United States
Environmental Protection
Agency
Effluent Guidelines Division
WH-562
Washington DC 20460
EPA-440/1^3/019-b
March 1983
Water and Waste Management
Development P
Document for
Effluent Limitations
Guidelines and
Standards for the
Nonferrous Metals
Point Source Category
Volume I
X
General Development
Document
-------
DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
GENERAL DEVELOPMENT DOCUMENT
Frederick A. Eidsness, Jr.
Assistant Administrator for Water
Steven Schatzow
Director
Office of Water Regulations and Standards
Jeffery D. Denit, Director
Effluent Guidelines Division
Ernst P. Hall, P.E., Chief
Metals and Machinery Branch
James R. Berlow, P.E.
Technical Project Officer
March 1983
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Effluent Guidelines Division
Washington, D.C. 20460
-------
This development document for nonferrous metals manufacturing
(phase I) consists of three volumes, a general development docu-
ment and two volumes of subcategory-specific supplements. The
Agency intends to modify the General Development Document, as
necessary, and produce additional volumes of subcategory-specific
supplements in order to support limitations and standards for
additional nonferrous metals manufacturing (phase II) subcate-
gories as they are proposed and promulgated.
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TABLE OF CONTENTS
Section Page
I SUMMARY 1
EXISTING REGULATIONS 1
METHODOLOGY 1
TECHNOLOGY BASIS FOR LIMITATIONS AND STANDARDS. 7
II CONCLUSIONS 11
III INTRODUCTION 69
PURPOSE AND AUTHORITY 69
PRIOR EPA REGULATIONS 71
Primary Aluminum Subcategory 71
Secondary Aluminum Subcategory 71
Primary Copper Smelting 71
Primary Electrolytic Copper Refining 72
Secondary Copper 72
Primary Lead 72
Primary Zinc 72
Metallurgical Acid Plants 72
METHODOLOGY 73
Approach of Study 73
Data Collection and Methods of Evaluation . . 74
GENERAL PROFILE OF THE NONFERROUS METALS
MANUFACTURING CATEGORY 77
IV INDUSTRY SUBCATEGORIZATION 83
SUBCATEGORIZATION BASIS 83
Metal Products, Co-Products, and By-Products. 85
Raw Materials 85
Manufacturing Processes 85
Product Form 86
Plant Location 86
Plant Age 86
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TABLE OF CONTENTS (Continued)
Section Page
Plant Size 87
Air Pollution Control . . 87
Meteorological Conditions 87
Solid Waste Generation and Disposal 88
Number of Employees 88
Total Energy Requirements 88
Unique Plant Characteristics. 88
PRODUCTION NORMALIZING PARAMETERS 89
V WATER USE AND WASTEWATER CHARACTERISTICS. ... 91
DATA SOURCES 91
Historical Data ..... 91
Data Collection Portfolios 91
Sampling and Analysis Program 92
WATER USE AND WASTEWATER CHARACTERISTICS. . . 100
VI SECTION OF POLLUTANT PARAMETERS 103
RATIONALE FOR SELECTION OF POLLUTANT
PARAMETERS 104
DESCRIPTION OF POLLUTANT PARAMETERS 105
SUMMARY OF POLLUTANT SELECTION 176
Pollutants Selected for Further Consideration
by Subcategory 177
Toxic Pollutants Not Detected 181
Toxic Pollutants Detected Below the
Analytical Quantification Limit 198
Toxic Pollutants Detected in Amounts too
Small to be Effectively Reduced by
Technologies Considered in Preparing this
Guideline 203
Toxic Pollutants Detected in the Effluent
From Only a Small Number of Sources 205
Toxic Pollutants Detected but Present Solely
as a Result of Their Presence in the Intake
Waters 208
ii
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TABLE OF CONTENTS (Continued)
Section Page
VII CONTROL AND TREATMENT TECHNOLOGY 215
END-OF-PIPE TREATMENT TECHNOLOGIES. ...... 215
MAJOR TECHNOLOGIES. 216
Activated Alumina Adsorption 216
Ammonia Steam Stripping 217
Carbon Adsorption 219
Chemical Precipitation 221
Advantages and Limitations 226
Cyanide Precipitation 227
Granular Bed Filtration 229
Pressure Filtration 232
Settling 234
Skimming 236
MAJOR TECHNOLOLOGY EFFECTIVENESS 238
LStS Performance - Combined Metals Data Base . 238
One Day Effluent Values 241
Average Effluent Values 244
Additional Pollutants 247
LS&F Performance 249
Analysis of Treatment System Effectiveness. . 250
Ammonia Steam Stripping Performance 253
Activated Carbon Performance 254
MINOR TECHNOLOGIES 254
Flotation 254
Centrifugation 257
Coalescing 259
Cyanide Oxidation by Chlorine 260
Cyanide Oxidation by Ozone 261
Cyanide Oxidation by Ozone with UV Radiation. 262
Cyanide Oxidation by Hydrogen Peroxide. . . . 263
Evaporation 264
Gravity Sludge Thickening 267
Ion Exchange 268
Insoluble Starch Xanthate 271
Peat Adsorption 271
Membrane Filtration 273
Reverse Osmosis 274
Sludge Bed Drying 277
Vacuum Filtration 279
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TABLE OF CONTENTS (Continued)
Section
VIII
IX
IN-PLANT TECHNOLOGY 281
Process Water Recycle 281
Process Water Reuse 284
Process Water Reduction 285
Air Cooling of Cast Metal Products 286
Dry Slag Processing and Granulation 286
Dry Air Pollution Control Devices 287
Good Housekeeping 288
COST, ENERGY, AND NONWATER QUALITY ASPECTS. . . 345
BASIS FOR COST ESTIMATION 345
Sources of Cost Data 345
Determination of Costs 345
Investment (Capital) Cost Basis 346
Annual Cost Basis 347
TECHNOLOGY BASIS FOR COST DEVELOPMENT 351
Recycle 351
Steam Stripping • J->^
Cyanide Precipitation 352
pH Adjustment 355
Chemical Precipitation, Sedimentation,
Gravity Thickening, Vacuum Filtration .... 355
Multimedia Filtration 357
Activated Carbon Adsorption 358
Activated Alumina Adsorption 359
Reverse Osmosis, Evaporation 360
NEW SOURCES 360
COST METHODOLOGY FOR SPECIFIC PLANTS 361
NONWATER QUALITY ASPECTS 361
Air Pollution, Radiation, and Noise 362
Solid Waste Disposal 362
Energy Requirements 363
EFFLUENT QUALITY ATTAINABLE THROUGH APPLICATION
OF THE BEST PRACTICABLE CONTROL CURRENTLY
AVAILABLE 377
IV
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TABLE OF CONTENTS (Continued)
Section Page
TECHNICAL APPROACH TO BPT 377
MODIFICATIONS TO EXISTING BPT EFFLUENT
LIMITATIONS 379
Primary Lead 380
Metallurgical Acid Plants 380
MODIFIED APPROACH TO STORMWATER 381
BPT OPTION SELECTION 383
Primary Lead 384
Primary Tungsten 384
Primary Columbium-Tantalum 384
Secondary Silver 385
Secondary Lead 385
EXAMPLES OF BUILDING BLOCK APPROACH IN
DEVELOPING PERMITS 386
X EFFLUENT QUALITY ATTAINABLE THROUGH APPLICATION
OF THE BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE 395
TECHNICAL APPROACH TO BAT 396
Industry Cost and Pollutant Reduction Benefits
of the Various Treatment Options 396
MODIFICATION OF EXISTING BAT EFFLUENT
LIMITATIONS 399
Primary Aluminum 399
Secondary Aluminum 400
Primary Electrolytic Copper Refining 400
Primary Lead 401.
Primary Zinc 401
Metallurgical Acid Plants 401
Modified Approach to Stormwater 401
BAT OPTION SELECTION 402
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TABLE OF CONTENTS (Continued)
Section
Primary Aluminum 403
Secondary Aluminum 404
Primary Electrolytic Copper Refining 405
Primary Lead 4°5
Primary Zinc 40°
Metallurgical Acid Plants 406
Primary Tungsten 4^/
Primary Columbium-Tantalum 407
Secondary Silver £08
Secondary Lead 4UV
REGULATED POLLUTANT PARAMETERS 409
EXAMPLES OF BUILDING BLOCK APPROACH IN
DEVELOPING PERMITS 41°
XI NEW SOURCE PERFORMANCE STANDARDS 419
TECHNICAL APPROACH TO NSPS. 419
Modifications to Existing NSPS 421
NSPS OPTION SELECTION 421
Primary Aluminum 422
Secondary Aluminum 422
Primary Copper Smelting 422
Primary Electrolytic Copper Refining 42J
Secondary Copper • 423
Primary Lead 42 J
Primary Zinc 424
Metallurgical Acid Plants 424
Primary Tungsten 424
Primary Columbium-Tantalum 425
Secondary Silver 425
Secondary Lead 425
XII PRETREATMENT STANDARDS 427
REGULATORY APPROACH 427
MODIFICATIONS TO EXISTING PRETREATMENT
STANDARDS 429
vi
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TABLE OF CONTENTS (Continued)
Section Page
Primary Aluminum • 430
Secondary Aluminum. . 430
Secondary Copper
OPTION SELECTION.
431
Primary Aluminum 432
Secondary Aluminum 432
Primary Copper Smelting 433
Primary Electrolytic Copper Refining 433
Secondary Copper 433
Primary Lead 433
Primary Zinc 434
Metallurgical Acid Plants 434
Primary Tungsten 435
Primary Columbium-Tantalum 435
Secondary Silver 436
Secondary Lead 437
XIII BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY. 441
XIV ACKNOWLEDGEMENTS 445
XV REFERENCES 447
XVI GLOSSARY 465
VI1
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LIST OF TABLES
Table Page
1-1 CURRENTLY PROMULGATED LIMITATIONS AND
STANDARDS - NONFERROUS METALS MANUFACTURING . . 10
II-l PROPOSED BPT EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 12
II-2 PROPOSED BPT EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 13
II-3 PROPOSED BPT EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 15
II-4 PROPOSED BPT EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY . . ' . 17
II-5 PROPOSED BPT EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 20
II-6 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 21
II-7 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 23
II-8 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 24
II-9 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 26
11-10 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 27
Vlll
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LIST OF TABLES (Continued)
Table Page
11-11 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 28
11-12 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 29
11-13 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 31
11-14 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 33
11-15 PROPOSED BAT/PSES EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 39
11-16 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 41
11-17 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 43
11-18 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 44
11-19 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 45
11-20 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 46
11-21 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 47
IX
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LIST OF TABLES (Continued)
Table ^Se-
ll-22 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY ^8
11-23 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 50
11-24 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 52
11-25 PROPOSED NSPS/PSNS EFFLUENT LIMITATIONS
COMPARISON NONFERROUS METALS MANUFACTURING POINT
SOURCE CATEGORY 55
11-26 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 56
H-27 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 58
11-28 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 59
11-29 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 60
11-30 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 61
11-31 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 62
11-32 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY 63
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LIST OF TABLES (Continued)
Table
11-33 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY
Page
11-34 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE
CATEGORY
11-35 BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
III-l
III-2
III-3
V-l
VI-1
VII-1
VII-2
VII-3
VII-4
VII-5
VII-6
VII-7
VII-8
INVJINT CJ\J\X» U O nij .iz^J-iu iurm»->i i*~ ••- «•.» — -.—
CATEGORY
CURRENTLY PROMULGATED LIMITATIONS AND STANDARDS
NONFERROUS METALS MANUFACTURING
NONFERROUS METALS CONSIDERED FOR REGULATION
UNDER PHASE II
BREAKDOWN OF DCP RESPONDENTS BY TYPE OF METAL
PRODUCED
DISTRIBUTION OF SAMPLED PLANTS IN THE NONFERROUS
METALS MANUFACTURING CATEGORY BY SUBCATEGORY. .
LIST OF 129 TOXIC POLLUTANTS
pH CONTROL EFFECT ON METALS REMOVAL
EFFECTIVENESS OF SODIUM HYDROXIDE FOR METALS
REMOVAL
EFFECTIVENESS OF LIME AND SODIUM HYDROXIDE FOR
METALS REMOVAL
THEORETICAL SOLUBILITIES OF HYDROXIDES AND
SULFIDES OF SELECTED METALS IN PURE WATER . . .
SAMPLING DATA FROM SULFIDE PRECIPITATION-
SEDIMENTATION SYSTEMS
SULFIDE PRECIPITATION-SEDIMENTATION
PERFORMANCE
FERRITE CO -PRECIPITATION PERFORMANCE
CONCENTRATION OF TOTAL CYANIDE (mg/1)
67
80
81
O J.
82
\j t-
101
209
289
290
£— S \S
001
£- 7 i
292
293
Z. ;/ J
294
<£. J ^T
295
296
XI
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LIST OF TABLES (Continued)
Table **&
VII-9 MULTIMEDIA FILTER PERFORMANCE 297
VII-10 PERFORMANCE OF SELECTED SETTLING SYSTEMS. ... 298
VII-11 SKIMMING PERFORMANCE 299
VII-12 COMBINED METALS DATA EFFLUENT VALUES (mg/1) . . 300
VII-13 L&S PERFORMANCE ADDITIONAL POLLUTANTS 301
VII-14 COMBINED METALS DATA SET - UNTREATED
WASTEWATER 302
VII-15 MAXIMUM POLLUTANT LEVEL IN UNTREATED
WASTEWATER ADDITIONAL POLLUTANTS (mg/1) .... 303
VII-16 PRECIPITATION-SETTLING-FILTRATION (LS&F)
PERFORMANCE PLANT A 304
VII-17 PRECIPITATION-SETTLING-FILTRATION (LSfcF)
PERFORMANCE PLANT B . . . . 305
VII-18 PRECIPITATION-SETTLING-FILTRATION (LSfeF)
PERFORMANCE PLANT C 306
VII-19 SUMMARY OF TREATMENT EFFECTIVENESS (mg/1) ... 307
VII-20 ION EXCHANGE PERFORMANCE (All Values mg/1). . . 308
VII-21 PEAT ADSORPTION PERFORMANCE 309
VII-22 MEMBRANE FILTRATION SYSTEM EFFLUENT 310
VIII-1 COSTS OF CONTRACT HAULING2 365
VIII-2 EXISTING SLUDGE TREATMENT METHODS* 366
VIII-3 MAXIMUM ENERGY REQUIREMENTS (Kwh/yr) and
ESTIMATED PERCENT OF PLANT TOTAL FOR ENTIRE
TREATMENT SYSTEM 368
IX-1 STORMWATER/PRECIPITATION ALLOWANCES 390
XI1
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LIST OF TABLES (Continued)
Table Paee
IX-2 MODIFICATION TO BPT PRECIPITATION EXEMPTION . . 392
IX-3 SUMMARY OF CURRENT TREATMENT PRACTICES 393
IX-4 REGULATED POLLUTANT PARAMETERS 394
X-l BAT OPTIONS CONSIDERED FOR EACH OF THE
NONFERROUS METALS MANUFACTURING SUBCATEGORIES . 412
X-2 MODIFICATIONS TO BAT PRECIPITATION EXEMPTION. . 413
X-3 REGULATED POLLUTANT PARAMETERS 414
X-4 TOXIC POLLUTANTS DETECTED BUT ONLY IN TRACE
AMOUNTS AND ARE NEITHER CAUSING NOR LIKELY TO
CAUSE TOXIC EFFECTS 416
X-5 TOXIC POLLUTANTS EFFECTIVELY CONTROLLED BY
TECHNOLOGIES UPON WHICH ARE BASED OTHER EFFLUENT
LIMITATIONS AND GUIDELINES 417
XII-1 REGULATED POLLUTANT PARAMETERS 439
XIII-1 SUMMARY OF BCT TEST IN THE NONFERROUS METALS
MANUFACTURING CATEGORY 443
Xlll
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LIST OF FIGURES
Figure
VII-1
VII-2
VII-3
VII-4
VII-5
VII-6
VII-7
VII-8
VII-9
VII-10
VII-11
VII-12
V1I-13
VII-14
VII-15
VII-16
VII-17
FLOW DIAGRAM OF ACTIVATED CARBON ADSORPTION
WITH REGENERATION
ACTIVATED CARBON ADSORPTION COLUMN
COMPARATIVE SOLUBILITIES OF METAL HYDROXIDES
AND SULFIDE AS A FUNCTION OF pH
EFFLUENT ZINC CONCENTRATION VS. MINIMUM
EFFLUENT pH
LEAD SOLUBILITY IN THREE ALKALIES
FILTER CONFIGURATIONS
GRANULAR BED FILTRATION
PRESSURE FILTRATION
REPRESENTATIVE TYPES OF SEDIMENTATION
GRAVITY OIL/WATER SEPARATOR
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS CADMIUM
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS CHROMIUM
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS COPPER
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS LEAD
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS NICKEL AND ALUMINUM
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS ZINC
HYDROXIDE PRECIPITATION SEDIMENTATION
F.FVKf.TTVKNF.SS IRON
rage
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
XIV
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LIST OF FIGURES (Continued)
Figurf
VII-18
VII-19
VII-20
VII-21
VII-22
VII-23
VII-24
VII-25
VII-26
VII-27
VII-28
VII-29
VII-30
VII-31
VII-32
VII-33
VIII-1
VIII-2
VIII-3
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS MANGANESE
HYDROXIDE PRECIPITATION SEDIMENTATION
EFFECTIVENESS TSS
DISSOLVED AIR FLOTATION
CENTRIFUGATION
TREATMENT OF CYANIDE WASTE BY ALKALINE
CHLORINATION
TYPICAL OZONE PLANT FOR WASTE TREATMENT ....
UV/OZONATION
TYPES OF EVAPORATION EQUIPMENT
GRAVITY THICKENING
ION EXCHANGE WITH REGENERATION
SIMPLIFIED REVERSE OSMOSIS SCHEMATIC
REVERSE OSMOSIS MEMBRANE CONFIGURATIONS ....
SLUDGE DRYING BED
VACUUM FILTRATION
FLOW DIAGRAM FOR RECYCLING WITH A COOLING
TOWER
SCHEMATIC DIAGRAM OF SPINNING NOZZLE ALUMINUM
REFINING PROCESS
GEOGRAPHICALLY DISTRIBUTED CAPITAL COST
FACTORS
GEOGRAPHICALLY DISTRIBUTED WAGE RATE FACTORS. .
SLUDGE HAULING COSTS 10 MILE ROUND TRIP
NONHAZARDOUS WASTES
Page
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
369
370
371
XV
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LIST OF FIGURES (Continued)
Figure
VIII-4 COST OF SEALING GROUND AT SLAG DUMP 372
VIII-5 COST OF LINED AND UNLINED STORAGE PONDS .... 373
VIII-6 COST OF TRANSPORTING WASTE MATERIALS 374
VIII-7 COST OF OIL SEPARATION 375
xvi
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SECTION I
SUMMARY
The United States Environmental Protection Agency has proposed
effluent limitations and standards for the nonferrous metals man-
ufacturing category pursuant to Sections 301, 304, 306, 307, and
501 of the Clean Water Act. The proposed regulation contains
effluent limitations for best practicable control technology
currently available (BPT), best conventional pollutant control
technology (BCT), and best available technology economically
achievable (BAT), as well as pretreatment standards for new and
existing sources (PSNS and PSES), and new source performance
standards (NSPS).
This Development Document highlights the technical aspects of
EPA's study of the nonferrous metals manufacturing category.
This volume addresses general issues pertaining to the category,
while the remaining volumes contain specific subcategory reports.
The Agency's economic analysis of the regulation is set forth^in
a separate document entitled Economic Analysis of Effluent Guide-
lines - Nonferrous Metals Manufacturing Point Source^Category.
That document is available from the Office of Analysis and
Evaluation, Economic Analysis Staff, WH-586, USEPA, Washington,
D.C., 20460.
EXISTING REGULATIONS
Since 1974, implementation of the technology-based effluent limi-
tations and standards has been guided by a series of settlement
agreements into which EPA entered with several environmental
groups the latest of which occurred in 1979. NRDC v. Costle. 12
ERC 1833 (D.D.C. 1979), aff'd and remd'd, EDF v. Costle, 14 ERG
2161 (1980). Under the settlement agreements, EPA was required
to develop BAT limitations and pretreatment and new source per-
formance standards for 65 classes of pollutants discharged from
specific industrial point source categories. The list of 65
classes was substantially expanded to a list of 129 specific
toxic pollutants. Table 1-1 presents a summary of the currently
promulgated effluent limitations and standards for the nonferrous
metals manufacturing point source category.
METHODOLOGY
To develop the effluent limitations and standards presented in
this document, the Agency characterized the category by subdi-
viding it, collecting raw and treated wastewater samples, and
examining water usage and discharge rates, and production pro-
cesses. To gather data about the category, EPA developed a
-------
questionnaire (data collection portfolio - dcp) to collect infor-
mation regarding plant size, age and production, the production
processes used, the quantity of process wastewater used and
discharged, wastewater treatment in-place, and disposal prac-
tices. The dcp's were sent to 319 firms (416 plants) known or
believed to perform nonferrous smelting and refining. These were
reviewed, and it was determined that there were 314 plants among
the 416 plants that were applicable to the nonferrous metals
manufacturing point source category.
As a next step, EPA conducted a sampling and analytical program
to characterize the raw (untreated) and treated process waste-
water. This program was carried out in two stages. Screen
sampling was performed at 10 facilities, each representing a
major metal manufacturing process. Samples were collected from
wastewater sources associated with the major manufacturing pro-
cess, as well as any associated processes, including cleaning,
etching, solution heat treatment, and annealing, among others.
The presence or absence of the concentration of 128 of ^ the 129
toxic pollutants, conventional and selected nonconventional
pollutants in each of the samples, was determined. The toxic
pollutant TCDD, number 129, was not analyzed for because an
analytical standard for TCDD was judged to be too hazardous to be
made generally available. A discussion of the sampling and
analysis, methods, and procedures is presented in Section V.
EPA then reviewed the rate of production and wastewater genera-
tion reported in the dcp's for each manufacturing operation, as
well as the wastewater characteristics determined durinf^sam-
pling, as the principal basis for subcategorizing the industry.
The data demonstrated that the industry should be subcategorized
by major metal manufacturing process. A discussion of the sub-
categorization scheme is presented in Section IV. For this rule-
making, the nonferrous metals manufacturing point source category
has been expanded to 12 subcategories:
1. Primary Aluminum Smelting
2. Secondary Aluminum
3. Primary Copper Smelting
4. Primary Electrolytic Copper Refining
5. Secondary Copper
6. Primary Lead
7. Primary Zinc
8. Metallurgical Acid Plants
9. Primary Tungsten
10. Primary Columbium-Tantalum
11. Secondary Silver
12. Secondary Lead
-------
The nonferrous metals manufacturing point source category is
divided into subcategories based on differences in wastewater
quantity and quality related to differences in industry manufac-
turing processes. This has resulted in the designation of 12
subcategories. Each subcategory is further subdivided into major
sources of wastewater for specific limitation within the regula-
tion. Other sources of wastewater not directly related to the
production of a metal, such as maintenance and cleanup water or
sanitary water, were not considered for specific limitation by
the regulation. The Agency believes wastewater sources of this
type are site-specific, and they are best handled on a case-by-
case basis. Each wastewater source identified for this rulemak-
ing was production-normalized. That is, each waste stream was
characterized by the volume of wastewater discharged per unit o±
production. The sources of process wastewater identified in the
nonferrous metals manufacturing category are outlined below by
subcategory:
Primary Aluminum Smelting
Anode Paste Plant Wet Air Pollution Control
Anode Bake Plant Wet Air Pollution Control
Anode Contact Cooling
Cathode Manufacturing
Cathode Reprocessing
Potline Wet Air Pollution Control
Potroom Wet Air Pollution Control
Direct Chill Casting
Continuous Rod Casting
Stationary Casting
Degassing Wet Air Pollution Control
Secondary Aluminum Smelting
Scrap Drying Wet Air Pollution Control
Scrap Screening and Milling
Dross Washing
Demagging Wet Air Pollution Control
Direct Chill Casting
Stationary Casting
Shot Casting
Primary Copper Smelting
Slag Granulation
Casting Contact Cooling
Casting Wet Air Pollution Control
-------
Primary Electrolg±ic_Cgpper Refining
Anode and Cathode Rinsing
Spent Electrolyte
Casting Contact Cooling
Casting Wet Air Pollution Control
By-Product Recovery
Secondary Cog£gr
Slag Milling and Classification
Smelting Wet Air Pollution Control
Casting Contact Cooling
Spent Electrolyte
Slag Granulation
Priiaary Lead
Blast Furnace Slag Granulation
Blast Furnace Wet Air Pollution Control
Zinc Fuming Wet Air Pollution Control
Dross Reverberatory Furnace Granulation
Hard Lead Refining Slag Granulation
Hard Lead Refining Wet Air Pollution Control
Zinc Reduction Furnace Wet Air Pollution Control
Leaching
Leaching Wet Air Pollution Control
Cathode and Anode Washing
Casting Wet Air Pollution Control
Casting Contact Cooling
Cadmium Plant
Me tal lur gical
Acid Plant Slowdown
Tungstic Acid Rinse
Acid Leach Wet Air Pollution Control
Alkali Leach Wash
Ion-Exchange
Calcium Tungstate Precipitate Wash
Crystallization and Drying of Ammonium Paratungstate
Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control
Reduction to Tungsten Wet Air Pollution Control
Reduction to Tungsten Water of Formation
-------
Primary Columbium-Tantalum
Concentrate Digestion Wet Air Pollution Control
Solvent Extraction
Solvent Extraction Wet Air Pollution Control
Precipitation and Filtration of Metal Salts
Metal Salt Drying Wet Air Pollution Control
Reduction of Salt to Metal
Reduction of Salt to Metal Wet Air Pollution Control
Consolidation and Casting Contact Cooling
Secondary Silver
Leaching
Leaching Wet Air Pollution Control
Nonphotographic Precipitation and Filtration
Nonphotographic Precipitation and Filtration Wet Air
Pollution Control
Film Stripping
Film Stripping Wet Air Pollution Control_
Film Stripping Precipitation and Filtration
Film Stripping Precipitation and Filtration Wet Air
Pollution Control
Photographic Silver Solution Precipitation
Photographic Silver Solution Precipitation Wet Air Pollution
Control
Electrolytic Refining
Furnace Wet Air Pollution Control
Casting Contact Cooling
Casting Wet Air Pollution Control
Secondary Lead
Battery Cracking
Blast and Reverberatory Wet Air Pollution Control
Kettle Wet Air Pollution Control
Casting Contact Cooling
As mentioned earlier, there are 314 plants identified in the ^
nonferrous metals manufacturing point source category discharging
an estimated 125.6 billion liters per year of process wastewater.
Untreated, this process wastewater contains approximately
1 058,000 kilograms of toxic organic pollutants, 2,100,000
kilograms of toxic metal pollutants, and 60,890,000 kilograms of
conventional and nonconventional pollutants.
The pollutants generated within the nonferrous metals manufactur-
ing subcategories are diverse in nature due to varying raw mate-
rials and production processes. Thus, the Agency examined
various end-of-pipe and pretreatment technologies to treat the
-------
pollutants present in the identified process wastewaters. The
pollutants selected for consideration for each subcategory are
presented in Section VI. The treatment technologies considered
for each subcategory are shown below:
Treatment Technologies Considered
Subcategory _A B C D F F
Primary Aluminum X X X X X X
Secondary Aluminum XXX X
Primary Copper Electrolytic XXX X
Refining
Secondary Copper X X X**
Primary Zinc X X X X X
Primary Lead XXX X
Secondary Lead X X X X X
Primary Tungsten XXX XX
Primary Columbium-Tantalum X X X X X X
Secondary Silver XXX XX
Metallurgical Acid Plants XXX X
Note: Option A - Lime precipitation and sedimentation and
cyanide precipitation, ammonia steam stripping, or
oil skimming where appropriate.
Option B - Option A preceded by flow reduction by
recycling variable quantities of process wastewater.
Option C - Option B plus filtration.
Option D - Option C plus activated alumina adsorption.
Option E - Option C plus activated carbon adsorption.
Option F - Option C plus reverse osmosis.
*0ption C plus activated carbon preliminary treatment of waste-
water from anode bake plant wet air pollution control, anode
paste plant wet air pollution control, potline wet air pollution
control, potroom wet air pollution control, and cathode
reprocessing.
**0ption G which includes lime precipitation and sedimentation in
conjunction with cooling towers and holding tanks to achieve
complete recycle of process wastewater.
-------
Engineering costs were prepared for each of the treatment options
considered for each subcategory. These costs were then used by
the Agency to estimate the impact of implementing the various
options on the industry. For each subcategory for each control
and treatment option, the number of potential closures, number of
employees affected, and impact on price were estimated. These
results are reported in the Economic Impact Assessement.
The Agency then reviewed each of the treatment options for each
subcategory to determine the estimated mass of pollutant removed
by the application of each treatment technology. The amount of
removal after the application of the treatment technology is
referred to as the benefit. The methodology used to calculate
the pollutant reduction benefits is presented in Section X.
TECHNOLOGY BASIS FOR LIMITATIONS AND STANDARDS
After examining the various treatment technologies, the Agency
has identified BPT to represent the average of the best existing
technology. Metals removal based on lime precipitation and
sedimentation technology is the basis for the BPT limitations for
10 subcategories. The other two subcategories, primary copper
smelting and secondary copper, are already subject to zero dis-
charge of all process wastewater pollutants. Steam stripping is
selected as the basis for ammonia limitations in four subcatego-
ries. To meet the newly-proposed BPT effluent limitations based
on this technology, it is estimated that the nonferrous metals
manufacturing point source category will incur a capital cost of
$3.34 million (1978 dollars) and an annual cost of $2.31 million
(1978 dollars).
One goal of BAT is to achieve increased levels of toxic pollutant
removal. For BAT, the Agency has built upon the BPT technology
basis by adding in-process control technologies which include
recycle of process water from air pollution control and metal
contact cooling waste streams, as well as other flow reductions,
where achievable. Filtration is added as an effluent polishing
step to the end-of-pipe treatment scheme. In addition, carbon
adsorption and cyanide precipitation are proposed for the primary
aluminum BAT treatment scheme. These two technologies are trans-
ferred to the primary aluminum subcategory because existing
treatment within the subcategory does not effectively remove
toxic organic pollutants and cyanide.
To meet the BAT effluent limitations based on this technology,
the nonferrous metals manufacturing point source category is
estimated to incur a capital cost of $44.91 million (1978
dollars) and an annual cost of $25.36 million (1978 dollars).
-------
Due to current adverse structural economic changes that are not
fully reflected in the Agency's current economic analysis, alter-
native BAT effluent limitations also are proposed for the primary
electrolytic copper refining, secondary silver, and secondary
lead subcategories. The alternative technology scheme upon which
the BAT limitations are based is lime precipitation and sedimen-
tation with in-process control technologies which include recycle
of process water from air pollution control and metal contact
cooling waste streams. To meet the BAT effluent limitations
based on the alternative technology, the estimated capital cost
is $42.48 million (1978 dollars) and the annual cost is $23.93
million (1978 dollars).
BDT, which is the technical basis of NSPS, is equivalent to BAT
with the exception of primary aluminum and primary lead. In
selecting BDT, EPA recognizes that new plants have the opportun-
ity to implement the best and most efficient manufacturing pro-
cesses and treatment technology. As such, new source performance
standards for the primary aluminum subcategory are based on dry
alumina air pollution scrubbing systems or 100 percent recycle.
Implementation of this technology eliminates the discharge of
toxic organics due to air emission scrubbing associated with
anode paste plants, anode bake plants, potlines and potrooms, as
well as from cathode reprocessing operations. New source per-
formance standards for the primary lead subcategory require zero
discharge of all process wastewaters. Zero discharge is achiev-
able through dry slag conditioning instead of using high pressure
water jets to granulate smelter slag. Table II-3 presents a
summary, for each subcategory and each waste stream within that
subcategory, of the discharge flow allowances, the option
selected, and the proposed NSPS.
For PSES, the Agency selected the same technology as BAT, which
is BPT end-of-pipe treatment in conjunction with several
in-process flow reduction control techniques followed by
filtration as an effluent polishing step. For PSNS, the Agency
selected end-of-pipe treatment and in-process flow reduction
control techniques equivalent to NSPS. To meet the pretreatment
standards for existing sources, the nonferrous metals manufactur-
ing point source category is estimated to incur a capital cost of
$9.78 million (1978 dollars) and an annual cost of $6.73 million
(1978 dollars).
Due to current adverse structural economic changes that are not
fully reflected in the Agency's current economic analysis, alter-
native PSES also are proposed for the secondary silver and
secondary lead subcategories. The alternative technology scheme
upon which the PSES are based is lime precipitation and sedimen-
tation with in-process control technologies which include
recycle of process water from air pollution control and metal
8
-------
contact cooling waste streams. To meet the PSES based on the
alternate technology, the estimated capital cost is $8.12 million
(1978 dollars) and the annual cost is $5.24 million (1978
dollars). Tables II-2 and II-3 present a summary, for each
subcategory and for each waste stream within that subcategory, of
the discharge flow allowances, the option selected, and the
proposed PSES and PSNS.
-------
Table 1-1
CURRENTLY PROMULGATED LIMITATIONS AND STANDARDS - NONFERROtTS METALS MANUFACTURING
Subcategory
*T--r " —.4.
Primary Aluminum
Secondary Aluminum
Primary Copper
BPT
LS
LS, PH
ND2
BAT
LS.FR
ND
ND2.3
NSPS
LS.FR1
LS.FR
.-
PSES
--
OS.pH.AS
--
PSNS
LS.FR!
LS.FR
--
Smelting
Primary Electro- LS LS,FR2.3,4
lytlc Copper
Refining
Secondary Copper ND2.' ND2»3 _- LS
Primary Lead ND2»3 ND2.3
Primary Zinc LS LS.FR
Metallurgical Acid LS
Plants4
Primary Tungsten
Primary Columblum-
Tantalum
Secondary Sliver
Secondary Lead
1Includes additional flow reduction beyond BAT.
2Allows a discharge without limitation during a 10-year, 24-hour rainfall (or
25-year, 24-hour rainfalls at BAT) for stormwater falling on the wontewnter cooling
or settling pond.
3Allows a discharge, subject to concentration limitations, for a flow equal to the
net monthly precipitation on the wastewater settling pond.
'•Copper acid plants only; zinc and lead acid plants are currently covered In the
primary zinc and primary lead subcategorles.
LS
FR
ND
OS
pH
AS
lime precipitation and sedimentation.
flow reduction.
no discharge.
oil skimming.
pH adjustment.
ammonia air stripping.
-------
SECTION II
CONCLUSIONS
EPA has divided the nonferrous metals manufacturing point^source
category into 12 subcategories for the purpose of developing
effluent limitations and standards. This section presents the
proposed effluent limitations and standards developed for 10 of
the 12 subcategories according to the following format:
Table Number
BAT and NSPS and
BPT PSES PSNS BCT
Effluent Effluent Effluent Effluent
Subcategory Limitations Limitations Limitations Limitations
Primary
Aluminum - 6 lo ^o
Secondary
Aluminum - 7 17 */
Primary Elec-
trolytic Copper
Refining - 8 18 28
Primary Lead 1 9 19 29
Primary Zinc - 10 20 30
Metallurgical
Acid Plants - H 21 Ji
2 12 22 32
Primary 3 13 23 33
Columbium-
Tantalum
Secondary 0/
Silver 4 14 24 34
Secondary „,. 0_
Lead 5 15 25 35
The other two subcategories, primary copper smelting and second-
ary copper, are proposed as zero discharge for all process waste-
water pollutants.
11
-------
Tfcble II-l
PROPOSED BPT H?FLtENT LIMITATIONS COME&RISON
NDNFERRDU5 MSTAIS MANUFACTURING IDIOT SOIRCE CA3EQCKY
Regulatory
Flow
Subcateflory/Waste Stream (1/kkg)
RIMARYLEAD
Blast Furnace Slag Granulation 3,730
Monthly Average
Blast Furnace Wet Air Pollution Control 0
Monthly Average
MaxLnun
Zinc Fuming Furnace Wet Air Pollution Control 426
Monthly Average
MaxLnun
Dross Reverberatory Furnace Wet Air Pollution 0
Control
Monthly Average
MaxLnun
Dross Beverberatory Furnace Granulation 3,134
Monthly Average
MaxLnun
Ifard lead Refining Wat Air Pollution Control 19,836
Monthly Average
Maximum
ftird lead Refining Slag °
Monthly Average
BPT EFFLUENT
Pb
484.9
559.5
0
55.38
63.9
o
\J
o
407.42
470.10
2,578.68
2,975.40
0
0
LJMETATIQNS
Zn
2,068.8
4,960.9
0
o
238.56
566.58
0
0
1,755.04
4,168.22
11,108.16
26,381.88
0
0
(mg/kkg)
TSS
74,600.0
152,930.0
0
8,520.0
17,466.0
0
0
62,680.0
128,494.0
3%, 720.0
813,276.0
0
0
Maximum
-------
Tkble II-2
PROPOSED BPT EFFUENT IJMITATIQJG COMPARISON
NMFERROUS METAIS MANUFACTURING JOINT SOLRCE GAIEOCRY
Subcategory /Waste Stream
PRIMARY TUNGSTEN
Tungsten Add Rinse
Monthly Average
MEDCUIU&
Acid Leach Wet Air Pollution Control
Monthly Average
Alkali leach Wash
Monthly Average
Ion-Exchange Raff Inate
Monthly Average
Calcium Tungstate Precipitate Wash
Monthly Average
Crystallization and Drying of Annonium I^iratungstate
Monthly Average
Regulatory
Flow
(1/kkg)
BPT EFFLUENT UMTTATIONS (ng/kkg)
Pb Se
Zn Ammonia
TSS
47,600
37,700
46,700
51,200
37,200
6,188.0 26,180.0 26,656.0 2,789,360.0 952,000.0
7,140.0 58,548.0 63,308.0 6,330,800.0 1,951,600.0
4,901.0 20,735.0 21,112.0 2,209,220.0 754,000.0
5,655.0 46,371.0 50,141.0 5,014,100.0 1,545,700.0
6,071.0 25,685.0 26,152.0 2,736,620.0 934,000.0
7,055.0 57,441.0 62,111.0 6,211,100.0 1,914,700.0
6,656.0 28,160.0 28,672.0 3,000,320.0 1,024,000.0
7,680.0 62,976.0 68,096.0 6,809,600.0 2,099,200.0
4,836.0 20,460.0 20,832.0 2,179,920.0 744,000.0
5,580.0 45,756.0 49,476.0 4,947,600.0 1,525,200.0
0
0
0
0
0
0
0
0
0
0
-------
"Bible II-2 (Continued)
PROPOSED BPT EPFUENT LMTIATIDI6 COMPARISON
NDNFERWHJ5 METALS MANUFACTURING POINT SOURCE CA1EOCRY
Subcategory/Waste Stream
PRIMARY TUNGSTEN (Cont.)
Aflnonlun Paratungatate Conversion to Oxides Wet Air
Pollution Oontrol
Monthly Average
Reduction to Tungsten Vfet Mr Pollution Control
Monthly Average
Maxinun
Reduction to TXmgaten Water of Formation
Monthly Average
Maxinun -
Regulatory
Flow
(lAkg)
BPT EFFUiNT UMTEAIIONS (og/kkg)
Pb
Se
Zn
Anmonia
TSS
29,900
73,200
19,400
2,717.0 11,495.0 11,704.0 1,224,740.0 418,000.0
3,135.0 25,707.0 27,797.0 2,779,700.0 856,900,0
9,516.0 40,260.0 40,992.0 4,289,520.0 1,464,000.0
10,980.0 90,036.0 97,356.0 9,735,600.0 3,002,200.0
2,522.0 10,670.0 10,864.0 1,136,840.0 388,000.0
2,910.0 23,862.0 25,802.0 2,580,200.0 795,400.0
-------
•Bible II-3
PROPOSED BPT EFFLUENT LIMITATIONS COMPARISON
N3NFERROUS METALS MANIFACTIKING POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY COUMBUM-TANIAHM
Concentrate Digestion Wet Air Pollu-
tion Control
Monthly Average
Maid mm
Solvent Extraction Raff irate
Monthly Average
Maximum
Solvent Extraction Wet Air Pollution
Control
Monthly Average
Maximm
Regulatory
Flow
d/kkg)
10,915
26,916
4,301
BPT EFFLIENT LIMITATIONS (ng/kkg)
Pb
1,418.95
1,637.25
3,499.08
4,037.40
559.18
645.21
Zn
6,112.40
14,516.95
15,072.%
35,798.28
2,408.78
5,720.86
Fl
288,156.0
649,442.50
710,582.40
1,601,502.0
113,556.%
255,933.30
Armenia
639,619.0
1,451,695.0
1,577,277.60
3,579,828.0
252,062.04
572,086.20
TSS
218,300.0
447,515.0
538,320.0
1,103,556.0
86,028.0
176,357.40
Precipitation and Filtration of
Metal Salts
Monthly Average
Metal Salt Drying Wet Air Pollution
Control
Monthly Average
Maximm
247,223
83,643
32,138.99 138,444.88 6,526,687.20 14,487,267.80 4,944,460.0
37,083.45 328,806.59 14,709,768.50 32,880,659.0 10,136,143.0
10,873.59 46,840.08 2,208,175.20 4,901,479.80 1,672,860.0
12,546.45 111,245.19 4,976,758.50 11,124,519.0 3,429,363.0
-------
Table II-3 (Continued)
PROPOSED BET EFFLIENT LIMITATIONS COMPARISON
NDNFERRDUS METALS MANUFACTURING POINT SOURCE CMEOORY
PRIMARY OOLLMBtlM-TMIAUM (Cont.)
Reduction of Salt to Metal
Monthly Average
Maximum
Reduction of Salt to Metal
Wet Air PaUutlon Control
Monthly Average
Consolidation and Casting Contact
Cooling
Monthly Average
Maxtnun
Regulatory
Flow
(1/kkg)
352,663
21,521
0
BPT EFFLUENT UMTTATIONS (mg/kkg)
Pb
45,846.19
52,899.45
2,797.73
3,228.15
0
0
Zn
197,491.28
469,041.79
12,051.76
28,622.93
0
0
Fl
9,310,303.20
20,983,448.50
568,154.40
1,280,499.50
0
0
Annonlfl
20,666,051.80
46,904,179.0
1,261,130.60
2,862,293.0
0
0
TSS
7,053,260.0
14,459,183.0
430,420.0
882,361.0
0
0
-------
Table II-4
IROPOSED BPT EFFUENT LJMTlATIQfB COmRISON
NDNFERROUS METALS MANUFACTURING JOINT SOURCE CATEQDRY
Subcategory/Waste Stream
SECONDARY SILVER
Film Stripping
Monthly Average
Maxinum
Film Stripping fcfet Air R>llution Control
Monthly Average
Maximum
Precipitation and Filtration of Film Strip-
ping Solutions
Monthly Average
Mayinmi
Precipitation and Filtration of Film Strip-
ping Solutions Wet Air Rjllxition Control
Monthly Average
Maxinun
Precipitation and Filtration of Hiotographic
Solutions
Monthly Average
Maxinun
Precipitation and Filtration of Rwtographic
Solutions Wet Air Pbllutlon Control
Monthly Average
Maidiram
Regulatory
Flow
(1/kkg)
1,619,000
15,580
1,851,000
15,580
854,000
390,300
BPT EFFLUENT LIMITATIONS (mg/kkg)
Cu Zn Anmonia TSS
1,619,000.00 906,640.0 94,873,400.0
3,076,100.0 2,153,270.0 215,327,000.0
15,580.0
29,602.0
1,851,000.0
3,516,900.0
15,580.0
29,602.0
854,000.0
1,622,600.0
390,300.0
741,570.0
8,724.80
20,721.40
1,036,560.0
2,461,830.0
8,742.80
20,721.40
478,240.0
1,135,820.0
218,568.0
519,099.0
912,988.0
2,072,140.0
108,468,600.0
246,183,000.0
912,988.0
2,072,140.0
50,044,400.0
113,582,000.0
22,871,580.0
51,909,900.0
32,380,000.0
66,379,000.0
311,600.0
638,780.0
37,020,000.0
75,891,000.0
311,600.0
638,780.0
17,080,000.0
35,014,000.0
7,806,000.0
16,002,300.0
-------
Table II-4 (Continued)
PROPOSED BPT EFFLUENT UMTIM1DNS COMPARISON
NDNFERRDUS METALS MANIFACTWING POINT SOURCE CATEGORY
oo
Subcategory /Waste stream
SHXNOftRY SILVER (Cont.)
Electrolytic Refining
Monthly Average
Mtnrlnim
Furnace Wet Air PoUutlon Control
Monthly Average
Casting Contact Cooling
Monthly Average
Maxlnun
Casting Wet Air Pollution Control
Monthly Average
Maximum
Leaching
Monthly Average
Maximum
Leaching Wet Air Pollution Control
Monthly Average
Regulatory
Flow
(1/kkg)
24,316
21,519
12,035
4,741
2,780
142,389
BPT
Cu
24,316.0
46,200.40
21,519.0
40,886.10
12,035.0
22,866.50
4,741.0
9,007.90
2,780.0
5,282.0
142,389.0
270,539.10
EFFLUENT LJMTE
Zn
13,616.%
32,340.28
12,050.64
28,620.27
6,739.60
16,006.55
2,654.%
6,305.53
1,556.8
3,697.4
79,737.84
189,377.37
iTIONS (mg/kkg)
Ammonia
1,424,917.60
3,234,028.0
1,261,013.40
2,862,027.0
705,251.0
1,600,655.0
277,822.60
630,553.0
162,908.0
369,740.0
8,343,995.40
18,937,737.0
TSS
486,320.0
9%, 956.0
430,380.0
882,279.0
240,700.0
493,435.0
94,820.0
194,381.0
55,600.0
113,980.0
2,847,780.0
5,837,949.0
-------
Table II-4 (Continued)
PROPOSED BPT EFFUENT LIMITATIONS COMPARISON
NDNFERRDUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Uaste Stream
SECONDARY SILVER (Cont.)
Precipitation and Filtration of Non-
photographic Solutions
Monthly Average
MaxLnun
Precipitation and Filtration of Ifon-
photographic Solutions Wfet Air Pollution
Control
Monthly Average
MaxLnun
Regulatory
Flow
d/kkg)
98,577
79,931
BPT
Cu
98,577.0
187,296.30
79,931.0
151,868.90
EFFLUENT UMTTATIONS (ngAkg)
Zn
55,203.12
131,107.41
44,761.36
106,308.23
Armenia
5,776,612.20
13,110,741.0
4,683,956.60
10,630,823.0
TSS
1,971,540.0
4,041,657.0
1,598,620.0
3,277,171.0
-------
Tkblfi II-5
PROPOSED BFT EFFUENT LMIIATIOtC
NDNFERROU5 MBIMS MANUFACTURING KHNT SOURCE CATEGORY
Subcategory/Waste stream
SECONDARY IEAD
Battery Cracking
Monthly Average
Blast and Reverberatory Rirnace Wet Air
Ibllution Control
Monthly Average
fettle Wet Air Ibllution Control
Monthly Average
Maud nun
Casting Contact Cooling
Monthly Average
Regulatory
Flow
(1/Wcg)
%0
3,380
0
221.2
HET EFFIiEHT LmTEATIDNS (nK/Ws^)
Sb
1,193.80
2,697.80
4,292.60
9,700.60
0
0
280.92
634.84
As
808.40
1,964.60
2,906.80
7,064.20
0
0
190.23
462.31
Pb
122.20
141.0
439.40
507.0
0
0
28.76
33.18
Zn
526.40
1,250.20
1,892.80
4,495.40
0
0
123.87
294.20
Armenia
0.0
0.0
0.0
0.0
0
0
0.0
0.0
7SS
18,800.0
38,540.0
67,600.0
138,580.0
0
0
4,424.0
9,069.20
-------
Tkble
PROPOSED BAT/PSES EFFLUENT TJMTIATIONS COMPARISON
NDtFERROUB METALS MANUFACTURING JOINT SOURCE CA3EQCRY
N>
SubcategoryAbate Stream
PRIMARY AULMINIM
Anode Paste Plant Wet Air Pollution Control
Monthly Average
Maxinuu
Anode Bake Plant Wet Air Pollution Control
Monthly Average
Cathode Manufacturing
Monthly Average
Cathode Reprocessing
Monthly Average
MEDCLHUO
Anode Contact Cooling
Monthly Average
Mavlmm
Potllne Wet Air Pollution Control
Monthly Average
Maxinun
Potroom Wet Air Pollution Control
Monthly Average
Manrimm
Regulatory Benzo-
Flow (a)
(1/kkg) pyrene
BAI/PSES EFFLUENT LIMITATIONS (ng/kkg)
103
49.4
77.4
952
621
838
1,305
Sb
CN
88.58 8.24
1.03 198.79 20.60
42.48 3.95
0.49 95.34 9.88
66.56 6.19
149.38 15.48
818.72 76.16
9.52 1,837.36 190.40
534.15 49.69
1,198.72 124.22
720.68 67.04
8.38 1,617.34 167.60
1,122.30 104.40
13.05 2,518.65 261.0
Ni
Al
Fl
38.11
56.65
18.28
27.17
28.64
42.57
127.72
312.09
61.26
149.68
1,812.80
4,089.10
869.44
1,961.18
95.98 1,362.24
234.52 3,072.78
352.24 1,180.48 16,755.20
523.60 2,884.56 37,794.40
229.81 770.16 10,931.36
341.61 1,881.93 24,657.67
310.06 1,039.12 14,748.80
460.90 2,539.14 33,268.60
482.85 1,618.20 22,968.0
717.75 3,954.15 51,808.5
-------
Table II-6 (Continued)
PROPOSED BAT/FSES EFFLUENT LMTIMIQNS OCMBMOSON
IOWEHHOUS PETALS MANUFACTURING POINT SOURCE CAIEOCRY
ISJ
Subcategory/Waste Stream
PRIMARY ALLMINLM (Cont . )
Degassing Wet Air Pollution Control
Monthly Average
Direct (hill Casting Contact Cooling
Monthly Average
Continuous Bod Casting Contact Cooling
Monthly Average
Stationary Casting Contact Cooling
Monthly Average
Regulatory Benzo-
Flow (a)
(1/ldtg) pyrene
BAT/FSES EFFLUENT UMTTATICfB (ng/kkg)
1,999
104
0
Sb
0
0
1,719.14
3,858.07
89.69
201.29
0
0
CN
0
0
159.92
399.80
8.34
20.86
0
0
Ni
0
0
739.63
1,099.45
38.59
57.37
0
0
Al
0
0
2,478.76
6,056.97
129.33
316.03
0
0
Fl
0
0
35,182.40
79,360.30
1,835.68
4,140.71
0
0
-------
Bible II-7
PROPOSED MT/PSES EFFtUENT UMTEATIONS COMPARISON
N3NFERROJS METALS MANJFACHJRING POINT SOURCE CATEGORY
Regulatory
BAT/PSES EFFUJENT LJMnflnONS (ng/kkg)
Subcategory/Waste Stream
300MKRY AUJMDUM
Scrap Drying Wet Air Pollution Control
Monthly Average
Maxlfflmi
Scrap Screening and Milling
Monthly Average
Maximum
Dross Washing
Monthly Average
Maximum
DemaggLng Wet Air Pollution Control
Monthly Average
Maximum
Direct Chill Casting Contact Cooling
Monthly Average
Maxinun
Stationary Casting Contact Cooling
Monthly Average
Maxinun
Shot Casting Contact Cooling
Monthly Average
Maximun
Flow
(1/kkg) Pb
0
0
0
0
0
0
10,868
978.12
1,086.80
800
72.0
80.0
1,999
179.91
199.90
0
0
0
0
0
0
Zn
0
0
0
0
4,564.56
11,085.36
336.0
816.0
839.58
2,038.98
0
0
0
0
Al
0
0
0
0
13,476.32
32,930.04
992.0
2,424.0
2,478.76
6,056.97
0
0
0
0
Anmonia
0
0
0
0
636,864.80
1,445,444.0
46,880.0
106,400.0
117,141.40
265.867.0
0
0
0
0
-------
•Bible II-8
PROPOSED BAT/PSES EFFTUENT LIMITATIONS COMPARISON
NDNFERROJS METAIS MANJFACIJRDG POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY ELECTROLYTIC COPPER REFINDG
Anode and Cathode Rinsing
Alternative A
Monthly Average
Alternative B
Monthly Average
Mmriinun
Spent Electrolyte
Alternative A
Monthly Average
Alternative B
Monthly Average
Maximum
Casting Contact Cooling
Alternative A
Monthly Average
Maxinun
Regulatory BAT/PSES EFFTUENT UMTEftTIONS (ng/Mtg)
Flow
(1/kkg) Cu Pb Ni
498
0
0
0
0
0
0
0
0
498.0
946.20
0
0
0
0
0
0
0
0
64.74
74.70
0
0
0
0
0
0
0
0
498.0
702.18
-------
Tkble II-8 (Continued)
PROPOSED BAT/PSES EFFLUENT LMTEATICTE OCMPARISON
N3NFERROUS METALS MANJFACI1JRIIG POINT SOURCE CATEGORY
Regulatory BAT/PSES EFFLUENT LJMTTATION5 (mg/kkg)
flow
Subcategpry/Waste Stream (1/kkg) Cu Pb Ki
PRBWRY ELECIROLYnC COPPER REFINDC (Cont.)
Alternative B
Itonthly Average 303.78 44.82 184.26
637.44 49.80 273.90
Casting Wet Air Pollution Control 0
KJ Alternative A
01 Monthly Average 0 0 0
000
Alternative B
Monthly Average 0 00
Maximum 000
By-Product Recovery 0
Alternative A
Monthly Average 0 0 0
Maximum 000
Alternative B
Monthly Average 000
Maxlmm 000
-------
Table II-9
PROPOSED BAT/PSES EFFLUENT LIMITATIONS OCMBMUSON
NOTFEKROU6 METALS MANLFACTURING R)INT SOURCE CATEGORY
BAT/PSES EFFUENT UMHATIQN5
Regulatory _ (mg/kkg) _
Flow
Subcategory/Waste Stream (1/kkg) Pb Zn
PRIMARY LEAD
Blast Furnace Slag Granulation 3,730
Monthly Average 335.7 1,566.6
Mffldrnm 373.0 3,804.6
Blast Furnace Wet Air Pollution Control 0
Monthly Average 0 0
Maxlnun 0 0
Zinc Fuming Furnace Wet Air Pollution Control 0
Monthly Average 0 0
Maxlnun 0 0
Etoss Beverberatory Wet Air Ibllution Control 0
Monthly Average 0 0
Maxima 0 0
Ekross Reverberatory Furnace Granulation 0
Monthly Average 0 0
Maxlnun 0 0
Hard lead Refining Wet Air Pollution Control 0
Monthly Average 0 0
Maxlnun 0 0
Hard Lead Refining Slag Granulation 0
Monthly Average 0 0
Maxlnun ° °
-------
Tfetble H-10
PROPOSED BAT/PSES EFFLUENT UMHATIDNS COMPARISON
METALS MANIFACHRING POINT SOIFCE CA3EGCRY
to
•vj
Skibcategory/Haste Stream
PRIMARY ZINC
Ztm Reduction Furnace Wet Air Pollution Control
Monthly Average
Maxinun
Leaching
Monthly Average
Maxinun
leaching Wet Air Pollution Control
Monthly Average
Maximxa
Cathode and Anode Washing
Mwithly Averags
Maxisum
Casting Wet Air dilution Control
Monthly Average
Maxinun
Casting Contact Cooling
Monthly Averaga
Maxinun
Cadmium Plant
ttonthly Average
Maxinun
Regulatory
Flow
(1/kkg)
1,668
1,310
0
19,850
257
181
6,171
BAT/PSES
Cd
133.46
333.66
104,80
262.0
0
0
1,588.0
3,970.0
20.56
51.40
14.48
36.20
493.68
1,234.20
EFFLUENT UMHATIONS (tng/kkg)
Cu
1,017.66
2,135,42
799.10
1,676.80
0
0
12,108.50
25,408.0
156.77
328.%
110.41
231.68
3,764.31
7,898.88
Pb
150.15
166.83
117.90
131.0
0
0
1,786.50
1,985.0
23.13
25.70
16.29
18.10
555.39
617.10
Zn
700.69
1,701.67
550.20
1,336.20
0
0
8,337.0
20,247.0
107.94
262.14
76.02
184.62
2,591.82
6,294.42
-------
Table 11-11
PROPOSED MT/PSES EFFTHENT LMTATICtB OCMPARISON
NDNFERHDUS MSEAIS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Haate Stream
METALLURGICAL ACID ILAOTS
Add Plant Blowdown
Monthly Average
Maximum
Regulatory
Flow
2,554
BAT/PSES EFFLUENT UMTEATICfB (mg/kfcg)
1,455.78
3,550.06
Cd
204.32
510.80
Cu
1,557.94
3,269.12
Pb
229.86
255.40
Zn
1,072.68
2,605.08
00
-------
•Bible 11-12
PROPOSED BAT/PSES EFFLUENT LMTEffiDONS COMPARISON
KMFERROUS METALS MANIFACTLRING POINT SOURCE CATEORY
N>
vO
Subcategory/Waste Stream
PRIMARY TUKSTEN
Tungsten Acid Rinse
Monthly Average
Acid teach Vfet Air Pollution Control
Monthly Average
MaxLoun
Alkali Leach Wash
Monthly Average
MEDQHUDQ
Ion-Exchange Raf f inate
Monthly Average
Maxinum
Calcium Tungstate Precipitate
Monthly Average
Maxinun
Crystallization and frying of Ammonium
Paratupgstate
Monthly Average
Maxinun
Regulatory
Flow
(1/kkg)
47,600
3,770
46,700
51,200
37,299
0
BAT/PSES EFFLUENT UMTTATIONS (fflg/kkg)
Pb
4,284.0
4,760.0
339.30
377.0
4,203.0
4,670.0
4,608.0
5,120.0
3,348.0
3,720.0
0
0
Se
17,612.0
39,032.0
1,394.90
3,091.40
17,279.0
38,294.0
41,984.0
18,944.0
13,764.0
30,504.0
0
0
Zn
19,992.0
48,552.0
1,583.40
3,845.40
19,614.0
47,634.0
21,504.0
52,224.0
15,624.0
37,944.0
0
0
Ammonia
2,789,360.0
6,330,800.0
220,922.0
501,410.0
2,736,620.0
6,211,100.0
3,000,320.0
6,809,600.0
2,179,920.0
4,947,600.0
0
0
-------
Table 11-12 (Continued)
PROPOSED BAI/PSES EFFLLENT UMITATIC^ OMPARISON
N3NFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY TUNGSTEN (Cont.)
Ammonium Paratungstate Conversion to
Oxides Wet Air Pollution Control
Monthly Average
Maximum
Reduction to Tungsten Wet Air Pollu-
tion Control
Monthly Average
Mgyjflflim
Reduction to Tungsten Water of forma-
tion
Monthly Average
MSQQJDLDl
Regulatory
Flow
(1/kkg)
20,900
7,320
19,400
BAT/PSES
Pb
2,717.0
3,135.0
658.80
732.0
1,746.0
1,940.0
EFFLUENT
Se
7,733.0
17,138.0
482.85
1,070.10
7,178.0
15,908.0
UMTTATIGNS (q
Zn
11,704.0
27,797.0
3,074.40
7,466.40
8,148.0
19,788.0
g/Wcg)
Aomonia
1,224,740.0
2,779,700.0
428,952.0
973,560.0
1,136,840.0
2,580,200.0
-------
Thble 11-13
PROPOSED BAT/PSES EFFUEMT LIMITATIONS OMBMOSON
IONFERROU6 METALS MANIFACTUUNG POINT SOURCE CATEGORY
Subcategory /Waste Stream
PRIMARY O>UranJM-TANIAUM
Concentrate Digestion Wet Air Pollu-
tion Control
Monthly Average
Mayimnn
Solvent Extraction Raf finate
Monthly Average
Solvent Extraction Wet Air Jbllution
Control
Monthly Average
Mstxioun
Precipitation and Filtration of
Metal Salts
Monthly Average
Maximum
Metal Salt Drying Wet Air Pollution
Control
Monthly Average
Maximum
Regulatory
Flow
(lAkg)
5,156
26,916
430
247,223
16,479
BAT/PSES EFFUENT
Pb
464.07
515.63
2,422.44
2,691.60
38.71
43.01
22,250.07
24,722.30
1,483.11
1,647.90
Zn
2,165.65
5,259.43
11,304.72
27,454.32
180.64
438.70
103,833.66
252,167.46
6,921.18
16,808.58
UMTIATIONS (mg/kkg)
Fl
90,750.88
204,705.11
473,721.60
1,068,565.20
7,569.76
17,074.97
4,351,124.80
9,814,753.10
290,030.40
654,216.30
Ammonia
302,159.18
685,787.90
1,577,277.60
3,579,828.0
25,203.86
57,203.30
14,487,267.80
32,880,659.0
965,669.40
2,191,707.0
-------
bble 11-13 (Continued)
PROPOSED BAT/PSES EFFUENT UMHAT1DNS COMPARISON
NDWERRDUS bfTIAlS MANUFACTURING POINT SOLRCE CAIEOCRY
Subcategory/Waste Stream
PRIMARY OOUMBILM-TANIMJM (Cont.)
Reduction of Suit to Metal
Monthly Average
MffluHUDl
Reduction of Salt to Metal Wet Air
Pollution Control
Monthly Average
MffldnuDi
Consolidation and Casting
Monthly Average
frtoylmwn
Regulatory
Flew
(lAkg)
332,663
21,521
0
BAT/PSES EFFLUENT LMTTAnONS (n«/kkg)
Pb
31,739.67
35,266.30
1,936.89
2,152.10
0
0
Zn
148,118.46
359,716.26
9,038.82
21,951.42
0
0
Fl
6,206,868.80
14,000,721.10
378,769.60
854,383.70
0
0
Ammonia
20,666,051.80
46,904,179.0
1,261, 13X60
2,862,293.0
0
0
-------
Table 11-14
PROPOSED BAI/PSES EFFLUENT LIMITATIONS COMPARISON
NDNFERHQUS METALS MANIFACTIRING POINT SOIKQB CATEGORY
OJ
Regulatory
Flow
Subcategory Abate Stream
SILVER
Film Stripping
Alternative A
Monthly Average
Maxbnun
Alternative B
Monthly Average
Maxinun
Film Stripping Wet Air Ibllution Cbatrol
Alternative A
Monthly Average
M-udnun
Alternative B
Monthly Average
Maxinun
Precipitation and Filtration of Film
Stripping Solutions
Alternative A
Monthly Average
1,619,000
15,580
1,851,000
BAT/PSES EFFLUENT UMTIATIONS (mg/kkg)
Cu Zn Annraiia
1,619,000.0
3,076,100.0
987,590.0
2,072,320.0
15,580.0
29,602.0
9,503.80
19,%2.40
906,640.0
2,153,270.0
679,980.0
1,651,380.0
8,724.8
20,721.0
6,543.60
15,891.60
94,873,400.0
215,327,000.0
94,873,400.0
215,327,000.0
912,988.0
2,072,140.0
912,988.0
2,072,140.0
1,851,000.0 1,036,560.0 108,468,600.0
3,516,900.0 2,461,830.0 246,183,000.0
-------
Table 11-14 (Continued)
PROPOSED BAT/PSES EFFUENT UMTEM10IB COMPARISON
NONFERROUS METALS MANIFACTURING POINT SOURCE CATEGORY
Subcategory/Haste Stream
,SECONDftRY SILVER (Cont.)
Alternative B
Monthly Average
Regulatory
Flow
(lAkg)
BAT/PSES EFFLUENT UMTIftTIONS
Precipitation and Filtration of Film Strip-
ping Solutions Wet Air Pollution Control
Alternative A
Monthly Average
15,580
Alternative B
Monthly Average
Maxima
Precipitation and Filtration of Photographic
Solutions
Alternative A
Monthly Average
854,000
Alternative B
Monthly Average
Cu
Zn
Ammonia
1,129,110.0 777,420.0 108,468,6CXXO
2,369,280.0 1,888,020.0 246^ 183,000-0
15,580.0
29,602.0
9,503.80
19,942.40
8,724.8
20,721.0
6,543.60
15,891.60
912,988.0
2,072,140.0
912,988.0
2,072,14aO
854,000.0
1,622,600.0
520,940.0
1,093,120.0
478,240.0
l,135,82aO
358,680.0
871,080.0
50,044,400.0
113,582,000.0
50,044,4CKXO
113,582,000.0
-------
Table 11-14 (Continued)
PROPOSED BAT/PSES EFFLUENT LIMITATIONS GOMB\RISON
NOIFERROUS METALS MANUFACTURING POINT SOURCE GA1EQORY
(jO
ui
Subcategory/Waste Stream
SECONDARY SILVER (Cbnt.)
Regulatory
Flow
(1/kkg)
Precipitation and Filtration of Photographic 390,300
Solutions Wet Air Pollution Control
Alternative A
Monthly Average
Alternative B
Monthly Average
Maxinun
Electrolytic Refining
Alternative A
Monthly Average
Maxinun
Alternative B
Monthly Average
24,316
BAT/PSES EFFLUENT LTMTTAnONS (qg/khjg)
Cu 2n Anmonia
390,300.0
741,570.0
238,083.0
499,584.0
218,568.0
519,099.0
163,926.0
398,106.0
22,871,580.0
51,909,900.0
22,871,580.0
51,909,900.0
24,316.0
46,200.4
14,832.76
31,124.48
13,616.%
32,340.28
10,212.72
24,802.82
1,424,917.60
3,234,028.0
1,424,917.60
3,234,028.0
-------
Table 11-14 (Continued)
PROPOSED BAI/PSES EFFLUENT LMirATIOtB COMPARISON
N3NFERRDUS METMS MANUFACTURING POINT SOURCE CATEGORY
SubcategoryAfeste Stream
SEOMARY SILVER (font.)
Furnace Wet Mr Pollution Control
Alternative A
Monthly Average
Alternative B
Monthly Average
Casting Contact Cooling
Alternative A
Monthly Average
Alternative B
Monthly Average
Casting Wet Mr Pollution Control
Alternative A
Monthly Average
Alternative B
Manthly Average
Regulatory BAT/PSES EFFIIBir LIMITATIONS (ng/kkg)
Flow
(l/kkg)
1,204
4,741
Cu
1,204.0
2,287.6
734.44
1,541.12
4,741.0
9,007.8
2,892.01
6,068.48
Zn
674.24
1,601.32
2,654.%
6,305.53
1,991.22
4,835.82
Amnonia
0
0
0
0
0
0
0
0
0
0
0
0
70,554.40
160,132.0
505.68 70,554.40
1,228.08 160,132.0
277,822.60
630,553.0
277,822.60
630,553.0
-------
Table 11-14 (Continued)
PROPOSED BAT/PSES EFFLUENT UMTTATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOIFCE CATEGORY
OJ
Subcategory/Waste Stream
SECONDARY SILVER (Gont.)
leaching
Alternative A
Monthly Average
Regulatory
Flow
d/kkg)
2,780
Alternative B
Monthly Average
Maxinum
Leaching Vfet Air Pollution Control
Alternative A
Monthly Average
MaxLnun
Alternative B
Monthly Average
Maxinun
Precipitation and Filtration of Nonphoto
graphic Solutions
Alternative A
Monthly Average
142,389
98,577
BAT/PSES EFFLUENT LTMrTATIONS (mg/kkg)
Cu Zn Amnonia
142,389.0
270,539.1
86,857.29
182,257.92
98,577.0
187,296.30
79,737.84
189,377.37
59,803.38
145,236.78
2,780.0
5,282.0
1,695.8
3,558.4
1,566.8
3,697.4
1,167.6
2,835.6
165,662.20
369,740.0
162,908.0
369,740.0
8,343,995.40
18,937,737.0
8,343,995.40
18,937,737.0
55,203.12
131,107.41
5,776,612.20
13,110,741.0
Alternative B
Monthly Average
60,131.97
126,178.56
41,402,34
100,548.54
5,776,612.20
13,110,741.0
-------
•Bible 11-14 (Continued)
PROPOSED BAT/PSES EFFLUENT LIMITATIONS CCMBARISON
NDNFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
U)
oo
Subcategory/Vfaate Stream
SKXMDMff SILVER (Cont.)
Precipitation and Filtration of Nonphoto-
graphlc Solutions Wet Mir tbllutlon Control
Alternative A
Manthly Average
Regulatory
Flow
(1/kkg)
79,931
BAT/PSES EFFLUENT LMTDglONS
Alternative B
Monthly Average
Cu
79,931.0
151,868.9
48,757.91
102,311.68
Zn
44,761.36
106,308.23
33,571.02
81,529.62
Ammonia
4,683,956.60
10,630,823.0
4,683,956.60
10,630,823.0
-------
Tkble 11-15
PROPOSED BAT/PSES EFFLUENT LJMnMIDKB COMPARISON
NDNFERROUS METALS MANIFACTURING fOINT SOURCE CATEGORY
Regulatory
Flow
BAT/PSES EFFLUEOT UMTDglONS (mg/kkg)
UJ
Subcategpry/Haste Stream
SECONDARY LEAD
Battery Cracking
Alternative A
Monthly Average
673
Alternative B
Monthly Average
Maxtnun
Blast and Reverberatory Furnace Wet Air Pollu-
tion Control
Alternative A
Monthly Average
Maxinun
Alternative B
Monthly Average
MaxLnun
fettle Wet Air Pollution Control
Alternative A
Monthly Average
2,610
Alternative B
Monthly Average
Sb
854.71
1,931.51
578.78
1,298.89
3,314.7
7,490.7
2,244.60
5,037.30
0
0
0
0
As
578.78
1,406.57
383.61
935.47
2,244.6
5,454.9
1,487.70
3,627.90
0
0
0
0
Pb
87.49
100.95
60.57
67.30
339.3
391.5
234.90
261.0
0
0
0
0
Zn
376.88
895.09
282.66
686.46
1,461.6
3,471.30
1,096.20
2,662.20
0
0
0
0
Ammonia
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0
0
0
0
-------
Table 11-15 (Continued)
PROPOSED BAT/FSES EFFLUENT UMTEATIOC OCMPARISON
NDNFERROJS MSTALS MANJFACHJKQG POINT SOURCE CATEGORY
Subcategpry/Waste Stream
SECONDARY I£AD (Cont.)
Casting Contact Cooling
Alternative A
Monthly Average
Alternative B
Monthly Average
Regulatory
Flow
(l/W
-------
•Bible 11-16
PROPOSED NSPS/PSNS EFFLUENT LMTIATlfflB COMPARISON
N3NFERHOUS METALS MANIFACTIRING IDIOT SOURCE GAIEGCRY
Sabcategory/Waste Stream
PRIMARY ALIMOTM
Anode Paste Plant Wet Mr
Fbllution Cbntrol
Monthly Average
Maxlnun
Anode Bake Plant Wet Air
Fbllution Control
Monthly Average
Cathode Manufacturing
Monthly Average
Cathode Reprocessing
Monthly Average
Anode Contact Cooling
Monthly Average
MEDCUDLKD
Pbtline Wat Air
Pollution Control
Monthly Average
Regulatory Benzo-
Flow (,
(1/kkg) pyrene
BAT/PSES EFFLUENT LJMnflTIONS (mg/kkg)
0
77.4
952
621
rene
0
0
9.52
0
Sb
0
0
0
0
66.56
149.38
818.72
1,837.36
534.15
1,198.72
0
0
CN
0
0
0
0
6.19
15.48
76.16
190.40
49.69
124.22
0
0
0
0
0
0
28.64
42.57
352.24
523.60
229.81
341.61
0
0
Al
0
0
0
0
95.98
234.52
1,180.48
2,884.56
770. 16
1,881.93
0
0
Fl
0
0
0
0
1,362.24
3,072.78
16,755.20
37,794.40
10,931.36
24,657.67
0
0
06G*
0
0
0
0
774.0
774.0
9,520.0
9,520.0
6,211.0
6,211.0
0
0
TSS*
0
0
0
0
928.80
1,610.0
11,424.0
14,280.0
7,453.20
9,316.50
0
0
-------
•Bible 11-16 (Continued)
FROBOSH) IBPS/PSNS ffFUENT LMTDMlMe OMBMUSON
NDNFERROUS MBTAIS MANUFACTURING POINT SOURCE CA1EGCRY
Subcategory/Waste Sti
PRIMARY AUMMM (Cant.)
PotroamUet Air
Pollution Control
Monthly Average
Maximum
Degassing Wet Air
^ Pollution Control
N> Monthly Average
Maximum
Direct Chill Casting
Contact Cooling
Monthly Average
Maximum
Continuous Rod Casting
Contact Cooling
Monthly Average
Maximal
Stationary Casting
Contact Cooling
Monthly Average
Maximum
Regulatory Benzo-
Flow (a)
(1/kkg) pyrene
BAT/PSES EFFUEOT UMTIATIONS (ng/kkg)
1,999
104
0
Sb
0
0
0
0
89.69
201.29
0
0
^Conventional pollutants are controlled by ICES only.
CN
Ni
Al
Fl
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O&G*
0
0
0
0
8.34
20.86
0
0
38.59
57.37
0
0
129.33
316.03
0
0
1,835.68 1,043.0
4,140.71 1,043.0
0
0
0
0
TSS*
0
0
0
0
1,719.14 159.92 739.63 2,478.76 35,182.40 19,990.0 23,988.0
3,858.07 399.80 1,099.45 6,056.97 79,360.30 19,990.0 29,985.0
1,251.60
1,564.50
0
0
-------
Bible 11-17
PROPOSED NSPS/PSNS EFFLUENT LMTTATICtB OCMPARISCN
NDNFERROUS M5TAIS MAHJFACTURING POINT SOURCE CATEGORY
SECONDARY ALUMINUM
Scrap Drying Wet Air Pollution
Control
Monthly Average
Maximum
Scrap Screening and Milling
Monthly Average
Maximum
Dross Washing
Monthly Average
Maximun
Danagging Wet Air Pollution
Control
Monthly Average
Maximun
Direct Chill Casting Contact
Cooling
Monthly Average
Mqiriimm
Stationary Casting Contact Cooling
Monthly Average
Maximun
Shot Casting Contact Cooling
Monthly Average
Maxtnun
Regulatory
Flow
(1/kkg)
0
0
10,868
800
1,999
0
0
BAT/PSES EFFDJENT UMTTATIONS (ng/kkg)
Pb
0
0
0
0
978.12
1,036.80
72.0
80.0
179.91
199.90
0
0
0
0
Zn
0
0
0
0
4,564.56
11,085.36
336.0
816.0
839.58
2,038.98
0
0
0
0
Al
0
0
0
0
13,476.32
32,930.04
992.0
2,424.0
2,478.76
6,056.97
0
0
0
0
Armenia
0
0
0
0
636,864.80
1,445,444.0
46,880.0
106,400.0
117,141.40
265,867.0
0
0
0
0
O&G*
0
0
0
0
108,680.0
108,680.0
8,000.0
8,000.0
19,990.0
19,990.0
0
0
0
0
TSS*
0
0
0
0
130,416.0
163,020.0
9,600.0
12,000.0
23,988.0
29,985.0
0
0
0
0
*Conventional pollutants are controlled by NSPS only.
-------
liable 11-18
PROPOSED NSPS/PSNS EFFLUENT UMTIATIONS OCMPAKSON
NDNFERROJS METAIS MANJFACHJRDG POINT SOME CA1H00RY
Regulatory BAT/FSES EFFUJENT UMTCftHONS (ag/kkg)
Subcategory/Haste Stream
PRIMARY ELECTROLYTIC tUfHSK REFTNDG
Anode and Cathode Rinsing
Monthly Average
Mfnrtinin
Spent Electrolyte
Monthly Average
Casting Contact Cooling
Monthly Average
Maxinun
Casting Wet Air Pollution Control
Monthly Average
Maxlraun
By-Product Recovery
Monthly Average
MaxLnun
Flow
(1/kkg)
0
0
498
0
0
Cu
0
0
0
0
303.78
637.44
0
0
0
0
Pb
0
0
0
0
44.82
49.80
0
0
0
0
NL
0
0
0
0
184.26
273.90
0
0
0
0
TSS*
0
0
0
0
5,976.0
7,470.0
0
0
0
0
*Conventlonal pollutants are controlled by NSPS only.
-------
liable 11-19
PROPOSED NSPS/PSN3 EFFUENT LJMTEATIDNS COMPARISON
NDNFERROUS META1S MANUFACTURING POINT SOURCE CATEGORY
BAT/PSES EFFUENT LIMITATIONS
Ul
Subcategory/Waste Stream
QM&RY LEAD
Blast Furnace Slag Granulation
Monthly Average
Maxinun
Blast Furnace Wat Air Pollution Control
Monthly Average
Maxinun
Zinc Fuming Furnace Wet Air Pollution Control
Monthly Average
Maxinun
Dross Reverberatory Wet Air Pollution Control
Monthly Average
Maxinun
Dross Reverberatory Furnace Granulation
Monthly Average
Maxinun
Hard lead Refining Wet Air Pollution Control
Monthly Average
Maidnim
Hard lead Refining Slag Granulation
Monthly Average
Maxinun
Regulatory
Flow
(1/kkg)
0
0
0
0
0
0
0
(mg/kkg)
Pb Zn TSS*
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
^Conventional pollutants are controlled by NSPS only.
-------
Table 11-20
PROPOSED NSPS/PSNS ffFUENT LJMIIftllQNS OCMB&RISON
NDWERROIB META1S MANUFACTURING POINT SOURCE CATEGORY
Regulatory BAT/PSES EEFUUENT UMTIATIONS (ng/kkg)
SubcategoryAfaste Stream
PRIMARY ZBC
Zitc. Reduction, Rirnsce Vfet Air RjUutlon Control
Monthly Average
Leaching
Monthly Average
MaxLnun
cr> Leaching Wet Air Pollution Control
Monthly Average
MaxLnun
Cathode and Anode Washing
Monthly Average
MaxLnun
Casting Wet Air Pollution Control
Monthly Average
Casting Contact Cooling
Monthly Average
Cadmium Plant
Monthly Average
MaxLnun
Flow
d/kkg)
1,668
1,310
0
19,850
257
181
6,171
Cd
133.46
333.66
104.80
262.0
0
0
1,588.0
3,970.0
20.56
51.40
14.48
36.20
493.68
1,234.20
Cu
1,017.66
2,135.42
799.10
1,676.80
0
0
12,108.50
25,408.0
156.77
328.%
110.41
231.68
3,764.31
7,898.88
Pb
150.15
166.83
117.90
131.0
0
0
1,786.50
1,985.0
23.13
25.70
16.29
18.10
555.39
617.10
Zn
700.69
1,701.67
550.20
1,336.20
0
0
8,337.0
20,247.0
107.94
262.14
76.02
184.62
2,591.82
6,294.42
TSS*
20,019.60
25,024.50
15,720.0
19,650.0
0
0
238,200.0
297,750.0
3,084.0
3,855.0
2,172.0
2,715.0
74,052.0
92,565.0
*Gonventional pollutants are controlled by NSPS only.
-------
Table 11-21
PROPOSED N5PS/PSN3 EFFUENT UMTTATIQNS (XMPARISON
N3NFERKOUS METALS MANIFACTIRING POINT SOURCE CAIEOQRY
Subcategory/Waste Stream
Regulatory
Flow
(1/kkg)
BAT/PSES EFFLUENT LIMITATIONS (ng/kkg)
As Cd
Cu
Pb
Zn
METALLLRGICAL ACID PLANTS
Add Plant Slowdown
Manthly Average
Maximum
2,554
1,455.78
3,550.06
204.32
510.80
1,557.94
3,269.12
229.86
255.40
1,072.68
2,605.08
TSS*
30,648.0
38,310.0
*Conventional pollutants are controlled by 1BPS only.
-------
Tkble 11-22
PROPOSED N3PS/PSNS EFFLUENT UMrWClONS COMPARISON
N3NFERROIJS METALS MANIFACTURING POINT 901BCE CATEGORY
00
Subcategory/Haste Stream
PRIMARY TtWGSTEN
Tbngsten Acid Rinse
Monthly Averaga
Maxinun
Acid leach Wet Air Pollution Control
Monthly Average
Maytmm
Alkali Lsachfesh
Monthly Average
MGDcinun
lon-Exdiange Raf f inate
Monthly Average
Maxinun
Calcium TUngstate Precipitate
Monthly Average
Crystallization and Drying of Annoniura
Paratungsute
Monthly Average
Maxinun
Regulatxiry
Flow
OA*g)
47,600
3,770
46,700
51,200
37,299
0
BAT/PSES EFFUUENT LIMITATIONS (fflg/kkg)
Pb
4,284.0
4,760.0
339.30
377.0
4,203.0
4,670.0
4,608.0
5,120.0
3,348.0
3,720.0
0
0
Se
17,612.0
39,032.0
1,394.90
3,091.40
17,279.0
38,294.0
41,984.0
18,944.0
13,764.0
30,504.0
0
0
Zn
19,992.0
48,552.0
1,583.40
3,845.40
19,614.0
47,634.0
21,504.0
52,224.0
15,624.0
37,944.0
0
0
Amnxiia
2,789,360,0
6,330,800.0
220,922.0
501,410.0
2,736,620.0
6,211,100.0
3,000,320.0
6,809,600.0
2,179,920.0
4,947,600.0
0
0
TSS*
571,200.0
174,000.0
45,240.0
56,550.0
560,400.0
700,500.0
614,400.0
768,000.0
446,400.0
558,000.0
0
0
-------
Table 11-22 (Continued)
PROroSED NSPS/PSN3 EFFUENT LJMTEATKHC OMBHUSON
N»FERO)iB METALS MANIFAOTKING JOINT SOURCE CAIEGCRY
vO
PRIMARY TUNGSTEN (Cont.)
Amonim Raratungstate Conversion to
Gbddes Vfet Air R>Uution Control
Monthly Average
Maodnun
Reduction to TVingsten Vfet Mr Ibllu-
tion Control
Monthly Average
Maximum
Reduction to T\mgsten Water of R>rma-
tion
Manthly Average
Msxinufi
Regulatory
Flow
(1/kkg)
20,900
7,320
19,400
BAT/K
Pb
2,717.0
3,135.0
658.80
732.0
1,746.0
1,940.0
5ES EFFLUENT L
Se
7,733.0
17,138.0
482.85
1,070.10
7,178.0
15,908.0
jMnATiute v
Zn
11,704.0
27,797.0
3,074.40
7,466.40
8,148.0
19,788.0
ig/KKg;
Ammonia
1,224,740.0
2,779,700.0
428,952.0
973,560.0
1,136,840.0
2,580,200.0
TSS*
418,000.0
856,900.0
87,840.0
109,800.0
232,800.0
291,000.0
"Conventional pollutants are controlled by J6PS only.
-------
Table 11-23
PROPOSED Nsre/psre EFFLUENT LJMTEMB»B
NOWERRDUS MEIALS MANUFACTURING POINT SOURCE CATEGORY
PWMARY COUMBIUMMIALtM
Concentrate Digestion Wet Air R>llu- 5,156
tlon Control
Monthly Average
Maximal
Solvent Extraction Raf flnate
Monthly Average
Solvent Extraction Wet Air ft>llution
Control
Monthly Average
Precipitation and Filtration of
fetal Salts
Monthly Average
Matal Salt Drying Vfet Air Ibllutlon
Control
Monthly Average
Regulatory
Flow
(1/kkg)
5,156
26,916
430
247,223
16,479
BAT/PSES EFFLUENT
Pb
464.07
515.63
2,422.44
2,691.60
38.71
43.01
22,250.07
24,722.30
1,483.11
1,647.90
Zn
2,165.65
5,259.43
11,304.72
27,454.32
180.64
438.70
103,833.66
252,167.46
6,921.18
16,808.58
LJMTIATIONS (tug
Fl
90,750.88
204,705.11
473,721.60
1,068,565.20
7,569.76
17,074.97
4,351,124.80
9,814,753.10
290,030.40
654,216.30
Me)
Aranonia
302,159.18
685,787.90
1,577,277.60
3,579,828.0
25,203.86
57,203.30
14,487,267.80
32,880,659.0
965,669.40
2,191,707.0
TSS*
61,875.60
77,344.50
322,992.0
403,740.0
5, 161.20
6,451.50
2,966,676.0
3,708,345.0
197,748.0
247,185.0
-------
Thble 11-23 (Continued)
PROPOSED teps/psie EFFUENT UMIIATKWS COMPARISON
NDNFERROU6 METALS MANIFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY COUMBUM-TANTALIM (Cont.)
RediK.ti.on of Salt to Metal
Monthly Average
Maxinun
Reduction of Salt to T-fetal Vfet Mr
Pollution Control
Monthly Average
Maxinun
Consolidation and Casting
Monthly Average
Maid mm
Regulatory BAT/
Flow
(1/kkg) Pb
352,663
31,739.67
35,266.30
21,521
1,936.89
2,152.10
0
0
0
'PSES EFFLUENT LTMTTATIONS (mg/kkg)
Zn
148,118.46
359,716.26
9,038.82
21,951.42
0
0
Fl
6,206,868.80
14,000,721.10
378,769.60
854,383.70
0
0
Anraonia
20,666,051.80
46,904,179.0
1,261,130.60
2,862,293.0
0
0
TSS*
4,231.956.0
5,289,945.0
258,252.0
322,815.0
0
0
*Gonventional pollutants are controlled by NSPS only.
-------
11-24
PROPOSED rePS/PSNS EFFUENT LMTBVOMG COMPARISON
NMFERROUS METMS MANUFACTURING POINT SOURCE CATEGORY
Ln
Subcategory/Haste stream
SECONEARY SILVER
Film Stripping
Monthly Average
Film Stripping Wet Air Pollution Control
Monthly Average
Precipitation and Filtration of Film
Stripping Solutions
Monthly Average
Maximum
Regulatory
Flow
(1/kkg)
1,619,000
15,580
1,851,000
Precipitation and Filtration of Film Strip- 15,580
ping Solutions Wat Air Pollution Control
Monthly Average
Maximum
Precipitation and Filtration of Photographic 854,000
Solutions
Monthly Average
390,300
Precipitation and Filtration of Photographic
Solutions Wat Air Pollution Control
Monthly Average
Maxinun
BAT/PSES EFFLUENT UMTDmONS (mgAkg)
Cu Zn Amnonia
987,590.0 679,980.0 94,873,400.0
2,072,320.0 1,651,380.0 215,327,000.0
9,503.80 6,543.60 912,988.0
19,942.40 15,891.60 2,072,140.0
TSS*
19,428,000.0
24,285,000.0
186,960.0
233,700.0
1,129,110.0 777,420.0 108,468,600.0 22,212,000.0
2,369,280.0 1,888,020.0 246,183,000.0 27,765,000.0
9,503.80 6,543.60 912,988.0 186,960.0
19,942.40 15,891.60 2,072,140.0 233,700.0
520,940.0 358,680.0 50,044,400.0 10,248,000.0
1,093,120.0 871,080.0 113,582,000.0 12,810,000.0
238,083.0 163,926.0 22,871,580.0 4,683,600.0
499,584.0 398,106.0 51,909,900.0 5,854,500.0
-------
Table 11-24 (Continued)
PROPOSED N5PS/PSN5 EFFLUENT UMTTATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
U)
Retaliatory BAT/PSES EFFLUENT LIMITATIONS (mg/kkg)
Subcategory/Waste Stream
SECONDARY SILVER (Cont.)
Rlectrolytic Refining
Monthly Average
Furnace Wet Air Pollution Control
Monthly Average
Casting Contact Cooling
Monthly Average
Maximm
Casting Wet Air Pollution Control
Monthly Average
Maxinun
Leaching
Monthly Average
Maxinun
Leaching Wet Air Pollution Control
Monthly Average
Maxinun
Flow
(1/kkg) Cu
24,316
14,832.76
31,124.48
0
0
0
1,204
734.44
1,541.12
4,741
2,892.01
6,068.48
2,780
1,695.8
3,558.4
142,389
86,857.29
182,257.92
Zn
10,212.72
24,802.82
0
0
505.68
1,228.08
1,991.22
4,835.82
1,167.6
2,835.6
59,803.38
145,236.78
Aumonia
1,424,917.60
3,234,028.0
0
0
70,554.40
160,132.0
277,822.60
630,553.0
162,908.0
369,740.0
8,343,995.40
18,937,737.0
TSS*
291,792.0
364,740.0
0
0
14,448.0
18,060.0
56,892.0
71,115.0
33,360.0
41,700.0
1,708,668.0
2,135,835.0
-------
Thble 11-24 (Continued)
PROPOSED NSB5/PSN3 EFFUENT LMTIATIJMB COMPARISON
NWFHBQU5 METALS MANLPACTIKIN6 POINT SOIFCE CAIEOCRY
ui
SubcategoryAbste Stream
SEDOMaRY SILVER (Cont.)
Precipitation and Filtration of Nbnphoto-
graphic Solutions
Monthly Average
Precipitation and Filtration of Nonphoto-
graphic Solutions Wat Air Pollution Control
Monthly Average
Regulatory
Flow
OAkg)
98,577
79,931
BAT/PSES EFFLUENT UMITATIOtB (iqgAkg)
Cu Zn Anmonia
60,131.97
126,178.56
48,757.91
102,311.68
41,402.34
100,548.54
33,571.02
81,529.62
5,776,612.20
13,110,741.0
4,683,956.60
10,630,823.0
TSS*
1,182,924.0
1,478,655.0
959,172.0
1,198,965.0
^Conventional pollutants are controlled by NSPS only.
-------
-Sable 11-25
PROPOSED frEPS/PSNS EFFLUENT LJMnATKKB OMBMHSON
NDNFERROUS METMS MANUFACTURING FOINT SOURCE CATEGORY
Subcategory/Waste Stream
SECONDARY LEAD
Battery Cracking
Monthly Average
Maximum
Blast and Reverberatory Rirnace Wet Air RxLlu-
tion Control
Monthly Average
Maximum
fettle Wet Air Ibllution Control
Monthly Average
Casting Contact Cooling
Monthly Average
Maximum
Regulatory
Blow
(1/kkg)
673
2,610
0
22.1
BAT/PSES EFFLUENT LJMTTATIONS (mgAckg)
Sb
578.78
1,298.89
2,244.60
5,037.30
0
0
19.066
42.653
As
383.61
935.47
1,487.70
3,627.90
0
0
12.60
30.72
Fb
60.57
67.30
234.90
261.0
0
0
1.99
2.21
Zn
282.66
686.46
1,0%. 20
2,662.20
0
0
9.28
22.54
Ammonia
0
0
0
0
0
0
0
0
TSS*
8,076.0
10,095.0
31,320.0
39,150.0
0
0
265.20
331.50
*Conventional pollutants are controlled by NSPS only.
-------
Table 11-26
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY ALUMINUM
Anode Paste Plant Wet Air Pollution
Control
Monthly Average
Maximum
Anode Bake Plant Wet Air Pollution
Control
Monthly Average
Maximum
Cathode Manufacturing
Monthly Average
Maximum
Cathode Reprocessing
Monthly Average
Maximum
Anode Contact Cooling
Monthly Average
Maximum
Potline Wet Air Pollution Control
Monthly Average
Maximum
Potroom Wet Air Pollution Control
Monthly Average
Maximum
Degassing Wet Air Pollution Control
Monthly Average
Maximum
Direct Chill Casting Contact Cooling
Monthly Average
Maximum
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
(1/kkg)
O&G
TSS
1,028
617
77.5
952
1,490
838
1,305
2,616
1,999
12,336.0
20,560.0
7,404.0
12,340.0
930.0
1,550.0
11,424.0
19,040.0
17,880.0
29,800.0
10,056.0
16,760.0
15,660.0
26,100.0
31,392.0
52,320.0
23,988.0
39,980.0
20,560.0
42,148.0
12,340.0
25,297.0
1,550.0
3,177.5
19,040.0
39,032.0
29,800.0
61,090.0
16,760.0
34,358.0
26,100.0
53,505.0
52,320.0
107,256.0
39,980.0
81,959.0
56
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Table 11-26 (Continued)
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
Subcategory/Waste Stream (1/kkg) O&G TSS
PRIMARY ALUMINUM (Cont.)
Continuous Rod Casting Contact Cooling 1,042
Monthly Average 12,504.0 20,840.0
Maximum 20,840.0 42,722.0
Stationary Casting Contact Cooling 0
Monthly Average 0 0
Maximum ° °
57
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Table 11-27
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
Subcategory/Waste Stream (1/kkg) O&G TSS
SECONDARY ALUMINUM
Scrap Drying Wet Air Pollution Control 0
Monthly Average 0 0
Maximum 0 0
Scrap Screening and Milling 0
Monthly Average 0 0
Maximum 0 0
Dross Washing 10,868
Monthly Average 130,416.0 217,360.0
Maximum 217,360.0 445,588.0
Demagging Wet Air Pollution Control 800
Monthly Average 9,600.0 16,000.0
Maximum 16,000.0 32,800.0
Direct Chill Casting Contact Cooling 1,999
Monthly Average 23,988.0 39,980.0
Maximum 39,980.0 81,959.0
Stationary Casting Contact Cooling 0
Monthly Average 0 0
Maximum 0 0
Shot Casting Contact Cooing 0
Monthly Average 0 0
Maximum 0 0
58
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Table 11-28
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Regulatory BCT EFFLUENT LIMITATIONS-
Flow (mg/kkg)
Subcategory/Waste Stream (1/kkg) TSS
PRIMARY ELECTROLYTIC COPPER REFINING
Anode and Cathode Rinsing 120
Monthly Average 2,400.0
Maximum 4,920.0
Spent Electrolyte 280
Monthly Average 5,600.0
Maximum 11,480.0
Casting Contact Cooling 1,000
Monthly Average 20,000.0
Maximum 41,000.0
Casting Wet Air Pollution Control 0
Monthly Average °
Maximum "
By-Product Recovery 600
Monthly Average 0
Maximum
59
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Table 11-29
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategorv/Waste Stream
PRIMARY LEAD
Blast Furnace Slag Granulation
Monthly Average
Maximum
Blast Furnace Wet Air Pollution
Control
Monthly Average
Maximum
Zinc Fuming Furnace Wet Air Pollu-
tion Control
Monthly Average
Maximum
Dross Reverberatory Furnace Wet Air
Pollution Control
Monthly Average
Maximum
Dross Reverberatory Furnace Granula-
tion
Monthly Average
Maximum
Hard Lead Refinning Wet Air Pollution
Control
Monthly Average
Maximum
Hard Lead Refining Slag Granulation
Monthly Average
Maximum
Regulatory
Flow
(1/kkg)
3,730
0
BCT EFFLUENT LIMITATIONS
(mg/kkg) .
426
3,134
19,836
TSS
74,600.0
152,930.0
0
0
8,520.0
17,466.0
0
0
62,680.0
128,494.0
396,720.0
813,276.0
0
0
60
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Table 11-30
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY ZINC
Zinc Reduction Furnace Wet Air
Pollution Control
Monthly Average
Maximum
Leaching
Monthly Average
Maximum
Leaching Wet Air Pollution Control
Monthly Average
Maximum
Cathode and Anode Washing
Monthly Average
Maximum
Casting Wet Air Pollution Control
Monthly Average
Maximum
Casting Contact Cooling
Monthly Average
Maximum
Cadmium Plant
Monthly Average
Maximum
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
(1/kkg) TSS
1,668
1,310
19,850
2,570
1,947
6,171
33,366.0
68,400.30
26,200.0
53,710.0
0
0
397,000.0
813,850.0
51,400.0
105,370.0
38,940.0
79,827.0
123,420.0
253,011.0
61
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Table 11-31
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
METALLURGICAL ACID PLANTS
Acid Plant Slowdown
Monthly Average
Maximum
Regulatory
Flow
d/kkg)
6,079
BCT EFFLUENT LIMITATIONS
(mg/kkg)
TSS
121,580.0
249,239.0
62
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Table 11-32
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Regulatory
Flow
Subcategory/Waste Stream (1/kkg)
PRIMARY TUNGSTEN
Tungsten Acid Rinse 47,600
Monthly Average
Maximum
Acid Leach Wet Air Pollution Control 37,700
Monthly Average
Maximum
Alkali Leach Wash 46,700
Monthly Average
Maximum
Ion-Exchange Raffinate 51,200
Monthly Average
Maximum
Calcium Tungstate Precipitate Wash 37,200
Monthly Average
Maximum
Crystallization and Drying of 0
Ammonium Paratungstate
Monthly Average
Maximum
Ammonium Paratungstate Conversion to 20,900
Oxides Wet Air Pollution Control
Monthly Average
Maximum
Reduction to Tungsten Wet Air Pollution 73,200
Control
Monthly Average
Maximum
BCT EFFLUENT LIMITATIONS
(mg/kkg)
TSS
Reduction to Tungsten Water of Formation 19,400
Monthly Average
Maximum
952,000.0
1,951,600.0
754,000.0
1,545,700.0
934,000.0
1,914,700.0
1,024,000.0
2,099,200.0
744,000.0
1,525,200.0
0
0
418,000.0
856,900.0
1,464,000.0
3,001,200.0
388,000.0
795,400.0
63
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Table 11-33
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
PRIMARY COLUMBIUM-TANTALUM
Concentrate Digestion Wet Air Pollu-
tion Control
Monthly Average
Maximum
Solvent Extraction Raffinate
Monthly Average
Maximum
Solvent Extraction Wet Air Pollu-
tion Control
Monthly Average
Maximum
Precipitation and Filtration of
Metal Salts
Monthly Average
Maximum
Metal Salt Drying Wet Air Pollution
Control
Monthly Average
Maximum
Reduction of Salt to Metal
Monthly Average
Maximum
Reduction of Salt to Metal Wet Air
Pollution Control
Monthly Average
Maximum
Consolidation and Casting Contact
Cooling
Monthly Average
Maximum
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
(1/kkg) TSS
10,915
26,916
4,301
247,223
83,643
352,663
21,521
0
218,300.0
447,515.0
538,320.0
1,103,556.0
86,028.0
176,357.40
4,944,460.0
10,136,143.0
1,672,860.0
3,429,363.0
7,053,260.0
14,459,183.0
430,420.0
882,361.0
0
0
64
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Table 11-34
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
SECONDARY SILVER
Film Stripping
Monthly Average
Maximum
Film Stripping Wet Air Pollution
Control
Monthly Average
Maximum
Precipitation and Filtration of Film
Stripping Solutions
Monthly Average
Maximum
Precipitation and Filtration of Film
Stripping Solutions Wet Air Pollution
Control
Monthly Average
Maximum
Precipitation and Filtration of
Photographic Solutions
Monthly Average
Maximum
Precipitation and Filtration of
Photographic Solutions Wet Air Pollu-
tion Control
Monthly Average
Maximum
Electrolytic Refining
Monthly Average
Maximum
Furnace Wet Air Pollution Control
Monthly Average
Maximum
Regulatory
Flow
(1/kkg)
1,619,000
15,580
1,851,000
15,580
BCT EFFLUENT LIMITATIONS
(mg/kkg)
TSS
854,000
390,300
24,316
21,519
32,380,000.0
66,379,000.0
311,600.0
638,780.0
37,020,000.0
75,891,000.0
311,600.0
638,780.0
17,080,000.0
35,014,000.0
7,806,000.0
16,002,300.0
486,320.0
996,956.0
430,380.0
882,279.0
65
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Table 11-34 (Continued)
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Subcategory/Waste Stream
SECONDARY SILVER (Cont.)
Casting Contact Cooling
Monthly Average
Maximum
Casting Wet Air Pollution Control
Monthly Average
Maximum
Leaching
Monthly Average
Maximum
Leaching Wet Mr Pollution Control
Monthly Average
Maximum
Precipitation and Filtration of
Nonphotographic Solutions
Monthly Average
Maximum
Precipitation and Filtration of
Nonphotographic Solutions Wet Air
Pollution Control
Monthly Average
Maximum
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
(1/kkg) TSS
12,035
4,741
2,780
142,389
98,577
79,931
240,700.0
493,435.0
94,820.0
194,381.0
55,600.0
113,980.0
2,847,780.0
5,837,949.0
1,971,540.0
4,041,657.0
1,598,620.0
3,277,171.0
66
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Table 11-35
BCT PROPOSED EFFLUENT LIMITATIONS COMPARISON
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
Regulatory BCT EFFLUENT LIMITATIONS
Flow (mg/kkg)
Subcategory/Waste Stream (1/kkg) TSS
SECONDARY LEAD
Battery Cracking 940
Monthly Average 18,800.0
Maximum 38,540.0
Blast and Reverberatory Furnace Wet 3, 380
Air Pollution Control
Monthly Average 67,600.0
Maximum 138,580.0
Kettle Wet Air Pollution Control 0
Monthly Average 0
Maximum 0
Casting Contact Cooling 221
Monthly Average 4,424.0
Maximum 9,069.20
67
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68
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SECTION III
INTRODUCTION
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," under Section 101(a). By July 1, 1977, existing indus-
trial dischargers were required to achieve "effluent limitations
requiring the application of the best practicable control tech-
nology currently available" (BPT), under Section 301(b)(1)(A);
and by July 1, 1983, these dischargers were required to achieve
"effluent limitations requiring the application of the best
available technology economically achievable . . . which will
result in reasonable further progress toward the national goal of
eliminating the discharge of all pollutants" (BAT), under 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; existing and new
dischargers to publicly owned treatment works (POTW) were subject
to pretreatment standards under Sections 307(b) (PSES) and (c)
(PSNS), respectively, of the Act. While the requirements for
direct dischargers were to be incorporated into National Pollu-
tant Discharge Elimination System (NPDES) permits issued under
Section 402 of the Act, pretreatment standards were made enforce-
able directly against discharges to a POTW (indirect discharg-
ers). Although Section 402(a)(1) of the 1972 Act authorized the
setting of NPDES permit requirements for direct dischargers on a
case-by-case basis, Congress intended that, for the most part,
control requirements would be based on the degree of effluent
reduction attainable through the application of BPT and BAT.
Moreover, Sections 304(c) and 306 of the Act required promulga-
tion of regulations for new sources (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 promulgate effluent standards
applicable to all dischargers of toxic pollutants. Finally,
Section 301(a) of the Act authorized the Administrator to pre-
scribe any additional regulations "necessary to carry out his
functions under the Act.
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
69
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program and adhere to a schedule for promulgating 21 major
industries' BAT effluent limitations guidelines, pretreatment ^
standards, and new source performance standards for 65 priority
pollutants and classes of pollutants. See Settlement Agreement
in Natural Resources Defense Council, Inc. v. Train, 8 ERG 2120
(D.D.C. 1976), modified 12 ERG 1833 CD.D.C. 1979).
On December 27, 1977, the President signed into law amendments to
the Federal Water Pollution Control Act (P.L. 95-217). The Act,
as amended, is commonly referred to as the Clean Water Act.
Although this Act 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 Settle-
ment Agreement program for toxic pollution control. Sections
301 (b) (2) (A) and 301 (b) (2) (C) of the Act now require the achieve-
ment by July 1, 1984, of effluent limitations requiring applica-
tion 'of BAT for toxic pollutants, including the 65 priority pol-
lutants and classes of pollutants (the same priority pollutants
as listed in Natural Resources Defense Council v. Train) , which
Congress declared toxic under Section 3U/U; of the Act. Like-
wise EPA's programs for new source performance standards and
pretreatment standards are now aimed principally at control of
these toxic pollutants. Moreover, to strengthen the toxics
control program, Congress added Section 304 (e) to the Act,
authorizing the Administrator to prescribe "best management
practices" (BMP) 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 also revised the control program for nontoxic pollutants.
Instead of BAT for "conventional" pollutants identified under
Section 304(a)(4) (including biological oxygen demand, suspended
solids, oil and grease, fecal coliform, and pH) the new Section
301 (b) (2) (E) requires achievement, by July 1, 1984, of ettluent
limitations requiring the application of the best conventional
pollutant control technology* (BCT) . The factors considered in
assessing BCT for an industry include a two-part cost-
"asonaSleness" test [Section 304(b) (4) (B) 3 American Paper
Institute v. EPA, 660 F.2d 954 (4th Cir. 1981). The first part
compares the c^t for private industry to reduce its conventional
pollutants with the costs to publicly owned treatment works for
tant8'
po
similar levels of reduction in their discharge of
The second part examines the cost effectiveness of additional
industrial treatment beyond BPT. For nontoxic, nonconventionai
POISES.. Sections 3oI(b)(2)(A) and (b) (2) (F) require achieve-
ment of BAT effluent limitations within three years after their
establishment or not later than July 1, 1984.
70
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The purpose of this report is to provide the supporting technical
data regarding water use, pollutants, and treatment technologies
for BPT, BAT, NSPS, PSES or PSNS effluent limitations that EPA is
proposing for the nonferrous metals manufacturing category under
Sections 301, 304, 306, 307, and 501 of the Clean Water Act.
PRIOR EPA REGULATIONS
EPA already has promulgated effluent limitations and pretreatment
standards for certain nonferrous metals manufacturing subcatego-
ries. These regulations, and the technological basis therefore-,
are summarized below.
Primary Aluminum Subcategory. EPA has promulgated BPT, BAT,
NSPS, and PSNS in this subcategory. 39 FR 12822 (March 26,
1974). BPT is based on lime precipitation and sedimentation
technology. BAT is based on this technology and flow reduction;
NSPS and PSNS are based on the same technology and additional
flow reduction.
Secondary Aluminum Subcategory. Existing regulations in this
subcategory cover BPT, BAT, NSPS, PSES and PSNS. 39 FR 12822
(March 26, 1974) and 41 FR 54854 (December 15, 1976) (establish-
ing pretreatment standards). BPT is based on lime precipitation
and sedimentation with pH adjustment to control ammonia. BAT is
no discharge of wastewater pollutants, PSES is based on oil skim-
ming, pH adjustment and ammonia air stripping, while NSPS and
PSNS are based on lime precipitation and sedimentation and flow
reduction. (Promulgated NSPS and PSNS are less stringent than
BAT and PSES because the processes believed to be necessary to
achieve zero discharge were not yet demonstrated in 1974 or 1976,
but it was believed that they would be demonstrated at the time
of the BAT and PSES compliance dates.)
Primary Copper Smelting. Existing regulations cover BPT and BAT.
The amended BPT,the most recently promulgated regulation, is no
discharge of process wastewater pollutants subject to an excep-
tion for unlimited discharge of the volume of water falling
within impoundments in excess of the 10-year, 24-hour storm
(known as a catastrophic precipitation event) when a storm of at
least that magnitude occurred. See 45 FR 44926 (July 2, 1980).
Existing BAT, promulgated earlier (40 FR 8523 (February 27,
1975)), is presently less stringent than BPT, allowing as exemp-
tions to zero discharge a similar unlimited discharge for storm-
water (except the allowance is for a volume of wastewater in
excess of a 25-year, 10-hour storm), and a further discharge
during any calendar month equal in volume to the difference
between precipitation on and evaporation from the impoundment
during that month. This later discharge is subject to
concentration-based limitations.
71
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Primary Electrolytic Copper Refining. Existing regulations cover
BPT and BAT. The BPT regulation for this subcategory allows a
mass-based continuous discharge based on lime precipitation and
sedimentation. 45 FR 44926 (July 2, 1980). The BAT regulation,
promulgated earlier (40 FR 8524 (February 27, 1975)) is impound-
ment rather than hardware-based, and establishes a mass-based
continuous discharge limitation, based on flow reduction, lime
precipitation, sedimentation, and the same allowances for
catastrophic stormwater discharge and net precipitation discharge
described for primary copper smelting, previously. (Refiners
located in areas of net evaporation, however, cannot discharge
process wastewaters, based on the use of solar evaporation. The
monthly net precipitation and catastrophic discharges may be
discharged.)
Secondary Copper. EPA has established BPT, BAT and PSES in this
subcategory. BPT and BAT, based on the presence of impoundments
(or cooling tower circuits), require no discharge of process
wastewater pollutants with allowances for catastrophic stormwater
discharge and net precipitation discharge as described above when
impoundments are used instead of cooling tower circuits. See 40
FR 8526 (February 27, 1975). PSES, promulgated later (41 FR
54854 (December 15, 1976)) is based on lime precipitation and
sedimentation.
Primary Lead. The existing BPT and BAT limitations in this sub-
category are based on impoundments. See 40 FR (February 27,
1975). These limitations provide for no discharge of process
wastewater pollutants, with exemptions for catastrophic storm-
water and net precipitation discharge of acid plant blowdown
(subject to mass limitations) and monthly net precipitation on
impoundments. The existing limitations do not apply to primary
lead refineries not on-site with a smelter.
Primary Zinc. We have promulgated BPT and BAT in this subcate-
gory. See 40 FR 8528 (February 27, 1975). These limitations are
based on lime precipitation and sedimentation technology for BPT,
with flow reduction added for BAT.
Metallurgical Acid Plants. This subcategory was established in
1980, and presently includes only acid plants (i.e., plants
recovering by-product sulfuric acid from sulfur dioxide smelter
air emissions) associated with primary copper smelting opera-
tions. See 45 FR 44926. Primary lead and zinc plants also have
associated acid plants, but their discharges presently are
covered under the primary lead and zinc subcategories. BPT for
copper smelting acid plants is based on lime precipitation and
sedimentation.
72
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METHODOLOGY
Approach of Study
The nonferrous metals manufacturing category includes plants
producing primary metals from ore concentrates and recovering
secondary metals from recycled metallic wastes (aluminum cans,
lead batteries, etc.)- Because of the diversity of the nonfer-
rous metals manufacturing category, EPA has divided it into
separate segments (nonferrous metals manufacturing Phase I and
nonferrous metals manufacturing Phase II).
The proposed regulatory strategy for Phase I nonferrous metals
manufacturing addresses 12 subcategories: primary aluminum,
copper smelting, copper electrolytic refining, lead, zinc,
columbium-tantalum, and tungsten; secondary aluminum, silver,
copper, and lead; and metallurgical acid plants. Nonferrous
metals manufacturing Phase II, containing an additional 21
primary metals or metal groups, 15 secondary metals or metal
groups, and bauxite refining (Table III-2) will be considered
separately and is scheduled for proposal in September, 1983. EPA
has also studied the segments of the nonferrous metals^industry
associated with forming and casting. Proposed regulations for
aluminum forming (47 FR 52626), copper forming (47 FR 51278) and
metal molding and casting (47 FR 51512) were issued in November,
1982. The forming of nonferrous metals other than copper and
aluminum will be addressed in a proposed regulation that is
scheduled for September, 1983. A group of metals including six
primary metals and five secondary metals, was included in a
Paragraph 8 affidavit submitted pursuant to the Settlement
Agreement: primary arsenic, antimony, barium, bismuth, calcium,
and tin; secondary beryllium, cadmium, molybdenum, tantalum, and
babbitt. These metals were excluded from regulation because the
manufacturing processes do not use water or are regulated by
toxics limitations in other categories (ferroalloys and inorganic
chemicals).
EPA gathered and evaluated technical data in the course of
developing these guidelines in order to perform the following
^ _ _ * _ _ _
tasks:
1. To profile the category with regard to the production,
manufacturing processes, geographical distribution,
potential wastewater streams, and discharge mode of
nonferrous metals manufacturing plants.
2. To subcategorize, if necessary, in order to permit
regulation of the nonferrous metals manufacturing
category in an equitable and manageable way.
73
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3. To characterize wastewater, detailing water use, waste-
water discharge, and the occurrence of toxic, conven-
tional, and nonconventional pollutants, in waste streams
from nonferrous metals manufacturing processes.
4. To select pollutant parameters--those toxic, nonconven-
tional, or conventional pollutants present at signifi-
cant concentrations in wastewater streams--that should
be considered for regulation.
5. To consider control and treatment technologies and
select alternative methods for reducing pollutant dis-
charge in this category.
6. To evaluate the costs of implementing the alternative
control and treatment technologies.
7. To present possible regulatory alternatives.
Data Collection and Methods of Evaluation
Data on the nonferrous metals manufacturing category were
gathered from previous EPA studies, literature studies, inquiries
to federal and state environmental agencies, trade association
contacts and the manufacturers themselves. Meetings were also
held with industry representatives and the EPA. All known com-
panies within the nonferrous metals manufacturing category were
sent data collection portfolios to solicit specific information
concerning each facility. Finally, a sampling program was
carried out at 46 plants. The sampling program consisted of
screen sampling and analysis at 10 facilities to determine the
presence of a broad range of pollutants and verification at 36
plants to quantify the pollutants present in the wastewater.
Specific details of the sampling program and information from the
above data sources are presented in Section V. Details on selec-
tion of plants for sampling, and analytical results, are con-
tained in Section V of each of the subcategory supplements.
Literature Review. EPA reviewed and evaluated existing litera-
ture for background information to clarify and define various
aspects of the nonferrous metals manufacturing category and to
determine general characteristics and trends in production
processes and wastewater treatment technology. Review of current
literature continued throughout the development of these limita-
tions and standards. Information gathered in this review was
used, along with information from other sources as discussed
below, in the following specific areas:
- Introduction (Section III of each of the subcategory
supplements) - description of production processes and
the associated lubricants and wastewater streams.
74
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Subcategorization (Section IV of each of the subcategory
supplements) - identification of differences in manufac-
turing process technology and their potential effect on
associated wastewater streams.
Selection of Pollutant Parameters (Section VI) - infor-
mation regarding the toxicity and potential sources of
the pollutants identified in wastewater from nonferrous
metals manufacturing processes.
Control and Treatment Technology (Section VII) - infor-
mation on alternative controls and treatment and
corresponding effects on pollutant removal.
Costs (Section VIII) - formulation of the methodology
for determining the current capital and annual costs to
apply the selected treatment alternatives.
Existing Data. Previous EPA studies of the following nonferrous
metals manufacturing subcategories were reviewed.
Primary Aluminum
Secondary Aluminum
Primary Copper
Secondary Copper
Primary Lead
Primary Zinc
Miscellaneous Nonferrous Metals (Including Secondary Lead,
Columbium-Tantalum, Primary and Secondary Germanium,
Primary Magnesium, Primary Beryllium, and Secondary Zinc)
The available information included a summary of the category
describing the production processes, the wastewater characteris-
tics associated with the processes, recommended pollutant param-
eters requiring control; applicable end-of-pipe treatment tech-
nologies for wastewaters ; effluent characteristics resulting from
this treatment, and a background bibliography. Also included in
these studies were detailed production and sampling information
for many plants.
The concentration or mass loading of pollutant parameters in
wastewater effluent discharges are monitored and reported as
required by individual state agencies. These historical data are
available from NPDES monitoring reports.
Frequent contact has been maintained with industry personnel.
Contributions from these sources were particularly useful for
clarifying differences in production processes.
75
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Data Collection Portfolios. EPA conducted a survey of the
nonferrous metals manufacturing plants to gather information
regarding plant size, age and production, the production
processes used, and the quantity, treatment, and disposal of
wastewater generated at these plants. This information was
requested in data collection portfolios (dcp) mailed to all
companies known or believed to belong to the nonferrous metals
manufacturing category. A listing of the companies comprising
the nonferrous metals industry (as classified by standard
industrial code numbers) was compiled by consulting trade
associations and the U.S. Bureau of Mines.
In all, dcp were sent to 319 firms (416 plants). In many cases,
companies contacted were not actually members of the nonferrous
metals manufacturing category as it is defined by the Agency.
Where firms had nonferrous metals manufacturing operations at
more than one location, a dcp was returned for each plant.
If the dcp were not returned, information on production pro-
cesses, sources of wastewater and treatment technology at these
plants was collected by telephone interview. The information so
gathered was validated by sending a copy of the information
recorded to the party consulted. The informaton was assumed to
be correct as recorded if no reply was received in 30 days. In
total, more than 95 percent of the category was contacted either
by mail or by telephone.
A total of 314 dcp applicable to the nonferrous metals manufac-
turing category were returned. A breakdown of these facilities
by type of metal processed is presented in Table IIT-3.
The dcp responses were interpreted individually, and the follow-
ing data were documented for future reference and evaluation:
- Company name, plant address, and name of the contact
listed in the dcp.
- Plant discharge status as direct (to surface water),
indirect (to POTW), or zero discharge.
Production process streams present at the plant, as well
as associated flow rates; production rates; process
capacities; operating hours; wastewater treatment, reuse,
or disposal methods; and the quantity and nature of
process chemicals.
- Capital and annual treatment costs.
- Availability of pollutant monitoring data provided by the
plant.
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The summary listing of this information provided a consistent,
systematic method of evaluating and summarizing the dcp
responses. In addition, procedures were developed to simplify
subsequent analyses. The procedures developed had the following
capabilities:
Selection and listing of plants containing specific pro-
duction process streams or treatment technologies.
Summation of the number of plants containing specific
process waste streams and treatment combinations.
Calculation of the percent recycle present for specific
waste streams and summation of the number of plants
recycling these waste streams within various percent
recycle ranges.
Calculation of annual production values associated with
each process stream and summation of the number of plants
with these process streams having production values
within various ranges.
Calculation of water use and discharge from individual
process streams.
The calculated information and summaries were used in developing
these effluent limitations and standards. Summaries were used in
the category profile, evaluation of subcategorization, and analy-
sis of in-place treatment and control technologies. Calculated
information was used in the determination of water use and
discharge values for the conversion of pollutant concentrations
to mass loadings.
GENERAL PROFILE OF THE NONFERROUS METALS MANUFACTURING CATEGORY
The nonferrous metals manufacturing point source category encom-
passes the primary smelting and refining of nonferrous metals
(Standard Industrial Classification (SIC) 333) and the secondary
smelting and refining of nonferrous metals (SIC 334). The cate-
gory does not include the mining and concentrating of ores,
rolling, drawing, or extruding of metals, or scrap metal
collection and preliminary grading.
Nonferrous metal manufacturers include processors of ore concen-
trates or other virgin materials (primary) and processors of
scrap (secondary). Metals produced as by- or co-products of
primary metals are themselves considered primary metals. For
example, silver produced from primary copper anode slimes is
considered to be primary silver, rather than secondary.
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The nonferrous metals manufacturing category is quite complex and
the production process for a specific metal is dictated by the
characteristics of raw materials, and economics of by-product
recovery, as well as the chemistry of the metals. Some metals,
such as primary aluminum, are produced by essentially one pro-
cess, while others, like copper and zinc, may be produced either
pyrometallurgically or electrometallurgically. By-products and
co-products are also important considerations for some indus-
tries. Many nonferrous metals are co-products or by-products of
the smelting or refining of the base metals (copper, lead, and
zinc). For example, all or almost all of the domestic production
of arsenic, rhenium, palladium, selenium, and tellurium during
1975 was as a by-product or co-product of copper. About one-
third of all domestic production of silver and gold was a copper
by- or co-product. Copper itself is a by-product of lead, zinc,
silver, and gold production. Other metals, such as aluminum and
tungsten, are produced without important by-products. The
co-product or by-product metals leave the production facilities
where they were generated in a variety of forms and states of
refinement, i.e., as concentrates, as unrefined materials in the
form of slags, drosses, slimes or sludges, or as refined or
alloyed metals.
Base-metal residues are interchanged among copper, lead, and zinc
processors. Other metal-rich residues are shipped to centralized
processing facilities where they are selectively extracted and
refined. The production of co- or by-product nonferrous metals
generally involves relatively small operations.
Employment data are given in the dcp responses for 314 plants.
These plants report a total of 61,000 workers involved in non-
ferrous metals manufacturing Phase I plants. Industry production
figures show that the aluminum, copper, lead and zinc producers
dominate the industry in terms of tonnage.
One hundred and eighty plants (57 percent) indicated that no
wastewater from nonferrous metals manufacturing operations is
discharged to either surface waters or a POTW. Of the remaining
135, 76 (25 percent) discharge an effluent from nonferrous metals
manufacturing directly to surface waters, and 58 (18 percent)
discharge indirectly, sending nonferrous metals manufacturing
effluent through a POTW.
EPA recognizes that plants sometimes combine process and non-
process wastewater prior to treatment and discharge. Pollutant
discharge allowances will be established under this regulation
only for nonferrous metals manufacturing process wastewater, not
the nonprocess wastewaters. The flows and wastewater character-
istics are a function of the plant layout and water handling
practices. As a result, the pollutant discharge effluent
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limitation for nonprocess wastewater streams will be prepared by
the permitting authority. A discussion of how a permitter might
construct a permit for an integrated facility is presented in
Section IX, Building Blocks.
Section III of each of the subcategory supplements presents a
detailed profile of the plants in each subcategory and describes
the production processes involved. In addition, the following
specific information is presented:
1. Raw materials,
2. Manufacturing process,
3. Geographic locations of manufacturing plants,
4. Age of plants by discharge status,
5. Production ranges by discharge status, and
6. Summary of waste streams for each process.
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Table III-l
CURRENTLY PROMULGATED LIMITATIONS AND STANDARDS -
NONFERROUS METALS MANUFACTURING
Subcategory _BPT_ BAT _NSPS_ _PSES_ _POTS_
Primary Aluminum LS LS.FR LS,FR* — LS.FRl
Secondary Aluminum LS, PH ND LS.FR OS.pH.AS LS.FR
Primary Copper ND2 ND2.3
Smelting
Primary Electro- LS LS.FR2.3'4
lytlc Copper
Refining
LS
Secondary Copper
Primary Lead
Primary Zinc
Metallurgical Acid
Plant-n'*
ND2.3
ND2.3
LS
LS
ND2.3
ND2.3
LS.FR
--
Primary Tungsten
Primary Colurablum-
Tnntalum
Secondary Sliver
Secondary Lead
1 Includes additional flow reduction beyond BAT.
or settling pond.
3Allows a discharge, subject to concentration limitations for a flow equal to the
net monthly precipitation on the wastewater settling pond.
^Copper acid plants only; zinc and lead acid plants are currently covered In the
primary zinc and primary lead subcategorles.
LS =• lime precipitation and sedimentation.
FR - flow reduction.
ND - no discharge.
OS - oil skimming.
pH « pH adjustment.
AS = ammonia air stripping.
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Table III-2
NONFERROUS METALS CONSIDERED FOR REGULATION
UNDER PHASE II
Beryllium
Boron
Cesium
Cobalt
Gallium
Germanium
Gold
Primary Metals
Hafnium
Indium
Lithium
Magnesium
Mercury
Molybdenum
Nickel
Platinum Group
Rare Earths
Rhenium
Rubidium
Titanium
Uranium
Zirconium
Secondary Metals
Boron
Cobalt
Columbium
Germanium
Indium
Magnes ium
Mercury
Nickel
Plutonium
Precious Metals
Tin
Titanium
Tungsten
Uranium
Zinc
Bauxite Refining
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Table III-3
BREAKDOWN OF DCP RESPONDENTS BY TYPE. OF METAL PROCESSED
Subcategory Number of Plants
Primary Aluminum 31
Secondary Aluminum 55
Primary Copper Smelting 20
Primary Electrolytic Copper Refining 15
Secondary Copper 31
Primary Lead 7
Secondary Lead 69
Primary Zinc 7
Primary Tungsten 8
Primary Columbium-Tantalum 5
Secondary Silver 44
Metallurgical Acid Plants* 22
TOTAL 314
Information about acid plants was reported along with the
primary copper, lead and zinc plant responses indicated above,
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SECTION IV
INDUSTRY SUBCATEGORIZATION
Subcategorization should take Into account pertinent industry
characteristics, manufacturing process variations, wastewater
characteristics, and other factors. Effluent limitations and
standards establish mass limitations on the discharge of pollu-
tants which are applied, through the permit issuance process, to
specific dischargers. To allow the national standard to be
applied to a wide range of sizes of production units, the mass of
pollutant discharge must be referenced to a unit of production.
This factor is referred to as a production normalizing parameter
and is developed in conjunction with subcategorization.
Division of the category into subcategories provides a mechanism
for addressing process and product variations which result in
distinct wastewater characteristics. The selection of production
normalizing parameters provides the means for compensating for
differences in production rates among plants with similar prod-
ucts and processes within a uniform set of mass-based effluent
limitations and standards.
This subcategorization analysis is actually an ongoing process.
The first subcategories (bauxite refining, primary aluminum
smelting, and secondary aluminum smelting) were established in a
1973 Agency rulemaking. Since that time, some subcategories have
been modified. New subcategories have been added in 1975 and
then again in 1980.
A comprehensive analysis of each factor that might warrant sepa-
rate limitations for different segments of the industry has led
the Agency to propose the following subcategorization scheme for
proposal of BPT and BAT effluent limitations guidelines and PSNS,
PSES and NSPS:
1. Primary Aluminum Smelting
2. Secondary Aluminum Smelting
3. Primary Copper Smelting
4. Primary Copper Electrolytic Refining
5. Secondary Copper
6. Primary Lead
7. Primary Zinc
8. Metallurgical Acid Plants
9. Primary Tungsten
10. Primary Columbium/Tantalum
11. Secondary Silver
12. Secondary Lead
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Most of these subcategories are further segmented into subdivi-
sions for the development of effluent limitations; these subdivi-
sions are enumerated and discussed in the subcategory supplements
to this document.
SUBCATEGORIZATION BASIS
Technology-based effluent limitations are based primarily upon
the treatability of pollutants in wastewaters generated by the
category under review. The treatability of these pollutants is,
of course, directly related to the flow and characteristics of
the untreated wastewater, which in turn can be affected by fac-
tors inherent to a processing plant in the category. Therefore,
these factors and the degree to which each influences wastewater
flow and characteristics form the basis for subcategorization of
the category, i.e., those factors which have a strong influence
on untreated wastewater flow and characteristics are applied to
the category to subcategorize it in an appropriate manner.
The list of potential subcategorization factors considered for
the nonferrous metals manufacturing category include:
1. Metal products, co-products, and by-products;
2. Raw materials;
3. Manufacturing processes;
4. Product form;
5. Plant location;
6. Plant age;
7. Plant size;
8. Air pollution control methods;
9. Meteorological conditions;
10. Treatment costs;
11. Solid waste generation and disposal;
12. Number of employees;
13. Total energy requirements (manufacturing process and
waste treatment and control); and
14. Unique plant characteristics.
For the reasons discussed below, the metal or other products, the
raw materials, and the manufacturing process were discovered to
have the greatest influence on wastewater flow charateristics and
treatability, and thus ultimately on the appropriateness of
effluent limitations. These three factors were used to subcate-
gorize the category. As mentioned previously, further division
of some subcategories is warranted based on the sources of
wastewaters (manufacturing processes) within the plant. Each
manufacturing process generates differing amounts of wastewater
and in some instances specific waste streams contain pollutants
requiring preliminary treatment to reduce concentrations of oil
and grease, ammonia, cyanide, and toxic organics prior to com-
bined treatment. Thus, each subcategory is further subdivided
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based on the manufacturing processes used. These subdivisions
are discussed in the appropriate supplement.
Metal Products, Co-Products, and By-Products
The metal products, co-products, and by-products is the most
important factor in identifying subcategories for this category.
Subcategorizing on this basis is consistent with the existing
division of plants, i.e., plants are identified as (and identify
themselves as) zinc plants, lead plants, silver plants, etc. The
production of each metal is based on its own raw materials and
production processes, which directly affect wastewater volume and
charateristics.
Production and refining of metal by-products and co-products gen-
erally will be covered by means of separate subcategorizations,
and included in the nonferrous metals phase II. There are two
exceptions. EPA found that production of the co-product metals
columbium and tantalum are inherently allied, so both were con-
sidered in a single subcategory. EPA also found that production
of by-product cadmium cannot realistically be separated from
primary zinc production (due to the relatively small wastewater
volume and loadings from cadmium production), and so this waste-
water is included under the limitations and standards for primary
zinc.
Raw Materials
The raw materials used (ore concentrates or scrap) in nonferrous
metals manufacturing determine the reagents used, and to a large
extent the wastewater characteristics. Raw materials are signi-
ficant in differentiating between primary and secondary produc-
ers. It is therefore selected as a basis for subcategorization.
Manufacturing Processes
The production processes for each metal are unique and are
affected by the raw materials used and the type of end product.
The processes used will, in turn, affect the volume and charac-
teristics of the resulting wastewater.
The processes performed (or the air pollution controls used on
the process emissions) in the production of nonferrous metals
determine the amount and characteristics of wastewater generated
and thus are a logical basis for the establishment of subcatego-
ries. In this category, however, similar processes may be
applied to differing raw materials in the production of different
metals yielding different wastewater characteristics. For exam-
ple, copper, silver, and zinc may all be produced by electroly-
sis. As a result of these considerations, specific process
operation was not generally found to be suitable as a primary
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basts for subcategorization. However, process variations which
result in significant differences in wastewater generation are
reflected in the allowances for discrete unit operations within
each subcategory (see the discussion of building blocks in
Section IX).
In the case of primary copper manufacturing, the production
processes used are deemed to be a reasonable basis for subcate-
gorization, even though these processes are sometimes practiced
at a single site. This resulted in the establishment of the
primary copper smelting subcatgory and the primary copper elec-
trolytic refining subcategory (see Section IV of the Primary
Copper Supplement. This is consistent with the structure of the
category since smelting and refining are also often conducted at
different sites.
Product Form
This factor becomes important when the final product from a plant
is actually an intermediate that another plant purchases and pro-
cesses to render the metal in a different form. An example of
this is the production of tungsten, which some plants produce by
reducing ammonium paratungstate (APT), an intermediate that may
have been produced by another plant. This practice, however, is
not found to be common in the category and its effect on waste-
water volume and characteristics is not as significant as the
factors chosen.
Plant Location
Most plants in the category are located near raw materials
sources, transportation centers, markets, and sources of inex-
pensive energy. While larger primary copper, lead and zinc pro-
ducers are mainly found near Midwestern and Western ores and are
remote from population centers, plentiful and inexpensive elec-
tricity in the Pacific Northwest, the Tennessee Valley and
upstate New York is important for primary aluminum producers.
Secondary producers, on the other hand, are generally located in
or near large metropolitan areas. Therefore, primary producers
often have more land available for treatment systems than second-
ary producers. Plant location also may be significant because
evaporation ponds can be used only where solar evaporation is
feasible and where sufficient land is available. However, loca-
tion does not significantly affect wastewater characteristics or
treatability, and thus different effluent limitations are not
warranted based on this factor.
Plant Age
Plants within a given subcategory may have significantly differ-
ent ages in terms of initial operating year. To remain competi-
tive, however, plants must be constantly modernized.
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Plants may be updated by modernizing a particular component, or
by installing new components. For example, an old furnace might
be equipped with oxygen lances to increase the throughput, or
replaced entirely by a new, more efficient furnace. Moderniza-
tion of production processes and air pollution control equipment
produces analogous wastes among all plants producing a given
metal, despite the original plant start-up date. While the
relative age of a plant may be important in considering the eco-
nomic impact of a guideline, as a subcategorization factor it
does not account for differences in the raw wastewater character-
istics. For these reasons, plant age is not selected as a basis
for subcategorization.
Plant Size
The size of a plant generally does not affect either the^produc-
tion methods or the wastewater characteristics. Generally, more
water is used at larger plants. However, when water use and
discharge are normalized on a production basis, no major differ-
ences based on plant size are found within the same subcategory.
Thus, plant size is not selected as a basis for subcategoriza-
tion.
Air Pollution Control Methods
Many facilities use wet scrubbers to control emissions which
influence wastewater characteristics. In some cases, the type of
air pollution control equipment used provides a basis for regula-
tion, because if wet air pollution control is used, an allowance
may be necessary for that waste stream, while a plant using only
dry systems does not need an allowance for a non-existent waste
stream. Therefore, this factor is often selected as a basis for
subdivision within some subcategories (i.e., developing an allow-
ance for this unit operation as part of the limitation or stan-
dard for the subcategory), but not as a means for subcategonzing
the category.
Meteorological Conditions
Climate and precipitation may affect the feasibility of certain
treatment methods, e.g., solar evaporation through the use of
impoundments is a feasible method of wastewater treatment only in
areas of net evaporation. This factor was not selected for
subcategorization, however, because plants in the category are
located in areas having widely varying meteorological conditions.
The differences in wastewater characteristics and treatability
are better explained by other factors such as metal products and
manufacturing processes, and thus different effluent limitations
based on this factor are not warranted.
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Solid Waste Generation and Disposal
Physical and chemical characteristics of solid waste generated by
the nonferrous metals category are determined by the raw mate-
rial, process, and type of air pollution control in use. There-
fore, this factor does not provide a primary basis for subcatego-
rization.
Number of Employees
The number of employees in a plant does not directly provide a
basis for subcategorization because the number of employees does
not necessarily reflect the production or process water usage
rate at any plant. Because the amount of process wastewater
generated is related to che production rates rather than employee
number, the number of employees does not provide a definitive
relationship to wastewater generation.
Total Energy Requirements
Total energy requirements was not selected as a basis for sub-
categorization primarily because energy requirements are found to
vary widely within this category and are not meaningfully related
to wastewater generation and pollutant discharge. Additionally,
it is often difficult to obtain reliable energy estimates spe-
cifically for production and waste treatment*. When available,
estimates are likely to include other energy requirements such as
lighting, air conditioning, and heating or cooling energy.
Unique Plant Characteristics
Unique plant characteristics such as land availability and water
availability do not provide a proper basis for subcategorization
because they do not materially affect the raw wastewater charac-
teristics of the plant. Process water availability may indeed be
a function of the geography of a plant. However, the impact of
limited water supplies is to encourage conservation by recycle
and efficient use of water. As explained in Section VII, this is
consistent with EPA's approach to establishing limitations for
all plants. Therefore, insufficient water availability only
tends to encourage the early installation of practices that EPA
believes are advisable for the entire category in order to reduce
treatment costs and improve pollutant removals.
Limited land availability for constructing a waste treatment
facility may affect the economic impact of an effluent limita-
tion. The availability of land for treatment, however, is gen-
erally not a major issue in the nonferrous metals manufacturing
category. Most primary plants are located on very large sites
and land availability would not be a factor. While secondary
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producers tend to be located in more urban settings, the amount
of land available to them for treatment is sufficient for the
types of treatment and control technologies considered.
PRODUCTION NORMALIZING PARAMETERS
To ensure equitable regulation of the category, effluent guide-
lines limitations and standards of performance are established on
a production-related basis, i.e., a mass of pollutant per unit of
production. In addition, by using these mass-based limitations,
the total mass of pollutants discharged is minimized. The under-
lying premise for mass-based limitations is that pollutant load-
ings and water discharged from each process are correlated to the
amount of material produced on that process. This correlation is
calculated as the mass of pollutant or wastewater discharged per
unit of production. The units of production are known as produc-
tion normalizing parameters (PNPs). The type and value of the
PNPs vary according to the subcaregory or subdivision. In one
case it may be the total mass of metal produced from that line
while in others it may be some other characteristic parameter.
Two criteria are used in selecting the appropriate PNP for a
given subcategory or subdivision: (1) maximizing the degree of
correlation between the production of metal reflected by the PNP
and the corresponding discharge of pollutants, and (2) ensuring
that the PNP is easily measured and feasible for use in
establishing regulations.
The production normalizing parameter identified for each subcate-
eory or subdivision, and the rationale used in selection are dis-
cussed in detail in Section IV of the appropriate supplements.
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SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section presents the data collection and data analysis
methods used for characterizing water use and wastewater associ-
ated with the nonferrous metals manufacturing category. Raw
waste and treated effluent sample data, and production normalized
water use and wastewater discharge data are presented for each
subcategory in Section V of each of the subcategory supplements.
DATA SOURCES
Historical Data
A useful source of long-term or historical d*ta * i
nonferrous metals manufacturing plants are the £ls.?harfe J
ine Reports (DMR's) completed as a part of the National Pollutant
Sfchlrge Elimination System (NPDES). All applicable DMR's were
obtained through the EPA regional offices and state regulatory
agencies for the year 1976, the last complete year for which
information was available at the time of the initial data collec-
tion for this category. (EPA intends to collect additional more
recent DMR data for some plants between proposal and promulgation
in order to supplement data submitted during the comment period).
The DMR's present a summary of the analytical results from a
se?ieTof samples taken during a given month for the pollutants
designated in the plant's permit. In general, minimum maximum,
and Iverage values, in mg/1 or Ibs/day, are presented for such
pollutant! as total suspended solids, aluminum oil and grease
pH copper, and zinc. The samples are collected from the plant
outfall(s) which represents the discharge(s) from the plant.
?or facilities with wastewater treatment, the DMR's Provide a
measure of the performance of the treatment system. In theory
?hele data could then serve as a basis for characterizing treated
wastewater from nonferrous metals manufacturing plants; however,
thlre is no influent to treatment information (i.e., paired
influent-effluent data) and too little information on the per-
formance of the plant at the time the samples were collected to
be ?he preferred source of data in formulating achievable perfor-
mance for various types of treatment. They do serve as a set of
data that can be used to verify the technology performances pre-
sented in Section VII, Control and Treatment Technology (Table
VII -19, p. 307).
Data Collection Portfolios
were added to the data base
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Data supplied by dcp responses were evaluated, and two flow-to-
production ratios were calculated for each stream in each
subcategory. The two ratios, water use and wastewater discharge
flow, are differentiated by the flow value used in calculation.
Water use is defined as the volume of water or other fluid
required for a given process per mass of metal product and is
therefore based on the sum of recycle and make-up flows to a
given process. Wastewater flow discharged after pretreatment or
recycle (if these are present) is used in calculating the
production normalized flow—the volume of wastewater discharged
from a given process to further treatment, disposal, or discharge
per mass of metal produced. Differences between the water use
and wastewater flows associated with a given stream result from
recycle, evaporation, and carryover on the product. The produc-
tion values used in calculation correspond to the production
normalizing parameter, PNP, assigned to each stream, as outlined
in Section IV of each of the subcategory supplements.
The production normalized water use and discharge flows were
compiled and summarized by stream type (i.e., flows associated
with discrete unit operations). The flows are presented in
Section V of each of the subcategory supplements. Where appro-
priate, an attempt was made to identify factors that could
account for variations in water use. Concentration data result-
ing from samples collected during sampling visits were also
compiled and summarized for each waste stream. They can also be
found in Section V of the subcategory supplements. BPT, BAT,
NSPS, BCT, and pretreatment discharge flows are selected for use
in calculating the effluent limitations and standards in Sections
IX, X, XI, XII, and XII of each of the subcategory supplements.
The regulatory production normalized discharge flows were also
used to estimate flows at nonferrous metals manufacturing plants
that supplied EPA with only production data in their dcp. Actual
discharge flows or estimated flows, when an actual flow was not
reported in the dcp, were then used to determine the cost of
various wastewater treatment options at these facilities (see
Section VIII).
Sampling and Analysis Program
The sampling and analysis program discussed in this section was
undertaken primarily to implement the requirements of the 1977
amendments to the Act and of the Settlement Agreement, and to
identify pollutants of concern in the nonferrous metals manufac-
turing point source category, with emphasis on toxic pollutants.
EPA and its contractors collected and analyzed samples from 46
nonferrous metals manufacturing facilities.
This section summarizes the purpose of the sampling trips and
identifies the sites sampled and parameters analyzed. It also
presents an overview of sample collection, preservation, and
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transportation techniques. Finally, it describes the pollutant
parameters quantified, the methods of analyses and laboratories
used, the detectable concentration of each pollutant, and the
general approach used to ensure the reliability of the analytical
data produced.
Site Selection. Information gathered in the data collection
portfolios was used to select sites for wastewater sampling for
each subcategory. The plants sampled were selected to be repre-
sentative of the category. Considerations included how well each
facility represented the subcategory as indicated by available
data, potential problems in meeting technology-based standards,
differences in production processes used, number and variety of
unit operations generating wastewater, and wastewater treatment
in place. Additional details on site selection are presented in
Section V of each of the subcategory supplements.
Field Sampling. After selection of the plants to be sampled,
each plant was contacted by telephone, and a letter of notifica-
tion was sent to each plant as to when a visit would be expected.
These inquiries led to acquisition of facility information neces-
sary for efficient on-site sampling. The information resulted in
selection of the sources of wastewater to be sampled at each
plant. The sample points included, but were not limited to,
untreated and treated discharges, process wastewater, and par-
tially treated wastewater.
During this program, 36 nonferrous metals manufacturing plants
were sampled by the technical contractor and 10 nonferrous metals
manufacturing plants (mine/mill/smelter complexes) were sampled
by other contractors or by EPA regional personnel, for a total of
46 plants. The distribution of these plants by subcategory is
presented in Table V-l.
Wastewater samples were collected in two phases: screening and
verification. The purpose of the first phase, screen sampling,
was to identify which toxic pollutants were present in the
wastewaters from production of the various metals. Screening
samples were analyzed for 128 of the 129 toxic pollutants and
other pollutants deemed appropriate. (Because an analytical
standard for TCDD was judged to be too hazardous to be made
generally available, samples were never analyzed for this pollu-
tant. There is no reason to believe that it would be present in
nonferrous metal category wastewaters.) A total of 10 plants
were selected for screen sampling. Some plants represent opera-
tions from more than one subcategory. At least one plant in
every subcategory was sampled during the screening phase. Two
plants were sometimes screen sampled within a subcategory because
the production process was different. For example, both
pyrolytic and electrolytic plants were screen sampled in the
primary zinc category.
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The second phase of sampling, verification sampling, was used Co
determine whether the pollutants identified by screen sampling
are present throughout a subcategory, and if so, at what concen-
trations. The samples gathered under the verification sampling
were analyzed only for those pollutants selected from the
screening results.
To reduce the volume of data handled, avoid unnecessary expense,
and direct the scope of the sampling program, a number of the
pollutants analyzed for during the screen sampling were not
analyzed for during the verification sampling. Three sources of
information were used for the verification pollutant selection:
the pollutants that plant personnel believes or knows are present
in their wastewater, the screen sampling analyses, and the pollu-
tants the Agency believes should be present after studying the
processes and materials used by the category. If a pollutant was
not detected during screen sampling, and if plant personnel and
the Agency did not believe it might be present in the wastewater
after studying the processes and materials used, verification
analyses for that pollutant were not performed.
On the data collection portfolio, the 129 toxic pollutants were
listed and each facility was asked to indicate for each particu-
lar pollutant "Known to be Present" (KTBP), "Believed to be
Present" (BTBP), "Believed to be Absent" (BTBA), or "Known to be
Absent" (KTBA). If the pollutant had been analyzed for and
detected, the facility was to indicate KTBP, if analyzed for and
not detected, KTBA. If the pollutant had not been analyzed, but
might be present in the wastewater, the facility was to indicate
BTBP, if it could not be present, BTBA. The reported results are
tabulated in Section V of each of the subcategory supplements.
After considering the available information, it was determined
that analysis of the volatile acid fraction of the toxic organic
pollutants could be discontinued for all subcategories in the
verification phase. None of these compounds were detected in
analysis of screening samples, information gathered from dcp
responses and an evaluation of the production processes and raw
materials. Other pollutants which were dropped from the verifi-
cation sample analysis for specific subcategories are discussed
in Section V of each of the subcategory supplements.
Sample Collection, Preservation, and Transportation. Collection,
preservation, and transportation of samples were accomplished in
accordance with procedures outlined in Appendix III of "Sampling
and Analysis Procedures for Screening of Industrial Effluents for
Priority Pollutants" (published by the Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio, March 1977, revised,
April 1977) and in "Sampling Screening Procedure for the
Measurement of Priority Pollutants" (published by the EPA
Effluent Guidelines Division, Washington, D.C., October 1976).
The procedures are summarized in the paragraphs that follow.
94
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Whenever practical, all samples collected at each sampling point
were taken from mid-channel at mid-depth in a turbulent, well-
mixed portion of the waste stream. Periodically, the temperature
and pH of each waste stream sampled were measured on-site.
Each large composite (Type 1) sample was collected in a new
11.4-liter (3-gallon), narrow-mouth glass jug that had been
washed with detergent and water, rinsed with tap water, rinsed
with distilled water, rinsed with methylene chloride, and air
dried at room temperature in a dust-free environment.
Before collection of Type 1 samples, new Tygon* tubing was cut to
minimum lengths and installed on the inlet and outlet (suction
and discharge) fittings of the automatic sampler. Two liters
(2.1 quarts) of blank water, known to be free of organic com-
pounds and brought to the sampling site from the analytical
laboratory, were pumped through the sampler and its attached tub-
ing into the glass jug; the water was then distributed to cover
the interior of the jug and subsequently discarded.
A blank was produced by pumping an additional 3 liters (0.8 gal)
of blank water through the sampler, distributed inside the glass
jug, and poured into a 3.8 liter (1 gal) sample bottle that had
been cleaned in the same manner as the glass jug. The blank
sample was sealed with a Teflon®-lined cap, labeled, and packed
in ice in a plastic foam-insulated chest. This sample subse-
quently was analyzed to determine any contamination contributed
by the automatic sampler.
During collection of each Type 1 sample, the glass jug was packed
in ice in a separate plastic foam-insulated container. After the
complete composite sample had been collected, it was mixed to
provide a homogeneous mixture, and two 0.95-liter (1 quart)
aliquots were removed for metals analysis and placed in new
labeled plastic 0.95-liter bottles which had been rinsed with
distilled water. One of these 0.95-liter aliquots was sealed
with a Teflon«-lined cap; placed in an iced, insulated chest to
maintain it at 4°C (39°F), and shipped by air for plasma-arc
metal analysis. Initially, the second sample was stabilized by
the addition of 5 ml (0.2 ounce) of concentrated nitric acid,
capped and iced in the same manner as the first, and shipped by
air to the contractor's facility for atomic-absorption metal
analysis.
Because of subsequent EPA notification that the acid pH of the
stabilized sample fell outside the limits permissible under
Department of Transportation regulations for air shipment,
stabilization of the second sample in the field was discontinued.
Instead, this sample was acid-stabilized at the analytical
laboratory.
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After removal of the two 0.95-liter (1 quart) metals altquots
from the composite sample, the balance of the sample in the
11.4-liter (3 gallon) glass jug was subdivided for analysis of
nonvolatile organics, asbestos, conventional, and nonconventional
parameters. If a portion of this 7.7-liter (2 gallon) sample was
requested by a plant representative for independent analysis, a
0.95-liter (1 quart) aliquot was placed in a sample container
supplied by the representative.
Sample Types 2 (cyanide) and 3 (total phenol) were stored in new
bottles which had been iced and labeled, 1-liter (33.8 ounce)
clear plastic bottles for Type 2, and 0.47-liter (16 ounce) amber
glass for Type 3. The bottles had been cleaned by rinsing with
distilled water, and the samples were preserved as described
below.
To each Type 2 (cyanide) sample, sodium hydroxide was added as
necessary to elevate the pH to 12 or more (as measured using pH
paper). Where the presence of chlorine was suspected, the sample
was tested for chlorine (which would decompose most of the
cyanide) by using potassium iodide/starch paper. If the paper
turned blue, ascorbic acid crystals were slowly added and dis-
solved until a drop of the sample produced no change in the color
of the test paper. An additional 0.6 gram (0.021 ounce) of
ascorbic acid was added, and the sample bottle was sealed (by a
Teflon»-lined cap), labeled, iced, and shipped for analysis.
To each Type 3 (total phenol) sample, phosphoric acid was added
as necessary to reduce the pH to 4 or less (as measured using pH
paper). Then, 0.5 gram (0.018 ounce) of copper sulfate was added
to kill bacteria, and the sample bottle was sealed (by a
Teflon«-lined cap), labeled, iced, and shipped for analysis.
Each Type 4 (volatile organics) sample was stored in a new 125-ml
(4.2 ounce) glass bottle that had been rinsed with tap water and
distilled water, heated to 105°C (221°F) for one hour, and
cooled. This method was also used to prepare the septum and lid
for each bottle. Each bottle, when used, was filled to overflow-
ing, sealed with a Teflon«-faced silicone septum (Teflon® side
down) and a crimped aluminum cap, labeled, and iced. Hermetic
sealing was verified by inverting and tapping the sealed con-
tainer to confirm the absence of air bubbles. (If bubbles were
found, the bottle was opened, a few additional drops of sample
were added, and a new seal was installed.) Samples were main-
tained hermetically sealed and iced until analyzed.
Sample Analysis. Samples were sent by air to contract labora-
tories. An aliquot of each metal sample received by contract
laboratory was sent to EPA's Chicago laboratory for inductively
coupled argon plasma emission spectrophotometry (ICAP) analysis;
while the contract laboratory retained an aliquot for atomic
96
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absorption spectrophotometry (AA). Twenty-two metals were
analyzed by ICAP, and five metals were analyzed by AA, as
follows:
Metals Analyzed by ICAP
Calcium Copper
Magnesium Iron
Sodium Manganese
Silver Molybdenum
Aluminum Nickel
Boron Lead
Barium Tin
Beryllium Titanium
Cadmium Vanadium
Cobalt Ytrium
Chromium Zinc
Metals Analyzed by AA
Antimony
Arsenic
Selenium
Silver
Thallium
Several of these metals analyzed by ICAP are not among the 129
toxic pollutants specified in the settlement agreements. They
are considered, however, because they consume lime and increase
sludge production in wastewater treatment facilities.
Mercury was analyzed by a special technique: the manual cold
vapor flameless atomic adsorption spectrometry technique.
Samples were also analyzed for asbestos by transmission electron
microscopy. Total fiber and chrysotile fiber counts were
reported by the testing laboratory. Chrysotile was chosen by the
Agency as the screening parameter for asbestos for mining related
activities because: (1) of its known toxicity when particles are
inhaled, (2) its industrial prevalance, (3) its distinguishing
selected area electron diffraction (SAED) pattern, and (4) the
cumbersome nature of the transmission electron microscopic (TEM)
analysis technique limits the identification to one mineral form
at the present time due to economics and time constraints.
While the asbestos data vary, the testing laboratory's report
indicates that when the total fiber count is performed in con-
junction with a count of chrysotile fibers a good initial screen-
ing parameter is produced. The report recommends re-examining
any facility with chrysotile fiber counts greater than 100
million fibers/liter (MFL) because this represents a significant
97
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departure from ambient counts of 3 MFL in the Great Lakes Basin.
The technique used had a threshold of detection of 0.22 MFL.
Wastewater samples from the plants sampled in the screening phase
were analyzed for asbestos. The verification phase wastewater
samples were not analyzed for asbestos.
Verification samples also went to EPA contract laboratories for
organics analysis or when metal analysis was performed by AA.
Since metals analysis of screening samples was complete before
verification metals analysis began, the samples were analyzed
only for metals shown to be significant in the nonferrous metals
manufacturing category or those expected to consume large amounts
of lime.
Due to their very similar physical and chemical properties, it is
extremely difficult to separate the seven polychlorinated
biphenyls (pollutants 106 to 112) for analytical identification
and quantification. For that reason, the concentrations of the
polychlorinated biphenyls are reported by the analytical
laboratory in two groups: one group consists of PCB-1242,
PCB-1254, and PCB-1221; the other group consists of PCB-1232,
PCB-1248, PCB-1260, and PCB-1016. For convenience, the first
group will be referred to as PCB-1254 and the second as PCB-1248.
The samples were not analyzed for Pollutant 129, 2,3,7,8-tetra-
chlorodibenzo-p-dioxin (TCDD) because no authentic reference sam-
ple was available to the analytical laboratory.
Three of the five conventional pollutants parameters were
selected for analysis for use in developing BCT and for evaluat-
ing treatment system performance. They are total suspended
solids (TSS), oil and grease, and pH. The other two conven-
tionals, fecal coliform and biochemical oxygen demand (BOD), were
not analyzed because there is no reason to believe that fecal
matter or oxygen demanding materials would be present. Ammonia,
fluoride, and total phenolics (4-AAP) were analyzed for in
selected samples if there was reason to believe they would be
present based on the processes used. While not classified as
toxic pollutants, they affect the water quality. Chemical oxygen
demand (COD) and total organic carbon (TOC) were also selected
for analysis for selected samples for subsequent use in evaluat-
ing treatment system performance. Total dissolved solids (TDS)
was analyzed to evaluate the potential for accumulation of
dissolved salts.
In addition, aluminum, calcium, magnesium, alkalinity, total dis-
solved solids, and sulfate were measured to provide data to
evaluate the cost of lime and settle treatment of certain waste-
water streams.
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The analytical quantification limits used in evaluation of the
sampling data reflect the accuracy of the analytical methods
used. Below these concentrations, the identification^ of the
individual compounds is possible, but quantification is diffi-
cult. Pesticides and PCB's can be analytically quantified at
concentrations above 0.005 mg/1, and other organic toxics at
concentrations above 0.010 mg/1. Analytical quantification
limits associated with toxic metals are as follows: 0.100 mg/1
for antimony; 0.10 mg/1 for arsenic; 10 MFL for asbestos; 0.010
mg/1 for beryllium; 0.002 mg/1 for cadmium; 0.005 mg/1 for
chromium; 0.009 mg/1 for copper; 0.100 mg/1 for cyanide; 0.02
mg/1 for lead; 0.0001 mg/1 for mercury; 0.005 mg/1 for nickel;
0.010 mg/1 for selenium; 0.020 mg/1 for silver; 0.100 mg/1 for
thallium; and 0.050 mg/1 for zinc.
These detection limits are not the same as published detection
limits for these pollutants by the same analytical methods (40
CFR Part 136 - Guidelines Establishing Test Procedures for the
Analysis of Pollutants; 40 CFR Part 136 - Proposed, 44 FR 69464,
December 3, 1979; 1982 Annual Book of ASTM Standards, Part 31,
Water, ASTM, Philadelphia, PA; Methods for Chemical Analysis of
Water and Wastes, Environmental Monitoring and Support Labora-
tory Office of Research and Development, U.S. EPA Cincinnati,
OH, March, 1979, EPA-600 4-79-020; Handbook for Monitoring Indus-
trial Wastewater, U.S. EPA Technology Transfer, August, 1973).
The detection limits used were reported with the analytical data
and hence are the appropriate limits to apply to the data.
Detection limit variation can occur as a result of a number of
laboratory-specific, equipment -specif ic , and daily operator-
specific factors. These factors can include day-to-day differ-
ences in machine calibration, variation in stock solutions, and
variation in operators.
Quality Control. Quality control measures used in performing all
analyses conducted for this program complied with the guidelines
given in "Handbook for Analytical Quality Control in Water and
Wastewater Laboratories" (published by EPA Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio, 197b;. As
part of the daily quality control program, blanks (including
sealed samples of blank water carried to each sampling site and
returned unopened, as well as samples of blank water used in the
field), standards, and spiked samples were routinely analyzed
with actual samples. As part of the overall program, all
analytical instruments (such as balances, spectrophotometers, and
recorders) were routinely maintained and calibrated.
The atomic -absorption spectrometer used for metal analysis ^
checked to see that it was operating correctly and performing
within expected limits. Appropriate standards were included
after at least every 10 samples. Also, approximately 15 percent
of the analyses were spiked with distilled water to assure
99
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recovery of the metal of interest. Reagent blanks were analyzed
for each metal, and sample values were corrected if necessary.
WATER USE AND WASTEWATER CHARACTERISTICS
In each of the subcategory supplements, wastewater characteris-
tics corresponding to the subcategories in the nonferrous metals
manufacturing category are presented and discussed. Tables are
presented in Section V of each of the subcategory supplements
which present the sampling program data for raw waste and treated
effluent sampled streams. For those pollutants detected above
analytically quantifiable concentrations in any sample of a given
wastewater stream, the actual analytical data is presented.
Where no data is listed for a specific day of sampling, it
indicates that the wastewater samples for the stream were not
collected.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. The base neu-
trals, acid fraction, and volatile organics are considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
Below this level, organic analytical results are not quantita-
tively accurate; however, the analyses are useful to indicate the
presence of a particular pollutant. Nonquantifiable results are
designated in the tables with an asterisk (double asterisk for
pesticides).
When calculating averages from the organic sample data, non-
quantifiable results were assumed to be zero. Organics data
reported as not detected (ND) are not averaged. For example,
three samples reported as ND, *, 0.021 mg/1 would average as
0.010 mg/1.
100
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Table V-l
DISTRIBUTION OF SAMPLED PLANTS IN THE NONFERROUS METALS
MANUFACTURING CATEGORY BY SUBCATEGORY
Total Number of Plants
Number of Sampled by Other
Plants Contractors or
Subcateeorv Sampled EPA Regions
ij H u \f CL I- ^* p ^ ** .7
Primary Aluminum
Secondary Aluminum
Primary Copper
Secondary Copper
Primary Lead
Secondary Lead
Primary Zinc
Primary Tungsten
Primary Co lumbium -Tantalum
Secondary Silver
Metallurgical Acid Plants*
TOTAL
6 2
5
4 2
5
3 3
6 1
5 2
4
4
4
^ —
46 10
Number
of Plants
Screened
Sampled
1
1
-
2
-
1
2
1
1
1
—
10
Number
of Plants
Verification
Sampled
3
4
2
3
—
4
1
3
3
3
—
26
*Acid plant wastewater samples were collected at the primary copper, lead, and zinc
plants listed above.
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Section VI
SELECTION OF POLLUTANT PARAMETERS
The Agency has studied nonferrous metals manufacturing waste-
waters to determine the presence or absence of toxic, conven-
tional and selected nonconventional pollutants. The toxic
pollutants and nonconventional pollutants are subject to BAT
effluent limitations and guidelines. Conventional pollutants are
considered in establishing BPT, BCT, and NSPS limitations.
One hundred and twenty-nine toxic pollutants (known as the 129
priority pollutants) were studied pursuant to the requirements of
the Clean Water Act of 1977 (CWA). These pollutant parameters,
which are listed in Table VI-1, are members of the 65 pollutants
and classes of toxic pollutants referred to in Section 307(a)(1)
of the CWA.
From the original list of 129 pollutants, three pollutants have
been deleted in two separate amendments to 40 CFR Subchapter N,
Part 401. Dichlorodifluoromethane and trichlorofluoromethane
were deleted first (46 FR 2266, January 8, 1981) followed by the
deletion of bis-(chloromethyl) ether (46 FR 10723, February 4,
1981). The Agency has concluded that deleting these compounds
will not compromise adequate control over their discharge into
the aquatic environment and that no adverse effects on the
aquatic environment or on human health will occur as a result of
deleting them from the list of toxic pollutants.
Past studies by EPA and others have identified many nontoxic pol-
lutant parameters useful in characterizing industrial wastewaters
and in evaluating treatment process removal efficiencies. For
this reason, a number of nontoxic pollutants were also studied
for the nonferrous metals manufacturing category.
EPA has defined the criteria for the selection of conventional
pollutants (43 FR 32857 January 11, 1980). These criteria are:
1. Generally those pollutants that are naturally occurring,
biodegradable; oxygen-demanding materials, and solids that have
characteristics similar to naturally occuring, biodegradable sub-
stances; or,
2. Include those classes of pollutants that traditionally have
been the primary focus of wastewater control.
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The conventional pollutants considered in this rulemaking (total
suspended solids, oil and grease, and pH) traditionally have been
studied to characterize industrial wastewaters. These parameters
impact water quality and are especially useful in evaluating the
effectiveness of some wastewater treatment processes.
Several nonconventional pollutants were also considered in devel-
oping these regulations. These included aluminum, chemical oxy-
gen demand (COD), and total organic carbon (TOG). In addition,
calcium, magnesium, alkalinity, total dissolved solids and
sulfate were measured to provide data to evaluate the cost of
chemical precipitation and sedimentation treatment of certain
jwastewater streams.
Fluoride, ammonia (NH3> and total phenolics (4-AAP) were also
identified as pollutants for some of the subcategories. Fluoride
compounds are used in the production of primary aluminum and
columbium-tantalum and are present in the raw wastewater of these
industries. In the primary and secondary aluminum, secondary
lead, secondary silver, primary columbium-tantalum, and primary
tungsten subcategories, NH3 is used in the process or formed
during a process step. In other subcategories, it has been used
for neutralization of the wastewater.
RATIONALE FOR SELECTION OF POLLUTANT PARAMETERS
In determining which pollutants to regulate, a pollutant^that was
never detected, or that was never found above its analytical
quantification level, was eliminated from consideration. The
analytical quantification level for a pollutant is the minimum
concentration at which that pollutant can be reliably measured.
Below that concentration, the identification of the individual
compounds is possible, but quantification is difficult. For the
toxic pollutants in this study, the analytical quantification
levels are: 0.005 mg/1 for pesticides, PCB's, chromium, and
nickel; 0.010 mg/1 for the remaining organic toxic pollutants and
cyanide, arsenic, beryllium, and selenium; 10 million fibers per
liter (10 MFL) for asbestos; 0.020 mg/1 for lead and silver;
0.009 mg/1 for copper; 0.002 mg/1 for cadmium; and 0.0001 mg/1
for mercury.
These detection limits are not the same as published detection
limits for these pollutants by the same analytical methods. The
detection limits used were reported with the analytical data and
hence are the appropriate limits to apply to the data. Detection
limit variation can occur as a result of a number of laboratory-
specific, equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
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Because the analytical standard for TCDD was judged to be too
hazardous to be made generally available, samples were never
analyzed for this pollutant. There is no reason to expect that
TCDD would be present in nonferrous metals manufacturing
wastewaters.
Pollutants which were detected below concentrations considered
achievable by available treatment technology were also eliminated
from further consideration. For the toxic metals, the chemical
precipitation, sedimentation, and filtration technology treata-
bility values, which are presented in Section VII (Table VII-22)
were used. For the toxic organic pollutants detected above their
analytical quantification limit, achievable concentrations for
activated carbon technology were used. These concentrations
represent the most stringent treatment options considered for
pollutant removal.
The pollutant exclusion procedure was applied to the raw waste
data for each subcategory. Detailed specific results are pre-
sented in Section VI of each of the subcategory supplements.
Summary results of selected pollutants for each subcategory are
presented later in this section.
Toxic pollutants remaining after the application of the exclusion
process were then selected for further consideration in estab-
lishing specific regulations.
DESCRIPTION OF POLLUTANT PARAMETERS
The following discussion addresses the pollutant parameters
detected above their analytical quantification limit in any
sample of nonferrous metals manufacturing wastewater. The
description of each pollutant provides the following information:
the source of the pollutant; whether it is a naturally occuring
element, processed metal, or manufactured compound; general
physical properties and the form of the pollutant; toxic effects
of the pollutant in humans and other animals; and behavior of the
pollutant in a POTW at concentrations that might be expected from
industrial discharges.
Acenaphthene (1). Acenaphthene (1,2-dihydroacenaphthylene, or
1,8-ethylene-naphthalene) is a polynuclear aromatic hydrocarbon
(PAH) with molecular weight of 154 and a formula of C^HlO-
Acenaphthene occurs in coal tar produced during high temperature
coking of coal. It has been detected in cigarette smoke and
gasoline exhaust condensates.
The pure compound is a white crystalline solid at room tempera-
ture with a melting range of 95 C to 97°C and a boiling range of
278°C to 280°C. Its vapor pressure at room temperature is less
105
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than 0.02 mm Hg. Acenaphthene is slightly soluble in water (100
mg/1), but even more soluble in organic solvents such as ethanol,
toluene, and chloroform. Acenaphthene can be oxidized by oxygen
or ozone in the presence of certain catalysts. It is stable
under laboratory conditions.
Acenaphthene is used as a dye intermediate, in the manufacture of
some plastics, and as an insecticide and fungicide.
So little research has been performed on acenaphthene that its
mammalian and human health effects are virtually unknown. The
water quality criterion of 0.02 mg/1 is recommended to prevent
the adverse effects on humans due to the organoleptic properties
of acenaphthene in water.
No detailed study of acenaphthene behavior in a POTW is avail-
able. However, it has been demonstratd that none of the organic
toxic pollutants studied so far can be broken down by biological
treatment processes as readily as fatty acids, carbohydrates, or
proteins. Many of the toxic pollutants have been investigated,
at least in laboratory-scale studies, at concentrations higher
than those expected to be contained by most municipal waste-
waters. General observations relating molecular structure to
ease of degradation have been developed for all of the toxic
organic pollutants.
The conclusion reached by study of the limited data is that bio-
logical treatment produces little or no degradation of acenaph-
thene. No evidence is available for drawing conclusions about
its possible toxic or inhibitory effect on POTW operation.
Its water solubility would allow acenaphthene present in the
influent to pass through a POTW into the effluent. The hydrocar-
bon character of this compound makes it sufficiently hydrophobic
that adsorption onto suspended solids and retention in the sludge
may also be a significant route for removal of acenaphthene from
the POTW.
Acenaphthene has been demonstrated to affect the growth of plants
through improper nuclear division and polyploidal chromosome
number. However, it is not expected that land application of
sewage sludge containing acenaphthene at the low concentrations
which are to be expectd in a POTW sludge would result in any
adverse effects on animals ingesting plants grown in such soil.
Benzene (4). Benzene (CfcHg) is a clear, colorless liquid
obtained mainly from petroleum feedstocks by several different
processes. Some is recovered from light oil obtained from coal
carbonization gases. It boils at 80°C and has a vapor pressure
106
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of 100 mm Hg at 26°C. It is slightly soluble in water (1.8 g/1
at 25°C) and it dissolves in hydrocarbon solvents. Annual U.S.
production is three to four million tons.
Most of the benzene used in the U.S. goes into chemical manufac-
ture. About half of that is converted to ethylbenzene which is
used to make styrene. Some benzene is used in motor fuels.
Benzene is harmful to human health according to numerous pub-
lished studies. Most studies relate effects of inhaled benzene
vapors. These effects include nausea, loss of muscle coordina-
tion, and excitement, followed by depression and coma. Death is
usually the result of respiratory or cardiac failure. Two spe-
cific blood disorders are related to benzene exposure. One of
these, acute myelogenous leukemia, represents a carcinogenic
effect of benzene. However, most human exposure data is based on
exposure in occupational settings and benzene carcinogenisis is
not considered to be firmly established.
Oral administration of benzene to laboratory animals produced
leukopenia, a reduction in mumber of leukocytes in the blood.
Subcutaneous injection of benzene-oil solutions has produced sug-
gestive, but not conclusive, evidence of benzene carcinogenisis.
Benzene demonstrated teratogenic effects in laboratory animals,
and mutagenic effects in humans and other animals.
For maximum protection of human health from the potential carcin-
ogenic effects of exposure to benzene through ingestion of water
and contaminated aquatic organisms, the ambient water concentra-
tion is zero. Concentrations of benzene estimated to result in
additional lifetime cancer risk at levels of 10"/, 10~°, and
10~5 are 0.15 ug/1, 1.5 ug/1, and 15 ug/1, respectively.
Some studies have been reported regarding the behavior of benzene
in a POTW. Biochemical oxidation of benzene under laboratory
conditions, at concentrations of 3 to 10 mg/1, produced 24, 27,
24, and 20 percent degradation in 5, 10, 15, and 20 days, respec-
tively, using unacclimated seed cultures in fresh water. Degra-
dation of 58, 67, 76, and 80 percent was produced in the same
time periods using acclimated seed cultures. Other studies pro-
duced similar results. Based on these data and general conclu-
sions relating molecular structure to biochemical oxidation, it
is expected that biological treatment in a POTW will remove ben-
zene readily from the water. Other reports indicate that most
benzene entering a POTW is removed to the sludge and that influ-
ent concentrations of 1 g/1 inhibit sludge digestion. There is
no information about possible effects of benzene on crops grown
in soils amended with sludge containing benzene.
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Carbon Tetrachloride (6). Carbon tetrachloride (0014), also
called tetrachloromethane, is a colorless liquid produced primar-
ily by the chlorination of hydrocarbons - particularly methane.
Carbon tetrachloride boils at 77°C and has a vapor pressure of 90
mm Hg at 20°C. It is slightly soluble in water (0.8 gm/1 at
25°C) and soluble in many organic solvents. Approximately
one-third of a million tons is produced annually in the U.S.
Carbon tetrachloride, which was displaced by perchloroethylene as
a dry cleaning agent in the 1930's, is used principally as an
intermediate for production of chlorofluoromethanes for refriger-
ants, aerosols, and blowing agents. It is also used as a grain
fumigant.
Carbon tetrachloride produces a variety of toxic effects in
humans. Ingestion of relatively large quantities - greater than
five grams - has frequently proved fatal. Symptoms are burning
sensation in the mouth, esophagus, and stomach, followed by
abdominal pains, nausea, diarrhea, dizziness, abnormal pulse, and
coma. When death does not occur immediately, liver and kidney
damage are usually found. Symptoms of chronic poisoning are not
as well defined. General fatigue, headache, and anxiety have
been observed, accompanied by digestive tract and kidney dis-
comfort or pain.
Data concerning teratogenicity and mutagenicity of carbon tetra-
chloride are scarce and inconclusive. However, carbon tetrachlo-
ride has been demonstrated to be carcinogenic in laboratory
animals. The liver was the target organ.
For maximum protection of human health from the potential carcin-
ogenic effects of exposure to carbon tetrachloride through inges-
tion of water and contaminated aquatic organisms, the ambient
water concentration of zero. Concentrations of carbon tetrachlo-
ride estimated to result,in additional lifetime cancer risk at
risk levels of 10-7, io~6, and 1Q-5 are 0.026 ug/1, 0.26
ug/1, and 2.6 ug/1, respectively.
Data on the behavior of carbon tetrachloride in a POTW are not
available. Many of the toxic organic pollutants have been inves-
tigated, at least in laboratory-scale studies, at concentrations
higher than those expected to be found in most municipal waste-
waters. General observations have been developed relating
molecular structure to ease of degradation for all of the toxic
organic pollutants. The conclusion reached by study of the
limited data is that biological treatment produces a moderate
decree of removal of carbon tetrachloride in a POTW. No informa-
tion was found regarding the possible interference of carbon
tetrachloride with treatment processes. Based on the water
solubility of carbon tetrachloride, and the vapor pressure of
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this compound, it is expected that some of the undegraded carbon
tetrachloride will pass through to the POTW effluent and some
will be volatilized in aerobic processes.
Chlorobenzene (7) . Chlorobenzene (CfcHsCl) , also called mono-
chlorobenzene is~a clear, colorless, liquid manufactured by the
liquid phase chlorination of benzene over a catalyst. It boils
at 132°C and has a vapor pressure of 12.5 mm Hg at 25°C. It is
almost insoluble in water (0.5 g/1 at 30°C) , but dissolves in
hydrocarbon solvents. U.S. annual production is near 150,000
tons.
Principal uses of Chlorobenzene are as a solvent and as an inter-
mediate for dyes and pesticides. Formerly it was used as an
intermediate for DDT production, but elimination of production of
that compound reduced annual U.S. production requirements for
Chlorobenzene by half.
Data on the threat to human health posed by Chlorobenzene are
limited in number. Laboratory animals, administered large doses
of Chlorobenzene subcutaneously , died as a result of central
nervous system depression. At slightly lower dose rates, animals
died of liver or kidney damage. Metabolic disturbances occurred
also. At even lower dose rates of orally administered chloroben-
zene similar effects were observed, but some animals survived
longer than at higher dose rates. No studies have been reported
regarding evaluation of the teratogenic, mutagenic, or carcino-
genic potential of Chlorobenzene.
For the prevention of adverse effects due to the organoleptic
properties of Chlorobenzene in water the recommended criterion is
0.020 mg/1.
Only limited data are available on which to base conclusions
about the behavior of Chlorobenzene in a POTW. Laboratory
studies of the biochemical oxidation of Chlorobenzene have been
carried out at concentrations greater than those expected to
normally be present in POTW influent. Results showed the extent
of degradation to be 25, 28, and 44 percent after 5, 10, and 20
days, respectively. In another, similar study using a phenol-
adapted culture 4 percent degradation was observed after 3 hours
with a solution containing 80 mg/1. On the basis of these
results and general conclusions about the relationship of molec-
ular structure to biochemical oxidation, it is concluded that
Chlorobenzene remaining intact is expected to volatilize from the
POTW in aeration processes. The estimated half-life of chloro-
benzene in water based on water solubility, vapor pressure and
molecular weight is 5.8 hours.
1,2,4-Trichlorobenzene (8). 1 ,2,4-Trichlorobenzene (C6H3C13) ,
1,2,4-TCB) is a liquid at room temperature, solidifying to a
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crystalline solid at 17°C and boiling at 214°C. It is produced
by liquid phase chlorination of benzene in the presence of a
catalyst. Its vapor pressure is 4 mm Hg at 25°C. 1,2,4-TCB is
insoluble in water and soluble in organic solvents. Annual U.S.
production is in the range of 15,000 tons. 1,2,4-TCB is used in
limited quantities as a solvent and as a dye carrier in the tex-
tile industry. It is also used as a heat transfer medium and as
a transfer fluid. The compound can be selectively chlorinated to
1,2,4,5-tetrachlorobenzene using iodine plus antimony trichloride
as catalyst.
No reports were available regarding the toxic effects of
1,2,4-TCB on humans. Limited data from studies of effects in
laboratory animals fed 1,2,4-TCB indicate depression of activity
at low doses and predeath extension convulsions at lethal doses.
Metabolic disturbances and liver changes were also observed.
Studies for the purpose of determining teratogenic or mutagenic
properties of 1,2,4-TCB have not been conducted. No studies have
been made of carcinogenic behavior of 1,2,4-TCB administered
orally.
For the prevention of adverse effects due to the organoleptic
properties of 1,2,4-trichlorobenzene in water, the water quality
criterion is 0.013 mg/1.
Data on the behavior of 1,2,4-TCB in POTW are not available.
However, this compund has been investigated in a laboratory scale
study of biochemical oxidation at concentrations higher than
those expected to be contained by most municipal wastewaters.
Degradations of 0, 87, and 100 percent were observed after 5, 10,
and 20 days, respectively. Using this observation and general
observations relating molecular structure to ease of degradation
for all of the organic priority pollutants, the conclusion was
reached that biological treatment produces a high degree of
removal in POTW.
1,2-Dichloroethane (10). 1,2-Dichloroethane is a halogenated
aliphatic used in the production of tetraethyl lead and vinyl
chloride, as an industrial solvent, and as an intermeidate in the
production of other organochlorine compounds. Some chlorinated
ethanes have been found in drinking waters, natural waters,
aquatic organisms and foodstuffs. Research indicates that they
may have mutagenic and carcinogenic properties.
1.1.1-Trichloroethane (11). 1,1,1-Trichloroethane is one of the
two possible trichlorethanes. It is manufactured by hydrochlori-
nating vinyl chloride to 1,1-dichloroethane which is then chlori-
nated to the desired product. 1,1,1-Trichloroethane is a liquid
at room temperature with a vapor pressure of 96 mm Hg at 20 C and
a boiling point of 74°C. Its formula is CClsCHs- It is
slightly soluble in water (0.48 g/1) and is very soluble in
organic solvents. U.S. annual production is greater than one-
third of a million tons.
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1 ,1 ,1-Trichloroethane is used as an industrial solvent and
degreasing agent.
Most human toxicity data for 1 ,1 ,1-trichloroethane relates to
inhalation and dermal exposure routes. Limited data are avail-
able for determining toxicity of ingested 1 , 1 ,1-trichloroethane,
and those data are all for the compound itself, not solutions in
water. No data are available regarding its toxicity to fish and
aquatic organisms. For the protection of human health from the
toxic properties of 1 ,1 ,1-trichloroethane ingested through the
comsumption of water and fish, the ambient water criterion is
15.7 mg/1. The criterion is based on bioassays for possible
carcinogenicity .
No detailed study of 1 ,1 ,1-trichloroethane behavior in a POTW is
available. However, it has been demonstrated that none of the
toxic organic pollutants of this type can be broken down by bio-
logical treatment processes as readily as fatty acids, carbohy-
drates, or proteins.
Biochemical oxidation of many of the toxic organic pollutants has
been investigated, at least in laboratory scale studies, at con-
centrations higher than commonly expected in municipal waste-
water. General observations relating molecular structure to ease
of degradation have been developed for all of these pollutants.
The conclusion reached by study of the limited data is that
biological treatment produces a moderate degree of degradation of
1 ,1 ,1-trichloroethane. No evidence is available for drawing con-
clusions about its possible toxic or inhibitory effect on POTW
operation. However, for degradation to occur, a fairly constant
input of the compound would be necessary.
Its water solubility would allow 1 ,1 ,1-trichloroethane, present
in the influent and not biodegradable, to pass through a POTW
into the effluent. One factor which has received some attention,
but no detailed study, is the volatilization of the lower molecu-
lar weight organics from a POTW. If 1 ,1 ,1-trichloroethane is not
biodegraded, it will volatilize during aeration processes in the
POTW.
Hexachloroethane (12) . Hexachloroethane (CCl^Cd^ , also
called perchloroethane is a white crystalline solid with a
camphor- like odor. It is manufactured from tetrachloroethylene,
and is a minor product in many industrial chlorination processes
designed to produce lower chlorinated hydrocarbons. Hexachloro-
ethane sublimes at 185°C and has a vapor pressure of about 0.2 mm
Hg at 20°C. It is insoluble in water (50 mg/1 at 22°C) and solu-
ble in some organic solvents.
Hexachloroethane can be used in lubricants designed to withstand
extreme pressure. It is used as a plasticizer for cellulose
esters, and as a pesticide. It is also used as a retarding agent
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in fermentation, as an accelerator in the rubber industry, and in
pyrotechnic and smoke devices.
Hexachloroethane is considered to be toxic to humans by ingestion
and inhalation. In laboratory animals liver and kidney damage
have been observed. Symptoms in humans exposed to hexachloro-
ethane vapor include severe eye irritation and vision impairment.
Based on studies on laboratory animals, hexachloroethane is
considered to be carcinogenic.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to hexachloroethane through
ingestion of water and contaminated aquatic organisms, the
ambient water concentration is zero. Concentrations of hexa-
chloroethane estimated.,to result in additional lifetime cancer
risks at levels of 10-7, iQ-b} and iQ-5 are 0.059 ug/1,
0.59 ug/1, and 5.9 ug/1, respectively.
Data on the behavior of hexachloroethane in POTW are not availa-
ble. Many of the organic priority pollutants have been investi-
gated, at least in laboratory scale studies, at concentrations
higher than those expected to be contained by most municipal
wastewaters. General observations have been developed relating
molecular structure to ease of degradation for all of the organic
priority pollutants. The conclusion reached by study of the
limited data is that biological treatment produces little or no
removal of hexachloroethane in POTW. The lack of water solubil-
ity and the expected affinity of hexachloroethane for solid
particles lead to the expectation that this compound will be
removed to the sludge in POTW. No information was found regard-
ing possible uptake of hexachloroethane by plants grown on soils
amended with hexachloroethane-bearing sludge.
1.1-Dichloroethane (13). 1,1-Dichloroethane, also called ethyli-
dene dichloride and ethylidene chloride, is a colorless liquid
manufactured by reacting hydrogen chloride with vinyl chloride in
1 1-dichloroethane solution in the presence of a catalyst. How-
ever it is reportedly not manufactured commercially in the U.S.
1.1-Dichloroethane boils at 57°C and has a vapor pressure of 182
mm Hg at 20°C. It is slightly soluble in water (5.5 g/1 at 20 C)
and very soluble in organic solvents.
1 1-Dichloroethane is used as an extractant for heat-sensitive
substances and as a solvent for rubber and silicone grease.
1 1-Dichloroethane is less toxic than its isomer (1,2-dichloro-
ethane) but its use as an anesthetic has been discontinued
because'of marked excitation of the heart. It causes central
nervous system depression in humans. There are insufficient data
to derive water quality criteria for 1,1-dichloroethane.
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Data on the behavior of 1,1-dichloroethane in a POTW are not
available. Many of the toxic organic pollutants have been
investigated, at least in laboratory scale studies, at concen-
trations higher than those expected to be contained by most
municipal wastewaters. General observations have been developed
relating molecular structure to ease of degradation for all of
the toxic organic pollutants. The conclusion reached by study of
the limited data is that biological treatment produces only a
moderate removal of 1,1-dichloroethane in a POTW by degradation.
The high vapor pressure of 1,1-dichloroethane is expected to
result in volatilization of some of the compound from aerobic
processes in a POTW. Its water solubility will result in some of
the 1,1-dichloroethane which enters the POTW leaving in the
effluent from the POTW.
^, 1,2-Trichloroethane (14) . 1,1,2-Trichloroethane is one of the
two possible trichloroethanes and is sometimes called ethane tri-
chloride or vinyl trichloride. It is used as a solvent for fats,
oils, waxes, and resins, in the manufacture of 1,1-dichloro-
ethylene, and as an intermediate in organic synthesis.
1,1,2-Trichloroethane is a clear, colorless liquid at room tem-
perature with a vapor pressure of 16.7 mm Hg at 20°C, and a boil-
ing point of 113°C. It is insoluble in water and very soluble in
organic solvents. The formula is CHC12CH2C1.
Human toxicity data for 1,1,2-trichloroethane does not appear in
the literature. The compound does produce liver and kidney dam-
age in laboratory animals after intraperitoneal administration.
No literature data was found concerning teratogenicity or muta-
genicity of 1,1,2-trichloroethane. However, mice treated with
1,1,2-trichloroethane showed increased incidence of hepatocellu-
lar carcinoma. Although bioconcentration factors are not avail-
able for 1,1,2-trichloroethane in fish and other freshwater
aquatic organisms, it is concluded on the basis of octanol-water
partition coefficients that bioconcentration does occur.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to 1,1,2-trichloroethane through
ingestion of water and contaminated aquatic organisms, the ambi-
ent water concentration is zero. Concentrations of this compound
estimated to result in additional lifetime cancer risks at risk
levels of 10-7, 1Q-6, and 10~5 are 0.06 ug/1, 0.6 ug/1, and
6 ug/1, respectively. If contaminated aquatic organisms alone
are consumed, excluding the consumption of water, the water con-
centration should be less than 0.418 mg/1 to keep the increased
lifetime cancer risk below 10~5. Available data show that
adverse effects on aquatic life occur at concentrations higher
than those cited for human health risks.
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No detailed study of 1 ,1 ,2-trichloroethane behavior in a POTW is
available. However, it is reported that small amounts are formed
by chlorination processes and that this compound persists in the
environment (greater than two years) and it is not biologically
degraded. This information is not completely consistant with the
conclusions based on laboratory scale biochemical oxidation
studies and relating molecular structure to ease of degradation.
That study concluded that biological treatment in a POTW will
produce moderate removal of 1 ,1 ,2-trichloroethane.
The lack of water solubility and the relatively high vapor
pressure may lead to removal of this compound from a POTW by
volatilization.
2 4,6-Trichlorophenol (21). 2 ,4,6-Trichlorophenol (
abbreviated here to 2, 4,6 -TCP) is a colorless, crystalline solid
at room temperature. It is prepared by the direct chlorination
of phenol. 2,4,6-TCP melts at 68°C and is slightly soluble in
water (0.8 gm/1 at 25°C) . This phenol does not produce a color
with 4-aminoantipyrene, and therefore does not contribute to the
nonconventional pollutant parameter "Total Phenols." No data
were found on production volumes.
2,4,6-TCP is used as a fungicide, bactericide, glue and wood pre-
servative, and for antimildew treatment. It is also used for the
manufacture of 2 ,3,4,6-tetrachlorophenol and pentachlorophenol.
No data were found on human toxicity effects of 2,4,6-TCP.
Reports of studies with laboratory animals indicate that
2,4,6-TCP produced convulsions when injected interperitoneally.
Body temperature was elevated also. The compound also produced
inhibition of ATP production in isolated rat liver mitochondria,
increased mutation rates in one strain of bacteria, and produced
a genetic change in rats. No studies on teratogenicity were
found. Results of a test for carcinogenicity were inconclusive.
For the prevention of adverse effects due to the organoleptic
properties of 2,4,6-trichlorophenol in water, the water quality
criterion is 0.100 mg/1.
Although no data were found regarding the behavior of 2,4,6-TCP
in a POTW, studies of the biochemical oxidation of the compound
have been made at laboratory scale at concentrations higher than
those normally expected in municipal wastewaters. Biochemical
oxidation of 2,4,6-TCP at 100 mg/1 produced 23 percent degrada-
tion using a phenol-adapted acclimated seed culture. Based on
these results, biological treatment in a POTW is expected to pro-
duce a moderate degree of degradation. Another study indicates
that 2,4,6-TCP may be produced in a POTW by chlorination of
phenol during normal chlorination treatment.
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Para-chloro-meta-cresol (22). Para-chloro-meta-cresol
CC1C7H60H) is thought to be a 4-chloro-3-methyl-phenol
(4-chloro-meta-cresol, or 2-chloro-5-hydroxy-toluene), but is
also used by some authorities to refer to 6-chloro-3-methyl-
phenol (6-chloro-meta-cresol, or 4-chloro-3-hydroxy-toluene),
depending on whether the chlorine is considered to be para to the
methyl or to the hydroxy group. It is assumed for the purposes
of this document that the subject compound is 2-chloro-5-hydroxy-
toluene. This compound is a colorless crystalline solid melting
at 66 to 68°C. It is slightly soluble in water (3.8 gm/l^and
soluble in organic solvents. This phenol reacts with 4-amino-
antipyrene to give a colored product and therefore contributes to
the nonconventional pollutant parameter designated "Total
Phenols." No information on manufacturing methods or volumes
produced was found.
Para-chloro-meta cresol (abbreviated here as PCMC) is marketed as
a microbicide, and was proposed as an antiseptic and disinfectant
more than 40 years ago. It is used in glues, gums, paints, inks,
textiles, and leather goods. PCMC was found in raw wastewaters
from the die casting quench operation from one subcategory of
foundry operations.
Although no human toxicity data are available for PCMC, studies
on laboratory animals have demonstrated that this compound is
toxic when administered subcutaneously and intravenously. Death
was preceded by severe muscle tremors. At high dosages kidney
damage occurred. On the other hand, an unspecified isomer of
chlorocresol, presumed to be PCMC, is used at a concentration of
0.15 percent to preserve muicous heparin, a natural product
administered intravenously as an anticoagulant. The report does
not indicate the total amount of PCMC typically received. No
information was found regarding possible teratogenicity, or
carcinogenicity of PCMC.
Two reports indicate that PCMC undergoes degradation in biochemi-
cal oxidation treatments carried out at concentrations higher
than are expected to be encountered in POTW influents. One study
showed 50 percent degradation in 3.5 hours when a phenol-adapted
acclimated seed culture was used with a solution of 60 mg/1 PCMC.
The other study showed 100 percent degradation of a 20 mg/1 solu-
tion of PCMC in two weeks in an aerobic activated sludge test
system. No degradation of PCMC occurred under anaerobic con-
ditions.
Chloroform (23). Chloroform also called trichloromethane, is a
colorless liquid manufactured commercially by chlorination of
methane. Careful control of conditions maximizes chloroform pro-
duction, but other products must be separated. Chloroform boils
at 61°C and has a vapor pressure of 200 mm Hg at 25 C. It is
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slightly soluble in water (8.22 g/1 at 20°C) and readily soluble
in organic solvents.
Chloroform is used as a solvent and to manufacture refrigerants,
Pharmaceuticals, plastics, and anesthetics. It is seldom used as
an anesthetic.
Toxic effects of chloroform on humans include central nervous
system depression, gastrointestinal irritation, liver and kidney
damage and possible cardiac sensit ization to adrenalin. Carcino-
genicity has been demonstrated for chloroform on laboratory
animals.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to chloroform through ingestion
of water and contaminated aquatic organisms, the ambient water
concentration is zero. Concentrations of chloroform estimated to
result in additional lifetime cancer risks at the levels of
1CT', 10~6, and 1CT5 were 0.021 ug/1, 0.21 ug/1, and 2.1
ug/1, respectively.
No data are available regarding the behavior of chloroform in a
POTW. However, the biochemical oxidation of this compound was
studied in one laboratory scale study at concentrations higher
than those expected to be contained by most municipal waste-
waters. After 5, 10, and 20 days no degradation of chloroform
was observed. The conclusion reached is that biological treat-
ment produces little or no removal by degradation of chloroform
in a POTW.
The high vapor pressure of chloroform is expected to result in
volatilization of the compound from aerobic treatment steps in a
POTW. Remaining chloroform is expected to pass through into the
POTW effluent.
2-Chlorophenol (24). 2-Chlorophenol (ClCgH^H) , also called
ortho-chlorophenol, is a colorless liquid at room temperature,
manufactured by direct chlorination of phenol followed by distil-
lation to separate it from the other principal product, 4-chloro-
phenol. 2-Chlorophenol solidifies below 7 C and boils at 176 C.
It is soluble in water (28.5 gm/1 at 20 C) and soluble in several
types of organic solvents. This phenol gives a strong color with
4-aminoantipyrene and therefore contributes to the nonconven-
tional pollutant parameter "Total Phenols." Production statis-
tics could not be found. 2-Chlorophenol is used almost
exclusively as a chemical intermediate in the production of
pesticides and dyes. Production of some phenolic resins uses
2-chlorophenol .
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Very few data are available on which to determine the toxic
effects of 2-chlorophenol on humans. The compound is more toxic
to laboratory mammals when administered orally than when adminis-
tered subcutaneously or intravenously. This affect is attributed
to the fact that the compound is almost completely in the un-ion-
ized state at the low pH of the stomach and hence is more readily
absorbed into the body. Initial symptoms are restlessness and
increased respiration rate, followed by motor weakness and con-
vulsions induced by noise or touch. Coma follows. Following
lethal doses, kidney, liver, and intestinal damage were observed.
No studies were found which addressed the teratogenicity or
mutagenicity of 2-chlorophenol. Studies of 2-chlorophenol as a
promoter of carcinogenic activity of other carcinogens were
conducted by dermal application. Results do not bear a deter-
minable relationship to results of oral administration studies.
For the prevention of adverse effects due to the organoleptic
properties of 2-chlorophenol in water, the criterion is 0.0003
mg/1.
Data on the behavior of 2-chlorophenol in a POTW are not avail-
able. However, laboratory scale studies have been conducted at
concentrations higher than those expected to be found in munici-
pal wastewaters. At 1 mg/1 of 2-chlorophenol, an acclimated
culture produced 100 percent degradation by biochemical oxidation
after 15 days. Another study showed 45, 70, and 79 percent
degradation by biochemical oxidation after 5, 10, and 20 days,
respectively. The conclusion reached by the study of these
limited data, and general observations on all toxic organic
pollutants relating molecular structure to ease of biochemcial
oxidation, is that 2-chlorophenol is removed to a high degree or
completely by biological treatment in a POTW. Undegraded
2-chlorophenol is expected to pass through a POTW into the efflu-
ent because of the water solubility. Some 2-chlorophenol is also
expected to be generated by chlorination treatments of POTW
effluents containing phenol.
1.1-Dichloroethylene (29). 1,1-Dichloroethylene (1,1-DCE), also
called vinylidene chloride, is a clear colorless liquid manufac-
tured by dehydrochlorination of 1,1,2-trichloroethane.Q 1,1-DCE
has the formula CC12CH2. It has a boiling point of 32 C, and
a vapor pressure of 591 mm Hg at 25 C. 1,1-DCE is slightly solu-
ble in water (2.5 mg/1) and is soluble in many organic solvents.
U.S. production is in the range of hundreds of thousands of tons
annually.
1 1-DCE is used as a chemical intermediate and for copolymer
coatings or films. It may enter the wastewater of an industrial
facility as the result of decomposition of 1,1,1-trichloro-
ethylene used in degreasing operations, or by migration from
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vinylidene chloride copolymers exposed to the process water.
Human toxicity of 1,1-DCE has not been demonstrated; however, it
is a suspected human carcinogen. Mammalian toxicity studies have
focused on the liver and kidney damage produced by 1,1-DCE.
Various changes occur in those organs in rats and mice ingesting
1,1-DCE.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to 1,1-dichloroethylene through
ingest ion of water and contaminated aquatic organisms, the ambi-
ent water concentration is zero. The concentration of 1,1-DCE
estimated to result in an additional lifetime cancer risk of 1 in
100,000 is 0.0013 mg/1.
Under laboratory conditions, dichloroethylenes have been shown to
be toxic to fish. The primary effect of acute toxicity of the
dichloroethylenes is depression of the central nervous system.
The octanol/water partition coefficident of 1,1-DCE indicates it
should not accumulate significantly in animals.
The behavior of 1,1-DCE in a POTW has not been studied. However,
its very high vapor pressure is expected to result in release of
significant percentages of this material to the atmosphere in any
treatment involving aeration. Degradation of dichloroethylene in
air is reported to occur, with a half-life of eight weeks.
Biochemical oxidation of many of the toxic organic pollutants has
been investigated in laboratory scale studies at concentrations
higher than would normally be expected in municipal wastewaters.
General observations relating molecular structure to ease of
degradation have been developed for all of these pollutants. The
conclusion reached by study of the limited data is that biologi-
cal treatment produces little or no degradation of 1,1-dichloro-
ethylene. No evidence is available for drawing conclusions about
the possible toxic or inhibitory effect of 1,1-DCE on POTW opera-
tion. Because of water solubility, 1,1-DCE which is not volatil-
ized or degraded is expected to pass through a POTW. Very little
1,1-DCE is expected to be found in sludge from a POTW.
1.2-trans-Dichloroethylene (30). 1,2-Dichloroethylene (1,2-
trans-DCE) is a clear, colorless liquid with the formula
CHClCHCl. 1,2-trans-DCE is produced in mixture with the cis-
isomer by chlorination of acetylene. The cis-isomer has dis-
tinctly different physical properties. Industrially, the mixture
is used rather than the separate isomers. 1,2-trans-DCE has a^
boiling point of 48°C, and a vapor pressure of 234 mm Hg at 25 C.
The principal use of 1,2-dichloroethylene (mixed isomers) is to
produce vinyl chloride. It is used as a lead scavenger in gaso-
line, general solvent, and for synthesis of various other organic
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chemicals. When it is used as a solvent, 1,2-trans-DCE can enter
wastewater streams.
Although 1,2-trans-DCE is thought to produce fatty degeneration
of mammalian liver, there are insufficient data on which to base
any ambient water criterion.
In the reported toxicity test of 1,2-trans-DCE on aquatic life,
the compound appeared to be about half as toxic as the other
dichloroethylene (1,1-DCE) on the toxic pollutants list.
The behavior of 1,2-trans-DCE in a POTW has not been studied.
However, its high vapor pressure is expected to result in release
of a significant percentage of this compound to the atmosphere in
any treatment involving aeration. Degradation of the dichloro-
ethylenes in air is reported to occur, with a half-life of eight
weeks.
Biochemical oxidation of many of the toxic organic pollutants has
been investigated in laboratory scale studies at concentrations
higher than would normally be expected in municipal wastewaters.
General observations relating molecular structure to ease of
degradation have been developed for all of these pollutants. The
conclusion reached by the study of the limited data is that
biochemical oxidation produces little or no degradation of
1 2-trans-dichloroethylene. No evidence is available for drawing
conclusions about the possible toxic or inhibitory effect of
1 2-trans-dichloroethylene on POTW operation. It is expected
that its low molecular weight and degree of water solubility will
result in 1,2-trans-DCE passing through a POTW to the effluent if
it is not degrld¥d~or volatilized. Very little 1,2-trans-DCE is
expected to be found in sludge from a POTW.
2.4-Dimethylphenol (34). 2,4-Dimethylphenol (2,4-DMP), also
called 2,4-xylenol, is a colorless crystalline solid at room
temperature \25°C)t but melts at 27°C to 28°C. 2,4-DMP is
slightly soluble in water and, as a weak acid, is soluble in
alkaline solutions. Its vapor pressure is less than 1 mm Hg at
room temperature.
2 4-DMP is a natural product, occurring in coal and petroleum
sources. It is used commercially as an intermediate for manufac-
ture of pesticides, dye stuffs, plastics and resins, and surfac-
tants It is found in the water runoff from asphalt surfaces.
It can find its way into the wastewater of a manufacturing plant
from any of several adventitious sources.
Analytical procedures specific to this compound are used for its
identification and quantification in wastewaters. This compound
does not contribute to "Total Phenols" determined by the
4-aminoantipyrene method.
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Three methylphenol isomers (cresols) and six dime thy Iphenol
isomers (xylenols) generally occur together in natural products,
industrial processes, commercial products, and phenolic wastes.
Therefore, data are not available for human exposure to 2,4-DMP
alone. In addition to this, most mammalian tests for toxicity of
individual dime thy Iphenol isomers have been conducted with
isomers other than 2,4-DMP.
In general, the mixtures of phenol, methylphenols, and dimethyl-
phenols contain compounds which produced acute poisoning in
laboratory animals. Symptoms were difficult breathing, rapid
muscular spasms, disturbance of motor coordination, and asym-
metrical body position. In a 1977 National Academy of Science
publication the conclusion was reached that, "In view of the
relative paucity of data on the mutagenicity , carcinogenicity ,
teratogenicity, and long term oral toxicity of 2 ,4-dimethyl-
phenol, estimates of the effects of chronic oral exposure at low
levels cannot be made with any confidence." No ambient water
quality criterion can be set at this time. In order to protect
public health, exposure to this compound should be minimized as
soon as possible.
Toxicity data for fish and freshwater aquatic life are limited;
however, in reported studies of 2, 4-dimethy Iphenol at concen-
trations as high as 2 mg/1 no adverse effects were observed.
The behavior of 2,4-DMP in a POTW has not been studied. As a
weak acid, its behavior may be somewhat dependent on the pH of
the influent to the POTW. However, over the normal limited range
of POTW pH, little effect of pH would be expected.
Biological degradability of 2,4-DMP as determined in one study,
showed 94.5 percent removal based on chemical oxygen demand
(COD). Thus, substantial removal is expected for this compound.
Another study determined that persistance of 2,4-DMP in the envi-
ronment is low, and thus any of the compound which remained in
the sludge or passed through the POTW into the effluent would be
degraded within moderate length of time (estimated as two months
in the report).
2 .4-Dinitrotoluene (35) . 2 ,4-Dinitrotoluene [ (NO^CgH, CH~] , a
yellow crystalline compound, is manufactured as a coproduct with
the 2,6-isomer by nitration of nitrotoluene. It melts at 71 C.
2 4-Dinitro toluene is insoluble in water (0.27 g/1 at 22 C) and
soluble in a number of organic solvents. Production data for the
2 4-isomer alone are not available. The 2,4-and 2,6-isomers are
manufactured in an 80:20 or 65:35 ratio, depending on the process
used. Annual U.S. commercial production is about 150 thousand
tons of the two isomers. Unspecified amounts are produced by the
U.S. government and further nitrated to trinitrotoluene (TNT) for
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military use. The major use of the dinitrotoluene mixture is for
production of toluene diisocyanate used to make polyurethanes.
Another use is in production of dyestuffs.
The toxic effect of 2,4-dinitrotoluene in humans is primarily
methemoglobinemia (a blood condition hindering oxygen transport
by the blood). Symptoms depend on severity of the disease, but
include cyanosis, dizziness, pain in joints, headache, and loss
of appetite in workers inhaling the compound. Laboratory animals
fed oral doses of 2,4-dinitrotoluene exhibited many of the same
symptoms. Aside from the effects in red blood cells, effects are
observed in the nervous system and testes.
Chronic exposure to 2,4-dinitrotoluene may produce liver damage
and reversible anemia. No data were found on teratogenicity of
this compound. Mutagenic data are limited and are regarded as
confusing. Data resulting from studies of carcinogenicity of
2,4-dinitrotoluene point to a need for further testing for this
property.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to 2,4-dinitrotoluene through^
ingestion of water and contaminated aquatic organisms, the ambi-
ent water concentration is zero. Concentrations of 2,4-
dinitrotoluene estimated to result in additional lifetime cancer
risk at risk levels of 10' ', 10-°, and 1(P are 7.4 ug/1,
74 ug/1, and 740 ug/1, respectively.
Data on the behavior of 2,4-dinitrotoluene in a POTW are not
available. However, biochemical oxidation of 2,4-dinitrophenol
was investigated on a laboratory scale. At 100 mg/1 of 2,4-
dinitrotoluene, a concentration considerably higher than that
expected in municipal wastewaters, biochemical oxidation by an
acclimated, phenol-adapted seed culture produced 52 percent^
degradation in three hours. Based on this limited information
and general observations relating molecular structure to ease of
degradation for all the toxic organic pollutants, it was con-
cluded that biological treatment in a POTW removes 2,4-dinitro-
toluene to a high degree or completely. No information is
available regarding possible interference by 2,4-dinitrotoluene
in POTW treatment processes, or on the possible detrimental
effect on sludge used to ammend soils in which food crops are
grown.
Ethvlbenzene (38). Ethylbenzene is a colorless, flammable liquid
manufactured commercially from benzene and ethylene. Approxi-
mately half of the benzene used in the U.S. goes into the manu-
facture of more than three million tons of ethylbenzene annually.
Ethylbenzene boils at 136°C and has a vapor pressure of 7 mm Hg
at 20°C. It is slightly soluble in water (0.14 g/1 at 15 C) and
is very soluble in organic solvents.
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About 98 percent of the ethylbenzene produced in the U.S. goes
into the production of styrene, much of which is used in the
plastics and synthetic rubber industries. Ethylbenzene is a con-
stituent of xylene mixtures used as diluents in the paint indus-
try, agricultural insecticide sprays, and gasoline blends.
Although humans are exposed to ethylbenzene from a variety of
sources in the environment, little information on effects of
ethylbenzene in man or animals is available. Inhalation can
irritate eyes, affect the respiratory tract, or cause vertigo.
In laboratory animals ethylbenzene exhibited low toxicity. There
are no data available on teratogenicity , mutagenicity , or car-
cinogenicity of ethylbenzene.
Criteria are based on data derived from inhalation exposure
limits. For the protection of human health from the toxic prop-
erties of ethylbenzene ingested through water and contaminated
aquatic organisms, the ambient water quality criterion is 1.1
mg/1.
The behavior of ethylbenzene in a POTW has not been studied in
detail. Laboratory scale studies of the biochemical oxidation of
ethylbenzene at concentrations greater than would normally be
found in municipal wastewaters have demonstrated varying degrees
of degradation. In one study with phenol-acclimated seed
cultures, 27 percent degradation was observed in a half day at
250 mg/1 ethylbenzene. Another study at unspecified conditions
showed 32, 38, and 45 percent degradation after 5, 10, and 20
days, respectively. Based on these results and general observa-
tions relating molecular structure of degradation, the conclu-
sion is reached that biological treatment produces only mod-
erate removal of ethylbenzene in a POTW by degradation.
Other studies suggest that most of the ethybenzene entering a
POTW is removed from the aqueous stream to the sludge. The
ethylbenzene contained in the sludge removed from the POTW may
volatilize.
Fluoranthene (39). Fluoranthene (1 ,2-benzacenaphthene) is one of
the compounds called polynuclear aromatic hydrocarbons Q (PAH) . A
pale yellow solid at room temperature, it melts at 111 C and has
a negligible vapor pressure at 25°C. Water solubility is low
(0.2 mg/1). Its molecular formula is
Fluoranthene, along with many other PAH's, is found throughout
the environment. It is produced by pyrolytic processing of
organic raw materials, such as coal and petroleum, at high tem-
perature (coking processes). It occurs naturally as a product of
plant biosyntheses. Cigarette smoke contains fluoranthene.
Although it is not used as the pure compound in industry, it has
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been found at relatively higher concentrations (0.002 mg/1) than
most other PAH's in at least one industrial effluent. Further-
more, in a 1977 EPA survey to determine levels of PAH in U.S.
drinking water supplies, none of the 110 samples analyzed showed
any PAH other than fluoranthene.
Experiments with laboratory animals indicate that fluoranthene
presents a relatively low degree of toxic potential from acute
exposure, including oral administration. Where death occurred,
no information was reported concerning target organs or specific
cause of death.
There is no epidemiological evidence to prove that PAH in
general, and fluoranthene, in particular, present in drinking
water are related to the development of cancer. The only studies
directed toward determining carcinogenicity of fluoranthene have
been skin tests on laboratory animals. Results of these tests
show that fluoranthene has no activity as a complete carcinogen
(i.e., an agent which produces cancer when applied by itself),
but exhibits significant cocarcinogenicity (i.e., in combination
with a carcinogen, it increases the carcinogenic activity).
Based on the limited animal study data, and following an estab-
lished procedure, the ambient water quality criterion for fluor-
anthene alone (not in combination with other PAH) is determined
to be 200 mg/1 for the protection of human health from its toxic
properties.
There are no data on the chronic effects of fluoranthene on
freshwater organisms. One saltwater invertebrate shows chronic
toxicity at concentrations below 0.016 mg/1. For some fresh-
water fish species the concentrations producing acute toxicity
are substantially higher, but data are very limited.
Results of studies of the behavior of fluoranthene in conven-
tional sewage treatment processes found in a POTW have been
published. Removal of fluoranthene during primary sedimentation
was found to be 62 to 66 percent (from an initial value of
0.00323 to 0.04435 mg/1 to a final value of 0.00122 to 0.0146
mg/1), and the removal was 91 to 99 percent (final values of
0.00028 to 0.00026 mg/1) after biological purification with
activated sludge processes.
A review was made of data on biochemical oxidation of many of the
toxic organic pollutants investigated in laboratory scale studies
at concentrations higher than would normally be expected in
municipal wastewaters. General observations relating molecular
structure to ease of degradation have been developed for all of
these pollutants. The conclusion reached by study of the limited
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data is that biological treatment produces little or no degrada-
tion of fluoranthene. The same study, however, concludes that
fluoranthene would be readily removed by filtration and oil-water
separation and other methods which rely on water insolubility, or
adsorption on other particulate surfaces. This latter conclusion
is supported by the previously cited study showing significant
removal by primary sedimentation.
No studies were found to give data on either the possible inter-
ference of fluoranthene with POTW operation, or the persistance
of fluoranthene in sludges or POTW effluent waters. Several
studies have documented the ubiquity of fluoranthene in the envi-
ronment and it cannot be readily determined if this results from
persistence of anthropogenic fluoranthene or the replacement of
degraded fluoranthene by natural processes such as biosynthesis
in plants.
Methylene Chloride (44). Methylene chloride, also called dichlo-
romethane (CH2C12), is a colorless liquid manufactured by
chlorination of methane or methyl chloride followed by separation
from the higher chlorinated methanes formed as coproducts.
Methylene chloride boils at 40°C, and has a vapor pressure ofQ362
mm Hg at 20°C. It is slightly soluble in water (20 g/1 at 20 C),
and very soluble in organic solvents. U.S. annual production is
about 250,000 tons.
Methylene chloride is a common industrial solvent found^in
insecticides, metal cleaners, paint, and paint and varnish
removers.
Methylene chloride is not generally regarded as highly toxic to
humans. Most human toxicity data are for exposure by inhalation.
Inhaled methylene chloride acts as a central nervous system
depressant. There is also evidence that the compound causes
heart failure when large amounts are inhaled.
Methylene chloride does produce mutation in tests for this
effect. In addition, a bioassay recognized for its extremely
high sensitivity to strong and weak carcinogens produced results
which were marginally significant. Thus potential carcinogenic
effects of methylene chloride are not confirmed or denied, but
are under continuous study. Difficulty in conducting and inter-
preting the test results from the low boiling point (40 C) of^
raethylene chloride which increases the difficulty ofQmaintaining
the compound in growth media during incubation at 37 C; and from
the difficulty of removing all impurities, some of which might
themselves be carcinogenic.
For the protection of human health from the toxic properties of
methylene chloride ingested through water and contaminated
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aquatic organisms, the ambient water criterion is 0.002 mg/1.
The behavior of methylene chloride in a POTW has not been studied
in any detail. However, the biochemical oxidation of this com-
pound was studied in one laboratory scale study at concentrations
higher than those expected to be contained by most municipal
wastewaters. After five days no degradation of methylene chlo-
ride was observed. The conclusion reached is that biological
treatment produces little or no removal by degradation of
methylene chloride in a POTW.
The high vapor pressure of methylene chloride is expected to
result in volatilization of the compound from aerobic treatment
steps in a POTW. It has been reported that methylene chloride
inhibits anerobic processes in a POTW. Methylene chloride that
is not volatilized in the POTW is expected to pass through into
the effluent.
Dichlorobromomethane (48). This compound is a halogenated
aliphatic. Research has been shown that halomethanes have
carcinogenic properties, and exposure to this compound may have
adverse effects on human health.
Isophorone (54). Isophorone is an industrial chemical produced
at a level of tens of millions of pounds annually in the U.S.
The chemical name for isophorone is 3,5,5-trimethyl-2-cyclohexen-
1-one and it is also known as trimethyl cyclohexanone and
isoacetophorone. The formula is 05^(013)30. Normally,
it is produced as the gamma isomer; technical grades contain
about 3 percent of the beta isoraer (3,5,5-trimethyl-3-cyclohexen-
1-one). The pure gamma isomer is a water-white liquid, with
vapor pressure less than 1 mm Hg at room temperature, and a
boiling point of 215.2°C. It has a camphor- or peppermint-like
odor and yellows upon standing. It is slightly soluble (12 mg/1)
in water and dissolves in fats and oils.
Isophorone is synthesized from acetone and is used commercially
as a solvent or cosolvent for finishes, lacquers, polyvinyl and
nitrocellulose resins, pesticides, herbicides, fats, oils, and
gums. It is also used as a chemical feedstock.
Because isophorone is an industrially used solvent, most toxicity
data are for inhalation exposure. Oral administration to labora-
tory animals in two different studies revealed no acute or
chronic effects during 90 days, and no hematological or patholog-
ical abnormalities were reported. Apparently, no studies have
been completed on the carcinogenicity of isophorone.
Isophorone does undergo bioconcentration in the lipids of aquatic
organisms and fish.
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Based on subacute data, the ambient water quality criterion for
isophorone ingested through consumption of water and fish is set
at 460 mg/1 for the protection of human health from its toxic
properties.
Studies of the effects of isophorone on fish and aquatic organ-
isms reveal relatively low toxicity, compared to some other toxic
pollutants.
The behavior of isophorone in a POTW has not been studied.^ How-
ever, the biochemical oxidation of many of the toxic organic
pollutants has been investigated in laboratory scale studies at
concentrations higher than would normally be expected in munici-
pal wastewaters. General observations relating molecular struc-
ture to ease of degradation have been developed for all of these
pollutants. The conclusion reached by the study of the limited
data is that biochemical treatment in a POTW produces moderate
removal of isophorone. This conclusion is consistent with the
findings of an experimental study of microbiological degradation
of isophorone which showed about 45 percent oxidation in 15 to 20
days in domestic wastewater, but only 9 percent in salt water.
No data were found on the persistence of isophorone in sewage
sludge.
Naphthalene (55). Naphthalene is an aromatic hydrocarbon with
two orthocondensed benzene rings and a molecular formula of
CinHg. As such it is properly classed as a polynuclear
aromatic hydrocarbon (PAH). Pure naphthalene is a white crystal-
line solid melting at 80°C. For a solid, it has a relatively
high vapor pressure (0.05 mm Hg at 20 C), and moderate water
solubility (19 mg/1 at 20°C). Napthalene is the most abundant
single component of coal tar. Production is more than a third of
a million tons annually in the U.S. About three fourths of the
production is used as feedstock for phthalic anhydride manufac-
ture. Most of the remaining production goes into manufacture of
insecticide, dyestuffs, pigments, and pharmaceuticals. Chlori-
nated and partially hydrogenated naphthalenes are used in some
solvent mixtures. Naphthalene is also used as a moth repellent.
Naphthalene, ingested by humans, has reportedly caused vision
loss (cataracts), hemolytic anemia, and occasionally, renal dis-
ease. These effects of naphthalene ingestion are confirmed by
studies on laboratory animals. No carcinogenicity studies are
available which can be used to demonstrate carcinogenic activity
for naphthalene. Naphthalene does bioconcentrate in aquatic
organisms.
For the protection of human health from the toxic properties of
naphthalene ingested through water and through contaminated
aquatic organisms, the ambient water criterion is determined to
be 143 mg/1.
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Only a limited number of studies have been conducted to determine
the effects of naphthalene on aquatic organisms. The data from
those studies show only moderate toxicity.
Naphthalene has been detected in sewage plant effluents at con-
centrations up to 0.022 mg/1 in studies carried out by the U.S.
EPA. Influent levels were not reported. The behavior of naph-
thalene in a POTW has not been studied. However, recent studies
have determined that naphthalene will accumulate in sediments at
100 times the concentration in overlying water. These results
suggest that naphthalene will be readily removed by primary and
secondary settling in a POTW, if it is not biologically degraded.
Biochemical oxidation of many of the toxic organic pollutants has
been investigated in laboratory scale studies at concentrations
higher than would normally be expected in municipal wastewaters.
General observations relating molecular structure to ease of
degradation have been developed for all of these pollutants. The
conclusion reached by study of the limited data is that biologi-
cal treatment produces a high removal by degradation of naphthal-
ene. One recent study has shown that microorganisms can degrade
naphthalene, first to a dihydro compound, and ultimately to car-
bon dioxide and water.
Nitrobenzene (56). Nitrobenzene (CeHsNOa), also called
nitrobenzol and oil of mirbane, is a pale yellow, oily liquid,
manufactured by reacting benzene with nitric acid and sulfuric
acid. Nitrobenzene boils at 210°C and has a vapor pressure of
0.34 mm Hg at 25°C. It is slightly soluble in water (1.9 g/1 at
20°C), and is miscible with most organic solvents. Estimates of
annual U.S production vary widely, ranging from 100 to 350
thousand tons.
Almost the entire volume of nitrobenzene produced (97 percent) _ is
converted to aniline, which is used in dyes, rubber, and medici-
nals. Other uses for nitrobenzene include: solvent for organic
synthesis, metal polishes, shoe polish, and perfume.
The toxic effects of ingested or inhaled nitrobenzene in humans
are related to its action in blood: methemoglobinemia and
cyanosis. Nitrobenzene administered orally to laboratory animals
caused degeneration of heart, kidney, and liver tissue; paraly-
sis' and death. Nitrobenzene has also exhibited teratogenicity
in laboratory animals, but studies conducted to determine muta-
genicity or carcinogenicity did not reveal either of these
properties.
For the prevention of adverse effets due to the organoleptic
properties of nitrobenzene in water, the criterion is 0.030 mg/1.
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Data on the behavior of nitrobenzene in POTW are not available.
However, laboratory scale studies have been conducted at con-
centrations higher than those expected to be found in municipal
wastewaters. Biochemical oxidation produced no degradation after
5, 10, and 20 days. A second study also reported no degradation
after 28 hours, using an acclimated, phenol-adapted seed culture
with nitrobenzene at 100 mg/1. Based on these limited data, and
on general observations relating molecular structure to ease of
biological oxidation, it is concluded that little or no removal
of nitrobenzene occurs during biological treatment in POTW. The
low water solubility and low vapor pressure of nitrobenzene lead
to the expectation that nitrobenzene will be removed from POTW in
the effluent and by volatilization during aerobic treatment.
4-Nitrophenol (58). 4-Nitrophenol (N02C6H40H), also called
paranitrophenol, is a colorless to yellowish crystalline solid
manufactured commercially by hydrolysis of 4-chloro-nitrobenzene
with aqueous sodium hydroxide. 4-Nitrophenol melts at 114 C.
Vapor pressure is not cited in the usual sources. 4-Nitrophenol
is slightly soluble in water (15 g/1 at 25°C) and soluble in
organic solvents. This phenol does not react to give a color
with 4-aminoantipyrene, and therefore does not contribute to the
nonconventional pollutant parameter "Total Phenols." U.S. annual
production is about 20,000 tons.
Paranitrophenol is used to prepare phenetidine, acetaphenetidine,
azo and sulfur dyes, photocheraicals, and pesticides.
The toxic effects of 4-nitrophenol on humans have not been exten-
sively studied. Data from experiments with laboratory animals
indicate that exposure to this compound results in methmoglobi-
nemia (a metabolic disorder of blood), shortness of breath, and
stimulation followed by depression. Other studies indicate that
the compound acts directly on cell membranes, and inhibits cer-
tain enzyme systems in vitro. No information regarding potential
teratogenicity was founcTAvailable data indicate that this
compound does not pose a mutagenic hazard to humans. Very
limited data for 4-nitrophenol do not reveal potential carcino-
genic effects, although the compound has been selected by the
national cancer institute for testing under the Carcinogenic
Bioassay Program.
No U.S. standards for exposure to 4-nitrophenol in ambient water
have been established.
Data on the behavior of 4-nitrophenol in a POTW are not avail-
able. However, laboratory scale studies have been conducted at
concentrations higher than those expected to be found in munici-
pal wastewaters. Biochemical oxidation using adapted cultures
from various sources produced 95 percent degradation in three to
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six days in one study. Similar results were reported for other
studies. Based on these data, and on general observations
relating molecular structure to ease of biological oxidation, it
is concluded that complete or nearly complete removal of
4-nitrophenol occurs during biological treatment in a POTW.
hydrolys: ,
2,4-Dinitrophenol sublimes at 114 C. Vapor pressure is not cited
in usual sources. It is slightly soluble in water (7.0 g/1 at
25°C) and soluble in organic solvents. This phenol does not
react with 4-aminoantipyrene and therefore does not contribute to
the nonconventional pollutant parameter "Total Phenols." U.S.
annual production is about 500 tons.
2,4-Dinitrophenol is used to manufacture sulfur and azo dyes,
photochemicals, explosives, and pesticides.
The toxic effects of 2,4-dinitrophenol in humans is generally
attributed to their ability to uncouple oxidative phosphoryla-
tion. In brief, this means that sufficient 2,4-dinitrophenol
short-circuits cell metabolism by preventing utilization of
energy provided by respiration and glycolysis. Specific symp-
toms are gastrointestinal disturbances, weakness, dizziness,
headache, and loss of weight. More acute poisoning includes
symptoms such as: burning thirst, agitation, irregular breath-
ing, and abnormally high fever. This compound also inhibits
other enzyme systems; and acts directly on the cell membrane,
inhibiting chloride permeability. Ingestion of 2,4-dinitrophenol
also causes cataracts in humans.
Based on available data it appears unlikely that 2,4-dinitro-_
phenol poses a teratogenic hazard to humans. Results of studies
of mutagenic activity of this compound are inconclusive as^far as
humans are concerned. Available data suggest that 2,4-dinitro-
phenol does not possess carcinogenic properties.
To protect human health from the adverse effects of 2,4-dinitro-
phenol ingested in contaminated water and fish, the suggested
water quality criterion is 0.0686 mg/1 .
Data on the behavior of 2,4-dinitrophenol in a POTW are not
available. However, laboratory scale studies have been conducted
at concentrations higher than those expected to be found in
municipal wastewaters. Biochemical oxidation using a phenol-
adapted seed culture produced 92 percent degradation in 3.5
hours. Similar results were reported for other studies. Based
on these data, and on general observations relating molecular
structure to ease of biological oxidation, it is concluded that
complete or nearly complete removal of 2,4-dinitrophenol occurs
during biological treatment in a POTW.
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N-nitrpsodiphenylamine (62) . N-nitrosodiphenylamine
F(C6H5)2NNO j , also called nitrous diphenylamide, is a
yellow crystalline solid manufactured by nitrosation of diphenyl-
amine. It melts at 66°C and is insoluble in water, but soluble
in several organic solvents other than hydrocarbons. Production
in the U.S. has approached 1,500 tons per year. The compound is
used as a retarder for rubber vulcanization and as a pesticide
for control of scorch (a fungus disease of plants) .
N-nitroso compounds are acutely toxic to every animal species
tested and are also poisonous to humans. N-nitrosodiphenylamine
toxicity in adult rats lies in the mid range of the values for 60
N-nitroso compounds tested. Liver damage is the principal toxic
effect. N-nitrosodiphenylamine, unlike many other N-nitroso-
amines , does not show mutagenic activity. N-nitrosodiphenylamine
has been reported by several investigations to be non-carcino-
genic. However, the compound is capable of trans-nitrosation and
could thereby—convert other amines to carcinogenic N-nitroso-
amines. Sixty-seven of 87 N-nitrosoamines studied were reported
to have carcinogenic activity. No water quality criterion have
been proposed for N-nitrosodiphenylamine.
No data are available on the behavior of N-nitrosodiphenylamine
in a POTW. Biochemical oxidation of many of the toxic organic
pollutants have been investigated, at least in laboratory scale
studies, at concentrations higher than those expected to be con-
tained in most municipal wastewaters. General observations have
been developed relating molecular structure to ease of degrada-
tion for all the toxic organic pollutants. The conclusion
reached by study of the limited data is that biological treatment
produces little or no removal of N-nitrosodiphenylamine in a
POTW. No information is available regarding possible interfer-
ence by N-nitrosodiphenylamine in POTW processes, or on the
possible detrimental effect on sludge used to amend soils in
which crops are grown. However, no interference or detrimental
effects are expected because N-nitroso compounds are widely dis-
tributed in the soil and water environment, at low concentra-
tions, as a result of microbial action on nitrates and
nitrosatable compounds.
Pentachlorophenol (64) . Pentachlorophenol (CeCl
white crystalline solid produced commercially by
is a
chlorination of
phenol or polychlorophenols . U.S. annual production is in excess
of 20,000 tons. Pentachlorophenol melts at 190 C and is slightly
soluble in water (14 mg/1). Pentachlorophenol is not detected by
the 4-amino antipyrene method.
Pentachlorophenol is a bactericide and fungicide and is^used^for
preservation of wood and wood products. It is competitive with
creosote in that application. It is also used as a preservative
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in glues, starches, and photographic papers. It is an effective
algicide and herbicide.
Although data are available on the human toxicity effects of pen-
tachlorophenol, interpretation of data is frequently uncertain.
Occupational exposure observations must be examined carefully
because exposure to pentachlorophenol is frequently accompanied
by exposure to other wood preservatives. Additionally, experi-
mental results and occupational exposure observations must be
examined carefully to make sure that observed effects are pro-
duced by the pentachlorophenol itself and not by the by-products
which usually contaminate pentachlorophenol.
Acute and chronic toxic effects of pentachlorophenol in humans
are similar; muscle weakness, headache, loss of appetite,
abdominal pain, weight loss, and irritation of skin, eyes, and
respiratory tract. Available literature indicates that penta-
chlorophenol does not accumulate in body tissues to any signifi-
cant extent. Studies on laboratory animals of distribution of
the compound in body tissues showed the highest levels of penta-
chlorophenol in liver, kidney, and intestine, while the lowest
levels were in brain, fat, muscle, and bone.
Toxic effects of pentachlorophenol in aquatic organisms are much
greater at pH 6 where this weak acid is predominantly in the
undissociated form than at pH 9 where the ionic form predomi-
nates. Similar results were observed in mammals where oral
lethal doses of pentachlorophenol were lower when the compound
was administered in hydrocarbon solvents (un-ionized form) than
when it was administered as the sodium salt (ionized form) in
water.
There appear to be no significant teratogenic, mutagenic, or car-
cinogenic effects of pentachlorophenol.
For the protection of human health from the toxic properties of
pentachlorophenol ingested through water and through contaminated
aquatic organisms, the ambient water quality criterion is deter-
mined to be 0.140 mg/1.
Only limited data are available for reaching conclusions about
the behavior of pentachlorophenol in a POTW. Pentachlorophenol
has been found in the influent to a POTW. In a study of one_POTW
the mean removal was 59 percent over a seven day period. Trickl-
ing filters removed 44 percent at the influent pentachlorophenol,
suggesting that biological degradation occurs. The same report
compared removal of pentachlorophenol at the same plant and two
additional POTW facilities on a later date and obtained values of
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4.4, 19.5 and 28.6 percent removal, the last value being for the
plant which was 59 percent removal in the original study. Influ-
ent concentrations of pentachlorophenol ranged from 0.0014 to
0.0046 mg/1. Other studies, including the general review_of data
relating molecular structure to biological oxidation, indicate
that pentachlorophenol is not removed by biological treatment
processes in a POTW. Anaerobic digestion processes are inhibited
by 0.4 mg/1 pentachlorophenol.
The low water solubility and low volatility of pentachlorophenol
lead to the expectation that most of the compound will remain in
the sludge in a POTW. The effect on plants grown on land treated
with pentachlorophenol-containing sludge is unpredictable.
Laboratory studies show that this compound affects crop germina-
tion at 5.4 mg/1. However, photodecompos ition of pentachloro-
phenol occurs in sunlight. The effects of the various breakdown
products which may remain in the soil was not found in the liter-
ture.
Phenol (65). Phenol, also called hydroxybenzene and carbolic
acid, is a clear, colorless, hygroscopic, deliquescent, crystal-
line solid at room temperature. Its melting point is 43 C and
its vapor pressure at room temperature is 0.35 mm Hg. It is very
soluble in water (67 gin/1 at 16°C) and can be dissolved in ben-
zene, oils, and petroleum solids. Its formula is C6H50H.
Although a small percent of the annual production of phenol is
derived from coal tar as a naturally occuring product, most of
the phenol is synthesized. Two of the methods are fusion of ben-
zene sulfonate with sodium hydroxide, and oxidation of cumene
followed by cleavage with a catalyst. Annual production in the
U.S. is in excess of one million tons. Phenol is generated dur-
ing distillation of wood and the microbiological decomposition of
organic matter in the mammalian intestinal tract.
Phenol is used as a disinfectant, in the manufacture of resins,
dyestuffs, and in pharmaceuticals, and in the photo processing
industry. In this discussion, phenol is the specific compound
which is separated by methylene chloride extraction of an
acidified sample and identified and quantified by GC/MS. Phenol
also contributes to the "Total Phenols," discussed elsewhere
which are determined by the 4-AAP colorimetrie method.
Phenol exhibits acute and sub-acute toxicity in humans and
laboratory animals. Acute oral doses of phenol in humans cause
sudden collapse and unconsciousness by its action on the central
nervous system. Death occurs by respiratory arrest. Sub-acute
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oral doses in mammals are rapidly absorbed and quickly distri-
buted to various organs, then cleared from the body by urinary
excretion and metabolism. Long term exposure by drinking phenol
contaminated water has resulted in statistically significant
increase in reported cases of diarrhea, mouth sores, and burning
of the mouth. In laboratory animals, long term oral administra-
tion at low levels produced slight liver and kidney damage. No
reports were found regarding carcinogenicity of phenol adminis-
tered orally - all carcinogenicity studies were skin test.
For the protection of human health from phenol ingested through
water and through contaminated aquatic organisms, the concen-
tration in water should not exceed 3.4 mg/1.
Fish and other aquatic organisms demonstrated a wide range of
sensitivities to phenol concentration. However, acute toxicity
values were at moderate levels when compared to other toxic
organic pollutants.
Data have been developed on the behavior of phenol in a POTW.
Phenol is biodegradable by biota present in a POTW. The ability
of a POTW to treat phenol-bearing influents depends upon acclima-
tion of the biota and the constancy of the phenol concentration.
It appears that an induction period is required to build up the
population of organisms which can degrade phenol. Too large a
concentration will result in upset or pass though in the POTW,
but the specific level causing upset depends on the immediate
past history of phenol concentrations in the influent. Phenol
levels as high as 200 mg/1 have been treated with 95 percent
removal in a POTW, but more or less continuous presence of phenol
is necessary to maintain the population of microorganisms that
degrade phenol.
Phenol which is not degraded is expected to pass through the POTW
because of its very high water solubility. However, in a POTW
where chlorination is practiced for disinfection of the POTW
effluent, chlorination of phenol may occur. The products of that
reaction may be toxic pollutants.
The EPA has developed data on influent and effluent concentra-
tions of total phenols in a study of 103 POTW facilities. How-
ever, the analytical procedure was the 4-AAP method mentioned
earlier and not the GC/MS method specifically for phenol.
Discussion of the study, which of course includes phenol, is
presented under the pollutant heading "Total Phenols."
Phthalate Esters (66-71). Phthalic acid, or 1,2-benzene-
dicarboxylicacid,is one of three isomeric benzenedicarboxylic
acids produced by the chemical industry. The other two isomeric
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forms are called isophthalic and terephthalic acids. The formula
for all three acids is C6H4(COOH)2. Some esters of
phthalic acid are designated as toxic pollutants. They will be
discussed as a group here, and specific properties of individual
phthalate esters will be discussed afterwards.
Phthalic acid esters are manufactured in the U.S. at an annual
rate in excess of one billion pounds. They are used as plasti-
cizers - primarily in the production of polyvinyl chloride (PVC)
resins. The most widely used phthalate plasticizer is bis
(2-ethylhexyl) phthalate (66) which accounts for nearly one-third
of the phthalate esters produced. This particular ester is com-
monly referred to as dioctyl phthalate (DOP) and should not be
confused with one of the less used esters, di-n-octyl phthalate
(69), which is also used as a plasticizer. In addition to these
two isomeric dioctyl phthalates, four other esters, also used
primarily as plasticizers, are designated as toxic pollutants.
They are: butyl benzyl phthalate (67), di-n-butyl phthalate
(68), diethyl phthalate (70), and dimethyl phthalate (71).
Industrially, phthalate esters are prepared from phthalic anhy-
dride and the specific alcohol to form the ester. Some evidence
is available suggesting that phthalic acid esters also may be
synthesized by certain plant and animal tissues. The extent to
which this occurs in nature is not known.
Phthalate esters used as plasticizers can be present in concen-
trations up to 60 percent of the total weight of the PVC plastic.
The plasticizer is not linked by primary chemical bonds to the
PVC resin. Rather, it is locked into the structure of intermesh-
ing polymer molecules and held by van der Waals forces. The
result is that the plasticizer is easily extracted. Plasticizers
are responsible for the odor associated with new plastic toys or
flexible sheet that has been contained in a sealed package.
Although the phthalate esters are not soluble or are only very
slightly soluble in water, they do migrate into aqueous solutions
placed in contact with the plastic. Thus, industrial facilities
with tank linings, wire and cable coverings, tubing, and sheet
flooring of PVC are expected to discharge some phthalate esters
in their raw waste. In addition to their use as plasticizers,
phthalate esters are used in lubricating oils and pesticide car-
riers. These also can contribute to industrial discharge of
phthalate esters.
From the accumulated data on acute toxicity in animals, phtha-
late esters may be considered as having a rather low order of
toxicity. Human toxicity data are limited. It is thought that
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the toxic effects of the esters is most likely due to one of the
metabolic products, in particular the monoester. Oral acute tox-
icity in animals is greater for the lower molecular weight esters
than for the higher molecular weight esters.
Orally administered phthalate esters generally produced enlarging
of liver and kidney, and atrophy of testes in laboratory animals.
Specific esters produced enlargement of heart and brain, spleen-
itis, and degeneration of central nervous system tissue.
Subacute doses administered orally to laboratory animals produced
some decrease in growth and degeneration of the testes. Chronic
studies in animals showed similar effects to those found in acute
and subacute studies, but to a much lower degree. The same
organs were enlarged, but pathological changes were not usually
detected.
A recent study of several phthalic esters produced suggestive but
not conclusive evidence that dimethyl and diethyl phthalates have
a cancer liability. Only four of the six toxic pollutant esters
were included in the study. Phthalate esters do bioconcentrate
in fish. The factors, weighted for relative consumption of
various aquatic and marine food groups, are used to calculate
ambient water quality criteria for four phthalate esters. The
values are included in the discussion of the specific esters.
Studies of toxicity of phthalate esters in freshwater and salt
water organisms are scarce. A chronic toxicity test with bis(2-
ethylhexyl) phthalate showed that significant reproductive
impairment occurred at 0.003 mg/1 in the freshwater crustacean,
Daphnia magna. In acute toxicity studies, saltwater fish and
organisms showed sensitivity differences of up to eight-fold to
butyl benzyl, diethyl, and dimethyl phthalates. This suggests
that each ester must be evaluated individually for toxic effects.
The behavior of phthalate esters in a POTW has not been studied.
However, the biochemical oxidation of many of the toxic organic
pollutants has been investigated in laboratory scale studies at
concentrations higher than would normally be expected in munici-
pal wastewaters. Three of the phthalate esters were studed.
Bis(2-ethylhexyl) phthalate was found to be degraded slightly or
not at all and its removal by biological treatment in a POTW is
expected to be slight or zero. Di-n-butyl phthalate and diethyl
phthalate were degraded to a moderate degree and their removal by
biological treatment in a POTW is expected to occur to a moderate
degree. Using these data and other observations relating molecu-
lar structure to ease of biochemical degradation of other toxic
organic pollutants, the conclusion was reached that butyl benzyl
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phthalate and dimethyl phthalate would be removed in a POTW to a
moderate degree by biological treatment. On the same basis, it
was concluded that di-n-octyl phthalate would be removed to a
slight degree or not at all. An EPA study of seven POTW facili-
ties revealed that for all but di-n-octyl phthalate, which was
not studied, removals ranged from 62 to 87 percent.
No information was found on possible interference with POTW oper-
ation or the possible effects on sludge by the phthalate esters.
The water insoluble phthalate esters - butyl benzyl and di-n-
octyl phthalate - would tend to remain in sludge, whereas the
other four toxic pollutant phthalate esters with water solubili-
ties ranging from 50 mg/1 to 4.5 mg/1 would probably pass through
into the POTW effluent.
Bis(2-ethylhexyl) phthalate (66). In addition to the general
remarks and discussion on phthalate esters, specific information
on bis(2-ethylhexyl) phthalate is provided. Little information
is available about the physical properties of bis(2-ethylhexyl)
phthalate. It is a liquid boiling at 387 C at 5mm Hg and is
insoluble in water. Its formula is C6H4(COOCsHi7)2•
This toxic pollutant constitutes about one-third of the phthalate
ester production in the U.S. It is commonly referred to as
dioctyl phthalate, or OOP, in the plastics industry where it is
the most extensively used compound for the plasticization of
polyvinyl chloride (PVC). Bis(2-ethylhexyl) phthalate has been
approved by the FDA for use in plastics in contact with food.^
Therefore, it may be found in wastewaters coming in contact with
discarded plastic food wrappers as well as the PVC films and
shapes normally found in industrial plants. This toxic pollutant
is also a commonly used organic diffusion pump oil, where its low
vapor pressure is an advantage.
For the protection of human health from the toxic properties of
bis(2-ethylhexyl) phthalate ingested through water and through
contaminated aquatic organisms, the ambient water quality criter-
ion is determined to be 15 mg/1. If contaminated aquatic organ-
isms alone are consumed, excluding the consumption of water, the
ambient water criteria is determined to be 50 mg/1.
Although the behavior of bis(2-ethylhexyl) phthalate in a POTW
has not been studied, biochemical oxidation of this toxic pollu-
tant has been studied on a laboratory scale at concentrations
higher than would normally be expected in municipal wastewater.
In fresh water with a non-acclimated seed culture no biochemical
oxidation was observed after 5, 10, and 20 days. However with
an acclimated seed culture, biological oxidation occured to the
extents of 13, 0, 6, and 23 percent of theoretical after 5, 10,
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15 and 20 days, respectively. Bis(2-ethylhexyl) phthalate
concentrations were 3 to 10 mg/1. Little or no removal of
bis(2-ethylhexyl) phthalate by biological treatment in a POTW is
expected.
Butyl Benzyl Phthalate (67). In addition to the general remarks
and discussion on phthalate esters, specific information on butyl
benzyl phthalate is provided. No information was found on the
physical properties of this compound.
Butyl benzyl phthalate is used as a plasticizer for PVC. Two
special applications differentiate it from other phthalate
esters. It is approved by the U.S. FDA for food contact in
wrappers and containers; and it is the industry standard^for
plasticization of vinyl flooring because it provides stain
resistance.
No ambient water quality criterion is proposed for butyl benzyl
phthalate.
Butyl benzyl phthalate removal in a POTW by biological treatment
is expected to occur to a moderate degree.
Di-n-butyl Phthalate (68). In addition to the general remarks
and discussion on phthalate esters, specific information on di-
n-butyl phthalate (DBP) is provided. DBP is a colorless, oil
liquid boiling at 340 C. Its water solubility at room tempera-
ture is reported to be 0.4 g/1 and 4.5 g/1 in two different chem-
istry handbooks. The formula for DBP, C6H4(COOC4H9)2
is the same as for its isomer, di-isobutyl phthalate. DBP
production is 1 to 2 percent of total U.S. phthalate ester
production.
Dibutyl phthalate is used to a limited extent as a plasticizer
for polvvinyl chloride (PVC). It is not approved for contact
with food. It is used in liquid lipsticks and as a diluent for
polysulfide dental impression materials. DBP is used as a plas-
ticizer for nitrocellulose in making gun powder, and as a fuel in
solid propellants for rockets. Further uses are insecticides,
safety glass manufacture, textile lubricating agents, printing
inks, adhesives, paper coatings, and resin solvents.
For protection of human health from the toxic properties of^
dibutyl phthalate ingested through water and through contami-^
nated aquatic organisms, the ambient water quality criterion is
determined to be 34 mg/1. If contaminated aquatic organisms
alone are consumed, excluding the consumption of water, the
ambient water criterion is 154 mg/1.
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Although the behavior of di-n-butyl phthalate in a POTW has not
been studied, biochemical oxidation of this toxic pollutant has
been studied on a laboratory scale at concentrations higher than
would normally be expected in municipal wastewaters. Biochemical
oxidation of 35, 43, and 45 percent of theoretical oxidation were
obtained after 5, 10, and 20 days, respectively, using sewage
microorganisms as an unacclimated seed culture.
Biological treatment in a POTW is expected to remove di-n-butyl
phthalate to a moderate degree.
Di-n-octyl Phthalate (69). In addition to the general remarks
and discussion on phthalate esters, specific information on
di-n-octyl phthalate is provided. Di-n-octyl phthalate is not to
be confused with the isomeric bis(2-ethylhexyl) phthalate which
is commonly referred to in the plastics industry as DOP. Di-n-
octyl phthalate is a liquid which boils at 220°C at 5 mm Hg. It
is insoluble in water. Its molecular formula is C6H4-
(COOC8Hl7)2- Its production constitutes about 1 percent of
all phthalate ester production in the U.S.
Industrially, di-n-octyl phthalate is used to plasticize poly-
vinyl chloride (PVC) resins.
No ambient water quality criterion is proposed for di-n-octyl
phthalate.
Biological treatment in a POTW is expected to lead to little or
no removal of di-n-octyl phthalate.
Diethyl Phthalate (70). In addition to the general remarks and
discussion on phthalate esters, specific information on diethyl
phthalate is provided. Diethyl phthalate, or DEP, is a colorless
liquid boiling at 296°C, and is insoluble in water. Its molecu-
lar formula is CeH4(COOC2H5)2• Production of diethyl
phthalate constitutes about 1.5 percent of phthalate ester
production in the U.S.
Diethyl phthalate is approved for use in plastic food containers
by the U.S. FDA. In addition to its use as a polyvinyl chloride
(PVC) plasticizer, DEP is used to plasticize cellulose nitrate
for gun powder, to dilute polysulfide dental impression materi-
als, and as an accelerator for dyeing triacetate fibers. An
additional use which would contribute to its wide distribution in
the environment is as an approved special denaturant for ethyl
alcohol. The alcohol-containing products for which DEP is^an
approved denaturant include a wide range of personal care items
such as bath preparations, bay rum, colognes, hair preparations,
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face and hand creams, perfumes and toilet soaps. Additionally,
this denaturant is approved for use in biocides, cleaning solu-
tions, disinfectants, insecticides, fungicides, and room deoder-
ants which have ethyl alcohol as part of the formulation. It is
expected, therefore, that people and buildings would have some
surface loading of this toxic pollutant which would find its way
into raw wastewaters.
For the protection of human health from the toxic properties of
diethyl phthalate ingested through water and through contaminated
aquatic organisms, the ambient water quality criterion is deter-
mined to be 350 mg/1. If contaminated aquatic organisms alone
are consumed, excluding the consumption of water, the ambient
water criterion is 1,800 mg/1.
Although the behavior of diethyl phthalate in a POTW has not been
studied, biochemical oxidation of this toxic pollutant has been
studied on a laboratory scale at concentrations higher than would
normally be expected in municipal wastewaters. Biochemical oxi-
dation of 79, 84, and 89 percent of theoretical was observed
after 5, 15, and 20 days respectively. Biological treatment in a
POTW is expected to lead to a moderate degree of removal of
diethyl phthalate.
Dimethyl Phthalate (71). In addition to the general remarks and
discussion on phthalate esters, specific information en dimethyl
phthalate (DMP) is provided. DMP has the lowest molecular weight
of the phthalate esters - M.W. = 194 compared to M.W. of 391Qfor
bis(2-ethylhexyl) phthalate. DMP has a boiling point of 282 C.
It is a colorless liquid, soluble in water to the extent of 5
g/1. Its molecular formula is C6H4(COOCH3)2•
m
Dimethyl phthalate production in the U.S. is just under one per-
cent of total phthalate ester production. DMP is used to some
extent as a plasticizer in cellulosics; however, its principal
specific use is for dispersion of polyvinylidene fluoride (PVDF).
PVDF is resistant to most chemicals and finds use as electrical
insulation, chemical process equipment (particularly pipe), and
as a case for long-life finishes for exterior metal siding. Coil
coating techniques are used to apply PVDF dispersions to aluminum
or galvanized steel siding.
For the protection of human health from the toxic properties of
dimethyl phthalate ingested through water and through contami-
nated aquatic organisms, the ambient water criterion is deter-
mined to be 313 mg/1. If contaminated aquatic organisms alone
are consumed, excluding the consumption of water, the ambient
water criterion is 2,900 mg/1.
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Based on limited data and observations relating molecular struc-
ture to ease of biochemical degradation of other toxic organic
pollutants, it is expected that dimethyl phthalate will be bio-
chemically oxidized to a lesser extent than domestic sewage by
biological treatment in a POTW.
Polynuclear Aromatic Hydrocarbons (72-84). The polynuclear aro-
matic hydrocarbons ^PAH)selected as toxic pollutants are a group
of 13 compounds consisting of substituted and unsubstituted poly-
- cyclic aromatic rings. The general class of PAH includes hetero-
cyclics, but none of those were selected as toxic pollutants.
PAH are formed as the result of incomplete combustion when
organic compounds are burned with insufficient oxygen. PAH are
found in coke oven emissions, vehicular emissions, and volatile
products of oil and gas burning. The compounds chosen as toxic
pollutants are listed with their structural formula and melting
point (m.p.). All are relatively insoluble in water.
72 Benzo(a)anthracene (1,2-benzanthracene)
m.p. 162°C
73 Benzo(a)pyrene (3,4-benzopyrene)
m.p,
176°C
74 3,4-Benzofluoranthene
m.p. 168°C
75 Benzo(k)fluoranthene (11,12-benzofluoranthene)
76 Chrysene (1,2-benzphenanthrene)
77 Acenaphthylene
m.p. 217
m.p. 255°C
m.p. 92°C
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78 Anthracene
81
82
83
m.p. 216°C
79 Benzo(ghi)perylene (1,12-benzoperylene)
m.p. not reported
.. 116°C
80 Fluorene (alpha-diphenylenemethane)
Phenanthrene
m.p. 101°C
Dibenzo(a,h)anthracene (1,2,5,6-
dibenzoanthracene)
m.p. 269°C
Indeno (1 ,2 ,3-cd)pyrene
(2,3-o-phenylenepyrene)
84 Pyrene
m.p. not available
m.p. 156°C
Some of these toxic pollutants have commercial or industrial
uses. Benzo(a)anthracene, benzo(a)pyrene, chrysene, anthracene,
dibenzo(a,h)anthracene, and pyrene are all used as antioxidants.
Chrysene, acenaphthylene, anthracene, fluorene, phenanthrene, and
pyrene are all used for synthesis of dyestuffs or other organic
chemicals. 3,4-Benzofluoranthrene, benzo(k)fluoranthene, benzo-
(ghi)perylene, and indeno (1,2,3-cd)pyrene have no known indus-
trial uses, according to the results of a recent literature
search.
Several of the PAH toxic pollutants are found in smoked meats, in
smoke flavoring mixtures, in vegetable oils, and in coffee.
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Consequently, they are also found in many drinking water
supplies. The wide distribution of these pollutants in complex
mixtures with the many other PAHs which have not been designated
as toxic pollutants results in exposures by humans that cannot be
associated with specific individual compounds.
The screening and verification analysis procedures used for the
toxic organic pollutants are based on gas chromatography (GC).
Three pairs of the PAH have identical elution times on the column
specified in the protocol, which means that the parameters of the
pair are not differentiated. For these three pairs [anthracene
(78) - phenanthrene (81); 3,4-benzofluoranthene (74) - benzo(k)-
fluoranthene (75); and benzo(a)anthracene (72) - chrysene (76)]
results are obtained and reported as "either-or." Either both
are present in the combined concentration reported, or one is
present in the concentration reported.
There are no studies to document the possible carcinogenic risks
to humans by direct ingestion. Air pollution studies indicate an
excess of lung cancer mortality among workers exposed to large
amounts of PAH containing materials such as coal gas, tars, and
coke-oven emissions. However, no definite proof exists that the
PAH present in these materials are responsible for the cancers
observed.
Animal studies have demonstrated the toxicity of PAH by oral and
dermal administration. The carcinogenicity of PAH has been
traced to formation of PAH metabolites which, in turn, lead to
tumor formation. Because the levels of PAH which induce cancer
are very low, little work has been done on other health hazards
resulting from exposure. It has been established in animal
studies that tissue damage and systemic toxicity can result from
exposure to non-carcinogenic PAH compounds.
Because there were no studies available regarding chronic oral
exposures to PAH mixtures, proposed water quality criteria were
derived using data on exposure to a single compound. Two studies
were selected, one involving benzo(a)pyrene ingestion and one
involving dibenzo(a,h)anthracene ingestion. Both are known
animal carcinogens.
For the maximum protection of human health from the potential
carcinogenic effects of expsure to polynuclear aromatic hydrocar-
bons (PAH) through ingestion of water and contaminated aquatic
organisms, the ambient water concentration is zero. Concentra-
tions of PAH estimated to result in additional risk of 1 in
100,000 were derived by the EPA and the Agency is considering
setting criteria at an interim target risk level in the range of
10~', 10~°, or 10"5 with corresponding criteria of 0.097
ng/1, 0.97 ng/1, and 9.7 ng/1, respectively.
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No standard toxtctty tests have been reported for freshwater or
saltwater organisms and any of the 13 PAH discussed here.
The behavior of PAH in a POTW has received only a limited amount
of study. It is reported that up to 90 percent of PAH entering a
POTW will be retained in the sludge generated by conventional
sewage treatment processes. Some of the PAH can inhibit bac-
terial growth when they are present at concentrations as low as
0.018 mg/1. Biological treatment in activated sludge units has
been shown to reduce the concentration of phenanthrene and
anthracene to some extent; however, a study of biochemical oxi-
dation of fluorene on a laboratory scale showed no degradation
after 5, 10, and 20 days. On the basis of that study and studies
of other toxic organic pollutants, some general observations were
made relating molecular structure to ease of degradation. Those
observations lead to the conclusion that the 13 PAH selected to
represent that group as toxic pollutants will be removed only
slightly or not at all by biological treatment methods in a POTW.
Based on their water insolubility and tendency to attach to sedi-
ment particles very little pass through of PAH to POTW effluent
is expected. Sludge contamination is the likely environmental
fate although no data are available at this time to support any
conclusions about contamination of land by PAH on which sewage
sludge containing PAH is spread.
Tetrachloroethylene (85). Tetrachloroethylene (CC12CC12),
aT¥o called perchTo7o¥thylene and PCE, is a colorless nonflam-
mable liquid produced mainly by two methods -_chlorination and
pvrolysis of ethane and propane, and oxychlorination of dichloro
Sane? U.S. annual production exceeds 300 000 tons PCE boils
at 121°C and has a vapor pressure of 19 mm Hg at ZU L. it is
insoluble in water but soluble in organic solvents.
Approximately two-thirds of the U.S. production of PCE is used
for dry cleaning. Textile processing and metal degreasing, in
equal amounts consume about one-quarter of the U.S. production.
The principal toxic effect of PCE on humans is central nervous
system depression when the compound is inhaled. Headache
ISl™; sleepiness, dizziness, and sensations of intoxication
are Reported. Severity of effects increases with vapor concert-
Nation? High integrated exposure concentration times duration)
oroduces kidney and liver damage. Very limited data on PCE
ingested by laboratory animals indicate liver damage occurs when
JOT is administered by that route. PCE tends to distribute to
fat in mammalian bodies.
One report found in the literature suggests, but does not con-
clude! ?hat PCE is teratogenic. PCE has been demonstrated to be
a liver carcinogen in B6C3-F1 mice.
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For the maximum protection of human health from the potential
carcinogenic effects of exposure to tetrachlorethylene through
ingestion of water and contaminated aquatic organisms, the ambi-
ent water concentration is zero. Concentrations of tetrachloro-
ethylene estimated to result in additional lifetime cancer risk
levels of 1CT7, 10'6, and 10~5 are 0.02 ug/1, 0.2 ug/1, and
2 ug/1, respectively.
No data were found regarding the behavior of PCE in a POTW. Many
of the toxic organic pollutants have been investigated, at least
in laboratory scale studies, at concentrations higher than those
expected to be contained by most municipal wastewaters. General
observations have been developed relating molecular structure to
ease of degradation for all of the toxic organic pollutants. The
conclusions reached by the study of the limited data is that
biological treatment produces a moderate removal of PCE in a POTW
by degradation. No information was found to indicate that PCE
accumulates in the sludge, but some PCE is expected to be
adsorbed onto settling particles. Some PCE is expected to be
volatilized in aerobic treatment processes and little, if any, is
expected to pass through into the effluent from the POTW.
Toluene (86). Toluene is a clear, colorless liquid with a
benzene-lTke odor. It is a naturally occuring compound derived
primarily from petroleum or petrochemical processes. Some
toluene is obtained from the manufacture of metallurgical coke.
Toluene is also referred to as totuol, methylbenzene, methacide,
and phenylmethane. It is an aromatic hydrocarbon with the
formula Cffl^Cn^. It boils at 111°C and has a vapor pres-
sure of 30 mm Hg at room temperature. The water solubility of
toluene is 535 mg/1, and it is miscible with a variety of organic
solvents. Annual production of toluene in the U.S. is greater
than two million metric tons. Approximately two-thirds of the
toluene is converted to benzene and the remaining 30 percent is
divided approximately equally into chemical manufacture, and use
as a paint solvent and aviation gasoline additive. An esti-
mated 5,000 metric tons is discharged to the environment anually
as a constituent in wastewater.
Most data on the effects of toluene in human and other mammals
have been based on inhalation exposure or dermal contact studies.
There appear to be no reports of oral administration of toluene
to human subjects. A long term toxicity study on female rats
revealed no adverse effects on growth, mortality, appearance and
behavior, organ to body weight ratios, blood-urea nitrogen
levels, bone marrow counts, peripheral blood counts, or morphol-
ogy of major organs. The effects of inhaled toluene on the cen-
tral nervous system, both at high and low concentrations, have
been studied in humans and animals. However, ingested toluene is
expected to be handled differently by the body because it is
absorbed more slowly and must first pass through the liver before
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reaching the nervous system. Toluene is extensively and rapidly
metabolized in the liver. One of the principal metabolic prod-
ucts of toluene is benzoic acid, which itself seems to have
little potential to produce tissue injury.
Toluene does not appear to be teratogenic in laboratory animals
or man. Nor is there any conclusive evidence that toluene is
mutagenic. Toluene has not been demonstrated to be positive in
any in vitro mutagenicity or carcinogenicity bioassay system, nor
to be carcinogenic in animals or man.
Toluene has been found in fish caught in harbor waters in the
vicinity of petroleum and petrochemical plants. Bioconcentration
studies have not been conducted, but bioconcentration factors
have been calculated on the basis of the octanol-water partition
coefficient.
For the protection of human health from the toxic properties of
toluene ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 14.3
mg/1. If contaminated aquatic organisms alone are consumed
excluding the consumption of water, the ambient water criterion
is 424 mg/1. Available data show that the adverse effects on
aquatic life occur at concentrations as low as 5 mg/1.
Acute toxicity tests have been conducted with toluene and a
variety of freshwater fish and Daphnia magna. The latter appears
to be significantly more resistant than fish. No test results
have been reported for the chronic effects of toluene on
freshwater fish or invertebrate species.
No detailed study of toluene behavior in a POTW is available.
However, the biochemical oxidation of many of the toxic pollu-
tants has been investigated in laboratory scale studies at
concentrations greater than those expected to be contained by
most municipal wastewaters. At toluene concentrations ranging
from 3 to 250 mg/1 biochemical oxidation proceeded to 50 percent
of theoretical or greater. The time period varied from a few
hours to 20 days depending on whether or not the seed culture was
acclimated. Phenol adapted acclimated seed cultures gave the
most rapid and extensive biochemical oxidation.
Based on study of the limited data, it is expected that toluene
will be biochemically oxidized to a lesser extent than domestic
sewage by biological treatment in a POTW. The volatility and
relatively low water solubility of toluene lead to the expecta-
tion that aeration processes will remove significant quantities
of toluene from the POTW. The EPA studied toluene removal in
seven POTW facilities. The removals ranged from 40 to 100
percent. Sludge concentrations of toluene ranged from 54 x
10-3 to 1.85 mg/1.
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Trichloroethylene (87). Trichloroethylene (1,1,2-trichloroethyl-
erie or TCE) is a clear, colorless liquid boiling at 87°C, It has
a vapor pressure of 77 mm Hg at room temperature and is slightly
soluble in water (1 gm/1). U.S. production is greater than 0.25
million metric tons annually. It is produced from tetrachloro-
ethane by treatment with lime in the presence of water.
TCE is used for vapor phase degreasing of metal parts, cleaning
and drying electronic components, as a solvent for paints, as a
refrigerant, for extraction of oils, fats, and waxes, and for dry
cleaning. Its widespread use and relatively high volatility
result in detectable levels in many parts of the environment.
Data on the effects produced by ingested TCE are limited. Most
studies have been directed at inhalation exposure. Nervous sys-
tem disorders and liver damage are frequent results of inhalation
exposure. In the short term exposures, TCE acts as a central
nervous system depressant - it was used as an anesthetic before
its other long term effects were defined.
TCE has been shown to induce transformation in a highly sensitive
in vitro Fischer rat embryo cell system (F1706) that is used for
identifying carcinogens. Severe and persistent toxicity to the
liver was recently demonstrated when TCE was shown to produce
carcinoma of the liver in mouse strain B6C3F1. One systematic
study of TCE exposure and the incidence of human cancer was based
on 518 men exposed to TCE. The authors of that study concluded
that although the cancer risk to man cannot be ruled out, expo-
sure to low levels of TCE probably does not present a very
serious and general cancer hazard.
TCE is bioconcentrated in aquatic species, making the consumption
of such species by humans a significant source of TCE. For the
protection of human health from the potential carcinogenic
effects of exposure to trichloroethylene through ingestion of
water and contaminated aquatic organisms, the ambient water con-
centration is zero. Concentrations of trichloroethylene esti-
mated to result in additional lifetime cancer risks of 10~',
10-5, and iQ-5 are 0.27 ug/1, 2.7 ug/1, and 27 ug/1, respec-
tively. If contaminated aquatic organisms alone are consumed,
excluding the consumption of water, the water concentration
should be less than 0.807 mg/1 to keep the additional lifetime
cancer risk below lO"-3.
Only a very limited amount of data on the effects of TCE^on
freshwater aquatic life are available. One species of fish (fat-
head minnows) showed a loss of equilibrium at concentrations
below those resulting in lethal effects.
The behavior of trichloroethylene in a POTW has not been studied.
However, in laboratory scale studies of toxic organic pollutants,
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TCE was subjected to biochemical oxidation conditions. After 5,
10, and 20 days no biochemical oxidation occurred. On the basis
of'this study and general observations relating molecular struc-
ture to ease of degradation, the conclusion is reached that TCE
would undergo no removal by biological treatment in a POTW. The
volatility and relatively low water solubility of TCE is expected
to result in volatilization of some of the TCE in aeration steps
in a POTW.
Polychlorinated Biphenyls (106 - 112). Polychlorinated biphenyls
(Ci2HionCln,Hin-nCln where n can range from 1 to 10) ,
designated PCBYs, are chlorinated derivatives of biphenyls. The
commercial products are complex mixtures of chlorobiphenyls, but
are no longer produced in the U.S. The mixtures produced for-
merly were characterized by the percentage chlorination. Direct
chlorination of biphenyl was used to produce mixtures containing
from 21 to 70 percent chlorine. Seven of these mixtures have
been selected as toxic pollutants:
Toxic
Pollu-
tant
No.
106
107
108
109
110
111
112
Name
Percent
Chlorine
Range (°C)
Distilla-
tion
Arochlor
1242
1254
1221
1232
1248
1260
1016
42
54
20.5-21.5
31.4-32.5
48
60
41
325-366
365-390
275-320
290-325
340-375
385-420
323-356
Pour
Point (°C)
•19
10
1
-35.5
• 7
31
Water
Solubility
240
12
<200
54
2.7
225-250
The arochlors 1221, 1232, 1016, 1242, and 1248 are colorless,
oily liquids; 1254 is a viscous liquid; 1260 is a sticky resin at
room temperature. Total annual U.S. production of PCB's averaged
about 20,000 tons in 1972 to 1974.
Prior to 1971 PCB's were used in several applications including
plasticizers/heat transfer liquids, hydraulic fluids, lubri-
cants vacuum pump and compressor fluids, and capacitor and
transformer oils. After 1970, when PCB use was restricted to
closed systems, the latter two uses were the only commercial
applications.
The toxic effects of PCB's ingested by humans have been reported
to ranee from acne-like skin eruptions and pigmentation of the
skin to numbness of limbs, hearing and vision Pjfl*ms> a^.
soasms Interpretation of results is complicated by the fact
that the ver? highly toxic polychlorinated dibenzofurans (PCDF's)
are found in many commercial PCB mixtures. Photochemical and
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thermal decomposition appear to accelerate the transformation of
PCB's to PCDF's. Thus the specific effects of PCB's may be
masked by the effects of PCDF's. However, if PCDF's are fre-
quently present to some extent in any PCB mixture, then their
effects may be properly included in the effects of PCB mixtures.
Studies of effects of PCB's in laboratory animals indicate that
liver and kidney damage, large weight losses, eye discharges, and
interference with some metabolic processes occur frequently.
Teratogenic effects of PCB's in laboratory animals have been
observed, but are rare. Growth retardations during gestation,
and reproductive failure are more common effects observed in
studies of PCB teratogenicity. Carcinogenic effects of PCB s
have been studied in laboratory animals with results interpreted
as positive. Specific reference has been made to liver cancer in
rats in the discussion of water quality criterion formulation.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to PCB's through ingestion of
water and contaminated aquatic organisms, the ambient water con-
centration should be zero. Concentrations of PCB s estimated to
result in additional lifetime cancer risk at risk levels of
10-/, ID'6, and 10-5 are 0.0026 ng/1, 0.026 ng/1, and 0.26
ng/1, respectively.
The behavior of PCB's in a POTW has received limited study. Most
PCB's will be removed with sludge. One study showed removals of
82 to 89 percent, depending on suspended solid removal. The
PCB's adsorb onto suspended sediments and other particulates. In
laboratory scale experiments with PCB 1221, 81 percent was
removed by degradation in an activated sludge system in47 hours.
Biodeeradation can form polychlorinated dibenzofurans which are
more toxic than PCB's (as noted earlier). PCB's at concentra-
tions of 0.1 to 1,000 mg/1 inhibit or enhance bacterial growth
rates, depending on the bacterial culture and the percentage
chlorine in the PCB. Thus, activated sludge may be inhibited by
PCB's. Based on studies of bioaccumulation of PCB s in food
crops grown on soils amended with PCB-containing sludge, the U.S.
FDA has recommended a limit of 10 mg PCB/kg dry weight of sludge
used for application to soils bearing food crops.
Antimony (114). Antimony (chemical name - stibium, symbol Sb),
classified-Ss-a non-metal or metalloid, is a silvery white, brit-
tle crystalline solid. Antimony is found in small ore bodies
throughout the world. Principal ores are oxides of mixed anti-
mony valences, and an oxysulfide ore. Complex ores with metals
areyi*Portant'becauseothe antimony is recovered "-•
Antimony melts at 631°C, and is a poor conductor of
and heat.
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Annual U.S. consumption of primary antimony ranges from 10,000 to
20,000 tons. About half is consumed in metal products - mostly
antimonial lead for lead acid storage batteries, and about half
in non-metal products. A principal compound is antimony trioxide
which is used as a flame retardant in fabrics, and as an opaci-
fier in glass, ceramics, and enamels. Several antimony compounds
are used as catalysts in organic chemicals synthesis, as fluori-
nating agents (the antimony fluoride), as pigments, and in fire-
works. Semiconductor applications are economically significant.
Essentially no information on antimony-induced human health
effects has been derived from community epidemiology studies.
The available data are in literature relating effects observed
with therapeutic or medicinal uses of antimony compounds and
industrial exposure studies. Large therapeutic doses of anti-
monial compounds, usually used to treat schistisomiasis, have
caused severe nausea, vomiting, convulsions, irregular heart
action, liver damage, and skin rashes. Studies of acute
industrial antimony poisoning have revealed loss of appetite,
diarrhea, headache, and dizziness in addition to the symptoms
found in studies of therapeutic doses of antimony.
For the protection of human health from the toxic properties of
antimony ingested through water and through contaminated aquatic
organisms the ambient water criterion is determined to be 0.146
mg/1. If contaminated aquatic organisms are consumed, excluding
the consumption of water, the ambient water criterion is deter-
mined to be 45 mg/1. Available data show that adverse effects on
aquatic life occur at concentrations higher than those cited for
human health risks.
Very little information is available regarding the behavior of
antimony in a POTW. The limited solubility of most antimony
compounds expected in a POTW, i.e., the oxides and sulfides, sug-
gests that at least part of the antimony entering a POTW will be
precipitated and incorporated into the sludge. However, some
antimony is expected to remain dissolved and pass through the
POTW into the effluent. Antimony compounds remaining in^the
sludge under anaerobic conditions may be connected to stibine
(SbH3> a very soluble and very toxic compound. There are no
data to show antimony inhibits any POTW processes. Antimony is
not known to be essential to the growth of plants, and has been
reported to be moderately toxic. Therefore, sludge containing _
large amounts of antimony could be detrimental to plants if it is
applied in large amounts to cropland.
Arsenic (115). Arsenic (chemical symbol As), is classified as a
non-metal or metalloid. Elemental arsenic normally exists in the
alpha-crystalline metallic form which is steel gray and brittle,
and in the beta form which is dark gray and amorphous. Arsenic
sublimes at 615°C. Arsenic is widely distributed throughout the
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world in a large number of minerals. The most important commer-
cial source of arsenic is as a by-product from treatment of
copper, lead, cobalt, and gold ores. Arsenic is usually marketed
as the trioxide (As£03). Annual U.S. production of the tri-
oxide approaches 40,000 tons.
The principal use of arsenic is in agricultural chemicals (herbi-
cides) for controlling weeds in cotton fields. Arsenicals have
various applications in medicinal and vetrinary use, as wood
preservatives, and in semiconductors.
The effects of arsenic in humans were known by the ancient Greeks
and Romans. The principal toxic effects are gastrointestinal
disturbances. Breakdown of red blood cells occurs. Symptoms of
acute poisoning include vomiting, diarrhea, abdominal pain,
lassitude, dizziness, and headache. Longer exposure produced
dry, falling hair, brittle, loose nails, eczema, and exfoliation.
Arsenicals also exhibit teratogenic and mutagenic effects in
humans. Oral administration of arsenic compounds has been
associated clinically with skin cancer for nearly one hundred
years. Since 1888 numerous studies have linked occupational
exposure and therapeutic administration of arsenic compounds to
increased incidence of respiratory and skin cancer.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to arsenic through ingestion of
water and contaminated aquatic organisms, the ambient water con-
centration is zero. Concentrations of arsenic estimated to
result in additional lifetime cancer risk levels of 10"',
lO-o and 10-5 are 2.2 x 10'? mg/1, 2.2 x.10-° mg/1, and
2 2 x ID'5 rog/1. respectively. If'contaminated aquatic organ-
isms alone are consumed, excluding the consumption of water, the
water concentration should be less than 1.75 x 10"^ to keep the
increased lifetime cancer risk below 10'5. Available data show
that adverse effects on aquatic life occur at concentrations
higher than those cited for human health risks.
A few studies have been made regarding the behavior of arsenic in
a POTW. One EPA survey of nine POTW facilities reported influent
concentrations ranging from 0.0005 to 0.693 mg/1; effluents from
three a POTW having biological treatment contained 0.0004 to O.U1
mg/1; two POTW facilities showed arsenic removal efficiencies of
50 and 71 percent in biological treatment. Inhibition of treat-
ment processes by sodium arsenate is reported to occur at 0.1
mg/1 in activated sludge, and 1.6 mg/1 in anaerobic digestion
processes. In another study based on data from 60 POTW facili-
ties, arsenic in sludge ranged from 1.6 to 65.6 mg/kg and the
median value was 7.8 mg/kg. Arsenic in sludge spread on cropland
may be taken up by plants grown on that land. Edible plants can
take up arsenic, but normally their growth is inhibited before
the plants are ready for harvest.
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Asbestos (116) . Asbestos is a generic term used to describe a
group of hydrated mineral silicates that can appear in a fibrous
crystal form (asbestifortn) and, when crushed, can separate into
flexible fibers. The types of asbestos presently used commer-
cially fall into two mineral groups: the sepentine and amphibole
groups. Asbestos is minerologically stable and is not prone to
significant chemical or biological degradation in the aquatic
environment. In 1978, the total consumption of asbestos in the
U.S. was 583,000 metric tons. Asbestos is an excellent insulat-
ing material and is used in a wide variety of products. Based on
1975 figures, the total annual identifiable asbestos emissions
are estimated at 243,527 metric tons. Land discharges account
for 98.3 percent of the emissions, air discharges account for 1.5
percent, and water discharges account for 0.2 percent.
Asbestos has been found to produce significant incidence of dis-
ease among workers occupationally exposed in mining and milling,
in manufacturing, and in the use of materials containing the
fiber. The predominant type of exposure has been inhalation,
although some asbestos may be swallowed directly or ingested
after being expectorated from the respiratory tract. Non-
cancerous asbestos disease has been found among people directly
exposed to high levels of asbestos as a result of excessive work
exposure; much less frequently, amongh those with lesser expo-
sures although there is extensive evidence of pulmonary disease
among people exposed to airborne asbestos. There is little evi-
dence of disease among people exposed to waterborne fibers.
Asbestos at the concentrations currently found in the aquatic
environment does not appear to exert toxic effects on aquatic
organisms. For the maximum protection of human health from the
potential carcinogenic effects of exposure to asbestos through
ingestion of water and contaminated aquatic organisms, the ambi-
ent water concentration should be zero based on the non-threshold
assumption of this substance. However, zero level may not be
attainable at the present time. Therefore, levels which may
result in incremental increase of cancer risk over the life time
are estimated at 10~5? 10~°, and 10~7. The corresponding
recommended criteria are 300,000 fibers/I, 30,000 fibers/1, and
3,000 fibers/1.
The available data indicate that technologies used at POTW for
reducing levels of total suspended solids in wastewater also
provide a concomitant reduction in asbestos levels. Asbestos
removal efficiencies ranging from 80 percent to greater than 99
percent have been reported following sedimentation of wastewater.
Filtration and sedimentation with chemical addition (i.e., lime
and/or polymer) have achieved even greater percentage removals.
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Beryllium (117) . Beryllium is a dark gray metal of the alkaline
earth family.It is relatively rare, but because of its unique
properties finds widespread use as an alloying element, espe-<
cially for hardening copper which is used in springs, electrical
contacts, and non-sparking tools. World production is reported
to be in the range of 250 tons annually. However, much more
reaches the environment as emissions from coal burning opera-
tions. Analysis of coal indicates an average beryllium content
of 3 ppm and 0.1 to 1.0 percent in coal ash or fly ash.
The principal ores are beryl (3BeO.Al203.6Si02) and
bertrandite [Be4Si20y(OH>2J• Only two industrial
facilities produce beryllium in the U.S. because of limited
demand and the highly toxic character. About two-thirds of the
annual production goes into alloys, 20 percent into heat sinks,
and 10 percent into beryllium oxide (BeO) ceramic products.
Beryllium has a specific gravity of 1.846, making it the lightest
metal with a high melting point (1,350°C). Beryllium alloys are
corrosion resistant, but the metal corrodes in aqueous environ-
ments. Most common beryllium compounds are soluble in water, at
least to the extent necessary to produce a toxic concentration of
beryllium ions.
Most data on toxicity of beryllium is for inhalation of beryllium
oxide dust. Some studies on orally administered beryllium in
laboratory animals have been reported. Despite the large number
of studies implicating beryllium as a carcinogen, there is no
recorded instance of cancer being produced by ingestion. How-
ever, a recently convened panel of uninvolved experts concluded
that epidemiologic evidence is suggestive that beryllium is a
carcinogen in man.
In the aquatic environment beryllium is chronically toxic to
aquatic organisms at 0.0053 mg/1. Water softness has a large
effect on beryllium toxicity to fish. In soft water, beryllium
is reportedly 100 times as toxic as in hard water.
For the maximum protection of human health from the potential
carcinogenic effects of exposure to beryllium through ingestion
of water and contaminated aquatic organisms the ambient water
concentration is zero. Concentrations of beryllium estimated to
result in additional lifetime cancer risk levels of 10~',
10-6, and 10~5 are 0.68 ng/1, 6.8 ng/1, and 68 ng/1, respec-
tively. If contaminated aquatic organisms alone are consumed
excluding the consumption of water, the concentration should be
less than 0.00117 mg/1 to keep the increased lifetime cancer risk
below 10"5.
Information on the behavior of beryllium in a POTW is scarce.
Because beryllium hydroxide is insoluble in water, most beryllium
152
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entering a POTW will probably be in the form of suspended solids.
As a result most of the beryllium will settle and be removed with
sludge. However, beryllium has been shown to inhibit several
enzyme systems, to interfere with DNA metabolism in liver, and to
induce chromosomal and mitotic abnormalities. This intereference
in cellular processes may extend to interfere with biological
treatment processes. The concentration and effects of beryllium
in sludge which could be applied to cropland has not been
studied.
Cadmium (118). Cadmium is a relatively rare metallic element
that is seldom found in sufficient quantities in a pure state to
warrant mining or extraction from the earth's surface. It is
found in trace amounts of about 1 ppm throughout the earth's
crust. Cadmium is, however, a valuable by-product of zinc pro-
duction'.
Cadmium is used primarily as an electroplated metal, and is found
as an impurity in the secondary refining of zinc, lead, and
copper.
Cadmium is an extremely dangerous cumulative toxicant, causing
progressive chronic poisoning in mammals, fish, and probably
other organisms. The metal is not excreted.
Toxic effects of cadmium on man have been reported from through-
out the world. Cadmium may be a factor in the development of
such human pathological conditions as kidney disease, testicular
tumors, hypertension, arteriosclerosis, growth inhibition,
chronic disease of old age, and cancer. Cadmium is normally
ingested by humans through food and water as well as by breathing
air contaminated by cadmium dust. Cadmium is cumulative in^the
liver, kidney, pancreas, and thyroid of humans and other animals.
A severe bone and kidney syndrome known as itai-itai disease has
been documented in Japan as caused by cadmium ingestion via
drinking water and contaminated irrigation water. Ingestion of
as little as 0.6 mg/day has produced the disease. Cadmium acts
synergistically with other metals. Copper and zinc substantially
increase its toxicity.
Cadmium is concentrated by marine organisms, particularly _
molluscs, which accumulate cadmium in calcareous tissues and in
the viscera. A concentration factor of 1,000 for cadmium in fish
muscle has been reported, as have concentration factors of J,UUU
in marine plants and up to 29,600 in certain marine animals. The
eggs and larvae of fish are apparently more sensitive than adult
fish to poisoning by cadmium, and crustaceans appear to be more
sensitive than fish eggs and larvae.
For the protection of human health from the toxic properties of
cadmium ingested through water and through contaminated aquatic
153
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organisms, the ambient water criterion is determined to be 0.010
mg/1. Available data show that adverse effects on aquatic life
occur at concentrations in the same range as those cited for
human health, and they are highly dependent on water hardness.
Cadmium is not destroyed when it is introduced into a POTW, and
will either pass through to the POTW effluent or be incorporated
into the POTW sludge. In addition, it can interfere with the
POTW treatment process.
In a study of 189 POTW facilities, 75 percent of the primary
plants, 57 percent of the trickling filter plants, 66 percent of
the activated sludge plants, and 62 percent of the biological
plants allowed over 90 percent of the influent cadmium to pass
through to the POTW effluent. Only two of the 189 POTW facili-
ties allowed less than 20 percent pass-through, and none less
than 10 percent pass-through. POTW effluent concentrations
ranged from 0.001 to 1.97 mg/1 (mean 0.028 mg/1, standard
deviation 0.167 mg/1).
Cadmium not passed through the POTW will be retained in the
sludge where it is likely to build up in concentration. Cadmium
contamination of sewage sludge limits its use on land since it
increases the level of cadmium in the soil. Data show that
cadmium can be incorporated into crops, including vegetables and
grains, from contaminated soils. Since the crops themselves show
no adverse effects from soils with levels up to 100 mg/kg cad-
mium, these contaminated crops could have a significant impact on
human health. Two Federal agencies have already recognized the
potential adverse human health effects posed by the use of sludge
on cropland. The FDA recommends that sludge containing over 30
mg/kg of cadmium should not be used on agricultural land. Sewage
sludge contains 3 to 300 mg/kg (dry basis) of cadmium mean = 10
mg/kg; median = 16 mg/kg. The USDA also recommends placing
limits on the total cadmium from sludge that may be applied to
land.
Chromium (119). Chromium is an elemental metal usually found as
a chromite (FeO.Cr203). The metal is normally produced by
reducing the oxide with aluminum. A significant proportion of
the chromium used is in the form of compounds such as sodium
dichromate (Na2Cr04), and chromic acid (Cr03) - both are
hexavalent chromium compounds.
Chromium is found as an alloying component of many steels and its
compounds are used in electroplating baths, and as corrosion
inhibitors for closed water circulation systems.
The two chromium forms most frequently found in industry waste-
waters are hexavalent and trivalent chromium. Hexavalent chro-
mium is the form used for metal treatments. Some of it is
154
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reduced to trtvalent chromium as part of the process reaction.
The raw wastewater containing both valence states is usually
treated first to reduce remaining hexavalent to trivalent chro-
mium, and second to precipitate the trivalent form as the hydrox-
ide. The hexavalent form is not removed by lime treatment.
Chromium, in its various valence states, is hazardous to man. It
can produce lung tumors when inhaled, and induces skin sensitiza-
tions. Large doses of chromates have corrosive effects on the
intestinal tract and can cause inflammation of the kidneys.
Hexavalent chromium is a known human carcinogen. Levels of chro-
mate ions that show no effect in man appear to be so low as to
prohibit determination, to date.
The toxicity of chromium salts to fish and other aquatic life
varies widely with the species, temperature, pH, valence of the
chromium, and synergistic or antagonistic effects, especially the
effect of water hardness. Studies have shown that trivalent
chromium is more toxic to fish of some types than is hexavalent
chromium. Hexavalent chromium retards growth of one fish species
at 0.0002 mg/1. Fish food organisms and other lower forms of
aquatic life are extremely sensitive to chromium. Therefore,
both hexavalent and trivalent chromium must be considered harmful
to particular fish or organisms.
For the protection of human health from the toxic properties of
chromium (except hexavalent chromium) ingested through water and
contaminated aquatic organisms, the ambient water quality crite-
rion is 170 mg/1. If contaminated aquatic organisms alone are
consumed, excluding the consumption of water, the ambient water
criterion for trivalent chromium is 3,443 mg/1. The ambient
water quality criterion for hexavalent chromium is recommended to
be identical to the existing drinking water standard for total
chromium which is 0.050 mg/1.
Chromium is not destroyed when treated by a POTW (although the
oxidation state may change) , and will either pass through to the
POTW effluent or be incorporated into the POTW sludge. Both oxi-
dation states can cause POTW treatment inhibition and can also
limit the usefulness of municipal sludge.
Influent concentrations of chromium to POTW facilities have been
observed by EPA to range from 0.005 to 14.0 mg/1, with a median
concentration of 0.1 mg/1. The efficiencies for removal of chro-
mium by the activated sludge process can vary greatly, depending
on chromium concentration in the influent, and other operating
conditions at the POTW. Chelation of chromium by organic matter
and dissolution due to the presence of carbonates can cause
deviations from the predicted behavior in treatment systems.
155
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The systematic presence of chromium compounds will halt nitrifi-
cation in a POTW for short periods, and most of the chromium will
be retained in the sludge solids. Hexavalent chromium has been
reported to severely affect the nitrification process, but tri-
valent chromium has little or no toxicity to activated sludge,
except at high concentrations. The presence of iron, copper, and
low pH will increase the toxicity of chromium in a POTW by
releasing the chromium into solution to be ingested by micro-
organisms in the POTW.
The amount of chromium which passes through to the POTW effluent
depends on the type of treatment processes used by the POTW. In
a study of 240 POTW facilities, 56 percent of the primary plants
allowed more than 80 percent pass-through to POTW effluent. More
advanced treatment results in less pass-through. POTW effluent
concentrations ranged from 0.003 to 3.2 mg/1 total chromium (mean
- 0.197, standard deviation = 0.48), and from 0.002 to 0.1 mg/1
hexavalent chromium (mean = 0.017, standard deviation = 0.020).
Chromium not passed through the POTW will be retained in the
sludge, where it is likely to build up in concentration. Sludge
concentrations of total chromium of over 20,000 mg/kg (dry basis)
have been observed. Disposal of sludges containing very high
concentrations of trivalent chromium can potentially cause prob-
lems in uncontrolled landfills. Incineration, or similar
destructive oxidation processes, can produce hexavalent chromium
from lower valence states. Hexavalent chromium is potentially
more toxic than trivalent chromium. In cases where high rates of
chrome sludge application on land are used, distinct growth
inhibition and plant tissue uptake have been noted.
Pretreatment of discharges substantially reduces the concentra-
tion of chromium in sludge. In Buffalo, New York, pretreatment
of electroplating waste resulted in a decrease in chromium con-
centrations in POTW sludge from 2,510 to 1,040 mg/kg. A similar
reduction occurred in Grand Rapids, Michigan, POTW facilities
where the chromium concentration in sludge decreased from 11,000
to 2,700 mg/kg when pretreatment was made a requirement.
Copper (120). Copper is a metallic element that sometimes is
found free, as the native metal, and is also found in minerals
such as cuprite (Cu20), malechite [CuCOs.Cu(OH)2], azurite
[2CuC03.Cu(OH)2], chalcopyrite (CuFeSz), and bornite
(CusFeS4). Copper is obtained from these ores by smelting,
leaching, and electrolysis. It is used in the plating, electri-
cal, plumbing, and heating equipment industries, as well as zn
insecticides and fungicides.
Traces of copper are found in all forms of plant and animal life,
and the metal is an essential trace element for nutrition.
Copper is not considered to be a cumulative systemic poxson for
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humans as it Is readily excreted by the body, but it can cause
symptoms of gastroenteritis, with nausea and intestinal irrita-
tions, as relatively low dosages. The limiting factor in domes-
tic water supplies is taste. To prevent this adverse organolep-
tic effect of copper in water, a criterion of 1 mg/1 has been
established.
The toxicity of copper to aquatic organisms varies significantly,
not only with the species, but also with the physical and chemi-
cal characteristics of the water, including temperature, hard-
ness, turbidity, and carbon dioxide content. In hard water, the
toxicity of copper salts may be reduced by the precipitation of
copper carbonate or other insoluble compounds. The sulfates of
copper and zinc, and of copper and calcium are synergistic in
their toxic effect on fish.
Relatively high concentrations of copper may be tolerated by
adult fish for short periods of time; the critical effect of
copper appears to be its higher toxicity to young or juvenile
fish. Concentrations of 0.02 to 0.03 mg/1 have proved fatal to
some common fish species. In general the salmonoids are very
sensitive and the sunfishes are less sensitive to copper.
The recommended criterion to protect freshwater aquatic life is
0.0056 mg/1 as a 24-hour average, and 0.012 mg/1 maximum concen-
tration at a hardness of 50 mg/1 CaC03- For total recoverable
copper the criterion to protect freshwater aquatic life is 0.0056
mg/1 as a 24-hour average.
Copper salts cause undesirable color reactions in the food indus-
try and cause pitting when deposited on some other metals such as
aluminum and galvanized steel. To control undesirable taste and
odor quality of ambient water due to the organoleptic properties
of copper, the estimated level is 1.0 mg/1 for total recoverable
copper.
Irrigation water containing more than minute quantities of copper
can be detrimental to certain crops. Copper appears in all
soils, and its concentration ranges from 10 to 80 ppm. In soils,
copper occurs in association with hydrous oxides of manganese and
iron, and also as soluble and insoluble complexes with organic
matter. Copper is essential to the life of plants, and the
normal range of concentration in plant tissue is from 5 to 20
ppm. Copper concentrations in plants normally do not build up to
high levels when toxicity occurs. For example, the concentra-
tions of copper in snapbean leaves and pods was less than 50 and
20 mg/kg, respectively, under conditions of severe copper toxic-
ity. Even under conditions of copper toxicity, most of the
excess copper accumulates in the roots; very little is moved to
the aerial part of the plant.
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Copper is not destroyed when treated by a POTW, and will either
pass through to the POTW effluent or be retained in the POTW
sludge. It can interfere with the POTW treatment processes and
can limit the usefulness of municipal sludge.
The influent concentration of copper to a POTW has been observed
by the EPA to range from 0.01 to 1.97 mg/1, with a median concen-
tration of 0.12 mg/1. The copper that is removed from the
influent stream of a POTW is absorbed on the sludge or appears in
the sludge as the hydroxide of the metal. Bench scale pilot
studies have shown that from about 25 percent to 75 percent of
the copper passing through the activated sludge process remains
in solution in the final effluent. Four-hour slug dosages of
copper sulfate in concentrations exceeding 50 mg/1 were reported
to have severe effects on the removal efficiency of an unaccli-
mated system, with the system returning to normal in about 100
hours. Slug dosages of copper in the form of copper cyanide were
observed to have much more severe effects on the activated sludge
system, but the total system returned to normal in 24 hours.
In a recent study of 268 POTW facilities, the median pass-through
was over 80 percent for primary plants and 40 to 50 percent for
trickling filter, activated sludge, and biological treatment
plants. POTW effluent concentrations of copper ranged from 0.003
to 1.8 mg/1 (mean 0.126, standard deviation 0.242).
Copper which does not pass through the POTW will be retained in
the sludge where it will build up in concentration. The presence
of excessive levels of copper in sludge may limit its use on
cropland. Sewage sludge contains up to 16,000 mg/kg of copper,
with 730 mg/kg as the mean value. These concentrations are
significantly greater than those normally found in soil, which
usually range from 18 to 80 mg/kg. Experimental data indicate
that when dried sludge is spread over tillable land, the copper
tends to remain in place down to the depth of the tillage, except
for copper which is taken up by plants grown in the soil. Recent
investigation has shown that the extractable copper content ot
sludge-treated soil decreased with time, which suggests a rever-
sion of copper to less soluble forms was occurring.
Cyanide (121). Cyanides are among the most toxic of pollutants
commonly observed in industrial wastewaters. Introduction of
cyanide into industrial processes is usually by dissolution of
potassium cyanide (KCN) or sodium cyanide (NaCN) in process
waters. However, hydrogen cyanide (HCN) formed when the above
salts are dissolved in water, is probably the most acutely lethal
compound.
The relationship of pH to hydrogen cyanide formation is very
important. As pH is lowered to below 7, more than 99 percent of
the cyanide is present as HCN and less than 1 percent as cyanide
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ions. Thus, at neutral pH, that of most living organisms, the
more toxic form of cyanide prevails.
Cyanide ions combine with numerous heavy metal ions to form com-
plexes. The complexes are in equilibrium with HCN. Thus, the
stability of the metal-cyanide complex and the pH determine the
concentration of HCN. Stability of the metal-cyanide anion com-
plexes is extremely variable. Those formed with zinc, copper,
and cadmium are not stable - they rapidly dissociate, with pro-
duction of HCN, in near neutral or acid waters. Some of the com-
plexes are extremely stable. Cobaltocyanide is very resistant to
acid distillation in the laboratory. Iron cyanide complexes are
also stable, but undergo photodecomposition to give HCN upon
exposure to sunlight. Synergistic effects have been demonstrated
for the metal cyanide complexes making zinc, copper, and cadmium
cyanides more toxic than an equal concentration of sodium
cyanide.
The toxic mechanism of cyanide is essentially an inhibition of
oxygen metabolism, i.e., rendering the tissues incapable of
exchanging oxygen. The cyanogen compounds are true noncumulative
protoplasmic poisons. They arrest the activity of all forms of
animal life. Cyanide shows a very specific type of toxic action.
It inhibits the cytochrome oxidase system. This system is the
one which facilitates electron transfer from reduced metabolites
to molecular oxygen. The human body can convert cyanide to a
non-toxic thiocyanate and eliminate it. However, if the quantity
of cyanide ingested is too great at one time, the inhibition^of
oxygen utilization proves fatal before the detoxifying reaction
reduces the cyanide concentration to a safe level.
Cyanides are more toxic to fish than to lower forms of aquatic
organisms such as midge larvae, crustaceans, and mussels. Toxic-
ity to fish is a function of chemical form and concentration, and
is influenced by the rate of metabolism (temperature) , the level
of dissolved oxygen, and pH. In laboratory studies free cyanide
concentrations ranging from 0.05 to 0.14 mg/1 have been proven to
be fatal to sensitive fish species including trout, bluegill, and
fathead minnows. Levels above 0.2 mg/1 are rapidly fatal to most
fish species. Long term sublethal concentrations of cyanide as
low as 0.01 mg/1 have been shown to affect the ability of fish to
function normally, e.g., reproduce, grow, and swim.
For the protection of human health from the toxic properties of
cyanide ingested through water and through contaminated aquatic
organisms, the ambient water quality criterion is determined to
be 0.200 mg/1.
Persistence of cyanide in water is highly variable and depends
upon the chemical form of cyanide in the water, the concentration
of cyanide and the nature of other constituents. Cyanide may be
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destroyed by strong oxidizing agents such as permanganate and
chlorine. Chlorine is commonly used to oxidize strong cyanide
solutions. Carbon dioxide and nitrogen are the products of com-
plete oxidation. But if the reaction is not complete, the very
toxic compound, cyanogen chloride, may remain in the treatment
system and subsequently be released to the environment. Partial
chlorination may occur as part of a POTW treatment, or during the
disinfection treatment of surface water for drinking water prep-
aration.
Cyanides can interfere with treatment processes in a POTW, or
pass through to ambient waters. At low concentrations and with
acclimated microflora, cyanide may be decomposed by microorga-
nisms in anaerobic and aerobic environments or waste treatment
systems. However, data indicate that much of the cyanide intro-
duced passes through to the POTW effluent. The mean pass-through
of 14 biological plants was 71 percent. In a recent study of 41
POTW facilities the effluent concentrations ranged from 0.002 to
100 mg/1 (mean = 2.518, standard deviation - 15.6). Cyanide also
enhances the toxicity of metals commonly found in POTW effluents,
including the toxic pollutants cadmium, zinc, and copper.
Data for Grand Rapids, Michigan, showed a significant decline in
cyanide concentrations downstream from the POTW after pretreat-
ment regulations were put in force. Concentrations fell from
0.66 mg/1 before, to 0.01 mg/1 after pretreatment was required.
Lead (122). Lead is a soft, malleable, ductile, blueish-gray,
metallic element, usually obtained from the mineral galena (lead
sulfide, PbS), anglesite (lead sulfate, PbS04), or cerussite
(lead carbonate, PbCOs). Because it is usually associated with
minerals of zinc, silver, copper, gold, cadmium, antimony, and
arsenic, special purification methods are frequently used before
and after extraction of the metal from the ore concentrate by
smelting.
Lead is widely used for its corrosion resistance, sound and
vibration absorption, low melting point (solders), and relatively
high imperviousness to various forms of radiation. Small amounts
of copper, antimony and other metals can be alloyed with lead to
achieve greater hardness, stiffness, or corrosion resistance than
is afforded by the pure metal. Lead compounds are used in glazes
and paints. About one third of U.S. lead consumption goes into
storage batteries. About half of U.S. lead consumption is from
secondary lead recovery. U.S. consumption of lead is in the
range of one million tons annually.
Lead ingested by humans produces a variety of toxic effects
including impaired reproductive ability, disturbances in blood
chemistry, neurological disorders, kidney damage, and adverse
cardiovascular effects. Exposure to lead in the diet results in
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permanent increase in lead levels in the body. Most of the lead
entering the body eventually becomes localized in the bones where
it accumulates. Lead is a carcinogen or cocarcinogen in some
species of experimental animals. Lead is teratogenic in experi-
mental animals. Mutagenicity data are not available for lead.
The ambient water quality criterion for lead is recommended to be
identical to the existng drinking water standard which is 0.050
mg/1. Available data show that adverse effects on aquatic life
occur at concentrations as low as 7.5 x 10"^ mg/1 of total
recoverable lead as a 24-hour average with a water hardness of 50
mg/1 as CaC03.
Lead is not destroyed in a POTW, but is passed through to the
effluent or retained in the POTW sludge; it can interfere with
POTW treatment processes and can limit the usefulness of POTW
sludge for application to agricultural croplands. Threshold con-
centration for inhibition of the activated sludge process is 0.1
mg/1, and for the nitrification process is 0.5 mg/1. In a study
of 214 POTW facilities, median pass through values were over 80
percent for primary plants and over 60 percent for trickling
filter, activated sludge, and biological process plants. Lead
concentration in POTW effluents ranged from 0.003 to 1.8 mg/1
(mean = 0.106 mg/1, standard deviation = 0.222).
Application of lead-containing sludge to cropland should not lead
to uptake by crops under most conditions because normally lead is
strongly bound by soil. However, under the unusual condition of
low pH (less than 5.5) and low concentrations of labile phos-
phorus, lead solubility is increased and plants can accumulate
lead.
Mercury (123). Mercury is an elemental metal rarely found in^
nature as the free metal. Mercury is unique among metals as it
remains a liquid down to about 39 degrees below zero. It is
relatively inert chemically and is insoluble in water. The
principal ore is cinnabar (HgS).
Mercury is used industrially as the metal and as mercurous and
mercuric salts and compounds. Mercury is used in several types
of batteries. Mercury released to the aqueous environment is
subject to biomethylation - conversion to the extremely toxic
methyl mercury.
Mercury can be introduced into the body through the skin and the
respiratory system as the elemental vapor Mercuric salts are
highly toxic to humans and can be absorbed through the gastro-
intestinal tract. Fatal doses can vary from 1 to 30 grams.
Chronic ?oxicity of methyl mercury is evidenced primarily by
neurological symptoms. Some mercuric salts cause death by kidney
failure.
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Mercuric salts are extremely toxic to fish and other aquatic
life. Mercuric chloride is more lethal than copper, hexavalent
chromium, zinc, nickel, and lead towards fish and aquatic life.
In the food cycle, algae containing mercury up to 100 times the
concentration in the surrounding sea water are eaten by fish
which further concentrate the mercury. Predators that eat the
fish in turn concentrate the mercury even further.
For the protection of human health from the toxic properties of
mercury ingested through water and through contaminated aquatic
organisms the ambient water criterion is determined to be 0.0002
mg/1.
Mercury is not destroyed when treated by a POTW, and will either
pass through to the POTW effluent or be incorporated into the
POTW sludge. At low concentrations it may reduce POTW removal
efficiencies, and at high concentrations it may upset the POTW
operation.
The influent concentrations of mercury to a POTW have been
observed by the EPA to range from 0.002 to 0.24 mg/1, with a
median concentration of 0.001 mg/1. Mercury has been reported in
the literature to have inhibiting effects upon an activated
sludee POTW at levels as low as 0.1 mg/1. At 5 mg/1 of mercury,
losses of COD removal efficiency of 15 to 40 percent have been
reoorted while at 10 mg/1 loss of removal of 59 percent has been
reported! Upset of an activated sludge POTW is reported^ the
literature to occur near 200 mg/1. The anaerobic digestion pro-
cess is much less affected by the presence of mercury, with
inhibitory effects being reported at 1,365 mg/1.
In a study of 22 POTW facilities having secondary treatment, the
r^ge or removal of mercury from the influent to the POTW ranged
from 4 to 99 percent with median removal of 41 percent. Thus
significant pass through of mercury may occur.
In sludges, mercury content may be high if industrial sources of
mercury coAtaminat ion are present. Little is known about the
form in which mercury occurs in sludge. Mercury may undergo
biological methylation in sediments, but no methylation has been
observed in soils, mud, or sewage sludge.
The mercury content of soils not receiving additions of P°™
ssRids.1^^.'^-- ' Hr i<°?r r
of mercury has been observed to approach 1.0 mg/kg. In the soil,
molecular - are retained by organic matter and clay or may be
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volatilized if gaseous. Because of the high affinity between
mercury and the solid soil surfaces, mercury persists in the
upper layer of the soil.
Mercury can enter plants through the roots, it can readily move
to other parts of the plant, and it has been reported to cause
injury to plants. In many plants mercury concentrations range
from 0.01 to 0.20 mg/kg, but when plants are supplied with high
levels of mercury, these concentrations can exceed 0.5 mg/kg.
Bioconcentration occurs in animals ingesting mercury in food.
Nickel (124). Nickel is seldom found in nature as the pure ele-
mental metal. It is a relatively plentiful element and is widely
distributed throughout the earth's crust. It occurs in marine
organisms and is found in the oceans. The chief commercial ores
for nickel are pentlandite [(Fe,Ni)9S8l> and a lateritic ore
consisting of hydrated nickel-iron-magnesium silicate.
Nickel has many and varied uses. It is used in alloys and as the
pure metal. Nickel salts are used for electroplating baths.
The toxicity of nickel to man is thought to be very low, and sys-
temic poisoning of human beings by nickel or nickel salts is
almost unknown. In non-human mammals nickel acts to inhibit
insulin release, depress growth, and reduce cholesterol. A high
incidence of cancer of the lung and nose has been reported in
humans engaged in the refining of nickel.
Nickel salts can kill fish at very low concentrations. However,
nickel has been found to be less toxic to some fish than copper,
zinc, and iron. Nickel is present in coastal and open ocean
water at concentrations in the range of 0.0001 to 0.006 mg/1
although the most common values are 0.002 to 0.003 mg/1. Marine
animals contain up to 0.4 mg/1 and marine plants contain up to 3
mg/1. Higher nickel concentrations have been reported to cause
reduction in photosynthetic activity of the giant kelp. A low
concentration was found to kill oyster eggs.
For the protection of human health based on the toxic properties
of nickel ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 0.0134
mg/1. If contaminated aquatic organisms are consumed, excluding
consumption of water, the ambient water criterion is determined
to be 0.100 mg/1. Available data show that adverse effects on
aquatic life occur for total recoverable nickel concentrations as
low as 0.0071 mg/1 as a 24-hour average.
Nickel is not destroyed when treated in a POTW, but will either
pass through to the POTW effluent or be retained in the POTW
sludge. It can interfere with POTW treatment processes and can
also limit the usefulness of municipal sludge.
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Nickel salts have caused inhibition of the biochemical oxidation
of sewage in a POTW. In a pilot plant, slug doses of nickel
significantly reduced normal treatment efficiencies for a few
hours, but the plant acclimated itself somewhat to the slug dos-
aee and appeared to achieve normal treatment efficiencies within
40 hours. It has been reported that the anaerobic digestion pro-
cess is inhibited only by high concentrations of nickel, while a
low concentration of nickel inhibits the nitrification process.
The influent concentration of nickel to a POTW has been observed
bv the EPA to range from 0.01 to 3.19 mg/1, with a median of 0.33
mg/1 In a study of 190 POTW facilities, nickel pass-through was
ereater than 90 percent for 82 percent of the primary plants.
Median pass-through for trickling filter, activated sludge and
biological process plants was greater than 80 percent. POTW
effluent concentrations ranged from 0.002 to 40 mg/1 (mean =
0.410, standard deviation = 3.279).
Nickel not passed through the POTW will be incorporated into the
sludge. In a recent two-year study of eight cities, four of the
cities had median nickel concentrations of over 350 mg/kg, and
two were over 1,000 mg/kg. The maximum nickel concentration
observed was 4,010 mg/kg.
Nickel is found in nearly all soils, plants, and waters. Nickel
has no known essential function in plants. In soils, nickel
typically is found in the range from 10 to 100 mg/kg. Various
environemntal exposures to nickel appear to correlate with
increased incidence of tumors in man. For example, cancer in the
maxillary antrum of snuff users may^ result from using plant
materials grown on soil high in nickel.
Nickel toxicity may develop in plants from application of sewage
sludge on acid*soils. Nickel has caused reduction of yields for
a variety of crops including oats, mustard, turnips, and cabbage.
?n one study nickel decreased the yields of oats significantly at
100 mg/kg.
Whether nickel exerts a toxic effect on plants depends on several
soil factors, the amount of nickel applied, and the contents of
other metals in the sludge. Unlike copper and zinc which are
morlavailable from inorganic sources than from sludge nickel
uptake by plants seems to be promoted by the presence of the
organic matter in sludge. Soil treatments, such « ^"^ .
reduce the solubility of nickel. Toxicity of nickel to plants is
enhanced in acidic soils.
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of 38 minerals and a minor component of 37 others found in
various parts of the world. Most selenium is obtained as a
by-product of precious metals recovery from electrolytic copper
refinery slimes. U.S. annual production at one time reached one
million pounds.
Principal uses of selenium are in semi-conductors, pigments,
decoloring of glass, zerography, and metallurgy. It also is used
to produce ruby glass used in signal lights. Several selenium
compounds are important oxidizing agents in the synthesis of
organic chemicals and drug products.
While results of some studies suggest that selenium may be an
essential element in human nutrition, the toxic effects of
selenium in humans are well established. Lassitude, loss of
hair, discoloration and loss of fingernails are symptoms of
selenium poisoning. In a fatal case of ingestion of a larger
dose of selenium acid, peripheral vascular collapse, pulmonary
edema, and coma occurred. Selenium produces mutagenic and tera-
togenic effects, but it has not been established as exhibiting
carcinogenic activity.
For the protection of human health from the toxic properties of
selenium ingested through water and through contaminated aquatic
organisms, the ambient water criterion is determined to be 0.010
mg/1, i.e., the same as the drinking water standard. Available
data show that adverse effects on aquatic life occur at concen-
trations higher than that cited for human toxicity.
Very few data are available regarding the behavior of selenium in
a POTW. One EPA survey of 103 POTW facilities revealed one POTW
using biological treatment and having selenium in the influent.
Influent concentration was 0.0025 mg/1, effluent concentration
was 0.0016 mg/1, giving a removal of 37 percent. It is not known
to be inhibitory to POTW processes. In another study, sludge
from POTW facilities in 16 cities was found to contain from 1.0
to 8.7 mg/kg selenium, compared to 0.01 to 2 mg/kg in untreated
soil. These concentrations of selenium in sludge present a
potential hazard for humans or other mammals eating crops grown
on soil treated with selenium-containing sludge.
Silver (126). Silver is a soft, lustrous, white metal that is
insoluble in water and alkali. In nature, silver is found in the
elemental state (native silver) and combined in ores such as
argentite (Ag2S), horn silver (AgCl), proustite (Ag3AsS3),
and pyrargyrite (Ag3SbS3). Silver is used_extensively in
several industries, among them electroplating.
Metallic silver is not considered to be toxic, but most of its
salts are toxic to a large number of organisms. Upon ingestion
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by humans, many silver salts are absorbed in the circulatory sys-
tem and deposited in various body tissues, resulting in general-
ized or sometimes localized gray pigmentation of the skin and
mucous membranes known as argyria. There is no known method for
removing silver from the tissues once it is deposited, and the
effect is cumulative.
Silver is recognized as a bactericide and doses from 0.000001 to
0.0005 mg/1 have been reported as sufficient to sterilize water.
The criterion for ambient water to protect human health from the
toxic properties of silver ingested through water and through
contaminated aquatic organisms is 0.010 mg/1.
The chronic toxic effects of silver on the aquatic environment
have not been given as much attention as many other heavy metals.
Data from existing literature support the fact that silver is
very toxic to aquatic organisms. Despite the fact that silver is
nearly the most toxic of the heavy metals, there are insufficient
data to adequately evaluate even the effects of hardness on
silver toxicity. There are no data available on the toxicity of
different forms of silver.
There is no available literature on the incidental removal of
silver by a POTW. An incidental removal of about 50 percent is
assumed as being representative. This is the highest average
incidental removal of any metal for which data are available.
(Copper has been indicated to have a median incidental removal
rate of 49 percent.)
Bioaccumulation and concentration of silver from sewage sludge
has not been studied to any great degree. There is some indica-
tion that silver could be bioaccumulated in mushrooms to the
extent that there could be adverse physiological effects on
humans if they consumed large quantities of mushrooms grown in
silver enriched soil. The effect, however, would tend to be
unpleasant rather than fatal.
There is little summary data available on the quantity of silver
discharged to a POTW. Presumably there would be a tendency to
limit its discharge from a manufacturing facility because of its
high intrinsic value.
Thallium (127). Thallium (Tl) is a soft, silver-white, dense,
malleable metal. Five major minerals contain 15 to 85 percent
thallium, but they are not of commercial importance because the
metal is produced in sufficient quantity as a by-product of lead-
zinc smelting of sulfide ores. Thallium melts at 304 C. U.S.
annual production of thallium and its compounds is estimated to
be 1,500 pounds.
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Industrial uses of thallium include the manufacture of alloys,
electronic devices and special glass. Thallium catalysts are
used for industrial organic syntheses.
Acute thallium poisoning in humans has been widely described.
Gastrointestinal pains and diarrhea are followed by abnormal
sensation in the legs and arms, dizziness, and, later, loss of
hair. The central nervous system is also affected. Somnolence,
delerium or coma may occur. Studies on the teratogenicity of
thallium appear inconclusive; no studies on mutagenicity were
found; and no published reports on carcinogenicity of thallium
were found.
For the protection of human health from the toxic properties of
thallium ingested through water and contaminated aquatic
organisms, the ambient water criterion is 0.004 mg/1.
No reports were found regarding the behavior of thallium in a
POTW It will not be degraded, therefore it must pass through to
the effluent or be removed with the sludge. However, since the
sulfide (T1S) is very insoluble, if appreciable sulfide is
present dissolved thallium in the influent to a POTW may be pre-
cipitated into the sludge. Subsequent use of sludge bearing
thallium compounds as a soil amendment to crop bearing soils may
result in uptake of this element by food plants. Several leafy
garden crops (cabbage, lettuce, leek, and endive) exhibit rela-
tively higher concentrations of thallium than other foods such as
meat.
Zinc (128). Zinc occurs abundantly in the earth's crust, con-
centrated in ores. It is readily refined into the pure, stable,
silver-white metal. In addition to its use in alloys, zinc is
used as a protective coating on steel. It is applied by hot dip-
ing (i.e., dipping the steel in molten zinc) or by electroplat-
ing.
Zinc can have an adverse effect on man and animals at high con-
centrations Zinc at concentrations in excess of 5 mg/1 causes
an undesirable taste which persists through conventional treat-
ment Tor the prevention of adverse effects due to these organo-
Teptic properties of zinc, 5 mg/1 was adopted for the ambient
water criterion. Available data.show that adverse effects on
aquatic life occur at concentrations as low as 0.047 mg/1 as a
24-hour average.
Toxic concentrations of zinc compounds cause adverse changes in
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clogging of the gills with mucous. Chronically toxic concentra-
tions of zinc compounds cause general enfeeblement and widespread
histological changes to many organs, but not to gills. Abnormal
swimming behavior has been reported at 0.04 mg/1. Growth and
maturation are retarded by zinc. It has been observed that the
effects of zinc poisoning may not become apparent immediately, so
that fish removed from zinc-contaminated water may die as long as
48 hours after removal.
In general, salmonoids are most sensitive to elemental zinc in
soft water; the rainbow trout is the most sensitive in hard
waters. A complex relationship exists between zinc concentra-
tion, dissolved zinc concentration, pH, temperature, and calcium
and magnesium concentration. Prediction of harmful effects has
been less than reliable and controlled studies have not been
extensively documented.
The major concern with zinc compounds in marine waters is not
with acute lethal effects, but rather with the long-term sub-
lethal effects of the metallic compounds and complexes. Zinc
accumulates in some marine species, and marine animals contain
zinc in the range of 6 to 1,500 mg/kg. From the point of view of
acute lethal effects, invertebrate marine animals seem to be the
most sensitive organism tested.
Toxicities of zinc in nutrient solutions have been demonstrated
for a number of plants. A variety of fresh water plants tested
manifested harmful symptoms at concentrations of 0.030 to 21.6
mg/1. Zinc sulfate has also been found to be lethal to many
plants and it could impair agricultural uses of the water.
Zinc is not destroyed when treated by a POTW, but will either
pass through to the POTW effluent or be retained in the POTW
sludge. It can interfere with treatment processes in the POTW
and can also limit the usefulness of municipal sludge.
In slug doses, and particularly in the presence of copper, dis-
solved zinc can interfere with or seriously disrupt the operation
of POTW biological processes by reducing overall removal effi-
ciencies, largely as a result of the toxicity of the metal to
biological organisms. However, zinc solids in the form of
hydroxides or sulfides do not appear to interfere with biological
treatment processes, on the basis of available data. Such solids
accumulate in the sludge.
The influent concentrations of zinc to a POTW has been observed
by the EPA to range from 0.017 to 3.91 mg/1, with a median con-
centration of 0.33 mg/1. Primary treatment is not efficient in
removing zinc; however, the microbial floe of secondary treatment
readily adsorbs zinc.
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In a study of 258 POTW facilities, the median pass-through values
were 70 to 88 percent for primary plants, 50 to 60 percent for
trickling filter and biological process plants, and 30 to 40 per-
cent for activated process plants. POTW effluent concentrations
of zinc ranged from 0.003 to 3.6 mg/1 (mean = 0.330, standard
deviation = 0.464).
The zinc which does not pass through the POTW is retained in the
sludge. The presence of zinc in sludge may limit its use on
cropland. Sewage sludge contains 72 to over 30,000 mg/kg of
zinc, with 3,366 mg/kg as the mean value. These concentrations
are significantly greater than those normally found in soil,
which range from 0 to 195 mg/kg, with 94 mg/kg being a common
level. Therefore, application of sewage sludge to soil will
generally increase the concentration of zinc in the soil. Zinc
can be toxic to plants, depending upon soil pH. Lettuce, toma-
toes, turnips, mustard, kale, and beets are especially sensitive
to zinc contamination.
Oil and Grease. Oil and grease are taken together as one pollu-
tant parameter. This is a conventional pollutant and some of its
components are:
1. Light Hydrocarbons - These include light fuels such as
gasoline, kerosene, and jet fuel, and miscellaneous solvents used
for industrial processing, degreasing, or cleaning purposes. The
presence of these light hydrocarbons may make the removal of
other heavier oil wastes more difficult.
2. Heavy Hydrocarbons, Fuels, and Tars - These include the
crude oils, diesel oils, #6 fuel oil, residual oils, slop oils,
and in some cases, asphalt and road tar.
3. Lubricants and Cutting Fluids - These generally fall
into two classes: non-emulsifiable oils such as lubricating oils
and greases and emulsifiable oils such as water soluble oils,
rolling oils, cutting oils, and drawing compounds. ^ Emulsifiable
oils may contain fat, soap, or various other additives.
4. Vegetable and Animal Fats and Oils - These originate
primarily from processing of foods and natural products.
These compounds can settle or float and may exist as solids or
liquids depending upon factors such as method of use, production
process, and temperature of water.
Oil and grease even in small quantities cause troublesome taste
fta"
169
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fowl are adversely affected by oils in their habitat. Oil emul-
sions may adhere to the gills of fish causing suffocation, and
the flesh of fish is tainted when microorganisms that were
exposed to waste oil are eaten. Deposition of oil in the bottom
sediments of water can serve to inhibit normal benthic growth.
Oil and grease exhibit an oxygen demand.
Many of the toxic organic pollutants will be found distributed
between the oil phase and the aqueous phase in industrial waste-
waters. The presence of phenols, PCB's, PAH's, and almost any
other organic pollutant in the oil and grease make characteriza-
tion of this parameter almost impossible. However, all of these
other organics add to the objectionable nature of the oil and
grease.
Levels of oil and grease which are toxic to aquatic organisms
vary greatly, depending on the type and the species susceptibil-
ity. However, it has been reported that crude oil in concentra-
tions as low as 0.3 mg/1 is extremely toxic to freshwater fish.
It has been recommended that public water supply sources be
essentially free from oil and grease.
Oil and grease in quantities of 100 1/sq km show up as a sheen on
the surface of a body of water. The presence of oil slicks
decreases the aesthetic value of a waterway.
Oil and grease is compatible with a POTW activated sludge process
in limited quantity. However, slug loadings or high concentra-
tions of oil and grease interfere with biological treatment
processes. The oils coat surfaces and solid particles, prevent-
ing access of oxygen, and sealing in some microorganisms. Land
spreading of POTW sludge containing oil and grease uncontaminated
by toxic pollutants is not expected to affect crops grown on the
treated land, or animals eating those crops.
pH. Although not a specific pollutant, pH is related to the
acidity or alkalinity of a wastewater stream. It is not, how-
ever, a measure of either. The term pH is used to describe the
hydrogen ion concentration (or activity) present in a given solu-
tion. Values for pH range from 0 to 14, and these numbers are
the negative logarithms of the hydrogen ion concentrations. A pH
of 7 indicates neutrality. Solutions with a pH above 7 are alka-
line, while those solutions with a pH below 7 are acidic. The
relationship of pH and acidity and alkalinity is not necessarily
linear or direct. Knowledge of the water pH is useful in deter-
mining necessary measures for corrosion control, sanitation, and
disinfection. Its value is also necessary in the treatment of
industrial wastewaters to determine amounts of chemicals required
to remove pollutants and to measure their effectiveness. Removal
of pollutants, especially dissolved solids is affected by the pH
of the wastewater.
170
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Waters with a pH below 6.0 are corrosive to water works struc-
tures, distribution lines, and household plumbing fixtures and
can thus add constituents to drinking water such as iron, copper,
zinc, cadmium, and lead. The hydrogen ion concentration can
affect the taste of the water, and at a low pH water tastes sour.
The bactericidal effect of chlorine is weakened as the pH
increases, and it is advantageous to keep the pH close to 7.0.
This is significant for providing safe drinking water.
Extremes of pH or rapid pH changes can exert stress conditions or
kill aquatic life outright. Even moderate changes from accept-
able criteria limits of pH are deleterious to some species.
The relative toxicity to aquatic life of many materials is
increased by changes in the water pH. For example, metallocya-
nide complexes can increase a thousand-fold in toxicity with a
drop of 1.5 pH units.
Because of the universal nature of pH and its effect on water
quality and treatment, it is selected as a pollutant parameter
for many industry categories. A neutral pH range (approximately
6 to 9) is generally desired because either extreme beyond this
range has a deleterious effect on receiving waters or the pollu-
tant nature of other wastewater constituents.
Pretreatment for regulation of pH is covered by the "General Pre-
treatment Regulations for Existing and New Sources of Pollution,
40 ?FR 403 58 This section prohibits the discharge to a POTW of
"pollutants which will cause corrosive structural damage to the
POTW but in no case discharges with pH lower than 5.0 unless the
works is specially designed to accommodate such discharges.
Total Suspended Solids (TSS) . Suspended solids include both
organic and inorganic materials. The inorganic compounds include
sand silt and Slay. The organic fraction includes such materi-
als as grease, oil/tar, and animal and vegetable waste products.
These solids may settle out rapidly, and bottom deposits are
of?en a mixture^ both organic and inorganic solids Solids may
be suspended in water for a time and then settle to the bed of
the strtam or lake. These solids discharged with man's wastes
may be inert, slowly biodegradable materials, or rapidly decom-
poLble substances. While in suspension, sus?en^ *°^ion
increase the turbidity of the water, reduce light penetration,
and impair the photosynthetic activity of aquatic plants.
Suspended solids in water interfere with many industrial pro-
cesses and cause foaming in boilers and incrustations on equip-
ment IxSSseTS such waler, especially as the temperature rises.
Thev a?e undesirable in process water used in the manufacture of
steel? L tne textile industry, in laundries, in dyeing, and in
cooling systems.
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Solids in suspension are aesthetically displeasing. When they
settle to form sludge deposits on the stream or lake bed, they
are often damaging to the life in the water. Solids, when trans-
formed to sludge deposit, may do a variety of damaging things,
including blanketing the stream or lake bed and thereby destroy-
ing the living spaces for those benthic organisms that would
otherwise occupy the habitat. When of an organic nature, solids
use a portion or all of the dissolved oxygen available in the
area. Organic materials also serve as a food source for
sludgeworms and associated organisms.
Disregarding any toxic effect attributable to substances leached
out by water, suspended solids may kill fish and shellfish by
causing abrasive injuries and by clogging the gills and respira-
tory passages of various aquatic fauna. Indirectly, suspended
solids are inimical to aquatic life because they screen out
light, and they promote and maintain the development of noxious
conditions through oxygen depletion. This results in the killing
of fish and fish food organisms. Suspended solids also reduce
the recreational value of the water.
Total suspended solids is a traditional pollutant which is com-
patible with a well-run POTW. This pollutant with the exception
of those components which are described elsewhere in this sec-
tion, e.g., heavy metal components, does not interfere with the
operation of a POTW. However, since a considerable portion of
the innocuous TSS may be inseparably bound to the constituents
which do interfere with POTW operation, or produce unusable
sludge, or subsequently dissolve to produce unacceptable POTW
effluent, TSS may be considered a toxic waste.
Aluminum. Aluminum, a nonconventional pollutant, is the most
common~metallic element in the earth's crust, and the third most
abundant element (8.1 percent). It is never found free in
nature. Most rocks and various clays contain aluminum in the
form of aluminosilicate minerals. Generally, aluminum is first
converted to alumina (Al203> from bauxite ore. The alumina
then undergoes electrolytic reduction to form the metal. Alumi-
num powders (used in explosives, fireworks, and rocket fuels)
form flammable mixtures in the air. Aluminum metal resists
corrosion under many conditions by forming a protective oxide
film on the surface. This oxide layer corrodes rapidly in strong
acids and alkalis, and by the electrolytic action of other metals
with which it comes in contact. Aluminum is light, malleable,
ductile possesses high thermal and electrical conductivity, and
is non-magnetic. It can be formed, machined, or cast. Aluminum
is used in the building and construction, transportation, and the
container and packaging industries and competes with iron and
steel in these markets. Total U.S. production of primary alumi-
num in 1981 was 4,948,000 tons. Secondary aluminum (from old
scrap) production in 1981 was 886,000 tons. Production of
primary aluminum is currently declining.
172
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Aluminum is soluble under both acidic and basic conditions, with
environmental transport occurring most readily under these condi-
tions. In water, aluminum can behave as an acid or base, can
form ionic complexes with other substances, and can polymerize,
depending on pH and the dissolved substances in water. Alumi-
num's high solubility at acidic pH conditions makes it readily
available for accumulation in aquatic life. Acidic waters con-
sistently contain higher levels of soluble aluminum than neutral
or alkaline waters. Loss of aquatic life in acidified lakes and
streams has been shown to be due in part to increased concentra-
tions of aluminum in waters as a result of leaching of aluminum
from soil by acidic rainfall.
Aluminum has been found to be toxic to freshwater and marine
aquatic life. In freshwaters acute toxicity and solubility
increases as pH levels increase above pH 7. This relationship
also appears to be true as the pH levels decrease below pH 7.
Chronic effects of aluminum on aquatic life have also been docu-
mented. Aluminum has been found to be toxic to certain plants.
A water quality standard for aluminum was estabished (U.S.
Federal Water Pollution Control Administration, 1968) for inter-
state agricultural and irrigation waters, which set a trace
element tolerance at 1 mg/1 for continuous use on all soils and
20 mg/1 for short term use on fine-textured soils.
There are no reported adverse physiological effects on man from
exposure to low concentrations of aluminum in drinking water.
Large concentrations of aluminum in the human body, however, are
alleged to cause changes in behavior. Aluminum compounds,
especially aluminum sulfate, are major coagulants used in the
treatment of drinking water. Aluminum is not among the metals
for which a drinking water standard has been established.
The highest aluminum concentrations in animals and humans occur
in the lungs, mostly from the inhalation of airborne particulate
matter. Pulmonary fibrosis has been associated with the inhala-
tion of very fine particles of aluminum flakes and powders among
workers in the explosives and fireworks industries. An occupa-
tional exposure Threshold Limit Value (TLV) of 5 mg/nH is
recommended for pyro powders to prevent lung changes, and a
Time-Weighted Average (TWA) of 10 mg/m3 is recommended for
aluminum dust. High levels of aluminum have been found in the
brains, muscles, and bones of patients with chronic renal failure
who are being treated with aluminum hydroxide, and high brain
levels of aluminum are found in those suffering from Alzheimers
disease (presenile dementia) which manifests behavioral changes.
Aluminum and some of its compounds used in food preparation and
as food additives are generally recognized as safe and are sanc-
tioned by the Food and Drug Administration. No limits on alumi-
num content in food and beverage products have been established.
173
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Aluminum has no adverse effects on POTW operation at concentra-
tions normally encountered. The results of an EPA study of 50
POTWs revealed that 49 POTWs contained aluminum with effluent
concentrations ranging from less than 0.1 mg/1 to 1.07 mg/1 and
with an average removal of 82 percent.
Ammonia . Ammonia (chemical formula NHs) is a nonconventional
pollutant. It is a colorless gas with a very pungent odor, ^
detectable at concentrations of 20 ppm in air by the nose, and is
very soluble in water (570 gm/1 at 25°C). Ammonia is produced
industrially in very large quantities (nearly 20 million tons
annually in the U.S.). It is converted to ammonium compounds or
shipped in the liquid form (it liquifies at -33 C) . Ammonia also
results from natural processes. Bacterial action on nitrates or
nitrites, as well as dead plant and animal tissue and animal^
wastes produces ammonia. Typical domestic wastewaters contain 12
to 50 mg/1 ammonia.
The principal use of ammonia and its compounds is as fertilizer.
High amounts are introduced into soils and the water runoff from
agricultural land by this use. Smaller quantities of ammonia are
used as a refrigerant. Aqueous ammonia (2 to 5 percent solution)
is widely used as a household cleaner. Ammonium compounds find a
variety of uses in various industries, as an example, ammonium
hydroxide is used as a react ant in the purification of tungsten.
Ammonia is toxic to humans by inhalation of the gas or ingestion
of aqueous solutions. The ionized form, ammonium (NH4+) , is
less toxic than the unionized form. Ingestion of as little as
one ounce of household ammonia has been reported as a fatal dose.
whether inhaled or ingested, ammonia acts distinctively on mucous
membrane with resulting loss of function. Aside from breaks in
liquid ammonia refrigeration equipment, industrial hazard trom
ammonia exists where solutions of ammonium compounds may be
accidently treated with a strong alkali, releasing ammonia gas.
As little as 150 ppm ammonia in air is reported to cause laryn-
geal spasms, and inhalation of 5,000 ppm in air is considered
sufficient to result in death.
The behavior of ammonia in POTW is well documented because it is
a natural component of domestic wastewaters. Only very high con-
centrations of ammonia compounds could overload POTW. One study
has shown that concentrations of unionized ammonia greater than
90 me/I reduce gasification in anaerobic digesters and concentra-
tion! of 140 mg/1 stop digestion completely. Corros ion of copper
piping and excessive consumption of chlorine also result from
high ammonia concentrations. Interference with aerobic nitrifi-
cation processes can occur when large concentrations of ^ ammonia
suppress dissolved oxygen. Nitrites are then produced instead of
nitrates. Elevated nitrite concentrations in drinking water are
known to cause infant methemoglobinemia.
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Fluoride. Fluoride ion (F-) is a nonconventional pollutant.
Fluorine is an extremely reactive, pale yellow, gas which is
never found free in nature. Compounds of fluorine - fluorides -
are found widely distributed in nature. The principal minerals
containing fluorine are fluorspar (CaF2) and cryolite
(Na2AlF6). Although fluorine is produced commercially in
small quantities by electrolysis of potassium bifluoride in anhy-
drous hydrogen fluoride, the elemental form bears little relation
to the combined ion. Total production of fluoride chemicals in
the U.S. is difficult to estimate because of the varied uses.
Large volume usage compounds are: calcium fluoride (estimated
1,500,000 tons in U.S.) and sodium fluoraluminate (estimated
100,000 tons in U.S.). Some fluoride compounds and their uses
are sodium fluoroaluminate - aluminum production; calcium fluor-
ide - steelmaking, hydrofluoric acid production, enamel, iron
foundry; boron trifluoride - organic synthesis; antimony penta-
fluoride - fluorocarbon production; fluoboric acid and fluobor-
ates - electroplating; perchloryl fluoride (C103F) - rocket
fuel oxidizer; hydrogen fluoride - organic fluoride manufacture,
pickling acid in stainless steelmaking, manufacture of aluminum
fluoride; sulfur hexafluoride - insulator in high voltage trans-
formers; polytetrafluoroethylene - inert plastic. Sodium
fluoride is used at a concentration of about 1 pm in many public
drinking water supplies to prevent tooth decay in children.
The toxic effects of fluoride on humans include severe gastroen-
teritis, vomiting, diarrhea, spasms, weakness, thirst, failing
pulse and delayed blood coagulation. Most observations of toxic
effects are made on individuals who intentionally or accidentally
ingest sodium fluoride intended for use as rat poison or insecti-
cide. Lethal doses for adults are estimated to be as low as
2.5 g. At 1.5 ppm in drinking water, mottling of tooth enamel is
reported, and 14 ppm, consumed over a period of years, may lead
to deposition of calcium fluoride in bone and tendons.
Fluorides found in irrigation waters in high concentrations have
caused damage to certain plants exposed to these waters. Chronic
fluoride poisoning of livestock has been observed. Fluoride from
waters apparently does not accumulate in soft tissue to a signi-
ficant degree; it is transferred to a very small extent into the
milk and to a somewhat greater degree in eggs. Data for fresh
water indicate that fluorides are toxic to fish.
Very few data are available on the behavior of fluoride in POTW.
Under usual operating conditions in POTW, fluorides pass through
into the effluent. Very little of the fluoride entering conven-
tional primary and secondary treatment processes is removed. In
one study of POTW influents conducted by the U.S. EPA, nine POTW
reported concentrations of fluoride ranging from 0.7 mg/1 to l.Z
mg/1, which is the range of concentrations used for fluoridated
drinking water.
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Phenols (Total). "Total Phenols" is a nonconventional pollutant
parameter. Total phenols is the result of analysis using the
4-AAP (4-aminoantipyrene) method. This analytical procedure
measures the color development of reaction products between 4-AAP
and some phenols. The results are reported as phenol. Thus
"total phenol" is not total phenols because many phenols (notably
nitrophenols) do not react. Also, since each reacting phenol
contributes to the color development to a different degree, and
each phenol has a molecular weight different from others and from
phenol itself, analyses of several mixtures containing the same
total concentration in mg/1 of several phenols will give differ-
ent numbers depending on the proportions in the particular
mixture.
Despite these limitations of the analytical method, total phenols
is a useful parameter when the mix of phenols is relatively con-
stant and an inexpensive monitoring method is desired. In any
given plant or even in an industry subcategory, monitoring of
total phenols" provides an indication of the concentration of
this group of priority pollutants as well as those phenols not
selected as priority pollutants. A further advantage is that the
method is widely used in water quality determinations.
In an EPA survey of 103 POTW the concentration of "total phenols"
ranged from 0.0001 mg/1 to 0.176 mg/1 in the influent, with a
median concentration of 0.016 mg/1. Analysis of effluents from
22 of these same POTW which had biological treatment meeting
secondary treatment performance levels showed "total phenols"
concentrations ranging from 0 mg/1 to 0.203 mg/1 with a median of
0.007. Removals were 64 to 100 percent with a median of 78 per-
cent.
It must be recognized, however, that six of the eleven priority
pollutant phenols could be present in high concentrations and not
be detected. Conversely, it is possible, but not probable, to
have a high "total phenol" concentration without any phenol
itself or any of the 10 other priority pollutant phenols present.
A characterization of the phenol mixture to be monitored to
establish constancy of composition will allow "total phenols" to
be used with confidence.
SUMMARY OF POLLUTANT SELECTION
After examining the sampling data, pollutants and pollutant
parameters were selected by subcategory for further consideration
for limitation. The selection of a pollutant was based on the
concentration of the pollutant in the raw sampling data and the
frequency of occurrence above concentrations considered treata-
ble. Paragraph 8(a)(iii) allows the exclusion of a toxic pollu-
tant if it is not detected, if it is present in amounts too small
to be effectively reduced by technologies known to the
176
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Administrator, if it is detected in the effluent from only a
small number of sources, or if it is present solely as a result
of its presence in the intake waters. The exclusion and selec-
tion of pollutants that took place under this rationale are
listed below. The analysis that led to the selection of these
toxic pollutants is presented in Section VI of each subcategory
supplement.
Pollutants Selected for Further Consideration by Subcategory
Primary Aluminum Smelting Subcategory
1. acenaphthene
39. fluoranthene
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo(a)pyrene
76. chrysene
77. acenaphthylene
78. anthracene (a)
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene (a)
82. dibenzo(a,h)anthracene (1,2,5,6-dibenzanthracene)
84. pyrene
114. antimony
115. arsenic
116. asbestos
118. cadmium
119. chromium (Total)
120. copper
121. cyanide (Total)
122. lead
124. nickel
125. selenium
128. zinc
aluminum
fluoride
oil and grease
TSS
pH
(a) Reported together
177
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Secondary Aluminum Subcategory
118. cadmium
122. lead
128. zinc
aluminum
ammonia (N)
oil and grease
TSS
pH
Primary Electrolytic Copper Refining Subcategory
115. arsenic
119. chromium (Total)
120. copper
122. lead
124. nickel
126. silver
128. zinc
TSS
PH
Primary Lead Subcategory
116. asbestos
118. cadmium
122. lead
128. zinc
TSS
PH
Primary Zinc Subcategory
115. arsenic
116. asbestos
118. cadmium
119. chromium (Total)
120. copper
122. lead
124. nickel
126. silver
128. zinc
TSS
pH
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Metallurgical Acid Plants Subcategory
114. antimony
115. arsenic
118. cadmium
119. chromium (Total)
120. copper
122. lead
123. mercury
124. nickel
125. selenium
126. silver
128. zinc
TSS
pH
Primary Tungsten Subcategory
1. acenaphthene
55. naphthalene
77. acenaphthylene
80. fluorene
118. cadmium
119. chromium (Total)
122. lead
125. selenium
127. thallium
128. zinc
ammonia (N)
TSS
pH
Primary Columbium-Tantalum Subcategory
7. chlorobenzene
8. 1,2,4-trichlorobenzene
10*. l',2-dichloroethane
38. ethylbenzene
51. chlorodibromomethane
87. trichloroethylene
114. antimony
115. arsenic
116. asbestos
118. cadmium
119. chromium (Total)
120. copper
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122. lead
124. nickel
125. selenium
127. thallium
128. zinc
ammonia (N)
fluoride
TSS
pH
Secondary Silver Subcategory
4. benzene
6. carbon tetrachloride (tetrachlorornethane)
10. 1,2-dichloroethane
29. 1,1-dichloroethylene
87. trichloroethylene
114. antimony
115. arsenic
118. cadmium
119. chromium (Total)
120. copper
121. cyanide
122. lead
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
ammonia (N)
TSS
pH
Secondary Lead Subcategory
114. antimony
115. arsenic
118. cadmium
119. chromium (Total)
120. copper
122. lead
124. nickel
126. silver
127. thallium
128. zinc
TSS
pH
180
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Toxic Pollutants Not Detected
Primary Aluminum Smelting Subcategory
2. acrolein
3. acrylonitrile
5. benzidine
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1.2-dichloroethane
11. 1,1,1-trichlorethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
43. bis(2-choroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromethane
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
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56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
63. N-nitrosodt-n-propylamine
64. pentachlorophenol
71. dimethyl phthalate
85. tetrachloroethylene
88. vinyl chloride (chloroethylene)
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
Secondary Aluminum Subcategory
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trichlorethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorotneta cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
28. 3,3'-dichlorobenzidine
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
40. 4-chlorophenyl phenyl ether
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41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
5 5. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
70. diethyl phthalate
72. benzo (a)anthracene (1,2-benzanthracene)
74. 3,4-benzofluoranthene
75. benzo (k) f luoranthene (11,12-benzofluoranthene)
78. anthracene (a)
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene (a)
82. dibenzo (a,h)anthracene (1,2 ,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
86. toluene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
94. 4,4'-DDD(p,p'TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
105. g-BHC-Delta
116. asbestos (Fibrous)
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
(a) Reported together.
183
-------
Primary Electrolytic Copper Refining Subcategory
2. aerolein
3. acrylonitrile
5. benzidine
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1.2-dichloroethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlororoeta cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
44. methylene chloride (dichloromethane)
45. methyl chloride (ch1oromethane)
46. methyl bromide (bromoroethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
56. nitrobenzene
57. 2-n i trophenoI
184
-------
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamtne
64. pentachlorophenol
65. phenol
70. diethyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
74. 3,4-benzofluoranthene
77. acenaphthylene
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
82. dibenzo (a,h)anthracene (1,2 ,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
86. toluene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
94. 4,4'-DDD(p,P'TDE)
105. g-BHC-Delta
113. toxaphene
116. asbestos (Fibrous)
117. beryllium
118. cadmium
121. cyanide (Total)
123. mercury
127. thallium
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
Primary Lead Subcategory
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1.2-dichloroethane
11. 1,1,1-trichlorethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
185
-------
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-diraethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chloride (ch1oromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. d ichlorobromomethane
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine_
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
186
-------
71. dimethyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo(a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
78. anthracene (a)
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene (a)
82. dibenzo(a,h)anthracene (1,2 ,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
84. pyrene
85. tetrachloroethylene
86. toluene
87. trichloroethylene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
94. 4,4'-DDD(p,p!TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
105. g-BHC-Delta
106. PCB-1242 (Arochlor 1242) (b)
107. PCB-1254 (Arochlor 1254) (b)
108. PCB-1221 (Arochlor 1221) (b)
109. PCB-1232 (Arochlor 1232) (c)
110. PCB-1248 (Arochlor 1248) (c)
111. PCB-1260 (Arochlor 1260) (c)
112. PCB-1016 (Arochlor 1016) (c)
113. toxaphene
121. cyanide (Total)
127. thallium
129. 2,3,7 ,8-tetrachlorodibenzo-p-dioxo.n (TCDD;
(a), (b), (c) Reported together.
187
-------
Primary Zinc Subcategory
1. acenaphthene
2. acrolein
3. acrylonitrile
4. benzene
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1.2-dichloroethane
11. 1,1,1-trichlorethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
23. chloroform (trichloromethane)
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. DELETED
188
-------
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo(a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
78. anthracene (a)
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene (a)
82. dibenzo(a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
84. pyrene
85. tetrachloroethylene
86. toluene
87. trichloroethylene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
189
-------
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
105. g-BHC-Delta
106. PCB-1242 (Arochlor 1242) (b)
107. PCB-1254 (Arochlor 1254) (b)
108. PCB-1221 (Arochlor 1221) (b)
109. PCB-1232 (Arochlor 1232) (c)
110. PCB-1248 (Arochlor 1248) (c)
111. PCB-1260 (Arochlor 1260) (c)
112. PCB-1016 (Arochlor 1016) (c)
113. toxaphene
114. antimony
117. beryllium
121. cyanide (Total)
127. thallium
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
(a), (b), (c) Reported together.
Metallurgical Acid Plants Subcategory
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
11. 1,1,1-trichlorethane
12. hexachlorethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
190
-------
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37 . 1,2-dtphenylhydraztne
38. ethylbenzene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
50. DELETED
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
72. benzo(a)anthracene (1,2-benzanthracene)
77. acenaphthylene
79. benzo(ghi)perylene (1,11-benzoperylene)
82. dibenzo(a,h)anthracene (1,2 ,5 ,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
88. vinyl chloride (chloroethylene)
89. aldrin
95. a-endosulfan-Alpha
97. endosulfan sulfate
102. a-BHC-Alpha
105. g-BHC-Delta
113. toxaphene
116. asbestos . ,~,rnn\
129. 2,3,7,8-tetrachlorodibenzo-p-dxoxxn (TCUV)
Primary Tungsten Subcategory
2. acrolein
3. acrylonitrile
5. benzidene N
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
11. 1,1,1-trichlorethane
12. hexachlore thane
191
-------
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
44. methylene chloride (dichloromethane)
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
48. dichlorobromomethane
49. DELETED
50. DELETED
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
67. butyl benzyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo(a)pyrene (3,4-benzopyrene)
192
-------
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
79. benzo(ghi)perylene (1,11-benzoperylene)
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
96. b-endosulfan-Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
105. g-BHC-Delta
113. toxaphene
114. antimony
116. asbestos (Fibrous)
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD;
Primary Columbium-Tantalum Subcategory
2. acrolein
3. acrylonitrile
5. benzidene
9. hexachlorobenzene
11. 1,1,1-trichloroethane
13. 1,1-dichloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
31. 2 ,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
193
-------
34. 2,4-dtmethylphenol
37. 1,2-diphenylhydrazine
40. 4-chlorophenyl phenyl ether
41. 4-broraophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
49. DELETED
50. DELETED
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
55. naphthalene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
67. butyl benzyl phthalate
69. di-n-octyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
79. benzo(ghi)perylene (1,11-benzoperylene)
82. dibenzo(a,h)anthracene (1,2,5,6-dibenzanthracene
83. indeno (1,2,3-cd)pyrene
84. pyrene
86. toluene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. B-BHC-Beta
104. r-BHC (lindane)-Gamma
105. delta-BHC
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
194
-------
Secondary Silver Subcategory
2. acrolein
3. acrylonitrile
5. benzidene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
48. dichlorobromomethane
49. DELETED
50. DELETED
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
195
-------
64. pentachlorophenol
65. phenol
71. dimethyl phthalate
72. benzo (a)anthracene (1,2-benzanthracene)
73. benzo (a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene
88. vinyl chloride (chloroethylene)
89. aldrin
94. 4,4'-DDD(p,p'TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
101. heptachlor epoxide
105. g-BHC-Delta
117. beryllium
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
Secondary Lead Subcategory
1. acenaphthene
2. acrolein
3. acrylonitrile
4. benzene
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trichlorethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethylene
16. chloroethane
17. DELETED
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chlor©naphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
196
-------
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
41. 4-brotnophenyl phenyl ether
42. bis(2-chlorotsopropyl) ether
43. bis(2-choroethoxy) methane
44, methylene chloride (dichloromethane)
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
48. dichlorobromomethane
49. DELETED
50. DELETED
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylaroine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
67. butyl benzyl phthalate
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo(a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthene (11,12-benzofluoranthene)
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene N
82. dibenzo(a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno(l,2,3-cd)pyrene
85. tetrachloroethylene
86. toluene
87. trichloroethylene
88. vinyl chloride (chloroethylene)
89. aldrin
197
-------
95- a-endosulfan-Alpha
97. endosulfan sulfate
105. g-BHC-Delta
113. toxaphene
116. asbestos (Fibrous)
125. selenium
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
Toxic Pollutants Detected Below the Analytical Quantification
Limit
Primary Aluminum Smelting Subcategory
54. isophorone
69. di-n-ocytl phthalate
70. diethyl phthalate
86. toluene
87. trichloroethylene
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites;
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
105. g-BHC-Delta
109. PCB-1232 (Arochlor 1232) (a)
110. PCB-1248 (Arochlor 1248) (a)
111. PCB-1260 (Arochlor 1260) (a)
112. PCB-1016 (Arochlor 1016) (a)
113. toxaphene
(a) Reported together.
Secondary Aluminum Subcategory
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4f-DDE(p,pIDDX)
98. endrin
198
-------
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
106. PCB-1242 (Arochlor 1242) (a)
107. PCB-1254 (Arochlor 1254) (a)
108. PCB-1221 (Arochlor 1221) (a)
109. PCB-1232 (Arochlor 1232) (b)
110. PCB-1248 (Arochlor 1248) (b)
111. PCB-1260 (Arochlor 1260) (b)
112. PCB-1016 (Arochlor 1016) (b)
113. toxaphene
121. cyanide (Total)
(a), (b) Reported together.
Primary Electrolytic Copper Refining Subcategory
1. acenaphthene
4. benzene
11. 1,1,1-trichlorethane
15. 1,1,2,2-tetrachloroethane
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
39. fluoranthene
55. naphthalene
71. dimethyl phthalate
73. benzo (a)pyrene (3,4-benzopyrene)
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
78. anthracene (a)
81. phenanthrene (a)
84. pyrene
85. tetrachloroethylene
87. trichloroethylene
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
95. a-endosulfan-Alpha
96. b-endosulfan—Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
199
-------
104. r-BHC (lindane)-Gamma
106. PCB-1242 (Arochlor 1242) (b)
107. PCB-1254 (Arochlor 1254) (b)
108. PCB-1221 (Arochlor 1221) (b)
109. PCB-1232 (Arochlor 1232) (c)
110. PCB-1248 (Arochlor 1248) (c)
111. PCB-1260 (Arochlor 1260) (c)
112. PCB-1016 (Arochlor 1016) (c)
(a), (b), (c) Reported together.
Primary Lead Subcategory
4. benzene
6. carbon tetrachloride (tetrachloromethane)
23,. chloroform (trichloromethane)
44. methylene chloride (dichloromethane)
Metallurgical Acid Plants Subcategory
4. benzene
10. 1.2-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
39. fluoranthene
49. DELETED
51. chlorodibromomethane
54. isophorone
55. naphthalene
64. pentachlorophenol
65. phenol
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
73. benzo (a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
80. fluorene
84. pyrene
87. trichloroethylene
90. dieldrin
91. chlordane (technical mixture and metabolites;
92. 4,4'-DDT
93. 4,4l-DDE(p,p'DDX)
200
-------
94. 4,4'-DDD(p,pfTDE)
96. b-endosul£an-Beta
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
106. PCB-1242 (Arochlor 1242) (a)
107. PCB-1254 (Arochlor 1254) (a)
108. PCB-1221 (Arochlor 1221) (a)
109. PCB-1232 (Arochlor 1232) (b)
110. PCB-1248 (Arochlor 1248) (b)
111. PCB-1260 (Arochlor 1260) (b)
112. PCB-1016 (Arochlor 1016) (b)
117. beryllium
121. cyanide (Total)
(a), (b) Reported together.
Primary Tungsten Subcategory
4. benzene
10. 1.2-dichloroethane
15. 1,1,2,2-tetrachloroethane
39. fluoranthene
78. anthracene (a)
81. phenanthrene (a)
84. pyrene
87. trichloroethylene
95. a-endosulfan-Alpha
106. PCB-1242 (Arochlor 1242) (b)
107. PCB-1254 (Arochlor 1254) (b)
108. PCB-1221 (Arochlor 1221) (b)
109. PCB-1232 (Arochlor 1232) (c)
110. PCB-1248 (Arochlor 1248) (c)
111. PCB-1260 (Arochlor 1260) (c)
112. PCB-1016 (Arochlor 1016) (c)
(a), (b), (c) Reported together.
Primary Columbium-Tantalum Subcategory
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
20. 2-chloronaphthalene
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
201
-------
39. fluoranthene
67. butyl benzyl phthalate
73. benzo (a)pyrene (3,4-benzopyrene)
78. anthracene (a)
80. fluorene
81. phenanthrene (a)
113. toxaphene
121. cyanide (Total)
(a) Reported together.
Secondary Silver Subcategory
7. chlorobenzene
15. 1,1,2,2-tetrachloroethane
51. chlorodibromomethane
78. anthracene (a)
81. phenanthrene (a)
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
98. endrin
99. endrin aldehyde
100. heptachlor
102. a-BHC-Alpha
103. b-BHOBeta
104. r-BHC (lindane)-Gamma
113. toxaphene
116. asbestos
(a) Reported together.
Secondary Lead
7. chlorobenzene
40. 4-chlorophenyl phenyl ether
70. diethyl phthalate
78. anthracene (a)
81. phenanthrene (a)
90. dieldrin
91. chlordane (technical mixture and metabolites;
92. 4,4'-DDT
93. 4,4f-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
96. b-endosulfan-Beta
98. endrin
202
-------
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
106. PCB-1242 (Arochlor 1242) (b)
107. PCB-1254 (Arochlor 1254) (b)
108. PCB-1221 (Arochlor 1221) (b)
109. PCB-1232 (Arochlor 1232) (c)
110. PCB-1248 (Arochlor 1248) (c)
111. PCB-1260 (Arochlor 1260) (c)
112. PCB-1016 (Arochlor 1016) (c)
(a), (b), (c) Reported together.
Toxic Pollutants Detected in Amounts Too Small to be Effectively
Reduced by Technologies Considered in Preparing this Guideline
Primary Aluminum Smelting Subcategory
4. benzene
23. chloroform (trichloromethane)
44. methylene chloride (dichloromethane)
123. mercury
Secondary Aluminum Subcategory
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
48. dichlorobromomethane
114. antimony
117. beryllium
123. mercury
125. selenium
126. silver
Primary Electrolytic Copper Refining Subcategory
114. antimony
125. selenium
Primary Lead Subcategory
115. arsenic
117. beryllium
119. chromium (Total)
123. mercury
124. nickel
203
-------
125. selenium
126. silver
Primary Zinc Subcategory
44. methylene chloride
123. mercury
125. selenium
Metallurgical Acid Plants Subcategory
23. chloroform (trichloromethane)
48. dichlorobromomethane
85. tetrachloroethylene
Primary Tungsten Subcategory
23. chloroform (trichloromethane)
29. 1,1-dichloroethylene
38. ethylbenzene
51. chlorodibromomethane
85. tetrachloroethylene
86. toluene
117. beryllium
121. cyanide (Total)
123. mercury
Primary Columbium-Tantalum Subcategory
4. benzene
48. dichlorobromomethane
54. isophorone
70. diethyl phthalate
117. beryllium
126. silver
Secondary Silver Subcategory
1. acenaphthene
30. 1,2-trans-dichloroethylene
38. ethylbenzene
204
-------
Secondary Lead Subcategory
23. chloroform (trichloromethane)
47. bromoform (tribromomethane)
56. nitrobenzene
71. dimethyl phthalate
117. beryllium
Toxic Pollutants Detected in the Effluent From Only a Small
Number of Sources
Primary Aluminum Smelting Subcategory
20. 2-chloronaphthalene
42. bis(2-chloroisopropyl) ether
55. naphthalene
62. N-nitrosodiphenylamine
65. phenol
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthene (11,12-benzofluoranthene)
83. indeno(l,2,3-cd)pyrene
106. PCB-1242 (Arochlor 1242) (a)
107. PCB-1254 (Arochlor 1254) (a)
108. PCB-1221 (Arochlor 1221) (a)
117. beryllium
126. silver
127. thallium
(a), (b) Reported together.
Secondary Aluminum Subcategory
4. benzene
23. chloroform (trichloromethane)
27. 1,4-dichlorobenzene
39. fluoranthene
44. methylene chloride (dichloromethane)
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
71. dimethyl phthalate
73. benzo (a)pyrene (3,4-benzopyrene)
76. chrysene
77. acenaphthylene
84. pyrene
85. tetrachloroethylene
205
-------
87. trichloroethylene
115. arsenic
119. chromium (Total)
120. copper
124. nickel
127. thallium
Primary Lead Subcategory
114. antimony
120. copper
Metallurgical Acid Plants Subcategory
6. carbon tetrachloride
13. 1,1-dichloroethane
44. methylene chloride (dichloromethane)
66. bis(2-ethylhexyl) phthalate
78. anthracene (a)
81. phenanthrene (a)
86. toluene
127. thallium
(a) Reported together.
Primary Tungsten Subcategory
47. bromoform (tribromomethane)
66. bis(2-ethylhexyl) phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
76. chrysene
115. arsenic
120. copper
124. nickel
126. silver
Primary Columbium-Tantalum Subcategory
1. acenapthene
6. carbon tetrachloride (tetrachloromethane)
12. hexachlorethane
23. chloroform (trichloromethane)
30. 1,2-trans-dichloroethylene
44. methylene chloride
47. bromoform
56. nitrobenzene
206
-------
66. bis(2-ethylhexyl) phthalate
68. di-n-butyl phthalate
71. dimethyl phthalate
85. tetrachloroethylene
106. PCB-1242 (Arochlor 1242) (a)
107. PCB-1254 (Arochlor 1254) (a)
108. PCB-1221 (Arochlor 1221) (a)
109. PCB-1232 (Arochlor 1232) (b)
110. PCB-1248 (Arochlor 1248) (b)
111. PCB-1260 (Arochlor 1260) (b)
112. PCB-1016 (Arochlor 1016) (b)
123. mercury
(a), (b) Reported together.
Secondary Silver Subcategory
11. 1,1,1-trichlorethane
23. chloroform (trichloromethane)
44. methylene chloride (dichloromethane)
47. bromofonn (tribromomethane)
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
84. pyrene
85. tetrachloroethylene
86. toluene
106. PCB-1242 (Arochlor 1242) (a)
107. PCB-1254 (Arochlor 1254) (a)
108. PCB-1221 (Arochlor 1221) (a)
109. PCB-1232 (Arochlor 1232) (b)
110. PCB-1248 (Arochlor 1248) (b)
111. PCB-1260 (Arochlor 1260) (b)
112. PCB-1016 (Arochlor 1016) (b)
123. mercury
(a), (b) Reported together.
Secondary Lead Subcategory
39. fluoranthene
66. bis(2-ethylhexyl) phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
76. chrysene
77. acenaphthylene
84. pyrene
121. cyanide (Total)
123. mercury
207
-------
Toxic Pollutants Detected But Present Solely as a Result of Their
Presence in the Intake Waters~~
Primary Electrolytic Copper Refining Subcategory
23. chloroform
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-ocytl phthalate
208
-------
Table VI-1
LIST OF 129 TOXIC POLLUTANTS
Compound Name
1. acenaphthene
2. acrolein
3. acrylonitrile
4. benzene
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
Chlorinated benzenes (other than dichlorobenzenes)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
Chlorinated ethanes (including 1,2-dichloroethane.
1,1,1-trichloroethane and hexachloroethane)
10. 1.2-dichloroethane
11. 1,1,1-trichlorethane
12. hexachlorethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
Chloroalkyl ethers (chloromethyl, chloroethyl and
mixed ethers)
17. bis (chloromethyl) ether
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
Chlorinated naphthalene
20. 2-chloronaphthalene
Chlorinated phenols (other than those listed elsewhere;
includes trichlorophenols and chlorinated cresols)
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
23. chloroform (trichloromethane)
24. 2-chlorophenol
209
-------
Table VI-1 (Continued)
LIST OF 129 TOXIC POLLUTANTS
Dichlorobenzenes
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
Dichlorobenzidine
28. 3,3'-dichlorobenztdine
Dichloroethylenes (1,1-dtchloroethylene and
1,2-dichloroethylene)
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
Dichloropropane and dichloropropene
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
Dlnitrotoluene
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydraztne
38. ethylbenzene
39. fluoranthene
Haloethers (other than those listed elsewhere)
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
Halomethanes (other than those listed elsewhere)
44. methylene chloride (dichloromethane)
45. methyl chloride (ch1oromethane)
46. methyl bromide (bromomethane)
210
-------
Table VI-1 (Continued)
LIST OF 129 TOXIC POLLUTANTS
Halomethanes (Cont.)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. trichlorofluoromethane
50. dichlorodifluoromethane
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
Nitrophenols (including 2,4-dinitrophenol and dinitrocresol)
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
Nitrosamines
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
65. phenol
Phthalate esters
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
Polynuclear aromatic hydrocarbons
72. benzo (a)anthracene (1,2-benzanthracene)
73. benzo (a)pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
211
-------
Table VI-1 (Continued)
LIST OF 129 TOXIC POLLUTANTS
Polynuclear aromatic hydrocarbons (Cont.)
76. chrysene
7 7. acenaphthylene
78. anthracene
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)
83. tndeno (1,2,3-cd)pyrene (w,e,-o-phenylenepyrene)
84. pyrene
85. tetrachloroethylene
86. toluene
87. trlchloroethylene
88. vinyl chloride (chloroethylene)
Pesticides and metabolites
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites;
DDT and metabolites;
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
Polychlorinated biphenyls (PCB's)
Endosulfan and metabolites
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
Endrin and metabolites
98. endrin
99. endrin aldehyde
Heptachlor and metabolies
100. heptachlor
101. heptachlor epoxide
212
-------
Table VI-1 (Continued)
LIST OF 129 TOXIC POLLUTANTS
Hexachlorocyclohexane (all isomers)
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Gamma
105. g-BHC-Delta
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
Metals and Cyanide, and Asbestos
114. antimony
115. arsenic
116. asbestos (Fibrous)
117. beryllium
118. cadmium
119. chromium (Total)
120. copper
121. cyanide (Total)
Metals and Cyanide, and Asbestos (Cont.)
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
Other
113. toxaphene
129. 2,3,7,8-tetra chlorodibenzo-p-dioxin (TCDD)
213
-------
SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
This section describes the treatment techniques currently used or
available to remove or recover wastewater pollutants normally
generated by the nonferrous metals manufacturing industrial point
source category. Included are discussions of individual end-of-
pipe treatment technologies and in-plant technologies. These
treatment technologies are widely used in this category and many
industrial categories; therefore, data and information to support
their effectiveness have been drawn from a wide range of sources
and data bases.
END-OF-PIPE TREATMENT TECHNOLOGIES
Individual recovery and treatment technologies are described
herein which are used or are suitable for use in treating waste-
water discharges from nonferrous metals manufacturing facilities.
Each description includes a functional description and discus-
sions of application and performance, advantages and limitations,
operational factors (reliability, maintainability, solid waste
aspects), and demonstration status. The treatment processes
described include both technologies presently demonstrated within
the nonferrous metals manufacturing category, and technologies
demonstrated in treatment of similar wastewater in other indus-
tries. These technologies will be evaluated in the appropriate
subcategory supplements as they relate to specific nonferrous
metals manufacturing subcategories.
Nonferrous metals manufacturing wastewater streams characteristi-
cally contain treatable concentrations of toxic metals. The
toxic metals antimony, arsenic, cadmium, chromium, copper, lead,
nickel, selenium, silver, and zinc are found in nonferrous metals
manufacturing wastewater streams at treatable concentrations.
Aluminum, ammonia, cyanide, fluoride, and some toxic organics
also may be present. These are the most significant wastewater
pollutants in this category.
The most effective technology for metals removal is chemical
precipitation, sedimentation, and filtration. Most metals are
effectively removed by precipitation of metal hydroxides or
carbonates utilizing the reaction with lime, sodium hydroxide, or
sodium carbonate. For some metals, improved removal is^provided
by the use of sodium sulfide or ferrous sulfide to precipitate
the pollutants as sulfide compounds.
Discussion of end-of-pipe treatment technologies is divided into
three parts: the major technologies; the effectiveness of major
technologies; and minor end-of-pipe technologies.
215
-------
MAJOR TECHNOLOGIES
In Sections IX, X, XI, and XII of each of the subcategory
supplements, the rationale for selecting treatment systems is
discussed. The individual technologies used in the system are
described here. The major end-of-pipe technologies considered
are: activated alumina, ammonia stripping, carbon adsorption,
chemical precipitation of dissolved metals, cyanide precipita-
tion, granular bed filtration, pressure filtration, settling of
suspended solids, and skimming of oil. In practice, precipita-
tion of metals and settling of the resulting precipitates is
often a unified two-step operation. Suspended solids originally
present in raw wastewaters are not appreciably affected by the
precipitation operation and are removed with the precipitated
metals in the settling operations. Settling operations can be
evaluated independently of hydroxide or other chemical precipita-
tion operations, but hydroxide and other chemical precipitation
operations can only be evaluated in combination with a solids
removal operation.
Activated Alumina Adsorption
Application, Performance, Advantages and Limitations. Activated
alumina adsorbs arsenic and fluorides.Alumina's removal effi-
ciency depends on the wastewater characteristics. High concen-
trations of alkalinity or chloride and high pH reduce activated
alumina's capacity to adsorb. This reduction in adsorptive
capacity is due to the alkalinity-causing (e.g., hydroxides,
carbonates, etc.) and chlorine anions competing with arsenic and
fluoride ions for removal sites on the alumina.
While chemical precipitation (as discussed on p. 221) can reduce
fluoride to less than 14 mg/1 by formation of calcium fluoride,
activated alumina can reduce fluoride levels to below 1.0 mg/1 on
a long-term basis. An initial concentration of 30 mg/1 of fluor-
ide can be reduced by as much as 85 to 99+ percent. Influent
arsenic concentrations of 0.3 to 10 mg/1 can be reduced by 85 to
99-1- percent. However, some complex forms of fluoride are not
removed by activated alumina. Caustic, sulfuric acid, hydro-
chloric acid, and alum are used to chemically regenerate
activated alumina.
Operational Factors—Reliability and Maintainability: Activated
alumina has been used at potable water treatment plants for many
years. Furthermore, the equipment is similar to that found in
ion-exchange water softening plants which are commonly used in
industry to prepare boiler water.
Demonstration Status. The use of activated alumina has not been
reported by any nonferrous metals manufacturing plants nor is it
widely applied in any other industrial categories. High capital
and operation costs generally limit the wide application of this
process in industrial applications.
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Ammonia Steam Stripping
Ammonia, often used as a process reagent, dissolves in water to
an extent governed by the partial pressure of the gas in contact
with the liquid. The ammonia may be removed from process waste-
waters by stripping with air or steam.
Air stripping takes place in a packed or lattice tower; air is
blown through the packed bed or lattice, over which the ammonia-
laden stream flows. Usually, the wastewater is heated prior to
delivery to the tower, and air is used at ambient temperature.
The term "ammonia steam stripping" refers to the process of
desorbing aqueous ammonia by contacting the liquid with a suffi-
cient amount of ammonia-free steam. The steam is introduced
countercurrent to the wastewater to maximize removal of ammonia.
The operation is commonly carried out in packed bed or tray
columns, and the pH is adjusted to 12 or more with lime._ Simple
tray designs (such as disk and doughnut trays) are used in steam
stripping because of the presence of appreciable suspended solids
and the scaling produced by lime. These allow easy cleaning of
the tower, at the expense of somewhat lower steam water contact
efficiency, necessitating the use of more trays for the same
removal efficiency.
Application and Performance. The evaporation of water and the
volatilization of ammonia generally produces a drop in both tem-
perature and pH, which ultimately limit the removal of ammonia in
a single air stripping tower. However, high removals are favored
by:
1. High pH values, which shift the equilibrium from
ammonium toward free ammonia;
2. High temperature, which decreases the solubility of
ammonia in aqueous solutions; and
3. Intimate and extended contact between the wastewater to
be stripped and the stripping gas.
Of these factors, pH and temperature are generally more cost-
effective to optimize than increasing contact time by an increase
in contact tank volume or recirculation ratio. The temperature
will, to some extent, be controlled by the climatic conditions;
the pH of the wastewater can be adjusted to assure optimum
stripping.
Steam stripping offers better ammonia removal (99 percent or ^
better) than air stripping for high-ammonia wastewaters found in
the primary columbium-tantalum, secondary silver, and primary
tungsten subcategories of this category. The performance of an
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ammonia stripping column is influenced by a number of important
variables that are associated with the wastewater being treated
and column design. Brief discussions of these variables follow.
Wastewater pH: Ammonia in water exists in two forms, NH3 and
NHA+ the distribution of which is pH dependent. Since only
the molecular form of ammonia (NH3> can be stripped, increasing
the fraction of NH3 by increasing the pH enhances the rate of
ammonia desorption.
Column temperature: The temperature of the stripping column
affects the equilibrium between gaseous and dissolved ammonia, as
well as the equilibrium between the molecular and ionized forms
of ammonia in water. An increase in the temperature reduces the
ammonia solubility and increases the fraction of aqueous ammonia
that is in the molecular form, both exhibiting favorable effects
on the desorption rate.
Steam rate: The rate of ammonia transfer from the liquid to gas
phase is directly proportional to the degree of ammonia under-
saturation in the desorbing gas. Increasing the rate of steam
supply, therefore, increases undersaturation and ammonia trans-
fer.
Column design: A properly designed stripper column achieves uni-
form distribution of the feed liquid across the cross section of
the column, rapid renewal of the liquid-gas interface, and
extended liquid-gas contacting area and time.
Steam stripping can recover significant quantities of reagent
ammonia from wastewaters containing extremely high initial
ammonia concentrations, which partially offsets the capital and
energy costs of the technology.
Advantages and Limitations. Strippers are widely used in indus-
try to remove a variety of materials, including hydrogen sulfide
and volatile organics as well as ammonia, from aqueous streams.
The basic techniques have been applied both in process and in
wastewater treatment applications and are well understood. The
use of steam strippers with and without pH adjustment is standard
practice for the removal of hydrogen sulfide and ammonia in the
petroleum refining industry and has been studied extensively in
this context. Air stripping has treated municipal and industrial
wastewater and is recognized as an effective technique of broad
applicability. Both air and steam stripping have successfully
treated ammonia-laden wastewater, both within the nonferrous
metals manufacturing category or for similar wastes in closely
related industries.
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The major drawback of air stripping is the low efficiency in cold
weather and the possibility of freezing within the tower.
Because lime may cause scaling problems and the types of towers
used in air stripping are not easily cleaned, caustic soda is
generally employed to raise the feed pH. Air stripping simply
transfers the ammonia from one medium to another, whereas, steam
stripping allows for recovery and, if so desired, reuse of
ammonia. Four primary tungsten plants use steam stripping to
recover ammonia from process wastewater and reuse the ammonia in
the manufacture of ammonium paratungstate. The two major limita-
tions of steam strippers are the critical column design required
for proper operation and the operational problems associated with
fouling of the packing material.
Operational Factors. Reliability and Maintainability: Strippers
are relatively easy to operate. The most complicated part of a
steam stripper is the boiler. Periodic maintenance will prevent
unexpected shutdowns of the boiler.
Packing fouling interferes with the intimate contacting of
liquid-gas, thus decreasing the column efficiency, and eventually
leads to flooding. The stripper column is periodically taken out
of service and cleaned with acid and water with air sparging.
Column cutoff is predicated on a maximum allowable pressure drop
across the packing of maximum "acceptable" ammonia content in the
stripper bottoms. Although packing fouling may not be completely
avoidable due to endothermic CaSC>4 precipitation, column runs
could be prolonged by a preliminary treatment step designed to
remove suspended solids originally present in the feed and those
precipitated after lime addition.
Demonstration Status. Steam stripping has proved to be an effi-
cient reliable process for the removal of ammonia from many
types'of industrial wastewaters that contain high concentrations
of ammonia. Industries using ammonia steam stripping technology
include the fertilizer industry, iron and steel, petroleum
refining, organic chemicals manufacturing, and nonferrous metals
manufacturing. One plant in the secondary aluminum subcategory,
one plant in the secondary lead subcategory, two plants in the
primary columbium-tantalum subcategory, and four plants in the
primary tungsten subcategory reported steam stripping in-place.
Carbon Adsorption
The use of activated carbon to remove dissolved organics from
water and wastewater is a well demonstrated technology. It is
one of the most efficient organic removal processes available.
This sorption process is reversible allowing activated carbon to
be regenerated for reuse by the application of heat and steam or
solvent. Activated carbon has also proved to be an effective
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adsorbent for many toxic metals, including mercury. Regeneration
of carbon which has adsorbed significant metals; however, may be
difficult.
The term activated carbon applies to any amorphous form of carbon
that has been specially treated to give high adsorption capaci-
ties. Typical raw materials include coal, wood, coconut shells,
petroleum base residues, and char from sewage sludge pyrolysis.
A carefully controlled process of dehydration, carbonization, and
oxidation yields a product which is called activated carbon.
This material has a high capacity for adsorption due primarily to
the large surface area available for adsorption, 500 to 1,500
m^/gm, resulting from a large number of internal pores. Pore
sizes generally range from 10 to 100 angstroms in radius.
Activated carbon removes contaminants from water by the process
of adsorption, or the attraction and accumulation of one sub-
stance on the surface of another. Activated carbon preferen-
tially adsorbs organic compounds over other species and, because
of this selectivity, is particularly effective in removing
organic compounds from aqueous solution.
Carbon adsorption requires preliminary treatment to remove excess
suspended solids, oils, and greases. Suspended solids concentra-
tions in the influent should be reduced to minimize backwash
requirements.
Oil and grease concentrations should also be reduced. High
concentrations of dissolved organic material in the influent may
cause problems with thermal carbon reactivation (i.e., scaling
and loss of activity) unless appropriate preventive steps are
taken. Such steps might include pH control, softening, or the
use of an acid wash on the carbon prior to reactivation.
Activated carbon is available in both powdered and granular form.
A flow diagram of activated carbon treatment and regeneration is
shown in Figure VII-1. A schematic of an individual adsorption
column is shown in Figure VII-2. Powdered carbon is less expen-
sive per unit weight and may have slightly higher adsorption
capacity, but it is more difficult to handle and to regenerate.
Application and Performance. Isotherm tests have indicated that
activated carbon is very effective in adsorbing 65 percent of the
toxic organic pollutants and is reasonably effective for another
22 percent. Specifically, activated carbon is very effective in
removing polynuclear aromatic compounds, 14 of which are classi-
fied as toxic pollutants.
Advantages and Limitations. The major benefits of carbon treat-
ment include applicability to a wide variety of organics and high
removal efficiency. Inorganics such as cyanide, chromium, and
220
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mercury are also removed effectively. Variations in concentra-
tion and flow rate are well tolerated. The system is compact,
and recovery of adsorbed materials is sometimes practical.
However, destruction of adsorbed compounds often occurs during
thermal regeneration. If carbon cannot be thermally regenerated,
it must be disposed of along with any adsorbed pollutants. The
capital and operating costs of thermal regeneration are rela-
tively high. Cost surveys show that thermal regeneration is
generally economical when carbon usage exceeds about 650 Ibs/day.
Carbon cannot remove low molecular weight or highly soluble
organics.
Operational Factors. Reliability: This system should be very
reliable with any upstream protection necessary from solids or
oil and grease and proper operation and maintenance procedures.
Maintainability: This system requires periodic regeneration or
replacement of spent carbon and is dependent upon raw waste load
and process efficiency.
Solid Waste Aspects: Solid waste from this process is contami-
nated activated carbon that requires disposal unless the carbon
is thermally regenerated. There is some periodic disposal of
spent carbon required with thermal regeneration; however, the
frequency and amount disposed is significantly smaller.
Demonstration Status. Carbon adsorption systems have been demon-
strated to be practical and economical in reducing COD, BOD, and
related parameters in secondary municipal and industrial waste-
waters- in removing polynuclear aromatic compounds from specific
industrial wastewaters (e.g., iron and steel); in removing and
recovering certain organics from wastewaters; and in the remov-
ing, and sometimes recovering, of selected inorganic chemicals
from aqueous waste streams. Carbon adsorption is a viable and
economic recovery process for organic waste streams containing up
to 1 to 5 percent of refractory or toxic organics. Its applica-
bility for removal of inorganics such as metals has also been
demonstrated. None of the plants in the nonferrous metals
manufacturing category reported having activated carbon
technology in place.
Chemical Precipitation
Dissolved toxic metal ions and certain anions may be chemically
precipitated for removal by physical means such as sedimentation,
filtration, or centrifugation. Several reagents which are
commonly used to effect this precipitation are described below.
1 Alkaline compounds such as lime or sodium hydroxide may
be used to precipitate many toxic metal ions as metal
hydroxides. Lime also may precipitate phosphates^as
insoluble calcium phosphate and fluorides as calcium
fluoride.
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2. Both "soluble" sulfides such as hydrogen sulfide or
sodium sulfide and "insoluble" sulfides such as ferrous
sulfide may be used to precipitate many heavy metal ions
as insoluble metal sulfides.
3. Ferrous sulfate, zinc sulfate, or both (as is required)
may be used to precipitate cyanide as a ferro or zinc
ferricyanide complex.
4. Carbonate precipitates may be used to remove metals
either by direct precipitation using a carbonate
reagent such as calcium carbonate or by converting
hydroxides into carbonates using carbon dioxide.
These treatment chemicals may be added to a flash mixer or rapid
mix tank, to a presettling tank, or directly to a clarifier or
other settling device. Because metal hydroxides tend to be col-
loidal in nature, coagulating agents may also be added to facili-
tate settling. After the solids have been removed, final pH
adjustment may be required to reduce the high pH created by the
alkaline treatment chemicals.
Chemical precipitation as a mechanism for removing metals from
wastewater is a complex process of at least two steps^-^precipi-
tation of the unwanted metals and removal of the precipitate.
Some small amount of metal will remain dissolved in the waste-
water after complete precipitation; the amount depends on the
treatment chemicals used and related factors. The effectiveness
of this method of removing any specific metal depends on the
fraction of the specific metal in the raw waste (and hence in the
precipitate) and the effectiveness of suspended solids removal.
In specific instances, a sacrificial ion such as iron or aluminum
may be added to aid in the precipitation process and reduce the
fraction of a specific metal in the precipitate.
Application and Performance. Chemical precipitation is used in
nonferrous metals manufacturing for precipitation of dissolved
metals. It can be used to remove metal ions such as aluminum,
antimony, arsenic, cadmium, chromium, copper, iron, lead, mer-
cury, selenium, silver, thallium, and zinc. The process is also
applicable to any substance that can be transformed into an
insoluble form such as fluorides, phosphates, soaps, and sul-
fides among others. Because it is simple and effective, chemi-
cal precipitation is extensively used for industrial wastewater
treatment.
The performance of chemical precipitation depends on several
variables. The most important factors controlling precipitation
effectiveness are:
1. Maintenance of an alkaline pH throughout the
precipitation reaction and subsequent settling;
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2. Addition of a sufficient excess of treatment ions to
drive the precipitation reaction to completion;
3. Addition of an adequate supply of sacrificial ions
(such as iron or aluminum) to ensure precipitation and
removal of specific target ions; and
4. Effective removal of precipitated solids (see^
appropriate technologies discussed under "Solids
Removal").
Control of pH. Irrespective of the solids removal technology
used, proper control of pH is absolutely essential for favorable
performance of precipitation-sedimentation technologies. This is
clearly illustrated by solubility curves for selected metals
hydroxides and sulfides shown in Figure VII-3, and by plotting
effluent zinc concentrations against pH as shown in Figure VII-4.
Figure VII-3 was obtained from Development Document for the Pro-
posed Effluent Limitations Guidelines and New Source Performance
Standards for the Zinc Segment ot the Nonterrous Metals Manufac-
turing Point Source Category, U.S. EPA, EPA 440/1-74/033,
November, 1974.Figure VII-4 was plotted from the sampling data
from several facilities with metal finishing operations. It is
partially illustrated by data obtained from three consecutive
days of sampling at one copper forming plant (47432) as displayed
in Table VII-1. Flow through this system is approximately 49,263
1/hr (13,000 gal/hr).
This treatment system uses lime precipitation (pH adjustment)
followed by coagulant addition and sedimentation. Samples were
taken before (in) and after (out) the treatment system. The best
treatment for removal of copper and zinc was achieved on day one,
when the pH was maintained at a satisfactory level. The poorest
treatment was found on the second day, when the pH slipped to an
unacceptably low level and intermediate values were achieved on
the third day, when pH values were less than desirable but in
between the first and second days.
Sodium hydroxide is used by one battery manufacturing facility
(plant 439) for pH adjustment and chemical precipitation,
followed by settling (sedimentation and a polishing lagoon) of
precipitated solids. Samples were taken prior to caustic
addition and following the polishing lagoon. Flow through the
system is approximately 22,700 1/hr (6,000 gal/hr . Metals
removal data for this system are presented in Table VII-2.
Effluent PH was controlled within the range of 8.6 to 9.3 and
while raw waste loadings were not unusually high, most toxic
metals were removed to very low concentrations.
Plant 40063, a porcelain enameling facility with a metal-bearing
wastewater exemplifies efficient operation of a chemical precip-
Uat?on and sealing system. Table VII-3 shows sampling data
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from this system, which uses lime and sodium hydroxide for pH
adjustment, chemical precipitation, polyelectrolyte flocculant
addition, and sedimentation. Samples were taken of the raw waste
influent to the system and of the clarifier effluent. Flow
through the system is approximately 19,000 1/hr (5,000 gal/hr).
At this plant, effluent TSS levels were below 15 mg/1 on each
day, despite average raw waste TSS concentrations of over 3,500
mg/1. Effluent pH was maintained at approximately 8, lime addi-
tion was sufficient to precipitate the dissolved metal ions, and
the flocculant addition and clarifier retention served to remove
effectively the precipitated solids.
Sulfide precipitation is sometimes used to precipitate metals
resulting in improved metals removals. Most metal sulfides are
less soluble than hydroxides and the precipitates are frequently
more effectively removed from water. Solubilities for selected
metal hydroxide, carbonate, and sulfide precipitates are shown in
Table V1I-4 (Source: Lange's Handbook of Chemistry). Sulfide
precipitation is particularly effective in removing specific
metals such as silver and mercury. Sampling data from three
industrial plants using sulfide precipitation appear in Table
VTI-5. The data were obtained from three sources:
1. Summary Report, Control and Treatment Technology for
the Metal Finishing Industry: Sulfide Precipitation,
U.S. EPA, EPA No. 625/8/80-003, 1979.
2. Industrial Finishing, Vol. 35, No. 11, November, 1979.
3. Electroplating sampling data from plant 27045.
In all cases except iron, effluent concentrations are below 0.1
mg/1 and in many cases below 0.04 mg/1 for the three plants
studied.
Sampling data from several chlorine-caustic manufacturing plants
using sulfide precipitation demonstrate effluent mercury concen-
trations varying between 0.009 and 0.03 mg/1. As shown in Figure
VTI-5, the solubilities of PbS and Ag2S are lower at alkaline
pH levels than either the corresponding hydroxides or other sul-
fide compounds. This implies that removal performance for lead
and silver sulfides should be comparable to or better than that
for the heavy metal hydroxides. Bench scale tests on several
types of metal finishing and manufacturing wastewater indicate
that metals removal to concentrations of less than 0.05 mg/1 and
in some cases less than 0.01 mg/1 are common in systems using
sulfide precipitation followed by clarification. Some of the
bench scale data, particularly in the case of lead, do not
support such low effluent concentrations. However, lead is
consistently removed to very low concentrations (less than 0.02
mg/1) in systems using hydroxide and carbonate precipitation and
sedimentation.
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Of particular interest is the ability of sulfide to precipitate
hexavalent chromium (Cr+6) without prior reduction to the trival-
ent state as is required in the hydroxide process. When ferrous
sulfide is used as the precipitant, iron and sulfide act as
reducing agents for the hexavalent chromium according to the
reaction:
CrOs + FeS + 3H20 -»• Fe(OH)3 + Cr(OH)3 + S
The sludge produced in this reaction consists mainly of ferric
hydroxides, chromic hydroxides, and various metallic sulfides.
Some excess hydroxyl ions are generated in this process, possibly
requiring a downward readjustment of pH.
Based on the available data, Table VII-6 shows the minimum relia-
bly attainable effluent concentrations for sulfide precipitation-
sedimentation systems. These values are used to calculate
performance predictions of sulfide precipitation-sedimentation
systems.
Carbonate precipitation is sometimes used to precipitate metals,
especially where precipitated metals values are to be recovered.
The solubility of most metal carbonates is intermediate between
hydroxide and sulfide solubilities; in addition, carbonates form
easily filtered precipitates.
Carbonate ions appear to be particularly useful in precipitating
lead. Sodium carbonate has been observed being added at
treatment to improve lead precipitation and removal in some
industrial plants. The lead hydroxide and lead carbonate
solubility curves displayed in Figure VII-5 ("Heavy Metals
Removal," by Kenneth Lanovette, Chemical Engineering/Deskbook
Issue, Oct. 17, 1977) explain this phenomenon.
Co-precipitation with Iron - The presence of substantial quanti-
ties of iron in metal-bearing wastewaters before treatment has
been shown to improve the removal of toxic metals. In some cases
this iron is an integral part of the industrial wastewater; in
other cases iron is deliberately added as a preliminary or first
step of treatment. The iron functions to improve toxic metal
removal by three mechanisms: the iron co-precipitates with toxic
metals forming a stable precipitate which desolubilizes the toxic
metal; the iron improves the settleability of the precipitate;
and the large amount of iron reduces the fraction of toxic metal
in the precipitate. Co-precipitation with iron has been prac-
ticed for many years; incidentally, when iron was a substantial
constituent of raw wastewater and, intentionally, when iron^salts
were added as a coagulant aid. Aluminum or mixed iron-aluminum
salt also have been used.
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Co-precipitation using large amounts of ferrous iron salts is
known as ferrite co-precipitation because magnetic iron oxide or
ferrite is formed. The addition of ferrous salts (sulfate) is
followed by alkali precipitation and air oxidation. The resul-
tant precipitate is easily removed by filtration and may be
removed magnetically. Data illustrating the performance of
ferrite co-precipitation is shown in Table VII-7.
Advantages and Limitations
Chemical precipitation has proven to be an effective technique
for removing many pollutants from industrial wastewater. It
operates at ambient conditions and is well suited to automatic
control. The use of chemical precipitation may be limited
because of interference by chelating agents, because of possible
chemical interference of mixed wastewaters and treatment chemi-
cals, or because of the potentially hazardous situation involved
with the storage and handling of those chemicals. Lime is usu-
ally added as a slurry when used in hydroxide precipitation. The
slurry must be kept well mixed and the addition lines periodi-
cally checked to prevent blocking of the lines, which may result
from a buildup of solids. Also, hydroxide precipitation usually
makes recovery of the precipitated metals difficult, because of
the heterogeneous nature of most hydroxide sludges.
The major advantage of the sulfide precipitation process is that
the extremely low solubility of most metal sulfides promotes very
high metal removal efficiencies ; the sulfide process also has the
ability to remove chromates and dichromates without preliminary
reduction of the chromium to its trivalent state. In addition,
sulfide can precipitate metals complexed with most complexing
agents. The process demands care, however, in maintaining the pH
of the solution at approximately 10 in order to prevent the gen-
eration of toxic hydrogen sulfide gas. For this reason, ventila-
tion of the treatment tanks may be a necessary precaution in most
installations. The use of insoluble sulfides reduces the problem
of hydrogen sulfide evolution. As with hydroxide precipitation,
excess sulfide ion must be present to drive the precipitation
reaction to completion. Since the sulfide ion itself is toxic,
sulfide addition must be carefully controlled to maximize heavy
metals precipitation with a minimum of excess sulfide to avoid
the necessity of post treatment. At very high excess sulfide
concentrations and high pH, soluble mercury-sulfide compounds
also may be formed. Where excess sulfide is present aeration of
the effluent stream can aid in oxidizing residual sulfide to the
less harmful sodium sulfate (Na2S04). The cost of sulfide
precipitants is high in comparison with hydroxide precipitants,
and disposal of metallic sulfide sludges may pose problems. An
essential element in effective sulfide precipitation is the
removal of precipitated solids from the wastewater and proper
disposal in an appropriate site. Sulfide precipitation will also
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generate a higher volume of sludge than hydroxide precipitation,
resulting in higher disposal and dewatering costs. This is
especially true when ferrous sulfide is used as the precipitant.
Sulfide precipitation may be used as a polishing treatment after
hydroxide precipitation-sedimentation. This treatment configura-
tion may provide the better treatment effectiveness of sulfide
precipitation while minimizing the variability caused by changes
in raw waste and reducing the amount of sulfide precipitant
required.
Operational Factors. Reliability: Alkaline chemical precipita-
tion is highly reliable, although proper monitoring and control
are required. Sulfide precipitation systems provide similar
reliability.
Maintainability: The major maintenance needs involve periodic
upkeep of monitoring equipment, automatic feeding equipment,
mixing equipment, and other hardware. Removal of accumulated
sludge is necessary for efficient operation of precipitation-
sedimentation systems.
Solid Waste Aspects: Solids which form the precipitate are
removed in a subsequent treatment step. Ultimately, these solids
require proper disposal.
Demonstration Status. Chemical precipitation of metal hydroxides
is a classic waste treatment technology used by at least 60
nonferrous metals manufacturing plants for wastewater treatment.
Chemical precipitation of metals in the carbonate form alone has
been found to be feasible and is commercially used to permit^
metals recovery and water reuse. Full scale commercial sulfide
precipitation units are in operation at numerous installations in
other categories (e.g., metal finishing) and at one Swedish
smelter. As noted earlier, sedimentation to remove precipitates
is discussed separately.
Cyanide Precipitation
Cyanide precipitation, although a method for treating cyanide in
wastewaters, does not destroy cyanide. The cyanide is retained
in the sludge that is formed. Reports indicate that during expo-
sure to sunlight the cyanide complexes can break down and form
free cyanide. For this reason the sludge from this treatment
method must be disposed of carefully.
Cyanide may be precipitated and settled out of wastewaters by the
addition of zinc sulfate or ferrous sulfate. In the presence of
iron, cyanide will form extremely stable cyanide complexes. The
addition of zinc sulfate or ferrous sulfate forms zinc ferrocya-
nide or ferro- and ferricyanide complexes.
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Adequate removal of the precipitated cyanide requires that the pH
be kept at 9 and an appropriate detention time be maintained. A
study has shown that the formation of the complex is very depen-
dent on pH. At pH's of 8 and 10 the residual cyanide concentra-
tions measured are twice those of the same reaction carried out
at a pH of 9. Removal efficiencies also depend heavily on the
retention time allowed. The formation of the complexes takes
place rather slowly. Depending upon the excess amount of zinc
sulfate or ferrous sulfate added, at least a 30-minute retention
time should be allowed for the formation of the cyanide complex
before continuing on to the clarification stage.
One experiment with an initial concentration of 10 mg/1 of
cyanide showed that 98 percent of the cyanide was complexed 10
minutes after the addition of ferrous sulfate at twice the theo-
retical amount necessary. Interference from other metal ions,
such as cadmium, might result in the need for longer retention
times.
Table VII-8 presents data from three coil coating plants using
well-operated cyanide precipitation treatment. These data form
the basis for the concentration achievable by this technology.
Of these three plants, one plant (Plant 1057) also does aluminum
forming. A fourth plant was visited for the purpose of observing
plant testing of the cyanide precipitation system. Specific data
from this facility are not included because: (1) the pH was
usually well below the optimum level of 9.0; (2) the historical
treatment data were not obtained using the standard cyanide
analysis procedure; and (3) paired untreated and treated data
were not made available by the plant. The available data
presented in Table VII-11 indicate that the raw waste cyanide
concentration was in the range of 0.12 to 3.28 mg/1, the pH 7.5;
and treated cyanide concentration was from 0.024 to 0.14. For
this reason, we selected the average of these data, 0.07, as the
long-term performance concentration achievable by this
technology.
Plant 1057 allowed a 27-minute retention time for the formation
of the complex. The retention time for the other plants is not
known. The data suggest that over a wide range of cyanide
concentration in the raw waste, the concentration of cyanide can
be reduced in the effluent stream to under 0.07 mg/1 on a
long-term basis.
Application and Performance. Cyanide precipitation can be used
when cyanide destruction is not feasible because of the presence
of cyanide complexes which are difficult to destroy. Effluent
concentrations of cyanide well below 0.07 mg/1 are possible.
Advantages and Limitations. Cyanide precipitation is an inexpen-
sive method of treating cyanide. Problems may occur when metal
ions interfere with the formation of the complexes.
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Demonstration Status. Although no plants currently use cyanide
precipitation to treat nonferrous metals manufacturing waste-
waters, it is used in at least six coil coating plants.
Granular Bed Filtration
Filtration occurs in nature as the surface ground waters are
cleansed by sand. Silica sand, anthracite coal, and garnet are
common filter media used in water treatment plants. These three
media are usually supported by gravel. The media may be used
singly or in combination. Multimedia filters may be arranged to
maintain relatively distinct layers by virtue of balancing the
forces of gravity, flow and buoyancy on the individual particles.
This is accomplished by selecting appropriate filter loading
rates (1/sq m-hr), media grain size, and bed density.
Granular bed filters are classified in terms of filtration rate,
filter media, flow pattern, or method of pressurization. Tradi-
tional rate classifications are slow sand, rapid sand, and high
rate mixed media. In the slow sand filter, flux or hydraulic
loading is relatively low, and removal of collected solids to
clean the filter is therefore relatively infrequent. The filter
is often cleaned by scraping off the inlet face (top) of the sand
bed. In the higher rate filters, cleaning is frequent and is
accomplished by a periodic backwash, opposite to the direction of
normal flow.
A filter may use a single medium such as sand or diatomaceous
earth (Figure VII-6a) , but dual (Figure VII-6d) and mixed (multi-
or multiple) media (Figure VII-6e) filters allow higher flow
rates and efficiencies. The dual media filter usually consists
of a fine bed of sand under a coarser bed of anthracite coal.
The coarse coal removes most of the influent solids, while the
fine sand performs a polishing function. At the end of the back-
wash, the fine sand settles to the bottom because it is denser
than the coal, and the filter is ready for normal operation. The
mixed media filter operates on the same principle, with the
finer, denser media at the bottom and the coarser, less dense
media at the top. The usual arrangement is garnet at the bottom
(outlet end) of the bed, sand in the middle, and anthracite coal
at the top. Some mixing of these layers occurs and is, in fact,
desirable.
The flow pattern is usually top-to-bottom, but other patterns are
sometimes used. Upflow filters (Figure VII-6b) and horizontal
filters are sometimes used. In a btflow filter (Figure
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the influent enters both the top and the bottom and exits later-
ally. The advantage of an upflow filter is that with an upflow
backwash the particles of a single filter medium are distributed
and maintained in the desired coarse-to-fine (bottom-to-top)
arrangement. The disadvantage is that the bed tends to become
fluidized, which lowers filtration efficiency. The biflow design
is an attempt to overcome this problem.
The classic granular bed filter operates by gravity flow; how-
ever, pressure filters are fairly widely used. They permit
higher solids loadings before cleaning and are advantageous when
the filter effluent must be pressurized for further downstream
treatment. In addition, pressure filter systems are often less
costly for low to moderate flow rates.
Figure VII-7 depicts a high rate, dual media, gravity downflow
granular bed filter, with self-stored backwash. Both filtrate
and backwash are piped around the bed in an arrangement that per-
mits gravity upflow of the backwash, with the stored filtrate
serving as backwash. Addition of the indicated coagulant and
polyelectrolyte usually results in a substantial improvement in
filter performance.
Auxiliary filter cleaning is sometimes used in the upper few
inches of filter beds. This is conventionally referred to as
surface wash and is accomplished by water jets just below the
surface of the expanded bed during the backwash cycle. These
jets enhance the scouring action in the bed by increasing the
agitation.
An important feature for successful filtration and backwashing is
the underdrain. This is the support structure for the bed. The
underdrain provides an area for collection of the filtered water
without clogging from either the filtered solids or the media
grains. In addition, the underdrain prevents loss of the media
with the water, and during the backwash cycle it provides even
flow distribution over the bed. Failure to dissipate the veloc-
ity head during the filter or backwash cycle will result in bed
upset and the need for major repairs.
Several standard approaches are used for filter underdrains. The
simplest one consists of a parallel porous pipe imbedded under a
layer of coarse gravel and manifolded to a header pipe for efflu-
ent removal. Other approaches to the underdrain system are known
as the Leopold and Wheeler filter bottoms. Both of these incor-
porate false concrete bottoms with specific porosity configura-
tions to provide drainage and velocity head dissipation.
Filter system operation may be manual or automatic. The filter
backwash cycle may be on a timed basis, a pressure drop basis
with a terminal value which triggers backwash, or a solids carry-
over basis from turbidity monitoring of the outlet stream. All
of these schemes have been used successfully.
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Application and Performance. Wastewater treatment plants often
use granular bed filters for polishing after clarification, sedi-
mentation, or other similar operations. Granular bed filtration
thus has potential application to nearly all industrial plants.
Chemical additives which enhance the upstream treatment equipment
may or may not be compatible with or enhance the filtration pro-
cess. Normal operation flow rates for various types of filters
are as follows:
Slow Sand 2.04 - 5.30 1/sq m-hr
Rapid Sand 40.74 - 51.48 1/sq m-hr
High Rate Mixed Media 81.48 - 122.22 1/sq m-hr
Suspended solids are commonly removed from wastewater streams by
filtering through a deep 0.3 to 0.9 m (1 to 3 feet) granular
filter bed. The porous bed formed by the granular media can be
designed to remove practically all suspended particles. Even
colloidal suspensions (roughly 1 to 100 microns) are adsorbed on
the surface of the media grains as they pass in close proximity
in the narrow bed passages.
Properly operated filters following some preliminary treatment to
reduce suspended solids below 200 mg/1 should produce water with
less than 10 mg/1 TSS. For example, multimedia filters produced
the effluent qualities shown in Table VII-9.
Advantages and Limitations. The principal advantages of granular
bed filtration are its comparatively (to other filters) low ini-
tial and operating costs, reduced land requirements over other
methods to achieve the same level of solids removal, and elimina-
tion of chemical additions to the discharge stream. However, _ the
filter may require preliminary treatment if the solids level is
high (over 100 mg/1). Operator training must be somewhat exten-
sive due to the controls and periodic backwashing involved, and
backwash must be stored and dewatered for economical disposal.
Operational Factors. Reliability: The recent improvements in
filter technology have significantly improved filtration relia-
bility. Control systems, improved designs and good operating
procedures have made filtration a highly reliable method of water
treatment .
Maintainability: Deep bed filters may be operated with either ^
manual or automatic backwash. In either case they must be peri-
odically inspected for media attrition partial plugging, and
leakage! Where backwashing is not used, collected solids must be
removed by shoveling, and filter media must be at least partially
replaced.
Solid Waste Aspects: Filter backwash is generally r
within the wastewater treatment system, so that the solids ulti-
mtely appearin the clarifier sludge stream for subsequent
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dewatering. Alternatively, the backwash stream may be dewatered
directly or, if there is no backwash, the collected solids may be
disposed of in a suitable landfill. In either of these situa-
tions there is a solids disposal problem similar to that of
clarifiers.
Demonstration Status. End-of-pipe filtration is demonstrated in
the nonferrous metals manufacturing category in a total of 22
discharging plants: one primary aluminum plant; one primary
electrolytic copper refinery; one secondary copper plant; one
primary lead plant; seven secondary lead plants ; three primary
zinc plants ; three secondary silver plants ; one primary
columbium-tantalum plant; three primary tungsten plants; and
three acid plants. Long-term paired data from a primary zinc
plant were considered in establishing treatment performance
concentrations for lime, settle and filtration technology (see
L,SSeF Performance, p.249).
Pressure Filtration
Pressure filtration works by pumping the liquid through a filter
material which is impenetrable to the solid phase. The positive
pressure exerted by the feed pumps or other mechanical means pro-
vides the pressure differential which is the principal driving
force. Figure VII-8 represents the operation of one type of
pressure filter.
A typical pressure filtration unit consists of a number of plates
or trays which are held rigidly in a frame to ensure alignment
and which are pressed together between a fixed end and a travel-
ing end. On the surface of each plate is mounted a filter made
of cloth or a synthetic fiber. The feed stream is pumped into
the unit and passes through holes in the trays along the length
of the press until the cavities or chambers between the trays are
completely filled. The solids are then entrapped, and a cake
begins to form on the surface of the filter material. The water
passes through the fibers, and the solids are retained.
At the bottom of the trays are drainage ports. The filtrate is
collected and discharged to a common drain. As the filter medium
becomes coated with sludge, the flow of filtrate through the
filter drops sharply, indicating that the capacity of the filter
has been exhausted. The unit must then be cleaned of the sludge.
After the cleaning or replacement of the filter media, the unit
is again ready for operation.
Application and Performance. Pressure filtration is used in
nonferrous metals manufacturing for sludge dewatering and also
for direct removal of precipitated and other suspended solids
from wastewater.
Because dewatering is such a common operation in treatment sys-
tems, pressure filtration is a technique which can be found in
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many industries concerned with removing solids from their waste
stream.
In a typical pressure filter, chemically preconditioned sludge
detained in the unit for one to three hours under pressures vary-
ing from 5 to 13 atmospheres exhibited a final dry solids content
between 25 and 50 percent.
Advantages and Limitations. The pressures which may be applied
to a sludge tor removal ot water by filter presses that are
currently available range from 5 to 13 atmospheres. As a result,
pressure filtration may reduce the amount of chemical pretreat-
ment required for sludge dewatering. Sludge retained in the form
of the filter cake has a higher percentage of solids than that
from a centrifuge or vacuum filter. Thus, it can be easily
accommodated by materials handling systems.
As a primary solids removal technique, pressure filtration
requires less space than clarification and is well suited to
streams with high solids loadings. The sludge produced may be
disposed of without further dewatering. The amount of sludge is
increased by the use of filter precoat materials (usually dia-
tomaceous earth). Also, cloth pressure filters often do not
achieve as high a degree of effluent clarification as clanfiers
or granular media filters.
Two disadvantages associated with pressure filtration in the past
have been the short life of the filter cloths and lack of auto-
mation. New synthetic fibers have largely offset the first of
these problems. The second problem has been reduced because of
the current availability of units with automatic feeding and
pressing cycles.
For larger operations, the relatively high space requirements, as
compared to those of a centrifuge, could be prohibitive in some
situations.
Operational Factors. Reliability: With proper pretreatment
design, and control, pressure filtration is a highly dependable
system.
Maintainability: Maintenance consists of periodic cleaning or
replacement of the filter media, drainage gr^s drainage piping,
filter pans and other parts of the system. If the removal ot
the sludge cake is not automated, additional time is required for
this operation.
Solid Waste Aspects: Because it is generally drier than other
t?pes of sludges the filter sludge cake can be handled with
relative ease? The accumulated sludge may be disposed by any of
the accepted procedures depending on its chemical composition.
The tevels of^oxic metals present in sludge from treating
233
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nonferrous metals manufacturing wastewater necessitate proper
disposal.
Demonstration Status. Pressure filtration is a commonly used
technologyin many commercial applications. Several nonferrous
metals manufacturing plants use pressure filtration for sludge
dewatering.
Settling
Settling is a process which removes solid particles from a liquid
matrix by gravitational force. This is done by reducing the
velocity of the feed stream in a large volume tank or lagoon so
that gravitational settling can occur. Figure VII-9 shows two
typical settling devices.
Settling is often preceded by chemical precipitation, which
converts dissolved pollutants to solid form, and by coagulation,
which enhances settling by coagulating suspended precipitates
into larger, faster settling particles.
If no chemical pretreatment is used, the wastewater is fed into a
tank or lagoon where it loses velocity and the suspended solids
are allowed to settle out. Long retention times are generally
required. Accumulated sludge can be collected either periodi-
cally or continuously and either manually or mechanically.
Simple settling, however, may require excessively large catch-
ments, and long retention times (days as compared with hours) to
achieve high removal efficiencies. Because of this, addition of
settling aids such as alum or polymeric flocculants is often
economically attractive.
In practice, chemical precipitation often precedes settling, and
inorganic coagulants or polyelectrolytic flocculants are usually
added as well. Common coagulants include sodium sulfate, sodium
aluminate, ferrous or ferric sulfate, and ferric chloride.
Organic polyelectrolytes vary in structure, but all usually form
larger floe particles than coagulants used alone.
Following this pretreatment, the wastewater can be fed into a
holding tank or lagoon for settling, but is more often piped into
a clarifier for the same purpose. A clarifier reduces space
requirements, reduces retention time, and increases solids
removal efficiency. Conventional clarifiers generally consist of
a circular or rectangular tank with a mechanical sludge collect-
ing device or with a sloping funnel-shaped bottom designed for
sludge collection. In advanced settling devices, inclined
plates, slanted tubes, or a lamellar network may be included
within the clarifier tank in order to increase the effective
settling area, increasing capacity. A fraction of the sludge
stream is often recirculated to the inlet, promoting formation of
a denser sludge.
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Application and Performance. Settling and clarification are used
in the nonferrous metals manufacturing category to remove precip-
itated metals. Settling can be used to remove most suspended
solids in a particular waste stream; thus it is used extensively
by many different industrial waste treatment facilities. Because
most metal ion pollutants are readily converted to solid metal
hydroxide precipitates, settling is of particular use in those
industries associated with metal production, metal finishing,
metal working, and any other industry with high concentrations of
metal ions in their wastewaters. In addition to toxic metals,
suitably precipitated materials effectively removed by settling
include aluminum, iron, and fluoride.
A properly operated settling system can efficiently remove sus-
pended solids, precipitated metal hydroxides, and other impuri-
ties from wastewater. The performance of the process depends on
a variety of factors, including the density and particle size of
the solids, the effective charge on the suspended particles, and
the types of chemicals used in pretreatment. The site of floccu-
lant or coagulant addition also may significantly influence the
effectiveness of clarification. If the flocculant is subjected
to too much mixing before entering the clarifier, the complexes
may be sheared and the settling effectiveness diminished. At the
same time, the flocculant must have sufficient mixing and reac-
tion time in order for effective set-up and settling to occur.
Plant personnel have observed that the line or trough leading
into the clarifier is often the most efficient site for floccu-
lant addition. The performance of simple settling is a function
of the retention time, particle size and density, and the surface
area of the basin.
The data displayed in Table VII-10 indicate suspended solids
removal efficiencies in settling systems. The mean effluent TSS
concentration obtained by the plants shown in Table VII-10 is
10.1 mg/1. Influent concentrations averaged 838 mg/1. The maxi-
mum effluent TSS value reported is 23 mg/1. These plants all use
alkaline pH adjustment to precipitate metal hydroxides, and most
add a coagulant or flocculant prior to settling.
Advantages and Limitations. The major advantage of simple set-
tling is its simplicity as demonstrated by the gravitational
settling of solid particular waste in a holding tank or lagoon.
The major problem with simple settling is the long retention time
necessary to achieve an acceptable effluent, especially if the
specific gravity of the suspended matter is close to that_of
water. Some materials cannot be effectively removed by simple
settling alone.
Settling performed in a clarifier is effective in removing slow-
settling suspended matter in a shorter time and in less space
than a simple settling system. Also, effluent quality is often
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better from a clarifier. The cost of installing and maintaining
a clarifier, however, is substantially greater than the costs
associated with simple settling.
Inclined plate, slant tube, and lamellar settlers have even
higher removal efficiencies than conventional clarifiers, and
greater capacities per unit area are possible. Installed costs
for these advanced clarification systems are claimed to be one
half the cost of conventional systems of similar capacity.
Operational Factors. Reliability: Settling can be a highly
reliable technology for removing suspended solids. Sufficient
retention time and regular sludge removal are important factors
affecting the reliability of all settling systems. Proper con-
trol of pH adjustment, chemical precipitation, and coagulant or
flocculant addition are other factors affecting settling effi-
ciencies in systems (frequently clarifiers) where these methods
are used.
Those advanced settlers using slanted tubes, inclined plates, or
a lamellar network may require prescreening of the waste in order
to eliminate any fibrous materials which could potentially clog
the system. Some installations are especially vulnerable to
shock loadings, as by storm water runoff, but proper system
design will prevent this.
Maintainability: When clarifiers or other advanced settling
devices are used, the associated system utilized for chemical
pretreatment and sludge dragout must be maintained on a regular
basis. Routine maintenance of mechanical parts is also neces-
sary. Lagoons require little maintenance other than periodic
sludge removal.
Demonstration Status. Settling represents the typical method of
solids removal and is used extensively in industrial waste
treatment. At least 60 nonferrous metals manufacturing plants
use settling, usually in conjunction with chemical precipitation.
The advanced clarifiers are just beginning to appear in signifi-
cant numbers in commercial applications. As an example, a
lamellar inclined-tube clarifier is used by one secondary copper
smelter.
Skimming
Pollutants with a specific gravity less than water will often
float unassisted to the surface of the wastewater. Skimming
removes these floating wastes. Skimming normally takes place in
a tank designed to allow the floating material to rise and remain
on the surface, while the liquid flows to an outlet located below
the floating layer. Skimming devices are therefore suited to the
removal of non-emulsified oils from raw waste streams. Common
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skimming mechanisms include the rotating drum type, which picks
up oil from the surface of the water as it rotates. A doctor
blade scrapes oil from the drum and collects it in a trough for
disposal or reuse. The water portion is allowed to flow under
the rotating drum. Occasionally, an underflow baffle is
installed after the drum; this has the advantage of retaining any
floating oil which escapes the drum skimmer. The belt type
skimmer is pulled vertically through the water, collecting oil
which is scraped off from the surface and collected in a drum.
Gravity separators (Figure VII-10), such as the API type, utilize
overflow and underflow baffles to skim a floating oil layer from
the surface of the wastewater. An overflow-underflow baffle
allows a small amount of wastewater (the oil portion) to flow
over into a trough for disposition or reuse while the majority of
the water flows underneath the baffle. This is followed by an
overflow baffle, which is set at a height relative to the first
baffle such that only the oil bearing portion will flow over ^ the
first baffle during normal plant operation. A diffusion device,
such as a vertical slot baffle, aids in creating a uniform flow
through the system and increasing oil removal efficiency.
Application and Performance. Skimming is applicable to any waste
stream containing pollutants which float to the surface. It iS>
commonly used to remove free oil, grease, and soaps. Skimming is
often used in conjunction with air flotation or clarification in
order to increase its effectiveness.
The removal efficiency of a skimmer is partly a function of the
retention time of the water in the tank. Larger, more buoyant
particles require less retention time than smaller particles.
Thus the efficiency also depends on the composition of the waste
stream. The retention time required to allow phase separation
and subsequent skimming varies from 1 to 15 minutes, depending on
the wastewater characteristics.
API or other gravity-type separators are more effective where the
amount of surface oil flowing through the system is continuous
and substantial. Drum and belt type skimmers are applicable to
waste streams which evidence smaller amounts of floating oil and
where surges of floating oil are not a problem. Using an API
separator system in conjunction with a drum type skimmer would be
a very effective method of removing floating contaminants from
non-emulsified oily waste streams. Sampling data shown in Table
V?I-11 illustrate the capabilities of the technology with both
extremely high and moderate oil influent levels.
This data is intended to be illustrative of the very high level
l-
s a
oi^.^«v.^s^.^^.o.xs^t.o-.«|«^i
SSSJ ormanufac?Sr?ng°nplant^ and on per.lt regents that
are constantly achieved, it is determined that effluent oil
237
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levels may be reliably reduced below 10 mg/1 with moderate
influent concentrations. Very high concentrations of oil such as
the 22 percent shown in Table VII-11 may require two-step
treatment to achieve this level. However, these concentrations
are not typically found in nonferrous wastewater.
Advantages and Limitations. Skimming as a pretreatment is effec-
tive in removing naturally floating waste material. It also
improves the performance of subsequent downstream treatments.
Many pollutants, particularly dispersed or emulsified oil, will
not float "naturally" but require additional treatments. There-
fore, skimming alone may not remove all the pollutants capable of
being removed by air flotation or other more sophisticated tech-
nologies .
Operational Factors. Reliability: Because of its simplicity,
skimming is a very reliable technique.
Maintainability: The skimming mechanism requires periodic
lubrication, adjustment, and replacement of worn parts.
Solid Waste Aspects: The collected layer of debris must be
disposed of by contractor removal, landfill, or incineration.
Because relatively large quantities of water are present in the
collected wastes, incineration is not always a viable disposal
method.
Demonstration Status. Skimming is a common operation utilized
extensively by industrial waste treatment systems.
MAJOR TECHNOLOGY EFFECTIVENESS
The performance of individual treatment technologies was pre-
sented above. Performance of operating systems is discussed
here. Five different systems are considered: IAS (hydroxide
precipitation and sedimentation or lime and settle), LS&F
(hydroxide precipitation, sedimentation, and filtration or lime,
settle, and filter), cyanide precipitation, ammonia steam strip-
ping, and activated carbon adsorption. Subsequently, an analysis
of effectiveness of such systems is made to develop one-day
maximum and ten-day and thirty-day average concentration levels
to be used in regulating pollutants. Evaluation of the LfcS and
the LSScF systems is carried out on the assumption that cyanide
precipitation and oil skimming are installed and operating
properly where appropriate.
LSiS Performance - Combined Metals Data Base
Chemical analysis data were collected of raw waste (treatment
influent) and treated waste (treatment effluent) from 55 plants
238
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(126 data days) sampled by EPA (or its contractor) using EPA
sampling and chemical analysis protocols. These data are the
data base for determining the effectiveness of LkS technology.
Each of these plants belongs to at least one of the following
industry categories: aluminum forming, battery manufacturing,
coil coating, copper forming, electroplating and porcelain
enameling. All of the plants employ pH adjustment and hydroxide
precipitation using lime or caustic, followed by settling (tank,
lagoon or clarifier) for solids removal. Most also add a
coagulant or flocculant prior to solids removal.
Analytical data from nonferrous metals manufacturing treatment
systems which include paired raw waste influent treatment and
treated effluent are limited to six nonferrous metals manufac-
turing plants with properly operated lime precipitation and
sedimentation systems.
The treated data from the six nonferrous plants were compared to
the achievable concentrations derived using the combined data
base. These data supported the combined data base concentra-
tions. These data and the analysis performed using the data are
in the administrative record supporting this rulemaking. Addi-
tionally, EPA examined the homogeneity among nonferrous subcate-
gories, as well as across nonferrous subcategories and the
combined metals data base. Homogeneity is the absence of
statistically discernable differences among mean pollutant
concentrations observed in a set of data. The P^P"*?*^"
analyses was to check the Agency's engineering judgement that the
untreated wastewater characteristics observed in the nonferrous
category were similar to those observed in the combined metals
data Establishment of similarity of raw wastes through a
statistical assessment provides further support to EPA s
assumption that lime and settle treatment reduces the toxic metal
SllSan? concentrations in untreated nonferrous wastewater to
concentrations achieved by the same technology applied to the
wastewater from the categories in the combined metals data base.
untreated nonfe?roSs metals manufacturing data combined across
subca?egories and the combined metals data also showed good
agreement.
239
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treatment of wastewater from the categories included in the
combined metals data base. After considering these points and
the fact that the combined data base consisted of more plants and
paired data points, the Agency decided to use the combined metals
data base.
Properly operated hydroxide precipitation and sedimentation will
result in effluent concentrations that are directly related to
pollutant solubilities. Since the nonferrous metals manufactur-
ing raw wastewater matrix contains the same toxic pollutants in
the same order of magnitude as the combined metals data base raw
wastewater and the technology is solubility-based, the mean
treatment process effluent and variability will be quite similar.
In addition, no interfering properties (such as chelating agents)
exist in nonferrous metals manufacturing wastewater that would
interfere with metal precipitation and so prevent attaining
concentrations calculated from the combined metals data base.
It should be noted, however, that statistical analyses indicate
that the raw wastewater matrix in nonferrous metals manufacturing
contains higher concentrations of lead and cadmium than the raw
wastewater of plants used for the combined metals data base.
Because the precipitation (and ultimate removal by sedimentation)
of these metals is directly related to their solubility, EPA
believes that the differences in raw waste concentrations, while
statistically significant, are not large enough to alter the
achievable concentrations following treatment.
An analysis of this combined data base was presented in the
development documents for the proposed regulations for coil
coating and porcelain enameling (January, 1981). In response to
the proposal, some commentors claimed that it was inappropriate
to use data from some categories for regulation of other catego-
ries. In response to these comments, the Agency reanalyzed the
data. An analysis of variance was applied to the data for the
126 days of sampling to test the hypothesis of homogeneous plant
mean raw and treated effluent levels across categories by pollu-
tant. This analysis is described in the report, "A Statistical
Analysis of the Combined Metals Industries Effluent Data" which
is in the administrative record supporting this rulemaking. The
main conclusion drawn from the analysis of variance is that, with
the exception of electroplating, the categories are generally
homogeneous with regard to mean pollutant concentrations in both
raw and treated effluent. That is, when data from electroplating
facilities are included in the analysis, the hypothesis of homo-
geneity across categories is rejected. When the electroplating
data are removed from the analysis, hypothesis of homogeneity
across categories is confirmed. On the basis of this analysis,
the electroplating data were removed from the data base used to
determine limitations. Where pollutants were present in higher
concentrations in raw wastewater from some categories (such as
240
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copper in copper forming and lead in lead battery manufacturing)
were expected and were accommodated in developing limitations by
using the larger values obtained from the marginally different
category to characterize the entire data set.
The statistical analysis provides support for the technical engi-
neering judgement that electroplating wastewaters are different
from most metal processing wastewater. These differences may be
further explained by differences in the constituents and relative
concentrations of pollutants in the raw wastewaters. Therefore,
the wastewater data derived from plants that only electroplate
are not used in developing limitations for the nonferrous metals
manufacturing category.
After removing the electroplating data, data from 21 plants and
52 days of sampling remained.
Prior to performing the homogeneity analysis, certain data were
deleted from the data base. The following criteria were used in
making these deletions:
o Plants where malfunctioning processes or^treatment
systems at time of sampling were identified.
o Data days where pH was less than 7.0 or TSS was greater
than 50 mg/1. (This is a prima facie indication of poor
operation).
For the purpose of developing treatment effectiveness, following
homogeneity, additional deletions were made. These deletions
were made, almost exclusively, in cases where effluent data
points were associated with raw waste values too low to assure
actual pollutant removal (i.e., less than 0.1 mg/1 of pollutant
in raw waste). A few data points were also eliminated following
the homogeneity analysis where malfunctions not previously
identified were recognized.
Collectively, these selection criteria ensure that the data are
from properly operating lime and settle treatment facilities.
The remaining data are displayed graphically in Figures VII-11 to
VII-19 This common or combined metals data base provides a more
sound and usable basis for estimating treatment effectiveness and
statistical variability of lime and settle technology than the
available data from any one category.
One-Day Effluent Values
The basic assumption underlying the determination of treatment
ina~ number of effluent guidelines categories. In the case of
the combined metal categories data base, there are too few data
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from any one plant to verify formally the lognormal assumption.
Thus, we assumed measurements of each pollutant from a particular
plant, denoted by X, follow a lognormal distribution with a log
mean y and log variance a2. The mean, variance, and 99th
percentile of X are then:
mean of X = E(X) = exp(y + a2/2)
variance of X = V(X) - exp(2y + a2) [exp(a2) - 1]
99th percentile = X^g = exp(y + 2.33o)
where exp is e, the base of the natural logarithm. The term
lognormal is used because the logarithm of X has a normal dis-
tribution with mean y and variance a2. Using the basic
assumption of lognormality, the actual treatment effectiveness
was determined using a lognormal distribution that, in a sense,
approximates the distribution of an average of the plants in the
data base, i.e., an "average plant" distribution. The notion of
an "average plant" distribution is not a strict statistical con-
cept but is used here to determine limits that would represent
the performance capability of an average of the plants in the
data base.
This "average plant" distribution for a particular pollutant was
developed as follows: the log mean was determined by taking the
average of all the observations for the pollutant across plants.
The log variance was determined by the pooled within-plant
variance. This is the weighted average of the plant variances.
Thus, the log mean represents the average of all the data for the
pollutant and the log variance represents the average of the
plant log variances or average plant variability for the
pollutant.
The one-day effluent values were determined as follows:
Let Xjj = the jth observation on a particular pollutant at
plant i, where
i. = 1, • . •, I
j=l, . . • , «J i
I = total number of plants
Ji = number of observations at plant i.
Then Y^j = In X^j
where In means the natural logarithm.
242
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Then
y = log mean over all plants
I J
where n = total number of observations
= L Ji
and V(y) = pooled log variance
= 2 (Ji-l)Si2
(Ji-D
where
log variance at plant L
J-l
* log mean at plant i-
Thus y and V(y) are the log mean and log variance, respectively,
of the lognormal distribution used to determine the treatment
effectiveness. The estimated mean and 99th percent ile of this
distribution form the basis for the long-term average and daily
maximum effluent limitations, respectively. The estimates are
mean
exp(y)^n(0.5V(y)>
99th percentile - £.99 - expty + 2.3
where 4>(.) is a Bessel function and exp is e, the base of the
natural logarithms (see Aitchison J. and J. A. C. Brown The
Lognormal Distribution, Cambridge University Press 1963). In
cases wh'ere~^r^r~w^Fi present in the data, a generalized form of
tht !ognormal SJtribution, known as the delta distribution, was
used (see Aitchison and Brown, op. cit., Chapter y;.
For certain pollutants, this approach was modified slightly to
accommodate situations in which a category or categories stood
out arbein* marginally different from the others. For instance,
afte? excluding the electroplating data and other data that did
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not reflect pollutant removal or proper treatment, the effluent
copper data from the copper forming plants were statistically
significantly greater than the copper data from the other plants.
Thus, copper effluent values shown in Table VII-12 are based only
on the copper effluent data from the copper forming plants. That
is, the log mean for copper is the mean of the logs of all copper
values from the copper forming plants only and the log variance
is the pooled log variance of the copper forming plant data only.
In the case of cadmium, after excluding the electroplating data
and data that did not reflect removal or proper treatment, there
were insufficient data to estimate the log variance for cadmium.
The variance used to determine the values shown in Table VII-12
for cadmium was estimated by pooling the within-plant variances
for all the other metals. Thus, the cadmium variability is the
average of the plant variability averaged over all the other
metals. The log mean for cadmium is the mean of the logs of the
cadmium observations only. A complete discussion of the data and
calculations for all the metals is contained in the administra-
tive record for this rulemaking.
Average Effluent Values
Average effluent values that form the basis for the monthly
limitations were developed in a manner consistent with the method
used to develop one-day treatment effectiveness in that the log-
normal distribution used for the one-day effluent values was also
used as the basis for the average values. That is, we assume a
number of consecutive measurements are drawn from the distribu-
tion of daily measurements.
In response to the proposed coil coating and porcelain enameling
regulations, the Agency received comments pointing out that per-
mits usually required less than 30 samples to be taken during a
month while the monthly average used as the basis for permits and
pretreatment requirements is based on the average of 30 samples.
In applying the treatment effectiveness values to regulations,
the Agency has considered the comments, examined the sampling
frequency required by many permits, and considered the change in
values of averages depending on the number of consecutive sam-
pling days in the averages. The frequency of sampling required
in most permits is about 10 samples per month or slightly greater
than twice weekly. The 99th percentiles of the distribution of
averages of 10 consecutive sampling days are not substantially
different from the 99th percentile of the distribution's 30-day
average. (Compared to the one-day maximum, the 10-day average is
about 80 percent of the difference between one-day and 30-day
values). Hence, the 10-day average provides a reasonable basis
for a monthly average and is typical of the sampling frequency
required by existing permits.
244
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The approach used for the 10 measurements values was used
previously for the electroplating category (see "Development
Document for Existing Sources Pretreatment Standards for the
Electroplating Point Source Category," EPA 440/1-79/003, U.S.
Environmental Protection Agency, Washington, D.C., August, 1979).
That is, the distribution of the average of 10 samples from a
lognormal was approximated by another lognormal distribution.
Although the approximation is not precise theoretically, there is
empirical evidence based on effluent data from a number of
categories that the lognormal is an adequate approximation for
the distribution of small samples. In the course of previous
work the approximation was verified in a computer simulation
study. The average values were developed assuming independence
of the observations although no particular sampling scheme was
assumed.
The monthly average is to be achieved in all permits and pre-
treatment standards regardless of the number of samples required
to be analyzed and averaged by the permitting or pretreatment
authority.
Ten-Sample Average:
The formulas for the 10-sample limitations were derived on the
basis of simple relationships between the mean and variance of
the distributions of the daily pollutant measurements and the
average of 10 measurements. It is assumed that the daily concen-
tration measurements for a particular pollutant, denoted by X,
follow a lognormal distribution with log mean and log variance
denoted by y and a2, respectively. Let XIQ denote the mean
of 10 consecutive measurements. The following relationships then
hold assuming the daily measurements are independent:
mean of X10 = E(X10) = E(X)
variance of X10 = V(X10) = V(X) T 10.
where E(X) and V(X) are the mean and variance of X, respectively,
defined above. It is then assumed that XIQ follows a lognormal
distribution with log mean VIQ and log standard deviation
o2lo- The mean and variance of XIQ are then
= exp(yio + 0.5a2io)
= exp(2yi0 + a2io) [exp(02lo) ~ 1]
r\
Now, yio and a2io can be derived in terms of y and oz as
y10 = y + a2/2 - 0.5 ln[l + (exp(a2) -
a2lo = ln[l + (exp(a2) -
245
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Therefore, V\Q and O2IQ can be estimated using the above
relationships and the estimates of y and a^ obtained for the
underlying lognormal distribution. The 10-sample limitation
value was determined by the estimate of the approximate 99th
percentile of the distribution of the 10-sample average given by
Xi0(.99) = exp(yio + 2.33 a10)
where yio and a!0 are t^ie estimates of VIQ and OIQ,
respectively.
30-Sample Average:
The average values based on 30 measurements are determined on the
basis of a statistical result known as the Central Limit Theorem.
This Theorem states that, under general and nonrestrictive
assumptions, the distribution of a sum of a number of random
variables, say n, is approximated by the normal distribution.
The approximation improves as the number of variables, n,
increases. The Theorem is quite general in that no particular
distributional form is assumed for the distribution of the
individual variables. In most applications (as in approximating
the distribution of 30-day averages) the Theorem is used to
approximate the distribution of the average of n observations of
a random variable. The result makes it possible to compute
approximate probability statements about the average in a wide
range of cases. For instance, it is possible to compute a value
below which a specified percentage (e.g., 99 percent) of the
averages of n observations are likely to fall. Most textbooks
state that 25 or 30 observations are sufficient for the
approximation to be valid. In applying the Theorem to the
determination of 30-day average effluent values, we approximate
the distribution of the average of 30 observations^drawn from the
distribution of daily measurements and use the estimated 99th
percentile of this distribution. The monthly limitations based
on 10 consecutive measurements were determined using the log-
normal approximation described above because 10 measurements
were, in this case, considered too small a number for use of the
Central Limit Theorem.
30-Sample Average Calculation
The formulas for the 30-sample average were based on an applica-
tion of the Central Limit Theorem. According to the Theorem, the
average of 30 observations drawn from the distribution of^daily
measurements, denoted by X3Q, is approximately normally dis-
tributed. The mean and variance of X3Q are
mean of XSQ - £(£30) = E(X)
variance of X3Q = V(X30) - V(X) ± 30.
246
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The 30-sample average value was determined by the estimate of the
approximate 99th percentile of the distribution of the 30-sample
average given by
Xso(-99) = E(X) + 2.33v/V~00~T~30~
A
where E(X) = exp(y)(jm(0.5V(y) )
and V(X) = exp(2y)|>n(2V(y)) - *n
The formulas for E(X) and V(X) are estimates of E(X) and V(X),
respectively given in Aitchison, J. and J. A. C. Brown, The
Lognormal Distribution, Cambridge University Press, 1963, page
457
Additional Pollutants
Nonferrous metals manufacturing wastewaters contain several other
toxic metals treatable by lime and settle technology but not part
of the combined metals data base. Paired performance data for
these parameters are not readily available, so data available to
the Agency in other categories have been selectively used to
determine the long-term average performance of lime and settle
technology for each pollutant. These data indicate that the
concentrations shown in Table VII-13 are reliably attainable by
nonferrous plants with well-operated hydroxide precipitation and
settling. The precipitation of silver appears to be accomplished
by alkaline chloride precipitation and adequate chloride ions
must be available for this reaction to occur.
In establishing which data were suitable for use in Table VII-13
two factors were heavily weighed: (1) the nature of the waste-
water; and (2) the range of pollutants or pollutant matrix in the
raw wastewater. These data have been selected from processes
that generate dissolved metals in the wastewater and which are
generally free from complexing agents. The pollutant matrix was
evaluated by comparing the concentrations of pollutants found in
the raw wastewaters with the range of pollutants in the raw
wastewaters of the combined metals data set. These data are
displayed in Tables VII-14 and VII-15 and indicate that there is
sufficient similarity in the raw wastes to assume a logical
transferability of the treated pollutant concentrations to the
combined metals data base. The available data on these added
pollutants do not allow homogeneity analysis as was performed on
the combined metals data base. The data source for each added
pollutant is discussed separately.
247
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Antimony (Sb) - The achievable performance for antimony is based
on data from a battery manufacturing and secondary lead plant.
Both EPA sampling data and recent permit data (1978 to 1982)
confirm the achievability of 0.7 mg/1 in the battery manufactur-
ing wastewater matrix included in the combined data set.
Arsenic (As) - The achievable performance of 0.5 mg/1 for arsenic
is based on permit data from two nonferrous metals manufacturing
plants. The untreated wastewater matrix shown in Table VII-15 is
comparable with the combined data set matrix based on the maximum
concentrations observed.
Beryllium (Be) - The treatability of beryllium is from the non-
ferrous metals manufacturing industry. The 0.3 mg/1 performance
is achieved at a beryllium plant with the comparable untreated
wastewater matrix shown in Table VII-15.
Mercury (Hg) - The 0.06 mg/1 treatability of mercury is based on
data from four battery plants. The untreated wastewater matrix
at these plants was considered in the combined metals data set.
Selenium (Se) - The 0.30 mg/1 treatability of selenium is based
on recent permit data from one of the nonferrous metals manufac-
turing plants also used for arsenic performance. The untreated
wastewater matrix for this plant is shown in Table VII-15.
Silver (Ag) - The treatability of silver is based on a 0.1 mg/1
treatability estimate from the inorganic chemicals industry.
Additional data supporting a treatability as stringent or more
stringent than 0.1 mg/1 are also available from seven nonferrous
metals manufacturing plants. The untreated wastewater matrix for
these plants is comparable to the combined metals data set plants
and is summarized in Table VII-15.
Thallium (Th) - The 0.50 mg/1 treatability for thallium is trans-
ferred from the inorganic chemicals industry. Although no
untreated wastewater data are available to verify comparability
with the combined metals data set plants, no other sources of
data for thallium treatability could be identified.
Aluminum (Al) - The 1.11 mg/1 treatability of aluminum is based
on the mean performance of one aluminum forming plant and one
coil coating plant. Both of the plants are from categories con-
sidered in the combined metals data set, assuring untreated
wastewater matrix comparability.
Fluoride (F) - The 14.5 mg/1 treatability of fluoride is based on
the mean performance of an electronics and electrical component
manufacturing plant. The untreated wastewater matrix for this
plant shown in Table VII-15 is comparable to the combined metals
data set.
248
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The mean concentrations from nonferrous plants with well operated
lime precipitation and sedimentation that the Agency sampled
indicates that the plants are meeting the limits for six pollu-
tants (antimony, arsenic, aluminum, selenium, silver, and fluor-
ide) . ^ EPA believes that the proposed limitations for arsenic and
selenium are achievable because they are based on permit data
from nonferrous metal plants including one of the six plants with
treatment sampled by EPA.
LSSeF Performance
Tables VII-16 and VII-17 show long-term data from two plants
which have well operated precipitation-settling treatment
followed by filtration. These data were used to provide
treatment effectiveness numbers for lime, settle and filtration
performance for the toxic metals chromium, copper, nickel, zinc,
and iron. The wastewaters from both plants contain pollutants
from metals processing and finishing operations (multi-category).
Both plants reduce hexavalent chromium before neutralizing and
precipitating metals with lime. A clarifier is used to remove
much of the solids load and a filter is used to "polish" or
complete removal of suspended solids. Plant A uses pressure
filtration, while Plant B uses a rapid sand filter.
Raw waste data was collected only occasionally at each facility
and is presented as an indication of the nature of the wastewater
treated. Data from Plant A was received as a statistical summary
and is presented as received. Raw laboratory data was collected
at Plant B and reviewed for spurious points and discrepancies.
The method of treating the data base is discussed below under
lime, settle, and filter treatment effectiveness.
Table VII-18 shows long-term data for zinc and cadmium removal at
Plant C, a primary zinc plant, which operates a LS&F system.
This data represents approximately four months (103 data days)
and has been arranged similarly to the data collected from plants
A and B for comparison and use. Lime, settle and filtration
treatment values for cadmium are based on this data.
It should be noted that the iron content of the raw waste of
plants A and B is high while that for Plant C is low. This
results, for plants A and B, in co-precipitation of toxic metals
with iron. Precipitation using high-calcium lime for pH control
yields the results shown in Table VII-18. Plant operating per-
sonnel indicate that this chemical treatment combination (some-
times with polymer assisted coagulation) generally produces
better and more consistent metals removal than other combinations
of sacrificial metal ions and alkalis.
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The LSSeF performance data presented here are based on systems
that provide polishing filtration after effective LScS treatment.
EPA believes that the use of polishing filtration data from
porcelain enameling plants is justified because porcelain enamel-
ing was included in the combined metals data base. Since it was
determined that lime precipitation and sedimentation will produce
identical results on both nonferrous metals manufacturing and
porcelain enameling wastewater, it is reasonable to assume that
polishing filters treating these identical intermediate waste
streams will produce an identical final effluent. Although the
one nonferrous plant sampled only supplied data for cadmium,
zinc, and TSS, its attainment of the limitations calculated from
the extensive porcelain enameling data suggests the ability to
attain the other limitations because of the nonpreferential
nature of toxic metal removal by filters.
Analysis of Treatment System Effectiveness
Data are presented in Table VII-12 showing the mean, one day, 10-
day, and 30-day values for nine pollutants examined in the LScS
metals data base. The mean variability factor for each of eight
pollutants (excluding cadmium because of the small number of data
points) was determined and is used to estimate one day, 10-day,
and 30-day values. (The variability factor is the ratio of the
value of concern to the mean: the average variability factors
are: one day maximum - 4.100; ten-day average - 1.821; and
30-day average - 1.618.) For values not calculated from the
common data base as previously discussed, the mean values for
pollutants shown in Table VII-13 were multiplied by the mean
variability factors of the eight combined data base pollutants to
derive the value to obtain the one, 10- and 30-day values. These
are tabulated in Table VII-19.
LSStF technology data are presented in Tables VII-16 and VII-17.
These data represent two operating plants (A and B) in which the
technology has been installed and operated for some years. Plant
A data was received as a statistical summary and is presented
without change. Plant B data was received as raw laboratory
analysis data. Discussions with plant personnel indicated that
operating experiments and changes in materials and reagents and
occasional operating errors had occurred during the data collec-
tion period. No specific information was available on those
variables. The Plant B data were analyzed to sort out high
values probably caused by methodological factors from random
statistical variability, or data noise. For each of the four
pollutants (chromium, nickel, zinc, and iron), the mean and
standard deviation (sigma) were calculated for the entire data
set. A data day was removed from the complete data set when any
individual pollutant concentration for that day exceeded the sum
of the mean plus three sigma for that pollutant. Fifty-one data
days (from a total of about 1,300) were eliminated by this
method.
250
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Another approach was also used as a check on the above method of
eliminating certain high values. The minimum values of raw
wastewater concentrations from Plant B for the same four pollu-
tants were compared to the total set of values for the corre-
sponding pollutants. When pollutant concentration exceeded the
minimum value selected from raw wastewater, concentrations for
that pollutant were discarded. Forty-five days of data were
eliminated by this procedure. Forty-three common days of data
were eliminated by both procedures. Since common engineering
practice (mean plus 3 sigma) and logic (treated waste should be
less than raw waste) seem to coincide, the data base with the 51
spurious data days eliminated is the basis for all further analy-
sis. Range, mean, standard deviation and mean plus two standard
deviations are shown in Tables VII-16 and VII-17 for Cr, Cu, Ni,
Zn, and Fe.
The Plant B data were separated into 1979, 1978, and total data
base (six years) segments. Combined with the statistical analy-
sis from Plant A for 1978 and 1979, this in effect created five
data sets, in which there is some overlap between the individual
years and total data sets from Plant B. By comparing these five
parts it is apparent that they are quite similar and all appear
to be from the same family of numbers. The largest mean found
among the five data sets for each pollutant was selected as the
long-term mean for LS&F technology and is used as the LS&F mean
in Table VII-19.
Plant C data were used as a basis for cadmium removal performance
and as a check on the zinc values derived from plants A and B.
The cadmium data are displayed in Table VII-18 and are incorpo-
rated into Table VII-19 for LSStF. The zinc data were analyzed
for compliance with the one-day and 30-day values in Table
VII-19; no zinc value of the 103 data points exceeded the one-day
zinc value of 1.02 mg/1. The 103 data points were separated into
blocks of 30 points and averaged. Each of the three full 30-day
averages was less than the Table VII-19 value of 0.31 mg/1.
Additionally, the Plant C raw wastewater pollutant concentrations
(Table VII-18) are well within the range of raw wastewater con-
centrations of the combined metals data base (Table VII-14),
further supporting the conclusion that Plant C wastewater data
are compatible with similar data from plants A and B.
Concentration values for regulatory use are displayed in Table
VII-19. Mean one-day, ten-day, and 30-day values for L&S for
nine pollutants were taken from Table VII-12; the remaining LScS
values were developed using the mean values in Table VII-13 and
the mean variability factors discussed above. (It is appropriate
to use these variability factors for the additional pollutants,
since the combined data base is a detailed data set for this
technology, and the additional pollutants all are in the same
solubility ranges as metals in the combined data base.)
251
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LS&F mean values for Cd, Cr, Ni, Zn, and Fe, appearing in Table
VII-19, are derived from plants A and B, as discussed above. The
Cd value is from Plant C. One-, ten-, and 30-day values for LS&F
are derived by applying the same variability factor developed
from the pooled LStS data base for the specific pollutant to the
LSStF mean calculated for that pollutant. EPA used variability
factors calculated from the pooled metals data base because the
pooled data base provided a better statistical basis for comput-
ing variability than the data from the three plants sampled. In
fact, the use of the lime and settle combined data base variabil-
ity factors is probably a conservative assumption because
filtration is a less variable technology than lime and settle,
since it is less operator dependent.
Mean values for LSStF for pollutants not already discussed are
derived by reducing the LStS mean by one-third. The one-third
reduction was established after examining the percent reduction
in concentrations going from LStS to LSStF data for Cd, Cr, Ni, Zn,
and Fe. The average reduction is 0.3338 or one-third. Variabil-
ity factors for these additional pollutants are identical to the
variabilities established for LStS treatment of these pollutants
(using the variance from the pooled metals data base or the mean
of other pollutant variances if a pollutant-specific variance is
not available). Since filtration is a non-preferential technol-
ogy with regard to metals treated, and furthermore is being used
to polish relatively clean wastewater (wastewater after lime and
settle treatment), EPA believes it is reasonable that these
additional pollutants will be removed at the same average rate.
Copper concentrations achieved at plants A and B may be lower
than generally achievable by plants in this category because of
the high iron content and low copper content of the raw waste-
waters. Therefore, the mean concentration value achieved is not
used; the LSStF mean used is derived from the LStS technology using
the one-third factor described previously.
LStS cyanide mean concentrations shown in Table VII-8 are ratioed
to one-day, ten-day, and 30-day values using the mean variability
factors developed for the additional pollutants not included in
the pooled metals data base. The LSSeF mean cyanide value is
calculated by using the one-third removal factor for LSStF trom
the LStS mean removal, as discussed previously for LSStF metals
limitations. The cyanide performance was arrived at by using the
same variability factors. The treatment method used here is
cyanide precipitation. Because cyanide precipitation is limited
by the same physical processes as the metal precipitation, it is
expected that the variabilities will be similar. Therefore, the
average of the metal variability factors from the pooled metals
data has been used as a basis for calculating the cyanide one-
day, ten-day, and 30-day average treatment effectiveness values.
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The filter performance for removing TSS as shown in Table VII-9
yields a mean effluent concentration of 2.61 mg/1 and calculates
to a ten-day average of 4.33, 30-day average of 3.36 mg/1; a one-
day maximum of 8.88. These calculated values more than amply
support the classic values of 10 and 15, respectively, which are
used for LSScF.
Although iron was reduced in some LSScF operations, some facili-
ties using that treatment introduce iron compounds to aid set-
tling. Therefore, the one-day, ten-day, and 30-day values for
iron at LS&F were held at the LScS level so as to not unduly pen-
alize the operations which use the relatively less objection-
able iron compounds to enhance removals of toxic metals.
Ammonia Steam Stripping Performance
Chemical analysis data were collected of raw waste (treatment
influent) and treated waste (treatment effluent) from one plant
of the iron and steel category. A contractor for EPA, using EPA
sampling and chemical analysis protocols, collected six paired
samples in a two-month period. These data are the data base for
determining the effectiveness of ammonia steam stripping tech-
nology and are contained within the public record supporting this
document. Ammonia treatment at this coke plant consisted of two
steam stripping columns in series with steam injected counter-
currently to the flow of the wastewater. A lime reactor for pH
adjustment separated the two stripping columns.
An arithmetic mean of the treatment effluent data produced an
ammonia long-term mean value of 32.2 mg/1. The one-day maximum,
10-day and 30-day average concentrations attainable by ammonia
steam stripping were calculated using the long-term mean of the
32.2 mg/1 and the variability factors developed for the combined
metals data base. This produced ammonia concentrations of 133.3,
58.6 and 52.1 mg/1 ammonia for the one-day maximum, 10-day and
30-day averages, respectively.
As discussed above under Demonstration Status for Ammonia
Stripping (p.217 ), steam stripping is demonstrated within the
nonferrous metals manufacturing category. EPA believes the
performance data from the iron and steel category provide a valid
measure of this technology's performance on nonferrous category
wastewater due to similar (concentrations of the same order of
magnitude) concentrations of ammonia in the respective raw
wastewater matrices. A comparison of raw untreated wastewater
samples from the nonferrous metals manufacturing point source
category and the iron and steel facility from which the ammonia
data was transferred is shown below:
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Category or Subcategory Ammonia Concentrations (mg/1)
Iron and Steel 599, 226, 819, 502, 984, and 797
Primary Tungsten 695 and 1,610
Primary Columbium-Tantalum 53.1, 496.1, 25,700, 18,500 and
16,900
Secondary Aluminum 195
Secondary Silver 1,202 and 4,630
Activated Carbon Performance
Activated carbon preliminary treatment was selected to control
discharges of polynuclear aromatic hydrocarbons from wet air pol-
lution control associated with anode paste plants, anode bake
plants, potlines, and potrooms, as well as the cathode reproces-
sing operations from primary aluminum plants. This treatment
technology was selected because discharges from these operations
do not appear to be effectively controlled by existing treatment.
Activated carbon is not demonstrated in this or any other appli-
cation within the primary aluminum subcategory. Therefore,
performance of this technology is transferred from the iron and
steel category.
MINOR TECHNOLOGIES
Several other treatment technologies were considered for possible
application in BPT or BAT. These technologies are presented here
with a full discussion for most of them. A few are described
only briefly because of limited technical development.
Flotation
Flotation is the process of causing particles such as metal
hydroxides or oil to float to the surface of a tank where they
can be concentrated and removed. This is accomplished by releas-
ing gas bubbles which attach to the solid particles, increasing
their buoyancy and causing them to float. In principle, this
process is the opposite of sedimentation. Figure VII-20 shows
one type of flotation system.
Flotation is used primarily in the treatment of wastewater
streams that carry heavy loads of finely divided suspended solids
or oil. Solids having a specific gravity only slightly greater
than 1.0, which would require abnormally long sedimentation
times, may be removed in much less time by flotation.
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This process may be performed in several ways: foam, dispersed
air, dissolved air, gravity, and vacuum flotation are the most
commonly used techniques. Chemical additives are often used to
enhance the performance of the flotation process.
The principal difference among types of flotation is the method
of generating the minute gas bubbles (usually air) in a suspen-
sion of water and small particles. Chemicals may be used to
improve the efficiency with any of the basic methods. The fol-
lowing paragraphs describe the different flotation techniques and
the method of bubble generation for each process.
Froth Flotation - Froth flotation is based on differences in the
physiochemical properties in various particles. Wettability and
surface properties affect the ability of the particles to attach
themselves to gas bubbles in an aqueous medium. In froth flota-
tion, air is blown through the solution containing flotation
reagents. The particles with water repellant surfaces stick to
air bubbles as they rise and are brought to the surface. A
mineralized froth layer, with mineral particles attached to air
bubbles, is formed. Particles of other minerals which are read-
ily wetted by water do not stick to air bubbles and remain in
suspension.
Dispersed Air Flotation - In dispersed air flotation, gas bubbles
are generated by introducing the air by means of mechanical agi-
tation with impellers or by forcing air through porous media.
Dispersed air flotation is used mainly in the metallurgical
industry.
Dissolved Air Flotation - In dissolved air flotation, bubbles are
produced by releasing air from a superstaturated solution under
relatively high pressure. There are two types of contact between
the gas bubbles and particles. The first type is predominant in
the flotation of flocculated materials and involves the entrap-
ment of rising gas bubbles in the flocculated particles as they
increase in size. The bond between the bubble and particle is
one of physical capture only. The second type of contact is one
of adhesion. Adhesion results from the intermolecular attraction
exerted at the interface between the solid particle and the gase-
ous bubble.
Vacuum Flotation - This process consists of saturating the waste-
water with air either directly in an aeration tank, or by permit-
ting air to enter on the suction of a wastewater pump. A partial
vacuum is applied, which causes the dissolved air to come out of
solution as minute bubbles. The bubbles attach to solid parti-
cles and rise to the surface to form a scum blanket, which is
normally removed by a skimming mechanism. Grit and other heavy
solids that settle to the bottom are generally raked to a central
sludge pump for removal. A typical vacuum flotation unit con-
sists of a covered cylindrical tank in which a partial vacuum is
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maintained. The tank is equipped with scum and sludge removal
mechanisms. The floating material is continuously swept to the
tank periphery, automatically discharged into a scum trough, and
removed from the unit by a pump also under partial vacuum.
Auxiliary equipment includes an aeration tank for saturating the
wastewater with air, a tank with a short retention time for
removal of large bubbles, vacuum pumps, and sludge pumps.
Application and Performance. Flotation is used primarily in the
treatment of wastewater streams that carry heavy loads of finely
divided suspended solids or oil. Solids having a specific grav-
ity only slightly greater than 1.0, which would require abnor-
mally long sedimentation times, may be removed in much less time
by flotation.
The primary variables for flotation design are pressure, feed
solids concentration, and retention period. The suspended solids
in the effluent decrease, and the concentration of solids in the
float increases, with increasing retention period. When the
flotation process is used primarily for clarification, a reten-
tion period of 20 to 30 minutes is adequate for separation and
concentrat ion.
Advantages and Limitations. Some advantages of the flotation
process are the high levels of solids separation achieved in many
applications, the relatively low energy requirements, and the
adaptability to meet the treatment requirements of different
waste types. Limitations of flotation are that it often requires
addition of chemicals to enhance process performance and that it
generates large quantities of solid waste.
Operational Factors. Reliability: Flotation systems normally
are very reliable with proper maintenance of the sludge collector
mechanism and the motors and pumps used for aeration.
Maintainability: Routine maintenance is required on the pumps
and motors. The sludge collector mechanism is subject to possi-
ble corrosion or breakage and may require periodic replacement.
Solid Waste Aspects: Chemicals are commonly used to aid the
flotation process by creating a surface or a structure that can
easily adsorb or entrap air bubbles. Inorganic chemicals, such
as the aluminum and ferric salts, and activated silica, can bind
the particulate matter together and create a structure that can
entrap air bubbles. Various organic chemicals can change the
nature of either the air-liquid interface or the solid-liquid
interface, or both. These compounds usually collect on. the
interface to bring about the desired changes. The added chemi-
cals plus the particles in solution combine to form a large
volume of sludge which must be further treated or properly
disposed.
256
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Demonstration Status. Flotation is a fully developed process and
is readily available for the treatment of a wide variety of
industrial waste streams. Dissolved air flotation technology is
used by can manufacturing plants to remove oil and grease in the
wastewater from can wash lines. It is not currently used to
treat nonferrous metals manufacturing wastewaters.
Centrifugation
Centrifugation is the application of centrifugal force to sepa-
rate solids and liquids in a liquid-solid mixture or to effect
concentration of the solids. The application of centrifugal
force is effective because of the density differential normally
found between the insoluble solids and the liquid in which they ^
are contained. As a waste treatment procedure, Centrifugation is
most often applied to dewatering of sludges. One type of centri-
fuge is shown in Figure VII -21.
There are three common types of centrifuges: the disc, basket,
and conveyor type. All three operate by removing solids under
the influence of centrifugal force. The fundamental difference
between the three types is the method by which solids are col-
lected in and discharged from the bowl.
In the disc centrifuge, the sludge feed is distributed between
narrow channels that are present as spaces between stacked con-
ical discs. Suspended particles are collected and discharged
continuously through small orifices in the bowl wall. The clar-
ified effluent is discharged through an overflow weir.
A second type of centrifuge which is useful in dewatering sludges
is the basket centrifuge. In this type of centrifuge sludge
feed is introduced at the bottom of the basket, and solids col-
lect at the bowl wall while clarified effluent overflows the lip
rina at the top. Since the basket centrifuge does not have pro-
vision for continuous discharge of collected cake, operation^
requires interruption of the feed for cake discharge for a minute
or two in a 10 to 30 minute overall cycle.
The third type of centrifuge commonly used in sludge dewatering
is the conveyor type. Sludge is fed through a stationary feed
pipe into rotating bowl iS which the solids are settled out
aeainst the bowl wall by centrifugal force. From the bowl wall,
?hey are moved by a screw to the Snd of the machine at which
point they are discharged. The liquid effluent is discharged
trough ports after passing the length of the bowl under cen-
trifugal force .
Application and Performance. Virtually all industrial waste
t1
range of industrial concerns.
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The performance of sludge dewatertng by centrifugation depends on
the feed rate, the rotational velocity of the drum, and the
sludge composition and concentration. Assuming proper design and
operation, the solids content of the sludge can be increased to
20 to 35 percent.
Advantages and Limitations. Sludge dewatering centrifuges have
minimal space requirements and show a high degree of effluent
clarification. The operation is simple, clean, and relatively
inexpensive. The area required for a centrifuge system instal-
lation is less than that required for a filter system or sludge
drying bed of equal capacity, and the initial cost is lower.
Centrifuges have a high power cost that partially offsets the low
initial cost. Special consideration must also be given to pro-
viding sturdy foundations and soundproofing because of the vibra-
tion and noise that result from centrifuge operation. Adequate
electrical power must also be provided since large motors are
required. The major difficulty encountered in the operation of
centrifuges has been the disposal of the concentrate which is
relatively high in suspended, non-settling solids.
Operational Factors. Reliability: Centrifugation is highly
reliable with proper control of factors such as sludge feed, con-
sistency, and temperature. Pretreatment such as grit removal and
coagulant addition may be necessary, depending on the composition
of the sludge and on the type of centrifuge used.
Maintainability: Maintenance consists of periodic lubrication,
cleaning, and inspection. The frequency and degree of inspection
required varies depending on the type of sludge solids being
dewatered and the maintenance service conditions. If the sludge
is abrasive, it is recommended that the first inspection of the
rotating assembly be made after approximately 1,000 hours of
operation. If the sludge is not abrasive or corrosive, then the
initial inspection might be delayed. Centrifuges not equipped
with a continuous sludge discharge system require periodic
shutdowns for manual sludge cake removal.
Solid Waste Aspects: Sludge dewatered in the centrifugation pro-
cess may be disposed of by landfill. The clarified effluent
(centrate), if high in dissolved or suspended solids, may require
further treatment prior to discharge.
Demonstration Status. Centrifugation is currently used in a
great many commercial applications to dewater sludge. One
secondary copper plant uses a centrifuge to dewater sludge. Work
is underway to improve the efficiency, increase the capacity, and
lower the costs associated with centrifugation.
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Coalescing
The basic principle of coalescence involves the preferential
wetting of a coalescing medium by oil droplets which accumulate
on the medium and then rise to the surface of the solution as
they combine to form larger particles. The most important
requirements for coalescing media are wettability for oil and
large surface area. Monofilament line is sometimes used as a
coalescing medium.
Coalescing stages may be integrated with a wide variety of grav-
ity oil separation devices, and some systems may incorporate^
several coalescing stages. In general, a preliminary oil skim-
ming step is desirable to avoid overloading the coalescer.
One commercially marketed system for oily waste treatment com-
bines coalescing with inclined plant separation and filtration.
In this system, the oily wastes flow into an inclined plate
settler. This unit consists of a stack of inclined baffle plates
in a cylindrical container with an oil collection chamber at the
top. The oil droplets rise and impinge upon the undersides ^ of
the plants. They then migrate upward to a guide rib that directs
the oil to the oil collection chamber, from which oil is dis-
charged for reuse or disposal.
The oily water continues on through another cylinder containing
replaceable filter cartridges that remove suspended particles
from the waste. From there the wastewater enters a final cylin-
der in which the coalescing material is housed. As the oily
water passes through the many small, irregular, continuous
passages in the coalescing material, the oil droplets coalesce
and rise to an oil collection chamber.
Application and Performance. Coalescing is used to treat oily
wastes that do not separate readily in simple gravity systems .
The three stage system described above has achieved effluent
concentration! of 10 to 15 mg/1 oil and grease from raw waste
concentrations of 1,000 mg/1 or more.
Advantages and Limitations. Coalescing allows removal of oil
droolets too finely dispersed for conventional gravity
°
I«
oils Tlavlid plugging, coalescers must be protected by pre
concentrations of
os ,
?reake .rhlgh concentrations of £rroOUrffd
faT necessawnen^a^stro?! concentrations are high.
may be
259
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Operational Factors. Reliability: Coalescing is inherently
highly reliable since there are no moving parts and the coalesc-
ing substrate (mono filament, etc.) is inert in the process and
therefore not subject to frequent regeneration or replacement
requirements. Large loads or inadequate preliminary treatment;
however, may result in plugging or bypass of coalescing stages.
Maintainability: Maintenance requirements are generally limited
to replacement of the coalescing medium on an infrequent basis .
Solid Waste Aspects: No appreciable solid waste is generated by
this process.
Demonstration Status. Coalescing has been fully demonstrated in
industries generating oily wastewater, although none are known to
be in use at any nonferrous metals manufacturing facility.
Cyanide Oxidation by Chlorine
Cyanide oxidation using chlorine is widely used in industrial
waste treatment to oxidize cyanide. Chlorine can be utilized in
either the elemental or hypochlorite forms. This classic proced-
ure can be illustrated by the following two step chemical reac-
tion:
1. Cl2 + NaCN + 2NaOH -»• NaCNO + 2NaCl + H20
2. 3C12 + 6NaOH + 2NaCNO •*• 2NaHC03 + N£ + 6NaCl +
The reaction presented as equation (2) for the oxidation of cya-
nate is the final step in the oxidation of cyanide. A complete
system for the alkaline chlorination of cyanide is shown in
Figure VII -22.
The alkaline chlorination process oxidizes cyanides to carbon
dioxide and nitrogen. The equipment often consists of an equali-
zation tank followed by two reaction tanks, although the reaction
can be carried out in a single tank. Each tank has an electronic
recorder-controller to maintain required conditions with respect
to pH and oxidation reduction potential (ORP). In the first
reaction tank, conditions are adjusted to oxidize cyanides to
cyanates. To effect the reaction, chlorine is metered to the
reaction tank as required to maintain the ORP in the range of 350
to 400 millivolts, and 50 percent aqueous caustic soda is added
to maintain a pH range of 9.5 to 10. In the second reaction
tank, conditions are maintained to oxidize cyanate to carbon
dioxide and nitrogen. The desirable ORP and pH for this reaction
are 600 millivolts and a pH of 8.0. Each of the reaction tanks
is equipped with a propeller agitator designed to provide approx-
imately one turnover per minute. Treatment by the batch process
is accomplished by using two tanks, one for collection of water
over a specified time period, and one tank for the treatment of
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an accumulated batch. If dumps of concentrated wastes are fre-
quent, another tank may be required to equalize the flow to the
treatment tank. When the holding tank is full, the liquid is
transferred to the reaction tank for treatment. After treatment,
the supernatant is discharged and the sludges are collected for
removal and ultimate disposal.
Application and Performance. The oxidation of cyanide waste by
chlorine is a classic process and is found in most industrial
plants using cyanide. This process is capable of achieving
effluent levels of free cyanide that are nondetectable.
Advantages and Limitations. Some advantages of chlorine oxidaton
for handling process effluents are operation at ambient tempera-
ture, suitability for automatic control, and low cost. Disadvan-
tages include the need for careful pH control, possible chemical
interference in the treatment of mixed wastes, and the potential
hazard of storing and handling chlorine gas. If organic com-
pounds are present, toxic chlorinated organics may be generated.
Alkaline chlorination is not effective in treating metallocyanide
complexes, such as the ferrocyanide.
Operational Factors. Reliability: Chlorine oxidation is highly
reliable with proper monitoring and control, and proper pretreat-
ment to control interfering substances.
Maintainability: Maintenance consists of periodic removal of
sludge and recalibration of instruments.
Solid Waste Aspects: There is no solid waste problem associated
with chlorine oxidation.
Demonstration Status. The oxidation of cyanide wastes ^y chlo-
rine is a widely used process in plants using cyanide in cleaning
and metal processing baths.
Cyanide Oxidation by Ozone
Ozone is a highly reactive oxidizing agent which is approximately
10 times more soluble than oxygen on a weight basis in water. ^
Ozone may be produced by several methods, but the silent electri-
cal discharge method is predominant in the field. The silent
electrical discharge process produces ozone by passing oxygen or
air between electrodes separated by an insulating material. A
complete ozonation system is represented in Figure VII-ZJ.
Application and Performance. Ozonation has been applied commer-
cially to oxidize cyanides, phenolic chemicals, and organometal
complexes. Its applicability to photographic wastewaters has
beeS studied in the laboratory with good results. Ozone is used
in industrial waste treatment primarily to oxidize cyanide to
cyan^e and to oxidize phenolsand dyes to a variety of colorless
nontoxic products.
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Oxidation of cyanide to cyanate is illustrated below:
CN~ + 63 ->• CNO~ + 02
Continued exposure to ozone will convert the cyanate formed to
carbon dioxide and ammonia; however, this is not economically
practical.
Ozone oxidation of cyanide to cyanate requires 1.8 to 2.0 pounds
ozone per pound of CN"; complete oxidation requires 4.6 to 5.0
pounds ozone per pound of CN~. Zinc, copper, and nickel cya-
nides are easily destroyed to a nondetectable level, but cobalt
and iron cyanides are more resistant to ozone treatment.
Advantages and Limitations. Some advantages of ozone oxidation
for handling process effluents are its suitability to automatic
control and on-site generation and the fact that reaction prod-
ucts are not chlorinated organics and no dissolved solids are
added in the treatment step. Ozone in the presence of activated
carbon, ultraviolet, and other promoters shows promise of reduc-
ing reaction time and improving ozone utilization, but the
process at present is limited by high capital expense, possible
chemical interference in the treatment of mixed wastes, and an
energy requirement of 25 kwh/kg of ozone generated. Cyanide is
not economically oxidized with 03 beyond the cyanate form.
Operational Factors. Reliability: Ozone oxidation is highly
reliable with proper monitoring and control, and proper prelimi-
nary treatment to control interfering substances.
Maintainability: Maintenance consists of periodic removal of
sludge, and periodic renewal of filters and desiccators required
for the input of clean dry air; filter life is a function of
input concentrations of detrimental constituents.
Solid Waste Aspects: Preliminary treatment to eliminate sub-
stances which will interfere with the process may be necessary.
Dewatering of sludge generated in the ozone oxidation process or
in an "in-line" process may be desirable prior to disposal.
Cyanide Oxidation by Ozone with UV Radiation
One of the modifications of the ozonation process is the simulta-
neous application of ultraviolet light and ozone for the treat-
ment of wastewater, including treatment of halogenated orgam.cs.
The combined action of these two forms produces reactions by
photolysis, photosensitization, hydroxylation, oxygenation, and
oxidation. The process is unique because several reactions and
reaction species are active simultaneously.
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Ozonation is facilitated by ultraviolet absorption because both
the ozone and the reactant molecules are raised to a higher
energy state so that they react more rapidly. In addition, free
radicals for use in the reaction are readily hydrolyzed by the
water present. The energy and reaction intermediates created by
the introduction of both ultraviolet and ozone greatly reduce the
amount of ozone required compared with a system using ozone
alone. Figure VII-24 shows a three-stage UV-ozone system. A
system to treat mixed cyanides requires preliminary treatment
that involves chemical coagulation, sedimentation, clarification,
equalization, and pH adjustment.
Application and Performance. The ozone-UV radiation process was
developed primarily for cyanide treatment in the electroplating
and color photo-processing areas. It has been successfully
applied to mixed cyanides and organics from organic chemicals
manufacturing processes. The process is particularly useful for
treatment of complexed cyanides such as ferricyanide, copper
cyanide, and nickel cyanide, that are resistant to ozone.
Demonstration Status. Ozone combined with UV radiation is a
relatively new technology. Four units are currently in operation
and all four treat cyanide-bearing waste.
Cyanide Oxidation by Hydrogen Peroxide
Hydrogen peroxide oxidation removes both cyanide and metals in
cyanide-containing wastewaters. In this process, cyanide-bearing
waters are heated to 49°C to 54°C (120°F to 130°F) and the pH is
adjusted to 10.5 to 11.8. Formalin (37 percent formaldehyde) is
added while the tank is vigorously agitated. After two to five
minutes, a proprietary peroxygen compound (41 percent hydrogen
peroxide with a catalyst and additives) is added. After an hour
of mixing, the reaction is complete. The cyanide is converted to
cyanate and the metals are precipitated as oxides or hydroxides.
The metals are then removed from solution by either settling or
filtration.
The main equipment required for this process is two holding tanks
equipped with heaters and air spargers or mechanical stirrers.
These tanks may be used in a batch or continuous fashion, with
one tank being used for treatment while the other is being
filled. A settling tank or a filter is needed to concentrate the
precipitate.
Application and Performance. The hydrogen peroxide oxidation
process is applicable to cyanide-bearing wastewaters, especially
those containing metal-cyanide complexes. In terms of waste
reduction performance, this process can reduce total cyam.de to
less than 0.1 mg/1 and the zinc or cadmium concentrations to less
than 1.0 mg/1.
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Advantages and Limitations. Chemical costs are similar to those
for alkaline chlorination using chlorine and lower than those for
treatment with hypochlorite. All free cyanide reacts and is com-
pletely oxidized to the less toxic cyanate state. In addition,
the metals precipitate and settle quickly, and they may be recov-
erable in many instances; however, the process requires energy
expenditures to heat the wastewater prior to treatment.
Demonstration Status. This treatment process was introduced in
1971 and is used in several facilities. No nonferrous metals
manufacturing plants use oxidation by hydrogen peroxide.
Evaporation
Evaporation is a concentration process. Water is evaporated from
a solution, increasing the concentration of solute in the remain-
ing solution. If the resulting water vapor is condensed back to
liquid water, the evaporation-condensation process is called dis-
tillation. However, to be consistent with industry terminology,
evaporation is used in this report to describe both processes.
Both atmospheric and vacuum evaporation are commonly used in
industry today. Specific evaporation techniques are shown in
Figure VI1-25 and discussed below.
Atmospheric evaporation could be accomplished simply by boiling
the liquid. To aid evaporation, heated liquid is sprayed on an
evaporation surface, and air is blown over the surface and subse-
quently released to the atmosphere. Thus, evaporation occurs by
humidification of the air stream, similar to a drying process.
Equipment for carrying out atmospheric evaporation is quite
similar for most applications. The major element is generally a
packed column with an accumulator bottom. Accumulated wastewater
is pumped from the base of the column, through a heat exchanger,
and back into the top of the column, where it is sprayed into the
packing. At the same time, air drawn upward through the packing
by a fan is heated as it contacts the hot liquid. The liquid
partially vaporizes and humidifies the air stream. The fan then
blows the hot, humid air to the outside atmosphere. A scrubber
is often unnecessary because the packed column itself acts as a
scrubber.
Another form of atmospheric evaporator also works on the air
humidification principle, but the evaporated water is recovered
for reuse by condensation. These air humidification techniques
operate well below the boiling point of water and can utilize
waste process heat to supply the energy required.
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In vacuum evaporation, the evaporation pressure is lowered to
cause the liquid to boil at reduced temperatures. All of the
water vapor is condensed and, to maintain the vacuum condition,
noncondensible gases (air in particular) are removed by a vacuum
pump. Vacuum evaporation may be either single or double effect.
In double effect evaporation, two evaporators are used, and the
water vapor from the first evaporator (which may be heated by
steam) is used to supply heat to the second evaporator. As it
supplies heat, the water vapor from the first evaporator con-
denses. Approximately equal quantities of wastewater are evapo-
rated in each unit; thus, the double effect system evaporates
twice the amount of water that a single effect system does, at
nearly the same cost in energy but with added capital cost and
complexity. The double effect technique is thermodynamically
possible because the second evaporator is maintained at Blower
pressure (higher vacuum) and, therefore, lower evaporation tem-
perature. Another means of increasing energy efficiency is vapor
recompression (thermal or mechanical), which enables heat to be
transferred from the condensing water vapor to the evaporating
wastewater. Vacuum evaporation equipment may be classified as
submerged tube or climbing film evaporation units.
In the most commonly used submerged tube evaporator, the heating
and condensing coil are contained in a single vessel to reduce
capital cost. The vacuum in the vessel is maintained by an
eductor-type pump, which creates the required vacuum by the flow
of the condenser cooling water through a venturi. Wastewater
accumulates in the bottom of the vessel, and it is evaporated by
means of submerged steam coils. The resulting water vapor con-
denses as it contacts the condensing coils in the top of the
vessel. The condensate then drips off the condensing coils into
a collection trough that carries it out of the vessel. Con-
centrate is removed from the bottom of the vessel.
The major elements of the climbing film evaporator are the evapo-
rator, separator, condenser, and vacuum pump. Wastewater is
"drawn" into the system by the vacuum so that a constant liquid
level is maintained in the separator. Liquid enters the steam-
jacketed evaporator tubes, and part of it evaporates so that a
mixture of vapor and liquid enters the separator. The design of
the separator is such that the liquid is continuously circulated
from the separator to the evaporator. The vapor entering the
separator flows out through a mesh entrapment separator to the
condenser, where it is condensed as it flows down through the
condenser tubes. The condensate, along with any entrained ^ air,
is pumped out of the bottom of the condenser by a liquid ring
vacuum pump. The liquid seal provided by the condensate keeps
the vacuum in the system from being broken.
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Application and Performance. Both atmospheric and vacuum
evaporation are used in many industrial plants, mainly for the
concentration and recovery of process solutions. Many of these
evaporators also recover water for rinsing. Evaporation has also
been applied to recovery of phosphate metal-cleaning solutions.
In theory, evaporation should yield a concentrate and a deionized
condensate. Actually, carry-over has resulted in condensate
metal concentrations as high as 10 mg/1, although the usual level
is less than 3 mg/1. Samples from one plant showed 1,900 mg/1
zinc in the feed, 4,570 mg/1 in the concentrate, and 0.4 mg/1 in
the condensate. Another plant had 416 mg/1 copper in the feed
and 21,800 mg/1 in the concentrate. Chromium analysis for that
plant indicated 5,060 mg/1 in the feed and 27,500 mg/1 in the
concentrate. Evaporators are available in a range of capacities,
typically from 15 to 75 gph, and may be used in parallel
arrangements for processing of higher flow rates.
Advantages and Limitations. Advantages of the evaporation pro-
cess are that it permits recovery of a wide variety of process
chemicals, and it is often applicable to concentration or removal
of compounds which cannot be accomplished by any other means.
The major disadvantage is that the evaporation process consumes
relatively large amounts of energy for the evaporation of water.
The recovery of waste heat from many industrial processes (e.g.,
diesel generators, incinerators, boilers, and furnaces) should be
considered as a source of this heat for a totally integrated
evaporation system. Also, in some cases solar heating could be
inexpensively and effectively applied to evaporation units. For
some applications, preliminary treatment may be required to
remove solids or bacteria which tend to cause fouling in the
condenser or evaporator. The buildup of scale on the evaporator
surfaces reduces the heat transfer efficiency and may present a
maintenance problem or increase operating cost. It has been
demonstrated that fouling of the heat transfer surfaces can be
avoided or minimized for certain dissolved solids by maintaining
a seed slurry which provides preferential sites for precipitate
deposition. In addition, low temperature differences in the
evaporator will eliminate nucleate boiling and supersaturation
effects. Steam distillable impurities in the process stream are
carried over with the product water and must be handled by
preliminary or post treatment.
Operational Factors. Reliability: Proper maintenance will
ensure a high degree of reliability for the system. Without such
attention, rapid fouling or deterioration of vacuum seals may
occur, especially when handling corrosive liquids.
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Maintainability: Operating parameters can be automatically
controlled. Preliminary treatment may be required, as well as
periodic cleaning of the system. Regular replacement of seals,
especially in a corrosive environment, may be necessary.
Solid Waste Aspects: With only a few exceptions, the process
does not generate appreciable quantities of solid waste.
Demonstration Status. Evaporation is a fully developed, com-
mercially available wastewater treatment system. It is used
extensively to recover plating chemicals in the electroplating
industry and a pilot scale unit has been used in connection with
phosphating of aluminum. Proven performance in silver recovery
indicates that evaporation could be a useful treatment operation
for the photographic industry, as well as for metal finishing.
Gravity Sludge Thickening
In the gravity thickening process, dilute sludge is fed from a
primary settling tank or clarifier to a thickening tank where
rakes stir the sludge gently to density it and to push it to a
central collection well. The supernatant is returned to the
primary settling tank. The thickened sludge that collects on the
bottom of the tank is pumped to dewatering equipment or hauled
away. Figure VII-26 shows the construction of a gravity
thickener.
Application and Performance. Thickeners are generally used in
facilities where the sludge is to be further dewatered by a com-
pact mechanical device such as a vacuum filter or centrifuge.
Doubling the solids content in the thickener substantially
reduces capital and operating cost of the subsequent dewatering
device and also reduces cost for hauling. The process is
potentially applicable to almost any industrial plant.
Organic sludges from sedimentation units of 1 to 2 percent solids
concentration can usually be gravity thickened to 6 to 10 per-
cent; chemical sludges can be thickened to 4 to 6 percent.
Advantages and Limitations. The principal advantage of a gravity
sludge thickening process is that it facilitates further sludge
dewatering. Other advantages are high reliability and minimum
maintenance requirements.
Limitations of the sludge thickening process are its sensitivity
to the flow rate through the thickener and the sludge removal
rate. These rates must be low enough not to disturb the
thickened sludge.
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Operational Factors. Reliability: Reliability is high with
proper design and operation. A gravity thickener is designed on
the basis of square feet per pound of solids per day, in which
the required surface area is related to the solids entering and
leaving the unit. Thickener area requirements are also expressed
in terms of mass loading, kilograms of solids per square meter
per day (Ibs/sq ft/day).
Maintainability: Twice a year, a thickener must be shut down for
lubrication of the drive mechanisms. Occasionally, water must be
pumped back through the system in order to clear sludge pipes.
Solid Waste Aspects: Thickened sludge from a gravity thickening
process will usually require further dewatering prior to dispo-
sal, incineration, or drying. The clear effluent may be recircu-
lated in part, or it may be subjected to further treatment prior
to discharge.
Demonstration Status. Gravity sludge thickeners are used
throughout industry to reduce sludge water content to a level
where the sludge may be efficiently handled. Further dewatering
is usually practiced to minimize costs of hauling the sludge to
approved landfill areas.
Ion Exchange
Ion exchange is a process in which ions, held by electrostatic
forces to charged functional groups on the surface of the ion
exchange resin, are exchanged for ions of similar charge from the
solution in which the resin is immersed. This is classified as a
sorption process because the exchange occurs on the surface ot
the resin, and the exchanging ion must undergo a phase transfer
from solution phase to solid phase. Thus, ionic contaminants in
a waste stream can be exchanged for the harmless ions of the
resin.
Although the precise technique may vary slightly according to the
application involved, a generalized process description follows.
The wastewater stream being treated passes through a filter to
remove any solids, then flows through a cation exchanger which
contains the ion exchange resin. Here, metallic impurities such
as copper, iron, and trivalent chromium are retained. The stream
then passes through the anion exchanger and its assocaited resin.
Hexavalent chromium (in the form of chromate or dichromate) for
example, is retained in this stage. If one pass does not reduce
the contaminant levels sufficiencly,the stream may then enter
another series of exchangers. Many ion exchange systems are
equipped with more than one set of exchangers for this reason.
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The other major portion of the ion exchange process concerns the
regeneration of the resin, which now holds those impurities
retained from the waste stream. An ion exchange unit with
in-place regeneration is shown in Figure VII-27. Metal ions such
as nickel are removed by an acid, cation exchange resin, which is
regenerated with hydrochloric or sulfuric acid, replacing the
metal ion with one or more hydrogen ions. Anions such as dichro-
mate are removed by a basic anion exchange resin, which is regen-
erated with sodium hydroxide, replacing the anion with one or
more hydroxyl ions. The three principal methods employed by
industry for regenerating the spent resin are:
(A) Replacement Service: A regeneration service replaces
the spent resin with regenerated resin, and regenerates
the spent resin at its own facility. The service then
has the problem of treating and disposing of the spent
regenerant .
(B) In-Place Regeneration: Some establishments may find it
less expensive to do their own regeneration. The spent
resin column is shut down for perhaps an hour, and the
spent resin is regenerated. This results in one or
more waste streams which must be treated in an appro-
priate manner. Regeneration is performed as the resins
require it, usually every few months.
(C) Cyclic Regeneration: In this process, the regeneration
of the spent resins takes place within the ion exchange
unit itself in alternating cycles with the ion removal
process. A regeneration frequency of twice an hour is
typical. This very short cycle time permits operation
with a very small quantity of resin and with fairly
concentrated solutions, resulting in a very compact
system. Again, this process varies according to appli-
cation but the regeneration cycle generally begins
with caustic being pumped through the anion exchanger,
carrying out hexavalent chromium, for example, as
sodium dichromate. The sodium dichromate stream then
oasses through a cation exchanger, converting the
?odKm Bichromate to chromic acid. After concentration
by evaporation or other means, the chromic acid can be
returned to the process line. Meanwhile, the cation
is regenerated with sulfuric acid resulting
™
erld The ion exchangers, with newly regenerated
resin, then enter the ion removal cycle again.
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Application and Performance. The list of pollutants for which
the ion exchange system has proven effective includes aluminum,
arsenic, cadmium, chromium (hexavalent and trivalent), copper,
cyanide, gold, iron, lead, manganese, nickel, selenium, silver,
tin, zinc, and others. Thus, it can be applied to a wide variety
of industrial concerns. Because of the heavy concentrations of
metals in their wastewater, the metal finishing industries util-
ize ion exchange in several ways. As an end-of-pipe treatment,
ion exchange is certainly feasible, but its greatest value is in
recovery applications. It is commonly used as an integrated
treatment to recover rinse water and process chemicals. Some
electroplating facilities use ion exchange to concentrate and
purify plating baths. Also, many industrial concerns use ion
exchange to reduce salt concentrations in incoming water sources.
Ion exchange is highly efficient at recovering metal-bearing
solutions. Recovery of chromium, nickel, phosphate solution, and
sulfuric acid from anodizing is common. A chromic acid recovery
efficiency of 99.5 percent has been demonstrated. Typical data
for purification of rinse water are displayed in Table VII-23.
Advantages and Limitations. Ion exchange is a versatile technol-
ogy applicable to a great many situations. This flexibility,
along with its compact nature and performance, makes ion exchange
a very effective method of wastewater treatment. However, the
resins in these systems can prove to be a limiting factor. The
thermal limits of the anion resins, generally in the vicinity of
60°C, could prevent its use in certain situations. Similarly,
nitric acid, chromic acid, and hydrogen peroxide can all damage
the resins, as will iron, manganese, and copper when present with
sufficient concentrations of dissolved oxygen. Removal of a par-
ticular trace contaminant may be uneconomical because of the
presence of other ionic species that are preferentially removed.
The regeneration of the resins presents its own problems. The
cost of the regenerative chemicals can be high. In addition, the
waste streams originating from the regeneration process are
extremely high in pollutant concentrations, although low in
volume. These must be further processed for proper disposal.
Operational Factors. Reliability: With the exception of occa-
sional clogging or fouling of the resins, ion exchange has proved
to be a highly dependable technology.
Maintainability: Only the normal maintenance of pumps, valves,
piping, and other hardware used in the regeneration process is
required.
Solid Waste Aspects: Few, if any, solids accumulate within the
ion exchangers, and those which do appear are removed by the
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regeneration process. Proper prior treatment and planning can
eliminate solid buildup problems altogether. The brine resulting
from regeneration of the ion exchange resin most usually must be
treated to remove metals before discharge. This can generate
solid waste.
Demonstration Status. All of the ion exchange applications
discussed in this section are in commercial use, and industry
sources estimate the number of ion exchange units currently in
the field at well over 120. The research and development in ion
exchange is focusing on improving the quality and efficiency of
the resins, rather than new applications. Work is also being
done on a continuous regeneration process whereby the resins are
contained on a fluid- transfusible belt. The belt passes through
a compartmented tank with ion exchange, washing, and regeneration
sections. The resins are therefore continually used and regener-
ated. No such system, however, has been reported beyond the
pilot stage.
Insoluble Starch Xanthate
Insoluble starch xanthate is essentially an ion exchange medium
used to remove dissolved heavy metals from wastewater. The water
may then either be reused (recovery application) or discharged
(end-of-pipe application). In a commercial electroplating
operation, starch xanthate is coated on a filter medium. Rinse
water containing dragged out heavy metals is circulated through
the filters and then reused for rinsing. The starch-heavy metal
complex is disposed of and replaced periodically. Laboratory
tests indicate that recovery of metals from the complex is
feasible, with regeneration of the starch xanthate. Besides
electroplating, starch xanthate is potentially applicable to^
nonferrous metals manufacturing, aluminum forming, coil_coating
porcelain enameling, copper fabrication, and any other industrial
plants where dilute metal wastewater streams are generated. Its
present use is limited to one electroplating plant.
Peat Adsorption
Peat moss is a complex natural organic material containing lignin
and cellulose as major constituents. These constituents partic-
ularly lignin, bear polar functional groups, such as alcohols,
aldehydes? ketones, acids, phenolic hydroxides and ethers, that
can be involved in chemical bonding. Because of the polar nature
of the material, its adsorption of dissolved solids such as
transition metals and polar organic molecules is quite high.
These properties have led to the use of peat as an agent for the
purification of industrial wastewater.
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Peat adsorption is a "polishing" process which can achieve very
low effluent concentrations for several pollutants. If the con-
centrations of pollutants are above 10 mg/1, then peat adsorption
must be preceded by pH adjustment for metals precipitation and
subsequent clarification. Pretreatment is also required for
chromium wastes using ferric chloride and sodium sulfide. The
wastewater is then pumped into a large metal chamber called a
kier which contains a layer of peat through which the waste
stream passes. The water flows to a second kier for further
adsorption. The wastewater is then ready for discharge. This
system may be automated or manually operated.
Application and Performance. Peat adsorption can be used in
aluminum forming plants for removal of residual dissolved metals
from clarifier effluent. Peat moss may be used to treat waste-
waters containing heavy metals such as mercury, cadmium, zinc,
copper, iron, nickel, chromium, and lead, as well as organic
matter such as oil, detergents, and dyes. Peat adsorption is
currently used commercially at a textile plant, a newsprint
facility, and a metal reclamation operation.
Table VII-24 contains performance figures obtained from pilot
plant studies. Peat adsorption was preceded by pH adjustment for
precipitation and by clarification.
In addition, pilot plant studies have shown that chelated metal
wastes, as well as the chelating agents themselves, are removed
by contact with peat moss.
Advantages and Limitations. The major advantages of the system
include its ability to yield low pollutant concentrations, its
broad scope in terms of the pollutants eliminated, and its capac-
ity to accept wide variations of wastewater composition.
Limitations include the cost of purchasing, storing, and dispos-
ing of the peat moss; the necessity for regular replacement of
the peat may lead to high operation and maintenance costs. Also,
the pH adjustment must be altered according to the composition of
the waste stream.
Operational Factors. Reliability: The question of long-term
reliability is not yet fully answered. Although the manufacturer
reports it to be a highly reliable system, operating experience
is needed to verify the claim.
Maintainability: The peat moss used in this process soon
exhausts its capacity to adsorb pollutants. At that time, the
kiers must be opened, the peat removed, and fresh peat placed
inside. Although this procedure is easily and quickly accom-
plished, it must be done at regular intervals, or the system s
efficiency drops drastically.
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Solid Waste Aspects: After removal from the kier, the spent peat
must be eliminated. If incineration is used, precautions should
be taken to ensure that those pollutants removed from the water
are not released again in the combustion process. Presence of
sulfides in the spent peat, for example, will give rise to sulfur
dioxide in the fumes from burning. The presence of significant
quantities of toxic heavy metals in nonferrous metals manufactur-
ing wastewater will in general preclude incineration of peat used
in treating these wastes.
Demonstration Status. Only three facilities currently use
commercial adsorption systems in the United States - a textile
manufacturer, a newsprint facility, and a metal reclamation firm.
No data have been reported showing the use of peat adsorption in
nonferrous metals manufacturing plants.
Membrane Filtration
Membrane filtration is a treatment system for removing precipi-
tated metals from a wastewater stream. It must therefore be
preceded by those treatment techniques which will properly pre-
pare the wastewater for solids removal. Typically, a membrane
filtration unit is preceded by pH adjustment or sulfide addition
for precipitation of the metals. These steps are followed by the
addition of a proprietary chemical reagent which causes the pre-
cipitate to be non-gelatinous, easily dewatered, and highly
stable. The resulting mixture of pretreated wastewater and
reagent is continuously recirculated through a filter module and
back into a recirculation tank. The filter module contains tubu-
lar membranes. While the reagent-metal hydroxide precipitate
mixture flows through the inside of the tubes, the water and any
dissolved salts permeate the membrane. When the recirculating
slurry reaches a concentration of 10 to 15 percent solids, it is
pumped out of the system as sludge.
Application and Performance. Membrane filtration appears to be
applicable to any wastewater or process water containing metal
ions which can be precipitated using hydroxide, sulfide, or car-
bonate precipitation. It could function as the primary treatment
system, but also might find application as a polishing treatment
(after precipitation and settling) to ensure continued compliance
with metals limitations. Membrane filtration systems are being
used in a number of industrial applications, particularly in the
metal finishing area. They have also been used for heavy metals
removal in the metal fabrication industry and the paper industry.
The oermeate is claimed by one manufacturer to contain less than
thl elnuen? concentrations shown in Table VII-25, regardless of
the influent concentrations. These claims have been largely sub-
stantiated by the analysis of water samples at various plants in
various industries.
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In the performance predictions for this technology, pollutant
concentrations are reduced to the levels shown in Table VII-25
unless lower levels are present in the influent stream.
Advantages and Limitations. A major advantage of the membrane
filtration system is that installations can use most of the
conventional end-of-pipe systems that may already be in place.
Removal efficiencies are claimed to be excellent, even with^sud-
den variation of pollutant input rates; however, the effective-
ness of the membrane filtration system can be limited by clogging
of the filters. Because pH changes in the waste stream greatly
intensify clogging problems, the pH must be carefully monitored
and controlled. Clogging can force the shutdown of the system
and may interfere with production. In addition, relatively high
capital cost of this system may limit its use.
Operational Factors. Reliability: Membrane filtration has been
shown to be a very reliable system, provided that the pH is
strictly controlled. Improper pH can result in the clogging of
the membrane. Also, surges in the flow rate of the waste stream
must be controlled in order to prevent solids from passing
through the filter and into the effluent.
Maintainability: The membrane filters must be regularly moni-
tored and cleaned or replaced as necessary. Depending on the
composition of the waste stream and its flow rate, frequent
cleaning of the filters may be required. Flushing with hydro-
chloric acid for six to 24 hours will usually suffice. In
addition, the routine maintenance of pumps, valves, and other
plumbing is required.
Solid Waste Aspects: When the recirculating reagent-precipitate
slurry reaches 10 to 15 percent solids, it is pumped out of the
system. It can then be disposed of directly to a landfill or it
can undergo a dewatering process. Because this sludge contains
toxic metals, it requires proper disposal.
Demonstration Status. There are more than 25 membrane filtration
systems presently in use on metal finishing and similar waste-
waters. Bench scale and pilot studies are being run in an
attempt to expand the list of pollutants for which this system is
known to be effective. There are no data on the use of membrane
filtration in nonferrous metals manufacturing plants.
Reverse Osmosis
The process of osmosis involves the passage of a liquid through a
semipermeable membrane from a dilute to a more concentrated solu-
tion. Reverse osmosis (RO) is an operation in which pressure is
applied to the more concentrated solution, forcing the permeate
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to diffuse through the membrane and into the more dilute solu-
tion. This filtering action produces a concentrate and a perme-
ate on opposite sides of the membrane. The concentrate can then
be further treated or returned to the original production opera-
tion for continued use, while the permeate water can be recycled
for use as clean water. Figure VII-28 depicts a reverse osmosis
system.
As illustrated in Figure VII-29, there are three basic configura-
tions used in commercially available RO modules: tubular,
spiral-wound, and hollow fiber. All of these operate on the
principle described above, the major difference being their
mechanical and structural design characteristics.
The tubular membrane module uses a porous tube with a cellulose
acetate membrane- lining. A common tubular module consists ^of a
length of 2.5 cm (1 inch) diameter tube wound on a supporting
spool and encased in a plastic shroud. Feed water is driven into
the tube under pressures varying from 40 to 55 atm (600 to 800
psi). The permeate passes through the walls of the tube and is
collected in a manifold while the concentrate is drained off at
the end of the tube. A less widely used tubular RO module uses a
straight tube contained in a housing, under the same operating
conditions.
Spiral-wound membranes consist of a porous backing sandwiched
between two cellulose acetate membrane sheets and bonded along
three edges. The fourth edge of the composite sheet is attached
to a large permeate collector tube. A spacer screen is then
placed on top of the membrane sandwich and the entire stack is
rolled around the centrally located tubular permeate collector.
The rolled up package is inserted into a pipe able to withstand
the high operating pressures employed in this process, up to 55
atm (800 psi) with the spiral-wound module. When the system is
operating, the pressurized product water permeates the membrane
and flow! through the backing material to the central collector
tube. The concentrate is drained off at the end of the container
pipe and can be reprocessed or sent to further treatment facili-
ties.
The hollow fiber membrane configuration is made up of a bundle of
polyamide fibers of approximately 0.0075 cm (0;^ fiS4r module
con aiS &SS a^'t^S^^t
1 su^ ?ed by
module througt a por™s "istriuto/tube. Permeate flows through
rte memSaneto the hollow Interiors of the fibers and. is col-
lected at the ends of the fibers.
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The hollow fiber and spiral-wound modules have a distinct advan-
tage over the tubular system in that they are able to load a very
large membrane surface area into a relatively small volume. How-
ever, these two membrane types are much more susceptible to foul-
ing than the tubular system, which has a larger flow channel.
This characteristic also makes the tubular membrane much easier
to clean and regenerate than either the spiral-wound or hollow
fiber modules. One manufacturer claims that their helical
tubular module can be physically wiped clean by passing a soft
porous polyurethane plug under pressure through the module.
Application and Performance. The largest application has been
for the recovery of nickel solutions. It has been shown that RO
can generally be applied to most acid metal baths with a high
degree of performance, providing that the membrane unit is not
overtaxed. The limitations most critical here are the allowable
pH range and maximum operating pressure for each particular
configuration.
Adequate prefiltration is also essential. Only three membrane
types are readily available in commercial RO units, and their
overwhelming use has been for the recovery of various acid metal
baths. For the purpose of calculating performance predictions of
this technology, a rejection ratio of 98 percent is assumed for
dissolved salts, with 95 percent permeate recovery.
Advantages and Limitations. The major advantage of reverse osmo-
sis for handling process effluents is its ability to concentrate
dilute solutions for recovery of salts and chemicals with low
power requirements. No latent heat of vaporization or fusion is
required for effecting separations; the main energy requirement
is for a high pressure pump. It requires relatively little floor
space for compact, high capacity units, and it exhibits good
recovery and rejection rates for a number of typical process
solutions.
A limitation of the reverse osmosis process for treatment of pro-
cess effluents is its limited temperature range for satisfactory
operation. For cellulose acetate systems, the preferred limits
are 18°C to 30°C (65°F to 85°F); higher temperatures will
increase the rate of membrane hydrolysis and reduce system life,
while lower temperatures will result in decreased fluxes with no
damage to the membrane.
Another limitation is inability to handle certain solutions.
Strong oxidizing agents, strongly acidic or basic solutions,
solvents, and other organic compounds can cause dissolution ot
the membrane. Poor rejection of some compounds such as borates
and low molecular weight organics is another problem. Fouling ot
membranes by slightly soluble components in solution or colloids
has caused failures, and fouling of membranes by feed waters with
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high levels of suspended solids can be a problem. A final limi-
tation is inability to treat or achieve high concentration ^ with
some solutions. Some concentrated solutions may have initial
osmotic pressures which are so high that they either exceed
available operating pressures or are uneconomical to treat.
Operational Factors. Reliability: Acceptable reliability can be
achieved so long as the proper precautions are taken to minimize
the chances of fouling or degrading the membrane. Sufficient
testing of the waste stream is the best method of ensuring a
successful application.
Maintainability: Membrane life is estimated to range from six
months to three years, depending on the use of the system. Down
time for flushing or cleaning is on the order of two hours as
often as once each week; a substantial portion of maintenance
time must be spent on cleaning any prefilters installed ahead of
the reverse osmosis unit.
Solid Waste Aspects: In a closed loop system utilizing RO there
is a constant recycle of permeate and a minimal amount of solid
waste. Prefiltration eliminates many solids before they reach
the module and helps keep the buildup to a minimum. These solids
require proper disposal.
Demonstration Status. There are presently at least one hundred
reverse osmosis wastewater applications in a variety of indus-
tries. In addition to these, there are 30 to 40 units being used
to provide pure process water for several industries. Despite
the many types and configurations of membranes, only the spiral-
wound cellulose acetate membrane has had widespread success in
commercial applications.
One secondary lead plant installed reverse osmosis following a
Ume precipitation and sedimentation system for treating waste
b™e?J electrolyte prior to discharge. However the reverse
osmosis membranes became fouled and never operated satisfactor-
ily L addition, plant personnel could not achieve design
throughpuffor the reverse osmosis system. The technology was
never made fully operational by the plant.
app™ca™ons in the category to achieve virtually complete
recycle.
Sludge Bed Drying
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landfill. These beds usually consist of 15 to 45 cm (6 to 18
in.) of sand over a 30 cm (12 in.) deep gravel drain system made
up of 3 to 6 mm (1/8 to 1/4 in.) graded gravel overlying drain
tiles. Figure VII-30 shows the construction of a drying bed.
Drying beds are usually divided into sectional areas approxi-
mately 7.5 meters (25 ft) wide x 30 to 60 meters (100 to 200 ft)
long. The partitions may be earth embankments, but more often
are made of planks and supporting grooved posts.
To apply liquid sludge to the sand bed, a closed conduit or a
pressure pipeline with valved outlets at each sand bed section is
often employed. Another method of application is by means of an
open channel with appropriately placed side openings which are
controlled by slide gates. With either type of delivery system,
a concrete splash slab should be provided to receive the falling
sludge and prevent erosion of the sand surface.
Where it is necessary to dewater sludge continuously throughout
the year regardless of the weather, sludge beds may be covered
with a fiberglass reinforced plastic or other roof. Covered
drying beds permit a greater volume of sludge drying per year in
most climates because of the protection afforded from rain or
snow and because of more efficient control of temperature.
Depending on the climate, a combination of open and enclosed beds
will provide maximum utilization of the sludge bed drying facili-
ties.
Application and Performance. Sludge drying beds are a means of
dewatering sludge from clarifiers and thickeners. They are
widely used both in municipal and industrial treatment facili-
ties.
Dewatering of sludge on sand beds occurs by two mechanisms: fil-
tration of water through the bed and evaporation of water as a
result of radiation and convection. Filtration is generally com-
plete in one to two days and may result in solids concentrations
as high as 15 to 20 percent. The rate of filtration depends on
the drainability of the sludge.
The rate of air drying of sludge is related to temperature, rela-
tive humidity, and air velocity. Evaporation will proceed at a
constant rate to a critical moisture content, then at a falling
rate to an equilibrium moisture content. The average evaporation
rate for a sludge is about 75 percent of that from a free water
surface.
Advantages and Limitations. The main advantage of sludge drying
beds over other types ot sludge dewatering is the relatively low
cost of construction, operation, and maintenance.
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Its disadvantages are the large area of land required and long
drying times that depend, to a great extent on climate and
weather.
Operational Factors. Reliability: Reliability is high with
favorable climatic conditions, proper bed design, and care to
avoid excessive or unequal sludge application. If climatic con-
ditions in a given area are not favorable for adequate drying, a
cover may be necessary.
Maintainability: Maintenance consists basically of periodic
removal of the dried sludge. Sand removed from the drying bed
with the sludge must be replaced and the sand layer resurfaced.
The resurfacing of sludge beds is the major expense item in
sludge bed maintenance, but there are other areas which may
require attention. Underdrains occasionally become clogged and
have to be cleaned. Valves or sludge gates that control the flow
of sludge to the beds must be kept watertight. Provision for
drainage of lines in winter should be provided to prevent damage
from freezing. The partitions between beds should be tight so
that sludge will not flow from one compartment to another. ^ The
outer walls or banks around the beds should also be watertight.
Solid Waste Aspects: The full sludge drying bed must either be
abandoned or the collected solids must be removed to a landfill.
These solids contain whatever metals or other materials were
settled in the clarifier. Metals will be present as hydroxides,
oxides, sulfides, or other salts. They have the potential for
leaching and contaminating ground water, whatever the location of
the semidried solids. Thus the abandoned bed or landfill^should
include provision for runoff control and leachate monitoring.
Demonstration Status. Sludge beds have been in common use in
both municipal and industrial facilities for many years. How-
ever, protection of ground water from contamination is not always
adequate.
Vacuum Filtration
In wastewater treatment plants, sludge dewatering by vacuum fil-
tration generally uses cylindrical drum filters. These drums
have a filter medium which may be cloth made of natural or syn-
thetic fibers or a wire-mesh fabric. The drum is suspended above
and dips into a vat of sludge. As the drum rotates slowly, part
of its circumference is subject to an internal vacuum that draws
sludee to the filter medium. Water is drawn through the porous
fiu£ cake thorugh the drum fabric to a discharge port and the
dewatered sludge, loosened by compressed air, is scraped from the
fiUer mesh. Because the dewatering of sludge on vacuum filters
is relatively expensive per kilogram of water removed^ the liquid
sludge is frequently thickened prior to processing. A vacuum
filter is shown in Figure VII-31.
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Application and Performance. Vacuum filters are frequently used
both tn municipal treatment plants and in a wide variety^of
industries. They are most commonly used in larger facilities,
which may have a thickener to double the solids content of clari-
fier sludge before vacuum filtering. Often a precoat is used to
inhibit filter blinding.
The function of vacuum filtration is to reduce the water content
of sludge, so that the solids content increases from about 5
percent to between 20 and 30 percent, depending on the waste
characteristics.
Advantages and Limitations. Although the initial cost and area
requirement o£ the vacuum filtration system are higher than those
of a centrifuge, the operating cost is lower, and no special pro-
visions for sound and vibration protection need be made. The
dewatered sludge from this process is in the form of a moist cake
and can be conveniently handled.
Operational Factors. Reliability: Vacuum filter systems have
proven reliable at many industrial and municipal treatment facil-
ities. At present, the largest municipal installation is at the
West Southwest wastewater treatment plant of Chicago, Illinois,
where 96 large filters were installed in 1925, functioned approx-
imately 25 years, and then were replaced with larger units.
Original vacuum filters at Minneapolis-St. Paul, Minnesota now
have over 28 years of continuous service, and Chicago has some
units with similar or greater service life.
Maintainability: Maintenance consists of the cleaning or
replacement of the filter media, drainage grids, drainage piping,
filter pans, and other parts of the equipment. Experience in a
number of vacuum filter plants indicates that maintenance
consumes approximately 5 to 15 percent of the total time. If
carbonate buildup or other problems are unusually severe, mainte-
nance time may be as high as 20 percent. For this reason, it is
desirable to maintain one or more spare units.
If intermittent operation is used, the filter equipment should be
drained and washed each time it is taken out of service. An
allowance for this wash time must be made in filtering schedules.
Solid Waste Aspects: Vacuum filters generate a solid cake which
is usually trucked directly to landfill. All of the metals
extracted from the plant wastewater are concentrated in the
filter cake as hydroxides, oxides, sulfides, or other salts.
Demonstration Status. Vacuum filtration has been widely used for
many years.It is a fully proven, conventional technology for
sludge dewatering.
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IN-PLANT TECHNOLOGY
The intent of in-plant technology for the nonferrous metals manu-
facturing point source category is to reduce or eliminate the
waste load requiring end-of-pipe treatment and thereby improve
the efficiency of an existing wastewater treatment system or
reduce the requirements of a new treatment system. In-plant
technology involves water conservation, automatic controls, good
housekeeping practices, process modifications, and waste treat-
ment.
Process Water Recycle
EPA is proposing BAT for most subcategories based on 90 percent
recycle of wet air pollution control and contact cooling waste-
water. The Agency has proposed a higher rate for certain waste
streams where reported rates of recycle are even higher. Water
is used in wet air pollution control systems to capture particu-
late matter or fumes evolved during manufacturing. Cooling water
is used to remove excess heat from cast metal products.
Recycle is part of the technical basis for many of the promul-
gated regulations in the nonferrous metals manufacturing cate-
gory. The Agency identified both demonstrated and feasible
recycle opportunities as early as 1973 in proposed effluent
limitations for secondary aluminum.
Recycling of process water is the practice of recirculating water
to be used again for the same purpose. An example of recycling
process water is the return of casting contact cooling water to
the casting process after the water passes through a cooling
tower. Two types of recycle are possible—recycle with a bleed
stream (blowdown) and total recycle. Total recycle may be pro-
hibited by the presence of dissolved solids. Dissolved solids
(e.g., sulfates and chlorides) entering a totally recycled waste
strlam may precipitate, forming scale if the solubility limits of
the dissolved solids are exceeded. A bleed stream may be neces-
sary to prevent maintenance problems (pipe plugging or scaling,
etc.) that would be created by the precipitation of dissolved
solids. While the volume of bleed required is a function of the
amount of dissolved solids in the waste stream 10 P^cent bleed
is a common value for a variety of process waste streams in the
nonferrous metals manufacturing category. The recycle of process
water is currently practiced where it is cost effective, where it
is necessary due to water shortage, or where the local permitting
authority Ss required it. Recycle, as compared to the once-
through use of process water, is an effective method of
conserving water.
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Application and Performance. Required hardware necessary for
recycle is highly site-specific. Basic items include pumps and
piping. Additional materials are necessary if water treatment
occurs before the water is recycled. These items will be dis-
cussed separately with each unit process. Chemicals may be
necessary to control scale buildup, slime, and corrosion prob-
lems, especially with recycled cooling water.
The Agency based its zero discharge of pollutants regulation for
PSES in the secondary copper subcategory on the use of cooling
towers in conjunction with lime precipitation and sedimentation.
The lime precipitation and sedimentation technology was included
to reduce the metals concentrations so that the wastewater could
be completely recycled and reused without corrosion and scaling
problems. Maintenance and energy use are limited to that
required by the pumps, and solid waste generation is dependent o
the type of treatment system in place.
Recycling through cooling towers is the most common practice.
One type of application is shown in Figure VII-32. Casting
contact cooling water is recycled through a cooling tower with a
blowdown discharge.
A cooling tower is a device which cools water by bringing the
water into contact with air. The water and air flows are
directed in such a way as to provide maximum heat transfer. The
heat is transferred to air primarily by evaporation (about 75
percent), while the remainder is removed by sensible heat trans-
fer.
Factors influencing the rate of heat transfer and, ultimately,
the temperature range of the tower, include water surface area,
tower packing and configuration, air flow, and packing height.
large water surface area promotes evaporation, and sensible heat
transfer rates are lower in proportion to the water surface area
provided. Packing (an internal latticework contact area) is
often used to produce small droplets of water which evaporate
more easily, thus increasing the total surface area per unit of
throughput. For a given water flow, increasing the air flow
increases the amount of heat removed by maintaining higher
thermodynamic potentials. The packing height in the tower shoul*
be high enough so that the air leaving the tower is close to
saturation.
A mechanical-draft cooling tower consists of the following major
components:
(1) Inlet-water distributor
(2) Packing
(3) Air fans
(4) Inlet-air louvers
(5) Drift or carryover eliminators
(6) Cooled water storage basin.
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Advantages and Limitations. Recycle offers economic as well as
environmental advantages.Water consumption is reduced and
wastewater handling facilities (pumps, pipes, clarifiers, etc.)
can thus be sized for smaller flows. By concentrating the pollu-
tants in a much smaller volume (the bleed stream), greater
removal efficiencies can be attained by any applied treatment
technologies. Recycle may require some treatment such as
sedimentation or cooling of water before it is reused.
The ultimate benefit of recycling process water is the reduction
in total wastewater discharge and the associated advantages of
lower flow streams. A potential problem is the buildup of dis-
solved solids which could result in scaling. Scaling can usually
be controlled by depressing the pH and increasing the bleed flow.
Operational Factors. Reliability and Maintainability: Although
the principal construction material in mechanical-draft towers is
wood, other materials are used extensively. For long life and
minimum maintenance, wood is generally pressure-treated with a
preservative. Although the tower structure is usually made of
treated redwood, a reasonable amount of treated fir has been used
in recent years. Sheathing and louvers are generally made of
asbestos cement, and the fan stacks of fiberglass. There is a
trend to use fire-resistant extracted PVC as fill which, at
little or no increase in cost, offers the advantage of permanent
fire-resistant properties.
The major disadvantages of wood are its susceptibility to decay
and fire. Steel construction is occasionally used, but not to
any great extent. Concrete may be used but has relatively high
construction labor costs, although it does offer the advantage of
fire protection.
Various chemical additives are used in cooling water systems to
control scale, slime, and corrosion. The chemical additives
needed depend on the character of the make-up water. All addi-
tives have definite limitations and cannot eliminate the need for
blowdown. Care should be taken in selecting nontoxic or readily
degraded additives, if possible.
Solid Waste Aspects: The only solid waste associated with cool-
ing towers may be removed scale.
Demonstration Status. Predominantly two types of waste streams
in the nonferrous metals manufacturing category are currently
being recycled; casting contact cooling water and air pollution
control scrubber liquor. Two variations of recycle are used:
(1) a wastewater is recycled within a given process, and (2) a
wastewa^er is combined with others, treated, and the combined
wastewater is Recycled to the processes from which it originated.
283
-------
For example, scrubber liquor may be recycled within the scrubber,
or treated by sedimentation and recycled back to the scrubber.
As a second example, plants in the primary aluminum subcategory
combine wastewater from potline scrubbers and from cathode
reprocessing for cryolite recovery, and recycle the treated
wastewater back to the scrubbers.
Total recycle may become more wide-spread in the future if
methods for removal of dissolved solids, such as reverse osmosis
and ion exchange, become more common and less expensive.
The Agency observed extensive recycle of contact cooling water
and scrubber liquor throughout the category. Indeed, some plants
reported 100 percent recycle of process wastewater from these
operations. The Agency believes, however, that most plants may
have to discharge a portion of the recirculating flow to prevent
the excessive buildup of dissolved solids unless dragout of
solids in products or slags is sufficient to prevent this
buildup.
Existing practice supports the selection of a 90 percent recycle
rate. Twenty-nine of 61 aluminum smelting and forming plants
practice greater than 90 percent recycle of the direct chill
casting contact cooling water. Two of the five aluminum smelters
practicing continuous rod casting recycle 90 percent or more of
their contact cooling water. Four of eight primary aluminum
plants using wet air pollution control on anode bake ovens, five
of 11 plants using wet scrubbers on potlines, and three of eight
plants using wet scrubbers for potrooms recycle 90 percent or
more of their scrubber water.
Five of 10 primary electrolytic copper plants currently recycle
90 percent or more of their casting contact cooling water. Two
of three primary zinc plants with leaching scrubbers recycle 90
percent or more. Two of five primary tungsten plants with
scrubbers on reduction furnaces practice 90 percent or greater
recycle. Six of seven secondary silver plants with furnace
scrubbers currently recycle 90 percent or more of the scrubber
water.
Process Water Reuse
Reuse of process water is the practice of recirculating water
used in one production process for subsequent use in a different
production proqess.
Application and Performance. Reuse of wastewater in a different
proces can include using a relatively clean wastewater for
another application, or using a relatively dirty water for an
application where water quality is of no concern.
284
-------
Advantages and Limitations. Advantages of reuse are similar to
the advantages of recycle. Water consumption is reduced and
wastewater treatment facilities can be sized for smaller flows.
Also, in areas where water shortages occur, reuse is an effective
means of conserving water.
Operational Factors. The hardware necessary for reuse of process
wastewaters varies, depending on the specific application. The
basic elements include pumps and piping. Chemical addition is
not usually warranted, unless treatment is required prior to
reuse. Maintenance and energy use are limited to that required
by the pumps. Solid waste generated is dependent upon the type^
of treatment used and will be discussed separately with each unit
process.
Demonstration Status. Reuse applications in the non ferrous
metals manfuacturing category are varied. For example, a primary
aluminum plant reuses wastewater from casting for air scrubbing.
A lead smelter uses wastewater from air scrubbing for slag granu-
lation, where all the water is evaporated. A primary copper
refinery reuses precipitated spent electrolyte, known as black
acid," in leaching operations that are part of an ore beneficia-
tion plant.
Process Water Use Reduction
Process water use reduction is the decrease in the amount of pro-
cess water used as an influent to a production process per unit
of production. Section V of each of the subcategory supplements
discusses water use in detail for each nonferrous metals
manufacturing operation. A range of water use values taken from
the data collection portfolios is presented for each operation.
The range of values indicates that some plants use process water
more efficiently than others for the same operation.
Application and Performance. Noncontact cooling water can
replace contact cooling water in some applications. The use of
SSScSSac? heat exchanfers eliminates concentration of J« solved
solids by evaporation and minimizes scaling problems. A copper
refinery is currently using this method to achieve zero dis- .
charge However, industry-wide conversion to noncontact cooling
may not be ossible because of a need for extensive retrofitting
t
shol ^roauct Shot generally cannot be produced Without contact
cooling water.
285
-------
Air Cooling of Cast Metal Products
Application and Performance. Air cooling, for some operations,
is an alternative to contact cooling water but limited potential
except in low tonnage situations. For example, air cooling is
not generally used in the production of high tonnage casting for
several reasons. The casting line can be inordinately long (or
large), a result of an increased number of molds to compensate
for the slower cooling of the metal.
Operational Factors. Maintenance costs are generally higher
because of the longer conveyor, the added heat load on equipment
and lubricants, and the need for added air blowers. Air cooling
without these process appurtenances might greatly reduce finished
metal production from rates now possible with water cooling.
Conversion to dry air pollution control equipment, discussed
further on in this section, is another way to eliminate water
use
Dry Slag Processing and Granulation
Slag from pyrometallurgical processes is a solid waste that must
be disposed of or reprocessed. Slag can be prepared for disposal
by slag granulation or slag dumping.
Application and Performance. Slag granulation uses a high-
velocity water jet to produce a finely divided and evenly sized
rock, which can be used as concrete agglomerate or for road
surfacing. Slag dumping is the dumping and subsequent solidifi-
cation of slag, composed almost entirely of insolubles, which can
be crushed and sized for such applications as road surfacing.
Slag can be reprocessed if the metal content is high enough to be
economically recovered. Wet or dry milling, and recovery of
metal by melting can be used to process slag with recoverable
amounts of metal. Of course, in all slag reuse processes,
ultimate disposal of the reprocessed slag must be considered.
Operational Factors. Although slag dumping eliminates the waste-
water associated with slag granulation, an additional factor is
that large volumes of dust are generated during subsequent crush-
ing operations and dust control systems may be necessary.
Demonstration Status. Four of the seven primary lead smelters
currently granulate slag prior to disposal. One of the four
plants granulates the slag, mixes the granulated slag in with ore
concentrate feed to sintering because the lead content of the
slag is high enough to be economically recovered.
286
-------
Dry Air Pollution Control Devices
Application and Performance. The use of dry air pollution con-
trol devices would allow the elimination of waste streams with
high pollution potentials. The choice of air pollution control
equipment is complicated, and sometimes a wet system is the
necessary choice. The important difference between wet and dry
devices is that wet devices control gaseous pollutants as well as
particulates .
Wet devices may be chosen over dry devices when any of the fol-
lowing factors are found: (1) the particle size is predominantly
under 20 microns, (2) flammable particles or gases are to be
treated at minimal combustion risk, (3) both vapors and particles
are to be removed from the carrier medium, (4) the gases are
corrosive and may damage dry air pollution control devices, and
(5) the gases are hot and may damage dry air pollution control
devices.
Equipment for dry control of air emissions includes cyclones, dry
electrostatic precipitators, fabric filters, and afterburners.
These devices remove particulate matter, the first three by
entrapment and the afterburners by combustion.
Afterburner use is limited to air emissions consisting mostly of
combustible particles. Characteristics of the particulate-laden
gas which affect the design and use of a device are gas density,
temperature, viscosity, flammability , corrosiveness, toxicity,
humidity, and dew point. Particulate characteristics which
affect the design and use of a device are particle size, shape,
density, resistivity, concentration, and other physio chemical
properties .
In the primary and secondary aluminum subcategories , melting
prior to casting requires wet air pollution control only when
Chlorine gas is present in the off gases. Dry air pollution
con?roTmethods with inert gas or salt furnace fluxing nave been
demonstrated in the category. .It is possible to perform all the
metal treatment tasks of removing hydrogen, non-metallic inclu
sions and undesirable trace elements and meet the most stringent
quality requirements without furnace fluxing, using only in-line
Si treatment units. To achieve this, the molten aluminum is
treated in the transfer system between the furnace and casting
uni?s by flowing the metal through a region of very fine, dense,
in Ficure VII-33? Another similar alternate degassing method is
to reduce the chlorine-rich degassing agent with a "»£«
as
287
-------
To the extent that nonferrous metals manufacturing processes are
designed to limit the volume or severity of air emissions, the
volume of scrubber water used for air pollution control also can
be reduced. For example, new or replacement furnaces can be
designed to minimize emission volumes.
Advantages and Limitations. Proper application of a dry control
device can result in particulate removal efficiencies greater
than 99 percent by weight for fabric filters, elecrtrostatic pre-
cipitators, and afterburners, and up to 95 percent for cyclones.
Common wet air pollution control devices are wet electrostatic
precipitators, venturi scrubbers, and packed tower scrubbers.
Collection efficiency for gases will depend on the solubility of
the contaminant in the scrubbing liquid. Depending on the con-
taminant removed, collection efficiencies ususally approach 99
percent for particles and gases.
Demonstration Status. Plants in the primary and secondary alumi-
num^primary zinc,primary lead, secondary copper and secondary
silver subcategories all report the use of dry air pollution
control devices on furnaces and casting operations.
Good Housekeeping
Good housekeeping and proper equipment maintenance are necessary
factors in reducing wastewater loads to treatment systems. Con-
trol of accidental spills of oils, process chemicals, and waste-
water from washdown and filter cleaning or removal can aid in
abating or maintaining the segregation of wastewater streams.
Curbed areas should be used to contain or control these wastes.
Leaks in pump casings, process piping, etc., should be minimized
to maintain efficient water use. One particular type of leakage
which may cause a water pollution problem is the contamination of
noncontact cooling water by hydraulic oils, especially if this
type of water is discharged without treatment.
Good housekeeping is also important in chemical, solvent, and oil
storage areas to preclude a catastrophic failure situation.
Storage areas should be isolated from high fire-hazard areas and
arranged so that if a fire or explosion occurs, treatment facili-
ties will not be overwhelmed nor excessive groundwater pollution
caused by large quantities of chemical-laden fire-protection
water.
A conscientiously applied program of water use reduction can be a
very effective method of curtailing unnecessary wastewater flows.
Judicious use of washdown water and avoidance of unattended
running hoses can significantly reduce water use.
288
-------
Table VII-1
pH CONTROL EFFECT ON METALS REMOVAL
Day 1 Day 2 Day 3
In Out In Out In Out
pH Range 2.4-3.4 8.5-8.7 1.0-3.0 5.0-6.0 2.0-5.0 6.5-8.1
(mg/1)
TSS 39 8 16 19 16 7
Copper 312 0.22 120 5.12 107 0.66
Zinc 250 0.31 32.5 25.0 43.8 0.66
Source: Development Document for Effluent Limitations Guidelines
and Standards for the Copper Forming Point Source Cate-
gory, U.S. EPA, EPA 440/l-82/074b.
289
-------
Table VII-2
EFFECTIVENESS OF SODIUM HYDROXIDE FOR METALS REMOVAL
Day 1
In Out
Day 2
In Out
Day 3
In Out
pH Range
(mg/1)
Cr
Cu
Fe
Pb
Mn
Ni
Zn
TSS
Source :
2.1-2.9 9.0-9.3
0.097 0.0
0.063 0.018
9.24 0.76
1.0 0.11
0.11 0.06
0.077 0.011
0.054 0.0
13
Development Document
and Standards for the
2.0-2.4 8.7-9.1 2.0-2.4
0.057 0.005 0.068
0.078 0.014 0.053
15.5 0.92 9.41
1.36 0.13 1.45
0.12 0.044 0.11
0.036 0.009 0.069
0.12 0.0 0.19
11
8.6-9.1
0.005
0.019
0.95
0.11
0.044
0.011
0.037
11
for Effluent Limitations, Guidelines
Battery Manufacturing Point
Source
290
-------
Table VII-3
EFFECTIVENESS OF LIME AND SODIUM HYDROXIDE
FOR METALS REMOVAL
Day 1 Day 2 Day 3
In Out In Out In Out
pH Range 9.2-9.6 8
Al
Co
Cu
Fe
Mn
Ni
Se
Ti
Zn
TSS
Source :
37.3
3.92
0.65
137
175
6.86
28.6
143
18.5
4,390
.3-9.8
0.35
0.0
0.003
0.49
0.12
0.0
0.0
0.0
0.027
9 3,
Development Document
and Standards
for the
9.2
38.1
4.65
0.63
110
205
5.84
30.2
125
16.2
595
7.6-8.1 9.6
0.35
0.0
0.003
0.57
0.012
0.0
0.0
0.0
0.044
13
29.9
4.37
0.72
208
245
5.63
27.4
115
17.0
2,805
7.8-8.2
0.35
0.0
0.003
0.58
0.12
0.0
0.0
0.0
0.01
13
for Effluent Limitations Guidelines
Porcelain
Enameling Point
Source
291
-------
Table VII-4
THEORETICAL SOLUBILITIES OF HYDROXIDES AND SULFIDES
OF SELECTED METALS IN PURE WATER
Metal
Cadmium (Cd++)
Chromium (Cr Ml)
Cobalt (Co-H-)
Copper (Cu++)
Iron (Fe++)
Lead (Pb++)
Manganese (Mn++)
Mercury (Hg++)
Nickel (Ni++)
Silver (Ag+)
Tin (Sn++)
Zinc (Zn++)
Solubility of Metal Ion, mg/1
As Hydroxide As Carbonate As Sulfide
2.3 x 10-5
8.4 x 10-4
2.2 x 10-1
2.2 x 10-2
8.9 x 10-1
2.1
1.2
3.9 x 10-4
6.9 x 10-3
13.3
1.1 x 10-4
1.1
1.0 x 10-4
7.0 x 10-3
3.9 x 10-2
1.9 x 10-1
2.1 x 10-1
7.0 x 10-4
6.7 x 10-10
No precipitate
1.0 x 10-8
5.8 x 10-18
3.4 x 10-5
3.8 x 10-9
2.1 x 10-3
9.0 x 10-20
6.9 x 10-8
7.4 x 10-12
3.8 x 10-8
2.3 x 10-7
Source: Lange's Handbook of Chemistry, McGraw-Hill, New York,
292
-------
to
Table VI1-5
SAMPLING DATA FROM SULFIDE PRECIPITATION-SEDIMENTATION SYSTEMS
Lime, FeS,
Polyelectrolyte,
Lime, FeS,
Polyelectrolyte,
Settle. Filter
NaOH, Ferric Chloride,
Na?ST Clarify (1 Stage)
Treatment
pH
(mg/D
Cr+6
Cr
Cu
Fe
Ni
Zn
Sources:
In Out In
5.0-6.8 8-9 7.7
25.6 <0.014 0.022
32.3 <0.04 2.4
__
0.52 0.10 108
0.68
39.5 <0.07 33.9
Out
7.38
<0.020 11
<0.1 18
0
0.6
<0.1
<0.1 0
In Out
.45 <.005
.35 <.005
.029 0.003
--
__
.060 0.009
Summary Report, Control and Treatment Technology for the Metal Finishing
Industry: Sulfide Precipitation,
Indus try F injjshing , Vol. 35, No.
U.S. EPA, EPA No. 625/8/8U-UU3, 19/9.
11, November,
1979.
Electroplating sampling data from plant 27045
-------
Table VII-6
SULFIDE PRECIPITATION-SEDIMENTATION PERFORMANCE
Parameter Treated Effluent (mg/l)_
Cd 0.01
Cr (Total) 0.05
Cu 0.05
Pb 0.01
Hg 0.03
Ni 0.05
Ag 0.05
Zn 0.01
Sources: Summary Report, Control and Treatment Technology for
the Metal Finishing Industry: Sulfide Precipitation,
U.S.. EPA, EPA No. S25/a/80-603. 19/9.
Addendum to Development Document for Effluent Limita-
fions'Guideiines and New Source Performance Standards^
Malor Inorganic Products Segment of Inorganics PointT
Source Category, U.S. EPA, EPA Contract No. EPA/68-U.1-
3281 (Task 7), June, 1978.
294
-------
Table VII-7
FERRITE CO-PRECIPITATION PERFORMANCE
Metal Influent (mg/1) Effluent (mg/1)
Mercury 7.4 0.001
Cadmium 240 0.008
Copper 10 0.010
Zinc 18 0.016
Chromium 10 <0.010
Manganese 12 0.007
Nickel 1,000 0.200
Iron 600 0.06
Bismuth 240 0.100
Lead 475 0.010
Source: Sources and Treatment of Wastewater in the Nonferrpug
Metals Industry, U.S. EPA, EPA No. 6UU/2-80-U74,
295
-------
Table VII-8
CONCENTRATION OF TOTAL CYANIDE (mg/1)
Plant Method In Out
1057 FeS04 2.57 0.024
2.42 0.015
3.28 0.032
33056 FeS04 0.14 0.09
0.16 0.09
12052 ZnS04 0.46 0.14
0.12 0.06
Mean
0.07
Source: Development Document for Proposed Effluent Limitations
r^dgllnes and Standards for the Coiling Coating Point
Source Category. U.S. EPA, EPA 440/1-81-uyib, November
• ftU n
296
-------
Table VII-9
MULTIMEDIA FILTER PERFORMANCE
Plant ID //
06097
13924
18538
30172
36048
Mean
TSS Effluent Concentration, mg/1
0.0, 0.0, 0.5
1.8, 2.2, 5.6, 4.0, 4.0, 3.0, 2.2, 2.8
3.0, 2.0, 5.6, 3.6, 2.4, 3.4
1.0
1.4, 7.0, 1.0
2.1, 2.6, 1.5
2.61
Source: Development Document for Effluent Limitations, Guidelines
and Standards for the Battery Manufacturing Point Source
Category, U.S. EPA, EPA 440/l-82/067b.
Development Document for Effluent Limitations Guidelines
and Standards for the Porcelain Enameling Point Source
Category. U.S. EPA, EPA 440/1-82/072.
297
-------
Table VII-10
PERFORMANCE OF SELECTED SETTLING SYSTEMS
Plant ID
J. JU0L1W A.*-'
01057
09025
11058
12075
to
°° 19019
33617
40063
44062
46050
Source :
Settling
Device
Lagoon
Clarifier +
Settling
Ponds
Clarifier
Settling
Pond
Settling
Tank
Clarifier EC
Lagoon
Clarifier
Clarifier
Settling
Tank
Development Docums
ro r the Porcelain
OL
Day
In
54
1,100
451
284
170
--
4,390
182
295
mt for Eff
Enameling
JOJT Cjlll^ti
1
Out
6
9
17
6
1
--
9
13
10
:luent
Point
Lf OW.UJLJ-'U Viwi
Day
In
56
1,900
--
242
50
1,662
3,595
118
42
Limitations
-2 —
Out
6
12
--
10
1
16
12
14
10
Guidelines
Source Category, U.S.
Day 3
In
50
1,620
— -»
502
*• "•
1,298
2,805
174
153
Out
5
5
""
14
""
4
13
23
8
and Standards
EPA, EPA '
4-^fU/
1-82/072.
-------
Table VII-11
SKIMMING PERFORMANCE
Oil Sc Grease (mg/1)
Plant Skimmer Type In Out
06058 API 224,669 17.9
06058 Belt 19.4 8.3
Source: Development Document for Effluent Limitations Guide-
lines and Standards for the Copper Forming Point Source
Category, U.S. EPA, EPA 440/1-82/074b.
299
-------
Table VII-12
COMBINED METALS DATA EFFLUENT VALUES (mg/1)
Cd
Cr
Cu
Pb
Ni
Zn
Fe
Mn
TSS
Mean
0.079
0.08
0.58
0.12
0.57
0.30
0.41
0.21
12.0
One -Day
Max.
0.32
0.42
1.90
0.15
1.41
1.33
1.23
0.43
41.0
10 -Day Avg.
Max.
0.15
0.17
1.00
0.13
1.00
0.56
0.63
0.34
20.0
30 -Day Avg.
Max.
0.13
0.12
0.73
0.12
0.75
0.41
0.51
0.27
15.5
300
-------
Table VII-13
LStS PERFORMANCE
ADDITIONAL POLLUTANTS
Pollutant Average Performance (mg/1)
Sb 0.7
As 0.51
Be 0.30
Hg 0.06
Se 0.30
Ag 0.10
Tl 0.50
Al 1-11
Co 0.05
F 14.5
301
-------
Table VII-14
COMBINED METALS DATA SET - UNTREATED WASTEWATER
Pollutant Min. Cone, (mg/1) Max. Cone, (mg/1)
Cd <0.1 3.83
Cr <0.1 116
Cu <0.1 108
Pb <0.1 29.2
Ni <0.1 27.5
Zn <0.1 337.
Fe <0.1 263
Mn <0.1 5.98
TSS 4.6 4,390
302
-------
Table VII-15
MAXIMUM POLLUTANT LEVEL IN UNTREATED WASTEWATER
ADDITIONAL POLLUTANTS
(mg/1)
Be Ag
10.24
Pollutant
As
Be
Cd
Cr
Cu
Pb
Ni
Ag
Zn
F
Fe
O&G
TSS
As Sc Se
4.2
--
<0.1
0.18
33.2
6.5
--
--
3.62
--
--
16.9
352
8.60 0.23 22.8
1.24 110.5 2.2
0.35 11.4 5.35
100 0.69
4.7
0.12 1,512 <0.1
760
646
16 2.8
796 587.8 5.6
303
-------
Table VII-16
PRECIPITATION-SETTLING-FILTRATION (LSSeF) PERFORMANCE
PLANT A
Parameters
No. Points
For 1979-Treated Wastewater
Cr
Cu
Nt
Zn
Fe
47
12
47
47
Range mg/1
0.015
0.01
0.08
0.08
0.13
0.03
0.64
0.53
Mean +
Std. Dev.
0.045 + 0.029
0.019 T 0.006
0.22 + 0.13
0.17 + 0.09
Mean + 2
Std. Dev.
0.10
0.03
0.48
0.35
u>
o
For 1978-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
47
28
47
47
21
0.01
0.005
0.10
0.08
0.26
- 0.07
- 0.055
- 0.92
- 2.35
- 1.1
0.06 + 0.10
0.016 + 0.010
0.20 + 0.14
0.23 + 0.34
0.49 + 0.18
0.26
0.04
0.48
0.91
0.85
Raw Waste
Cr
Cu
Ni
Zn
Fe
5
5
5
5
5
32.0
0.08
1.65
33.2
10.0
72.0
0.45
20.0
32.0
95.0
-------
Table VII-17
PRECIPITATION-SETTLING-FILTRATION (LSScF) PERFORMANCE
PLANT B
u>
o
Ln
Parameters No.
Points
Range mg/1
Mean +
Std. Dev.
For 1979-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
TSS
175
176
175
175
174
2
0.0
0.0
0.01
0.01
0.01
1.00
- 0.40
- 0.22
-1.49
- 0.66
- 2.40
- 1.00
0.068
0.024
0.219
0.054
0.303
-1- 0.075
+ 0.021
+ 0.234
+ 0.064
+ 0.398
For 1978-Treated Wastewater
Cr
Cu
Ni
Zn
Fe
Total 1974-1979-Treated
Cr 1,
Cu 1,
Ni 1,
Zn 1,
Fe 1,
Raw Waste
Cr
Cu
Ni
Zn
Fe
TSS
144
143
143
131
144
Wastewater
288
290
287
273
287
3
3
3
2
3
2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.80
0.09
1.61
2.35
3.13
111
- 0.70
- 0.23
- 1.03
- 0.24
- 1.76
- 0.56
- 0.23
- 1.88
- 0.66
- 3.15
9.15
0.27
4.89
3.39
- 35.9
- 446
0.059
0.017
0.147
0.037
0.200
0.038
0.011
0.184
0.035
0.402
5.90
0.17
3.33
22.4
+ 0.088
+ 0.020
+ 0.142
+ 0.034
+ 0.223
+ 0.055
+ 0.016
+ 0.211
+ 0.045
+ 0.509
Mean + 2
Std. Dev.
0.22
0.07
0.69
0.18
1.10
0.24
0.06
0.43
0.11
0.47
0.15
0.04
0.60
0.13
1.42
-------
Table VII-18
PRECIPITATION-SETTLING-FILTRATION (LS&F) PERFORMANCE
PLANT C
Parameters No.
For Treated Wastewater
Cd
Zn
TSS
Points
103
103
103
pH 103
u>
ON For UnTreated Wastewater
Cd
Zn
Fe
TSS
pH
103
103
3
103
103
Range
0.010 -
0.039 -
0.100 -
7.1
0.039 -
0.949 -
0.107 -
0.80 -
6.8
mg/1
0.500
0.899
5.00
7.9
2.319
29.8
0.46
19.6
8.2
Mean +
Std. Dev.
0.049 + 0.049
0.290 + 0.131
1.244 + 1.043
9.2*
0.542 + 0.381
11.009 + 6.933
0.255
5.616 + 2.896
7.6*
Mean + 2
Std. Dev.
0.147
0.552
3.33
1.304
24.956
11.408
*pH value is median of 103 values.
-------
U)
o
Table VII-19
SUMMARY OF TREATMENT EFFECTIVENESS (mg/1)
LStS Technology System
Pollutant
Parameter
114 Sb
115 As
117 Be
118 Cd
119 Cr
120 Cu
121 CN
122 Pb
123 Hg
124 Ni
125 Se
126 Ag
127 Th
128 Zn
Al
Co
F
Fe
Mn
P
OScG
TSS
Mean
0.70
0.51
0.30
0.079
0.080
0.58
0.07
0.12
0.06
0.57
0.3
0.1
0.50
0.30
1.11
0.05
14.5
0.41
0.21
4.08
12.0
One-
Day
Max.
2.87
2.09
1.23
0.32
0.42
1.90
0.29
0.15
0.25
1.41
1.23
0.41
2.05
1.33
4.55
0.21
59.5
1.23
0.43
16.7
20.0
41.0
YO-
Day
Avg.
1.27
0.86
0.51
0.15
0.17
1.00
0.12
0.13
0.10
1.00
0.55
0.17
0.84
0.56
1.86
0.09
26.4
0.63
0.34
6.83
12.0
20.0
30-
Day
Avg.
1.13
0.83
0.49
0.13
0.12
0.73
0.11
0.12
0.10
0.75
0.49
0.16
0.81
0.41
1.80
0.08
23.5
0.51
0.27
6.60
10.0
15.5
LSScF Technology System
Mean
0.034
0.34
0.20
0.049
0.07
0.39
0.047
0.08
0.036
0.22
0.007
0.07
0.34
0.23
0.74
0.05
9.46
0.28
0.14
2.72
2.6
One-
Day
Max.
0.14
1.39
0.82
0.20
0.37
1.28
0.20
0.10
0.15
0.55
0.03
0.29
1.40
1.02
3.03
0.21
38.8
1.23
0.30
11.2
10.0
15.0
10-
Day
Avg.
0.06
0.57
0.34
0.08
0.15
0.61
0.08
0.09
0.06
0.37
0.01
0.12
0.57
0.42
1.24
0.09
15.8
0.63
0.23
4.6
10.0
12.0
JU-
Day
Avg.
0.06
0.55
0.32
0.08
0.1.0
0.49
0.08
0.08
0.06
0.29
0.01
0.10
0.55
0.31
1.20
0.08
15.3
0.51
0.19
4.4
10.0
10.0
-------
Table VI1-20
ION EXCHANGE PERFORMANCE
(All Values mg/1)
Plant A
Plant B
Parameter
Al
Cd
Cr+3
Cr+6
Cu
CN
Au
Fe
Pb
Mn
Ni
Ag
S04
Sn
Zn
Prior to
Purifica-
tion
5.6
5.7
3.1
7.1
4.5
9.8
--
7.4
--
4.4
6.2
1.5
--
1.7
14.8
After
Purifica-
tion
0.20
0.00
0.01
0.01
0.09
0.04
--
0.01
--
0.00
0.00
0.00
--
0.00
0.40
Prior to
Purifica-
tion
--
--
--
--
43.0
3.40
2.30
--
1.70
--
1.60
9.10
210.00
1.10
--
After
Purifica-
tion
--
--
0.10
0.09
0.10
--
0.01
--
0.01
0.01
2.00
0.10
--
308
-------
Table VII-21
PEAT ADSORPTION PERFORMANCE
Pollutant Influent (mg/1) Effluent (mg/1)
Cr+6 35,000 0.04
Cu 250 0.24
CN 36.0 0.7
Pb 20.0 0.025
Hg 1.0 0.02
Nt 2.5 0.07
Ag 1.0 0.05
Sb 2.5 0.9
Zn 1.5 0.25
309
-------
Table VII-22
MEMBRANE FILTRATION SYSTEM EFFLUENT
00
I-1
0
Specific
Metal
Al
Cr,(+6)
Cr (T)
Cu
Fe
Pb
CN
Ni
Zn
TSS
Manufacturer s
Guarantee
0.5
0.02
0.03
0.1
0.1
0.05
0.02
0.1
0.1
--
Plant 19066
In Out
0.46 0.01
4.13 0.018
18.8 0.043
288 0.3
0.652 0.01
<0.005 <0.005
9.56 0.017
2.09 0.046
632 0.1
Plant 31022
In Out
5.25 <0.005
98.4 0.057
8.00 0.222
21.1 0.263
0.288 0.01
<0.005 <0.005
194 0.352
5.00 0.051
13.0 8.0
Predicted
Perfor-
mance
0.05
0.20
0.30
0.05
0.02
0.40
0.10
1.0
-------
FILTER
ADSORPTION
COLUMN
INFLUENT
WASTE WATER
REGENERATED CARBON SLURRY
f
LO
FINES
REMOVAL
SCREEN
"
TERTIARY
TREATED
EFFLUENT
DEWATERING
SCREEN
CARBON
STORAGE
REGENERATION
FURNACE
REGENERATED
CARBON
SLURRY TANKS
FINES TO
WASTE
Figure VII-1
FLOW DIAGRAM OF ACTIVATED CARBON ADSORPTION WITH REGENERATION
-------
FLANGE
WASTE WATER
INFLUENT
DISTRIBUTOR
WASH WATER
BACKWASH
SURFACE WASH
MANIFOLD
BACKWASH
REPLACEMENT CARBON
CARBON REMOVAL PORT
TREATED WATER
SUPPORT PLATE
Figure VII-2
ACTIVATED CARBON ADSORPTION COLUMN
312
-------
o-
»' —
10
10 «
o io->
5,.-
0
„•'
1
:
.-II
n it ia
Source:
Figure VII-3
COMPARATIVE SOLUBILITIES OF METAL HYDROXIDES
AND SULFIDE AS A FUNCTION OF pH
Development Document for the Proposed Effluent Limita-
tions Guidelines and New Source Performance Standards
p ~' i 1-7 • '_ r*~ ^vt-» -P^>--v-/-Mia T-To i~ Q 1 c T^Tami T ^ C" —
for the Zinc Segment of the Nonferrous I-L
turing Point Source Category.EPA 440/1-74-0
November,1974.
313
-------
•
4
"j
0
z
o
H
4 )
K
H
Z
W
u
z
o
u
u
z
•• f
N «
h
z
u
3
-J
h.
k
U
1
x
O
(
u
>
0
0
O
O
O
0 0
^J
r\n t
0 <
» o OQ
O
0
8°
On ^
O
0
O
s • i • 7 10 it i,
MINIMUM EFFLUENT pH
Figure VII-4
EFFLUENT ZINC CONCENTRATION VS. MINIMUM EFFLUENT pH
-------
0.40
SODA ASH AND
CAUSTIC SODA
10.5
Figure VII-5
LEAD SOLUBILITY IN THREE ALKALIES
Source: Lanovette, Kenneth, "Heavy Metals Removal," Chemical
Engineering/Deskbook Issue, October 17, 1977.
315
-------
(a)
30-40 in-*
UNOERDRA
CHAMBER
COARSE
INTERMIX
FINER U
FINEST M
INFLUENT
1
EFFLUENT
(b)
r
6-10 ft —
DEPTH
FINE/.. "•'."•':'.'
'.•};• SAND •'•':/
.;•;'• '• COARSE"
I
tt
Ll
(d)
HEDIA— -
EOIA —
EDIA— —
UNOERDRAI
CHAMBER
/-OVERFLOW
/ TROUGH
nnrff.
Fl'ME.':;; .•.*•;.•:'
' i" ' ' 1 • . ••
ws.
-/ 'v COARSE1
f
'FLUENT VrMFLU
UNOERDRAIN\
CHAMBER—1
INFLUENT
•ANTHRACl'tr "T
•v'-;:'??4V.;-.v.
7 •— ..— — -.TT- 30 •<
•''.-.-' •'.•'.••' -:\ • ' 1
.-.-••rSlLICA -•..'.
^xStyCt::^ 1
1 EFFLUENT
Ll
(Oil
X-SRIT TO
RETAIN / \
SAND (** )
STRAINER -v
'
EFFLUENT
4-6H y
DEPTH-'
£NT UNDERDRJ
CHAMBE
(e)
COARSE MEDIA —
FINER MEDIA— ^
FINEST MEDIA —
UNOERORAU)
CHAMBER
.'.'.•• FINE".-.-
>-'.••'• ' • •_
'..";•: SAND •'.-•;•
:•.'••: : r."-*«
••/.tOARSE.-/
^~
UN \
R — »
INFLUENT
. 1
ANTHRACITE
.•"..-'.'•COAL;.-.'
- T.T- T^r~. — •""
..-•'..;.'siLicA',:.f
— •— . 5T^IS ^.'^
s
*n
1 INFLUENT
sll
T
: 1
"28-4Sin
GARNET SAND
\ 'EFFLUENT
(a) Single-Media Conventional Filter (d) Dual-Media Filter.
(b) Single-Media Upflow Filter. (e) Mixed-Media (Triple
(c) Single-Media Biflow Filter Media) Filter.
Figure VII-6
FILTER CONFIGURATIONS
316
-------
INFLUENT
ALUM
CFFLUENT!
'1
K <
U
H
-< V
5
i /
FILTER \
COMPARTMENT y
'
e SAND-,
^WATER \
LEVEL \
STORED /
BACKWASH /
WATER
\ ,
.. — FILTER /
— HBACKWASH-*- 11
FILTER
MEDIA V U
;:---::- ;-TCOAL
^^^ ^X;>sV^
u u u U U u U u u U
0 COLLECTION CHAMBER
DRAIN
Figure VII-7
GRANULAR BED FILTRATION
317
-------
PERFORATED
BACKING PLATE
FABRIC
FILTER MEDIUM
SOLID
RECTANGULAR
END PLATE
INLET
SLUDGE
FABRIC
FILTER MEDIUM
SOLIDS
FILTERED LIQUID OUTLET
PLATES AND FRAMES ARE
TOGETHER DURING
FILTRATION CYCLE
RECTANGULAR
METAL PLATE
RECTANGULAR FRAME
Figure VII-8
PRESSURE FILTRATION
318
-------
SEDIMENTATION BASIN
INLET ZONE
INLET LIQUID
BAFFLES TO MAINTAIN
QUIESCENT CONDITIONS
OUTLET ZONE
**»V^, " SETTLING PARTIBLE
• """•**»»* • TRAJECTORY . * «
jf
OUTLET LIQUID
BELT-TYPE SOLIDS COLLECTION
MECHANISM
SETTLED PARTICLES COLLECTED
AND PERIODICALLY REMOVED
CIRCULAR CLARIFIES
SETTLING ZONE
INLET LIQUID
CIRCULAR BAFFLE
i—'
INLET ZONE
• •
•*•*.* \* * . *. • . •„* * ' */• UQLUD '
-i1—-. • *.V. . ' .T-*' ' .V.'FLOW /
• IT.T.T .INJ • '4 / v*. • •>/.T T.T-T.'.'
L-..J• • h7:>*3^N^v^.' •J.-I/rrs-
ANNULAR OVERFLOW WEIR
OUTLET LIQUID
SETTLING PARTICLES
REVOLVING COLLECTION
MECHANISM
I
SETTLED PARTICLES
COLLECTED AND PERIODICALLY
REMOVED
SLUDGE DRAWOFF
Figure VII-9
REPRESENTATIVE TYPES OF SEDIMENTATION
319
-------
SEPARATOR CHANNEL
GATEWAY PIER
^-FOREBAY
*SLOT FOR
CHANNEL GATE
SLUDGE COLLECTING
HOPPER
DIFFUSION DEVICE
(VERTICAL-SLOT BAFFLE)
FLIGHT SCRAPER
CHAIN SPROCKET
ROTATABLE OIL
SKIMMING PIPE
FLIGHT SCRAPER
CHAIN
WATER
LEVEL
WOOD FLIGHTS
I I 1 l\±zd
FLOW
OIL RETENTION
BAFFLE
/-EFFLUENT
WEIR AND
WALL
•EFFLUENT
SEWER
EFFLUENT FLUME
SLUDGE - COLLECTING HOPPER
DISCHARGE WITH LEAD PIPE.
SLUDGE PUMP
SUCTION PIPE
Figure VII-10
GRAVITY OIL/WATER SEPARATOR
-------
I .
1.0
0.1
E
I 0.01
0.001
0
f-
0.01
Data pninls with • raw waste concenlialion
less Ilian 0.1 nig/1 weie not inclinleil in
lif nlmeiit ellectiveness calculations.
n
1.0
Cadmium Raw Waste Concentration (ing/1)
us
100
(Numlier ol nliseivalions = 2)
FIGURE VII-11
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
CADMIUM
-------
to
r )
I 3
10
E
01
0.01
01
-(h
0
-4»-
6
0
e
0
D
10 10
Cliruiiiiiim Raw Waste Concenlialinn (rng/l)
100
FIGURE VII -12
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
CHROMIUM
1000
of oliseivalinnt =• 26)
-------
to
s »1
a
a
'1
0.01
0.1
0,k
cnda
0
1.0
©
I
C
)
10
Copper Raw Waste Concentration (mg/l)
100
1000
(Nunihnr of ohsetvatiom = 19)
FIGURE VII-13
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
COPPER
-------
U)
10
on
J:
I •'
C
§
I
a
U
I
£
0.01
onoi
001
©
fiL\ fiflvfn
< > l«v>
O.I
1.0
Lead flaw Waste Concentration (mg/l)
10 100
(Number of observations « 23)
FIGURE VII -14
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
LEAD
-------
to
a
•a
c o
fi u
1.0
LO
)
i n
u
< 2
X 0
0.1
.01
——X —
•t
0
0.1
10 10
0 Nickel Raw Waste Concentration (nig/I)
x Aluminum Raw Waste Concentration (ing/I)
100
(Number of unset valions =13)
(Nuinlier of ohscivalioiii = S)
1000
FIGURE VII-15
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
NICKEL AND ALUMINUM
-------
S3
IV
§ 10
o
g
E
S
§
0
1
111
*~ 01
a
e
Oni
.ui
0
©
1
•)
(.
,j
(•i
1
1
*
1
4
4
0
D
|
e
0
©
W
V
T
0
©
G
©
0
<*t
19
0
I*
-• *
II
- . _.
10
•
•
10(1
Zinc Raw Waste Concentration (ing/I)
(Number of obseivalinns - 29)
FIGURE VII-16
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
ZINC
-------
„
•^
I 1.0
g
3
3
:
8
3
!
u
§
? ...
B
B
k.
^
001
0
0
— «r-
1
©
^0
(
• O -
0
©
*
1.0
)
t)
S
5"
•r
In... IJtI.,
.
ID
©
10
m
©
•
©
-J3
100
©
— _
_ —
— — _
"
1001
(Number of nbiervalions - 29)
FIGURE VII -17
HYDROXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
IRON
-------
1.0
g 0.1
U)
N3
00
0.01
0001
B
01
5
i
•
1.0 10
Manganese Raw Watte Cnncentralinn (nig/I)
100
1000
of olisetvalioin a 10)
FIGURE VII-18
IIYDROXIOE PRECIPITATION SEDIMENTATION EFFECTIVENESS
MANGANESE
-------
IUUU
— 100
fg
a
•a
R
g
I
CJ
Ni -0
|_
OT
1*
f n
(
n
"Si
I
i
•
j
1
>
'
1
©
©
a
©
_
,
i
(
6
®
'i
•'
§
\Sr •
© ©
_
*
A
,
f)
©
©
j) ©
©
^.
ft)
A
*
©
(I\
1.0
too
TSS Raw Waste Concentration (mg/l)
1000
10.1100
(Number of oliservntiiMH -
vii-19
IIYOnOXIDE PRECIPITATION SEDIMENTATION EFFECTIVENESS
TSS
-------
OILY WATER
INFLUENT
WATER
DISCHARGE
MOTOR
DRIVEN
RAKE
OVERFLOW
SHUTOFF
VALVE
AIR IN
BACK PRESS
VALVE
TO SLUDGE
TANK "
EXCESS
AIR OUT
LEVEL
CONTROLLER
_J
Figure VII-20
DISSOLVED AIR FLOTATION
330
-------
CONVEYOR DRIVE
r— BOWL DRIVE
LIQUID
OUTLET
SLUDGE
INLET
AAAAJVJV
CYCLOGEAR
SLUDGE
DISCHARGE
BOWL
REGULATING IMPELLER
RING
Figure VII-21
CENTRIFUGATION
331
-------
RAW WASTE
CAUSTIC
SODA
»M
CONTROLLER
LO
LO
N3
OOP CONTROLLERS
00
WATER
CONTAINING
CYANATE
>k
CHLORINE
CIRCULATING
PUMP
REACTION TANK
CHLORINATOR
CAUSTIC
SODA
Olr-D
t
00
REACTION TANK
PH
CONTROLLER
TREATED
WASTE
Figure VII-22
TREATMENT OF CYANIDE WASTE BY ALKALINE CHLORINATION
-------
CONTROLS
OZONE
GENERATOR
DRY AIR
OZONE
REACTION
TANK
RAW WASTE-
X
TREATED
WASTE
Figure VII-23
TYPICAL OZONE PLANT FOR WASTE TREATMENT
333
-------
MIXER,
WASTEWATER
FEED TANK
^ EXHAUST
GAS
TEMPERATURE
CONTROL
PH MONITORING
TEMPERATURE
CONTROL
PH MONITORING
TEMPERATURE
CONTROL
PH MONITORING
TREATED WATER
OZONE
OZONE
GENERATOR
Figure VII-24
UV/OZONATION
334
-------
EXHAUST
CONDENSER
WATER VAPOR
'.'
PACKED TOWER
EVAPORATOR
WASTCWATER
HEAT
EXCHANGER
STEAM
• TEAM
CONDENSATE
CONCENTRATE
EVAPORATOR
STEAM-
STEAM
CONDENSATE
VAPOR-LIQUID
MIXTURE ^SEPARATOR
\ MIXTURE l
y/7/.
PUMP
ATMOSPHERIC EVAPORATOR
WASTEWATER
WATER VAPOH
BHHSS
77/A
LIQUID
RETURN
VACUUM LINE
VACUUM
CONOENSATE
WASTCWATEH
CONCENTRATE
COOLING
WATER
STEAM
WASTE
WATER
STEAM
CONDENSATE
SUBMERGED TUBE EVAPORATOR
; •
-------
CONDUIT
TO MOTOR
INFLUENT
CONDUIT TO
OVERLOAD
ALARM
COUNTERFLOW
INFLUENT WEL
DRIVE UNIT
OVERLOAD ALARM
EFFLUENT WEIR
DIRECTION OF ROTATION
EFFLUENT PIPE
EFFLUENT CHANNEL
PLAN
TURNTABLE
BASE
HANDRAIL
INFLUENT
CENTER COLUMN
CENTER CAGE
WEIR
L
STILTS
CENTER SCRAPER
SQUEEGEE
SLUDGE PIPE
Figure VII-26
GRAVITY THICKENING
336
-------
WASTE WATER CONTAINING
DISSOLVED METALS OR
OTHER IONS
REGENERANT
"SOLUTION
-OIVERTER VALVE
•DISTRIBUTOR
-SUPPORT
REGENERANT TO REUSE,
TREATMENT. OR DISPOSAL
-DIVERTER VALVE
METAL-FREE WATER
REUSE OR DISCHARGE
Figure VII-27
ION EXCHANGE WITH REGENERATION
337
-------
MACROMOLECULE5
AND SOLIDS
MOST
..LT.
« 450 PS1
MEMBRANE
FEED
WATER
PERMEATE (WATER)
MEMBRANE CROSS SECTION,
IN TUBULAR. HOLLOW FIBER,
OR SPIRAL-WOUND CONFIGURATION
•f ' •(
O SALTS OR SOLIDS
• WATER MOLECULES
Figure VII-28
SIMPLIFIED REVERSE OSMOSIS SCHEMATIC
CONCENTRATE
(SALTS)
338
-------
PERMEATE
TUBE
ADHESIVE BOUND
SPIRAL MODULE
PERMEATE
FLOW
FEED
CONCENTRATE
ruow
BACKING MATERIAL
MESH SPACER
M EMBRANE
SPIRAL MEMBRANE MODULE
POROUS SUPPORT TUBE
WITH MEMBRANE
PRODUCT WATER
PERMEATE FLOW
BRACKISH
WATER
FEED FLOW
BRINE
CONCENTRATE
FLOW
PRODUCT WATER
TUBULAR REVERSE OSMOSIS MODULE
SNAP
RING
OPEN ENDS
OF FIBERS
r— EPOXY
TUBE SHEET
POROUS
BACK-UP DISC
CONCENTRATE
OUTLET —FLOW SCREEN
-END PLATE
-f IBER
POROUS FEED
DISTRIBUTOR TUBE—'
••O" RING^\ 1
SEAL •* \_
PERMEATE
END PLATE
HOLLOW FIBER MODULE
Figure VII-29
REVERSE OSMOSIS MEMBRANE CONFIGURATIONS
339
-------
ik.
U
TT
i)
n
] (
!j
i
i
n
] i!
II
JL___
• -IN. VtTRIFl
:
c
I
Tf
} 1
3
i
___JL.__
•^r-->^-
D PIPE LAID— '
WITH PLASTIC JOINTS
3 to !!
n
n
u
u
n
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Figure VII-30
SLUDGE DRYING BED
340
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FABRIC OR WIRE
FILTER MEDIA
STRETCHED OVER
REVOLVING DRUM
DIRECTION OF ROTATION
ROLLER
SOLIDS SCRAPED
OFF FILTER MEDIA
STEEL
CYLINDRICAL
FRAME
SOLIDS COLLECTION
HOPPER
INLET LIQUID
TO 8E
FILTERED
-TROUGH
FILTERED LIQUID
Figure VII-31
VACUUM FILTRATION
341
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EVAPORATION
CONTACT COOLING
WATER
COOLING
TOWER
RECYCLED FLOW
SLOWDOWN
DISCHARGE
MAKE-UP WATER
Figure VII-32
FLOW DIAGRAM FOR RECYCLING WITH A COOLING TOWER
342
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GAS
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Figure VII-33
SCHEMATIC DIAGRAM OF SPINNING NOZZLE ALUMINUM PxEFINING PROCESS
-------
SECTION VIII
COST, ENERGY, AND NONWATER QUALITY ASPECTS
Cost information for the treatment options considered in estab-
lishing these effluent limitations and standards is presented in
the following discussion. This section presents general informa-
tion pertaining to the development of capital and annual costs.
Several levels of effluent reduction are presented for each waste
stream in every subcategory. The cost curves drafted for use in
estimating plant costs are presented in each of the subcategory
supplements. After discussing the basis of the cost estimates,
this section presents the specific procedures for developing
costs for each technology for existing sources. The section
concludes with a discussion of the energy and nonwater quality
aspects of the treatment options.
BASIS FOR COST ESTIMATION
Sources of Cost Data
Capital and annual cost data for the selected treatment processes
were collected from four sources: (1) literature, (21 data col-
lection portfolios, (3) equipment manufacturers, and (4) in-house
desien projects. The majority of the cost information was
obtained from literature sources. Many of the literature sources
cited obtained their costs from surveys of actual design proj-
ects. Data collection portfolios completed by companies^in the
nonferrous metals manufacturing category contained a l^ted
amount of chemical and unit process cost information. Most of
the dcp did not include treatment plant capital and annual^cost
information. Therefore, little data from the data collection
portfolios was applicable for the determination of individual
unit process costs. Additional data was obtained from equipment
manufacturers and design projects performed by an EPA contractor.
Determination of Costs
The annualized costs developed for each level of treatment and
combination of waste streams include amortization and deprecia-
tion of the investment cost, operation and maintenance costs and
monitoring costs. The summation curves included in each of the
supplements present the cost of each alternative as a plot of
annual cos? ($/yr) versus plant flow (mgd). The dollar base is
4th quarter 1976.
345
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Investment (Capital) Cost Basis
Investment costs (capital expenditures) include:
1. Major and auxiliary equipment,
2. Piping and pumping,
3. Freight,
4. Sitework,
5. Installation,
6. Contractor's fees,
7. Electrical and instrumentation,
8. Yard piping,
9. Engineering, and
10. Contingency.
For technologies currently in use, i.e., chemical precipitation,
sedimentation, cyanide precipitation, vacuum filtration, multi-
media filtration, pH adjustment, activated alumina adsorption,
activated carbon adsorption, steam stripping, reverse osmosis,
and flow reduction using holding tank and cooling towers, cost
data were gathered from current bids, from the literature and
from other sources as described above.
The cost information was equalized by updating or backdating all
the costs to the 4th quarter of 1976. The national average
EPA-Sewage Treatment Plant (STP) index and the EPA-Large City
Advanced Treatment (LCAT) index were both considered for use in
updating the costs for preliminary engineering estimates. The
EPA-LCAT index was chosen most often because its component mix is
indicative of the treatment processes presented herein, and was
used by a majority of the references from which costs were
obtained. The 4th quarter 1976 value of this index is 130, while
the 1976 value of the EPA-STP index is 262. It should also be
noted that the costs presented here are averages for the nation
and, under specific regional market conditions, could vary as
much as 40 percent. The factors in Figure VIII-1 can be used to
modify the average capital costs for a particular location.
Total installed costs were broken into equipment and construction
fractions shown in the table below. These figures represent the
percentage of the installed cost of each item. For example, the
installed cost of chemical precipitation is estimated to be 20
percent equipment and 80 percent construction.
Process Equipment Construction
Chemical Precipitation 20 80
Vacuum Filtration 35 65
Multi-Media Filtration 20 80
pH Adjustment 35 65
Activated Alumina Adsorption 50 50
346
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Process Equipment Construction
Activated Carbon Adsorption 50 50
Steam Stripping 35 65
Reverse Osmosis 50 50
Holding Tank 50 50
Sedimentation 10 90
Cooling Tower 35 65
A contingency allowance of 15 percent of the installed cost was
used to cover unexpected costs due to local plant conditions and
differences between actual systems and those used for the cost
estimates. No allowance was made for plant shutdown during con-
struction. The need for a shutdown is dependent on the layout of
each plant. Engineering costs were estimated by using a percent-
age of the installed cost plus contingencies. The percentage
used was to the nearest 0.5 percent from curve A in Consulting
Engineering (ASCE MOP //45), which is a plot of percent engineer-
ing costs versus construction costs.
Annual Cost Basis
Amortization. The annual cost of capital is a function of the
investment cost, the interest rate, and the period of amortiza-
tion. For the cost curves contained in this document and in the
supplements, the capital costs were amortized at an interest rate
of 7.75 percent over a 20-year period. This results in an annual
cost of capital of 10 percent of the investment. The amortiza-
tion and depreciation costs in this document are presented for
the sake of completeness. The economic impact analysis document
should be consulted for the methods of amortization and deprecia-
tion that were actually used to assess the economic impact for
this category. A summary of these methods is presented in the
specific plant costing section below.
Depreciation. The estimated useful lives of the components of
each alternative were established to calculate depreciation, a
non-cash annual expense that accounts for obsolescence and
retirement of the asset. The useful lives for each component are
estimated as follows:
Technology Useful Life (Years)
Chemical Precipitation 25
Vacuum Filtration 15
Filtration 15
pH Adjustment 15
Activated Alumina Adsorption 15
347
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Technology Useful Life (Years)
Activated Carbon Adsorption 15
Steam Stripping 15
Reverse Osmosis 20
Holding Tank 20
Sedimentation 25
Cooling Tower 15
To calculate the useful life of a treatment option, the sum of
the products of the cost and the useful life for each component
is divided by the sum of the costs. This weights the useful life
by the cost of each component in the alternative. The installed
cost plus contingencies were depreciated on a straight line basis
for the calculated life of each alternative.
Operation and Maintenance Labor. Estimates of the annual man-
hours required to operate and maintain the various systems were
developed from the literature. A productive work value of 6.5
hr/man/day, or 1,500 hr/yr/man was assumed. A rate of $15/hr was
used as the total cost for wages, benefits, and overhead
expenses. Supervisory, administrative, clerical, and laboratory
man-hours were developed and are included in the O&M labor costs.
Figure VIII-2 shows how the wage rates will vary with location
throughout the U.S. The factors shown can be multiplied by the
assumed rate of $15/hr to obtain the wage rate at that location.
Maintenance Materials. The annual costs of materials and parts
needed to maintain each process were developed from the litera-
ture and equipment manufacturers.
Chemicals. The assumptions used to estimate chemical require-
ments are listed below for each module that requires chemicals.
The costs of chemicals were assumed to be as follows:
Chemical Cost ($/ton) - 4th quarter 1976
Lime (CaO) 30
S02 130
Activated Alumina 340
Activated Carbon 1,000
NaOH (50% liquid) 160
H2S04 (66° Be1) 47
Energy and Power. Operating time for all equipment of all the
treatment alternatives, with the exception of vacuum filtration,
was assumed to be 24 hrs/day and 300 days/yr. Vacuum filters
were sized to operate 10 hrs/day, 300 days/yr.
348
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Annual electrical energy consumption values for each component
were developed utilizing the technical literature and equipment
manufacturers' specifications. In developing the costs, all
electric motors were assumed to have an efficiency of 88 percent
and the cost of electricity was assumed to be 3.3 cents/kwh.
This cost value is an average value for the entire U.S. taken
from the industry data collection portfolio responses.
Fuel oil and natural gas costs were also developed from a
representative cross-section of the data collection portfolio
responses and applicable technical literature. National average
costs were determined to be 24 cents/therm for fuel oil and 18
cents/therm for natural gas.
Vacuum filtration energy consumption varies with filter area.
The area, or size of the filter, is dependent on the amount of
sludge to be dewatered which itself is a function of the chemical
precipitation and filtration systems, and of the flow rate being
evaluated. Consequently, energy consumption is dependent on
these criteria also.
Energy consumption for activated carbon is dependent on the flow
and whether the exhausted carbon is regenerated or discarded.
The remaining technologies' consumption is based solely on flow.
Sludge Disposal. In the cost development and economic impact
analysis,sludges from this industry were assumed to be nonhaz-
ardous. However, costs were developed late in the program for
hazardous waste disposal. Based on comments it receives, the
Agency will consider incorporation of these costs into the
economic impact analysis.
For primary smelters and refiners, sludge disposal costs cover
hauling dewatered sludge, exhausted activated carbon, and concen-
trated reverse osmosis brine, when applicable, to an approved
sanitary landfill. These sludges may be disposed of in this
fashion since wastes generated by primary smelters and refiners
are currently exempted from regulation as hazardous waste by an
act of Congress (Resource Conservation and Recovery Act (RCRA),
Secton 3001(b)). The hauling costs for these wastes were
obtained from the literature, and plotted as tons/yr of dry
sludge hauled vs. $/dry ton. A round trip hauling distance of 10
miles was assumed. These costs are depicted in Figure VIII-3.
For secondary smelters and refiners, no such exemption currently
applies, i.e., waste generated by secondary metals operations is
subject to designation as hazardous waste based on its toxicity,
ignitability, corrosivity, or reactivity. Costs for disposal by
sludge hauling of nonhazardous waste are found in Figure VlII-3;
costs for disposal of hazardous wastes were calculated depending
upon the disposal method selected.
349
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Several potentially hazardous wastes, such as furnace slags,
skimming slags, and scrap preparation solids, may be disposed of
in ground sealed dump areas. Capital costs for this method
include sealing, collection ditches, and pumps and piping. Oper-
ation and maintenance costs are estimated at 5 percent of the
capital cost. The investment cost as a function of slag output
is presented in Figure VIII-4.
Wastewater treatment sludges, reverberatory furnace solids,
neutralized spent battery electrolyte (from secondary lead opera-
tions) , and other waste may be disposed of on-site in lined or
unlined disposal ponds, or by contract hauling. The capital
costs for the impoundment method include pond excavation and
diking, liner (as necessary), and monitoring wells and equipment.
Direct operating costs were estimated at 8 percent of the capital
cost, and largely consisted of maintenance, taxes, and insurance.
The capital costs for this method are presented in Figure VIII-5.
Contract hauling costs for hazardous sludges and solid waste are
a function of the distance to the disposal site, the costs
incurred by the hauler to meet the RCRA requirements for trans-
portation of hazardous materials, and the disposal site costs.
Figure VIII-6 displays the transportation costs for hazardous
sludges, based on a 20 to 25 ton shipment. These costs should be
combined with the appropriate contract hauling costs presented in
Table VIII-1. Costs are tabulated for disposal of sludge (i.e.,
greater than 5 percent free liquid) in 55-gallon drums or in bulk
shipment, and for solids (i.e., less than 5 percent free liquid)
in bulk shipment.
Casting lubricants consist of oil-water mixtures that are often
emulsified. In some cases these lubricants may represent a
hazardous material. Costs for separation of the oil and water
fraction are presented in Figure VIII-7. Capital costs include a
staged mixer-settler, with addition of a flocculant or
de-emulsifier. Direct operating costs are estimated at 40 per-
cent of the capital cost, of which approximately 75 percent is
labor-related. The oil separated in the settler may be contract
hauled or sold.
Sludge disposal costs are included for technology options using
chemical precipitation and sedimentation with and without
filtration, activated alumina, activated carbon, and reverse
osmosis. The sludge generation assumptions and factors are
discussed within each module description below.
Monitoring. The costs are based on collecting samples of the
influent and effluent streams of the treatment plant. The
sampling schedule is for 24-hour composite samples to be taken
once per week. Continuous monitoring of the pH and flow is also
provided for the influent and effluent of all treatment plants.
350
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The equipment items include two flow meters, two primary and one
backup refrigerated samplers, two pH meters, refrigerated sample
storage containers, and a refrigerator. The costs are based on
equipment manufacturers' price lists. The annual labor require-
ments for laboratory work range from 40 hours at 0.01 mgd to
3,500 hours at 20 mgd.
Monitoring costs include outside laboratory analytical charges
and time for reporting results to regulatory agencies. The costs
associated with collecting and delivering samples are included
under operation and maintenance labor.
Sampling frequency was assumed to be once per week of both the
influent and effluent. Criteria pollutants (conventional and
nonconventional pollutants) are analyzed once per week and prior-
ity pollutants are analyzed once per month.
Laboratory cost estimates were June, 1978 commercial laboratory
price lists. Reporting costs were based on $15/hr and included 2
hr/week for compiling data plus 8 hr/month for preparing reports.
TECHNOLOGY BASIS FOR COST DEVELOPMENT
The treatment alternatives considered as the basis for BPT and
BAT limitations consist of in-process control steps and end-of-
pipe treatment technologies. The following subsections present
the elements of each control and treatment step for which costs
were prepared. These include:
--Recycle
--Steam Stripping
--Cyanide Precipitation
--Primary Sedimentation
—pH Adjustment
--Chemical Precipitation, Sedimentation, Gravity Thickening,
Vacuum Filtration
—Multimedia Filtration
--Activated Carbon Adsorption
—Activated Alumina Adsorption
--Reverse Osmosis, Evaporation
Recycle
The in-plant control measures that exist in or are available to
plants in the nonferrous metals category are discussed in Section
VII of the supplements. The incorporation of in-plant controls
into the processes of an existing source can be a cost-effective
means of reducing pollutant and hydraulic loadings and thereby
the cost of treatment facilities. Recycle of various process
streams is the most common in-plant control suggested for BAT. A
description of the recycled streams is provided in Section VIII
351
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of each supplement, and the costs of the recommended in-plant
controls are included for each treatment scheme in the summation
curves of annual costs. In some cases, the costs associated with
equipment installed to provide flow reduction are presented
separately from the summation curves.
Holding tanks or a cooling tower are the principal cost elements
for recycle or reuse of certain plant wastewaters. These two
items will be discussed together as they are incorporated into
the various treatment schemes to provide flow reduction through
recycle. A cooling tower is costed for reduction of flow from
casting contact cooling water, and holding tank(s) is costed for
reduction of flow from wet air pollution control equipment.
The investment costs for a holding tank include tanks, pumps, and
1,000 ft of piping with the tanks sized to store one day of flow.
There are no operation and maintenance costs associated with a
holding tank. The investment costs for a cooling tower assume
the use of a mechanical draft tower and include the tower, pumps,
305 meters (1,000 ft) of piping, fans and packing. The sizing of
the tower is based on a range of 13.9°C (25°F), an approach
(driving force) temperature of 5.6°C (10 F), and a wet bulb tem-
perature of 21.11°C (70°F). The OScM labor requirements varied
from 82 hr/yr at 0.6 mgd to 1,340 hr/yr at 20 mgd. Maintenance
materials were assumed as 3 percent of the installed cost.
Energy requirements are for the forced draft fans, which vary
from 1.7 hp at 0.1 mgd to 200 hp at 10 mgd.
Steam Stripping
A stripping tower and steam are used to remove ammonia from the
wastewater. The investment costs include a stripping tower, a
boiler, and a blower. A surface loading rate of 81.5 1/min-m2
(2 gpm/ft^) was assumed along with a steam requirement of 1
pound of steam per gallon of wastewater treated.
OStM labor requirements ranged from 21 hr/yr at .1 mgd to 1,330
hr/yr at 20 mgd. Maintenance materials were assumed at 3 percent
of the investment cost. Costs for steam, electrical require-
ments, and chemicals were also included.
Cyanide Precipitation
In this wastewater treatment technology, cyanide is reacted with
ferrous (or zinc) sulfate in the presence of H2S03 and then
raised to pH 9.0 to form a variety of precipitates that may best
be represented as Fe4(FeCNg)3 (Prussian Blue). This sys-
tem, which closely resembles a conventional chemical precipita-
tion operation, includes chemical feed equipment for sodium
hydroxide and ferrous sulfate addition, a reaction vessel,
agitator, control system, clarifier, and pumps.
352
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Costs are estimated for both batch and continuous systems with^
the operating mode selected on a least cost basis. This decision
is a direct function of flow rate. Capital costs are composed of
five subsystem costs: (1) FeSC-4 feed system, (2) NaOH feed
system, (3) reaction vessel with agitator, (4) clarifier, and
(5) recycle pump. These subsystems include the following equip-
ment :
(1) Ferrous sulfate feed system
ferrous sulfate steel storage hoppers with dust
collectors (largest hopper size is 6,000 ftj; 15
days storage)
enclosure for storage tanks
volumetric feeders (small installations)
- mechanical weigh belt feeders (large installations)
- dissolving tanks (5 minute detention time, 6 percent
solution)
- dual-head diaphragm metering pumps
instrumentation and controls
(2a) Caustic feed system (less than 200 Ib/day usage)
volumetric feeder
- mixing tank with mixer (24-hour detention, 10
percent solution)
- feed tank with mixer (24-hour detention)
dual-head metering pumps
instrumentation and controls
(2b) Caustic feed system (greater than 200 Ib/day usage)
- storage tanks (15 days, FRP tanks)
- dual-head metering pumps including standby pump
instrumentation and controls
(3) Reaction tank (5 minutes detention time, stainless
steel, agitator mounting, agitator, concrete slab)
(4) Clarifier tank (based on 700 gpd/ft2; to include a
steel or concrete vessel (depending on flow rate),
support structure, sludge scraper assembly and
drive unit)
(5) Recycle pumps (for sludge and supernatant)
Operation and maintenance costs for cyanide precipitation include
labor requirements to operate and maintain the system, electric
power for mixers, pumps, clarifier and controls and treatment
chemicals. Electrical requirements are also included for the
353
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chemical storage enclosures for lighting and ventilation and in
the case of caustic storage, heating. The following criteria are
used in establishing O&M costs.
(1) Ferrous sulfate feed system
maintenance materials - 3 percent of manufactured
equipment cost
labor for chemical unloading
--5 hr/50,000 Ib for bulk handling
--8 hr/16,000 Ib for bag feeding to the hopper
--routine inspection and adjustment of feeders is
10 min/feeder/shift
maintenance labor
--8 hr/yr for liquid metering pumps
--24 hr/yr for solid feeders and solution tank
power (function of instrumentation and control,
metering pump hp and volumetric feeder (bag feed-
ing))
(2) Caustic feed system
maintenance materials - 3 percent of manufactured
equipment cost (excluding storage tank cost)
labor/unloading
--dry NaOH - 8 hr/16,000 Ib
--liquid 50 percent NaOH - 5 hr/50,000 Ib
labor operation (dry NaOH only) - 10 min/day/feeder
labor operation for metering pump - 15 min/day
annual maintenance - 8 hr
power (includes metering pump hp, instrumentation
and control, volumetric feeder (dry NaOH))
(3) Clarifier
maintenance materials range from 0.8 percent to 2
percent as a function of increasing size
labor - 150 to 500 hr/yr (depending on size)
power - based on horsepower requirements for sludge
pumping and sludge scraper drive unit
(4) Reaction vessel with agitator
maintenance materials - 2 percent of equipment cost
labor
--15 min/mixer/day routine O&M
--4 hr/mixer/6 mos - oil changes
--8 hr/yr - draining, inspection, cleaning
power - based on horsepower requirements for
agitator
354
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(5) Recycle pump
maintenance materials - percent of manufactured
equipment cost variable with flow rate
50 ft TDH; motor efficiency of 90 percent and pump
efficiency of 85 percent
Annual costs for treatment chemicals are determined from cyanide
concentration, pH, metals concentrations, and flow rate of the
raw waste stream.
pH Adjustment
H2S04 (66° Be1) or NaOH (50 percent NaOH) are utilized to
obtain desired pH values at various points in any given alterna-
tive sequence. The investment costs include:
(1) Chemical feed system
bulk storage tank
dry tank
mixer
flow regulator
(2) Concrete tank (detention time, 15 minutes)
(3) Mixing equipment
(4) Instrumentation
(5) Sump pump
Operating costs are based on the following assumptions:
(1) Sulfuric acid dose rate of 0.5 pound per 1,000 gallons
of wastewater.
(2) Caustic dose rate of 0.5, 5, and 20 pounds per 1,000
gallons of wastewater.
Labor and energy costs were assumed to be equal for all alkali
and acid dose rates. Energy requirements on a system basis are
linear from 10,000 gal/day at 660 Kw-hr/yr and increase to 14,000
Kw-hr/yr at 10 mgd.
Chemical Precipitation, Sedimentation, Gravity Thickening, Vacuum
Filtration
This process is used to remove dissolved metals as metal hydrox-
ides. Precipitation occurs through addition of lime (Ca(OH)2)
to the wastewater; the hydroxides are removed by settling in a
355
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sedimentation device, usually a clarifier. The overflow is
routed to further treatment or discharged while the underflow
sludge is sent to sludge dewatering in a vacuum filter, sometimes
preceded by concentration in a sludge thickener.
Lime was selected as the precipitant because of its comparatively
low cost coupled with its proven effectiveness in the category.
While it is recognized that caustic, iron salts, and sulfides may
be more appropriate in some applications, costs for these precip-
itants and feed systems are comparable to the lime-based system
relative to the overall costs of a chemical precipitation unit.
The equipment included in this system is as follows:
(1) Lime feed system
- storage units (30 days storage)
- dilution tanks (slaker as necessary)
metering pumps
(2) Rapid mix tank and agitator (5 minutes detention time)
(3) Clarifier (hydraulic loading rate of 0.5 gpm/ft2)
concrete or steel
sludge rake
(4) Gravity thickener
(5) Vacuum filter
motor and drive
piping and pumps
vacuum system
- rotary filter (4 lb/hr/ft2)
(6) Auxiliaries
(7) Control system
To specify lime dosages, specific model wastewater matrices (or
cases) were developed from examination of untreated wastewater
data in the industry. The lime dosages for the various waste
stream combinations could be classified into the different cases
based on the lime requirements for each component stream, which
in turn were calculated from the concentrations of pollutants in
the stream that consume lime. These lime dosages will also
affect the amount of sludge produced from the system. The cases,
lime dosages, and sludge generation factors are presented in the
following tabulation:
356
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Case Lime Dosage (mg/1) Sludge (Ib/mil gal)
1 16,000 500,000
2 7,300 250,000
3 2,500 100,000
4 1,100 50,000
5 580 25,000
6 285 10,000
7 50 1,500
Units were sized for these cases based on an overflow rate of
40.75 nH/day-m2 (1,000 gpd/ft2) for sedimentation and an
application rate of 122 kg/day-m2 (25 Ib/ft2/day) for gravity
thickening. OScM labor requirements for lime precipitation and
sedimentation vary from 1,450 hours at 0.01 mgd to 4,950 hours at
20 mgd.
The investment costs for vacuum filtration were developed in
terms of the amount of sludge to be dewatered. The sludge
generation factors listed on the preceding table are exclusive of
multimedia filtration backwash solids and other sludges produced
in the treatment system but dewatered on the vacuum filter. The
extra capacity required to handle these sludges is calculated for
each sludge-generating module, so that the vacuum filter is
adequately sized. The generation of these other sludges is
described in the appropriate module discussion. The filter area
was calculated using a dry solids loading rate of 19.53
kg/m2/hr (4 Ib/ft2/hr) and an operating period of 10 hrs/day.
0&M labor requirements for vacuum filtration vary from 1,635
manhours at 0.01 mgd to 29,100 manhours at 10 mgd.
Multimedia Filtration
Multimedia filtration is used as a wastewater treatment polishing
device to remove suspended solids not removed in previous treat-
ment processes. The filter beds consist of graded layers of
gravel, coarse anthracite coal, and fine sand. The equipment
used to determine capital and annual costs follow:
1. Filter tank and media
2. Surface wash system
3. Backwash system
4. Valves
5. Piping
6. Controls
7. Electrical system
357
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The hydraulic loading rate used was 163 1/min-m2 (4 gpm/ft2).
Specific cases were developed for filtration as follows:
Case TSS Removed (mg/1)
1 100
2 50
3 15
4 5
The solids carried over to the filter from chemical precipitation
have a direct influence on the solids being recycled in the back-
wash to the secondary clarifier and therefore add to the sludge
volume applied to the vacuum filter. The additional sludge was
accounted for in each case by multiplying the TSS removed by the
flow rate. For options where multimedia filtration is included,
the extra capacity required for the vacuum filter to dewater the
backwash solids was included.
O&M labor requirements vary from 45 manhours at 0.01 mgd to 3,400
manhours at 20 mgd.
Activated Carbon Adsorption
Activated carbon is used primarily for the removal of organic
compounds from wastewater. The capital and annual costs for this
process are based on a system using granular activated carbon
(GAG) in a series of downflow contacting columns.
The effectiveness of activated carbon in removing the organic
priority pollutants has not yet been demonstrated in the non-
ferrous metals category. Reports are available, however, that
discuss the degree of adsorbability of activated carbon for the
individual priority toxic organics. Based upon these reports,
conservative estimates have been made for removals by carbon and
its exhaustion rates under different operating conditions. An
exhaustion rate of .18 kg/m3 (1,500 Ib/mil gal) was assumed for
all subcategories except secondary silver. A .66 kg/in-* (5,500
Ib/mil gal) and 1.49 kg/m3 (12,400 Ib/mil gal) exhaustion rate
was assumed for secondary silver, nonphotographic and
photographic unit processes, respectively.
Two methods of replacing spent carbon were considered: (1) ther-
mal regeneration of spent carbon and (2) replacement of spent
carbon with new carbon and disposal of spent carbon. Thermal
regeneration of spent activated carbon is economically practical
only at relatively large carbon exhaustion rates. Simply replac-
ing spent carbon with new carbon is more practical than thermal
regeneration for plants with low carbon usage.
358
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An economic analysis was performed to determine the carbon usage
rate at which thermal regeneration of spent carbon becomes prac-
tical. It was determined that thermal regenerating facilities
are practical above a carbon usage of 105,000 kg/yr (230,000
Ibs/yr). Plants not regenerating carbon on-site were assumed to
dispose of the spent carbon using the exhaustion rates described
above. Plants for which regeneration would occur on-site were
assumed to generate no carbon wastes to be disposed.
Thermal regeneration is assumed to be accomplished with multiple
hearth furnaces at a loading rate of 40 pounds of carbon per
square foot of hearth area per day. Activated carbon thermal
regeneration facilities include a multiple hearth furnace, spent
carbon storage and dewatering equipment, quench tank, screw
conveyors, and regenerated carbon refining and storage tanks.
A 30-minute empty-bed contact time was used to size the downflow
contacting units. The activated carbon used in the columns was
assumed to have a bulk density of 26 pounds per cubic foot.
Included in the capital for a carbon contacting system are carbon
contacting columns, initial carbon fill, carbon inventory and
storage backwash system, and wastewater pumping.
OStM labor requirements are dependent upon whether carbon is
regenerated. In the adsorption only case, annual manhour
requirements vary from 100 at 0.1 mgd to 4,700 at 20.0 mgd. If
carbon is regenerated, annual manhour requirements vary from 140
at 0.01 mgd to 17,500 at 20 mgd. The activated carbon process
incurs chemical costs for the replacement of carbon. For small
plants that find it more economical to discard the carbon after
exhaustion, the entire carbon inventory is replaced according to
the exhaustion rate. For those plants that utilize on-site
regeneration, it was assumed that 8 percent of the carbon is lost
during each regeneration and must be replaced.
Activated Alumina Adsorption
Contact columns containing alumina are used to remove arsenic and
fluoride. The backwash and spent regenerant are both recycled to
the chemical precipitation unit for removal of the concentrated
pollutants.
The investment costs are based on a system using activated
alumina in contacting columns, acid and caustic feed systems, a
control system, and pumping and piping. A surface loading rate
of 122 1/min-m2 (3 gpm/ft2) was assumed with an alumina
adsorption capacity of 0.5 percent by weight for fluoride and
arsenic.
Activated alumina manpower requirements are based on activated
carbon and ion exchange labor requirements. The values vary from
359
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210 manhours per year at 0.01 mgd to 5,200 manhours per year at
20 mgd. Activated alumina chemical usage includes sulfuric acid
(66° Be1) and sodium hydroxide (50 percent NaOH) for regenera-
tion, and replacement of activated alumina. For regeneration,
four bed volumes of 1 percent NaOH and one bed volume of .05N
H2S04 are needed every two days. A replacement rate of 10
percent per year for activated alumina was assumed.
Reverse Osmosis, Evaporation
To remove selected ions from the wastewater streams, a reverse
osmosis unit with prefiltration cartridges is used. The result-
ing brines are further concentrated into a disposable sludge by
multiple-effect evaporators.
The equipment in this module includes:
1. Holding tank
2. Prefiltration cartridge
3. Membranes
4. Membrane housing
5. Feed and brine pumps
6. Mechanical evaporation system
7. Instrumentation and control system
Costs were based on a recovery of 85 percent of the flow through
the reverse osmosis unit at 600 psi, a 95 percent solids rejec-
tion rate, and a 98 percent reduction in the brine flow through
the mechanical evaporator. The brine is evaporated to 25 percent
solids, which is contract hauled.
The reverse osmosis labor requirements varied from 7,300 manhours
per year at 0.6 mgd to 22,000 manhours per year at 20 mgd. Main-
tenance items include the membranes, which were assumed to have a
2-year life. Energy requirements include steam for evaporation
and electricity for the pumps.
NEW SOURCES
The technology options considered for new sources are identical
to those considered for existing sources. Additional flow reduc-
tion is being proposed for primary aluminum based on the elimina-
tion of wet scrubbers in this subcategory, and for the primary
lead subcategory based on the elimination of slag granulation,
since the use of dry scrubbers and slag dumping is currently
demonstrated at several plants in the affected subcategories.
EPA assumes, therefore, that the application of these technol-
ogies in some existing plants is based on a determination that
any incremental cost of these technologies over other practices
is offset by savings in end-of-pipe treatment costs or specific
manufacturing costs.
360
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COST METHODOLOGY FOR SPECIFIC PLANTS
The capital and operating costs for each treatment option are
used to analyze the economic impact of the proposed regulations
on each subcategory (see Economic Impact Analysis for Effluent
Guidelines and Standards for the Nonferrous Metals Manufacturing
Point Source Category, EPA" 1983) . The approach used is to
estimate the compliance costs for each plant in the subcategory,
accounting for the specific combination of wastewaters, the
wastewater flow, and the existing treatment system at the plant.
These plant-specific cost estimates for the nonferrous metals
category were developed over an extended time period during which
several changes in the approach to regulation of the category
have been made. The cost estimation procedure reflects these
changes.
First, amortization of the capital investment was originally
assumed to be based on a 7.75 percent interest rate over a
20-year period. Although costs presented in the curves in each
supplement reflect these assumptions, updated values of 10
percent interest over 10 years were used for the specific plant
costs in the economic impact analysis. The revised amortization
interest rate and period will also be reviewed and updated as
necessary before final promulgation of the regulation.
Second, the Agency originally chose to use actual wastewater
flows in the sizing and costing of cooling towers to treat con-
tact cooling water prior to recycle. Similarly, actual flows
were also used to size and cost holding tanks to treat wet air
pollution control wastewater prior to recycle. As a result, the
estimated costs may be high for some plants. The Agency is
currently considering the use of regulatory flows in sizing this
equipment, i.e., a cooling tower or holding tank would be sized
to handle the BPT regulatory flow for the appropriate wastewater.
EPA requests comments on this approach.
NONWATER QUALITY ASPECTS
The elimination or reduction of one form of pollution may aggra-
vate other environmental problems. Therefore, Sections 304(b)
and 306 of the Act require EPA to consider the nonwater quality
environmental impacts (including energy requirements) of certain
regulations. In compliance with these provisions, EPA has con-
sidered the effect of this regulation^on air pollution, solid
waste generation, and energy consumption.
361
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Air Pollution, Radiation and Noise
Various forms of both wet and dry air pollution control methods
are utilized throughout the category. Replacement of wet systems
by dry systems will reduce the pollutant loading discharged in
the plant effluent. The alternatives for BAT presented in this
document assume that those plants presently using wet air pollu-
tion control systems would not change to dry systems since retro-
fit costs would be high. As previously discussed, it is assumed
that new sources will install dry systems instead of wet systems
where dry systems have been demonstrated.
In general, none of the wastewater treatment or control processes
causes air pollution. Steam stripping of ammonia has a potential
to generate atmospheric emissions. With proper design and opera-
tion, however, air pollution impacts are eliminated. None of the
wastewater treatment processes causes objectionable noise and
none of the treatment processes has any potential for radiation
hazards.
Solid Waste Disposal
As shown in the supplements, the waste streams being discharged
contain large quantities of toxic and other metals ; the most
common method of removing the metals is by lime precipitation.
Consequently, large volumes of heavy metal-laden sludge are
generated that must be disposed of properly. Table VIII-2
summarizes the methods currently in use, along with their
frequency of occurrence, for treating and disposing of sludges.
The technologies that directly generate sludge are:
1. Cyanide precipitation
2. Chemical precipitation
3. Multimedia filtration
4. Primary sedimentation
5. Reverse osmosis
Sludge is also indirectly generated by the recycling of the spent
activated alumina regenerant, containing fluoride or arsenic, to
the chemical precipitation unit. Spent carbon from activated
carbon adsorption also represents a solid waste stream requiring
disposal.
The sludge resulting from the five technologies listed above will
vary in characteristics depending on the subcategory and combina-
tion of streams being treated. However, in most cases, the
majority of the sludge produced is a result of chemical precipi-
tation. This sludge will, in general, contain large quantities
of precipitated metals. The sludge indirectly generated from
activated alumina adsorption will contain large quantities of
fluoride or arsenic.
362
-------
A major concern in the disposal of sludges is the contamination
of soils, plants, and animals by the heavy metals contained in
the sludge. The leaching of heavy metals from sludge and subse-
quent movement through soils is enhanced by acidic conditions.
Sludges formed by lime precipitation possess high pH values and
thus are more resistant to acid leaching. Since the largest
amount of sludge that results from the alternatives is generated
by lime precipitation, it is not expected that metals will be
readily leached from the sludge. Disposal of sludges in a lined
sanitary landfill will further reduce the possibility of heavy
metals contamination of soil, plants and animals.
Other methods of treating and disposing of sludge are available.
Table VIII-2 shows that one method currently being used at a
number of plants is reuse or recycle, usually to recover metals.
Since the metal concentrations in some sludges may be substan-
tial, it may be cost effective for some plants to recover the
metal fraction of their sludges prior to disposal.
The Solid Waste Disposal Act Amendments of 1980 prohibited EPA
from regulating certain wastes under Subtitle C of RCRA until
after completion of certain studies and certain rulemaking.
Among these wastes are "solid waste from the extraction, benefi-
ciation and processing of ores and minerals." EPA has therefore
exempted from hazardous waste status any solid wastes from pri-
mary smelting and refining, as well as from exploration, mining,
and milling.
The Agency has not made a determination of the hazardous char-
acter of sludges and solid wastes generated from the secondary
metals processing plants covered by this proposal. Each sludge
generator in the secondary metals subcategories is subject to the
RCRA tests for ignitability, corrosivity, reactivity, and
toxicity. Costs for treatment and disposal of such sludges and
solid wastes, as well as nonhazardous sludges and solid wastes,
have been presented in this section.
Energy Requirements
The incremental energy requirements of a wastewater treatment
system have been determined in order to consider the impact of
this regulation on natural resource depletion and on various
national economic factors associated with energy consumption.
Based on the data collection portfolios, the median values for
total plant energy consumption and wastewater flow rate were
calculated for each subcategory. Within each subcategory, each
treatment system option may vary somewhat depending on the
wastewater combination being treated. For example, Option A in
the primary tungsten subcategory includes steam stripping of
ammonia only for discharges from specific unit operations.
363
-------
Energy requirements were always calculated using the configura-
tion for each option that would consume the most energy, i.e.,
the maximum energy requirement was always calculated.
Table VIII-3 presents these energy requirements in Kwh/yr for
each subcategory and option. The percent increase in total plant
energy requirements attributable to the treatment system is also
presented on the table. Blanks appear in the table where that
option was not relevant to that subcategory. By reviewing this
table, it can be seen that the additional energy required is
greater than 1 percent only for Option F (which includes reverse
osmosis), and then only for certain subcategories. As a result,
the Agency has concluded that the energy requirements of the pro-
posed treatment options will not significantly affect the natural
resource base nor energy distribution or consumption in communi-
ties where plants are located.
364
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u>
&
Ul
Type of Waste
Sludge Disposal
Solids Disposal^
Table VIII-1
COSTS OF CONTRACT HAULING2
Method
of Shipment $/Gal
Drums - 55 Gallon 0.91
20-25 Ton Shipments 0.70
20-25 Ton Shipments
$/Ton
(Wet Basis)
Percent Solids
10
1,750
1,350
2C)
875
675
580
450
$/Ton
(Dry Basis)
1751
1351
100
iDensity = 78 Ib/ft3
not include cost of transportation.
than five percent free liquid.
-------
Table VIII-2
EXISTING SLUDGE TREATMENT METHODS*
Gravity Vacuwa Filter Centri- Kilo Incio- Calci- Contractor Drying Land- Reuse/
PriMry
Aluminum
Secondary
Columbia*/
Tantalum
(Ore)
Columbium/
Tantalum
(Salt)
Primary
Copper
(Smeltera)
PriMry
Copper
(Refinera)
Secondary
Copper
PriMry Lead
7
7
0
1
6
3
4
2
5
2
0
0
0
0
2
3
1
0
1
0
1
1
1
0
0121
0000
0000
1000
00 00
0000
1000
00 00
1 1
1 1
0 0
0 0
0 1
1 0
0 0
0 1
13 11
4 6
1 1
0 0
6 0
3 2
3 6
0 1
1
1
0
0
0
0
3
0
5
0
0
1
3
0
4
4
*Number of plants using sludge disposal and treatment methods.
-------
Table VIII-2 (Continued)
EXISTING SLUDGE TREATMENT METHODS*
LO
Gravity VecutMi Filter Centri- Kilo locin- Calci- Contractor Drying Land- Reuse
Thickening Filter Preaa fuge Drying eration nation Dispoaal Beda Lagooning fill Sale Recycle
Secondary
Lead
Secondary
Silver
(Photo)
Secondary
Silver
(Non-Photo)
Primary
Tungaten
(Ore)
Priawry
Tung* tea
(Salt)
Primary Zinc
TOTAL
4
3
2
2
1
3
45
6
2
1
3
0
3
27
1
2
0
2
0
0
10
0
0
2
0
0
1
5
0
0
0
0
0
0
1
0 0
2 0
0 0
0 0
0 0
0 0
4 1
3
1
2
0
0
1
10
3
0
4
0
0
1
12
2
0
2
1
I
1
37
7
0
2
2
0
3
41
0
5
0
1
1
1
13
• 11. i —»>
9
4
4
0
1
2
37
^Number of plants using sludge disposal and treatment methods.
-------
Table VIII-3
MAXIMUM ENERGY REQUIREMENT (Kwh/yr) AND ESTIMATED PERCENT OF
PLANT TOTAL FOR ENTIRE TREATMENT SYSTEM
oo
Total Plant
Bwrgy OonouBptton
Subcategpry
Prinary Alunlmn
Secondary Alumliui
Primary CojUnbturTantalm
Prinary Copper
Secondary Copper
Primary Lead
Secondary Lead
Secondary Silver
Primary Toigs ten
Primary Zinc
QMi/yr)
1.28 x 108
8.15 x 107
6.19 x 107
2.55 x 10s
3.35 x 1011
2.30 x 108**
2.29 x 107
1.02 x 107
3.64 x 107
5.51 x 10"
Median
Site Plant
by Flo*
(B»»)
1,200,000
4,280
59,000
1,640,000
7,600
1,240,000
5,760
521
172,000
675,000
Option*
Uaage
2.41 x 10s
3.66x10*
6.56 x 10*
1.64 x 10*
2.42 x 10*
7.14 x 103
1.90 x 10s
Poxcnt.
0.19
0.045
0.11
0.05
0.11
0.07
0.52
Option B
Uaag
3.75 x
6.56 x
3.87 x
3.92 x
2.23 x
1.90 x
1.51 x
!
10*
10*
ID*
10*
10*
10*
10*
Percent
0.29
0.11
0.15
0.17
0.22
0.52
0.003
Option C Option D Option B Option P
Uaage
4.1 xlO5
3.66 x 10*
6.73 x 10*
3.9 x 10s
1.66 x 10*
3.95x10*
2.23 x 10*
2.01 x 108
3.51 x 10*
Percent Ueaae
0.32 4.53 x 10s
0.045
0.11 6.94 x 10*
0.15
0.05
0.17 4.13 x 10*
0.22
0.35
0.006 8.20 x 10*
Pezuont Unga Peccant UMge
0.35* 1.05 x 10* 0.82* 3.72 x 10*
5.33 x 10*
0.11 9.63 x 10* 0.16 2.62 x 10s
6.50 x 10s
6.4 x 10*
0.18 6.15 x 10*
2.58 x 10* 0.25
2.93 x 105 0.805 7.41 x 10s
0.01 1.99 x 10*
Percent
2.9
0.065
0.42
0.25
2.8
0.27
2.0
0.36
"Option D and Option E correspond to Option t>i and Option Dj in the priaary aludiua wpplaaent.
**Ihia la the energy conraiptlon of the alngle discharger In the priaary lead eubcategary.
-------
Boston
(1.12)
Now York (1.30)
TronlofidOe)
Philadelphia (1.19)
Baltimore (1.03)
UJ
a-
Atlanta
plnnlnghaftyo.82)
(0.79)
National Avtragc *I.OO
Miami (0.69)
Figure VIII-1
GEOGRAPHICALLY DISTRIBUTED CAPITAL COST FACTORS
-------
Notional Avarag* *I.OO
Figure VIII-2
GEOGRAPHICALLY DISTRIBUTED WAGE RATE FACTORS
Boston
(107)
Now York (1.16)
Trenton (1.06)
Philadelphia (I.II)
Baltlmor«(l.02)
Miami 10.92)
-------
100
90
80
70
6O
50
40
30
20
10
I ' • ' ' I ' ' ' ' I • ' '
I
l .
500 1000 1500 2000 2500
DRY TONS HAULED /YEAR
Figure VIII-3
SLUDGE HAULING COSTS
10 MILE ROUND TRIP
NONHAZARDOUS WASTES
3000
371
-------
CAPITAL COST (thousands of 1982 dollars)
T 1 T
SLAG OUTPUT {million tons per year)
NOTE: Direct operating cost is equal to 5 percent of capital cost.
Figure VIII-4
COST OF SEALING GROUND AT SLAG DUMP
-------
CAPITAL COST (thousands of 1982 dollars)
10*
T
10'
T 1 1—i—rr
Lined
10"
. . . .1 I
t nrl
J L
. . ..I L
0"
10
NOTE: Direct operating cost is equal to 8 percent of capital cost
Figure VIII-5
COST OF LINED AND UNLINED STORAGE PONDS
10'
POND VOLUME (million cubic feet)
-------
U>
DIRECT OPERATING COST (1982 dollars per ton of watte)
20 r~i i i i i n i i i i i i r~i i i i • i r
18
16
14
12
8
6
0
T
T I II I I I I
T| I
I I I I I I I I I I I I I
I 1 1 I I I I I I I I I I I I I I I I I I I I I I I 1 I I I
10 20 30 40 50 60
70 80 90 100
DISTANCE FROM PLANT TO DISPOSAL (miles)
NOTE: Costs are based on 20 to 25 ton shipment.
Figure VIII-6
COST OF TRANSPORTING WASTE MATERIALS
-------
01
CAPITAL COST (thousands of 1982 dollars)
i ^3
10'
T T
J I _L
NOTE: Direct operating cost is equal to 40 percent of capital cost.
10"
Figure VIII-7
COST OF OIL SEPARATION
1 1 r
J I L
FLOWRATE (gallons per day)
-------
SECTION IX
EFFLUENT QUALITY ATTAINABLE THROUGH APPLICATION OF THE
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
This section sets forth the effluent limitations attainable
through the application of best practicable control technology
currently available (BPT). It also serves to summarize changes
from previous rulemakings in the nonferrous metals manufacturing
category, and presents the development and use of the mass-based
effluent limitations.
A number of considerations guide the BPT analysis. First, efflu-
ent limitations based on BPT generally reflect performance levels
achieved at plants in each subcategory equipped with the best
wastewater treatment facilities. The BPT analysis emphasizes
treatment facilities at the end of a manufacturing process but
can also include in-plant control techniques when they are con-
sidered to be normal practice within the subcategory. Finally,
the Agency closely examines the effectiveness of the various
treatment technologies by weighing the pollutant reduction
benefits achievable by each treatment alternative and assesses
the installation and operational costs to enable it to determine
the economic achievability of each option.
The limitations are organized by subcategory, i.e., limitations
are presented by subcategory in Section II. The limitations were
developed based on the sampling, treatability, and cost data that
have been presented in this document. The analysis has resulted
in a number of modifications to existing BPT effluent
limitations.
TECHNICAL APPROACH TO BPT
In the past, the technical approach for the nonferrous metals
manufacturing category considered each plant as a single waste-
water source, without specific regard to the different unit
processes that are used in plants within the same subcategory.
This approach is appropriate for BPT which is generally based
upon end-of-pipe technology. In-process controls are generally
not used to establish BPT; however, they may be used as the basis
of BPT when they are widely demonstrated in the category. In
reevaluating the existing BAT regulations and developing new BAT
regulations, the Agency closely examined each process and the
ootential for implementing in-process controls. It became
apparent that it^as best to establish effluent limitations and
standards recognizing specific waste streams associated with
specific manufacturing operations. This also results in more
effective pollution abatement by tailoring the regulation to
reflect these various wastewater sources. Currently promulgated
377
-------
BPT effluent limitations using this approach will not be modified
unless there is sufficient data supplied to the Agency demon-
strating the need for change.
This approach, referred to as the building block approach,
establishes pollutant discharge limitations for each source of
wastewater identified within the subcategory. Each wastewater
source is allocated a discharge based on the average reported
discharge rates for that source. These flows are normalized
(related to a common basis) using a characteristic production
rate associated with the wastewater source (volume of wastewater
discharged per unit mass of production). The mass limitations
established for a wastewater source are obtained by multiplying
the effluent concentrations attainable by the selected BPT
technology by the regulatory flow for each wastewater source.
Thus, the specific pollutant discharge allowances for a plant's
final discharge permit are calculated by multiplying the appro-
priate production rates with the corresponding mass limitations
for each wastewater source in that plant, and then summing the
results. This calculation is performed to obtain the one-day and
the maximum monthly average limitations. It is important to note
that the plant need only comply with the mass limitations and not
the flow allowances or concentrations. In cases where process
and nonprocess wastewater sources not specifically regulated by
this proposal exist within the facility, the permit authority
must treat these on a case-by-case basis.
Although each waste stream may not include each selected pollu-
tant, a discharge allowance is provided for all pollutants in
every waste stream because each waste stream contributes to the
total loading of a combined waste treatment system. Since a
discharge allowance is included for each pollutant in every waste
stream, facilities would not be required to reduce pollutant
concentrations below the performance limits of the technology.
Instead, this approach allows plants to achieve the performance
determined for the technology at the plant discharge point.
Therefore, the mass limitations used are the product of the
concentration achievable by the technology and basis of the
limitation and the sum of regulatory flows for each unit process
actually operated at the plant.
In determining the technology basis for BPT, the Agency reviewed
a wide range of technology options and selected six alternatives
which could be applied to nonferrous metals manufacturing as BPT
options. These options include:
1. Option A - End-of-pipe treatment consisting of lime
precipitation and clarification, and preliminary treat-
ment, where necessary, consisting of oil skimming,
cyanide precipitation, and ammonia steam stripping.
This combination of technology reduces toxic metals
and conventional pollutants.
378
-------
2. Option B - Option B is equal to Option A preceded by
flow reduction of process wastewater through the use
of cooling towers for contact cooling water and holding
tanks for all other process wastewater subject to
recycle.
3. Option C - Option C is equal to Option B plus end-of-
pipe polishing filtration for further reduction of
toxic metals and TSS.
4. Option D - Option D is equal to Option C plus treatment
of isolated waste streams with activated carbon adsorp-
tion for reduction of toxic organics and activated
alumina for reduction of fluorides and arsenic
concentrations.
5. Option E - Option E consists of Option C plus activated
carbon adsorption applied to the total plant discharge
as a polishing step to reduce toxic organic concentra-
tions.
6. Option F - Option F consists of Option C plus reverse
osmosis treatment to attain complete recycle of all
process wastewater.
A combination of these options was examined for each subcategory
based on the concentration of pollutants found in raw wastewaters
of each subcategory. For example, toxic organic pollutants were
not found above treatable concentrations in the primary lead sub-
category. Therefore, treatment Options D2 and E, which contain
activated carbon adsorption, were not considered. For each of
the selected options, the mass of pollutant removed and the costs
associated with application of the option were estimated. A
description regarding the pollutant reduction benefits associated
with the application of each option is presented in Section X,
while the cost methodology is presented in Section VIII.
MODIFICATIONS TO EXISTING BPT EFFLUENT LIMITATIONS
Prior to this rulemaking session, BPT effuent limitations have
been promulgated for eight of the 12 nonferrous manufacturing
subcategories:
1. primary aluminum smelting,
2. secondary aluminum,
3. primary copper smelting,
4. primary electrolytic copper refining,
5. secondary copper,
6. primary lead,
7. primary zinc, and
8. metallurgical acid plants.
379
-------
At this time, four new subcategories are proposed for inclusion
in the nonferrous metals manufacturing point source category.
There have been no previous effluent limitations developed for
these four subcategories listed below:
1. primary tungsten,
2. primary columbium-tantalum,
3. secondary silver, and
4. secondary lead.
It is not EPA's intention to modify effluent limitations promul-
gated in previous rulemakings unless new information warrants
change. As such, EPA is proposing to modify BPT effluent
limitations for the primary lead subcategory in light of new
information submitted to the Agency. EPA is proposing that the
metallurgical acid plants subcategory be modified to include acid
plants associated with primary zinc and primary lead. In addi-
tion, modifications are proposed for existing stormwater exemp-
tions promulgated in the primary lead subcategory.
PRIMARY LEAD
The currently promulgated BPT for this subcategory is based on
the complete recycle and reuse of slag granulation wastewater
(or dry slag dumping), dry air scrubbing, and treatment and
impoundment (subject to allowances for net precipitation and
catastrophic precipitation events) of acid plant blowdown. As
mentioned earlier, acid plant blowdown is now included in the
metallurgical acid plants subcategory. This suggests that BPT
for primary lead should be zero discharge. Since promulgation,
however, additional data collected by the Agency supports the
need for discharge of wastewater from slag granulation. Although
it was previously thought that slag granulation is a net water
consuming operation, the additional data show that at least one
plant uses an ore with a lead content sufficient to justify
recycling blast furnace slag into the sintering machine to
recover the remaining lead content. For this reason, EPA is
proposing modification of promulgated BPT for this subcategory to
allow a discharge from slag granulation operations.
METALLURGICAL ACID PLANTS
EPA is proposing that the metallurgical acid plants subcategory
be expanded to include metallurgical acid plants at primary lead
and primary zinc smelters as well as those at primary copper
smelters. These operations, which were previously regulated
under their respective primary metal subcategories, would now be
subject to limitations for acid plants. This reorganization was
based on the following reasons (additional detail may be found in
Section IV):
380
-------
1. Process similarity - The purpose of acid plants is to
remove sulfur dioxide from smelter emissions and produce
sulfuric acid as a marketable by-product regardless of
the associated metal processing. Consequently, the
processing methods of lead and zinc acid plants are
similar to those used in copper acid plants.
2. Waste stream similarity - The process similarities lead
to generation of the same waste streams, i.e., acid
plant blowdown.
3. Similar waste stream characteristics - The normalized
(based on 100 percent acid produced) wastewater flows
generated by acid plants of all three metal types are
quite similar. Further, the pollutant matrices, while
varying in the concentrations of some pollutant metals,
exhibited general similarities between the three types.
More importantly, the ranges of concentrations found
were not broad enough to warrant distinctive treatment
techniques or suggest different performances achievable
with BPT.
MODIFIED APPROACH TO STORMWATER
Stormwater, as in all effluent limitations guidelines, is only
considered process wastewater when commingled with actual process
wastewater. If commingling occurs, the stormwater, which usually
does not contain significant pollutant loadings, is contaminated
with the pollutants contained in the process wastewater, and as
such should be subject to treatment. No allowance, however, is
given for this additional flow, since stormwater is or can be
segregated from the process wastewater. Should a sufficient
number of plants demonstrate that segregation of stormwater would
result in excessive costs, is not technically feasible, or demon-
strate that contamination of stormwater with process pollutants
is an unavoidable result of manufacturing processes, the Agency
will consider modification of the proposed regulation as
appropriate.
Existing BPT effluent limitations for the nonferrous metals sub-
categories primary copper smelting, secondary copper,_and^primary
lead have promulgated stormwater exemptions. Facilities_ in these
three subcategories are subject to a zero discharge requirement
according to promulgated BPT effluent limitations; however,
facilities meeting certain design capacity requirements could
discharee regardless of effluent quality, a volume of water
falling8within the impoundment in excess of the 10-year, 24-hour
storm, when a storm of at least that magnitude occurred.
Further facilities in the secondary copper and primary lead sub-
categories can discharge once per month, subject to concentra-
tion-based effluent limitations, a volume of water equal to the
381
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difference between precipitation and evaporation falling on the
impoundment in that month.
The Agency began to revise some of these impoundment-based regu-
lations in 1980 for primary copper smelting and electrolytic
refining BPT, this rulemaking session is proposing to revise
others. The revised regulations are based on mechanical end-of-
pipe treatment using hardware (lime precipitation and sedimenta-
tion technology using clarifiers). By eliminating impoundments,
the need for a net precipitation allowance and (subject to an
exception discussed below) stormwater discharge is eliminated.
Table IX-1 summarizes the current stormwater precipitation
allowances.
The Agency is reluctant to issue limitations based on impound-
ments for a number of reasons:
1. Discharge from impoundments can be as a "slug,"
allowing potentially heavy and damaging pollutant
loadings to be discharged all at once;
2. Impoundments allow dilution of heavily contaminated
process wastewaters with relatively cleaner process
streams;
3. Net precipitation limitations are hard to calculate
because of periodic shifts between net precipitation
and net evaporation;
4. Impoundments pose a risk of groundwater contamination;
and
5. Impoundment-based regulations effectively require the
Agency to specify impoundment design.
(See generally 45 FR at 44926 (July 2, 1980), revising
impoundment-based regulations in the primary copper smelting and
electrolytic refining subcategories.) In addition, plants within
these subcategories, have in many cases, already installed
hardware-based lime precipitation and sedimentation technology,
so that these technologies are now BPT or BAT for these sub-
categories.
In light of these considerations, an allowance for net precipita-
tion is not included for BPT for the primary lead subcategory
because the effluent limitations for BPT are not based on set-
tling and evaporation impoundments. EPA is not proposing any
modifications to promulgated BPT effluent limitations for the
primary copper smelting and secondary copper subcategories.
Table IX-2 summarizes the proposed changes to the catastrophic
stormwater and precipitation allowances.
382
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It is recognized that this approach to catastrophic rainfalls
varies from the approach used for the ore mining and dressing
category (47 FR 54603). In that regulation EPA required only
that the impoundments be designed and operated so as to contain a
10-year, 24-hour storm, while this proposed regulation requires
that no discharge from the impoundment may occur except when a
10-year, 24-hour storm occurs. This difference is justified by
the fact that the nonferrous metals manufacturing allowance
applies only to water falling on the surface of the impoundment
while the ore mining allowance applies to stormwater drainage
from various processing locations at the ore mine and mill. The
relative surface area of a nonferrous manufacturing impoundment
is a small fraction of the area drained at an ore mine and mill.
Therefore, the quantity of stormwater that must be contained at a
nonferrous plant impoundment is much smaller, making containment
of the stormwater under the provisions of this proposed regula-
tion achievable. The Agency believes that decisions regarding
stormwater are site-specific and are best handled based on the
judgment of individual permit writers.
BPT OPTION SELECTION
The treatment option selected for the technology basis of BPT
throughout the category is Option A (lime precipitation and
sedimentation, with ammonia steam stripping where appropriate).
Lime precipitation, sedimentation, and ammonia steam stripping
are widely demonstrated at plants with the best treatment
practices in the nonferrous metals manufacturing category. Lime
precipitation and sedimentation for dissolved toxic metals
removal is demonstrated at 61 discharging facilities within the
nonferrous metals manufacturing point source category. Ammonia
steam stripping is demonstrated at three facilities and unspeci-
fied ammonia removal is demonstrated at five facilities. To
illustrate the frequency of various treatment techniques, Table
IX-3 summarizes the current treatment technology in-place for
plants in each subcategory. As can be seen, the preponderance of
technology is lime precipitation and sedimentation equipment.
Multimedia filtration (Option C) as an add-on polishing step to
the precipitation and sedimentation system was not selected at
BPT since it was less widely demonstrated.
Effluent BPT limitations have not been promulgated for the
following four subcategories:
1. Primary tungsten,
2. Primary columbium-tantalum,
3. Secondary silver, and
4. Secondary lead.
In the discussions that follow, a brief description of the option
selected for each of these four subcategories will be presented.
383
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A discussion of primary lead BPT option selection will also be
presented since limitations for this subcategory are being
modified. The mass limitations developed for these subcategories
are presented in Section II of this document and the correspond-
ing supplements. Table IX-4 presents the pollutants selected for
limitation in each of these subcategories.
PRIMARY LEAD
The technology basis for the BPT limitations is lime precipita-
tion and sedimentation technology to remove metals and solids
from combined wastewaters and to control pH. This technology is
demonstrated at three primary lead smelters and is estimated to
remove 1,350 kg/yr of toxic pollutants and 84,000 kg/yr of con-
ventional pollutants over estimated raw discharges. With the
only discharger in this subcategory utilizing lime precipitation,
sedimentation, and filtration, no costs are anticipated for the
primary lead subcategory to meet the proposed BPT effluent
limitations.
More stringent technology options were not selected for BPT,
since they require in-process changes or end-of-pipe technologies
not widely practiced in the primary lead subcategory. These
technologies are more appropriately considered under BAT.
PRIMARY TUNGSTEN
The technology basis for the BPT limitations is lime precipita-
tion and sedimentation technology to remove metals and solids
from combined wastewaters and to control pH, and ammonia steam
stripping to remove ammonia. These technologies are already
in-place at both of the direct dischargers for this subcategory.
Implementation of the proposed BPT limitations will remove from
raw wastewaters an estimated 3,560 kg of toxic metals, 741,470 kg
of ammonia, and 2,658,600 kg of TSS. No capital or annual costs
are projected for achieving proposed BPT because the technology
is in-place at both discharging facilities.
More stringent technology options were not selected for BPT since
they require in-process changes or end-of-pipe technologies not
widely practiced in the subcategory, and, therefore, are more
appropriately considered under BAT.
PRIMARY COLUMBIUM-TANTALUM
EPA is proposing BPT effluent mass limitations based on lime pre-
cipitation and sedimentation to control toxic metals, TSS, pH and
fluoride, and ammonia steam stripping. These technologies are
currently in-place at both of the direct dischargers in the pri-
mary columbium-tantalum subcategory.
384
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Application of BPT technology will result in the removal of
145,000 kg of toxic pollutants, 1.5 million kg of conventional
pollutants, and 1.3 million kg of nonconventional pollutants per
year from current raw wastewaters. There is no cost associated
with compliance with the proposed BPT mass limitations because
the technology is already in-place at both of the direct dis-
charging plants in the primary columbium-tantalum subcategory.
More stringent technology options were not selected since they
require in-process changes or end-of-pipe technologies which are
not widely practiced by the industry and, therefore, are more
appropriately considered under BAT.
SECONDARY SILVER
The proposed BPT effluent mass limitations are based on lime pre-
cipitation and sedimentation to remove toxic metals, pH and TSS.
Ammonia steam stripping is applied as pretreatment or removal of
ammonia. Ammonia steam stripping is currently in place at two of
the five direct dischargers in the secondary silver subcategory.
The proposed BPT will result in the removal of 27,000 kg of toxic
pollutants and 578,350 kg of ammonia per year from raw discharge
levels. The estimated capital investment cost of BPT is $0.124
million and the estimated annual cost is $0.263 million. These
costs represent wastewater treatment equipment not currently in
place. More stringent options were not selected for BPT because
they involve in-process changes or end-of-pipe treatment technol-
ogies which are not widely practiced by the industry and, there-
fore, are more appropriately considered under BAT.
SECONDARY LEAD
The proposed BPT effluent mass limitations for the secondary lead
subcategory are based on lime precipitation and sedimentation to
control toxic metals, pH, and TSS. This technology is currently
in-place at 23 discharging facilities in the secondary lead sub-
category. In addition, dry kettle air pollution control is
required, which eliminates the discharge of ammonia.
The proposed BPT will result in the removal of 14,400 kg of toxic
pollutants and 5.4 million kg of conventional pollutants per year
from raw discharge levels. The estimated capital investment cost
of BPT is $0.470 million and the estimated annual cost is $0.228
million. These costs represent wastewater treatment equipment
not currently in-place. More stringent options were not selected
for BPT because they involve in-process changes or end-of-pipe
treatment technologies which are not widely practiced by the
industry and, therefore, are more appropriately considered under
BAT.
385
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EXAMPLES OF BUILDING BLOCK APPROACH IN DEVELOPING PERMITS
A plant is to receive a discharge allowance for a particular
building block only if it is actually operating that particular
process? In this way, the building block approach recognizes and
accommodates the fact that not all plants use identical steps in
manufacturing a given metal. The plant need not be discharging
wastewater from the process to receive the allowance, however.
Thus if the regulation contains a discharge allowance for wet
scrubber effluent and a particular plant has dry scrubbers, it
cannot include a discharge allowance for wet scrubbers as part of
its aggregate limitation. On the other hand, if it has wet
scrubbers and discharges less than the allowable limit or does
not discharge from the scrubbers, it would receive the full
regulatory allowance in developing the permit.
There are several facilities within this category that have inte-
grated manufacturing operations; that is, they combine wastewater
from smelting and refining operations, which are part of this
point source category, with wastewater from other manufacturing
operations which are not a part of this category, and treat the
combined stream prior to discharge.
The building block approach is only to be used when the individ-
ual discharger combines wastewater from various processes and
co-treats the wastewater before discharge through a single dis-
charge pipe. The building block approach allows the determina-
tion of appropriate effluent limitations for the discharge point
by combining appropriate limitations based upon the various
processes that contribute wastewater to the discharge point.
In establishing limitations for integrated facilities for which a
portion of the plant is covered by concentration-based limita-
tions, the permit writer can determine the appropriate mass limi-
tations for the entire facility or point source. The portion of
the wastewater covered by this category receives mass limitations
according to the building block methodology described above. The
permit writer must then determine an appropriate flow for the
portion of the facility subject to concentration-based limita-
tions and multiply it by the concentration limitations to yield
mass limitations. The mass limitations applicable to the dis-
charge are obtained by summing these two sets of mass
limitations.
As an example, consider a facility which combines both secondary
lead smelting and battery manufacturing wastewater and treats
this water in a waste treatment system prior to discharge. The
permit writer must first identify the manufacturing operations
using process water in the facility. The facility in this exam-
ple utilizes and discharges wastewater from the processes shown
386
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below. By multiplying the production for each of these opera-
tions by the limitations or standards in 40 CFR 421 for secondary
lead production and 40 CFR 461 for battery manufacturing, the
permit writer can obtain the allowable mass discharge.
Process Production
Battery Cracking 8,400 kkg/yr
Kettle Wet Air Pollution Control 18,300 kkg/yr
Casting Contact Cooling 18,300 kkg/yr
Lead Oxide Purchased . 2,600,000 kg/yr
Paste Preparation and Application 5,200,000 kg/yr
Curing Stacked 5,200,000 kg/yr
Formation - Closed, Single 4,160,000 kg/yr
Formation - Open, Dehydrated 1,040,000 kg/yr
Battery Wash - With Detergent 5,200,000 kg/yr
Using the maximum for any one day limitation based on the best
practicable control technology (BPT) for the pollutant lead is
3.75 kg/yr as calculated below:
Battery Cracking
(141.0 mg/kkg) (8,400 kkg/yr) (10~6 kg/mg) =1.18
Kettle Wet Air Pollution Control
(0 mg/kkg) (18,300 kkg/yr) (10'6 kg/mg) = 0
Casting Contact Cooling
33.18 mg/kkg) (18,300 kkg/yr) (lO'6 kg/mg) = 0.61
Secondary Lead Production Subtotal = 1.79 kg/yr
Paste Preparation and Application
(0 mg/kg) (5,200,000 kg/yr) (10~6 kg/mg) = 0
Curing Stacked
(0 mg/kg) (5,200,000 kg/yr) (10~6 kg/mg) = 0
387
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Formation - Closed, Single
(0 mg/kg) (4,160,000 kg/yr) (10~6 kg/mg) = 1
Formation - Open, Dehydrated
(1.35 mg/kg) (1,040,000 kg/yr) (10~6 kg/mg) =1.404
Battery Wash - With Detergent
(0.108 mg/kg) (5,200,000 kg/yr) (10~6 kg/mg) = 0.56
Battery Manufacturing Subtotal - 1.96 kg/yr
Facility Total = 3.75 kg/yr
In establishing limitations for integrated facilities for which a
portion of the plant is covered by concentration-based limita-
tions, the permit writer can determine the appropriate mass limi-
tations for the entire facility or point source as follows. The
portion of the wastewater covered by this category receives mass
limitations according to the building block methodology described
above. The permit writer must then determine an appropriate flow
for the portion of the facility subject to concentration-based
limitations and multiply it by the concentration limitations to
yield mass limitations. The mass limitations applicable to the
discharge are obtained by summing these two sets of mass limita-
tions. If, instead, the waste stream is not covered by any limi-
tations, the permit writer must then also determine the appropri-
ate concentration as well.
As an example, we will use a facility which combines process
wastewater from a mill using froth flotation to concentrate lead
ore with blast furnace slag granulation wastewater from a primary
lead smelter. The portion of the limitations attributable to the
casting water is calculated by multiplying the limitations in
Subpart E of 40 CFR 421 in today's notice by the casting produc-
tion. The permit writer must then determine the appropriate flow
for the discharge from the mill and multiply it by the concentra-
tions set forth in Subpart J of 40 CFR 440 at 47 FR 54618. If
the casting production is 175,000 kkg per year and the flow from
the froth flotation mill is 2,000,000 1/yr, the maximum for any
one day limitation based on the best available technology econom-
ically achievable (BAT) for the pollutant lead is 99.1 kg/yr as
calculated below:
Blast Furnace Slag Granulation
(559.5 mg/kkg) (175,000 kkg/yr) (10~6 kg/mg) = 97.9 kg/yr
388
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Froth Flotation Mill Vastewater
(0.6 mg/1) (2,000,000 1/yr) (10~6 kg/mg) - 1.2 kg/yr
Total - 99.1 kg/yr
389
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OJ
>£>
o
Table IX-1
STORMWATER/PRECIPITATION ALLOWANCES
Existing Regulations
BPT
Subcategory
Primary Copper Smelting
Primary Copper Electro-
lytic Refining
Secondary Copper
Primary Lead
Catas-
trophic
Storm
Yes
No
Yes
Yes
Net
Precipi-
tation
No
No
Yes
Yes
BAT
Catas-
trophic
Storm
Yes
Yes
Yes
Yes
Net
Precipi-
tation
Yes
Yes
Yes
Yes
Proposed Regulations
BPT
Catas-
trophic
Subcategory Storm
Net
Precipi-
tation
Primary Copper Smelting
Primary Copper Electro-
lytic Refining
Secondary Copper
Pr imar
y Lead No
No
BAT
Catas-
trophic
Storm
Yes
No
Yes
No
Net
Precipi-
tation
No
No
No
No
NSPS
Catas-
trophic
Storm
No
No
No
No
Net
Precip-
tation
No
No
No
No
-------
Table IX-1 (Continued)
STORMWATER/PRECIPITATION ALLOWANCES
Proposed Regulations
PSES
PSNS
Subcategory
Primary Copper Smelting
Primary Copper Electro-
lytic Refining
Secondary Copper
Primary Lead
Catas-
trophic
Storm
__*
__*
No
__*
Net
Precipi-
tation
No
Catas-
trophic
Storm
No
No
No
No
Net
Precipi-
tation
No
No
No
No
Yes = Regulation contains this allowance.
No = Regulation does not contain this allowance.
*No existing indirect dischargers.
-------
Table IX-2
MODIFICATION TO BPT PRECIPITATION EXEMPTION
Existing BPTProposed BPT
Regulation Regulation
Catas-NetCatas- Net
trophic Precipi- trophic Precipi
* - • t* A— —. _~*_ ^ ** ^ ^ *"*»%
Subcategory
Storm tation Storm tation
Secondary Copper Yes Yes Yes No
Primary Lead Yes Yes No No
Yes - Regulation contains this allowance.
No - Regulation does not contain this allowance
392
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vD
Table IX-3
SUMMARY OF CURRENT TREATMENT PRACTICES
Ammonia Stripping 5iseharge_S^tatus
SUBCATKWKI
Primary Aluminum
Secondary Aluminum
Primary Copper
Smelters
Primary Copper
Refiners
Secondary Copper
Primary Lead
Secondary Lead
Primary Zinc
Secondary Silver
Primary
Co lumb lum /Tant al urn
Primary Tungsten
Metallurgical Acid
Plants
Lime and
Settle1
13 (0)2
4 (4)
4 (4)
2 (1)
4 (3)
2 (1)
23 (6)
7 (1)
7 (0)
4 (0)
3 (0)
8 (0)
'and/rater" Summing Air Steam "iKT Direct Indirect
1 (0) "
1 8 13
2
1 (0) 1 (1) 4
1 (1) 5 6
1 (0) 1
7 (0) 1 ' l6
3 (1) 5
3 (0) * 17
1 (0) 1 «» I <°> 3 2
3 (0) « <2> 2 3
3 (0) 81
Zero Total
4 31
34 55
18 20
11 15
20 31
6 7
46 69
2 7
23 44
5
3 8
13 22
number on this column Include plants tallied In the lime, *ettU and filter column.
2Numbers In parentheses Indicate zero dischargers with treatment.
-------
Table IX-4
REGULATED POLLUTANT PARAMETERS
Subcategory
Primary Lead
Primary Tungsten
Primary Columbium-Tantalum
Secondary Silver
Secondary Lead
Pollutant Parameters
122. lead
128. zinc
TSS
pH
122. lead
125. selenium
128. zinc
ammonia (N)
TSS
pH
122. lead
128. zinc
ammonia (N)
fluoride
TSS
pH
120. copper
128. zinc
ammonia (N)
TSS
pH
114. antimony
115. arsenic
122. lead
128. zinc
TSS
pH
394
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SECTION X
EFFLUENT QUALITY ATTAINABLE THROUGH APPLICATION OF
THE BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
This section sets forth the effluent limitations attainable
through the application of best available technology economically
achievable (BAT). It also serves to summarize changes from
previous rulemakings in the nonferrous metals manufacturing
category, and presents the development and use of the mass-based
effluent limitations.
A number of factors guide the BAT analysis including the age of
equipment and facilities involved, the process employed, process
changes, nonwater quality environmental impacts (including energy
requirements), and the costs of application of such technology.
BAT technology represents the best available technology economi-
cally achievable at plants of various ages, sizes, processes, or
other characteristics. In those categories whose existing per-
formance is uniformly inadequate EPA may transfer technology from
a different subcategory or category. BAT may include process
changes or internal controls, even when these are not common
industry practice. This level of technology also considers those
plant processes and control and treatment technologies which, at
pilot plant and other levels, have demonstrated both technologi-
cal performance and economic viability at a level sufficient to
justify investigation.
The required assessment of BAT "considers" costs, but does not
reauire a balancing of costs against effluent reduction benefits
(see Weyerhaeuser v. Costle, 11 ERG 2149 (D.C. Cir. 1978)). In
developing the proposed BAT, however, EPA has given substantial
weight to the economic achievability of the technology. The
Agency has considered 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.
The BAT effluent limitations are organized by subcategory for
individual sources of wastewater. The limitations were developed
based on the attainable effluent concentrations and production
normalized flows.that have been presented in this document. The
analysis has resulted in a number of modifications to the exist-
395
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TECHNICAL APPROACH TO BAT
In the past, the technical approach for the nonferrous metals
manufacturing category considered each plant as a single waste-
water source, without specific regard to the different unit
processes that are used in plants within the same subcategory.
For this rulemaking, end-of-pipe treatment technologies and
in-process controls were examined in the selection of the best
available technology. After examining in-process controls, it
becomes apparent that it was best to establish effluent limita-
tions and standards recognizing specific waste streams associated
with specific manufacturing operations. The approach adopted for
this proposal considers the individual wastewater sources within
a plant, resulting in more effective pollution abatement by
tailoring the regulation to reflect these various wastewater
sources. This approach, known as the building block approach,
was presented in Section IX.
INDUSTRY COST AND POLLUTANT REDUCTION BENEFITS OF THE VARIOUS
TREATMENT OPTIONS
Under these guidelines, six treatment options were evaluated in
selection of BAT for the category. Because of the diverse pro-
cesses and raw materials used in the nonferrous category, the
pollutant parameters found in various waste streams are not uni-
form. This required the identification of significant pollutants
in the various waste streams so that appropriate treatment tech-
nologies could be selected for further evaluation. The options
considered applicable to the nonferrous metals manufacturing sub-
categories are presented in Table X-l. A thorough discussion of
the treatment technologies considered applicable to wastewaters
from the nonferrous metals manufacturing category is presented in
Section VII of this document. In Section VII, the attainable
effluent concentrations of each technology are presented along
with their uniform applicability to all subcategories. Mass
limitations developed from these options may vary, however,
because of the impact of different production normalized
wastewater discharge flows.
In summary, the treatment technologies considered for nonferrous
metals manufacturing are:
Option A is based on:
Lime and settle (chemical precipitation of metals
followed by sedimentation), and, where required,
Ammonia steam stripping, and
Oil skimming.
(This option is equivalent to the technology on which
BPT is based.)
396
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Option B is based on:
Option A (lime and settle) plus cyanide precipitation,
where required, and process wastewater flow reduction
by the following methods:
Contact cooling water recycle through cooling
towers.
Holding tanks for all other process wastewater
subject to recycle.
Option C is based on:
Option B (lime and settle preceded by flow reduction),
plus multimedia filtration.
Option DI is based on:
Option C (lime precipitation, sedimentation, in-process
flow reduction, and multimedia filtration); plus acti-
vated alumina treatment, where required.
Option D2 is based on:
Option C (lime precipitation, sedimentation, in-process
flow reduction, and multimedia filtration); plus acti-
vated carbon adsorption preliminary treatment, where
required.
Option E is based on:
Option C (lime precipitation, sedimentation, in-process
flow reduction, and multimedia filtration); plus acti-
vated carbon adsorption at the end of the Option C
treatment scheme.
Option F is based on:
Option C (lime precipitation, sedimentation, in-process
flow reduction, and multimedia filtration); plus
reverse osmosis treatment to attain complete recycle of
all process wastewater.
As a means of evaluating the economic achievability of each of
these treatment options, the Agency developed estimates of the
compliance costs and pollutant reduction benefits. An estimate
of capital and annual costs for the applicable BAT options was
prepared for each subcategory as an aid in choosing the best BAT
option. The cost estimates are presented in Section X of each of
the subcategory supplements. All costs are based on fourth
quarter 1978 dollars.
397
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The cost methodology has been described in detail in Section
VIII. For most treatment technologies, standard cost literature
sources were used for module capital and annual costs. Data from
several sources were combined to yield average or typical costs
as a function of flow or other characteristic design parameters.
In a small number of modules, the technical literature was
reviewed to identify the key design criteria, which were then
used as a basis for vendor contacts. The resulting costs for
individual pieces of equipment were combined to yield module
costs. In either case, the cost data were coupled with flow data
from each plant to establish system costs for each facility.
Pollutant reduction benefit estimates were calculated for each
option for each subcategory. The estimated pollutant removal
that the treatment technologies can achieve is presented in
Section X of each of the subcategory supplements.
The first step in the calculation of the benefit estimates is the
calculation of production normalized raw waste values (mg/kkg)
for each pollutant in each waste stream. The raw waste values
were calculated using one of three methods. When analytical con-
centration data (mg/1) and sampled production normalized flow
values (1/kkg) were available for a given waste stream, individ-
ual raw waste values for each sample were calculated and aver-
aged. This method allows for the retention of any relationship
between concentration, flow and production. When sampled produc-
tion normalized flows were not available for a given waste
stream, an average concentration was calculated for each pollu-
tant, and the average raw waste normalized flow taken from the
dcp information for that waste stream was used to calculate the
raw waste. When analytical values were not available for a given
waste stream, the raw waste values for a stream of similar water
quality was used.
The total flow (1/yr) for each option for each subcategory was
calculated by summing individual flow values for each waste
stream in the subcategory for each option. The individual flow
values were calculated by multiplying the total production asso-
ciated with each waste stream in each subcategory (kkg/yr) by the
appropriate production normalized flow (1/kkg; for each waste
stream for each option.
The raw waste mass values (kg/yr) for each pollutant in each sub-
category were calculated by summing individual raw waste masses
for each waste stream in the subcategory. The individual raw
waste mass values were calculated by multiplying the total pro-
duction associated with each waste stream in each subcategory
(kkg/yr) by the raw waste value (mg/kkg) for each pollutant in
each waste stream.
398
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The mass discharged (kg/yr) for each polultant for each option
for each subcategory was calculated by multiplying the total flow
(1/yr) for those waste streams which enter the central treatment
system, by the treatment effectiveness concentration (mg/1)
(Table VII-22) for each pollutant for the appropriate option.
The total mass removed (kg/yr) for each pollutant for each option
for each subcategory was calculated by subtracting the total mass
discharged (kg/yr) from the total raw mass (kg/yr).
Total treatment performance values for each subcategory were cal-
culated by using the total production (kkg/yr) of all plants in
the subcategory for each waste stream. Treatment performance
values for direct dischargers in each subcategory were calculated
by using the total production (kkg/yr) of all direct dischargers
in the subcategory for each waste stream.
MODIFICATION OF EXISTING BAT EFFLUENT LIMITATIONS
Modifications are proposed to all existing promulgated BAT
effluent limitations in the nonferrous metals manufacturing
category. In general, the existing BAT effluent limitations are
being modified to incorporate the building block approach. A
detailed discussion regarding the development of mass limitations
from this approach is presented in Section IX. Other modifica-
tions to the primary lead subcategory and secondary aluminum sub-
category are a result of new information supplied to the Agency.
To reflect the changes in stormwater allowances promulgated for
BPT in the primary copper smelting and secondary copper subcate-
gories, the Agency is proposing modifications to the stormwater
allowances promulgated under BAT. The proposed changes allow a
discharge resulting from a catastrophic rainstorm, but they
eliminate the monthly net precipitation discharge allowance. The
building block approach is not developed for these two subcatego-
ries since they are required to maintain zero discharge of all
process wastewater pollutants.
The technology basis for BAT is also being modified. Lime pre-
cipitation, sedimentation and filtration is being proposed. The
Agency believes this represents the best available technology
economically achievable. The proposed limitations are based on
achievable concentrations from two porcelain enameling plants and
one nonferrous metals plant and variability factors from the com-
bined data base.
Primary Aluminum
The existing BAT effluent limitations were developed by consider-
ing each plant as a single wastewater source and allocating one
399
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discharge rate from which the effluent limitations were calcu-
lated. The technology basis from which these effluent limita-
tions were developed are lime and settle performance values. The
proposed BAT effluent limitations are developed for individual
wastewater sources identified within the primary aluminum
subcategory, and effluent concentrations attainable with lime
precipitation, sedimentation, filtration, cyanide precipitation,
and activated carbon adsorption. This technology is discussed in
greater detail in the BAT option selection of this section.
Secondary Aluminum
The currently promulgated BAT for this subcategory prohibits the
discharge of process wastewater. However, new information sup-
ports the need for discharge of wastewater from chlorine demag-
ging, an operation considered and included in the promulgated
zero discharge regulation. Three dry processes existed at the
time of promulgation; the Durham process; the Alcoa process; and
the Teller process. The Agency believed that each of these pro-
cesses were sufficiently well demonstrated to be installed and
become operational by 1984; the compliance date for BAT. Conse-
quently, there was no justification for a discharge allowance
associated with this waste stream.
New information shows that the technologies are not sufficiently
demonstrated nor are they applicable to plants on a nationwide
basis. For this reason, the promulgated BAT is being modified;
the proposed BAT is based on the use of wet scrubbing on chlorine
demagging operations.
Information has become available to the Agency that supports the
need for discharge of wastewater from direct chill casting, an
operation not considered nor included in the promulgated BAT
regulation. Direct chill casting is a relatively new process and
companies have been installing this technology into their plants
over the past five years. The process has been considered as a
part of the rulemaking and effluent limitations that allow a dis-
charge are being proposed.
Primary Electrolytic Copper Refining
The existing BAT effluent limitations were developed by consider-
ing each plant as a single wastewater source and allocating one
discharge rate from which the effluent limitations were calcu-
lated. The technology basis was lime precipitation and sedimen-
tation performance values. The proposed BAT effluent limitations
are developed for individual wastewater sources identified within
the primary electrolytic copper refining subcategory, and efflu-
ent concentrations attainable with lime precipitation, sedimenta-
tion, in-process flow reduction, and multimedia filtration. This
technology is discussed in greater detail in the BAT option
selection of this section.
400
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Primary Lead
With the exception of stormwater exemptions, the existing BAT
effluent limitations require zero discharge of all process waste-
water pollutants. Information supplied to the Agency shows that
slag removed from the smelting furnace may contain recoverable
concentrations of lead. For the smelter slag to be recycled back
into the production process, it must be granulated so that it is
compatible with concentrated ore. The Agency has determined that
this waste stream requires a discharge to control the buildup of
suspended solids.
Primary Zinc
The existing BAT effluent limitations were developed from one
wastewater discharge rate and lime and settle performance values.
The proposed BAT effluent limitations are developed for individ-
ual wastewater sources identified within the primary zinc
subcategory, and effluent concentrations attainable with lime
precipitation, sedimentation, in-process flow reduction, and
multimedia filtration. This technology is discussed in greater
detail in the BAT option selection of this section.
Metallurgical Acid Plants
As discussed in Section IX, the metallurgical acid plants sub-
category is being modified to include acid plants associated with
primary zinc and lead smelters as well as primary copper smel-
ters. This is based on the similarity between discharge rates
and effluent characterisitcs of wastewaters from primary lead,
zinc, and copper smelting acid plants.
MODIFIED APPROACH TO STORMWATER
For the same reasons discussed in detail in Section IX, no allow-
ance will be given for stormwater under BAT. Stormwater is or
can be segregated from the process wastewater. Furthermore,
stormwater is site-specific and is best addressed on a case-by-
case basis by the permit writer. Should a sufficient number of
plants demonstrate that segregation of stormwater would result in
excessive costs, is not technically feasible, or demonstrate that
contamination of stormwater with process pollutants is an
unavoidable result of manufacturing processes, the Agency will
consider modification of the proposed regulation as appropriate.
The BAT regulations on catastrophic and net precipitation exemp-
tions are modified for several subcategories. These changes are
presented in Table X-2. The reasons for modifying the BAT relief
provisions for primary copper smelting, primary copper electro-
lytic refining, secondary copper and primary lead are as
follows:
401
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1. The technology basis for BAT has been changed from
wastewater impoundments to equipment such as holding
tanks, cooling towers, and clarifiers. This type of
equipment is not influenced to the same degree as cool-
ing impoundments. As a result, storm relief is not
necessary to treat process wastewater (with the excep-
tion noted in (2) below).
2. For primary copper smelting and secondary copper,
impoundments to treat cooling water are used at many
facilities as an alternative to cooling towers. EPA
has thus provided that stormwater may be discharged
from these impoundments when a 25-year, 24-hour storm
or larger has been experienced by the facility. The
volume of water that may be discharged is only that
which falls directly on the impoundment surface.
Further, since the size required for cooling water
impoundments is substantially smaller than impoundments
that treat other process wastewaters, no net precipita-
tion relief is necessary. The amount of freeboard
available in the proper design and operation of these
cooling water ponds is sufficient for most facilities
to accommodate the fluctuations in volume resulting
from the precipitation cycle without having to dis-
charge .
BAT OPTION SELECTION
The option generally selected throughout the category is Option C
or lime precipitation, sedimentation, in-process flow reduction,
multimedia filtration, and ammonia steam stripping, where applic-
able. The Agency has selected BPT plus in-process wastewater
flow reduction and the use of filtration as an effluent polishing
step as BAT for all of the subcategories except primary aluminum,
where additional treatment is proposed for the control of toxic
organics and cyanide.
This combination of treatment technologies has been selected
because they are technically feasible and are demonstrated within
the nonferrous metals manufacturing category. Implementation of
this treatment scheme would result in the removal of an estimated
175,500 kg/yr of toxic pollutants and 2,582,000 kg/yr of conven-
tional pollutants above BPT discharge estimates. Although the
Agency is not required to balance the costs against effluent
reduction benefits (see Weyerhaeuser v. Costle, supra), the
Agency has given substantial weight to the reasonableness of
cost. The Agency's current economic analysis shows that this
combination of treatment technologies is economically achievable.
No closures of indirect dischargers are expected as a result of
402
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compliance with recommended BAT technologies. Price increases
are not expected to exceed 0.5 percent with production decreases
of less than 0.5 percent.
The general approach taken by the Agency for BAT regulation of
this category is presented below. The actual proposed limita-
tions may be found in Section II of this document. The BAT
op.tion selected for each subcategory is presented below.
Primary Aluminum
The BAT option selected is flow reduction, lime precipitation,
sedimentation, and filtration for control of toxic metals and
fluoride; activated carbon preliminary treatment for toxic
organics removal; and cyanide precipitation pretreatment.
This combination of treatment technologies was selected because
it provides additional pollutant removal achievable by the
primary aluminum subcategory and it is economically achievable.
Lime precipitation and sedimentation are widely practiced at pri-
mary aluminum plants, and as indicated in the previous section,
form the basis for the BPT limitations. Filtration serves as an
important polishing step in BAT. For this subcategory, it
results in the removal of 1,214,000 kg/yr of toxic pollutants and
1,390,000 kg/yr of nonconventional pollutants over the estimated
BPT discharge. Further, lime precipitation and sedimentation are
demonstrated at 13 primary aluminum smelters, while filtration is
demonstrated at 23 plants in the nonferrous metals manufacturing
category including one plant in the primary aluminum subcategory.
The estimated capital investment cost of BAT is $34.85 million
and the annualized cost is $18.71 million.
The activated carbon pretreatment step is directed at better
control of discharges from wet air emission scrubbing associated
with anode paste plants, anode bake plants, potlines and pot-
rooms- as well as from cathode reprocessing operations. As an
alternative method of controlling these discharges, a plant could
install a dry alumina air scrubber or institute 100 percent recy-
cle of wet scrubbing discharges. Although the activated carbon
adsorption is not demonstrated in this subcategory, the Agency
has compiled data from two iron and steel plants with activated
carbon. These data demonstrate its applicability to and perfor-
mance for removing the polynuclear aromatic hydrocarbons produced
by primary aluminum plants.
Cyanide precipitation pretreatment is directed at control of free
and complexed cyanides in waste streams within the primary alumi-
num subcategory that result from use of coke and pitch in the
electrolyti? reduction process. These waste streams collectively
discharge approximately 121,000 kg/yr of cyanide. While cyanide
403
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precipitation has not been demonstrated in the primary aluminum
subcategory, it is used at six coil coating plants. The Agency
believes this technology is transferable to the primary aluminum
subcategory because raw wastewater cyanide concentrations are of
the same order of magnitude in both categories prior to dilution
with waste streams without cyanide. Further, no pollutants were
identified in primary aluminum wastewater that would interfere
with the operation or performance of this technology.
Flow reduction is an important element of BAT because it results
in reduced dilution of pollutants and smaller hydraulic flows,
which in turn lead to more efficient treatment, smaller treatment
systems, and an associated reduction in the net cost of treat-
ment. Wastewater flow reduction is based on increased recycle of
scrubber liquor from degassing, potline, potroom, and anode bake
scrubbers, in addition to casting contact cooling water.
More complex technologies were also considered as BAT, including
end-of-pipe activated alumina for the control of fluoride and
reverse osmosis. These two technologies were rejected because
they are not demonstrated in the nonferrous metals manufacturing
category nor are they clearly transferable.
Secondary Aluminum
EPA is proposing BAT effluent mass limitations for the secondary
aluminum subcategory based on lime precipitation, sedimentation,
filtration and ammonia steam stripping. Ammonia steam stripping
is selected by the Agency over air stripping because air strip-
ping reduces ammonia concentrations by simply transferring pollu-
tants from one media (water) to another (air). Steam stripping
reduces ammonia concentrations by stripping the ammonia from
wastewater with steam. The ammonia is concentrated in the steam
phase and may be condensed, collected, and sold as a by-product
or disposed off-site. Ammonia steam stripping is demonstrated by
three facilities in the nonferrous metals manufacturing category
and one plant in the secondary aluminum subcategory. Filtration
is not demonstrated in the secondary aluminum subcategory,
however, it is demonstrated in the nonferrous metals
manufacturing category.
Application of the proposed BAT will result in the removal of 173
kg of toxic pollutants and 45.6 kg of nonconventional pollutants
above the estimated BPT removal. The estimated capital invest-
ment cost of the proposed BAT is $1.60 million and the estimated
annualized cost is $1.35 million.
Reverse osmosis was also examined for BAT. This technology, how-
ever, is not demonstrated in the category, nor is it clearly
transferable.
404
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Primary Copper Electrolytic Refining
Due to adverse economic conditions that are not reflected by the
Agency's current economic analysis, EPA is proposing alternative
BAT effluent mass limitations for the primary copper electrolytic
refining subcategory. After revision of the economic analysis
and consideration of public comment, EPA will select a technology
basis for the promulgated BAT. In the interim, the Agency is
soliciting comment on two options in order to assure that corn-
mentors consider both options. Alternative A is based^on the
existing BPT of lime precipitation and sedimentation with
additional reduction in pollutant discharge achieved through
in-process wastewater flow reduction. Alternative B adds the use
of filtration as an effluent polishing step. Wastewater flow
reduction is based on increased recycle of spent electrolyte,
anode rinse water and casting contact cooling water. None of the
four direct discharging plants in the primary copper electrolytic
refining subcategory currently practice filtration of wastewater.
Application of the proposed Alternative A BAT will result in the
removal of 2,691 kg of toxic pollutants and 23,442 kg of noncon-
ventional pollutants above the estimated BPT discharge. The
estimated capital investment cost of the proposed BAT^is^$0.328
million and the estimated annualized cost is $0.239 million.
Application of the proposed Alternative B BAT will result in the
removal of 2,864 kg of toxic pollutants and 25,935 kg of noncon-
ventional pollutants above the estimated BPT discharge. The
estimated capital investment cost of the proposed BAT is $0.487
million and the estimated annualized cost is $0.290 million.
Reverse osmosis was also considered for BAT. It was rejected,
however, because it is not demonstrated in the category, nor is
it clearly transferable.
Primary Lead
EPA is proposing BAT effluent mass limitations for the primary
lead subcategory based on the existing BPT with additional
reduction in pollutant discharge achieved through in-process
wastewater flow reduction and the use of filtration as an efflu-
ent polishing step. Wastewater flow reduction is based on the
complete recycle of process wastewater from zinc fuming wet air
pollution control, dross reverberatory furnace granulation, and
hard lead refining wet air pollution control. Wastewater gener-
ated from slag granulation is the only waste stream allocated a
discharge allowance. Filtration is currently demonstrated by one
facility in the primary lead subcategory.
405
-------
Application of the proposed BAT will result in the removal of 173
kg of toxic pollutants and 4,985 kg of nonconventional pollutants
above the estimated BPT discharge. The primary lead subcategory
is not expected to incur any costs to implement the technology
basis from which BAT is developed. Reverse osmosis was also
considered for BAT; however, it is not demonstrated in the
category, nor is it clearly transferable.
Primary Zinc
EPA is proposing BAT effluent mass limitations for the primary
zinc subcategory based on BPT with additional reduction in
pollutant discharge achieved through in-process wastewater flow
reduction and the use of filtration as an effluent polishing
step. (Wastewater flow reduction is based on increased recycle
of casting scrubber water and casting contact cooling water.)
Filtration is currently in place at two of the five direct
discharging plants in the primary zinc subcategory.
Application of the proposed BAT effluent mass limitations will
result in the removal of 5,390 kg of toxic pollutants above the
estimated BPT discharge. The estimated capital investment cost
of the proposed BAT is $2.56 million and the estimated annualized
cost is $1.63 million. Activated alumina and reverse osmosis
were also considered for BAT but were rejected. These technolo-
gies are not demonstrated in the category, nor are they clearly
transferable.
Metallurgical Acid Plants
EPA is proposing BAT effluent mass limitations for metallurgical
acid plants based on BPT with additional reduction in pollutant
discharge achieved through in-process wastewater flow reduction
and the use of filtration as an effluent polishing step. Waste-
water flow reduction is based on increased recycle of acid plant
scrubber liquor. Filtration is currently demonstrated at three
of the eight direct discharging plants in the metallurgical acid
plants subcategory.
Application of the proposed BAT mass limitations will result in
the removal of 9,400 kg of toxic pollutants per year above the
estimated BPT discharge. The estimated capital investment cost
of BAT is $3.55 million and the annualized cost is $2.18 million.
The filtration option was selected instead of BPT plus flow
reduction because it is demonstrated and results in removal of
l,114kg/yr of toxic pollutants. Reverse osmosis was considered
but it was rejected because it is not demonstrated in the
category, nor is it clearly transferable.
406
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Primary Tungsten
EPA is proposing BAT mass limitations for the primary tungsten
subcategory based on BPT with additional reduction in pollutant
discharge achieved through in-process wastewater flow reduction
and the use of filtration as an effluent polishing step. Waste-
water flow reduction is based on 90 percent recycle of scrubber
liquors. Filtration is currently in place at three plants in the
subcategory.
Application of the proposed BAT will remove an estimated 144
kg/yr of toxic pollutants, which is 127 kg/yr of toxic metals
over the estimated BPT discharge. No additional ammonia is
removed at BAT, nor are any toxic organics removed. The proposed
BAT represents a 22 percent incremental toxics removal over BPT,
and 89 percent total toxics removal from raw waste. Approxi-
mately half of these removals are attributable to flow reduction,
the remainder to filtration. The estimated capital investment
cost of BAT is $447,000, and the estimated annual cost is
$193,000.
The filtration option was selected instead of BPT plus flow
reduction because it is demonstrated and results in removal of 54
kg/yr of toxic metals. More stringent options were also consid-
ered but were rejected. Activated carbon adsorption was consid-
ered for the control of toxic organics. The Agency determined
that the current discharge rate of toxic pollutants by the
primary tungsten subcategory are not causing, nor are they likely
to cause toxic effects in navigable waters. Reverse osmosis was
rejected for BAT because it is not demonstrated in the category,
nor is it clearly transferable.
Primary Columbium-Tantalum
EPA is proposing BAT mass limitations for the primary columbium-
tantalum subcategory based on BPT with additional reduction in
pollutant discharge achieved through in-process wastewater flow
reduction and the use of filtration as an effluent polishing
step. Wastewater flow reduction is based on increased recycle of
scrubber liquors associated with three sources: concentrate
digestion scrubber, solvent extraction scrubber, and metal salt
drying scrubber. Filtration is currently in place at one of the
two direct discharging plants in the primary columbium-tantalum
subcategory.
Application of the proposed BAT will result in the removal of 285
kg/yr of toxic pollutants and 2,360 kg/yr of conventional pollu-
tants over the estimated BPT discharge. The estimated capital
investment cost of BAT is $797,000 and the estimated annual cost
is $396,000.
407
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The filtration option was selected instead of BPT plus flow
reduction because it is demonstrated and results zn removal ol
129 kg/yr of toxic pollutants and 1,575 kg/yr of nonconventional
pollutants. Activated carbon adsorption was considered for the
control of toxic organics. The Agency determined that the
current discharge rate of toxic pollutants by the primary
columbium-tantalum subcategory are not causing, nor are they
likely to cause toxic effects in navigable waters. Reverse
osmosis was rejected for BAT because it is not demonstrated in
the category, nor is it clearly transferable.
Secondary Silver
Due to adverse economic conditions that are not reflected by the
Agency's current economic analysis, EPA is proposing alternative
BAT mass limitations for the secondary silver subcategory in a
manner similar to that explained for primary copper refining.
Alternative A for secondary silver is based on BPT with
additional reduction in pollutant discharge achieved through
in-process wastewater flow reduction. Alternative B adds the use
of filtration as an effluent polishing step. Wastewater flow
reduction is based on increased recycle of leaching scrubber
water, furnace scrubber water and casting contact cooling water.
Filtration is currently in place at one of the five direct
discharging plants in the secondary silver subcategory.
Application of the proposed Alternative A BAT will result in the
removal of 13 kg/yr of toxic pollutants, 4 kg/yr of conven-
tional pollutants, and 79 kg/yr of ammonia above the estimated
BPT discharge. The estimated capital investment cost of the
proposed Alternative A BAT is $184,000 and the annual cost is
$278,000.
Application of the proposed Alternative B BAT will result in the
removal of 92 kg/yr of toxic pollutants, 1,880 kg/yr of conven-
tional pollutants, and 79 kg/yr of ammonia above the estimated
BPT discharge. The estimated capital investment cost of the
proposed Alternative B BAT is $206,000 and the annual cost is
$345,000.
The filtration option was selected instead of BPT plus flow
reduction because it is demonstrated and results in removal of 78
kg/yr of toxic pollutants. Activated carbon adsorption was con-
sidered for the control of toxic organics. The Agency determined
that the current discharge rate of toxic pollutants by the
secondary silver subcategory are not causing, nor are they likely
to cause toxic effects in navigable waters. Reverse osmosis was
rejected for BAT because it is not demonstrated in the category,
nor is it clearly transferable.
408
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Secondary Lead
Due to current adverse economic conditions that are not reflected
in the Agency's current economic analysis, EPA is proposing
alternative BAT effluent mass limitations for the secondary lead
subcategory in a manner similar to the approach used for primary
copper refining and secondary silver. Alternative A is based on
BPT with additional reduction in pollutant discharge achieved
through in-process wastewater flow reduction. Alternative B adds
to Alternative A with the use of filtration as an effluent
polishing step. Wastewater flow reduction is based on increased
recycle of smelter scrubber water and casting contact cooling
water, and reducing the amount of water used for battery
cracking. Filtration is currently in place at two of the five
direct discharging plants in the secondary lead subcategory.
Application of the proposed Alternative A BAT will result in the
removal of 131.5 kg/yr of toxic pollutants and 918 kg/yr of con-
ventional pollutants above the estimated BPT discharge. The
estimated capital investment cost of BAT is $470,000, and the
estimated annual cost is $228,000.
Application of the proposed Alternative B BAT will result in the
removal of 250 kg/yr of toxic pollutants and 2,850 kg/yr of
conventional pollutants above the estimated BPT discharge. The
estimated capital investment cost of this alternative is $2.12
million, and the estimated annual cost is $1.36 million.
Reverse osmosis was considered for BAT, but it was rejected.
Reverse osmosis is not demonstrated in the category, nor is it
clearly transferable.
REGULATED POLLUTANT PARAMETERS
Presented in Section VI of this document is a list of the pollu-
tant parameters at concentrations and frequencies above treatable
concentrations that warrant further consideration. Although
these pollutants were found at treatable concentrations, the
Agency is not proposing to regulate each pollutant selected for
further consideration. The high cost associated with analysis of
toxic metal pollutants has prompted EPA to develop an alternative
method for regulating and monitoring toxic pollutant discharges
from the nonferrous metals manufacturing category. Rather than
developing specific effluent mass limitations and standards for
each of the toxic metals found in treatable concentrations in the
raw wastewater from a given subcategory, the Agency is proposing
effluent mass limitations only for those pollutants generated in
the greatest quantities as shown by the pollutant reduction
benefit analysis.
409
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By establishing limitations and standards for certain toxic metal
pollutants, dischargers will attain the same degree of control
over toxic metal pollutants as they would have been required to
achieve had all the toxic metal pollutants been directly limited.
This approach is technically justified since the treatable con-
centrations used for lime precipitation and sedimentation tech-
nology are based on optimized treatment for concommitant multiple
metals removal. Thus, even though metals have somewhat different
theoretical solubilities, they will be removed at very nearly the
same rate in a lime precipitation and sedimentation treatment
system operated for multiple metals removal. Filtration as part
of the technology basis is likewise justified because this
technology removes metals non-preferentially.
The same arguments stated above also apply to activated carbon
adsorption for the primary aluminum subcategory. Several poly-
nuclear aromatic hydrocarbons were found above treatable concen-
trations in the primary aluminum subcategory. Since these
organic pollutants are structurally similar, the Agency believes
that by regulating the toxic organic in the largest quantity, the
other toxic organics will be effectively controlled.
The Agency has excluded several toxic organic pollutants from
specific regulation in the primary tungsten, primary columbium-
tantalum, and secondary silver subcategories because they were
found in trace (deminimus quantities) amounts and are neither
causing nor likely to cause toxic effects. Table X-3 presents
the pollutants selected for specific regulation and Table X-4
presents those pollutants excluded because they are neither
causing nor likely to cause toxic effects. Table X-5 presents
those pollutants that are effectively controlled by technologies
upon which are based other effluent limitations and guidelines.
A more detailed discussion on the selection and exclusion of
toxic pollutants is presented in Section X of each subcategory
supplement.
EXAMPLES OF BUILDING BLOCK APPROACH IN DEVELOPING PERMITS
As an example, consider a facility which combines both aluminum
smelting and aluminum forming wastewater and treats this water in
a waste treatment system prior to discharge. The facility in
this example discharges wastewater from potroom wet air pollution
control, direct chill casting, rolling with neat oils, and
annealing wet air pollution control. By multiplying the produc-
tion for each of these operations by the limitations or standards
in 40 CFR 421 for potroom wet air pollution control and direct
chill casting and 40 CFR 436 for rolling with neat oils and by
summing product obtained for each of these waste streams, the
permit writer can obtain the allowable mass discharge.
410
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If, for example, the production associated with the potroom wet
air pollution system, the production of aluminum reduced, is
200,000 kkg/yr, the production of aluminum resulting from direct
chill casting is 150,000 kkg/yr and the rolling with neat oils
production is 50,000 kkg/yr, the maximum for any one day limita-
tion based on the best available technology economically achiev-
able (BAT) for the pollutant aluminum is 1,703.15 kg/yr as
calculated below:
Potroom Wet Air Pollution Control
(200,000 kkg/yr) (3,954.15 mg/kkg) (10~6 kg/mg) = 790.83 kg/yr
Direct Chill Casting
(150,000 kkg/yr) (6,056.97 mg/kkg) (lO'6 kg/mg) = 908.545 kg/yr
Rolling With Neat Oils
(50,000 kkg/yr) (75.5 mg/kg) (10~6 kg/mg) = 3-775 kg/yr
Total = 1,703.15 kg/yr
The Agency recognizes that there may be different technology
bases for the limitations and standards applicable to an inte-
grated facility. Continuing with the example from above, the^
technology basis for BAT for aluminum smelting is lime precipita-
tion, sedimentation, and filtration whereas the technology^basis
for BAT for aluminum forming is lime precipitation and sedimenta-
tion. This does not necessarily imply that the facility install
end-of-pipe filtration on all or a part of the discharge flow.
EPA developed these limiations based on specified in-plant con-
trols and end-of-pipe treatment technology; however, it does not
require that the facility implement these specific in-plant con-
trols and end-of-pipe technology. The facility combining waste-
water from manufacturing operations covered by the two categories
must install technology and modify the manufacturing operations
so as to comply with the mass limitations.
411
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Table X-l
BAT OPTIONS CONSIDERED FOR EACH OF THE NONFERROUS
METALS MANUFACTURING SUBCATEGORIES
Options Considered
Subcategory
Primary Aluminum
Secondary Aluminum
Primary Copper Electrolytic
Refining
Primary Zinc
Primary Lead
Secondary Lead
Primary Tungsten
Primary Columbium/Tantalum
Secondary Silver
Metallurgical Acid Plants
A
X
X
X
X
X
X
X
X
X
X
B
X
X
X
X
X
X
X
X
X
X
C D E
X X
X
X
X X
X
X X
X X
XXX
X X
X
F
X
X
X
X
X
X
X
X
X
X
412
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Table X-2
MODIFICATIONS TO BAT PRECIPITATION EXEMPTION
Subcategory
Primary Copper Smelting
Primary Copper Electro-
lytic Refining
Secondary Copper
Primary Lead
Existing BAT
Regulation
Catas- Net
trophic Precipi
Strom tation
Proposed BAT
Regulation
Catas- Net
trophic Precipi-
Strom tation
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
No
No
No
No
No
Yes = Regulation contains this allowance.
No = Regulation does not contain this allowance.
413
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Table X-3
REGULATED POLLUTANT PARAMETERS
Subcategory
Primary Aluminum Smelting
Secondary Aluminum
Primary Electrolytic Copper
Refining
Primary Lead
Primary Zinc
Metallurgical Acid Plants
Pollutant Parameters
73. benzo(a)pyrene
114. antimony
121. cyanide (Total)
124. nickel
aluminum
fluoride
oil and grease
TSS
pH
122. lead
128. zinc
aluminum
ammonia (N)
TSS
PH
120. copper
122. lead
124. nickel
TSS
pH
122. lead
128. zinc
TSS
pH
118. cadmium
120. copper
122. lead
128. zinc
TSS
pH
115. arsenic
118. cadmium
120. copper
122. lead
128. zinc
TSS
pH
414
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Table X-3 (Continued)
REGULATED POLLUTANT PARAMETERS
Subcategory Pollutant Parameters
Primary Tungsten 122. lead
125. selenium
128. zinc
ammonia (N)
TSS
pH
Primary Columbium-Tantalum 122. lead
128. zinc
ammonia (N)
fluoride
TSS
pH
Secondary Silver 120. copper
128. zinc
ammonia (N)
TSS
pH
Secondary Lead 114. antimony
115. arsenic
122. lead
128. zinc
TSS
PH
415
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Table X-4
TOXIC POLLUTANTS DETECTED BUT ONLY IN TRACE AMOUNTS
AND ARE NEITHER CAUSING NOR LIKELY TO CAUSE TOXIC EFFECTS
Subcategory
Primary Tungsten
Pollutants
1. acenaphthene
55. naphthalene
77. acenaphthylene
80. fluorene
Primary Columbium-Tantalum
1. acenaphthene
7. chlorobenzene
8. 1,2,4-trichlorobenzene
10. 1,2-dichloroethane
30. 1,2-trans-dichloroethylene
38. ethylbenzene
56. nitrobenzene
85. tetrachloroethylene
Secondary Silver
4. benzene
6. carbon tetrachloride
(tetrachloroemethane)
10. 1,2-dichloroethane
29. 1,1-dichloroethylene
87. trichloroethylene
416
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Table X-5
TOXIC POLLUTANTS EFFECTIVELY CONTROLLED BY TECHNOLOGIES
UPON WHICH ARE BASED OTHER EFFLUENT LIMITATIONS AND GUIDELINES
Subcategory
Primary Aluminum Smelting
Pollutants
1. acenaphthene
39. fluoranthene
72. benzo (a)anthracene
(1,2-benzanthracene)
76. chrysene
77. acenaphthylene
78. anthracene (a)
79. benzo(ghi)perylene
(1,11-benzoperylene)
80. fluorene
81. phenanthrene (a)
82. dibenzo (a,h)anthracene
(1,2,5,6-dibenzanthracene)
84. pyrene
115. arsenic
118. cadmium
119. chromium (Total)
120. copper
122. lead
125. selenium
128. zinc
(a) Reported together.
Secondary Aluminum
118. cadmium
Primary Electrolytic
Copper Refining
114. antimony
115. arsenic
119. chromium (Total)
125. selenium
126. silver
128. zinc
Primary Lead
118.
125.
cadmium
selenium
417
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Table X-5 (Continued)
TOXIC POLLUTANTS EFFECTIVELY CONTROLLED BY TECHNOLOGIES
UPON WHICH ARE BASED OTHER EFFLUENT LIMITATIONS AND GUIDELINES
Subcategory
Primary Zinc
Pollutants
115. arsenic
119. chromium (Total)
124. nickel
125. selenium
126. silver
Metallurgical Acid Plants
114. antimony
119. chromium (Total)
123. mercury
124. nickel
125. selenium
126. silver
Primary Tungsten
118. cadmium
119. chromium (Total)
127. thallium
Primary Columbium-
Tantalum
114. antimony
115. arsenic
119. chromium (Total)
120. copper
124. nickel
125. selenium
127. thallium
Secondary Silver
118. cadmium
119. chromium (Total)
122. lead
124. nickel
Secondary Lead
118. cadmium
119. chromium (Total)
120. copper
124. nickel
126. silver
127. thallium
418
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SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the Clean Water Act is the best available demon-
strated technology (BDT). New plants have the opportunity to
design the best and most efficient production processes and
wastewater treatment technologies. Therefore, BDT^includes
process changes, in-plant controls (including elimination of
wastewater streams), operating procedure changes, and^end-of-pipe
treatment technologies to reduce pollution to the maximum extent
possible. This section describes the control technology for^
treatment of wastewater from new sources and presents mass dis-
charge limitations of regulated pollutants for NSPS, based on the
described control technology.
TECHNICAL APPROACH TO NSPS
All wastewater treatment technologies applicable to a new source
in the nonferrous metals manufacturing category have been consid-
ered previously for the BAT options. For this reason, six
options were considered as the basis for NSPS, all identical to
BAT options in Section X. In summary, the treatment technologies
considered for new facilities are outlined below:
NSPS Option A is based on:
Lime and settle (chemical precipitation of metals,
followed by sedimentation), and, where required
Ammonia steam stripping, and
Oil skimming.
NSPS Option B is based on:
NSPS Option A (lime precipitation and sedimentation),
plus process wastewater flow minimization by the
following methods:
--Casting contact cooling water recycle
--Air pollution control scrubber liquor recycle
Cyanide precipitation.
NSPS Option C is based on:
NSPS Option B (lime precipitation, sedimentation, and
in-process flow reduction), plus multimedia filtration
as an effluent polishing step.
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NSPS Option DI is based on:
NSPS Option C (lime precipitation, sedimentation,
in-process flow reduction, and multimedia filtration),
plus activated alumina preliminary treatment for the
control of arsenic and fluoride.
NSPS Option D2 is based on:
NSPS Option C (lime precipitation, sedimentation,
in-process flow reduction, and multimedia filtration),
plus activated carbon adsorption preliminary treatment
for the control of toxic organics.
NSPS Option E is based on:
NSPS Option C (lime precipitation, sedimentation,
in-process flow reduction, and multimedia^iltration) ,
plus end-of-pipe activated carbon adsorption.
NSPS Option F is based on:
NSPS Option C (lime precipitation, sedimentation,
in-process flow reduction, and multimedia filtration),
plus reverse osmosis so that all wastewaters can be
recycled.
The options listed above are general and can be applied to all
subcategories. Wastewater flow reduction within the nonferrous
metals manufacturing category is generally based on the recycle
of scrubbing liquors and casting contact cooling water. Addi-
tional flow reduction is achievable for new sources through
alternative process methods which are subcategory-specific.
Additional flow reduction attainable for each subcategory is
discussed later in this section regarding the NSPS option
selection.
For several subcategories, the regulatory production normalized
flows for NSPS are the same as the production normalized flows
for the selected BAT option. The mass of pollutant allowed to be
discharged per mass of product is calculated by multiplying the
appropriate treatment effectiveness value (one day maximum and
10-day average values) (mg/1) by the production normalized flows
(1/kkg). When these calculations are performed, the mass-based
NSPS can be derived for the selected option. Effluent concentra-
tions attainable by the NSPS treatment options are identical to
those presented in Section VII.
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MODIFICATIONS TO EXISTING NSPS
New source performance standards have been promulgated for the
primary and secondary aluminum smelting subcategories. The tech-
nology basis for these standards was lime precipitation, sedimen-
tation, and in-process flow reduction of process wastewater. EPA
is proposing modifications to these NSPS to incorporate changes
proposed for BAT and to include additional flow reductions possi-
ble at new sources in the primary aluminum subcategory.
NSPS OPTION SELECTION
In general, EPA is proposing that the best available demonstrated
technology for all 12 subcategories in the nonferrous metals
manufacturing category be equivalent to BAT technology (NSPS
Option C). The principal treatment method for this option is
in-process flow reduction, lime precipitation, sedimentation, and
multimedia filtration. Option C also includes cyanide precipita-
tion, ammonia steam stripping, and oil skimming, where required.
As discussed in Sections IX and X, these technologies are cur-
rently used at plants within this point source category. The
Agency recognizes that new sources have the opportunity to imple-
ment more advanced levels of treatment without incurring the
costs of retrofit equipment, and the costs of partial^or complete
shutdown to install new production equipment. Specifically, the
design of new plants can be based on recycle of contact cooling
water through cooling towers, recycle of air pollution control
scrubber liquor or the use of dry air pollution control
equipment. New plants also have the opportunity to^consider
alternate degassing or slag granulation methods during the
preliminary design of the facility.
The data relied upon for selection of NSPS were primarily the
data developed for existing sources which included costs on a
plant-by-plant basis along with retrofit costs where applicable.
The Agency believes that compliance costs could be lower for new
sources than the cost estimates for equivalent existing^sources,
because production processes can be designed on the basis of
lower flows and there will be no costs associated with retro-
fitting the in-process controls. Therefore, new sources will
have costs that are not greater than the costs that existing
sources would incur in achieving equivalent pollutant discharge
reduction. Based on this analysis, the Agency believes that the
selected NSPS (NSPS Option C) is an appropriate choice.
Section II of this document presents a summary of the NSPS for
the Nonferrous Metals Manufacturing Point Source Category. The
pollutants selected for regulation for each subcategory are
identical to those selected for BAT. Presented below is a brief
discussion describing the technology option selected for NSPS for
e ach sub ca t ego ry.
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PRIMARY ALUMINUM
New source performance standards for primary aluminum are based
on BAT plus additional flow reduction. Additional flow reduction
is achievable through the use of dry air pollution scrubbing on
potlines, anode bake plants, and anode paste plants and elimina-
tion of potroom and degassing scrubber discharges. Potroom
scrubbing discharges are eliminated by design of efficient pot-
line scrubbing (eliminating potroom scrubbing completely) or 100
percent recycle (with blowdown recycled to casting). Degassing
scrubbers are limited by replacing chlorine degassing with inert
gases.
These flow reductions are demonstrated at existing plants, but
are not included in BAT because they might involve substantial
retrofit costs at other existing plants. However, new plants can
include these reductions in plant design at no significant addi-
tional cost. Dry scrubbing also prevents the contamination of
scrubbing discharges with toxic organics, eliminating the need
for activated carbon pretreatment included in the proposed BAT to
control these toxic organics except for plants discharging
wastewater from cathode reprocessing.
The Agency does not believe that the proposed NSPS will provide a
barrier to entry for new facilities. In fact, installation of
dry scrubbing instead of wet scrubbing in new facilities reduces
the cost of end-of-pipe treatment by reducing the overall volume
of wastewater discharged and eliminates the need for activated
carbon pretreatment proposed for BAT except for process
wastewater from cathode reprocessing.
Possible additional pollutant reduction for the primary aluminum
subcategory could be accomplished with activated alumina or
reverse osmosis. These technologies, however, are not demon-
strated in the category nor are they clearly transferable.
SECONDARY ALUMINUM
The technology basis and discharge allowances for NSPS are equiv-
alent to that of the proposed BAT; lime precipitation, sedimenta-
tion and filtration. Reverse osmosis, as noted above, is not
demonstrated and is not deary transferable to nonferrous metals
manufacturing wastewater. The Agency also does not believe that
new plants could achieve any additional flow reduction for chlo-
rine demagging and direct chill casting beyond that proposed for
BAT.
PRIMARY COPPER SMELTING
The proposed NSPS for the primary copper smelting subcategory is
zero discharge of all process pollutants. The Agency believes
422
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that new smelting facilities can be constructed using cooling
towers to cool and recirculate casting contact cooling water and
slag granulation wastewater instead of large volume cooling
impoundments. This technology is also in place in this sub-
category. Thus, this proposal eliminates the allowance for the
catastrophic precipitation discharge allowed at BAT. The costs
associated with construction and operation of a cooling tower
system are not significantly greater than those for cooling
impoundments, and as such, the Agency does not believe that the
proposed NSPS will constitute a barrier for entry of new
facilities.
PRIMARY ELECTROLYTIC COPPER REFINING
The proposed NSPS for the primary electrolytic copper refining
subcategory are equivalent to BAT (based on BAT Alternative B
that includes filtration). Review of the subcategory indicates
that no additional demonstrated technologies exist that improve
on this BAT technology. Reverse osmosis, as noted above, is not
demonstrated and is not clearly transferable to nonferrous metals
manufacturing wastewater. The Agency also does not believe that
new plants could achieve any additional flow reduction beyond
that proposed for BAT.
SECONDARY COPPER
New source performance standards for the secondary copper sub-
cateeory are proposed as zero discharge of all process wastewater
pollutants. It is believed that new sources can be constructed
with cooling towers exclusively and that the cost of cooling ^
towers instead of cooling impoundments is minimal. This elimi-
nates the allowance needed for catastrophic stormwater provided
at BAT. Therefore, NSPS, as defined, does not constitute a
barrier to entry for new plants.
PRIMARY LEAD
The proposed NSPS prohibits the discharge of all process waste-
water pollutants from primary lead smelting. Zero discharge is
achievable through complete recycle and reuse of slag granula-
tlon wastewater or through slag dumping. Elimination ofdis-
charge from slag granulation is demonstrated in six of the seven
extsllng plants! but it is not included at BAT because it would
involve substantial retrofit costs for the one existing dis-
chlrglr by requiring the installation of a modified sintering
machine. New plants can include elimination of the discharge
from ?he slag granulation process in the plant design at no
significant additional cost. Therefore, NSPS does not present
any barrier to entry for new plants.
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PRIMARY ZINC
New source performance standards for the primary zinc subcategory
are proposed equal to BAT. Review of the subcategory indicates
that no new demonstrated technologies exist that improve on BAT.
Reverse osmosis, as noted above, is not demonstrated in this
subcategory and is not clearly transferable to nonferrous metals
manufacturing wastewater.
Dry scrubbing is not demonstrated for controlling emissions from
zinc reduction furnaces, leaching and product casting. The
nature of these emissions (acidic fumes, hot particulate matter)
technically precludes the use of dry scrubbers. Therefore, a
discharge allowance is included from this source at NSPS equiva-
lent to that proposed for BAT. The Agency does not believe that
new plants could achieve any additional flow reduction beyond
that proposed for BAT.
METALLURGICAL ACID PLANTS
New source performance standards for the metallurgical acid
plants subcategory are proposed equal to BAT. Review of the
subcategory indicates that no new demonstrated technologies exist
that improve on BAT. Reverse osmosis, as noted above, is not
demonstrated in this subcategory and is not clearly transferable
to nonferrous metals manufacturing wastewater. The Agency also
does not believe that new plants could achieve any additional
flow reduction beyond that proposed for BAT.
PRIMARY TUNGSTEN
For the primary tungsten subcategory, NSPS are proposed as equal
to BAT. Review of the subcategory indicates that no new demon-
strated technologies that improve on BAT exist. Reverse osmosis,
as noted above, is not demonstrated in this subcategory and is
not clearly transferable to nonferrous metals manufacturing
wastewater.
Dry scrubbing is not demonstrated for controlling emissions from
acid leaching, APT conversion to oxides and tungsten reduction
furnaces. The nature of these emissions (acid fumes, hot par-
ticulate matter) technically precludes the use of dry scrubbers.
Therefore, a discharge allowance is included for these sources at
NSPS equivalent to that proposed for BAT. Also, the Agency does
not believe that new plants could achieve any additional flow
reduction beyond the 90 percent scrubber effluent recycle
proposed for BAT.
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PRIMARY COLUMBIUM-TANTALUM
The proposed NSPS for the primary columbium-tantalum subcategory
is equivalent to BAT. Review of the subcategory indicates that
no new demontrated technologies that improve on BAT exist.
Reverse osmosis, as noted above, is not demonstrated in this
subcategory and is not clearly transferable to nonferrous metals
manufacturing wastewater.
Dry scrubbing is not demonstrated for controlling emissions from
concentration digestion, metal salt drying and salt to metal
reduction. The nature of these emissions (acidic fumes, hot par-
ticulate matter) technically precludes the use of dry scrubbers.
Therefore, a discharge allowance is included for these sources at
NSPS equivalent to that proposed for BAT. The Agency also does
not believe that new plants could achieve any additional flow
reduction beyond that proposed for BAT.
SECONDARY SILVER
The proposed NSPS for the secondary silver subcategory is equiva-
lent to BAT (based on BAT Alternative B which includes filtra-
tion). Review of the subcategory indicates that no new demon-
strated technologies that improve on BAT exist. Reverse osmosis,
as noted above, is not demonstrated in this subcategory and is
not clearly transferable to nonferrous metals manufacturing
wastewater.
Dry scrubbing is not demonstrated for controlling emissions^from
film stripping, precipitation and filtration of film stripping
solutions, precipitation and filtration of photographic solu-
tions, reduction furnaces, leaching and precipitation and
filtration. The nature of these emissions (acidic fumes, hot
particulate matter) technically precludes the use of dry
scrubbers. Therefore, a discharge allowance is included for
these sources at NSPS equivalent to that proposed for BAT. The
Agency also does not believe that new plants could achieve any
additional flow reduction beyond that proposed for BAT.
SECONDARY LEAD
The proposed NSPS for the secondary lead subcategory is equiva-
lent to BAT (based on BAT Alternative B which includes filtra-
tion). Review of the subcategory indicates that no new demon-
strated technologies that improve on BAT exist. Reverse osmosis,
as noted above, is not demonstrated in this subcategory and is
not clearly transferable to nonferrous metals manufacturing
wastewater.
425
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Dry scrubbing is demonstrated for controlling emissions from
kettle smelting. In fact, it is applied so widely throughout
this subcategory that it was selected as the best practicable
control technology currently available for kettle smelting. Dry
scrubbing, however, is not demonstrated for controlling emissions
from blast and reverberatory furnaces, and the nature of these
emissions (hot particulate matter) precludes the use of dry
scrubbing. Therefore, a discharge allowance is included for
these sources at NSPS equivalent to that proposed for BAT. The
Agency also does not believe that new plants could achieve any
additional flow reduction beyond that proposed for BAT.
426
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SECTION XII
PRETREATMENT STANDARDS
Section 307(b) of the Clean Water 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, inter-
fere with, or are otherwise incompatible with the operation of
publicly owned treatment works (POTW). The Clean Water Act of
1977 adds a new dimension by requiring pretreatment for pollu-
tants, such as heavy metals, that limit POTW sludge management
alternatives, including the beneficial use of sludges on agricul-
tural lands. 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 pollutants.
Section 307(c) of the Act requires EPA to promulgate pretreatment
standards for new sources (PSNS) at the same time that it promul-
gates NSPS. New indirect discharge facilities, like new direct
discharge facilities, have the opportunity to incorporate the
best available demonstrated technologies, including process
changes, in-plant controls, and end-of-pipe treatment technolo-
gies, and to use plant site selection to ensure adequate treat-
ment system installation.
General Pretreatment Regulations for Existing and New Sources of
Pollution were published in the Federal Register, Vol. 46, No.
18, Wednesday, January 28, 1981.These regulations describe the
Agency's overall policy for establishing and enforcing pretreat-
ment standards for new and existing users of a POTW and delin-
eates the responsibilities and deadlines applicable to each party
in this effort. In addition, 40 CFR Part 403, Section 403.5(b),
outlines prohibited discharges which apply to all users of a
POTW.
This section describes the treatment and control technology for
pretreatment of process wastewaters from existing sources and new
sources, and presents mass discharge limitations of regulated
pollutants for existing and new sources, based on the described
control technology. It also serves to summarize changes^from
previous rulemakings in the nonferrous metals manufacturing
category.
REGULATORY APPROACH
There are 58 facilities, representing 18 percent of the non-
ferrous metals manufacturing category, who discharge wastewaters
to POTW. Pretreatment standards are established to ensure
427
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removal of pollutants discharged by these facilities which may
interfere with, pass through, or be incompatible with POTW opera-
tions. A determination of which pollutants may pass through or
be incompatible with POTW operations, and thus be subject to pre-
treatment standards, depends on the level of treatment used by
the POTW. In general, more pollutants will pass through or
interfere with a POTW using primary treatment (usually physical
separation by settling) than one which has installed secondary
treatment (settling plus biological treatment).
Many of the pollutants contained in nonferrous metals manufac-
turing wastewaters are not biodegradable and are, therefore, not
effectively treated by such systems. Furthermore, these
pollutants have been known to pass through or interfere with the
normal operations of these systems. Problems associated with the
uncontrolled release of pollutant parameters identified in non-
ferrous metals manufacturing process wastewaters to POTW were
discussed in Section VI.
The Agency based the selection of pretreatment standards for the
nonferrous metals manufacturing category on the minimization of
pass-through of toxic pollutants at POTW. For each subcategory,
the Agency compared removal rates for each toxic pollutant
limited by the pretreatment options to the removal rate for that
pollutant at well-operated POTW. The POTW removal rates were
determined through a study conducted by the Agency at over 40
POTW and a statistical analysis of the data. (See Fate of
Priority Pollutants in Publicly Owned Treatment Works, EPA
440/1-80-301, October. 1980; and Determining National Removal
Credits for Selected Pollutants for Publicly Owned Treatment
Works, EPA 440/82-008, September. 1982.)The POTW removal rates
are presented below:
Toxic Pollutant POTW Removal Rate
Cadmium 38%
Chromium 65%
Copper 58%
Cyanide 52%
Lead 48%
Nickel 19%
Silver 66%
Zinc 65%
Total Regulated Metals 62%
Other pollutants found in nonferrous metals manufacturing waste-
waters include arsenic, antimony, and selenium. There is no data
available to EPA concerning POTW removals for these three toxic
metals. It was assumed, therefore, that these toxic metals pass
428
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through a POTW because they are soluble in water and are not de-
gradable. Specific comments are solicited on the pass-through of
these metals and actual POTW removal performance.
A pollutant is deemed to pass through the POTW when the average
percentage removed nationwide by well-operated POTW, meeting
secondary treatment requirements, is less than the percentage
removed by direct dischargers complying with BAT effluent limita-
tions guidelines for that pollutant. (See generally, 46 FR
9415-16 (January 28, 1981).) For example, if the selected PSES
option removed 90 percent of the cadmium generated by the
subcategory, cadmium would be considered to pass through because
a well-operated POTW would be expected to remove 38 percent.
Conversely, if the selected PSES option removed only 30 percent
of the cadmium generated by the subcategory, it would not be
considered to pass through. In the latter case, cadmium would
not be selected for specific regulation because a well- operated
POTW would have a greater removal efficiency.
The analysis described above was performed for each subcategory
starting with the pollutants selected for regulation at BAT. The
conventional pollutant parameters (TSS, pH, and oil and grease)
and aluminum were not considered for regulation under pretreat-
ment standards. The conventional pollutants are effectively
controlled by POTW while aluminum is used to enhance settling.
For those subcategories where ammonia was selected for specific
limitation, it wUl also be selected for limitation under pre-
treatment standards. Most POTW in the United States are not
designed for nitrification. Hence, aside from incidental
removal, most, if not all, of the ammonia introduced into POTW
will pass through into receiving waters without treatment.
An examination of the percent removal for the selected pretreat -
raent options indicated that the pretreatment option selected
removed at least 95 percent of the toxic pollutants generated in
the nonferrous metals manufacturing point source category. Con-
sequently, the toxics regulated for each subcategory under BAT
will also be regulated under pretreatraent standards. Table XII-1
presents the pollutants selected for regulation for pretreatment
standards.
MODIFICATIONS TO EXISTING PRETREATMENT STANDARDS
Existing pretreatment standards proposed for the nonferrous
metals manufacturing category are being revised to incorporate
the building block approach as discussed earlier. In addition,
information has become available regarding proposed pretreatment
standards that warrant revision of promulgated standards.
429
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Primary Aluminum
Pretreatment standards for new sources were promulgated to limit
the quantity of fluoride discharged from primary aluminum smel-
ters to POTW. The technology basis for this limitation was based
on lime precipitation and sedimentation. PSNS for primary alumi-
num is being revised to incorporate the building block approach
and the technology basis proposed for new sources. Since the
PSNS regulation has been proposed, three additional technologies
have been identified as demonstrated or transferable to the
primary aluminum subcategory. These technologies, filtration,
activated carbon, and dry alumina for scrubbing systems, would
greatly reduce the amount of toxic pollutants discharged by a new
source. A thorough discussion of the building block approach and
selection of regulated pollutant parameters is presented in the
primary aluminum supplement.
Secondary Aluminum
The promulgated pretreatment for existing secondary aluminum
facilities limits the quantity of oil and grease discharged from
metal cooling, the pH from demagging fume scrubbers, and the
quantity of ammonia discharged from residue milling. These mass
limitations are being revised to include additional waste streams
that warrant regulations and to upgrade the technology basis so
that it is analogous to the proposed BAT.
Pretreatment standards promulgated for new sources require zero
discharge of all process generated pollutants into POTW with the
exception of demagging fume scrubber liquor. A discharge from
this scrubber was allowed only when chlorine is used as a demag-
ging agent. Mass limitations developed for this discharge were
based on chemical precipitation and sedimentation technology.
Revision of the proposed pretreatment standard is necessary in
light of comments and information received and to incorporate the
more thorough building block approach. Since the promulgation of
PSNS, the secondary aluminum subcategory has reportedly installed
direct chill casting processes, which cannot meet zero discharge
requirements. An extensive description of the development of
these standards can be found in the secondary aluminum
supplement.
Secondary Copper
The promulgated pretreatment standards for existing sources
allows the discharge of process wastewaters subject to limita-
tions developed from chemical precipitation and sedimentation
technology. Currently promulgated BAT limitations, however,
require zero discharge of all process wastewaters. Therefore,
PSES is being proposed as zero discharge through recycle and
reuse making it equivalent to BAT.
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OPTION SELECTION
The treatment schemes considered for pretreatment standards for
existing sources are identical to those considered for BAT. The
treatment schemes considered for pretreatment standards for new
sources are also identical to those considered for BAT with the
exception of primary aluminum smelting and primary lead where
additional flow reduction is required. Each of the options
considered builds upon the BPT technology basis of chemical
precipitation and sedimentation. Depending on the pollutants
present in the subcategories raw wastewaters, a combination of
the treatment technologies listed below were considered:
o Option A = Lime precipitation, sedimentation, ammonia
steam stripping, and cyanide removal.
o Option B = Option A (lime precipitation, sedimentation,
ammonia steam stripping, and cyanide precipitation), plus
flow reduction.
o Option C = Option B (lime precipitation, sedimentation,
ammonia steam stripping, cyanide precipitation, and flow
reduction), plus multimedia filtration.
o Option DI = Option C (lime precipitation, sedimenta-
tion, ammonia steam stripping, cyanide^precipitation,
flow reduction, and multimedia filtration), plus
activated alumina.
o Option D£ - Option C (lime precipitation, sedimenta-
tion, ammonia steam stripping, cyanide precipitation,
flow reduction, and multimedia filtration), plus
activated carbon preliminary treatment.
o Option E = Option C (lime precipitation, sedimenta-
tion, ammonia steam stripping, cyanide precipitation,
flow reduction, and multimedia filtration), plus
activated carbon at end-of-pipe treatment.
o Option F = Option C (lime precipitation, sedimenta-
tion, ammonia steam stripping, cyanide precipitation,
flow reduction, and multimedia filtration), plus reverse
osmosis.
A more complete discussion of the treatment technologies consid-
ered is presented in Section X regarding the selection of BAT
treatment technologies. The general approach taken by the Agency
for pretreatment standards for this category is presented below.
The mass-based standards for each subcategory may be found xn
Section II of this document. The options selected for the cate-
gory on which to base pretreatment standards are discussed below.
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Primary Aluminum
Pretreatment standards for existing sources will not be proposed
for the primary aluminum smelting subcategory since there are no
existing indirect dischargers.
The technology basis for PSNS is identical to NSPS and includes
flow reduction, lime precipitation, sedimentation, and filtration
for control of toxic metals and fluoride; activated carbon pre-
treatment for toxic organics removal; and cyanide precipitation
pretreatment.
Secondary Aluminum
The technology basis for PSES is lime precipitation and sedimen-
tation, ammonia steam stripping, and filtration. The achievable
concentration for ammonia steam stripping is based on iron and
steel manufacturing category data. Flow reduction is based on the
same zero discharge of scrubber effluent for scrap drying wet air
pollution control which is equivalent to the flow basis of BAT.
Only one indirect discharger uses a wet system to control air
emissions from scrap drying, and it does not practice any recycle
for this system. Ammonia steam stripping and lime precipitation
and sedimentation, and filter technologies are presently
demonstrated in the subcategory. Ammonia air stripping was the
technology basis for the promulgated PSES. Steam stripping is
proposed instead of air stripping because it is a superior
technology in that it does not transfer the pollutant from one
media to another.
As an alternative to mass-based standards, a POTW may elect to
implement concentration-based standards for the secondary
aluminum subcategory. The purpose of mass-based standards is to
encourage recycle and reuse of process wastewaters. Since there
is no additional flow reduction from current practices to the
regulatory flows used to develop the mass-based standards,
concentration-based standards are an appropriate way to ensure
pollutant reduction for this subcategory.
Implementation of the proposed PSES would remove annually an
estimated 1,214 kg of toxic pollutants over estimated raw
discharges. Capital cost for achieving proposed PSES is $2.4
million, and annual cost of $1.6 million.
The technology basis used to develop standards for new sources is
identical to those used for existing sources. There is no
demonstrated technology that is better than the PSES technology
because the only other flow reduction technology available,
reverse osmosis, is neither demonstrated nor clearly transferable
to this subcategory.
432
-------
Primary Copper Smelting
No pretreatment standards for existing sources are proposed for
the primary copper smelting subcategory since there are no
existing indirect dischargers.
The technology basis for proposed PSNS is identical to NSPS (and
BAT), which is zero discharge of all process wastewater pollu-
tants, with no allowance for catastrophic stormwater discharge.
New indirect dischargers will be constructed with cooling towers,
not cooling impoundments, since they will be located near POTW,
suggesting that they will be near heavily populated areas where
land is scarce making the cost of acquiring land to install an
impoundment relatively high. Thus, we do not believe there are
any incremental costs associated with PSNS.
Primary Electrolytic Copper Refining
No pretreatment standards for existing sources are proposed for
the primary electrolytic copper refining subcategory since there
are no existing indirect dischargers.
The technology basis of pretreatment for new sources is based on
lime precipitation, sedimentation, filtration, and 90 percent
recycle for casting contact cooling water. As in NSPS, all other
waste streams generated at copper refineries are not included in
the flow allowance. Flow reduction for new sources is feasible,
based on reverse osmosis because reverse osmosis is not demon-
strated in the nonferrous metals manufacturing category nor it is
clearly transferable.
Secondary Copper
As mentioned earlier in this section, PSES for secondary copper
is being modified to make it equivalent to BAT, or zero dis-
charge. Implementation of the proposed PSES would remove annu-
ally an estimated 4,837 kg of toxic pollutants from raw dis-
charges. Furthermore, it is anticipated that the costs associ-
ated with installation and operation of cooling towers and
holding tanks for indirect dischargers to achieve zero discharge
will be insignificant.
The technology basis for proposed PSNS is identical NSPS, PSES,
and BAT. No allowance for catastrophic stormwater discharges is
provided as is discussed in Chapter XT for NSPS.
Primary Lead
No pretreatment standards for existing sources are proposed for
the primary lead subcategory since there are no existing indirect
dischargers.
433
-------
The technology basis for proposed PSNS is equivalent to NSPS or
zero discharge. As discussed in Chapter XI for NSPS, slag
removed from blast furnaces contains economical recoverable
amounts of lead that are granulated before recycling. New
facilities will have the opportunity to install dry slag condi-
tioning devices to eliminate the usage of wastewater in this
process or implement a 100 percent recycle system of slag
granulation wastewater.
Primary Zinc
No pretreatment standards for existing sources are proposed for
the primary zinc subcategory since there are no existing indirect
dischargers.
The technology basis for proposed pretreatment standards for new
sources is equivalent to NSPS or flow reduction, lime precipita-
tion, sedimentation, and filtration. The PSNS flow allowances
are based on minimization of process wastewater wherever possible
through the use of cooling towers to recycle contact cooling
water and sedimentation basins for wet scrubbing wastewater. The
discharges from contact cooling and scrubbers is based on 90
percent recycle. No additional flow reduction for new sources is
feasible because the only other available flow reduction technol-
ogy, reverse osmosis, is not demonstrated nor is it clearly
transferable to this subcategory. Elimination of wastewater from
scrubbers by installing dry scrubbers is not demonstrated for
controlling emissions from zinc reduction furnaces, leaching and
product casting. Th nature of emissions from these sources
(acidic fumes, hot particulate matter) technically precludes the
use of dry scrubbers.
Metallurgical Acid Plants
Pretreatment standards for existing sources are not proposed for
metallurgical acid plants. There is only one existing indirect
discharger, and its estimated current mass discharge is less than
the level that would be achieved by indirect dischargers with
BAT-equivalent technology (lime precipitation and sedimentation,
flow reduction, and filtration). Consequently, the Agency
believes that the amount of pollutants discharged by this plant
are too insignificant to justify developing PSES.
The proposed technology basis for pretreatment for new sources is
equivalent to NSPS or flow reduction, lime precipitation, sedi-
mentation, and filtration. There is no demonstrated technology
that provides better pollutant removal than that proposed for
PSNS. The acid plant blowdown allowance allocated for PSNS is
based on 90 percent recycle. The Agency believes that no addi-
tional flow reduction is feasible for new sources because the
only other available flow reduction technology, reverse osmosis,
434
-------
is not demonstrated nor is it clearly transferable for this
subcategory.
Primary Tungsten
The technology basis for PSES is equivalent to BAT or wastewater
flow reduction, lime precipitation and sedimentation, ammonia
steam stripping, and filtration. Flow reduction is based on 90
percent recycle of scrubber effluent that is the flow basis of
BAT. This flow rate is achieved by one of the three indirect
dischargers in the subcategory, and filters are demonstrated at
one indirect discharger.
Implementation of the proposed PSES limitations would remove an
estimated 4,075 kg/yr of toxic pollutants over estimated raw
discharge, and an estimated 79,530 kg/yr of ammonia. Capital
cost for achieving proposed PSES is $.396 million, and annual
cost of $.329 million. The intermediate option considered for
PSES was Option B which is equivalent to the selected PSES
technology without filters.
The technology basis for proposed PSNS is identical to PSES. The
PSES flow allowances are based on minimization of process waste-
water wherever possible through the use of cooling towers to
recycle contact cooling water and sedimentation basins for wet
scrubbing wastewater. These discharges are based on 90 percent
recycle of these waste streams. No additional flow reduction for
new sources is feasible because the only other flow reduction
technology, reverse osmosis, is not demonstrated nor is it
clearly transferable for this subcategory. (See Section XII of
the primary tungsten supplement.) Dry scrubbing is not demon-
strated for controlling emissions from acid leaching, APT con-
version to oxides and tungsten reduction furnaces. The nature of
these emissions (acidic fumes, hot particulate matter) techni-
cally precludes the use of dry scrubbers. The only other end-
of-pipe technology, activated carbon, does not significantly
reduce toxic pollutant discharges while increasing costs
ten-fold.
Primary Columbium-Tantalum
The technology basis for proposed PSES is equivalent to BAT or
wastewater flow reduction, lime precipitation and sedimentation,
ammonia steam stripping, and filtration. Flow reduction is based
on 90 percent recycle of scrubber effluent that is the flow basis
of BAT. This flow rate is achieved by both indirect dischargers
in the* subcategory, and filters are demonstrated at direct dis-
chargers in this subcategory.
435
-------
Implementation of the proposed PSES limitations would remove
64,890 kg/yr of toxic pollutants and 8,808 kg/yr of ammonia from
raw discharges. Capital cost for achieving proposed PSES is
$2.47 million, and annual cost of $1.41 million.
The technology basis for proposed PSNS is identical to NSPS, PSES
and BAT. There is no known economically feasible, demonstrated
technology that is better than PSES technology. The PSES flow
allowances are based on minimization of process wastewater
wherever possible through the use of cooling towers to recycle
contact cooling water and sedimentation basins for wet scrubbing
wastewater. The discharges are based on 90 percent recycle of
these waste streams. No additional flow reduction for new
sources is feasible because the only other available flow reduc-
tion technology, reverse osmosis, is not demonstrated nor is it
clearly transferable for this subcategory. Dry scrubbing is not
demonstrated for controlling emissions from concentration diges-
tion, metal salt drying and salt to metal reduction. The nature
of these emissions (acidic fumes, hot particulate matter) tech-
nically precludes the use of dry scrubbers.
Secondary Silver
For PSES, two alternative standards are proposed. As stated in
more detail in Section X of the Secondary Silver Supplement, the
secondary silver subcategory is experiencing structural economic
changes not anticipated in this analysis. Consequently, this
analysis does not adequately reflect the ability of the tolling
segment of the industry to achieve economically proposed stan-
dards based on filtration. Filtration is, however, demonstrated
in the secondary silver subcategory, removes additional toxic
pollutants, and it appears economically achievable based on the
existing economic analysis.
The technology basis for Alternative A is in-process flow
reduction, lime precipitation and sedimentation, and ammonia
steam stripping. Wastewater flow reduction is based on increased
recycle of leaching scrubber water, furnace scrubber water and
casting contact cooling water. Flow reduction is demonstrated
for each of these unit operations in the subcategory, while
chemical precipitation and sedimentation is currently in place at
seven plants in the secondary silver subcategory. Implementation
of Alternative A would remove an estimated 9,731 kg/yr of toxic
pollutants and 1,500 kg/yr over current estimated discharges.
The estimated capital cost for achieving this option is $1.03
million; the estimated annualized cost is $0.958 million.
Alternative B is equivalent to Alternative A with the addition of
filtration as an effluent polishing step. Wastewater flow reduc-
tion is based on increased recycle of leaching scrubber water,
furnace scrubber water and casting contact cooling water. Flow
436
-------
reduction is demonstrated for each of these unit operations in
the subcategory. Filtration is currently in place at three dis-
charging plants in the secondary silver subcategory. Alternative
B would remove annually an estimated 1,561 kg of toxic pollutants
over estimated current discharge, and it would remove 9,792 kg of
toxic pollutants generated by the industry. For both options, an
estimated 149,300 kg of ammonia above estimated current dis-
charges is removed. Capital cost for achieving proposed PSES
Alternative B is $1.14 million, with an annual cost of $1.07
million.
The proposed technology basis for PSNS is equivalent to NSPS or
in-process flow reduction, lime precipitation and sedimentation,
filtration, and ammonia steam stripping. Review of the subcate-
gory indicates that no new demonstrated technologies that improve
on this BAT technology exist. Reverse osmosis, as noted above,
is not demonstrated in this subcategory and is not clearly
transferable to nonferrous metals manufacturing wastewater.
Dry scrubbing is not demonstrated for controlling emissions^from
film stripping, precipitation and filtration of film stripping
solutions, precipitation and filtration of photogrpahic
solutions, reduction furnaces, leaching and precipitation and
filtration. The nature of these emissions (acidic fumes, hot
particulate matter) technically precludes the use of dry scrub-
bers Therefore, an allowance is included for these sources at
PSES equivalent to that proposed for BAT and PSES. The Agency
also does not believe that new plants could achieve any addi-
tional flow reduction beyond that proposed for BAT.
Secondary Lead
Two alternative pretreatment standards are proposed for existing
sources. As stated in Section X of the Secondary^Lead Supple-
ment the secondary lead subcategory is experiencing long-run
market shifts which may affect the structure and composition of
this subcategory. Because these shifts have definite impacts on
the subcategory, the current econoimc analysis may not reflect
the ability of secondary lead plants to achieve standards based
on filtration. Filtration is, however, demonstrated by seven
facilities in the secondary lead subcategocy.
The technology basis for Alternative A is lime precipitation and
sedimJntationpreceded by wastewater flow reduction Flow reduc-
tion is based on 90 percent recycle of scrubber effluent and
castine contact cooling water, and is achieved by two of the 16
indirect dischargers. ^Implementation of Alternative A removes an
estimated 2 470 kg of toxic pollutants over estimated raw dis-
charge The estimated capital cost of this technology is $1.49
million, with an estimated annual cost of $0.56 million.
437
-------
The technology basis for Alternative B is equivalent to Alterna-
tive A plus filtration. Implementation of the proposed Alterna-
tive B PSES would remove annually an estimated 2,625 kg of toxic
pollutants over estimated raw discharge. Removals over estimated
raw discharge are approximately 17,290 kg of toxic pollutants.
Capital cost for achieving proposed PSES Alternative B is $3.04
million, with an annual cost of $1.94 million.
Pretreatment standards for new sources are equivalent to NSPS or
wastewater flow reduction, lime precipitation, sedimentation and
filtration. Flow reduction is based on 90 percent recycle of
scrubber effluent and casting contact cooling water using cooling
towers and holding tanks. There is no known demonstrated tech-
nology that is better than the technology basis proposed for new
secondary lead plants. Furthermore, no additional flow reduction
for new sources is feasible because the only other available flow
reduction technology, reverse osmosis, is not demonstrated for
this subcategory, nor is it clearly transferable. Dry scrubbing
is not demonstrated for controlling emissions from blast and
reverberatory furnaces, and the nature of these emissions (hot
particulate matter) precludes the use of dry scrubbing.
438
-------
Table XII-1
REGULATED POLLUTANT PARAMETERS
Subcategory
Primary Aluminum Smelting
Secondary Aluminum
Primary Electrolytic Copper
Refining
Primary Lead
Primary Zinc
Metallurgical Acid Plants
Primary Tungsten
Primary Columbium-Tantalum
Secondary Silver
Secondary Lead
Pollutant Parameters
73. benzo(a)pyrene
114. antimony
121. cyanide (Total)
124. nickel
fluoride
122. lead
128. zinc
ammonia (N)
120. copper
122. lead
124. nickel
122. lead
128. zinc
118. cadmium
120. copper
122. lead
128. zinc
115. arsenic
118. cadmium
120. copper
122. lead
128. zinc
122. lead
125. selenium
128. zinc
ammonia (N)
122. lead
128. zinc
ammonia (N)
fluoride
120. copper
128. zinc
ammonia (N)
114. antimony
115. arsenic
122. lead
128. zinc
439
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SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
The 1977 amendments to the Clean Water Act added Section
301(b)(2)(E), establishing "best conventional pollutant control
technology" (BCT) for discharge of conventional pollutants from
existing industrial point sources. Biochemical oxygen-demanding
pollutants (6005), total suspended solids (TSS), fecal coli-
form, oil and grease (O&G), and pH have been designated as
conventional pollutants (see 44 FR 44501).
BCT is not an additional limitation, but replaces BAT for the
control of conventional pollutants. In addition to the other
factors specified in Section 304(b)(4)(B), the Act requires that
limitations for conventional pollutants be assessed in light of a
two-part cost-reasonableness test. On October 29, 1982, the
Agency proposed a revised methodology for carrying out BCT analy-
ses (47 FR 49176). The purpose of the proposal was to correct
errors in the BCT methodology originally established in 1977.
Part 1 of the proposed BCT test requires that the cost and level
of reduction of conventional pollutants by industrial dischargers
be compared with the cost and level of reduction to remove the
same type of pollutants by publicly-owned treatment works (POTW).
The POTW comparison figure has been calculated by evaluating the
change in costs and removals between secondary treatment (30 mg/1
BOD and 30 mg/1 TSS) and advanced secondary treatment (10 mg/1
BOD and 10 mg/1 TSS). The difference in cost is divided by the
difference in pounds of conventional pollutants removed, result-
ing in an estimate of the "dollars per pound" of pollutant
removed, that is used as a benchmark value. The proposed POTW
test benchmark is $0.30 per pound (1978 dollars). The annual
incremental cost for each subcategory to remove conventional
pollutants beyond BPT is calculated as:
[(Candidate BCT Annual Cost) - (BPT Annual Cost)]
[(Candidate BCT Conventional Pollutants Removed) -
(BPT Conventional Pollutants Removed)]
Part 2 of the BCT test requires that the cost and level of reduc-
tion of conventional pollutants by industrial dischargers be
evaluated internally to the industry. In order to develop a
benchmark that assesses a reasonable relationship between cost
and removal, EPA has developed an industry cost ratio which
compares the dollar per pound of conventional pollutant removed
in going from primary to secondary treatment levels with that of
eoine from secondary to more advanced treatment levels. The
basis of costs for the calculation of this ratio are the costs
incurred by a POTW. EPA used these costs because: they reflect
441
-------
the treatment technologies most commonly used to remove conven-
tional pollutants from wastewater; the treatment levels associ-
ated with them compare readily to the levels considered for
industrial dischargers; and the costs are the most reliable for
the treatment levels under consideration. The proposed industry
subcategory benchmark is 1.42. If the industry figure for a
subcategory is lower than 1.43, the subcategory passes the BCT
test. This ratio is calculated as:
Total Annual Cost/Pound Removed (BPT to BCT)
Total Annual Cost/Pound Removed (pre-BPT to BPT)
The Agency usually considers two conventional pollutants in the
cost test, TSS and an oxygen-demanding pollutant. Although both
oil and grease and BOD5 are considered to be oxygen-demanding
substances by EPA (see 44 Fed. Reg. 50733), only one can be
selected in the cost analysis to conform to procedures used to
develop POTW costs. Oil and grease is used rather than 8005 in
the cost analysis performed for nonferrous metals manufacturing
waste streams due to the common use of oils in casting operations
in this industry.
BPT is the base for evaluating limitations on conventional
pollutants (i.e., it is assumed that BPT is already in place).
The test evaluates the cost and removals associated with treat-
ment and controls in addition to that specified as BPT.
If the conventional pollutant removal cost of the candidate BCT
is less than the POTW cost, Part 1 of the cost-reasonableness
test is passed and Part 2 (the internal industry test) of the
cost-reasonableness test must be performed. If the internal
industry test is passed, then a BCT limitation is promulgated
equivalent to the candidate BCT level. If all candidate BCT
technologies fail both parts of the cost-reasonableness test, the
BCT requirements for conventional pollutants are equal to BPT.
The BCT test was performed on the 10 subcategories with direct
dischargers and the results are summarized in Table XIII-1. The
cost test was not required for primary copper smelting and
secondary copper since these subcategories have promulgated BPT
effluent limitations requiring zero discharge of process waste-
water pollutants. All of the 10 subcategories failed Part 1 of
the test for both the proposed BAT and intermediate options,
eliminating the need for testing in Part 2. Consequently, BCT is
equivalent to BPT in all subcategories.
442
-------
Table XIII-1
SUMMARY OF BCT TEST IN THE NONFERROUS METALS MANUFACTURING CATEGORY
Comparable
POTW
Incremental
Cost
Proposed
BAT
Proposed
BAT Option
Part 1
Incremen-
tal Cost
Intermedi-
ate Option
Proposed
Intermedi-
ate Option
Part 1
(Pass or
Subcategory
Primary Aluminum
Secondary Aluminum
Primary Electro-
lytic Copper
•£ Refining
u>
Primary Lead
Primary Zinc
Metallurgical
Acid Plants
Primary Tungsten
Primary Columbium-
Tantalum
Secondary Silver
Secondary Lead
Benchmark
$0.
$0.
$0.
$0.
$0.
$0.
$0.
$0.
$0.
$0.
27
27
27
27
27
27
27
27
27
27
(Part 1)
$
$
$
$
$
$
$
$
$
$1
3
15
5
13
8
19
15
76
4
79
.07
.68
.07
.26
.20
.60
.04
.16
.09
.94
(Pass or Fail) (Part
Fail
Fail
Fail
Fail
Fail
Fail
Fail
Fail
Fail
Fail
2
22
0
4
23
19
8
1,700
15
1)
.20
--
.06
.0
.30
.77
.73
.73
.34
Fail)
Fail
Fail
Fail
Fail
Fail
Fail
Fail
Fail
Fail
Fail
-------
SECTION XIV
ACKNOWLEDGEMENTS
The initial draft of this document was prepared by Sverdrup and
Parcel and Associates under Contract No. 68-01-4409. The docu-
ment has been checked and revised at the specific direction of
EPA personnel by Radian Corporation under Contract No.
68-01-6529.
The field sampling programs were conducted under the leadership
of Mr. Garry Aronberg of Sverdrup and Parcel. Preparation and
writing of the initial drafts of this document were accomplished
by Mr. Donald Washington, Project Manager, Mr. Garry Aronberg,
Ms. Claudia O'Leary, Mr. Antony Tawa, Mr. Charles Amelotti, and
Mr. Jeff CarIton of Sverdrup and Parcel. Mr. James Sherman,
Program Manager, Mr. Mark Hereth, Project Director, Mr. Ron
Dickson, Mr. Mike Zapkin, Mr. John Collins, Mr. Tom Grome,
Mr. Marc Papai, Mr. Dave Pierce, Mr. Matt Phillips, and
Ms. Laurie Morgan have contributed in specific assignments in the
final preparation of this document.
The project was conducted by the Environmental Protection Agency,
Metals and Machinery Branch, Mr. Ernst P. Hall, Chief. The tech-
nical project officer is Mr. James Berlow; the previous technical
project officer was Ms. Patricia Williams. The project's legal
advisor is Mr. Steven Silverman, who contributed to this project.
The economic project officer is Mr. John Kukulka. Contributions
from the Monitoring and Data Support Division came from Mr. Rich
Healey.
The cooperation of the Aluminum Association, American Mining
Congress, Aluminum Recycling Association, Tantalum Producers
Association, Secondary Lead Smelters Association, their technical
committees and the individual companies whose plants were sampled
and who submitted detailed information in response to question-
naires is gratefully appreciated.
Acknowledgement and appreciation is also given to the secretarial
staff of Radian Corporation (Ms. Nancy Reid, Ms. Sandra Moore,
Ms. Daphne Phillips, and Ms. Pam Amshey).
445
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SECTION XV
REFERENCES
1. Sampling & Analysis Procedures for Screening of Industrial Efflu-
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Support Laboratory, Cincinnati, OH 45268 (March, 1977, revised
April, 1977).
2. "Mineral Facts and Problems," Bureau of Mines Bulletin 667,
Washington, D.C., Department of the Interior (1975).
3. Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Primary Aluminum Smelting Sub-
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1974).
4. Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Secondary Aluminum Subcategory,
EPA-400/l-74-019e, Environmental Protection Agency (March, 1974).
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Guidelines and Proposed New Source Performance Standards for the
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(February, 1975).
6. Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards for the
Secondary Copper Subcategory, EPA-440/l-75/032c, Environmental
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9 Draft Development Document for Effluent Limitations Guidelines
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Metals Segment, EPA-440/I-76/067, Environmental Protection Agency
(March, 1977).
447
-------
10. "Natural Resources Defense Council v. Train," Environmental
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11. Development Document for Effluent Limitations Guidelines and New
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13. Wilson, Phillip R., Brush Wellman, Inc., Elmore, OH, Personal
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14. Description of the Beryllium Production Processes at the Brush
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15. Phillips, A. J., "The World's Most Complex Metallurgy (Copper,
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17. Technical Study Report: BATEA-NSPS-PSES-PSNS-Textile Mills Point
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18. The Merck Index, 8th edition, Merck Sc Co., Inc., Rahway, NJ
(1968).
19. Rose, A. and Rose, E., The Condensed Chemical Dictionary, 6th
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20. McKee, J. E. and Wolf, H. W. (eds.), Water Quality Criteria, 2nd
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21. Quinby-Hunt, M. S., "Monitoring Metals in Water," American
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22. Fassel, V. A. and Kniseley, R. N., "Inductively Coupled Plasma -
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448
-------
23. Study of selected Pollutant Parameters in Publicly Owned
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24. Schwartz, H. G. and Buzzell, J. C., The Impact of Toxic Poll-
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25. Class notes and research compiled for graduate class, Autumn
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27. Second Interim Report - Textile Industry BATEA-NSPS-PSES-PSNS
Study, report submitted to EPA-Effluent Guidelines Division by
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28. Proposed Criteria for Water Quality, Vol. 1, Environmental Pro-
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29. Morrison, R. T. and Boyd, R. N. , Organic Chemistry, 3rd ed.,
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30. McKee, J. E. and Wolf, H. W. (eds), Water Quality Criteria, 2nd
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Browning, E. , "Toxicity of Industrial Metals," Butterworth, London,
England '(1961).
31 citing Stokinger, H. E. and Woodward, R. L., "Toxicologic
Methods for Establishing Drinking Water Standards," Journal AWWA, 50,
515 (1958).
32 citing Waldichuk, M., "Sedimentation of Radioactive
Wastes in the Sea," Fisheries Research Board of Canada, Circular No.
59 (January, 1961).
449
-------
33. _____ citing "Quality Criteria for Water," U.S. Environmental
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34. Bronstein, M. A., Priviters, E. L., and Terlecky, P. M., Jr.,
"Analysis of Selected Wastewater Samples of Chrysotile Asbestos and
Total Fiber Counts - Nonferrous Metals Point Source Category,"
Calspan Advanced Technology Center, Report No. ND-5782-M-19 for USEPA,
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35. Hallenbeck, W. H. and Hesse, C. S., "A Review of the Health
Effects of Ingested Asbestos," Review of Environmental Health, 2, 3,
157 (1977).
36. McKee, J. E. and Wolf, H. W. (eds), Water Quality Criteria, 2nd
edition, California State Water Resources Control Board, (1963) citing
The Merck Index, 7th ed., Merck & Co., Inc., Rahway, NJ (1960).
37. citing Pomelee, C. S., "Toxicity of Beryllium," Sewage &
Industrial Wastes 25, 1424 (1953).
38. citing Rothstein, "Toxicology of the Minor Metals,"
University of Rochester, AEC Project, UR-262 (June 5, 1953).
39. _^___ citing Truhout, R. and Boudene, C., "Enquiries into the
Fats of Cadmium in the Body During Poisoning: Of Special Interest to
Industrial Medicine," Archiv. Hig. Roda 5, 19 (1954); AMA Archives of
Industrial Health 11, 179 (February, 1955).
40. _____ citing Fairhall, L. T., "Toxic Contaminants of Drinking
Water,*' Journal New England Water Works Association, 55, 400 (1941).
41. citing Ohio River Valley Water Sanitation Commission,
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Laboratory, College of Medicine, University of Cincinnati, Cincinnati,
OH (January 28, 1953).
42. citing "Copper and the Human Organism," Journal American
Water Works Association, 21, 262 (1929).
43. citing Taylor, E. W., "The Examination of Waters and Water
Supplies," P. Blakiston's Son and Co. (1949).
44. citing "Water Quality and Treatment," 2nd ed., AWWA (1950).
450
-------
45. citing Hale, F. E. , "Relation of Copper and Brass Pipe to
Health," Water Works Eng., 95, 240, 84, 139, 187 (1942).
46. citing "Drinking Water Standards," Title 42 - Public
Health; Chapter 1 - Public Health Service, Department of Health,
Education, and Welfare; Part 72 - Interstate Quarantine Federal
Register 2152 (March 6, 1962).
47. citing Derby, R. L., Hopkins, 0. C. , Gullans, 0., Baylis,
J. R., Bean, E. L., and Malony, F., "Water Quality Standards," Journal
American Water Works Association, 52, 1159 (September, 1960).
48. McKee, J. E. and Wolf, H. W. , (eds.), Water Quality Criteria, 2nd
edition, California State Water Resources Control Board, (1963) citing
Klein, L., "Aspects of River Pollution," Butterworth Scientific
Publications, London and Academic Press, Inc., New York (1957).
49. citing Fuchess, H., Bruns, H., and Haupt, H. , "Danger of
Lead Poisoning From Water Supplies," Theo. Steinkopff (Dresden)
(1938); Journal American Water Works Association, 30, 1425 (1938).
50. citing "Ohio River Valley Water Sanitation Commission,
Subcomittee on Toxicities, Metal Finishing Industries Action
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51. Pickering, Q. H. and Henderson, C., "The Acute Toxicity of
Some Heavy Metals to Different Species of Warm Water Fish," Intnat. J.
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52. Murdock, H. R. Industrial Wastes," Ind. Eng. Chem. 99A-102A
(1953T:
53. Calabrese, A., et. al., "The Toxicity of Heavy Metals of
Embryos of the American Oyster, Crassostrea Virginicia," Marine
Biology 38: 162-166 (1973).
54. citing Russell, F. C., "Minerals in Pasture, Deficiencies
and Excesses in Relation to Animal Health," Imperial Bureau of Animal
Nutrition, Aberdeen, Scotland, Tech. Communication 15 (1944).
55t citing Hurd-Kaner, A., "Selenium Absorption by Plants and
their Resulting Toxicity to Animals," Smithsonian Inst. Ann. Rept., p.
289 (1934-35).
451
-------
56. citing Byers, H. G., "Selenium Occurrence i Certain Soils
in the United States with a Discussion of Related Topics," U.S.
Department of Agr. Tech. Bull. No. 582 (August, 1935).
57. citing Fairhall, L. T., "Toxic Contaminants of Drinking
Water," Journal New England Water Works Association, 55, 400 (1941).
58. citing Smith, M. I., Franke, K. W., and Westfall, B. B.,
"Survey to Determine the Possibility of Selenium Detoxification in the
Rural Population Living on Seleniferous Soil," Public Health Repts.
51, 1496 (1936).
59. citing Kehoe, R. A., Cholak, J., and Largent, E. J., "The
Hygienic Significance of the Contamination of Water with Certain
Mineral Constituents," Journal American Water Works Association, 36,
645 (1944).
60. citing Schwarz, K. , "Effects of Trace Amounts of Selenium,"
Proc. Con£. Physiol. Effects of Water Quality, U.S.P.H.S., p. 79
(September, 1960).
61. Water Quality Criteria of 1972. NAS Report.
62. US Department of Agriculture, Agricultural Research
Science, Consumer and Food Economics Research Division, "Food
Consumption of Households in the United States," (Spring, 1965),
Preliminary Report, Agricultural Research Service, Washington, D.C.
63. Hill, W. R. and Pillsburg, D. M., "Argyria Investigation -
Toxicity Properties of Silver," American Silver Producers Research
Project Report, Appendix II.
64. citing Brown, A. W. A., "Insect Control by Chemicals," John
Wiley and Sons (1951).
65. Lougis, P., "The Physiological Effect of Zinc in Seawater,"
Comptes Rendu, Paris, 253:740-741 (1961).
66. _ Wisely, B. and Blick, R. A., "Mortality of Marine
Invertebrate Larvae in Mercury, Copper and Zinc Solutions," Aust. J.
of Mar. Fresh. Res., 18:63-72 (1967).
67. Clarke, G. L., "Poisoning and Recovery in Barnacles and
Mussels," Biol. Bull., 93:73-91 (1947).
452
-------
68. Foreman, C. T., "Food Safety and the Consumer," EPA Jour. 4, 10,
16 (November/December, 1978).
69. Marnahan, S. E., Environmental Chemistry, 2nd ed., Willard Grant
Press, Boston (1975).
70. Methods for Chemical Analysis of Water and Wastes, Environmental
Monitoring and Support Laboratory, EPA-625/6-74-003a USEPA,
Cincinnati, OH (1976).
71. Krocta, H. and Lucas, R. L., "Information Required for the
Selection and Performance Evaluation of Wet Scrubbers," Journal of
Pollution Control Association, 22, 6, 459.
72. Pourbaix, M. , Atlas of Electrochemical Equilibria in Aqueous
Solutions, Pergamon Press, New York (1966) cited in Development Docu-
ment for Interim Final Effluent Limitations Guidlines and Proposed New
Source Performance Standards for the Primary Copper Smelting Subcate-
gory and Primary Copper Refining Subcategory, EPA-440/I-75/032b,
Environmental Protection Agency (February, 1975).
73. Draft Development Document for Effluent Limitations Guidelines
and New Source Performance Standards for the Miscellaneous Nonferrous
Metals Segment, EPA-440/1-76/067, Environmental Protection Agency
(March, 1977) citing Miller, D. G., "Fluoride Precipitation in Metal
Finishing Waste Effluent," Water-1974:1. Industrial Waste Treatment,
American Institute of Chemical Engineers Symposium Series, 70, 144
(1974).
74. Parker & Fong, "Fluoride Removal: Technology and Cost Estimates,"
Industrial Wastes (November/December, 1975).
75. Rohrer, L., "Lime, Calcium Chloride Beat Fluoride Wastewat.er,"
Water and Wastes Engineering (November, 1974), p. 66 cited in Draft
Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Miscellaneous Nonferrous Metals
Segment, EPA-440/1-76/067, Environmental Protection Agency (March,
1977).
76. Zabben, W. and Jewett, H. W. , "The Treatment of Fluoride Wastes,"
Proceedings of 22nd Industrial Waste Conference, Purdue University
(May 2-4, 1967), pp. 706-716.
453
-------
77. Manual of Treatment Techniques for Meeting the Interim Primary
Drinking Water Regulations, EPA-600/8-77-005, Environmental Protection
Agency (April, 1978).
78. Patterson, J.W., "Technology and Economics of Industrial Pollu-
tion Abatement," IIEQ Document #76/22 Project //20.070A (1976).
79. Maruyama, T., Hannah, S. A., and Cohen, J. M. , "Metal Removal by
Chemical Treatment Processes," Journal Water Pollution Control
Federation, 47, 5, 962.
80. Gulp, G. L. and Gulp, R. L., New Concepts in Water Purification,
(Van Nostrand, Reinhold and Company, New York (1974), pp. 222-224.
81. Jenkins, S. N. , Knight, D. G., and Humphreys, R. E., "The
Solubility of Heavy Metal Hydroxides in Water, Sewage, and Sewage
Sludge, I. The Solubility of Some Metal Hydroxides, International
Journal of Air and Water Pollution, 8, 537 (1964).
82. Sittig, M., Pollutant Removal Handbook. Noyes Data Corp., Park
Ridge, NJ (1973).
83. Link, W. E. and Rabosky, J. G. , "Fluoride Removal from Wastewater
Employing Calcium Precipitation and Iron Salt Coagulation," Proceed-
ings of the 31st Industrial Waste Conference, Purdue University, pp.
485-500 (1976).
84. Beychak, M. R., Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley and Sons (1967) cited in Draft Development Document
for Effluent Limitations Guidelines and New Source Performance Stan-
dards for the Miscellaneous Nonferrous Metals Segment, EPA-440/1-76-
067, Environmental Protection Agency (March, 1977).
85. "Stripping, Extraction, Adsorption, and Ion Exchange," Manual on
Disposal of Refinery Wastes - Liquid Wastes, American Petroleum Insti-
tute, Washington, D. C. (1973) cited by Draft Development Document for
Effluent Limitations Guidelines and New Source Performance Standards
for the Miscellaneous Nonferrous Metals Segment, EPA-440/1-76/067 ,
Environmental Protection Agency (March, 1977).
454
-------
86. Grantz, R. G., "Stripper Performance Tied to NH3 Fixation," Oil
and Gas Journal, 73, 24, 80 (1975) cited by Draft Development Document
for Effluent Limitations Guidelines and New Source Performance Stan-
dards for the Miscellaneous Nonferrous Metals Segment, EPA-440/1-
76/067, Environmental Protection Agency (March, 1977).
87. Wrek, W. J. and Snow, R. H. , "Design of Cross Flow Cooling Towers
and Ammonia Stripping Towers," Industrial engineering Process Design
Development, 11, 3 (1972) cited by Draft Development Document for
Effluent Limitations Guidelines and New Source Performance Standards
for the Miscellaneous Metals Segment, EPA-440/1-76-067, Environmental
Protection Agency (March, 1977).
88. Mioderszewski, D., "Ammonia Removal - What's Best," Water and
Wastes Engineering (July, 1975) cited by Draft Development Document
for Effluent Limitations Guidelines and New Source Performance
Standards for the Miscellaneous Metals Segment, EPA-440/1-76-067,
Environmental Protection Agency (March, 1977).
89. Schlauch, R. M. , and Epstein, A. C., Treatment of Metal
Finishing Wastes by Sulfide Precipitation, EPA 600/2-77-049.
90. Coleman, R. T., Colley, D. J., Klausmeier, R. F. , Malish, D. A.,
Meserole, N. P., Micheletti, W. C., and Schwitzgebel, K. , Draft Copy
Treatment Methods for Acidic Wastewater Containing Potentially Toxic
Metal Compounds, Report by Radian Corporation, Austin, TX, submitted
to USEPA Industrial Environmental Research Laboratory, Cincinnati, OH
(1978).
91. Bettler, C. R. , "Lime Neutralization of Low-Acidity Wastewater,"
Proceedings of 32nd Industrial Waste Conference, Purdue University
(1977), p. 830.
92. Permuitt Co., Inc., Proceedings of seminar on metal waste
treatment featuring the Sulfex process, Paramus, NJ, undated.
93. Larson, H. P., Shou, K. P., Ross, L. W., "Chemical Treatment of
Metal Bearing Mine Drainage," Journal Water Pollution Control Feder-
ation 45, 8, 1682 (1974) cited by Coleman, R. T., et. al., Draft Copy
Treatment Methods for Acidic Wastewater Containing Potentially Toxic
Metal Compounds, Report by Radian Corporation, Austin, TX, submitted
to USEPA Industrial Environmental Research Laboratory, Cincinnati, OH
(1978).
455
-------
94. Murao, K. and Sei, N., "Recovery of Hevy Metals from the Waste-
water of Sulfuric Acid Process in Ahio Smelter," Proceedings of Joint
MMIJ AIME Meeting on World Mining and Metallurgical Technology,
Denver, September, 1976, Volume 2, pp. 808-16 (1976) cited by Coleman,
R. T., et. al., Draft Copy Treatment Methods for Acidic Wastewater
Containing Potentially Toxic Metal Compounds, Report by Radian
Corporation, Austin, TX, submitted to USEPA Industrial Environmental
Research Laboratory, Cincinnati, OH (1978).
95. LaPerle, R. L., "Removal of Metals from Photographic Effluent by
Sodium Sulfide Precipitation," Journal Appl. Photogr. Eng. 2, 134,
(1976) cited by Coleman, R. T., et. al.. Draft Copy Treatment Methods
for Acidic Wastewater Containing Potentially Toxic Metal Compounds,
Report by Radian Corporation, Austin, TX, submitted to USEPA Indus-
trial Environmental Research Laboratory, Cincinnati, OH (1978).
96. Scott, M. (Senior Marketing Specialist, Permutit Company),
Private communications with R. Klausmeier (November, 1977) cited by
Coleman, R. T., et. al., Draft Copy Treatment Methods for Acidic
Wastewater Containing Potentially Toxic Metal Compounds, Report by
Radian Corporation, Austin, TX, submitted to USEPA Industrial
Environmental Research Laboratory, Cincinnati, OH (1978).
97. Development Document for Interim Final and Proposed Effluent
Limitations Guidelines and New Source Performance Standards for the
Ore Mining and Dressing Industry, EPA-440/1-75-061, Environmental
Protection Agency (1975) cited by Coleman, R. T., et. al.. Draft Copy
Treatment Methods for Acidic Wastewater Containing Potentially Toxic
Metal Compounds, Report by Radian Corporation, Austin, TX, submitted
to USEPA Industrial Environmental Research Laboratory, Cincinnati, OH
(1978).
98. Coleman, R. T. and Malish, D. A., Trip Report to Paul Bergoe and
Son, Boliden Aktiebolag and Outokumpu as part of EPA Contract
68-02-2608, Radian Corporation (November, 1977) cited by Coleman, R.
T., et. al., Draft Copy Treatment Methods for Acidic Wastewater
Containing Potentially Toxic Metal Compounds, Report by Radian
Corporation, Austin, TX, submitted to USEPA Industrial Environmental
Research Laboratory, Cincinnati, OH (1978).
99. Maltson, M. E., "Membrane Desalting Gets Big Push," Water and
Wastes Engineering (April, 1975), p. 35.
456
-------
100. Cruver, J. E. , "Reverse Osmosis for Water Reuse," Gulf
Environmental System (June, 1973).
101. _^_^ "Water Renovation of Municipal Effluents by Reverse
Osmosis," Gulf Oil Corporation, San Diego (February, 1972).
102. Spatz, D. D. , "Methods of Water Purification," Presented to the
American Association of Nephrology Nurses and Technicians at the ASA10
AANNT Joint Conference, Seattle, Washington (April, 1972).
103. Donnelly, R. G., Goldsmith, R. L. , McNulty, K. J., Grant, D. C. ,
and Tan, M. , Treatment of Electroplating Wastes by Reverse Osmosis,
EPA-600/2-76-261, Environmental Protection Agency (September, 1976).
104. Rook, J. J., "Haloforms in Drinking Water," Journal American
Water Works Association, 68:3:168 (1976).
105. Rook, J. J., "Formation of Haloforms During Chlorination of
Natural Waters," Journal Water Treatment Examination, 23:234 (1974).
106. Trussell, R. R. and Umphres, M. D. , "The Formation of
Trihalomethanes," Journal American Water Works Association 70:11:604
(1978).
107. Nebel, C. , Goltschlintg, R. D. , Holmes, J. L. , and Unangst, P.
C., "Ozone Oxidation of Phenolic Effluents," Proceedings of the 31st
Industrial Waste Conference, Purdue University (1976), pp. 940-951.
108. Rosen, H. M., "Wastewater Ozonation: a Process Whose Time Has
come," Civil Engineering, 47, 11, 65 (1976).
109. Hardisty, D. M. and Rosen, H. M. , "Industrial Wastewater
Ozonation," Proceedings of the 32nd Industrial Waste Conference,
Purdue University (1976), pp. 940-951.
110. Traces of Heavy Metals in Water Removal Processes and Monitoring,
EPA-902/9-74-D01, Environmental Protection Agency (November, 1973).
Ill Symons J. M. , "Interim Treatment Guide for Controlling Organic
Contaminants in Drinking Water Using Granular Activated Carbon, Water
Supply Research Division, Municipal Environmental Research Laboratory,
Office of Research and Development, USEPA, Cincinnati, OH (January,
1978).
457
-------
112. McCreary, J. J. and V. L. Snoeyink, "Granular Activated Carbon in
Water Treatment," Journal American Water Works Association, 69, 8,
437 (1977).
113. Grieves, C. G. and Stevenson, M. K., "Activated Carbon Improves
Effluents," Industrial Wastes (July/August, 1977), pp. 30-35.
114. Beebe, R. L. and Stevens, J. I., "Activated Carbon System for
Wastewater Renovation," Water and Wastes Engineering (January, 1967),
pp. 43-45.
115. Gulp, G. L. and Shuckrow, A. J., "What lies ahead for PAC," Water
and Wastes Engineering (February, 1977), pp. 67-72, 74.
116. Savinelli, E. A. and Black, A. P., "Defluoridation of Water with
Activated Alumina," Journal American Water Works Association, 50, 1,
33 (1958).
117. Paulson, E. G., "Reducing Fluoride in Industrial Wastewater,"
Chemical Engineering, Deskbook Issue (October 17, 1977).
118. Bishop, P. L. and Sansovey, G., "Fluoride Removal from Drinking
Water by Fluidized Activated Alumina Adsorption," Journal American
Water Works Association, 70,10,554 (1978).
119. Harmon, J. A. and Kalichman, S. G., "Defluoridation of Drinking
Water in Southern California," Journal American Water Works
Association, 57:2:245 (1965).
120. Maier, F. J., "Partial Defluoridation of Water," Public Works,
91:90 (1960).
121. Bellack, E., "Arsenic Removal from Potable Water," Journal
American Water Works Association, 63, 7 (1971).
122. Gupta, S. K. and Chen, K. Y., "Arsenic Removal by Adsorption,"
Journal Water Pollution Control Association (March, 1978), pp.
493-506.
123. Johnson, D. E. L., "Reverse Osmosis Recycling System for
Government Arsenal," American Metal Market (July 31, 1973) cited in
Draft Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Miscellaneous Nonferrous Metals
Segment, EPA-440/1-76-067, Environmental Protection Agency (March,
1977).
458
-------
124. Nachod, F. C. and Schubert, J., Ion Exchange Technology, Academic
Press, Inc. (1956).
125. Volkert, David, and Associates, "Monograph on the Effectiveness
and Cost of Water Treatment Processes for the Removal of Specific
Contaminants," EPA 68-01-1833, Office of Air and Water (1974) cited by
Contaminants Associated with Direct and Indirect Reuse of Municipal
Wastewater, EPA-600/1-78-019 (March, 1978).
126. Clark, J. W., Viessman, W. , Jr., and Hammer, M., Water Supply and
Pollution Control, (3rd ed.) IEP, New York (1977).
127. AWARE (Associated Water and Air Resources Engineers, Inc.),
Analysis of National Industrial Water Pollution Control Costs," (May
21, 1973).
128. AWARE, "Alternatives for Managing Wastewater in the Three Rivers
Watershed Area," (October, 1972).
129. Bechtel, "A Guide to the Selection of Cost-Effeetive Wastewater
Treatment Systems," EPA 430/9-75-002 (July, 1975).
130. Smith, R. , "Cost of Conventional and Advanced Treatment of
Wastewater," Journal Water Pollution Control Federation, 40, 9, 1546
(1968).
131. Icarus, "Capital and Operating Costs of Pollution Control
Equipment Modules," Vol. I and II, EPA-R5-73-023a & b (July, 1973).
132. Monti, R. P. and Silberman, P. T. , "Wastewater System
Alternatives: What Are They... and What Cost0" Water and Waste
Engineering (May, 1974), p. 40.
133. Process Design Manual for Removal of Suspended Solids,
EPA-625/175-003a (January, 1975).
134. Process Design Manual for Carbon Adsorption, EPA 625/l-71-002a
(October, 1973).
135. Grits, G. J., "Economic Factors in Water Treatment," Industrial
Water Engineering (November, 1971), p. 22.
459
-------
136. Barnard, J. L. and Eckenfelder, W. W., Jr., "Treatment Cost
Relationships for Industrial Waste Treatment,: Environmental and Water
Resources Engineering, Vanderbilt University (1971).
137. Grits, G. J. and Glover, G. G., "Cooling Slowdown in Cooling
Towers," Water and Wastes Engineering (April, 1975), p. 45.
138. Kremen, S. S., "The True Cost of Reverse Osmosis," Industrial
Wastes (November/December, 1973), p. 24.
139. Cruver, J. E. and Sleigh, J. H., "Reverse Osmosis - The Emerging
Answer to Seawater Desalination," Industrial water Engineering
(June/July, 1976), p. 9.
140. Doud, D. H., "Field Experience with Five Reverse Osmosis Plants,"
Water and Sewage works (June, 1976), p. 96.
141. Lacey. R. E. and Loed, S., (eds.), "Industrial Processing with
Membranes, in The Cost of Reverse Osmosis, John Wiley and Sons
(1972).
142. Disposal of Brines Produced in Renovation of Industrial
Wastewater, FWQA Contract #14-12-492 (May, 1970).
143. Process Design Manual for Sludge Treatment and Disposal, EPA
625/1-74-006 (October, 1974).
144. Black & Veatch, "Estimating Cost and Manpower Requirements for
Conventional Wastewater Treatment Facilities," EPA Contract //14-12-462
(October, 1971).
145. Osmonics, Inc., "Reverse Osmosis and Ultrafiltration Systems
Bulletin No. G7606," (1978).
146. Buckley, J. D., "Reverse Osmosis; Moving from Theory to
Practice," From Fluid Systems Div., UOP, Inc. (Reprint from Consulting
Engineer), 45, 5, 55 (1975).
147. Process Design Manual for Nitrogen Control, EPA-Technology
Transfer (October, 1975).
148. Rizzo & Shepherd, "Treating Industrial Wastewater with Activated
Carbon," Chemical Engineering (January 3, 1977).
460
-------
149. Richardson, "1978-79 Process Equipment, Vol. 4 of Richardson
Rapid System."
150. Thiansky, D. P. , "Historical Development of Water Pollution
Control Cost Functions," Journal Water Pollution Control Federation,
46, 5, 813 (1974).
151. Zimmerman, 0. T., "Wastewater Treatment," Cost Engineering
(October, 1971), p. 11.
152. Watson, I. C. , (Control Research, Inc.) "Manual for Calculation
of Conventional Water Treatment Costs," Office of Saline Water (March,
1972).
153. Gulp, R. L., Wesner, G. M., Gulp, G. L., Handbook of Advanced
Wastewater Treatment, McGraw-Hill (1978).
154. Dynatech R/D Company, A Survey of Alternate Methods for Cooling
Condenser Discharge Water Large-Scale Heat Rejection Equipment, EPA
Project No. 16130 DHS (July, 1969).
155. Development Document for Steam Electric Power Generating, EPA
440/1-73/029 (March, 1974).
156. "Cooling Towers - Special Report," Industrial Water Engineering
(May, 1970).
157. AFL Industries, Inc., "Product Bulletin #12-05.Bl (Shelter
Uses)," Chicago,m IL (December 29, 1977).
158. Fisher Scientific Co., Catalog 77 (1977).
159. Isco, Inc., Purchase Order Form, Wastewater Samplers (1977).
160. Dames & Moore, Construction Cost for Municipal Wastewater
Treatment Plants: 1973-1977, EPA-430/9-77-013, MCD-37 (January, 1978).
161. Metcalf Sc Eddy, Inc., Wastewater Engineering: Collection,
Treatment, Disposal, McGraw-Hill, New York (1972).
162. Obert, E. F. and Young, R. L., Elements of Thermodynamics and
Heat Transfer, McGraw-Hill (1962), p. 270.
461
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163. Paulson, E. G. , "How to Get Rid of Toxic Organics," Chemical
Engineering, Deskbook Issue (October 17, 1977), pp. 21-27.
164. CH2-M-Hill, "Estimating Staffing for Municipal Wastewater
Treatment Facilities," EPA #68-01-0328 (March, 1973).
165. "EPA Indexes Reflect Easing Costs," Engineering News Record
(December 23, 1976)-, p. 87.
166. Chemical Marketing Reporter, Vol. 210, 10-26 (December 6 and
December 20, 1976).
167. Smith, J. E., "Inventory of Energy Use in Wastewater Sludge
Treatment and Disposal," Industrial Water Engineering (July/August,
1977).
168. Jones, J. L. , Bomberger, D. C. , Jr., and Lewis, F. M. , "Energy
Usage and Recovery in Sludge Disposal, Parts 1 St 2," Water and Sewage
Works (July and August, 1977), pp. 44-47 and 42-46.
169. Hagen, R. M. and Roberts, E. B., "Energy Requirements for
Wastewater Treatment, Part 2," Water and Sewage Works (December,
1976), p. 52.
170. Banersi, S. K. and O'Conner, J. T., "Designing More Energy
Efficient Wastewater Treatment Plants," Civil Engineering (September,
1977), p. 76.
171. "Electrical Power Consumption for Municipal Wastewater
Treatment," EPA-R2-73-281 (1973).
172. Hillmer, T. J., Jr., "Economics of Transporting Wastewater
Sludge," Public Works (September, 1977), p. 110.
173. Ettlich, W. F., "Economics of Transport Methods of Sludge,"
Proceedings of the Third National Conference on Sludge Management,
Disposal and Utilization (December 14-16, 1976), pp. 7-14.
174. NUS/Rice Laboratory, "Sampling Prices," Pittsburgh, PA (1978).
175. WARF Instruments, Inc., "Pricing Lists and Policies," Madison, WI
(June, 15, 1973).
462
-------
176. Orlando Laboratories, Inc., "Service Brochure and Fee Schedule
#16," Orlando, FL (January 1, 1978).
177. St. Louis Testing Laboratory, "Water and Wastewater Analysis -
Fee Schedule," St. Louis, MO (August, 1976).
178. Ecology Audits, Inc., "Laboratory Services - Individual Component
Analysis," Dallas, TX (August, 1976).
179. Laclede Gas Company, (Lab Div.), "Laboratory Pricing Schedule,"
St. Louis, MO (August, 1977).
180. Industrial Testing Lab, Inc., "Price List," St. Louis, MO
(October, 1975).
181. Luther, P. A., Kennedy, D. C., and Edgerley, E., Jr. "Treatabi-
lity and Functional Design of a Physical-Chemical wastewater Treatment
System for a Printing and Photodeveloping Plant," 31st Purdue Indus-
trial Waste Conference, pp. 876-884 (1976).
182. Hindin, E. and Bennett, P. J., "Water Reclamation by Reverse
Osmosis," Water and Sewage Works, 116, 2, 66 (February, 1969).
183. Cruver, J. E. and Nusbaum, I., "Application of Reverse Osmosis to
Wastewater Treatment," Journal Water Pollution Control Association,
476, 2, 301 (February, 1974).
184. Cruver, J. E., "Reverse Osmosis - Where It Stands Today," Water
and Sewage Works, 120, 10, 74 (October, 1973).
185. Vanderborght, B. M. and Vangrieken, R. E. , "Enrichment of Trace
Metals by Adsorption on Activated Carbon," Analytic Chemistry, 49, 2,
311 (February, 1977).
186. Hannah, S. A., Jelus, by Physical and Chemical Treatment
Processes," Journal Water Pollution Control Federation, 50, 11, 2297
(1978).
187. Argo, D. G. and Gulp, G. L., "Heavy Metals Removed in Wastewater
Treatment'Processes - Parts 1 and 2," Water and Sewage Works, August,
1972, pp. 62-65, and September, 1972, pp. 128-132.
463
-------
188. Hager, D. G., "Industrial Wastewater Treatment by Granular
Activated Carbon," Industrial Water Engineering, pp. 14-28
(January/February, 1974) 189. Rohrer, K. L., "Chemical Precipitants
for Lead-Bearing Wastewaters," Industrial Water Engineering, 12, 3 13
(1975).
189. Brody, M. A. and Lumpkins, R. J., "Performance of Dual-Media
Filters," Chemical Engineering Progress (April, 1977).
190. Bemardin, F. E., "Cyanide Detoxification using Absorption and
Catalytic Oxidation," Journal Water Pollution Control Federation, 45,
2 (February, 1973).
191. Russel, D. L. , "PCB's: The Problem Surrounding Us and What Must
be Done," Pollution Engineering (August, 1977).
192. Chriswell, C. D., et. al., "Comparison of Macroreticular Resin
and Activated Carbon as Sorbents," Journal American Water Works
Association (December, 1977).
193. Gehm, H. W. and Bregman, J. I., Handbook of Water Resources and
Pollution Control, Van Nostrand Reinhold Company (1976).
464
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SECTION XVI
GLOSSARY
This section is an alphabetical listing of technical terms (with
definitions) used in this document which may not be familiar to
the reader.
4-AAP Colorimetric Method
An analytical method for total phenols and total phenolic com-
pounds that involves reaction with the color developing agent
4-aminoantipyrine.
Acidity
The quantitative capacity of aqueous solutions to react with
hydroxyl ions. Measured by titration with a standard solution of
a base to a specified end point. Usually expressed as milligrams
per liter of calcium carbonate.
The Act
The Federal Water Pollution Control Act Amendments of 1972 as
amended by the Clean Water Act of 1977 (PL 92-500).
Amortization
The allocation of a cost or account according to a specified
schedule, based on the principal, interest and period of cost
allocation.
Analytical Quantification Level
The minimum concentration at which quantification of a specified
pollutant can be reliably measured.
Anglesite
A mineral occurring in crystalline form or as a compact mass.
Antimonial Lead
An alloy composed of lead and up to 25 percent antimony.
Backwashing
The oneration of cleaning a filter or column by reversing the
flow of liquid through it and washing out matter previously
trapped.
465
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Baghouses
The area for holding bag filters, an air pollution control
equipment device.
Ball Mill
Pulverizing equipment for the grinding of raw material. Grinding
is done by steel balls, pebbles, or rods.
Barton Process
A process for making lead oxide to be used in secondary lead
oxide batteries. Molten lead is fed, agitated, and stirred in a
pot with the resulting fine droplets oxidized. Material is col-
lected in a settling chamber where crystalline varieties of lead
oxide are formed.
Batch Treatment
A waste treatment method where wastewater is collected over a
period of time and then treated prior to discharge. Treatment is
not continuous, but collection may be continuous.
Bench Scale Pilot Studies
Experiments providing data concerning the treatability of a
wastewater stream or the efficiency of a treatment process con-
ducted using laboratory-size equipment.
Best Available Demonstrated Technology (BADT)
Treatment technology upon new source performance standards as
defined by Section 306 of the Act.
Best Available Technology Economically Achievable
Level of technology applicable to toxic and nonconventional pol-
lutants on which effluent limitations are established. These
limitations are to be achieved by July 1, 1984 by industrial dis-
charges to surface waters as defined by Section 301(b)(2)(C) of
the Act.
Best Conventional Pollutant Control Technology (BCT)
Level of technology applicable to conventional pollutant effluent
limitations to be achieved by July 1, 1984 for industrial dis-
charges to surface waters as defined in Section 301(b)(2)(E) of
the act.
466
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Best Management Practices (BMP)
Regulations intended to control the release of toxic and hazard-
ous pollutants from plant runoff, spillage, leaks, solid waste
disposal, and drainage from raw material storage.
Best Practicable Control Technology Currently Available (BPT)
Level of technology applicable to effluent limitations to have
been achieved by July 1, 1977 (originally) for industrial dis-
charges to surface waters as defined by Section 301(b)(l)(A) of
the Act.
Betterton Process
A process used to remove bismuth from lead by adding calcium and
magnesium. These compounds precipitate the bismuth which floats
to the top of the molten bath where it can be skimmed from the
molten metal.
Billet
A long, round slender cast product used as raw material in
subsequent forming operations.
Biochemical Oxygen Demand (BOD)
The quantity of oxygen used in the biochemical oxidation of
organic matter under specified conditions for a specified time.
Blast Furnace
A furnace for smelting ore concentrates. Heated air is blown in
at the bottom of the furnace, producing changes in the combustion
rate.
Blister Copper
Copper with 96 to 99 percent purity and appearing blistered; made
by forcing air through molten copper matte.
Slowdown
The minimum discharge of circulating water for the purpose of
discharging dissolved solids or other contaminants contained in
the water the further buildup of which would cause concentration
in amounts exceeding limits established by best engineering
practice.
467
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Calcining
Heating to a high temperature without fusing so as to remove
material or make other changes.
Carbon Reduction
The process of using the carbon of coke as a reducing agent in
the blast furnace.
Cementation
A proces in which metal is added to a solution to initiate the
precipitation of another metal. For example, iron may be added
to a copper sulfate solution to precipitation Cu:
CuS04 + Fe -> Cu + FeS04
Cerussite
A mineral occurring in crystalline form and made of lead
carbonate.
Charged
Material that has been melted by being placed inside a furnace.
Charging Scrap
Scrap material put into a furnace for melting.
Chelation
The formation of coordinate covalent bonds between a central
metal ion and a liquid that contains two oc more sites for com-
bination with the metal ion.
Chemical Oxygen Demand (COD)
A measure of the oxygen-consuming capacity of. the organic and
inorganic matter present in the water oc wastewater.
Cold-Crucible Arc Me1ting
Melting and purification of metal in a cold refractory vessel or
pot.
Colloid
Suspended solids whose diameter may vary between less than one
micron and fifteen microns.
468
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Composite Samples
A series of samples collected over a period of time but combined
into a single sample for analysis. The individual samples can be
taken after a specified amount of time has passed (time compo-
sited), or after a specified volume of water has passed the sam-
pling point (flow composited). The sample can be automatically
collected and composited by a sampler or can be manually
collected and combined.
Consent Decree (Settlement Agreement)
Agreement between EPA and various environmental groups, as insti-
tuted by the United States District Court for the District of
Columbia, directing EPA to study and promulgate regulations for
the toxic pollutants (NRDC, Inc. v. Train, 8 ERG 2120 (D.D.C.
1976), modified March 9, 1979, 12 ERG 1833, 1841).
Contact Water
Any water or oil that comes into direct contact with the alumi-
num, whether it is raw material, intermediate product, waste
product, or finished product.
Continuous Casting
A casting process that produces sheet, rod, or other long shapes
by solidifying the metal while it is being poured through an
open-ended mold using little or no contact cooling water. Thus,
no restrictions are placed on the length of the product and it is
not necessary to stop the process to remove the cast product.
Continuous Treatment
Treatment of waste streams operating without interruption as
opposed to batch treatment. Sometimes referred to as flow-
through treatment.
Contractor Removal
Disposal of oils, spent solutions, or sludge by a commercial
firm.
Conventional Pollutants
Constitutents of wastewater as determined by Section 304(a)(4) of
the Act, including but not limited to pollutants classified as
biological-oxygen-demanding, oil and grease, suspended solids,
fecal coliforms, and pH.
469
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Converting
The process of blowing air through molten metal to oxidize
impurities.
Cooling Tower
A hollow, vertical structure with internal baffles designed to
break up falling water so that it is cooled by upward-flowing air
and the evaporation of water.
Copper Matte
An impure sulfide mixture formed by smelting the sulfide ores in
copper.
Cupelled
Refined by means of a small shallow porous bone cup that is used
in assaying precious metals.
Cupola Furnace
A vertical cylindrical furnace for melting materials on a small
scale. This furnace is similar to a reverberatory furnace but
only on a smaller scale.
Cyclones
A funnel-shaped device for removing particulates from air or
other fluids by centrifugal means.
Data Collection Portfolio_(_dcp_)_
The questionnaire used in the survey of the aluminum forming
industry.
Degassing
The removal of dissolved hydrogen from the molten aluminum prior
to casting. This process also helps to remove oxides and
impurities from the melt.
Direct Chill Casting
A method of casting where the molten aluminum is poured into a
water-cooled mold. The base of this mold is the top of a
hydraulic cylinder that lowers the aluminum first through the
mold and then through a water spray and bath to cause solidifica-
tion. The vertical distance of the drop limits the length of the
ingot. This process is also known as semi-continuous casting.
470
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Direct Discharger
Any point source that discharges to a surface water.
Pore
Gold and silver bullion remaining in a cupelling furnace after
oxidized lead is removed.
Drosjs
Oxidized impurities occurring on the surface of molten metal.
Drying Beds
Areas for dewatering of sludge by evaporation and seepage.
Effluent
Discharge from a point source.
Effluent Limitation
Any standard (including schedules of compliance) established by a
state or EPA on quantities, rates, and concentrations of chemi-
cal physical, biological, and other constituents that are dis-
charged from point sources into navigable waters, the waters of
the contiguous zone, or the ocean.
Electrolysis
A method of producing chemical reactions by sending electric
current through electrolytes or molten salt.
Electrolytic Refining
A purification process in which metals undergo electrolysis.
Electrolytic Slime
Insoluble impurities removed from the bottom of an electrolytic
cell during electrolytic refining.
Electron Beam Melting
A melting process in which an electron beam is used as a heating
source.
471
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Electrostatic Precipitator (ESP)
A gas cleaning device that induces an electrical charge on a
solid particle which is then attracted to an oppositely charged
collector plate. The collector plates are intermittently
vibrated to discharge the collected dust to a hopper.
End-of-Pipe Treatment
The reduction of pollutants by wastewater treatment prior to dis-
charge or reuse.
Film Stripping
Separation of silver-bearing material from scrap photographic
film.
Fluid Bed Roaster
A type of roaster in which the material is suspended in air
during roasting.
Fluxes
Substances added to molten metal to help remove impurities and
prevent excessive oxidation, or promote the fusing of the metals.
Galena
A bluish gray mineral occurring in the form of crystals, masses,
or grains; it constitutes the principal ore of lead,
Gangue
Valueless rock and mineral mined with ore. When separated from
ore, the material is known as "slag."
Gas Chromatography/Mass Spectroscopy (GC/MS)
Chemical analytical instrumentation used foe quantitative organic
analysis.
Grab Sample
A single sample of wastewater taken without regard to time oc
flow.
Hardeners
Master alloys that are ad
-------
Harris Process
A process in which sodium hydroxide and sodium nitrate are added
to molten lead to soften or refine it. These two compounds react
with impurities in the molten metal forming a slag that floats to
the top of the molten metal.
Humidification Chamber
A chamber in which the water vapor content of a gas is increased.
Hydrogenat ion
The addition of hydrogen to a molecule.
Hydrometallurgical
The use of wet processes to treat metals.
Indirect Discharger
Any point source that discharges to a publicly owned treatment
works.
Inductively-Coupled Argon Plasma. Spectrophotometer (ICAP)
A laboratory device used for the analysis of metals.
Ingot
A large, block-shaped casting produced by various methods.
Ingots are intermediate products from which other products are
made.
In-Process Control Technology
Any procedure or equipment used to conserve chemicals and water
throughout the production operations, resulting in a reduction of
the wastewater volume.
Litharge
A yellowish compound with a crystalline form; also known as lead
monoxide.
Matte
A metal sulfide mixture produced by smelting sulfide ores.
473
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Mitsubishi Process
A process used in primary copper refining which incorporates
three furnaces to combine roasting, smelting, and converting into
one continuous proces. The Mitsubishi process results in reduced
smelting rates and heating costs.
New Source Performance Standards (NSPS)
Effluent limitations for new industrial point sources as defined
by Section 306 of the Act.
Nonconventional Pollutant
Parameters selected for use in performance standards that have
not been previously designated as either conventional or toxic
pollutants.
Non-Water Quality Environmental Impact
The ecological impact as a result of solid, air, or thermal pol-
lution due to the application of various wastewater technologies
to achieve the effluent guidelines limitations. Also associated
with the non-water quality aspect is the energy impact of waste-
water treatment.
NPDES Permits
Permits issued by EPA or an approved state program under the
National Pollution Discharge Elimination System.
Off-Gases
Gases, vapors, and fumes produced as a result of an aluminum
forming operation.
Oil and Grease (OScG)
Any material that is extracted by freon from an acidified sample
and that is not volatilized during the analysis, such as hydro-
carbons, fatty acids, soaps, fats, waxes, and oils.
Outokumpu Furnaces
A furnace used for flash smelting, in which hot sulfide concen-
trate is fed into a reaction shaft along with preheated air and
fluxes. The concentrate roasts and smelts itself in a single
autogeneous proces s.
474
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Parke ' s Process
A process in which zinc is added to molten lead to form insoluble
zinc-gold and zinc-silver compounds. The compounds are skimmed
and the zinc is removed through vacuum de-zincing.
Pelletized
An agglomeration process in which an unbaked pellet is heat
hardened. The pellets increase the reduction rate in a blast
furnace by improving permeability and gas-solid contact.
The pH is the negative logarithm of the hydrogen ion activity of
a solution.
Pollutant Parameters
Those constituents of wastewater determined to be detrimental
and, therefore, requiring control.
Precipitation Supernatant
A liquid or fluid forming a layer above precipitated solids.
Priority Pollutants
Those pollutants included in Table 2 of Committee Print number
95-30 of the "Committee on Public Works and Transportation of the
House of Representatives," subject to the Act.
Process Water
Water used in a production process that contacts the product, raw
materials, or reagents.
Production Normalizing Parameter (PNP)
The unit of production specified in the regulations used to
determine the mass of pollution a production facility may
discharge.
PSES
Pretreatment standards (effluent regulations) for existing
sources.
PSNS
Pretreatment standards (effluent regulations) for new sources.
475
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Publicly Owned Treatment Works (POTW)
A waste treatment facility that is owned by a state or
municipality.
Pug Mill
A machine for mixing and tempering a plastic material by the
action of blades revolving in a drum or trough.
Pyrometallurgical
The use of high-temperature processes to treat metals.
Raffinate
Undissolved liquid mixture not removed during solvent refining.
Recycle
Returning treated or untreated wastewater to the production pro-
cess from which it originated for use as process water.
Reduction
A reaction in which there is a decrease in valence resulting from
a gain in electrons.
Reuse
The use of treated or untreated process wastewater in a different
production process.
Reverberatory Furnaces
Rectangular furnaces in which the fuel is burned above the metal
and the heat reflects off the walls and into the metal.
Roasting
Heating ore to remove impurities prior to smelting. Impurities
within the ore are oxidized and leave the furnace in gaseous
f o on.
Rod
An intermediate aluminum product having a solid, round cross sec-
tion 9.5 mm (3/8 inches) or more in diameter.
476
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Rotary Furnace
A circular furnace which rotates the workpiece around the axis of
the furnace during heat treatment.
Scrubber Liquor
The untreated wastewater stream produced by wet scrubbers clean-
ing gases produced by aluminum forming operations.
Shot Casting
A method of casting in which molten metal is poured into a
vibrating feeder, where droplets of molten metal are formed
through perforated openings. The droplets are cooled in a quench
tank.
Sintering
The process of forming a bonded mass by heating metal powders
without melting.
Skimmings
Slag removed from the surface of smelted metal.
Slag
The product of fluxes and impurities resulting from the smelting
of metal.
Smelting
The process of heating ore mixtures to separate liquid metal and
impurities.
Soft Lead
Lead produced by the removal of antimony through oxidation. The
lead is characterized by low hardness and strength.
Spent Hypo Solution
A solution consisting of photographic film fixing bath and wash
water which contains unreduced silver from film processing.
Stationary Casting
A process in which the molten aluminum is poured into molds and
allowed to air-cool. It is often used to recycle in-house scrap.
477
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Subcategorization
The process of segmentation of an industry into groups of plants
for which uniform effluent limitations can be established.
Supernatant
A liquid or fluid forming a layer above settled solids.
Surface Water
Any visible stream or body of water, natural or man-made. This
does not include bodies of water whose sole purpose is wastewater
retention or the removal of pollutants, such as holding ponds or
lagoons.
Surfactants
Surface active chemicals that tend to lower the surface tension
between liquids.
Sweating
Bringing small globules of low-melting constituents to an alloy
surface during heat treatment.
Total Dissolved Solids (TDS)
Organic and inorganic molecules and ions that are in true solu-
tion in the water or wastewater.
Total Organic Carbon (TOC)
A measure of the organic contaminants in a wastewater. The TOC
analysis does not measure as much of the organics as the COD or
BOD tests, but is much quicker than these tests.
Total Recycle
The complete reuse of a stream, with makeup water added for
evaporation losses. There is no blowdown stream from a totally
recycled flow and the process water is not periodically or con-
tinuously discharged.
Total Suspended Solids (TSS)
Solids in suspension in water, wastewater, or treated effluent.
Also known as suspended solids.
478
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Traveling Grate Furnace
A furnace with a moving grate that conveys material through the
heating zone. The feed is ignited on the surface as the grate
moves past the burners; air is blown in the charge to burn the
fuel by downdraft combustion as it moves continuously toward
discharge.
Tubing Blank
A sample taken by passing one gallon of distilled water through a
composite sampling device before initiation of actual wastewater
sampling.
Tuyeres
Openings in the shell and refractory lining of a furnace through
which air is forced.
Vacuum Dezincing
A process for removing zinc from a metal by melting or heating
the solid metal in a vacuum.
Venturi Scrubbers
A gas cleaning device utilizing liquid to remove dust and mist
from process gas streams.
Volatile Substances
Materials that are readily vaporizable at relatively low
temperatures.
Vastewater Discharge Factor
The ratio between water discharged from a production process and
the mass of product of that production process. Recycle water is
not included.
Water Use Factor
The total amount of contact water or oil entering a process
divided by the amount of aluminum product produced by this pro-
cess. The amount of water involved includes the recycle and
makeup water.
479
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Wet Scrubbers
Air pollution control devices used for removing pollutants as the
gas passes through the spray.
Zero Discharger
Any industrial or municipal facility that does not discharge
wastewater.
The following sources were used for defining terms in the
glossary:
Gill, G. B., Nonferrous Extractive Metallurgy. John Wiley St
Sons, New York, NY, 1980.
Lapedes, Daniel N., Dictionary of Scientific and Technical Terms,
2nd edition. New York, NY, McGraw-Hill Book Co., 1978.
McGannon, Harold E., The Making, Shaping, and Treating of Steel,
9th edition. Pittsburgh, PA, U.S. Steel Corp., 1971.
480
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METRIC UNITS
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
i nches 1n
inches of mercury in Hg
pounds lb
million gallons/day mgd
mi 1e mi
pound/square
Inch (gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
0.405
1233.5
0.252
ha
cu m
kg cal
0
3
0.555
0.028
1.7
0.028
28.32
16.39
,555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
,785
1.609
kg cal /kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
(0.06805 psig +1)* atm
0.0929 sq m
6.452 sq cm
0.907 kkg
0.9144 m
hectares
cubic meters
kilogram - calories
kilogram calories/kilo<
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilog
meter
* Actual conversion, not a multiplier
481
* U.S. ODVERlMENr PRINTnC CFPEE: 1983
381-545/3817
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