United States Effluent Guidelines Division EPA-440/1-84/019-b
Environmental Protection WH-552 July 1984
Agency Washington, D.C. 20460
Water and Waste Management
£EPA Development Proposed
Document for
Effluent Limitations
Guidelines and
Standards for the
Nonferrous Metals
Point Source Category
Phase II
Supplemental Development
Document For:
Primary and Secondary Tin
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DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
PHASE II
Primary and Secondary Tin Supplement
Jack E. Ravan
Assistant Administrator for Water
Edwin L. Johnson
Director
Office of Water Regulations and Standards
tj 5 Environmental Protection Agency
\ /2- 230 Soj.'i Dearborn Street
Chicago, Illinois 60604
Jeffery D. Denit, Director
Effluent Guidelines Division
Ernst P. Hall, P.E., Chief
Metals and Machinery Branch
James R. Berlow, P.E.
Technical Project Officer
July 1984
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Effluent Guidelines Division
Washington, D.C. 20460
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U,S. EnvfRwnrrema! Protection Agency
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PRIMARY AND SECONDARY TIN SUBCATEGORY
TABLE OF CONTENTS
Section Page
I SUMMARY AND CONCLUSIONS 1
II RECOMMENDATIONS 5
BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY 5
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY 10
NSPS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY 15
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY 20
PSNS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY 24
III INDUSTRY PROFILE 29
DESCRIPTION OF PRIMARY AND SECONDARY TIN
PRODUCTION 29
RAW MATERIALS 29
TIN SMELTING 30
ALKALINE DETINNING 30
ELECTROWINNING 31
PRECIPITATION OF TIN HYDROXIDE 31
REDUCTION TO TIN METAL 32
PROCESS WASTEWATER SOURCES 32
OTHER WASTEWATER SOURCES 32
AGE, PRODUCTION, AND PROCESS PROFILE 32
IV SUBCATEGORIZATION 41
FACTORS CONSIDERED IN SUBCATEGORIZATION 41
FACTORS CONSIDERED IN SUBDIVIDING THE PRIMARY
AND SECONDARY TIN SUBCATEGORY 42
OTHER FACTORS 44
PRODUCTION NORMALIZING PARAMETERS 44
V WATER USE AND WASTEWATER CHARACTERISTICS .... 47
WASTEWATER FLOW RATES 48
WASTEWATER CHARACTERISTICS DATA 48
DATA COLLECTION PORTFOLIOS 49
FIELD SAMPLING DATA 49
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PRIMARY AND SECONDARY TIN SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
WASTEWATER CHARACTERISTICS AND FLOWS BY
SUBDIVISION 50
TIN SMELTER S02 SCRUBBER 50
DEALUMINIZING RINSE. 51
TIN MUD ACID NEUTRALIZATION FILTRATE 51
TIN HYDROXIDE WASH 52
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP . . 52
SPENT ELECTROWINNING SOLUTION FROM MUNICIPAL
SOLID WASTE 53
TIN HYDROXIDE SUPERNATANT FROM SCRAP 53
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING
SOLUTIONS 53
TIN HYDROXIDE SUPERNATANT FROM TIN PLATING
SLUDGE SOLIDS 54
TIN HYDROXIDE FILTRATE 54
VI SELECTION OF POLLUTANT PARAMETERS 189
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT
PARAMETERS 189
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT
PARAMETERS SELECTED 189
TOXIC POLLUTANTS 1 91
TOXIC POLLUTANTS NEVER DETECTED 191
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR
ANALYTICAL QUANTIFICATION CONCENTRATION 193
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS
ACHIEVABLE BY TREATMENT 193
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OF
SOURCES 194
TOXIC POLLUTANTS SELECTED FOR FURTHER
CONSIDERATION IN ESTABLISHING LIMITATIONS
AND STANDARDS 196
VII CONTROL AND TREATMENT TECHNOLOGIES 203
CURRENT CONTROL AND TREATMENT PRACTICES 203
TIN SMELTER S0£ SCRUBBER 203
DEALUMINIZING RINSE 204
TIN MUD ACID NEUTPJ^LIZATION FILTRATE 204
TIN HYDROXIDE WASH 204
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP . . 204
SPENT ELECTROWINNING SOLUTION FROM MUNICIPAL
SOLID WASTE 204
ii
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Section
PRIMARY AND SECONDARY TIN SUBCATEGORY
TABLE OF CONTENTS (Continued)
TIN HYDROXIDE SUPERNATANT FROM SCRAP 205
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING
SOLUTIONS 205
TIN HYDROXIDE SUPERNATANT FROM SLUDGE SOLIDS . . 205
TIN HYDROXIDE FILTRATE 205
CONTROL AND TREATMENT OPTIONS 206
OPTION A 206
OPTION C 206
VIII COST OF WASTEWATER TREATMENT AND CONTROL .... 207
TREATMENT OPTIONS FOR EXISTING SOURCES 207
OPTION A 207
OPTION C 207
COST METHODOLOGY 207
NONWATER QUALITY ASPECTS 209
ENERGY REQUIREMENTS 209
SOLID WASTE 209
AIR POLLUTION 211
IX BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE 215
TECHNICAL APPROACH TO BPT 215
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES. . 217
BPT OPTION SELECTION 21 7
WASTEWATER DISCHARGE RATES 219
TIN SMELTER S02 SCRUBBER 21 9
DEALUMINIZING RINSE 219
TIN MUD ACID NEUTRALIZATION FILTRATE 219
TIN HYDROXIDE WASH 220
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP . . 220
SPENT ELECTROWINNING SOLUTION FROM MUNICIPAL
SOLID WASTE 220
TIN HYDROXIDE SUPERNATANT FROM SCRAP 221
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING
SOLUTIONS 221
TIN HYDROXIDE SUPERNATANT FROM SLUDGE SOLIDS . . 221
TIN HYDROXIDE FILTRATE 221
REGULATED POLLUTANT PARAMETERS 222
EFFLUENT LIMITATIONS 222
iii
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PRIMARY AND SECONDARY TIN SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
XI
XII
BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE 231
TECHNICAL APPROACH TO BAT 231
OPTION A 232
OPTION C 232
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES. . 233
POLLUTANT REMOVAL ESTIMATES 233
COMPLIANCE COSTS 233
BAT OPTION SELECTION 234
WASTEWATER DISCHARGE RATES 234
REGULATED POLLUTANT PARAMETERS 235
EFFLUENT LIMITATIONS 236
NEW SOURCE PERFORMANCE STANDARDS 247
TECHNICAL APPROACH TO NSPS 247
OPTION A 247
OPTION C 248
NSPS OPTION SELECTION 248
REGULATED POLLUTANT PARAMETERS 248
NEW SOURCE PERFORMANCE STANDARDS 248
PRETREATMENT STANDARDS 255
TECHNICAL APPROACH TO PRETREATMENT 255
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES. . 256
PRETREATMENT STANDARDS FOR EXISTING AND NEW
SOURCES 256
OPTION A 256
OPTION C 256
PSNS AND PSES OPTION SELECTION 257
REGULATED POLLUTANT PARAMETERS 257
PRETREATMENT STANDARDS 257
XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY .
273
iv
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PRIMARY AND SECONDARY TIN SUBCATEGORY
LIST OF TABLES
Number Page
III-1 INITIAL OPERATING YEAR (RANGE) SUMMARY OF
PLANTS IN THE PRIMARY AND SECONDARY TIN
SUBCATEGORY BY DISCHARGE TYPE 34
III-2 PRODUCTION RANGES FOR PRIMARY AND SECONDARY
TIN PLANTS FOR 1982 35
III-3 SUMMARY OF PRIMARY AND SECONDARY TIN
SUBCATEGORY PROCESSES AND ASSOCIATED
WASTE STREAMS 36
V-1 WATER USE AND DISCHARGE RATES TIN SMELTER S0£
SCRUBBER 55
V-2 WATER USE AND DISCHARGE RATES DEALUMINIZING
RINSE 56
V-3 WATER USE AND DISCHARGE RATES TIN MUD ACID
NEUTRALIZATION FILTRATE 57
V-4 WATER USE AND DISCHARGE RATES TIN HYDROXIDE
WASH 58
V-5 WATER USE AND DISCHARGE RATES SPENT ELECTRO-
WINNING SOLUTION FROM NEW SCRAP 59
V-6 WATER USE AND DISCHARGE RATES SPENT ELECTRO-
WINNING SOLUTION FROM MUNICIPAL SOLID WASTE. . . 60
V-7 WATER USE AND DISCHARGE RATES TIN HYDROXIDE
SUPERNATANT FROM SCRAP 61
V-8 WATER USE AND DISCHARGE RATES TIN HYDROXIDE
SUPERNATANT FROM SPENT PLATING SOLUTIONS .... 62
V-9 WATER USE AND DISCHARGE RATES TIN HYDROXIDE
SUPERNATANT FROM SLUDGE SOLIDS 63
V-10 WATER USE AND DISCHARGE RATES TIN HYDROXIDE
FILTRATE 64
V-11 SPENT ELECTROWINNING SOLUTION RAW WASTEWATER
SAMPLING DATA 65
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PRIMARY AND SECONDARY TIN SUBCATEGORY
LIST OF TABLES (Continued)
Number Page
V-12 TIN HYDROXIDE PRECIPITATION SUPERNATANT (FROM
SCRAP) RAW WASTEWATER SAMPLING DATA 85
V-13 TIN HYDROXIDE PRECIPITATION SUPERNATANT (FROM
SPENT PLATING SOLUTION AND SLUDGES) RAW
WASTEWATER SAMPLING DATA 96
V-14 TIN HYDROXIDE FILTRATE RAW WASTEWATER
SAMPLING DATA 112
V-15 MUD POND SUPERNATANT RAW WASTEWATER SAMPLING
DATA 123
V-16 ELECTROWINNING SOLUTION AFTER CHLORINATION -
PLANT C TREATED WASTEWATER SAMPLING DATA .... 134
V-17 ELECTROWINNING SOLUTION AFTER CHLORINATION AND
NEUTRALIZATION - PLANT C TREATED WASTEWATER
SAMPLING DATA 144
V-18 ELECTROWINNING SOLUTION AFTER CHLORINATION,
NEUTRALIZATION, AND SEDIMENTATION - PLANT C
TREATED WASTEWATER SAMPLING DATA 154
V-19 FINAL EFFLUENT - PLANT C TREATED WASTEWATER
SAMPLING DATA 164
V-20 ELECTROWINNING SOLUTION AFTER CARBONATION -
PLANT D TREATED WASTEWATER SAMPLING DATA .... 174
VI-1 FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS
PRIMARY AND SECONDARY TIN SUBCATEGORY
RAW WASTEWATER 199
VII1-1 COST OF COMPLIANCE FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY DIRECT DISCHARGERS . . 212
VIII-2 COST OF COMPLIANCE FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY INDIRECT DISCHARGERS . 213
IX-1 BPT WASTEWATER DISCHARGE RATES FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY 223
vi
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PRIMARY AND SECONDARY TIN SUBCATEGORY
LIST OF TABLES (Continued)
Number Page
IX-2 BPT MASS LIMITATIONS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY 224
X-1 PRIMARY AND SECONDARY TIN SUBCATEGORY POLLUTANT
REMOVAL ESTIMATES DIRECT DISCHARGERS 237
X-2 COST OF COMPLIANCE FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY DIRECT DISCHARGERS 238
X-3 BAT WASTEWATER DISCHARGE RATES FOR THE PRIMARY
AND SECONDARY TIN SUBCATEGORY 239
X-4 BAT MASS LIMITATIONS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY 240
XI-1 NSPS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY 249
XI-2 NSPS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY 250
XI1-1 PRIMARY AND SECONDARY TIN SUBCATEGORY POLLUTANT
REMOVAL ESTIMATES INDIRECT DISCHARGERS 259
XII-2 COST OF COMPLIANCE FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY INDIRECT DISCHARGERS 260
XII-3 PSES AND PSNS WASTEWATER DISCHARGE RATES FOR
THE PRIMARY AND SECONDARY TIN SUBCATEGORY. ... 261
XII-4 PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY 262
XI1-5 PSNS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY 267
vii
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PRIMARY AND SECONDARY TIN SUBCATEGORY
LIST OF FIGURES
Number Page
III-1 PRIMARY TIN PRODUCTION PROCESS 37
III-2 SECONDARY TIN PRODUCTION PROCESSES 38
III-3 GEOGRAPHIC LOCATIONS OF THE PRIMARY AND
SECONDARY TIN SUBCATEGORY PLANTS 39
V-1 SAMPLING SITES AT SECONDARY TIN PLANT A 184
V-2 SAMPLING SITES AT SECONDARY TIN PLANT B 185
V-3 SAMPLING SITES AT SECONDARY TIN PLANT C 186
V-4 SAMPLING SITES AT SECONDARY TIN PLANT D 187
IX-1 BPT TREATMENT SCHEME 229
X-1 BAT TREATMENT SCHEME FOR OPTION A 245
X-2 BAT TREATMENT SCHEME FOR OPTION C 246
IX
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION I
SUMMARY AND CONCLUSIONS
Pursuant to Sections 301, 304, 306, 307, and 501 of the Clean
Water Act and the provisions of the Settlement Agreement in
Natural Resources Defense Council v. Train, 8 ERC 2120 (D.D.C.
1976) modified, 12 ERC 1833 (D.D.C. 1979), EPA has collected and
analyzed data for plants in the primary and secondary tin
subcategory. EPA has never proposed or promulgated effluent
limitations or standards for this subcategory. This document and
the administrative record provide the technical' basis for
proposing 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).
The primary and secondary tin subcategory is comprised of twelve
plants. Of the twelve plants, three discharge directly to
rivers, lakes, or streams/ two discharge to publicly owned
treatment works (POTW); and seven achieve zero discharge of
process wastewater.
EPA first studied the primary and secondary tin 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 (1) the
sources and volume of water used, the processes used, and the
sources of pollutants and wastewaters in the plant; and (2) the
constituents of wastewaters, including toxic pollutants. As a
result, ten subdivisions have been identified for this
subcategory that warrant separate effluent limitations. These
include:
Tin smelter S02 scrubber,
Dealuminizing rinse,
Tin mud acid neutralization filtrate,
Tin hydroxide wash,
Spent electrowinning solution from new scrap,
Spent electrowinning solution from municipal solid
waste,
Tin hydroxide supernatant from scrap,
Tin hydroxide supernatant from spent plating solutions,
Tin hydroxide supernatant from sludge solids, and
Tin hydroxide filtrate.
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EPA also identified several distinct control and treatment
technologies (both in-plant and end-of-pipe) applicable'to the
primary and secondary tin 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
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 Proposed Effluent Limitations Guidelines and
Standards for the Nonferrous Smelting and Refining 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.
Steam stripping was selected as the technology basis for ammonia
limitations and cyanide precipitation was selected as the basis
for cyanide limitations. To meet the BPT effluent limitations
based on this technology, the primary and secondary tin
subcategory is expected to incur capital and annual costs.
However, these costs are not presented here because they are
based on information claimed to be confidential.
For BAT, the Agency has built upon the BPT technology basis by
adding filtration as an effluent polishing step to the
end-of-pipe treatment scheme. To meet the BAT effluent
limitations based on this technology, the primary and secondary
tin subcategory is estimated to incur capital and annual costs.
However, these costs are not presented here because the data on
which they are based has been claimed to be confidential.
NSPS, which are based on best demonstrated technology, are
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.
However, the technology basis of BAT has been determined as the
best demonstrated technology for this subcategory.
The technology basis for PSES is equivalent to BAT. To meet the
pretreatment standards for existing sources, the primary and
secondary tin subcategory is estimated to incur a capital cost of
$341,700 and an annual cost of $119,900. For PSNS, the Agency
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selected end-of-pipe treatment and in-process flow reduction
control techniques equivalent to NSPS.
The mass limitations and standards for BPT, BAT, NSPS, PSES and
PSNS are presented in Section II.
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION II
RECOMMENDATIONS
1 . EPA has divided the primary and secondary tin subcategory
into ten subdivisions for the purpose of effluent limitations and
standards. These subdivisions are:
(a) Tin smelter S02 scrubber,
(b) Dealuminizing rinse,
(c) Tin mud acid neutralization filtrate,
(d) Tin hydroxide wash,
(e) Spent electrowinning solution from new scrap,
(f) Spent electrowinning solution from municipal solid waste
(g) Tin hydroxide supernatant from scrap,
(h) Tin hydroxide supernatant from spent plating solutions,
(i) Tin hydroxide supernatant from sludge solids, and
(j) Tin hydroxide filtrate.
2. BPT is proposed based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology, along with preliminary treatment consisting
of ammonia steam stripping and cyanide precipitation for selected
waste streams. The following BPT limitations are proposed:
BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 62.190 27.740
Lead 9.102 4.334
Nickel 41.610 27.520
Cyanide (total) 6.284 2.600
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 106.600 47.240
Total suspended 888.500 422.600
solids
pH Within the range of 7.5 to 10.0
at all times
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BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(b) Dealuminizing Rinse
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of dealurninized scrap produced
Antimony 0.101 0.045
Lead 0.015 0.007
Nickel 0.067 0.044
Cyanide (total) 0.010 0.004
Ammonia (as N) 4.666 2.051
Fluoride 1.225 0.700
Tin 0.172 0.076
Total suspended 1.435 0.683
solids
pH Within the range of 7.5 to 10.0
at all times
BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of neutralized dewatered tin
mud produced
Antimony 14.490 6.460
Lead 2.120 1.010
Nickel 9.690 6.410
Cyanide (total) 1.464 0.606
Ammonia (as N) 672.800 295.800
Fluoride 176.700 101.000
Tin. 24.830 11.000
Total suspended 206.900 98.420
solids
pH Within the range of 7.5 to 10.0
at all times
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BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(d) Tin Hydroxide Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony 34.310 15.300
Lead 5.020 2.391
Nickel 22.950 15.180
Cyanide (total) 3.466 1.434
Ammonia (as N) 1,593.000 700.400
Fluoride 418.400 239.100
Tin 58.810 26.058
Total suspended 490.100 233.100
solids
pH Within the range of 7.5 to 10.0
at all times
BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 48.220 21.510
Lead 7.056 3.360
Nickel 32.260 21.340
Cyanide (total) 4.872 2.016
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 82.660 36.620
Total suspended 688.800 327.600
solids
pH Within the range of 7.5 to 10.0
at all times
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BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as
raw material
Antimony 0.342 0,152
Lead 0.050 0.024
Nickel 0.229 0.151
Cyanide (total) 0.035 0.014
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.585 0.259
Total suspended 4.879 2.321
solids
pH Within the range of 7.5 to 10.0
at all times
BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly' Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 159.700 71.220
Lead 23.370 11.130
Nickel 106.800 70.660
Cyanide (total) 16.140 6.677
Ammonia (as N) 7,417.000 3,261.000
Fluoride 1,948.000 1,113.000
Tin 273.700 121.300
Total suspended 2,281.000 1,085.000
solids
pH Within the range of 7.5 to 10.0
at all times
8
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BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from spent
plating solutions
Antimony 109.000 48.610
Lead 15.950 7.596
Nickel ' 72.920 48.230
Cyanide (total) 11.010 4.557
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 186.900 82.790
Total suspended 1,557.000 740.600
solids
pH Within the range of 7.5 to 10.0
at all times
BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 477.500 213.000
Lead 69.870 33.270
Nickel 319.400 211.300
Cyanide (total) 48.240 19.960
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 818.500 362.700
Total suspended 6,821.000 3,244.000
solids
pH Within the range of 7.5 to 10.0
at all times
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BPT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 71.880 32.060
Lead 10.520 5.009
Nickel 48.090 31.810
Cyanide (total) 7.263 3.005
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 123.200 54.600
Total suspended 1,027.000 488.400
solids
pH Within the range of 7.5 to 10.0
at all times
3. BAT is proposed based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology along
with preliminary treatment consisting of ammonia steam stripping
and cyanide precipitation for selected waste streams. The
following BAT effluent limitations are proposed:
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
10
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BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(b) Dealuminizing Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
0,
0,
0,
0,
4,
1
0.
068
010
019
0070
666
225
115
0,
0,
0,
0,
2,
0,
0,
030
005
013
0028
051
700
051
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million
mud produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Ibs) of neutralized dewatered tin
9
1 ,
2,
1 ,
672,
176,
16,
741
413
776
009
800
700
550
4.341
" 0.656
1 .868
0.404
295.800
101.000
7.370
1 1
-------
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(d) Tin Hydroxide Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony 23.070 10.280
Lead 3.347 1.554
Nickel 6.574 4.423
Cyanide (total) 2.391 0.956
Ammonia (as N) 1,593.000 700.400
Fluoride 418.400 239.100
Tin 39.210 17.450
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 14.450
Lead 4.704 2.184
Nickel 9.240 "6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 55.100 24.530
12
-------
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
ing/kg (Ib/million Ibs) of MSW scrap used as
raw material
Antimony 0.230 0.102
Lead 0.033 0.015
Nickel 0.065 0.044
Cyanide (total) 0.0238 0.0095
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.390 0.174
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 107.400 47.850
Lead 15.580 7.233
Nickel 30.600 20.590
Cyanide (total) 11.130 4.451
Ammonia (as N) 7,417.000 3,261.000
Fluoride 1,948.000 1,113.000
Tin 182.500 81.230
13
-------
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from spent
plating soultions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 124.600 55.450
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 321.100 143.100
Lead 46.580 21.630
Nickel 91.500 61.560
Cyanide (total) 33.270 13.310
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 545.700 242.900
14
-------
BAT LIMITATIONS FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
to
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
4. NSPS are based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle and filter) technology, along
with preliminary treatment consisting of ammonia steam stripping
and cyanide precipitation for selected waste streams. The
following effluent standards are proposed for new sources:
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
Total suspended 325.100 260.100
solids
pH Within the range of 7.5 to 10.0
at all times
15
-------
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(b) Dealuminizing Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Total suspended
solids
pH
0.068
0.010
0.019
0.0070
4.666
1 .225
0.115
0.525
0.030
0.005
0.013
0.0028
2.051
0.700
0.051
0.420
Within the range of 7.5 to 10.0
at all times
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million
mud produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Total suspended
solids
PH
Ibs) of neutralized dewatered tin
9,
1 ,
2,
1 ,
672,
176,
16
741
413
776
009
800
700
550
75.710
4.341
0.656
1 .868
0.404
295.800
101.000
7.370
60.570
Within the range of 7.5 to 10.0
at all times
16
-------
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(d) Tin Hydroxide Wash
Pollutant or Maximum for . Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony 23.070 10.280
Lead 3.347 1.554
Nickel 6.574 4.423
Cyanide (total) 2.391 0.956
Ammonia (as N) 1,593.000 700.400
Fluoride 418.400 239.100
Tin 39.210 17.450
Total suspended 179.300 143.500
solids
pH Within the range of 7.5 to 10.0
at all times
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 "14.450
Lead 4.704 2.184
Nickel 9.240 6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 55.100 24.530
Total suspended 252.000 201.600
solids
pH Within the range of 7.5 to 10.0
at all times
17
-------
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as raw material
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Total suspended
solids
pH
0.230
0.033
0.065
0.0238
15.860
4.165
0.390
1 .785
0. 102
0.015
0.044
0.0095
6.973
2.380
0.174
1 .428
Within the range of 7.5 to 10.0
at all times
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Total suspended
solids
pH
7,
1,
107.
15.
30.
1 1 .
417.
948.
182.
400
580
600
130
000
000
500
47
7
20
4
.,261
,113
81
850
233
590
451
000
000
230
834.600
667.700
Within the range of 7.5
at all times
to 10.0
18
-------
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from spent
plating solutions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin . 124.600 55.450
Total suspended 569.700 455.800
solids
pH Within the range of 7.5 to 10.0
at all times
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 321.100 143.100
Lead 46.580 21.630
Nickel 91.500 61.560
Cyanide (total) 33.270 13.310
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 545.700 242.900
Total suspended 2,496.000 1,997.000
solids
pH Within the range of 7.5 to 10.0
•at all times
19
-------
NSPS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
Total suspended 375.700 300.500
solids
pH Within the range of 7.5 to 10.0
at all times
5. PSES are proposed based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle and filter) technology, along
with preliminary treatment consisting of ammonia steam stripping
and cyanide precipitation for selected waste streams. The
following pretreatment standards are proposed for existing
sources:
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
20
-------
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(b) Dealuminizing Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
0,
0,
0,
0,
4,
1 ,
0,
068
010
019
0070
666
225
115
0,
0,
0,
0,
2,
0,
0,
030
005
013
0028
051
700
051
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg {Ib/million Ibs) of neutralized dewatered tin
mud produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
9.741
1 .413
2.776
1 .009
672.800
176.700
16.550
4.341
0.656
1 .868
0.404
295.800
101.000
7.370
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(d) Tin Hydroxide Wash
Pollutant or
Pollutant Property
Maximum for
Any One Day
• Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
23.070
3.347
6.574
2.391
1,593.000
418.400
39.210
10.280
1.554
4.423
0.956
700.400
239.100
17.450
21
-------
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 14.450
Lead 4.704 2.184
Nickel 9.240 6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride • 588.000 336.000
Tin 55.100 24.530
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as raw material
Antimony 0.230 0.102
Lead 0.033 . 0.015
Nickel 0.065 0.044
Cyanide (total) 0.0238 " 0.0095
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.390 0.174
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 107.400 47.850
Lead 15.580 7.233
Nickel 30.600 20.590
Cyanide (total) 11.130 4.451
Ammonia (as N) 7,417.000 3,261.000
Fluoride 1,948.000 1,113.000
Tin 182.500 81.230
22
-------
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or ' Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/mill
spent plating
Antimony
Lead
Nickel
Cyanide
Ammon i a
Fluoride
Tin
(
(
ion Ibs) of tin metal
solutions
total)
as
N)
5,
1,
73.
10.
20.
7.
062.
329.
124.
300
640
890
596
000
000
600
recovered
32.
4.
14.
3.
2,226.
759.
55.
from
660
937
050
038
000
600
450
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
sludge solids
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Ibs) of tin metal
321.100
46.580
91.500
33.270
22,180.000
5,823.000
545.700
recovered from
143.100
"21 .630
61 .560
13.310
9,749.000
3,327.000
242.900
PSES FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
23
-------
6. PSNS are proposed based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle and filter) technology, along
with preliminary treatment consisting of ammonia steam stripping
and cyanide precipitation for selected waste streams. The
following pretreatment standards are proposed for new sources.
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(b) Dealuminizing Rinse
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony 0.068 0.030
Lead 0.010 0.005
Nickel ' 0.019 0.013
Cyanide (total) 0.0070 0.0028
Ammonia (as N) 4.666 2.051
Fluoride 1.225 0.700
Tin 0.115 0.051
24
-------
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of neutralized dewatered tin
mud produced
Antimony 9.741 4.341
Lead 1.413 0.656
Nickel 2.776 1.868
Cyanide (total) 1.009 0.404
Ammonia (as N) 672.800 295.800
Fluoride 176.700 101.000
Tin 16.550 7.370
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(d) Tin Hydroxide Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony 23.070 10.280
Lead 3.347 1.554
Nickel 6.574 4.423
Cyanide (total) 2.391 0.956
Ammonia (as N) 1,593.000 700.400
Fluoride 418.400 239.100
Tin 39.210 17.450
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or . Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 14.450
Lead 4.704 2.184
Nickel 9.240 6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 55.100 24.530
25
-------
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as
raw material
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
0.230
0.033
0.065
0.0238
15.860
4.165
0.390
0.102
0.015
0.044
0.0095
6.973
2.380
0.174
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
107,
15,
30,
11 ,
7,417,
1 ,948
400
580
600
130
000
000
182.500
47,
7,
20
4
3,261
1,113
81
850
233
590
451
000
000
230
26
-------
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
spent plating solutions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 124.600 55.450
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 321.100 143.100
Lead 46.580 "21.630
Nickel 91.500 61.560
Cyanide (total) 33.270 13.310
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 545.700 242.900
27
-------
PSNS FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
28
-------
PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION III
INDUSTRY PROFILE
This section of the primary and secondary tin supplement
describes the raw materials and processes used in the production
of primary and secondary tin and presents a profile of the
primary and secondary tin plants identified in this study. A
discussion of the purpose, authority and methodology for this
study, and a general description of the nonferrous metals
manufacturing category is presented in Section III of the General
Development Document.
The largest total use of tin is in solders which are manufactured
from both primary tin and secondary tin. The low melting point
of tin (232°C) makes it ideal for this application. Tin plated
steel products represent the second largest use of tin. Only
primary tin is used for this application.
Tin is also used in a number of alloys including brass, bronze,
and white metal alloys including babbit. White metal alloys are
low melting point alloys consisting primarily of tin or lead.
These alloys may also contain lesser amounts of copper, zinc and
antimony and are used primarily in bearings.
DESCRIPTION OF PRIMARY AND SECONDARY TIN PRODUCTION
Primary tin is . produced by smelting tin concentrates with
limestone and coke. The crude tin is then electrolytically
refined and cast. The process is presented schematically in
.Figure III-l .
Secondary tin may also be produced by smelting tin residues,
particularly detinners mud from secondary tin recovery
operations. Most secondary tin, however, is produced by
dissolving tin from tin plated steel scrap, and recovering the
tin by electrowinning. Tin may also be recovered from solution
by precipitation of tin as tin hydroxide, Sn(OH)4. A smaller
amount of secondary tin is recovered from tin plating sludges
which are generated by tin plated steel production operations.
Secondary tin production can be divided into four major
operations: alkaline detinning, electrowinning, tin hydroxide
precipitation, and reduction to tin metal. These operations are
shown schematically in Figure III-2.
RAW MATERIALS
Tin concentrates used in primary tin production are produced as a
by-product from molybdenum mining operations in Colorado or from
gold placer mining operations in Alaska.
29
-------
The principal raw material for the secondary tin industry is tin
plated steel scrap. Virtually all of this scrap comes from
fabrication plants which produce cans and a variety of other tin
plated steel products. Such scrap may include punched sheets,
rolls and bundles. One producer also reported tin recovery from
tin plated steel separated from municipal solid waste. Two
producers reported that they recovered tin from spent tin
electroplating solutions and plating sludges.
TIN SMELTING
There is currently one tin smelter in the United States. Tin
concentrates and residues are smelted in a reverbertory furnace
with limestone and coke at 1200 to 1300°C. Sulfur dioxide
emissions from the smelting furnace are controlled with a caustic
scrubber. Crude molten tin is removed from the furnace, fire
refined and cast into anodes. The anodes are consumed in an
electrolytic refining process and the purified tin is cast into
ingots.
ALKALINE PETINNING
The first step in recovering tin from tin plated scrap is hot
alkaline detinning. Tin plated scrap is loaded into perforated
steel detinning baskets and placed in a detinning tank which
contains a solution of sodium hydroxide and sodium nitrate. The
solution is heated to near the boiling point and the tin
dissolves into solution as sodium stannate, Na2Sn03. The
chemical reaction (not balanced) is as follows:
Sn + NaN03 + NaOH + H20 —> Na2Sn03 . H20 + NH3 + N2
The detinning cycle is complete after 4 to 12 hours. Scrap
containing aluminum is pretreated in a solution of sodium
hydroxide, in which the aluminum dissolves. After rinsing, the
dealuminized scrap is sent to the detinning tanks.
There are two variations of the alkaline detinning process: the
saturated process and the unsaturated process. In the saturated
process, the sodium stannate solution is allowed to become
supersaturated and sodium stannate crystals precipitate from
solution. The sodium stannate is recovered from the solution in
a filter press and the solution is returned to the detinning
tanks. The sodium stannate filter cake may then be sold as a
product or redissolved in water for further processing or
electrowinning.
In the unsaturated process, the sodium stannate concentration in
the solution is kept below the saturation point and the solution
is pumped directly to further processing or electrowinning. In
both the saturated and the unsaturated process, the sodium
stannate solution is purified by adding sodium sulfide, Na2S or
30
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sodium hydrosulfide, NaHS, to precipitate lead and other metal
impurities as insoluble metal sulfides. The precipitated residue
is called tin mud or detinners mud and is sold to tin smelters.
Detinners mud may also include residues removed from the bottoms
of detinning tanks. This mud contains 3 to 5 percent tin and is
sold as a by-product to tin smelters. The tin mud is usually
rinsed to recover any soluble tin which may be present. The
rinse water is recycled to the detinning tanks. One producer
reported an acid neutralization step in which sulfuric acid is
added to the mud. The neutralized mud is then dewatered in a
filter press and sold as a by-product containing approximately 10
percent tin.
When the detinning cycle is complete, the detinned steel is
removed from the detinning tanks. The steel is then rinsed to
recover any tin solution which may be adhering to it, pressed or
baled, and sold as a product. The rinse water is recycled to the
detinning tanks to recover tin.
ELECTROWINNING
The purified sodium stannate solution is sent to electrolytic
cells where pure tin metal is deposited onto cathodes. The tin
is then removed from the cathodes, melted and cast. The
electrowinning solution is then recycled to the detinning tanks.
A blowdown stream must periodically be discharged from the
electrowinning circuit in order to control the concentration of
aluminum, carbonates, and other impurities in the solution.
One producer reported the use of tin hydroxide, Sn(OH)4/ as a raw
material. The tin hydroxide is first washed with water and then
dissolved in a solution of sodium hydroxide. The resultant
sodium stannate solution is then purified and added to the sodium
stannate solution from alkaline detinning and the combined
solution enters the electrowinning tanks.
PRECIPITATION OF TIN HYDROXIDE
As an alternative to electrowinning, tin can be recovered from
solution as tin hydroxide, Sn(OH)4. Sulfuric acid is added to
lower the pH to 7 and sodium carbonate is then added to raise the
pH to 7.8. At this point tin hydroxide will precipitate from the
solution. One plant which uses this process precipitates tin
from a solution which is a mixture of alkaline detinning solution
and a solution generated by dissolving tin electroplating sludge
in water. The other plant which precipitates tin hydroxide uses
spent tin electroplating solution as a raw material and
facilitates precipitation throuch the addition of ammonia.
31
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REDUCTION TO TIN METAL
The tin hydroxide is dried and calcined in a furnace to produce
tin dioxide, Sn02. The tin dioxide is then charged to a
reduction furnace with carbon where it is reduced to tin metal.
PROCESS WASTEWATER SOURCES
Although a variety of processes are involved in primary and
secondary tin production, the process wastewater sources can be
subdivided as follows:
1. Tin smelter S02 scrubber
2. Dealuminizing rinse,
3. Tin mud acid neutralization filtrate,
4. Tin hydroxide wash,
5. Spent electrowinning solution from new scrap,
6. Spent electrowinning solution from municipal solid waste
7. Tin hydroxide supernatant from scrap,
8. Tin hydroxide supernatant from spent plating solutions
9. Tin hydroxide supernatant from sludge solids, and
10. Tin hydroxide filtrate.
OTHER WASTEWATER SOURCES
There are other waste streams associated with the primary and
secondary tin subcategory. These streams include, but are not
limited to:
1. Noncontact cooling water,
2. Stormwater runoff, and
3. Maintenance and cleanup water.
These waste streams are not considered as a part of this
rulemaking. EPA believes that the flows and pollutant loadings
associated with these waste streams are insignificant relative to
the waste streams selected, or are best handled by the
appropriate permit authority on a case-by-case basis under
authority of Section 403 of the Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
Table III-l shows the relative age and discharge status of the
primary and secondary tin plants. the average plant age is
between 16 and 25 years. All of the plants have been built since
1940. Table III-2 shows the 1982 production for primary and
secondary tin. The 11 secondary tin plants have production
levels less than 1,000 kkg/yr. The only primary tin producer has
a production level between 1,000 and 5,000 kkg/yr from both
primary and secondary materials.
Table III-3 provides a summary of the number of plants with the
various production processes and the number of plants which
32
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generate wastewater from each process. The one plant which
practices tin smelting is the only domestic primary tin producer.
Alkaline detinning is practiced by 10 of the 11 secondary tin
plants. Of these 10 plants, eight also practice electrowinning.
Figure II1-3 shows the geographic locations of the primary and
secondary tin facilities in the United States by discharge
status.
33
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Table III-2
PRODUCTION RANGES FOR PRIMARY AND SECONDARY TIN
PLANTS FOR 1982
Discharge 0-100 100-1,000 1,000-5,000
Type (kkg/yr) (kkg/yr) (kkg/yr) Total
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35
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PRIMARY TIN PRODUCTION PROCESS
37
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION IV
SUBCATEGORIZATION
As discussed in Section IV of the General Development Document,
the nonferrous metals manufacturing category has been
subcategorized to take into account pertinent industry
characteristics, manufacturing process variations, and a number
of other factors which affect the ability of the facilities to
achieve effluent limitations. This section summarizes the
factors considered during the designation of the primary and
secondary tin subcategory and its related subdivisions.
FACTORS CONSIDERED IN SUBCATEGORIZATION
The following factors were evaluated for use in subcategorizing
the nonferrous metals manufacturing category:
1. Metal products, co-products, and by-products;
2. Raw materials;
3. Manufacturing processes;
4. Product form;
5. Plant location;
6. Plant age;
7. Plant size;
8. Air pollution control methods
9. Meteorological conditions;
10. Treatment costs;
11. Nonwater quality aspects;
12. Number of employees;
13. Total energy requirements; and
14. Unique plant characteristics.
Evaluation of all factors that could warrant subcategorization
resulted in the designation of the primary and secondary tin
subcategory. Three factors were particularly important in
establishing these classifications: the type of metal produced,
the nature of raw materials used, and the manufacturing processes
involved.
In Section IV of the General Development Document, each of these
factors is described, and the rationale for selecting metal
product, manufacturing process, and raw materials as the
principal factors used for subcategorization is discussed. On
this basis, the nonferrous metals manufacturing (phase II)
category was divided into 21 subcategories, one of them being
primary and secondary tin.
41
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FACTORS CONSIDERED IN. SUBDIVIDING THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
The factors listed previously were each evaluated when
considering subdivision of the primary and secondary tin
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 primary
and secondary tin 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 tin 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:
1. Tin smelter S02 scrubber,
2. Dealuminizing rinse,
3. Tin mud acid neutralization filtrate,
4. Tin hydroxide wash,
5. Spent electrowinning solution fron new scrap,
6. Spent electrowinning solution from municipal solid waste,
7. Tin hydroxide supernatant from scrap,
8. Tin hydroxide supernatant from spent plating solutions.
9. Tin hydroxide supernatant from sludge solids, and
10. Tin hydroxide filtrate.
These subdivisions follow directly from differences with-in the
five distinct production processes which may be used in the
production of primary or secondary tin: tin smelting, alkaline
detinning, electrowinning, precipitation and reduction.
The smelting of tin gives rise to the first subdivision. The
control of sulfur dioxide emissions from smelter flue gases is
accomplished through the use of a wet caustic scrubbing system.
Slowdown of caustic scrubbing solution comprises the wastewater
stream associated with this subdivision.
Although alkaline detinning is a net consumer of water because of
evaporation losses, a number of wastewater streams may be
generated. When tin scrap containing aluminum is used, the scrap
is leached with a sodium hydroxide solution prior to entering the
detinning tanks. The aluminum dissolves in the caustic solution
and the scrap is then rinsed with water. The spent caustic
leaching solution and rinse water are discharged as a waste
stream.
Another wastewater stream associated with alkaline detinning is
tin mud acid neutralization filtrate. Tin mud may consist of
42
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residues from the detinning tanks, precipitates formed when
sodium sulfide or sodium hydrosulfide is added to the sodium
stannate solution to precipitate base metal impurities, or a
combination of the two. This "detinners mud" typically contains
from 3 to 5 percent tin by weight. The mud is rinsed with fresh
water to recover soluble tin compounds which are returned to the
detinning tanks. The rinsed mud is filtered and eventually sold
to smelters. One producer neutralizes this mud with sulfuric
acid prior to dewatering in a pressure filter. The filtrate
cannot be returned to the detinning tanks and is therefore
discharged as a waste stream. The mud has been upgraded to a
product that is approximately 10 percent tin.
Electrowinning is the principal means of recovering tin from the
sodium stannate solution which is generated in alkaline detinning
operations. One producer reported the use of tin hydroxide as an
additional raw material to the electrowinning solution. Prior to
being dissolved in the sodium stannate solution the tin hydroxide
is washed with water to remove impurities. The wash water is
then discharged as a wastewater stream. The most significant
wastewater stream associated with electrowinning is spent
electrowinning solution. The partially depleted sodium stannate
solution is recycled to the detinning tanks where additional tin
is taken into solution. A bleed stream is required, however, in
order to control the buildup of impurities, particularly aluminum
and carbonates, in the solution. This bleed stream comprises a
wastewater stream associated with the electrowinning operation.
When municipal solid waste is used as a raw material to alkaline
detinning operations, a much larger discharge of spent
electrowinning solution results. This larger blowdown stream is
necessitated by impurities which are introduced into the sodium
stannate solution by the raw material. Consequently, spent
electrowinning solution from municipal solid waste processing is
identified as a separate subdivision.
As an alternative to electrowinning, tin may be precipitated from
solution as tin hydroxide. The tin hydroxide sludge is dewatered
in a filter press, dried and sold or calcined to tin oxide in a
furnace, and reduced with carbon in a reduction furnace to
produce tin metal. The supernatant and filtrate streams
associated with tin hydroxide precipitation comprise wastewater
streams associated with this operation.
The flow rates and characteristics of the tin hydroxide
supernatant stream vary significantly depending on the raw
materials used. Because of this, separate subdivisions have been
identified for tin hydroxide supernatant from each of the three
possible raw materials: tin plated steel scrap, spent plating
solutions, and tin plating sludge solids. Tin hydroxide filtrate
from dewatering the precipitated tin hydroxide is also designated
as a separate subdivision.
43
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OTHER FACTORS
The other factors considered in this evaluation either support
the establishment of the 10 subdivisions or were shown to be
inappropriate bases 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 tin product, intermediate
or raw material processed will be used as the PNP. Thus, the
PNPs for the ten subdivisions are as follows:
Subdivision
1. Tin smelter S02 scrubber
2. Dealuminizing rinse
3. Tin mud acid neutralization
filtrate
4. Tin hydroxide wash
5. Spent electrowinning solution
from new scrap
6. Spent electrowinning
solution from municipal
solid waste
7. Tin hydroxide supernatant from
scrap
8. Tin hydroxide supernatant from
PNP
kkg of tin metal produced
kkg of dealuminized scrap
produced
kkg of neutralized, dewatered
tin mud produced
kkg of tin hydroxide washed
kkg of cathode tin produced
kkg of MSW scrap
used as raw material
kkg of tin metal recovered
from scrap
kkg of tin metal recovered
44
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spent plating solutions from spent plating solutions
9. Tin hydroxide supernatant from kkg of tin metal recovered
sludge solids from sludge solids
10. Tin hydroxide filtrate kkg of tin metal produced
45
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the primary and secondary tin 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.
Section V of the General Development Document contains a detailed
description of the data sources and methods of analysis used to
characterize wastewater from the nonferrous metals manufacturing
category. To summarize this informaiton breifly, two principal
data sources were used; 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 and
secondary tin plants, a field sampling program was conducted. A
complete list of the pollutants considered and a summary of the
techniques used in sampling and laboratory analyses are included
in Section V of the General Development Document. 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 wastewater in the
primary and secondary tin subcategory. In general, the samples
were anlayzed for cyanide and three classes of pollutants: toxic
organic pollutants, toxic metal pollutants, and criteria
pollutants (which includes both conventional and nonconventional
pollutants).
As described in Section IV of this supplement, the primary and
secondary tin subcategory has been split into 10 subdivisions or
wastewater sources, so that the proposed regulation contains mass
discharge limitations and standards for 10 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. Tin smelter S02 scrubber,
2. Dealuminizing rinse,
3. ' Tin mud acid neutralization filtrate,
47
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4. Tin hydroxide wash,
5. Spent eleetrowinning solution from new scrap,
6. Spent electrowinning solution from municipal solid waste,
7. Tin hydroxide supernatant from scrap,
8. Tin hydroxide supernatant from spent plating solutions,
9. Tin hydroxide supernatant from sludge solids, and
10. Tin hydroxide filtrate.
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 the calculation. Water
use is defined as the volume of water or other fluid required for
a given process per mass of tin product and is therefore based on
the sum of recycle and make-up flows to a given process to
further treatment, disposal, or discharge per mass of tin
produced. Differences between the water use and wastewater flows
associated with a given stream result from recycle, evaporation,
and carryover 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, tin smelter S02 scrubber water flow is related to the
production of tin metal. As such, the discharge rate is
expressed in liters of scrubber water per metric ton of tin
produced (gallons of scrubber water per ton of tin metal).
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-1 through V-10 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 X, XI, and XII
where representative 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
primary and secondary tin production come from two sources—data
collection portfolios and analytical data from field sampling
trips.
48
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DATA COLLECTION PORTFOLIOS
In the data collection portfolios, the tin plants that discharge
wastewater were asked to specify the presence or absence -of toxic
pollutants in their wastewater. Three of the five discharging
plants responded. The responses are summarized below:
Pollutant Known Present Believed Present
antimony 1 2
arsenic 1 0
cadmium 1 0
chromium 1 0
copper 1 1
cyanide 1 0
lead 1 1
mercury 0 1
nickel 2 0
selenium 0 1
silver 1 0
zinc 1 1
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from primary and secondary tin plants, wastewater
samples were collected at four plants, which represent one-third
of the primary and secondary tin plants in the United States.
Diagrams indicating the sampling sites and contributing
production processes are shown in Figures V-l through V-4 (at the
end of this section).
Raw wastewater data are summarized in Tables V-l1 through V-l5
(at the end of this section). Data from samples of treated and
partially treated wastewater streams are presented in Tables V-l6
through V-20. Notfe that the stream numbers listed in the tables
correspond to those given in individual plant sampling site
diagrams. Figures V-l through V-4. Where no data are listed for
a specific day of sampling, the wastewater samples for the stream
were not collected.
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.
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.
49
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Second, 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
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.
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. 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
one of these pollutants is reported as not detected, it is
assigned a value of zero in calculating the average. Finally,
toxic metal values reported as less than a certain value were
considered as below quantification, 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 primary and secondary tin production involves 10 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 also be
discussed.
TIN SMELTER SO, SCRUBBER
There is one facility which produces tin metal tnrough the
smelting of tin concentrates and residues. This facility
reported the use of a wet scrubbing system to control S02
emissions in the smelter flue gas. The scrubber uses a
50
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recirculating caustic solution. A portion of the solution must
be discharged in order to maintain effective S02 removal. The
water use and wastewater discharge rates for this stream are
shown in liters per metric ton of tin metal produced in Table
V-l .
The one facility reporting this stream is a direct discharger
after treatment consisting of chemical precipitation and
sedimentation. There are no analytical data for this waste
stream; however, it is expected to be similar to S02 scrubber
blowdown which was sampled at a secondary lead facility with
treatable concentrations of several toxic metals present. Also,
the one facility reporting this waste stream indicated that
nickel was known to be present in the waste stream and that
copper, lead, zinc and antimony were believed to be present based
on the raw materials and process chemicals used in the operation.
DEALUMINIZING RINSE
Aluminum present in tin plated steel scrap may be removed by
leaching in a sodium hydroxide solution prior to alkaline
detinning. The aluminum dissolves in the caustic solution and
the scrap is then rinsed and charged to the alkaline detinning
tanks. One plant reported this practice. A portion of their raw
material is tin plated steel scrap separated from municipal solid
waste. The spent caustic leaching solution and rinse water are
discharged as a waste stream. The one facility reporting this
waste stream is a direct discharger. The dealuminizing waste
stream is treated with sodium sulfide to precipitate metals,
chlorinated to destroy cyanide, and neutralized with sulfuric
acid. Solids are removed from the neutralized stream in a
sedimentation pond prior to discharge. The water use and
discharge rates are presented in Table V-2 in liters per metric
ton of dealuminized scrap produced.
There are no analytical data for this stream; however, it is
expected to be similar to the spent electrowinning solution with
a very alkaline pH and treatable levels of cyanide and certain
toxic metals including arsenic, lead, nickel and selenium.
TIN MUD ACID NEUTRALIZATION FILTRATE
One facility reported neutralization of tin mud with sulfuric
acid prior to dewatering in a filter press. The neutralized,
dewatered mud is sold as a by-product. The filtrate from the
dewatering step is discharged as a wastewater stream. Water use
and discharge rates are presented in Table V-3 in liters per
metric ton of neutralized, dewatered tin mud produced.
Although there are no analytical data for this specific stream,
data are available for samples of tin mud pond supernatant which
were collected at a facility which stores tin mud in open ponds
prior to sale to a tin smelter. These data are presented in
51
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Table V-15. The same pollutants found in the mud pond
supernatant are expected to be present in the tin mud acid
neutralization filtrate. It can be seen that treatable levels of
toxic metals are present including antimony, arsenic, lead,
nickel, thallium and zinc. Treatable levels of cyanide are also
present. The one facility reporting this waste stream is an
indirect discharger with no treatment in place.
TIN HYDROXIDE WASH
One facility reported the use of tin hydroxide, Sn(OH)4, as a raw
material in their electrolytic tin production process. The tin
hydroxide is washed with water to remove impurities, dissolved in
a sodium hydroxide solution and mixed with the tin solution from
the alkaline detinning operation prior to entering the
electrowinning cell. The tin hydroxide wash water is discharged
as a waste stream. The one facility reporting this stream
achieves zero discharge through the use of an evaporation pond.
The water use and discharge rates are shown in liters per metric
ton of tin hydroxide washed in Table V-4.
There are no analytical data available for this stream. It is
expected to have an alkaline pH and a treatable level of total
suspended solids. Also, some toxic metals may be present if they
are present in the tin hydroxide.
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP
Electrowinning is the principal method for recovering tin from
the alkaline detinning solution. After the tin has been plated
onto the cathode and the solution has been 'depleted, the solution
is either recycled to the detinning tank or discarded depending
on the amount and type of impurities present. Of the 10 plants
which practice alkaline detinning, eight recover tin from
solution via electrowinning. Of these eight facilities, six
achieve zero discharge through various combinations of recycle,
evaporation, contractor disposal and sales. Of the two remaining
plants one is a direct discharger; and the other is an indirect
discharger. Water use and discharge rates are presented in Table
V-5 in liters per metric ton of cathode tin produced.
Table V-l1 summarizes the raw wastewater sampling data for the
toxic and selected conventional and nonconventional pollutants.
It can be seen that there are treatable concentrations of several
toxic metals present including antimony, arsenic, lead, nickel,
selenium, thallium and zinc. Also, treatable concentrations of
cyanide are present. This wastewater stream has a very alkaline
pH (approximately 12) and high concentrations of total suspended
^olids.
52
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SPENT ELECTRONINNING SOLUTION FROM MUNICIPAL SOLID WASTE
When tin plated steel scrap which was recovered from municipal
solid waste (MSW) is used as a raw material for alkaline
detinning and electrowinning, a significantly larger discharge of
spent electrowinning solution is necessary because of additional
impurities introduced into the solution. There is currently one
facility using MSW as a source of raw material. The water use
and discharge rates for this stream are shown in Table V-6 in
liters per metric ton of MSW scrap used as raw material. This
flow rate is estimated using a procedure described in Section IX
of this document.
The one facility reporting this extra discharge of spent
electrowinning solution is a direct discharger after treatment
consisting of chlorination, acid neutralization and
sedimentation. The characteristics of this wastewater are
assumed to be similar to the characteristics of spent
electrowinning solution as discussed previously.
TIN HYDROXIDE SUPERNATANT FROM SCRAP
Tin may be recovered from solution by precipitation as tin
hydroxide, Sn(OH)4. Tin is present in solution as sodium
stannate, Na2Sn03. Tin hydroxide will precipitate when the pH is
lowered to 7.0 with sulfuric acid and sodium carbonate is added
to pH 7.8. The characteristics and production normalized flow
rates of the resultant supernatant stream are dependent upon the
raw material used. The three possible raw materials are tin
plated steel scrap, spent plating solutions, and plating sludge
solids.
The water use and wastewater discharge rates for tin hydroxide
supernatant from scrap are shown in Table V-7 in liters per
metric ton of tin metal recovered from scrap. The one facility
reporting this stream is a direct discharger after treatment by
sedimentation. Table V-12 summarizes the raw wastewater sampling
data for the toxic and selected conventional and nonconventional
pollutants. It can be seen that treatable levels of toxic metals
are present, particularly antimony at 4.4 mg/1. This waste
stream has a pH of 8.3 and treatable levels of oil and grease and
total suspended solids (TSS).
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING SOLUTIONS
Two plants reported the use of spent tin plating solutions as raw
material. One facility recovers tin as tin hydroxide from both
spent plating solutions and plating sludge solids. This facility
dissolves tin from the sludge solids into the plating solution by
adding additional water, while heating and lancing with air. Tin
hydroxide is then precipitated from the resultant solution. The
second facility uses only spent plating solutions. The liquids
are decanted from the solids, which are rinsed and dried in an
53
-------
oven. Tin hydroxide is precipitated from the spent plating
solution and rinse water by the addition of ammonia. Water use
and discharge rates in liters per metric ton of tin metal
recovered from spent plating solutions are presented in Table
V-8.
Sampling data for tin hydroxide supernatant from tin plating
solutions and sludges is presented in Table V-13. The samples
were collected at the facility which uses both spent plating
solutions and tin sludge solids as raw materials to tin hydroxide
precipitation operations. The data are assumed to be
representative of both tin hydroxide supernatant from spent
plating solutions and tin hydroxide supernatant from plating
sludge solids. It can be seen that treatable concentrations of
toxic metals are present, particularly antimony which was
detected at a maximum concentration of 3.1 mg/1. Cyanide is also
present with a maximum observed concentration of 16 mg/1. Very
high concentrations of fluoride are present in this wastewater
with concentrations from 12,000 to 15,000 mg/1. This fluoride
originates from tin fluoroborate and fluoroboric acid which are
used in the tin plating baths. This wastewater has a
nearly-neutral pH and treatable concentrations of suspended
solids.
TIN HYDROXIDE SUPERNATANT FROM TIN PLATING SLUDGE SOLIDS
One facility reported the use of both tin plating sludge solids
and spent plating solutions raw materials for tin hydroxide
precipitation operations. Water use and discharge rates are
presented in Table V-9 in liters per metric ton of tin recovered
from sludge solids. The flow attributable to production of tin
from tin sludge solids was calculated by subtracting the flow
expected from tin production from spent plating solutions from
the total tin hydroxide supernatant flow from both sludge solids
and spent plating solution. This wastewater stream is
characterized by treatable concentrations of antimony, cyanide,
fluoride, and TSS.
TIN HYDROXIDE FILTRATE
When tin hydroxide slurry is separated from the supernatant
stream, it may be further dewatered in a filter press prior to
drying. The resultant filtrate is discharged as a wastewater
stream. Water use and discharge rates are presented in Table
V-10 in liters per metric ton of tin metal produced.
The one facility reporting this stream is a direct discharger
after treatment by sedimentation. Table V-14 summarizes the
sampling data for this waste stream. Treatable concentrations of
cyanide and toxic metals are present including antimony at 2.4
mg/1. Treatable concentrations of fluoride and TSS are also
present.
54
-------
Table V-1
WATER USE AND DISCHARGE RATES
TIN SMELTER S02 SCRUBBER
(1/kkg of tin metal produced)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1118 50 43,340 21,670
55
-------
Table V-2
WATER USE AND DISCHARGE RATES
DEALUMINIZING RINSE
(1/kkg of dealuminized scrap produced)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1047 0 35 35
56
-------
Table V-3
WATER USE AND DISCHARGE RATES
TIN MUD ACID NEUTRALIZATION FILTRATE
(1/kkg of neutralized, dewatered tin mud produced)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1046 0 5,047 5,047
57
-------
Table V-4
WATER USE AND DISCHARGE RATES
TIN HYDROXIDE WASH
(1/kkg of tin hydroxide washed)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1049 0 11,953 11,953
58
-------
Table V-5
WATER USE AND DISCHARGE RATES
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP
(1/kkg of cathode tin produced)
Production
Production
Normalized
Plant Code
1047
1049
1048
1054
1046
1056
1057
1144
Percent
Recycle
0
0
NR
0
0
0
0
NR
Normalized
Water Use
NR
24,069
NR
16,609
15,145
12,489
10,498
NR
Discharge
Rate
NR
24,069
21 ,982
16,609
15,145
12,489
10,498
NR
NR = Data not reported.
59
-------
Table V-6
WATER USE AND DISCHARGE RATES
SPENT ELECTROWINNING SOLUTION FROM MUNICIPAL SOLID WASTE
(1/kkg of MSW scrap used as a raw material)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1047* 0 119 119
*Calculated from estimates of both MSW and scrap flow combined at
plant.
60
-------
Table V-7
WATER USE AND DISCHARGE RATES
TIN HYDROXIDE SUPERNATANT FROM SCRAP
(1/kkg of tin metal recovered from scrap)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1036 0 55,640 55,640
61
-------
Table V-8
WATER USE AND DISCHARGE RATES
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING SOLUTIONS
(1/kkg of tin metal recovered from spent plating solutions)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1014 0 37,978 37,978
1036 0 NR NR
NR = Data not reported.
62
-------
Table V-9
WATER USE AND DISCHARGE RATES
TIN HYDROXIDE SUPERNATANT FROM SLUDGE SOLIDS
(1/kkg of tin metal recovered from sludge solids)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1036 0 166,362 166,362
63
-------
Table V-10
WATER USE AND DISCHARGE RATES
TIN HYDROXIDE FILTRATE
(1/kkg of tin metal produced)
Production
Production Normalized
Percent Normalized Discharge
Plant Code Recycle Water Use Rate
1036 0 25,044 25,044
64
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Tin
Hydroxide
Supernatant
From Scrap
x\
395
Precipitation
Supernatant
Tank No. 1
(Sludge and
Plating Solutions)
Precipitation
Supernatant
Tank No. 2
(Sludge and
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398
<&
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Source
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Figure V-l
SAMPLING SITES AT SECONDARY TIN PLANT A
184
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Source
Water
454
Spent
Electrowinning
Solution
455
To Sales
Mud Pond
Figure V-2
SAMPLING SITES AT SECONDARY TIN PLANT B
185
-------
Source
Water
Spent
Electrowinning
Solution
NaOCl
843
Chlorination
849
Neutralization
Sedimentation
Ponds
Noncontact
Cooling
Water
844
Discharge
to River
Figure V-3
SAMPLING SITES AT SECONDARY TIN PLANT C
186
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Source
Water
Spent
Electrowinning
Solution
Na2C03
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I
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858
Discharge to
Surface Water
Figure V-4
SAMPLING SITES AT SECONDARY TIN PLANT D
187
-------
188
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
Section V of this supplement presented data from primary and
secondary tin plant sampling visits and subsequent chemical
analyses. This section examines that data and discusses the
selection or exclusion of pollutants for potential limitation.
Each pollutant selected for potential limitation is discussed in
Section VI of the General Development Document. That discussion
provides information concerning the nature of the pollutant
(i.e., whether it is a naturally occurring substance, processed
metal, or a manufactured compound)/ general physical properties
and the form of the pollutant; toxic effects of the pollutant in
humans and other animals; and behavior of the pollutant in POTW
at the concentrations expected in industrial discharges.
The discussion that follows describes 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 lime precipitatio'n,
sedimentation, and filtration (see Section VII Of the General
Development Document - Combined Metals Data Base). The treatable
concentrations used for the toxic organ'ics were the long-term
performance values achievable by carbon adsorption. Also,
conventional and nonconventional pollutants and pollutant
parameters are selected or excluded from limitation.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
This study examined samples from the primary and secondary tin
subcategory for two conventional pollutant parameters (total
suspended solids, and pH) and three nonconventional pollutant
parameters, (ammonia, tin and fluoride). Fluoride is known to be
present in certain of the raw materials used by secondary tin
facilities and ammonia is used as a reagent in some tin recovery
operations. Also, ammonia is generated in the alkaline tin
dissolving reaction.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
• ammonia
• fluoride
189
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• tin
• total suspended solids (TSS)
• pH
Ammonia was found in six of the eight raw waste samples analyzed
for this subcategory in concentrations ranging from 1.1 to 92
mg/1. One of the values recorded is well above the 32.2 mg/1
concentration attainable by the available treatment technology.
Also, one facility which uses ammonia to precipitate tin
hydroxide supplied wastewater analytical data with their dcp
response which indicated that 3,000 mg/1 of ammonia nitrogen was
present. Consequently, ammonia is selected for limitation in
this subcategory.
Fluoride was detected in all eight raw wastewater samples
analyzed for this study. Five of the eight values are equal to
or greater than 12,000 mg/1. These high concentrations of
fluoride are found in wastewaters associated with secondary tin
production from tin plating solutions and sludges. The fluoride
originates as tin fluoroborate or fluoroboric acid which are
constituents of tin plating baths. For these reasons, fluoride
is selected for limitation in this subcategory.
Tin was analyzed for in all ten raw waste samples, and was found
in concentrations ranging from 5.8 mg/1 to 8800 mg/1. All ten
values are greater than the 0.80 mg/1 concentration considered
achievable by lime, settle and filter technology. Also, tin is
expected to be present in the wastewaters from this subcategory
because-of its prevalence in the process and its solubility. For
these reasons, tin is selected for limitation in this
subcategory.
TSS concentrations ranging from 25 to 50,000 mg/1 were observed
in the 10 raw waste samples analyzed for this study. All 10
concentrations are well above the 2.6 mg/1 treatable
concentration. Furthermore, 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 eight pH values observed during this study ranged from 7.6 to
13.3. Two of the eight values were 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.
190
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TOXIC POLLUTANTS
The frequency of occurrence of the toxic pollutants in the raw
wastewater samples taken is presented in Table VI-1. Table VI-1
is based on the raw wastewater data from streams 455, 456, 395,
396, 398, 399, 843, and 856 (see Section V). 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 below were not detected in any raw
wastewater samples from this subcategory; therefore, they are are
not selected for consideration in establishing limitations:
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
10. 1,2-dichloroethane
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-chl-oroethyl) ether
19. 2-chloroethyl vinyl ether
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-cichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
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)
191
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48. dichlorobromomethane
49. trichlorofluoromethane (deleted)
50. dichlorodifluoromethane (deleted)
51. chlorodibromomethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
56. nitrobenzene
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
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)fluoranthene (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
79. benzo(ghi)perylene (1,11-benzoperylene)
82. dibenzo(a,n)anthracene (1,2,5,6-dibenzanthracene)
83. indeno(1,2,3-cd)pyrene (w,e,-o-phenylenepyrene)
85. tetrachloroethylene
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4,4'-DDT
93. 4,4!-DDE(p,p'DDX)
94. 4,4'-DDD(p,p'TDE)
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100,, heptachlor
101. heptachlor epoxide
102. Alpha - BHC
103. Beta - BHC
104. 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
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
192
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TOXIC POLLUTANTS NEVER FOUND 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.
9. hexachlorobenzene
11. 1,1,1-trichloroethane
23. chloroform
29. 1,1-dichloroethylene
34. 2,4-dimethylphenol
37. 1,2-diphenylhydrazine
39. fluoranthene
55. naphthalene
62. n-nitrosodimethylamine
68. di-n-butyl phthalate
78. anthracene
80. fluorene
81. phenanthrene
87. trichloroethylene
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 individually
following the list.
117. beryllium
123. mercury
Beryllium was detected above its analytical quantification level
(0.1 mg/1) in four out of 10 raw wastewater samples. The
observed concentrations ranged from 0.02 .mg/1 to 0.20 mg/1.
Three of these values are below the treatable concentration for
beryllium (0.20 mg/1). One is right at the treatability
concentration and would therefore not be reduced by available
treatment technology. Beryllium is therefore not selected for
limitation.
Mercury was detected in two out of 10 raw wastewater samples.
The two observed concentrations are .026 mg/1 and .0004 mg/1,
both below the concentration considered achievable by identified
treatment technology (.036 mg/1). Mercury is therefore not
selected for limitation.
193
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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 they are uniquely
related to only those sources.
4. benzene
38. ethylbenzene
44. methylene chloride
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
65. phenol
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
84. pyrene
86. toluene
88. vinyl chloride
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.
Benzene was detected above its treatable level of 0.01 mg/1 in
two out of 10 raw wastewater samples. The observed treatable
concentrations are .051 and .047 mg/1, just slightly higher than
the treatability concentration.. Because these values are only
slightly higher than could be achieved by treatment and only two
in 10 samples showed benzene at a treatable concentration,
benzene is not selected for limitation.
Ethylbenzene was detected above its treatable concentration of
0.01 mg/1 in only one out of ten raw wastewater samples. The
observed treatable concentration is 0.011 mg/1. Because it was
found at a treatable concentration in only one out of ten samples
and because the observed value is only slightly above the
treatable concentration, ethylbenzene is not selected for
limitation.
Methylene chloride was found above its treatable concentration of
0.01 mg/1 in three out of 10 raw wastewater samples. Methylene
chloride is a common laboratory reagent often detected in blank
and raw water samples. The treatable concentrations observed
(0.031, 0.025 and 1.724 mg/1) are probably due to laboratory
contamination. Methylene chloride is therefore not selected for
limitation.
2-Nitrophenol was detected above the concentration considered
achievable by identified treatment technology (.01 mg/1) in three
out of 10 raw wastewater samples. The treatable concentrations
observed were .031 mg/1, .06 mg/1 and .02 mg/1. The Agency has
194
-------
no reason to believe that treatable concentrations of
2-nitrophenol should be present in primary and secondary tin
wastewaters. For this reason, and because it was detected in
such a small number of samples, 2-nitrophenol is not selected for
limitation.
4-Nitrophenol was detected above its treatable concentration of
0.01 mg/1 in two out of ten raw wastewater samples. The observed
treatable concentrations are 0.026 and 0.025 mg/1. Because it
was found at a treatable concentration in only two out of ten
samples and because the Agency has no reason to believe that
treatable concentrations of 4-nitrophenol should be present in
primary and secondary tin wastewaters, 4-nitrophenol is not
selected for regulation.
2,4-Dinitrophenol was detected above its treatable concentration
of 0.01 mg/1 in two out of 10 raw wastewater samples. The
treatable concentrations observed are .033 mg/1 and .086 mg/1.
Because very little removal could be expected with treatment and
because it was detected at treatable concentrations in only two
out of 10 samples, 2,4-dinitrophenol is not selected for
limitation.
Phenol was detected above the concentration considered achievable
by available treatment technology (.01 mg/1) in three out of 10
raw wastewater samples. The observed treatable concentrations
are 0.017, 0.02 and 0.13 mg/1. Because it was detected in only
three of 10 samples, and because the Agency has no reason to
believe that treatable concentrations of phenol should be present
in primary and secondary tin wastewaters, phenol is not selected
for limitation.
Bis(2-ethylhexyl) phthalate was detected above its treatability
concentration of .01 mg/1 in only one out of 10 raw wastewater
samples. The observed treatable concentration is 0.268 mg/1.
This compound is a plasticizer commonly used in laboratory and
field sampling equipment, and is not used or formed as a
by-product in this subcategory. For this reason and because it
was detected at a treatable concentration in only one out of 10
raw wastewater samples, bis(2-ethylhexyl) phthalate is not
selected for limitation.
Butyl benzyl phthalate was detected above the concentration
considered achievable by available treatment technology (.01
mg/1) in three out of 10 raw wastewater samples. The observed
concentrations are .011 mg/1, .012 mg/1, and .025 mg/1. This
compound is a plasticizer commonly used in laboratory and field
equipment, and is not used or formed as a by-product in this
subcategory. For this reason, and because it was detected in
only three out of 10 samples, butyl benzyl phthalate is not
selected for limitation.
195
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Pyrene was detected above its treatability concentration of .01
mg/1 in only one out of 10 raw wastewater samples. The observed
treatable concentration is .063 mg/1. The Agency has no reason
to believe that treatable concentration of pyrene should be
present in primary and secondary tin wastewaters. For this
reason, and because it was detected at a treatable concentration
in only one out of 10 samples, pyrene is not selected for
limitation.
Toluene was detected above its treatable concentration of 0.01
mg/1 in two out of ten raw wastewater samples. The observed
treatable concentrations are 0.018 and 0.017 mg/1. Because
toluene was detected in only two out of ten raw wastewater
samples at concentrations only slightly above treatabilty and
because it was detected in the source water sample at 0.093 mg/1,
toluene is not selected for regulation.
Vinyl chloride was detected above the concentration considered
achievable by identified treatment technology (.01 mg/1) in only
one out of 10 raw wastewater samples. The treatable
concentration observed is .036 mg/1. Because it was detected in
only one out of 10 samples, vinyl chloride 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
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. antimony
115. arsenic
118. cadmium
119. chromium
120. copper
121. cyanide
122. lead
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
Antimony was detected above the concentration considered
achievable by identified treatment technology (0.47 mg/1) in
eight out of 10 raw v,'2?tewater samples. The treatable
concentrations observed range from 0.9 mg/1 to 12.0 mg/1.
Antimony is therefore selected for further consideration for
limitation.
196
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Arsenic was detected above the concentration considered
achievable by identified treatment technology (0.34 mg/1) in four
out of 10 raw wastewater samples. The treatable concentrations
observed range from 1.9 mg/1 to 6.6 mg/1. Arsenic is therefore
selected for further consideration for limitation.
Cadmium was detected above the concentration considered
achievable by identified treatment technology (0.049 mg/1) in
eight out of 10 raw wastewater samples. The treatable
concentrations observed range from 0.08 mg/1 to 0.42 mg/1.
Cadmium is therefore selected for further consideration for
limitation.
Chromium was detected above the concentration considered
achievable by identified treatment technology (0.07 mg/1) in
three out of 10 raw wastewater samples. The treatable
concentrations observed range from 0.30 mg/1 to 0.94 mg/1.
Chromium is therefore selected for further consideration for
limitation.
Copper was detected above the concentration considered achievable
by identified treatment technology (0.39 mg/1) in three out of 10
raw wastewater samples. The treatable concentrations observed
range from 0.41 mg/1 to 0.52 mg/1. Copper is therefore selected
for further consideration for limitation.
Cyanide was detected above the concentration considered
achievable by identified treatment technology (0.047 mg/1) in all
nine raw wastewater samples analyzed for this study. The
treatable concentrations observed range from 0.22 mg/1 to 24
mg/1. Cyanide is therefore selected for "further consideration
for limitation.
Lead was detected above the concentration considered achievable
by identified treatment technology (0.08 mg/1) in six out of 10
raw wastewater samples. The treatable concentrations observed
range from 1.0 mg/1 to 11 mg/1. Lead is therefore selected for
further consideration for limitation.
Nickel was detected above the concentration considered achievable
by identified treatment technology (0.22 mg/1) in nine out of 10
raw wastewater samples. The treatable concentrations observed
range from 0.35 mg/1 to 4.1 mg/1. Nickel is therefore selected
for further consideration for limitation.
Selenium was detected above the concentration considered
achievable by identified treatment technology (0.07 mg/1) in
three out of 10 raw wastewater samples. The treatable
concentrations observed range from 0.43 mg/1 to 32 mg/1.
Selenium is therefore selected for further consideration tor
limitation. Selenium was detected at 3.1 mg/1 in the source
water sample associated with the wastewater sample in which
selenium was observed at 32 mg/1.
197
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Silver was detected above the concentration considered achievable
by identified treatment technology (0.07 mg/1) in four out of 10
raw wastewater samples. The treatable concentrations observed
range from 0.30 mg/1 to 0.40 mg/1. Silver is therefore selected
for further consideration for limitation.
Thallium was detected above the concentration considered
achievable by identified treatment technology (0.34 mg/1) in five
out of 10 raw wastewater samples. The treatable concentrations
observed range from 0.59 mg/1 to 3.1 mg/1. Thallium is therefore
selected for further consideration for limitation.
Zinc was detected above the concentration considered achievable
by identified treatment technology (0.23 mg/1) in five out of 10
raw wastewater samples. The treatable concentrations observed
range from 0.24 mg/1 to 190 mg/1. Zinc is therefore selected for
further consideration for limitation.
198
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PRIMARY AND SECONDARY TIN SUBCATEGORY
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 and secondary tin subcategory. This section summarizes
the description of these wastewaters and indicates the level of
treatment which is currently practiced for each waste stream.
CURRENT CONTROL AND TREATMENT PRACTICES
Control and treatment technologies are discussed in general in
Section VII of the General Development Document. The basic
principles of these technologies and the applicability to
wastewater similar to that found in this subcategory are
presented there. 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
and secondary tin subcategory is characterized by the presence of
the toxic metal pollutants, cyanide, ammonia, fluoride, tin 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 economies of scale, and, in some instances, to
combine streams of differing alkalinity to reduce treatment
chemical requirements. Three plants in this subcategory
currently have combined wastewater treatment systems. One has
cyanide oxidation with chlorine, followed by acid neutralization
and sedimentation. One has lime precipitation and sedimentation
and one has sedimentation lagoons only. Two options have been
selected for consideration for BPT, BAT, NSPS, and pretreatment
in this subcategory, based on combined treatment of these
compatible waste streams.
TIN SMELTER SO, SCRUBBER
The one plant which practices tin smelting from concentrates and
residues uses a caustic scrubber to control S02 emissions from
the smelting operations. The facility reported practicing 50
percent recycle of the scrubber liquor. The scrubber liquor
contains treatable concentrations of toxic metals and suspended
solids. This stream is directly discharged after treatment
consisting of lime addition and sedimentation.
203
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DEALUMINIZING RINSE
The one facility which reported the use of municipal solid waste
as a raw material uses an alkaline leaching and rinsing process
to remove aluminum from the scrap prior to detinning operations.
The spent leachate and rinsewater have a very alkaline pH and
contain treatable concentrations of cyanide and toxic metals.
The one facility reporting this stream discharges it directly
after treatment consisting of sulfide addition to precipitate
aluminum, cyanide oxidation with sodium hypochlorite, acid
neutralization, vacuum filtration and sedimentation.
TIN MUD ACID NEUTRALIZATION FILTRATE
Tin mud may be neutralized with sulfuric acid and dewatered in a
filter press prior to sales to a tin smelter. The filtrate
contains treatable concentrations of toxic metals and cyanide.
The one facility reporting this waste stream is an indirect
discharger with no treatment in place.
TIN HYDROXIDE WASH
The one facility which reported the use of tin hydroxide,
Sn(OH)4, as a raw material, washes the tin hydroxide with water
prior to dissolving it in a caustic solution. This solution is
then mixed with the sodium stannate solution from alkaline
detinning and tin is recovered from the combined stream by
electrowinning. The spent wash water contains treatable
concentrations of toxic metals and suspended solids. The one
facility reporting this waste stream achieves zero discharge
through the use of evaporation ponds.
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP
New tin plated steel scrap is used as a raw material at 10 out of
11 secondary tin plants. After alkaline detinning, the tin is
recovered by electrowinning and either all or a portion of the
spent solution is discharged, as a waste stream. The spent
solution has a very alkaline pH and contains treatable
concentrations of cyanide, toxic metals, and suspended solids.
Of the eight plants which practice electrowinning, six achieve
zero discharge by contractor disposal, sales or evaporation
ponds. Of the two plants which discharge this stream, one is an
indirect discharger with no treatment in place and the other is a
direct discharger with treatment consisting of cyanide oxidation
with chlorine, acid addition, vacuum filtration and
sedimentation.
SPENT ELSCTROWINNING SOLUTION FROM MUNICIPAL SOLID WASTE
The one facility which reported the use of municipal solid waste
as a raw material to alkaline detinning and electrowinning
discharges a spent electrowinning solution waste stream. This
204
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stream has a very alkaline pH and contains treatable
concentrations of cyanide, toxic metals, and suspended solids.
This stream is discharged directly after treatment consisting of
cyanide oxidation with chlorine, acid addition, vacuum filtration
and sedimentation.
TIN HYDROXIDE SUPERNATANT FROM SCRAP
Tin hydroxide may be precipitated from alkaline detinning
solution as an alternative to electrowinning for tin recovery.
Sulfuric acid and sodium carbonate are added to the sodium
stannate solution and the tin hydroxide forms an insoluble
precipitate which is separated from the liquid phase by
sedimentation. The supernatant waste stream contains treatable
concentations of cyanide and toxic metals. The one plant
reporting this waste stream is a direct discharger after
treatment in sedimentation lagoons.
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING SOLUTIONS
Tin hydroxide may be precipitated from spent plating solutions
generated from tin plated steel manufacturing operations. Either
sulfuric acid and sodium carbonate or ammonia is added to the
solution and an insoluble precipitate of tin hydroxide is formed.
The precipitate is separated from the liquid phase by
sedimentation. The supernatant stream contains treatable
concentrations of cyanide and toxic metals as well as high
concentrations of fluoride. 'Treatable concentrations of ammonia
may also be present if ammonia is used as the reagent causing the
formation of tin hydroxide. Of the two plants reporting this
waste stream, one is an indirect discharger with no treatment in
place and the other is a direct discharger after treatment in
sedimentation lagoons.
TIN HYDROXIDE SUPERNATANT FROM SLUDGE SOLIDS
Tin plating sludge solids are dissolved and the resultant
solution is treated with sulfuric acid and sodium carbonate to
precipitate tin hydroxide. The resultant supernatant waste
stream contains treatable concentrations of antimony, cyanide,
fluoride, and suspended solids. The one facility reporting this
waste stream is a direct discharger after treatment in
sedimentation lagoons.
TIN HYDROXIDE FILTRATE
Tin hydroxide slurry which has been separated from the
supernatant stream may be further dewatered in a filter press
prior to drying. The resultant filtrate waste stream contains
treatable concentrations of antimony, cyanide, fluoride, and
suspended solids. The one facility reporting this waste stream
is a direct discharger after treatment in sedimentation lagoons.
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CONTROL AND TREATMENT OPTIONS
The Agency examined two control and treatment technology
alternatives that are applicable to the primary and secondary tin
subcategory. The options selected for evaluation represent a
combination of flow reduction, pretreatment technology applicable
to individual waste streams, and end-of-pipe treatment
technologies.
OPTION A
Option A for the primary and secondary tin subcategory requires
treatment technologies to reduce pollutant mass. The Option A
treatment scheme consists of ammonia steam stripping preliminary
treatment applied to the tin hydroxide supernatant from spent
plating solutions waste stream. Also, preliminary treatment
consisting of cyanide precipitation is applied to the combined
stream of dealuminizing rinse, spent electrowinning solution from
new scrap and municipal solid waste, tin hydroxide supernatant
from scrap, tin hydroxide supernatant from spent plating
solution, tin hydroxide supernatant from sludge solids, tin
hydroxide filtrate, and tin mud acid neutralization filtrate.
Preliminary treatment is followed by chemical precipitation and
sedimentation applied to the combined stream of cyanide
precipitation effluent, tin smelter S02 scrubber and tin
hydroxide wash. Chemical precipitation is used to remove metals
and fluoride by the addition of lime or sulfuric acid followed by
gravity sedimentation. Suspended solids are also removed by the
process.
OPTION C
Option C for the primary and secondary tin subcategory consists
of all control and treatment requirements of Option A (ammonia
steam stripping, cyanide precipitation, 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 and fluoride, 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 as well. The
addition of filters also provides consistent removal during
periods in which there are rapid increases in flows or loadings
of pollutants to the treatment system.
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION VIII
COST OF WASTEWATER TREATMENT AND CONTROL
This section presents a summary of compliance costs for the
primary and secondary tin subcategory and a description of the
treatment options and subcategory-specific assumptions used to
develop these estimates. Together with the estimated pollutant
removals presented in Section 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
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 and secondary tin subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, two treatment options have been
developed for existing primary and secondary tin sources. The
treatment schemes for each option are summarized below and
schematically presented in Figures X-l and X-2.
OPTION A
Option A consists of preliminary treatment consisting of ammonia
steam stripping and cyanide precipitation where required and
chemical precipitation and sedimentation end-of-pipe technology.
OPTION C
Option C consists of Option A preliminary treatment consisting of
ammonia steam stripping and cyanide precipitation where required
and chemical precipitation and sedimentation with the addition of
multimedia filtration to 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 the General
Development Document. Plant-by-plant compliance costs have been
estimated for the nonferrous metals manufacturing category and
are documented in detail in the administrative record supporting
this regulation. The costs developed for the proposed regulation
are presented in Tables VIII-1 and VII1-2.
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Each of the general assumptions used to develop compliance costs
is presented in Section VIII of the General Development Document.
Each subcategory also contains a unique set of waste streams
requiring certain subcategory-specific assumptions to develop
compliance costs. The five major assumptions specific to the
primary and secondary tin subcategory are discussed briefly
below.
(1) The generation of calcium fluoride (CaF2) during chemical
precipitation was accounted for in cases where significant
amounts of fluoride were present. If the sludge resulting
from chemical precipitation was mostly composed of CaF2 (>
50 percent), it was assumed to be suitable for resale for
use as a fluxing agent. Thus, annual costs for contract
hauling of these sludges were not included in these
instances.
(2) Ammonia removal costs were not included for treating the tin
hydroxide supernatant from spent plating solutions waste
stream, which contains treatable levels of ammonia. The
ammonia is present as a precipitating agent for tin
hydroxide; however it was assumed that sodium carbonate may
be used instead of ammonia. It was further assumed that the
transition to sodium carbonate can be accomplished at
negligible costs.
(3) All sludges produced from wastewater treatment are
considered to be nonhazardous except for those resulting
from cyanide precipitation, . which contain cyanide. Such
cyanide bearing sludges are disposed separately based on
hazardous waste contract hauling costs.
(4) The sampling values for TSS and aluminum concentration in
spent electrowinning solutions were revised. It was assumed
that the values reported were in error by a factor of 1000
based on conversations with personnel at one of the two
sampled plants and evaluation of the reported data. The
concentrations were revised as follows:
Old New
TSS 36,500 mg/1 36.5 mg/1
Al 28,700 mg/1 28.7 mg/1
(5) The lime and settle treatability value for tin is 1.07 mg/1,
which is based on the average of two sampling values for the
effluent at a particular plant.
(6) Cost estimates for cyanide precipitation for plants 1014,
1046, and 1047 do not include costs for a reaction tank and
agitator. This was done because in each case the low total
flow rates into the treatment system resulted in retention
208
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(or holdup) times in the chemical precipitation tank large
enough to allow both cyanide precipitation and chemical
precipitation to occur without significantly increasing the
tank size. For example, the retention time in the chemical
precipitation tank for Plant 1014 was two days or 48 hours.
Since the required batch duration for cyanide precipitation
was 8.5 hr. and 16 hr. for chemical precipitation, both
processes could be accomplished within the time available.
The above procedure resulted in a significant reduction in
capital investment. Information on the variation of
retention times in the chemical precipitation unit operating
at low flow rates, is contained in Section VIII of the
general development document.
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 the General
Development Document. Nonwater quality impacts specific to the
primary and secondary tin 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 790,000 kWh/yr. Option C, which includes
filtration, is estimated to increase energy consumption over
Option A by approximately one percent. Further, the total energy
requirement for Option C is approximately one 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 primary and secondary tin subcategory is
due to the precipitation of metals as hydroxides and carbonates
using lime. Sludges associated with the primary and secondary
tin subcategory will necessary contain quantities of toxic metal
pollutants. Sludges from primary operations 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. Wastes from secondary
metal operations can be regulated as hazardous. However, the
Agency examined the solid wastes that would be generaged 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,
209
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with one exception. This judgment is based on the results of
Extraction Procedure (EP) toxicity tests performed on similar
sludges (i.e. toxic-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
8261.24. 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. The one exception is
that sludges produced as a result of cyanide precipitation are
expected to exhibit hazardous characteristics, and have been
treated as such in our analysis.
Although it is the Agency's view that most of the 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 2-62.11).
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 diposition. 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. For more details, see Section VIII of
the General Development Document.
It is estimated that 467 metric tons per year of sludge will be
generated as a result of these proposed BAT and PSES regulations
for the primary and secondary tin subcategory.
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AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of ammonia steam
stripping, cyanide precipitation, chemical precipitation,
sedimentation, and multimedia filtration. Ammonia steam
stripping yields an aqueous ammonia stream. The other
technologies transfer pollutants to solid waste and are not
likely to transfer pollutants to air.
-------
TABLE VII1-1
COST OF COMPLIANCE
FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
DIRECT DISCHARGERS
Compliance costs for direct dischargers in this subcategory are
not presented here because the data on which they are based has
been claimed to be confidential.
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TABLE VII1-2
COST OF COMPLIANCE
FOR THE PRIMARY AND SECONDARY TIN SUBCATEGORY
INDIRECT DISCHARGERS
(MARCH 1982 DOLLARS)
Total Required Total
Option Capital Cost Annual Cost
A 333,400 112,200
C 341,700 119,900
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PRIMARY AND SECONDARY TIN SUBCATEGORY
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)(1)(A). BPT reflects
the existing performance by plants of various sizes, ages, and
manufacturing processes within the primary and secondary tin
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 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 (see Tanner's Council of America v. Train, 540 F.2d 1188
(4th Cir. 1976). BPT focuses on end-of-pipe treatment rather
than process changes or internal controls, except where such
practices are common 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 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 tin
subcategory has been subdivided into ten potential wastewater
sources. Since the water use, discharge rates, and pollutant
215
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characteristics of each of these wastewaters is potentially
unique, effluent limitations will be developed for each of the
ten subdivisions.
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. 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 regualtory 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). Ammonia steam
stripping is applied to streams with treatable concentrations of
ammonia and cyanide precipitation is applied to streams with
treatable concentrations of cyanide.
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 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 400 as the
effluent limitations guidelines.
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
216
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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 tin 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 effluent reduction benefits,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollution control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed BPT. See Weyerhaeuser
Company v. Costle, 590 F.2d 1011 '(D.C. Cir. 1978).
The methodology for calculating pollutant removals and compliance
costs is discussed in Section X. Table X-1 shows the pollutant
removal estimates for each treatment option for direct
dischargers. Compliance costs for direct dischargers are
presented in Table X-2.
BPT OPTION SELECTION
The technology basis for the proposed BPT limitations is Option
A, chemical precipitation and sedimentation technology to remove
metals, fluoride, and solids from combined wastewaters and to
control pH, with preliminary treatment consisting of cyanide
precipitation and ammonia steam stripping. Chemical
precipitation and sedimentation technology is already in-place at
two of the three direct dischargers in the subcategory. The
pollutants specifically proposed for regulation at BPT are
antimony, cyanide, lead, nickel, tin, ammonia, fluoride, TSS, and
pH. The BPT treatment scheme is presented schematically in
Figure IX-1.
Implementation of the proposed BPT limitations will remove
annually an estimated 1,169 kg of toxic metals, 144 kg of
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cyanide, 237,220 kg of fluoride, and 58,600 kg of TSS. Capital
and annual costs for achieving BPT are not presented here because
the data on which they are based has been claimed to be
confidential.
More stringent technology options were not selected for BPT since
they require in-process changes or end-of-pipe technologies not
demonstrated in the subcategory, and, therefore, are more
appropriately considered under BAT.
Ammonia steam stripping is demonstrated at seven facilities in
the nonferrous metals manufacturing category. These facilities
are treating ammonia-bearing wastewaters associated with the
production of primary tungsten, primary columbium and tantalum,
primary molybdenum, secondary tungsten and cobalt, secondary
molybdenum and vanadium, and primary zirconium and hafnium. 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 because raw wastewater concentrations of
ammonia are of the same order of magnitude in the respective raw
wastewater matrices.
Chemical analysis data were collected of raw waste (treatment
influent) and treated waste (treatment effluent) from one 'coke
plant of the iron and steel manufacturing category. A contractor
for EPA, using EPA sampling and chemical analysis protocols,
collected six paired samples in a two-month period. These data
are the data base for determining the effectiveness of ammonia
steam stripping technology and are contained within the public
record supporting this document. Ammonia -treatment at this coke
plant consisted of two steam stripping columns in series with
steam injected countercurrently to the flow of the wastewater. A
lime reactor for pH adjustment separated the two stripping
columns.
The Agency has verified the proposed steam stripping performance
values using steam stripping data collected at a primary
zirconium and hafnium plant which has raw ammonia levels as high
as any in the nonferrous metals manufacturing category. Data
collected by the plant represent almost two years of daily
operations, and support the long-term mean used to establish
treatment effectiveness.
We are transferring cyanide precipitation technology and
performance to the primary and secondary tin subcategory from
coil coating plants. We believe the technology is transferable
to these subcategories because the raw wastewater concentrations
are of the same order of magnitude as those observed in coil
coating wastewater. In that cyanide precipitation converts all
cyanide species to complex cyanides and that precipitation of the
complexed cyanides is solubility related, we believe that the
218
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technology will achieve identical effluent concentrations in both
categories.
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 for each
wastewater source, separate production normalized discharge rates
for each of the 10 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 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-10.
TIN SMELTER SO, SCRUBBER
The BPT wastewater discharge rate for tin smelter S02 scrubber
water is 21,670 1/kkg (5,210 gal/ton) of tin metal produced.
This rate is allocated only to those plants which use wet air
pollution control to control S02. emissions from tin smelting
operations. Only one facility reported tin smelting operations
and the use of wet scrubbing. Water use and discharge rates are
presented in Table V-l. This facility reports a recycle rate of
50 percent in their smelter scrubber. The BPT flow allowance is
based on the wastewater discharge rate reported by this facility.
DEALUMINIZING RINSE
The BPT flow allowance for dealuminizing rinse wastewater is 35
1/kkg (9 gal/ton) of dealuminized scrap produced. This rate is
allocated only to those plants which practice dealuminizing of
tin bearing steel scrap prior to alkaline detinning. Only one
facility reported this practice, which is apparently only
necessary when municipal solid waste is used as a raw material.
The water use and discharge rates reported by this facility are
presented in Table V-2. The BPT flow rate is based on the
wastewater discharge rate reported by this -facility.
TIN MUD ACID NEUTRALIZATION FILTRATE
The BPT wastewater discharge rate for tin mud acid neutralization
filtrate is 5,047 1/kkg (1,210 gal/ton) of neutralized, dewatered
tin mud produced. This rate is allocated only to those
facilities which neutralize tin mud with sulfuric acid and
219
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dewater the neutralized mud. One facility reported this
practice. Water use and discharge rates are presented in Table
V-3. The BPT flow rate is based on the production normalized
flow reported by this facility.
TIN HYDROXIDE WASH
The BPT wastewater discharge rate for tin hydroxide wash water is
11,953 1/kkg (2,869 gal/ton) of tin hydroxide washed. This rate
is only allocated to those facilities which use tin hydroxide as
a raw material in tin electrowinning operations and wash the tin
hydroxide prior to dissolution in a caustic solution. One plant
reported this practice. The water use and wastewater discharge
rates reported by this facility are presented in Table V-4. The
BPT flow rate is based on the wastewater discharge rate reported
by this facility.
SPENT ELECTROWINNING SOLUTION FROM NEW SCRAP
The BPT wastewater discharge rate for spent electrowinning
solution from new scrap is 16,800 1/kkg (4,029 gal/ton) of
cathode tin produced. This rate is allocated only to those
plants which produce tin metal by electrowinning. There are
eight facilities which produce tin by electrowinning. Six of
these eight plants reported sufficient information to calculate a
discharge rate from this process. The BPT flow allowance is
based on the average of the production normalized flows reported
by these six facilities (see Table V-5). These production
normalized flows ranged from 10,498 1/kkg to 24,069 1/kkg.
SPENT ELECTROWINNING SOLUTION FROM MUNICIPAL SOLID WASTE
The BPT flow rate for spent electrowinning solution from
municipal solid waste is 119 1/kkg (29 gal/ton) of MSW scrap used
as a raw material in alkaline detinning operations. This rate is
allocated only to those plants which recover secondary tin from
municipal solid waste by alkaline detinning and electrowinning.
One facility reported the use of municipal solid waste as a raw
material in addition to new scrap. This facility discharges four
to five times as much spent electrowinning solution per mass of
electrolytic tin produced than the average of the other six
plants which reported flows for this waste stream. The large
flow is a direct result of impurities which are introduced into
the electrowinning solution from the municipal solid waste.
This wastewater flow allowance for facilities which process
municipal solid waste was calculated by subtracting the
facility's BPT flow allowance for spent electrowinning solution
from new scrap from the total spent electrowinning solution flow
rate reported by the facility. The difference represents the
flow due to municipal solid waste processing. This flow was
divided by the amount of municipal solid waste scrap which the
facility uses as a raw material to alkaline detinning operations.
220
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The resultant production normalized flow rate is 119 1/kkg of
municipal solid waste scrap used as a raw material, as shown in
Table V-6.
TIN HYDROXIDE SUPERNATANT FROM SCRAP
The BPT wastewater discharge rate for tin hydroxide supernatant
from scrap is 55,640 1/kkg (13,354 gal/ton) of tin metal
recovered from scrap. This rate is allocated only to those
facilities which precipitate tin hydroxide from tin solutions
generated from alkaline detinning of tin plated steel scrap. One
facility reported this practice. Water use and discharge rates
are presented in Table V-7. The BPT flow rate is based on the
production normalized flow rate at the one facility currently
generating this waste stream.
TIN HYDROXIDE SUPERNATANT FROM SPENT PLATING SOLUTIONS
The BPT wastewater discharge rate for tin hydroxide supernatant
from spent plating solutions is 37,978 1/kkg (9,115 gal/ton) of
tin metal recovered from spent plating solutions. This rate is
allocated only to those facilities which recover tin from spent
plating solutions by precipitation of tin hydroxide.
Two facilities reported this practice. Water use and wastewater
discharge rates are presented in Table V-8. Only one of the two
facilities reported sufficient information to calculate a flow
rate for this stream The BPT flow rate is based on the production
normalized flow rate reported by .this facility.
TIN HYDROXIDE SUPERNATANT FROM SLUDGE SOLID'S
The BPT wastewater discharge rate for tin hydroxide supernatant
from sludge solids is 166,362 1/kkg (39,927 gal/ton) of tin metal
recovered from sludge solids. This rate is allocated for those
facilities which recover tin from tin plating sludge solids by
dissolving and precipitating tin hydroxide. One facility
reported this practice. Water use and discharge rates are
presented in Table V-9. The BPT flow rate is based on the
production normalized flow rate reported by this facility.
TIN HYDROXIDE FILTRATE
The BPT wastewater discharge rate for tin hydroxide filtrate is
25,044 1/kkg (6,011 gal/ton) of tin metal produced. This rate is
allocated only for those plants which dewater tin hydroxide
slurries from tin hydroxide precipitation operations in a filter
press. There is currently only one plant which reported this
practice. Water use and discharge rates are presented in Table
V-10. The BPT wastewater discharge rate for tin hydroxide
filtrate is based on the value reported by the one facility which
currently generates this waste stream.
221
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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 is
presented in Sections VI and X. A total of nine pollutants or
pollutant parameters are selected for limitation under BPT and
are listed below:
114. antimony
121. cyanide
122. lead
124. nickel
tin
ammonia
fluoride
TSS
PH
EFFLUENT LIMITATIONS
The treatable concentrations achievable by application of the
proposed BPT are discussed in Section VII of the General
Development Document and summarized there in Table VII-19. These
treatable concentrations (both one day maximum and monthly
average values) are multiplied by the BPT normalized discharge
flows summarized in Table IX-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 BPT effluent limitations and
are presented in Table IX-2 for each individual waste stream.
222
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Table IX-2
BPT MASS LIMITATIONS FOR THE PRIMARY
AND SECONDARY TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony ' 62.190 27.740
Lead 9.102 4.334
Nickel 41.610 27.520
Cyanide (total) 6.284 2.600
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 106.600 47.240
Total suspended 888.500 422.600
solids
pH Within the range of 7.5 to 10.0
at all times
(b) Dealuminizing Rinse
Pollutant or Maximum for. Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony 0.101 0.045
Lead 0.015 0.007
Nickel 0.067 0.044
Cyanide (total) 0.010 0.004
Ammonia (as N) 4.666 2.051
Fluoride 1.225 0.700
Tin 0.172 0.076
Total suspended 1.435 0.683
solids
pH Within the range of 7.5 to 10.0
at all times
224
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Table IX-2 (continued)
BPT MASS LIMITATIONS FOR THE PRIMARY
AND SECONDARY TIN SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of neutralized dewatered tin
mud produced
Antimony 14.490 6.460
Lead 2.120 1.010
Nickel 9.690 6.410
Cyanide (total) 1.464 0.606
Ammonia (as N) 672.800 295.800
Fluoride 176.700 101.000
Tin 24.830 11.000
Total suspended 206.900 98.420
solids
pH Within the range of 7.5 to 10.0
at all times
(d) Tin Hydroxide Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony 34.310 15.300
Lead 5.020 2.391
Nickel 22.950 15.180
Cyanide (total) 3.466 1.434
Ammonia (as N) 1,593.000 700.400
Fluoride 418.400 239.100
Tin 58.810 26.058
Total suspended 490.100 233.100
solids
pH Within the range of 7.5 to 10.0
at all times
225
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Table IX-2 (continued)
BPT MASS LIMITATIONS FOR THE PRIMARY
AND SECONDARY TIN SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 48.220 21.510
Lead 7.056 3.360
Nickel 32.260 21.340
Cyanide (total) 4.872 2.016
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 82.660 36.620
Total suspended 688.800 327.600
solids
pH • Within the range of 7.5 to 10.0
at all times
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as
raw material
Antimony 0.342 0.152
Lead 0.050 0.024
Nickel 0.229 0.151
Cyanide (total) 0.035 0.014
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.585 0.259
Total suspended 4.879 2.321
solids
pH Within the range of 7.5 to 10.0
at all times
226
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Table IX-2 (continued)
BPT MASS LIMITATIONS FOR THE PRIMARY
AND SECONDARY TIN SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 159.700 71.220
Lead 23.370 11.130
Nickel 106.800 70,660
Cyanide (total) 16.140 6.677
Ammonia (as N) 7,417.000 3,261.000
Fluoride 1,948.000 1,113.000
Tin 273.700 121.300
Total suspended 2,281.000 1,085.000
solids
pH Within the range of 7.5 to 10.0
at all times
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from spent
plating solutions
Antimony 109.000 48.610
Lead 15.950 7.596
Nickel 72.920 48.230
Cyanide (total) 11.010 4.557
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 186.900 82;790
Total suspended 1,557.000 740.600
solids
pH Within the range of 7.5 to 10.0
at all times
227
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Table IX-2 (continued)
BPT MASS LIMITATIONS FOR THE PRIMARY
AND SECONDARY TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 477.500 213.000
Lead 69.870 33.270
Nickel 319.400 211.300
Cyanide (total) 48.240 19.960
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 818.500 362.700
Total suspended 6,821.000 3,244.000
solids .
pH Within the range of 7.5 to 10.0
at all times
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 71.880 32.060
Lead 10.520 5.009
Nickel 48.090 31.810
Cyanide (total) 7.263 3.005
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 123.200 54.600
Total suspended 1,027.000 . 488.400
solids
pH Within the range of 7.5 to 10.0
at all times
228
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230
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
The effluent limitations which must be achieved by July 1, 1984
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 (Section
304(b)(2)(B) of the Clean Water Act). At a minimum BAT
technology represents the best available technology at plants of
various ages, sizes, processes, or other characteristics. As
with BPT, 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 dommon industry
practice.
The statutory assessment of BAT considers costs, but does not
require a balancing of costs against effluent reduction benefits
(see Weyerhaeuser v. Costle, 11 ERC 2149 (D.C. Cir. 1978)).
However, in assessing the proposed 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 two
technology options which could be applied to the primary and
secondary tin 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 increase treatment
231
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effectiveness achievable with the more sophisticated BAT
treatment technology.
In summary the treatment technologies considered for BAT are
presented below:
Option A (Figure X-l) is based on
• Preliminary treatment with ammonia steam stripping and
cyanide precipitation
• Chemical precipitation and sedimentation
Option C (Figure X-2) is based on
• .Preliminary treatment with ammonia steam stripping and
cyanide precipitation
• Chemical precipitation and sedimentation
• Multimedia filtration
The two options examined for BAT are discussed in greater detail
below. The first option considered is the same as the BPT
treatment which was presented in the previous section. The
latter option represents substantial progress toward the
prevention of polluting the environment above and beyond the
progress achievable by BPT.
OPTION A
Option A for the primary and secondary tin subcategory is
equivalent to the control and treatment technologies which were
analyzed for BPT in Section IX. The BPT end-of-pipe treatment
scheme includes chemical precipitation and sedimentation, with
ammonia steam stripping and cyanide precipitation preliminary
treatment (see Figure X-l). 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 tin subcategory consists
of all control and treatment requirements of Option A (ammonia
steam stripping, cyanide precipitation, chemical precipitation
and sedimentation) plus multimedia filtration technology added at
the end of the Option A treatment scheme (see Figure X-2).
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 filters, such as
rapid sand filters or pressure filters, would perform as well.
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INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant reduction benefits and the compliance
costs associated with each option. The methodologies are
described below.
POLLUTANT REMOVAL ESTIMATES
A complete 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 the
General Development Document. In short, 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 primary and secondary tin 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 first 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. Finally, 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 the primary and secondary tin
subcategory are presented in Table X-1, for direct dischargers.
COMPLIANCE COSTS
In estimating subcategory-wide compliance costs, the first step
was to develop a cost model, relating the total costs associated
with installation and operation of wastewater treatment
technologies to plant process wastewater discharge. EPA applied
the model on a per plant basis, a plant's costs - both capital,
and operating and maintenance - being determined by what
treatment it has in place and by its individual process
wastewater discharge (from dcp). The final step was to annualize
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the capital costs, and to sum the annualized capital costs, and
the operating and maintenance costs, yielding the cost of
compliance for the subcategory (see Table X-2). These costs were
used in assessing economic achievability.
BAT OPTION SELECTION
Our proposed BAT limitations for this subcategory are based on
preliminary treatment consisting of ammonia steam stripping and
cyanide precipitation when required, and end-of-pipe treatment
consisting of chemical precipitation and sedimentation, and
polishing filtration.
The pollutants specifically limited under BAT are antimony,
cyanide, lead, nickel, tin, ammonia, and fluoride. The toxic
pollutants arsenic, cadmium, chromium, copper, selenium, silver,
thallium and zinc 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.
Implementation of the proposed BAT limitations would remove
annually an estimated 1,260 kg of toxic metals, which is 91 kg of
toxic metals more than the estimated BPT discharge. Capital and
annual costs for this subcategory are not presented here because
the data on which they are based has been claimed to be
confidential.
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 dcp. 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 wastewater sources were determined and are summarized in
Table X-3. 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 (PNP) are also listed in Table X-4.
The BAT wastewater discharge rate equals the BPT wastewater
discharge rate for all of the waste streams in the primary and
secondary tin subcategory. Based on the available data, the
Agsr.cy did not find that further flow reduction would be feasible
for any of these wastewater sources. The rationale for
determining these regulatory flows is presented in Section IX.
234
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REGULATED POLLUTANT PARAMETERS
In implementing the terms of the Consent Agreement in NRDC v.
Train, Op. cit., and 33 U.S.C. 1314(b)(2)(Aand B) (1976), 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 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 mass limitations and standards for each of the toxic
metals found in treatable concentrations in the raw wastewater
from a given subcategory, the Agency is proposing effluent mass
limitations only for those pollutants generated in the greatest
quantities as shown by the pollutant removal estimate analysis.
The pollutants selected for specific limitation are listed below:
114. antimony
121. cyanide
122. lead
124. nickel
ammonia (as N)
fluoride
tin
By establishing limitations and standards for certain toxic metal
pollutants, dischargers will attain the same degree of control
over toxic metal pollutants as they would have been required to
achieve, had all the toxic metal pollutants been directly
limited.
This approach is technically justified since the treatable
concentrations used for lime 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
non-preferentially.
The toxic metal pollutants selec^d for specific limitation in
the subcategory to control the dischargges of toxic metal
pollutants are antimony, lead, and nickel. Cyanide is selected
for limitation because the methods used to control antimony,
lead, nickel and ammonia are not effective in the control of
235
-------
cyanide. The following toxic pollutants are excluded from
limitation on the basis that they are effectively controlled by
the limitations developed for antimony, lead and nickel.
115. arsenic
118. cadmium
119. chromium (Total)
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 the General Development Document and summarized
there in Table VII-19. The treatability concentrations (both one
day maximum and monthly average values) are multiplied by the BAT
normalized discharge flows summarized in Table X-3 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 for each waste stream.
236
-------
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237
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Table X-2
COST OF COMPLIANCE FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY DIRECT DISCHARGERS
Compliance costs for direct dischargers in this subcategory are
not presented here becuase the data on which they are based have
been claimed to be confidential.
238
-------
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239
-------
Table X-4
BAT MASS LIMITATIONS FOR- THE
PRIMARY AND SECONDARY TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
41.830
6.068
11.920
4.334
2,8-89.000
758.500
71.080
18.640
2.817
8.018
1 .734
270!000
433.400
31.640
(b) Dealuminizing Rinse
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
0.068
0.010
0.019
0.0070
4.666
1 .225
0.115
0.030
0.005
0.013
0.0028
2.051
0.700
0.051
240
-------
Table X-4 (continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY
c) Tin Mud Acid Neutralization Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million
mud produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Ibs) of neutralized dewatered tin
9
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413
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009
800
700
550
4.341
0.656
1 .868
0.404
295.800
101.000
7.370
(d) Tin Hydroxide Wash
Pollutant or
Pollutant Property
Maximum for.
Any One Day
Maximum for
Monthly. Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
23.070
3.347
6.574
2.391
1,593.000
418.400
39.210
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423
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400
100
17.450
241
-------
Table X-4 (continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 14.450
Lead 4.704 2.184
Nickel 9.240 6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 55.100 24.530
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as'
raw material
Antimony 0.230 0.102
Lead 0.033 0.015
Nickel 0.065 0.044
Cyanide (total) 0.0238 0.0095
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.390 0.174
242
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Table X-4 (continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 107.400 47.850
Lead 15.580 - 7.233
Nickel 30.600 20.590
Cyanide (total) 11.130 4.451
Ammonia (as N) 7,417.000 3,261.000
Fluoride 1,948.000 1,113.000
Tin 182.500 81.230
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from spent
plating soultions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 124.600 55.450
243
-------
Table X-4 (continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 321.100 143.100
Lead 46.580 21.630
Nickel 91.500 61.560
Cyanide (total) 33.270 13.310
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 545.700 242.900
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
244
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PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
The basis for new source performance standards (NSPS) under
Section 306 of the Act 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, Congress directed EPA to consider the best
demonstrated process changes, in-plant controls, and end-of-pipe
treatment technologies which reduce pollution to the maximum
extent feasible.
This section describes the technologies for treatment of
wastewater from new sources and presents mass discharge standards
for regulatory pollutants for NSPS in the primary and secondary
tin subcategory, based on the selected treatment technology.
TECHNICAL APPROACH TO NSPS
New source performance standards are equivalent to the best
available technology (BAT) selected for currently existing
primary and secondary tin plants. This result is a consequence
of careful review by the Agency of a wide range of technology
options for new source treatment systems which is discussed in
Section XI of the General Development Document. This review of
the primary and secondary tin subcategory found no new,
economically feasible, demonstrated technologies which could be
considered an improvement over those chosen for consideration
for BAT. 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.
Treatment technologies considered for the NSPS options are
identical to the treatment technologies considered for the BAT
options. These options are:
OPTION A
• Preliminary treatment with ammonia steam stripping and
cyanide precipitation (where required)
• Chemical precipitation and sedimentation
247
-------
OPTION C
• Preliminary treatment with ammonia steam stripping and
cyanide precipitation (where required)
• Chemical precipitation and sedimentation
• Multimedia filtration
NSPS OPTION SELECTION
We are proposing that NSPS be equal to BAT. Our review of the
subcategory indicates that no new demonstrated technologies that
improve on BAT technology exist. We do not believe that new
plants could achieve any flow reduction beyond the allowances
proposed for BAT. Because NSPS is equal to BAT we believe that
the proposed NSPS will not pose a barrier to 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. The
mass of pollutant allowed to be discharged per mass of product is
based upon the product of the appropriate treatable concentration
(mg/1) and the production normalized wastewater discharge flows.
The treatable concentrations are listed in Table VI1-19 of the
General Development Document. The results of these calculations
are the production-based new source performance standards. These
standards are presented in Tables XI-2.
248
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Table XI-2
NSPS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
Total suspended 325.100 260.100
solids
pH Within the range of 7.5 to 10.0
at all times
(b) Dealuminizing Rinse
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of dealuminized scrap produced
Antimony 0.068 0.030
Lead 0.010 0.005
Nickel 0.019 0.013
Cyanide (total) 0.0070 0.0028
Ammonia (as N) 4.666 2.051
Fluoride 1.225 0,700
Tin 0.115 0.051
Total suspended 0.525 0.420
solids
pH Within the range of 7.5 to 10.0
at all times
250
-------
Table XI-2 (continued)
NSPS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of neutralized dewatered tin
mud produced
Antimony 9.741 4.341
Lead 1.413 0.656
Nickel 2.776 1.868
Cyanide (total) 1.009 0.404
Ammonia (as N) 672.800 295.800
Fluoride 176.700 101.000
Tin 16.550 7.370
Total suspended 75.710 60.570
solids
pH Within the range of 7.5 to 10.0
at all times
(d) Tin Hydroxide Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony 23.070 10.280
Lead 3.347 1.554
Nickel 6.574 4.423
Cyanide (total) 2.391 0.956
Ammonia (as N) 1,593.000 700.400
Fluoride 418.400 239.100
Tin 39.210 17.450
Total suspended 179.300 143.500
solids
pH Within the range of 7.5 to 10.0
at all times
251
-------
Table XI-2 (continued)
NSPS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY.
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 14.450
Lead 4.704 2.184
Nickel 9.240 6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 55.100 24.530
Total suspended 252.000 201.600
solids
pH Within the range of 7.5 to 10.0
at all times
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as raw material
Antimony 0.230 0.102
Lead 0.033 0.015
Nickel 0.065 0.044
Cyanide (total) 0.0238 0.0095
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.390 0.174
Total suspended 1.785 1.428
solids
pH Within the range of 7.5 to 10.0
at all times
252
-------
Table XI-2 (continued)
NSPS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 107.400 47.850
Lead 15.580 7.233
Nickel 30.600 20.590
Cyanide (total) 11.130 4.451
Ammonia (as N) 7,417.000 3,261.000
Fluoride ' 1,948.000 1,113.000
Tin 182.500 81.230
Total suspended 834.600 667.700
solids
pH Within the range of 7.5 to 10.0
at all times
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from spent
plating solutions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 124.600 55.450
Total suspended 569.700 455.800
solids
pH Within the range of 7.5 to 10.0
at all times
253
-------
Table XI-2 (continued)
NSPS FOR THE PRIMARY AND
SECONDARY TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 321.100 143.100
Lead 46.580 21.630
Nickel 91.500 61.560
Cyanide (total) 33.270 13.310
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 545.700 242.900
Total suspended 2,496.000 1,997.000
solids
pH Within the range of 7.5 to 10.0
at all times
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
Total suspended 375.700 300.500
solids
pH Within the range of 7.5 to 10.0
at all times
254
-------
PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION XII
PRETREATMENT STANDARDS
Section 307(b) of the Act requires EPA to promulgate pretreatment
standards for existing sources (PSES), which must be achieved
within three years of promulgation. PSES are designed to prevent
the discharge of pollutants which pass through, interfere with,
or are otherwise incompatible with the operation of publicly
owned treatment works (POTW). The Clean Water Act of 1977
requires pretreatment for pollutants, such as heavy metals, that
limit POTW sludge management alternatives. Section 307(c) of the
Act requires EPA to promulgate pretreatment standards for new
sources (PSNS) at the same time that it promulgates NSPS. New
indirect 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 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 and secondary tin subcategory.
Pretreatment standards for regulated pollutants are presented
based on .the selected control and treatment" technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing 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 .we11-operated POTW meeting secondary
treatment requirements, is less than the percentage removed by
direct dischargers complying with BAT effluent limitations
guidelines for that pollutant. (See generally, 46 FR at 9415-16
(January 28, 1981)).
This definition of pass through satisfies two competing
objectives set by Congress: (1) that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time, (2) that the treatment capability and
255
-------
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.
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 shows the estimated pollutant removals for indirect
dischargers. Compliance costs for indirect dischargers are
presented in Table XI1-2.
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
Preliminary treatment with ammonia steam stripping and
cyanide precipitation (where required)
Chemical precipitation and sedimentation
OPTION C
• Preliminary treatment with ammonia steam stripping and
cyanide precipitation (where required)
• Chemical precipitation and sedimentation
• Multimedia filtration
256
-------
PSNS AND PSES OPTION SELECTION
We are proposing PSES equal to BAT for this subcategory. It is
necessary to propose PSES to prevent pass-through of antimony,
cyanide, lead, nickel, tin, ammonia, and fluoride. The four
toxic pollutants and fluoride are removed by a well-operated POTW
achieving secondary treatment at an average of 17 percent while
BAT technology removes approximately 97 percent.
The technology basis for PSES thus is chemical precipitation and
sedimentation, with preliminary treatment consisting of ammonia
steam stripping and cyanide precipitation, and filtration.
Implementation of the proposed PSES limitations would remove
annually an estimated 152 kg of toxic metals, 6,282 kg of tin, 32'
kg of cyanide and 25,105 kg of fluoride. Removals over estimated
raw discharge, are the same as removals over current discharge
because neither of the indirect dischargers in this subcategory
has any treatment in-place. Capital cost for achieving proposed
PSES is $341,700, and annual cost is $119,900. The proposed PSES
will not result in adverse economic impacts.
We are proposing PSNS equivalent to PSES, NSPS and BAT. The
technology basis for proposed PSNS is identical to NSPS, PSES,
and BAT. The same pollutants pass through at PSNS as at PSES,
for the same reasons. We know of no economically feasible,
demonstrated technology that is better than PSES technology. The
PSNS flow allowances are identical to the flow allowances for
BAT, NSPS, and PSES.
There would be no additional cost for" PSNS above the costs
estimated for BAT. We believe that the proposed PSNS are
achievable, and that they are not a barrier to entry of new
plants into this subcategory.
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 propose PSES and PSNS
to prevent the pass-through of antimony, cyanide, lead, nickel,
tin, fluoride, and ammonia, which are the limited pollutants.
PRETREATMENT STANDARDS
Pretreatment standards are based on the treatable concentrations
from the selected treatment technology, (Option C), 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 the subcategory. This pollutant
allocation is based on the product of the treatable concentration
from the proposed treatment (mg/1) and the production normalized
wastewater discharge rate. The achievable treatment
,257
-------
concentrations for BAT are identical to those for PSES and PSNS.
These concentrations are listed in Tables XII-19 of the General
Development Document. PSES and PSNS are presented in Tables XII-
4 and XII-5.
253
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Table XII-2
COST OF COMPLIANCE FOR THE
PRIMARY AND SECONDARY TIN SUBCATEGORY
INDIRECT DISCHARGERS
(March, 1982 Dollars)
Total Required Total
Option Capital Cost Annual Cost
A 333,400 112,200
C 341,700 119,900
260
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Table XII-4
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
(b) Dealuminizing Rinse
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of dealumi.nized scrap produced
Antimony 0.068 " 0.030
Lead 0.010 0.005
Nickel 0.019 0.013
Cyanide (total) 0.0070 0.0028
Ammonia (as N) 4.666 2.051
Fluoride 1.225 0.700
Tin 0.115 0.051
262
-------
Table XII-4 (continued)
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million
mud produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Ibs) of neutralized dewatered tin
9.741
1 .413
2.776
1 .009
672.800
176.700
16.550
4.341
0.656
1 .868
0.404
295.800
101.000
7.370
(d) Tin Hydroxide Wash
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
23,
3,
6,
2,
593,
418,
39,
070
347
574
391
000
400
210
10
1
4
0.
700
239,
17,
280
554
423
956
400
100
450
263
-------
Table XII-4 (continued)
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs) of cathode tin produced
Antimony 32.430 14.450
Lead 4.704 2.184
Nickel 9.240 6.216
Cyanide (total) 3.360 1.344
Ammonia (as N) 2,239.000 984.500
Fluoride 588.000 336.000
Tin 55.100 24.530
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
ing/kg (Ib/million Ibs) of MSW scrap used as" raw material
Antimony 0.230 0.102
Lead 0.033 0.015
Nickel 0.065 0.044
Cyanide (total) 0.0238 0.0095 '
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.390 0.174
264
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Table XII-4 (continued)
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from scrap
Antimony 107.400 47.850
Lead 15.580 7.233
Nickel 30.600 20.590
Cyanide (total) 11.130 4.451
Ammonia (as N) 7,417.000 3,261.000
Fluoride 1,948.000 1,113.000
Tin 182.500 81.230
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (lb/mi11 ion Ibs) of tin metal recovered from
spent plating solutions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) . 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 124.600 55.450
265
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Table XII-4 (continued)
PSES FOR THE PRIMARY AND SECONDARY TIN
SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
321.100
46.580
91.500
33.270
22,180.000
5,823.000
545.700
143.100
21.630
61.560
13.310
9,749.000
3,327.000
242.900
(j) Tin Hydroxide Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
48.340
7.013
13.780
5.009
3,338.000
876.600
82.140
"21.540
3.256
9.266
2.004
1,468.000
500.900
36.560
266
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Table XII-5
PSNS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY
(a) Tin Smelter S02 Scrubber
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 41.830 18.640
Lead 6.068 2.817
Nickel 11.920 8.018
Cyanide (total) 4.334 • 1.734
Ammonia (as N) 2,889.000 1,270.000
Fluoride 758.500 433.400
Tin 71.080 31.640
(b) Dealuminizing Rinse
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of dealumi.nized scrap produced
Antimony 0.068 '0.030
Lead 0.010 0.005
Nickel 0.019 0.013
Cyanide (total) 0.0070 0.00-28
Ammonia (as N) 4.666 2.051
Fluoride 1.225 0.700
Tin 0.115 0.051
267
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Table XII-5 (continued)
PSNS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY
(c) Tin Mud Acid Neutralization Filtrate
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million
mud produced
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Ibs) of neutralized dewatered tin
9.
1.
2.
1,
672,
176,
741
413
776
009
800
700
16.550
4.341
0.656
1.868
0.404
295.800
101.000
7.370
(d) Tin Hydroxide Wash
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of tin hydroxide washed
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
23,
3,
6,
2,
1 ,593,
418,
070
347
574
391
000
400
10.
1 .
4.
0.
700,
239.
280
554
423
956
400
100
39.210
17.450
268
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Table XII-5 (continued)
PSNS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY
(e) Spent Electrowinning Solution from New Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Antimony
Lead
Nickel
Cyanide (total)
Ammonia (as N)
Fluoride
Tin
Ibs) of cathode
32.430
4.704
9.240
3.360
2,239.000
588.000
55.100
tin produced
14.450
2.184
6.216
1.344
984.500
336.000
24.530
(f) Spent Electrowinning Solution from Municipal Solid
Waste
Pollutant or Maximum for Maximum for
Pollutant Property Any One .Day Monthly Average
mg/kg (Ib/million Ibs) of MSW scrap used as
raw material
Antimony 0.230 0.102
Lead 0.033 0.015
Nickel 0.065 0.044
Cyanide (total) 0.0238 0.0095
Ammonia (as N) 15.860 6.973
Fluoride 4.165 2.380
Tin 0.390 0.174
269
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Table XII-5 (continued)
PSNS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY
(g) Tin Hydroxide Supernatant from Scrap
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Antimony
Lead
Nickel
Cyanide
Ammonia
Fluoride
Tin
(
(
total)
as
N)
Ibs) of t
107
15
30
11
7,417
1,948
182
in metal
.400
.580
.600
.130
.000
.000
.500
recovered
3,
1,
47,
7.
20,
4.
261 .
113.
81.
from
850
233
590
451
000
000
230
scrap
(h) Tin Hydroxide Supernatant from Spent Plating
Solutions
Pollutant or Maximum .for Maximum for
Pollutant Property Any One Day Mont.hly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
spent plating solutions
Antimony 73.300 32.660
Lead 10.640 4.937
Nickel 20.890 14.050
Cyanide (total) 7.596 3.038
Ammonia (as N) 5,062.000 2,226.000
Fluoride 1,329.000 759.600
Tin 124.600 55.450
270
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Table XII-5 (continued)
PSNS FOR THE PRIMARY AND SECONDARY
TIN SUBCATEGORY
(i) Tin Hydroxide Supernatant from Sludge Solids
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tin metal recovered from
sludge solids
Antimony 321.100 143.100
Lead 46.580 21.630
Nickel 91.500 61.560
Cyanide (total) 33.270 13.310
Ammonia (as N) 22,180.000 9,749.000
Fluoride 5,823.000 3,327.000
Tin 545.700 242.900
(j) Tin Hydroxide Filtrate
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day. Monthly Average
mg/kg (Ib/million Ibs) of tin metal produced
Antimony 48.340 21.540
Lead 7.013 3.256
Nickel 13.780 9.266
Cyanide- (total) 5.009 2.004
Ammonia (as N) 3,338.000 1,468.000
Fluoride 876.600 500.900
Tin 82.140 36.560
271
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272
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, PRIMARY AND SECONDARY TIN SUBCATEGORY
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not proposing best conventional pollutant control
technology (BCT) limitations for the primary and secondary tin
subcategory at this time.
273
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