(Dffice of Water1
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-------
ORGANIZATION OF THIS DOCUMENT
This development document for the nonferrous metals manufacturing
category consists of a general development document which
considers the general and overall aspects of the regulation and
31 subcategory specific supplements. These parts are organized
into 10 volumes as listed below.
The information in the general document and in the supplements is
organized by sections with the same type of information reported
in the same section of each part. Hence to find information on
any specific aspect of the category one would need only look in
the same section of the general document and the specific
supplements of interest.
The ten volumes contain contain the following subjects:
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
General Development Document
Bauxite Refining
Primary Aluminum Smelting
Secondary Aluminum Smelting .
Primary Copper Smelting
Primary Electrolytic Copper Refining
Secondary Copper Refining
Metallurgical Acid Plants
Primary Zinc
Primary Lead
Secondary Lead
Primary Antimony
Primary Precious Metals and Mercury
Secondary Precious Metals
Secondary Silver
Secondary Mercury
Primary Tungsten
Secondary Tungsten and Cobalt
Primary Molybdenum and Rhenium
Secondary Molybdenum and Vanadium
Primary Beryllium
Primary Nickel and Cobalt
Secondary Nickel
Secondary Tin
Volume VIII Primary Columbium and Tantalum
Secondary Tantalum
Secondary Uranium
Volume IX
Volume X
Primary and Secondary Titanium
Primary Zirconium and Hafnium
Primary and Secondary Germanium and Gallium
Primary Rare Earth Metals
Secondary Indium
-------
DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
VOLUME X
Primary and Secondary Germanium and Gallium
Primary Rare Earth Metals
Secondary Indium
William K. Reilly
Administrator
Rebecca Hanmer, Acting
.Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
-------
11
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TABLE OF CONTENTS
Supplement
Primary and Secondary Germanium and Gallium
Primary Rare Earths
Secondary Indium
Paqe
5231
5353
5525
For detailed contents see detailed contents list in
individual supplement.
111
-------
IV
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NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
.DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Primary and Secondary Germanium and Gallium Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
5231
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5232
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
TABLE OF CONTENTS
Section
I
II
III
IV
V
SUMMARY 5241
CONCLUSIONS 5243
SUBCATEGORY PROFILE 5225
Description of Germanium and Gallium Production 5255
Raw Materials 5255
Germanium Production 5256
Chlorination 5256
Hydrolysis 5256
Reduction to Metal 5256
Purification 5257
Gallium Production 5257
Chlorination 5257
Hydrolysis 5257
Reduction to Metal 5257
Purification 5258
Solvent Extraction 5258
Process Wastewater Sources 5258
Other Wastewater Sources 5258
Age, Production, and Process Profile 5258
SUBCATEGORIZATION 5265
Factors Considered in Subdividing the Primary 5265
and Secondary Germanium and Gallium
Subcategory
Other Factors 5266
Production Normalizing Parameters 5266
WATER USE AND WASTEWATER CHARACTERISTICS 5269
Wastewater Flow Rates 5270
Wastewater Characteristics Data 5271
Data Collection Portfolios 5271
Field Sampling Data 5271
Wastewater Characteristics and Flows by 5273
Subdivision
Still Liquor 5273
Chlorinator Wet Air Pollution Control 5273
Germanium Hydrolysis Filtrate 5273
Acid Wash and Rinse Water. 5274
Gallium Hydrolysis Filtrate 5274
Solvent Extraction Raffinate 5274
TABLE OF CONTENTS (Continued)
5233
-------
r
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
Section
VI
VII
VIII
SELECTION OF POLLUTANT PARAMETERS
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Priority Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Never Pound Above Their
Analytical Quantification Concentration
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for Further
Consideration in Establishing Limitations
and Standards
CONTROL AND TREATMENT TECHNOLOGIES
Current Control and Treatment Practices
Still Liquor
Chlorinator Wet Air Pollution Control
Germanium Hydrolysis Filtrate
Acid Wash and Rinse Water
Gallium Hydrolysis Filtrate
Solvent Extraction Raffinate
Control and Treatment Options
Option A
Option C
COSTS, ENERGY, AND NONWATER QUALITY
ASPECTS
Treatment Options for Existing Sources
Option A
Option C
Cost Methodology
Nonwater Quality Aspects
Energy Requirements
Solid Waste
Air Pollution
5284
5284
5285
5285
5285
5286
5297
5297
5297
5298
5298
5298
5298
5298
5298
5298
5299
5301
5301
5301
5301
5301
5302
5302
5302
5304
5234
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
Section
TABLE OF CONTENTS (Continued)
IX
XI
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY 5307
AVAILABLE
Technical Approach to BPT • 5309
Industry Cost and Pollutant Removal Estimates 5309
BPT Option Selection 5309
Wastewater Discharge Rates 5310
Still Liquor 5310
Chlorinator Wet Air Pollution Control 5311
Germanium Hydrolysis Filtrate 5311
Acid Wash and Rinse Water 5311
Gallium Hydrolysis Filtrate 5311
Solvent Extraction Raffinate 5311
Regulated Pollutant Parameters 5312
Effluent Limitations 5312
BEST AVAILABLE TECHNOLOGY ECONOMICALLY 5319
ACHIEVABLE
Technical Approach to BAT 5319
Option A 5320
Option C 5320
Industry Cost and Pollutant Removal Estimates 5320
Pollutant Removal Estimates 5320
Compliance Costs 5321
Wastewater Discharge Rates 5321
BAT Option Selection - Proposal 5322
BAT Option Selection - Promulgation 5322
Regulated Pollutant Parameters 5323
Effluent Limitations 5324
NEW SOURCE PERFORMANCE STANDARDS 5331
Technical Approach to NSPS 5331
NSPS Option Selection - Proposal 5331
NSPS Option Selection - Promulgation 5331
Regulated Pollutant Parameters 5332
New Source Performance Standards 5332
5235
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
XII
PRETREATMENT STANDARDS
Technical Approach to Pretreatment
Industry Cost and Pollutant Removal. Estimates
Pretreatment Standards for Existing and New
Sources
PSES Option Selection
PSES Option Selection
PSNS Option Selection
PSNS Option Selection
Regulated Pollutant Parameters
Pretreatment Standards
Proposal
Promulgation
Proposal
Promulgation
XIII
BEST CONVENTIONAL POLLUTANT CONTROL
TECHNOLOGY
5337
5337
5338
5338
5338
5339
5339
5339
5339
5339
5351
5236
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
LIST OF TABLES
Table
Title
Paqe
III-l Initial Operating Year (Range) Summary of Plants 5260
in the Primary and Secondary Germanium and
Gallium Subcategory by Discharge Type
III-2 Summary of Subcategory Processes and Associated 5261
Waste Streams
V-l Water Use and Discharge Rates for Still Liquor 5275
V-2 Water Use and Discharge Rates for Chlorinator 5276
Wet Air Pollution Control
V-3 Water Use and Discharge Rates for Germanium 5277
Hydrolysis Filtrate
V-4 Water Use and Discharge Rates for Acid Wash and 5278
Rinse Water
V-5 Water Use and Discharge Rates for Gallium 5279
Hydrolysis Filtrate
V-6 Water Use and Discharge Rates for Solvent 5280
Extraction Raffinate
V-7 Primary and Secondary Germanium and Gallium 5281
Raw Wastewater Data from Self-Sampling
VI-1 Frequency of Occurrence of Priority Pollutants 5289
Primary and Secondary Germanium and Gallium
Subcategory Raw Wastewater
VI-2 Toxic Pollutants Never Detected 5293
5237
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
LIST OF TABLES (Continued)
Table
Title
Pac
VIII-1 Cost of Compliance for the Primary and Secondary 5305
Germanium and Gallium Subcategory Indirect
Dischargers
IX-1 BPT Wastewater Discharge Rates for the Primary 5313
and Secondary Germanium and Gallium Subcategory
IX-2 BPT Mass Limitations for the Primary and 5314
Secondary Germanium and Gallium Subcategory
X-l BAT Wastewater Discharge Rates for the Primary 5325
and Secondary Germanium and Gallium Subcategory
X-2 BAT Mass Limitations for the Primary and 5326
Secondary Germanium and Gallium Subcategory
XI-1 NSPS Wastewater Discharge Rates for the Primary 5333
and Secondary Germanium and Gallium Subcategory
XI-2 NSPS for the Primary and Secondary Germanium and 5334
Gallium Subcategory
XII-1 Pollutant Removal Estimates for Indirect 5341
Dischargers Primary and Secondary Germanium and
Gallium Subcategory
XII-2 Cost of Compliance for the Primary and Secondary 5342
Germanium and Gallium Subcategory
XII-3 PSES and PSNS Wastewater Discharge Rates for the 5343
Primary and Secondary Germanium and Gallium
Subcategory
XII-4 PSES for the Primary and Secondary Germanium and 5344
Gallium Subcategory
XII-5 PSNS for the Primary and Secondary Germanium and 5347
Gallium Subcategory
5238
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
LIST OF FIGURES
Figure
III-l
III-2
III-3
IX-1
X-l
X-2
Title
Primary and Secondary Germanium Production
Process
Paqe
5262
Primary and Secondary Gallium Production Process 5263
Geographic Locations of the Primary and 5264
Secondary Germanium and Gallium Plants Operating
in the United States
BPT Treatment Scheme for the Primary and
Secondary Germanium an Gallium Subcategory
BAT Treatment Scheme for Option A
BAT Treatment Scheme for Option C
5318
5329
5330
5239
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
5240
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
effluent limitations based on best practicable technology (BPT)
and best available technology (BAT) for existing direct
dischargers, pretreatment standards for existing and for new
indirect dischargers (PSES and PSNSJand standards of performance
for new sources direct dischargers (NSPS).
The primary and secondary germanium and gallium subcategory
consists of 5 plants. One of the five plants discharges to
a publicly owned treatment works (POTW), and four achieve
zero discharge of process wastewater.
EPA first studied the primary and secondary germanium and gallium
subcategory to determine whether differences in raw materials,
final products, manufacturing processes/ equipment, age and size
of plants, and water usage required the development of separate
effluent limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including the
sources and volume of water used, the processes used, the
sources of pollutants and wastewaters in the plant, and the
constituents of wastewaters, including toxic pollutants. As a
result, six subdivisions have been identified for
this subcategory that warrant separate effluent limitations.
These include:
o Still liquor,
o Chlorinator wet air pollution control,
o Germanium hydrolysis filtrate,
o Acid wash and rinse water,
o Gallium hydrolysis filtrate, and
o Solvent extraction raffinate.
EPA also identified several distinct control and treatment
technologies (end-of-pipe) applicable to the primary and
secondary germanium and gallium subcategory. The Agency analyzed
both historical and newly generated data on the performance of
these technologies, and on their nonwater quality impacts
including air quality, solid waste generation, and energy
requirements.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of
implementing the various options on the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
of pollutants, we estimated the number of potential closures,
number of employees affected, and impact on price. These results
are reported in a separate document entitled the "The Economic
5241
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - I
Impact Analysis of Effluent Limitations and
Nonferrous Metals Manufacturing Industry."
Standards for the
After examining the various treatment technologies, the Agency
has selected BPT requirements for the primary and secondary
germanium and gallium subcategory based on chemical
precipitation and sedimentation (lime and settle) technology.
Although there are no existing direct dischargers in this
subcategory, BPT is promulgated because it is a necessary base
against which pleas for variances can be measured. This action is
deemed necessary because wastewaters from germanium and
gallium operations which contain significant loadings of
toxic pollutants are currently being disposed of in a RCRA
permitted surface impoundment. Future modifications to the RCRA
standards may result in a discharge from germanium plants.
There are no capital or annual costs for BPT in this subcategory
because there are no direct dischargers.
EPA is promulgating BAT limitations for this subcategory based
on chemical precipitation and sedimentation technology. BAT is
equivalent to BPT technology. Although there are no existing
direct dischargers in this subcategory, BAT is promulgated for
any existing zero discharger who, at some point in the future,
elects to discharge. This action was deemed necessary because
wastewaters from germanium and gallium operations which contain
significant loadings of toxic pollutants are currently being
disposed of in a RCRA permitted surface impoundment. There are
no capital or annual costs for BAT in this subcategory because
there are no direct dischargers.
NSPS are equivalent to the BAT mass limitations. In selecting
NSPS, EPA recognizes that new plants have the opportunity to
implement the best and most efficient manufacturing processes and
treatment technology. As such, the technology basis of BAT has
been determined as the best demonstrated technology.
The technology basis for PSES is equivalent to BAT. To meet the
pretreatment standards for existing sources, the primary and the
secondary germanium and gallium subcategory is estimated to incur
a capital cost of $24,600 and an annual cost: of $20,300. For
PSNS, the Agency selected end-of-pipe treatment equivalent to
NSPS.
The best conventional technology (BCT) replaces BAT for the
control of conventional pollutants. BCT is riot being promulgated
because the methodology for BCT has not yet been finalized. The
mass limitations and standards for BPT, BAT, NSPS, PSES, and PSNS
are presented in Section II.
5242
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
SECTION II
CONCLUSIONS
EPA has divided the primary and secondary germanium and
gallium subcategory into six subdivisions for the purpose of
effluent limitations and standards. These subdivisions are:
(a) Still liquor,
(b) Chlorinator wet air pollution control,
(c) Germanium hydrolysis filtrate,
(d) Acid wash and rinse water,
(e) Gallium hydrolysis filtrate, and
(f) Solvent extraction raffinate.
BPT is promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology. The following BPT effluent limitations are
promulgated:
(a) Still Liquor BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
TSS
pH
131.700
26.460
91.980
2,205.000
2,583.000
Within the range of 7.5
58.590
12.600
38.430
1,254.000
1,229.000
to 10.0 at all times
(b) Chlorinator Wet Air Pollution Control BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
TSS
pH
27.530
5.531
19.230
461.000
540.000
12.250
2.634
8.034
262.100
256.800
Within the range of 7.5 to 10.0 at all times
5243
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(c) Germanium Hydrolysis Filtrate BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
TSS
pH
39.440
7.9Z5
27.550
660.500
773.700
17.550
3.774
11.510
375.500
368.000
Within the range of 7.5 to 10.0 at all times
(d) Acid Wash and Rinse Water BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium washed
Arsenic 325.500 144.800
Lead 65.400 31.140
Zinc 227.400 94.990
Fluoride 5,450.000 3.099.000
TSS 6,385.000 3,037.000
pH Within the range of 7.5 to 10.0 at all times
(e) Gallium Hydrolysis Filtrate BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
TSS
pH
70.450
14.160
49.220
1,180.000
1,382.000
31.350
6.742
20.560
670.800
657.300
Within the range of 7.5 to 10.0 at all times
5244
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
f) Solvent Extraction Raffinate BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium produced by solvent
extraction
Arsenic
Lead
Zinc
Fluoride
TSS
pH
39.330
7.904
27 480
658.700
771.600
17.500
, 3.764
11.480
374.500
367 ..000
Within the range of 7.5 to 10.0 at all times
EPA is promulgating BAT for the primary and secondary germanium
and gallium subcategory, based on the performance achievable by
the application of chemical precipitation and sedimentation (lime
and settle) technology. The following BAT effluent limitations
are promulgated:
(a) Still Liquor BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
(Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
131.700
26.460
91.980
2,205.000
58.590
12.600
38.430
1,254.000
(b) Chlorinator Wet Air Pollution Control BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
27.530
5.531
19.230
461.000
12.Z20
2.634
8.034
262.100
5245
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(c) Germanium Hydrolysis Filtrate BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
39.440
7.925
27.550
660.500
17.550
3.774
11.510
375.500
(d) Acid Wash and Rinse Water BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs)
Arsenic
Lead
Zinc
Fluoride
(e) Gallium Hydrolysis
of germanium washed
325.500
65.400
227.400
5,450.000
Filtrate BAT
144.800
31.140
94.990
3,099.000
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
70.450
14.160
49.220
1,180.000
31.350
6.742
20.560
670.800
5246
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(f) Solvent Extraction Raffinate BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium produced by solvent
extraction
Arsenic
Lead
Zinc
Fluoride
39.330
7.904
27.480
658.700
17.500
3.764
11.480
374.500
EPA is promulgating NSPS for the primary and secondary germanium
and gallium subcategory based on the performance achievable by
the application of chemical precipitation and sedimentation (lime
and settle) technology. The following effluent standards for new
sources are promulgated:
(a) Still Liquor NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
TSS
PH
131.700
26.460
91.980
2,205.000
2,583.000
Within the range of 7.5
58.590
12.600
38.430
1,254.000
1,229.000
to 10.0 at all times
(b) Chlorinator Wet Air Pollution Control NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg {Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
TSS
pH
27.530
5.531
19.230
461.000
540.500
12.250
2.634
8.034
262.100
256.800
Within the range of 7.5 to 10.0 at all times
5247
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(c) Germanium Hydrolysis Filtrate NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
nig/kg (Ib/million Ibs) of germanium hydrolyzed
Arsenic 39.440 17.550
Lead 7.925 3.774
Zinc 27.550 11.510
Fluoride 660.500 375.500
TSS
pH
773.700 368.000
Within the range of 7.5 to 10.0 at all times
(d) Acid Wash and Rinse Water NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium washed
Arsenic
Lead
Zinc
Fluoride
TSS
pH
325.500
65.400
227.400
5,450.000
6,385.000
144.800
31.140
94.990
3,099.000
3,037.000
Within the range of 7.5 to 10.0 at all times
(e) Gallium Hydrolysis Filtrate NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
TSS
pH
70.450
14.160
49.220
1,180.000
1,382.000
31.350
6.742
20.560
670.800
657.300
Within the range of 7.5 to 10.0 at all times
5248
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(f) Solvent Extraction Raffinate NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium produced by solvent
extraction
Arsenic
Lead
Zinc
Fluoride
TSS
pH
39.330
7.904
27.480
658.700
771.600
17.500
3.764
11.. 480
374.500
367.000
Within the range of 7.5 to 10.0 at all times
EPA is promulgating PSES for the primary and secondary germanium
and gallium subcategory based on the performance achievable by
the application of chemical precipitation and sedimentation (lime
and settle) technology. The following pretreatment standards for
existing sources are promulgated:
(a) Still Liquor PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
lead
Zinc
Fluoride
131.700
26.460
91.980
2,205.000
58.590
12.600
38.430
1,254.000
(b) Chlorinator Wet Air Pollution Control PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
27.530
5.531
19.230
461.000
12.250
2.634
8.034
262.100
5249
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(c) Germanium Hydrolysis Filtrate PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
39.440
7.925
27.550
660.500
17.550
3.774
11.510
375.500
(d) Acid Wash and Rinse Water PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium washed
Arsenic
Lead
Zinc
Fluoride
325.500
65.400
227.400
5,450.000
144.800
31.140
94.990
3,099.000
(e) Gallium Hydrolysis Filtrate PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
70.450
14.160
49.220
1,180.000
31.350
6.742
20.560
670.800
5250
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(f) Solvent Extraction Raffinate PSES
, Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium produced by solvent
extraction
Arsenic
Lead
Zinc
Fluoride
39.330
7.904
27.480
658.700
17.500
3.764
11.480
374.500
EPA is promulgating PSNS for the primary and secondary germanium
and gallium subcategory based on the performance achievable by
the application of chemical precipitation and sedimentation (lime
and settle) technology. The following pretreatment standards are
promulgated for new sources:
(a) Still Liquor PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
nig/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
131.700
26.460
91.980
2,205.000
58.590
12.600
38.430
1,254.000
(b) Chlorinator Wet Air Pollution Control PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium chlorinated
Arsenic
Lead
Zinc
Fluoride
27.530
5.531
19.230
461.000
12.250
2.634
8.034
262.100
5251
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
(c) Germanium Hydrolysis Filtrate PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
39.550
7.925
27.550
660.500
17.550
3.774
11.510
375.500
(d) Acid Wash and Rinse Water PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibsj of germanium washed
Arsenic
Lead
Zinc
Fluoride
325.500
65.400
227.400
5,450.000
144.800
31.140
94.990
3,099.000
(e) Gallium Hydrolysis Filtrate PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Arsenic
Lead
Zinc
Fluoride
70.450
14.160
49.22O
1,180.000
31.350
6.742
20.560
670.800
5252
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT ,- II
(f) Solvent Extraction Raffinate PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of gallium produced by solvent
extraction
Arsenic
Lead
Zinc
Fluoride
39.330
7.904
27.480
658.700
17.500
3.764
11.480
374.500
EPA is not promulgating best conventional pollutant control
technology (BCT) at this time.
5253
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - II
THIS PAGE INTENTIONALLY LEFT BLANK
5254
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the primary and secondary germanium and gallium
supplement describes the raw materials and processes used in the
production of germanium and gallium and presents a profile of the
germanium and gallium plants identified in this study.
There are many commercial uses for germanium, including infrared
systems (40 percent), fiber optics (15 percent), semiconductors
(23 percent), detectors (10 percent), and other uses (12
percent). Because germanium is transparent to infrared light, it
is important in germanium lenses and windows which transmit
thermal radiation in a manner similar to optical glass
transmitting visible light. Germanium based infrared
optical components are finding an increasing number of military
and commercial applications.
The principal uses of gallium are in electronic applications.
High-purity gallium is used in such items as fiber-optic light
transmission cables, gallium-based light-emitting diodes and
lasers, electronic devices for computers, and research and
development in solid-state devices.
DESCRIPTION OF GERMANIUM AND GALLIUM PRODUCTION
Germanium and gallium are produced from both primary and
secondary raw materials. Both metals are produced in a similar
manner; however, their production processes are treated
separately in this study. The germanium production process is
presented schematically in Figure III-l (page 5262) and described
below. The gallium production process is presented schematically
in Figure III-2 (page 5263). Germanium and gallium production can
be divided into four distinct stages: chlorination to tri- or
tetra-chlorides, hydrolysis to produce an oxide, reduction to
metal, and further purification.
RAW MATERIALS
The primary raw materials for germanium and gallium are residues
from primary zinc roasters. Zinc ores in the
Kansas-Missouri-Oklahoma and Central Tennessee zinc districts,
as well as some foreign zinc ores, contain germanium and gallium.
Concentrates typically contain 0.3 to 7 percent germanium and 0.2
to 1 percent gallium. Some facilities also use purchased
intermediates such as germanium dioxide or crude gallium metal.
Secondary raw materials for germanium include both low and
high-grade scrap. High grade scrap includes cuttings and saw
dust from the forming of lenses and windows from pure germanium.
Secondary raw materials for gallium include silicon-caroidp
5255
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
abrasives, and glass scrap consisting primarily of gallium
arsenide.
GERMANIUM PRODUCTION
Germanium is normally produced using four major steps or
processes: chlorination, hydrolysis, reduction to metal,
and further purification. Each of these steps is described
below:
CHLORINATION
The first step in winning germanium from concentrates and scrap
is chlorination with hydrochloric acid or chlorine gas.
Chlorination converts germanium to germanium tetrachloride
vapors, which are recovered in a condenser. Germanium
tetrachloride is a clear, colorless liquid at room temperature.
Vapors which pass through the condenser are sent through a wet
scrubber which controls acid and chlorine fumes. There are two
wastewater sources associated with germanium chlorination, as
shown in Figure III-l (page 5264). Excess hydrochloric acid along
with impurities in the raw material which are not vaporized by
the chlorination are discharged as still liquor. If gallium is
present in the feed materials, it will remain in the still liquor
and the still liquor may be used as a raw material for gallium
recovery rather than discharged. Additionally, scrubber liquor
from the wet scrubber associated with the chlorination still may
be discharged.
After converting the germanium in the feed material to the
tetrachloride, the germanium tetrachloride is purified using
stripping and distillation. Several stripping and
distillation processes may occur in series in order to achieve
the desired purity.
HYDROLYSIS
Purified germanium tetrachloride
dioxide by hydrolysis with water.
is:
is converted to germanium
The reaction that takes place
GeCl4 + 2 H2O ---- > GeO2 + 4 HC1.
After hydrolysis, the insoluble germanium dioxide is separated
from the liquid phase by filtration and dried. The hydrolysis
filtrate may be discharged as a wastewater stream.
REDUCTION TO METAL
Pure germanium dioxide is reduced to metal in a furnace with a
hydrogen atmosphere. The reaction that takes place is:
The
+ 2 H2 ---- > Ge + 2 H2O
germanium dioxide is reduced to germanium metal powder, and
5256
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
the water formed is vented to the atmosphere. The germanium
metal powder is then melted and cooled to produce germanium bars.
There are no wastewater sources associated with reducing
germanium dioxide to metal, or with subsequent melting and
casting to produce germanium ingots or bars.
PURIFICATION
Germanium bars are cleaned by acid washing and purified by zone
refining. The bars are washed with a hydrofluoric acid-nitric
acid mixture to remove any oxide coating on the bar, and then
rinsed with water to remove residual acid. The etched bars are
further purified by induction heated zone refining. In this
process, impurities are concentrated at one point because the
impurities are more soluble in the liquid phase. The germanium
bar may be acid washed and zone refined several times in order
to achieve the desired purity. The only wastewater source
associated with this process is the spent acid and rinse water.
GALLIUM PRODUCTION
Gallium production, shown schematically in Figure III-2 (page
5263), usually consists of four stages; chlorination, hydrolysis,
reduction to metal, and further purification. A solvent
extraction process can also be used to ref.ine gallium. Each of
these stages is described below.
CHLORINATION
Crude gallium or gallium arsenide scrap may be used as feed
material for the gallium chlorination process. Hydrochloric acid
and chlorine gas are used to convert the gallium to gallium
trichloride. Gallium trichloride is purified using a series of
distillation steps. No process wastewater is associated with
gallium chlorination or purification of gallium trichloride.
HYDROLYSIS
Gallium trichloride from chlorination of crude gallium metal,
chlorination of gallium scrap or other chlorination is routed to
the hydrolysis process. Water and sodium hydroxide are
reacted with gallium trichloride to produce an insoluble
gallium hydroxide. The reaction is as follows:
GaCl3 + NaOH + H2O > GaOOH + NaCl + 2 HC1
The insoluble gallium solids are separated from the liquid phase
by filtration. The hydrolysis filtrate is the only wastewater
stream associated with gallium hydrolysis.
REDUCTION TO METAL
Gallium oxide hydroxide is dissolved and electrolyticaly
reduced to gallium metal which collects at the cathode. Beca^sp
gallium metal is a liquid at room temperature with a deri^.^y
5257
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
greater than water, it sinks to the bottom of the electrolytic
cell. When electrolysis is complete, the residual electrolyte
is recycled and the gallium metal is routed to further
purification.
PURIFICATION
Electrolytic gallium is washed to remove residual water soluble
impurities and further purified by zone crystallization to remove
metal soluble impurities. The wash water is recycled to the
process. High purity gallium (99.9999+ percent) is produced in
this manner. There is no process wastewater associated with
crystallization.
SOLVENT EXTRACTION
A solvent extraction process can also be used, to recover gallium
from gallium scrap. The scrap is first dissolved in acid, and
gallium is then extracted from solution into an organic solvent.
Gallium is recovered from the solvent and the solvent is reused.
The depleted acid or raffinate is the only wastewater stream
associated with the solvent extraction process.
PROCESS WASTEWATER SOURCES
Although a variety of processes are involved in primary and
secondary germanium and gallium production, the process
wastewater sources can be delineated as follows:
1. Still liquor,
2. Chlorinator wet air pollution control,
3. Germanium hydrolysis filtrate,
4. Acid wash and rinse water,
5. Gallium hydrolysis filtrate, and
6. Solvent extraction raffinate.
OTHER WASTEWATER SOURCES
Other wastewateirs may be associated with the production of
primary and secondary germanium and gallium. These streams may
include aspirator water, noncontact cooling water, and equipment
and floor wash water. These wastewaters are not considered as
a part of this rulemaking. EPA believes that the flows and
pollutant loadings associated with these streams are
insignificant relative to the wastewater streams selected and
are best handled by the appropriate permit authority on
a case-by-case basis under authority of Section 402 of the CWA.
AGE, PRODUCTION, AND PROCESS PROFILE
Figure III-3 (page 5264) shows the location of the five
primary and secondary germanium and gallium plants operating
in the United States. One plant is located in Pennsylvania, two
are in the Oklahoma-Texas region, and two are in the far
western part of the country. Germanium and gallium plants are
5258
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
SECT - III
usually located near sources of raw materials, either zinc ore
deposits, or major electronics manufacturing.
Table III-l (page 5260) shows the initial operating year for the
plants in this subcategory by discharge type. All of the
plants were built within the last twenty-five years, with two
built within the last three years. The average plant age is 12
years. Table III-2 (page 5261) lists the various unit
operations in this subcategory, and shows the number of plants
with that process and the number of plants generating wastewater.
5259
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
Table III-1
INITIAL OPERATING YEAR (RANGE) SUMMARY OF PLANTS IN THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
BY DISCHARGE TYPE
Initial Operating Year (Range)
(Plant Age in Years)
Type of Plant
Direct
Indirect
Zero
Total
1983-
1973
(0-10)
0
1972-
1968
(11-15)
0
1967-
1958
(16-25)
0
0
2
1957-
1948
(26+)
0
0
0
To_tal
0
1
4
5260
-------
PRIMARY 'AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
Table III-3
SUMMARY OF SUBCATEGORY PROCESSES AND ASSOCIATED WASTE STREAMS
Process or
Waste Stream
Number of Germanium and
Gallium Plants with
Process or Waste Stream
Chlorination 3
Still liquor 2
Wet air pollution 2
Hydrolysis 3
Germanium filtrate 2
Gallium filtrate , 2
Reduction to metal (dry) 4
Purification 4
Acid wash and rinse
water 3
Ga solvent extraction 1
raffinate 1
Number of Plants
Reporting Generation
of Wastewater*
2
2
2
2
3
1
*Through reuse or evaporation practices, a plant may "generate" a
wastewater from a particular process but not discharge it.
5261
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
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5262
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - III
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5263
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
SECT - III
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5264
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the related subdivisions of the primary and
secondary germanium and gallium subcategory. Production
normalizing parameters for each subdivision are also
discussed.
FACTORS CONSIDERED IN SUBDIVIDING THE PRIMARY AND SECONDARY
GERMANIUM AND GALLIUM SUBCATEGORY
The factors listed previously for general subcategorization were
each evaluated when considering subdivision of the primary and
secondary germanium and gallium subcategory. In the
discussion that follows, the factors will be discussed as they
pertain to this particular subcategory.
The rationale for considering subdivision of the primary and
secondary germanium and gallium subcategory is based
primarily on differences in the production processes and raw
materials used within this subcategory. A number of different
operations are performed, which may or may not have a water use
or discharge, and which may require the establishment of separate
effluent limitations. While primary and secondary germanium and
gallium is still considered a single subcategory, a more thorough
examination of the production processes has illustrated the
need for limitations and standards based on a specific set of
waste streams. Limitations will be based on specific flow
allowances for the following subdivisions or building blocks:
1. Still liquor,
2. Chlorinator wet air pollution control,
3. Germanium hydrolysis filtrate,
4. Acid wash and rinse water,
5. Gallium hydrolysis filtrate, and
6. Solvent extraction raffinate.
These subdivisions follow directly from differences within the
distinct production stages of germanium and gallium
chlorination, hydrolysis, reduction to metal, and further
purification.
Chlorination of germanium concentrate or scrap to produce
germanium tetrachloride results in the first two subdivisions
still liquor and chlorination wet air pollution control. Still
liquor contains impurities present in the raw material as well as
excess hydrochloric acid used to chlorinate the germanium.
After recovering germanium tetrachloride, the acid fumes are
scrubbed with a water or caustic scrubber. This creates the
5265
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IV
need for the chlorination wet air pollution control subdivision.
Hydrolysis of germanium tetrachloride to germanium dioxide, and
gallium trichloride to a gallium hydroxide, results in two
more subdivisions germanium hydrolysis filtrate, and gallium
hydrolysis filtrate. Both hydrolysis products, germanium dioxide
and gallium hydroxide, are produced as solids which are
separated from the liquid phase by filtration. Both germanium
and gallium hydrolysis filtrates may be discharged as
wastewater streams.
After germanium dioxide is reduced to metal, it may be washed
with hydrofluoric acid and nitric acid, and then rinsed with
water. The wash -and rinse water may be discharged, and this
creates the need for another subdivision acid wash and rinse
water.
Gallium can be recovered from some scrap by a solvent extraction
process. In this process, scrap is dissolved in acid and
then recovered into an organic solvent. The spent acid may be
discharged. The solvent extraction raffinate gives rise to
the last subdivision.
OTHER FACTORS
The other factors considered in this evaluation were shown to be
inappropriate as a basis for subdivision. Air pollution control
methods, treatment costs, and total energy requirements are
functions of the selected subcategorization factors — metal
product, raw materials, and production processes. Therefore,
they are not independent factors and do not affect the
subcategorization which has been applied. As discussed in Section
IV of the General Development Document, certain other factors,
such as plant age, plant size, and the number of employees, were
also evaluated and determined to be inappropriate for use as
bases for subdivision of nonferrous metals plants.
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow these
regulations to be applied to plants with various production
capacities, the mass of pollutant discharged must be related to a
unit of production. This factor is known as the production
normalizing parameter (PNP).
In general, for each production process which has a wastewater
associated with it, the actual mass of germanium and gallium
product or intermediate will be used as the PNP. Thus, the PNPs
for the six subdivisions are as follows:
5266
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IV
Subdivision
1. Still liquor
2. Chlorinator wet air
pollution control
3. Germanium hydrolysis
filtrate
4. Acid wash and rinse
water
5. Gallium hydrolysis
filtrate
6. Solvent extraction
raffinate
PNP
germanium chlorinated
germanium chlorinated
germanium hydrolyzed
germanium washed
gallium hydrolyzed
gallium produced by
solvent extraction
Other PNPs were considered. The use of production capacity
instead of actual production was eliminated from consideration
because the mass of the pollutant produced is more a function of
true production than of installed capacity. The use of some
common intermediate (i.e., germanium tetrachloride or gallium
trichloride) as a basis for PNPs for all processes was rejected
since not all plants follow the same production path to get to
the specific end-product. Additionally, some plants divert part
of their intermediate products (e.g., germanium dioxide) and sell
them as by-products instead of processing all input raw
materials to one final product. If an "end-product" were chosen
as the PNP, plants that had these upstream diversions would be
allowed to discharge more per mass of product than their
competitors who did not.
5267
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IV
THIS PAGE INTENTIONALLY LEFT BLANK
5268
-------
PRIMARY" AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the primary and secondary germanium and gallium
subcategory. Data used to characterize the wastewaters are
presented. Finally, the specific source, water use and discharge
flows, and wastewater characteristics for each separate
wastewater source are discussed.
The two principal data sources used are data collection
portfolios (dcp) and field sampling results. Data collection
portfolios contain information regarding wastewater flows and
production levels.
In order to quantify the pollutant discharge from germanium and
gallium plants, a field sampling program was conducted prior to
proposal. A complete list of pollutants considered and a summary
of the techniques used in sampling and laboratory analyses are
included in Section V of Vol. I. Samples were analyzed for 124 of
the 126 priority pollutants and other pollutants deemed
appropriate. Because the analytical standard for TCDD was judged
to be too hazardous to be made generally available, samples were
never analyzed for this pollutant. Samples were also never
analyzed for asbestos. There is no reason to expect that TCDD or
asbestos would be present in nonferrous metals manufacturing
wastewater. A total of two plants were selected for sampling in
the primary and secondary germanium and gallium subcategory. In
general, the samples were analyzed for three classes of
pollutants: toxic organic pollutants, toxic metal pollutants, and
criteria pollutants (which includes both conventional and
nonconventional pollutants).
After proposal, EPA gathered additional wastewater sampling data
for four subdivisions in this subcategory. These data were
acquired through a self sampling program undertaken at the
specific request of EPA. The data include analyses for the toxic
metals antimony, arsenic, cadmium, chromium, copper, lead,
nickel, selenium, silver, thallium and zinc. The data also
include analyses for the nonconventional pollutants fluoride,
germanium and gallium. These data presented in Table V-7 (page
5281), show pollutant concentrations similar to those indicated
by the data which EPA had acquired for these subdivisions prior
to proposal. The data also support the assumptions which
EPA had made concerning the presence and concentrations of
pollutants in those subdivisions where we did not have
analytical data for specific pollutants. For this reason,
the selection of pollutant parameters for limitation in this
subcategory (Section VI) has not been revised based on this new
data.
5269
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
As described in Section IV of this supplement, the primary and
secondary germanium and gallium subcategory has been divided into
six subdivisions or wastewater sources, so that the promulgated
regulation contains mass discharge limitations and standards for
six unit processes discharging process wastewater. Differences
in the wastewater characteristics associated with these
subdivisions are to be expected. For this reason, wastewater
streams corresponding to each subdivision are addressed
separately in the discussions that follow. These wastewater
sources are:
1. Still liquor,
2. Chlorinator wet air pollution control,
3. Germanium hydrolysis filtrate,
4. Acid wash and rinse water,
5. Gallium hydrolysis filtrate, and
6. Solvent extraction raffinate.
WASTEWATER FLOW RATES
Data supplied by dcp responses were evaluated, and two
flow-to-production ratios, water use and wastewater discharge
were calculated for each stream. The two ratios 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. 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 germanium and gallium produced. Differences between
the water use and wastewater flows associated with a given stream
result from recycle, evaporation, and carry-over on the
product. The production values used in calculation
correspond to the production normalizing parameter, PNP, assigned
to each stream, as outlined in Section IV. As an example,
chlorinator scrubber water flow is related to the production of
germanium chlorinated. As such, the discharge rate is expressed
in liters of scrubber water per metric ton of germanium
chlorinated (gallons of scrubber water per ton of germanium
chlorinated).
The production normalized discharge flows were compiled and
statistically analyzed by stream type. These production
normalized water use and discharge flows are presented by
subdivision in Tables V-l through V-6 (pages 5275 - 5280).
Where appropriate, an attempt was made to identify factors
that could account for variations in water use and
discharge rates. These variations are discussed later in this
section by subdivision. A similar analysis of factors affecting
the wastewater flows is presented in Sections IX, X, XI, and XII
where representative BPT, BAT, NSPS, and pretreatment flows are
selected for use in calculating the effluent limitations.
The water use and discharge rates shown do not include nonprocess
wastewater, such as rainfall runoff and noncontact cooling water.
5270
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
WASTEWATER CHARACTERISTICS DATA
Data used to characterize the various wastewaters associated with
germanium and gallium production come from two sources—data
collection portfolios and analytical data from field sampling
trips.
DATA COLLECTION PORTFOLIOS
In the data collection portfolios, the germanium and gallium
plants that discharge wastewater were asked to specify the
presence of priority pollutants in their wastewater. No
plant indicated that any priority organic pollutants were present
in their wastewater. However, two of the three responding
plants stated that they either knew priority metal pollutants to
be present or they believed priority metal pollutants to
be present. The responses for the priority metals are
summarized below1":
Pollutant
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Known
Present
1
1
0
0
0
0
0
0
0
1
0
0
0
Believed
Present
1
1
0
0
1
1
0
0
1
1
0
0
0
•'•Two plants were omitted due to lack of data,
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from primary and secondary germanium and gallium
plants, wastewater samples were collected at two plants. Both
of these facilities claimed the analytical data collected to be
confidential and therefore these data are not presented in this
document. Diagrams and tabulated information usually included to
describe these operations are also omitted for this same reason.
Several points regarding these tables should be noted. First,
the data tables include some samples measured at concentrations
considered ;not quantifiable. The base-neutral extractable, acid
extractable, and volatile organics generally are considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
5271
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
Below this concentration organic analytical results are not
quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1.
Second, the detection limits shown on the data tables for
priority metals and conventional and nonconventional
pollutants are not the same in all cases as the 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 operator specific factors. These factors can
include day-to-day differences in machine calibration, variation
in stock solutions, and variation in operators.
Third, the statistical analysis of data includes some samples
measured at concentrations considered not quantifiable. For data
considered as detected but below quantifiable concentrations, a
value of zero is used for averaging. Priority
nonconventional, and conventional pollutant data
with a "less than" sign are considered as
but not further quantifiable. A value of zero is also
U£><=« ^w^ averaging. If a pollutant is reported as not
detected, it is assigned a value of zero in calculating the
average. Finally, priority metal values reported as less
certain value were considered as not quantifiable, and
organic,
reported
detected,
used for
zero in the calculation
than _
consequently were assigned a value of
of the average.
Finally, appropriate source water concentrations are presented
with the summaries of the sampling data. The method by which
each sample was collected is indicated by number, as follows:
1 - One-time grab
2 - Manual composite during intermittent process operation
3 - 8-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since primary and secondary germanium and gallium production
involves six principal sources of wastewater and each has
potentially different characteristics and flows, the wastewater
5272
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
characteristics and discharge rates corresponding to each
subdivision will be described separately. A brief description of
why the associated production processes generate a wastewater and
explanations for variations of water use within each subdivision
will also be discussed.
STILL LIQUOR
All of the plants which chlorinate germanium raw materials
generate a still liquor. The production normalized water use and
discharge rates for still liquor are given in Table V-l (page
5275) in liters per metric ton of germanium chlorinated. Still
liquor can be characterized by treatable concentrations of
arsenic, nickel, zinc and germanium, suspended solids, and acidic
pH. Additional data for this stream collected after proposal
confirm this characterization.
CHLORINATOR WET AIR POLLUTION CONTROL
All of the plants which chlorinate germanium raw materials use a
wet scrubbing system for the control of HC1 and Cl2 fumes. No
plant reporting this stream practices recycle of this water.
Table V-2 (page 5276) presents the production normalized water
use and discharge flows for chlorinator scrubber water in liters
per metric ton of germanium chlorinated. This water is
characterized by treatable concentrations of cadmium, lead,
nickel, germanium, suspended solids, and an alkaline pH.
GERMANIUM HYDROLYSIS FILTRATE
Germanium tetrachloride is hydrolyzed to germanium dioxide by
adding water. Germanium dioxide solids are separated from the
liquid phase by filtration, and the filtrate may be discharged.
Production normalized water use and discharge rates for this
waste stream are presented in Table V-3 (page 5277), in liters
per metric ton of germanium hydrolyzed. This stream contains
treatable concentrations of nickel and germanium.
ACID WASH AND RINSE WATER
Germanium ingots or bars are washed with an HF-HNOs mixture and
then rinsed with water to remove the residual acid from the bar.
The spent acid and rinse water are discharged as a wastewater
stream. The production normalized water use and discharge rates
are presented in Table V-4 (page 5278), in liters per metric ton
of germanium washed. Sampling data for this wastewater stream
show that this stream contains treatable concentrations of lead,
germanium and fluoride.
GALLIUM HYDROLYSIS FILTRATE
Gallium trichloride is hydrolyzed to an insoluble gallium
hydroxide by adding water and sodium hydroxide. Gallium oxide
hydroxide solids are separated from the waste solution by
filtration, and the filtrate may be discharged. Production
5273
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
normalized water use and discharge rates for this waste stream
are presented in Table V-5 (page 5279), in liters per metric ton
of gallium hydrolyzed. This wastewater stream contains toxic
metals, particularly arsenic, and suspended solids above
treatable concentrations.
SOLVENT EXTRACTION RAFFINATE
Gallium is recovered from gallium arsenide scrap by a
solvent extraction process. In this process, scrap is dissolved
in acid, and gallium is extracted from the acid into an organic
phase. Gallium is then recovered from the organic phase. The
spent acid or raffinate is discharged as a wastewater
stream. Production normalized water use and discharge rates for
solvent extraction raffinate are shown in Table V-6 (page 5280).
This wastewater stream was not sampled, however, it is
expected to have similar characteristics to gallium hydrolysis
filtrate and should be characterized by toxic metals,
particularly arsenic, and suspended solids above treatable
concentrations.
5274
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
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5277
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
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5278
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
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5279
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
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53
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
TABLE V-7
PRIMARY AND SECONDARY GERMANIUM SAMPLING DATA
RAW WASTEWATER DATA FROM SELF-SAMPLING
POLLUTANT
Sample Number
88154
Concentration (mg/1)
88155 88156
88157
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium
120. copper
122. lead
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
<0
1
<0
0
<0
0
<0
2
0
<0
0
150
.030
.700
.050
.230
.500
.160
.200
.000
.089
.001
.011
.000
<0
<0
<0
0
<0
0
0
1
0
0
0
0
•
•
•
•
•
•
•
•
•
•
•
•
020
100
050
460
500
200
450
800
036
0026
015
170
<0.
<0.
<0.
<0.
<0.
<0.
<0.
1.
0.
0.
0.
<0.
010
200
050
050
500
100
200
000
116
0022
024
050
0
0
<0
<0
<0
<0
0
<0
<0
0
<0
0
.044
.390
.050
.050
.500
.100
.780
.200
.005
.066
.010
.060
Nonconventional Pollutants
aluminum
cobalt
gallium
germanium
iron
fluoride
manganese
molybdenum
tin
titanium
vanadium
1
<0
<0
31
1
2
<0
<5
<2
<1
88154 = Still Liquor
88155 = Chlorinator Wet
.500
.500
.200
.000
.800
.200
.500
.000
.000
.000
Air
88156 = Germanium Hydrolysis
88157 = Acid Wash and Rinse
4
<0
<0
470
11
0
<0
<5
2
<1
*
•
•
•
*
•
•
*
•
•
100
500
200
000
000
250
500
000
000
000
0.
<0.
<0.
950.
0.
<0.
0.
<5.
<2.
<1.
780
500
200
000
370
050
520
000
000
000
350
<0
<0
454
2
40000
0
<0
<5
<3
<1
.000
.500
.200
.000
.900
.000
.090
.500
.000
.000
.000
Pollution Control
Filtrate
Water
5281
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
528?
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
This section examines the chemical analysis data presented in
Section V and discusses the selection or exclusion of priority
pollutants for potential limitation. The discussion that follows
presents and briefly discusses the selection of conventional
and nonconventional pollutants for effluent limitations. Also
described is the analysis that was performed to select or exclude
toxic pollutants for further consideration for limitations and
standards. Pollutants will be considered for limitation if they
are present in concentrations treatable by the technologies
considered in this analysis. The treatable concentrations used
for the toxic metals were the long-term performance values
achievable by chemical precipitation, sedimentation, and
filtration. The treatable concentrations used for the toxic
organics were the long-term performance values achievable by
carbon adsorption.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
As part of this study, the Agency examined samples for two
conventional pollutant parameters (total suspended solids and pH)
and the nonconventional pollutants fluoride, gallium and
germanium. At proposal, the Agency had selected germanium for
limitation in this subcategory. On March 18, 1985, the Agency
published a notice of data availability which stated that EPA was
also considering regulating gallium in this subcategory.
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in the subcategory are:
fluoride
total suspended solids (TSS)
pH
Fluoride was detected,in acid wash and rinse wastewater at a
concentration of 40,000 mg/1. This concentration is
significantly higher than the concentration of fluoride which is
achievable with identified treatment technology (14.5 mg/1). For
this reason, fluoride is selected for limitation in this
subcategory. The source of fluoride in this wastewater is
hydrofluoric acid which is used to wash germanium bars.
Neither germanium nor gallium is not selected for limitation in
this subcategory. The Agency proposed to limit germanium because
it was expected to be present in the raw wastewater.
Germanium and gallium were proposed for regulation but the
Agency has decided to not regulate these pollutants at
promulgation because they are expected to be controlled by the
BPT technology. However, it is possible that these pollutants may
be present in large concentrations at an individual plant.
5283
The r e fore, benzene i~s no t coTfrs1Ue"r'eU~~ fo~r~
5285
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
Therefore, the permitting or control authority may establish
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
Hexachlorobenzene was detected in the one sample for which it was
analyzed at a concentration of 0.011 mg/1. Although this value
is above the concentration achievable by identified treatment
technplogy (0.01 mg/1), it is below the concentration of
hexachlorobenzene in the source water at the plant where the
sample was taken (0.26 mg/1). Also, hexachlorobenzene is not
expected to be present in the wastewater based on the raw
materials and production processes used. For these reasons,
hexachlorobenzene is not considered for limitation.
Methylene chloride was detected in the one sample for which it
was analyzed at a concentration treatable by identified treatment
technology (0.01 mg/1). However, methylene chloride is not
attributable to specific materials or processes associated with
germanium and gallium production, but is a common solvent used in
analytical laboratories. No germanium and gallium plants
believed this pollutant was present in their wastewater. For
these reasons, methylene chloride is not considered for
limitation.
Cyanide was detected in the one sample for which it was analyzed
at a concentration of 0.069 mg/1. This concentration exceeds
that which is attainable by identified treatment technology
(0.047/1). However, cyanide cannot be attributed to any raw
material or production process associated with the germanium and
gallium subcategory, and is not expected to be present in any
wastewater from these industries. Therefore, cyanide is not
considered for limitation.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for
further consideration in establishing limitations and standards
for this subcategory. The toxic pollutants selected for
further consideration for limitation are each discussed
following the list.
114.
115.
118.
119.
120.
122.
124.
125.
126.
127.
128.
antimony
arsenic
cadmium
chromium
copper
lead
nickel
selenium
silver
thallium
zinc
Antimony was detected above its treatable concentration (0.47
mg/1) in four of six samples analyzed. The quantifiable
concentrations ranged from 1.0 mg/1 to 16 mg/1. Since antimony
was present in concentrations exceeding the concentrations
5286
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
achievable by identified treatment technology, it is selected for
consideration for limitation.
Arsenic was detected above its treatable concentration (0.34
mg/1) in five of six samples analyzed. The quantifiable
concentrations ranged from 0.72 mg/1 to 47.4 mg/1. Since arsenic
was present in concentrations exceeding the concentrations
achievable by identified treatment technology, it is selected for
consideration for limitation.
Cadmium was detected above its treatable concentration (0.049
mg/1) in three of six samples analyzed. The quantifiable
concentrations ranged from 0.015 mg/1 to 2.05 mg/1. Since
cadmium was present in concentrations exceeding the
concentrations achievable by identified treatment technology, it
is selected for consideration for limitation.
Chromium was detected above its treatable concentration (0.07
mg/1) in two of four samples analyzed. The quantifiable
concentrations ranged from 0.05 mg/1 to 1.06 mg/1. Since
chromium was present in concentrations exceeding the
concentrations achievable by identified treatment technology, it
is selected for consideration for limitation.
Copper was detected above its treatable concentration (0.39 mg/1)
in three of six samples analyzed. The quantifiable
concentrations ranged form 0.084 mg/1 to 3.27 mg/1. Since copper
was present in concentrations exceeding the concentrations
achievable by identified treatment technology, it is selected for
consideration for limitation.
Lead was detected above its treatable concentration (0.08 mg/1)
in four of six samples analyzed. The quantifiable concentrations
ranged from 0.03 mg/1 to 16.5 mg/1. Since lead was present in
concentrations exceeding the concentrations achievable by
identified treatment technology, it is selected for consideration
for limitation.
Nickel was detected above its treatable concentration (0.22 mg/1)
in one of three samples analyzed. The quantifiable
concentrations ranged from 0.05 mg/1 to 1.8 mg/1. Since nickel
was present in concentrations exceeding the concentrations
achievable by identified treatment technology, it is selected for
consideration for limitation.
Selenium was detected above its treatable concentration (0.2
mg/1) in the one sample for which it was analyzed. The
quantifiable concentrations is 0.51 mg/1. Since selenium is
present in concentrations exceeding the concentrations achievable
by identified treatment technology, it is selected for
consideration for limitation.
Silver was detected above its treatable concentration (0.07 mg/1)
in the one sample for which it was analyzed. The observed
quantifiable concentration is 0.12 mg/1. Since silver was
5287
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
present in concentrations exceeding the concentrations achievable
by identified treatment technology, it is selected for
consideration for limitation.
Thallium was detected above its treatable concentration (0.34
mg/1) in the one sample for which it was analyzed. The observed
quantifiable concentration is 1.0 mg/1. Since thallium was
present in concentrations exceeding the concentrations achievable
by identified treatment technology, it is selected for
consideration for limitation.
Zinc was detected above its treatable concentration (0.23 mg/1)
in six of six samples analyzed. The quantifiable concentrations
ranged from 0.39 mg/1 to 289 mg/1. Since zinc was present in
concentrations exceeding the concentrations achievable by
identified treatment technology, it is selected for consideration
for limitation.
5288
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
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5289
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
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5290
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
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5291
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
10. 1,2-dichloroethane
11. 1,1,1,-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
17. bis (choromethyl) ether (deleted)
18. bis {2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
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 (lf3-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-chloroethoxy) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromethane
49. trichlorofluoromethane (deleted)
5293
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
50. dichlorodifluoromethane (deleted)
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlprocyclopentadiene
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
65. phenol
67. butyl benzyl 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. acenapthylene
78. anthracene
79. benzo(g,h,i)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene
82. dibenzo (a,h)anthracene
83. indeno (1,2,3-cd)pyrene
84. pyrene
85. tetrachloroethylene
86. toluene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4'-ODD (p,p'DDX)
94. 4,4'-DDD (p,p'TDE)
95. alpha-endosulfan
96. beta-endosulfan
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
(1,2,5,6-dibenzanthracene)
(w,e,-o-phenylenepyrene)
5294
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
TABLE VI-2(Continued)
TOXIC POLLUTANTS NEVER DETECTED
100. heptachlor
101. heptachlor epoxide
102. alpha-BHC
103. beta-BHC104. gamma-BHC (lindane)
105. delta-BHC
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. toxaphene
116. asbestos (fibrous)
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
5295
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VI
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5296
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT.TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters from primary and
secondary germanium and gallium plants. This section summarizes
the description of these wastewaters and indicates the treatment
technologies which are currently practiced in the primary and
secondary germanium and gallium subcategory for each waste
stream. Secondly, this section presents the control and
treatment technology- options which were examined by the Agency
for possible application to the primary and secondary germanium
and gallium subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently being applied to each of the
sources, generating wastewater in this subcategory. As discussed
in Section V, wastewater associated with the primary and
secondary germanium and gallium subcategory is characterized by
the presence of the priority metal pollutants and
suspended solids. This analysis is supported by the raw
(untreated) wastewater data presented for specific sources
as well as combined waste streams in Section V. Generally,
these pollutants are present in each of the waste streams at
concentrations above treatability and these waste streams are
commonly combined for treatment. Construction of one wastewater
treatment system for combined treatment allows plants to
take advantage of economic scale and in some instances to
combine streams of different alkalinity to reduce treatment
chemical requirements. Two plants in this subcategory currently
have combined wastewater treatment systems, none have lime
precipitation and sedimentation, but two have limestone pH
adjustment. As such, two options have been selected for
consideration for BPT, BAT, NSPS, and pretreatment based on
combined treatment of these compatible waste streams.
STILL LIQUOR
Germanium tetrachloride is generated by chlorinating germanium
concentrates or scrap with hydrochloric acid or chlorine _ gas.
Still liquor consists of impurities present in the raw materials
as well as excess hydrochloric acid solution which remains when
the chlorination reaction is complete. One of the two plants
which produces germanium tetrachloride disposes of the resultant
still liquor by means of contractor disposal; the other plant
adjusts the pH with lime and then holds the neutralized waste in
a RCRA permitted surface impoundment.
5297
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VII
CHLORINATOR WET AIR POLLUTION CONTROL
Plants which chlorinate germanium with hydrochloric acid and
chlorine use wet scrubbers to control air emissions. No
plants practice recycle of the chlorinator scrubber liquor.
The scrubber liquor was found to be disposed by contractor
disposal, or by disposal into , a RCRA permitted surface
impoundment after adjusting the pH with lime.
GERMANIUM HYDROLYSIS FILTRATE
Germanium tetrachloride is hydrolyzed with water to produce
germanium dioxide solids and the solids separated from the
excess solution by filtration. As with the still liquor and
chlorinator scrubber liquor, the wastewater may be contractor
disposed or the pH adjusted with lime and the waste held in an
RCRA permitted surface impoundment.
ACID WASH AND RINSE WATER
Plants wash germanium bars with a hydrofluoric acid-nitric
acid mixture and then rinse them with water. No recycle is
practiced for this wastewater. In addition to disposal by a
contractor or into a RCRA impoundment, this wastewater is also
treated and discharged.
GALLIUM HYDROLYSIS FILTRATE
Gallium is recovered by hydrolyzing gallium trichloride
producing a solid gallium hydroxide. Spent or excess solution
is separated from the gallium product by filtration, and the
filtrate wastewater stream treated and discharged or treated in
an evaporation pond.
SOLVENT EXTRACTION RAFFINATE
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VII
The Option A treatment scheme consists of chemical precipitation
and sedimentation technology. Specifically, lime or some other
alkaline compound is used to precipitate toxic metal ions as
metal hydroxides. The metal hydroxides and suspended
solids settle out and the sludge is collected. Vacuum
filtration is used to dewater sludge.
OPTION C
Option C for the primary and secondary germanium and gallium
subcategory consists of all control and treatment requirements of
Option A, (chemical precipitation and sedimentation) plus
multimedia filtration technology added at the end of the Option A
treatment scheme. Multimedia filtration is used to remove
suspended solids, including precipitates of metals, beyond the
concentration attainable by gravity sedimentation. The filter
suggested is of the gravity, mixed-media type, although other
forms of filters, such as rapid sand filters or pressure filters
would perform satisfactorily. The addition of filters also
.provides consistent removal during periods of time in which there
are rapid increases in flows or loadings of pollutants to the
treatment system.
5299
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VII
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5300
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
primary and secondary germanium and gallium subcategory and a
description of the treatment options and subcategory-specific
assumptions used to develop these estimates. Together with the
estimated pollutant removal performance presented in Sections IX,
X, XI, and XII of this supplement, these^ cost estimates provide a
basis for evaluating each regulatory option. These cost
estimates are also used in determining the probable economic
impact of regulation on the subcategpry at different •- pollutant
discharge levels. In addition, this section addresses nonwater
quality environmental impacts of wastewater treatment and control
alternatives, including air pollution, solid wastes, and energy
requirements, which are specific to the primary and secondary
germanium and gallium subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As. discussed in Section VII, two treatment options have been
developed for existing primary and secondary germanium and
gallium sources. The treatment schemes for each option are
summarized below and schematically presented in Figures X-l; and
X-2 ( pages 5329 and 5330). ;
OPTION A
Option A consists of
technology.
OPTION C
chemical precipitation and sedimentation
Option C for the primary and secondary germanium and gallium
subcategory consists of all control and treatment requirements of
Option A, (chemical precipitation and sedimentation) plus
multimedia filtration technology added at the end of the Option A
treatment scheme.
COST METHODOLOGY
A detailed discussion of the methodology used to develop the
compliance costs is presented in Section VIII of Vol. I-,
Promulgation cost estimates did not change from those developed
for the proposed regulation. These cost estimates are presented
in Table VIII-1 (page 5305). Each subcategory contains a unique
set of waste streams requiring certain subcategory-specific
assumptions to develop compliance costs. The major assumptions
relevant to the cost estimates for the primary and secondary
germanium and gallium subcategory are discussed briefly below.
5301
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VIII
(1) Raw waste data for the acid wash and rinse; waste stream were
transferred from a simil'ar stream, wastewater from titanium
etching with hydrofluoric acid in the primary and secondary
titanium subcategory.
(2) The germanium concentration in the acid wash and rinse waste
stream is estimated to be 4000 mg/1 based on germanium solubility
data and estimates from plant personnel. One-day and ten-day
treatment effectiveness concentrations for germanium are assumed
to be 0.44 and 0.18 mg/1, for lime and settle and 0.37 and 0.15
mg/1 for lime, settle, and filter.
A second set of costs were generated in the primary and
secondary germanium and gallium subcategory.
In general, the Agency does not prepare compliance costs for
zero dischargers. In this subcategory, however, wastes
generated tend to be hazardous and fall under RCRA
regulations. In the event that the plants presently achieving
zero discharge would lose their capability to impound
their wastewaters due to a change in the RCRA regulations, EPA
wanted to study the cost impact these plants would face
in having to provide treatment for their wastewater prior
to discharge. These costs were used for assessing the
potential economic achievability of these plants to change their
discharge status.
NONWATER QUALITY ASPECTS
Nonwater quality impacts specific to the primary and
secondary germanium and gallium subcategory, including
energy requirements, solid waste and air pollution are discussed
below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for the two options
considered are estimated at 6,253 kwh/yr and 7,496 kwh/yr for
Options A and C, respectively. Option C, which includes
filtration, is estimated to increase energy consumption over
Option A by approximately 20 percent. Option C represents
roughly three percent of a typical plant's electrical energy
usage. It is therefore concluded that the energy requirements of
the treatment options considered will not have a significant
impact on total plant energy consumption.
SOLID WASTE
Sludge generated in the primary and secondary germanium and
gallium subcategory is due to the precipitation of metal
hydroxides and carbonates using lime. Sludges associated with
the primary and secondary germanium and gallium subcategory will
necessarily contain 'quantities of priority metal
pollutants. Sludges from primary operations are not subject to
5302
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VIII
regulation as hazardous wastes since wastes generated by primary
smelters and refiners are currently exempt from regulation by
Act of Congress (Resource Conservation and Recovery Act (RCRA),
Section 3001(b)), as interpreted by EPA. Wastes from secondary
metal operations can be regulated as hazardous. However, the
Agency examined the solid wastes that would be generated at
secondary nonferrous metals manufacturing plants by the
suggested treatment technologies and believes they are not
hazardous wastes under the Agency's regulations implementing
Section 3001 of RCRA. This judgment is based on the
results of Extraction Procedure (EP) toxicity tests performed
on similar sludges (i.e., priority-metal-bearing lime
sludges) generated by other industries such as the iron and
steel industry. A small amount of excess lime was added during
treatment, and the sludges subsequently generated passed the
toxicity test. See CFR S261.24. Thus, the Agency believes that
the wastewater sludges from both primary and secondary
operations will not be EP toxic if the recommended technology
is applied.
Although it is the Agency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these, wastes must test the waste to determine if
the wastes meet any of the. characteristics of hazardous waste
(see 40 CFR S262.ll).
If these wastes identified should be or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements.; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 8262.20 [45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980)]. The
transporter regulations require transporters of hazardous waste
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR S263.20 (45 FR
33151 (May 19, 1980), amended at 45 FR 86973 (December 31,
1980)]. Finally, RCRA regulations establish standards for
hazardous waste treatment, storage, and disposal facilities
allowed to receive such wastes. See 40 CFR Part 464 [46 FR 2802
(January 12, 1981), 47 FR 32274 (July 26, 1982)].
!
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 84004 of RCRA. See 44 FR 53438
(September 13, 1979). The Agency has calculated.as part of the
costs for wastewater treatment the cost of hauling and disposing
of these wastes.
The Agency estimates that the promulgated PSES regulation for
5303
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VIII
primary and secondary germanium and gallium manufacturing
facilities will generate 108 metric tons of solid wastes (wet
basis) in 1982 as a result of wastewater treatment. The
promulgated BPT and BAT regulations will not generate any solid
wastes because there are currently no direct dischargers.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of chemical
precipitation and sedimentation. These technologies transfer
pollutants to solid waste and are not likely to transfer
pollutants to air.
5304
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VIII
TABLE VIII-1
The cost of compliance data are not presented here because the
data on which they are based have been claimed to be
confidential.
5305
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - VIII
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5306
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through the application of best practicable control technology
currently available (BPT), Section 301(b)(a)(A). BPT reflects
the existing performance by plants of various sizes, ages, and
manufacturing processes within the primary and secondary
germanium and gallium subcategory, as well as the established
performance of the model BPT systems. Particular consideration is
given to the treatment already in place at plants within
the data base.
The factors considered in identifying BPT include the total cost
of applying the technology in relation to the effluent reduction
benefits from such application, the age of equipment and
facilities involved, the manufacturing processes used, nonwater
quality environmental impacts (including energy requirements),
and other factors the Administrator considers appropriate. In
general, the BPT level represents the average of the existing
performances of plants of various ages, sizes, processes", or
other common characteristics. Where existing performance is
uniformly inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology are supported by a rationale concluding that the
technology is, indeed, transferable, and a reasonable prediction
that it will be capable of achieving the prescribed effluent
limits BPT focuses on end-of-pipe treatment rather than
process changes or internal controls, except where such
practices are common industry practice.
TECHNICAL APPROACH TO BPT
The Agency studied the,primary and secondary germanium and
gallium subcategory to identify the processes used, the
wastewaters generated, and the treatment processes installed.
Information was collected from the category using data
collection portfolios, and specific plants were sampled and
the wastewaters analyzed. In making technical assessments of
data, reviewing manufacturing processes, and assessing wastewater
treatment technology options, both indirect and direct
dischargers have been considered as a single group. An
examination of plants and processes did not indicate any
process differences based on the type of discharge, whether it be
direct or indirect.
As explained in Section IV, the primary and secondary germanium
and gallium subcategory has been subdivided into six potential
wastewater sources. Since the water use, discharge rates, and
pollutant characteristics of each of these wastewaters is
5307
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IX
potentially unique, effluent
each of the six subdivisions.
limitations will be developed for
For each of the subdivisions, a specific approach was followed
for the development of BPT mass limitations. The first
requirement to calculate these limitations is to account for
production and flow variability from plant to plant. Therefore,
a unit of production or production normalizing parameter (PNP)
was determined for each waste stream which could then be related
to the flow from the process to determine a production normalized
flow. Selection of the PNP for each process element is discussed
in Section IV. Each plant within the subcategory was then
analyzed to determine which subdivisions were present, the
specific flow rates generated for each subdivision, and the
specific production normalized flows for each subdivision. This
analysis is discussed in detail in Section V. Nonprocess
wastewaters such as rainfall runoff and noncontact cooling water
are not considered in the analysis.
Production normalized flows for each subdivision were then
analyzed to determine the flow to be used as part of the basis
for BPT mass limitations. The selected flow (sometimes referred
to as the BPT regulatory flow or BPT discharge rate) reflects the
water use controls which are common practices within the
category. The BPT regulatory flow is based on the average of all
applicable data. Plants with normalized flows above the average
may have to implement some method of flow reduction to achieve
the BPT limitations.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the BPT
level of treatment technology. Section VII discusses the various
control and treatment technologies which are currently in place
for each wastewater source. In most cases in the nonferrous
metals manufacturing category, the current control and treatment
technologies consist of chemical precipitation and sedimentation
(lime and settle technology).
In the germanium and gallium subcategory current control and
treatment technology is inadequate, and lime and settle
technology must be transferred to this subcategory. Lime and
settle technology is widely demonstrated on wastewaters with
similar characteristics to that found in this subcategory, and it
is realistic to believe that a similar performance is achievable.
Using these regulatory flows and the achievable concentrations,
the next step is to calculate mass loadings for each wastewater
source or subdivision. This calculation was made on a
stream-by-stream basis, primarily because plants ^ in this
subcategory may perform one or more of the operations in various
combinations. The mass loadings (milligrams of pollutant per
kilogram of production mg/kg) are based on multiplying the BPT
regulatory flow (1/kkg) by the concentration achievable by the
BPT level of treatment technology (mg/1) , for each pollutant
parameter to be limited under BPT. These mass loadings are
5308
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IX
published in the Federal Register and in CFR Part 421 as the
effluent limitations.
The mass loadings which are allowed under BPT for each plant will
be the sum of the individual mass loadings for the various
wastewater sources which are found at particular plants.
Accordingly, all the wastewater generated within a plant may be
combined for treatment in a single or common treatment system but
the effluent limitations for these combined wastewaters are based
on the various wastewater sources which actually contribute to
the combined flow. This method accounts for the variety of
combinations of wastewater sources and production processes which
may be found at primary and secondary germanium and gallium
plants.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow and effluent concentration
achievable by the treatment technology and summed to derive an
appropriate limitation for each plant.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal estimates,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollution control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed or promulgated BPT.
The methodology for calculating pollutant removal estimates and
. plant compliance costs is discussed in Section X. Because the
data on which the cost and pollutant removal estimates are based
have been claimed confidential, these values are not included
here. Pollutant removal estimates and compliance costs for
promulgation are the same as those developed for the proposed
regulation.
BPT OPTION SELECTION
EPA proposed a two tier approach for regulating this subcategory.
Level A provisions were applicable to facilities which only
reduce germanium dioxide in a hydrogen furnace and wash and rinse
the germanium product in conjunction with zone refining. Level B
provisions were applicable to all other facilities in the
subcategory. At proposal the BPT technology basis for both
Levels A and B was chemical precipitation and sedimentation.
5309
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IX
We are promulgating BPT requirements for the primary and
secondary germanium and gallium subcategory equivalent to
those proposed for BPT but we no longer have two regulatory
levels. The technology basis for the BPT limitations are
chemical precipitation and sedimentation technology to remove
metals, fluoride, and solids from combined wastewaters and to
control pH (Option A). The pollutants specifically promulgated
for regulation at BPT are arsenic, lead, zinc, fluoride,
TSS, and pH.
Although there are no existing direct dischargers in this
subcategory, BPT is promulgated for any existing zero discharger
that elects to discharge at some point in the future. This
action was taken because wastewaters from germanium and gallium
operations which contain significant loadings of toxic
pollutants are currently being disposed of in a RCRA permitted
surface impoundment.
More stringent technology options were not selected for BPT since
they require in-process changes or end-of-pipe technologies
less widely practiced in the subcategory, and, therefore, are
more appropriately considered under BAT. EPA is not
promulgating a two tier regulatory scheme for this subcategory,
because there is not much additional removal of pollutants using
the additional treatment technology of Option C. The BPT
treatment scheme is presented in Figure IX-1 (page 5318).
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
from analysis of dcp. The discharge rate is used with the
achievable treatment concentrations to determine BPT effluent
limitations. Since the discharge rate may be different from each
wastewater source, separate production normalized discharge rates
for each of- the six wastewater sources are discussed below and
summarized in Table IX-1. The discharge rates are normalized on
a production basis by relating the amount of wastewater generated
to the mass of the intermediate or product which is produced by
the process associated with the waste stream in question. These
production normalizing parameters, or PNPs, are also listed in
Table IX-1.
Section V of this document further describes the discharge flow
rates and presents the water use and discharge flow rates for
each plant by subdivision in Tables V-l through V-6.
STILL LIQUOR
The BPT wastewater discharge rate used for both proposal and
promulgation for still liquor is 63,000 1/kkg (15,097
gal/ton) of germanium chlorinated. This rate is allocated
only for those plants which chlorinate germanium concentrate _or
scrap with hydrochloric acid or chlorine to produce germanium
5310
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IX
tetrachloride. Water use and wastewater discharge rates are
presented in Table V-l. The BPT flow is based on the rate
reported by one plant with this process.
CHLORINATOR WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate used for both proposal and
promulgation for chlorinator wet air pollution control is
13,170 1/kkg (3,156 gal/ton) of germanium chlorinated, based on
zero percent recycle. This rate is allocated only for those
plants which chlorinate germanium raw material to produce
germanium tetrachloride, and use a wet scrubber to control air
emissions from the chlorinator. Water use and wastewater
discharge rates are presented in Table V-2. The BPT flow is
based on the rate reported by one plant with this process.
GERMANIUM HYDROLYSIS FILTRATE
The BPT wastewater discharge rate used for both proposal and
promulgation for germanium hydrolysis filtrate is 18,870 1/kkg
(4,522 gal/ton) of germanium hydrolyzed. This rate is
allocated only for those plants which hydrolyze germanium
tetrachloride to germanium dioxide by reacting it with
water. Water use and wastewater discharge rates are presented
in Table V-3. The BPT flow is based on the rate reported
by one plant with this process.
ACID WASH AND RINSE WATER
The BPT wastewater discharge rate used for both proposal and
promulgation for acid wash and rinse water is 155,720 1/kkg
(37,316 gal/ton) of germanium washed. This rate is allocated
only for those plants which wash germanium bars with acid and
then rinse them with water. Water use and wastewater
discharge rates are presented in Table V-4. The BPT flow is
based on the rate reported by one plant with this process.
Other plants reported insufficient information to calculate
this discharge rate.
GALLIUM HYDROLYSIS FILTRATE
The BPT wastewater discharge rate used for both proposal and
promulgation for gallium hydrolysis filtrate is 33,710 1/kkg
(8,078 gal/ton) of gallium hydrolyzed. This rate is allocated
only for those plants which hydrolyze gallium trichloride to
gallium oxide hydroxide by reacting it with water and sodium
hydroxide. Water use and wastewater discharge rates are
presented in Table V-5. The BPT flow is based on the average
of the rates reported by plants with this wastewater stream.
SOLVENT EXTRACTION RAFFINATE
The BPT wastewater discharge rate used for both proposal and
promulgation for solvent extraction raffinate is 18,820 1/kkg
(4,510 gal/ton) of gallium produced by solvent extraction. This
5311
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - IX
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5318
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another industry where
it is readily transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used, as well as reduction of the amount of water used
and discharged, process control, and treatment technology
optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the process used, process changes, nonwater
quality environmental impacts (including energy requirements),
and the costs of application of such technology. At a minimum,
BAT represents the best available technology economically
•achievable at plants of various ages, sizes, processes, or other
characteristics. Where the Agency has found the existing
performance to be uniformly inadequate, BAT may be transferred
from a different subcategory or category. BAT may include
feasible process changes or internal controls, even when not in
common industry practice.
The statutory assessment of BAT considers costs, but does not
require a balancing of costs against pollutant removals. However,-
in assessing the proposed and promulgated BAT, the Agency has
given substantial weight to the economic achievability of the
technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency elected to examine two
technology options which could be applied to the secondary
molybdenum and vanadium subcategory as alternatives for the basis
of BAT effluent limitations.
For the development of BAT effluent limitations, mass loadings
were calculated for each wastewater source or subdivision in the
subcategory using the same technical approach as described in
Section IX for BPT limitations development. The differences in
the mass loadings for BPT and BAT are due to increased treatment
effectiveness achievable with the more sophisticated BAT
treatment technology.
The treatment technologies considered for BAT are summarized
below:
5319
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
Option A (Figure X-l, page 5329) is based on
o Chemical precipitation and sedimentation
Option C (Figure X-2, page 5330) is based on:
o Chemical precipitation and sedimentation
o Multimedia filtration
The two options examined for BAT are discussed in greater detail
on the following pages. The first option considered (Option A) is
the same as the BPT treatment and control technology which was
presented in the previous section. The second option represents
substantial progress toward the reduction of pollutant discharges
above and beyond the progress achievable by BPT.
OPTION A
Option A for the primary and secondary germanium and gallium
subcategory is equivalent to the control and treatment
technologies which were analyzed for BPT in Section IX (see
Figure IX). The BPT end-of-pipe treatment scheme includes
chemical precipitation and sedimentation. The discharge rates for
Option A are equal to the discharge rates allocated to each
stream as a BPT discharge flow.
OPTION C
Option C for the primary and secondary germanium and gallium
subcategory consists of all control and treatment requirements of
Option A, (chemical precipitation and sedimentation) plus
multimedia filtration technology added at the end of Option A
treatment scheme (see Figure X-2r page 5326). Multimedia
filtration is used to remove suspended solids, including
precipitates of toxic metals, beyond the concentrations
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed media type, although other forms of filters,
such as rapid sand filters or pressure filters, would perform
satisfactorily.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removals and the compliance costs
associated with each option. The methodplogies are described
below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant removal, or benefit, achieved by the
application of the various treatment options is presented in
Section X of Vol.1. In short, sampling data collected during the
field sampling program were used to characterize the major waste
5320
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
streams considered for regulation. At each sampled facility, the
sampling data was production normalized for each unit operation
(i.e., mass of pollutant generated per mass of product
manufactured). This value, referred to as the raw waste, was used
to estimate the mass of toxic pollutants generated within the
primary and secondary germanium and gallium subcategory. The
pollutant removal estimates were calculated for each plant by
first estimating the total mass of each pollutant in the
untreated wastewater. This was calculated by first multiplying
the raw waste values by the corresponding production value for
that stream and the summing these values for each pollutant for
every stream generated by the plant.
Next, the volume of wastewater discharged after the application
of each treatment option was estimated for each operation at each
plant by comparing the actual discharge to the regulatory flow.
The smaller of the two values was selected and summed with the
other plant flows. The mass of pollutant discharged was then
estimated by multiplying the achievable concentration values
attainable with the option(mg/1) by the estimated volume of
process wastewater discharged by the subcategory. The mass of
pollutant removed is the difference between the estimated mass of
pollutant generated within the subcategory and the mass of
pollutant discharged after application of the treatment option.
The pollutant removal estimates for indirect dischargers in the
primary and secondary germanium and gallium subcategory are
presented in Table XII-1 (Page 5341).
COMPLIANCE COSTS,
In estimating subcategory-wide compliance costs, the first step
was to develop a cost estimation model, relating the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge. EPA
applied the model to each plant. A plant's investment and
operating costs are determined by what treatment it has in place
and by its individual process wastewater discharge. As discussed
above, this flow is either the actual or the BAT regulatory flow,
whichever is less. The final step was to annualize the capital
costs, and to sum the annualized capital costs, and the operating
and maintenance costs for each plant, yielding the cost of
compliance for the subcategory. Compliance costs for indirect
dischargers are shown in Section XII. These costs were used in
assessing economic achievability.
WASTEWATER DISCHARGE RATES
A BAT discharge rate was calculated for each subdivision based
upon the flows of the existing plants, as determined from
analysis of the data collection portfolios. The discharge rate is
used with the achievable treatment concentrations to determine
BAT effluent limitations. Since the discharge rate may be
different for each wastewater source, separate production
normalized discharge rates for each of the six wastewater sources
were determined and are summarized in Table X-l (Page 5225). The
5321
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
BAT wastewater discharge rates are identical to those determined
for BPT. No additional flow reduction measures are considered
feasible for this subcategory.
BAT OPTION SELECTION - PROPOSAL
EPA proposed Level a BAT limitations for this subcategory based
on chemical precipitation and sedimentation (Option A) for plants
that only reduce germanium dioxide in a hydrogen furnace and then
wash and rinse the germanium product in conjunction with zone
refining. Level B BAT limitations were proposed for all other
facilities in this subcategory. The level B effluent limitations
at proposal were based on Option A with the addition of
filtration (Option C).
The pollutants specifically limited under the proposed BAT were
arsenic, lead, zinc, germanium and fluoride. Gallium was also
considered for regulation as discussed in the March 18, 1985
Notice of Data Availability and Request for Comment (50 FR
10918). The Agency considered applying the same technology levels
to this entire subcategory but decided to propose this two tiered
regulatory scheme because there was little additional pollutant
removal from the Level A wastewater streams when treated by the
added Level B technology.
Although there are no existing direct dischargers in this
subcategory, BAT was proposed for any existing zero discharger
who elects to discharge at some time in the future. This action
was taken because wastewaters from germanium and gallium
operations which contain significant loadings of toxic
pollutants are currently being disposed of in a RCRA permitted
surface impoundment.
BAT OPTION SELECTION - PROMULGATION
We are promulgating BAT limitations for this subcategory based on
chemical precipitation and sedimentation (Option A) for all
facilities in this subcategory. This is equivalent to BPT
technology. We are not promulgating two tiered limitations for
this subcategory because there is not much additional removal of
pollutants using the more expensive regulatory scheme.
The pollutants specifically limited under BAT are arsenic, lead,
zinc, and fluoride. The priority pollutants antimony, cadmium,
chromium, copper, nickel, selenium, silver and thallium were
also considered for regulation because they were found at
treatable concentrations in the raw wastewaters from this
subcategory. These pollutants were not selected for specific
regulation because they will be effectively controlled when the
regulated toxic metals are treated to the concentrations
achievable by the model BAT technology.
Although there are no existing direct dischargers in this
subcategory, BAT is promulgated for any existing zero discharger
who elects to discharge at some time in the future. This action
5322
-------
PRIMARY A'ND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
was taken because wastewaters from germanium and gallium
operations which contain significant loadings of toxic pollutants
are currently being disposed of in a RCRA permitted surface
impoundment.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutants and pollutant parameters for limitation. This
examination and evaluation was presented in Section VI. The
Agency, however, has chosen not to regulate all 11 toxic
pollutants selected in this analysis. The high cost associated
with analysis for priority metal pollutants has prompted EPA to
develop an alternative method for regulating and monitoring
priority pollutant discharges from the nonferrous metals
manufacturing category. Rather than developing specific effluent
mass limitations and standards for each of the priority metals
found in treatable concentrations in the raw wastewater from a
given subcategory, the Agency is promulgating effluent mass
limitations only for those pollutants generated in the greatest
quantities as shown by the pollutant removal estimate analysis.
The pollutants selected for specific limitation are listed below:
115. arsenic
122. lead
128. zinc
fluoride
By establishing limitations and standards for certain priority
metal pollutants, dischargers will attain the same degree of
control over priority metal pollutants as they would have been
required to achieve had all the priority metal pollutants been
directly limited.
This approach is technically justified since the treatable
concentrations used for. chemical precipitation and sedimentation
technology are based on optimized treatment for concomitant
multiple metals removal. Thus, even though metals have somewhat
different theoretical solubilities, they will be removed at very
nearly the same rate in a chemical precipitation and
sedimentation treatment system operated for multiple metals
removal.
The toxic metal pollutants selected for specific limitation in
the primary and secondary germanium and gallium subcategory to
control the discharges of priority metal pollutants are arsenic,
lead and zinc. The following toxic metal pollutants are excluded
from limitation on the basis that they are effectively controlled
by the limitations developed for arsenic, lead and zinc:
114. antimony
118. cadmium
119. chromium (total)
120. copper
5323
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
124. nickel
125. selenium
126. silver
127. thallium
EFFLUENT LIMITATIONS
The concentrations achievable by application of BAT are discussed
in Section VII of this supplement. The treatable concentrations
for both one day maximum and monthly average values are
multiplied by the BAT normalized discharge flows summarized in
Table X-l (page 5325) to calculate the mass of pollutants allowed
to be discharged per mass of product. The results of these
calculations in milligrams of pollutant per kilogram of product
represent the BAT effluent limitations and are presented in Table
X-2 (Page 5326) for each wastewater stream.
5324
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
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5325
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
TABLE X-2
BAT FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(a) Still Liquor BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Pluoride
Gallium
Germanium
180.800
131.700
21.420
27.720
119.700
26.460
121.000
77.490
25.830
129.200
91.980
2,205.000
27.720
27.720
80.640
58.590
9.450
11.340
63.000
12.600
80.010
34.650
10.710
57.330
38.430
1,254.000
11.340
11.340
(b) Chlorinator Wet Air Pollution Control BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Pluoride
Gallium
Germanium
37.800
27.530
4.478
5.795
25.020
5.531
25.290
16.200
5.400
27.000
19.230
461.000
5.795
5.795
16.860
12.250
1.976
2.371
13.170
2.634
16.730
7.244
2.239
11.980
8.034
262.100
2.371
2.371
*Regulated Pollutant
5326
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
TABLE X-2 (Continued)
BAT FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(c) Germanium Hydrolysis Filtrate BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
54.160
39.440
6.416
8.303
35.850
7.925
36.230
23.210
7.737
38.680
27.550
660.500
8.303
8.303
24.150
17.550
2.831
3.397
18.870
3.774
23.960
10.380
3.208
17.170
11.510
375.500
3.397
3.397
(d) Acid Wash and Rinse Water BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium washed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
446.900
325.500
52.940
68.520
295.900
65.400
299.000
191.500
63.850
319.200
227.400
5,450.000
68.520
68.520
199.300
144.800
23.360
28.030
155.700
31.140
197.800
85.650
26.470
141.700
94.990
3,099.000
28.030
28.030
*Regulated Pollutant
5327
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
TABLE X-2 (Continued)
BAT FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(e) Gallium Hydrolysis Filtrate BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
96.750
70.450
11.460
14.830
64.050
14.160
64.720
41.460
13.820
69.110
49.220
1,180.000
14.830
14.830
43.150
31.350
5.057
6.068
33.710
6.742
42.810
18.540
5.731
30.680
20.560
670.800
6.068
6.068
(f) Solvent Extraction Raffinate BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium produced by solvent extraction
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
54.010
39.330
6.399
8.281
35.760
7.904
36.130
23.150
7.716
38.580
27.480
658.700
8.281
8.281
24.090
17.500
2.823
3.388
18.820
3.764
23.900
10.350
3.199
17.130
11.480
374.500
3.388
3.388
*Regulated Pollutant
5328
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - X
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5330
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
This section describes the technologies for treatment of
wastewater from new sources and presents mass discharge standards
for regulated pollutants for NSPS in the primary and secondary
germanium and gallium subcategory, based on selected treatment
technology. New plants have the opportunity to design the best
and most efficient production processes and wastewater treatment
technologies without facing the added costs and restrictions,
encountered in retrofitting and existing plant. Therefore, EPA
has considered the best demonstrated process changes, in-plant
controls and end-of-pipe treatment technologies which reduce
pollution to the maximum extent feasible as the basis for NSPS.
TECHNICAL APPROACH TO NSPS
New source performance standards are equivalent to the best
available technology (BAT) selected for primary and secondary '
germanium and gallium plants. This result is a consequence of
careful review by the Agency of wide range of technical options
for new source treatment systems which is discussed in Section XI
of the General Development Document. Additionally, there was
nothing found to indicate that the wastewater flows and-
characteristics of new plants would not be similar to those from _
existing plants, since the processes used by new sources are not!
expected to differ from those used at existing sources.
Consequently, BAT production normalized discharge rates, which
are based on the best existing practices of the subcategory, can
also be applied to new sources. These rates are presented in '
Table XI-.1 (Page 5333).
Treatment technologies considered for the NSPS options are
identical to the treatment technologies considered for the BAT
options. These options are:
OPTION A '""•
o Chemical precipitation and sedimentation
OPTION C
o Chemical precipitation and sedimentation
o Multimedia filtration
,NSPS OPTION SELECTION - PROPOSAL
EPA proposed that the best available demonstrated technology for
the primary and secondary germanium and gallium subcategory be
equivalent to Option A (chemical precipitation and sedimentation)
5331
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XI
for Level A plants, and Option C (chemical precipitation,
sedimentation, and multimedia filtration) for Level B plants. The
technology basis for the proposed NSPS is equivalent to that for
the proposed BAT.
The wastewater flow rates for NSPS were the same as the proposed
BAT flow rates. Flow reduction measures for NSPS were not
considered feasible because no new demonstrated technologies
existed within the subcategory that improved on water use and
discharge practices.
NSPS OPTION SELECTION - PROMULGATION
EPA is promulgating NSPS for the primary and secondary germanium
and gallium based on Option A (chemical precipitation and
sedimentation). This technology basis for the promulgated NSPS is
equivalent to that for the promulgated BAT.
We do not believe that new plants could achieve any flow
reduction beyond the allowances promulgated for BAT. Therefore,
wastewater flow rates for NSPS are equivalent to those for the
promulgated BAT. Because NSPS is equal to BAT we believe that the
promulgated NSPS will not have a detrimental impact on the entry
of new plants into this subcategory.
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with existing sources.
Accordingly, pollutants and pollutant parameters selected for
limitation under NSPS, in accordance with the rationale of
Sections VI and X, are identical to those selected for BAT. The
conventional pollutant parameters TSS and pH are also selected
for limitation.
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows for each wastewater source are the same
as the discharge rates for BAT and are shown in Table XI-1 (page
5333). The mass of pollutant allowed to be discharged per mass of
product is calculated by multiplying the appropriate achievable
concentration (mg/1) by the production normalized wastewater
discharge flows (1/kkg). The results of these calculations are
the mass-based production-related new source performance
standards. These standards are presented in Table XI-2 (Page
5334).
5332
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XI
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5333
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XI
TABLE XI-2
NSPS FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(a) Still Liquor NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
*TSS
*pH Within the
180.800
131.700
21.420
27.720
119.700
26.460
121.000
77.490
25.830
129.200
91.980
2,205.000
27.720
27.720
2f583.000
range of 7.5 to 10
80.640
58.590
9.450
11.340
63.000
12.600
80.010
34.650
10.710
57.330
38.430
1,254.000
11.340
11.340
1,229.000
,0 at all times
(b) Chlorinator Wet Air Pollution Control NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
g/kg (Ib/million Ibs) of germanium chlorinated
m<
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
*TSS
*pH Within the
37.800
27.530
4.478
5.795
25.020
5.531
25.290
16.200
5.400
27.000
19.230
461.000
5.795
5.795
540.000
range of 7.5 to 10.0 at all
16.860
12.250
1.976
2.371
13.170
2.634
16.730
7.244
2.239
11.980
8.034
262.100
2.371
2.371
256.800
times
*Regulated Pollutant
5334
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XI
TABLE XI-2
NSPS FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(c) Germanium Hydrolysis Filtrate NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
*TSS
*pH Within the
54.160
39.440
6.416
8.303
35.850
7.925
36.230
23.210
7.737
38.680
27.550
660.500
8.303
8.303
773.700
range of 7.5 to 10.0
24.150
17.550
2.831
3.397
18.870
3.774
23.960
10.380
3.208
17.170
11.510
375.500
3.397
3.397
368.000
at all times
(d) Acid Wash and Rinse Water NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium washed
Antimony -
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
*TSS
*pH Within the
446.900
325.500
52.940
68.520
295.900
65.400
299.000
191.500
63.850
319.200
227.400
5,450.000
68.520
68.520
6,385.000
range of 7.5 to 10
199.300
144.800
23.360
28.030
155.700
31.140
197.800
85.650
26.470
141.700
94.990
3,099.000
28.030
28.030
3,037.000
,0 at all times
*Regulated Pollutant
5335
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XI
TABLE XI-2
NSPS FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(e) Gallium Hydrolysis Filtrate NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
*TSS
*pH Within the
96.750
70.450
11.460
14.830
64.050
14.160
64.720
41.460
13.820
69.110
49.220
1,180.000
14.830
14.830
1,382.000
range of 7.5 to 10.0 at all
43.150
31.350
5.057
6.068
33.710
6.742
42.810
18.540
5.731
30.680
20.560
670.800
6.068
6.068
657.300
times
(f) Solvent Extraction Raffinate NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs)gallium produced by solvent extraction
* Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
*TSS
*pH Within the
54.010
39.330
6.399
8.281
35.760
7,904
36.130
23.150
7.716
38.580
27.480
658.700
8.281
8.281
771.600
range of 7.5 to 10.0 at all
24.090
17.500
2.823
3.388
18.820
3,764
23.900
10.350
3.199
17.130
11.480
374.500
3.388
3.388
367.000
times
* Regulated Pollutant
5336
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY. SECT - XII
SECTION XII
PRETREATMENT STANDARDS
This section describes the control and treatment technologies for
pretreatment of process wastewaters from new sources in the
primary and secondary germanium and gallium subcategory. PSES are
designed to prevent the discharge of pollutants which pass
through, interfere with or are otherwise incompatible with the
operation of publicly owned treatment works (POTW). The Clean
Water Act also requires pretreatment for pollutants, such as
toxic metals, that limit POTW sludge management alternatives. 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 technologies, and to
use plant site selection to ensure adequate treatment system
function. Pretreatment standards are to be technology based, and
analogous to the best available or best demonstrated technology
for removal of toxic pollutants. Pretreatment standards for
regulated pollutants are presented based on the selected control
and treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing and promulgating pretreatment standards, the
Agency examines whether the pollutants discharged by the industry
pass through the POTW or interfere with the POTW operation or its
chosen sludge disposal practices. In determining whether
pollutants pass through a well-operated POTW achieving secondary
treatment, the Agency compares the percentage of a pollutant
removed by POTW with the percentage removed by direct dischargers
applying the best available technology economically achievable. 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
limitations guidelines for that pollutant.
This definition of pass through satisfies two competing
objectives set by Congress that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time, the treatment capability and performance
of the POTW be recognized and taken into account in regulating
the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
5337
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
POTW from non-industrial sources or the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
The industry cost and pollutant removal estimates of each
treatment option were used to determine the most cost-effective
option. The methodology applied in calculating pollutant removal
estimates and plant compliance costs is discussed in Section X.
Table XII-1 (Page 5341) shows the estimated pollutant removals
for indirect dischargers. Compliance costs for indirect
dischargers are presented in Table XII-2 (Page 5342).
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES
Options for pretreatment of wastewaters from both existing and
new sources are based on increasing the effectiveness of
end-of-pipe treatment technologies. All in-plant changes and
applicable end-of-pipe treatment processes have been discussed
previously in Sections X and XI. The options for PSNS and PSES,
therefore, are the same as the BAT options discussed in Section
X.
A description of each option is presented in Section X, while a
more detailed discussion, including pollutants controlled by each
treatment process is presented in Section VII of the General
Development Document.
Treatment technologies considered for the PSNS and PSES options
are:
OPTION A
o Chemical precipitation and sedimentation
OPTION C
o Chemical precipitation and sedimentation
o Multimedia filtration
PSES OPTION SELECTION - PROPOSAL
EPA proposed PSES based on Option A (chemical precipitation and
sedimentation) for Level A plants, and Option C (chemical
precipitation), sedimentation, and multimedia filtration) for
Level B plants.
EPA proposed PSES to prevent pass-through of arsenic, lead, zinc,
fluoride, and germanium. These pollutants were specifically
limited in the proposed PSES. Wastewater discharge rates for the
proposed PSES were equivalent to those proposed for BAT.
5338
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
PSES OPTION SELECTION - PROMULGATION
We are pomulgating PSES for this subcategory
precipitation and sedimentation technology
pollutants controlled at PSES are the same as
BAT. We are promulgating PSES to prevent pass-
lead, zinc and fluoride. These POTW achieving
to an average of 33 percent, while BAT
approximately 70 percent.
based on chemical
(Option A). The
those controlled at
through of arsenic,
secondary treatment
technology removes
Implementation of the promulgated PSES would remove annually an
estimated 20 kg of toxic metals and 376 kg of fluoride. The
capital and annual costs for the promulgated PSES are $28,300 and
$22,200 (1982 dollars), respectively.
PSNS OPTION SELECTION - PROPOSAL
EPA proposed that the pretreatment standards technology base for
new sources in the primary and secondary germanium and gallium
subcategory be equivalent to Option A (chemical precipitation and
sedimentation) for Level A plants, and Option C (chemical
precipitation, sedimentation, and multimedia filtration) for
Level B plants. The proposed PSNS technology basis was equivalent
to that of the proposed BAT.
PSNS OPTION SELECTION - PROMULGATION
We are promulgating PSNS equivalent to PSES, NSPS and BAT. The
technology basis for the promulgated PSNS is identical to NSPS
PSES, and BAT. The same pollutants pass through as at PSES, for
the same reasons.
We believe that the promulgated PSNS are achievable, and that
they are not a barrier to entry of new plants into this
subcategory because they do not include any additional costs
compared to PSES.
The wastewater discharge rates for PSNS are identical to the BAT
discharge rates for each waste stream. The PSES and ^PSNS
discharge rates are shown in Table XII-3 (Page 5343).
REGULATED POLLUTANT PARAMETERS
Pollutants selected for limitation, in accordance with the
rationale of Sections VI and X, are identical to those selected
for limitation for BAT. It is necessary to promulgate PSES and
PSNS to prevent the pass-through of arsenic, lead, zinc, and
fluoride, which are the limited pollutants.
PRETREATMENT STANDARDS
Pretreatment standards are based on the treatable concentrations
from the selected treatment technology, and the discharge rates
determined in Section X for BAT. A mass of pollutant per mass of
product (mg/kg) allocation is given for each subdivision within
5339
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
the subcategory. This pollutant allocation is based on the
product of the achievable concentration from the model treatment
(mg/1) and the production normalized wastewater discharge rate
(1/kkg). The achievable treatment concentrations for BAT are
identical to those for PSES and PSNS. PSES and PSNS are presented
in Tables XII-4 and XII-5 (Pages 5344 and 5347).
5340
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
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PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
Table XII-2
COST OF COMPLIANCE FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
Indirect Dischargers
Option
A
C
Total Required
Capital Cost
(1982 Dollars)
24,600
28,300
Total Annual
Cost
(1982 Dollars)
20,300
22,200
5342
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
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5343
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
TABLE XI1-4
PSES FOR THE PRIMARY AND SECONDARY GERMANIUM
AND GALLIUM SUBCATEGORY
(a) Still Liquor PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
180.800
131.700
21.420
27.720
119.700
26.460
121.000
77.490
25.830
129.200
91.980
2,205.000
27.720
27.720
80.640
58.590
9.450
11.340
63.000
12.600
80.010
34.650
10.710
57.330
38.430
1,254.000
11.340
11.340
(b) Chlorinator Wet Air Pollution Control PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
37.800
27.530
4.478
5.795
25.020
5.531
25.290
16.200
5.400
27.000
19.230
461.000
5.795
5.795
16.860
12.250
1.976
2,371
13.170
2.634
16.730
7.244
2.239
11.980
8.034
262.100
2.371
2.371
*Regulated Pollutant
5344
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
TABLE XI1-4 (Continued)
PSES FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(c) Germanium Hydrolysis Filtrate PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
54.160
39.440
6.416
8.303
35.850
7.925
36.230
23.210
7.737
38.680
27.550
660.500
8.303
8.303
24.150
17.550
2.831
3.397
18.870
3.774
23.960
10.380
3.208
17.170
11.510
375.500
3.397
3.397
(d) Acid Wash and Rinse Water PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium washed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
446.900
325.500
52.940
68.520
295.900
65.400
299.000
191.500
63.850
319.200
227.400
5,450.000
68.520
68.520
199.300
144.800
23.360
28.030
155.700
31.140
197.800
85.650
26.470
141.700
94.990
3,099.000
28.030
28.030
*Regulated Pollutant
5345
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
TABLE XII-4 (Continued)
PSES FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(e) Gallium Hydrolysis Filtrate PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
96.750
70.450
11.460
14.830
64.050
14.160
64.720
41.460
13.820
69.110
49.220
1,180.000
14.830
14.830
43.150
31.350
5.057
6.068
33.710
6.742
42.810
18.540
5.731
30.680
20.560
670.800
6.068
6.068
(f) Solvent Extraction Raffinate PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium produced by solvent extraction
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
54.010
39.330
6.399
8.281
35.760
7.904
36.130
23.150
7.716
38.580
27.480
658.700
8.281
8.281
24.090
17.500
2.823
3.388
18.820
3.764
23.900
10.350
3.199
17.130
11.480
374.500
3.388
3.388
^Regulated Pollutant
5346
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
TABLE XI1-5
PSNS FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(a) Still Liquor PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
180.800
131.700
21.420
27.720
119.700
26.460
121.000
77.490
25.830
129.200
91.980
2,205.000
27.720
27.720
80.640
58.590
9.450
11.340
63.000
12.600
80.010
34.650
10.710
57.330
38.430
1,254.000
11.340
11.340
(b) Chlorinator Wet Air Pollution Control PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium chlorinated
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
37.800
27.530
4.478
5.795
25.020
5.531
25.290
16.200
5.400
27.000
19.230
461.000
5.795
5.795
16.860
12.250
1.976
2.371
13.170
2.634
16.730
7.244
2.239
11.980
8.034
262.100
2.371
2.371
*Regulated Pollutant
5347
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
TABLE XI1-5 (Continued)
PSNS FOR THE
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(c) Germanium Hydrolysis Filtrate PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of germanium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
54.160
39.440
6.416
8.303
35.850
7.925
36.230
23.210
7.737
38.680
27.550
660.500
8.303
8.303
24.150
17.550
2.831
3.397
18.870
3.774
23.960
10.380
3.208
17.170
11.510
375.500
3.397
3.397
(d) Acid Wash and Rinse Water PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
(Ib/million Ibs) of germanium washed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
446.900
325.500
52.940
68.520
295.900
65.400
299.000
191.500
63.850
319.200
227.400
5,450.000
68.520
68.520
199.300
144.800
23.360
28.030
155.700
31.140
197.800
85.650
26.470
141.700
94.990
3,099.000
28.030
28.030
*Regulated Pollutant
5348
-------
PRIKARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
TABLE XI1-5 (Continued)
PSNS FOR THE ;
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY
(e) Gallium Hydrolysis Filtrate PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium hydrolyzed
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
96.750
70.450
11.460
14.830
64.050
14.160
64.720
41.460
13.820
69.110
49.220
1,180.000
14.830
14.830
43.150
31.350
5.057
6.068
33.710
6.742
42.810
18.540
5.731
30.680
20.560
670.800
6.068
6.068
(f) Solvent Extraction Raffinate PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of gallium produced by solvent extraction
Antimony
*Arsenic
Cadmium
Chromium
Copper
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Fluoride
Gallium
Germanium
54.010
39.330
6.399
8.281
35.760
7.904
36.130
23.150
7.716
38.580
27.480
658.700
8.281
8.281
24.090
17.500
2.823
3.388
18.820
3.764
23.900
10.350
3.199
17.130
11.480
374.500
3.388
3.388
*Regulated Pollutant
5349
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XII
THIS PAGE INTENTIONALLY LEFT BLANK
5350
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the primary and secondary germanium and
gallium subcategory at this time.
5351
-------
PRIMARY AND SECONDARY GERMANIUM AND GALLIUM SUBCATEGORY SECT - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
5352
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Primary Rare Earth Metals Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell/ Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
5353
-------
5354
-------
Section
PRIMARY RARE EARTH METALS SUBCATEGORY
TABLE OF CONTENTS
I
II
III
IV
V
SUMMARY
CONCLUSIONS
SUBCATEGORY PROFILE
Description of Primary Rare Earth Metals
Production
Raw Materials
Calcium Reduction
Mischmetal Reduction
Production of Mischmetal
Process Wastewater Sources
Other Wastewater Sources
Age, Production, and Process Profile
SUBCATEGORIZATION
Factors Considered in Subdividing the Primary
Rare Earth Metals Subcategory
Other Factors
Production Normalizing Parameters
WATER USE AND WASTEWATER CHARACTERISTICS
Wastewater Flow Rates
Wastewater Characteristics Data
Data Collection Portfolios
Field Sampling Data
Wastewater Characteristics and Flows by
Subdivision
Dryer Vent Water Quench and Scrubber
Dryer Vent Caustic Wet Air Pollution Control
Electrolytic Cell Water Quench and Scrubber
Electrolytic Cell Caustic Wet Air Pollution
Control
Sodium Hypochlorite Filter Backwash
5363
5365
5375
5375
5376
5376
5376
5376
5377
5377
5378
5387
5387
5388
5388
5389
5390
5390
5391
5391
5392
5392
5393
5393
5393
5394
5355
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
Section
VI
VII
VIII
TABLE OF CONTENTS (Continued)
SELECTION OF POLLUTANT PARAMETERS
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Priority Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Never Found Above Their
Analytical Quantification Concentration
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for Further
Consideration in Establishing Limitations
and Standards
CONTROL AND TREATMENT TECHNOLOGIES
Current Control and Treatment Practices
Dryer Vent Water Quench and Scrubber
Dryer Vent Caustic Wet Air Pollution Control
Electrolytic Cell Water Quench and Scrubber
Electrolytic Cell Caustic Wet Air Pollution
Control
Sodium Hypochlorite Filter Backwash
Treatment Practices
Control and Treatment Options
Option A
Option B
Option C
Option E
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
Treatment Options for Existing Sources
Option A
Option B
Option C
Option E
Cost Methodology
Nonwater Quality Aspects
Energy Requirements
Solid Waste
Air Pollution
5450
5450
5450
5450
5451
5452
5463
5463
5463
5464
5464
5464
5464
5464
5464
5465
5465
5465
5465
5467
5467
5467
5467
5467
5467
5468
5468
5468
5468
5470
5356
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
IX
X
XI
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE
Technical Approach to BPT
Industry Cost and Pollutant Removal Estimates
BPT Option Selection
Wastewater Discharge Rates
Dryer Vent Water Quench and Scrubber
Dryer Vent Caustic Wet Air Pollution Control
Electrolytic Cell Water Quench and Scrubber
Electrolytic Cell Caustic Wet Air Pollution
Control
Sodium Hypochlorite Filter Backwash
Regulated Pollutant Parameters
Effluent Limitations
BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE
Technical Approach to BAT
Option A
Option B
Option C
Option E
Pollutant Removal Estimates
Compliance Costs
BAT Option Selection - Proposal
BAT Option Selection - Promulgation
Wastewater Discharge Rates
Dryer Vent Water Quench and Scrubber
Electrolytic Cell Water Quench and Scrubber
Regulated Pollutant Parameters
Effluent Limitations
NEW SOURCE PERFORMANCE STANDARDS
Technical Approach to NSPS
NSPS Option Selection - Proposal
NSPS Option Selection - Promulgation
Regulated Pollutant Parameters
New Source Performance Standards
Page
5473
5473
5475
5475
5476
5476
5477
5477
5477
5478
5478
5478
5486
5485
5486
5486
5486
5487
5487
5488
5489
5489
5490
5490
5491
5491
5492
5503
5503
5504
5504
5505
5505
5357
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
Page
XII
XIII
PRETREATMENT STANDARDS 5511
Technical Approach to Pretreatment 5511
Industry Cost and Pollutant Removal Estimates 5512
Pretreatment Standards for Existing and New 5512
Sources
PSNS and PSES Option Selection - Proposal 5512
PSNS Option Selection - Promulgation 5512
PSES Option Selection - Promulgation 5513
Regulated Pollutant Parameters 5513
Pretreatment Standards 5513
BEST CONVENTIONAL POLLUTANT CONTROL 5523
TECHNOLOGY
5358
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
LIST OF TABLES
Table
Title
Page
III-l
III-2
III-3
V-l
V-2
V-3
V-4
V-5
V-6
V-7
V-9
V-10
VI-1
VI-2
Initial Operating Year (Range) Summary of Plants 5379
in the Primary Rare Earth Metals Subcategory by
Discharge, Type
Production Ranges for the Primary Rare Earth 5380
Metals Subcategory
Summary of Primary Rare Earth Metals Subcategory 5381
Processes and Associated Waste Streams
Water Use and Discharge Rates for Dryer Vent 5395
Water Quench and Scrubber
Water Use and Discharge Rates for Dryer Vent 5395
Caustic Wet Air Pollution Control
Water Use and Discharge Rates for Electrolytic 5395
Cell Water Quench and Scrubber
Water Use and Discharge Rates for Electrolytic 5396
Cell Caustic Wet Air Pollution Control
Water Use and Discharge Rates for Sodium 5396
Hypochlorite Filter Backwash
Primary Rare Earth Metals Sampling Data Dryer 5397
Vent Water Quench Raw Wastewater
Primary Rare Earth Metals Sampling Data Dryer 5407
Vent Caustic Scrubber Raw Wastewater7
Primary Rare Earth Metals Sampling Data 5417
Electrolytic Cell Water Quench Raw Wastewater
Primary Rare Earth Metals Sampling Data Combined 5427
Raw Wastewater
Primary Rare Earth Metals Sampling Data Final 5437
Effluent
Frequency of Occurrence of Priority Pollutants 5455
Primary Rare Earth Metals Raw Wastewater
Toxic Pollutants Never Detected 5459
5359
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
LIST OF TABLES (Continued)
Table
Title
Page
VIII-1
IX-1
IX-2
X-l
X-2
X-3
X-4
XI-1
XI-2
XII-1
XII-2.
XII-3
XII-4
XII-5
5471
5479
5480
Cost of.Compliance for the Primary Rare Earth
Metals Subcategory Direct Dischargers
BPT Wastewater Discharge Rates for "the Primary
Rare Earth Metals Subcategory
BPT Mass Limitations for the Primary Rare Earth
Metals Subcategory
Pollutant Removal Estimates for Direct 5493
Dischargers Primary Rare Earth Metals Subcategory
Cost of Compliance for the Primary Rare Earth 5494
Metals Subcategory Direct Dischargers
BAT Wastewater Discharge Rates for the Primary
Rare Earth Metals Subcategory
BAT Mass Limitations for the Primary Rare Earth
Metals Subcategory
NSPS Wastewater Discharge Rates for the Primary
Rare Earth Metals Subcategory
NSPS for the Primary Rare Earth Metals
Subcategory
Pollutant Removal Estimates for Indirect
Dischargers Primary Rare Earth Metals Subcategory
Cost of Compliance for the Primary Rare Earth
Metals Subcategory Indirect Dischargers
PSES and PSNS Wastewater Discharge Rates for the 5516
Primary Rare Earth Metals Subcategory
5495
5496
5506
5507
5514
5515
PSES for the Primary Rare Earth Metals
Subcategory
PSNS for the Primary Rare Earth Metals
Subcategory
5517
5520
5360
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
LIST OF FIGURES
Figure Title Page
III-l Calcium Reduction Process Primary Rare Earth 5382
Metals Subcategory
III-2 Mischmetal Reduction Process Primary Rare Earth 5383
Metals Subcategory
III-3 Mischmetal Production Process Primary Rare 5384
Earth Metals Subcategory
III-4 Geographic Locations of the Primary Rare Earth 5385
Metals Subcategory Plants
V-l Sampling Sites at Primary Rare Earth Metals 5447
Plant
IX-1 BPT Treatment Scheme for the Primary Rare Earth 5483
Metals Subcategory
X-l BAT Treatment Scheme for Option A 5499
X-2 BAT Treatment Scheme for Option B 5500
X-3 BAT Treatment Scheme for Option C 5501
X-4 BAT Treatment Scheme for Option E 5502
5361
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
5362
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
effluent limitations based on best practicable technology (BPT)
and best available technology (BAT) for existing direct
dischargers, pretreatment standards for existing indirect
dischargers (PSES), pretreatment standards for new indirect
dischargers (PSNS), and standards of performance for new source
direct dischargers (NSPS).
At the time of promulgation, the primary rare earth metals
subcategory consisted of four plants. Of the four plants, one
discharges directly to a surface water, one discharges to a
publicly owned treatment works (POTW), and two plants do not
discharge process wastewater. Since then, one additional plant,
which does not discharge process wastewater, has been located.
EPA first studied the primary rare earth metals subcategory to
determine whether differences in raw materials, final products,
manufacturing processes, equipment, age and size of plants, or
water usage, required the development of separate effluent
limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including the
sources and volume of water used, the processes used, the sources
of pollutants and wastewaters in the plant, and the constituents
of wastewaters, including priority pollutants. As a result, five
subdivisions have been identified for this subcategory that
warrant separate effluent limitations. These include:
o Dryer vent water quench and scrubber,
o Dryer vent caustic wet air pollution Control,
o Electrolytic cell water quench and scrubber,
o Electrolytic cell caustic wet air pollution control, and
o Sodium hypochlorite filter backwash.
EPA also identified several distinct control and treatment
technologies (both in-plant and end-of-pipe) applicable to the
primary rare earth metals subcategory. The Agency analyzed both
historical and newly generated data on the performance of these
technologies, including their nonwater quality environmental
impacts and air quality, solid waste generation, and energy
requirements. EPA also studied various flow reduction techniques
reported in the data collection portfolios (dcp) and plant
visits.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of
implementing the various options on the subcategory. For each
control and treatment option that the Agency found to be most
5363
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - I
effective and technically feasible in controlling the discharge
of pollutants, we estimated the number of potential closures,
number of employees affected, and impact on price. These results
are reported in a separate document entitled "The Economic Impact
Analysis of Effluent Limitations and Standards for the Nonferrous
Metals Manufacturing Industry."
After examining the various treatment technologies, the Agency
has identified BPT to represent the average of the best existing
technology. Metals removal based on chemical precipitation and
sedimentation technology is the basis for the BPT limitations. To
meet the BPT effluent limitations based on this technology, the
primary rare earth metals subcategory is not expected to incur
any additional capital or annual costs.
For BAT, the Agency has built upon the BPT technology basis by
adding in-process control technologies which include recycle of
process water from quench and wet air pollution control waste
streams. Filtration is added as an effluent polishing step to
the end-of-pipe treatment scheme followed by activated carbon
adsorption technology for removal of toxic organics.
NSPS is equivalent to BAT. In selecting NSPS, EPA recognizes
that new plants have the opportunity to implement the best and
most efficient manufacturing processes and treatment technology.
As such, the technology basis of BAT has been determined as the
best demonstrated technology.
The technology basis for PSES is equivalent to BAT. For PSNS,
the Agency selected end-of-pipe treatment and in-process flow
reduction control techniques equivalent to NSPS.
To meet the effluent limitations and pretreatinent standards based
on the BAT-PSES technology, the primary rare earth metals
subcategory is estimated to incur a capital cost of $231,100 and
an annual cost of $117,200.
The best conventional technology (BCT) replaces BAT for the
control of conventional pollutants. BCT is not being promulgated
because the methodology for BCT has not yet been finalized.
After promulgation, the agency withdrew the BPT and BAT effluent
limitations because of a procedural error in the promulgation
process. The promulgated limitations and rationales are included
in this document for completeness and as best professional
judgment advise to permit writers should the need for such advise
arise. The mass limitations and standards for BPT, BAT, NSPS,
PSES, and PSNS are presented in Section II.
The 16 lanthanide group metals included as rare earth metals are
cerium, dysprosium, erbium, europium, gadolinium, holmium,
lanthanum, lutetium, neodymium, praseodymium, samarium, scandium,
terbium, thulium, ytterbium, and yttrium.
5364
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
SECTION II
CONCLUSIONS
EPA has divided the primary rare earth metals subcategory into
five subdivisions for the purpose of effluent limitations and
standards. These subdivisions are:
(a) Dryer vent water quench and scrubber,
(b) Dryer vent caustic wet air pollution control,
(c) Electrolytic cell water quench and scrubber,
(d) Electrolytic cell caustic wet air pollution control, and
(e) Sodium hypochlorite filter backwash.
BPT was promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology. After promulgation the Agency withdrew BPT
because of a procedural error. The following BPT effluent
limitations were promulgated and are presented here as best
professional advice:
(a) Dryer Vent Water Quench and Scrubber BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
(Ib/million Ibs) of mischmetal produced from
wet rare earth chlorides
Chromium (Total)
Lead
Nickel
TSS
4.648
4.436
20.280
433.100
1.901
2.113
13.420
206.000
pH
Within the range of 7.5 to 10.0 at all times
(b) Dryer Vent Caustic Wet Air Pollution Control BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal produced
from wet rare earth chlorides
Chromium (Total)
Lead
Nickel
TSS
PH
0.323
0.308
1.409
30.090
0.132
0.147
0.932
14.310
Within the range of 7.5 to 10.0 at all times
5365
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - II
(c) Electrolytic Cell Water Quench and Scrubber BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Chromium (Total) 5.580 2.283
Lead 5.326 2.536
Nickel 24.350 16.110
TSS 520.000 247.300
pH Within the range of 7.5 to 10.0 at all times
(d) Electrolytic Cell Caustic Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced"~
Chromium (Total) 0.000 0.000
Lead 0.000 0.000
Nickel 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.5 to 10.0 at all times
(e) Sodium Hypochlorite Filter Backwash BPT
Pollutant orMaximum forMaximum for~
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Chromium (Total) 0.159 0.065
Lead 0.152 0.072
Nickel 0.695 0.460
TSS 14.840 , 7.059
pH Within the range of 7.5 to 10.0 at all times
BAT was promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, multimedia
filtration, activated carbon adsorption technology, and inprocess
flow reduction methods. After promulgation, the Agency withdrew
BAT because of a procedural error. The following BAT effluent
limitations are presented here as best professional advice for
the permit writer:
5366
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
(a) Dryer Vent Water Quench and Scrubber BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (lb/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.042
1.544
1.168
2.295
0.042
0.626
0.542
1.544
(b) Dryer Vent Caustic Wet Air Pollution Control BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (lb/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.007
0.272
0.206
0.404
0.007
0.110
0.095
0.272
(c) Electrolytic Cell Water Quench and Scrubber BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (lb/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.094
3.474
2.629
5.165
0.094
1.409
1.221
3.474
(d) Electrolytic Cell Caustic Wet Air Pollution Control BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (lb/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
5367
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
(e) Sodium Hypochlorite Filter Backwash BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
(Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.004
0.134
0.101
0.199
0.004
0.054
0.047
0.134
NSPS are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, multimedia
filtration, activated carbon technology, and in-process flow
reduction methods. The following standards are promulgated for
new sources:
(a) Dryer Vent Water Quench and Scrubber NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
TSS
0.042
1.544
1.168
2.295
62.600
0.042
0.626
0.542
1.544
50.080
pH
Within the range of 7.5 to 10.0 at all times
(b) Dryer Vent Caustic Wet Air Pollution Control NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
rag/kg (Ib/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
TSS
0.007
0.272
0.206
0.404
11.010
0.007
0.110
0.095
0.272
8.808
pH
Within the range of 7.5 to 10.0 at all times
5368
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
(c) Electrolytic Cell Water Quench and Scrubber NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
TSS
0.094
3.474
2.629
5.165
140.900
0.094
1.409
1.221
3.474
112.700
pH
Within the range of 7.5 to 10.0 at all times
(d) Electrolytic Cell Caustic Wet Air Pollution Control NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
TSS
pH Within the
Ibs) of total
0.000
0.000
0.000
0.000
0.000
range of 7.5
mischmetal produced
0.000
0.000
0.000
0.000
0.000
to 10.0 at all times
(e) Sodium Hypochlorite Filter Backwash NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
TSS
0.004
0.134
0.101
0 199
5.430
0.004
0.054
0.047
0.134
4.344
pH
Within the range of 7.5 to 10.0 at all times
5369
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
PSES are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, multimedia
filtration, activated carbon adsorption technology, and inprocess
flow reduction methods. The following pretreatment standards are
promulgated for existing sources:
(a) Dryer Vent Water Quench and Scrubber PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.042
1.544
1.168
2.295
0.042
0.626
0.542
1.544
b) Dryer Vent Caustic Wet Air Pollution Control PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg(Ib/million Ibs)of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.007
0.474
0.206
0.404
0.007
0.110
0.095
0.272
c) Electrolytic Cell Water Quench and Scrubber PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.094
3.474
2.629
5.165
0.094
1.409
1.221
3.474
5370
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
(d) Electrolytic Cell Caustic Wet Air Pollution Control PSES
Pollutant or
Pollutant Property
mg/kg (Ib/million Ibs) of total mischmetal produced
Maximum for
Any One Day
Maximum for
Monthly Average
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
(e) Sodium Hypochlorite Filter Backwash PSES
Pollutant or
Pollutant Property.
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.004
0.134
0.101
0.199
0.004
0.054
0.047
0.134
PSNS are promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, multimedia
filtration, activated carbon adsorption technology, and in-
process flow reduction methods. The following pretreatment
standards are promulgated for new sources:
(a) Dryer Vent Water Quench and Scrubber PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.042
1.544
1.168
2.295
0.042
0.626
0.543
1.544
5371
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - II
(b) Dryer Vent Caustic Wet Air Pollution Control PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
rag/kg (Ib/million Ibs) of mischmetal produced from
wet rare earth chlorides
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.007
0.272
0.206
0.404
0.007
0.110
0.095
0.272
(c) Electrolytic Cell Water Quench and Scrubber PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.094
3.474
2.629
5.165
0.094
1.409
1.221
3.474
(d) Electrolytic Cell Caustic Wet Air Pollution Control PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
5372
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - II
(e) Sodium Hypochlorite Filter Backwash PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Hexachlorobenzene
Chromium (Total)
Lead
Nickel
0.004
0.134
0.101
0.199
0.004
0.054
0.047
0.134
EPA is not promulgating best conventional technology (BCT) at
this time for the primary rare earth metals subcategory.
5373
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - II
THIS PAGE INTENTIONALLY LEFT BLANK
5374
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the primary rare earth metals supplement
describes the raw materials and processes used in producing
primary rare earth metals and presents a profile of the primary
rare earth metals plants identified in this study.
Rare earth metals are presently used in areas such as metallurgy,
ceramics, and electrical and lighting applications A mixture of
individual rare earth metals and iron called mischmetal is the
rare earth metal predominately used in metallurgy. It is added
to select alloys to increase hardness, electrical and thermal
conductivity, and to improve high temperature characteristics
with respect to strength and resistance to oxidation. Mischmetal
is also the main ingredient of lighter flints. In ceramics, rare
earth metals are used in pigments, heating elements, and in
dielectric and conductive ceramics. Electrical and lighting
applications include using rare earth metal phosphors in color
television tubes, radar screens thermometers, low and high
pressure mercury vapor lamps, and trichromatic fluorescent
lights. Rare earth permanent magnets are used in electric motors,
alternators, line printers, and disk drive actuators as well as
other applications.
DESCRIPTION OF PRIMARY RARE EARTH METALS PRODUCTION
In this supplement the production of rare earth metals will
focus primarily on the production of individual metals of the
lanthanide group and on the production of mischmetal. The
production processes for manufacturing individual rare earth
metals include calcium reduction, mischmetal reduction and
solvent extraction.
Two process operations are used in the production of mischmetal.
Mischmetal is an alloy typically composed of cerium, lanthanum,
neodymium, praseodymium, other rare earth metals, and iron, with
cerium being the greatest constituent and iron the smallest. In
the first operation, the raw material is dehydrated, and in the
second operation, the dried raw material is electrolytically
reduced to metal. Wastewater is generated during the production
of mischmetal while the production of individual rare earth
metals does not generates process wastewater.
The following paragraphs will further explain these operations
and processes. A schematic diagram for the calcium reduction
process is shown in Figure III-l (page 5382). The mischmetal
reduction process is shown in Figure III-2 (page 5383). The
mischmetal production process is shown in Figure III-3 (page
5384).
5375
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
RAW MATERIALS
The raw materials that are used by the plants in the primary rare
earth metals subcategory are rare earth metal oxides, metal
hydroxides, metal chlorides, and metal fluoride.
Depending on their availability. rare earth metal oxides,
hydroxides, chlorides, and fluorides are obtained from foreign or
domestic companies which mine, separate, and concentrate ores
containing rare earth metals.
CALCIUM REDUCTION
Ten of the 14 lanthanide group metals are produced by calcium
reduction. These include lanthanum, cerium, praseodymium,
neodymium, gadolinium, terbium, dysprosium, holmium, erbium, and
lutetium, as well as scandium and yttrium. The raw material form
of these metals is the metal fluoride. The individual metal
fluoride is placed with calcium metal into a reduction vessel
where a heat-driven reaction produces pure rare earth metal and
calcium fluoride. The metals are further purified by melting in
a vacuum to remove impurities. Casting is dependent upon the
form in which a buyer wants the metal. Non-contact cooling water
is used to cool both the reduction vessel and the melting and
casting equipment. No process wastewater is generated in the
calcium reduction process.
MISCHMETAL REDUCTION
The last four of the lanthanide group metals, samarium, europium,
thulium, and ytterbium, are produced by mischmetal reduction.
Mischmetal reduces the oxide form of these metals to an elemental
form. In this reaction the mischmetal acts as a reducing agent
and is oxidized to a mixture of rare earth metal oxides. The
process is performed at low pressure and a temperature below the
melting point so that the metals vaporize or sublime. The pure
metal is condensed and collected in a crystalline mass of high
purity. These solids may be crushed into powder or melted and
cast if a solid product form is desired. Water use in this
process is limited to noncontact cooling, thus no process
wastewater streams are generated by this production process.
PRODUCTION OF MISCHMETAL
Raw Material Dehydration: Wet rare earth chlorides or hydrated
rare earth chloride compounds must be stripped of their water
before electrolytic reduction can take place. This is to prevent
decay of the graphite anode during electrolysis. The anode could
be decayed by the reaction of the liberated oxygen in the
electrolyte with the carbon anode to form carbon dioxide. Batch
or continuous mode dryers may be used. Both gas heat and
electric heat have been used to run the dehydration furnaces.
The off-gases from the furnaces are treated by water or alkaline
scrubbers to scrub particulates and acid from the off-gases.
The treated gases are vented and and the scrubber liquor may be
5376
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - III
discharged to wastewater treatment.
Electrolytic Reduction: Dry rare earth chlorides are reduced to
mischmetal in electrolytic cells. Batch process electrolysis
reduces the rare earth salts to metal in eight to 12 hours.
Excess slag is removed and may be sold for its rare earth
chlorides content. Off-gases from electrolytic reduction include
chlorine gas, carbon monoxide and carbon dioxide gases from the
carbon in the graphite anodes, and hydrochloric acid fumes.
These gases are contacted with water to cool the gases and absorb
particulates and hydrochloric acid vapors. The partially
cleansed gases are then contacted with sodium hydroxide solution
where sodium hypochlorite is formed. After a sufficient
hypochlorite concentration is attained, the solution may be sold
as a by product.
Since the composition of-mischmetal is defined within certain
limits, the quantities and types of rare earth chloride raw
materials must be properly proportioned as they are added to the
electrolytic reduction cell to produce the specified mischmetal
composition. Following the reduction process, the mischmetal is
cast into bars or ingots for future uses primarily in metallurgy.
PROCESS WASTEWATER SOURCES
The process wastewater sources for the primary
subcategory are subdivided as follows:
rare earth metals
1.
2.
3.
4.
5.
Dryer vent water quench and scrubber,
Dryer vent caustic wet air pollution control,
Electrolytic cell water quench and scrubber,
Electrolytic cell caustic wet air pollution control,
Sodium hypochlorite filter backwash.
and
The building blocks used at proposal were revised because of new
information provided to the Agency after proposal. Subdivisions 1
and 2 which were a single building block at proposal were
separated at promulgation because not all plants incorporate both
subdivisions in their process operations.
Information was also supplied in comments after proposal for a
sodium hypochlorite filter backwash wastewater stream. The Agency
did not give this wastewater stream an allowance at proposal
because no plant had reported it in their dcp. However, in
response to industry comments, EPA has promulgated discharge
standards for this wastewater stream.
OTHER WASTEWATER SOURCES
There may be other wastewater streams associated with the primary
rare earth metals subcategory. These streams may include
noncontact cooling water, maintenance and cleanup water, and
stormwater runoff. These wastewater streams are not considered as
a part of this rulemaking. EPA believes that the flows and
pollutant loadings associated with these streams are
5377
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
insignificant relative to the wastewaters selected and are best
handled by the appropriate permit authority on a case-by-case
basis under authority of Section 402 of the Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
Figure III-4 (page 5385) shows the locations of the primary rare
earth metals plants identified in this study. Three are located
in the Eastern United States while one is in the southwestern
region.
Table III-l (page 5379) shows the relative age and discharge
status of the primary rare earth metals plants. Two of the
plants are noticeably older than the others,, Table III-2 (page
5380) shows the relative production for the primary rare earth
metals plants for 1982.
Mischmetal is the rare earth metal that is produced in greatest
volume, but most of the plants that manufacture mischmetal also
manufacture other alloys and pure rare earth metals and powders.
Table III-3 (page 5381) provides a summary of the
plants generating wastewater for the waste streams
with various processes, and the number of plants
process.
number of
associated
with the
5378
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
cd
H
.-1
CO
•u
O
H
Cd Cd
33 CU
H >*
H
1-1 Cd
O
CO OS
H < ^ co
CQ VJ
c2 >i cO CO
<5 os CD >•<
^?j f^ %^
so c
M^ r^ oo ^^
CO H C
<* -^ CO
cd oa co <;
03 W
Z CO CO 4J
<; a c
OM CO ^^ Co
^*-^ HJ ^^
< r-4 A,
oi f-i co v— '
^ Cd **"^
Cd S U
33 C
O &H 1— 1
Z OS
1— t *
O i~ »- CM
x-\
1 >>O
r^ oo ^o
CM »— 1
^^[n
S../
O O O O
""N
r^ oo ^^
^ C*-J 1
^^ c^ r*^
t— ,— en
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O O O O
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«— T- CM
\^S
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r^ oo CM
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ON ON r^
t— »— r-
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CO OO ^O
OO \O ^~
ON ON 1
«— »- O
t- 0 0 .-
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1-104
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O-i
*4-4
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w
0 J
u co <:
O V4 H
CO -^ O O
to 13 , to H
•r^ C CD
Q HH NI
5379
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
TABLE II1-2
PRODUCTION RANGES
FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
These data are not presented here because
they have been claimed to be confidential.
5380
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
Table II1-3
SUMMARY OF PRIMARY RARE EARTH METALS SUBCATEGORY
PROCESSES AND ASSOCIATED WASTE STREAMS
Process
Calcium Reduction
Mischmetal Reduction
Production of Mischmetal
Dryer Vent Water Quench and
Scrubber
Dryer Vent Caustic Wet Air
Pollution Control ,
Electrolytic Cell Water
Quench and Scrubber
Electrolytic Cell Caustic
Wet Air Pollution Control
Sodium Hypochlorite Filter
Backwash
Number of Rare
Earth Metals
Plants
With Process
1
2
2
2
1
2
2
1
Number of Plants
Reporting
Generation
of Wastewater*
0
0
2
2
1
2
0
1
*Through reuse, evaporation practices, or by-product recovery,
a plant may "generate" wastewater from a particular process
but not discharge it.
5381
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
Rare Earth
Fluorides
Calcium
1.1
Non-Contact
Cooling
Calcium
Reduction
Non-Contact
Cooling
Reduced
Metal
Melting
and
Casting
Impurities
Pure Rare Earth
Metal Ingot
Calcium
Fluoride
Figure III-l
CALCIUM REDUCTION PROCESS
PRIMARY RARE EARTH METALS SUBCATEGORY
5382
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
Rare Earth
Metal Oxide
Mischmetal
1 I
Non-Contact
Cooling
Mischmetal
Reduction
(Vacuum
Distillation)
Mixed Rare
Earth Oxides
Crystalline
Rare Earth Metal
Crushing
and
Packaging
I
Rare Earth
Metal Product
Figure III-2
MISCHMETAL REDUCTION PROCESS
PRIMARY RARE EARTH METALS SUBCATEGORY
5383
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
od
O
a
CO Cd
CO EH
cd <3
o a
O 03
OS 3
CM CO
Z CO
T> O tJ
M H EH
HH CJ Cd
a
O 33
OS H
CM Oti
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
00
CO
CM
CQ
3
CO
CO
J
IS
Cd
Ed
CO
a
o
33
CM
o
w
o
5385
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - III
THIS PAGE INTENTIONALLY LEFT BLANK
5386
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the related subdivisions of the primary rare earth
metals subcategory. Production normalizing parameters for each
subdivision are also discussed.
FACTORS CONSIDERED IN SUBDIVIDING THE PRIMARY RARE EARTH METALS
SUBCATEGORY
The factors listed previously for general subcategorization were
each evaluated when considering subdivision of the primary rare
earth metals subcategory. In the discussion that follows, the
factors will be discussed as they pertain to this particular
subcategory. '
The rationale for considering further subdivision of the primary
rare earth metals subcategory is based primarily on differences
in the production process and raw materials used. Within this
subcategory, five primary operations are performed which include
water use and wastewater discharge, and which require the
establishment of separate effluent limitations. While the
primary rare earth metals subcategory is still considered_ a
single subcategory, a more thorough examination of the production
processes has illustrated the need for limitations based on
specific flow allowances for the following subdivisions:
1. Dryer vent water quench and scrubber,
2. Dryer vent caustic wet air pollution control,
3. Electrolytic cell water quench and scrubber,
4. Electrolytic cell caustic wet air pollution control, and
5. Sodium hypochlorite filter backwash.
The first two subdivisions result from the use of different gas
cleaning systems when the raw material — hydrated rare earth
chlorides —is dried. When these salts are in a hydrated form,
they require drying to inhibit anode decay. The use of a water
quench to cool the gases and collect particulates and the use of
a caustic scrubber each require a different wastewater flow rate.
The third and fourth subdivisions arise from the cleaning of
gases generated by the operation used to reduce dried, mixed rare
earth chlorides to mischmetal. In the electrolytic reduction,
chlorine gas and hydrochloric acid are primary constituents of
the off-gases. A water quench or water scrubber is employed to
cool the gases, absorb much of the hydrochloric acid fumes, and
collect particulates. Caustic is used to react the chlorine gas
to form sodium hypochlorite which is sold as a by-product. A
separate subdivision has been assigned to each of these
operations to account for their wastewater discharge.
The fifth subdivision results from filtration of the sodium
5387
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IV
hypochlorite by-product prior to sale. Depending on the type of
filter in use, backwash may be necessary for efficient operation
of the filter. This subdivision accounts for the discharge from
backwashing such a filter.
OTHER FACTORS
The other factors considered in this evaluation were shown to be
inappropriate as a basis for subdivision. Air pollution control
methods, treatment costs, and total energy requirements are
functions of the selected subcategorization factors—metal
product, raw materials, and production processes. Therefore,
they are not independent factors and clo not affect the
subcategorization which has been applied. Certain other factors,
such as plant age, plant size, and the number of employees, were
also evaluated and determined to be inappropriate for use as
a basis for subdivision of nonferrous metals plants.
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow these
regulations to be applied to plants with various production
capacities, the mass of pollutant discharged must be related to a
unit of production. This factor is known as the production
normalizing parameter (PNP).
In general, for each production process which has a wastewater
associated with it, the actual mass of rare earth mineral or
intermediate product will be used as the PNP,, Thus, the PNPs for
the five subdivisions are as follows:
Subdivision
1. Dryer vent water quench and
scrubber
2. Dryer vent caustic wet air
pollution control
3. Electrolytic cell water
quench and scrubber
4. Electrolytic cell caustic
wet air pollution control
5. Sodium hypochlorite filter
backwash
PNP
mischmetal produced from wet
rare earth chlorides
mischmeteil produced from wet
rare earth chlorides
total mischmetal produced
total mischmetal produced
total mischmetal produced
5388
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the primary rare earth metals subcategory. Water
use and discharge rates are explained and then summarized in
tables at the end of this section. Data used to characterize the
wastewaters are presented. Finally, the specific source, water
use and discharge flows, and wastewater characteristics for each
separate wastewater source are discussed.
The two principal data sources used in collecting data for this
study are data collection portfolios (dcp) and field sampling
results. Data collection portfolios contain information
regarding wastewater flows and production levels.
In order to quantify the pollutant discharge from primary rare
earth metals plants, a field sampling program was conducted.
Wastewater samples were analyzed for 124 of the 126 priority
pollutants and other pollutants deemed appropriate. Because the
analytical standard for TCDD was judged to be too hazardous to be
made generally available, samples were never analyzed for this
pollutant. Samples were also never analyzed for asbestos. There
is no reason to expect that TCDD or asbestos would be present in
nonferrous metals manufacturing wastewater. One plant was
selected for sampling in the primary rare earth metals
subcategory. In general, the samples were analyzed for three
classes of pollutants: toxic organic pollutants, toxic metal
pollutants, and criteria pollutants (which includes both
conventional and nonconventional pollutants).
No additional sampling data for this subcategory were obtained
between proposal and promulgation. Characterization of primary
rare earth metals subcategory wastewaters (Section V), and
selection of pollutant parameters for limitation (Section VI) are
based upon the same data used for proposal.
Additional wastewater flow and production data were received
through industry comments between proposal and promulgation. This
aided EPA in determining subdivisions needed to proper
characterize the subcategory and to calculate the the appropriate
discharge allowances for all of the subdivisions.
As described in Section IV of this supplement, the primary rare
earth metals subcategory has been split into five subdivisions or
wastewater sources, so that the promulgated regulation contains
mass discharge limitations and standards for five unit processes
discharging process wastewater. Differences in the wastewater
characteristics associated with these subdivisions are to be
expected. For this reason, wastewater streams corresponding to
each subdivision are addressed separately in the discussions that
follow. These wastewater sources are:
5389
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - V
1. Dryer vent water quench and scrubber,
2. Dryer vent caustic wet air pollution control,
3. Electrolytic cell water quench and scrubber,
4. Electrolytic cell caustic wet air pollution control, and
5. Sodium hypochlorite filter backwash.
WASTEWATER PLOW RATES
Data supplied by dcp responses were evaluated, and two flow-
to-production ratios, water use and wastewater discharge, were
calculated for each stream. The two ratios 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 rare earth 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 rare earth product.
Differences between the water use and wastewater flows associated
with a given stream result from recycle, evaporation, and
carry-over on the product. The production values used in
calculation correspond to the production normalizing parameter,
PNP, assigned to each stream, as outlined in Section IV. As an
example, sodium hypochlorite filter backwash flow is related to
the total production of mischmetal. As such, the discharge rate
is expressed in liters of filter backwash wastewater per metric
ton of total mischmetal produced (gallons of filter backwash
wastewater per ton of total mischmetal produced).
The production normalized discharge flows were compiled and
statistically analyzed by stream type. These production
normalized water use and discharge flows are presented by
subdivision in Tables V-l through V-5 at the end of this section.
Where appropriate, an attempt was made to identify factors that
could account for variations in water use and discharge rates.
These variations are discussed later in . this section by
subdivision. A similar analysis of factors affecting the
wastewater flows is presented in Sections IX, X, XI, and XII
where representative BPT, BAT, NSPS, and pretreatment flows are
selected for use in calculating the effluent limitations.
The water use and discharge rates shown do not include nonprocess
wastewater, such as rainfall runoff and noncontact cooling water.
WASTEWATER CHARACTERISTICS DATA
Data used to characterize the various wastewaters associated with
the primary rare earth metals subcategory come from these
sources—data collection portfolios, analytical data from field
sampling trips, and comments submitted on the proposed
regulation.
5390
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
DATA COLLECTION PORTFOLIOS
In the data collection portfolios, the rare earth metals plants
that discharge wastewater were asked to specify the presence or
absence of toxic pollutants in their wastewater. Only one plant
submitted partial information in response to this request. For
this reason, insufficient data were available from the data
collection portfolios to be presented at proposal as being
representative of the wastewater characteristics of the
subcategory. However, after proposal additional data and
information were submitted by the industry which allowed EPA to
determine the wastewater characteristics of the subcategory.
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from primary rare earth metals plants, wastewater
samples were collected at one of the plants belonging to this
subcategory. A diagram indicating the sampling sites, waste
streams and production processes is shown in Figure V-l (page
5447)
Tables V-6 through V-10 (pages 5397 - 5437) summarize the data
for 124 priority pollutants as well as other pollutants that
were considered appropriate to this subcategory. Sampling was
done at five points which included the primary waste streams
associated with the production process and other sampling points
as will be clarified further. Tables V-6 and V-7 (pages 5397 -
5407) show data taken from the dryer vent water quench stream and
the dryer vent caustic scrubber waste stream. Table V-8
tabulates the analysis of the quench water from the electrolytic
reduction process of rare earth chlorides. Table V-9 shows the
analysis of the combined waste streams from the entire plant just
before treatment, and Table V-10 is the analysis of the final
effluent from this plant. Note that the stream numbers listed in
the tables correspond to those given in the plant sampling site
diagram, Figure V-l. Where no data are listed for a specific day
of sampling, the wastewater samples for the stream were not
collected.
The data tables include some samples measured at concentrations
considered not quantifiable. The base-neutral extractable, acid
extractable, and volatile organics generally are considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
Below this concentration, organic analytical results are not
quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1.
The detection limits shown on the data tables for toxic metals
and conventional and nonconventional pollutants are not the same
in all cases as the 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
5391
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. For data
considered as detected but below quantifiable concentrations, a
value of zero is used for averaging. Priority organic,
nonconventional, and conventional pollutant data reported with a
"less than" sign are considered as detected, but not further
quantifiable. A value of zero is also used for averaging. If a
pollutant is reported as not detected, it is assigned a value of
zero in calculating the average. Finally, priority metal values
reported as less than a certain value were considered as not
quantifiable, and consequently were assigned a value of zero in
the calculation of the average.
Finally, appropriate source water concentrations are presented
with the summaries of the sampling data. The method by which
each sample was collected is indicated by number, as follows:
1 one-time grab
2 manual composite during intermittent process operation
3 8-hour manual composite
4 8-hour automatic composite
5 24-hour manual composite
6 24-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since rare earth metals production involves five principal
sources of wastewater and each has potentially different
characteristics and flows, each waste stream, or subdivision, is
discussed separately. Below is a discussion of each subdivision
including a description of the process, where the wastewater is
generated, and the wastewater flow and characteristics.
DRYER VENT WATER QUENCH AND SCRUBBER
Wet rare earth chlorides are dried before reduction to metal by
passing the wet chlorides through a furnace or drier. A wet air
pollution control system first cools the drier fumes and collects
flue dust. The scrubber liquor is discharged to wastewater
treatment and the gases vented to the atmosphere. The pH of this
quench water is approximately 1-5. The second stage will be
discussed in the next subdivision.
Table V-l (page 5395) presents the production normalized water
use and discharge flows for the operations described above in
liters per metric ton of mischmetal produced from wet rare earth
chlorides. Table V-6 (page 5397) shows detailed analyses of the
constituents of this wastewater stream. From the data it can be
5392
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
seen that this stream is characterized by acidic pH, treatable
concentrations of some toxic metals such as nickel, and treatable
concentrations of suspended solids.
DRYER VENT CAUSTIC WET AIR POLLUTION CONTROL
Following the dryer vent water scrubber or quench, a caustic
scrubber is used to remove acid vapors from the. vent gases.
Scrubber liquor is presently recycled and the bleed stream is
discharged to treatment.
Table V-2 (page 5395) presents the production normalized water
use and discharge flows for the caustic scrubber in liters per
metric ton of mischmetal produced from wet rare earth chlorides.
Table V-7 (page 5407) presents detailed analyses of the
constituents in this wastewater stream. These data characterize
the caustic scrubber wastewater as having a high pH, treatable
concentrations of toxic metals such as chromium, lead, nickel,
and thallium, and treatable concentrations of suspended solids.
ELECTROLYTIC CELL WATER QUENCH AND SCRUBBER
Dry rare earth chlorides are placed into cells usually lined with
graphite carbon. The salts are electrolytically reduced to
mischmetal, the composition of which is dictated by the mixture
of rare earth chlorides fed into the cells. The reduction
process produces chlorine gas, as well as carbon monoxide and
carbon dioxide gases. Water quench or water scrubbers cool these
gases and trap particulate matter as well as vaporized
hydrochloric acid.
Wastewater from this operation contains treatable concentrations
of lead, acidic pH, and treatable concentrations of
hexachlorobenzene. Table V-3 (page 5395) presents production
normalized water use and discharge rates for this operation in
liters per metric ton of total mischmetal produced. Table V-8
reports field sampling data on electrolytic cell water quench and
scrubber.
ELECTROLYTIC CELL CAUSTIC WET AIR POLLUTION CONTROL
The caustic wet air pollution control system following the water
quench or water scrubber is designed to recover chlorine present
in the gas stream. Sodium hydroxide is circulated through the
scrubber and the reaction with chlorine forms sodium
hypochlorite. When a 12 to 15 percent sodium hypochlorite
concentration is attained, the solution is drawn off and sold for
industrial use.
Table V-4 (page 5396) shows that the production normalized
discharge flow for this subdivision is zero. This is because
both plants having the scrubber operation achieve zero discharge
-through recovery of the scrubber liquor as a salable by-product,
sodium hypochlorite.
5393
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
SODIUM HYPOCHLORITE FILTER BACKWASH
Sodium hypochlorite produced in the electrolytic cell caustic
scrubber may contain particulate matter. In order to produce a
marketable product, the sodium hypochlorite is filtered.
Depending on the type of filter used, backwashing may be
necessary to insure efficient operation of the filter.
This wastewater stream was not directly sampled. However, EPA
believes its characteristics will be similar to those of the
dryer vent caustic scrubber wastewater. The filter backwash
wastewater may be characterized by high pH, high values of
chloride and other dissolved solids, and treatable concentrations
of suspended solids.
5394
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
TABLE V-l
WATER USE AND DISCHARGE RATES FOR
DRYER VENT WATER QUENCH AND SCRUBBER
(1/kkg of mischmetal produced from
wet rare earth chlorides)
Production
Normalized
Plant Code
1106
1113
Recycle
NA
0
Water Use
NA
10563
Production
Normalized
Discharge Flow
4173
10563
TABLE V-2
WATER USE AND DISCHARGE RATES FOR
DRYER VENT CAUSTIC WET AIR POLLUTION CONTROL
(1/kkg of mischmetal produced from
wet rare earth chlorides)
Plant Code
1113
Recycle
90
Production
Normalized
Water Use
10563
Production
Normalized
Discharge Flow
10563
TABLE V-3
WATER USE AND DISCHARGE RATES FOR
ELECTROLYTIC CELL WATER QUENCH AND SCRUBBER
(1/kkg of total mischmetal produced)
Production
Normalized
Plant Code
1106
1113
Recycle
NA
0
Water Use
NA
12682
Production
Normalized
Discharge .Flow
9390
12682
5395
-------
PRIMARY RARE DEARTH METALS SUBCATEGORY SEPT - V_
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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5408
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
CN
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5410
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
3
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5411
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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5412
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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T3
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
5448
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
This section examines chemical analysis data presented in Section
V and discusses the selection or exclusion of toxic and other
pollutants for potential limitation. The discussion that follows
presents and briefly discusses the selection of conventional and
nonconventional pollutants for effluent limitations. Also
described is the analysis that was performed to select or exclude
priority pollutants for further consideration for limitations and
standards. Pollutants will be considered for limitation if they
are present in concentrations treatable by the technologies
considered in this analysis. The treatable concentrations used
for the priority metals were the long-term performance values
achievable by chemical precipitation, sedimentation, and
filtration. The treatable concentrations used for the priority
organics were the long-term performance values achievable by
carbon adsorption.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
This study examined samples from the primary rare earth metals
subcategory for two conventional pollutant parameters (total
suspended solids and pH) and several nonconventional pollutant
parameters.
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
total suspended solids (TSS), and
pH
None of the nonconventional pollutants or pollutant parameters
was selected for limitation in -this subcategory.
TSS concentrations ranging from 20 mg/1 to 27 mg/1 were observed
in the three raw waste samples analyzed for this study. All
three concentrations are above the 2.6 mg/1 treatable
concentration. Most of the specific methods used to remove toxic
metals do so by converting these metals to precipitates, and
these toxic-metal-containing precipitates should not be
discharged. Meeting a limitation on total suspended solids helps
ensure that removal of these precipitated toxic metals has been
effective. For these reasons, total suspended solids are selected
for limitation in this subcategory.
The pH values of the raw wastewater observed during .this study
ranged from 1.3 to 1.6, consistently outside the 7.5 to 10.0
range considered desirable for discharge. Many deleterious
effects are caused by extreme pH values or rapid changes in pH.
Also, effective removal of toxic metals by precipitation requires
careful control of pH. Since pH control is readily attainable,
5449
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
I
pH is selected for limitation in this subcategory.
TOXIC PRIORITY POLLUTANTS
The frequency of occurrence of the priority pollutants in the raw
wastewater samples taken is presented in Table VI-1 (page 5455).
Table VI-1 is based on the raw wastewater data from streams 429,
430, 431, and 432. These data provide the basis for the
categorization of specific pollutants as discussed below.
Treatment plant samples were not considered in the frequency
count.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table VI-2 (page 5459) were not
detected in any raw wastewater samples from this subcategory.
Therefore, they are not selected for consideration in
establishing limitations.
TOXIC POLLUTANTS NEVER POUND ABOVE THEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
The toxic pollutants listed below were never found above their
analytical quantification concentration in any raw wastewater
samples from this subcategory. Therefore, they are not selected
for consideration in establishing limitations.
7. chlorobenzene
21. 2,4,6-trichlorophenol
47. bromoform
65. phenol
86. toluene
114. antimony
117. beryllium
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individually
following the list.
121. cyanide (Total)
123. mercury
Cyanide was detected above its analytical quantification
concentration of 0.02 mg/1 in four samples ranging from 0.020
mg/1 to 0.032 mg/1. Another seven samples were detected below
the quantification concentration. Since no samples were detected
above the treatable concentration of 0.047 mg/1, cyanide is not
considered for limitation.
5450
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
Mercury was detected above its quantification concentration of
0.001 mg/1 in six samples analyzed. The remaining five samples
were below quantification. The greatest concentration detected
was 0.0042 mg/1 of mercury. Since this is substantially below
the 0.036 mg/1 treatable concentration, mercury is not selected
for limitation.
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The following pollutants were not selected for limitation because
they were detected in the effluent from only a small number of
sources within the subcategory and are uniquely related to only
those sources.
6. carbon tetrachloride
23. chloroform
44. methylene chloride
48. dichlorobromomethane
49. trichlorofluoromethane (Deleted)
51. chlorodibromomethane
66. bis(2-ethylhexyl) phthalate
Although these pollutants were not selected for limitation in
establishing nationwide regulations, it may be appropriate, on a
case-by-case basis, for the local permitter to specify effluent
limitations
Carbon tetrachloride was detected in only four of 11 samples
analyzed. The detected concentrations ranged from 0.013 mg/1 to
0.082 mg/1. Treatability for carbon tetrachloride is 0.01 mg/1.
Since carbon tetrachloride is present in concentrations not
significantly higher than treatable concentrations, and it is
present in a small number of sources, carbon tetrachloride is not
selected for limitation.
Chloroform was detected in 10 samples. Two samples were below
the quantification concentration, two were below the treatable
concentration, and six samples were above the treatable
concentration of 0.01 mg/1. Of these six samples, only four
showed concentrations greater than that of the source water,
0.041 mg/1. Chloroform is a common laboratory solvent, and the
frequency of detection may be due to sample contamination. The
presence of chloroform in the source water attests to this.
Therefore, chloroform is not selected for limitation.
Methylene chloride was detected above its treatability
mg/1 in nine samples. The concentrations ranged from 0
to 0.019 mg/1. These concentrations are close to the
concentration and would not lend themselves to
treatment. In addition, methylene chloride is not a
expected to be present in wastewaters of this industry
consideration of raw materials and production processes
by this industry. Therefore, methylene chloride is not
for limitation.
of 0.01
.010 mg/1
treatable
effective
pollutant
based on
employed
selected
5451
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
Dichlorobromomethane was detected in only one of 11 wastewater
samples at a concentration of 0.330 mg/1. The treatability for
dichlorobromomethane is 0.01 mg/1. However, there is no reason
to believe that this pollutant should be present in wastewater of
this subcategory, and this result cannot be generalized as
characteristic of the entire subcategory. Therefore,
dichlorobromomethane is not selected for limitation.
Trichlorofluoromethane was detected in only one of the four waste
streams sampled. Out of 11 samples analyzed, it was detected
twice, both times above the treatability concentration of 0.01
mg/1. The two samples contained 0.012 mg/1 and 0.021 mg/1. Since
this is just slightly higher than could be achieved by treatment
and such a small number of sources indicate that
trichlorofluoromethane is present, trichlorofluoromethane is not
selected for limitation.
Chlorodibromomethane was detected in only two of 11 samples
analyzed. One sample containing 0.002 mg/1 was below the
quantification concentration of 0.010 mg/1. The other detected
sample was 0.250 mg/1, above the treatable concentration of 0.01
mg/1. Since Chlorodibromomethane was detected in such a small
number of sources, its presence cannot be generalized to be
characteristic of the entire subcategory. Therefore,
Chlorodibromomethane is not selected for limitation.
Bis(2-ethylhexyl) phthalate was detected in. seven samples below
the quantification concentration (0.010 mg/1), and four samples
above the treatable concentration (0.01 mg/1). Treatable
concentrations ranged from 0.013 mg/1 to 0.040 mg/1. The source
water contained 0.008 mg/1 of bis(2-ethylhexyl) phthalate. This
compound is a plasticizer commonly used in laboratory and field
sampling equipment, and is not considered a pollutant specific to
this subcategory. Therefore, bis(2-ethylhexyl) phthalate is not
selected for limitation.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below have been detected in
quantities above their treatability concentrations. All these
pollutants are under consideration to be selected in establishing
limitations and standards for this subcategory. The toxic
pollutants listed below are each discussed following the list.
4. benzene
9. hexachlorobenzene
115. arsenic
118. cadmium
119. chromium (Total)
12O. copper
122. lead
124. nickel
125. selenium
126. silver
5452
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
127. thallium
128. zinc
Benzene was detected above treatable concentrations in
samples. The treatability for benzene is below the analytical
quantification limit of 0.01 mg/1, and the range of sample
concentrations is from 0,011 mg/1 to 9.018 mg/1. Comparable
concentrations of benzene were detected in samples from the final
effluent. For these reasons, benzene is selected for further
consideration for limitation.
Hexachlorobenzene was found above treatability in six samples
These ranged from 1.3 mg/1 to 2.6 mg/1 while the treatable
concentration of hexachlorobenzene is below the analytical
quantification limit of 0.01 mg/1. Equally high concentrations
of this toxic organic were found in the final effluent samples.
Therefore, hexachlorobenzene is selected for further
consideration for limitation.
Arsenic was detected above treatability of 0.34 mg/1 in one
sample indicating 1.45 mg/1. Five samples ranging from 0.022
mq/1 to 0.096 mg/1 were observed below treatability. Because of
its frequent occurrence, arsenic is being considered for
limitation.
Cadmium was detected above treatability in two samples from the
same waste stream showing 0.36 mg/1 cadmium. Five samples were
below the treatable concentration of 0.049 mg/1, ranging from
0.002 mg/1 to 0.03 mg/1. Thus, cadmium is selected for
consideration for limitation.
Chromium was detected in one waste stream above treatability of
0.07 mg/1 at 1.2 mg/1 and 1.3 mg/1. Seven samples were below the
treatable concenttation and ranged from 0.005 mg/1 to 0.033 mg/1.
Because of its frequency of occurrence above treatable
concentrations, chromium is considered for limitation.
- in 11 samples analyzed for copper, two samples were above the
treatable concentration of 0.39 mg/1. Both indicated 0.66 mg/1
copper and were observed in dehydration furnace wet air pollution
control wastewater. In addition, eight samples ranging from
0.010 mg/1 to 0.23 mg/1 were detected below treatable
concentrations. Therefore, copper is being further considered
for limitation.
Lead was detected above treatability of 0.08 mg/1 in eight
samples ranging from 0.09 mg/1 to 2.3 mg/1. These samples were
taken from three of the four waste streams analyzed. Thus lead
is selected for consideration for limitation.
Two samples from two waste streams detected nickel above its
treatable concentration of 0.22 mg/1. These samples showed 0.69
mg/1 and 3S. 1 mg/1 nickel in the wastewater. Eight samples
ranging from 0.005 mg/1 to 0.190 mg/1 were observed below the
treatable concentration of nickel. Because nickel was found
5453
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
above its treatable concentrations, it is
consideration for limitation.
selected
for
Selenium was detected above its treatability of 0.20 mg/1 in two
wastewater samples showing 0.22 mg/1 and 0.510 mg/1. Six samples
below the treatable concentration ranged from 0.012 mg/1 to 0.13
m/1. The source water was found to have less than 0.005 mg/1
silver detected concentrations below the quantification
concentration. Because treatable concentrations of silver were
detected, silver is considered for limitation.
Thallium was detected above treatable concentrations in two
samples taken from the same waste stream. Both samples showed
1.4 mg/1 thallium, while the treatable concentration is 0.34
mg/1. All other samples analyzed were below the quantification
concentration. However, thallium is selected for further
consideration for limitation.
Zinc was detected above treatable concentrations in two samples
from one waste stream. Both samples indicated 0.56 mg/1 zinc,
and the treatable concentration is 0.23 mg/1. Four samples
showed zinc to be below the treatable concentration in
concentrations ranging from 0.05 mg/1 to 0.19 mg/1. Thus zinc is
selected for consideration for limitation.
5454
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
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5455
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
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5456
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PRIMARY,RARE EARTH METALS SUBCATEGORY SECT - VI
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5458
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
8. 1,2,4-trichlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trichloroethane
12. hexachloroethane
13. 1.1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
17. bis (chloromethyl) ether (Deleted)
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether
20. 2-chloronaphthalene
22. para-chloro meta-cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3f3'dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. l,2.dichloropropylene
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-chloroethoxy) methane
44. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
50. dichlorodifluoromethane (Deleted)
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
5459
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4.nitrohpenol
59. 2,4-dinitrophenol
60. 4,6.dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
72. benzo (a)anthracene
73. benzo (a)pyrene
74. 3,4-benzofluoranthene
75. benzo (k)fluoranthane
76. chrysene
77. acenaphthylene
78. anthracene
79. benzo(ghi)perylene
80*. fluorene
81. phenanthrene
82. dibenzo (a,h)anthracene
83. indeno (1,2,3-cd)pyrene
84. pyrene
85. tetrachloroethylene
87. trichloroethylene
88. vinyl chloride
89. aldrin
90. dieldrin
91. chlordane
92. 4,4'-DDT
93. 4,4 -DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
95. alpha-endosulfan
96. beta-endosulfan
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
5460
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
100. heptachlor
101. heprachlor epoxide
102. alpha-BHC
103. beta-BHC
104. gamma-BHC (lindane)
105. delta-BHC
106. PCB-1242 (Arpchlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1234 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. toxaphene
116. asbestos (Fibrous)
129. 2.3,7,8-tetra chlorodibenzo-p-dioxin (TCDD)
5461
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VI
THIS PAGE INTENTIONALLY LEFT BLANK
5462
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters generated in the
primary rare earth metals plants. This section summarizes the
description of these wastewaters and indicates the treatment
technologies which are currently practiced in the primary rare
earth metals subcategory for each waste stream. Secondly, this
section presents the control and treatment technology options
which were examined by the Agency for possible application to the
primary rare earth metals subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently applied to each of the sources
generating wastewater in this subcategory. As discussed in
Section V, wastewater associated with the primary rare earth
metals subcategory ,is characterized by the presence of the toxic
metal pollutants, treatable concentrations of hexachlorobenzene
and benzene, and suspended solids. This analysis is supported by
the raw (untreated) wastewater data presented for specific
sources as well as combined waste streams in Section V.
Generally, these pollutants are present in each of the waste
streams at concentrations above treatability and these waste
streams are commonly combined for treatment. Construction of one
wastewater treatment system for combined treatment allows plants
to take advantage of economic scale, and in some instances, to
combine streams or different alkalinity to reduce treatment
chemical requirements. Both discharging plants in this
subcategory currently have combined wastewater treatment systems.
One has lime precipitation and sedimentation, and the other
employs a pH control system. Four options have been selected for
consideration for BPT, BAT, NSPS, and pretreatment based on
combined treatment of these compatible waste streams.
The two plants in the rare earth metals subcategory that produce
mischmetal do not practice treatment of individual waste streams.
The treatment of wastewater occurs after all waste streams have
been combined; for this reason a short summary of the waste
streams generated will be followed by a discussion of the present
treatment levels at the two plants in this subcategory.
DRYER VENT WATER QUENCH AND SCRUBBER
Drying of wet rare earth chlorides produces off-gases which are
quenched with water or scrubbed. The gases are cooled,
particulates removed, and hydrochloric acid is absorbed in these
operations.
5463
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VII
! ' I
DRYER VENT CAUSTIC WET AIR POLLUTION CONTROL
After dryer off-gases are quenched or scrubbed with water they
may be routed to a caustic scrubber. This provides for more
complete removal of particulates and acid vapors. Scrubber
liquor is discharged to treatment and the gases vented to the
atmosphere.
ELECTROLYTIC CELL WATER QUENCH AND SCRUBBER
Reduction of dry rare earth chlorides by electrolysis produces
off-gases which are quenched by continuous water spray or passed
through a water scrubber. Similar to the drier operation, the
gases are cooled, particulates removed, and hydrochloric acid is
absorbed by the quench or scrubber water. Upon discharge to
treatment, this wastewater stream has a pH in the range of 1.5.
ELECTROLYTIC CELL CAUSTIC WET AIR POLLUTION CONTROL
After the quench or scrubber step described above, a caustic
Scrubber may be used to remove chlorine gas from the gas stream.
Sodium hypochlorite is formed in the scrubber and after recycling
to obtain a desired concentration, it is removed and sold for
industrial uses. Thus the potential wastewater stream generated
by this operation becomes a by-product.
SODIUM HYPOCHLORITE FILTER BACKWASH
Sodium hypochlorite produced in the electrolytic cell caustic
scrubber is filtered to remove residual particulates prior to
storage as a salable product. Depending on the type of filter
used, backwashing may be necessary for effective and efficient
filtration. This wastewater stream is discharged to treatment.
TREATMENT PRACTICES
Plants . in this subcategory treat the combined wastewater if low
from all the production operations. The wastewater streams are
combined for treatment in a holding tank, then pumped to a mixing
tank into which sodium hydroxide or lime is added to raise the
pH. After sediment removal,the neutralized wastewater is then
discharged.
CONTROL AND TREATMENT OPTIONS
The Agency examined four control and treatment technology options
that are applicable to the primary rare earth metals subcategory.
As the sampling and analytical data in Section V indicate, the
wastewaters from this subcategory contain various types of
contaminants including dissolved toxic metals, and suspended
solids, as well as treatable concentrations of benzene and
hexachlorobenzene. The treatment options selected for evaluation
represent a combination of in-process flow reduction and end-of-
pipe treatment technologies.
5464
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VII
OPTION A
The Option A treatment scheme consists of chemical precipitation
and sedimentation technology. Specifically, lime or some other
alkaline compound is used to precipitate priority metal ions as
metal hydroxides. The metal hydroxides and suspended solids
settle out and the sludge is collected. Vacuum filtration is
used to dewater the sludge.
OPTION B
Option B for the primary rare earth metals subcategory consists
of the Option A (chemical precipitation and sedimentation)
treatment scheme plus flow reduction techniques to reduce the
discharge of wastewater volume. In-process changes which allow
for water recycle and reuse are the principal control mechanisms
for flow reduction.
OPTION C
Option C for the primary rare earth metals subcategory consists
of all control and treatment requirements of Option B (in-process
flow reduction, chemical precipitation and sedimentation) plus
multimedia filtration technology added at the end of the Option B
treatment scheme. Multimedia filtration is used to remove
suspended solids, including precipitates of metals, beyond the
concentration attainable by gravity sedimentation. The filter
suggested is of the gravity, mixed-media type, although other
forms of filters, such as rapid sand filters or pressure filters
would perform satisfactorily. The addition of filters also
provides consistent removal during periods of time in which there
are rapid increases in flows or loadings of pollutants to the
treatment system.
OPTION E
Option E for the primary rare earth metals subcategory consists
of all of the control and treatment requirements of Option C (in-
process flow reduction, chemical precipitation and sedimentation,
followed by multimedia filtration) with the addition of granular
activated carbon technology at the end of the Option C treatment
scheme. The activated carbon process is utilized to control the
discharge of hexachlorobenzene and other toxic organic
pollutants.
5465
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VII
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5466
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
primary rare earth metals subcategory and a description of the
treatment options and subcategory-specific assumptions used to
develop these estimates. Together with the estimated pollutant
removal performance presented in Sections X and XII of this
supplement, these cost estimates provide a basis for evaluating
each regulatory option. These cost estimates are also used in
determining the probable economic impact of regulation on the
subcategory at different pollutant discharge levels. In
addition, this section addresses nonwater quality environmental
impacts of wastewater treatment and control alternatives,
including air pollution, solid wastes, and energy requirements,
which are specific to the primary rare earth metals subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, four treatment options have been
developed for existing primary rare earth metals sources. The
treatment schemes for each option are summarized below and
schematically presented in Figures X-l through X-4 (pages 5499 -
5502).
OPTION A
Option A consists of chemical precipitation and sedimentation
technology.
OPTION B
Option B consists of in-process flow reduction via holding tanks
with pH adjustment for the electrolytic cell water quench and
scrubber, and dryer vent water quench and scrubber waste streams,
followed by chemical precipitation and sedimentation.
OPTION C
Option C consists of Option B (in-process flow reduction,
chemical precipitation and sedimentation) with the addition of
multimedia filtration at the end of the Option B treatment
scheme. .
OPTION E
Option E consists of Option C (in-process flow reduction,
chemical precipitation and sedimentation, followed by multimedia
filtration) with the addition of granular activated carbon
technology at the end of Option C treatment scheme. The
activated carbon process is utilized to control the discharge of
hexachlorobenzene and other toxic organic pollutants.
5467
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VIII
COST METHODOLOGY
Plant-by-plant compliance costs for the nonferrous metals
manufacturing category have been revised as necessary following
proposal. These revisions calculate incremental costs, above
treatment already in place, necessary to comply with the
promulgated effluent limitations and standards and are presented
in the administrative record supporting this regulation. A
comparison of the costs developed for proposal and the revised
costs for the final regulation are presented in Table VIII-1
(page 5471) for direct indirect dischargers.
Each subcategory contains a unique set of wastewater streams'
requiring certain subcategory-specific assumptions to develop
compliance costs. The major assumptions specific to the primary
rare earth metals subcategory are discussed briefly below.
(1) Activated carbon adsorption columns were sized to remove
hexachlorobenzene to 0.01 mg/1. The activated carbon
exhaustion rates were determined from the influent
hexachlorobenzene concentration based on sampling data, the
desired effluent concentration (0.01 mg/1), and a carbon
adsorption isotherm for hexachlorobenzene. A 50 percent
excess factor was also included in the exhaustion rate.
• ' . i1""1 , , |
(2) Activated carbon materials costs were based on once-through
carbon use and subsequent disposal of the spent carbon as a
hazardous waste. This option resulted from a least-cost
evaluation of three alternatives: (1) once-through use and
disposal, (2) off-site regeneration of spent carbon, and (3)
on-site regeneration of spent carbon.
(3) Recycle of quench water and air pollution control
scrubber liquor is based on recycle through holding
tanks. Annual costs reflect a sodium hydroxide feed
system included to adjust scrubber effluent to neutral
pH prior to reuse.
NONWATER QUALITY ASPECTS
A general discussion of the nonwater quality aspects of the
control and treatment options considered for the nonferrous
metals category is contained in Section VIII of Vol. I. Nonwater
quality impacts specific to the primary rare earth metals
subcategory, including energy requirements, solid waste and air
pollution are discussed below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for Option A are
5468 .
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VIII
estimated at 66,000 kwh/yr, and for Option E the estimated
requirement is 92,000 kwh/yr. Option E energy requirements
increase over those for Option A because even though Option E
includes wastewater recycle, the benefits of treating less water
do not surpass the added cost of recycle equipment. In addition,
Option E includes multimedia filtration and activated carbon
adsorption which are energy intensive processes. However, both
options represent less than 1 percent of a typical plant's energy
usage. It is therefore concluded that the energy requirements of
the treatment options considered will have no significant impact
on total plant energy consumption.
SOLID WASTE
Sludge generated in the primary rare earth metals subcategory is
due to the precipitation of metal hydroxides and carbonates using
lime or other chemicals. Sludges associated with the primary
rare earth metals subcategory will necessarily contain quantities
of toxic metal pollutants. These sludges are not subject to
regulation as hazardous wastes since wastes generated by primary
smelters and refiners are currently exempt from regulation by Act
of Congress (Resource Conservation and Recovery Act (RCRA),
Section 3001(b)), as interpreted by EPA. If a small excess of
lime is added during treatment, the Agency does not believe these
sludges would be identified as hazardous under RCRA in any case.
(Compliance costs include this amount of lime.) This judgment is
based on the results of Extraction Procedure (EP) toxicity tests
performed on similar sludges (toxic metal-bearing sludges)
generated by other industries such as the iron and steel
industry. A small amount of excess lime was added during
treatment, and the sludges subsequently generated passed the
toxicity test. See CFR 8261.24. Thus, the Agency believes that
the wastewater sludges will similarly not be EP toxic if the
recommended technology is applied.
Although it is the Agency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 CFR 262.11).
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards would require generators of_ hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20 45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
5469
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VIII
delivered to a permitted facility. See 40 CFR 263.20 45 FR 33151
(May 19, 1980), as amended at 45 FR 86973 (December 31, 1980).
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464 46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 4004 of RCRA. See 44 FR 53438
(September 13, 1979). It is estimated that the primary rare
earth metals subcategory will generate 8.5 metric tons of sludge
per year when implementing the promulgated BPT treatment
technology. The Agency has calculated as part of the costs for
wastewater treatment the cost of hauling and disposing of these
wastes.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of chemical
precipitation, sedimentation, multimedia filtration, and
activated carbon adsorption. These technologies transfer
pollutants to solid waste and are not likely to transfer
pollutants to air.
5470
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VIII
TABLE VIII-1
COST OF COMPLIANCE FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
DIRECT AND INDIRECT DISCHARGERS
These costs are not presented here because the data on which they
are based have been claimed to be confidential.
5471
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - VIII
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5472
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through the application of best practicable control technology
currently available (BPT). BPT reflects the existing performance
by plants of various sizes, ages, and manufacturing processes
within the primary rare earth metals subcategory, as well as the
established performance of the recommended BPT systems.
Particular consideration is given to the treatment already in
place at the plants within the data base.
The factors considered in identifying BPT include the total cost
of applying the technology in relation to the effluent reduction
benefits from such application, the age of equipment and
facilities involved, the manufacturing processes used, nonwater
quality environmental impacts (including energy requirements),
and other factors the Administrator considers appropriate. In
general, the BPT level represents the average of the existing
performances of the plants of various ages, sizes, processes, or
other common characteristics. Where existing performance is
uniformly inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology are supported by a rationale concluding that the
technology is, indeed, transferable, and a reasonable prediction
that it will be capable of achieving the prescribed effluent
limits. BPT focuses on end-of-pipe treatment rather than process
changes or internal controls, except where such practices are
common industry practice.
TECHNICAL APPROACH TO BPT •
The Agency studied the nonferrous metals category to identify the
processes used, the wastewaters generated, and the treatment
processes installed. " Information was collected from industry
using data collection portfolios, and specific plants were
sampled and the wastewaters analyzed. In making technical
assessments of data, reviewing manufacturing processes, and
assessing wastewater treatment technology options, both indirect
and direct dischargers have been considered as a single group. An
examination of plants and processes did not indicate any process
differences based on the type of discharge, whether it be direct
or indirect.
As explained in Section IV, the primary rare earth metals
subcategory has been subdivided into five potential wastewater
sources. Since the water use, discharge rates and pollutant
characteristics of each of these wastewaters is potentially
unique, effluent limitations will be developed for each of the
five subdivisions.
5473
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
For each of the subdivisions, a specific approach was followed
for the development of BPT mass limitations. The first
requirement to calculate these limitations is to account for
production and flow variability from plant to plant. Therefore,
a unit of production or a production normalizing parameter (PNP)
was determined for each waste stream which could then be related
to the flow from the process to determine a production normalized
flow. Selection of the PNP for each process element is discussed
in Section IV. Each plant within the subcategory was then
analyzed to determine which subdivisions were present, the
specific flow rates generated for each subdivision, and the
specific production normalized flows for each subdivision. This
analysis is discussed in detail in Section V. Nonprocess
wastewater such as rainfall runoff and noncontact cooling water
is not considered in the analysis.
Production normalized flows for each subdivision were then
analyzed to determine the flow to be used as part of the basis
for BPT mass limitations. The selected flow (sometimes referred
to as the BPT regulatory flow or BPT discharge rate) reflects the
water use controls which are common practices within the
category. The BPT regulatory flow is based on the average of all
applicable data. Plants with normalized flows above the average
may have to implement some method of flow reduction to achieve
the BPT limitations.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the BPT
level of treatment technology. Section VII discusses the various
control and treatment technologies which are currently in place
for each wastewater source. In most cases, the current control
and treatment technologies consist of chemical precipitation and
sedimentation (lime and settle technology) and a combination of
reuse and recycle to reduce flow.
Using these regulatory flows and the achievable concentrations,
the next step is to calculate mass loadings for each wastewater
source or subdivision. This calculation was made on a stream-by-
stream basis, primarily because plants in this subcategory may
perform one or more of the operations in various combinations.
The mass loadings (milligrams of pollutant per kilogram
production - mg/kg) are based on multiplying the BPT regulatory
flow (1/kkg) by the concentration achievable by the BPT level of
treatment technology (mg/1) for each pollutant parameter to be
limited under BPT. These mass loadings are published in the
Federal Register and in CFR Part 421 as the effluent limitations.
The mass loadings which are allowed under BPT for each plant will
be the sum of the individual mass loadings for the various
wastewater sources which are found at particular plants.
Accordingly, all the wastewater generated within a plant may be
combined for treatment in a single or common treatment system,
but the effluent limitations for these combined wastewaters are
based on the various wastewater sources which actually contribute
to the combined flow. This method accounts for the variety of
5474
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
combinations of wastewater sources and production processes which
may be found at primary rare earth metals plants.
The Agency usually establishes wastewater limitations in terms of
mass" rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow and effluent concentration
achievable by the treatment technology and summed to derive an
appropriate limitation for each plant.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal estimates,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollutant control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed or promulgated BPT.
The methodology for calculating pollutant removal estimates and
plant compliance costs is discussed in Section X. The pollutant
removal estimates made for proposal have been revised based on
new flow and production data, and adjustments in the number of
subdivisions. Table X-l (page 5493) shows the pollutant removal
estimates for each treatment option for direct dischargers.
Compliance costs for direct dischargers are presented in Table X-
2 (page 5494).
BPT OPTION SELECTION
The technology basis for the promulgated BPT limitations, Option
A, is equivalent to the proposed BPT technology. Option A
includes chemical precipitation and sedimentation technology to
remove metals and solids from combined wastewaters and to control
pH. These technologies are demonstrated and economically
achievable since they are already in place at direct dischargers
in this subcategory.
There are no expected capital or additional annual costs for
achieving the promulgated BPT because the technology is already
in-place. The end-of-pipe treatment configuration for Option A is
presented in Figure IX-1 (page 5483).
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based_ on
the average of the flows of the existing plants, as determined
from analysis of the data collection .portfolios. The discharge
5475
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
rate is used with the achievable treatment concentrations to
determine BPT effluent limitations. Since the discharge rate may
be different for each wastewater source, separate production
normalized discharge rates for each of the five wastewater
sources are discussed below and summarized in Table IX-1 '(page
5381). The discharge rates are normalized on a production basis
by relating the amount of wastewater generated to the mass of the
intermediate product which is produced by the process associated
with the waste stream in question. These production normalizing
parameters, or PNPs, are also listed in Table IX-1.
Section V of this document further describes the discharge flow
rates and presents the water use and discharge flow rates for
each plant by subdivision in Tables V-l through V-5.
i I
DRYER VENT WATER QUENCH AND SCRUBBER
At proposal, this subdivision was combined with the second
subdivision and called dehydration furnace quench and scrubber.
The BPT wastewater discharge rate for the combined subdivision
was 14,800 1/kkg of mischmetal produced from wet rare earth
chlorides. This discharge rate was based on the average reported
water use. The reported water use ranged from 11,600 1/kkg to
17,900 1/kkg. Since proposal, new flow and production information
prompted a study of the combined subdivision. EPA then decided to
create two separate subdivisions to better address the
differences between plants in this subcategory.
The BPT wastewater discharge rate for dryer vent water quench and
wet air pollution control is 10,563 1/kkg (2,531 gal/ton) of
mischmetal produced from wet rare earth chlorides. This rate is
allocated only for those plants which use a furnace to dehydrate
rare earth chloride raw material prior to electrolytic refining,
and treat the off-gases with a continuous water quench or with a
water scrubber. The BPT wastewater discharge rate is based on
the water use at a plant reporting no recycle of wastewater.
This plant uses 10,563 1/kkg. Because other plants presently
operate with recycle, recycle is more appropriately used as a
basis for the BAT discharge allowance.
DRYER VENT CAUSTIC WET AIR POLLUTION CONTROL
No separate BPT wastewater discharge rate was proposed for this
subdivision because this present subdivision was combined with
the above subdivision at proposal. Since EPA has decided to use
separate subdivisions, a separate discharge rate for this
wastewater stream has been developed.
The BPT wastewater discharge rate for dryer vent caustic wet air
pollution control wastewater is 734 1/kkg (176 gal/ton) of
mischmetal produced from wet rare earth chlorides. This rate is
allocated only for those plants which use a caustic scrubber, in
addition to a water quench.or water scrubber, to treat vent gases
from a wet rare earth chlorides dehydration furnace. This BPT
wastewater discharge rate is based on the reported discharge
5476
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
flow.
ELECTROLYTIC CELL WATER QUENCH AND SCRUBBER
The BPT wastewater discharge rate used at proposal for
electrolytic cell water quench and scrubber wastewater was 16,400
1/kkg (3f930 gal/ton) of total mischmetal produced. This rate
was based on the average of the reported water use data for this
wastewater stream. At proposal, EPA understood that no plant
recycled this wastewater based on dcp information. Post-proposal
comments and information indicated otherwise; therefore, a new
BPT rate was chosen for promulgation.
The BPT wastewater discharge rate at promulgation for
electrolytic cell water quench and scrubber is 12,682 1/kkg
(3,039 gal/ton) of total mischmetal produced. This rate is
allocated only for those plants which electrolytically reduce
rare earth chlorides to mischmetal and treat the off-gases with a
continuous water quench or a water scrubber system before any
further treatment of the exhaust gases. This BPT wastewater
discharge rate is based on the water use at a plant reporting no
recycle of scrubber or quench water. This plant uses 12,682
1/kkg.
ELECTROLYTIC CELL CAUSTIC WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate for electrolytic cell caustic
wet air pollution control wastewater is zero liters per kkg of
total mischmetal produced. This rate is allocated only for those
plants which electrolytically reduce rare earth chlorides to
mischmetal and, after water quenching or scrubbing, pass the
exhaust gases through a caustic scrubber to produce sodium
hypochlorite. Plants reporting use of this system operate with
zero discharge. The scrubber liquor is used in a by-product
recovery operation that produces sodium hypochlorite from a
reaction between chlorine gas produced in electrolytic refining
and the sodium hydroxide used as the scrubber liquor. This
solution is then sold for industrial use; thus no waste stream is
generated by this operation. Because of this, it is appropriate
that the BPT regulatory flow should be zero.
SODIUM HYPOCHLORITE FILTER BACKWASH
A BPT discharge rate for sodium hypochlorite filter backwash was
never proposed because dcp information used for proposal did not
quantify any wastewater discharge from this operation. Comments
received from industry after proposal requested an allowance for
the filter backwash and supplied information so that water use
and discharge rates could be calculated. This wastewater
discharge rate is being added in response to the comments
received on the proposed regulation.
The BPT wastewater discharge rate for sodium hypochlorite filter
backwash is 362 1/kkg (87 gal/ton) of total mischmetal produced.
This rate is allocated only for those plants which operate a
5477
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
filter for filtering sodium hypochlorite which requires periodic
backwashing in order to operate properly and efficiently. The
promulgated discharge rate is based on the reported water use for
this wastewater stream.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutant parameters for limitation. This examination and
evaluation was presented in Section VI. A total of five
pollutants or pollutant parameters are selected for limitation
under BPT and are listed below:
119. chromium (Total)
122. lead
124. nickel
TSS
pH
EFFLUENT LIMITATIONS
The pollutant concentrations achievable by application of the
promulgated BPT are discussed in Section VII of this supplement.
These treatment effectiveness concentrations (both one day
maximum and monthly average values) are multiplied by the BPT
normalized discharge flows summarized in Table IX-1 (page 5479)
to calculate the mass of pollu-tants allowed to be discharged per
mass of product. The results of these calculations in milligrams
of pollutant per kilogram of product represent the BPT effluent
limitations and are presented in Table IX-2 (page 5480) for each
individual waste stream.
5478
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
TABLE IX-2
BPT MASS LIMITATIONS FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY
(a) Dryer Vent Water Quench and Wet Air Pollution Control BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmeta1
produced from wet rare earth chlorides
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH
22.080
3.591
4.648
20.070
4.436
20.280
12.990
4.331
21.650
15.420
433.100
Within the range of 7.5
9.824
1.584
1.901
10.560
2.113
13.420
5.810
1.796
9.612
6.443
206.000
to 10.0 at all times
(b) Dryer Vent Caustic Wet Air Pollution Control BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH Within the
1.534
0.250
0.323
1.395
0.308
1.409
0.903
0.301
1.505
1.072
30.090
range of 7.5
0.683
0.110
0.132
0.734
0.147
0.932
0.404
0.125
0.668
0.448
14.310
to 10.0 at all times
*Regulated Pollutant
5480
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY
(c) Electrolytic Cell Water Quench and Wet APC BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH Within
(d) Electrolytic Cell
26.510
4.312
5.580
24.100
5.326
24.350
15.600
5.200
26.000
18.520
520.000
the range of 7.5
Caustic Wet Air
11.790
1.902
2.283
12.680
2.536
16.110
6.975
2.156
11.540
7.736
247.300
to 10.0 at all times
Pollution Control BPT
Pollutant Property
Maximum for
Any One Day
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
5481
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY
(e) Sodium Hypochlorite Filter Backwash BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH Within the
0.757
0.123
0.159
0.688
0.152
0.695
0.445
0.148
0.742
0.529
14.840
range of 7.5
0.337
0.054
0.065
0.362
0.072
0.460
0.199
0.062
0.329
0.221
7.059
to 10.0 at all times
*Regulated Pollutant
5482
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - IX
THIS PAGE INTENTIONALLY LEFT BLANK
5484
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another category from
which it is transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used, as well as reduction of the amount of water used
and discharged, process control, and treatment technology
optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the process used process changes nonwater
quality environmental impacts (including energy requirements),
and the costs of application of such technology. BAT represents
the best available technology at plants of various ages, sizes,
processes, or other characteristics. BAT may be transferred from
a different subcategory or category and may include feasible
process changes or internal controls even when not in common
industry practice.
The statutory assessment of BAT considers costs, but does not
require a balancing of costs against pollutant removals. However
in assessing the proposed and promulgated BAT the Agency has
given substantial weight to the economic achievability of the
selected technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency elected to examine four
technology options which could be applied to the primary rare
earth metals subcategory as treatment options for the basis of
BAT effluent limitations.
For the development of BAT effluent limitations, mass loadings
were calculated for each wastewater source or subdivision in the
subcategory using the same technical approach as described in
Section IX for BPT limitations development. The differences in
the mass loadings for BPT and BAT are due to increased treatment
effectiveness achievable with the more sophisticated BAT
treatment technology and reductions in the effluent flows
achieved by recycle and reuse technologies.
5485
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
The treatment technologies considered for BAT are summarized
below:
Option A (Figure X-l, page 5499) is based on:
| , I
o Chemical precipitation and sedimentation
Option B (Figure X-2, page 5500) is based on:
o Chemical precipitation and sedimentation
o In-process flow reduction of quench water and scrubber
liquor
Option C (Figure X-3,. page 5501) is based on:
o Chemical precipitation and sedimentation
o In-process flow reduction of quench water and scrubber
liquor
o Multimedia filtration
Option E (Figure X-4, page 5502) is based on:
o Chemical precipitation and sedimentation
o In-process flow reduction of quench water and scrubber
liquor
o Multimedia filtration
o Activated carbon adsorption
The four options examined for BAT are discussed in greater detail
on the following pages. The first option considered (Option A)
is the same as the BPT treatment and control technology which was
presented in the previous section. The last three options each
represent substantial progress toward the reduction of pollutant
discharges above and beyond the progress achievable by BPT.
OPTION A
Option A for the primary rare earth metals subcategory is
equivalent to the control and treatment technologies which were
analyzed for BPT in Section IX (see Figure X-l, page 5499). The
BPT end-of-pipe treatment scheme includes chemical precipitation
and sedimentation. The discharge rates for Option A are equal to
the discharge rates allocated to each stream as a BPT discharge
flow.
OPTION B
Option B for the primary rare earth metals subcategory achieves
lower pollutant discharge by building upon the Option A end-of-
pipe treatment technology. Flow reduction measures are added to
the Option A treatment scheme, which consists of chemical
precipitation and sedimentation. These flow reduction measures,
including in-process changes, result in the concentration of
pollutants in some wastewater streams. Treatment of a more
concentrated effluent allows achievement of a greater net
5486
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
pollutant removal and introduces the possible economic benefits
associated with treating a lower volume of wastewater.
The method used in Option 5 to reduce process wastewater
generation or discharge rates is recycle of water used in wet air
pollution control. There are two wet air pollution control
wastewater sources regulated under these effluent limitations for
which recycle is considered feasible:
o Dryer vent water quench and scrubber, and
o Electrolytic cell water quench and scrubber.
Reduction of flow through recycle represents the best available
technology economically achievable for these streams. Recycle of
dryer vent scrubber water and electrolytic cell scrubber water is
demonstrated by one plant in the primary rare earth metals
subcategory. Therefore, the Agency believes that recycle for
these two streams is feasible for other plants. Necessary
treatment for recycled quench or scrubber water could include pH
neutralization with sodium hydroxide solution; solids build up
from flue dust would not be critical because of continuous
blowdown and makeup. A holding tank for pH neutralization would
also aid in water temperature equilibration to inhibit the need
for cooling the recycled water.
OPTION C
Option C for the primary rare earth metals subcategory consists
of all control and treatment requirements of Option B (flow
reduction, chemical precipitation and sedimentation) plus
multimedia filtration technology added at the end of the Option B
treatment scheme (see Figure X-3, page 5501). Multimedia
filtration is used to remove suspended solids, including
precipitates of toxic metals, beyond the concentrations
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed media type, although other forms of filters,
such as rapid-sand filters or pressure filters, would perform
satisfactorily.
OPTION E
Option E for the primary rare earth metals subcategory consists
of all the control and treatment requirements of Option C (flow
reduction, chemical precipitation, sedimentation, and multimedia
filtration) with the addition of granular activated carbon
technology at the end of the Option C treatment scheme (see
Figure X-4, page 5502). The activated carbon process is provided
to control the discharge of hexachlorobenzene and other toxic
organic pollutants.
POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removals and the compliance costs
associated with each option. The methodologies are described
5487
-------
PRIMARY RARE EARTH METALS SUBCATEGORY -SECT - X
below.
A description of the methodology used to calculate the estimated
pollutant removal achieved by the application of the various
treatment options is presented in Section X of Vol. I. The
pollutant removal estimates have been revised from proposal
because of additional waste streams and new production normalized
flows are used for promulgation. The methodology for calculating
pollutant removals has not changed, and the data used for
estimating removals are the same as those used to revise
compliance costs.
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data were
production normalized for each unit operation (i.e., mass of
pollutant generated per mass of product manufactured). This
value, referred to as the raw waste, was used to estimate the
mass of toxic pollutants generated within the primary rare earth
metals subcategory. The pollutant removal estimates were
calculated for each plant by first estimating the total mass of
each pollutant in the untreated wastewater. This was calculated
by first multiplying the raw waste values by the corresponding
production value for that stream and then summing these values
for each pollutant for every stream generated by the plant.
Next, the volume of wastewater discharged after the application
of each treatment option was estimated for each operation at each
plant by comparing the actual discharge to the regulatory flow.
The smaller of the two values was selected and summed with the
other plant flows. The mass of pollutant discharged was then
estimated by multiplying the achievable concentration values
attainable with the option (mg/1) by the estimated volume of
process wastewater discharged by the subcategory. The mass of
pollutant removed is the difference between the estimated mass of
pollutant generated by each plant in the subcategory and the mass
of ' pollutant discharged after application of the treatment
option. The pollutant removal estimates for all dischargers
in the primary rare earth metals subcategory are presented in
Table X-l (page 5493).
COMPLIANCE COSTS
In estimating subcategory-wide compliance costs, the first step
was to develop a cost estimation model, relating the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge.
EPA applied the model to each plant. The plant's investment and
operating costs are determined by what treatment it has in place
and by its individual process wastewater discharge flow. As
discussed above, this flow is either the actual or the BAT
regulatory flow, whichever is lesser. The final step was to
annualize the capital costs, and to sum the annualized capital
costs, and the operating and maintenance costs for each plant,
yielding the cost of compliance for the subcategory. A
5488
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
comparison of the costs developed for proposal and the revised
costs for promulgation are presented in Table X-2 (page 5494) for
all dischargers in the primary rare earth metals subcategory.
Compliance costs for direct and indirect dischargers are shown in
combined because some of the data on which this table is based
are claimed to be confidential.
BAT OPTION SELECTION - PROPOSAL
EPA selected Option E for the proposed BAT which includes in-
process flow reduction, chemical precipitation, sedimentation,
and multimedia filtration, followed by activated carbon
technology to remove treatable concentrations of
hexachlorobenzene-.
The estimated capital cost of proposed BAT was $101,200 (1982
dollars) and the annual cost was $46,410 (1982 dollars).
Implementation of the proposed BAT technology was estimated to
remove 18.3 kilograms of priority pollutants (14.9 kilograms of
priority organics and 3.4 kilograms of priority metals) and 198
kilograms of suspended solids over the estimated BPT removal.
BAT OPTION SELECTION - PROMULGATION
After proposal, EPA received comments reporting a waste stream
that had not been included in the proposed regulations. In
addition, wastewater flow rates and production data were obtained
for several streams and used to calculate new production
normalized flow rates and regulatory flow allowances. These data
were also used for recalculating pollutant removal estimates and
for revising compliance costs.
EPA is promulgating BAT limitations for this subcategory based on
Option E, in-process flow reduction, chemical precipitation,
sedimentation, and multimedia filtration followed by activated
carbon technology for control of toxic organics. The technology
basis for promulgated BAT limitations is the same as that for the
proposed limitations. In addition, the treatment effectiveness
concentrations, upon which the mass limitations are based, are
equal to values used to calculate the proposed limitations. t
EPA is promulgating multimedia filtration as part of the BAT
technology because it results in additional removal of toxic
metals. Support for promulgating this type of treatment
technology comes from presently demonstrated applications of
multimedia filtration by 25 plants in the nonferrous metals
manufacturing category. Filtration adds reliability to the
treatment system by making it less susceptible to operator error
and to sudden changes in raw wastewater flow and concentrations.
Activated carbon end-of-pipe treatment was selected to control
discharges of hexachlorobenzene from the electrolytic reduction
cell quench wastewater. The Agency selected this treatment
technology because discharges of this toxic organic pollutant
cannot be effectively controlled by more conventional treatment
5489
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
technologies promulgated for BAT. Although activated carbon is
not demonstrated in this or any other application within the
nonferrous metals manufacturing category, EPA believes that
performance data from the iron and steel manufacturing category
provide a valid measure of this technology's performance on
nonferrous metals manufacturing category wastewater.
WASTEWATER DISCHARGE RATES
A BAT discharge rate was calculated for each subdivision based
upon the flows of the existing plants, as determined from
analysis of data collection portfolios. The discharge rate is
used with the pollutant concentration achievable by treatment to
determine BAT effluent limitations. Since the.discharge rate may
be different for each wastewater source, separate production
normalized discharge rates for each of the five wastewater
sources were determined and are summarized in Table X-3 (page
5495). The discharge rates are normalized on a production basis
by relating the amount of wastewater generated to the mass of the
product which is processed through the process associated with
the waste stream in question. These production normalizing
parameters (PNP) are also listed in Table X-3.
The BAT discharge rates reflect the flow reduction requirements
of the selected BAT option. For this reason, the two water
quench and scrubber wastewaters which were targeted for flow
reduction through recycle for BAT have lower flow rates than the
corresponding BPT flows. A discussion of these wastewaters is
presented below.
DRYER VENT WATER QUENCH AND SCRUBBER
The BAT wastewater discharge allowance for dryer vent water
quench and scrubber wastewater is 4,173 1/kkg (1,000 gal/ton) of
mischmetal produced from wet rare earth chlorides. All of the
rare earth metal plants producing mischmetal incorporate this
operation. One plant presently recycles the scrubber liquor.
Other plants do not presently practice recycle. The BAT
wastewater discharge rate is based on the discharge rate of the
plant practicing recycle. EPA has determined that this rate is
economically achievable using the best available technology. The
water use and discharge rates for this subdivision are shown in
Table V-l (page 5395).
ELECTROLYTIC CELL WATER QUENCH AND SCRUBBER
The BAT wastewater discharge allowance for electrolytic cell
water quench and scrubber is 9,390 1/kkg (2,250 gal/ton) of total
mischmetal produced. All of the rare earth metals plants
producing mischmetal incorporate this operation. One plant
presently practices 96 percent recycle while other plants do not
recycle. The BAT wastewater discharge rate is based on the
discharge rate of the plant practicing recycle. EPA has
determined that this rate is economically achievable using the
best available technology.
5490
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
REGULATED POLLUTANT PARAMETERS
In the development of this regulation the Agency placed
particular emphasis on the toxic pollutants. The raw wastewater
concentrations from individual operations and the subcategory as
a whole were examined to select certain pollutants and pollutant
parameters . for limitation. This examination and evaluation was
presented in Section VI. The Agency, however, has chosen not to
regulate all 12 toxic pollutants selected in this analysis.
The primary rare earth metals subcategory generates only two
toxic organic pollutants in concentrations that the Agency
considers likely to cause toxic effects, benzene and
hexachlorobenzene. There are also trace quantities of other
organic compounds present in wastewater of this subcategory.
Because of the high cost associated with analysis for toxic
organic pollutants, EPA is promulgating effluent limitations only
for those pollutants generated in the greatest quantities as
shown by the pollutant removal analysis. Thus, hexachlorobenzene
is the only toxic organic pollutant selected for specific
limitation.
By regulating only hexachlorobenzene, the toxic organic pollutant
found in greatest concentration in raw wastewater, the Agency
believes that the concentration of benzene will be effectively
controlled by the technology needed to limit the discharge of
hexachlorobenzene. In addition, the levels of benzene detected
in raw wastewater from the primary rare earth metals industry are
significantly lower than those for hexachlorobenzene. Therefore,
removal of benzene will not adversely impact the performance of
the activated carbon technology implemented to control
hexachlorobenzene.
The high cost associated with analysis for 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 limitations and standards for each of the toxic metals
found in treatable concentrations in the raw wastewater from a
given subcategory, the Agency is promulgating effluent
limitations only for those pollutants generated in the greatest
quantities as shown by the pollutant removal analysis. The
pollutants selected for specific limitation are listed below:
119. chromium (Total)
122. lead
124. nickel
By establishing limitations and standards for certain toxic metal
pollutants, discharges 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 achievable
5491
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
• I
concentrations used for chemical precipitation and sedimentation
technology are based on optimized treatment for concomitant
multiple metals removal. Thus, even though metals have somewhat
different theoretical solubilities, they will be removed at very
nearly the same rate in a chemical 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
nonpreferentially.
The toxic pollutants selected for specific limitation in the
primary rare earth metals subcategory to control the discharges
of toxic pollutants are hexachlorobenzene, lead, chromium, and
nickel. The following toxic pollutants are excluded from
limitation on the basis that they are effectively controlled by
the limitation developed for hexachlorobenzene, lead, chromium,
and nickel:
4. benzene
115. arsenic
118. cadmium
120. copper
125. selenium
126. silver
127. thallium
128. zinc
EFFLUENT LIMITATIONS
The concentrations achievable by application of BAT are discussed
in Section VII of this supplement. The achievable concentrations,
both one day maximum and monthly average values, are multiplied
by the BAT normalized discharge flows summarized in Table X-3
(page 5495) to calculate the mass of pollutants allowed to be
discharged per mass of product. The results of these calculations
in milligrams of pollutant per kilogram of product represent the
BAT effluent limitations and are presented in Table X-4 (page
5496) for each wastewater stream.
5492
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
TABLE X-l
POLLUTANT REMOVAL ESTIMATES FOR DIRECT DISCHARGERS
PRIMARY RARE EARTH METALS SUBCATEGORY
These removals are not presented here because the data on which
they are based have been claimed to be confidential.
5493
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
TABLE X-2
COST OF COMPLIANCE FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY DIRECT DISCHARGERS
] •
These costs are not presented here because the data on which they
are based have been claimed to be confidential.
5494
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
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5495
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - X
TABLE X-4
BAT MASS LIMITATIONS FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY
(a) Dryer Vent Water Quench and Wet Air Pollution Control BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.042
0.042
5.800
0.835
1.544
5.341
1.168
2.295
3.422
1.210
5.842
4.256
0.042
0.042
2.587
0.334
0.626
2.546
0.542
1.544
1.544
0.501
2.546
1.753
(b) Dryer Vent Caustic Wet Air Pollution Control 'BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene.
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.007
0.007
1.020
0.147
0.272
0.940
0.206
0.404
0.602
0.213
1.028
0.749
0.007
0.007
0.455
0.059
0.110
0.448
0.095
0.272
0.272
0.088
0.448
0.308
*Regulated Pollutant
5496
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY
(c) Electrolytic Cell Water Quench and Wet APC
BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
* Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.094
0.094
13.050
1.878
3.474
12.020
2.629
5.165
7.700
2.723
13.150
9.578
0.094
0.094
5.822
0.751
1.409
5.728
1.221
3.474
3.474
1.127
5.728
3.944
(d) Electrolytic Cell Caustic Wet Air Pollution Control BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.000
0.000
0.000
0.000
0.000
0.000
0.000
o.doo
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
*Regulated Pollutant
5497
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY RARE EARTH METALS SUBCATEGORY
(e) Sodium Hypochlorite Filter Backwash BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.004
0.004
0.503
0.072
0.134
0.463
0.101
0.199
0.297
0.105
0.507
0.369
0.004
0.004
0.224
0.029
0.054
0.221
0.047
0.134
0.134
0.043
0.221
0.152
*Regulated Pollutant
5498
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
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PRIMARY RARE EARTH METALS SUBGATEGORY SECT - X
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - X
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
This section describes the technologies for treatment of
wastewater from new sources and presents mass discharge standards
for regulated pollutants for NSPS in the primary rare earth
metals subcategory, based on the selected treatment technology.
The basis for new source performance standards (NSPS) is the best
available demonstrated technology (BDT). New plants have the
opportunity to design the best and most efficient production
processes and wastewater treatment technologies without facing
the added costs and restrictions encountered in retrofitting an
existing plant. Therefore, EPA has considered the best
demonstrated process changes, in-plant controls, and end-of-pipe
treatment technologies which reduce pollution to the maximum
extent feasible.
TECHNICAL APPROACH TO NSPS
New source performance standards are equivalent to the best
available technology (BAT) selected for currently existing
primary rare earth metals plants. This result is a consequence
of careful review by the Agency of a wide range of technical
options for new source treatment systems which is discussed in
Section XI of the General Development Document. Additionally,
there was nothing found to indicate that the wastewater flows and
characteristics of new plants would not be similar to those from
existing plants, since the processes used by new sources are not
expected to differ from those used at existing sources.
Consequently, BAT production normalized discharge rates, which
are based on the best existing practices of the subcategory, can
also be applied to new sources. These rates are presented in
Table XI-1 (page 5506).
Treatment technologies considered for the NSPS options are
identical to the treatment technologies considered for the BAT
options. These options are:
Option A
o Chemical precipitation and sedimentation
Option B
o Chemical precipitation and sedimentation
o In-process flow reduction of quench water and scrubber
liquor
5503
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
Option C
o Chemical precipitation and sedimentation
o In-process flow reduction of quench water and scrubber
liquor
o Multimedia filtration
Option E
o Chemical precipitation and sedimentation
o In-process flow reduction of quench water and scrubber
liquor
o Multimedia filtration
o Activated carbon adsorption
NSPS OPTION SELECTION - PROPOSAL
EPA proposed that the best available demonstrated technology for
the primary rare earth metals subcategory be equivalent to Option
E (in-process flow reduction, chemical precipitation,
sedimentation, multimedia filtration, and activated carbon
adsorption).
The wastewater flow rates for NSPS were the same as the proposed
BAT flow rates. Flow reduction measures for NSPS were not
considered feasible because it was believed that no new
demonstrated technologies existed within the subcategory that
improved on water use and discharge practices. Therefore, EPA
concluded that flow reduction beyond the allowances proposed for
BAT was unachievable, and NSPS flow rates should be equal to
those for BAT.
NSPS OPTION SELECTION - PROMULGATION
EPA is promulgating best available demonstrated technology for
the primary rare earth metals subcategory equivalent to Option E
(chemical precipitation, sedimentation, flow reduction,
multimedia filtration, and activated carbon adsorption).
Filtration is demonstrated by 25 plants in the nonferrous metals
manufacturing category.. Activated carbon adsorption technology
is promulgated to control the discharge of hexachlorobenzene.
The wastewater flow rates for NSPS are the same as the BAT flow
rates. Further flow reduction measures for NSPS are not
feasible, because dry scrubbing is not demonstrated for
controlling emissions from dehydration furnaces and electrolytic
reduction operations. The nature of these emissions (acid fumes,
hot particulate matter) technically precludes the use of dry
scrubbers. Therefore, EPA is including an allowance from this
source at NSPS equivalent to that promulgated for BAT. EPA also
does not believe that new plants could achieve any additional
flow reduction beyond the quench water and scrubber effluent
recycle promulgated for BAT.
5504
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with existing sources.
Accordingly, pollutants and pollutant parameters selected for
limitation under NSPS, in accordance with the rationale of
Sections VI and X, are identical to those selected for BAT. The
conventional pollutant parameters TSS and pH are also selected
for limitation.
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows for each wastewater source are the same
as the discharge rates for BAT and are shown in Table XI-1 (page
5506). The mass of pollutant allowed to be discharged per mass
of product is based on the product of the appropriate treatable
concentration (mg/1) and the production normalized wastewater
discharge flows (1/kkg). The results of these calculations are
the production-based new source performance standards. These
standards are presented in Table XI-2 (page 5507).
5505
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
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5506
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
TABLE XI-2
NSPS FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(a) Dryer Vent Water Quench and Wet Air Pollution Control
NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH Within
0.042
0.042
5.800
0.835
1.544
5.341
1.168
2.295
3.422
1.210
5.842
4.256
62.600
the range of 7.5
0.042
0.042
2.587
0.334
0.626
2.546
0.542
1.544
1.544
0.501
2.546
1.753
50.080
to 10.0 at all times
(b) Dryer Vent Caustic Wet Air Pollution Control
NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
* Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH Within the
0.007
0.007
1.020
0.147
0.272
0.940
0.206
0.404
0.602
0.213
1.028
0.749
11.010
range of 7.5
0.007
0.007
0.455
0.059
0.110
0.448
0.095
0.272
0.272
0.088
0.448
0.308
8.808
to 10.0 at all times
*Regulated Pollutant
5507
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(c) Electrolytic Cell Water Quench and Wet APC NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
0.094
0.094
13.050
1.878
3.474
12.020
2.629
5.165
7.700
2.723
13.150
9.578
140.900
0,
1,
0.094
0.094
5.822
,751
,409
5.728
1.221
3.474
3.474
1.127
5.728
3.944
112.700
*pH Within the range of 7.5 to 10.0 at all times
(d) Electrolytic Cell Caustic Wet Air Pollution Control NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH Within the range of 7
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
.5 to 10.0 at
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
all times
*Regulated Pollutant
5508
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(e) Sodium Hypochlorite Filter Backwash NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
*TSS
*pH
0.004
0.004
0.503
0.072
0.134
0.463
0.101
0.199
0.297
0.105
0.507
0.369
5.430
0.004
0.004
0.224
0.029
0.054
0.221
0.047
0.134
0.134
0.043
0.221
0.152
4.344
Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
5509
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XI
THIS PAGE INTENTIONALLY LEFT BLANK
5510
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
PSES are designed to prevent the discharge of pollutants which
pass through interfere with or are otherwise incompatible with
the operation of publicly owned treatment works (POTW). The
Clean Water Act requires pretreatment for pollutants, such as
toxic metals, that limit POTW sludge management alternatives.
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 technologies, and to
use plant site selection to ensure adequate treatment system
function. Pretreatment standards are to be technology based,
analogous to the best available or best demonstrated technology
for removal of toxic pollutants.
This section describes the control and treatment technologies for
pretreatment of process wastewaters from existing sources and new
sources in the primary rare earth metals subcategory.
Pretreatment standards for regulated pollutants are presented
based on the selected control and treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing and promulgating pretreatment standards, the
Agency examines whether the pollutants discharged by the industry
pass through the POTW or interfere with the POTW operation or its
chosen sludge disposal practices. In determining whether
pollutants pass through a well-operated POTW achieving secondary
treatment, the Agency compares the percentage of a pollutant
removed by POTW with the percentage removed by direct dischargers
applying the best available technology economically achievable. 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
limitations guidelines for that pollutant.
This definition of pass through satisfies the two competing
objectives set by Congress that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time the treatment capability and performance
of the POTW be recognized and taken into account in regulating
the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources or the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
5511
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
The industry cost and pollutant removal estimates of each
treatment option were used to determine the most cost-effective
option. These estimates have been revised since proposal because
of additional wastewater streams and new production normalized
flows used for promulgation. The methodology applied in
calculating pollutant removal estimates and plant compliance
costs is discussed in Section X.
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES
Options for pretreatment of wastewaters from both existing and
new sources are based on increasing the effectiveness of end-of-
pipe treatment technologies. All in-plant changes and applicable
end-of-pipe treatment processes have been discussed previously in
Sections X and XI. The options for PSNS and PSES, therefore, are
the same as the BAT options discussed in Section X.
A description of each option is presented in Section X, while a
more detailed discussion, including pollutants controlled by each
treatment process is presented in Section VII of Vol. I.
PSNS AND PSES OPTION SELECTION - PROPOSAL
EPA proposed that the pretreatment standards technology base for
the primary rare earth metals subcategory be equivalent to Option
E (in-process flow reduction, chemical precipitation,
sedimentation, multimedia filtration, and activated carbon
adsorption).
The wastewater discharge rates for both PSNS and PSES were
equivalent to the proposed BAT discharge rates. No flow
reduction measures for PSNS or PSES were considered feasible
beyond the recycle proposed for BAT.
PSES OPTION SELECTION - PROMULGATION
The technology basis for promulgated PSES is Option E, in-process
flow reduction, chemical precipitation, sedimentation, multimedia
filtration, and activated carbon adsorption technology to remove
metals, solids, and organics from combined wastewaters and to
control pH. The basis of this selection is that it achieves
effective removal of toxic pollutants without resulting in
negative impacts on the cost of new facilities. Filtration is
demonstrated by 25 plants in the nonferrous metals manufacturing
category, and will not result in adverse economic impacts.
Activated carbon adsorption technology is necessary to control
the discharge of hexachlorobenzene.
Table XII-1 (page 5514)shows the estimated pollutant removals for
indirect dischargers at promulgation. Compliance costs for
indirect dischargers at promulgation are presented in Table XII-2
(page 5515).
5512
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
PSNS OPTION SELECTION - PROMULGATION
Option E (in-process flow reduction, chemical precipitation,
sedimentation, multimedia filtration, and activated carbon
adsorption) has been selected by the Agency as the treatment
technology for the basis of promulgated pretreatment standards
for new sources. The basis of this selection is that it achieves
effective removal of priority pollutants without resulting in
negative impacts on the cost of new facilities. The wastewater
discharge rates for promulgated PSNS are identical to the
promulgated BAT discharge rates for each waste stream. The PSNS
discharge rates are shown in Table XII-3 (page 5516).
REGULATED POLLUTANT PARAMETERS
Pollutants selected for limitation, in accordance with the
rationale of Sections VI and X, are identical to those selected
for limitation for BAT. It is necessary to promulgate PSES and
PSNS to prevent the pass-through of hexachlorobenzene, chromium,
lead, and nickel, which are the limited pollutants. These toxic
pollutants are removed by a well-operated POTW achieving
secondary treatment at an average of 28 percent while BAT
technology removes approximately 74 percent.
PRETREATMENT STANDARDS
Pretreatment standards are based on the treatable concentrations
from the selected treatment technology (Option E) and the
discharge rates determined in Section X for BAT. A mass of
pollutant per mass of product (rag/kg) allocation is given for
each subdivision within the subcategory. This pollutant
allocation is based on the product of the treatable concentration
from the promulgated treatment (mg/1) and the production
normalized wastewater discharge rate (1/kkg). The achievable
treatment concentrations for BAT are identical to those for PSES
and PSNS. PSES and PSNS are presented in Tables XII-4 and XI1-5
(pages 5517 and 5520).
5513
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
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PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
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-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
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5516
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
TABLE XI1-4
PSES FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(a) Dryer Vent Water Quench and Scrubber PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.042 .
0.042
5.800
0.835
1.544
5.341
1.168
2.295
3.422
1.210
5.842
4.256
0.042
0.042
2.587
0.334
0.626
2.546
0.542
1.544
1.544
0.501
2.546
1.753
(b) Dryer Vent Caustic Wet Air Pollution Control PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg(Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
. Arsenic
Cadmium
*Chromium
Coppe r
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.007
0.007
1.020
0.147
0.272
0.940
0.206
0.404
0.602
0.213
1.028
0.749
0.007
0.007
0.455
0.059
0.110
0.448
0.095
0.272
0.272
0.088
0.448
0.308
*Regulated Pollutant
5517
-------
PRIMARY RARE EARTH METALS SUBCATEGORY
SECT - XII
TABLE XII-4 (Continued)
PSES FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(c) Electrolytic Cell Water Quench and Wet APC PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
rag/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.094
0.094
13.050
1.878
3.474
12.020
2.629
5.165
7.700
2.723
13.150
9.578
0.094
0.094
5.822
0.751
1.409
5.728
1.221
3.474
3.474
1.127
5.728
3.944
(d) Electrolytic Cell Caustic Wet Air Pollution Control PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel :
Selenium
Silver
Thallium
Zinc
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo .
o.ooo
0.000
0.000
0.000
0.000
0.000
0.000
0.000
*Regulated Pollutant
5518
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
TABLE XII-4 (Continued)
PSES FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(e) Sodium Hypochlorite Filter Backwash PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.004
0.004
0.503
0.072
0.134
0.463
0.101
0.199
0.297
0.105
0.507
0.369
0.004
0.004
0.224
0.029
0.054
0.221
0.047
0.134
0.134
0.043
0.221
0.152
*Regulated Pollutant
5519
-------
PRIMARY RARE EARTH METALS SOBCATEGORY SECT - XII
TABLE XI1-5
PSNS FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(a) Dryer Vent Water Quench and Wet Air Pollution Control PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.042
0.042
5.800
0.835
1.544
5.341
1.168
2.295
3.422
1.210
5.842
4.256
0.042
0.042
2.587
0.334
0.626
2.546
0.542
1.544
1.544
0.501
2.546
1.753
(b) Dryer Vent Caustic Wet Air Pollution Control PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of mischmetal
produced from wet rare earth chlorides
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.007
0.007
1.020
0.147
0.272
0.940
0.206
0.404
0.602
0.213
1.028
0.749
0.007
0.007
0.455
0.059
0.110
0.448
0.095
0.272
0.272
0.088
0.448
0.308
*Regulated Pollutant
5520
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
TABLE XII-5 (Continued)
PSNS FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(c) Electrolytic Cell Water Quench and Wet APC
PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
* Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.094
0.094
13.050
1.878
3.474
12.020
2.629
5.165
7.700
2.723
13.150
9.578
0.094
0.094
5.822
0.751
1.409
5.728
1.221
3.474
3.474
1.127
5.728
3.944
(d) Electrolytic Cell Caustic Wet Air Pollution Control
PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
*Regulated Pollutant
5521
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XII
TABLE XII-5 (Continued)
PSNS FOR THE PRIMARY RARE EARTH METALS SUBCATEGORY
(e) Sodium Hypochlorite Filter Backwash PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of total mischmetal produced
Benzene
*Hexachlorobenzene
Arsenic
Cadmium
*Chromium
Copper
*Lead
*Nickel
Selenium
Silver
Thallium
Zinc
0.004
0.004
0.503
0.072
0.134
0.463
0.101
0.199
0.297
0.105
0.507
0.369
0.004
0.004
0.224
0.029
0.054
0.221
0.047
0.134
0.134
0.043
0.221
0.152
*Regulated Pollutant
5522
-------
PRIMARY RARE EARTH METALS SUBGATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the primary rare earth metals subcategory at
this time.
5523
-------
PRIMARY RARE EARTH METALS SUBCATEGORY SECT - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
5524
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Secondary Indium Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
5525
-------
5526
-------
Section
SECONDARY INDIUM SUBCATEGORY
TABLE OF CONTENTS
I
II
III
IV
V
VI
SUMMARY
CONCLUSIONS
SUBCATEGORY PROFILE
Description of Secondary Indium Production
Raw Materials
Dissolving, Precipitation, and Electrolytic
Recovery
Electrolytic Refining
Melting and Casting
Process Wastewater Sources
Other Wastewater Sources
Age, Production, and Process Profile
SUBCATEGORIZATION
Factors Considered in Subdividing the Secondary
Indium Subcategory
Other Factors
Production Normalizing Parameters
WATER USE AND WASTEWATER CHARACTERISTICS
Wastewater Flow Rates
Wastewater Characteristics Data
Field Sampling Data
Wastewater Characteristics and Flows by
Subdivision
Displacement Supernatant
Spent Electrolyte
SELECTION OF POLLUTANT PARAMETERS
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Priority Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Never Found Above Their
Analytical Quantification Concentration
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for further
Consideration in Establishing Limitations and
Standards
5533
5535
5539
5539
5539
5539
5540
5540
5540
5540
5540
5543
5543
5543
5544
5545
5545
5546
5546
5547
5547
5547
5551
5551
5552
5552
5552
5552
5553
5554
5527
-------
SECONDARY- INDIUM SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
Page
VII
VIII
IX
X
XI
CONTROL AND TREATMENT TECHNOLOGIES 5563
Current Control and Treatment Practices 5563
Displacement Supernatant 5563
Spent Electrolyte 5563
Control and Treatment Options 5563
Option A 5654
Option C 5564
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS 5565
Treatment Options for Existing Sources 5565
Option A 5565
Option C 5565
Cost Methodology 5566
Nonwater Quality Aspects 5566
Energy Requirements 5566
Solid Waste 5566
Air Pollution 5568
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY 5571
AVAILABLE
BEST AVAILABLE TECHNOLOGY ECONOMICALLY 5571
ACHIEVABLE
NEW SOURCE PERFORMANCE STANDARDS 5573
Technical Approach to NSPS 5573
Industry Cost and Pollutant Removal Estimates 5575
Pollutant Removal Estimates 5575
Compliance.Costs 5375
NSPS Option Selection - Proposal 5576
NSPS Option Selection - Promulgation 5576
Wastewater Discharge Rates 5577
Displacement Supernatant 5577
Spent Electrolyte 5577
Regulated Pollutant Parameters 5577
New Source Performance Standards 5578
5528
-------
SECONDARY INDIUM SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
XII
XIII
PRETREATMENT STANDARDS 5583
Technical Approach to Pretreatment 5583
Industry Cost and Pollutant Removal Estimates 5584
Pretreatment Standards for Existing and New 5584
Sources
PSES Option Selection - Proposal 5584
PSES Option Selection - Promulgation 5584
PSNS Option Selection - Proposal 5585
PSNS Option Selection - Promulgation 5585
Pretreatment Standards 5586
BEST CONVENTIONAL POLLUTANT CONTROL 5593
TECHNOLOGY
5529
-------
SECONDARY INDIUM SUBCATEGORY
LIST OF TABLES
VI-2
VIII-1
XI-1
XI-2
XII-1
XII-2
XII-3
XII-4
XII-5
Title Page
Water Use and Discharge Rates for Displacement 5549
Supernatant
Water Use and Discharge Rates for Spent 5549
Electrolyte
Frequency of Occurrence of Priority Pollutants 5556
Secondary Indium Subcategory Raw Wastewater
Toxic Pollutants Never Detected 5560
Cost of Compliance for the Secondary Indium 5569
Subcategory Indirect Dischargers
NSPS Wastewater Discharge Rates for the 5579
Secondary Indium Subcategory
NSPS for the Secondary Indium Subcategory 5580
Pollutant Removal Estimates Secondary Indium 5587
Subcategory Indirect Dischargers
Cost of Compliance for the Secondary Indium 5588
Subcategory Indirect Dischargers
I i
PSES and PSNS Wastewater Discharge Rates for the 5589
Secondary Indium Subcategory
PSES for the Secondary Indium Subcategory 5590
PSNS for the Secondary Indium Subcategory 5591
5530
-------
Figure
SECONDARY INDIUM SOBCATEGORY
LIST OF FIGURES
Title
III-l Block Diagram for Indium Production
XI-1 NSPS Treatment Scheme for Option A
XI-2 NSPS Treatment Scheme for Option C
Paqe
5541
5581
5582
5531
-------
SECONDARY INDIUM SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
5532
-------
SECONDARY INDIUM SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
pretreatment standards for existing indirect dischargers (PSES),
pretreatment standards for new indirect dischargers (PSNS), and
standards of performance for new source direct dischargers
(NSPS).
The secondary indium subcategory consists of two plants. One
discharges to a publicly owned treatment works (POTW), and one
achieves zero discharge of process wastewater.
EPA first studied the secondary indium subcategory to determine
whether differences in raw materials, final products,
manufacturing processes, equipment, age and size of plants, and
water usage required the development of separate effluent
limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including the
sources and volume of water used, the processes used, and the
sources of pollutants and wastewaters in the plant, and the
constituents of wastewaters, including toxic pollutants. As a
result, two subdivisions have been identified for this
subcategory that warrant separate effluent limitations. These
include:
o Displacement supernatant, and
o Spent electrolyte.
Several distinct control and treatment technologies (both in-
plant and end-of-pipe) applicable to the secondary indium
subcategory were identified. The Agency analyzed both historical
and newly generated data on the performance of these
technologies, including their nonwater quality environmental
impacts and air quality, solid waste generation, and energy
requirements. EPA also studied various flow reduction techniques
reported in the data collection portfolios (dcp) and plant
visits.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of
implementing the various options in the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
of pollutants, the number of potential closures, number of
employees affected, and impact on price were estimated. These
results are reported in a separate document entitled "The
Economic Impact Analysis of Effluent Limitations and Standards
for the Nonferrous Metals Manufacturing Industry."
There is no plant currently discharging wastewater to a surface
5533
-------
SECONDARY INDIUM SUBCATEGORY
SECT - I
water in the secondary indium subcategory. Therefore, BPT, BAT,
and BCT do not apply to this subcategory, and are not
promulgated.
Metals removal based on chemical precipitation and
technology is the basis for the PSES limitations.
sedimentation
To meet the
PSES effluent limitations based on this technology, the secondary
indium subcategory is estimated to incur minimal capital and
annual cost.
i
NSPS and PSNS are based on chemical precipitation and
sedimentation technology. In selecting technology for new source
standards, EPA recognizes that new plants have the opportunity to
implement the best and most efficient manufacturing processes and
treatment technology. As such, the technology basis of PSES has
been selected as the best demonstrated technology.
The manufacturers of indium originally claimed much of the
information made available to the Agency as the basis of this
regulation to be confidential. However, they have released their
claims of confidentially for the preparation of this text.
The mass limitations and standards for NSPS,
presented in Section II.
PSES, and PSNS are
5534
-------
SECONDARY INDIUM SUBCATEGORY
SECT - II
SECTION II
CONCLUSIONS
EPA has divided the secondary indium subcategory into two
subdivisions for the purpose of effluent limitations and.
standards. These subdivisions are:
(a) Displacement supernatant, and
(h) Spent electrolyte.
We are not promulgating BPT or BAT limitations for the secondary
indium subcategory since there are no existing direct
dischargers.
NSPS are promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology. The following effluent standards are
promulgated for new sources:
(a) Displacement Supernatant NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of indium metal produced
Cadmium
Lead
Zinc
Indium
TSS
pH
(b) Spent
2.105
2.600
9.037
2.724
253.800
Within the range of 7.5
Electrolyte NSPS
0.929
1.238
3.776
1.114
120.700
to 10.0 at all times
Pollutant or
Pollutant Property
Maximum for
Any One Day
Monthly Average
(Ib/million Ibs) of cathode indium produced
Cadmium
Lead
Zinc
Indium
TSS
pH
12.170
15.040
52.270
15.750
1,468.000
5.370
7.160
21.840
6.444
698.100
Within the range of 7.5 to 10.0 at all times
5535
-------
SECONDARY INDIUM SUBCATEGORY
SECT - II
PSES are promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology. The following pretreatment standards are
promulgated for existing sources:
(a) Displacement Supernatant PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of indium metal produced
Cadmium
Lead
Zinc
Indium
2.105
2.600
9.037
2.724
0.929
1.238
3.776
1.114
(b) Spent Electrolyte PSES
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of cathode indium produced
Cadmium
Lead
Zinc
Indium
12.170
15.040
52.270
15.750
5.370
7.160
21.840
6.444
PSNS are promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology. The following pretreatment standards are
promulgated for new sources:
(a) Displacement Supernatant PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of indium metal produced
Cadmium
Lead
Zinc
Indium
2.105
2.600
9.037
2.724
0.929
1.238
3.776
1.114
5536
-------
SECONDARY INDIUM SUBCATEGORY
SECT - II
(b) Spent Electrolyte PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of cathode indium produced
Cadmium
Lead
Zinc
Indium
12.170
15.040
52.270
15.750
5.370
7.160
21.840
6.444
EPA is not promulgating best conventional pollutant control
technology (BCT) limitations at this time.
5537
-------
SECONDARY INDIUM SUBCATEGORY SECT - II
THIS PAGE INTENTIONALLY LEFT BLANK
5538
-------
SECONDARY INDIUM SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the secondary indium supplement describes the raw
materials and processes used in producing secondary indium and
presents a profile of the secondary indium plants identified in
this study.
Indium is used primarily in solders, seals, lubricants, and
electrical conductors. The low melting point of indium (156°C)
makes indium an ideal metal for use in solders. In addition,
indium can increase the electrical conductivity of other metals.
DESCRIPTION OF SECONDARY INDIUM PRODUCTION
The production of indium metal from secondary sources can be
divided into three distinct processes; dissolution and
precipitation of low-grade indium, electrolytic refining of high-
grade indium and melting and casting operations. A schematic
diagram of the secondary indium production processes is presented
in Figure III-l (page 5443).
RAW MATERIALS
The principal raw materials used for secondary indium production
are scrap indium metal and spent electrolytic solutions from
secondary silver refining operations.
DISSOLVING, PRECIPITATION, AND ELECTROLYTIC RECOVERY
Indium scrap is dissolved in hydrochloric acid to produce an
indium-laden solution. The indium-rich solution then undergoes a
series of precipitation steps to selectively remove metallic
impurities such as tin and lead. Spent electrolytic solutions
from secondary silver refineries may be added to the the indium
solution. The resulting indium solution is then processed to
precipitate out the indium. Zinc ions are added to the indium-
rich solution to displace and precipitate indium. The indium
sponge is then removed and sent to the melting and casting
operation. This operation produces indium which is suitable for
further purification by electrolytic refining.
One plant recovers indium from solution using an electrolytic
recovery process. This plant obtains indium-rich solutions from
dissolution of low grade indium metal or scrap, and also uses
spent plating solutions. Electrolytic recovery of indium from
solution produces a salable product or one that may be further
purified by electrolytic refining. Spent solution from the
electrolytic recovery process is recycled to the dissolving
operation.
5539
-------
SECONDARY INDIUM SUBCATEGORY
SECT - III
ELECTROLYTIC REFINING
This process is used to produce high purity indium (up to 99.9999
percent). In this process, the low grade indium acts as the
anode in an electrolyte solution. The electrolyte solution
contains very high concentrations of dissolved salts and metals
and has a pH in the range of 1.5 to 2.5.
A current is applied to the electrolytic bath and high purity
indium plates out on the cathode. This process may be repeated
until the desired grade of indium is obtained.
MELTING AND CASTING
Indium from the dissolution-precipitation, electrolytic recovery,
or electrolytic refining processes, as well as scrap indium metal
can be melted down and cast into desired product forms. All
indium melting and casting operations are dry.
PROCESS WASTEWATER SOURCES
The significant wastewater sources associated with the secondary
indium subcategory can be subdivided into two subdivisions as
follows:
1. Displacement supernatant, and
2. Spent electrolyte.
OTHER WASTEWATER SOURCES
There may be other wastewater streams associated with the
secondary indium subcategory. These streams may include
stormwater runoff, and maintenance and cleanup water. These
wastewaters are not considered as a part of this rulemaking. EPA
believes that the flows and pollutant loadings associated with
these wastewaters are insignificant relative to the waste
wastewater streams selected and are best handled by the
appropriate permit authority on a case-by-case basis under
authority of Section 402 of the Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
The secondary indium plants operating in the United States are
located in the northeastern United States. One plant uses
precipitation and electrolytic refining processes and is an
indirect discharger of treated process wastewater. Other plants
operate electrolytic recovery and electrolytic refining processes
and achieve zero discharge of process wastewater.
5540
-------
SECONDARY INDIUM SUBCATEGORY " SECT - III
Indium Scrap
Spent Solution
HC1
Product
Indium
Impurity Removal
(Pb, Sn) by
Precipitation
Spent Electrolyte from
Secondary Silver Recovery
. Precipitated
Impurities
_L
Zinc
Precipitation of
Indium
(Displacement)
' Wastewater
Low Grade Indium
High Grade Indium
Indium Scrap
Product Indium
Figure III-1
BLOCK DIAGRAM FOR INDIUM PRODUCTION
5541
-------
SECONDARY INDIUM SUBCATEGORY SECT - III
THIS PAGE INTENTIONALLY LEFT BLANK
5542
-------
SECONDARY INDIUM SUBCATEGORY SECT - IV
' SECTION IV "
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the related subdivisions of the secondary indium
subcategory. Production normalizing parameters for each
subdivision will also be discussed.
FACTORS CONSIDERED IN SUBDIVIDING THE SECONDARY INDIUM
SUBCATEGORY
The factors listed previously for general subcategorization were
each evaluated when considering subdivision of the secondary
indium subcategory. In the discussion that follows, the factors
will be described as they pertain to this particular subcategory.
The rationale for considering further subdivision of the
secondary indium subcategory is based primarily on differences in
the production processes and raw materials used. Within this
subcategory, several different operations are performed, which
may or may not have a water use or discharge, and which may
require the establishment of separate effluent limitations.
While indium is considered a single subcategory, a more thorough
examination of the production processes has illustrated the need
for limitations and standards based on a specific set of waste
streams. Limitations will be based on specific flow allowances
for the following subdivisions:
1. Displacement supernatant, and
2. Spent electrolyte.
These subdivisions follow directly from differences within the
processes used in the production of secondary indium.
Dissolution and precipitation (displacement) of scrap indium
gives rise to the first subdivision. The supernatant from the
displacement of indium is the only source of wastewater
associated with this refining process. The electrolytic refining
method results in the second subdivision. The spent electrolyte
is the only potential discharge from this operation. The final
production stage, melting and casting of indium is a dry
operation, and therefore, does not warrant a separate
subdivision.
OTHER FACTORS
The other factors considered in this evaluation were shown to be
inappropriate bases for subdivision. Certain other factors, such
as plant age, plant size, and the number of employees, were also
evaluated and determined to be inappropriate for use as bases for
subdivision of nonferrous metals plants.
5543
-------
SECONDARY INDIUM SUBCATEGORY
SECT - IV
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow these
regulations to be applied to any plant which might have varying
production capacities, the mass of pollutant discharged must be
related to a unit of production. This factor is known as the
production normalizing parameter (PNP).
For each production process which has a wastewater associated
with it, the actual mass of indium product will be used as the
PNP. Thus, the PNPs for the two subdivisions are as follows:
Subdivision
1. Displacement supernatant
2. Spent electrolyte
PNP
kkg of indium produced
',
kkg of cathode indium produced
The use of production capacity instead of actual production was
eliminated from consideration as an alternate PNP because the
mass of the pollutant produced is more a function of true
production than of installed capacity.
5544
-------
SECONDARY INDIUM SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the secondary indium subcategory. Data used to
characterize the waste-wastewater flow and pollutant
concentrations are presented , summarized and discussed.
The two principal data sources used are data collection
portfolios (dcp) and field sampling results. Data collection
portfolios contain information regarding wastewater flows and
production levels.
In order to quantify the pollutant discharge from secondary
indium plants, a field sampling program was conducted. Wastewater
samples were analyzed for 124 of the 126 toxic pollutants and
other pollutants deemed appropriate. Because the analytical
standard for TCDD was judged to be too hazardous to be made
generally available, samples were never analyzed for this
pollutant. Samples were also not analyzed for asbestos. There
is no reason to expect that TCDD or asbestos would be present, in
nonferrous metals manufacturing wastewater. Sampling was
conducted in the secondary indium subcategory. In general, the
samples were analyzed for three classes of pollutants: toxic
organic pollutants, toxic metal pollutants, and criteria
pollutants (which includes both conventional and nonconvent-ional
pollutants).
No additional sampling data for this subcategory were obtained
from EPA sampling efforts or industry comments between proposal
and promulgation. Characterization of secondary indium
subcategory wastewaters (Section V), and selection of pollutant
parameters for limitation (Section VI) is be based upon the same
data used for proposal.
As described in Section IV of this supplement, the secondary
indium subcategory has been divided into two subdivisions or
wastewater sources, so that the promulgated regulation contains
mass discharge limitations and standards for two unit processes
discharging process wastewater. It is expected that the
wastewater characteristics for these subdivisions will be
similar. However, since each subdivision has differing discharge
and production rates, wastewater streams corresponding to each
subdivision are addressed separately in the discussions that
follow. These wastewater sources are:
1. Displacement supernatant, and
2. Spent electrolyte.
WASTEWATER FLOW RATES
Data supplied by dcp responses were evaluated, and two flow-to-
5545
-------
SECONDARY INDIUM SUBCATEGORY SECT - V
production ratios, water use and wastewater discharge flow, were
calculated for each stream. The two ratios 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 indium product and is therefore b«ised 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 indium produced.
Differences between the water use and wastewater flows associated
with a given stream result from recycle, evaporation, and
carry-over on the product. The production values used in the
calculation correspond to the production normalizing parameter,
PNP, assigned to each stream, as outlined in Section IV.
1 i
The production normalized discharge flows were compiled and
statistically analyzed by stream type. These production
normalized water use and discharge flows are presented by
subdivision at the end of this section, in Tables V-l and V-2
(page 5451).
The water use and discharge rates shown do not include nonprocess
wastewater, such as rainfall runoff and noncontact cooling water.
WASTEWATER CHARACTERISTICS DATA
:
The data used to characterize the various wastewaters associated
with secondary indium production come from a field sampling trip.
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from secondary indium plants, wastewater samples were
collected. One sampled plant is currently not operating. At the
time of sampling, this facility produced indium by leaching of
indium-rich slags with hydrochloric acid and precipitation of
indium from solution by displacement with zinc. A diagram showing
the sampling sites nd processes contributing wastewaters is shown
in Figure V-l (page 5561). The spent electrolyte wastewater
stream was not sampled, however, spent electrolyte wastewater is
expected to be similar to the displacement tank supernatant which
was sampled. The displacement tank supernatant data will be used
to characterize the spent electrolyte wastewater stream.
Analytical results for displacement tank supernatant are
summarized in table V-3 (page 5550). When there no data are
listed for a specific day of sampling, the wastewater samples for
that stream were not collected.
The data tables include some samples measured at concentrations
considered not quantifiable. The base-neutral extractable, acid
extractable, and volatile organics generally are considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
Below this concentration, organic analytical results are not
5546
-------
SECONDARY INDIUM SUBCATEGORY
SECT - V
quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1.
The detection limits shown on the data tables are not the same in
all cases as the 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.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. These data are
considered as detected but below quantifiable concentrations, and
a value of zero is used for averaging. Toxic organic,
nonconventional, and conventional pollutant data reported with a
"less than" sign are considered as detected, but not further
quantifiable. A value of zero is also used for averaging. If a
pollutant is reported as not detected, a value of zero is used in
calculating the average. Finally, toxic metal values reported as
less than a certain value were considered as below
quantification, and consequently a value of zero was used in the
calculation of the average.
Appropriate source water concentrations are presented with the
summaries of the sampling data. The method by which each sample
was collected is indicated by number, as follows:
1 one-time grab
2 manual composite during intermittent process operation
3 8-hour manual composite
4 8-hour automatic composite
5 24-hour manual composite
6 24-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since secondary indium production involves two principal sources
of wastewater and each has potentially different characteristics
and flows, the wastewater characteristics and discharge rates
corresponding to each subdivision will be described separately. A
brief description of why the associated production processes
generate a wastewater and explanations for variations of water
use within each subdivision will be presented.
DISPLACEMENT SUPERNATANT
Scrap indium materials are dissolved in hydrochloric acid to
solubilize the indium. The indium-rich solution then goes
through ionic displacement steps to remove pollutant metals such
as tin and lead. Next, indium is precipitated out of the
5547
-------
SECONDARY INDIUM SUBCATEGORY SECT - V
solution by zinc ions. The production normalized water use rate
reported for this process step is 6190 1/kkg of indium produced.
The production normalized discharge rate reported for this
displacement operation is also 6190 1/kkg of indium produced and
no recycle or reuse is practiced. These rates are shown in Table
V-l (page 5541). This wastewater stream is characterized by a pH
of about 4 and contains treatable concentrations of zinc and
suspended solids.
SPENT ELECTROLYTE
In this process low grade indium is used to produce indium with a
purity of up to 99.9999 percent. The low grade indium is used as
the anode in an electrolyte solution. High purity indium is
deposited on the cathode when a current is applied to the
solution. All spent electrolyte from this step has additional
indium recovered in the dissolution-precipitation process at the
indium precipitation stage. The production normalized water use
rate reported by the one plant for spent electrolyte is
equivalent to the production normalized discharge rate and equals
35,800 1/kkg of cathode indium produced. These rates are shown
in Table V-2 (page 5452). No sampling data were collected for
this wastewater stream; however, it is expected to have pollutant
characteristics similar to those of the displacement tank
supernatant. Therefore, this wastewater stream is expected to
contain toxic metals and suspended solids at treatable
concentrations.
5548
-------
SECONDARY INDIUM SUBCATEGORY
SECT - V
Plant Code
1132
TABLE V-l
WATER USE AND DISCHARGE RATES FOR
DISPLACEMENT SUPERNATANT
(1/kkg of indium produced)
Percent Recycle
0
Production
Normalized
Water Use
6190
Production
Normalized
Discharge Flow
6190
TABLE V-2
WATER USE AND DISCHARGE RATES FOR
SPENT ELECTROLYTE
(1/kkg of cathode indium produced)
Plant Code
1132
Percent Recycle
0
Production
Normalized
Water Use
35800
Production
Normalized
Discharge Flow
35800
5549
-------
SECONDARY INDIUM SUBCATEGORY
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SECONDARY INDIUM SUBCATEGORY SECT - V
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5555
-------
SECONDARY INDIUM SUBCATEGORY SECT - V
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5556
-------
SECONDARY INDIUM SUBCATEGORY" SECT - V
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5557
-------
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SECONDARY INDIUM SUBCATEGORY" SECT - V
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5558
-------
SECONDARY INDIUM SUBCATEGORY SECT - V
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5559
-------
SECONDARY INDIUM SUBCATEGORY " SECT - V
IT)
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-------
SECONDARY INDIUM SUBCATEGORY' SECT
Source
Water
NaOH to
pH = 4.0
Displace-
ment Tank
Supernatant
Additional
Indium
Recovery
In(OH)3 to
Recycle
Chemical
Precipita-
tion and
Filtration
Other Nonferrous
Metals Manufacturing"
Wastewater
.Solids
Removed
Lagoon
Discharge
Figure V-1
SAMPLING SITES AT INDIUM MANUFACTURING FACILITY
5561
-------
SECONDARY INDIUM SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
5562
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
Section V of this supplement presented data
from sampling and subsequent chemical analyses of wastewaters
from secondary indium production.
This section examines that data and discusses the selection or
exclusion of pollutants for potential limitation.
The discussion that follows describes the analysis that was
performed to select or exclude toxic pollutants for further
consideration for limitations and standards. Also, conventional
and nonconventional pollutants will be selected for regulation.
Toxic pollutants will be considered for limitation if they are
present in concentrations treatable by the technologies
considered in this analysis. The treatable concentrations used
for the priority metals were the long-term performance values
achievable by chemical precipitation, sedimentation, and
filtration. The treatable concentrations used for the priority
organics were the long-term performance values achievable by
carbon adsorption.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
This study examined samples from the secondary indium subcategory
for two conventional pollutant parameters (total suspended solids
and pH) and one nonconventional pollutant parameter (indium).
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
indium
total suspended solids (TSS)
pH
Although indium was not analyzed for in the sample of raw
wastewater from this subcategory, it is expected to be present in
treatable concentrations based on the raw materials and
production processes used. Indium is soluble in aqueous
solutions at the raw wastewater pH (4.1) and, therefore, is
expected in the supernatant from the displacement tank at a
concentration exceeding 0.07 mg/1 (treatable concentration). For
these reasons, indium is selected for limitation in this
subcategory.
A TSS concentration of 15,000 mg/1 was observed in the raw waste
sample analyzed for this study. This concentration is well above
the 2.6 mg/1 concentration considered achievable by identified
treatment technology. Furthermore, most of the specific methods
used to remove toxic metals do so by converting these metals to
precipitates, and the toxic-metal-containing precipitates should
not be discharged. Meeting a limitation on total suspended
5563
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
solids helps ensure that removal of these precipitated toxic
metals has been effective. For these reasons, total suspended
solids are selected for limitation in this subcategory.
The pH value observed during this study was 4.1, which is outside
the 7.5 to 10.0 range considered desirable for discharge to
receiving waters. Many deleterious effects are caused by extreme
pH values or rapid changes in pH. Also, effective removal of
toxic metals by precipitation requires careful control of pH.
Since pH control within the desirable limits is readily
attainable by available treatment, pH is selected for limitation
in this subcategory.
TOXIC PRIORITY POLLUTANTS
The frequency of occurrence of the priority pollutants in one raw
wastewater sample is presented in Table VI-1 (page 5470). Table
VI-1 is based on the raw wastewater sample data from stream 77
(see Section V). These data provide the basis for the
categorization of specific pollutants, ass discussed below.
Treatment plant samples are not considered in the frequency
count.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table VI-2 (page 5474) were not
detected in any raw wastewater samples from this subcategory.
Therefore, they are not selected for consideration in
establishing limitations.
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
The tox'c pollutants listed below were never found above their
analytical quantification concentration in any raw wastewater
samples from this subcategory; therefore, they are not selected
for consideration in establishing limitations.
68. di-n-butyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
103. beta-BHC
114. antimony
115. arsenic
123. mercury
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any raw
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individualv
following the list.
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
117. beryllium
120. copper
Beryllium was detected at a concentration of 0.16 mg/1. This is
below the 0.2O mg/1 concentration considered achievable by
available treatment. Therefore, beryllium is not selected for
limitation.
Copper was detected at a concentration of 0.14 mg/1. Since this
concentration is below the 0.39 mg/1 concentration considered
achievable by identified treatment technology, copper is not
selected for limitation.
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The following pollutants were not selected for limitation on the
basis that they are detectable in the effluent from only a small
number of sources within the subcategory, and are uniquely
related to only these sources:
44. methylene chloride
64. pentachlorophenol
65. phenol
121. cyanide
Although these pollutants were not selected for limitation in
establishing nationwide regulations, it may be appropriate, on a
case-by-case basis, for the local permitting authority to specify
effluent limitations.
Methylene chloride was detected at a concentration of 0.021 mg/1.
Methylene chloride is a common laboratory reagent often detected
in blank and source water samples. At the sampled plant, the
source water was measured at 0.55 mg/1 methylene chloride. The
observed concentration of methylene chloride is probably due to
laboratory contamination. Methylene chloride is therefore not
selected for limitation.
Pentachlorophenol was found to be present at a concentration of
0.041 mg/1. This is above its treatability concentration of
0.010 mg/1; however, pentachlorophenol. was also detected in the
source water. Pentachlorophenol is not expected to be present
because it is not used as a raw material or produced as a
by-product or an intermediate. Additionally, because the
detected concentration is only slightly above the treatability
level, very little removal would be achieved. For these reasons,
pentachlorophenol is not selected.
Phenol was detected at a concentration of 0.029 mg/1. Because
this value is only slightly greater than the concentration
considered achievable by identified treatment technology (0.010
mg/1) and because the Agency has no- reason to believe that
treatable concentrations of phenol should be present in secondary
indium wastewaters, phenol is not selected for limitation.
5565
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
Cyanide was detected at a concentration of 2*i5rt,mg/lr,-, !
higher than its treatability concentration of 0.047 mg/1.
was also detected in the source water ar a concentration of 0.026
mq/1. Its presence in the wastewater is not expected to be due
S the process since it is not used as a raw material or produced
as a product or intermediate. Treatment for cyanide would result
in very little removal since the detected concentration is only
slightly higher than the treatability limit. Therefore, cyanide
is not selected for limitation.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for further
consideratioS in establishing limitations and standards for this
subcategory. The toxic pollutants selected for .further
consideration for limitation are each discussed following the
list.
118. cadmium
119. chromium
122. lead,
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
Cadmium was detected above treatability level of 0.049 mg/1.
Therefore, cadmium is selected for further consideration for
limitation.
Chromium was detected above chromium's treatability concentration
of 0.07 mg/1. Therefore, chromium is selected for further
consideration for limitation.
Lead was detected above the 0.08 mg/1 attainable by identified
treatment technology. Because of this finding, lead is selected
for further consideration for limitation.
Nickel was found at a concentration, greater than _ nickel ;s
treatability concentration of 0.22 mg/1. Therefore, nickel is
selected for further consideration for limitation.
Selenium was detected at a concentration above selenium;s
treatability concentration of 0.20 mg/1. Selenium, therefore, is
selected for further consideration for limitation.
Silver was detected at a concentration higher than the
treatability concentration of silver which is 0.07 mg/1. Silver,
therefore, is selected for further consideration for limitation.
5566
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
Thallium was detected at a concentration above its treatability
concentration of 0.34 mg/1. Therefore, thallium is selected for
further consideration for limitation.
Zinc was detected at a concentration substantially above the
treatability concentration of 0.23 mg/1. Zinc, therefore, is
selected for further consideration for limitation.
5567
-------
SECONDARY INDIUM SUBCATEGORY ' SECT - VI
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5568
-------
SECONDARY INDIUM SUBCATEGORY" SECT - VI
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5569
-------
SECONDARY INDIUM SUBCATEGORY " SECT - VI
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5570
-------
SECONDARY INDIUM SUBCATEGORY ' SECT - VI
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5571
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
1. acenaphthene
2. acrolein
3. acrylonitrile
4. benzene
5. benzidine
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1/1,2,2-tetrachloroethane
16. chloroethane
17. bis (chloromethyl) ether (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. trichlorofluoromethane (deleted)
5572
-------
SECONDARY INDIUM SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
50. dichlorodifluoromethane (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
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
69. di-n-octyl 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 (l,2,3-cd)pyrene (w,e,-o-phenylenepyrene)
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. alpha-endosulfan
96. beta-endosulfan
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
5573
-------
100.
101.
102.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
116,
SECONDARY INDIUM SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
heptachlor
heptachlor epoxide
alpha-8HC
gamma-8HC (lindane)
delta-BHC
PCB-1242
PCB-1254
PCB-1221
PCB-1232
PCB-1248
PCB-1260
PCB-1016
toxaphene
asbescos
(b)
(b)
(b)
(c)
(c)
(c)
(c)
(Fibrous)
129. 2,3,7,8-tetra
chlorodibenzo-p-dioxin (TCDD)
(a)r(b),(c) - Reported together,
5574
-------
'SECONDARY INDIUM SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters from secondary
indium plants. This section summarizes the description of these
wastewaters and indicates the treatment technologies which are
currently practiced in the secondary indium subcategory for each
wastewater stream. Additionally, this section presents the
control and treatment technology options which were examined by
the Agency for possible application to the secondary indium
subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently being applied to each of the
sources generating wastewater in this subcategory. One plant in
this subcategory currently practices chemical precipitation and
sedimentation. Two options have been selected for consideration
for pretreatment and new source standards.
DISPLACEMENT SUPERNATANT
Indium is recovered by dissolving indium-bearing scrap in
hydrochloric acid. The indium-rich solution is processed through
several displacement steps to remove metallic contaminates and
the purified indium precipitated by zinc ions. One indium plant
practices chemical precipitation and sedimentation on
displacement supernatant.
SPENT ELECTROLYTE
In this process high grade indium is produced by passing a
current through an electrolyte so that indium is deposited on the
cathode. All spent electrolyte from this process is further
processed in the dissolution-precipitation process to recover
indium remaining in solution. This is an additional product
recovery operation. As a result of this process, spent
electrolyte is combined with displacement tank supernatant and
treated with chemical precipitation and sedimentation.
CONTROL AND TREATMENT OPTIONS
The Agency examined two control and treatment technology options
that are applicable to the secondary indium subcategory. The
options selected for evaluation represent end-of-pipe treatment
technologies. No wastewater streams which are suitable for the
application of flow reduction technology are present in secondary
indium refining processes. Therefore,- Option B, which includes
flow reduction, was not further considered.
5575
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SECONDARY INDIUM SUBCATEGORY SECT - VII
OPTION A
The Option A treatment scheme consists of chemical precipitation
and sedimentation technology. Specifically, lime or an
equivalent alkali is added to precipitate toxic metal ions as
metal hydroxides. The metal hydroxides and suspended solids
settle out and the sludge is collected. Vacuum filtration is
used to dewater sludge.
Due to the large zinc loading in the wastewater, EPA considered
the necessity of a two-stage chemical precipitation system at
proposal. One stage would include use of an alkaline chemical
lime, and the second stage would include some other
such as sodium sulfide. Comments received after
from the current discharger in this subcategory
that the plant would have no difficulty meeting the
effluent regulations using lime and settle technology alone.
Therefore, EPA decided not to promulgate effluent regulations
based on a two-stage precipitation system.
such as
chemical,
proposal
indicated
OPTION C
Option C for the secondary indium subcategory consists of all
control and treatment requirements of Option A (chemical
precipitation and sedimentation) plus multimedia filtration
technology added at the end of the Option A treatment scheme.
Multimedia filtration is used to remove suspended solids,
including precipitates of metals, beyond the concentration
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed-media type, although other forms of filters,
such as rapid sand filters or pressure filters would perform
satisfactorily. The addition of filters also provides consistent
removal during periods of time in which there are rapid increases
in flows or loadings of pollutants to the treatment system.
Due to the large zinc loading in the wastewater, EPA considered
the necessity of a two-stage chemical precipitation system at
proposal. One stage would include use of an alkaline chemical
lime, and the second stage would include some other
such as sodium sulfide. Comments received after
from the current discharger in this subcategory
that the plant would have no difficulty meeting the
regulations using lime and settle technology alone.
EPA decided not to promulgate effluent regulations
such as
chemical,
proposal
indicated
effluent
Therefore,
based on a two-stage precipitation system.
5576
-------
SECONDARY INDIUM SUBCATEGORY
SECT - VIII
SECTION VIII
COSTS. ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
secondary indium subcategory and a description of the treatment
options and subcategory-specific assumptions used to develop
these estimates. Together with the estimated pollutant reduction
performance presented in Sections XI and XII of this supplement,
these cost estimates provide a basis for evaluating each
regulatory option. These cost estimates are also used in
determining the probable economic impact of regulation on the
subcategory at different pollutant discharge levels. In
addition, this section addresses nonwater quality environmental
impacts of wastewater treatment and control alternatives.
including air pollution, solid wastes, and energy requirements,
which are specific to the secondary indium subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, two treatment options have been
considered for existing secondary indium sources. The treatment
schemes for each option are summarized below and schematically
presented in Figures XI-1 and XI-2 (pages 5495 and 5496).
OPTION A
Option A consists of chemical precipitation
end-of-pipe technology.
and sedimentation
Due to the large zinc loading in the wastewater, EPA considered
the necessity of a two-stage chemical precipitation system at
proposal. One stage would include use of an alkaline chemical
lime, and the second stage would include some other
such as sodium sulfide. Comments received after
from the current discharger in this subcategory
that the plant would have no difficulty meeting the
regulations using lime and settle technology alone.
EPA decided not to promulgate effluent regulations
such as
chemical,
proposal
indicated
effluent
Therefore,
based on a two-stage precipitation system.
OPTION C
Option C consists of chemical precipitation, sedimentation,
multimedia filtration end-of-pipe treatment technology.
and
Due to the large zinc loading in the wastewater, EPA considered
the necessity of a two-stage chemical precipitation system at
proposal. One stage would use of an alkaline precipitant, such
as lime, and the second stage would use another precipitant, such
as sodium sulfide. Comments received after proposal from the
current discharger in this subcategory indicated that the plant
would have no difficulty meeting the effluent limitations using
5577
-------
SECONDARY INDIUM SDBCATEGORY
SECT
VIII
lime and settle technology alone. Therefore, EPA decided not to
promulgate effluent regulations based on a two-stage
precipitation system.
COST METHODOLOGY
A detailed discussion of the methodology used to develop the
compliance costs is presented in Section VIII of Vol. I.
Promulgation cost estimates did not change from those developed
for the proposed regulation. These cost estimates are presented
in Table VIII-l(page 5483).
Each subcategory may contain a unique set of wastewater streams
requiring certain subcategory-specific assumptions to develop
compliance costs. The major assumption specific to the secondary
indium subcategory is:
(1) Information was made available indicating the indium
concentration in the raw wastewater to be 130,000 mg/1.
Lime and settle and lime, settle, and filter long term
achievable concentrations of 0.084 and 0.07 mg/1,
respectively, were used in the costing process.
NONWATER QUALITY ASPECTS
Nonwater quality impacts specific to the secondary indium
subcategory, including energy requirements, solid waste and air
pollution are discussed below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for Option A are
estimated at 5,900 kwh/yr. Option C, which includes filtration,
is estimated to increase energy consumption over Option A by
approximately 25 percent. Further, the total energy requirement
for Option C is approximately 1 percent of the estimated total
plant energy usage. It is therefore concluded that the energy
requirements of the treatment options considered will have no
significant impact on total plant energy consumption.
SOLID WASTE
Sludge generated in the secondary indium subcategory is due to
the precipitation of metal hydroxides and carbonates using lime
or other chemicals. Sludges associated with the secondary indium
subcategory will necessarily contain quantities of toxic metal
pollutants. Wastes generated by secondary metal industries can
be regulated as hazardous. However, the Agency examined the
solid wastes that would be generated at secondary nonferrous
metals manufacturing plants by the suggested treatment
technologies and believes they are not hazardous wastes under the
5578
-------
SECONDARY INDIUM SUBCATEGORY SECT - VIII
Agency's regulations implementing Section 3001 of the Resource
Conservation and Recovery Act. None of the secondary indium
subcategory wastes are listed specifically as hazardous. Nor are
they likely to exhibit a characteristic of hazardous waste. This
judgment is based on the recommended technology of chemical
precipitation, sedimentation, and filtration. By the addition of
a small excess of lime during treatment, similar sludges,
specifically toxic metal-bearing sludges, generated by other
industries such as the iron and steel industry passed the
Extraction Procedure (EP) toxicity test. See 40 CFR S261.24.
Thus, the Agency believes that the wastewater sludges will
similarly not be EP toxic if the recommended technology is
applied.
Although it is the Aaency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 CFR 262.11) .
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation, from
the point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20, 45 FR 33142 (May 19,
1980)., as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 263.20, 45 FR
33151 (May 19, 1980), as amended at 45 FR 86973 (December 31,
1980). Finally, RCRA regulations establish standards for
hazardous waste treatment, storage, and disposal facilities
allowed to receive such wastes. See 40 CFR Part 464, 46 FR 2802
(January 12, 1981), and 47 FR 32274 (July 26, 1982).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing Section 4004 of RCRA. See 44 FR
53438 (September 13, 1979). The Agency has calculated as part of
the costs for wastewater treatment the cost of hauling and
disposing of these wastes. It is estimated that 170 metric tons
per year of sludge will be generated as a result of the
promulgated PSES for the secondary indium subcategory.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of chemical
5579
-------
SECONDARY INDIUM SUBCATEGORY SECT - VIII
orecipitation, sedimentation, and multimedia filtration. These
technologies transfer pollutants to solid waste and are not
likely to transfer pollutants to air.
5580
-------
SECONDARY INDIUM SUBCATEGORY
SECT - VIII
Table VIII-1
COST OF COMPLIANCE FOR THE SECONDARY INDIUM SUBCATEGORY
INDIRECT DISCHARGERS
(March, 1982 Dollars)
Total Required
Option Capital Cost
Total
Annual Cost
These costs are not presented here because the data on which they
are based have been claimed to be confidential.
5581
-------
SECONDARY INDIUM SUBCATEGORY S.ECT - VIII
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5582
-------
SECONDARY INDIUM SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EPA is not promulgating effluent limitations based on best
practicable control technology currently available (BPT) for the
secondary indium subcategory at this time because there are no
existing direct dischargers in this subcategory.
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EPA is not promulgating effluent limitations based on best
available technology economically achievable (BAT) for the
secondary indium subcategory at this time because there are no
existing direct dischargers in this subcategory.
5583
-------
SECONDARY INDIUM SUBCATEGORY SECT - X
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5584
-------
SECONDARY INDIUM SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) is the best
available demonstrated technology (BDT). New plants have the
opportunity to design the best and most efficient production
processes and wastewater treatment technologies without facing
the added costs and restrictions encountered in retrofitting an
existing plant. Therefore EPA has considered the best
demonstrated process changes, in-plant controls, and end-of-pipe
treatment technologies which reduce pollution to the maximum
extent feasible as the basis for NSPS.
TECHNICAL APPROACH TO NSPS
New source performance standards are based on the most effective
and beneficial technologies currently available. The Agency
reviewed and evaluated a wide range of technology options. The
Agency elected to examine two technology options, applied to
combined wastewater streams, which could be applied to the
secondary indium subcategory as alternatives for the basis of
NSPS effluent limitations.
Treatment technologies considered for the NSPS options are
summarized below:
OPTION A (Figure XI-1, page 5495) is based on:
o Chemical precipitation and sedimentation
OPTION C (Figure XI-2, page 5496) is based on:
o Chemical precipitation and sedimentation
o Multimedia filtration
As explained in Section IV, the secondary indium subcategory has
been subdivided into two potential wastewater sources. Since the
water use, discharge rates, and pollutant characteristics of each
of these wastewaters is potentially unique, effluent limitations
will be developed for each of the two subdivisions.
For each of the subdivisions, a specific approach was followed
for the development of new source performance standards. The
first requirement to calculate these standards is to account for
production and flow variability from plant to plant. Therefore,
a unit of production or production normalizing parameter (PNP)
was determined for each waste stream which could then be related
to the flow from the process to determine a production normalized
flow. Selection of the PNP for each process element is discussed
in Section IV. Each plant within the subcategory was then
analyzed to determine which subdivisions were present, specific
flow rates generated for each subdivision, and the specific
production normalized flows for each subdivision. This analysis
5585
-------
SECONDARY INDIUM SOBCATEGORY SECT - XI
is discussed in detail in Section V. Nonprocess wastewater such
as rainfall runoff and noncontact cooling water is not considered
in the analysis.
Production normalized flows for each subdivision were analyzed to
determine which flow was to be used as part of the basis for
NSPS. The selected flow (sometimes referred to as a NSPS
regulatory flow or NSPS discharge flow) reflects the water use
controls which are common practices within the industry. The
NSPS normalized flow is based on the average of all applicable
data. Nothing was found to indicate that the wastewater flows
and characteristics of new plants would not be similar to those
from existing plants, since the processes used by new sources are
not expected to differ from those used at existing sources.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the NSPS
level of treatment technology. Section VII discusses the various
control and treatment technologies which are currently in place
for each wastewater source. The current control and treatment
technology consists of chemical precipitation and sedimentation
(lime and settle) technology.
Using these regulatory flows and the achievable concentrations,
the next step is to calculate mass loadings for each wastewater
source or subdivision. This calculation was made on a stream-by-
stream basis, primarily because plants in this subcategory may
perform one or more of the operations in various combinations.
The mass loadings (milligrams of pollutant per metric ton of
production - mg/kkg) were calculated by multiplying the NSPS
regulatory flow (1/kkg) by the concentration achievable by the
NSPS level of treatment technology (mg/1) for each pollutant
parameter to be limited under NSPS. These mass loadings are
published in the Federal Register and in CFR Part 421 as the
effluent limitations.
The mass loadings which are allowed under NSPS for each plant
will be the sum of the individual mass loadings for the various
wastewater sources which are found at particular plants.
Accordingly, all the wastewater generated within a plant may be
combined for treatment in a single or common treatment system,
but the effluent limitations for these combined wastewaters are
based on the various wastewater sources which actually contribute
to the combined flow. This method accounts for the variety of
combinations of wastewater sources and production processes which
may be found at secondary indium plants.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH) .
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow arid effluent concentration
achievable by the treatment technology and summed to derive an
5586
-------
SECONDARY INDIUM SUBCATEGORY SECT - XI
appropriate limitation for each subcategory.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option. EPA developed
estimates of the pollutant removal and the compliance costs
associated with each option. The methodologies are described
below.
POLLUTANT REMOVAL ESTIMATES
Since there are no existing direct dischargers in the secondary
indium subcategory, the estimated pollutant removal analysis was
only carried out for indirect dischargers.
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data was
production normalized for each unit operation (i.e., mass of
pollutant generated per mass of product manufactured). This
value, referred to as the raw waste was used to estimate the
mass of toxic pollutants generated within the secondary indium
subcategory. The pollutant removal estimates were calculated for
each plant by first estimating the total mass of each pollutant
in the untreated wastewater. This was calculated by first
multiplying the raw waste values by the corresponding production
value for that stream and then summing these values for each
pollutant for every stream generated by the plant.
The volume of wastewater discharged after the application of each
treatment option was estimated for each operation at each plant
by comparing the actual discharge to the regulatory flow. The
smaller of the two values was selected and summed with the other
plant flows. The mass of pollutant discharged was then estimated
by multiplying the achievable concentration values attainable
with the option (mg/1) by the estimated volume of process
wastewater discharged by the subcategory. The mass of pollutant
removed is the difference between the estimated mass of pollutant
generated within the subcategory and the mass of pollutant
discharged after application of the treatment option. The
pollutant removal estimates for indirect dischargers in the
secondary indium subcategory are presented in Table XII-1 (page
5501).
COMPLIANCE COSTS
In estimating subcategory-wide compliance costs, the first step
was to develop a cost estimation model, relating the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge.
EPA applied the model to each plant. The plant's investment and
operating costs are determined by what treatment it has in place
and by its individual process wastewater discharge flow. As
discussed above, this flow is either the actual or the NSPS
regulatory flow, whichever is lesser. The final step was to
5587
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SECONDARY INDIUM SUBCATEGORY SECT - XI
annualize the capital costs, and to sum the annualized capital
costs, and the operating and maintenance costs for each plant,
yielding the cost of compliance for the subcategory (See Table
XII-2, page 5502). These costs were used in assessing economic
achievability.
NSPS OPTION SELECTION - PROPOSAL
EPA proposed that the best available demonstrated technology for
the secondary indium subcategory be equivalent to Option C
(chemical precipitation, sedimentation, and multimedia
filtration). The pollutants and pollutant parameters specifically
proposed for limitation under NSPS were cadmium, lead, zinc,
indium, total suspended solids, and pH. The Agency believed that
the proposed NSPS were economically achievable, and would not
have a detrimental impact on new plants in this subcategory.
Due to the large zinc loading in the wastewater, EPA considered
the necessity of a two-stage chemical precipitation and
sedimentation system at proposal. One stage would use an alkali
such as lime, and the second stage would use another chemical,
such as sodium sulfide.
NSPS OPTION SELECTION - PROMULGATION
i
EPA is promulgating that NSPS for the secondary indium
subcategory be based on Option A, chemical precipitation and
sedimentation. The end-of-pipe treatment configuration for the
NSPS option selected is presented in Figure XI-1 (page 5495).
The pollutants and pollutant parameters specifically promulgated
for limitation under NSPS are cadmium, lead, zinc, indium, total
suspended solids and pH. The toxic pollutants chromium, nickel,
selenium, silver, and thallium were also considered for
regulation because they are present at treatable concentrations
in the raw wastewaters from this subcategory. These pollutants
were not selected for specific regulation because they will be
effectively controlled when the regulated priority metals are
treated to the concentrations achievable by the model technology.
The toxic metal pollutants cadmium, lead, and zinc, as well as
the nonconventional metal pollutant indium, are specifically
limited to ensure the control of the excluded priority metal
pollutants. These pollutants are indicators of the performance
of the treatment technology.
These NSPS are equivalent to PSES technology. We believe that
the promulgated NSPS are economically achievable, and will not
have a detrimental impact on the entry of new plants into this
subcategory.
The proposed NSPS model technology was lime precipitation,
sedimentation, and filtration. Since the addition of a filter
would only remove an additional 0.2 kg/yr of toxic pollutants,
the Agency determined that the costs involved do not warrant
selection of filtration as part of the NSPS model technology. At
5588
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SECONDARY INDIUM SUBCATEGORY SECT - XI
proposal, EPA considered the necessity of a two-stage chemical
precipitation system. One stage would include use of an alkaline
chemical such as lime, and the second stage would include some
other chemical, such as sodium sulfide. Comments received after
proposal from the current discharger in this subcategory
indicated that the plant would have no difficulty meeting the
effluent regulations using lime and settle technology alone.
Therefore, EPA decided not to promulgate effluent regulations
based on a two-stage precipitation system.
WASTEWATER DISCHARGE RATES
A NSPS discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
from analysis of dcp data. The discharge rate is used with the
achievable treatment concentrations to determine NSPS. Since the
discharge rate may be different for each wastewater source,
separate production normalized discharge rates for each of the
two wastewater sources are discussed below and summarized in
Table XI-1 (page 5493). The discharge rates are normalized on a
production basis by relating the amount of wastewater generated
to the mass of the product which is produced by the process
associated with the waste stream in question. These production
normalizing parameters, or PNPs, are also listed in Table XI-1.
Section V of this document further describes the discharge flow
rates and presents water use and discharge flow rates for each
plant by subdivision in Tables V-l and V-2.
DISPLACEMENT SUPERNATANT
The proposed and promulgated NSPS wastewater discharge rate for
displacement tank supernatant is 6,190 1/kkg (1,483 gal/ton) of
indium produced. Indium production is measured as the amount
recovered in the displacement tanks and does not include the
amount recovered electrolytically. This rate is allocated to
those plants which recover indium from scrap via a dissolution-
precipitation process. Water use and discharge rates are
presented in Table V-l.
SPENT ELECTROLYTE
The proposed and promulgated NSPS wastewater discharge rate for
spent electrolyte is 35,800 1/kkg (8,579 gal/ton) of cathode
indium produced. This rate is allocated to those plants which
recover indium from scrap using an electrolytic refining process.
Water use and discharge rates are presented in Table V-2. The
NSPS flow is based on the rate at the only plant reporting this
waste stream.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutant parameters for limitation. This examination and
5589
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SECONDARY INDIUM SUBCATEGORY SECT - XI
evaluation was presented in Section VI. A total of six
pollutants or pollutant parameters are selected for limitation
under NSPS and are listed below:
118. cadmium
122. lead
128. zinc
indium
TSS
pH
The Agency has chosen not to regulate all eight toxic metals
selected in Section VI for further consideration.
The high cost associated with analysis for priority metal
pollutants has prompted EPA to develop an alternative method for
regulating and monitoring priority pollutant discharges from the
nonferrous metals manufacturing category. Rather than developing
specific effluent mass limitations and standards for each of the
priority metals found above treatable concentrations in the raw
wastewater from a given subcategory, the Agency is promulgating
effluent mass limitations only for those pollutants generated in
the greatest quantities as shown by the pollutant removal
analysis.
By establishing limitations and standards for certain toxic metal
pollutants, dischargers will attain the same degree of control
over toxic metal pollutants as they wouli have been required to
achieve had all the toxic metal pollutants been directly limited.
This approach is technically justified since the treatable
concentrations used for chemical precipitation and sedimentation
technology are based on optimized treatment for concomitant
multiple metals removal. Thus, even though metals have somewhat
different theoretical solubilities, they will be removed at very
nearly the same rate in a chemical precipitation and
sedimentation treatment system operated for multiple metals
removal.
NEW SOURCE PERFORMANCE STANDARDS
The treatable concentrations achievable by application of the
promulgated NSPS are discussed in Section VII of this supplement.
These treatable concentrations (both one day maximum and monthly
average values) are multiplied by the NSPS normalized discharge
flows summarized in Table XI-1 to calculate the mass of
pollutants allowed to be discharged per mass of product. The
results of these calculations in milligrams of pollutant per
kilogram of product represent the new source performance
standards and are presented in Table XI-2 (page 5494) for each
individual waste stream.
5590
-------
SECONDARY INDIUM SUBCATEGORY SECT - XI
TABLE XI-1
NSPS WASTEWATER DISCHARGE RATES FOR THE
SECONDARY INDIUM SUBCATEGORY
Wastewater Stream
NSPS Normalized
Discharge Rate
1/kkg gal/ton
Production
Normalizing
Parameter
Displacement Super- 6/190 1,483
natant
Spent Electrolyte 35,800 8,579
indium produced
cathode indium
produced
5591
-------
SECONDARY INDIUM SUBCATEGORY
SECT - XI
TABLE XI-2
NSPS FOR THE SECONDARY INDIUM SUBCATEGORY
(a) Displacement Supernatant NSPS
Maximum for
monthly average
Pollutant or
pollutant property
Maximum for
any one day
mg/kg (Ib/million Ibs) of indium produced
*Cadmium
Chromium
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Indium
*TSS
*pH Within
(b) Spent Electrolyte
2.105
2.724
2.600
11.880
7.614
2.538
12.690
9.037
2.724
253.800
the range of 7.5
NSPS
0.929
1.114
1.238
7.861
3.405
1.052
5.633
3.776
1.114
120.700
to 10.0 at all times
Pollutant or
pollutant property
any one day
monthly average
mg/kg (Ib/million Ibs) of cathode indium produced
*Cadmium
Chromium
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
* Indium
*TSS
*pH Within
12.170
15.750
15.040
68.740
44.030
14.680
73.390
52.270
15.750
1,468.000
the range of 7.5
5.370
6.444
7.160
45.470
19.690
6.086
32.580
21.840
6.444
598.100
to 10.0 at all times
*Regulated Pollutant
5592
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SECONDARY INDIUM SUBCATEGORY SECT - XI
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5593
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SECONDARY INDIUM SUBCATEGORY SECT - XI
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5594
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SECONDARY INDIUM SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
This section describes the control and treatment technologies for
pretreatment of process wastewaters from existing sources and new
sources in the secondary indium subcategory. PSES are designed to
prevent the discharge of pollutants which pass through, interfere
with, or are otherwise incompatible with the operation of
publicly owned treatment works (POTW). The Clean Water Act
requires pretreatment for pollutants, such as toxic metals, that
limit POTW sludge management alternatives. 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 technologies, and to use plant site
selection to ensure adequate treatment system installation.
Pretreatment standards are to be technology based, analogous to
the best available or best demonstrated technology for removal of
toxic pollutants. Pretreatment standards for regulated pollutants
are presented based on the selected control and treatment
technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing and promulgating pretreatment standards, the
Agency examines whether the pollutants discharged by the industry
pass through the POTW or interfere with the POTW operation or its
chosen sludge disposal practices. In determining whether
pollutants pass through a well-operated POTW achieving secondary
treatment, the Agency compares the percentage of a pollutant
removed by POTW with the percentage removed by direct dischargers
applying the best available technology economically achievable. 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
limitations guidelines for that pollutant.
This definition of pass through satisfies the two competing
objectives set by Congress that standards for indirect
dischargers be equivalent to standards or direct dischargers
while at the same time the treatment capability and performance
of the POTW be recognized and taken into account in regulating
the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources or the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
*
5595
-------
SECONDARY INDIUM SUBCATEGORY SECT - XII
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
i
The industry cost and pollutant removal estimates of each
treatment option were used to determine the most cost-effective
option. The methodology applied in calculating pollutant removal
estimates and plant compliance costs is discussed in Section XI.
Table XII-1 (page 5501) shows the estimated pollutant removal
estimates for indirect dischargers. Compliance costs for
indirect dischargers are presented in Table XII-2 (page 5502).
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES
Options for pretreatment of wastewaters from both existing and
new sources are based on increasing the effectiveness of end-of-
pipe treatment technologies. All in-plant changes and applicable
end-of-pipe treatment processes have been discussed previously in
Section XI. The options for PSNS and PSES, therefore, are the
same as the NSPS options discussed in Section XI. A description
of each option is presented below.
Treatment technologies considered for the PSNS and PSES options
are listed below and shown schematically in Figures XI-1 and XI-
2 (pages 5495 and 5496)
OPTION A
o Chemical precipitation and sedimentation
OPTION C
o Chemical precipitation and sedimentation
o Multimedia filtration
* , , ;
PSES OPTION SELECTION - PROPOSAL
EPA proposed PSES for the secondary indium subcategory based on
Option A, chemical precipitation and sedimentation. The
pollutants specifically proposed for regulation under PSES were
cadmium, lead, zinc, and indium.
Implementation of the proposed PSES limitations was estimated to
remove 586 kg of toxic metals and 288 kg of indium annually.
Due to the large zinc loading in the wastewater, EPA considered
the necessity of a two-stage chemical precipitation system at
proposal.
i
PSES OPTION SELECTION - PROMULGATION
. i
EPA is promulgating PSES for this subcategory based on Option A,
chemical precipitation and sedimentation. The pollutants
specifically regulated under PSES are cadmium, lead, zinc, and
indium. The toxic pollutants chromium, "nickel, selenium, silver,
and thallium were also considered for regulation because they are
5596
-------
SECONDARY INDIUM SUBCATEGORY SECT - XII
present at treatable concentrations in the raw wastewaters from
this subcategory. These pollutants were not selected for
specific regulation because they will be effectively controlled
when the regulated toxic metals are treated to the concentrations
achievable by the model technology. We are promulgating PSES to
prevent pass-through of cadmium, lead, zinc, and indium. These
toxic pollutants are removed by a well-operated POTW at an
average of 30 percent while PSES technology removes approximately
99 percent.
The wastewater discharge rates for promulgated PSES are identical
to the promulgated NSPS discharge rates for each waste stream.
The PSES discharge rates are shown in Table XII-3 (page 5503).
Implementation of the promulgated PSES limitations would remove
annually an estimaled 586 kg of toxic metals and 288 kg of
indium.
At proposal, EPA considered the necessity of a two-stage chemical
precipitation system. Comments received after proposal indicated
that plants would have no difficulty meeting the effluent
regulations using lime and settle technology alone. Therefore,
EPA decided not to promulgate effluent regulations based on a
two-stage precipitation system.
PSNS OPTION SELECTION - PROPOSAL
EPA proposed PSNS for the secondary indium subcategory based on
Option C, chemical precipitation, sedimentation, and multimedia
filtration.
The wastewater discharge rates proposed for PSNS were equivalent
to the proposed NSPS discharge rates. No flow reduction measures
for PSNS were considered feasible.
PSNS OPTION SELECTION - PROMULGATION
EPA is promulgating PSNS based on Option A, chemical
precipitation and sedimentation technology. The proposed PSNS
model technology included filtration. Since the addition of a
filter would only remove an additional 0.2 kg/yr of toxic
pollutants, the Agency determined that the costs involved do not
warrant selection of filtration as part of the PSNS model
technology. The same pollutants pass through at PSNS as at PSES,
for the same reasons. The PSNS flow allowances are based on
minimization of process wastewater wherever possible.
We believe that the promulgated PSNS are achievable, and that
they are not a barrier to entry of new plants into this
subcategory.
The wastewater discharge rates for PSNS are identical to the NSPS
discharge rates for each waste stream. The PSNS discharge rates
are shown in Table XII-3 (page 5503).
5597
-------
SECONDARY INDIUM SUBCATEGORY
SECT - XII
PRETREATMENT STANDARDS
Prefcreatment standards for existing source's are based on the
achievable concentrations from the selected treatment technology,
(Option A), and the discharge rates determined in Section XI for
NSPS (see Table XII-3 for discharge rates for PSES and PSNS). A
mass of pollutant per mass of product (mg/kg) allocation is given
for each subdivision within the subcategory. This pollutant
allocation is based on the product of the treatable concentration
from the promulgated treatment (mg/1) and the production
normalized wastewater discharge rate (1/kkg). Because PSNS and
NSPS are both based on Option A, the eichievable treatment
concentrations for NSPS are identical to those for PSNS.
5598
-------
SECONDARY INDIUM SUBCATEGORY " SECT - XII
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5599
-------
SECONDARY INDIUM SUBCATEGORY
SECT - XII
TABLE XII-2
COST OP COMPLIANCE FOR THE
SECONDARY INDIUM SUBCATEGORY
INDIRECT DISCHARGERS
(March 1982 Dollars)
Total Required
Option Capital Cost
Total
Annual Cost
These costs are not presented here because the data on which
they are based have been claimed to be confidential.
5600
-------
SECONDARY INDIUM SUBCATEGORY
SECT - XII
TABLE XII-3
PSES AND PSNS WASTEWATER DISCHARGE RATES FOR THE
SECONDARY INDIUM SUBCATEGORY
Wastewater Stream
Displacement Super-
natant
Spent Electrolyte
PSES and PSNS
Normalized
Discharge Rate
1/kkg gal/ton
6,190
35,800
1,483
8,579
Production
Normalizing
Parameter
indium produced
cathode indium
produced
5601
-------
SECONDARY INDIUM SUBCATEGORY
SECT - XII
TABLE XI1-4
PSES FOR THE SECONDARY INDIUM SUBCATEGORY
(a) Displacement Supernatant PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of indium produced
*Cadmium
Chromium
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Indium
2.105
2.724
2.600
11.880
7.614
2.538
12.690
9.037
2.724
0.929
1.114
1.238
7.861
3.405
1.052
5.633
3.776
1.114
(b) Spent Electrolyte PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cathode indium produce
*Cadmium
Chromium
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Indium
12.170
15.750
15.040
68.740
44.030
14.680
73.390
52.270
15.750
5.370
6.444
7.160
45.470
19.690
6.086
32.580
21.840
6.444
*Regulated Pollutant
5602
-------
SECONDARY INDIUM SUBCATEGORY
SECT - XII
TABLE XI1-5
PSNS FOR THE SECONDARY INDIUM SUBCATEGORY
(a) Displacement Supernatant PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of indium produced
*Cadmium
Chromium
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
* Indium
2 105
2.724
2.600
11.880
7.614
2.538
12.690
9.037
2.724
0.929
1 114
1.238
7.861
3.405
1.052
5.633
3.776
1.114
(b) Spent Electrolyte PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cathode indium produced
*Cadmium
Chromium
*Lead
Nickel
Selenium
Silver
Thallium
*Zinc
*Indium
12.170
15.750
15.040
68.740
44.030
14.680
73.390
52.270
15.750
5.370
6.444
7.160
45.470
19.690
6.086
32.580
21.840
6.444
*Regulated Pollutant
5603
-------
SECONDARY INDIUM SUBCATEGORY " SECT - XII
THIS PAGE INTENTIONALLY LEFT BLANK
5604
-------
SECONDARY INDIUM SUBCATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the secondary indium subcategory at this
time.
5605
-------
SECONDARY INDIUM SUBCATEGORY "SECT - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
5606
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