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 proposes  the  replacement  of  two  subcategories  with  new
 consolidated  subcategories.  Subpart AJ (Copper Sulfate) will be
 replaced.by Subpart  AJ   (Copper  Salts)   which   includes  copper
 sulfate,  copper  chloride,   copper  iodide,  copper nitrate, and
 copper  carbonate.  Subpart AU (Nickel Sulfate) will  be  replaced
by  Subpart  AU   (Nickel  Salts),  which includes  nickel sulfate,
nickel  chloride, nickel  nitrate,  nickel  fluoborate,  and  nickel
carbonate.                                                 "iv.js.ej.
This proposed subcategorization is 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
                               34

-------
      b.
      c.
      d.
                are  typically  commingled   and   sent   to   a   common
                wastewater  treatment  system.

                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.
      e.
               Levels of treatability are the same for copper  or
               nickel  sulfate  and  the  other
               salts.
                                                  copper or  nickel
             -        ab°VLis  the  copper  or  nickel  carbonate
             industry.   The  Agency  is  proposing  that  copper
           be  a  separate  segment  within  th-   C^er   Salts
                -, chf^  ^kel  carbon«^  -  a separate segment
       the Nickel Salts Subcategory because the  wastewater  unit
cnan?* , ?°pp.er  carbonate  and nickel carbonate facilities are
substantially greater  than  at  other  copper  or  nickel  salts
facilities covered in these subparts.                nicxei  salts
 carbonate
rnnii        -S  prop°sin9  to  exclude   104  subcategories  from
regulation primarily because the discharges from  all  plants   in
Sn««?"SCJ*efl0ry  ar? insi9nificant.  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
frnmdl«?imilar\ In-the Plaining cases' th* combined  discharge!
from  all  plants  in  the  consolidated  subcategories  are also
insignificant and would  therefore  be  proposed  for  exclusion
These   cases   are   noted   in  Section  19  infrS!   Only  thi
consolidations of the 17 subcategories just descTIbid  above  arl
*?nn^eCh?ICa-lyK feasible  and ^esult 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
                               35

-------
                             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 for sampling on the
basis of the following general criteria:
     A.
     B.
     C.
Minimal product mix and no organic product lines which
could increase the potential for interprocess cross
contamination of wastewater;

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

Manufacture of industrial grade products in volume,
rather than low volume reagent grade* products;
                               36

-------
      D.


      E.


      F.




      G.
           Median production capacity within  the subcategory;

           Segregated wastewater streams to facilitate sampling;

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

           f|°?[!lPhical .clustering of selected plants to
Prior  to  the  actual  sampling  of   wastewater
Sampling Program

A.   Collection of Samples

     In the sampling program,

                               the  specific   objective   was   the
                                                   .
    individual 24-hour composites) .  Thee smples were analzld
                              37

-------
     for  the  13  toxic metal pollutants, cyanide and phenol, as
     well as  the  conventional  and  non-conventional  pollutant
     parameters   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,
                               38

-------
     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
                               39

-------
40

-------
 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.

 2.   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
          positive1  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.


4.
UTD   =   "Unable
interferences.
To   Determine"   due   to   matrix
Criteria Employed in Spike Selection:

a.   Samples were chosen to be spiked  based  upon  the
     following criteria:

          All samples where  there  was  any  suspicion
          that   interference   or  matrix  effect  was
          present.
                          41

-------
                     All   samples   containing
                     concentration of analyte.
                     In addition,  at least  one
                     seven.
                                         a    measurable

                                       sample  in  every
           b.
      The  level  of  spike  chosen  was
      following  factors:
                                               controlled  by  the
                     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:
c.
      1.
      2.
      3.
     4.
     5.
Ten of the   13  toxic  metals  were  determined  by  AA
spectrophotometry  in  the furnace mode, namely Ag, Be,
Cd, Cu, Cr,  Ni, Pb, T1, Sb and Zn.

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

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.
Selenium  and  arsenic  were  determined   by
generation using sodium borohydride (NaBH«).
                                                          hydride
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.
                               42

-------
       TABLE 5-1.  ANALYTICAL DETECTION LIMITS FOR TOXIC  METALSd)
Method Detection Limit (ug/1) (2)
Element
Flame Furnace
Method Method (HGA) *
Gaseous
Hydride
Method
Cold
Vapor
Method
IAntimony,  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



                                                      0.2
                 40

                 10
                100
                  5
0.2
1
0.05
*  Heated Graphite Atomizer
(1)   Assuming no matrix interferences requiring dilution of sample.
 (2)   "Methods  for
      Envi ronmental
               Chemical  Analysis  of  Wastes  and  Water,"  USEPA
               Monitoring   and  Support  Laboratory  office   of
Research and Devlopraent, 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.
                               43

-------
 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
      £01lowed 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:

          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
1.
                               44

-------
      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.

SuIfides - 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  Mg/l
      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
      1 36) .

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
f,,Jh  ?£ f W?iCh ar? 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   bv
participation in the EPA Reference Sample Program that  utilizes a
                               45

-------
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   in  trace organic
chemical analysis dictates that  contamination of the samples from
any   possible  •  source    must   be  diligently  guarded against.
Accordingly, only glass sample containers with  Teflon-lined lids
were  used  and  these were  subjected   to a three  step cleaning
procedure prior to use, even  though only  new   liners   and  glass
containers  were  used.  All glassware used for  sample preparation
and analysis was  subjected to a  dual  cleaning 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
                               46

-------
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.
                               47

-------
TABLE 5-2.  POLLUTANT FREQUENCY BASED ON SAMPLING
      RESULTS (RAW AND TREATED WASTEWATER)*
Pollutant Occurrence Based on
Concentration (uq/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 f 1 , 1- t r ichloroethane
hexachloroethane
1 , 1-dichloroethane
1,1, 2-tr ichloroethane
chloroethane
bis (2-chloroethyl) ether
2,4, 6- tr ichlorophenol
chloroform
2-chlorophenol
1 , 4-dichlorobenzene
1 , 1-dichloroethylene
1 , 2-trans-dichloroethylene
2 , 4-dichlorophenol
1 , 2-dichloropropane
1,2-diphenylhydrazine
fluoranthene
methylene chloride
methyl chloride
bromoform
dichlorobromome thane
tr ichlorof luorome thane
chlorodibromomethane
isophorone
nitrobenzene
4-nitrophenol
2 , 4-dini trophenol
4 , 6-dinitro-o-cresol
n-nitrosodiphenylamine
pentachlorophenol
phenol
bis(2-ethylhexyl) phthalate
butyl benzyl phthalate
di-n-butyl phthalate
>50
but
<50 ,,500
4
2
17 2
6 3
6
1
4
1
8 .
6
5
2
3
43 9
1
1
7
5
2
3
2
1
45 2
5 2
4 1
21
6 1
16
2
1
1
1
1
1
4
7
37 1
7
31
>500
but
<2500 < 2500





2 4
*• ^*
*





1 1
•" «A>







5
3















                      48

-------
 TABLE 5-2 (continued)
                                     Pollutant  Occurrence Based on
Priority Organics Detected
69B di-n-octyl phthalate
70B diethyl phthalate
71B 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 B-endosulfan
97P endosulfan sulfate
98P endrin
100P heptachlor
101P heptachlor epoxide
102P a-BHC
103P B-BHC
104P y-BHC
105P 6-BHC
>50 >500
but but
£50 £500 £2500 £ 2500
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 = Pesticide fraction
                                49

-------
     TABLE 5-3.  PRIORITY ORGANICS DETECTED BY
SUBCATEGORY (RAW AND TREATED WASTEWATER; £ 10 ug/1)
Priority Organics Detected
3V acrylonitrile
4V benzene
6V carbon tetrachloride
10V 1,2-dichloroethane
12B hexachloroethane
16V chloroethane
18B bis (2-chloroethyl) ether
21A 2,4,6-trichlorophenol
23V chloroform
31A 2,4-dichlorophenol
37B 1,2-diphenylhydrazine
44V methylene chloride
45V methyl chloride
47V bromoform
48V dichlorobromomethane
49V trichlorofluoromethane
51V chlorodibromomethane
54B isophorone
58A 4-nitrophenol
59A 2,4-dinitrophenol
60A 4,6,-dinitro-o-cresol
64A pentachlorophenol
6SA phenol
66B bis(2-ethylhexyl) phthalate
68B di-n-butyl phthalate
69B di-n-octyl phthalate
85V tetrachloroethylene
86V toluene
88V vinyl chloride
103P P-BHC
Subcategory
1 - Cadmium Pigments and Salts
2 * Cobalt Salts
3 s copper Salts
4 « Nickel, Salts
5 - sodium Chlorate
6 = Zinc Chloride
Subcategory
5
5
5. 6
*J f V
5
5
5
1
3, 5
If 3, 4, 5
W ** r • 9 *J
5
3
1» 3, 4, 5, 6
5
3
3. 5
** 9 **
5
3
1
1
1
1
1
5
1» 3
1
5
3
3
5
3






                       50

-------
          TABLE 5-4.   OCCURRENCE OF ASBESTIFORM FIBERS BY PLANT
.ant
22
02
L02
07
L07
Shaken)
.07
[Settled)
.34
.34
.34
.34
.17
.17
.17
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
'L =  million fibers per  liter
(1)  Untreated
(2)  Two different waste streams
                                   51

-------
                            SECTION 5
                           REFERENCES
1.   Sampling Screening Procedure for the Measurement of Priority
     Pollutants, U.S. Environmental Protection Agency, 1976, 6pp.

2.   Anderson,  C.  H.  and  Long,  J.  M.   Interim  Method  for
     Determining   Asbestos   in  Water.  EPA-eOO/^-BO-OOS,  U.S.
     Environmental Protection Agency, Athens, Ga., 1980.
                               52

-------
                            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,  and self-monitoring (NPDES)  reports.
 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
                               53

-------
 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—I.

 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.

 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
                               54

-------
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.
                               55

-------
      TABLE 6-1.  308 QUESTIONNAIRE RESPONSE DATA ELEMENTS

               INORGANIC CHEMICALS GUIDELINES STUDY
Datum Reference
Description
                                                  Comments
Manufacturer
                    Confidential
Effluent Treatment
                                               Inorganic
                                                 Chemicals
                                               Primarily
                                               FY 1980
                                               Operating Days
                          Name
                          Location
                          EPA Region

Product                   Name
                          Subcategory

                          Number of other
                           Products

Plant                     Capacity

                          Production
                          Age

Process                   Name
                          Volume of Process
                           Effluent
                          Volume of Noncontact
                           Effluent

                          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.
                               56

-------
      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
                               57

-------
 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.
      2.
      3.
      4.
      5.
Production rates and mode of operation
Specific process type and wastewater sources
Wastewater flow per unit of production
Solid waste generation and handling
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 dealina
 with individual  industries.        •

 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
 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
                               58

-------
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.
                               59

-------
                              SECTION  7


    ASSESSMENT OF TECHNOLOGY  FOR ADVANCED  TREATMENT  AND CONTROL
 INTRODUCTION


 In   the   inorganic   chemicals   industry,  pollution  abatement

 lound1Ce?a^'y ^ 3 Wlde range °f trea^«t technologies can  £e
 found,  ranging  from  no  treatment to the application of hiqhlv
 advanced technologies for the removal of specific pollutants!

 Until the  NRDC  Settlement  Agreement,  industry  attention  was
              =         '     not toward  treatment  of  over  100
              specific  organic  compounds  now  listed  as  toxic
 pollutants.   Even   with   the   classical   (conventional   aid
         ni0nal>   P°llutants-   treatment  technology  hS  beSn
       h     removal down to the part per million  level,  whereas

             ?USJh 1S  tOWard part per biHi°n level requirements
            °f<- tl?eSe1 reasons'  high^  level  technologies   are
           -?°^  in Place in the inorganic chemicals industry,  and
 aoled  i    ^^^^^ examine technologies that haveY been
 applied  in  other  industries  or developed at the laboratory or
 S!h2E£lant«:8Cal? specifically for the  removal  of  these  toxic
 ?^n KO  T  l^ industrial wastewater, and determine whether they
 can be adopted as viable technological options.
  ;^       °?  ^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.
h
be
                   ^hatufew of the organic  toxic pollutants would
            inorganic chemical wastes  in treatable  concentrations
              b¥Tthe results of the analytical programs   in  both
 A   ^r    • ":  AS a^e?ult, the initial search for candidate
BAT technologies became limited to treatment technologies for the
                               60

-------
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
subcategor ies.

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                        (I)

     Metal ion + two hydroxyl ions"=  insoluble metal hydroxide

                                    for  hydroxide  precipitation
If the pH  is  below  the  optimum
soluble complexes form:
         + OH- » M(OH)+

     Metal ion + hydroxyl ion
                                                (2)

                                  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:
     M++ + 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.
                               61

-------
               TABLE 7-1.  SOLUBILITY PRODUCTS OF TOXIC METALS
        Metal
                                         Solubility Product Constant (K__)
                                                                       sp
Metal Hydroxide
                                                             Metal Sulfide
 Antimony (III)

 Arsenic

 Beryllium

 Cadmium

 Chromium (III)

 Copper

 Lead

 Mercury

 Nickel

 Selenium

 Silver

 Thallium (I)

 Zinc
         22
1.6 X 1(

2.5 X 1(T14  (1)

6.3 X ID'31  (1)
2.2 X 10
        -20
1.2 X ID
        '15
3.0 X 10
        ~26
2.0 X 10
        "35
2.0 X 10
        ~8
1.2 X 10
        -17
3.6 X 10-29  (2)




8.5 X ID"45  (2)

3.4 X ID'28  (2)

2.0 X ID'49  (2)
1.4 X 10
        -24
1.6 X 10-49 (2>
                           5.0 X 10
                                   -21
1.2 X 10
        ~28
NOTE:  References for above values are shown below.
(1)  Dean, J.A., Ed., Lange's Handbook of Chemistry, 12th ed., McGraw-Hill
     Book Co., New York, 1979.

(2)  Wsast, R.C., Ed., Handbook of Chemistry and Physics, 57th ed., CRC Press,
     Cleveland, Ohio, 1976.
                                     62

-------
Figure 7-1.  Theoretical solubilities of toxic metal hydroxides/oxides as a
             function of pH.
3
              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.
                                 63

-------
 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  i>g/l  standards,   and  hydroxide
 precipitation  is  often  supplemented  by the use of coagulating
 agents or filtration to improve solids removal.

 In practice,  the technology uses unit  process  steps  which  are
 simple,  well-established,  and well-understood by the industry.

 Depending on the quantity of waste flow,  the treatment can either
 be  a  batch  or continuous operation, with batch  treatment being
 favored  when wastewater flows are small.   In batch treatment  the
 equipment  usually consists of two tanks,  each with a capacity to
•treat the total wastewater volume expected during   the  treatment
 period.    These systems can be economically designed for flows up
 to 50,000 gallons per day (1 )..

 The treatment tanks  serve the multiple  functions   of  equalizing
 the flow,  acting as  a reactor and as a settler. During operation
 the  wastewater is stirred,  and a homogeneous sample is taken and
 analyzed to determine  the  chemical  dosage  requirements.    The
 chemicals are then added,  mixed and stirred for about 10 minutes.
 After the reaction  is complete,  the solids are allowed to settle
 for  a  few  hours.    The  clear  liquid   is  then  decanted  and
 discharged.    Settled  sludge  is retained to serve as a seed for
 crystal  growth  for   the  next  batch, but  must   be  drawn  off
 periodically  and disposed of,  usually in  a chemical landfill.

 For  larger  daily  flows,   a  typical continuous flow treatment
 scheme consists of a flash mixing tank and reagent  feed  system,
 settling  unit  with  sludge   storage  and  disposal  and,  in some
 cases, final  pH adjustment and/or a filtration system.
                                64

-------
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, Na2C03) is sometimes found to be the
reagent of choice particularly for lead removal.  Lead carbonate,
PbC03, and lead hydroxide/carbonate,  2PbCO3  .  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)
               (S04)— = CaS04 + 20H~
(4)
     Hydrated lime + sulfate ion  =  calcium sulfate  (gypsum)  +
     hydroxyl ions

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.   Industries  that  are  using  hydroxide
precipitation include:

               Inorganic Chemicals,
               Plating and Metal Finishing,
               Ore Mining and Dressing,
               Textiles,
               Iron and Steel,
               Non-Ferrous Metal Processing,
               Electronics,
               Copper Forming,
               Coal Mining
                               65

-------
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.

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  ferrite
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)

     Metal ion + sodium sulfide  =   insoluble metal  sulfide
                                      + sodium  ions
                               66

-------
 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
      M++ + 5—
                                                  (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+  == H2S
     Bisulfide  ion  + hydrogen  ion
                                            (8)

                                 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, K. =9.1 x 10-*
k2 • 1.1 x 10-*2 (see Reference 2 in Table 7-1) the solubility of
the metal ion can be calculated as a funci-ion of the hydrogen  ion
concentration emd, therefore, as a function of pH.

     For a divalent metal ion the equation is:


(M++) = [Ksp [1 + (H+)/(l.l x 10-12)] + (H+)*/(l x 10-»»)]%

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
sulfide ions to  precipitate  metal  sulfides  which  have  lower
solubilities than ferrous sulfide.   Typical reactions are:
                               67

-------
Figure 7-2.  Theoretical solubilities of toxic metal sulfides as a
             function of pH.
 •—•
 s
 s

 I
I
5
                                              10   11   12   13
                                     pH
                           68

-------
      FeS +  Cu++  =  CuS +  Fe++
                                                            (10)
      Ferrous   sulfide  +  copper  ion  =   insoluble copper sulfide +
      iron  ion
      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
industry  is  applying this technology  to remove mercury from its
wastewater streams.
                               69

-------
 Literature citations  on  the  efficiency  of   sulfide  precipitation
 and that liif JSf ?£?£   * *°St  resVlts are in  the sub  ppm  range,
 fhf ™  sulfide treatment is superior  to  hydroxide treatment  for
 the removal of several trace metals.  A recent   report   concluded
                                                          Allowing
                       Metals Concentration
                      Cadmium
                      Copper
                      Zinc
                      Nickel
                      Chromium (total)
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
          m?£alS 3PPearS fc? f? a Poising, economical te?hnoT£gy
 ™«h'    S     1S *."°  full-scale suifide treatment system as a
 R™?Si"?-!tep,.08?ratin«,ln the in°rc»anic chemicals industry, and
 treatability studies conducted by the Agency on  chrome  oiaments
 ?aS22SeEh and ?5^Srf lkali ^i«Phrag»%ell) wastewa?er incase
 LS5^Lthat 8u^f Jfe treatment as  a  polishing  step  following
 SS?JJX«*ipr?Clpltation   and   cl«ification   did  not  yield
 lalncv CaSJiy injreased to2lc  metal  removals.   Therefore/ the
 ??2So«i-  f  hn°?  Pr°P°?ed  sulfide  treatment  as  an  advanced
 sSbca?Igori!s  °  9y °P     ^ ^ PhaSe U  ino^ani^  chemical

 THE XANTHATE PROCESS
     r  °^xaf;thates  for  th®  removal  of  metals  from  waste streams
appears  to  be  -a  new,  promising  technology for  treating metal-
o!afi?S
-------
     The general removal mechanism  is as  follows:


     2  ROCS(=S)Na  + M++ = ROCS{=S)2M +  2Na+
                             (12)
     Xanthate + metal ion
insoluble metallic xanthate
 + sodium ions
     where R = starch or cellulose


Unlike hydroxide precipitation, this process is  reoorted  to  h»
effective  in  removing  metals  over a wide oH ranae of\ *Z i?
with an optimum range between 7 and 9        P     9  of 3 to 11,
                      Concentration, mg/1
         Metals
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Zinc
1 .35
0.30
1.6
3.1
3.9
2.4
1.0
	 	 aiiment
0.027
0.022 -
0.06-0. 14
0.08-0.36
0.008-0.021
0.077
0.03-0.04
                              71

-------
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 intos

          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,  (-S03H  and  -S03Na), 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).

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
                               72

-------
 operation  generally  follows  a   four-step   cycle:    exchanae
 (service), backwash, regeneration, and rinse.            exchange

 During  the  exchange  step,  the  reaction  between  the ions in
 solution and the ionic sites in the  resin  takes  place  as  the

 reaar^Her  P3SSeS  d??n  th&  bed"   The  reactionP 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
 Shirh  ?« 1?n iS att"cted more  singly  than  a  bivalen?  ion
 For ?ons with thf" attract*d moce strongly than a monovalent ion.
 r2»h?£  «J     e  Sam?  cnarge,   the  smaller  hydrated  ion  is
 favored.      m°Ving    °S6r  tO  the  exchan9e  site,  and is thus


 Many  synthetic  resins  contain   functional  groups   that    are
 a   IurinLt0 Certain metals'  For  «^mple,  a resin Manufactured by
 a   European company reacts preferentially with mercury (Hg++)  and

 equates-     "^  (H9C1 + )   10nS  accordin9  to  they
 2RSH + Hg++ = RSHgSR

 Resin + mercury ion
                             2H+
                              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
        "     9++ and H9Ci+ WhiCh are "pidly removed. °A  5  ppb
                   C0ncentration  m  the effluent is achieved^
              "Changeable sites in the resin are  used  up,  the
       bac^washed by passing clean water through to loosen up thl
the beS      rem°Ve any fine Peculates that are trapped inside
with  the


   (15)
RSHgCl + HC1
                      RSH + HgCl2
                               73

-------
       Insoluble  resin  complex   =
         + hydrochloric acid
            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  il
 treated              creates a secondary stream which needs  to  be


 A recent study found that  sodium   alumino  silicates   (zeolites)
 ?tm«  c  /?o^°W"m??t 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
 ?h?I  removed to  ^low 10 ppb.  Thermodynamic considerations  show
 Si!.™**!!"9?^0 haVS  a -high  affinifcy  for  cadmium,  copper,
 mercury, nickel,  silver, zinc, cesium, and barium.
                   ,a  ?roven  technology  that  can  reduce metal
 concentrations to low levels.  However this  technology  is  used
 b£«u*in JimJh€d  *ndustrial  Pollution  abatement  applications
 because  of  the  high  cost   associated   with   the   process.

                                                           in this
 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,
' hiiLfTf cipiJate 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.

 Chromium   (HI)   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 metabisulf ite,   sulfur
dioxide and ferrous salts.  The  reduction is accomplished  readily
at low pH with these reagents.   Typical  reduction  reactions are:
     3SO-
Cr207~
2H+
                                     3S04—  + H20
                                   (16)
                               74

-------
      Sulfur dioxide + dichromate ion
      + hydrogen ion
3S03— + Cr207— + 8H+ =
     Sulfite ion + dichromate ion
     + hydrogen ion
                                          trivalent  chromium  ion
                                           + sulfates and water
                                       ' 3S04— + 4H20
                                                            (17)
                                       trivalent chromium ion
                                        + sulfates + water
6Fe++ + Crz07—
                         4H+
                                                  7H20
                                                            (18)
     Ferrous ion + dichromate ion
      + hydrogen ion
                                       trivalent chromium ion
                                        + ferric ion + water
     , ^educ?f.  chromium  and the ferric ions produced in the third
 equation will  exist as the soluble sulfate at acid pH's.   If  the
 SiVhi3 v,9^!-  5?t  tne,  ration rate is drastically reduced,  and
 although dithionite will effect reduction at neutral pH's  it   is
 very costly and its use may be contraindicated.
thp
the
           finm1  4"® ^or  caustic soda is added to raise
        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
£<"r™L«?9   i      * iS r?P°rted that applying sulfur dioxide to a
pigment waste consistently  reduces Cr  (VI) and Cr(T) to  0.5   ma/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

Achieved ?sf  y         tha" °*°5   mg/I  °f  either  sPec^s  is

A one-step precipitation reduction process using sodium  bisulfide
wJcf«!I5Lin a f^i^-fichromate plant to remove chromium from its
wastewater.   An  effluent  quality  with less than  1 mg/1 Cr(VI),
and less than 5 rng/1 Cr(T) was reported (20).
boohw           redu^tion 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 solublJ

                                                      SOlution
                                                     (20)
            BH4-
                    8 OH- = 4Hg + B (OH)4 + 4H20
                               75

-------
      Mercury  ion  +  borohydride  ion
        + hydroxyl  ion
          insoluble mercury metal
           + borate ion + water
 A mercury  level of  0.01 mg/1
 reported (20).
 in  the  final  effluent  has  been
 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 bv
 thermal processes such as wet oxidation and incineration,  or  bv
 biological  processes  such  as  the  activated  sludge   process
 trickling filters, biodiscs, and aerated lagoons.         Process,

 Incineration  is  actually  a  combination   of   oxidation   and
 SH££?™'-   B?th  involYe  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.
 ™f-  P5ocefs  uhas,  been   shown  to  be  successful  in  reducing
 pesticides to  harmless molecules (22).                       "<-*"y
 Wet oxidation is a process in
 oxidized  in the liquid phase
 pressure vessel.   This reduces
 pollution  from  exhaust  gas)
 oxidation has been used for a
 waste  and acrylonitrile liquor
 99.8  percent  of  some of the
 (24).
 which  an  aqueous  waste  can  be
in a closed, high-temperature, high
 some of the problems (such as  air
,  inherent  in  incineration.  Wet
variety of wastes including pulping
 (23).   A reduction  in  excess  of
 toxic pollutants has been reported
  M* •««*?»,  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.                         organic
                  °5  chemical  oxidation to  industrial wastes  is
                  .for  cyanides,  sulfite,   ammonia,  and  other
 olvsulfi         i"  rilUt€  rs^e streams (Phenols, mercaptans,
polysulfides, etc.).  Common chemicals used as  oxidizing  agents
                               76

-------
 included   chlorine,   hypochlorite,   hydrogen  peroxide,  potassium
 permanganate,  ozone,  and  chlorine dioxide.   Air   and  oxvaen  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-

Cyanide + chlorine  =  cyanogen chloride + chloride

CNC1 + 2OH- = CNO- + Cl-
                                                            (21 )
Cyanogen chloride
 + hydroxyl ion
                           H0
                           cyanate  ion  +  chloride
                             ion  + water
                                                          ion

                                                            (22)
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
                                         2H20
                                                            (23)
     Cyanate + hydroxyl ion  »  chloride ion + carbon dioxide
      + chlorine                 + nitrogen + water
CNO- + 2H,0+ - C02 +

Cyanate + hydronium ion
                            H0
                                                            (24)
                                 carbon dioxide + ammonium ion
                                 + water
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
nypocnlonte,  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:
                               77

-------
     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:

     NH3 + HOC1 = NHZC1 + H2O                              (27)

     Ammonia + hypochlorous acid = monochloramine + water, etc.
     NH2C1 + HOC1 = NHC12 + H20

     NHC12 + HOC1 = NCI3 + H20
                                               (28)

                                               (29)
If excess chlorine is added, chloramines can  be  converted  into
nitrogen oxide(s):
2NH3
4HOC1
                    N2O + 4HC1 + 3H2O
(30)
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
                               78

-------
The free cyanide level after treatment  is  generally  below  O.I
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).

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.
                               79

-------
              FEED
                     1
                   I
               PRODUCT
                V5ATER
               I
                   WASTE
Figure 7-3.  ELectroiialysis process,
                 80

-------
 U-4

 O
'"sloT?
       „  oo cp

       CN  CN CN
       O  O O
       o  o o
       en  in «H
       III
       o  o o
       o  o o
       in  in in
       o  o o
       ooo
       in  in in
       *
          II
3  a §
                 fi
                 o
                 m
         2
         fc
o
o
o
in
                O
                O
               o
               in
              o
              o
              in
              r»
              o
              in
              
-------
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
weight  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,
rejection 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,
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
solute 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
                               82

-------
                                                JAVOM3H
activated  carbon.   A  chlor-alkali
activated carbon as a polishing step to r
                                                       ntlv  usi,ng
                                                         f  ^

Activated   carbon   is   made  by  charring  basic subsWates,  such^as
wood,  coke,  coal,  shell,  husks,  etc.,  at 600°C  in  af,oG
-------
FLUORIDE REMOVAL
                        of treating fluoride-bearing wastes is to
                fluoride as calcium fluoride by the  addition  of
          2F-

Hydrated lime
                     CaF
                     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  =
      + fluoride ion
                       aluminum monofluorohydroxide
                        + hydroxyl ion, etc.
     A1(OH)2F + F- = A1(OH)FZ + OH~

     A1(OH)F2 + 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
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
                               84

-------
sulfur  dioxide  or  a  related  reducing  agent  such  as sodium
bisulfite or sodium metabisulf ite.  Typical reactions  are  shown
in Equations 35 and 36.
S0
OC1" + H20
                           Cl-
                                                           (35)
     Sulfur dioxide + hypochlorite ion  =  sulfuric acid
      + water                               + chloride ion

     Na2S03 + OC1- • NazS04 + Cl-                          (36)

     Sodium sulfite +    =  sodium sulfate +
      hypochlorite ion       chloride ion

Alternatively,  hydrogen peroxide, although relatively expensive,
may also be used for dechlorination according to Equation 37.
H2O2 + OC1- «
                       + 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.
                                85

-------
                            SECTION 7
                           REFERENCES
     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.
10.   Wing,  R.E.
     Xanthate.
Heavy Metal Removal from Wastewater with  Starch
In:   Proceedings  of  the  29th  Annual  Purdue
                               86

-------
12.
13.
14.
15.
      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
      American 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 Heeitn,  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.

20.  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.
16,
                               87

-------
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.
                                88

-------
34.


35.


36.
Maier, F.J.  Partial Defluoridation of Water.  Public  Works
91(11), 1960.
Maier,  F.J.   New  Fluoride  Removal  Method  Cuts
Engineering News-Record 148(24):40, 1952.
Costs.
Kennedy, D.C., M.A. Kimler,  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.
                               89

-------
                            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.

     2.


     3.
Review and analyze applicable performance data.

                                              treatment
Estimate  best  performance  under  optimum
conditions.

Estimate average achievable performance under
industrial operating conditions.
                                               expected
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
                               90

-------
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
30-day   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 30-day achievable
performance using the same general treatment technology.

The  estimated  ranges  of  average  achievable  performance  are
presented   in   Table   8-11.    In   formulating  the  proposed
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

Following publication of the proposed Phase I regulations on July
24, 1980 {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.   Treatability Study for the Inorganic Chemicals Manufacturing
Point 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
at the public hearing on proposed pretreatment standards  (October
15,  1980)  are part of the official public record of the Phase  I
rulemaking.  The comments are summarized and responses are  given
in  "Responses  to  Public Comments, Proposed Inorganic Chemicals
                               91

-------
TABLE 8-1.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            ANTBCN* AND ARSENIC REMOVAL
Treatment Technology
Antimony
Lime/filter
Ferric chloride/filter
Aluttv^Pilter
Arsenic
Lime Softening
Sulfide/Filter
Lime (260 mgA) /Filter
Lime (600 ng/1) /Filter
Ferric sulf ate
Ferric sulf ate
Lime/Ferric Chloride/
Filter
Activated alunina
(2 mg/1)
Activated carbon
(Smj/l)
Ferric Chloride
Ferric Chloride
pH

11.5
6.2
6.4
^
6-7
10.0
n.s
5-7.5
6.0
10.3
6.8
3.1-3.6
-
-
Initial
Concen-
tration
(raj/l)

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
(m?A)

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
                                   92

-------
TABLE 8-2.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            BERYLLIUM AND CADMIUM REMOVAL

Treatment Technology
Beryllium
Lime/Filter
Cadmium
Lime (260 mg/1) /Filter
Line (600 mg/1) /Filter
Lime Softening
PH

U.5
10.0
11.5
5-6.5
Lime/Sulfide 8.5-11.3
Ferrous Sulfide (Sulfex)
Ferrite coprecipitation/
Filter
8.5-9.0
neutral
Initial
Concen-
tration
(mg/1)

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 1
95 4
98 4
92-98 7
98+ 8
99+ 7,9,10
99+ 11
                                     93

-------
TABLE 8-3.   WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
             COPPER REMOVAL

Treatment Technology
Lima/Filter 8
Line (260 mg/1) /Filter
Lime (600 mg/1) /Filter
Ferric sulfate/Filter
FH
.5-9.0
10.0
11.5
6.0
Lima >8.5
Lime
Alum 6
Lane/Sulf ide 5
Ferrous sulfide (Sulfex)8
Ferrous sulfide (Sulfex)8
Ferrite Coprecipitation/
Filter
9.5
.5-7.0
.0-6.5
.5-9.0
.5-9.0
—
Initial
Concen-
tration
(rogA)
3.2
5.0
5.0
5.0
10-20
3.0
3.0
50-130
3.2
4.0

Final
Concen-
tration
(103/1)
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
                                     94

-------
TABLE 8-4.  WASTE 'WATER TREMMNT OPTIONS AND PERFOBMBNCE DATA SttMABY -
           CHBCMim III AND CHKMIM VI RBCWL
Treatment Technology
Chrcmivn
Line (260 ng/1) /Filter
Lisa (600 mg/1) /Filter

Reduction/Lime
Line Softening
Lime/Filter
Lime
Lime
Ferrite coprecipifcition/
Filter
Ferric sulf ate
Ferric sulf ate/filter
Chromim VI
Activated cartxn
(pulverized, Pitts-
burgh type EC)
Same as above
Activated carbon
(granular)
Ferrite coprecipitiition
Sulfur ^ifxi^0 reduction
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
	
3.0
2.0
6.0
	
	
	
Concen-
tration
(mg/1)
5.0
5.0
140 (as
CrVI)
1300 (as
CrVI)
—
—
15
3.2
25
• —
5.0
10
10
3
0.5
	
	
Final Removal References
Concert- (%)
tration
(mg/1)
0.1 98 *»
0.1 98 **
1.0 	 2,- 3
0.06 Crm 	 2jr3,13
0.15 98+ I1*
0.05 	 15
0.1 	 12
<0.1 	 12
0.01 	 1 1
	 98+ 14
0.05 99 *
1.5 85 16
0.4 96 16
0.05 98 *t
not — 11
detectable
0.01-0.1 	 2, 3
0.05-1.0 	 2,3'
                       95

-------
TABLE 8-5.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
            LEAD REMOVAL
Treatment Technology
Lime (260 mg/1)
Line/filter
Lime (260 mg/1) /Filter
Line (600 mg/1) /Filter
Ferrous sulf ate/Filter
Sodium hydroxide (1 hour
settling)
Sodium hydroxide (24 hour
settling)
Sodium hydroxide/Filter
Sodium carbonate/Filter
Sodium carbonate/Filter
Sodium carbonate/Filter
Ferrous sulfide (Sulfex)
F«a-rri-fce coorecicdtation/
FH
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 Removal References
Concen- (%)
tration
(ncr/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
95.0
99.9
98.5
98.0
98.5
iJ--1LJ "r
J— "-"•-"
99+
99+
82-99+
99+
99.9
99.9
4
11
4
4
4
3
3
17
17
3
2,3
7
11
   Filter
                                       96

-------
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
dng/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
(mg/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
-
-
-
Reference!
2,3
18
18
18
18
11
2,3
14
18
                                 97

-------
TABLE 8-7. WASTE WATER TREATMENT OPTIONS AND
NICKEL REMOVAL
Treatment Technology pH


Lime 8.5-9.0
Lime (260 mg/1) /Filter 10.0
Lime (600 mg/1) /Filter 11.5
Caustic Soda/Filter 11.0
Ferrous sulfide (Sulfex) 8.5-9.0
Ferrite coprecipitation

Initial
Concen-
tration
(mg/1)
75
5.0
5.0
-
75
1000
TABLE 8-8. WASTE WATER TREATMENT OPTIONS AND
SILVER REMOVAL
Treatment Technology pH


Sodium hydroxide 9.0
Ferric sulfate (30 mg/1) 6-9
Lime Softening 9.0-11.5
Chloride precipitation -
(alkaline chlorination
in the presence of
cyanide)
Ferric chloride/Filter 6.2
Sulfide precipitation 5-11

Initial
Concen-
tration
(mg/1)
54
0.15
0.15
105-250
0.5
—
PERFORMANCE

Final
Concen-
tration
(mg/1)
1.5
0.3
0.15
0.3
0.05
0.20
PERFORMANCE

Final
Concen-
tration
(mg/1)
15
0.03-0.04
0.01-0.03
1.0-3.5
0.04
-
DATA SUMMARY -

Removal References


98 8
94 4
97 4
17
99.9 7,10
99.9 11
DATA SUMMARY -

Removal References


72 19
72-83 14
80-93 14
97+ 2,3
98.2 1
very high 2, 3
98

-------
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
(ngA)
0.1
0.05
0.5
0.10
0.10
0.5
0.06
0.5
0.6
0.6
Final
Concen-
tration
(n»?A)
0.03
0.01
0.26
0.02
0.03
u.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
                                      99

-------
TAPTE 8-10.  WASTE WATER TREATMENT OPTIONS AND PERFORMANCE DATA SUMMARY -
                               ZINC REMOVAL
Treatment Technology
Lime/Filter
Lime (260 mg/1)
Lime (260 mg/1) /Filter
Lime (600 mg/1)
Lima C600 ing/D/Filter
T/lTiva/Fi H"-»T*
Sodiw hydroxide
Sulfide
Ferrous sulf ide (Sulfex)
Ferrite ooprecipitation
pH Initial
Concen-
tration
(irg/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
                                   100

-------


co
w
5
o
i-3
0
z:
ac
u
H
0
w
I— 1

PH
w
EC
H
Pi
O
CO
w
i
i
w
H
i
C3
2:
o

w
P9
m
3
<
rH
CO
i
1




.
52

+
•C
2 gj
jH
fl3 rH
B fej
CO
•f


tn "O 4->
M Q V
•s to co

1 1
 o M
(0 -H • in o o
o o o o
in o in in
rH rH 0 0
CO in rH rH
O O O O
£1 S
Gl! TJ
, > Is
0 -H 1
C! C *^ • «»j
i 1 II







VD
•
*?
rH
O

CO
Q
4
*
o


in rH O rH
O O CM O
O O O O
V V


in sr o in rj
o o o o d
in in rH in in
o o o o o
• • • • •
o o o o o



in VD
t*- • . in ^*
• o o « •
O I | O O
""S1 O O rH d
O O O O O
o in VD in oo
rH 0 rH rH O
A JH ri, rl, 4
O O O O O
M
3 *j a ^ j?

w c ^^ ^ 3 G) fl)
I IS 1 Iff 5 d
O tJ LJ SS 5! tn
in
o
i
''f
o













in
X
o
d


(N
CM
O
d



in in 
-------
00
1
      H
           o
         CO
       ro
         J
                                M
^1

£
s
                                          A.
•^
i
                                     102

-------
ii
a
^v
S3
S 2
4J 9
S
•3-
•*4 »•*
~_
Srtl
Q
fl O
|a
K
sV
8m
rj

•04
If
2 —

Tg
P
1
il
gm
5
8 «
if
*5 ^J
Ts

i
CJ «-^
1!




^^
*
i


0
d
P
&
jn
O
0
Ift
~s

0
0
!
s
1

M
M
O

i


in
~a


eo
^
o

1*
I
*+ f* f^
2* ^* ^j
§"5§

s
s » «
0 t* •»
o' d o
 in r. " ^
0*4 »•* W N M ^ Q ^
O 0 0 0 0 O
•Htnininininininf^iHtfiinin
S5sS555i§109 |?
i s
I «
•• • 	 	 s M
Soeoooe G. **.
(^wr*>^oKov^ro o o
ooooooo^H^iio^F^tn
ooooooooooo*^*^

SS S§*:2 «
§*" ~5 *5**5"5~5 ~5
5 5555 5
s s is
«- | s a s K e
. . °. °. °. ° °
o o d d d d d
!*• O3 ^4
S 5 § i i
00 to
S S £
do d
£ S si 5
i g il
s s s s §

So o
_ a s «
o o o **
d odd
e
3 j i & i.i
P R "5 !rt «« 5 "a
S I a 1 a « I
s — 5

§11 §


S S 2 S
d d d d
s - «
Ve"*e
s - «
*; »* »
o o d
oj »< in in in
6* ^ £ & S* O
= * S * Z § |
i «
in r>
*-* ^< . -
>4 o in o> o do
O i-l ^ ^H IN
O O O O O
1
a


§

s g g g 3 _ 3
•— y u cj— ~ £i
B B 8 8 x & 6
r* to d
O 3 O 
-------
I
s§
w
«M " wj
                                                         ',  _  | 2 52
                                 104

-------
1
   I

   £
  s"S
  si

  If
  ffi
  84
  cfl
i  §
I  rf
31 J
if °'


II!
IM 

       ?l fl]
          >•

          z
   II - «5
   la R >l
   I i 38
       T  H*
       Is £*
       sa |&
       «-. *g
       °S  :§
       Bj. Sa
      £J
     E Ifl
 j ih

 J —
 i SB
                  3
     ii«ir * * «*s»
     B jc  - 5 E  -  • >  -a ~
     |s 8 ni 8 g 8 a 51
     || .H |2 H M H „ **

     W"K 9 15 S 8 39
     si £ c2 £ £ fi I S 5

     c  § §  1I1§
                      105

-------
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
Contro1/Remova1 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 maximum 30-day averages in Table  ff-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 actually more  like  long-term  averages
than   maximum   30-day , averages  for  the  inorganic  chemicals
industry.  The  proposed  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
                              106

-------
 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
 ~feSa ? lv-a^
-------
           TABLE 8-13.   ESTIMATED ACHIEVABLE LONG TERM AVERAGE
                        CONCENTRATIONS FOR PEIORITY METALS
                        WITH TREATMENT OPTIONS
Toxic
Metal
Antimony
Arsenic
Beryllium
Cadmiun
Chromiun
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Line/Clarification
(rog/1)
ID(1)
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
ID
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
^   ID:   Insufficient data for a reliable estimate

(2)   wn.   XT,
                                    108

-------
          TABLE 8-14.  THEORETICAL SOLIBILITIES OF TOXIC METAL
                       HYDROXtEES/OXIEES AT VARIOUS pH VALUES
pH
Metal
Group A
Cr4"44
Cu44
Ifc44
Zn44
Group B
Cd44
Ni44
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
W

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
                                   109

-------
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 cut 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
polishing  step  for  chlor-alkali(diaphragm  cell)  and   chrome
pigments   wastewater   treatment.    Both   subcategories   have
wastewaters  similar  to  those  encountered  in  the  Phase   II
industries.  -  That   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  are
not proposing 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
                              110

-------
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 regulations.  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.
                              m

-------
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  value's  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.

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
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
st.i'i j, 7tical  procedures.   A  final assumption was that treatment
                               112

-------
facilities and monitoring techniques had  remained
constant throughout the monitoring period.
substantially
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 validity of the
lognormal assumption for daily data.

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
the   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 long-
term average, depending only upon the day-to-day  variability  of
the  process  and  the  expected  number  of  excessive discharge
periods.  For a  lognormal  population,  the  variability  factor
(P/A),  the  performance standard P, and the long-term average A,
are related by:

          ln(P/A) = S'(Z - S'/2)
                               113

-------
           where
           "In"  represents  the  natural  logarithm
           numerical  quantity.
(base  e)   of  a
     B.    S1   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".

     C.    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.

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 A1
and  S'  are  the  mean  and  standard   deviation    of   Y=ln(X)
respectively,    then    the  probability  is   k  percent  that  an
                              114

-------
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'+ZS1  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'   +ZS').    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 -i- S1 (SV2))

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

   * exp [ZS1 - S' (SV2)]

   » 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  InO.O  +  (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  From  Long-Term
Data

Given  the  following  descriptive  statistics  for  a particular
parameter, as might be found for zinc (mg/l)in Appendix AJ
          No
Min
Avq
Max
CV
          442  0.014  0.224   4.4    1.26

Calculate the estimated standard deviation of logarithms

          (S')z = In (1.0 + (1.26)2) = 0.951
*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
                              115

-------
o
 •
r-l
O
 *

O
                                            DUTZ
                                 116

-------
                                                                                                  o>
M
I  H


                     ^
                            K
                                i

                                                             II
1

                                                                                    rtrfc
                                                                                       S
                                                                                                 01
                                                                                                 o
                                                                                                 en
                                        TJ
                                         O
                                     W -H
                                     1^  f-
                                     O  O
                                     •H  p,

                                     oJ ,G
                                     ^H +->
                                     +->  cJ
                                     a  o
                                     o  6
                                     o
                                     rt IH
                                     O t«~

                                         rt

                                     rH  fH
                                     •H  O
                                     rt  >
                                     TJ  O
        M-l +J
        O C
    O      fl>
    bo  fi 3
    01   O tH
    •P   -H 
        to rt
        •H a>
                                                                                                         >  PJ
                                                                                                        •H -H
                                                                                                            CO
                                                                                                            H
                                                                                                        U  0
                                                                                                        CM
                                                                                                         1
                                                                                                        oo
                                           117

-------
              NORMAL DISTRIBUTION
              (MODEL DENSITY OF LOGARITHMS OF POLLUTION VALUES)
    0
     I
                                       ln(P) - A' + 2.33(S')
                                          Y  - ln(X) - Logarithm  (ng/1)
             A1
  u          *»                »
  •   LOGNORMAL DISTRIBUTION  ^
      (MODEL DENSITY OF        N
      POLLUTION VALUES)
                                                  X(mg/l)

                                          _ P(Pearformance Standard)
                      I-A (Long Term Arithmetic Average)
         SAMPLE DISTRIBUTION OF N MEASUREMENTS
            (LONG TEFM MONITORING DATA)
             f         Max-^
             X (Sample Average)
                                      X(rog/l)
Note: (a)  S* is estimated as  (S1)

           CV=S/X"

           S2- Z (X-X)2/(N-D
                                 12
                                                 CV2fl
Figurfe 8-3.  Statistical distribution for daily pollution measurements.
                                  118

-------
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,  S',  was then
derived (S1 is the standard deviation of the logarithms).
          S1 = 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   po-llutant   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
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
                               119

-------
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 is:

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

          VF = 1 .0 + Z(CV)

          Where:

     1 .    Z  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.

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
                               120

-------
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.
1 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.
                                121

-------
                                                           60

                                                          |

                                                           0)
                                                                  §"
                                                                  •H *O
                                                                  *J 0
                                                                  9 4J
                                                                  .0 «
                                                                  •H 0)
                                                                  V)
                                                                  •H C
                                                                  V E
                                                                  > 9
                                                                  •H .H
                                                                  *j e
                                                                  cat)
                                                                  r-l Cfl
s


 O
 «M
  •
 O
   I


   i
   .1  .,


   CO
          >_.!.._ .1-.....J
                     i-H
                      *
                     O
(l/Sui)
                               uintuipiBO
.j	!„:..-!
O
 •
o
                                                                  i
                                                                 •eo

                                                                  V
                       00
                       •H
                       tu
                         122

-------
                                          .•!.::f:h::
                                        ;..;:JHH:
LO
o
to
o
                                               o
                                                •
                                               o
               uoT3.B.i:j.ti3ouo3  p-ea-j


                         123

-------
                    NOFMAL DISTRIBUTION
     (MODEL DENSITY OF SO-DAY AVERAGE POLLUTION MEASUREMENTS)
                                      X(mg/l)

                                 — P  (Performance Standard)

                    _ A  (long Term Average)
            SAMPLE DISTRIBUTION OF M MONTHLY AVERAGES
                   (LONG TERM MONITORING DATA)
                                    X (mg/1)

                       (Average of 30-Day Averages)
          Note:   (a)  P/A = 1+1.64 (CV)

                       CV
                     X=Z  X/M
Figure 8-6.  Statistical distributions for 30-day average pollution measurements.
                                  124

-------
                            SECTION 8

                            REFERENCES
1.   Hannah, S.A., M. Jelus, and J.M. Cohen.  Removal of Uncommon
     Trace Metals by Physical and Chemical  Treatment  Processes.
     Journal Water Pollution Control Federation 49(IT):2297-2309.

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

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

4.   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 j:2297--2305, 1977.

5.   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.

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

7.   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.

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

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

10.  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.

11.  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
                              125

-------
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.
                               126

-------
22.   Edmonson,  B.C.,  "Letter to Jacobs  Engineering  Group  Inc./
     detailing   statistical methodology developed for Phase I and
     II Inorganic Chemicals," March 15, 1983.
                               127

-------
                            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  and  potential
environmental   significance  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   below    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
                               128

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

Cadmium Pigments
 and Salts
Cobalt Salts
Copper Salts
Nickel Salts
Sodium Chlorate
Zinc Chloride
Group  1(1)

Cadmium
Selenium
Zinc
Cobalt
Copper
Nickel

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

 Antimony
 Arsenic
 Barium
 Chromium
 Copper
 Lead
 Nickel

 Lead
 Zinc
 Antimony
 Arsenic
 Chromium
 Lead
 Zinc

 Antimony
 Cadmium
 Chromium
 Lead
 Zinc
 Copper
 Lead
-Nickel
 Zinc
 Chromium (VI)

 Antimony
 Cadmium
 Chromium
 Copper

 Nickel
 Silver
(1)   Group 1 - dominant raw waste pollutants 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.
                              129

-------
point for advanced level treatment additions and incremental cost
estimates.

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 30-day 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
                               130

-------
characteristics
subcategory.
                 for the indicated treatment applications in each


Advanced Level Removal of BPT Pollutants
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 reduction by filtration.

Advanced Level Removal of_ Toxic Pollutants

Performance estimates for toxic pollutants were also based,  when
possible,  on  effluent  quality  achieved  at  pl-'./Jo  currently
practicing these technologies.  However  •' ,  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  we11-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
                              131

-------
Conventional Pollutants

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

     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 has  been  established as  the  general   control
limitation   and   the  permissible  frequency  and  duration  of
excursions beyond this range is to be specified  in  individual
plant  discharge  permits.   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
                               132

-------
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.

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
                               133

-------
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
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.
                              134

-------
                            SECTION 10

               COST OF TREATMENT AND CONTROL SYSTEMS
 INTRODUCTION
 The costs,  cost factors,  and costing methodology used  to  derive
                 f[inual costs of treatment and control systems are
                       sectlon*    A11  costs  are expressed in
 The following  cat€?gorization 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.
                              135

-------
D.





E.



F.
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.

                                        single  product
          Manufacturing plants are assumed to be
          plants.

          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.

     G.    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
                           136

-------
 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  provided  to  permit  alternate
 dewatering for sludge removal.

 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/mz ($0.20/ft*)
$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.
                               137

-------
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
     Vacuum Filter
(31
(31
I1)
3')
     Filter Cartridges
   $40,000*
   $60,000*
   $45,000
   $55,000

$100 - 300
     Agitated Falling-Film Evaporator (316SS) 6 m2**
     Agitated Falling-Film Evaporator (316SS) 7 m2**
     Agitated Falling-Film Evaporator (316SS) 11
     Multiple Effect Evaporator 9.3 m2***
     Multiple Effect Evaporator 32.5 m2***
                                    $76,000
                                    $85,000
                              m2** $104,000
                                   $100,000
                                   $190,000
   *For large-scale use of lime.
  **Heat transfer area.
 ***Total heating surface.
                              138

-------
 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%

                  I  to 2%

                  2  to 4%
                              139

-------
                         7  to 12%
                         2 to 3%

                         1 to 2%
                              cost
Engineering design and specifications

Inspection and engineering support during
construction

Operation and maintenance manual

From these totals of  14 percent to 25 percent, a midvalue  of  20
percent  of  in-place  construction  costs   (equipment  cost plus
installation cost) 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
 (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  $1 2,000/acre.

 ANNUAL COSTS

 Operations and Maintenance
140

-------
       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.S6
8.68
24.31
PIPE SIZE
Gal/
Min
18
27
64
119
458
824
1,468
2,292
6,418
CM
2.5
5.0
7.5
10.0
15.2
20.3
25.4
30.5
45.7
IN
1
2
3
4
6
8
10
12
18
PIPE
$/LM
44
48
59
72
109
167
220
280
470
COST*
$/LF
13.50
14.60
18.10
22.00
33.00
51.00
67.10
85.40
143.30
*Installcd above ground, includes allowance for fittings.
                               141

-------
       Figure 10-1.  LAND REQUIREMENTS FOR SMALL AND MEDIUM LAGOONS
    30
    10



    7


    5
I    3
O
o
O
<   1.0
    0.7


    0.5




    0.3
    0.1
                                                                         !    !  j
                                                                         t    *  I
                                                                         •>•	!"•••*
  :  !  :  : ! !
......	J..+..J..J..;.
                                 10           30    50  70  100


                                     LAGOON VOLUME (1000 m3)
                                                 300   500
       ha x 2.471 = acre$


       m3x 264.172-gal
                                       142

-------
       « • I •  '
       ttitl

                • -.---. —r	
          —:—••+	
'•••II*   *   *


irt"eT~rt""]	'"
• i • • J  !  •   >   •
                                                  »
                                                • j« •*•*
                                                 «••


                                                      --"-——"
CO


O
O
u.

O

(A
Ul
§
UJ
£





                                                                  in
                                                                  i   I
                                                                  «1
                                                                       in



                                                                           1
                                                                       CO   N
                                                                           CM
                                                                           r»
§
            §
      .
     o  o   o
     o  tZ   
                      5  o.  e.
                      o  r*  &
S
o
                                           §
                                   awrnoA axia

                                    143

-------
                               DIKE CIRCUMFERENCE (m)
CO

o
O
O
u.
O
CO
Ul
o

Ul
cc
Ul
UL


U
cc

u
o

<
w
<
Ul
cc
 Ul
 u
 <
 u.
 cc

 M
 Ul
 e
 «
 u.


                                                                                       X X

                                                                                     *»M CO

                                                                                 r-   E E E
                                 (ziu) vauv aovduns•


                                          144

-------
         Figure 10-4. CONCRETE PITS AND BUILDING COSTS
 7.5
 I
  4
                       a. COSTS OF CONCRETE PITS
                                        _L
                     20        30        40

                        PIT SIZE IN CUBIC METERS
                          50
                           60
  90


  80


  70



a 60


i50


5 40


8 30


  20


  10


   0
                       b.  STORAGE BUILDING COST
I
J_
             50       100       150       200
                     FLOOR AREA IN SQUARE METERS
                          250
                           300
                              145

-------
p
o
^
1
HI
0
                                       co
                                       111
                                       u
                                       5
o
5
o
 I
                       ID
  u>
•Ann'i
                                      (Z861 JOOO'IS) 1SOO
                                          146

-------
                                                                                    I
P

8
oc
UJ
oc
<

o
o
oc
01


UJ
x


of
UJ
 £
 §,
                                                                                                           lu
                                                                                                           O
                                                               Ul

                                                               H

                                                               oe
                                                               UJ

                                                               Ul
                                                        §     I
                                                        i-     £ oc
                                                               ^m uj
                                                               Ul IE
                        to
                        OC
                        Ul


                        i
                        o
                        ffl

                        o
                                                                  -
                                                                Q K

                                                                33
                                                                CO O


                                                                fl  I

                                                                O Q
                                                         §z
                                                         101   tt
                                                            3   tu

                                                            3   5

                                                            >   E
                                                            >   Ul
              s     s     s
                                  in
   §     8     8

(Z861 -O00'l$) JLSOD
8u>     e
r-     i-
                                                                                            Ifl
                                                                a.  Z

                                                                <§
                                                                O  CC
                                                                Ul  <
                                                                S  o

                                                                oc  Q
                                                                <  "
                                                                                                            <  H-
                                                                                                            DC  O

                                                                                                            O  <
                                                                                                            tl

                                                                                                            <
                                                    147

-------
Figure 10-7.  CHEMICAL FEED AND NEUTRALIZATION SYSTEM COSTS
  21


  20 -


  19


  18


  17


  16


  15


  14


  13


?512
8

111
__*

~10


u
7


6


5


4


3


2


1


0
                            (1)
                                            NEUTRALIZATION SYSTEM
                                         (4) I (FEED AND TANK ASSY)
                                                  NEUTRALIZATION TANK
                                                  AND MIXER

                                                  LIME OR CAUSTIC FEED
                                                  (TANK, AGITATOR AND
                                                  FEED PUMP)
                                          (1)
                                             POLY OR ALUM FEED
                                               (  ) - HP
                                               1 HP - 0.7457 Kw
                            j	I
                                                  l
100   200  300  400  500  600  700  800  900  1000
           DAILY FLOW IN CUBIC METERS
                             148

-------
        Figure 10-8.  PUMP AND CHROME REDUCTION SYSTEM COSTS
  20

  18

  16

  14

J2 12
S10
   a. PUMP COSTS
              25
   60        75       100
        ' PUMP HP (1 HP - 0.7457 Kw)
125
150
175
   90

   80

   70
 _ 60
 CM
 7.50
  »
 § 40
 »-
 8 30

   20


   10

    0
b. CHROME REDUCTION SYSTEM COSTS
                      (  )  - HP
                      1 HP  - 0.7457 Kw
         100  200  300  400  500   600   700  800  900 1000
                    DAILY FLOW IN CUBIC METERS
                                    149

-------
                                                                          5

                                                                          5
 I
 O
 O
r
Ul

o
m
u
z
 UJ
 oc
 a.
 OC
 UJ
I
Q
 o
 6


.1
 u.
Ul
ce
u.
o
Ul

3


§
                                                                           o
                                                                           o*
                                                                           o
                                                                           o
                      §
                                       (£861 -'000'1$) 1SOO
                                          150

-------
 M
 rt
•H
+J
rt
 o
 bO
13
 3
(V)
)ischar

ib
cd
ac
a

o
bO
C
•H
J-.
monito
 +J
 in
HO"
gco
0  N
Uffi
                            3
 00
 c
 •P
 •M
 o
 •H
 P
 rt
 p.
 •H
 O


 Cu

 0)

 • H
 rH
 cd
 ft
 O
 •H
 •P
 cd
 N 0
 •H -H
 r-t in
 cd cd
 f-c «
••p
 3
 O
 2
 bO
 •H
                                                       151

-------
                                                                0>
                                                               >
                                                                                                  IS)
                                                                                               0)  t-l
                                                                                               4J  rt
                                                   in C  C
                                                   rt    -H
                                                   S 6  w
                                                   ^ O  ctf
                                                   U f-4 ^3
                                                   CO UH
                                                                                                         \/
                                                                                                         \/
                                                           3 BJ (!)
                                                           C-H +->
                                                                 r-l
                                                              O -H
 o
•H
•P
 ri
 f-4
+J
iH
•H
PH

 rt
•H
Td
 0)
S
 rt
r-l
 3
r
 I
O
 0>
 M
 3
 bO
•H
(L,
V
A
                                                                   tXl   =»
                cd
               iH    Vi
                3 cS 0)
                                                               
                                                rt  4) M-i
                                               «  oi o

-------
V)
W
0>
U
o
O
.»->
CO
 in
 bO
 C
•H
 
  3
  bO
                                                          V
                          R)  rt
                          •PrfS
                          rt  U
                          C  w
                          Vl -H
                          0) Q
                          CU
                          3  o
                                                                  o

                                                                  o
                                                                  H
                                                                                                 r-l
                                                                                                 -rt
                                                                                               u c!
g
 cS
z:
      0) U
rt m P <

-------
                                                                                      0>
                                                                                      00
                                                                                      *H
                                                                                      03


                                                                                      o
                                                                                      to
o
cd
                                                                                                 M	
                                                                                                               CO
0)
                                                                                                               o
                                             rt «
                                                   0)
                                                O r-<


                                                 " V*

-------
 rt
•H
P-.
 CO
 c
 O
CO
 §
•H
 •P
 rt
 +J
•H
 &.
•H
 O
 4) bO
 V" C
 P< -H
    t->
 (U (U
 C +J
 •H OJ
 M >
 (4 0)
  O
 •H
 4->
  O

 *^
  o>
 OS
 •H  +J
  6  w
  o  3
  »H  -r->
  1-1
  i
  o
  t90
  •H
  tin
                                                                           155

-------
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
                              156

-------
 ($46  per cubic yard) for deposit  in a secure  landfill  (permitted
 for hazardous material) and $15 per cubic meter  ($11.50 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  (}h  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:

     CA = B ((r(l+r)n/n((l+r)n-l))

     Where:

     CA = 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.

Batch Processing of_ Wastewater
                              157

-------
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.
For the purpose" of this study,  equipment  is  sized  to  require
treatment operations about twice a week.

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
                              158

-------
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, pJH 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
                              159

-------
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, NaOH 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 wet 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,
Final pH Adjustment, and Sludge Dewaterinq
Settling,
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
                              160

-------
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
(oermitted for hazardous wastes).
                              161

-------
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  each
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
plant.   Model  plant  ^costs  for
presented in Section 15".
is  represented  by  one  model
 two treatment alternatives are
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.
                               162

-------
This subsection demonstreates 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.
l±    Alkaline   precipitation,   clar-j c: c
Level
dewatering and p_H adjustment.
                                                           sludge
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  (Hj,S04,  TOO  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 in*)

Equipment
                                            Cost
                                              Source
                                        $  7,000
                                           1,600
                                          18,000
                                           (Fig. 10-4a)
                                           (Fig. 10-4a)
                                           (Fig. 10-4b)
                              163

-------
NaOH feed system (300 mVday) (1 HP)
Clarifier (300 mVday) (6 HP)
Filter press (0.5 m3)
Neutralization system (300 mVday)
(2 HP)
Installation (materials and
erection labor)
Instrumentation
Engineering (20%)
Contractor overhead and profit (15%)
Contingency (10%)
Total Capital Costs
Annual Costs:
Operating personnel (3.25 Hrs./Day
at $25/Hr. )
Facility and equipment maintenance
(10%)
Materials
NaOH (50% solution) (140 kkg/year)
H2SO« (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
Level 2: Filtration
The wastewater flows through a sand filter
Capital Costs;
Facilities
Equipment
Sand filter (300 mVday)
Installation (materials and erection
labor)
Engineering (20%)
7,000
42,000
18,000

(Fig. 10-7)
(Fig. 10-6)
(Fig. 10-9)

13,900 (Fig. 10-7)

77,500
10,000
39,000
35,100
26,900
$296,000


$28,400

29,600

52,500
300
4,100
8,000
8,900
4,600
48,200
$184,600

before
Cost
None

$15,800

15,100
6,200

(p. 139)
(p. 139)
(p. 139)
(p. 140)
(p. 140)



(p. 156)

(p. 156)
(p. 156)


(p. 156)
(p. 157)
(p. 157)
(p. 156)
(p. 157)


discharge.
Source


(Fig. 10-6)

(p. 139)
(p. 139)
164

-------
  Contractor overhead and profit (15%)       5,600   (p. 140)
 Contingency (10%)                           4,300   (p. 140)
     Total Capital Cost                    $47,000

Annual Costs;

Operating personnel (0.5 Hrs/Day at
  $25/Hr)
Facility and equipment maintenance
  (10%)                                      4,700   (p. 156)
Taxes and insurance (3%)                     1,400   (p. 157)
Residual waste (2 mVyr at $60/m3)             100   (p. 156)
Amortization                                 7,600   (p. 157)
    Total Annual Cost                      $18,200
$ 4,400   (p. 156)
                              165

-------
                           SECTION 10

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

2.    "Building Construction Cost Data, 1982," by Robert Snow,
     Means Company, Inc.

3.    "Modern Cost-Engineering Techniques," by Robert Popper,
     McGraw-Hill Book Company.

4.    "Development Document for Effluent Limitations Guidelines
     and Standards for the Inorganic Chemicals Manufacturing
     Point Source Category"
     EPA 440/1-82/007, June 1982.

5.    Vendor Quotations.

6.    "Plant Design and Economics for Chemical Engineers", by M.S. Peters
     and K. D. Timmerhaus, McGraw - Hill Book Co., Third Edition.
                              166

-------
                           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
                              167

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

     Minimum
     Maximum
>4fOOO kkg/yr

 NA
>l,000"kleg/yr
Total Subcategory Wastewater Discharge

     Minimum
     Maximum
>1,200 m3/day
450 mVday
Types  of Wastewater Discharge
      Direct
      Indirect
      Zero
6
4
2
 NA  Not Available
                                168

-------
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 = CdCl2 + H2

     Cd + 2HN03 - Cd(N03)2 + Hj,

     Cd + H2S04 == CdSO* + 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
                              169

-------
 CADMIUM CHLORIDE
               Cadmium Source
HC1 gas
HCl 	 >
Water 	 >
» 	
Reactor

1 ^^
Evaporation
•>

Drying
                                                                    Anhydrous
                                                                   ^Product
 CADMIUM NITRATE

           Cadmium Source
                         liquid
                         product
                                      1
HCL -gas
hydrated
 product
                   1
Nitric Acid
(HN03) ^
Reactor

1
Evaporation

. >

Drying
                                                                    Anhydrous
                                                                   * Product
                          liquid
                          product
                                          Hydrated Product
 CADMIUM SULFATE
            Cadmium Source
Sulfuric
 Acid
                                   Evaporation
                                   Crystallization
                                                         Drying
                             ^Anhydrous
                                                                     Product
                                                  hydrated
                                                  product
 CADMIUM SULFIDE
                 Cadmium Sulfate
Na2S
  H2S
                    I
or ^.
~^
Reactor
^^



^

          FIGURE 11-1.  GENERALIZED PROCESS FLOW DIAGRAM FOR CADMIUM SALTS.
                                    170

-------
a
S
r







g
D> -rf
C U
5-0 g
,C C M
n ig **
4 <-4
* 2



*^ C


Q
T







c
•H
t)
«
c
o
«
o







/i . . .. -

u
01

*

n
0
'>
1 f
« ti -<
i Si
2 5

it
S
-, s
-- aj
1
c
2 8
•? S §•
« a -H ...
01 ij' J»
J 1|
•HO) is •6

r-« « *-•
01 U ^
1!
~

B«

u

"


1
>a'
••'fl fl
O J

2

£0.
3s
1 1
? 5
o
to o
u
=
v /


I
g

•H










'
5
•^ w
» «-l 
-------
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  yellow  lithopone  pigments   are
manufactured by coprecipitating 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 10 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)
                               172

-------
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) + Na2S04


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

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

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

Cadmium Lithopone Pigments
reds  and  cadmium
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) * CdSxSe(l-x) • BaS04  (when x < 1)

while the reaction for yellow lithopone pigments is:

CdS04 + 2BaS + Zn S04 = 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.
                              173

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

Water Use

In  the  cadmium  salts  industry, water is used primarily as the
reaction medium.  A small amount may be  used  in  air  pollution
control  (scrubbers)  and  in  washdown  of equipment and process
areas.

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  the  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
                               174

-------
     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
0
1.
0
0
0
0
1.
(4)

08




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).


Sourcej  Section 308 Questionnaires and Plant Visit Reports
                             175

-------
  TABLE 11-3.  WATER USAGE AT CADMIUM PIGMENTS FACILITIES
Flow (m3/kkg)
Water Use
Noncontact Cooling
Direct Process Contact
Indirect process Contact
Maintenance
Air Pollution Scrubbers
Noncontact Ancillary
TOTALS
Plant
F102
0
71.2
42.2
1.6
1.07
0
116.1
Designation (2)
F101
34.4
132.4
0
3.19
<0.067
0.16
170.2
F134
0.116
27.9
0
0.116
0.35
0.87
29.35
F110
0
34.65
0
1.07
0
0
35.7
(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
                              176

-------
  TABLE 11-4.  WASTEWATER FLOW AT CADMIUM SALTS FACILITIES
                                    Flow (m3/kkg)



                                  Plant Designation
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.
F125(2)
0
0
0
0.036
0.036
0
0
for those plants
information.
Fll
0
0
0.
0
0.
0,
0
7^J .F117U
0
0
085 0.054
0
085 0.054
0
0
that reported
Source:   Section 308 Questionnaires and Plant Visit Reports
                            177

-------
   TABLE 11-5.  WASTEWATER FLOW AT CADMIUM PIGMENTS FACILITIESU)
	 	 — 	 	 	 — 	 _
Wastewater Source
Direct Process Contact
Indirect Process Contact
Maintenance
Air Pollution Scrubbers
TOTAL PROCESS
WASTEWATER DISCHARGED
Noncontact Cooling
Noncontact Ancillary
Flow (m3/kkg)
Plant Desiqnahion
F102
71.2
42.2
1.60
1.07
116.1
0
F101
132.4
0
3.19
0
135.6
34.4
0.16
(2)
F134 F110
25.5 34.65C3)
0 o
0.12 0
NA o
25.62 o
0 0
0.87 0
 NA   Flow volume not available.                          *.


 (1)  Values indicated only for those^Jlants that reported
      complete information.                            .-•

 C2)  Values indicated are for all cadmium pigments production
      and include production of cadmium sulfate as starting
      material.                                           ft

 (3)   Discharge to on-site pond.
Source:  Section 308 Questionnaires and Plant Visit Reports
                              178

-------
 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.

 All wastewater is collected in a  sump,   then  is pumped   to  the
 pigment  plant treatment  system (for  cadmium recovery) and is then
 discharged   to the  main  plant  treatment  system.   Cadmium  recovery
 treatment consists  of  a   10,000-gallon   equalization  tank   where
 soda  ash   (during  the  sampling period  caustic  soda was  used)  is
 added to raise the  pH.   A polyelectrolyte  is added  in a flash  mix
 chamber  and  then flows through  a  tube settler.   The overflow from
 the tube settler is discharged  to an  in-plant  receiver, while  the
 underflow is  sent through a filter  press   for   dewatering.    The
 filter   cake   is  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.

 Since the time of sampling, the wastewater  treatment  system  has
 been  changed.   The discharge  from the  cadmium  process treatment
plant is now  comingled with other  wastewater  generated  at   the
 facility.   The  overflow from  the tube settler  is  now discharged
 to the main wastewater treatment facility, and the  filtrate  from
 the  filter press is sent to the beginning of the main wastewater
treatment  facility.   The  main  wastewater  treatment   facility
                              179

-------














\f
m

I-1











b
0
5
s
ft
Q
A A
•i «H 

\*
01
: 3
CO







h
U
*


CO
• a
	 >
Seleniua
— >Product
|
o
/k

>
JS 6
O TJ *
a c -
S a.
/ 1


e
SU I
e c
C £i
< a
3



I aS 5
! °i 4
o« ^
a u
®j^u 1
S

S 8 S
a ja j< " ^
5H— !i r~* i
b o « 5
ft £ /
1
b
u U)
olu
e * .
a o no .
Si S3 * g
si «j • 3s
«2 ° a 	 9 *
-, I3 - "I
.La "
I A ?
- & = 1 ^
II *
& O

« cS *
b. (M S «
j
? w 2 9 \
3 1 J!/
s I -i/
as
9 u
1 S Q
*J Q)
'1
u H

' b
i 1
< £ S|
» 5 ^
u -H 3
"-» tH -r*
£ 
-------
                                                                         0.

                                                                         a
                                                                         ta


                                                                         9
                                          181
_

-------
o
bl
                                                             in
                                                              I
                            182

-------
                                9  $
                                a   
-------
 racent S JST^f  , f 5?"  , th?   cadmium  Pigments  plant  (about  30
 percent of the total flow) along with process wastewater  from all
 ?S  nPnrtVf the  ?lant'  The  70 Percent of the wastewater  from
 the  non-cadmium  pigment  products and the filtrate from cadmium
 recovery filter press is treated with caustic and then  clarified
 i?  *  J1?riflf^   The  effluent  from  the  clarifier,   and the
 effluent from the   cadmium  treatment  plant  are  then   filtered
 through  a sand filter.  The filtrate is discharged to a  publicly
 owned treatment works (POTW), and the backwash is recycled- to the
 SJa™fl€r-  ThS underflow from  the  clarifier  is  dewatered  and
 treatment *S  hazardous wastes  and the water is recycled  for more


 During the sampling period,  only pure cadmium red  pigments  were
 being  produced.    Figure  n-3 shows wastewater sources  from the

           ?oeS?hS  at* ?lant  F1°2  3nd  the  samPle  P°int™  in
           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
                                                        Processes
 Process  wastewater and treatment for each color (red and yellow)
 are,sim>larly. segregated.    Process  wastewater  originates  from
 ??i?^      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  lo  I
 if™96/,    ding  tan£:   The resulting precipitate/slurry material is
 pumped    to    a  final  scavenger  filter   press.    The  filtrate
 represents the  final  effluent which is discharged directly,  while
 fnGMe??,V     f£ltercake 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
wastewater   sources   and   treatment  system  along  with   the

                                       Pigment  product  are  shown
 ™4-i   4-        F134  resulted in separate wastewater and
treated effluent samples from the pure cadmium yellow pigment and
                              184

-------
 S
EH CO
  EH

O W

W U



Ss


za
to i
z
EH EH
Z Z
W <
U J
z eu
  SEH
  (0
to co
W

I
EH
           Icn


CO







10
JC
o
 10
g,,
ON
Q^*



CM

to
O
O
i-l O
r-l O
o o


o
CM
o
«r o
co o
o o

r-
^*
r-l
O
in o
CM 0



in
CO
r-l
eno
CM O

CMO



in-
oo
to
too
to o
i-l
f-l


in
CO
•W
0 O
*s*
p»



c
§
•o
*8 4)
to
Floor Washings
Maintenance Ho
From Upstairs



CO


CM
CM
CO CM
f O
* •
t-4 O



r-l
p*.
r-l
i-l O
•-4 0


O
CM
P- O
CM O




f*»
CO
•-I 0

fO O
V V



r-l
co
00 T
* *
r- o


en
en
p»
tO f\
r-l
i-l








Filter Wash



•"

o
o
CO O
00
o o
• *
o o


to
o
o
CM 0
r-IO
O 0

co
r-l
o
•* o
CM O
o o



VD
O
o
r-40
i-4 O

O O


f«»
"4*
CM
0
to o
I1 O

CM
CM
O
in o
if 0



41
o»

(0
o
m
.rl
a
41
3 -.
u >,
o a
wo
4Ji-4



in

o
o
P> O
0 O
o o
0 0

CM
o
o
CM O
0 0
0 O
O O
to
o
o
to o
o o
0 O
o o


in
o
o
in o
o o
o o

o o
V V

00
o
co o
r-o
o o
00

o
r-l
O
O 0
ft O
V V



to
0)
41
o
X *~
W >!
m
Hot Water Tank
Discharge (1 di



to


p*
CO
en o
r-l O
o o



in
ft
in r-l
CM 0
o o



in
•-4 r-l
in.iH
CM




to
to

en r-i
CM




00
O P>
"» <"
0
f-l



r-l
• •
^* *9*
O r-l








Total Combined
Raw Waste



i-

co
en
CO
•-I 0
CM O
O O


o

r^
CO O
r-l O
00


f_l
tO rH
CM 0
O O



co

00
en o
•-I O

0 0




CO
o en •
CM CO
en

-

00
o
• •
en co
00
f-i






u
^«
Treated Effluei
,<



CO



a*
c
i— i
a

(0
W

IU
O
W
10
•o

01
41
u
4J

D>
C
•rl
U
3
•O
•O
41
C
(0
4J
ft
O
(0
41
3
ft

-------
                      oo
                                         MO   r4<
                                         •no    •>«
                                         eo
                                                            «no
                                                            no
                                                                          MO
               oo    ^<
?  «SJ
8  u mi
                          ?* •;
                                      « «    M
rax
                                             •* •    > I
                                             c •    a
                                             luO,
                                                    too,—
                                                                OB.
                                                                       ». 0<
                                                                       > •» €1
                                                                       « 
-------
 lithopone cadmium yellow pigment,  as well as from  the  lithopone
 cadmium red pigment operations.
 Table   11-7   presents   the   wastewater
 concentrations for each type of pigment.

 Other Plants Visited
flow  and  pollutant
 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
 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.
                              187

-------
 Plant FIT7 manufactures cadnuum 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  FIT9  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 FT 45  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.
     Pollutant

     Antimony
     Arsenic
Maximum Concentration
    Observed (ug/1)

          540
          190
                              188

-------
  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(i)
0
0
1040
47
0
0
29
1
25
1
0
0
0
0
0
0
.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<2)
0
0
11
0
0
0
0
0
2
0
0
0
0
0
0
0
.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.
                               189

-------
        TABLE 11-9.  TOXIC POLLUTANT TREATED EFFLUENT DATA
                         CADMIUM PIGMENTS
         Average Daily Pollutant Concentrations and Loads
                               mg/1
                              kg/kkg
Pollutant
Antimony
Cadmium
Thallium
Selenium
Zinc
Lead
Nickel
Copper
(PR)
F102(i)
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
(PY)
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
<0.13
<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.
                               190

-------
      Cadmium
      Chromium
      Copper
      Lead
      Nickel
      Selenium
      Thallium
      Zinc
      Bis(2-chloroethyl)  ether
      Bis  (2-ethyhexyl) phthalate
      Chloroform
      Methylene chloride
1,400,000
      400
      250
      530
      420
   81,000
      190
   62,000
       84
       24.4
       40.3
       14.8
 Data  was   obtained   at  Plants  FT02  (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   cleaninq
 procedures.                                                     y

 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

 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
                              191

-------
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
pafticulates.

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  F125  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.

Plant No. F123 produces  small  quanities  of  cadmium  chloride.
This  plant  discharges no wastewater.  All process wastewater is
incorporated in the product.
                               192

-------
 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
wastewater  treatment filtrates.   For example, plant F102 employs
polyelectrolyte addition to improve clarification performance  in
a   tube  settler.    The  identification  and  use  of  effective
flocculants   and   other   settling   aids   could    contribute
                              193

-------
significantly    toward   enhancing   effluent   quality  in  this
subcategory.                                           *

An overall  reduction  in  water  use at  cadmium pigments  facilities
might be obtained  by  the following approaches:
      1
     2.
     3.
Recycle of filter washwater
process, where possible;
                                        during   pigment   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
                            of  impurity,  and the demands of the
     the  amount
 the  product,
      ^       '	  — —   —•«£*• •-— *. wjf f   MIAVA wtis^ wdiiciiiuo
 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.

 A11°tner  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
 toxic  pollutants  should be directed to the  treatment  system for
further treatment.
                              194

-------
       Advanced Treatment Technology

       Cadmium pigments wastewater contains fugitive  pigment  particles
       which  in  turn  contain  significant  concentrations of cadmium?
                    Z.nC'  L°W concentrations of suspended  solids  must
                      P  ensure  reduction  of  these  toxic  metals  in
                  dlschar<3es-   Level 1  plus Level 2 technology  will  be
                 as  a minimum to achieve these low concentrations.   The
       effectiveness oi: these  technologies can be enhanced  by  addition
            locculaHng  aaents Prior to clarification and bythe use of
                 ? Urmedria ^tration  (as  opposed  to  filter  press
                 )   for  Level  2.    To illustrate the above,  plant FT 02
       practices  cadmium  recovery  followed   by   further   treatment
       consisting  of  pH adjustment,  clarification,  and sand  flltralion
       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
                  treatment   consists   of   alkalinp
                     °C  Settl^g-i  and  final  1-  adjustmen   of   the
                i  necessarv-  Sludges  generated  are  dewatered  in a
              P  !S  °r. c?"«cted and disposed of  in a hazardous waste
      t  r; /f rrt ofthe treatment system, a holding basin sized
      even? of tr^f^"^ of.infli;«nt is provided as a safeguard in  the

                    m
   i
followed
                            ?te? ^s the addition of caustic soda.  This
                           clarification/settling  (if  the  wastewater
      fclrif i     SUitable' a tub? Settl2r may  be  sJJStltSS
      tor  a  clarifier to conserve space .   Sludge is removed from the
      clanfier and directed to a filter press  for  dewatering    Pits
                    ^  the  filter Pres^ for thftempo^y s?orage ol
                   ??r?ge t? Peri°dicaliY transported  to  a  hazardous

                                                            tO the head
      aceDtabl    li           wastewater  stream  is  adjusted to an
      acceptable  level   by  acid  addition  prior  to   discharge   if
                      moitorin   Astern  is installed at the discharge
                                     ]  techn°10^ is  to  remove  heavy
           ^-^           Wa?  not  selected as the basis for BPT because
         provides   inadequate  removal   of  fine   suspended   cadmium
                                    195
_

-------
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

Treatment sludges for cadmium pigments generated by Level  1  are
dewatered  in a filter press.  The solids may be disposed of off-
                              196

-------
 site in a hazardous material landfill  or  sent  to  an  off-site
 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
             ranges.  and  wastewater  flow characteristics have been
           earlier  in this  section and  are  summarized in Table 11-
  :,,  lhere*rir  six  direct dischargers,  four indirect   dischargers,
 and  two plants which achieve  zero discharge.            ouu«y«rfi,,

 A.   Cadmium Pigments

 During development of the  model plant  characteristics,  only   data
 rSS-H   5®  £acilities. wnich  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 source!
 nfanrrh^ffr -T"e  COI?bined  for the purpose of defining  modi!
 S,,S  \- 5 K acteristics.   In fact, most  wastewater flow information
 supplied by  industry for pigment  plants  did  not   differentiate

                       *     fc       0   salts  production and  to
The model plant production rate  of  711  metric  tons  per  year
represents  the  average  production  for all discharging pigment

tin d™r;^JhV?del Pla^ Unit fl°W Of 92'4 cubic »2t2?s/S25ic
ton 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 fJSlUtiS
were "°t included in the computation, the average unit flow value
is greater than if zero discharge  (zero  unit  flow)  facilities
ODerate^f «n *M°8t  discha^ing  cadmium  pigment  facUitiS
««, ! S  ?        ay per year basis'  so the model plant was  also
assumed  to  operate  on a similar schedule.  The daily discharge
                              197

-------
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.)
     H2S04  (100%)
 445 kg/day
52.4 kg/day
(1)
(1)
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 169 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
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.)
     H2SO* (100%)
 0.12 kg/day
 0.014 kg/day
(1)
(1)
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.
                              198

-------
     TABLE 11-10.  WATER EFFLUENT TREATMENT COSTS AND RESULTING
                   WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
 SUBCATEGORY:  Cadmium Pigments  Subgroup
 ANNUAL PRODUCTION:	

 DAILY FLOW:	262

 PLANT AGE:
                711
                                            METRIC TONS
       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 Waste Disposal) 112 4   89
Residual Waste Disposal               2*7   0*3
                         COSTS ($1,000)  TO ATTAIN LEVEL

                         1234       5

                         23.0

                         168.6  29.4
                         38.3   5.9
                         34.5   5.3
                         26.4   4.1


                         290.8  44.7

                         47.3   7.3
  Total Annual Cost
               b.
                        162.4  16.5
Parameter

   pH
   TSS
   Cd
   Se
   Zn
       RESULTING WASTE-LOAD CHARACTERISTICS
                               •   Long-Terra Avg.
                               Concentration (mg/1)
„ „   «. , ,   ,                After Treatment To Level
Untreated(mg/11         12345
            Avg. Cone.
5-6
750
265
  8
  6.9
                                    6-9
                                    13
                                     4.3
                                     0.2
                                     0.26
                              6-9
                               9.3
                               0.076
                               0.2
                               0.04
                        c.   TREATMENT DESCRIPTION
                                199

-------
     TABLE 11-11.   WATER EFFLUENT TREATMENT COSTS AND  RESULTING
                   WASTE-LOAD CHARACTERISTICS  FOR MODEL  PLANT
 SUBGATEGORY:   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 Waste Disposal) 4.1
 Residual Waste  Disposal

                                    4.7    0.1

                    RESULTING WASTE-LOAD CHARACTERISTICS
                                              Long-Term Avg.
                                           Concentration  (mg/1)
                                         After Treatment To Level
                         m         1.2      3      4      5
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


Parameter
PH
TSS
Cd
Se
Zn
b . RES
Avg. Cone.
Untreated (
5-6
750
265
8
6.9
6-9
13
4.3
0.2
0.26
6-9
9.3
0.076
0.2
0.04
                        c.  TREATMENT DESCRIPTION
LEVEL 1:  Alkaline precipitation, clarification,  pH adjustment
LEVEL 2:  Filtration
                                200

-------
 incremental to Level  l .                  COSt  of  Levgl  2  is
 Basis for Regulations
 Basis for BPT Limitations
 A.   Technology Basis
                ,,»
Sir 1 -:£S
would not be affected        P   tS  have  "°
B.   Flow Basis
                                                and thus
C.   Selection of Pollutants to be Regulated
                        201

-------
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.   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  m'/kkg for  cadmium pigments  and 0.058
mVkkg for cadmium salts.

BPT  limitations,   which   apply   to    all   process   wastewater.
discharged,  are  presented in Table 11-V2  (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

          Since no long-term monitoring data for TSS is available
          from   any   cadmium   pigments   or   cadmium    salts
          manufacturing  plant,  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 .
                              202

-------
                                                   USe the same Level 2
                for frh   *  •               contro1 TSS that is proposed




                for  plants employing filtration.   Variability factorS
                                                              -
               30-dav average;
                 mVkkg)
               24-hour maximum;
                                                   (1000
                                                  (100° 1/m3)
               Similarly, for the cadmium salts segment:

               30-dav average.


                                                    (100°
               24-hour max imum :
                                                    (1000


     2.    Toxic  Pollutants


          a.   Cadmium














                                                        respectively.
                                                        Lons  for  the
                                                       follows:
30-day average;
(0.15 mg/l)(92.4
                                      )  (kg/10« mg) (TOOO
                                  203
_

-------
     * 0.014 kg/kkg

     24-hour maximum;
     (0.46 mg/l)(92.4 mVkkg) (kg/10* mg) (1000
     = 0.043 kg/kkg

     Similarly, for the cadmium salts segment:

     30-day average;
     (0.15 mg/l)(0.058 mVkkg) (kg/10« mg) (1000 1/m')
      = 0.0000087 kg/kkg

     24-hour maximum;
     (0.46 mg/l)(0.058 mVkkg) (kg/10« mg) (1000 1/m3)
     « 0.000027 kg/kkg
b.   Selenium
     The  BPT  limitations  for  selenium  are  based   upon
     screening and verification sampling at Plant F102 since
     no   plant  could  be  found  with  long-term  effluent
     monitoring   data   for   selenium.    Screening    and
     verification  data from plant F134 was 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/m*)
     = 0.037 kg/kkg

     24-hour maximum;
     (1.2 mg/1) (92.4 mVkkg) (kg/10« mg) (1000 1/m*)
     =0.11 kg/kkg

     Similarly, for cadmium salts:

     30-day average;
     (0.4 mg/1) (0.058 mVkkg) (kg/10«) (1000 1/m*)
     = 0.000023 kg/kkg

     24-hour maximum:
                         204

-------
                 TABLE 11-12.  BPT EFFLUENT LIMITATIONS FOR
                               CADMIUM PIGMENTS
Conventional
Pollutants
TSS
    (4)
Toxic
Pollutants
Cadmium

Selenium

Zinc
Long-Term
Avg.(mq/11
9.3
   (U
0.076(2)

0.2(3)

0.04(2)
                                 VFR
                               1.8/3.0.
        (ID
                                             Cone.  Basis
                                                (mq/1)
             30-day
              avg.
                           17
24-hr,
 max.


28
2/6(2)       0.15    0.46

2/6(2)       o.4     1.2

1.67/3.0(2)   0.067   0.12
                                           Effluent Limit
                                              (kg/kkg)
30-day
 avg.
                             1.57
24-hr.
 max.
                                                                    2.59
        0.014   0.043

        0.037   0.11

        0.0062   0.011
VFR - Variability Factor Ratio

(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.
                                205

-------
          TABLE 11-13.    BPT EFFLUENT LIMITATIONS FOR CADMIUM  SALTS
 Conventional
 Pollutants
Long-Term
Avg.
  VFR
           Cone. Basis   Effluent  Limit
                (mg/1)	Ckg/kkg)
           3u-day z'4-hr. 30-day  24-hr.
                                            avg.
                                   max.
                          avg.
                                                                  max.
 TSS
    (4)
 Toxic
 Pollutants
Cadmium

Selenium *• '
9.3CD
0.076*-2)

0 2C3)
\f • Lt

0.04
1.8/3.0^)  17
                                                  28
                                         0.001
                0.0016
                                2/6

                                2/6
                   (2)

                   (2)
            0.15

            0.4
0.46  0.0000087  0.000027

1.2   0.000023   0.000070
                                       ,C2)
                1.67/3.01 J 0.067  0.12  0.0000039  0.0000070
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.
                                 206

-------
(k9/'°*
                                                (100°
       c.    Zinc
            concentfauon   for   "nc^o?9  0  04  IST^S   .'*•"*
            factors   deveiopld  fS^inSVthlt p?ak werfllj'"
           30-dav average;

            0°
                                                ('°00
           2 4 -hour max imum
           Similarly, for the cadmium salts segment

           30-dav average;
           24-hour maximum;
Basis  for BCT  Effluent Limitations


EPA  is not prooosina an        <-  •
TSS under BCT  since we haveTLn^f "gfnt  limitations than BPT  for
would  remove additional amounts of JS? "^     technology  which
is equal to the BPT llmitationl.          S * r€SUlt' BCT for  TSS

Basis for BAT Effluent Limitations

Application of Advanced Level Treatment
                              207

-------
          TABLE 11-14.   BAT EFFLUENT LIMITATIONS FOR CADMIUM PIGMENTS
                            AND SALTS SUBCATEGORY
a.   Cadmium Pigments (Flow basis 92.4 m3/kkg)
                                            Concentration
                                                (mg/1)
 Effluent
Limitations
Toxic
Pollutants
Cadmium
Selenium
Zinc
L.T.A.
(mg/1)
0.076
0.2
0.04
VFR
2/6
2/6
1.67/3.0
30-day
avg.
0.15
0.4
0.067
24-hr.
max.
0.46
1.2
0.12
30-day
avg.
0.014
0.037
0.0062
24-hr.
max.
0.043
0.11
0.011
b-  Cadmium  Salts  (Flow basis  0.058  mVkkg)
Cadmium
Selenium
Zinc
0.076
0.2
0.04
2/6
2/6
1.67/3.0
                                            0.15     0.46  0.0000087  0.000027

                                            0.4      1.2   0.000023   0.000070

                                            0.067    0.12  0.0000039  0.0000070
L.T.A. * Long-terra average achievable  level.

VFR s Variability  Factor   Ratio;  ratio   of  the  30-day  average
      variability factor to the 24-hour maximum variability factor.
                                  208

-------
 For  BAT,   the Agency  is proposing  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
 proposed  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  proposing  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
 listed in Table 11-12  (cadmium  pigments) and Table 11-13 (cadmium
 salts).

Basis for Pretreatment Standards

 The  Agency  is  proposing  PSES  and   PSNS that are equal  to BAT
 limitations because  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.
                              209

-------
  Using  the  summary data presented in Tahi<=  11 in  4-u  *







           Cadmium;   Raw Waste = 265  mg/1
                     BAT       = 0.076 mg/1


                  Percent Removal =  [ (265-0. 076)•*( 265) 1 (100)
                                 "  99.97%

           Selenium;  Raw Waste = 8  mg/1
                     BAT       =0.2 mg/1

                  Percent Removal =  [(8-0.2)*(8)](100)
                                 =  97.5%

           ZiH£s      Raw Waste =6.9 mg/1
                     BAT       =0.04 mg/1


                 Percent Removal  =  I (6.9-0.04M6.9) ] (100)
                                 » 99.4%
       i^iiSrK^ts.'Ssss,?1 s/srs tS pSsriM
 study for other toxic metals ranged from  19% to 66%.  We  pres^l
      sSle?luln  removals are in that range.  Therefore  siSce th»
Existing Sources

There are currently four indirect  discharger cadmium pigments and

                      b Ca'°r   F°r  «m         lor
New Sources
                            210

-------
    -    K ??n?!?t standards for New Sources  (PSNS), the Agency  is
  M^l^tations based on NSPS.  Since NSPS is equal  to  BAT,
Table  ll-i2  (cadmium  pigments) and Table  11-13 (cadmium salts

                            £or  the
                             211

-------
                           SECTION 11

                           REFERENCES
1.    Kirk and Othmer, Encyclopedia of Chemical Technology, Wiley-
     Interscience, 3rd ed., Vol. 4, pp 397-411, (1978).

2.    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.

3.    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.
                              212

-------
                           SECTION 12


                       COBALT SALTS INDUSTRY
 INDUSTRIAL PROFILE

 General  Description

 The  cobalt  salts  considered  in  this  subcateqorv  are cobalf
 chloride,  cobalt nitrate, and  cobalt  sulfate    Each  lilt   has

             i??11^1^ how?ver many uses are «~» £ *» s;
             ind* in  fhhreS SaJtS.are  USed  as  Catalysts,   soil
 salts ha™ f« «*      *e ..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

                                                        *  *
 Table  12-1 presents the industry profile for cobalt  salts.
wastewater flow as a function of unit  production  is ve?y low

General Process Description and Raw Materials
hdrhi-    af?  Prod"ced by reacting  cobalt metal with either
hydrochloric, sulfuric,  or nitric  acid.   The  reactions  for  the

formation of the cobalt  salts under  consideration arl?

     Co + 2HC1 - CoCl2 + H2


     Co + H2S04'= CoS04  + Hj,


     Co + 2HN03 = Co(N03)2 + H2



                             Sid.)"*  Pr°d"~d  b^«°»P°^tion


The production of a  cobalt salt  is a batch process consistino  of
step
                       a:
             chemical addition and filtration may be SecessSry
                             213

-------
      TABLE 12-1.   SUBCATEGORY PROFILE &&TA FOR ©SHALT
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
>4@
19 m 3/3 ay
5
3
2
                            214

-------
         WATER USE AND WASTEWATER SOURCES

         Water Use
        Wastewater Sources
        Noncontact Cooling Water

                           "

        Direct Process Contact
                                              cto
                                      215
_

-------
o
=1
•o
o
                                            W
                                            I
3 2
O t«
« ^
T

U
01
4J J3
> 5 "*"
U
CO |
*TJ
2
§ §
O 0)
•O W
0 C§
A


•3J
u XI
C^, J*
0)^ 	 3 <^
y Vi
to 01
U «^
<3 -^
O
•H C4/^ ^




M
OJ
^ AJ
J § 3
^ ^ O &0
~ u G
•J. ^ 	 en fl
' 1
U
	 -a y
•H 3
^" UJ VJ
•H U
h-i CM
t-4
to n) o>
•aw r-i
^^ -H o »-i y
on y
W -H 0)
Q Crf





                                            erf
                                            o
                                            w
                                            H
                                            £

                                            I
                                             U
                                             n
                                             3
                                             o
                                             d
                                             o
                                             H
                                             si

                                             §
                                             erf
                                             g
                                             3
                                             Cft
                                             en
                                             u
                                             o
                                             CM
                                             N
                                             W
                                             Z
                                             td
                                             O
   216

-------
     TABLE  12-2.  WATER USAGE AT COBALT  SALTS FACILITIES


                           Flow (mVkkg 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
                              217

-------
   TABLE 12-3.  WASTEWATER FLOW AT COBALT SALTS FACILITIES(D


                            Flow (m3/kkg of  Cobalt Salts)
WASTEWATER SOURCE
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
F117(2) F117(3)
0 0
0 0
0.083 NA
0^ QC4)
 TOTAL PROCESS
 WASTEWATER DISCHARED
0.083
 Noncontact
 Cooling

 Noncontact
 Ancillary
 NA   Plow volume  not  available.
 	   No information.


 (1)   Values   indicated  only  for   those  plants   that   reported
      separate and complete  information.                      p«"eu
 (2)   Cobalt Chloride.
 (3)   Cobalt Sulfate.
 (4)  Wastewater recycled within plant.
Source:  Section 308 Questionnaires and Plant Visit Reports
                              218

-------
 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  sampll
 wastewater streams associated with cobalt salt production.
plant
                                                          tO those
 At Plant Fl 19 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-
 fs311™? £°  8'7 I*?:0 with. Caustic.   The  neutralized  wastewater
 aL ??«£ ^  *> Set"in9 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
 ifnrfSrLiS?  \  siudge  hol<3ing  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
Plant  F113  produces  cobalt  chloride  and  cobalt  sulfate.  All
process wastewater  is discharged   to  a  POTW without   treatment
except neutralization.
          1c  produces  cobalt chloride, cobalt nitrate and  cobalt
™*    K?epa^ate t'i;eatment systems are provided  for  both  the
cobalt  chloride  and  cobalt  nitrate processes.  Each treatment
system consists of caustic addition (to  pH   10)  and  filtration

                                                  SUlfate
Plant F107 produces cobalt nitrate as well as other metal  salts.
All process wastewater is discharged to a POTW without treatment.
 hni«IJ8  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
                              219

-------
 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 F124 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 FT39 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
                              220

-------
 Process Modifications and Technology Transfer Options


 2L.J?™"1/  ai^ie _?^c?ss_.wastewater  is  generated  in this
      1.
      2.
                                                      back into
Minimizing product changes by careful product
scheduling and by increasing the number of reactors.
      1.



      2.
                 lime) may be advantageous when used as
             wastewater  treatment  for  the  following


             reduces or eliminates the problem of scale
                                               reaction   time
Caustic  soda  treatment  results  in   a
reduction in sludge volume; and
                                                      significant
                       contfins  high.  concentrations   of . the

                                  WhiCh   may  be  "claimed  and
Best Management Practices
recycle.   To  implement  this  technology,  rwcle  olilno

                              221

-------
 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    1    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
                              222

-------
or  equivalent  treatment technology.
                                        Two additional plants have


                                                       not   incur
 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

 SS^S?  f11^-?!;888^8 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

 S?SSlSeS l!,filte?ed prior to  PH Adjustment (if necessary)  and
 discharged.   All  equipment is conventional  and readily available.


 B.    Chemical Handling
        soda<50 Pfrcent  NaOH)   is  used   to  precipitate   heavy

  d    fi£  »eV?\l'  Sujfuric 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

                      "**  be disP°sed of off-site in a hazardous
                      or   sent    to    an   off-site   cobalt

                           ion.   Level  2  filter backwash may  be

                K      uplant or' if the solids concentration   is
             high, may be sent directly to  the filter press.


Treatment Cost Estimates


General
n™«n,   ran«es. 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  providina

separate and complete production data is 358 metric tons per yea?

nr«v^L3Vera?e 2? "5 operating days per year.  Only  one  plant
provided  relieable  flow  data  but  that  flow data is believed

rh£^SrtatiVS  °f- °°balt  salts  Production  based  on  process
chemistry  and engineering visits to six plants by the Agency and
                              223

-------
        TABLE 12-4.  WATER EFFLUENT TKfcATMENT COSTS AND RESULTING
                     WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT


   SUBCATEGORY:   Cobalt Salts
   ANNUAL PRODUCTION: 	

   DAILY FLOW: 	p.26

   PLANT AGE:
                 358
               METRIC  TONS
       NA
	 CUBIC METERS

 YEARS   PLANT LOCATION:
                                                            NA
              a.
   COST CATEGORY
    COST OF TREATMENT TO ATTAIN  SPECIFIED  LEVELS


                         COSTS  ($1,000)  TO ATTAIN LEVEL

                         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 Waste Disposal) 6.0
  Residual Waste Disposal             - -
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
                 b.
                        8.6
                0.3
       RESULTING WASTE-LOAD CHARACTERISTICS

Avg. Cone.
Parameter     Untreated (mg/1)
pH
TSS
Co
Cu
Ni
5-8
290
4,000
5'
5
                   Long-Term Avg.
                Concentration (mg/1)
              After Treatment To Level
                2345
                                     6-9
                                      13
                                       1.3
                                       0.96
                                       0.96
                              6-9
                               9.3
                               0.97
                               0.69
                               0.69
                          c.   TREATMENT DESCRIPTION


  LEVEL 1:  Alkaline precipitation,  clarification, pH adjustment
  LEVEL 2:  Filtration
                                  224

-------
      Material usage  for both  levels was  estimated  as  follows:

      Chemical                   Amount       Treatment'
 NaOH  (50 percent sol.)
 H2SO« (100 percent)
           Level

             1
             2
3.3 kg/day
0.05 kg/day
                                                      (1)
                                                      (1)
                          Solid Waste

                            0.024
                            0.00004
 Basis for Regulation

 Basis for BPT Limitations

 A.    Technology  Basis









B.    Flow Basis
               sub                               c°*ts,  for  the
representative of the group.       ° /kkg  W3S  sele^ted as being
C.
Selection of Pollutants to be Regulated
                              225

-------
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  inplace 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 0.083m3/kkg.
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
                              226

-------
          Guidelines  for  Phase  I  Inorganic
          1)  and  the  JRB  study  (Ref.  2).
                                        Chemicals  (Ref
     b.   TSS
2.
      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
      proposed  BPT  for  the cobalt   salts  subcategory.
      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  Phase II 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   tb^sc  values,  one
      obtains TSS mass limitation;, ..or  the cobalt  salts
      subcategory of:

      30-day  average;

      (17 mg/1 )(0.083mVkkgHkg/10«  mgHlOOO  l/m*)
      = 0.0014  kg/kkg

      24-hour- maximum   , <.

      (28 mg/1 )(0.083mVkkg)( kg/10«  mg)(1000  l/m*)
      • 0.0023 kg/kkg

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.
     Thus,  utilizing these values, mass limitations may
     be obtained as follows:
                         227

-------
          30-day average;

          (1.4 mg/1)(0.083mVkkg)(kg/1 0« mg)(1000 1/m')
          = 0.00012 kg/kkg

          24-hour maximum;

          (3.6 mg/1 )(0.083mVkkg) (kg/1 6* 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  treat-  ability  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 thes
          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  a  24-hour  maximum.   Using  these
          figures,  the  corresponding copper concentrations
          are 1.0  and  3.3  mg/1  respectively.   Utilizing
          these  figures,  mass  limitations  for copper are
          calculated as follows:

          30-day average;

          (1.0 mg/1) (0.083mVkkgXkg/10* mg)(1000 l/m*)
          = 0.000083 kg/kkg

          24-hour maximum;
                         228

-------
             TABLE 12-5.   BPT EFFLUENT LIMITATIONS FOR COBALT SALTS
 Conventional
 Pollutants
             Long-Term
             Avg.(mq/1)
 TSS1
.(3)
              9.3
 Non-Convent i onal
 Pollutants
      .(4)
 Cobalt
Toxic
Pollutants

Copper^)
Nickel'-4-'
             0.97(2)
             0.69C2)
             0.69(2)
                                  VFR
                               1.8/3.0
        (1)
               Cone.  Basis
                  (mg/1)
              30-day   24-hr,
               avg.     max.
                                         17
                               1.44/3.75(2)   1.4
1.5.2/4,83(2)  1.0
1.52/4.83(2)  i.o
                      28
        Effluent Limit
           (kg/kkg) 	
        30-day  24-hr.
         avg.     max.
        0.0014    0.0023
                                                  3.6     0.00012  0.0003
3.3    0.000083  0.00027
3.3    0.000083  0.00027
LTA - Long-term average achievable level.

VFR - Variability Factor Ratio (30-day avK./24-hr, max.)

(1) Bas^d 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.
                               229

-------
                (3.3 mg/l)(0.083 mVkkg) (kg/10« mg)(1000 1/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/10« mg)(1000 1/m')
                *  0.000083  kg/kkg

                24-hour maximum;

                (3.3 mg/l)(0.083 mVkkg) (kg/1 0« mg)(1000 1/m')
                (-  0.00027  kg/kkg

Basis for  BCT Effluent Limitations

EPA is not proposing more  stringent limitations for TSS under  BCT
since we   identified  no  other  technology  which  would remove
significant  additional  amounts of TSS.  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 proposing 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 by  the
proposed 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
                              230

-------
 necessary,  is used for BAT which  is  the same technology used  for
 B.    Flow Basis
                                                           SB
                                           °f
 C.   Selection of Pollutants to be Regulated

     Toxic Pollutants

 *nn n?n-c?™entional pollutant cobalt,  and
 and nickel have been selected at the  same
 and  loadings  proposed  for  BPT.    Table
 limitations for Cobalt Salts Subcategory

 Basis for NSPS Effluent Limitations







Basis for Pretreatment Standards
           iS Pr°P°sin9  pSES and  PSNS  that  are  equal
                                                             BAT
             has
o^r'T" ""^  raw  waste   concentrations  for  the  cobalt  c?aifo
                             231

-------
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)] t  (4000)]  (100)
                          -  99.98%

          Copper t   Raw waste « 5 mg/1
                         BAT =0.69 mg/1

          Percent Removal =  [(5 - 0.69) t  (5)]  (100)
                          =  86.2%

          Nickel;   Raw waste = 5 mg/1
                         BAT « 0.69 mg/1

          Percent Removal =  [(5 - 0.69) t  (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  "40
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
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.  Therefore,  since
BAT  technology   achieves   a greater  percent removal  of cobalt,
copper, and nickel than is  achieved  by a  well operated  POTW  with
                               232

-------
                                      metalswould pass
     Existing Sources




     New Sources

                         ^^
                                 233
.

-------
                      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,  Inc.,  "An  Assessment  of  pH  Control  of
ProceS  tier's  in  Selected  Plants,"  Draft Report to the
Office of  Water  Programs,  U.S.  Environmental  Protection
Agency,  1979.
                           234

-------
                           SECTION 13

                      COPPER SALTS INDUSTRY
INDUSTRIAL PROFILE

General Description

The copper salts included in this subcategory are copper sulfate,
copper  chloride,  copper  carbonate,  copper nitrate, and copper
iodide.   These  compounds  are  produced  by  several  different
processes.

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
acid:

          Cu + H2 S04 = CuSO* + H2

The copper 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 copper
salts included in this subcategory.

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 denitration of cellulose> and  for
many  other  applications.   The other form of copper chloride is
cupric chloride, produced as  an  intermediate  in  some  cuprous
chloride   processes.    Cupric   chloride   (CuClz)   has   many
applications such as a catalyst in a number of organic  oxidation
reactions, in sweetening petroleum oils, a wood preservative, and
in  other uses.  Both 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  electroplating
                              235

-------
      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

Types of Wastewater Discharge
          Direct
          Indirect
          Zero
    15

>3000 kkg/yr
   <4.5 kkg/yr
  640 kkg/yr

~2000 m3/day
    0
 1060 n»3/day
    4
    5
    6
                              236

-------
TABLE 13-1.
      (b)
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       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
     Chemical Producers, 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  Proposed
     Revised  Effluent Guidelines  and  Standards  for the Inorganic
     Chemicals Industry," March,  1980.
                            237

-------
 industry as a source of copper, and agriculturally as a fungicide
 for treating seed.

 Copper  nitrate  (Cu(N02)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  (CuCl,)
 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 C1
                    CuCl
     Cu + C12 = CuCl2

     CuCl 2 + 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 .
                              238

-------
                     o
                    •a

                     o
        o
       • 3
        •o
        o
        14
       ft-
                    0)
                   43
                   43
                   O
                   CO
                  I
       •a
       c
      O
                                   (U
                                  .g
                                   10
                  W
                  CO
                       
                 M
                 01
                 U
                CO
                                  a>
                                  U
     c
     1-1
  CO
  0
  a
 01
 y
                             01
                             C
l-i
O
                            43
                            O
                                 0) t
                                 a.
                                 O  01

*j
B<




u
«<
0»^»
>






4J

>
CO
a
0
y
Solution Prt
e
•o
0
i-i
_ »
A
3 ^
O
CO _

t__

u
0)
43
3 < "
U
CO



4
B ;
§ c
TJ . 	 .
I *
i-l
«
1.
0
•i-
u-
-— -H
1 £
* < /!
u
CO
~~~^OI
" — 5, Vi
fl3 ^ O
s 2
y
»H d)
33
01
a

c. ^J
01 x ^
M' "^ o p
Q h
' 1


o» a) w
N W Q
•H m M
^ S o
2 5 £ g
5 a- < 3 «
i o a
o o
>r 4J U
•o y oj
-i. Tl 3 O
— o- 'o fa
1) T3 01 ^
u -H 4J M
H 	 ^»H w 0
"* ° ™ &
* co s g
I
CO
CO
H
U
§
< ft<
§
N
M
h4
2
M
Z
W
o
•
•H
l-l
3
M

                                                                                         O,
                                                                                         o
                                                  239

-------
                          w
                          c-l

240

-------
                   c
                   a
                   o
                  •o
  e
  Of
XI
 a
                  o
                 CO
 4)
 X
 fe
a
                 c
                 3
                 O
                T3
c
                Jj
                (U
                U
               co
                                                               o
                                                           5*.  3
                                                           O O
                                                              M
                                                              a,
                       l-c
                       «
                       N
                                        (0
                                        4J

                                        0)
                a)
               u
                a
                                       60
                                       C
                                      o
                                      o
                                      U
I
                        o
                       •a
                        2
                                                                tr
                                       o
                                       4J
               o
              •a
              eg
     CO
    r-l
     U
     X
     o
     o
    Bt
                                                       e
                                                     •a
                                                       
-------
                                          U
                                          9
                                          •a
                                          o
                  o
                 •a
                I
                  0)
                 .0
                  O
                 CO
                                          0)
                                          >»
                                          M
                                         Q
 t:
 CT
                 o
                 •o
 M


1
 Vl
 
-------
           sr
     CuS04 + Na2C03 = CuC03 + NazS04



     Cu(N03)2 + NazC03 = CuCO, + 2NaN03
copper arei



    3Cu * S HNO, . 3Cu{NOj)2 t 2NO * 4H,0



    Cu * 4HNO, . Cu(NO,)2 + 2H20 + 2NOZ
                                     .
                           general  reactions  for pure
is  rS^'^-^'-jrdis^1  L^i1?^"^ ^s"
general diagram for the SodSrtlS^f copPerrMtra;l.PreSentS the


S5?tloifi2, 1'B"a»~d * two  "«"*•   The  genera!
   CuS04 + 2KI = Cul



   2Cu + I2 = 2CuI
                        0.5I
                      243

-------
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
noncontact 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
                              244

-------












r-l
W
W
hH
E->
+•4
»4
M
g
in
s
<
CO
«
w
cu
Ch
O
o
£4
s
•M
s
W
^
CJ
EH
g

•
04
1
n
*H
TABLE



















^^
10
JJ
,— I
18
to
J- 0
Ol »*H
a u
Cu 18
o c
O CT

C
•H 01
^ CO
O (0 a,
3 § 8 §
S § * § 3 ^
2 Sw |{- I ^2 8&
c -u o So S "o S £ J3
8 83 ^5 ^ *s g^
S K C TD C .5 u 2 e M
o —  ^
H ' .*4
•» .2
5' >
•" u
c
« fl
— **
S o-
18
•H M
Ul c
«, «
0 S.
5 S
« 0 ' g'
2 "" o
* >. S
1 3 1
<« -a 01' . a
aj e S « Oi-oo
•WC •U18«fngJ ^
go I8COI--44.! m
e 7* OO-OU18
„, tJ -H J3 -rt O K C
ul (Q *U LJ t3 t-4 4J ft
g B C 18 O X -H ."
= g -HO-HOC 4J
>C 0)0)OIO>O) U)
3 i-4 04 Q, a. O,
o in o o o o
rja >uooo oi
w o
g| id--- o
245

-------
                   b
                   b
                                           rt      •»
w
u
                                                                                                a
        u
u

8
                                                                                               •o
V
                   b.
        b
                  b
rH C   rH C
rH 3   rH 3
 <0 O    10 O

W 5   W if
                                                                                                            *•
                                                                                               a
                  b

                  b
rH C    i-H C
rH 3    i-H 3
10 O    10 O
si    si
S
                          BJ      4J
                            JJ    0 4J
                          oj u    a)  o
                          o la    u  10
                          0) 4J    -H 4J
                         .ri  o
                                  CO
                             1

                             I
                          W M
                          co a
                          w
                          CJ
RO
ER
                          DO    MCJ
             o .a
                                               •H o
                                               < co
P
A
                                                            «C H
C
                                                                       o    o
                                                                                    4JC
                                                                                    OO
                                                                                    g E
                                                                                    3U
                                                                                    •HO
                                                                                    Ou-i

                                                                                    ft, \
4J 10   . fj 0)  O
ro c  ID .^ jj  ni
o O  'o u ro  u
•rl J3  —I O VI
•O VI  "O rH 4J  VI
c ro  o j= —i  a)
•rl U  -H U C -U
              re
CO VI  VI VI VI  2


•H a a a. a  w
10 o  o o o  re
> u  u u u S
                                                     246

-------
  The  direct   contact  water

  ESS-ASS- 2! S
  whil. refining solut?ons
  Noncontact Ancillary
  Indirect  Process Contact
                          m?l°
 most copper  salts    incln
-------
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
contract  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.

During  the  sampling episode the pump seals were not  leaking  and
water wa's 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
water is used as direct  contact water   in dissolving,   reacting,
and  filter washing.  Noncontact cooling  water  is not  used  in  the
                               248

-------
HC1
I
£

Spent cop
'lating
u n i
olution HCJL
1 \\
Tank

— ^
per
Wa
' \
Tank
ter
	 	 ^.
                                              Liquid
                                              Cuprous  Chloride
    Recycled  ^
   to Process
    Pump 5>eal Leaks-

    Maintenance, 	
    Washdowns
Wastewater
   Tank® #4
   Sump
                         City Water
      = Sampling Point
   FIGURE 13-5.  PROCESS AND  SAMPLING LOCATIONS FOR PLANT F130.
                        249

-------





CO
X
W


Tl
a
as



•~>. c
O Tl
t>o oo
« a
n jt
o u
OJ b
A

U
B
•H
U
X
U


«
a
rH
T<
,

h
0)
Tl
tb


B
a
u H
01
w -a
rt 0)
•H U

/ ^


Reactor
«n
r o <
U 1
a
JJ kl Q) U
"•» s u u u
a u OB
V JC U
a -H u a
u i-i ao>
" < o OH
1 X
1 ;i,
Y
u a.
« B
1 "
™ /k /k
in PI
u h
0] Q)
O O

-1-1
O i-l h H
C Tl 0) (11
9 a B B
o m _^ u a)
x a o u
m jt TI Ti
« « JC X
30) H 1 H

Wen V\ / \ o
ya\ / s^o
0 li . / oo
0) IM O \ / «W C
UBS MM y bk
a a u o OK a) &
n ._ 3 u TJ -e
	 u-* o to BO BC
•HM>. 3U >i S*
•H > «
fa ^
o
1-1
<44
b
U
>
O
^
> J«
•aw B
Q) TJ CO
4J O 00
aw- -a c
t/1 a) T|
1W 4J
a u
CQ CO
J
^

AJ
s ~<
o
0)
a
0)
u
a
3
a
OS
3
J
d
a
E
                                  B

                                  Tl

                                  O
                                  00

                                  (3
                                  a
                                  e
                                 (0

                                  i
250

-------

3
to
n
HI
EH
HI
lJ
HI
2

CO
EH
if
to
I
Ok
8
p
5
I
(0
0!
£
to
0
s

Q
5
•^
CO
§
H
p
i
u
EH
L3-4. POLLUTAN
^n


frn
1
EH



e
N





to





ft



1 d
|| S
i*



55
u





to
to




tream
ascription
CO Q




10 •
« o
CO
01
tt
o
•s
1-
03
U


0>
a
o
u




f
»"
4.
C
II
s














in o M ^T
t~O (M in«N »?
wo wo ^ o .1
00 00 00 C
• • • • • • e
o o oo o o ,5
—
u
^ — W
o <• m .5
t-- HN 05
0»H r*0 OrH g
e\o oo MO S.
. . . . . . Jr*
OO OO O O ,j


rH O
OI f CA
rH ^» f»,
er» rH *»i o in o
in O rHO rH O O
• • . • . . ft
O O OO O O r-
fc
0 00 00 C
w tn -v a
i- r* o m r-
CO O HO CO O Qj
«n o oo HO
• . . . * .
O O O O O O


in en f*i
^'l "S* !"•• *n* ^3 \^
• . . • . *
crt c4 rH tn r^- in
d w o
H H H




in f"» G\ H Gf\ r*«
• . . . . .
T M o w in eft
** eo co
H H H
CO v
CO o
vo in . m
r- o H ! MO
00 0 i HO
^ O O (*) O


f» CO

ro o vo . f>o
CO O O ! OO
•w o o i r~ o
o o o o o


r- o
in n
in co o
MO O 00
r~ o c-> i en p
in o M o o

m in
m M
o in . HO
£0 2; wo
••> O O ! MO
. * •• . •
OO 0 OO

ro
4* m
en ro o * co o
• • . t . «
HO o ! r- o
mo in
ro ci



!*• in
f> CO
t- o in ( t- o
r- o o i m o
f) CO
V
u
o! ft> c
Jj M 5
** «v Q
* rA ?. *" 0>
? 0) 0» £ c
S 2> *j m 43
w 5 w * "°
» w *w e — «
n s n oi u *~ a)
S u ^B Q W «
Sgw'o* -o*™^.
O O A! 01 01 C 0) tt-m
U jH 

1
0)
u
0)
X!
S
4J
a
01
u
M
01
n
>t
10
•o
C 01
O 0)
•_J *_1
cient informat:
values for thi
sampling.
d to process.
-I 0> >ifl)
 (8 iH
o O
9 u | >,
m o> oi u
c > c oi
HI < O «

1 ^^ ^^ ^^
                                    251
_

-------
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 F127.  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
described.  Off- gases from the  copper  nitrate  production  are
exhausted though a condenser to recover nitric acid, and the off-
                              252

-------
                        t0
ca-rbonat

                                    destr°y nitrogen oxides before

                                          cotlecteTin
 previously   described   process.    Wastwater  from  all   cheical
 processes   are   combined   and  passed   through a treatment svstem
 consisting  of equalization,  alkaline precipitation! SrtUinS  and
 final pH adjustment  before discharge to surface waters?
Th=nt Pfoduces cuprous chloride and other  inorganic  salts
The manufacturing process  is similar to the previously   described

of°CcoDt>er0r,n,?»?dUCi29 "£lte? CUprous M°'**° from  the reScuIn
of  copper  metal  and  chlorine.   All  contact   and noncontact

                                                          '
faci
 wastewater
                       pretreated prior to discharge to  a  POTW

                              253

-------
process  wastewater   streams  when  visited.   Since  the  lagoons  are
unlined, 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.
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 (uq/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

Section 5  of  this
sampling  program.
report  describes  the  methodology  of  the
In  the Copper Salts Subcategory, a total of
                              254

-------
    TABLE 13-5.
                                                DATA FOR SAMPLED
          Average Daily Pollutant Concentrations and Loads

                                            mg/1
kg/kkg
Plant Designation
Pollutant
Antimony

Arsenic

Chromium
Copper

Lead

Nickel

Selenium
Silver
Thallium
Zinc

F130(D
	 	 	 ,
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
	 	 	 • 	 	 	
F127C2)
— — — — — — — .
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
w • -t W *•
0.00276
0.134
0.00135
229.167
2.99
2.947
0.00668
0.267
** • *• w »
0.00481
<0.037
<0.0018
0.04-1
0.00071
<0.073
<0.0011
3.556
0.00463
(1)   Data from three daily grab samples,
(2)   Copper carbonate wastewater.
Cuprous chloride wastewater.
                             255

-------
 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.

P1fntV  F132 Prod"ces 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,
                              256

-------
and filtration.
air scrubber.
                  These treated wastewaters are  recycled  to  the
 ---"" -,".      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.                              .             y

 Process Modifications and Technology Transfer Options

 9ne 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  8r-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
 riitration) 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:

           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.

As shown on Table   13-3,  all  four   plants   with   scrubbers   are
£f™H"g theuscrubber water.  Product scheduling  is  a management
perogative subject  to customer demands.  Consequently, the Agency
     1
                             257

-------
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  leaks,  spills,   and
washdowns should be contained and treated.

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
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.
                              258

-------

B.
Level 2


                             259

-------
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 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
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  in a hazardous
material  landfill 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
                               260

-------
                                 3.0 kg/day
                                 0.08 kg/day

            of  solid waste generated for both
            salts segment are provided below:
      Waste Source
                            ^Amount
      Level  1  sludge
      Level  2  sludge
                                0.0176  m*/day
                                0.0018  mVday


                                                         in   Table
Therefore, the Agency has combined
     cubic  meters  calculated  frSIhh. 3 ^? "astewater flow  of
unit flow of 0.94 mVkkg (as found =<• ™   Uy PJ°du=tion and the
an  operating   schedule^   o£   ?02      Per sulfate Plants) with
                                            «- I.  th.
     an   annual   production   of

                             a
                                                ^ea^ent
Chemical

NaOH (50 percent sol.)
H2SO« (100 percent sol.)
                             Amount

                             87.3 kg/day
                             29.1 kg/day
Level

1
1
                                                      levels  in
                             261


-------
      TABLE 13-6.  WATER EFFLUENT TREATMENT COSTS AND RESULTING
                   WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
 SUBCATEGORY:  Copper Salts Subgroup
 ANNUAL PRODUCTION:

 DAILY FLOW: 	

 PLANT AGE:
                             85.2
               METRIC  TONS
                       0.8
                     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 Waste Disposal)  6.3
 Residual Waste Disposal
                                      COSTS  ($1,000) TO ATTAIN LEVEL

                                      1      23      4      5

                                      0.7
6.6
1.5
1.3
1.0
11.1
1.8
6.3
0.7
0.4
0.1
0.1
0.1
0.7
0.1
0.2
0.1
   Total Annual Cost
                                      8.8
                0.4
                b.   RESULTING  WASTE-LOAD CHARACTERISTICS
                                               Long-Term  Avg.
             Avg. Cone.                      Concentration (mg/1)
                                         After  Treatment To Level
                                     12345
Parameter     Untreated(mg/1)
pH
TSS
Cu
Ni
2.5
225
1,175
51.2
                                    6-9
                                            6-9
                                       *     20
                                       1.2   0.89
                                       2.3   1.8
                        c.   TREATMENT DESCRIPTION


LEVEL  1:  Alkaline precipitation,  clarification, pH adjustment

LEVEL  2:  Filtration

*No performance data available for TSS  in this  subcagegory with  Level 1
 technology.
                                 262

-------
      TABLE  13-7.   WATER  EFFLUENT TREATMENT COSTS AND RESULTINf
                   WASTE-LOAD  CHARACTERISTICS FOR MODEL


SUBCATEGORY:  Copper Carbm.»t»

ANNUAL PRODUCTION:	155

DAILY FLOW:  	

PLANT AGE:
                                          METRIC TONS
                      291
                    NA
                              	 CUBIC METERS

                              YEARS   PLANT LOCATION:
                                                            NA
            a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
   COST CATEGORY

   Facilities
   Installed Equipment
                                     COSTS .($1,000) TO ATTAIN LEVEL
                                    1

                                   25.4

                                  163.7
                                   37.8
                                   34.0
                                   26.1
.Contractor Overhead and Profit
 Contingency
 Land

   Total  Invested  Capital

Annual Capital Recovery
Annual Operating and Maintenance
 (Excluding Residual Waste Disposal) 78 3
Residual Waste Disposal              J 9
                                     287.0

                                      46.7
                                             31.3
                                              6.3
                                              5.6
                                              4.3
                                          47.5

                                           7.7

                                           9.3
                                           0.1
    Total Annual Cost                17r  Q    .-  ,
                                     •i- £ 3 • ^7    Jl / « 1

                 b.  RESULTING WASTE-LOAD CHARACTERISTICS
              Ave  Conr                      ^  Long-Term Avg.
              *vg.  uonc.                    ^Concentration (mg/1)

Parameter     Untreatedfmc/ll          i
                                         Af|°r Trea.tment To Level
PH
TSS
Cu
Ni
                  2.5
               225
             1,175
                51.2
                                 6-9
                                   *
                                   1.2
                                   2.3
6-9
20
 0.89
 1.8
                       c.  TREATMENT DESCRIPTION
                 a available for TSS in this subcategory with


                                263

-------
 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,
 dewatenng  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  m3/kkg  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.                                                     w

 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,
consideration   of   the  raw  materials  used  in  the  process,
literature data,  historical  discharge  monitoring  reports  and
                              264

-------
 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,   average concentrations  of   arsenic at two
 copper   salts fsicilities   during  Phase    II    sampling   were
 approximately 0.1  ing/1.   Therefore,   arsenic was rejected as a
 regulated  pollutant.    Arsenic  was also  not  selected  as  a
 regulated pollutemt in Phase  I.

 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
                              265

-------
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 m'/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 mVkkgH kg/10* mgXlOOO l/m3)
               - 0.023 kg/kkg

               24-hour maximum;

               (73 mg/1) (0.94 m'/kkg)(kg/10« mg)OOOO 1/m*)
                              266

-------
2.
      =  0.069 kg/kkg


      2-   Copper Carbonate Segment

      30-day average;


      (24 mg/l)(58.1 mVkkg) (kg/10« mg)(1000 1/m')
      =1.4 kg/kkg


      24-hour maximum;


      (73 mg/1) (58.1 mVkkg)  (kg/10« mg)(1000 1/m*)
      =    4.2 kg/kkg

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  l  2
     and  3.6  were  used  to  compute the 30-day average
     and 24-hour  maximum values of  l.l  and  3.2  mg/1
     respectively.                                   *
     rno       ic  uvaiues'  mass limitations for the
     Copper   Salts   Subcategory  may  be  obtained   as
     follows?


     1 •    Copper  Salts Segment

     30-day  average;


                    mVkkg)(k9/10'  nig) (1000  1/m,)
    24-hour maximum;
    2'   Copper Carbonate Segment

    30-day average;


    (1.1 mg/1) (58.1 mVkkg) (kg/10* mg)(1000 1/m')
    = 0.064 kg/kkg
                   267

-------
     24-hour maximum;

     (3.2 mg/l)(58.1 m'/kkg)(kg/10«mg)(1000 l/m»)
     =0.19 kg/kkg
b.   Nickel
     The  BPT  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/l
     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/l)(0.94  mVkkg) (kg/10« mg)(1000  1/m')
     * 0.0020 kg/kkg

     24-hour maximum;

     •(6.4 mg/1) (0.94  mVkkg)(kg/10« mg)(1000  1/m3)
     - 0.0060 kg/kkg

     2.   Copper  Carbonate  Segment

     30-day  average;

      (2. l'mg/1) (58.1  mVkkg) (kg/10« mg)(1000  l/m*)
           0.12  kg/kkg

      24-hour maximum

      (6.4 mg/1) (58.1  mVkkg) (kg/10«  mg)(1000 1/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 I, a  long-term
      average  concentration  of  0.44 mg/1 selenium was
                     268

-------
                derived,  and  estimated  variability  factors  of   1  2

                UUI5  ™'t  Were   used  to comPute  the 30-day  average
                and  24-hour maximum values  of  0.53   and   1.6   ma/1
                respectively.                                   y



                Utilizing  these  values, mass limitations  for the

                follows-       Subcategory  may  be obtained   as



                1-   Copper Salts Segment


                30-day average;
                                                -BM'OOO 1/k.)
                24-hour maximum;
                    «n,,
                * 0.0015 kg/kkg


                2-    Copper Carbonate Segment


                30-clay average



                                        ( kg/1°*
                24-hour  maximim
Basis for BCT Effluent Limitations



    l      P^°P°Sing ai?X m°re Strin9ent  limitations  for  TSS under
Basis for BAT Effluent Limitations


Application of Advanced Level Treatment
                              269

-------
       TABLE 13-8.    BPT EFFLUENT LIMITATIONS FOR COPPER SALTS
Coventional
Pollutants
Long-Term (1)
Avg.(mg/1)


 20
VFR
   CD
                               1.2/3.6
Cone. Basis
    Qng/1)
30-day  ^
avg.     max.
            24
73
      Effluent Limit
         (kg/kkg)
      30-day  24-hr.
       avg.    max.
                                           0.023   0.069
Toxic
Pollutants

Copper^-3)

Nickel^3)

Selenium^3)
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.
                               270

-------
       TABLE 13-9.    BPT EFFLUENT LIMITATIONS FOR COPPER CARBONATE
Conventional
Pollutants
    (3)
TSS
Toxic
Pollutants
Copper
       (2)
Nickel^

Seleniunr J
Long-Term
Avg.(mg/11
 20
         CD
  VFR
     (1)
1.2/3.6
 Cone. Basis
    (mg/l)
30-day  24-hr.
 avg.     max.
                                            24
                                    73
                             Effluent Limit
                                fkg/kkg-)
                             30-d
   ay
avg .
1.4
        24-hr.
         max .
       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.
                               271

-------
      TABLE  13-10.    BAT EFFLUENT LIMITATIONS FOR COPPER SALTS
Toxic
Pollutants
Long-Term
          (1)
Avg.(rng/1)
VFR
           Cone. BasisLJJ Effluent Limit
              Cmg/lj         rkg/kkg-)
          30-day24-hr.  30-day  24-hr.
Copper
Nickel
Selenium
0.
1.
0.
89
8
44
1.
1.
1.
2/3.
2/3.
2/3.
6
6
6
1.
2.
0.
1
1
53
3.2
6.4
1.6
0.
0.
0.
•" K •
0010
0020
00050
0.0030
0.0060
0.0015
VFR - Variability  Factor Ratio
(1)  Based upon  limitations  promulgated for  the  copper  sulfate  sub-
     category  in Phase  I.
                               272

-------
         TABLE 13-11.   BAT EFFLUENT LIMITATIONS FOR COPPER CARBONATE
                                              Cone.  Basis(1)   Effluent Limit
                                                 Cmg/D           fkg/kkg)
1UJLJ.U
Pollutants
Copper
Nickel
Selenium
i-ong-iernr
Avg.Cmg/i)
0.89
1.8
0.44
*
1.2/3.6
1.2/3.6
1.2/3.6
30-day
avg.
1.1
2.1
'0.53
24-hr.
max.
3.2
6.4
1.6
• 30-day
avg.
0.064
0.12
0.031
24-hr.
max.
0.19
0.37
0.093
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated for the copper sulfate sub-
     category in Phase I.
                                 273

-------
 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 mVkkg  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 proposing 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  proposing  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  Table  13-6,   the   Agency  has
 estimated  the  percent removal  for 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
                              274

-------
 concentrations  presented  in  Table 13-6  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
1175
0.89
mg/1
mg/1
           Percent Removal
           Nickel:
Raw Waste
     BAT
           PercentRemoval
[(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   "40
 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 .

 Selenium has  also been  selected for regulation under  PSES for the
 reasons  previously given for its  selection for regulation under
Existing Sources

There are currently five indirect discharging copper salts plants
in  the subcategory.  There is also one indirect discharge copper
sulfate plant.  For Pretreatment Standards for  Existing  Sources
(PSES),   the  Agency  is  proposing  limitations  based  on  BAT
described above.   The  pollutants  to  be  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
Tables  13-8  and.  13-9  summarize  the limitations for the toxic
pollutants copper, nickel,  and selenium.
                              275

-------
                      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.
                         276

-------
                           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, + H2S04 » NiS04 + H2

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
l(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
                              277

-------
TABLE 14-1.   SUBCATEGORY PROFILE DATA FOR NICKEL SALTS
      (a)     NICKEL SALTS EXCLUSIVE OF NICKEL SULFATE
Number of Plants in Subcategory

Total Subcategory Production Rate
         Minimum  (3 plants)
         Maximum
   12

>5000   kkg/yr
   <4.5 kkg/yr
 1550   kkg/yr
Total  Subcategory Wastewater  Discharge
          Minimum
          Maximum
  600 m /day
    0
  195 m3/day
 Types of Wastewater Discharge
          Direct
          Indirect
          Zero
     6
     4
     2
                            278

-------
 TABLE 14-1.
        (b)
           SUBCATEGORY PROFILE DATA SUMMARY FOR NICKEL SALTS
           NICKEL SULFATE^
 Total Subcategory Capacity
 Total Subcategory Production
 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
           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
                                             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
                            279

-------
                             g
                             w
280

-------
                                         u
                                         3
                                        •O
                                         o
                                        A
                                                                                       1
                                                                                       o
                                                                                       BQ
                                                                                       1
                 O  C0
                 •o  5
                 ca
                  3
                  Vi
                  U
                 CO
 ^ l-l
 £ 
            w
            0)
 l-l
 u
en
                             u
                             (1)
                  •a PQ O
                  •H ac z
                   O   • S3
                  rH O.  O  >»
                                                   on     u
                                                   to 1-1     
-------
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:

          NiSO4 + 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

NiO
2HC1 = NiClj
                                H,0
                 2HN03 = Ni(N03)2 + H20

           NiO + 2HBF4 = Ni(BF4)2 + H20

 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  P^cess
 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
                                282

-------














^^
fH
*"*
CO
ta
EJ
t^
S
w
^
tjj
**•
&*
CO
f*
£

u
o
H4
z
g

U4
CO


CM
I


*
*N
1
•"^
s
CO
g
t"*




































10
jj
•-I
10
CO
c
•H O
01 -rJ
A: jj
O 10
•^4 C

•H
IU Ul
o oi
D
.* JJ
.* C
V. 10
CO r-l

3
O
r-l
b



































01
to
0>
JJ
10
3
in
CM
b.
§
1—
r-l
b

—•
X
CO
r-l
1-1
b


^
CO
r-
r-4
r-4
b



_
CO
CO
H
r-l


CM
£
r-l
b


^
CM


r-l
b


^^
cs
~
1-1
i-4
b


_
CM
4.x
f-4
O
i-4
b

CM O
is o z z o z
in
fO CO
en oo tt < o <
»o Z Z Z


CO CM IO CO VO
»-i o in CM o CM
. . . . . •
o in CM r-l in r-4
CO




in
CO O
. .
vo r-l 
O 10 O C
o o> o o
O 14 t
O u C 3 U u
(0 £UJJ JJJJ <0 r-4r-l (010
JJ OOOCr-lOJJi-l
1- JJ(0 0)10 0> O u Cr-l
O UJJ u JJ JJ & JJ O-n
u o>e-
jj
jj
to c
JJ 10
C r-l
10 Cu
r-l
a. -D
0) 10
in
o a>
JJ -rl
10
* u c
o> o c
iH IU O
r> »r<
10 >i JJ
r-l r-l CO
•n C 0>
10 O 3
> a
CO TJ 0) «
01 JJ 01 • 00
jj . jj a ai o
o e  u-i a> 01 a> at co
C 3 .* J* id
» -n r-4 O O O
O 10 -H -H -H ..
r-i o > z z z ai
b Z 0
u
I ^^***, 3
«< 1 i-4 CM CO TJI O
Z 1 «-».«-*- CO
283

-------












^
rH
*W
w
M
M
5
r£
b

to
S
•£
tn

t3
H
fcfi
O

Z
*
o

b
g
tj|
S*


(O
•C
s


1
*


1

















_^
to
4J

<8
rH O
0) -4
Jtf JJ
U 10
-4 C

IU 01
O 0)
Q
.* JJ
J£ C
>» 10
m rH
£ ^

*
o
rH
b























-





0)
0
:ewatec Souc
**
01
U
a*
rM
rH
1-4
*
rH
b



^i
*— *
cn
rH
rH
b


^^
cn
i—
rH
b



^^
2.
m
rH

b




CM
in
rH



5
r-
rH
b



__
CM

rH
,H



s
O
rH









OV
P
g Z Z o
-l O
jj (0 01 10 0) O u
0) C -H C C C
U O "O O -4 14 O
O H S '•«
, * -
11 18
5 rH O
•O 0) « O

OC JJCOTJOtO 0
CO (8C-r4JJO) m
•H O O V4 18 V4
(1) JJ -r4 JO O M C
618 rrJUrHJJU O
o o "* ° ° « g
>IU COrHrHrH^ OI
C fl> 0) 01 0) 0) CO
g""* rH 0 0 0 01
r-| O (8 -r4 -r4 «r4 ro «
b Z o
u
,£1 r-l o) m •« in O

284

-------
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
                              285

-------
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  F113  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
 adjustment.   Figure   14-4  is  a  diagram   of   the  process  and
 treatment  system   showing  sampling  points.   Table 14-4 presents
 data on the major  pollutant  concentrations  and  loads  for  the
 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
                               286

-------
                                                                              V
                                                                              08
                                                                              4-
                                                                                A
4J H
 V
CO
                                                                                          00
                                                                                          C
                                                                                         •H  to
                                                                                         rH  4J
                                                                                          o. a
                                                                                          e  -H
                                                                                          CO  O
                                                                                         co  en
                                        w
                                        co
                                        U
                                        o
                                        §
                                        a,
                                                                                                                  ro

                                                                                                                  -a-
                                                                                                                  rH
                                        g
                                             C
                                         CO O
                                     ^ e -H
                                      0) -H  AJ
                                     J£ i->  S
                                      O « t-H
                                     •H iH  O
                                     SS OH CO
                                                   287

-------
                                                    o
                                                    3
                                                   "O
                                                    O
                                                    M
                                                   CD
                                                  -a-
                                                 o
                                                 en
                                                  CM
                                                 33 "
                                                    (U
                                                    >-,
                                                    Id
                                                    Q
                                                   A
  e
  o
 •H
  4J
  td
  N
                                                                                 3
                                                                                 01
                                                                                   0)
                                                                                   60
ro
««=
                                                                                                ^=^  o
                                                                                                      CO
    M
•a  01
 C  «
 Cd  rH
                               M
                               O)
                                fe
                                                    A
                                0)
                                U.
                                cd
                                                    CM
                                                    =«=
                                                                            *-i  0)  O
                                                                             >>
                                                                            J
-------
0)
4J
>> CO 4J
«-« rH C CJ
O. 0) O 3
CX ,'ii Xi T3
3 O M O
CO t-l CO M
S5 CJ O,
0)
4J
CO
3:
>
cO
(A
i\



r~x '
• **








. 	 5,
^


co
l-i co
CO -H
1 1 j^
0) CD
1-1 4J
M CO
D.S
O
M 3
On CO
4
«*-,



C
U /
E—l
^<
O

OS
u
A
4-1
CO
U
,—J ^ \
^n *»
ss o
L, ^3
s. - s ?-g
4J w "te CO ^ u

w yS ^»* u CM a)
t. n <" ^ 60
* ^ « 2: ™ l>>
CO
/^ *
•*




c ' ^
0 , o

CO a)
•H c ;
5-5 M ;
A 2 S
X 43 fa
U
(0 H
»_J ^^
*rt ^3
0 3
A ^
<^. PS
js =«J! ) o
w **<
5 w
& a
>v o
0 M
h co g
5 » .. y
2 > S
2 - J |
« ,


' ^ fl)

•D
3
O
to


,
k /^ H4
\ CL,
1
CO

CO Q
C -H Z
S ^H <
5n M
"O tx co

CO U
—t f^
— I 5 §
J 3 P'H
" 2
"00 £
« -H -a co i
" H H ^ fll -*
'• 4J CJ .-•* B(J 1~l
1 ,
1
63
H
"^
H
M
ss
, 1
L &
k 0
t-l
00
c
•rl CO
?™i 4J
o. c
6 -H
0) CO O
s ss a 1" ®fc
I 5s " -1
85 r! o 2 2OT
CO
                289

-------
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 F145 produces nickel carbonate, nickel chloride, and 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  aci'd,  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 F118 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  F113,  F117,  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:
                               290

-------
 Q
 W
W


K
CQ
a
%*
o!
   .
Is
j
s
f

•V
tH

H

n


3
o




.0
CO






•H
z



CO
to















Stream
Description

g
n •
0) O
*j z
CO

l>
H 1
0 1
• |
O


•^
1 s
Z 0 t
Z. . |
0 1
PI
•H
to
•j i**
c *^
ig o J
H o 1



O 1
• 1
H |














Supply Water



•
H



CM
f 1
0 1
0



o
0 1
. f
H 1




f)
0 1
t~ 1



O 1
* 1
0 1














Rinse Decant



,
CM


in
en H in H
HO CMO
o o o o
o o o o



in
PI p-
ov t^v
voo vo o
oo o o



vo
r» i1 oo

PI O VO H


_^
0 0
oo en PI in
• • • •

a
Ni Nitrate Wastew




CM




VO 1
CM |
• 1
O



V 1
in i
o
V




1
O 1
vo
** (


,
0 1
r-
PI








u
01

a
S
Ni Carbonate Wast




PI

































.
c
o
•4-4
ufficient informa
to
c
M

1
1
1




XI
Q.
0)
o
X
01
to
a
•o

«
0)
u
n)
CO
01
3

(0


C
o
w and concentratil
re noted.
-day sampling.
O 01 O
H .C S
En S E-I

_ __
H N
•-^ ^^
                                291

-------
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 were  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
                               292

-------
    TABLE 14-5,
TOXIC POLLUTANT RAW WASTE DATA FOR SAMPLED
   NICKEL SALTS FACILITIES
        Average Daily Pollutant Concentrations and Loads


                              rog/1

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
kg/kkg
Plant
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
Designati
F107d)
<0.531
	
<0.850
0.047
	
0.460
<0.003
540.3
	
<0.001
<0.003

0.387
on
Overall
Average
<0.420
0.0309
<0.291
<0.002
0.048
0.00575
0.170
0.00394
<0.023
0.00785
199.3
5.79
<0.013
0.0021
<0 113
0.0316
0.149
0.00421
	  Insufficient information.


(1)  Flow-proportioned averages from two nickel product
     wastewater streams.
                         293

-------
producing nickel salts.


prior to discharge.
Plant
             produces  nickel  chloride   and  nickel  fluoborate  in
                     ^^
 technology.
 Pl»t
 to discharge.


 prior to discharge.


 there is no discharge.
                     nickel fluoborate in small  quantities  along
 fluoborate and therefore  there  is no discharge.
 other Applicable  Control  and  Treatment  Technologies


  effluent for further solids and metals  removal.
  Process Modifications and Technology Transfer Options
                                294

-------
                                                             y

                                      C°ntaCt »«tew.ter generated
                      °f
 1 '
 2.
           S!S^iing  alJ  direct  Process  contact  wastewater or  use
           possible;  ^     aS  make"UP f°r  Pr°duct  solutions,  wherl

           Minimizing  product    changes    by   careful    oroduct
           scheduling and  by  increasing the number  of  realtors
           This can result  in  reducing  the volume   of   wlshdown
           water required by minimizing  product  changeover






JK39^^ pe£°9ative sV3ect  to customer  demand?   ConseqCIntfy



Best Management Practices


                            trea^e"t of scrubber wastewater from
                           recycle, where  technically
          odi-nn
        production
cta
                       Ieaa9e' spillage of raw materials or
                         295

-------
All  other  contact  wastewater  including  leaks,  spills,   and
washdowns should be contained and treated.
treatment.

Plant   F117   which   produces   a   variety   of  inorganic  chemicals
(including all  four  Phase  II nickel  salts),  practices segregation
anS  commingling of   various  wastewater  Breams  depending   upon
rhemical  characteristics.   Some wastewater,   particularly tnat
orfg noting  from nickel  carbonate and nickel sulfate  Potion,
is combined  and treated  in the same  wastewater treatment facility
 sludges.

 Advanced Technology

 For  facilities  using  impure  raw  materials  such  as  Plating
 solutions, etc., significant concentrations of « variety °| toxic
 metals may be present in wastewater,  .particularly  in  dissolved
 form    Careful  control  of  pH  to reduce the solubility of the
 metais 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,
  ?J  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
                                296

-------
 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
                              297

-------
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.
                               298

-------
        TABLE  14-6.  WATER  EFFLUENT TREATMENT COSTS  AND RESULTING
                    WASTE-LOAD  CHARACTERISTICS FOR  MODEL PLANT
   SUBCATEGORY:  Nickel Salts Subgroup
  ANNUAL PRODUCTION:

  DAILY FLOW: 	

  PLANT AGE:
        429
                                       METRIC TONS
   1.67
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 Waste Disposal) 7.4
  Residual Waste Disposal
                 COSTS  ($1,000) TO ATTAIN  LEVEL

                 12345

                 1.1
12.2
2.7
2.4
1.8
20.2
3.3
7.4
0.5
0.4
0.1
0.1
0.1
0.7
0.1
0.2
Negl
Total Annual Cost

             b,,
                                     11.2
                        0.3
                     RESULTING WASTE-LOAD CHARACTERISTICS
                                       •     '    Long-Term Avg.,
              Avg. Cone.                     Concentration  (mg/1)
                              ft\           After Treatment To Level
Parameter     Untreated (mg/1) ^ J      l_    _2_    _3_    _4_      _5_

                                     6-9    6-9
                                      .*    39.2
                                       2.4   0.3
                                       0.62  0.3
PH
TSS
Cu
Ni
4.0
148.7
27
343
                          c.   TREATMENT DESCRIPTION
  LEVEL 1:   Alkaline precipitation, clarification,  pH adjustment
  LEVEL 2:-  Filtration

 *No data available for TSS in this subcategory with Level  1  technology.

 (1)  Untreated wastewater  characteristics are  average of Phase  I
     nickel  sulfate  and Phase  II nickel salts  plants.
                               299

-------
      TABLE 14-7   WATER EFFLUENT TREATMENT  COSTS AND  RESULTING
                   WASTE-LOAD  CHARACTERISTICS  FOR MODEL  PLANT
 SUBCATEGORY:   Nickel  Carbonate Subgroup
ANNUAL PRODUCTION:

DAILY FLOW:  	

PLANT AGE:   	.
                            . 142
                                          METRIC  TONS
                       94.8
                    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
                                     12345
                                     11.7

                                    122.9
                                     26.9
                                     24.2
                                     18.6
                                             22.5
                                             4.5
                                             4.1
                                             3.1
                                    204.3   34.2
                                     33.2
  Annual Capital Recovery
  Annual Operating and Maintenance
  (Excluding Residual Waste Disposal)  56.8
  Residual Waste Disposal              0.3
                                            5.6

                                            7.5
                                           Negl.
    Total Annual Cost                 90.3   13.1

                 b.  RESULTING WASTE-LOAD CHARACTERISTICS

              Avg. Cone.

Parameter     Untreated (mg/1)        __L.
                                               Long-Term Avg.
                                            Concentration (mg/1)
                                          After Treatment To Level
                                                         -4-     -^-
  pH
  TSS
  Cu
  Ni
                  4.0
                148.7
                 27
                343
                                   6-9
                                     *
     6-9
     39.2
2.4   0.3
0.62  0.3
                         c.
                             TREATMENT DESCRIPTION
 LEVEL 1:  Alkaline precipitation, clarification, sludge dewatering,
             pH  adjustment
 LEVEL 2:  Filtration

*No data available for TSS in this subcategory with Level  1  technology.

                                 300

-------
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 mVkkg 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 F107.  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 (50 percent sol.)
     H2S04 (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.)

     H2S04 (100 percent)
Amount

53.0 kg/day

 9.8 kg/day
Estimates of solid waste generated for all treatment  levels  are
provided below:
     Waste Source

     Level 1  sludge

     Level 2 sludge
Amount

0.019 mVday

0.0019 mVday
                              301

-------
Model Plant Treatment Costs
    rs 'ass -ss
incremental  to Level 1 .

Basis for Regulations

Basis for BPT Limitations

A.   Technology  Basis

         the Aaencv is setting
ss  sre
                                                            -s
                                           based  upon  alkaline
       e

     r rtssti              ib-
 p?lmul,a?ed eflfuen? limitations guidelines  and standards for the
 nickel sulfate subcategory.

 B.    Flow Basis
 representaive of  the group.   This  flow  rate  was  derived  as
 described above under model plant treatment costs.

     the nickel carbonate segment of the Nickel Salts  Subcategory,

                               ^^
 model plant treatment costs.

 C.   Selection of  Pollutants  to be Regulated

 The  selection  of  pollutants  for   which   specific    e"l"ent
 limitations  are  being established is based on an evaluation of



 I
 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
                               302

-------
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.

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 m* 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
                              303

-------
    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:
                                     t
         1.   Nickel  Salts Segment

         30-day  average;

         (47 mg/1) (0.68 mmVkkg) (kg/10* mg)(1000  l/m')
         =  0.032 kg/kkg

         24-hour maximum;

         (141 mg/1) (0.68  mVkkg) (kg/1 0« mg)(1000  l/m*)
         =  0.096 kg/kkg

         2.   Nickel Carbonate Segment

         30-day  average

          (47 mg/1) (120 mVkkg)(kg/10«)(1000 1/m')
         =5.6  kg/kkg

          24-hour maximum

          (141 mg/1) (120  mVkkgHkg/10* mg)(1000 1/m')
          - 17 kg/kkg

2.    Toxic  Pollutants

     a.   Nickel
                         304

-------
         TABLE  14-8.   BPT EFFLUENT LIMITATIONS FOR NICKEL SALTS
Conventional
Pollutants
Long-Term
Avg.(mg/l)
         CD
 VFR
           Cone.  Basis
              (mg/1
             -d
               Effluent Limit
        __ (kg/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
                                           3.0
141
0.032   0.096
          9.0  0.002   0.006
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated for the nickel sulfate sub-
     category in Phase I.
                              305

-------
       TABLE 14-9.   BPT EFFLUENT LIMITATIONS FOR NICKEL CARBONATE
Coventional     Long-Term
Pollutants      Avg"Cmg/lJ
                          CD
             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
 3.0
141     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.
                                 306

-------
              n™ B?T limitations for nickel are based  on  the
              S,,i>»ilinitation? Promul9ated 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
              ^fi1^ 5a^°rs of 1-2 for a  monthly  averagl
              and 3.6 for daily maximum computations.   Utilizing
              InlS sub™?5'  maSS  iimitati°ns for  the NickSl
              Salts Subcategory may be obtained as follows:
              1 •    Nickel Salts Segment
              30-day averae;
                                          mgMlOOO
                                         mg)(1000
                       x
                     Kg/Rkg
              24-hour maximumi
              2-   Nickel Carbonate Segment
              30-dav averae
                                        nig) (1000
              24-hour maximum
              (9.0 mg/1) (120 m.3/kkg)(kg/lO« mg)(lOOO l/m»)
              =  i.i Kg/Kkg
Basis for BCT Effluent Limitations
S ilnST.rgEr&SSflSS' ITSSE 'S&SSss;
5s^«ti?-jnrttfjr1sftss!Bs'^sp
Basis for BAT Effluent Limitations
Application of Advanced Level Treatment
                                                   =1
                          307

-------
as
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  Level  1  has  been
selected as the basis of BAT  (same as BPT).

B.   Flow Basis

Unit wastewater flow rates of  0.68 mVkkg of nickelnf?ltfca^
mVkkg for nickel carbonate has been selected  for  BAT   (same
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   m'/kkg 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
 Sited  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  (Treatability Studies for th|
 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
  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
                                308

-------
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 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/l)(0.68 m'/kkg)(kg/10* mg) (1000 1/m')
           = 0.00024 kg/kkg

          24-hour maximum;

          (1.1  mg/l)(Q.68 n^/kkg) (kg/10* ing) (1000 1/m')
          = 0.00074 kg/kkg

          2.   Nickel Carbonate Segment

          30-day average

          (0.36 mg/1) (120 mVkkg) (kb/1 0« mg)(1000 1/m*)
          = 0.042 kg/kkg

          24-hour maximum

          (1.1  mg/1)(120 m3/kkg)(kg/10* ing) (1000 l/m»)
          =0.13 kg/kkg
     b.    Nickel
          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
                              309

-------
        TABLE  14-10.    BAT EFFLUENT  LIMITATIONS  FOR NICKEL  SALTS
Cone.  Basis
    Qng/1)
                                                           Effluent  Limit
                                                              .(kg/kkg)
Toxic
Pollutants
Copper
Nickel
Long- Term1 J
Avg. (mg/1)
0.3
0.3

1.
1.
VFRc
2/3.
2/3.
1)
6
6
30-day
avg.
0.36
0.36
24-hr.
max.
1.1
1.1
30-day
avg.
0.00024
0.00024
24-hr.
max.
0.00074
0.00074
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated for the nickel sulfate sub-
     category in Phase I.
                                310

-------
     TABLE  14-11.    BAT EFFLUENT LIMITATIONS FOR NICKEL CARBONATE
Toxic
Pollutants
Long-Term (1)
Avg .(ing/11
                                 VFR
    CD
Cone. Basis( ^  Effluent Limit
   Ong/1)          fkg/kkgl
                60-day  24-hr.
                 avg.     max.
30-dayZ4-hr
 avg.     max.
Copper

Nickel
   0.3

   0.3
1.2/3.6     0.36     1.1    0.042   0.13

1.2/3.6     0.36     1.1    0.042   0.13
VFR - Variability Factor Ratio
(1)  Based upon limitations promulgated for the nickel sulfate sub-
     category in Phase I.
                                 311

-------
          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/l)(0.68 mVkkg) (kg/10« mg)(1000 1/m3)
          =  0.00024 kg/kkg

          24-hour maximum;

          (1.1  mg/1)(0.68 m3/kkg)(kg/1 0* mg)(1000 1/m3)
          ~  0.00074 kg/kkg

          2.    Nickel Carbonate Segment

          30-day average

          (0.36 mg/1) (120 mVkkg) (kg/1 0' ing) (1000 1/m3)
          = 0.042 kg/kkg

          24-hour maximum

          (1.1 mg/1) (120 mVkkg) (kg/106 mg)(1000 1/m3)
          * 0.13 kg/kkg

Basis for NSPS Effluent Limitations

For NSPS, the Agency is proposing 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 proposing 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.

Using  the  summary  data presented  in Table 14-6, the Agency has
estimated the percent removals of copper and nickel by  comparing
the  untreated  waste  concentrations  for those two toxic metals
                              312

-------
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  «
          PercentRemoval
27 mg/1
0.3 mg/1
          = [(27 -
          = 98.8%
       0.3) T (27)](100)
          Nickel:
Raw Waste
     BAT
          PercentRemoval
343 mg/1
0.3 mg/1

[(343 - 0.3)
99.9%
                         ? (343)] (100)
The  percent  removals are greater than the removals achieved for
copper (58%) and nickel (19%) by 25% of  the  POTWs  in  the  "40
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 greather
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  proposing  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.
                              313

-------
                      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.
                         314

-------
                            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
  r  fd d .manufacture of Pyrotechnics.   Industry profile data are


 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

 facilities     th€   Sam&   SUe aS cnlor-alkali   manufacturing

 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
rhrH«          /I5 .Pr?duced  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
                              315

-------
           TABLE 15-1.  SUBCATEGORY PROFILE DATA FOR
                        SODIUM CHLORATE
Number of Plants in Subcategory

Total Subcategory Production Rate
     Minimum
     Maximum
     13

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
                              316

-------
uniformly
follows:
      across  the  industry.   The  overall  reaction  is as
          NaCl + 3H20 = NaC103
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 to 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 (1).

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.
                              317

-------
318

-------
 After  electrolysis,   the  sodium  chlorate  liquor  is  fed into
  dehypo     tanks    to     destroy     residual     hypochlorite
 (dehypochlonnation)   (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 dependinq uoon
 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
 tor plants producing sodium chlorate are  summarized from  industry
 responses   to  the  Agency's request for  information under section
 JUB o£ 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
 ,U™ «-•  th?  13  •?1u?ts. in  the  ind"stry.    (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).
                              319

-------
                  CM
                  CM
                  co
                  •-4
                  tu
                           <   O
                           Z
                    CM
                    oo
                                 Ok
                           CM   in
                                              fii
                                          CM
                                          in
                                        oo
                                        o
                                        m    CM
                                        oo    co
                                                    to
                                                    oo
en
H
KJ
U
s
6
                                  m
                                  CM
              O
!    "'
01
CO
•-4
CM
                            CM    m
                            co    ft
 s
 §
 H

 i
  a
  to
  i
      4J
       e
        tH
                                                o
                                                 V
                                          ro    co
                                          -*    o
                                   co
                                     •
                                   co
                                   O   CO
                                   co   in
                                           CM    CM
                                               oo
                                               o
                                               \o
                                               o
                     o
                     CM
  I
                      H
                      w

                      K


                      I
                             oo
                             o
                                    4J
                                    e

                                    8
                                                Z
                                                 CM   PI
                                           ^,   r-l   VO
                                           CM      •     •
                                           —   <•   O


                                            Z
                                          r-    in
                                          o    o
                                                        a
                                                        u
                                                        41
                                                 9
                                                 U
                                                 O
                                                 U
                                                             Ok
                                                             V
                                                             «o
                                                               •
                                                             «
                                                             CO
                                                              in
                                                               •
                                                              o
                                                                     o
                                                                     M
                                                              00
                                                              CO
                                                                                      O»
                                                                                     •fl

                                                                                     A
                                                                                      O

                                                                                      s
                                                                                      u
                                                                                      O
                                                                                      m
                                                                                 •    a
                                                                                c    4i
                                                                                2    8,

                                                                                «    S
                                                                                S    O
                                                                                o    c
                                                                                iu    4)
                                                                           u


                                                                           I
                                                                                         0.
                                                                                 «o

                                                                                  10
                                                                      S,
                                                                      41
                                                                      a

                                                                      •o
                                                                      41
                                                                                  a
                                                                                  4)
                                                                                  u
             u
             41

             41

             §
             ft
             •O
             41
             0>
             9

             in       a
             •a       *>

             *       o
             u       Ot
              4)   •
             4J  U
              «  4)
              S  JJ    JJ
                 id    •*«
             *J  »    0)
              o
                                                                                                        4)
                                                                                                        OS
                             0
                             o
                             4>
                                          IU
                                          u
                                          O
                                      O
                                041    -4
                       (1,       o     *>


           S    *    tit;    i     3
           e    *»    4> «    41     o
           o    o    w *>    *»     P<
           o    4)    -H e    c
           e    u    «o o    -^     u
           o    ~«    co    «     rj
           Sow       x     <
                                                       U
                                                       M
                                                       U


                                                       JJ
                                                       u
                                                       o
                                                               O
                                                               z
                                                                               H
                                                                               *
                                                                      4J  U  C 4)
                                                                          4)  O M
                                                                       01  4J  O
                                                                      4J  «J    CTl
                                                                       C  3  0) C
                                                                       «     B!"*
                                                                      r^  *>  4) U
                                                                       CUO  O
                                                                          
                                                                       4)  4J  u 0)
                                                                       u  e  cu9
                                                                       o  o
                                                                       £  O  4J O
                                                                       JJ     O W
                                                                          m  4i
                                                                       u  a  u "o
                                                                       O  4)-^  41
                                                                        C
41  .    J) U i-l  18    00
O  C    4J -H CD       O
CO    id *O Ok  'O    co
C^J    o    .-«  c

 «*>    55 >,"     o
 g  B    C    WO    -^
^4  u    -rf "O fl 0)    -U
 O  O        4) 9^1     O
 >IU    M t) C f*     41
    C    fl)  9 <8 10   C/l
    S»)    9 H >-J *>
         •H  U    «
HO     «  c e c    ••
 hZ    >HM-M    4)

                        U
    I                   3
 «< I      •  • •       O
 35 I    »-4 d f*^       W
                                                  320

-------
CM

 I

LO
O)
tJ





to
•»->
c
re
r—
Q.
+-> CD
U 4->
•C 2
0 0
Q- IE
O
0.-0
•> L.
O! «£
0
3 5
C
C_
 -0
to c
3 re
« to
(A 3
re re
•r- 4J
I- 00
GJ
-M O)
^fe
re o
o: to
o







t 3
= LJ-
•
3C
O
00
>— i


•
LU O
Q- O
>- C£.
t— 0-



• *
0 _J
0_ LL.


02 3T
r> o
cc oo
O »-t
00 Q


• •
•Si oo
O C2

«t 0
co o



•
h- a:
z o
i— c 00
<: t-i
y^ ^j


• •
LU u- a:
Z i— i O
5g£
co D- e

LU
\- cz.
—t r>
•a: o
OO 00
1
_J
o.
CO O LO CO LO CM ro
^0. CM^Hr-\ 'isi ^1 r^. ^! r"~ f~*
Illjs^iJcJas
o^oroizaiQiQiQi^^



#
r— r—

0000000 CO OJO
^^ZZZZQiCliZ




f"— f^ f^~ ^i^

WjajOJCULUCUCU CPUJLU
o£o£0£o£>-a:afc£>->-




§§iii§ISgg
1— 1— f— I— ZZZI— l_i_
<-a:VClOCMCOr»-
,-H^.,H(,o^.co^.CXJg^:
u. ZL^ LT m £ £ £ ,r ,-r ,r
- LO
t— 1
o
fl— 1

oo
LU



•o
•r™
£




00
LU




00
LU






00
LU






OO
LU




00
LU

LU
z
t— 1
CO
<— 1
r— t
i — 1
1 1
                                                                                                                            Ol
                                                                                                                            u
                                                                                                                            to
     O) r—  o

     r- J3 2

     J2  (Q

     03  U  II

     i— *f—

  C -i- r-^-^

  O   Q.
                                                                                                                           co
                                                                                                                  II   II   II

                                                                                                                  c
                                                                                             u.
                                                                                                       *  *
                                                                                                                     Ol
                                                                                                                 re  i_  ,
                                                                                                                 t.  t.  o o
                                                                                                                 3  3  O CO
                                                                                                                 o. Q. ce a:

                                                                                                                 u   u   u  u
 re  t.  re i—
oo co  oo >,
          u
  «   •   • CO
O- Q.  0£ C£
                                                   321

-------
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  P««f i^0"
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
Ssults  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

                             S* "JHf '.^2- £"*
 remove HC1  and Cl« from cell off-gases.  Other process wastewater
 is generated from cell  washdown,  filter  bag  wash,  leaks  and
 snills    This  liquor  and the scrubber water may be recycled or
 discharged  Generally with neutralization  and  sedimentation  as
 thS oSly treatment.  Barometric condenser water is a major source
 of  S?o?e£  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  Campled  plants
 (F122   F149   F146 and F112) produce  sodium  chlorate  (NaC10?) by
 the electrolysis of brine similar to the process shown in  Figure
 15-1 .

 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
 nrocess   The brine  is  purified to  remove calcium   carbonate and
 SlciSm' sulfate,  passSd   through  a sand filter and then further
 Seated  to  inhibit corrosion.   The  feed  solution then  undergoes
 chlorination  and electrolysis  at the cells  and the  cell  liquor  is
                                322

-------
               CM

               Ml
                                       i
                                                     M
                                                     n
      «
           o
           c
           o
«
s
                                      ^
                                 09    f
                                  .    ^,
                                 r-     *e

                                       Z
                                     in
                                      •
                                     OI
                            00.0
                      ss    «
                                                        10
 C  rH
•H  rH
H  •H


 8   c
o  <
JJ
o
id
jj

!

i
JJ
U
id
jj

!

i
 u
 0
 JJ
 Id
 S

 E
 u
 O
jj
(A
                                                                         c
                     S
                                                                         5

                                                                         0
                                                                        JJ
                                                                        g
                                                                        (0
                                                              5
                                                                                    g1
                                                                          B»

                                                                          *
                                                                                   «

                                                                                   a
                                                                         e
                                                                         0

                                                                         S1
                                                                         >
                                                                                  15
                                                                                  o>
                                                                                  M
                                                                        s
                                                                     I
                                    n
                                    jj
                                    u
                                    o
                                    Qi
                    i"S
                    as!
                    4) JJ n
                    n C O
                    Is;

                    *«5
                    M 01 *
                    o « S
                   «u o *
                      o
                                                                            _ •
                                                                            -3     8
                                                                          JJ   JJ

                                                                        O *   m
                                                                        10 0   il
                                                                        JJ JJ   >


                                                                        ei   s
                                                                              IB
                                                                        n 0
                                                                           o<

                                                                           "8
                                                                           a
                                                       gg
                                                       EG
                                                       3 U
                                                         O
                                                               O.-H

                                                             C   rH
                                                             O JJ O
                                                               o to

                                                               « -
                                                                       10
                   ^-i c
                   «o^>o   u
                   C   «>a)
                                                         * 2
                                                        •00
                                                       •u u e
                                                       S Q.0
                                                       *w   O*   CO
                                                       iH jj     a>


                                                       :s2   3
                                                       '-J-H'O   C
                                                       •Cm 0   C
                                                       i c£   °
                                                         O

                                                         CO


                                                         m


                                                         C
                                                                 > C
                                                                 00

                                                                HZ
                                                                •< 1
                                                                Z 1
                             Uin   -H
                       {J»O JJ « «   JJ

                     «U«<09rH   O
                   OTI OrH J CrH   n)
                   W 3£ 0 S <0 m   w
                   3H 0 >,4J»0 JJ   ™
                   -H o ra o n   n
                                                                      > M Q U S M -H
                                                            r-l (s ro  «r in
                                                                                       4)
                                   g

                                   en
                                        323

-------
                      en    CD


                      .r- OVr- C7>
                      •§£
C X O C E
nj LU O I— ' "—- '
eZ t_ 4-9 -o 
40 5 C t- C
t2 4^ o 4-9 -a
to re c
re 3 q
_-. CO CM
£ CO tO rH CM
.3- CM «— ' CD «-H
a;
LO
t-<

ai
LO
i— 1
i— 1
                                                                                                        O>
                                                                                                      CO

                                                                                                        E
                             O)
                             4->
                           a) 

                      "re  re
                      4-9  3
                       o  

                          re
                       o
                       O "O  O>
                      CJ  C 4-9
                          re  re
                      4-9     t/>
                       o  c_  c
                       re  
C3
co
^-t
LO
1— 1
CO
«-l
I-l
vo
CTi
LO
LO
I— I
c
o
•r- *"""*
O >>
•0 en
O -^
O- •— '
LO
vo
LO
co
CO


CO
CM
00
C3


CM
o
«t
en


r- <
00
t— i


o
o
o
LO


0
C2
CO
LO
•=»-


co
CM
CM
r- <
CM
co
CO
to
*
CO
CM
1 CM


                                                VO


LO
CO
t— 1
U.


O\
t— I
Lu


CO
O
?™l
u.


CM
CM
U.
in
4-9
c

I— 1
^
Li-
re
"o.
1^.























•






4-9
C
re
o.
"al
•0
£
0)
4-9
re
t_
o
o

s
3

•5
3
c.
.>>
CO
Jȣ
J^
o
O
o

CM
CO



t_
,>>
a>
^t
^
tc
i —
«a-
en
*i
„,-!
CO
U

t_
>^
en
^t
j*
CO
co
(£>
VI
CO
CM


»*.




||

uoi^onpc
0-
r—
re
4-»
|2
tn
4-9
c
re
I!
il-
CS
(U
ja
3

ii
c
o
•r-
4JI
O
3
•a
o
a.




{_
>,





o>
^
^

"O
•o
LO
ro
CM
CM
x



>l
re
T3
LO
1C
CO

^

X
«l
,
X


en
^
^:
O
0
«t
CM
CO
X
COJ
i —
•
CM

II

(U


*o
t-
e
t_
0>
Q.

4-9
C
re
"o.
>,
o
C7>
0)
4-9
re
u
.0
(A
T3
C
re
>> >»
re c-
0 ^
£ 1
ro o»
0

v)
(/)

U
O
(_ t-
>> ca.
i
3
T3
O)
(/)
en re
^ -0
^t
V
^>

2
"s. -r:
o
r—
U-
4-9
•r~
C
O 4-»
^- w>
| . A\
LL
ii W
>, »
P~

•r™ •" "
re 
-------
 evaporated  to  produce  sodium  chlorate
 product is sold as solid sodium chlorate.
crystals.   Almost all
  i«                  USS?  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
 S?nS!n?  fc£at re^cled   iS  discharged  to  an  on-site  lagoon
 Effluents  from other product processes also flow into the laaoon
 from where they are discharged  to  surface  water.    Figure  15-2
 presents the sodium chlorate process and sampling points at Plant
 3? I  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
Jf JS !SJyS1S* f°£v, pHu 9ontro1 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 hypoch lor it es, and filtered to  produce  a  sodium
cniorate solution.
                              325

-------
326

-------
                                         s
                                      f
          C

          iH
          0.
          t-
          o
          u

      .CM
 co
 CO
I-
                                                     CO
                                           -e-
                          0)  jfi
                          w  to
                          iH  tfl
                                       U  E
                                       3  S
                                      •O  B)
                                       O  0)
                                       M  M
                                      CU H
XI

l-l
U
co
                                                                 c
                                                                •H
                                                                 o
                                                                a,

                                                                 60
                                                                 c
                                                                         Q.

                                                                         §
 O
 14
 4J
 O

41
a
                                       /,
                          sj-
                         O
                          M
                         U
                          cs-
                          ra
                                       0)
                                       c
Vi
o
^
0
u
0) 0.
rH CO
•H
D.
CO
?i
•P -H
C i-l
I]) -H
01 O
«
£ o fa

0) O
o 5
^i T5
u o>
                                                    327

-------
328

-------
                                                     CO
                                                     4J
                                                     c
                                                     o
                                                     a,
                                                     60
                                                     r.
5 4J
55
                                 329

-------
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 F112 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 HZS04 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 F112.

Table   15-4 shows  the  wastewater  stream   flow  and  pollutant
concentrations for  the four sampled  plants.

Other  Plants Visited

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
                               330

-------








Q
U
a.
§
CO
«
2
CO
o
§5
Q CO
Z W

CO HI
z u
O M
«£ bi
&• U
Z E*
U •£
z
O S
u x
z x
< 0
f M
a o
•J O
2"


W
in
TABLE ]





CM
rH
10
rH 3
CJTJ

n
01
K

.0
CO
*>dj5
ofv.
e]s
u
o




CO
CQ
*"
















Stream
Description
e
10 «
41 O
u z
CO








CM
CV
h
JJ
c
a




























m i
0 |
V





r- I
O 1
O 1
•
o


CM 1
CM |
• I
O



1
vo t
• i
?











0)
-W
ID
0)
C
01
•a
Barometric con


<


in t in i in i f i
• i • i • i • i
O 1 O 1 O 1 rH 1
V V V





I r- I i in i
rH | o i in i o i
01 01 rH 1 01
• • • , •
o o o o


en f
rH 1 rH 1 O 1 O 1
VI O 1 rH 1 VI
• 1 • 1 • 1 • 1
o o m CM



1 1 1 1
r-l o i r-l 01
• l • i • i • i
PI VO CO CM











S —
O VD
irj ^^
S -u
o c
rH 01
a 3
rH
U U-l
U O) vu
0) 4J W
U N 18
o -H si E
4J rH O
10 rH O> O
U «J C «
O 4J -rf
Q4 0) rH rH
« >1 O rH
> u 0 0)
W 0 U 0


Bj o •» r-



rH 1 V in
00 V





in
1- 1 en
in i co oo
r-l vo o
o o o


in
en
o i oo oo
o I vo o
i-H O O



00
1 en
n l m vo
o in o
vo











4J
c
V
4_J PJ
a> vu
4»J 1 1 1
rH U
VU
VU «
pQ g}
U
e <
O m
K 01
«
3 §
a> u
u cu


oo en


vo v CM r-
in v oo v
OO CM rH
rH V
V



VO
rH
CM o ve CM en
0 0 f rH V
o o o o fc.

4J
C

-------


































4. (continued)
i
m
tH
«t
2
•s
f


s
•H
tH 3
VO
n
«

S
'.I5*
*"Jj«
8Jo;


u
u






M
H










Stream
Description


9
n •
t) 0
ti
to








5
r

c

cu





























•s,
»:§§§§§§
a
{3

CD
Ml t~l 01 01 l-l Ml «£>0
r-i i ni mi mi WBI «ni oo cj
01 r-l r-ti 01 mi wi »HO H
o en ro * 'f <^ oo h
v . v . v v *»
c
ro «
Cft f"
(D m «O OOW«HOi
in I cni .HI 01 mi ini «jo
01 tHI iHI 01 mi Ml «0
• 1 *l •! •! •! •! ••
o r» o o o o oo
CM 0
in


o>

*>! cni mi in i <*i 01 eoie
CM ! CM ! mi cni ic l eo i as o
iH »H tH o> eo «•• eo
.H M f* "1







U VI

u | 5
« n a
* 35 5
g I1 5 u u
5 3 0. — S S
2 W S 2 S \ 1
a V* W Qt 3 3 S
rj O E VI U 41
• 3 U 3 0 0 3
4J D" O W W W r^
S 3 fi -g S 5 S
e o» tJ d o o ^
1 1 « a g. s s
O 4J €) O €) V "^
z w * o o > «M



CM m •» » t- « o




5!
8 ' §
«
a

00
l mo
mi mo
tH i mo
en oo



CftO
1 f^ ^3
mi CMO
r> o o
eo
tH

f^
in

t- 1 00
• 1 • •
o i too
o
tH









Salt Feed Tank
Cooling Tower Slowdown



M m


•0 0>
v e
• •H — •
"88- t!
Is "
. w **!
» u "^
U.3 0)
OlTj -l
jC ^L *W
*j^ «
o) t2 o
*_. §
fi> ^J JS
» * *
0) oT
>I4J C
* 10 • -H
•O "D u
« g e 5
u"u ° *
5 O tj
rH it ^J
^* M "*
u o 3

•O «w O S
41 UJ CO (fl
4J 00 O r-l 01
U 01 10 • u

O 5 C flj LI ^ AJ
41 »S* 5s «

SB 10 y 0) O ,_( *
u 2. _j v. ""
z « j: 10 D E . o
*> e »o ,_ w c
« id —"I e
a u . ?. o Ti 2
"o? £vo -
ufficient information
w and concentration values
Id tests were conducted i
ept at F122 where laborato
-day sampling.
oratory testing for total
oratory testing indicated
icated the presence of chl
-day sampling.
Id testing indicated chlor

e .H-H x » ra m c c-i
M fefaOituJJ-nOfc
t
i 1-4 CM m » in «* r-

332

-------
 filtered.  The filtrate is evaporated and  the  hot  solution
                           primarily of noncontact cooling
 "o   r            •    f-s- »-da2rat p^srf
                                         the



Summary of Toxic Pollutant Data
                        333

-------
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
mq/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
1. Cooling Tower Blowdown only
2. Includes only those plants
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
with process

F112(D
0.333
0.00084
<0.004
<0. 00001
<0.023
<0. 00006
oleooso
0.357
OaOOOSO
• 0.215
0.0Q054
<0.008
<0. 00002

-------
      Pollutant
       Maximum Concentration Observed
                    (ug/1)
      Antimony
      Arsenic
      Chromium
      Copper
      Lead
      Mercury
      Nickel
      Silver
      Thallium
      Zinc

      Benzene
      Chloroform
      1,2-Dichloroethane
      Dichlorobromoethane
      Chlorod i bromoethane
      Carbon Tetrachloride
      Methyl Chloride
      Methylene Chloride
      Trichlorofluoromethane
                     2,000
                       610
                    20,000
                     2,800
                     1,300
                       220
                       690
                       500
                     1,100
                     1,100

                        83
                       220
                     4,710
                        95
                        27
                        19
                       183
                        12
                        27
mhi«      ?   .uhlS   report   describes   the   sampling  program
methodology.   In  the  sodium  chlorate   industry,   twelve  davs   of
sampling  were conducted.   Twenty-one  streams we?e lampled  and
     ™v™i.   tOXiC metal P°H«tants was SasJd   on
     analytical   data points  while   toxic  organics  evaluation
consisted of 2,280 analytical data points.  Table ?5- 5  presents
the   toxic  pollutant   raw  waste  data  as  the averaae  dailS
       rai0n8f°nd  in  the  combin^  raw  wSltewale?9 at   tie
                                       averages   for  the
POLLUTION ABATEMENT OPTIONS

Toxic Pollutants of_ Concern
high  concentrations  in  the  wastewaters
                               WaS
Toxic metals found in

res~u??s S|±in?heH-          ,
results  trom  the  addition  of  sodium  dichromate  to  inhibif
corrosion and to reduce the formation of hypochlorite ion   Other
metals  detected  in  the wastewaters may be con?ainld in'the rlw
          ^ (br^6S °C r°Ck salt) whic^' in some cases? may  be
 »«         °m u°ther  Product Process wastewater streams .   ThesI
impurities may be released to sodium chlorate wastewater  streaml
                              335

-------
during purification processes.  The extensive use of recycling in
this  industry  would tend 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
fSSfSt significantly higher "concentrations.  This pollutant was
nresent  in  all wastewater streams sampled at one facility.  Its
lourceis considered to be the  river  water  which  is  used  to
Tislolve  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.   s^n£e  *ne
1  2-Dichloroethane was found  at only one plant and is  related  to
its  presence   in  the  intake  water  at  that plant  the Agency
proposes to exclude that pollutant under Paragraph 8(a)  (in)  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
 (FU1? F114?  F131,  Fill,   F136,  F105   and  F135)   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 F114 are recycled and blended
 with a brine solution obtained from an adjacent plant.  In  1980,
 tne p?ant 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.
                                336

-------
 Plant Fi 31 does not discharge any wastewater  streams  to  either
 i£  S?SrE   5 °^ treatment facilities.  Noncontact cooling wat«
 controf  ThJ t i   t- ^  in~Plant  holding  pond  for  use in dust
 m?n«m i' K *  Pla"t uses a pure salt as the  raw  material,  with
 SJriSSir.:    S  P^ification wastes.  The plant does not have air
 nrnHnS  4 ^ Produces ?nly solution grade sodium chlorate.   The
 product is not filtered before shipment.

 Plant Fill discharges all wastewater streams  to  surface  water
 waLr   Sn™J°Ur?e  °f  wastewater  flow  is noncontact cooling
 water.   Sources  of  process  contact  wastewater  include  brine
                    PK°dUCt /ilter bac^ashes,  chlorate trench and
            streams'  barometric  condensate,   and  water  used  to
                   from  cell  off -gases.   No  information on any
 bu     mf treatment  including in-plant treatment,  is  available
 levels  Tn ?he filr^  data,  indicate that  chlorine and chromium
 levels  in the discharge are low.   The plant  uses an  impure brine

          m   C1       M°St  °f  the Pr°duCt is Sold as s°lid
 At  Plant  F136,  the source  of  raw material  is purified brine  from
 an  ad3acent  chlor-alkali plant.   Most  wastewater is recycled  but
 washf  aandSCr±nr «as^*j >  washwater  (cell  wash and tank car
 wash)   and   pump  seal   water   is  combined with  chlor-alkali
                n°ncontact  cooling water  before PH adjustment  and
At  Plant  FT 05,  wastewater streams consisting  of  equipment wash
water and cooling water are combined with pulp   mill  wastewater

  aaaa
Plant  F135  combines  wastewater  streams  from  sodium chlorate
production with pulp mill effluent.  No  information  is  availablJ
2?fi!!2!Je?at?'  treatment  technologies  at this plant.  The final
effluent is discharged to surface water.

other Applicable Control/Treatment Technologies
ron«==                 technol°gy ^ 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  whe?e  treatment  effects  the
removal of toxic metals and chlorine.  Over half of the plants in
the industry also practice either complete or extensive ?ecycliiS
?LhP ?°e?S  wa»tewater.    Other  identified control or treatment
technologies  which  might  be  applicable   include   hexavalent
                              337

-------
chromium   reduction,   dual-media   filtration,   and   chlorine
reduction.

The Zero Discharge Option
barometric  condenser  water,   to dissolve the salt; plants using
brines cannot recycle much water for  this purpose.  Plants  using
Durilied brine or purified salt generate minimal amounts x>f brine
nurif ication  process  wastewater  whereas  plants  using natural
brines or ?ockPsalt  must  purify the   brine  before  electrolysis,
thus  generating a significant ^ount 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
Slants  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  salt9 anyhow),  and does not filter its product
 solution,  thus eliminating that source of wastewater  also.   The
 customers   for  the  fourth   plant  apparently  do  not  "quire
 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 le?o 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  reduce the amount  of   process   wastewater
 discharged  include  the  following:
                                338

-------
5.
           Recycle of scrubber wastewater within the
           improve reagent utilization.
                                                scrubber   to
           Use of sodium hydroxide as the alkali in the  scrubbers
           so  that  the  water is amenable to reuse in the plant.
           Calci urn-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.

           Operations using rock salt use the recycled  wastewater
           in dissolving the salt.

           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.

           procesf  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 storaae
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 hiah
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
                              339

-------
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,
                               340

-------
 and  suspended  solids.   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.

 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   antimonv
 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  sludqe
 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
hazardous materials landfill.   The  sludge  was  assumed  to  be
hazardous because of its high metal content.
                              341

-------
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.

General

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
                               342

-------
 The model  plant  for  the  sodium  chlorate  subcategorv  has  a
 production  rate  of 32,000 metric tons per year and a daily flow
 Sofof   ZuCU^lc meters Per day-   These figures were used as the
 Figure ?5-3U)atment  CO8t .. ^iinates  at  both  levels.    See


 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  mVdav  for
Level  1 and an additional  0.002  mVday  for  Level  2.

M2de3,  Plant Treatment Costs.  On the basis  of  the  model  nlant
specifications  and  design  concepts   presented  earlier  £A ?„
fwo^LL?' the estimated  c°sts  °f treatmeTfor  one  moLl  witS
increment? t^Lev^T  "  ™*   ^6'   ^e cost of  Level T^

Basis  for Regulations

Basis  for BPT Limitations

A.   Technology Basis

For BPT,  the Agency is setting limitations based upon  hexavalent
       t
                                     .
discharge and thus would not be affected.
B.   Flow Basis
                                                             zero
        sodium chlorate  subcategory,  a  unit  flow  rate  of  2 7
        -''b                                    *
                             343

-------
„-,.
                        s™gs,jgSSgS«S9iS
 SUBCATEGORY:  Sodium Chlorate

 ANNUAL PRODUCTION:        32,000

 DAILY FLOW: 	

 PLANT AGE:	
          237
                      CUBIC  METERS
        NA
                YEARS   PLANT LOCATION:'
J2A.
                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

   Total Annual Cost

                b.  RESULTING WASTE-
                         COSTS ($1,000)  TO  ATTAIN  LEVEL

                         1      2

                          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.
Parameter
              Avg.  Cone.

              Untreated(mg/1)
   pH             7.0
   TSS           50
   Cr  (Total)     4.7
   .Chlorine      20
      (Total Residual)
                          c.
                          161.8  16.6

                         LOAD  CHARACTERISTICS
                                    Long-Term Avg.
                                 Concentration  (mg/1)
                               After Treatment  To Level

                         _L     -L

                         6-9    6-9 ,
                          13     9.3
                           0.25  0.16
                           0.64  0.64
                              TREATMENT DESCRIPTION
  LEVEL l:  Hexava^t^roMu^duction,  ^lorine^eductlon,

  LEVEL 2:  Filtration
                                344

-------
 c.
      Selection of Pollutants to be Regulated
                   u P°llutants  for   which   specific   effluent
              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  pS'
 ii£2[?ture data   historical  discharge  monitoring  reports

 poUutantsPP      °nS'   ^   the   treatability  of  the
                    8:,14 ST13^26 the  achievable  concentrations
    h«             P°llutants  from the literature using available
 technology options, other industries, and  treatability  studies
                                                           ™
                                                         are
                                             ,
 screening and verification sampling at several

              f11^  J" tMs Se^ti0"-   Data f?o         xon   e
             S   tn"?lac?u l"dustry  treatment  systems  was  also
             developing the list of pollutants to be regulated.
 me UP°?-  the occurrence of treatable levels of specific toxic
 metals,  antimony and chromium were selected  as  candidate  toxic
bv
                  un         c..
                ml™.,.and  Chlorine will  be  reduced  slmultLieouIly
                  UttnChaS  *1S°   SSl               "
antimony and chromium as the toxic pollutants to be regulated.

D.   Basis of BPT Pollutant Limitations


                                  concentrations <»g/D and loads

                                       th€ tW° iS based on a unit
flow rte o
                            -
                 mVkkg"°nShlP
BPT  limitations,  which  apply   to   all
discharged, are presented in Table 15-8.
                                             process   wastewater
                              345

-------
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  (F125,  F115  and  F140)
          considered  to  be  efficiently  operating   their
          wastewater treatment facilities provided long-term
          Level 1 treatment system performance data for TSS.
          Since  no  other  data  from well-operated Level 1
          treatment systems was  available,  and  since  the
          clarification  provided  at  plants FT25, FITS 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 F140.  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
          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/1) (2.7 mVkkg)(kg/10« mg)(1000 1/m3)
          - 0.068 kg/kkg

          24-hour maximum:
                         346

-------
          (43 mg/l)(2.7 mVkkg) (kg/10« mgHlOOO 1/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« mgMlOOO 1/m*)
          =  0.0027 kg/kkg

          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 data 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
                        347

-------
               respectively.    Utilizing    these    values,  mass
               limitations  for antimony are  obtained as  follows:

               30-day average;

               (1.6 mg/l)(2.7 mVkkg) (kg/10«mg) (1000 1/m*)
               « 0.0043 kg/kkg

               24-hour maximum;

               (3.2 mg/l)(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).
               factors are  based  on  that   same
               plant  is  achieving  a  long-term
               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:

               30-day average;

               (0.9 mg/l)(2.7 mVkkg) (kg/10« mg)(1000 1/m*)
               = 0.0024 kg/kkg

               24-hour maximum;

               (1.5 mg/1) (2.7 mVkkg) (kg/10« mg)(1000 1/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
The variability
facility.   The
 average  total
                              348

-------
           TABLE 15-7.  BPT EFFLUENT LIMITATIONS FOR SODIUM CHLORATE
 Conventional    Long-Term
 Pollutants      Avg-(mg/l)
TSS

Toxic
Pollutants

Antimony
 (Total)


Chromium
 (Total)
                13
                 0.8*
                 0.25(2)
Non-Conventional
Pollutants	

Chlorine
 (Total
  Residual)     0.64
                     (3)
   VFR
 1.9/3.3
                                       CD
2/4
   (2)
2/4(2)
                               1.4/2.3
       (3)
                                             Cone. Basis
                                                (mq/1)
                                            30-day  24-hr,
                                             avg.     max.
                                            25-
                                             1.6
                                             0.5
              0.9
43
                                                     1.0
                                                    1.5
        Effluent Limit
           (kq/kkg)
        30-day  24-hr.
         avq.    max.
0.068   0.12
                                                     3.2     0.0043   0.0086
                              0.0014   0.0027
       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 Bichromate
    Subcategory - Phase I.
(3) LTA and limitations based upon promulgated total residual  chlorine
                                                     I  - Chlor-Alkali
*From Table 8-11.

See Phase I Inorganic Chemicals Development Document; EPA 440/1-82-007.
                               349

-------
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
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     =
          Level 2 long-term average*
          Difference
13   mg/1
 9.3 mg/1
3.7 mg/1
*(See Sections  11 and  12 for derivation)

     (b)  Annual flow  for model plant:
          (2.7  mVkkg)  (32,000 kkg/yr) = 86,400 mVyr

     (c)  Total annual  additional TSS removed for model plants

          (3.7  mg/1)  (86,000 mVyr)  (kg/10«mg)(1000  1/m3)
          *  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,
          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.

 Since   the  candidate  BCT technology  failed the BCT cost test, EPA
 is  not  proposing any  more  stringent  limitations for  TSS under BCT
 since  we  have  identified no other technology which   would   remove
 additional   amounts of TSS.  As  a result, BCT for TSS  is equal  to
 the BPT Limitations.
                               350

-------
 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   consideration   in    the
 determination of the BAT regulations.

 For  BAT,  the Agency is proposing limitations based on  treatment
           °J ^T ] ?JVS i?Yel  2'  Level 2 adds 9^™^   media
           of the Level  1 efflunet.  The toxic pollutants limited
 by   the  proposed   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

 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
                              351

-------
             for  the  30-day  average  and 4.0 for the 24-hour



             limitations'  for  chromium   in the sodium chlorate
             subcategory  are calculated as follows:

             30-day  average;

              (0.32 mg/l>(2.7 m'/kkgXkg/10* mg)(lOOO  l/m»)
             = 0.00086  kg/kkg

             24-hour maximum;

              (0.64 mg/l)(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
              ?SeS  from  industry  performance  data  in Table
              a-il      The    lowest     reported     achievable
              concentration  of  0.4 mg/1 for antimony utilizing
               lime addition plus  filtration  is  taken  as  the
               loSa-term average.  The variability factors of 2.0
               flT 30™ay  average  and   4.0  for  24-hour maximum
               used for chromium are used  for  antimony,  JieWinj
               effluent  antimony  concentrations  of 0.8 mg/1 and
               1.6 mg/1 respectively.  The mass  limitations  are
               calculated  as follows;

               30-dav average;

               (0.80  mg/1) (2.7  m'/kkg)(kg/1 (>•)( 1000  l/m»)
               = 0.0022  kg/kkg

               24-hour maximum;

               (1.6 mg/1)(2.7  m3/kkg)(kg/lO«  mg)(1000
               = 0.0044 kg/kkg

     Non-Conventional Pollutants

Total  residual  chlorine has been selected for controller

concentra?!onraanld ,SdiSTSc4«?Sr BA^a.e the sane as £or
BPT for this parameter.
                               352

-------
    TABLE  15-8.  BAT EFFLUENT LIMITATIONS  FOR  SODIUM CHLORATE  SUBCATEGORY
Toxic
Pollutants
          Long-Term
          Avg.(mg/1)
Antimony  (T)    0,4*
                                 VFR
                        2/4
                                  (2)
      Cone. Basis
          (mg/1)
      30-day   24-hr.
      avg.    max.
                                                           Effluent  Limit
                                                               [kg/kkg)
      0.80
        30-day24-hr.
         avg.    max.
 1.6     0.0022   0.0043
Chromium  (T)     0.16d)
                        2/4(2)
      0.32     0.64     Q-..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

VFR
Long-term average achievable level.

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.
                                353

-------
Basis for NSPS Effluent Limitations

For NSPS, the Agency is proposing limitations equal to BAT  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
pH  TSS and chlorine limitations are found  in Table 15-7, and the
antimony and chromium limitations are found in Table  15-8.

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  15-6,  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)  t (0.8)]  (100)
                           =  52%

          Chromium (Total);  Raw Waste =6.2 mg/1
                             BAT       =  0-. 1 6 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  "40  Cities   study
 (Fate  of  Priority Pollutants iri Publicly Owned Treatment Works,
 Final Report,  EPA  440/1-82/303,  September,  1982).   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
 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 Table 15-6,  the  Agency  has
 also  estimated  the  percent  removals  for  antimony  and total
                                354

-------
 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)
50%
f (0.8)] (TOO)
          Chromium  (Total)  BPT  =0.25  mg/1
                            BAT  =0.16  mg/1
          Percent Removal
[(0.25 - 0.16)
36%
  -r (0.25) ]  (TOO)
The  percent  removals  for   total   chromium   are   less   than  the
removals achieved by  25% of the  POTWs  in  the   "40   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^   *t?+ez   '.hat  the
average  hexavalent   chromium  removal fo»- ^l^nts  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 FOTw'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
"40 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
discharge  of  antimony  to  POTW in the  sodium chlorate  industry
with pretreatment limitations based on BAT technology.

Existing Sources
                              355

-------
Since there are no indirect dischargers in this subcategory,
                                                              the
Agreement .

New Sources

The Agency is proposing PSNS that are equal to NSPS because these
standards provide for the removal of antimony and chromium, which
would likely pas! through a well  operated  POTW  with  secondary
treatment  in  the absence of pretreatment.  Pollutants regulated
SESSfpSHS are antimony and chromium,  Chlorine is not  regulated
under PSNS because POTW influent is often chlorinated.
                                356

-------
 1.


 2.


 3.



4.
SECTION 15
REFERENCES



                *••
                            357

-------
                           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
S3?  batteries; oil well completion fluids; tinning; galvanizing
and soldering fluxes;'and for the preservation and  flameproofing
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 = ZnCl2  +  H2

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
                                358

-------
            TABLE 16-1.   SUBCATEGORY PROFILE DATA FOR
                          ZINC CHLORIDE
 Number  of Plants  in Subcategory

 Total Subcategory Production Rate
     Minimum
     Maximum
Total Subcategory Wastewater Dischargt
     Minimum
     Maximum
Types of Wastewater Discharge
     Direct
     Indirect
     Zero
>25,000 kkg/yr'
    <4.5 kkg/yr
 Confidential

  >1500 m3/day
     26 m3/day
    719 m3/day
      5
      2
      0
                           359

-------
-p
u
-^ n

Filter
'1
04
t-l

0
en
Concentrator

0 W
•H rH
4J nt
n) u
O -H
••-I E -^
j./
Evaporator
—>
^

Scrubber
•u
•H
l-l
•H
r,.
H
0)
4J
•H
b

0) 0)
•|J Jtff
•HO
b

                            1
360

-------
      TABLE 16-2.  WATER USAGE AT ZINC CHLORIDE FACILITIES(D
WATER USE
Noncontact
Cooling
Direct Process
Contact
Indirect Process
Contact
Maintenance
Air Pollution
Scrubbers
Noncontact
Ancillary
TOTALS

F125
0
0
4.94
NA
NA
NA
4.94
Flow (m3/kkg of zinc
Plant Desianat
F140 F120
0 0
!-6 0.03
13.65 0.69
0.03 0.05
0 1.38
0.32 0.10
15.6 2.25
Chloride)
ion
F144
0
5.67
7.56
0.05
0
NA
13.3

F143
5.73
0
1.62
0.42
3.33
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
                             361

-------
     TABLE 16-3.   WASTEWATER AT ZINC CHLORIDE FACILITIES

WASTEWATER SOURCE F125
Direct Process
Contact 0
Indirect Process
Contact 4.94
Maintenance NA
Air Pollution
Scrubbers NA
TOTALS 4.94
Noncontact
Cooling 0
Noncontact
Ancillary NA
Storm Water NA
Flow (m3/kkg of Zinc Chloride)
Plant Designation
F140 F120 F144 F14J
1.6 0 1.89 0
13.65 0.69(2) 7.56 1.62
0 NA(2) 0.05 0.42
0 1.24(2) 0 3.33
15.3 1.93 9.5 5.37
00 0 5.73
0.032 0.01 NA 1.39
NA ^ 7.14 0.53 2.67
NA   Flow volume not available.


1.   Values   indicated   only  for  those   plants  that  reported
     separate and complete information.
2.   Wastewater recycled within plant.
3.   Stormwater unknown but not zero.


Source:  Section 308 Questionnaires and Plant Visit Reports
                              362

-------
 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   8308   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
 C5i?f^de 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   existina
 seven plants.                                               =>*-iny

 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
                              363

-------
                       o 33
364

-------
              ZnCl.,  Other Product Process Wastewater

                            »2
                                               <—®    Supply Water
                          O//3
                       Limestone
                       Neutralization
                       Clarifier
                           (Underflow)
          (Centrate) L
                       Centrifuge
                       Solids
                                                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.
                                   365

-------
purification/evaporation stage.






          So!rP?ocesf »^e a? -fst S| , I  one ana a hal£ yea..

5iSS£i: InloThe S'            n^rtnffact that there
has been no discharge.
                     -In        -iS.t2t ^s  'Si.
         rlSovI?"r?ir to recycle o? discharge (optional

                                              asociae   sa.pl in,
 locations at Plant F120
 sold as a solution or as a solid product.
                                366

-------
and  the  centrate  is  recycled to the beginning of the process.
Plant Fl44 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 F144 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.

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 F145 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
                              367

-------






D .
J
§
CO
tf
£
to
§
«4
a-*
ss to
M
to EH
5S H
0 ^
M M
P
«z r^i
W Q
2 P4
00
o 3
EH O
EH a
53 H
r4 N

2

**
VD
rH
W
1
EH







VI





X)


u>
rH JC
e en




g





to
to
EH




Stream
Description


e
(0 •
0) O
vi 5S
to











0
CO
rH
4J
C
R
ft




















rH CT»
CO O O
00 O rH O
O O CO O
O O O O


00 CO
CO f~ CO
o o vo o
00 O 00 O
rHO HO


in co
H 0 -*
en o oo o ^*
O O CO O rH
rH 0 00 fe
O O O O 4J
R
rH
CM
2
r- r- o
o ^* o
CO rH 0
CO O O O
CO
VN


r*
r-i
r*- *"~i
^^ ^4*
CO O O rH
in co
o
* •

VI
0)

Vi 3
flj VI
XI O
xi to
S 0
0 "H
to -u
(0
-U D
(1) R)



rH CO


o o
CO T** Cft CM VD
CO rH VO CO r- 0
in o o rH o o
o o co o o o


CO 0
«fl« 00 CO
t«. co in oo ^* o
O O rH rH O O
rH 0 *» 0 00
o o o o o o

o
r- VD r-
co o m m o o
CO O CO O rH O
00 HO 00
o o o o o o
V V

vo
m
t— c*
t— CO CO CA O O
*y *4< O O HO
00 ^" H
H CO



vo **
eo H oo
co oo r- co r* oo
00 O VO H HO
CO CO H

4J
c
0)
3
V4 H
<1) UH
* PS vi
0) 4) VI
4J *O ^ ^
OJ 4) RJ .1-1
«J C S MH
a -«H v> ••H
JQ-U »j
S g w 
VI
(d
0)
4J

4J
0)
(0
0)
VI
a
Q)
VI
0)
•0
(0
o
rH
•o
m
ncentrations
0
o

^
rH

368

-------
 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
 Ko?™VS • loVfrom  the clarifiers receives biological treatment
 before being discharged directly to a receiving stream.

 Summary of Toxic Pollutant Data

 Eleven toxic metals were found at  detectable  concentrations  in
   vi  faw *astewater 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,
525l"m«1c
-------
TABLE 16-5.  TOXIC POLLUTANT RAW WASTE DATA FOR SAMPLED
                ZINC  CHLORIDE FACILITIES
Average
Daily Pollutant Concentrations and Loads
mg/1
kg/kkg
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
0.142
0.00039
0.325
0.00090
111.724
0.308
Plant
Designation
F144
0.
0.
<0.
tf.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
<0.
0.
<0.
0.
184.
4.
045
00104
006
00014
032
00074
520
0121
067
00155
107
00248
017
00039
001
00002
100
00232
700
29
Overall
Average
0 .74
o!o0250
<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
                          370

-------
  Section   5   of   this   report  describes  the  methodology  of the
  sampling  program.   In  the  zinc chloride industry,  a totll of  six
  days   of  sampling  were conducted at  Plants FT 20  and F144?  Five
                     ^ samPled and analyzed.   The evaluation  of
      ti a
 POLLUTION ABATEMENT OPTIONS

 Toxic Pollutants of Concern


 The principal pollutant of concern  is  zinc.   Other  pollutants
 found  in  significant  concentrations in the process wastewaterl

 so^ef^lhelox'^ ^^ PUrU? °f the  ZinC  Stll ^T SSd
 nickel fonrJ H,,^n        ? arsenic, antimony, lead, chromium and
 «if«?«af     during screening and  verification  sampling  likely

 ?aw9 zinc aLt^tUeStSH0Vhe 9alvanizer skimmings usld as the
 f~ n*   ?  material.   Highest concentrations of these metals were
 found primarily in the scrubber  wastewater  streams  from  PlSt

       in 5L.;C?UbSr St?P Preceeds the heavy metals removal stSp
         J eve^al other plant  processes.    Therefore,  such  high
         °f the above-mentioned heavy metals would not be expected

   actor gfses!  ^    °perations included scrubbing of  the  Zn/HCl


 Existing Wastewater Control  and Treatment Practices
           Pfa£ticef.at the visited plants were presented earlier
 presented .belSl!    °" ^ treatment Practices at other plants Ire
consisting of
sedimentation
               	  —  •" — ~»»-»*  wj.  J.O.JICVJ
before discharge to a receiving stream.
to a chemical landfill.
                                            is
                                          and  unlined impoundments
                                          Solid  wastes are  hauled
a   hr*«    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.  Process
       ^ equallzed and neutralized  prior  to  discharge  tS  5
otner Applicable Control/Treatment Technologies
                              371

-------
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
be applicable to this industry is filtration for  further  solids
and toxic metal removal.

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.   None  of  the  existing  zinc  chloride  manufacturers  has
achieved  zero discharge.

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   stornu 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
                               372

-------
constituents  can  be  transmitted  to  the  wastewater.  Further
reduction of metals would require  treatment  by  granular  media
filtration.

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, dewatering of the sludge in a filter
press, and  pH  adjustment  if  necessary.   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.  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.

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
                              373

-------
plants have equivalent treatment installed.

Equipment for Different Treatment Levels

A    Equipment Functions
 readily  available.

 B.    Chemical  Handling

       -^..
 Ssed tS reduce the pH of the wastewater prior to discharge.
 C.    Solids Handling
 high, may be sent directly to the, filter press.

 Treatment Cost Estimates
                                374

-------
      TABLE  16-6.  WATER EFFLUENT TREATMENT COSTS AND RESULTING
                  WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY:   Zinc  Chloride
ANNUAL PRODUCTION: 	

DAILY FLOW:	I.QQQ

PLANT AGE:         NA
                          26.000
METRIC TONS
                                 CUBIC METERS
                           YEARS   PLANT LOCATION:
                 NA
           a.  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
COST CATEGORY

Facilities
Installed Equipment
   Concluding Instrumentation)
Engineering
Contractor Overhead and Profit
Contingency
Land

  Total Invested Capital
Annual Capital Recovery
Annual Operating and Maintenance
(Excluding Residual Waste Disposal)120.8  22.5
Residual Waste Disposal               5.9*  0.2
                                   216.6  43.0
                                    COSTS  ($1,000) TO ATTAIN LEVEL

                                    1234       5

                                    59.0

                                   305.0   82.2
                                    72.'8   16.4
                                    65.5   14.8
                                    50.2   11.3


                                   552.5 124.7

                                    89.9   20.3
Total Annual Cost


Parameter
pH
TSS
As
Pb
Zn
b . RES
Avg . Cone .
Untreated (
2.6
300
2.8
0.86
150
                   RESULTING WASTE-LOAD CHARACTERISTICS
                                              Long-Term Avg.
                                           Concentration  (mg/1)
                                         After Treatment To Level
                         rl)         12345
                                   6-9
                                    13
                                     0.5
                                     0.3
                                     0.93
                                          6-9
                                           9.3
                                           0.5
                                           0.035
                                           0.23
LEVEL 2:
                        c.  TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, sludge dewatering,
inirei 9. c-PS  adjustment
              ration
                                 375

-------
     TABLE  16-7.  WATER EFFLUENT TREATMENT COSTS AND RESULTING
                  WASTE-LOAD CHARACTERISTICS FOR MODEL PLANT
SUBCATEGORY: ''  Zinc  Chloride
ANNUAL PRODUCTION:   5,700

DAILY FLOW: 	

PLANT AGE:
                       METRIC TONS
     260
N/A
	 CUBIC METERS

 YEARS   PLANT LOCATION:
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)  95.7
Residual Waste Disposal
                  COSTS  ($1,000) TO ATTAIN LEVEL

                  12345

                   21.6
156.8
35.7
32.1
24.6
270.8
44.1
95.7
2.1
29.4
5.9
5.3
4.1
44.7
7.3
8.9
0.1
Total Annual Cost


Parameter
pH
TSS
As
Pb
Zn
b. RES
Avg. Cone.
Untreated (
2.6
300
2.8
1.6
185
                                    141.9   16.3

                   RESULTING WASTE-LOAD  CHARACTERISTICS
                                              Long-Term Ayg.
                                           Concentration (mg/1)
                                         After Treatment To Level
                         Ml         12345
                                    6-9
                                   13
                                    0.5
                                    0.3
                                    0.93
                        6-9
                        9.3
                        0.5
                        0.035
                        0.23
                        c.  TREATMENT DESCRIPTION
LEVEL 1: Alkaline precipitation, clarification, sludge dewatering,  pH
         adjustment.
LEVEL 2: Filtration
                                   376

-------
 several  larger  plants which  produce over 90 percent of   the  zinc
 chloride in the U.S.

 Costs  for   two  model  plants  were developed  because of the wide
 variation  of   plant   sizes   in  this   subcategory.   The  annual
 production   rates  used   were  26,000   kkg   and   5,700   kkg.   The
 wastewater   flows  used   were  1000   mVday  and    260   mVday
 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 model
 plants are  estimated  as  follows:
                               Large Plant   Small Plant
     Ca(OH)2
     H2S04  (100 percent)
       400 kg/day
       100 kg/day
88 kg/day (1)
22 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 mVday
    0.011 m»/day
    Small Plant

    0.086 mVday
    0.0024 m'/day
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 16-6 and 16-7.  The cost of Level
2 is incremental to Level 1.

Basis for Regulations

Basis for BPT Limitations

A.   Technology Basis
                              377

-------
 For BPT,  the Agency  is  setting  limitations   based   upon  alkaline
 precipitation   and   clarification,   followed by  pH  adjustment  (if
 necessary), 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

 For the  Zinc Chloride Subcategory,   a   unit   flow   rate  of  13.5
 mVkkg   was selected as being representative of  the group for  the
 reasons  given  above  under treatment  cost estimates.

 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
                              378

-------
^i  x£f i°ns 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 13.5 mVkkg.
BPT   limitations,   which   apply   to  all
discharged, are presented in Table 16-8.

     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
               Guidelines for Phase I Inorganic  Chemicals  (Ref
               1) and the JRB study {Ref.  2).

          b.   TSS
               Three  Phase  II  plants  (F125,   F115  and  F140)
               considered   to   be  efficently   operating  their
               wastewater treatment facilities provided long-term
               Level 1  treatment system performance data for TSS.
               Since no other data  from  well-operated  Level   1
               treatment  systems  was  available,   and since the
               clarification provided at Plants   F125,   F115  and
               F140   for  TSS  removal  would be similar to that
               necessary for TSS removal at  zinc  chloride  plants
               (Plants   F125  and F140 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   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.)    Thus,   utilizing
               these values,  one obtains TSS mass limitations for
               the zinc  chloride subcategory of:

               30-day average;

               (25 mg/l){13.5  mVkkg) (kg/1 0«  mgMlOOO 1/m3)
               = 0.34 kg/kkg
                             379

-------
          24-hour maximum;

          (43 mg/l)(13.5 mVkkg) (kg/10* mg)(1000
          =0.58 kg/kkg
2.   Toxic Pollutants

     a.   Arsenic
          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 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.    Mass
          limitations are computed as follows:
          30-day average;

          (1.0 mg/1) (13.5 m-Vkkg)(kg/10« mg)
          = 0.014 kg/kkg

          24-hour maximum:
(1000 l/m')
          (3.0 mg/1) (13.5 mVkkg) (kg/1 0® mg) (1000 1/m')
          = 0.041 kg/kkg
     b.    Lead
          Because there are no  long-term  performance  data
          for lead from any 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 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
          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.  Using these values, mass
          limitations for lead are calculated as follows:
                         380

-------
                (0.6 mg/l)(l3.5 mVkkg) (kg/10* mg)(1000
                = 0.0081 kg/kkg

                24-hour maximum;

                (1.8 mg/l)O3.5 mVkkg) (kg/1 0«) (1000 l/m»)
                = 0.024 kg/kkg
           c.    Zinc
                The BPT limitations for zinc are  based  on  long-
                term  monitoring data from Plant F118 presented in
                Appendix A.   The plant has  a  Level   1   treatment
                system.     The  plant  is   achieving   a  long-term
                average  concentration  for  zinc  of  0.93  mg/1
                Variability  factors  for   zinc developed at Plant
                F144,  and  presented  in  Appendix A,   were  used
                because the data from Plant F118 was  not in a form
                that could  be used  to develop variability factors.
                These   are   2.0  for a 30-day average  and 6.0 for a
                24-hour maximum.  From these  values,   limitations
                or   1.9  mg/1,  30-day average and 5.6  mg/1,  24-hour
                maximum,  were derived.   Utilizing these  values
                mass limitations for the Zinc Chloride  Subcategory
                may  be  obtained  as  follows:
               M-day average;
                       ,
               - 0.026 kg/kkg

               24-hour maximum;
                               m3/kkg)( kg/10* mg)  (1000  l/m»)
               (5.6 mg/1) (13.5 mVkkg) (kg/10« mg)  (1000 I/in*)
               * 0.076 kg/kkg
Basis for BCT Effluent Limitations
                          a,.1?
are  required  according  to the revised methodology, a POTW test
and an industry cost effectiveness test.  The POTW test is passed
   theinren>ental  cost  per  pound  of  conventional  pollutant

      dolrTh0m-B?T ^° BCT iS less than $°'46 Per Pound ?n
      dollars.    The  industry  test  is  passed  if  this
incremental  cost  per  pound  is  less  than  143 percent of
incremental cost per pound associated with achieving I3PT
                              381

-------
    TABLE  16-8.   BPT  EFFLUENT  LIMITATIONS  FOR ZINC CHLORIDE
Coventional
Pollutants
Long-Term
Avg-Cmg/1)
VFR
           Cone. Basis  Effluent Limit
               Cmg/1J        (kg/kkg) '
           3TF~day 24-hr.30-day  24-hr.
                   max.  avg.
                      max.
TSS

Toxic
Pollutants

Arsenic

Zinc

Lead
                  13.0
                  0.93
                       (4)
                  0.3
                      ^
               1.9/3.3
               2/6

               2/6

               2/6
 (3)

 (3)

 (3)
25




 1.0

 1.9

 0.6
                  43
     0.34
0.58
3.0  0.014   0.041

5.6  0.026   0.076

1.8  0.0081  0.024
VFR - Variability Factor Ratio
(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 F118.
                              382

-------
The methodology for the first BCT cost test is as follows:
(1)
     Calculate that amount of additional TSS removed by the BCT technology,

     (a)   BPT long-term average       =' 13 mg/i
          Level 2 long-term average * = 9.3 mg/1
          *(See Sections 11  and 12 for derivation)
     (b)
          Difference                «  3<7 mg/1

          Annual  flow for  model  plant:
          (13.5 mVkkg)(5,700 kkg/yr)
          (13.5 m3/kkg)(26,000 kkg/yr)
                                          76,950 m'/vr "Small
                                          351,000 mVyr "
     (0  Total annual additional TSS removed for model plant:

         Small Plant:

         (3;LmE/:l)(76/950 m3/yr)(kg/10« ing) (1000 l/m3)
         = 2B5 kg/yr
         = 628 Ibs/yr

         Large Plant:


         l^Lj^k1/*351'000 m3/yr)(k9/10«mg)(1000 l/m')
         * 2864 Ibs/yr


                                                         of TSS
                              Cost'
                               cost for Levei 2
         $16,300 "Small",  and $43,000 "Large"

    (b)   Divide annual ized cost by annual additional TSS removals:

         ($16,300 per yr)  * (628 Ibs/yr)  = $25.96 per Ib of TSS
                               removed for small model plant.
         ($43,000 per year)  t (2864 Ibs/yr)  = $15.01  per Ib of TSS
                                              removed for the  large
                                              model  plant.

                            383

-------
the  first BCT cost test there is no need to apply the second BCT
cost test.
Since the candidate BCT technology failed the  BCT  -  POTW  cost
test, EPA is not proposing any more stringent limitations for TSS
under  BCT  since  we  have  identified no other technology which
would remove additional amounts of TSS.  As a result, BCT for TSS
is equal to the BPT limitations.

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.
               impacts on the Zinc Chloride Subcategory have been
               detail  and  taken  into  consideration   in   the
The  economic
evaluated  in
determination of the BAT regulations.

For  BAT,  the Agency is proposing limitations based on treatment
consisting of Level 1 plus Level 2 technology.  Toxic  pollutants
limited  by  the  proposed  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 followed by pH adjustment if necessary form the selected
BAT technology basis.
B.
     Flow Basis
A unit wastewater flow rate of 13.5 m3/kkg of zinc  chloride  has
been selected for BAT (same as BPT).

C.   Selection of Pollutants to be Regulated

     Toxic Pollutants

The toxic pollutants arsenic, lead, and zinc have  been  selected
for  BAT limitation.  Table 16-9 presents the BAT limitations for
the Zinc Chloride Subcategory.
D.
     Basis of BAT Pollutant Limitations
As  in  BPT,  the  BAT  limitations   are   presented   as   both
concentrations  (mg/1) and loads (kg/kkg).  Loadings were derived
                              384

-------
                               USing
                                          model  plant  flow
Toxic Pollutants


a.   Arsenic



     Because there  is  no.  long-term  monitoring  data  for

                ?n /AT limitati°ns for arsenic are based on

      ron    2~?ay  avera9es  achievable  with  Level  2
     treatment   taken  from  Table  8-11,   and  variability

     factors computed from long-term data for zinc at  Plant

     ma/t  Presented  *n  Appendix  A.   Using a value of 0 5

     factor  ?nr ?n9^term  average'   2'°  ™  a  variability
     lac?°F.1for 30~day average concentrations,  and 6 0 as a
        m-»               maximum)   are
      imitations are computed as follows:


     30-day average;
                                           obtined.     Mass
    24-hour maximum;
                                   mg)(1000 l/m')
b.
    Lead
    The BAT limitations for lead  are  based
               lan                                         x
              plant achieves a  long-term  average  effluent
     lead  concentration of 0.035 mg/1.   Variability factors

            d at Plant/144 were used.   These are K25 fo? 1

            average and 4.8 for  a  24-hour  maximum.    F?om
             values,    limitations  of   0.044  ma/1

                       mg/1'  24-hour ^aximum  we?e '
                      are computed as follows;


          30-day averae;
    tk
    these
     ™
    Mass
         24-hour maximuma
                       385

-------
               (0.17 mg/l)(13.5 mVkkg) (kg/10« mg)(1000 1/m*)
               = 0.0023 kg/kkg
     c.
Zinc
          The BAT limitations for zinc are based  upon  long-term
          monitoring  data from Plant F144, presented in Appendix
          A.   This plant achieves a  long-term  average  effluent
          zinc  concentration of 0.225 mg/1.  Variability factors
          developed for 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 0.45 mg/1, 30-day average, and
          1.35  mg/1,  24-hour  maximum,  are   obtained.    Mass
          limitations are computed as follows:

          30-day average;

          (0.45 mg/1) (13.5 mVkkg) (kg/10« mg)(1000 1/m')
          « 0.0061 kg/kkg

          24-hour maximum;

          (1.35 mg/l)(13.5 mVkkgH kg/10* mgMlOOO 1/m')
          - 0.018 kg/kkg

Basis for NSPS Effluent Limitations

For  NSPS,  the  Agency is proposing limitations equal to BAT for
toxic pollutants and BPT for  conventional  pollutants  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 Tables 16-8 and 16-9.

Basis for Pretreatment Standards

Existing Sources

     The Agency  is  proposing  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 Table  16-6,  the  Agency  has
estimated  that  percent  removals for arsenic, lead, and zinc by
comparing the untreated  waste  concentrations  for  those  three
                              386

-------
            TABLE 16-9.   BAT EFFLUENT LIMITATIONS FOR ZINC CHLORIDE
                                             Cone.  Basis    Effluent Limit
Pollutants
Arsenic
Zinc
Lead
jjong-Term
Ave. (mg/1)
0.5(D
0.225(2)
0.035C2)
VFR
2/6(2)
2/6(2)
1.25/4.79(2:>
30-day
avg.
1.0
0.45
0.044
24-hr,
max.
3.0
1.35
0.17
30-day
avo
0.014
0.0061
0. 00060
24-hr.
0.041
0.018
0.0023
VFR - Variability Factor Ratio

(1)  Based upon Table 8-11.
(2)  Based upon long-term data at Plant F144
                               387

-------
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 = 0.035 mg/1
     Percent Removal  =  [(0.86 -  0.035)/(0.86)](100)
                      =  96%
     Zinc:
Raw Waste = 150 mg/1
    BAT   =0.23 mg/1
      Percent Removal  =  [(150  -  0.23)7(150)]  (100)
                      =  99.8%

The percent removals  are  greater  than  the  removals for  lead  (48%)
and   zinc   (65%)   achieved  by 25% of the POTWs  in the "40 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
treatment, those  three  toxic  metals would  pass-through  the  POTW
in the absence  of pretreatment.

Using the  summary  data presented in Table 16-6, 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  BAT   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)
                               388

-------
                   82%
Lead;
               BPT
               BAT
Percent Removal =  [(0.3 -
Zinc;
               BPT
               BAT
Percent Removal • [(o 93
                = 75%
                                =0.3 mg/1
                                : 0.035 mg/1

                                0.035) t (0.3)]  (100)


                               3 0.93 mg/1
                               s 0.23 mg/1

                               - 0.23)  ^ (0.93)[(100)

 toxic metals ranged  from
in the absence of pretreatment

New Sources
                          s
zinc and are listed in Table 1^9
                                           °f
                                     in that  study *°r other
                                                   the  POTW
                                                  *>r to.ic
                                       arsenic,  lead,  and
                       389

-------
                      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.    ORB 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.
                               390

-------
                          SECTION 17




                        BAT REVISIONS
BACKGROUND
 nd  are  stn    n                Pc°<™lgated on March  12  1974

                                                      ' If
''Ihe19lli
                       -  Ins"tute  Petitioned  the  Agency  to
          o                                       y






             °s water
                           391

-------
calcium 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

The sodium chloride (solution brine-mining  process-)  subcategory
includes  22  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 24,224 mVday
(6.4  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.  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
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.
      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 1,454,000
mVday (384 MGD).
                              392

-------
 Water Use and Wastewater Characteristics
   rnm         wastewater  discharged  consists essentially of the
 barometric  condenser  water  used  to  condense  the  steam  and
 CatSrabCbbLSVab^T  ^ /he multiple-effect evaporators   As ?h2
 carried  ovJr' ft  ?A      evaporates,  some  salt  crystals  are
              •. v.   uthe  escaPin9 vapor (become entrained) and are
              the  barometric  condenser  water  and  subsequently
 be  oesn   .f^11^! ties  such as toxic pollutants, that may
 Pni-r^nS    i     !  evaporating  solution,  could  also  become
 ?K Si3f2  ?    contami«?ate  the barometric condenser wastewater
 The order of concentration of  contaminants  in  the  wastewatJr
 from  highest  to  lowest, will be the same as the orde? of thJir
 concentrations in the evaporating solution.   The  residue  after
 JontamTnan? in^-h^H  Pr°^Ct S°^'   Acc°rdingly, the most Ukefy
 itself             barometric condenser wastewater is the product


 The technology used  as  a  model  for  the  zero  discharge  BAT
 promulgated  in 1974 assumed replacement  of barometric cSndlnsers
 by surface condensers (e.g.,  shell  and  tube  condensers ).    The
 S£ JS?  
-------
studies  which  directly  bear  on   the   issue   of   pollutant
entrapment.    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.

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):

                                    Concentration (mq/1)
Stream
Intake
Effluent
TSS
0
0
DH
8.0
8.1
Ca Cl S
128 65
147 120
0^ Fe
13
37
0
0
                                394

-------
                              Tables
                             Because
                             in   the
 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
 14-17,   14-18,   14-33b,   14-34,  and  14-37,  Reference 3).
 the toxic metal,   iron,   sodium  and  calcium  compounds  ,.„  ,.„,=
 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.

 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
 S?««,?5i?r"a}S?li*.   >    (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
395

-------
          TABLE  17-1
               DISCHARGES
Pollutant

   Sb
   As
   Be
   Cd
   Cr
   Cu
   Pb
Hg

Ni
   Se
   Ag

   Tl
   zn
            <20
          <2

         <50

         <50
             18
<20

 30
         B

       <20
       <25

       <50

       <50
<0.4
            <50    <50
50
 <2

:75
                                                  BAROMETRIC


                           Concentration  (ug/l(ppb))(D
                     TOXIC METAL
                      CONDENSER WASTEWATER
       <20
        <2
                           <50

                           <50
                                Plant
                                 <20
                                     28
                                    <2
                                   <50
                                   ^50
                            <0.4

                           <50
 <2

<50
                         <0.4

                         65
                                     <2
                                    135
                                             E
                         <3

                         <0.2

                          0.3

                          6.5

                          6.5
                                             10
                                             20
                         <2
                        <50
                                                     0.7
                                                   1.1
                                 18
                                 28
                                                     13
                                  1.6
                                                     10
                                                    <9
                                  0.9
                                                    270
                                                             <2
                                                             <2
                                                              <2

                                                              24

                                                              22
                                                           <3
                                         <5
                                                           49

                                                           33

                                                           25
< = less than

Plants A to E = Chlor-Alkali (Diaphragm Cell)

Plant F = Sodium Thiosulfate

Plant G = Ammonium Bromide

(1)  All values  are  maximum daily values observed  from  three  24-
     hour composite  samples  obtained  during  verification sampling
     at plants B,  Cf Df  and G.  Values  reported  for  Plants Af  E,
     and P  are  the  values observed  during  screen sampling  (72-
     hour composites).

                               396

-------

          iCtiSns^bein'  Ivl Seated"" concentrations of toxic metals
 Plant

  A
 B,C,D
  E
  F
  G
  Cu

1,700
  600
  530

  140
Cr
1,900
940
260
•»
Pb
2,000
160
260
220
Ni
22,000
-
-
Zn
1,600
500
240
550
650
                                 ?upKrt the conclusions that the
                             avfilabje from an  ammonium  bromide




carry-over °
     Ammonia
                   3.2 mg/1 •
                       Bromide        6.0 mg/1

                        is the product, and  would  be

                             397

-------
 TABLE 17-2,
CHEMICAL COMPOSITION OF BAROMETRIC CONDENSATE
FROM PLANT F122 CALL 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.
                            398

-------
  "^orators.
                      beCaUSe
                                         te.1  is  used  in   the
  significant'levefs
                                                          COntain
                                           data submitted by  two

 permitting authrites  ,3  art  oT"^1"9  P^ocess)  Plar*s to the
 permits  for  those  plant!    That  SJt- a^ticati°™  for  NPDES

 pollutants are below  Iiqni?ican? ?L0fata  !hows  a11 toxic metal
 detection limit.      Si^^iCant levels, and most  are  below  the



 Treatment Cost Estimates




 sCrfacfcondenser^in'the £diu£°Jhl"?i ^^  °f  installati- «£
 brine-mining  process)  a                  subcategory  (solution


                "



                                .
                                 Utilized

                                                       the cost
                                                    asrss
installation of the solace condanS^S  °"  Occurrln9  while  the

utilized in preparation o^theSe estimates. proceedin9  «»•  "een
Saner"!    °™
                                            1A C°ndenser
                             399

-------
120
                                                  CS = Cold Steel
                                                  SS304 = Stainless
                                                    Steel 304
          roo
           200      300  400  500 600   800  1000
                Surface Area in Square Meters

Figure 17.1.   SURFACE CONDENSER COST (SOURCE:  REFERENCE 4).
                                  400

-------
          TABLE.17-3.  WATER EFFLUENT TREATMENT COSTS AND RESULTTNr
                      WASTE-LOAD CHARACTERISTICS FOR MODEL P LA Si
    SUBCATEGORY:    Sodium Chi or*A*

    ANNUAL PRODUCTION:       397.266

    DAILY  FLOW: 	

    PLANT  AGE:
         45.420
                                METRIC  TONS  (438,000 short tons)
                     N/A
	 CUBIC METERS (total flow);  757  ri*  cpndensate

 YEARS   PLANT LOCATION:  	N/A
  a.
                  COST OF TREATMENT TO ATTAIN SPECIFIED LEVELS
   COST CATEGORY
                           COSTS ($1,.000) TO ATTAIN LEVEL
                           1A
                                              IB
   Facilities
   Installed Equipment
                           30.0  150.0
   Contractor Overhead and Profit
   Contingency
   Land

     Total  Invested Capital

  Annual Capital Recovery
  Annual Operating and Maintenance
   (Excluding Residual Waste Disposal)
  Residual Waste Disposal      v»"*±)
                                      172.3
                                       40.5
                                 861.3
                                 202.3
                           36.4   182.6
                           27.9   139.6
                          307.1 1,535.2

                          50'. 0  249.8
                          58.2  245.2
    Total Annual Cost                108.2  495.0

                 b.  RESULTING WASTE-LOAD CHARACTERISTICS
              Ave. Cone                      n  Long-Term Avg.
              *vg. uonc.                      Concentration (mg/1)

Pollutant     Untreated fBg/n          1A   Afj£r Tre2atment J° Level
   TSS
                  27
 LEVEL 1A:
 LEVEL IB:
                         c.
                 TREATMENT DESCRIPTION
Surface condenser'- loss of 10% capacity during sununer months
Surface condenser - no loss of capacity
                                 401

-------
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, a building is provided  for  the  housing  of  the
condensers.
     Facilities

     Building

     Equipment
Level 1A

  85 m2
     Surface Condenser
           (cold steel)   920
           (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
would  require  a  total capital and annual investment as follows
(1982 dollars):
     Total Capital Costs
     Total Annual Costs
       Level 1A

       $7,277,600
       $2,514,600
       Level IB*

       $36,388,000
       $11,613,800
 *    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  propose  to  withdraw   the currently
 effective BAT regulation for this subcategory.
 2If  the  temperature  of  the  incoming  cooling  water  is  greater  than
 25°C (77°F),  a  greater  loss of  capacity  would  result.
                               402

-------
 Sf.1.     5r°£™ to exclude tne 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.  For new sources, the cost of surface condensers  is
 about the same as the cost for barometric condensers.  Therefore
 a  new  plant  can install surface condensers from the start, and
 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
    ,?? termination of  BCT  for  conventional   pollutants  (47  FR
    76).    The methodology has been described  in detail in several

             C
 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
 A.   Option  1  -  Surface  Condensers

 The  use of surface  condensers at  22 plants   is   estimated   to   be
"SSc  »i«  ?T  removin9  approximately  540,000 kg  (1,188,000  Ib)  of
 TSS  annually at  a cost   of  $2,514,600   (for the  Level   1A,   or
 smaller  condenser).   The annual cost  for  the industry using the
 larger condenser with no loss of  capacity would  be   $11,613,800.
 Therefore, the computation of TSS removed would  be as follows:

     (BPT limitation) (ann. production)  » TSS removed/yr.

     (0.17 kg/kkg)  (3,175,000 kkg/yr) =  539,750  kg/yr

     For the surface condenser option as BCT:
     $2,514,600/vr
     540,000 kg/yr
$4.66/kg (1 kg = 2.2 Ibs.)

 $2.12/lb.  TSS removed (1982)
As   a  result  of  the  above  computation,  the  candidate  BCT
technology failed the BCT - POTW cost test.  Since the  LevJl  1A
option  failed  the BCT cost test, inclusion of costs due to loss
of production and production capacity, or applying the BCT  cost-
                              403

-------
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.

B.   Option 2 - Granular Media Filtration

The use of granular media filtration at 22 plants is estimated to
be capable of removing 300,000 kg (660,000 Ib.) of additional TSS
(over BPT) annually at a cost of $5,500,000.   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 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) (3,175,000 kkg/yr) = 300,000 kg/yr.
     For the granular media filtration option as BCT:

                         $18.33/kg  (1 kg = 2.2  Ibs.)

                         $8.33/lb.  TSS removed  (1982)
$5,500,000/vr
300,000 kg/yr
     As  a  result  of  the above computations, the candidate BCT
technology failed the BCT-POTW test  ($0.43 per poundJ1982)).

Since both candidate BCT technologies failed the cost  test,  and
no  other  less expensive  technology options have been identified
which would remove additional amounts of TSS and pass  the  test,
EPA proposes to establish  BCT limitations for the sodium  chloride
(solution   brine-mining   process)   subcategory  equal  to  the
currently effective BPT.

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
                               404

-------
  tons)  or 71.6 percent were produced from natural sources (brines)
                      Cacf ''aT" elther  3S Solid








                               ^
 grocess Description









                                                                 '
     A typical concentration of the brine  is  (2):



          CaCla   19.3%     Bromides             n •>**


          Nlcl2    I'll     gther Minerals       o.ll*
          NaCl     4.9%     water               70.8%
Water Use and Wastewater Characteristic
                              405

-------
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
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).
3Includes three plants known   to   be   zero   discharge   and   three
others   located   in   inland,   arid and   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.
                               406

-------
There are no known dischargers in this industry.


Recommendations
Chan9es
                                      the
                                                   "- -ass
                                              are  no
                           existing
•3-r^ .  Effluent    Limitations.    Since   there
dischargers,  there  is no need for a BCT.

SODIUM SULFITE

General
                                          .«
                           407

-------
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
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*  Direct/Indirect
  B

  C
         27,210 kkg
33,560 kkg

 9,070 kkg
69,840 kkg/yr
Direct



Direct

Indirect
              Flow
                               16.4 m'
330.0 m*

 70.0 m*
           Treatment

           pH adjust,
              oxidation,
             filtration
pH adjust, oxidation,
  settling
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.
                               408

-------
follows:
                    f°r devel°Pment of the BPT limitations were as
      Process  condensate
      Dryer  ejector and
       filter  wash
                               m Vkko
                              0.17
                              0.29 - 0.63
                         based  upon  the  wastewater  stream from  the
 range  (63mVkKg) ?*** "***  °*erations  *  the  high  end  of   Si


 ash*-  su?furbi?nv?Lthe  t^'ee  remaining P^nts utilizing the soda
 of 2 2 m3fvka*i  f«? rea^ion  process yield  an average unit  flow
 ot 2.2 m^ kkg**  (581 gal/ton)  for all wastewater discharged.
 /    TT~ Ltnis subcategory is oxidation of the sulfite to sulfate
 (usually by aeration) and filtration of the wastewater to  removl
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 m'/kkg
                             409

-------
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
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 toxic 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
observed  in   treated
the  toxic  pollutant  concentration  data
effluent during verification sampling from
                               410

-------
    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 fmg/1)
PliHtPlant
.1987          |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
                         411

-------
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 Subcateqories

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.

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
$2,817,100*
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
5Annual costs  include energy costs which are very  high
BAT technology (evaporation).
                           for  the
                              412

-------
                TABLE 17-5.   COMPARISON  OF  SODIUM SULPITE
                   AND SODIUM BISULFITE SUBCATEGORIES
Plants
Unit Flow
Process
Raw Materials
Treatment Tech.
  In Place
BAT
Sodium Sulfite
3
2.2 m3/kkg
Soda Ash - S02
NaC03, S02
OH Pptn., Aeration,
  Filt.  or Settling
Zero Discharged)
Sodium Bisulfite
7
1.5 m3/kkg
Soda Ash - S02
OH Pptn., Aeration
  Settling
Discharge subject
  to 40 CFR 415.542
(1)   Currently in effect.   To be modified by this  proposal
                             413

-------
        JABLE 17-6..WATER EFFLUENT TREATMENT COSTS AND RESULTING
                    WASTP.-I.OAD CHARACTERISTICS FOR MODEL PLANT
  SUBCATEGORY:   Sodium Sulfite
  ANNUAL PRODUCTIONS-27.210:6-33.560:0-9, METRIC TONS
                      oTo
  .DAILY FLOW: A-16.4;B-550;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 kgAkg
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
                             414

-------

  £33


  Basis for ProEosed BCT Effluent Limitations
 «»I76>.  The
                         has

                                                     -thodology
                                                          <47 *
wastewater  and  contained
metals.    TSS  is  the  only
wastewater.   Filtration was ..w
because   the BPT   limitations  were
precipitation, aeration, and filtration.
                                                           this
                                                            all
                                                 so  ids  COD and
 		,„ thfBPrUmf?atiLsh;ndandiHat?.teChn°10^ ma* be
 the- subcategory:        limitations and production  capacity  for

 (0.016 kg/kkg) (69,840  kkg/yr) . 1,117.4

 Therefore:


     **''}7'.l°%%r. "  $2'512-'2/*9 TSS removed , 2.2 Ib/kg

                       =  $l,141.87/lb  TSS removed (1982)
ssr ssssr
Basis for Proposed. BAT Effluent  Limitations
                            415

-------
 TABLE 17-7.   BAT AND BCT EFFLUENT LIMITATIONS FOR SODIUM SULFITE
Conventional*- '
Pollutants

PH
TSS
30-day avg.
0.016
       Effluent Limitations
                                 _
                        24-hour max.
                          0.032
Non-Conventional
Pollutants	

COD
1.7(2)
                          3.4(2)
Toxic Pollutants

Chromium  (T)
Zinc  (T)
0.00063(3)
0.0015(3)
                          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
     (40 CFR Sec. 415.542).
(4)  BCT only.
                              416

-------
   e        "        s-    a
 ft* y'ss^^ -S.»E
 discharge for this subcategory should be withdrawn

 to.ic-i.tS'a nonfcSioLf p^L^^ed ^isr &
 w1sa-th^aiJi?s:iioSc^jrs'1»sssoss!:'2g.«i;f;1siioS:
 already in effect for the sodium bisulfite subcategory. Jm   tl°ns
 subcategory. Su""narlzes  the  limitations being proposed for this
                                             -SB

the BAT limitations are based upon the BPT technology
Basis for NSPS Effluent Limitations
   .      —^	~~,,..^ TIWWJ.U  we: me same  as
technology basis for BAT is the same as for BPT.

Basis for Pretreatment Standards


           facility  adds  small  amounts  of  copper  in  the
          S  Parameter will  be effectively controlled bv
                1 the limitations f- the other
                        417

-------
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:
Raw Waste = 1960 ppm
BAT       =  550 ppm
                 Percent Removal  =  [(1960-550)t{1960)](100)
                                  =  71.9%
               Chromium;
Raw Waste =1.95 ppm
BAT       =0.22 ppm
                  Percent  Removal  =
       [(1.95-0.22)*(1.95)1(100)
       88 = 7%
               Zincs
Raw Waste * 1.81 ppm
BAT       =0.52 ppm
                  Percent Removal
    -  [(1.81-0.52)*(1.81)1(100)
    =  71.3%
 The percent removals of chromium,  zinc,  and COD are greater  than
 the- removals  for  chromium  (65%),   zinc. (65%),   and COD (72-s)
 achieved by 25% of the POTWs in the "40  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
                               418

-------
low  toxic  pollutant  loading,  we  propose  to   exclude   this
subcategory   from   further  PSES  development  under  Paragraph
8(b)(n) of the EPA-NRDC Settlement Agreement.             -yrapn
New Sources

The Agency is proposing PSNS that are equal to NSPS because these
standards provide for the removal of toxic metals which may  Sals
through  a  well  operated  POTW  with secondary treatment in ?he
           Pretreatment   The pollutants regulated under PSNS
                             419

-------
SECTION 17

REFERENCES
1.
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.
      Meals and Minerals.
      Stanford  Research
      Producers - 1982".
                      Institute,    "Directory    of
      I,


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 ID," Frontier Technical Associates,  Inc.
      Report No.  FTA-82-E-2/03 Revised January 14, 1983.
                               420

-------
                            SECTION 18

                      PRETREATMENT STANDARDS
                    FOR DEFERRED SUBCATEGOR I ES
 INTRODUCTION

 General
              stlnlardHSre
                          ,              t        ,o


Subcateqor i es Surveyed
     The 23 subcategories surveyed are as follows:
     Borax
     Bromine
     Calcium Carbide**
     Calcium Chloride**
     Chromic Acid
     Fluorine
     Hydrogen***
     Iodine
     Calcium Oxide**
     Calcium Hydroxide
     Potassium Chloride
12.   Potassium (metal)**
 1
 2
 3
 4,
 5.
 6,
 7.
 8,
 9.
10.
11 .
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.
                                             Category.
                              421

-------
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 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
                              422

-------
  Subcateqories _N-]_8

  1.    Borax
  2.   Bromine
                e
 3.   Calcium Carbide
uncovered6
subcategory.  Calcium
under the Lrroa!^

4.   Calcium Chloride
in this subcategory.

5.   Chromic Acid

                                                     Carblde
                                                         s in this
                                £
                                            chloride by the  brine
                                           or indirect dischargers
6.   Fluorine


h!^5%1are- tw°  known  Producers
hydrofluoric  acid  electrolysis
dischargers in this subcategory.

7.   Hydrogen
                              423

-------
subcategory is subject to effluent limitations for the
Refining Point Source Category (40 CF1 Pt. 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  toxide. ,(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  (Hvdrated  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 eyfP?"^0";  ,Th®
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 mm.)
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
                                424

-------
 ?OTWC  Pr°CeSS  wastewater,  treats   it  and then discharges to a








                             Parameter
                   Average Concentration (mg/1)
                         <0.029  <0.0011
 15.   Sodium Chloride
 employing both processes are included here!

      a.
                                                             which
                                                  bringing ana

                                                      Sy °f plants
     b.
                                               .
           None  of  these plants discharge  to  POTWs

           Solar Evaporation  Process.    There  are    39    known
           producers  of  sodium chloride  by  the solar evaporation
           process.  There are no  indirect discha?ge?s.   P

Both processes  (a  and b) are employed at  some  facilities.

16.  Sodium Sulf ite







felt on °" o£etntsl?eo1rt eth2££Sati°n.and a"alyS?S PrSe"ted5?°
this subcatlgory frol^SK.      '  Cy  1S  Pr°P°sin9  'o  exclude
17.   Stannic Oxide
                              425

-------
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 19-23

Thi's 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.

PSES 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
                              426

-------
                Cu  (Total)
                Ni  (Total)
                Zn  (Total)
                                      0.5/1.0 mg/1
                                      1.0/2.0 mg/1
                                      2.5/5.0 mg/1
believed to be adequate

2 1 .   Lead Monoxide
                                                         for  other
                                          ,  the  existing PSES are
                                                            -
                                                    dr^els and"

 £SES  in Effect,  current  PSES  in  this subcategory  are  as  follow,

                 Parameter         DQPC  iir* j
                 - — L        PSES  (30-day avn. /74-hr. ma».

                     (TOtal)
                                          .            for other
                                        the  existing  PSES  are
 believed to be adequate.


 22 •   Potassium Dj.chr ornate
 ESHS in Effect,   current PSES in thl. subcategory are as follow,

                                    PSES
              Cr  (VI)
              Cr  (Total)
                                           0.090/0.25  mg/1
                                            • 0/3.0 mg/1
                     Se.ner     h             for other
believed to be adequate.      ^nerefore,  the  existng   PSES   are


23.  Sodium Fluoride


There are four known producers of which two discharge indirectly


     IB Mfect.   current PSES in this subcategory are as follows:

                             PSES
                              427

-------
             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.

PROPOSED EXCLUSIONS

The Agency proposes to  exclude  from  national  PSES  regulation
development the twelve subcategories listed below  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
             jl^j L X 11^—                  *^ w»*»* •» * *• ^* ^f •• •• —• —
The  Agency   proposes  to exclude 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)
 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 proposes to exclude 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.
                               428

-------
                 TABLE 18-1.  SUMMARY OP THE DISCHARGE STATUS OF ALL
                              PSES SUBCATEGORIES
   1.
   2.
   3.
   4.
   5.
   6.
   7.
   8.
   9.
 10.
 11.
 12.
 13.
 14.
 15.

 16.
 17.
 18.
 19.
 20.
 21.
 22.
 23.
 Borax
 Bromine
 Calcium Carbide
 Calcium Chloride
 Chromic Acid
 Fluorine
 Hydrogen
 Iodine
 Lime
 Hydrated Lime
 Potassium Chloride
 Potassium (Metal)
 Potassium Sulfate
 Sodium  Bicarbonate
 Sodium  Chloride  (brine)
 Sodium  Chloride  (evap.)
 Sodium  Sulfite
 Stannic Oxide
 Zinc Sulfate
Aluminum Sulfate(3)
Ferric Chloride(3)
Lead Monoxide(3)
Potassium Dichromate(3)
Sodium Fluoride(3)
                                                         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)  One plant unable to be contacted, thought to be zero or direct.
(2)  Plow at both plants Is 1OM, and iess than 1, of plant flow to POTW.
(3)  PSES currently in effect.
                                   429

-------
Subcategories with PSES  In Effect

Information was developed during the survey to show  that  the PSES
in  effect are adequate, therefore, no change is proposed for the
PSES following five subcategories:

     Aluminium Sulfate
     Ferric Chloride
     Lead Monoxide
     Potassium Bichromate
     Sodium Fluoride

PROPOSED PSNS

The 12 subcategories for which no PSNS are  currently   in effect
are:
     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  proposes  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
effective  BPT  effluent limitations of zero discharge of process
wastewater pollutants.
                              430

-------
                            SECTION  18

                            REFERENCES

 3.
4.
 Minerals,  Mineral Intry Suveys,   JVp
                                                    °£
                                                              Salt
                                                          for
                                      t
     the    inorganic   Chemials    M«nSf   J'1?p"ent
     Category, "  Calspan  Selort  No  ND-B^wV  ^   ?°Urce
     (Survey conducted in 1 976 ) .          5782-M-85,  17  March 1977
5.
6.
Industry  -
Report So.
                                                       »
                                                    Manufacturing
                                                            .  Inc?
               pM,
by the New York DEC, Region 7?    '  SU"""ary °f data
                                                          Dr.  T.
                             431

-------
                           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 60 of those subcategories  (the Phase
I  guidelines).  The Agency is now proposing effluent limitations
guidelines and standards for  17  additional  subcategories   (the
Phase  II guidelines).  The Agency is proposing to exclude 104 of
•the  remaining   107  subcategories   from   national    regulation
development.   One  subcategory   is deferred for regulation under
another, more appropriate guideline.  The Agency also proposes to
amend the applicability  section  of  one  promulgated   inorganic
chemical   subcategory   to   include   an   additional  product
representing two subcategories.

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.


Subcateqories Surveyed

The  1-07 subcateogries 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
                               432

-------
      Table 19-1.   Inorganic Chemical  Subcategories Surveyed
  1.
  2.
  3.
  4.
  5.
  6.
  7.
  8.
  9.
 10.
 11.
 12.
 13.
 14.
 15.
 16.
 17.
 18.
 19.
 20.
 21.
 22.
 23.
 24.
 25.
 26.
 27.
 28.
 29.
 30.
 31.
 32.
 33.
 34.
 35.
 36.
 37.
 38.
 39.
 40.
 41.
 42.
 43.
 44.
 45.
 46.
 47.
 48.
49.
50.
 Aluminum Chloride
 Aluminum Compounds
 Aluminum Hydroxide (Hydrated Alumina)
 Aluminum Oxide (Alumina)
 Alums (also 6, 55, 77)
 Ammonia Alum (also 5)
 Ammonia Compounds
 Ammonia Molybdate
 Ammonia Perchlorate
 Ammonia Thiosulfate
 Barium Compounds
 Barium Sulfate
 Barytes Pigments
 Beryllium Oxide
 Bleaching Powder  (Calcium Hypochlorite, No. 20)
 Boron Compounds (not produced at mines)
 Borosilicate
 Brine Chemicals
 Calcium Compounds (Inorganic)
 Calcium Hypochlorite  (Bleaching Powder. No. 15)
 Cerium Salts                          '       '
 Chlorosulfonic  Acid
 Chrome Oxide (Chrome Pigments)
 Chromium Sulfate
 Deuterium Oxide (Heavy Water)
 Hydrated Alumina  Silicate Powder
 Hydrogen Sulfide
 Hydrophosphites
 Indium Chloride
 Industrial Gases
 Inorganic Acids (except  nitric  and  phosphoric  acid)
 Iodides
 Iron  Colors
 Iron  Oxide (Black)  (iron Oxide  Pigments)
 Iron  Oxide (Magnetic) (Iron Oxide Pigments)
 Iron  Oxide (Yellow) (iron Oxide Pigments)
 Lead  Arsenate
 Lead  Dioxide, Brown
 Lead  Dioxide, Red
 Lead  Silicate
 Lithium Compounds
 Magnesium  Compounds, Inorganic
 Manganese  Dioxide  (Powdered Synthetic)
 Mercury Chloride
 Mercury Oxide
 Nickel Ammonium Sulfate
 Nitrous Oxide
 Ochers (Iron Oxide Pigments, No. 34-36)
Oleum  (Sulfuric Acid)
Oxidation Catalyst made from Porcelain
                              433

-------
Table 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
                              434

-------
Table 19-1.   (continued)
Radioactive Materials.
 98.
 99.
100.
101.
102.
103.
104.
105.
106.
107.
Cobalt 60
Fissionable Materials
Isotopes, Radioactive (also 98)
        ES
Radium Chloride (also 101,  106)
Radium Luminous Compounds (also  101
Uranium Slugs, Radioactive
                                      10S)
                                      <-•»
                            435

-------
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
the  16  were  sampled.  Supplemental information was provided by
NPDES permit authorities and by POTW authorities.   The  proposed
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  presently  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 proposes to  exclude  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.

2.   Aluminum  Compounds.   Specific   aluminum   compounds   not
     addressed elsewhere are:

     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  proposes  to  exclude  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 proposed for exclusion from any
     further regulation development under the inorganic chemicals
     point source category because the wastewater from the plants
                              436

-------
4.
5.
6.

7.
     in  the  subcategory  is  controlled
     limitations guidelines and standards.
                                       by   other   effluent
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  proposed  for  exclusion  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.

"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  proposes to exclude this subcategory
under Paragraphs 8 (a)(iv) and 8(b)(ii) because there are no
known dischargers.
Ammonia Alum.  (See subcategory No. 5 above)

                                  ammonium   compounds,  not
Ammonia  Compounds.     Specific
addressed~elsewhere are:
          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 proposes to exclude this
          chemical-from national BAT regulation  under  Paragraph
          8(a)(iv) of the Settlement Agreement.  In addition, the
          single  indirect  discharger  is proposed for exclusion
          from categorical PSES under Paragraph 8(b)(ii)  because
          the low flow is too insignificant to justify a national
          regulation.

          Ammonium Dichromate - 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 proposed
          for  exclusion  from  national  BAT and PSES regulation
                              437

-------
          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.

     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  proposed  for
          exclusion 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  proposed  for  exclusion
          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
          proposed  for  exclusion  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 proposed for  exclusion  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
     proposes to exclude this subcategory Paragraphs 8(a)(iv) and
     8{b)(ii)  of  the Settlement Agreement because there is only
     one discharger.
                              438

-------
°


'"•
    £*?* deE^eY'V^re^a-bl  N°, ^ ' °^"Jc  SlS?^S
    SBi^^™^8:iffl«£SBas
11•  Barium Compounds.  Inorganic
    at   a limited number  of
    addressed elsewhere are:
    arb,

 Barium

 these
   c.

   d.
Barium Hydroxide - This chemical  is  produced  at  (•„,.,-
   e.

       produce  reagent  grade   chemicals
                       439

-------
12,13.
        nroduction    One  of   these plants  is  known  to  achieve
        lert  SiscKarge   The other  three  plants (two  direct  and
        one indirect) are  estimated to  discharge  a   total   of
        less  than  10,000 gallons  per year.

        Barium Perchlorate - There  are  two  plants   producing
        this   chJmical.    One   achieves no discharge  by  recycle
        whi?e tnS  second discharges to  a  POTW.    Production   at
        the   second plant  is  less than  2.3 kkg/yr (5000  Ib/yr).
        BecauS! of the  very  low production,  discharges of toxic
        pollutants would  be  insignificant.

        The   Aaency  proposes   to  exclude  all  of  the  above
         chemict!  VodScts    under   Paragraphs  8 a)(iv)  and
         8(b)(ii)  of  the  Settlement  Agreement  (low  loading
         because of low flow) .

              Barium  Sulfate,.  Barvtes   Pigments.    In   each
         subcateqory  there is only one plant which produces the
         chemfcH In bulk,  and toother plants that  have  very
         low  production  rates.   None  of  the  small producers
         d?schlrges process wastewater.  The Agency proposes  to
         exclude  each subcategory under Paragraphs 8(a)  iv) and
         8(b)(ii) because there is only one discharger   in  eacn
         subcategory.    The  Agency  considered   combining  the
         Jubcategories because the products «"e^nSi
         the  production processes, raw materials,  and
         pollutants  are significantly different  for  each plant .
         Hence  combining the subcategories was  not   technically
         feasible.

 15.
            =Non-Ferrous"Metals Category (40 CFR  Part  ._...
     new  stud?  of ?hls  category  by EPA is currently underway
     (proposal expected February,  1984).

                            Calcium Hypochlorite, No.  20).    See
                           jte 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,
                               440

-------

     e.
f.
17.
                                  Produced two or three times  per
                    lon,
                 gallons per year.
                                                   etimated to be
                                   Plant  Produces  this  chemical
               ha™        an  evaP°ration  pond  to  achieve  no
           discharge of process wastewater.


           chemicaldondf ," ^f ^ °nly one Plant Producing this
           chemical  on a specialty basis with very low production.

           Boron Nitride -  There are three' plants  producing  this
           chemical  at present.   All three discharge to a POTW bit
           flows are low (two  plants discharge less than 3 8 cubic
           Tfnn* Per day.each  <<1000  gpd).   The third plant Sow
           is  unknown but is expected to be similar (and  low)   to

           known  toC h£r°dUCeiS  beCaUSS Pr°cess technologies  are
           known  to  be similar.    Hence,   the   total   flow   is
           estimated to be  about 3,000  gallons per day.
            nnn              ' The Prod"ction of  this chemical  is
            non-aqueous process  with  no  discharge  of  process
          wastewater.    There    are    two   plants
                                           but    there
                                                         two
                                                          No
                                                         its
                                                          of
                                                          to
                                                          to
                                         produced  in  small
                                               So waStewa?er
          Lithium Metaborate - This chemical is produced  at
          Drforfi-v0" i? .sPfcialty ba^is with lo5 production.
          priority pollutants are known to  be  involved  in
          production.   One  plant  achieves  zero  discharge
          process wastewater.  The other plant  is  estimated
          All of  the  above  chemicals  are

          fHtlfcihS aat  few Plants with

                              441

-------
18,
19,
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
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  proposes  to  exclude  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.
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 galIons'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
                              442

-------
                                              is


 and loading).
                                ,  low
 20.
21.
 are chlor-alkali plants
                                                 ion,  low  flow
                                                     «•  four
                                          '  and the other
     siar
                             •»"»«•* the
                                                      .111 (an
 8(b)(ii).
                               tor  exclusion  under
EPA proposes  to
                           the
                                                *

process  wastewaters are    ?n«
standards for  chlor-Ilkal?  n?
presented in Tabfe l!4c "Jlant
                                          •               these
                                        exifting guidelines and
                                          Relev^t  data   are
                            443

-------
22,
    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 proposes to  exclude  this  subcategory   from  further
    regulation  development   under  Paragraph 8(a)(iv)   and  8
     (b)(ii) of the Settlement Agreement.

    Chlorosulfonic Acid.   No  toxic pollutants  were  detected   at
    treatablelevels 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  proposed   for  exclusion
    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.

     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 proposes to exclude this subcategory
     from further  consideration (Paragraph 8(a)(i)>.  The current
     effluent  limitations  would continue to  apply.

     Chromium  Sulfate.   There is only one  plant  producing  this
     chemical,   therefore   the  Agency  proposes  to exclude this
     subcategory  under  Paragraphs 8(a)(iv) and 8(b)(ii).

     Heavy Water  (Deuterium Oxide).   There are  no  producers  of
     deuterium  oxide  (heavy water)  in the U.S. today.   Therefore
     the  Agency   Proposes  to  exclude  this  subcategory  under
     Paragraphs 8(a)(iv) and 8{b)(ii).

26.  Hvdrated   Alumina  Silicate  Powder.    There   is  one  plant
     currently  producing  this  chemical,  and this plant has no
     discharge of  process  wastewater.    Therefore,   the  Agency
23
24.
25.
                               444

-------
 27,
28,
29,
30,
31
      proposes    to   exclude
      8(a)(iv)  and 8(b)(ii).
                         this  subcategory  under  Paragraphs
 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 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 proposes to exclude 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 proposes  to exclude
 this subcategory under  the provisions  of Paragraphs 8(a)(iv)
 and  8(b)(ii)  because  there are no  k'nown  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 proposes to
 exclude   this  subcategory  under   Paragraphs  8(a)(iv)   and
 8(b)(n)  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 proposes to  exclude  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:
     a.    Hydrobromic Acid - There is  no  discharge  of
          wastewater from production of this chemical.
                                                     process
                              445

-------
     b.
33.
34,
          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  proposes  to  exclude  it
          under   the   provisions  of  Paragraphs  8(a)(iv)  and
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
          proposed  for  exclusion  under   the   provisions   of
          Paragraphs 8(a)(iv) and 8(b)(ii).

     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 proposes
     to exclude this subcategory under  Paragraphs  8(a)(iv)  and
     8(b)(ii) because there  is only one plant.

    35, 36,  48, 67, and 94.  Iron Oxide(s)  (Iron Oxide Pigments) .
     These   subcategories include the Iron Oxides  (Black, Yellow,
     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
     four  inorganic  chemical  plants,  there^.  are   no   toxic
     pollutants  at treatable levels discharged from any of these
                               446

-------
42.
     f?Vr ?Jants:  Relevant data are presented  in  Table  IQ ?f
"•
 41 '
                                   Lead  Wfl-nt,,'  subcategory


                      -  SPficific "">!•» compounds not addressed
                                                                tt

                                       three
    b.
                                         ^
    Magnesium   Compounds   (Inorganic)
    compounds not addressed elsewhere are
                                             Specific   magnesium
    a.
                            447

-------
d.
e.
f.
         four    plants    produce    the  product   from  magnesium
         hydroxide and  hydrochloric  acid  by a  process   which
         generates   no   wastewater.     Hence   there  are  no
         dischargers.

         Maanesium Fluoride - This  chemical  is  produced  from
         Sonuoric   acid   and   magnesium  hydroxide   on  a
         specialty basis at two plants.   The total Auction is
         less  than ten  tons  per  year,  which   results  in  an
         insignificant discharge.

         Maanesium Nitrate - There  are  five  plants  producing
         2h?S   chSnical,  however,  the two large plants have no
         discharge of process wastewater from this product.  The
         othSr  three Pplants  (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.

         Maanesium Sulfate - There  are  five   plants   producing
         this cSical,  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
         usSs   an entirely different   process and  raw material
         sou?ce?  thl identity  and quantity  of  pollutants   would
         be different  for   each process.   Hence, this chemical
         would  require different  subcategories  each  with  one
         p?ant.    The   one  indirect  discharger is  estimated to
         discharge less than 5,000 gallons per  year   because  of
          its  very low production rate.

     The Agency  proposes  to  exclude  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.

43.  Magnesium
          and 8(b)(ti), because there is only one discharging
 plant
                          448

-------
 44'
46
47.
     §iiriSiSllsiRis-nJh?re-lsonly.05e  plant  pacing  this
     cnemical.   The  plant  is  an  indirect  discharger  and is
     required by the POTW  to  control  its  discharge9 using  an
     add-on*!  Jevei   technology.    That  technology  inv?lve£
     ?h?i   ?? 1  treatment beyond that used as the basis  for  the
     chlor-alkali  BAT  limitations and therefore toxic pollutant
                            are  expected  to  be  insigSif {£££?
                                                      -bcategory
45.   Mercury Oxides.   There is  only  one  plant  producing  this

     S^r^'hi  T^ /Pla2fc  is  the  sameP PlantP that^oduces
     S«S ryf.chlorjde (Product No.  44  above)   and  combines  the
     wastewaters   from  boch  products  for  treatment.    For the

     S?SSS2Lpr!8ented,f2r  excludin9 mercury chloride,  the Agency
     proposes  to  exclude   this   chemical   subcategory   under
     Paragraphs 8(a)(iv)  and 8(b).      •                     unaer
     Nicel  Ammonium  Sulfate.   There   are   two  plants  producing

                           has  n°  discharge of process wastewate?
                           -The second  P^duces    reagent    and
      h«   .        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  toxi?
     pollutants  at   treatable  levels at  this plant.  Therefor^

                                                           under
    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
    Sli? K?r  nonc9nventional  pollutants  are  discharged   at
    treatable  levels  in process wastewater from plants in this

    f?nJ?te??^' <-Th? ^!ening and v^ification sampling of tne
    levSL   i!J?  «?fc b°th PJant? detected ammonia at  excessive
    levels,  but  at  very  low levels in all process wastewater
    sources contributing to that final effluent.  Relevant  data
    fh6  Pre?ented  in  Table 19-2e.   At one plant, the water in
    the discharge trench was so low that the trench  had  II  be

    2S5fS ^   ™ai!S  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  hiah

    thatenlan?Und'    ^ ^T^ C°Uld n°? be *™c*ss related 2
    Sm«iS     because  all  process  wastewater  sources  were
    sampled  and.  no  ammonia  was  found at treatable levels in
                             449

-------
     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 proposes to  exclude  this  subcategory
     under Paragraphs 8(a)(iv) and 8 b(ii).

48.  Ochers  (Iron Oxide  Pigments).   See  Iron  Oxide  Pigments,
     Subcategories No. 34, 35 and 36.
49,
50,
51
52.
    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
    plantsproducing   this   material  in  the   U.S.  The Agency
    proposes   to  exclude  this  subcategory under   Paragraphs
    8(a)(iv) and 8(b)(ii).

    Perchloric Acid.  There is only   one   plant which  produces
    thischemical.    The  Agency   proposes  to   exclude  this
    subcategory under  Paragraphs 8(a)(iv) and 8(b)(ii).

    Peroxides  (Inorganic).    Specific  peroxides  not   addressed
    elsewhere  are:

          Sodium Peroxide - There is   only  one   plant   producing
          this   chemical by a dry process.  Therefore there is no
          discharge of  process wastewater.

          Potassium Peroxide - There  are  no  producers  of  this
          chemical in the United States today.

     The  Agency  proposes  to  exclude  this  subcategory  under
     Paragraphs  8(a)(iv)  and  8(b)(ii)  because  there  are  no
     discharging facilities.-

53.  Potash Alum.  This subcategory has been addressed under  the
     "Alums" Subcategory, No. 5.

54.  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.
     a.
      b.
                               450

-------
                   -><-
 "•
 56.
57.  Potassium

                                chemical ^ produced at only  one

58,
59
      and the discharge is insignificant.


Potassium Chlorate - There is only one  pro*
                                                         onlyndne
                                                          direct

     a-
                                              8.ot
          f ^chargers.  One plant produces less than  45
                     /7   °f     Pr°dUCt and all wastewaterrm
     hundreds
     Hundreds
        uction
                       chemicals  produced  at  that   <5it-«    =.

                                  '  dvanced ^astewater treatment


                                             0*5  c^«^



                   to be less than 5/000 gllons pe? yelr      S
                    h              ,            is produced on  a
                    basis  (i.e.,  low production quantities) at

         drhKnS-u EaCh Plant (one direct and SS5 iSdlreSt
         discharger) makes numerous other reagent and  SDerialfG




         oe j.ess tnan 10,000 gallons  per year.
                             451

-------
61
62.
    c.
    d.
    e.
60.
    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 no dischargers.

    Potassium Silicof luoride  - There  is one  plant  Producing
    this  chemical but no process wastewater   is  discharged
    from  this product.

    Potassium Silicate  - No  toxic  pollutants  Attributable
    to potassium   silicate  production  were  detected during
    screening   and   verification   at  on© 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  Aaencv  proposes  to  exclude all of the above chemical
product; in thisPsubcategory 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.

Potassium Cyanide.   There are only two plants producing this
chemical at present.  One achieves zero discharge  by   total
recycle,  and the second plant discharges proce *s  wastewater
to a POTW after treating for  cyanide   removal  by  alkaline
chlorination.
     The
                            to  exclude  this  subcategory  under
pretreating wastewater  before  discharge  to the POTW.

Potassium Hvpochlorate.   This  chemical  is no lo"9^ produced
in the  United States.   The Agency proposes to  exclude  this
subcategory   under the  provisions of  Paragraphs 8(a)(iv)  and
 Potassium  Nitrate  and  Sulfate.    The  potassium   sulfate
 s^i!e^ry£LlJaT^xcTUdedn^r^hase 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
                               452

-------
64.
      ms-charger^1*   in  th*   U'S'    This  ^   1-  -  Direct
                                                             "

                                                              23
 "'   Piff 1SrThi!SsaTS1iai%.  There are £ive kn°™ Producers  of
                  mecaj.  salts in th& n ^  ^r^or*-i m       •
      are  discussed above in Suhrat-ennr-ii M«  -n \     mi.       salts
      jr •      -i  ^^-^ tiwwvc in ouocategory wo. 21 ) .   Threp  nf  t-h^

      diJcha?iS? !!nSChleV? !er° discha^e' ^d there is one direct
             "     " one indirect discharoer  in   i-ho    K  *•

      year (
-------
65.


66.



67.

68.
69,
70,
71.
72.
     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).
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 proposes to exclude
this subcategory under Paragraphs 8(a)(iv) and 8(b)(ii).

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  proposed  for  exclusion  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
proposes  to  exclude  this  subcategory  under   Paragraphs
8(a)(iv) 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
proposes  to  exclude  this  subcategory  under   Paragraphs
8(a)(iv) and 8(b).

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
                              454

-------
 74.
 75.
76.
            suchChsamra9n  'produ^on
      pollutant  loads  a?e  aStiUpat
  73.

      silver  recovery   and
 pretreatment  requirements
 with the POTW's pret?eS£nJnt
 value of  the - ?e?ovj?ed  si

 cost of the treatment Sy?emSth
 cease operatino the  ?re

 Agency propose^to excludJ
 8(a)(iv) and 8(b). eXC1Ude
                                                       system

                                         *.i,with   the   POTW's

                                            Plants must comP!y
                                                   Since  *ie

                                     pant         ^l °f the
                                     Plants  are  unlikely  to

                                              Jhe"fore/ the
                                         ory under  Paragraphs
 Silver Iodide.
 quantTtIes~~Tor "research"^  hh  p£?auced  in
 There is only one dischara^r i n +h* higj]1y specialized U»«B.
 Plant  discharges to a POTW   Sin?i iSUbcate9°ry.  That one
 from  such  small  production  voinmL,*   fwater 1S exP®cted
 pollutant  loads  are antiri™,^    mu   ^  no  significant

 rara? an^ .s??* saeis£2t^5^S'  ssysss



             ^fSjas -S-.S  a-s-^Ba

 treatable  levels   in  the^trSaJed^^stewaLr^'1"'3"'8 3t
               wastewater  discharged  at  that pi
                       BPT effluent  limitations.
                      : this subcategory.  40 CF*  «I3 ^-«,,

th;-slIver"Stratr:uSca?ego?y.Umitati0nS and standards'for

The Agency
regulatory
    discharoe to .a
                           455

-------
    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  limeprecipitation-alum
    coagulation  treatment  system  before  discharge.   Process
    wastewater volume discharged is negligible.

    The  Agency  proposes  to  exclude  this  subcategory  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,  /J, /*,
    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.
79.
Sodium Antimonate.  This product is generated  at  only  two
sites  by a process releasing no wastewater.  Therefore, the
Agency proposes to exclude this  subcategory  from  national
BAT   and   PSES   effluent  limitations  development  under
Paragraphs 8(a)(iv) and 8(b)(ii).

Sodium Compounds  (Inorganic).  Specific sodium compounds not
addressed elsewhere are:

a.   Sodium Molybdate - There are two plants producing  this
     chemical.    One  has  no  discharge,  while  the second
     produces  research   quantities   and   is   a   direct
                               456

-------
80.
     ssar sr
                                                            TS
                                                              *
                                                             °
      b.
c.
d.
     Sodium  Perborate  -  There  is  one  plant
     discharger, producing this chemical.
                                                         a  direct
                                                         a  direct
           Sodium  Perchlorate   -   There   are  only    two   d
           producing  this  chemical  and neither Sasa discharge

           Sodium Stannate - Three  plants  (two direct  dischargers

           TOciSlti ndl^-,diS?hargerLPro^uce this chemical on I
           specialty   basis  along with  many  other  chemicals
           Production quantities at each plant are very low    The
lels thfn°To
j.ess cnan 10,
                      n n          plants is
                      gallons per  year.
                                                            to
          wasewatr
                             " There are three  Plants  Producing
                                  °f th  plants discharge procesl
          cemcabrt        frc ^° plants Prod"cing  this
          cnemical,  but  one  plant  achieves  no  discharge  of

          lesseS?hanSt?Wfer'K- The  remaini^  P?«n?  dJschlrges
          less  than  1.9  cubic  meters  per  day  (<500 and)  nf
          process wastewater from this product.           9P

     The Agency proposes, to exclude ..the above  chemical  oroducts
     under Paragraphs 8(a)(iv)  and 8(b)(ii)  because the volume  of
     wastewater discharged is insignificant.
                              tw°  plants
                                                             this
          .             system  and   then   to   a   POTW    Alkaline
     chlorination is  used  at  this plant to destroy cyanide before
                                          '"  "SlSSSJ with
                                                           under
    This plant is also the only potassium cyanide producer  with
    a  discharge.   Therefore,  the  Agencyy did not combine the
                             457

-------
81
82.
83,
84.
85.
     potassium cyanide and sodium '"cyanide
     there is only one discharged.
                                       subcategories,  since
Sodium tiydrosulfite  (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
^grtilizer 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 s.ilicofluoride.
Thus there is only one discharger in this subcategory.
     Therefore, the Agency proposes to exclude
     under Paragraphs 8(a)(iv) and 8(b)(ii).
                                            this   subcategory
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  proposes   to exclude  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).   All   three dischargers  also produce
barium carbonate  and  combine  the  wastewatecs 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 proposes  to  exclude 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
                               458

-------
 87,
 88,
89.
       cii         -
  discharge of about 5,oJS gallon! per yea?!
                                                       which
                                                     *" estimated

                                         this  subcategory  under
  86.
                                                        -Ifites
                                               sulfide or sulfite
                                                  barium sulfide/
                                                ?romul9ated  for

                                                  ^SUlf ide' and
                                                   heref°^e  the
                     weu

 such as sodium hydrSsulfite
 sodium hydrosulfide? ReJul4tion
 sodium  sulfite;   sodium  hydrosSlJ?^
 sodium  hydrosuifide have  been  ^c?u                '
 Agency proposes to excludl thlJauSSJlS      Jheref°^e  the
 8(a)(i),  8(a)(iv)  and 8(b)(ii)  subcate^^ under Paragraphs



 (Potassium  Thiocylnate)  o? Io
 There are no discharges   ?S;
 exclude  the  sulfocyanides (fhl
 Paragraphs  8(a)(iv) and  8
-------
90,
    d.   Sulfuryl Chloride - Thetre cfre only two plants, but only
         one has a discharge.

    The one discharger produces all four chemicals.   Therefore,
    the  Agency  proposes  to  exclude  this  subcategory  under
    Paragraphs 8 (a)(iv) and 8(b)(ii) because there is only  one
    discharger in the subcategory,

    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  proposes  to  exclude  this  subcategory  under
    Paragraphs 8(a)(iv) and  8(b)(ii) because there is  only  one
    discharger in the subcategory.

    Thiocvanates.   (See Subcategory No. 59  (c),  79 (f) and 87).

    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
    fluoroborate.    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 proposes to  exclude  this
    subcategory  under   Paragraphs   8(a)(iv)   and   8(b)(n).
    Screening   and  verification sampling data   for  the   one
    discharger are  presented in Table  19-2i. •

93;—Ultramarine Pigments.   These  substances are not produced  in
     the—U7slat   present.    Therefore,   the  Agency proposes to
    exclude  this   subcategory under   Paragraphs   8(a)(iv)  .and
91
92.
 94.   Umbers.   This subcategory  has  been  addressed  under  Iron
      Oxides - see subcategory No.  34.

 95.   White Lead Pigments.   The white  lead  pigments  subcategory
      includesthe  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
                               460

-------
                                                                 has
  96.
       exclude   the   white

       subcategories undlrla.agrhs
 97.
                                         a
       Calcium  Carbonate  Subctegov  a?e   ^9U^elines  for
       Calcium carbonate  has  been  fxcluded from  /?H  CFR    415-300.
       regulation   development    in   Phfsf  ?  Kther  national BAT
       pollutants were found  at treatable  Kv.?  becaVse  ™   toxic




      provisions of Paragraphs 8?I) Uv)°and I(b) (??)"'   Under  the
                                                               one

                                                      r makes «»ny
                                 i
      Plant in the subcategory?         € XS °nly one  Discharging

 Radioactive Materials
98.  Cobalt 60
                                   104. Nuclear Fuel Scrap

                                          Reprocessing
M.  Ftssionable Materials         I05. Radium Chloride


-00. isotopes. Radioactive         106. Radtum LumlnQus ^^


101. Luminous Compounds (Radium)    ,07. Uranium Slugs,
                              461

-------
                                          Radioactive
102.  Nuclear Cores, Inorganic

103.  Nuclear Fuel Reactor Cores,
       Inorganic
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 proposed actions for each group of
subcategories is presented below.

     Cobalt 60 and other radioactive   isotopes  are  produced  in
     nuclear  reactors by inserting the non-radioactive precursor
     (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.
A.
 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.
                               462

-------
c.
D.
 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
 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 at 10 CFR  820.3(a)(3),  (15),  and
 (16).   The Supreme Court decided in  Train v.  Colorado  PIRG
 426  U.S.I.   (1976)   that  these materials,  "at—Ieast~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 durina 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 at  10 CFR   820.3(a)(3)
 (15),  and   (16).   The   Supreme  Court decided,  in Train v'
Colorado PIRG,  426 U.S.I.  (1976) that   these  materialsT" at
least  when regulated by  the NRC, are not  "pollutants"  under
the Clean Water Act.
                              463

-------
 Table  19-2.  SUMMARY OF TOXIC AND NON-CONVENTIONAL POLLUTANT DATA
             FOR SCREENING/VERFICATION SAMPLING (Table 19-2a,  AMMONIUM
             THIOSULFATE).

 SUBCATEGORY:  10 - Ammonium Thlosulfate
Pollutant

   Sb
   As
   Be
   Cd
   Cr
   Cu
   Pb
   Hg
   Ni
   SI
   Ag
  Tl
   Zn
   Ethyl benzene
   Tolune
   2,4 Dinltro phenol
   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.
                                    464

-------
 Table 19-2.  SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA
             FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 b.,  BRINE CHEMICALS)

 SUBCATEGORY: 18 - Brine Chemicals
 Pollutant

   Sb
   As
   Be
   Cd
   Cr
   Cu
   Pb
   Hg
   N1
   Se
  Ag
  Tl
  Zn
Concentration (mg/1)

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.
                                   465

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA FOR
            SCREENING/VERIFICATION SAMPLING (Table 19-2 £, CALCIUM HYPOCHLORITE),
SUBCATEGORY:  20 - Calcium Hypochlorlte

Pol 1utant                     Plant A
   Sb
   As
   Be
   Cd
   Cr
   Cu
   Pb
   Hg
   Ni
   Se
   Ag
   Tl
   Zn
   Chloroform
   Methylene Chloride
   Di chlorobromomethane
   Chiorodibromomethane
0.1
0.004
0.001
0.006
0.039
0.041
0.14
0.002
0.015
0.004
0.0003
0.002
0.085
0.090
0.014
0.025
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
                                    466

-------
Table 19-2. SUMMARY OF TOXIC AND NONC.ONVENTIONAL POLLUTANT DATA  FOR
            SCREENING/VERIFICATION SAMPLING  (Table 19-2 d, CHLOROSULFONIC ACID),

Subcategory: 22 - Chlorosulfonlc Acid
Pollutant

  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  Ni
  Se
  Ag
  Tl
  Zn
  Chloroform
  Methylene Chloride
  Di-n-octyl phthalate
Concentration (mg/1)

 Plant A

  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
                                  467

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL  POLLUTANT  DATA
            FOR SCREENING/VERIFICATION SAMPLING (TABLE  19-2 e^, NITROUS  OXIDE),

SUBCATEGORY: 47- Nitrous Oxide

                   Concentration (ing/1)

Pollutant                   Plant A
  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  Ni
  Se
  Ag
  Tl
  Zn
  0.06
  0.01
  0.002
  0.002
  0.24
  0.021
  0.007
  0.002
  0.035
  0.015
  0.002
  0.01
  0.08
360.
  Plant  B

   0.008
   0.004
   0.001
   0.009
   0.060
   0.075
   0.061
   0.005
   0.009
   0.003
   0.0007
   0.003
   0.015
3400.
*  See Text.
                                     468

-------
 Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA FOR
        .     SCREENING/VERIFICATION SAMPLING (Table 19-2 f,  IRON WIDE  PIGMENTS),

 SUBCATEGORY: 34.35.36.48.67.94 - Iron Oxide
 Pollutant

   Sb
   As
   Be
   Cd
   Cr
   Cu
   Pb
   Hg
   Ni
   Se
   Ag
   Tl
   Zn
   Fe
   Methylene Chloride
**
        Concentration  (mg/l)

      A*            Riant B
 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
 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
                        fUnCt1°n1n9 <*«»«"*•  Effluent not in co.pliance with
   Long-term treatment system performance data.
                                   469

-------
TABLE 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL POLLUTANT DATA       .MnDI)llftllO
            FOR SCREENING/VERFICATION SAMPLING (Table 19-2 £, SILICA, AMORPHOUS),
SUBCATE60RY:  68 - Silica, Amorphous
Pollutant

  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  W
  Se
  Ag
  Tl
  Zn
  Chloroform
  Methylene  Chloride
  Methyl  Chloride
  Di chlorobromomethane
  2,4 Dinitrophenol
  Di-n-octyl  phthalate
   1,1,1 - Trichloroethane
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.
                                     470

-------
Table 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL  POLLUTANT  DATA
            FOR SCREENING/VERIFICATION SAMPLING (Table 19-2 h,SILICA GEL),

SUBCATEGORY: 69 - Silica Gel
Pollutant

  Sb
  As
  Be
  Cd
  Cr
  Cu
  Pb
  Hg
  N1
  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
                                 471

-------
TABLE 19-2. SUMMARY OF TOXIC AND NONCONVENTIONAL  POLLUTANT  DATA
            FOR SCREENING/VERIFICATION SAMPLING (Table  19-21, TIN COMPOUNDS),

SUBCATEGORY: 92 - Tin Compounds  (Tin Fluobbrate)

                            Concentration  (mg/1)

Pollutant                  Plant A

  Sb                        0.008
  As                        0.016
  Be                        0.005
  Cd                        0.006
  Cr                        0.007
  Cu                        0.17
  Pb                        0.12
  Hg                        0.0005
  Ni                        0.22
  Se                        0.005
  Ag                        0.0004
  Tl                        0.045
  Zn                        0.12
  Phenol                    0.045
  Butyl Benzyl Phthalate    0.043
                                    472

-------
                             SECTION 19


                             REFERENCES
 5.
 6.
  1972.
  Park,  cSTTIoFnlS.
                              "    S-   "Standard   mistrial
                             ,    U.S.   Government  Printing Office,



                                          *i  Chfffiical  Producer^
                               '  stanfor<3 Research Institute,  Menlo
  Chical  Marketing Reporter,
                                       cheaical  Buyers  Directorv
                            rea       tfi    ack9""^  ->ata)  to
            Inorganic   Chmiclls   ManSf^f el°pment D°=™ents for
      Category,"  Calspan  Seport  No  ND l™^,* P°lnt   Source
      (Survey conducted in 1976K      KD-5782-M-85, 17 March 1977
                                                      "» Deluded

               Associates,  ,c.
7.
8.
Terlecky, P.M. and  Frederick    v B
Rare   Earth   Metal   Salts'   »;R"
Subcategories,"   Menorfndum
Assoc.ates to Dr. Thomas
                                            »n-  u
                                            u?ischarge  Status  of
Associates, Inc., November 30,
                                                                .
                                             Frontier   Technical
                                                              and
                                                              and
                             473

-------
11    U.S. Bureau of Mines, Minerals Yearbook, vol. 1 (Metals  and
     Minerals), "Minor Metals" (1976).

12   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 Communication:  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  Communications   X-ray  Industries  Detroit,   MI  to
     D.M. Harty,  FTA, December  7,  1982.

 22  U.S. Bureau of Mines,  Mineral Facts and Problems,  "Depleted
     Uranium"   by  William "sT—KlrkT^UMINES Bull. 671, 1980,  p.
      997-1003.
13.


14.


15.



16.


17.


18.



19.


20


21
                                474

-------
                  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 F.115
   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-S1

A-52
A-53
A-56
A-57
A-58
                             A-

-------
  Treatment Technology Abbreviations Used!
  Eq
  Neut
  Neut  (2)
  FL(m)
  FL(s)
  FL(p)
 CL
 S
 Sd
 RCL
 PH
 Floe
Act.
 Sludge
AR
Cr-Red
Pep
!  Equalization
;  Neutralization
  Two stage neutralization, if used in sequence
  Filtration with multi-media
  Filtration with sand filter
  Filtration with filter press
  Filtration-method unknown
  Clarifier
  Sulfide  addition
  Sedimentation  (basin,  pond,  lagoon)
  Recycle
  pH adjustment
  Flocculant addition
 Biological activated sludge
 Aeration
 Hexavalent chromium reduction
 Alkaline  precipitation
                          A-iii

-------

-------
CADMIUM PIGMENTS AND SALTS
           A-l

-------
                                               a) M
                                               6 rt
                                               o a
                                               «U rt
                                               r4 P
                                               0> CO
s
s
                  in
                 •p

                  rt
                 to
                  t/>
                 •p
                  rt
                  o
    •H
rH   E
O  »U
     rt
          V)
         •P
          rt
          o>
          6
          «
         •rt   -P
     6  &.   u
              (D
          f-<   M
                              O
                              CO
                              0>
                              t-H
                               rt
                               rt
                                               rt rt
                                               •H PH
                                               ^
                                               rt
                                                                   .
                                                        22222222
                                   U
                                                        <<<<<<<<
                                                        \ ^  -v.  •»*.  -^  •»%. •»».  -x.
                                                        22222222
                                            22222222
                                                                 CO  vO   rH  O   rH
                                                                 CO  CO   CO  CO   CD   CD
                                            O  rH  «O   rH  1/5
                                            rH  O  CO
                                                to
                                                        2222222
                 U   O  I-H  »-3   2
             O
             U
             •P
             •rt
    /—%       W
     w   ..   3
     fl>   W   -P
    •rt   -P   rt

    "s  3   to

     O   O   O
     bo  fH   bo
     0)
                               o  o
                              •H  g
                               r«  43
                               fl)  O
                  bO
                  .5  S
                               •rt  r< P
                                rt  o rt

                               Q    S
                rt o
                •rt rt
                rH <1>
              rt
rrt   RJ   f-i  43
•rt   O   0)   O  «rt
 O  43  43   W  FJ
 rt   3  +•»  -rt  o
(i,  CO  O  Q  S
     o
O   6
•p   p
     rt
     0)
                                               to
                                     OH
                                            rHi-HrHi-HrHrHi-Hi-H
                                            •rt  -rt  «rt   -rt  -rt  «rt  -rt  -rt
                                            rtrtrtrtrtrtrtrt
                                            QQQOQQQQ
 OOHJOJODaJD
 ooooooo^o
 rtrtrtrtrtrtrtrt
OCDOOOOOO
                                               •P i-H

                                               6 be
                                               rt if
                                  rt
                                  Pu
                                                                                       a>
                                                             to
                                                        £C   CO  T>   O   O
                                                         CX  H  U  PU   CO
                                                                      2  •
                                                                       i   '
                                                                       to i
                                                                                       CO
43
 rt
 O
•rt
rH
 (X
 ex.
                                                                                        P
                                                                                        o
                                                                                        2

                                                                                        H



                                                                                       2?
                                                                                                                 rt *
                                                                                                                 rt *2
                                                                                                                 *J g
                                                                                                                 tn rt
                                                                                                                    P

                                                                                                                 O
                                                                                                                 rt ^
                                                                                                                 rt u

                                                                                                                 Si
                                                                                                                    Q>
                                                                                                                 0)  CXi

                                                                                                                "5  a>


                                                                                                                 rt  ^
                                                                                                                •^  s
                                                                                                                4J  rt
                                                                                                                    43
                                                                                                                 W  4J
                                                                                                                 V)
                                                                                                                 0)  (/>

                                                                                                                rt  o
                                                                                                                    0)
                                                                                                                 o
                                                                                                                 *J

                                                                                                                T3
                                                                                                                 (D
                                                                                               n. L)
                                                                                               «  0)
                                                                                               a,  g,

                                                                                               (A  0>


                                                                                               rt  »
                                                                                               S  0>

                                                                                               u  rt
                                                                                                                 w  >

                                                                                                                   .
                                                                                                                 rt  O
                                                                                                                ti  e
                                                                                                                •P 4-»


                                                                                                                *o  o


                                                                                                                O» "1
                                                             A-2

-------
                                                     O

                                                     03
                                                     e
                                                       CO
                                                              CM CM
                                                              rH CM
                                                                      urj o
                                                                      O rH
                                                             O O    O O
    e
    rH
       CO
       Q
                                                   rH  O
                                                   •H
                                                   ja  o
                                                   cd  cd
                                                   R)
                                                             vo o»
                                                             vO to
                                                                   O> vo
                                                                   VO rH
CD 61
CO CO

< w
f-« CJ
   p w
   HCL,
   M

   §§
  H CO

  « O
  OH
  •-PCJ
                    CO   3
              g
              o
                      C.
                      cd
                      be

                      O
                    I
                          •P
                          O
                          :
CM
m
3
                  y
                   01
                                                             A-3

-------
                                                cd
                                                6
                                                o  c
                                               m  cd
                                                (4  P
                                                o  co
          cd
         •p
          a>
         S

         T3

          9
     (A
     •P   tO

     g  1
     i   u
     00  >rl
     •H   g
     Pn   0)
     ftf  
rH
  •k
 rl
 0>

•g
 0>

I
                               CO
                                               •rl JH
                                               f-l O
                                               •H 4->
                                               .0 U
                                                cd cd
                                               •H y,
                                                ri
                                                cd
                       CJ
                       ex:
     3            P  co
     • rl   ri          3   O
                                               cd
                                              •P
                                              CO
                                              CO
                cd
                u
               •rl
                rl
                O

                (0
               •H
               ffi
                                                                                                                       £i
                                                                                                                     in
                                                                                                                     cd "g

                                                                                                                     C  *
                                                                                                                     cd *^
                                                                                                                     w  cd
                                                                                                                        P
                                                                                                                     4>  (A

                                                                                                                     pio
                                                                                                                        £
                                                                                                                     r!  «
                                                                                                                                     O
                                                                                                                                    m
                                                                                                                                     g
                                                         o
                                                         V
(A
O
rH

V
                                                                                                                                     0)
                                                    O
                                                   551
ft,   CJ  O
<

w


,t
V
tJ
o
u

X
4J
•rl
rH
•H
U
cd

..
to
4)
•H
* -*
r7
O
bo

•P
cd
O
^0
3
CO

,*
to

u

o
ri
ex,

rl
4)

^J
O
(A
3
4J
cd
•P
CO
4>
bO
ri
cd
y^*
o
(A
•rl
Q
0
•H
rl
4>
P|
bO
C
•H
ri
O
P
•H
C
O
S
bo
0
rH
O
p<
^5
U
Q)
H
P
C
4)
a

cd
4>
rl
H
                                             •H  r< P
                                              Cd  O C
                                             Q    O
                                    fi U
                                   •rl C4
                                   rH 4)
                                    &E
                                    6 c^
                                    cd a>
                                   CO ri
                                                             4)
                                                            rH

                                                            •8
                                            p  cd
                                                         •H
                                                         cd
                                                                                         4)
                                                                                        3
                                                                                         u
 0.0
    o
 O  4)
 4)  <-*
 ft O
 V?  fl>
 0)  ft
    X
 W  4)
                                                                                                                     0)  4)

                                                                                                                     §  cd°

                                                                                                                     *3  O
                                                                                                                     w  >
                                                                                                                     Cd  ^«
                           o  cd
                                                •P '
                                                 0)'
                                                 6  exj
                                                 cd
                                                 Cd
                                                CX,
•H  Pi
 cd  O
                                                                                                                                  o  o>
                                                                                                                     o o
                                                                                                                                 o»  in
                                                                                                                                 o  en
                                                            A-4

-------
                                                 «'
                                                 u
                                     £


                                     U,
                                     P.
                                     U
                                                S rt
                                                ht>
                                    <  <  <
                  f-.
                  0) I
                 ft.
                     §
                                     c
                                     o>

                                     rt
                 rH O
                 •fH j *
                 «O O
                 rt rt
                 •H PL,
                                    (U

                                    rt
                    CO
                   co
                   
               u
              •H
               ^
               u>\
              •HI
              •*-"
               rt
              +J
              co
                                             Ml
                                             rt
                                3
                                     a
                                                 ^
                                                       °°
10  o»  o
000
 •   •    .
O  O  O
                                l-t
                                 «|  A
                                 
                                wl
                                •H|
                                K
a
                      X
                      00
                  ..   Q
              ••  tJ   rt
     <—>       woo
     to  • •   »3  «.j   «^
 ••  o>  M  £   £  JH
 «J  -H  +J   rt   4)   O
"g  'r'  o  +J  cw   «
 O  X  ^  CO      H

     O  O  fl)  C  4.J
 X  bo  ^  bo  .H   p<
4J  Q>  p|  K4  IH   A)


•H  U  fl)  U  >H  R)
O ^  X   W  CJ  03
rt  3   4-*  >H  O  t-i
^  CO  O  Q  S  £
Sampling
Frequency
                                                      5"  5" 3  £ $
                                                      «  «  S  2  2
                                                          W  W   w   w

                                                          *H  H
                                                          S  2   w   W
                                                          «  rt   rt   «
                                                          M  «  «  pq
                                                             -2
                                                              rt
                                        rt
                                        t.
                                       0
                                                                             V
                                                                             rt
                                                                             u
                                                                            •H
                                                                                                                           CM
                                                                                                                     *

-------
                   cd
                   CO
                                     
                                     J3
                                     rt
                                     •H H,
                                     !-i
                                     rt
                                                                  oo
                                                                               oo
                                                                               to
                                                                                     cn    \o
                                                                                     10    vo
                                                                                     rH    tO
                                                                                                  to
                                                                                                               uo
                                                                                                        to
                                                                                                                                         cd  *J»
                                                                                                                                         cd
                                                                                                                                         o
   co
  ; os
CO
                   O   rt
                        o
                    •.  -H
                   rt
                           O
                                  rH   rH
                   3   O   
E    •>
0)  4->
O   3

              rH   rt
              cd   3   •*->
                             rt
                                      O
                                 -P   -P
                                  O    rH
                  CO  O  Q   S   H
                                                 o
                                    cd
                                    +J
                                   CO
                                    cd
                                                      cd
                                               •H J-i 4->
                                                cd o rt
                                      oo >>
                                      fi O
                                     •H C
                                      Cd V
                                     CO (H
                                      0) /-^
                                      -P rH
                                      0)	
                                                    cd
                                                           cn
                                                           oo
                                                                  00
                                                                  oo
                                                           00    00
                                                           r-j    vo
                                                                               cn
                                                   vo
                                                   to
                                      cn
                                      vo
                                                                oo
                                                                  •
                                                                to
                                                                                                        to
                                                                                                               VO
                                                                                                 00    VO
                                                                                                 vo    CM
                                                                                                        LO
                                                           vo
                                                                        in    in
                                                                        vo    vo
                                                                                     10     to
                                                                                                  vO    vo
                                              to
                                                           vO
                                                                  to
                                                                   cd
                                             cn
                                             vo
                                                                                    to
                                                                                           in
                                                                        to
                                                                        \o
                                                                        to    vo    vo    to
                                                                         •      •
                                                                        CM    O    i
                                                                               to
                                                                                     vO
                                                                                            to
                                                                                                  vO
                                                                                                         to
                                                                                                               to
                                                   00
                                                   to
                                                                                                               vO
                                                                                                                     to
                                                                                                                     to
                                                                               cd
                                                                                            cd
                                                                                                         cd
                                                                                                                      cd
                                                                         Cd
                                                                                cd
                                                                         QrHCT
                                                                                      cd
                                                                                            cd
                                                                                                   cd
                                                                                                         cd
                                                                                                                cd
                                                                                                                      cd
                                                                                                               txl
                                                                    A-6
                                                                                                                                  cn
                                                                                                                                   cd
 rH  0)        In  (D       rH  0)        rH  (D        rH CD        (H O
 Oft        Oft       Oft       Oft       Oft       Oft
tt i     «. •   ^ii     «.    ^j     tj    LLJ     LJ     U_i     11    *iji     tj



rH  <0 rH  .  rH  0) JH    rH  fl)  rH    rHOrH     rH 0  rH    MtUf-4
•H  ^ Cd                     '             "            "           " "
 cd     3
                                                                                                                            cd
                                                                                                                                   cd
                                                                                                               Qr-IO*    nrH
 !-,  cd
 O  S
4-1  M
 rH  O
 0  4H
 ft ^
    0)
 a>  ft
                                                                                                                           w
                                                                                                                           V)
                                                                                                                           4)
                                                                                                                                            o
                                                                                                                                         (1)
                                                                                                                               o
                                                                                                                           ^j Tj
                                                                                                                           o  o
                                                                                                                           
                                                                                                                           a,  ft
                                                                                                       o  cd
                                                                                                       rH  rH
                                                                                                       3  0
                                                                                                       W  >
                                                                                                       cd  cd
                                                                                                       0  ^
                                                                                                       B  >>
                                                                                                                                        1-1 -P
                                                                                                                                        m «w
                                                                                                                                         o  o
                                                                                                                                        «M> e'P
                                                                                                                                        CT. 10
                                                                                                                                        cn en

-------
   & to
      CO
LO


































f-

4-
P
CJ
v_
3
£



• •
O
0
u
X
4J
•H
•H
cd




w
r-l
cd
to

rt
.£
U
•H
2;

C3
cd

£*
(U
S
O rt
o ca
-o
•> -rl
£ §
cd A
rO CJ
O
0 0
•H
§cd oo
W m
'S O
•5 G CD
•cd w c
u 3
CUT r-3
WO O
4J -H +3
C G *j
^ e bV S °
• bo n o> *
'•HO rt 0
W 4J * 3
'3 0 0 J3 **
"d ^ rH € «
e o> -H S 4J
^ 6 T3 O 3
,*? 5 G 
" s: rt Q 2:

X
.. o
•• »O rt
'~\ WOO
W .. 3 .H c
« W 4J ^ £
•H 4J Cd ' CD 0
*— ' O 4J CV a)
b ^ w H
H T3 bO
O O CD G P
^0 JH bO -H G
O CL, fn fn fl)
4-* cd O S
U V 0 -rt td
•S •£ w G CD
3 £ -H 0 fn
W O Q S H


CD
O
«J
M •
O

(-.
CD C
cx,
k_^
Hrf
^
•O *o cn
C
cd <= o
P
o
"-,


X
t t
H>»
•H '
rt 1
•H 4
rQ |
cd c
•H p
cd
>

H
3 °°
J Oi ps*
J '
3 ** rt
H tH






CVI ^>
(/) >
0 U
•H
^O I/?
•
rt to
4J
W
•rH •
Co 1 Cfl
tol "*
00 00
«*7 ^3
0 rt

xl
W .1 _. „
| a « s
§ <" 0* 0
W
1 — • >
rt .
rt C
Ol «H
Hs
o
4->|
W .
•H O
E| 2:
•-• 1-1
0 0
0 0
0 0

in o
*
X rt
•"H H*P
cd o G
Q o
2
X
I i


ampling
equency
CO *H
H-,
g b(
cd 6
JH O
O CL
X W 4J
rt CD fH
Qrt 0-
^
v_^
  2:


A-7
                                                                                                                              rt
                                                                                                                              rt
                                                                                                                              •P
                                                                                                                                  rt
                                                                                                                                  rt
                                                                                                                              U
                                                                                                                                 0)
                                                                                                                                 u
                                                                                                                             a
                                                                                                                                 (U
                                                                                                                             •P
                                                                                                                                5
                                                                                                                             W  -P

                                                                                                                             VI
                                                                                                                             0)  M

                                                                                                                            rH  W

                                                                                                                                 tJ
                                                                                                                            O  0)
                                                                                                                            a> -P
                                                                                                                            P.  o
                                                                        to  a>
                                                                       •P
                                                                        G  w
                                                                       O  (U
                                                                       e  w>
                                                                       0)  W
                                                                       ^  fn
                                                                       3  O
                                                                       W  >
                                                                       rt  rt
                                                                                                                          •H G
                                                                                                                           rt O
                                                                                                                          •a 0

                                                                                                                           0) O
                                                                                                                          .C J5
                                                                                                                          +J -p

                                                                                                                          
-------
  PU
ri P
4} CO
       ^J-VO
               O «O

               i-l tO
                       rH tO

                       O O
•H h
rH O
•H P
43 U
 rt rt
•H U«
 rl
 rt
          in   CM to   oo in
         • ir*^   in oo
                       r-4 LO
F-f
?:
S
^
=|
S
<
1

CD
z
HH
DJ
0
H
fr*H
1
H
I
U,
fi,
w
^^

1— 1
Crf
O
H
CO
l-l
X


VO
*
arH
I

»jn
•i
5
H








CO
1
Q
^|J
s
co
w
o
2
5^
o
fe
os
u
(X
o
CO
«
o
H
CJ
g
s
HH
. i
HH
HH
5
r-l
cd
<;
>:































CM
rH
UH





4«
CD

O
U

^.
•H
rH
•H
U
rt











to
P
rH
rt
CO

rX
U
•H
55
rt
P
rH
rt
O
CJ
Cadmium,



..
V)
CD
•H

^
J-4
O
bo
P
rt
U
43
CO








rH
rt
CJ
•H
CD
43
CJ
O
•H
CJ
rt
bO
0
(3
1
U
•H
rt
bo
O
JH
0
43
•P
0




• •
to
•p
u

*o
o

(X
^
0
•3
0


















^
0
o
t 	 /
Direct 1



-
^
•p
rt
P


. CD
bO
ri
rt
43
U
to
•H
Q








to
OO
0
rH
..
oo
CM
J-c
rt
43
CD
U«
•P
rH
OO
en
rH
•h
January



o
•H
^1
CD
PW

bO
(3
•H
r<
O
P
•H
ti
O
S









•0
CO

aT
P.

w
^J
n,
CJ
•i
p.
u
Cu,

O
rH
HH
cr


^
o
rH
O
f3
43
U
CD
H

P
(3
i

rt
CD
H








J^N
rH
to
U
•H
in
•H
P
-P
CO
^
rt
c?
rH
rt
O
•H
P
in
•H


rH
•H
rt
n





•
r


C










(
















k
0



M
3
H
H

3
rt
o


M
CD
P
CD
=
S
»4
rt
X


^
J


X
rt

•|
H
(3
S
0
^1
rH
43
P
(3
O



^
o
a
o
j3
cr
CD
rl
PL,


/-^
rH
^^
bi
g
v_



t~- Tj- CJ OO t»- CM
CM t-» HI Ol «* rH
O O O O O rH

O "* !>• O>
^^ ^^ rH '^fr rH in
i-l t~- rH O O O
rH
to to
r-» f- en en vo vo
O> CTl VO .VO O O
O O O O O O
09 CM CM t^
O O CT> rH tO O
m o to o o o
o o o o o o
vo t^ \o f** vo r^
(M in (M in CM tn
vO vO vO
^t ?N ^*
rH iH rH
43 >> XX 43 X
+J rH P rH P rH
f3 -H P3 -H f3 -H
o rt o rt c rt






Sk.
»4 ^* ^*^
« Q 0
^*^ ^N, ^^»
" rH rH






0 .H "0 .
CJ g u


(3

O

o
rt

o
p
                                                           CD CD
                                                           J3 bo
                                                           O 14
                                                          •H rt
                                                           P43
                                                           fH U
                                                           O W
                                                           P.-rj
                                                           O T)
                                                           (H
                                                           p, CD
                                                             JH
                                                           > O
                                                           O'H
                                                             CD
                                                              CD
                                                             P
                                                           0)
                                                           t-i bO

                                                           43 -H

                                                           ^^ O
                                                           CD O
                                                           P U

                                                           O +•>
                                                           P.U
                                                           CD rt
                                                           »H P

                                                           10 O
                                                           f3 O
                                                           O  i
                                                           •H J3
                                                           P O

                                                           (H
                                                           •P43
                                                           C P
                                                            CD-H

                                                            a*
                                                            o bo
                                                            U (3
                                                              •H
                                                           P i-l

                                                            
 rt  O
 g  g
ll
tl  o
 a) "4-1
     P/
                                                                       £3 ">
                                                                       0 0)
                                                                       6 S?
                                                                       0) CO
                                                                       w >
                                                                       rt rt
                                                                       CD .
                                                                       2£
                                                                          o
                                                                       rt
                                                                       CD
                                                                       43
                                                                       P
                                                                        6  o

                                                                       «*> <«»
                                                                       CT> ">
                                                                       cx> en
         A-8

-------
                   o
                   -o
                   o
                  rH


                  CJ


                  (J
                  C
                  C
                  cfl


                  to
                  •P
                  rH
                  03
                  CO
                                               u
                                               C13
                                               rt  rl
                                               S  rt
                                               r»'
                                               O  C
                                              MH  rt
                                               p P
                                               v to
                         X
                         p
                        •H  I
                        rH  <
                        •H P
                        JO  U
                         rt  rt
                        •H U.
                         f-.
                         rt
                                                                                 oo
                                                                                 CM
                  CO

                 A<

                  U
                      w
 0
-H
 6
 (1)
                              to
                              CO
 f-,
 a
 3
 c!
 ctt
•-5

 O
P
                 tj  CJ
                  rt
                  rt   u
                             OO
            tO
                 g   rt       X .-J
                 3   rt  -P   rl  O
                 •H   bo  o   rt
             ">  6   >H  o   3    «
             -j  {V,
                                           to
                      o
                      P
                      w
                          a1?
                           X    .
                          JS   oo

13
CO
p
u
4J
(0
Q
•P
O
?
w
rt
13
CO
p
J*4
o
a.
CO
f-1
to
CO
3
_J
r~1
rt
>
13











^
*3-
•
rH






LO
» bo
E
p
O.O
CO rH
o .
Xo
u
H
r* x
TJ rt
a 2£
P
U (0
(D r*n?
p P
Q 13
•P rt
O
S5rH
r ^
bO
W S
rt
. 13 O
co .
P O
rH
0 II .
CO .
JH bt
>











. '
»rj
CU
P

CO
P
Q
p
0

<0
TJ
CO
p
o
CO*
J^

                                                                0)
                                                                            LO
                                                                            o
                                                                        0)
                                                                                             g,
                                                                    -o u "
                                                                              •C   o O
                                                                                  t- u

                                                                              §   &*
                                                                              !««.-

                                                                              2
                                                                                     •a  -a
                                                                                         •
                                                                                                              6 w
                 ?1
 rH

 1
O3
•s





• •
CO
13
O
CJ
X
•p
•H
rH
•H
U
rt
pv



f— \
co
CO
•H
v— '
X
r-l
O
bO
CO
P
rt
U
rO
3




• •
(0
p
u
3
T3
O
r.
CX.

>H
CO.
jc!
4J



U)
3
P
rt
P
CO

CO
bO
r4
rt
X
u
V)
•H


• •
o
•H
r<
CO
PL,

bO
rt
•H
r«
O
P
•H
rt
0
X
bO
o
rH
O
rt
.rt
u
o
t-*

•p
rt
CO
K
P
Cli
4>
r<
                    O  O  S  E-
                                         x
                                         •H   X
                                         •rt rt 4J
                                         at 0 C
                                         Q   0
                                              S
Sampling
Frequency
                                           rW


                                           P i-H

                                           4)
                                           rt
                                          0.
                              i
                             5.
                                                   O
                                                   O
                                      o
                                              o
                                             s
                                                      at
                                                      o
                                                      -c
                                                      •p
                                                      c
rH
x
p
e
                                                                               X
                                                                              rH
                                                                              JZ
   •}
  Q
   „  U ^l-H
  «e  c   u)
  5  o «x
  ~    « tH
 ' w  e u ca
  «s  o o
  _     1* in
  ^  *J &-H
  W  «) «J 4J

  £-35B

  s  Se'H
  "  4)-rt-O

  «  h-o 2
  «  CU -•
 S 4JJ3 «)
     D.
  •Ov_
   fc.
   IST3
  •O »«
   e «
   OT3
  *» e
  in m
     w
  u in
  u
  e o

  §^
  i-> a

  ^g
  >- o
  U

  e5
  19
 J= C
  W 13
   X
  m w
  w
  1> in
 >-i in
    4)

 •Q1"1
    o
 O J)
                                                      0)
                                                      J
                                                                                                    (U
                                                                                                    0
                    CO
                    CO      TJ

                    H      CJ
                                                     A-9
                                                                   O
                                                                  CJ
                                                                          CJ
                                                                                    « -0 4>
                                                                                    J;  

 c in
 4) t>
 E M
 4> OJ
 V. >-.
 3 4>
 VI >
 o) »
 4)
 B X
  rH
 XA
rH +>
•H e
 a o
•O H

 (U 0
JGJS
                                                                     JQ

                                                                     0,
                                                                                                   *.•*    ri  «>I
                                                                                                   N    <—• *—i
                                                                                                                     O O
                                                                                       Out
                                                                                       en en

-------
                                                 o
                                                 rt
                                                 O CO
                                                          LO to
                                                          rH LO    OO
                               VO CM
                               O rH
                                                          O O
                                                                   oo
                                                                            O O
    CO
oo
S





























.

oo
CM
f-l
(I,



















10
p
f-l
rt
CO
13
£
ments a
bo
•H
PL,
6
•H
6

rt
CJ


w
P
£
 -p
0
O  CMLO
o
00
cn
rH

fH
V
0
e
0)
U
V
Q
O
p
o>
t-
en
rH
£
rt
3
£
rt
'T*
;-,
V

O
O
os
e
3
•H
S
rt
CO /^
VB_>S Cf
•\ »-3
**^ P^
**— -* ^
PL, CO

•V
p,
o
a,

tf)
U
•H
p

•H
•P
rt
•P

Summary
^•rf
,
rt
U
•H
t .
M
O
+•*
w
, 'H
• Jr^
\OCM
^
O


vO
•
X
rt
S
i—l
CM
O

o
.1 t^
Is
LO

£
•H
O
o
o



•
O
ST.
CM
rH



^j»
LO
O

00
00
o
o
en
«=»•
o
o
o



to
en





CM
01 rH
THO
rH






OJ "*
to oo
CM «j-

LO'
to
oto
OiH
00
OOl"--
00
00
oo
rHS
oo
oo
oo .
oo



•^t-oo





J^
vO
t-H







t-H

O







cn
cn
CM







^
LO
o


o o
en
o
o

o
o
o
f-
rH
O
O



CM
f-l
rH
O

cn
to
o
o
LO
o
o
o



rH
O
                                                                                                                                  rt
                                                                                                                                  ID
                                                                                                                                  u
                                                                                                                                  4)
                                                                                                                                      a>
                                                                                                                                     A
Facility Code:
Subcategory(ies)
Other Products:
Discharge Status
Monitoring Perio
Treatment Techno
•HUP
 rt  O  £
                                                 £  U
                                                •H  £
                                                .
                                                to
 O

PL,
      •P rH
      £'H
      o  rt
      ^g fr\
                                                          V
XX   X  >N
P rH    P rH
£ -H     £ -H
O  rt     O  rt
so    so
                                                                                                                                  £
                                                                                                                                  rt
                                                                                                                                  A
                                                                                                                                  fj  rt

                                                                                                                                  «  +J
                                                                                                                                  to
                                                                                                                                  0)  (0
                                                                                                                                  O
                                                                                                                                  •P

                                                                                                                                  Q) P

                                                                                                                                  S* «
                                                                                                                                  OP,

                                                                                                                                  in <1>
                                                                                                                                  •P
                                                                                                                                  £ w
                                                                                                                                  o  rt
                                                                                                                                  (H (-<
                                                                                                                                  3 «
                                                                                                                                  w >
                                                                                                                                  rt rt
                                                                   o
                                                                  £
                               O

                              is
                                                 fH
                                                 d>
                                                •P rH


                                                 1^
                                                 rt
                                                         U
               bO
               35
                                                                                     rt  o
                                                                                    t»  e
                                                                                     a)  a>
                                                                                     O  O

                                                                                    ««» cN>
                                                                                    en LO
                                                                                    cn cn
                                                                                    16
                                                           A-10

-------
                               V
                               u
                               G'U
                               rt
                               E rt
                               HIS

                              .83
                               f-l -P
                               tt> CO
                                                              CM
                                                              VO LO
                                                             O r-l
                                                                         \o
98
in












to
rH
*-•
rH
cO
CO
_
C
R)
w
«

                                      00    O rH
                                      iH LO
                                X    00 \0    to LT»
                                t8|     •   •    Ol O
                                              vo oo
                                      «0 to     .  .
                                      M M   o 10
                                > I     •  •   io rj-
                               <|    00   rs^
                                                          VO
                                                          f- iH
                                                 00.
                                    .00    00
                                              CM
Ol   IO OO    10 f>
•W|   IO «*    to VO
                                                                                                              CO
                                                                                                                                      T)
                                                                                                                                  ^  H
                                                                                                                                  V)  CD
                                                                                                                                      •p
                                                                                                                                  0)  W
                                                                                                                                  U
                                                                                                                                  C  4)
                                                                                                                                  rt  U
                                                                                                                                  €  A
                                                                                                                                  f-c  rt
                                                                                                                                  o  e
                                                                                   O.

                                                                                   0)
                                                                                                                O
                                                                                                                                 CO

                                                                                                                                 4->  n)
                                                                                                                                    ^3
                                                                                                                                 W -M
                                                                                                                                 W
                                                                                                                                 V V)
                                                                                                               O
                                                                                                            OJ
                                                                                                               flj
                                                                                                                                    O
                                                                                                                                13  •P

                                                                                                                                +J 13
                                                                                                                                o  a>
                                                                                                                                0) •*->
 <
 w

I-




• •
0)
•o
o
u
X
+J
•H
rH
•H
U
CO
ft*

>t
^A
V)
•
o



Jf
cd
X
u
w
•H
Q

"
O
•H

4)
(X
bO
fi
•H
rH
O
-P
•H
ft
£
bo
0
o

(-4
o
V
EH
*J
A
O
1
to
0
^
H
                        «»  o
                               0
Sampling
Frequency
                                               •P rH


                                               cO B

                                               CO
                                             M.
                                             fi X
                                                          C-H
                                                          o  n)
                                                         SQ
                                   AS
                                    0)
                                             0)
                                             0)
                                                                                                              g.
                                                                                                              w
                                                                                                           u  cd
                                                                                                           f-.  fn
                                                                                                           3  «
                                                                                                           OT  >
                                                                                                           rt  cu
                                                                                                         •H  C
                                                                                                          (U  O
                                                                                                         13  6

                                                                                                          0)  0)
                                                                                                         ^5 JZ
                                                                                                         *J -P

                                                                                                         IH ««
                                                                                                         o  o

                                                                                                         e»f> «9P .
                                                                                                         O) to
                                                                                                         O> O>
                                      A-11

-------
COBALT SALTS
   A-12

-------
                                      p.

                                      u,
                                      p.
                                      u
                                     fx,
                                                  fl> '
                                                  u

                                                  cd
                                                   i *O
                                    rH 4->
                                    O CO
                    to
                   ,
                   OT
                   0)
                   ^

                   •rt
                   cd   cd
                  .0   4J
                   o   «
                  u  a
                  6   3
                  3   O   +J
                  •H   ^   O
                       fl>   O
                        (U

                        4J
                        cd
                        H
r-l   Cd
u,  u
                               3   e
                                                •H  t->
                                                r-l  O
                                                •H 4->
                                                ,r>  (j
                                                cd  «d
                                                •H (I,

                                                cd
                                 w
                                 0| O
                                 •1*1
                                 •p
                                 V)
                                 •rt
                                 •P
                                 cd|  cd

                                 W  S
                        H   'I
                        cd  bd

                        ill
                       CO

 3  -H
S:  a
                                   «
                                 rH
                                 O
                                 •P
                                 W
                                 •HI   o
                                 ffil  »
                                           00      o   P<
•H   +J
•-<   «   h  ..,
•H   O   O  O
 O  ,0   rf3  W
_td   3   4-»  -H
                                   O

                                   O
                         rt
                 o
                +j
            B
            5
            CD
                              cd
                             Q
                          I 4-1
                          > £
                           O
                           S
                                             cd
                                            >>  >>   X  X  X
                                           r-l .r-l  r-l  f-H  PH
                                           •H  -H  -H  -H  -H

                                           Q  Q  Q  Q  Q
 W   OT   W   V)
•H   «rt  .H  .rt
 W   to   W   W)
 <5   cd   cd   cd
«   PQ  pq  pq

^   ,a  .o  rfi
™   cd  cd   cd
                                                                        w
                                                                        •H
                                                                        pq

                                                                        -0
                                                                                                 V
                                                                                                l-l
                                                                                                XI
                                                                                                 rt
                                                                                                 O
                                                                                                             I
                                                          OT
                                                              S
                                                       •A-13

-------
                  o>
                 •13
                               1/1
                               4>
                                  B.8
                                 .813
                                  Ki 4J
                                  fl> CO
                                                                        to
                                                                                                  vO
                               o
                               rt
                               CO
                                 i-l  O
                                 •H  +J
                                 rf5  O
                                  rt  rt
                                                                                 to
                                                                                 to
                                                                                                  vO
                                                                                                           to
                                                                         to
                                                                                                       rt f>
                                                                                                      TJ  P
                                                                                                       C  rt
                                                                                                       « "2
                                                                                                      ^  S
                                                                                                       vt  rt
                                                                                                         •P
                                                                                                       0}  VI

                                                                                                       e  »
O I
o
                  rt

                  w
                  rt
                 co

                 i-l   W
                  4)   i-l
                 A<   rt
                  o   o

                  0)
                               oo
                               Ol
                               0>
                      rt
                               oo
                               01
     fX   W) 0-3   I-l
     O   fH  O
     CJ   O  O
             OO
                      IH   U   U
                               6  O
                      Q)   OJ   +J
                  O   -P
                               P,   «
             U.  O   O  Q   CO  W
                                VI
                                VI
                                             to
                                to
                                             rt
                                             V)
                                     rt
                                                       CO
                                          to
                                                       vO
                                                                \0
                                                            VO
                                                                                 CM
                                                                     O>
                                                                                     00

                                                                                       *

                                                                                     00
                                                                                          VO
                                                                                                  to
                                                                                                  Ol
                                                                                                  to
                                                                                 0>
                                                                                                                W 4J
                                                                                                                «/)
                                                                                                                0) Ift
                                                                                                                             0)  rH
                                                                                                                0)

                                                                                                                (J  0)
                                                                                                                0) 4J
                                                                                                                p,  o
                                                                                                                57  a)
 -
s
                                   >s      i-l
                                   CO      >H
                          MOO
             Q)  -H   -P
                      tn  +>
U   f4
     O
 S  60
•P   O
•H   -P
                      3  CO
                               bO
O  O   P!
M  bo  -H

    rt   O
                                   U
                                   O
•H   O  O •  O   «H   rt
 O  .0  A   V)   ft   J)
 OJ   3  *J  «H   O   »H
H.  W  O  Q   2  H
                                                                                                           r-l
                                                  0)
                                               rt  o>
                                              co  H
                                               o /— <
                                               •P I-l
                                               rt 6
                                               rt
                                                        rt
                                                                a>
                                                                CJ
                                                                                                           CO
                                                                                                           CO
                                                                                                                             en
                                                                                                                             a)
                                                                                                                3  »
                                                                                                                w  >
                                                                                                                rt  rt
                                                                                                                0)
                                                                                                                -
                                                                                                                             o>
                                                          A-14

-------
                                                      - §
   CO CO

   •< w
   H CJ
   < 2:
   Q<
  2:0
  r-l Lt,
  cici
  O ty
  HO,
  o 2:
 H  co

 w  o
 =3  E-
 ^  CJ
 fe  <

 W

 J E-

 O -3
 r-t I-H

 O <
 E-1 i—i
CO OS
I-H <
a >:
 «^i
  i
«

$
o>
*°
•rH
»H
O
rH
CJ
U
c
•rt
KI

c
R)

(0
+•>
rH
R)
CO
i-H W
(1) rH
A! RJ
0 0
•l-l IM!
n •PI
2: e
o
tJ &
C CJ
RJ
O ,
 I-H
+J 4J
rH rl O
00 RJ 
P* JTj
^ t

0 H^
+-> CJ
O> .,
t-. p.
Ol O
rH CXj

^» •>
RJ cr*
*5* nj

«•
U
*O
o
CJ
X
4->
•H
rH
•H
U
rt
b.
• •
(0
0
•H
v«/
^
^i
o
be
V
4->
a
u
J3
3
CO

to
+J
(.}
3

0
S-i
CL,
>H
(0
^i
4-»
O
3
4->

+J
CO

d>
bo
(H
R>
JZ
o
W
•H
Q
TJ
0
^
(U
P(

bo
c
•H
ri
O
+J
•H
A
0
rH
0
c

U

f ,

+J
c
0)
4->
R)

                                                     X5 O
                                                     R) R)
                                                     •H [L.
                                                  W
                                                  U
                                                 •H
                                                 4J
                                                  (/)
                                                 •H
                                                 4->
                                                 R)
                                                  Ctf
                                                 £
      X
      R)

                                                 O
                                                 4J
                                                 W
                                                •H
                                                a  2!
                                              •H JH 4->
                                               « O C
                                              Q    o
 c o
•H c
rH  i   10  o
  •    •    •
rH   ^3  (^
                                                           0   0  0
                                                                                  0   0
         3   I   3  i   S  3   *

                                                                   S
                                                                            13   S
                                                d)
                                                4-> rH


                                                I

                                                r.'

                                               (X,
                                                         R)   (0

                                                         O   M
                                                        H  IX,
                                                             §
                           3   -H
                          cj   2:
                                                                 A-15

-------
                                             rt rt
                                             6 rt

                                             o p)
                                             *4H rt

                                             0) CO
pa
s
PQ
               •0
               •H
   U

   U
   G
   N

   •U

   s
                r-l
                 rt
                CO
                 0>
                     W
        rt
    o  o
   •rH  «H
   z  e
        O

    g  O

        U
                 bo

                •H
                 rt
                 O
                 4J
                •H
                 P!

                 £

                 co
                 0
                 00
                 o»
 rt
S

 O   H
 •P   P.
                 p,   rt   /—>  oo    •>
                 p,   bo  CJ  r-   J
                 o   rt   o  en   u
                 CJ   O   O  rH
                      P«   ^—'        ^
                  «  I—I         •>  Pi
                          4J   4->   U
                 •P
                 rH   rt
            co   rt   OJ
            rH   ^)  ^S
            rH   O   -P
            ttt   o   o
              u
              Q>
 (A  Pv.

 bO    -
 3   O4
 <  W
                 <-%       IA   O   O
                  M   ..   3   -H   g
                  O   (A   -P   rt  ^3
                 .H   4J   rt   0)   O
 O
U
     >>  3

     o  o
>•»  bO  rt
4->   0)  PU

i   ^  -
r-l   rt
•H   O
O   ,0
rt   3
tL,   CO
                          W
                           bo  -H
                           ^   ^
                           OJ
          0)
             P
              P!

         o   I

              rt
     O  «ri

"   W   S   S
+J  .H   O   ?-"
O  Q  2   H
•rl ri
rH 0
•H P
.0 U
rt rt
•H PU
rt
>
tn
•
^







(A
U
•H
V)
•H
4J
rt
P
CO

^
J>4
rt
3
CO

r™
rt
U
•r
c
(/
•r
rc
^-
5
O>
0

X
42
rH
•
2 o

i M

bd *~*

4J
O

rH
rt


rH

<,
•

to
rH





/— %
to
O
o
V
(A
rt
0)
4->
O
P.
r<

(A
0)
3
i-H
rt


rH

<,


to
rH





/— \
rH
O
O
V
(A
rt

-P
rl
0 0
PO P,
0>
rl

\O (A
. 0>
0 3
rH i-H
rt
^

rH
rH
Ift <^


to to
rH rH





f— \
rH
O
O
V
(A
rt
0)
P
rl
0
P.
rl

in
0)
3
rH
rt
^

rH
rH
^,


IO
rH
               rt  o  C
              a     o
 bO >>
 C  O
•H  P4
rH  0)

 §*a
 rt  o>
CO  ri
    PH
                                           rH  r-l   rH  rH   rH  rH   i-H
                                           •H  -H   -H  -H   -H  -H   -H
                                           rt   rt   rt   rt   rt   rt   rt
                                           Q  O   Q  n   Q  O   O
                                            P   -P   P
                                            P!   P!   P!
                                        A  A
                                        +J  4J
                                        P!  PS
                                                                               P!  PJ
                                                P i
                                                O'
                                                 rl'
                                                 rt
                                                Pu
                                                    6
"^ ^^
rH rH

i^^
rH

ij
O
H
\—>

2r »rt
0 0
rH rH rH


(A
0)
-d
•H
rl
0
3
rl .O rH
CJ p [ (JLt
rH
IA
a)
-P
rt
ri
0
J3
0
3
rH
U,
rH



<1)
P
rt
C
a>
(0
(H
<
                                                                      U
                                                                      o
                                                                      H
                                                                                                    §
                                                                                                    o
                                                                                                    o
                                                                                        0

                                                                                        rt

                                                                                        a)



                                                                                         *t
                                                                                        V)
                                                                                                     rt
                                                                                                     r<
                                                                                                     O
                                                                                                     PQ
                                                                                                     rt
                                                                                                     PQ
                                                                       •H
                                                                        P4

                                                                        i

                                                                        O
                                                                        V)
                                                                                                                              S
                                                                                                                             : fl) W

                                                                                                                             • g •>
                                                                                                                             ; § o
                                                                                                                              € ^
                                                                                                                              c «
                                                                                                                              O 6
                                                                                                                              IW rt
                                                                                                                              
                                                                                                                  rt  rt
                                                                                                                  o

                                                                                                                   rt
                                                                                                                   Q>  QJ

                                                                                                                  •^ •
                                                                                                                                o  o
                                                                                                                                o>
                                                           A-16

-------
        to
        4J
        rt
        rt
        co
                                      u

                                      rt  ft
                                      E  rt

                                      o  e
                                     *r-t  rt
                                      r-l  4->
                                      V CO
                                     Ac   :
   t>»    o>



   O    O
                                                               «
o
  *
\o
CO
  •

rO
                                                                                                                      g
                                                                                                                      O
                                                                                                                      V
                                                                                                               g
                                                                                                               O
                                                                                                                V
                     V

                     u
        c
        rt
                        -H
                    +»   e
                    rH   0)
                    Cd  J3
                    ,0  U
                    O
                    U   U
                        •H

                    E   3
                    •3   «
                   >H   M
      O
      W
                                                                                                                    cx,
                                                 •H V.
                                                 rH O
                                                 •H I *
                                                 J3 O
                                                  rt rt
                                    rt
                                            5
                   o
                   oo
                   en
      o>
                    .   8
                   I   a
                   •H   O
                   Ac
           W  +J
                    O
                    +J


                   t->  b
                   Ot
                                *   °
      E    3   U     .o
01
      td
                        iw
                        V -H
                        @ •«
B.   0   SI
                   E   •>
                   0)
                   Q
                                  rt
                                   rt
                                   E

                                   3
                                  co
                                       a
                                                  00
                                                                    uj
                                                                                     to

                                                                                           oo

                                                                                                 K)
                                            o
                                           o
                                      OJ  ,0
                                                             O



                                                             V
                                                                                                                    o
                                                                                                                    V
                                        o


                                        V
                                                                                                             o
                                                                                                              V
to
tsj

w

i
                       M)
                   ••   O

     <-%      woo
   .  M   ••   3  -H   fi

 flj   -H   4J   rt   <1J   U
T3   «—'  O   4J  At   0)
 O   X  3   CO      E-i
O   rH  *O        bO
     o   o   a>   c  4->
 X  bo  h   bo  -H   c,'

•H   4->       rt   o   E
                  +J  4J)
     rt
•H   U
 U
             y
             M
rt  3   
                                                                               C

                                                                               i


                                                                                                 to



                                              »H
                                              «
•H  
                                                                                                                     OJ  W
                                                                                                                     o
                                                                                                                     c  o

                                                                                                                     11
                                                                                                                     (H CO

                                                                                                                    rt
                                                                                                                   OT  -P
                                                                                                                       (/)
                                                                                                                       o
                                                                                                                       o
                                                                                                                       +J
                                  rt
                                 a,
                                          Tj
                                          O
                                                                               £
                                                                               <->
                                                                                                                   O
                                                                                                                                P. 0
                                              in o
                                              4-1
                                              C <"
                                              5 o
                                              E bo
                                              o> rt
                                              r-. ^
                                              3 0>
                                              W >
                                              rt rt
                                              o

                                              6£
                                              S- -C
                                             rH £
                                             •H  C
                                                                                                                  V  O

                                                                                                                  •J ^J

                                                                                                                 ^ ^M
                                                                                                                  o o


                                                                                                                 o> to'
                                             A-17

-------
in






























<7
p
o
CJ
\~r

O*
rH
rH
PH





««
Q)

O
CJ

^,
p
•rl
rH
•H
U
c«
P-.







in
p
rH
CO
CO
i_|
0
U
•rl
-a
C3
r.

•Cj
,CJ
u
•rl
3
be


rH
US'

O
•H
P!
cd
bO
r«
O
in
3
O
r<
<0

5-5
52




,.
V)
4J
u

o

O-*
rl
0)
^
p
o






































4J
u
0)
rl
•H
id
Pi
I-H



• •
in
3
P
CO
P
CO
0>
bO
^4
(0
u
in
•H
Q


























O
oo
Ol
f—i

V

3

O
P

00
O
rH
^
0)
-O
E

u
• o
Q


• «
tJ
O
•H
^|
0
OH
bO
Pi
•H
^(
0
P
•H
Pi
O
S



































i^
CJ
•«
u
o
^^
a,

•^
P
3
u
•z.

bO
O
rH
O
P!
^P*
O
0)
H
P
P!
a>
E
P
CO
a>
M
H






cO r>
€ cO
O P!
I
* p
0) CO
p



\O
10
O


-1


X
p
._J Li
•n ri
i-H O
•H P
£> U
cO cO
•H U,
CO





in
u
•M
P
in
P
cO
P
CO
>,
rl
cO
E
E
CO
(0
u
•H
ri
O
P
(0
•H
sc


00
CTl
(0





CSJ
,^
CJ
00
•
i-H


X
CO
S
OO

O


*I Oi
bd o
1 *
<\ 0
rH
c
•H
s
O
0
•
0



•
O

irt
2
*
rH S
•H rl P
CO 0 C
a



(
t
«f
r

o
^
i-H
4J

O
s s


SOX
3 U
H Pi
H 0)
3, 3
E CT
CO 0)
CO ri



|
pLt
.
O
m

^
rH
•H
CO
Q



fl) «-^
P iH
e"«
to e
t
^'-'
co


H*

2
CJ

Ol
o






f.
rH
^H




^i*
to
•


oo

rH


OO
O
•
0
rH
O
0
*
0
V



o
™

rH
•H
CO
Q

€ .
a>
&
fM 
-------
ex
CD v-
O
GTS
cd n
E rt
MH cd
tj j j
CD CO
O,
X
4J
•H r«
rH O
•H 4->
43 CJ
cd cc
•H U,





•* VO 0 to rH tO
i-H tO rH tO O O





"5MO CM tO 0010
*» IN. tO 00 f- ^fr
* * • • •
rH tO rHrf rH to

P
rH
SCO
II
CO CO
< w
H U
§0
I-H U,
O U]
£-0,
KH
0§
H CO
20:
W O
3E-
•J CJ
U, <
(X^ PU
J>^
-J H
^£ HH
0 Hj
I-H I-H
HISTOR
VARIAB

VO
1
w
p*»
6-1









CM
i— 1
B,



Q)
TJ
0
U
X
4J
•H
rH
•H
U
cd
d,

H
r
C
r
C
rS
(.
•p
2
T
P
ct
4-
rH
Ct
C
O
I
f=
3
•H
•d
cd
CJ


w
•H
bcategoryf
3
CO
m
M ,
-1 I
«
0 (
•i
3 !
< t
) f,
^ c
: t
': T.
I P
R
L
•H
C
ct
U
O

J-.
CD
4>)
o



4J
U
13
O
Cw
CD
43
^J
O
t/>
rH
cd
CJ
H
e
o
c
J
H
•4
d
)0
-i
3
4
•I
t
i
^-^
iH
o
3 0

^J
O
CD
r<
•H
O


(0
3
rd
CO
CD
bO
cd
A
U
to
•H

»
C
c
r
O
C"
k
*•
CT
^
4:
(V
tv
c
I-l
oo
> rH

CM
X
rt
cd
3
cd
"-5


O
•H
CD
Ai
bO
G
•H
fH
0
4->
•H
G
o

O
10
•h
-I
t\ Tf\
" VJ
0
•J A
X
s a,
4
1
to
,_3
CJ
•t
(J
CX
•>
o

U-r

CJ*


..
bo
O
rH
O
CJ
CD
H
4J
G
CD
•P
a
Q)
f-i
H
/-*
iH
v_
tr
CJ
•H
4-1
to
•H
4->
cd
4J
CO
§
1
rt
Cd
U
•H
M
o

to)
•HI
ffil



X
rH
•H H
cd o
0

bo
G
•H
rH
&
cd
CO
1


tu
\
1 ^


<
•
•H
s


•
o


*
£
4J
C
O
S

Jt-requencv


t~- ^»
J| 00
• o
* I—I t^
CJ C3> 0>
1 00
oo
0 0
to o
0 0


VD I-~
CM to
VO



X
rH
G'H
O Cd
SQ

X
cd
Q
i-H


CM 00
.to 01
0 0
rHO
rH
O) O)
VO VO
O O
CM
Ot rH
to o
OO


vO'f--
CM tO
VO



X
45 X
4J i-H
G'H
o cd
SQ

X
cd
Q
rH


fx CM
**!-!
OrH
rHIO
00
to to
VO VO
00
00
CM. f-
to o
00
OO


VO t-~
CM IO
VO



X
43 X
4JrH
G-H
C Cd
so

X
cd
Q
rH


                                                               G

                                                               O
                                                               O
                                                               U
                                                               cd
                                                               CD CD
                                                               G bo
                                                               O rH
                                                              •H Cd
                                                               O V)

                                                               OTJ

                                                               Oi CD



                                                                 CD
                                                              (U f-i
                                                              J-< CD
                                                              CD 4J
                                                                 oo
                                                              0)
                                                             ^3 O
                                                              CD O
                                                             4-» O

                                                             O 4->
                                                             &, CJ
                                                             CD Cd
                                                             to o
                                                             G O
                                                             O t
                                                            •H G
                                                             Si
                                                             O bo
                                                             O G
                                                               •H
                                                            ^ i . t
                                                             G bo

                                                            3'H
 cd
CX
 O
o
                •H
                2
           A-19
                                                               o
                                                               CJ

-------
                                              O'
                                                 rt
                                              (U CO
                                                      \O  *&
                                                      tO  00
                                                                tO  T-l
                                                                          CM
                                             rH  O
                                              rt rt
                                              rt
                                                      co  o
                                                                LO
                                                                               to
                                                      CM  to    CM   I-H   CM   o
                                                                                                                           CO
                                                                                                                           C  rt
                                                                                                                           S.-
                                                                                                                           IA
                                                                                                                               (A
                                                                                                                               o
                                                                                                                           6
   CO
  i w
  i A.
U«
                     (A
                     i-<
                     cd
                 rt   €
                CO   1)
                 CO  O
                ,0  -H
                 O  C
                CJ  O)
                              10
                              CO
                              O)
                  W
                  B
                              4J  CM
                 oo   -P
     be  rH  en  3
*O   r<  O  rH  0)
 COO       2
 ca   c:  v_/   «
     fcH       >s    •
,-1       +J   fn  >J
 0)   r«   O   OS  O
,x   a>   o>   3
 O   JS   rl   *3    »
.H   -P  -H   CO  CT
a   o  a  "-3  w
co
                  10   ..
                  O   (A
              (A   O   O
              si   -H   a
             O   X  3
                      O  +•>
                                   0)
             4J   a)
             ,H   •(->
                  -
                  o   o   o   fi
                  bo
M  -H   C

cd  o   B
f!  .P   .p
         CO
pa
•ri   U   O   U  >ri
 O  ^3  .C   «A   A
 rt   3   +J  -H   O
PL,  CO  O  O  2
                            rt
                            •P
                            CO
                                             rt
                                co
                                                      o   oo
                                                      O   iH
                                                    f~  CM
                                                    en  CM
                                                                  oo
                                         o  »-(    o  to    o  CM
                                                      to
                                                                 oo,
                                                        LfJ
                                                        to
                                          rH  O
                                                    CM  rH
                                                    O  C7)
                                                                 rH  rH
                                                    O  OO
                                                    in  o
                                                              oo  o
                                                               •    •
                                                              to  oo
                                                                           o  o
                                                           o  to
                                                           CM  o
                                                       to  to
                            to   tO
                            CM   CM
                                                                 o . o
to
CM
                                           •H ri
                                               o n
                                                        o   rt
                                                                      rt
                                                                           o  o
OO  tO
rH  tO
    IO
                                                                            o  rt
                                                                 SO   SO
                                                                                         0>
                                                                                         (A
                                                                                         0)
                                                                                         c
                                                                                         rt
                                                                                         00

                                                                                         rt
                                  rH fl)
                                               .
                                               CO rl
                                                  (it
                                                        O   O    CO   CO    CO  CO
                                           to  to
                                                     rH  rH
                                                                                                      (A
                                               as
                                               rl^
                                               CO
                                           CO  CO
                                                        A- 20
                                                      O   O
                                                                                                          «4H rl
                                                                                                           rl .0
                                                                                                                           0)  P-
                                                                                                           «A +*
                                                                                                           (A
                                                                                                           0) IA
                                                                                                           rH W
                                                                                                              O
                                                                                                           (1) rH
                                                                                                               +j vd
                                                                                                               o o>
                                                                                                               a> •*->
                                                                                                               c. o
                                                                                                               X «
                                                                                                            6  5?
                                                                                                            0)  CO
                                                                                                            IH  >-*
                                                                                                            jj  «
                                                                                                            in  >
                                                                                                            rt  cd
                                                                                                            Q)
                                                                                                            -
                                                                                                           •o  e
                                                                                                            o>  o>
                                                                                                               en ">
                                                                                                               o> en

-------
COPPER SALTS
      A-21

-------
                                                 (X,
                                              d) «—
                                              u
                                              C-d
                                              rt )H
                                              E rt
                                              ««  rt
                                               h P
                                               - ci
=i <
< a
to w

<; ty
r- U
<
I-H U,
O 2
E- co
2 es
u; o
ty
          CO
                      U
          (U

         o

          u
                      a
                              CO
                              en
 rt   rt  o
co       »-'

 J-i  'tH  +J
                              en
                               rt
                                   CO
                          
                                                                       to
                                                                          (M
                                                                                10
                                                                                                               O
                                                                                                                4J  rt

                                                                                                                tn  P
                                                                                                                (0
                                                                                                                o  ">
                                                                                                                rH  W
                                                                                                                    O
                                                                                                                                o
< n
CJ J
I-H >H
erf o
O <
H «-«
co ei
tj<
s >
     w
             O
              W
 >%  to
 P   0}
•H   P
                          60  -H
•H   U   
                                   P!  O
                                  •H  fi
                                  t-l  0)
                                   P.3
                                   6  cr
                                   rt  a)
                                  co  f-.
                                               (U,
                                               P I-l
                                               rt
                                                         (U
                                                         co
                                                         co
                                                                  V
                                                                  a)
                                                                           0)
                                                                                    v
                                                                            u
                                                                            a>
                                                                 CJ
                                                                                                                (/)  O
                                                                                                                o  o
                                                                                                                e  «
                                                                                                                             w  >
                                                                                                                             rt  «
                                                                                                                             o
                                                                                                                             rt  o
                                                                                                                             o
                                                                                                                             o  o
                                                                                                                            o>
                                                 A-22

-------















H
rH
Sc to
Q
>«OS
SUMMAR
STANDA
< w
HCJ
35
2i
u 2
"Z.O
rH U,
es o:
o t»
Hft,
i_f
EFFLUENT MONj
FACTORS AND
>*
•JE-
< rH
0 *4
1— 1 t— <
HISTOR:
VARIAB:

CM
to
f
W
HH '
J^











/"*\
P
r*
O
V
"° >»
•H rH
H H
O Q)
rH 4-1
41 K.
U cd
0 &
•H CO
Q
^3 o .
S *
cd v- •

W CM
P oo
rH en
Cd rH
to
rH W "fl>
0) rH 43
AJ cd E
U U 
25 S . 0
T) JS ^
C U 0
U 5C
« *d ° &
 a; ' 4J
rH 45 J3 r< P^ •.
rH O P .H 0) O*
U. O. O Q CO W

**
60
•• O
«—> woo
w .. 3 -H a
«) 'H 4J Cd flj *U
0 X 3 to H
O r< *O W)
o o o 'e *j
P 0 O. h 'fj S
•HP rd o B .
rH rt f-i 43 P p
•H O fl> O .H Cd
U 4i 4J y> pj 

•4
3 CM
J rH
J
d CM
4





w >
0 U
p
•H| •
•P 'X
to S
00
VO
*
O
rH
O
H J o
| H 2
Historical S
No. Min.
CM
O
O
en

*
iiH M p
rt o «
X
p
o
S

S'ampling
Frequency
4:
p
c
o
*v»
l-H


f. _j
a>^>
P rH

E W
r4<-^
cd
» >
cd
P
O
H

O



rH ^> pj _.

° ° « r4 2' °



o,
&?
TJ ^
Vi
° S B § S 3 |1
" • rt ~ V; ^ S?
w cd
<_i
0) (0
u
c c^
cd o
• s s
f-> cd
s i: s s 5 s ^°
• • . . . ^  +J
x SL
rH* rn" rn" rt" ' ±? X J1
- 1-1 "3 " rH rH rH ' W flJ
4j *^ •*-• »s5 "^ p
e £ £ £ P P cw
0 0 n S C ^ "W0
S-S^OOo EM
^ •* •* S S S o cd
3 
cd cd
43 J3 j- U ' jfi ' r. Ss.
« « fi II ^ ^
0 0 n SGC X^
^ 4 4 | ^ £ ss
rHrH'^7^^^ «°
rt ^ -"I rHTjE

0) 8)
V P +•>
0>

U. 0 O
«*P Of>
5 5 3 S 5 s Sc5
A-23

-------
                              O '
                              u

                              rt
                              6 rt
                               O C
                              «« rt

                               (H P
                               fl> CO
                              PU
           0}
II
CO CO
J
pa






























CO
rH
t-H
U.






• *
O

O
o
>s
P
•H
•H
U
rt
u.






•H
rl
0
rH
ff^
CJ
U

•H


TJ
e
rt
w
rt
CO
rH (/>
0) rH
r< rt
O O

z 'e
tt>
ft O
rt
u
rl >H
g/S
a. t>o
0 rl
U 0
c
«. I-H
rH H
rt o
•O *£•
O P
CJ O



..
f—t
to ••
O V)
•rl P
v-> (J
X 3
rl *C?
0 O
bO rl
o cu
P
rt rl
U 0

3 +•»
CO O































^
CM
O
O
\M/

•P
U
0>
t^
•H
O



..
in
3
P
rt
P
CO
bO
rl
rt
U
U)
•H
n








/••">
bO
c
•H
O
P
•H
g
O
S

.ance
•rl
i— I

0
CJ

rH
00
Gl
rH

O
3
•-5
0 "
P

en
f*»
01
rH
^^
rt
2


..
"ti
O
•rl
f^
0)
0«

toring
•H
ft
O
S





























X
PU
•k
•J
0

A
P-
U
•k
cr
w
"
bO
0
rH
O
g
^r*
U
0)
H
tment
rt
0>
rl
H






rH O
•H P
J* 0
rt rt
•rl (it
rl
rt

^^
•>»
2



•^





(A
u
•H
P
tn
•rl
P
rt
4J
CO
.
^*
rt
g
*3
CO

rH
0)
U
*H
»_.
H

4-*
(/)
*H
a:

51 1

*
X
_rt
to
in
«£i

.
bfl *"*
?j fsj
^.1


•
C
is

rH
0



o

to

.
^
rH «C
•rl rl P
rt o C
0 £
j£i

X
•H
rt
Q




bO>-
5 °
rt 
rl
rH


rl ~^
«/-<
P rH
S^
vS

'rt
rt
P
O
i_I<

z

•^
^
2









-V.

to
LO



CM
CM



vb
rH
0



so



>>
•H
rt
Q




rl
rt
rH
bO
(U
rl
rl
I-l



0)
0>
u!
£/

z

*^ ^5 ^s
^- ^^ ^»
^ ^ X









ss^
^J.
rH <
O Z rH
rH
t*^
t- rH
O O CM
o o tn



O << rH
0 Z rH



to rH IO



>N X >»
•H >H -H
rt rt *rt
000




rl rl rl
rt rt rt
rH rH rH
333
bo bo bo
a> o o
JH rl rl
i-l rl rl
W IH H








O rl 3

^^ -1
^
^









»>^

CM
rH


CO
vO
0



CM
O



to



X
•H
rt
Q




rl
rt
rH
3
bO
0)
r<
W








•H
•_«

srt, ^J
^ ^?
r^ S









^^
CO
LO O
0 t^


CM
Ul rH
O ^t



\o
* •
0 rH



to to



>> X
•H -H
rt rt
Q 0




rl rl
rt rt
rH rH
3 3
bo bO
u o
rl rl
rH rH







CO
« CO
                                     A-24

-------
                                      a,
                                   o
                                   o
                                   c-o
                                   cd -JH
                                   6 rt
                                   rlTJ

                                   ££
                                   rl 4-1
                                   • Di
 oi <
 

                    C
                    o
                   V
                   6

                   i-H
                   P.
                   a.

                   w
                              o
                              00
                   X
                   cd
                  S

                   o  s
      ft  cd  <—\  oo.  «
      P,  bo   CJ
     CJ   O  O   rH
          d  v—1       >
              4J
              O
                -H   3   o*
            t%  CJ  O  Q  .<   W
     (/)   ..
 ••   0)   W
 O  -H   4->
•O  V-/  O

^   b 5
CJ   rl  t)
     O   O
     be  M
     V  (X,
 X
 4->
•H  4J
rH   Cd
•H   O
 O  XI

(1.  CO
                         WOO
                         3  -H   rt
                         JJ  t.   («^

                         cd  a>   o
                         4->  (X,   0
                         CO      H
                             bo
                         «  C  4J
                         OO  'H   C
                    (D

                    4->
                    O
 Ri

 O
 W
•H
a
 o   6
 4->   4J
•H   Cd
 C     4->
                                               J-  J,  JH
                                               0  0  0
                                               P«  P«  CX
                                               0>  0>  0)
                                                          w   w  e/j  \o
                                                          0)   O  (D   .
                                                          3330
                                                         rH   rH  rH  rH
                                                          cd   cd  cd
                                                          >   >  t>
                                                                           0   0
                                                                           P.  CX,
                                                                           00
                                                   w
                                                   o

                                                  rH
                                                   Cd
                                                   in

                                                   3
                                                  rH
                                                   cd
                                                     O   rH  rH  rH
                                                       •   rH  rH  rH
                                                     o   <;  
                             X  X   XX  X
                             rH  rH  rH  rH   rH

                             

                                            &?J
                                            E a
                                            R) 
                                                                  cd
                                                                  C!
                                                                  0)
                                                                  V)
                                                                        O
                                                                        o
                                                                        H
                                                                                                §
                                                                                                CJ
                                                                                    §
                                                                                    W
                                                                                    4)
                                                                                    4->
                                                                                    rt
                                                                                    4J^
                                                                                    0)
                                                                                    O
                                                                                                0)
                                                                                               4J
                                                                                                rt
                                                                                              co

                                                                                                «k
                                                                                               cd
 o
•H
•rl

i
                                                                                                              •o ^
                                                                                                               Pi
                                                                                                               cd -p
                                                                                                              •o  »-
                                                                                                               c  «
                                                                                                               «8 *O
                                                                                                              4->  C
                                                                                                               in  «
                                                                                              u
                                                                                              c  o
                                                                                              C8  O
                                                                                              e  c
                                                                                              In  (9
                                                                                              O  E
                                                                                             Hi  r<
                                                                                              rl  0
                                                                                              O <4H
                                                                                              a  r.
                                                                                                 o
                                                                                              o  c.

                                                                                             4J  O
                                                                                                JZ
                                                                                              G *-•
                                                                                             rt
                                                                                            x:
                                                                                                                             O
                                                                                                                            O
                                                                                                                        ^J  4J

                                                                                                                        S-o
                                                                                                                        o  o
                                                                                                                        O  4->
                                                                                                                        c.  "
                                                                                                                        X  C>
                                                                                                             M O
                                                                                                             4->
                                                                                                             C W
                                                                                                             o o
                                                                                                             e u
                                                                                                             U A
                                                                                                             r. r.
                                                                                                             3 «>
                                                                                                             W >
                                                                                                             cd n
                                                                                                             o
                                                                                                            'H  C
                                                                                                            cs  O
                                                                                            a>  o

                                                                                           55
                                                                                           it . t{j
                                                                                            o  o
                                                                                                           O
                                            A-25

-------
                               IX
H
i— i
o: <
< o

ll
< w

S
z.o
ow
Hft
r-l

§§
H W
zctf
wo
0<
f-l rH
co ei





IO

to
 I
S
           V)





o>
rH
rH






..
0)

O
CJ

K.^
p
•rt
rH
•rt
U
rt
igments, Cadmittra, Cobalt, 'Copper and Nickel Sa.
ft

e
3
•rt
c£
•o
rt
CJ


..
^^
to
0)
•H

J>^
rl
0
bO
0)
•P
rt
u

CO
Organic § Inorganic Chemicals

U)
3
o
rl
0>
0
3
2:




• *
to

O
3

O
rl


ri
0)
43
-P
0


•P
U
0)
rl
•rt
-d
r*
rH


m.
W
3

rt
1 \
to

o
bo
rl
rt
43
O
to
•rt
Q
O
OO
O>
rH
0)
"5
O
P
OO
0>
i-H
M
rl
0)
"I
0)
U
(U
Q

«•
•d
o
•rt
rl
(D
ft

bO
rt
•rt
rl
O
P
•rt
{3
O
S
CJ
A
U
O
rH
tii
^
•P
3
0)
2
bo
0
rH
0
rt
43
L)
0)
E-

P
.' rt
0)
e
p
'- rt
o>
rl
H
fl> v-'
o
rt rl
e rt
0 C
IH rt
rl P
0> (/}


p
•rt rl
rH O
•H P
43 U
rt rt
•rt [I,
i-l
rt



Wfc^fc,
i^
0 CJ
•rt
P
(/)
•H •

Co Co
P SS
to

r7 -
rt bt
"J ^"
1 1
y
co
rH *
rt • C
"ri
O
•P
W •
•H O
ffi 2
*
>•
X rH
rH 43
rt o a
C5 Q
bO >•
rt 0
•rt rt
i-l 
oo
o



• ,
N
o


'a
=•


to
o
o

VO

rH
43
O
&
rl
O
<4H

X
i-H
•rt
rt
O

•»
:



en
00
o





to
o
oo





CM
oo
i-H



oo
o
rH


rH
O .


 rl
I-H cr






in o>
t- f-





vO 00
rH tO





OO OO
CM VO
O O




rH Oi
r*> i-
rH

VO m
in m

m
rH vO
rH 0
to o

vO 0
to

rH
f3 -rt
o rt
SS Q
ri
rl U
O ft
^|> «.
AX fl)
X4> P
rH 4) rl
•rt £ rt
rt 3
QI-H cr






o
vO





o»
in
rH





vO
to
O



^.
t-
tn


vO
to


rH
to
CM

VO

rH
43
O
rl
O

rH
•rt
rt
O






00
to





vO
vO
to





CM
*"»
o




t
rH
rH

vO
to


s
0

0
to

*
•rt
rt
. Q
rl
O
ft
rl
|X  rt
rH CT






^.
to





to
rH
CM





0>
vO
O




OO
to


VO
rH


to
VO
O

VO

rH
i
rl
O

to





o
to





to
*•-
o




t~-
LO


VO
rH


to
0

0
to

X
•rt
rt
0
ri
0>
rX fl)
0) rl
I-H cr






o o
t^. vO
0 rH





to **
CM ^1-
CM 10





VO CM
I*** ^^
0 rH



OO vO
vO CM
0 rH


rH rH
IO tO
0 0

00
IO CM
O 0
O 0

vo O
to

rH
43 X
Pi -rt
O rt
S3 0
rl 0)
o p<
<4H rl
r4 fl>
Xfl) +J
l-H 
Cj «
*^
'rt 0
^o ^
0) O
o o
da 
-------
                     w
                     rt
                     co
                    rX
                     U
                    •rt
                     rt
                    o
                    P<
                         (0
                                                   o
                                                   CT3
                                                   rt !-.
                                                   £ rt
                                                   t-> -a
                                                   o c
                                                  »tH rt
                                                   (H 4-1
                                                   O CO
                                                  •rt
                                                  iH  O
                                                  •rt  4->
                                                  ,O  u
                                                   rt  rt
                                                  •rt tL,
                                                   ^
                                                   rt
                                                to
                                                 •
                                                o
O)
  •
o
CJ.-J
to
 r
w
«
'CJ

4->
iN
:rt
»Q
O
CJ

e

•rt
'6
•d
rt
. u
•rH
o
tl"<
CJ

u
•rt
9
be
|_^
O
A









O
oo
o
i-^

V
                                               00
                                               a»
                   "rt  n
                   a
                   s
                        0
                       -rt
                                 ^

                                 o
                                 4J

                                 00

                                 O>
           rt
           00
       00  l-l
      •rt   O
      (1*
           W  4->   fn
       6300
             O>
                        O
                        ^
                        0
                  CJ
                   fn  ^
                  'rt   4->   rt   O
                  k-/   U   4J  &,
                  £3   CO      H

                           O
                                    u
                  O   O
                  b«   ^
                  d>  CU
                  4J
                               60
                          bo .H
                          ^   J-i
                          rt
                               O   6
                               4J   5
                 0   0>   0  «H   nj
                     fi   Vt   CO
                 3-   +J  .H   O   (-1
V)
c.
4-
-• «r
4J
a
CO
&
5
E
v\
iH
rt
o
•rt
^
O
4->
W
•rt
S
i^
E
>•
R
» °°
3 rt
i "
•* O
bfil °*
rj o

rt o G
^^ o
X
•rt
4->
O
"*• S
bO X
C 0
•rt C
rH O
0,3
S CT
rt o
CO ft
tl<
M
4-> r-l
tH 0
«S &
X*0
rrt 0
•rt &
rt


LO
to*
00
OS)
iH
OO
0
•
O

iH
O
O
o
V


o
(M



X
rrt
•rt
rt
O
t_.
quarter


                                                        CJ
                                                     A-27

-------
                                             ,  bO
             +J   0)
                  cd
O   V
P5
                           Ifl
                                     cd
                                     V
                  W  O  Q   S
                                            •H J-i 4J
                                             cd O £
                                                bO >>
                              P.3
                              6  a
                              cd  o
                              to  t-i
                                 P-.
                                                 
                                                                                                                        .cd
                                                                                                                         X
                                                                                                                         cd
                                                                                                                         cd
                                                                                                       in
                                                                                                       •r)
                                                                                                       V)
                                                                                                       cd

                                                                                                                                  (4-1
                                                                                                                               
-------
fe to
   Q
>- os
CO CO
    (3
 P  a>
 (3  E
 Q> P
 E  rt

 rt  ft
 <1) H
 rH
H rH
                                     rt  p.
                                     (3  O
                                    •HCJ
                                    tt,
                                    *->  60
 10 TJ


>-4 rH
tt.  U
                                    P
                                    3  «
                                    0) to
                                    15 E
                                       v
                                      CO
             u
             CT3
             rt  ft
             E  rt

             O  J3
            «4-i  rt
             ft +J
 X
 P
•H  rH
rH  O
•H  P
43  O
 rt  rt
•H u,
 ft
 rt
                                                                                                                  rt
                                                                                                                  0)
                                                                     o
                                                                     IO
                                                                                                  eo
                                                                                 o o   o o
                                                                                 V  V
                                                    I IO

                                                   00
                                                         cr>
                                                        rH CM
                                                                     to
                                                                                 00
                                                    o
                                                    01
                                                                                 rH rH  rH«ct
                                                                                                • rHfNj
            tt,  CJ













to
•p
rt
to

r-l
P.
O
to
•p
o
E
•H
OH
•a
9
w
JLJ
T^
«o •
>s
rH
rt
•P
rt
CJ

V) P
3 0
O fl)
rH rH
O -H
§tJ
A



o
to
O)
rH
w

rt E
rH +J
(X rt
P rH
(3H
g AJ
P fi
rt v
£ C
Pu
rH fl)
0)TJ
P C
rtrH
0) rH
P rt
(0 ft
rt a)
& >•
fito
•H

to
(.
•p
(0
•r*
P
rt
P
to

>•
(0
3
to

rH
. rt
u
•H
ft
O
P
in
•H
ffi
CJ
\O \O
to 10
O"    to rt

                                                                                o o   o o    o o
                                                                                        t-» 00
                                                                                rH rH   O rH
                                                                                                    to
                                  S o


• *
a>
^J
o
CJ

X
p
•H
rH
•H.
U
rt
tt,
..
V)
0)
•H
v«y
£
O
bfl
a>
P
rt
u
43

CO

• •
to
•p
u
3
TJ
O

^!

rH

jf*
P
0
to
3
P
rt
P
to
4)
60
ft
rt

u
to
•H
Q
*•
•a
o
•H
ft

OH
60

•H

O
P
•H

O

X
00
o
rH
O

J2
u
V
t-H
P
C
4>
E
4J
rt
a>

5-1
                                           rt
                                              o C
                                                 o
          bo
          C O
          •H fi
          rH 0)
          P,3

          .rt 4>
          CO rH
             tt,
                                             P rH
                  4= X
                   P rH
                   fi'H
                   o rt
                  so
                                                       (!)  tt E
                                                       0)4- §
                                                             0
                                •P
                                e
                                                                                o o  o o   o o
                                                                                V V
                                                                                       •O tO    CM tO
                                                                                rHiH  00    rHrH

                                                                                O O  O O    O O
                                                                                V V
                                                                                       rHrH
                                                                                rHrH  O O    rH rH

                                                                                op  o o    oo
                                                                                V  V  V V    V V
                                                                                 • oo  oo 10    rv o
                                                                                 I rH  rH t--    rH CM
                                5r^5^   5>T
                                 fi «H   C ,H    C .H
                                 o  rt   o rt   .o rt
                                SO  SO   SO
                                           ft
                                           O
                                                43
                                        *x        1 ji
                                        0)        c
                                        «        O
          E  bq
          «^E

          rt
         OH
TJ
C
rt
Q
0
CJ

oT
Hi
^
O
ex,
luoride,
tt,
«*
NJ
*
o
s
A
rt
CQ
^

rrj
O
>

o
V)
CO

TJ
•d
(3
rt

rH
rt
•P
O
P
Vi— '

rH


•t
to
n

to
rH
0
•P
•H
13
O
E

O
to
























rH

O
V

w
rt

TJ
V
p
ft
o
p.
(U
rH

10
0)
rH

E
to

U

'fi
0)
«0
rH
rt

rH


/— ^
c.
^•^ r -1
a.
rH
rt "3
ti J-
(•3 ^*
« "O
P C
to rt
'ormance
•mance si
VM rH
ft O
p. J-
o
0 C.
+J O
C 5
43 C
p rt
W 4J
V)
O «O
rH OT
O
Q) rH
43
O
O J3
P
O
-3 4J
0
o o
O 4J
c. o
x o
C) CX.
X
(0 0
+J
C «
ft) O
E «>
o rt
ft ft
3 
•H C
rt o
TJ E

fl> O
pC •£«
4J 4J
                  to
                  CO
                   CO
                   to
                   H
                                                             A-29
                                                                                                                              0  0
                                                                               W
                                                                              <
                                                 -rj
                                                 CJ
 O
CJ
                                                                                                                             04
                                                                                                                             *

-------
                               4-> O
                               CS r<
                               O H
                                  0)
                               rH P<
                                rt p<
                                a o
                               •H U
                               PH
                               v_^ CJO
                                w 'd
                               v_/S
                               •JrH
                                0) (A
                                z e
                                   V
                                             (X.
                                           o-
                                           O
                                           03  r<
                              M-l CJ
                               J-i +J
                               CD CO
                              •H  r<
                              rH  O
                              •H  P
                              .0  O
                               cd  cd
                              •H  U,
                               iH
                               rt
                                                  LO OO
                                                  O O
                                              U1 OO

                                              CM vO
                                                      ^t VO
                                                      O O
                                                      O O    rH

                                                      O O    Ol I-
                                                                       r-i in    oo en
                                                                       CM IO    CM VO
                                                                                   o o
                                         CM
                                                                        oo to
                                                                                CM
                                                                   rH tO    IO O
                                                                                    rH CM
               g!
                                                                                            o o   «*«•-•
                                                                                        in to
                                      \u \^i    c*>J r»J       *"'   ^»       ~ - .    -- - -
                                      to vo    CTICM    ooo   men    <* r-«    o \o    CM en
                                                                                                     CM tO
                                                                                                 CO
                                                                                                             CJ
                                                                                                                     rt
                                                                                                                     tn  rt
                                                                                                                        4->
                                                                                                                     0)  tA
to to
< W
2SO
o w
HA.
t-H
2IQ
O 2
        O
            +J  rH  U
                            CO
                            en
                                   CO
                    rH 4J
                    PJ CCl
                    .   0)
                             0)   4->  P!
                             J3   rt  0)
    £-4 3)
o     P.
+J   J-i 0)
     a) TJ
en   P c
t-»   CO t-H

rH   fl) rH
     •P CO
                                                 CO  O
,_|   tf   J-i   ,C  -P
.H   O   CD   O  -H
 O  ,O  rfS   «A  Pi
 tt$   3   -P   -H  O
ti,  CO   O   Q  S
                             •H (H -P
                                             bO ^
                                             rt  o
                                            •H  C
                                            rH  0)
                                             P.3
                                             S  v7
                                             rt  o>
                                            CO  r<
                                               tu
                                             4J rH
                                             fl) ---
                                             6 «
                                                    r- en
                                                             oo oo
                                                                     rH rH
                                                                             OO
                                                                 •p
                                                                                 r- o
                                                                                 rH CM
          -P i-H
          C-H
                                        II    IS    IS   .IS   SS    S3
                                                 O       C!
                                                 0)       O
                                                 &      S
                                                                  0)
                                                                                   0)
                                                                                                      00 VO
                                                                                                      i-H
                                                                                           a>
                                                                                           0)
                                                                                            to
                                                                                                               cj
                                                                                                                      o -P
                                                                                                          (A  O

                                                                                                          «•»
                                                                                                          o  o
                                                                                                          6  M
                                                                                                          Q)  CO
                                                                                                          r<  r<
                                                                                                          3  «,
                                                                                                          
                                                                                                          CO  CO
                                                                                                          O
                                                                                                               CO
                           +J  0)
                           •H  (A   .H C
                           £  CO   CO O
                           O  fl)   n3 6
                           e  t-i
                              CJ3
                                                                                                                (A
                                                                                                                   §
                                                                                                                          O
                                                                                                           o  o
                                             CO
                                                          A-30

-------
                                                w
                                                E
                                                w
                                                X
                                               CO
                                      o
                                      G -r)
                                      n
                                      E  co
                                      f-i TJ
                                      O  G
                                     "4H  rt
                                      (H ~l i1
                                      -H
2c r"i
0 2
E-i CO
W O
S H
•-^ CJ
PH (i,
^ ^
< I-H
O hj
-1 E
[T, ^J
OS
4-T ?J
(U
2; 4->
^ c
CT'S
W C
PH
* • 0)
J ^ tl t »
° G G *•
oo rtt-t,-^"-
O» rH 4J 4-
rH fr, rH C "
TO O *
- 4J fn E
rH f^ fl\ j |
o o> > rt •
*^ £s O Q) '
E 4J CO ^
o ro H
w O 'fn O rn n
•*-" s: t-t «
(/) jj X
k ' 4™^ r»i
^>' 0 (H C rv
rH 4J O 0) O CO
,n . , 4J £ U
W 4J 0 tfl 4J rH
+-1 oj oo i nj (jn ro
rH CJ O> 0) 0) fj O
CO W4j'Ht)H^'^
K 3 £ SJ ^Mr^ 2
R & '£ A •§ « g g 43
^ 0* i'S ** 'H-HrH X
fe U 2 n O S ^— '


•H rH
rH O r^ \Q f^j j^ Q^ ^. fm^ ^^ ^^
•H4J '*VC)'*l'>vOtOor^CsICT>
roro '*t^totorsirHP_|LOrs,^(.
(-.
>


t^ o to
iCJ 	 "t°.
1 0 rHO 00 00 rHO rH

) . rH
. «H «0 o ,*
X ° ^ <=> rH tO 00 0 VO CM 0
S ° ° --IOO OOOCNJO 0
V ^


•1 ^^, *° «-l
N SJ^^1^ ° MCM
^1 0 0 LOOPM rHO 10 rHO
OOOOOOOOIT500
V v

^ do to 2 oo
•H °OtOOrHCTiOt-rHO
OOOOOVOOrHOO
W
2; »^tOt«5totOtOtOtOtOtO

*
X
 Ci
 CO  OS
w
-H"
M

25
                    V)
                * *  *"J^

                10   o

                3  -H
                                        O
               V
Co
•H  4->   ro
^   O  4->
 X   3  CO
 fH  -U
                                   O   O
                                  OH   (U
 X   bfi
 4->   O
•H  4J
rH   ro
•H  O
 O  ,0
 ro  3
0
^
0,
V4
<0
fi
4->
0>
bo
f-i
ro
rfl
U
U)
•H
lonitorinj
reatment
              tt.   CO   O   Q   S  E-H
                                                  rt O  C
                                                 O     O
 °0 X
 G  O
•H  C
rH  
                                 4J r-t

                                 E b(
                                 TO^E

                                 TO
                                OH
                                                   i3  t?  b ** ^  ^  ^ »-• ^
                                                   ro  ca^  ed ctf c*  TO  ro ro es
                                                              M to bo to
                                                                    «>. « •
                                                                              o>
                                                                j   >   >
                                                                                                                                               TO  13