United States Effluent Guidelines Division EPA-440/1-84/019-b
Environmental Protection WH-552 July 1984
Agency Washington, O.C. 20460
Water and Waste Management " , ( T'T'L/ I OT"U I vy D I
>EPA Development Proposed
Document for
Effluent Limitations
Guidelines and
Standards for the
Nonferrous Metals
Point Source Category
Phase II
Supplemental Development
Document For:
Secondary Precious Metals
-------
DEVELOPMENT DOCUMENT
for i
EFFLUENT LIMITATIONS GUIDELINES.AND STANDARDS
for the
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
PHASE II
Secondary Precious Metals Supplement
Jack E. Ravan
Assistant Administrator for Water
Edwin L. Johnson
Director
Office of Water Regulations and Standards
U.S. Environmental Protection Agency
\ R':?\on V. ' is--?ry
f 2E2J 23° —'" • :-•-.'.•". -rn Street
\ ^ Cii.-:.:;_,o, .Ilinois 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
-------
U.S. E
»w
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
TABLE OF CONTENTS
Section
I SUMMARY AND CONCLUSIONS 1
II RECOMMENDATIONS 5
BPT MASS LIMITATIONS FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY 6
BAT MASS LIMITATIONS FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY 12
NSPS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY 17
PSES FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY 23
PSNS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY 28
III INDUSTRY PROFILE 33
DESCRIPTION OF SECONDARY PRECIOUS METALS
PRODUCTION 33
RAW MATERIALS 33
RAW MATERIAL PREPARATION STEPS 33
Incineration and Smelting 34
Raw Material Granulation 34
Stripping With Cyanide Solutions 34
Recovery From Spent Plating Solutions 34
REFINING STEPS 35
Hydrometallurgical Processing 35
Solvent Extraction 37
Electrolytic Refining 37
Further Processing 37
PROCESS WASTEWATER SOURCES 37
OTHER WASTEWATER SOURCES 38
AGE, PRODUCTION, AND PROCESS PROFILE 38
IV SUBCATEGORIZATION 47
FACTORS CONSIDERED IN SUBCATEGORIZATION 47
FACTORS CONSIDERED IN SUBDIVIDING THE SECONDARY
PRECIOUS METALS SUBCATEGORY 48
OTHER FACTORS 49
PRODUCTION NORMALIZING PARAMETERS 50
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
V WATER USE AND WASTEWATER CHARACTERISTICS .... 53
WASTEWATER FLOW RATES 54
WASTEWATER CHARACTERIZATION DATA 55
DATA COLLECTION PORTFOLIOS 55
FIELD SAMPLING DATA 55
WASTEWATER CHARACTERISTICS AND FLOWS BY
SUBDIVISION 57
FURNACE WET AIR POLLUTION CONTROL 57
RAW MATERIAL GRANULATION 57
SPENT PLATING SOLUTIONS 58
SPENT CYANIDE STRIPPING SOLUTIONS 58
REFINERY WET AIR POLLUTION CONTROL 58
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH
WATER 59
GOLD SPENT ELECTROLYTE 59
GOLD PRECIPITATION AND FILTRATION 59
PLATINUM PRECIPITATION AND FILTRATION 60
PALLADIUM PRECIPITATION AND FILTRATION 60
OTHER PLATINUM GROUP METALS PRECIPITATION
AND FILTRATION 60
SPENT SOLUTION FROM PGC SALT PRODUCTION 61
EQUIPMENT AND FLOOR WASH 61
VI SELECTION OF POLLUTANT PARAMETERS 211
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT
PARAMETERS 211
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT
PARAMETERS SELECTED 211
TOXIC POLLUTANTS 212
TOXIC POLLUTANTS NEVER DETECTED 213
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR
ANALYTICAL QUANTIFICATION LIMIT 215
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS
ACHIEVABLE BY TREATMENT 215
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER
OF SOURCES 216
TOXIC POLLUTANTS SELECTED FOR FURTHER
CONSIDERATION IN ESTABLISHING LIMITATIONS
AND STANDARDS 218
11
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
VII CONTROL AND TREATMENT STANDARDS 225
CURRENT CONTROL AND TREATMENT PRACTICES 225
FURNACE WET AIR POLLUTION CONTROL 225
RAW MATERIAL GRANULATION 226
SPENT PLATING SOLUTIONS 226
SPENT CYANIDE STRIPPING SOLUTIONS 226
REFINERY WET AIR POLLUTION CONTROL 227
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH
WATER 227
GOLD SPENT ELECTROLYTE 227
GOLD PRECIPITATION AND FILTRATION 228
PLATINUM PRECIPITATION AND FILTRATION 228
PALLADIUM PRECIPITATION AND FILTRATION 228
OTHER PLATINUM GROUP METALS PRECIPITATION
AND FILTRATION 229
SPENT SOLUTION FROM PGC SALT PRODUCTION 229
EQUIPMENT AND FLOOR WASH 229
CONTROL AND TREATMENT OPTIONS CONSIDERED .... 229
OPTION A 229
OPTION B 230
OPTION C 230
VIII COSTS, ENERGY, AND NONWATER QUALITY ASPECTS. . . 231
TREATMENT OPTIONS FOR EXISTING SOURCES 231
OPTION A 231
OPTION B 231
OPTION C 231
COST METHODOLOGY 232
NONWATER QUALITY ASPECTS 233
ENERGY REQUIREMENTS 233
SOLID WASTE 234
AIR POLLUTION 235
IX BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE 239
TECHNICAL APPROACH TO BPT 239
INDUSTRY COST AND POLLUiANT REMOVAL ESTIMATES. . 241
BPT OPTION SELECTION 241
WASTEWATER DISCHARGE RATES 243
FURNACE WET AIR POLLUTION CONTROL 244
RAW MATERIAL GRANULATION 244
ill
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
SPENT PLATING SOLUTIONS 244
SPENT CYANIDE STRIPPING SOLUTIONS 245
REFINERY WET AIR POLLUTION CONTROL 245
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH
WATER 246
GOLD SPENT ELECTROLYTE 246
GOLD PRECIPITATION AND FILTRATION 246
PLATINUM PRECIPITATION AND FILTRATION 247
PALLADIUM PRECIPITATION AND FILTRATION 247
OTHER PLATINUM GROUP METALS PRECIPITATION
AND FILTRATION 248
SPENT SOLUTION FROM PGC SALT PRODUCTION 248
EQUIPMENT AND FLOOR WASH 248
REGULATED POLLUTANT PARAMETERS 249
EFFLUENT LIMITATIONS 249
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE 261
TECHNICAL APPROACH TO BAT 261
OPTION A 262
OPTION B 263
Recycle of Water Used in Wet Air Pollution
Control 263
OPTION C 264
INDUSTRY COST AND ENVIRONMENTAL BENEFITS .... 264
POLLUTANT REMOVAL ESTIMATES 264
COMPLIANCE COSTS 265
BAT OPTION SELECTION 265
WASTEWATER DISCHARGE RATES 266
FURNACE WET AIR POLLUTION CONTROL 267
REFINERY WET AIR POLLUTION CONTROL 267
REGULATED POLLUTANT PARAMETERS 267
EFFLUENT LIMITATIONS 269
XI NEW SOURCE PERFORMANCE STANDARDS 283
TECHNICAL APPROACH TO NSPS 283
OPTION A 284
OPTION B 284
OPTION C 284
IV
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
XII
XIII
NSPS OPTION SELECTION 284
REGULATED POLLUTANT PARAMETERS 285
NEW SOURCE PERFORMANCE STANDARDS 285
PRETREATMENT STANDARDS 295
TECHNICAL APPROACH TO PRETREATMENT 295
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES. . 296
PRETREATMENT STANDARDS FOR EXISTING AND NEW
SOURCES 296
OPTION A 296
OPTION B 297
OPTION C 297
PSES OPTION SELECTION 297
PSNS OPTION SELECTION 298
REGULATED POLLUTANT PARAMETERS 298
PRETREATMENT STANDARDS 298
BEST CONVENTIONAL POLLUTANT CONTROL
TECHNOLOGY 315
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
LIST OF TABLES
Number Page
II1-1 INITIAL OPERATING YEAR (RANGE) SUMMARY OF
PLANTS IN THE SECONDARY PRECIOUS METALS
SUBCATEGORY BY DISCHARGE TYPE 40
III-2 PRODUCTION RANGES FOR THE SECONDARY PRECIOUS
METALS SUBCATEGORY DURING 1982 (TROY OUNCES
OF TOTAL PRECIOUS METALS/YEAR) 41
III-3 SUMMARY OF SECONDARY PRECIOUS METALS
SUBCATEGORY PROCESSES AND ASSOCIATED
WASTE STREAMS 42
V-1 WATER USE AND DISCHARGE RATES FOR FURNACE WET
AIR POLLUTION CONTROL 62
V-2 WATER USE AND DISCHARGE RATES FOR RAW MATERIAL
GRANULATION 63
V-3 WATER USE AND DISCHARGE RATES FOR SPENT PLATING
SOLUTIONS 64
V-4 WATER USE AND DISCHARGE RATES FOR SPENT '
CYANIDE STRIPPING SOLUTIONS 65
V-5 WATER USE AND DISCHARGE RATES FOR REFINERY WET
AIR POLLUTION CONTROL 66
V-6 WATER USE AND DISCHARGE RATES FOR GOLD SOLVENT
EXTRACTION RAFFINATE AND WASH WATER 68
V-7 WATER USE AND DISCHARGE RATES FOR GOLD SPENT
ELECTROLYTE 69
V-8 WATER USE AND DISCHARGE RATES FOR GOLD
PRECIPITATION AND FILTRATION WASTEWATER 70
V-9 WATER USE AND DISCHARGE RATES FOR PLATINUM
PRECIPITATION AND FILTRATION 72
V-10 WATER USE AND DISCHARGE RATES FOR PALLADIUM
PRECIPITATION AND FILTRATION 73
vii
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
LIST OF TABLES (Continued)
Number Page
V-11 WATER USE AND DISCHARGE RATES FOR OTHER
PLATINUM GROUP METALS PRECIPITATION AND
FILTRATION 74
V-12 WATER USE AND DISCHARGE RATES FOR SPENT
SOLUTION FROM PGC SALT PRODUCTION 75
V-13 WATER USE AND DISCHARGE RATES FOR EQUIPMENT
AND FLOOR WASH 76
V-14 SECONDARY PRECIOUS METALS SAMPLING DATA
FURNACE WET AIR POLLUTION CONTROL RAW
WASTEWATER 77
V-15 SECONDARY PRECIOUS METALS SAMPLING DATA
SPENT PLATING SOLUTIONS RAW WASTEWATER 93
V-16 SECONDARY PRECIOUS METALS SAMPLING DATA
SPENT CYANIDE STRIPPING SOLUTION RAW
WASTEWATER 103
V-17 SECONDARY PRECIOUS METALS SAMPLING DATA
REFINERY WET AIR POLLUTION CONTROL RAW
WASTEWATER 106
V-18 SECONDARY PRECIOUS METALS SAMPLING DATA
GOLD PRECIPITATION AND FILTRATION RAW
WASTEWATER 126
V-19 SECONDARY PRECIOUS METALS SAMPLING DATA
PALLADIUM PRECIPITATION AND FILTRATION
RAW WASTEWATER 130
V-20 SECONDARY PRECIOUS METALS SAMPLING DATA
SPENT SOLUTION FROM PGC SALT PRODUCTION
RAW WASTEWATER 137
V-21 SECONDARY PRECIOUS METALS SAMPLING DATA
EQUIPMENT AND FLOOR WASH RAW WASTEWATER 140
V-22 SECONDARY PRECIOUS METALS SAMPLING DATA
CEMENTATION TANK EFFLUENT 144
V1LL
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
LIST OF TABLES (Continued)
Number Page
V-23 SECONDARY PRECIOUS METALS SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT A 164
V-24 SECONDARY PRECIOUS METALS SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT B 175
V-25 SECONDARY PRECIOUS METALS SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C 188
V-26 SECONDARY PRECIOUS METALS SAMPLING DATA
CASTING CONTACT COOLING WATER 201
VI-1 FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS
SECONDARY PRECIOUS METALS SUBCATEGORY
RAW WASTEWATER 221
VI11-1 COST OF COMPLIANCE FOR THE SECONDARY PRECIOUS
METALS SUBCATEGORY DIRECT DISCHARGERS 236
VIII-2 COST OF COMPLIANCE FOR THE SECONDARY PRECIOUS
METALS SUBCATEGORY INDIRECT DISCHARGERS 237
IX-1 BPT WASTEWATER DISCHARGE RATES FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY 250
IX-2 BPT MASS LIMITATIONS FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY 252
X-1 CURRENT RECYCLE PRACTICES WITHIN THE SECONDARY
PRECIOUS METALS SUBCATEGORY 270
X-2 POLLUTANT REMOVAL ESTIMATES FOR DIRECT
DISCHARGERS 271
X-3 COST OF COMPLIANCE FOR DIRECT DISCHARGERS IN
THE SECONDARY PRECIOUS METALS SUBCATEGORY. ... 272
X-4 BAT WASTEWATER DISCHARGE RATES FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY 273
X-5 BAT MASS LIMITATIONS FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY 275
IX
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
LIST OF TABLES (Continued)
Number Page
XI-1 NSPS WASTEWATER DISCHARGE RATES FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY 286
XI-2 NSPS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY 288
XII-1 POLLUTANT REMOVAL ESTIMATES FOR INDIRECT
DISCHARGERS 299
XII-2 COST OF COMPLIANCE FOR THE SECONDARY PRECIOUS
METALS SUBCATEGORY INDIRECT DISCHARGERS 300
XII-3 PSES WASTEWATER DISCHARGE RATES FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY 301
XI1-4 PSES FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY 303
XII-5 PSNS WASTEWATER DISCHARGE RATES FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY 308
XI1-6 PSNS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY 310
x
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
LIST OF FIGURES
Number
III-1 SECONDARY PRECIOUS METALS PRODUCTION PROCESSES . 43
III-2 GEOGRAPHIC LOCATIONS OF THE SECONDARY PRECIOUS
METALS INDUSTRY 45
V-1 SAMPLING SITES AT SECONDARY PRECIOUS METALS
PLANT A 205
V-2 SAMPLING SITES AT SECONDARY PRECIOUS METALS
PLANT B 206
V-3 SAMPLING SITES AT SECONDARY PRECIOUS METALS
PLANT C 207
V-4 SAMPLING SITES AT SECONDARY PRECIOUS METALS
PLANT D 208
V-5 SAMPLING SITES AT SECONDARY PRECIOUS METALS
PLANT E 209
IX-1 BPT TREATMENT SCHEME FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY 259
X-1 BAT TREATMENT SCHEME FOR OPTION A 280
X-2 BAT TREATMENT SCHEME FOR OPTION B 281
X-3 BAT TREATMENT SCHEME FOR OPTION C 282
XI
-------
SECONDARY PRECIOUS METALS 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 ERG 2120 (D.D.C.
1976) modified, 12 ERG 1833 (D.D.C. 1979), EPA has collected and
analyzed data for plants in the secondary precious metals sub-
category. EPA has never proposed or promulgated effluent limita-
tions 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 discharg-
ers, pretreatment standards for existing indirect dischargers
(PSES), pretreatment standards for new indirect dischargers
(PSNS), and standards of performance for new source direct
dischargers (NSPS).
The secondary precious metals subcategory is comprised of 48
plants. Of the 48 plants, three discharge directly to rivers,
lakes, or streams; 29 discharge to publicly owned treatment works
(POTW); and 16 achieve zero discharge of process wastewater.
EPA first studied the secondary precious metals subcategory to
determine whether differences in raw materials, final products,
manufacturing processes, equipment, age and size of plants, or
water usage, required the development of separate effluent limi-
tations 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, 13
subdivisions have been identified for this subcategory that
warrant separate effluent limitations. These include:
Furnace wet air pollution control,
Raw material granulation,
Spent plating solutions,
Spent cyanide stripping solutions,
Refinery wet air pollution control,
Gold solvent extraction raffinate and wash water,
Gold spent electrolyte,
Gold precipitation and filtration,
Platinum precipitation and filtration,
Palladium precipitation and filtration,
-------
• Other platinum group metals (PGM) precipitation and
filtration,
• Spent solution from PGC salt production, and
• Equipment and floor wash.
EPA also identified several distinct control and treatment
technologies (both in-plant and end-of-pipe) applicable to the
secondary precious metals subcategory. The Agency analyzed both
historical and newly generated data on the performance of these
technologies, including their nonwater quality environmental
impacts and air quality, solid waste generation, and energy
requirements. EPA also studied various flow reduction techniques
reported in the data collection portfolios (dcp) and plant
visits.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of imple-
menting 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 pollu-
tants, 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. Cyanide precipitation was selected as the tech-
nology basis for cyanide limitations. To meet the BPT effluent
limitations based on this technology, the secondary precious
metals subcategory is expected to incur a capital and annual
cost. These costs cannot be disclosed because the data on which
they are based have been claimed to be confidential.
For BAT, the Agency has built upon the BPT technology basis by
adding in-process control technologies which include recycle of
process water from air pollution control waste streams. Filtra-
tion is added as an effluent polishing step to the end-of-pipe
treatment scheme. To meet the BAT effluent limitations based on
this technology, the secondary precious metals subcategory is
expected to incur a capital and annual cost. These costs cannot
be disclosed because the data on which they are based have been
claimed to be confidential.
-------
NSPS is equivalent to BAT, with one exception. The one exception
is that dry air pollution control replaces a wet scrubber in one
application. In selecting NSPS, EPA recognizes that new plants
have the opportunity to implement the best and most efficient
manufacturing processes and treatment technology. As such, the
technology basis of BAT has been determined as the best demon-
strated technology.
The technology basis for PSES is equivalent to BAT. To meet the
pretreatment standards for existing sources, the secondary
precious metals subcategory is estimated to incur a capital cost
of $1,419,000 and an annual cost of $984,000. For PSNS, the
Agency selected end-of-pipe treatment and in-process flow
reduction control techniques equivalent to NSPS.
The best conventional technology (BCT) replaces BAT for the con-
trol of conventional pollutants. BCT is not being proposed
because the methodology for BCT has not yet been finalized.
The mass limitations and standards for BPT, BAT, NSPS, PSES, and
PSNS are presented in Section II.
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION JI
RECOMMENDATIONS
1. EPA has divided the secondary precious metals sub-
category into 13 subdivisions for the purpose of
effluent limitations and standards. These
subdivisions are:
(a) Furnace wet air pollution control,
(b) Raw material granulation,
(c) Spent plating solutions,
(d) Spent cyanide stripping solutions,
(e) Refinery wet air pollution control,
(f) Gold solvent extraction raffinate and wash
water,
(g) Gold spent electrolyte,
(h) Gold precipitation and filtration,
(i) Platinum precipitation and filtration,
(j) Palladium precipitation and filtration,
(k) Other platinum group metals precipitation and
filtration,
(1) Spent solution from PGC salt production, and
(m) Equipment and floor wash.
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
effluent limitations are proposed:
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(a) Furnace Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
incinerated or smelted
Copper 136.400 71.800
Cyanide (total) 20.820 8.616
Zinc 104.800 43.800
Ammonia (as N) 9,571.000 4,207.000
Total suspended 2,944.000 1,400.000
solids
pH Within the range of 7.5 to 10.0
at all times
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(b) Raw Material Granulation
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metal in the granulated
raw material
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
Total suspended 0.000 0.000
solids
pH Within the range of 7.5 to 10.0
at all times
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(c) Spent Plating Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/liter of spent plating solution used as a
raw material
Copper 1.900 1.000
Cyanide (total) 0.290 0.120
Zinc 1.460 0.610
Ammonia (as N) 133.300 58.600
Total suspended 41.000 19.500
solids
pH Within the range of 7.5 to 10.0
at all times
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(d) Spent Cyanide Stripping Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by
cyanide stripping
Copper 2.090 1.100
Cyanide (total) 0.319 0.132
Zinc 1.606 0.671
Ammonia (as N) 146.600 64.460
Total suspended 45.100 21.450
solids
pH Within the range of 7.5 to 10.0
at all times
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(e) Refinery Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 39.900 21.000
Cyanide (total) 6.090 2.520
Zinc 30.660 12.810
Ammonia (as N) 2,799.000 1,231.000
Total suspended 861.000 409.500
solids
pH Within the range of 7.5 to 10.0
at all times
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(f) Gold Solvent Extraction Raffinate and Wash Water
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by solvent extraction
Copper 1.197 0.630
Cyanide (total) 0.183 0.076
Zinc 0.920 0.384
Ammonia (as N) 83.980 36.920
Total suspended 25.830 12.290
solids
pH Within the range of 7.5 to 10.0
at all times
8
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(g) Gold Spent Electrolyte
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by electrolysis
Copper 0.017 0.009
Cyanide (total) 0.003 0.001
Zinc 0.013 0.005
Ammonia (as N) 1.160 0.510
Total suspended 0.357 0.170
solids
pH Within the range of 7.5 to 10.0
at all times
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(h) Gold Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold precipitated
Copper 8.360 4.400
Cyanide (total) 1.276 0.528
Zinc 6.424 2.684
Ammonia (as N) 586.500 257.800
Total suspended 180.400 85.800
solids
pH Within the range of 7.5 to 10.0
at all times
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(i) Platinum Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of platinum precipitated
Copper 9.880 5.200
Cyanide (total) 1.508 0.624
Zinc 7.592 3.172
Ammonia (as N) 693.200 304.700
Total suspended 213.200 101.400
solids
pH Within the range of 7.5 to 10.0
at all times
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(j) Palladium Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of palladium precipitated
Copper 6.650 3.500
Cyanide (total) 1.015 0.420
Zinc 5.110 2.135
Ammonia (as N) 466.600 205.100
Total suspended 143.500 68.250
solids
pH Within the range of 7.5 to 10.0
at all times
10
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(k) Other Platinum Group Metals Precipitation and
Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of other platinum group metals
precipitated
Copper 9.880 5.200
Cyanide (total) 1.508 0.624
Zinc 7.592 3.172
Ammonia (as N) 693.200 304.700
Total suspended 213.200 101.400
solids
pH Within the range of 7.5 to 10.0
at all times
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(1) Spent Solution from PGC Salt Production
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold contained in PGC product
Copper 1.710 0.900
Cyanide (total) 0.261 0.108
Zinc 1.314 0.549
Ammonia (as N) 120.000 52.740
Total suspended 36.900 17.550
solids
pH Within the range of 7. 5 to 10.0
at all times
11
-------
BPT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(m) Equipment and Floor Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/troy ounce of precious metals, including silver,
produced in refinery
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
Total suspended 0.000 0.000
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, sedi-
mentation, and multimedia filtration (lime, settle,
and filter) technology and in-process flow reduc-
tion methods, along with preliminary treatment
consisting of ammonia steam stripping and cyanide
precipitation for selected waste streams. The
following BAT effluent limitations are proposed:
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(a) Furnace Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
incinerated or smelted
Copper 5.760 2.745
Cyanide (total) 0.900 0.360
Zinc 4.590 1.890
Ammonia (as N) 599.900 263.700
12
-------
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(b) Raw Material Granulation
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals in in the granulated
raw material
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(c) Spent Plating Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/liter of spent plating solution used as a
raw material
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc 1.020 0.420
Ammonia (as N) 133.300 58.600
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(d) Spent Cyanide Stripping Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by
cyanide stripping
Copper 1.408 0.671
Cyanide (total) 0.220 0.088
Zinc 1.122 0.462
Ammonia (as N) 146.600 64.460
13
-------
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(e) Refinery Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc 1.020 0.420
Ammonia (as N) 133.300 58.600
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(f) Gold Solvent Extraction Raffinate and Wash Water
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by solvent extraction
Copper 0.806 0.384
Cyanide (total) 0.126 0.050
Zinc 0.643 0.265
Ammonia (as N) 83.980 36.920
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(g) Gold Spent Electrolyte
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by electrolysis
Copper 0.0111 0.0053
Cyanide (total) 0.0017 0.0007
Zinc 0.0089 0.0037
Ammonia (as N) 1.160 0.510
14
-------
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(h) Gold Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold precipitated
Copper 5.632 2.684
Cyanide (total) 0.880 0.352
Zinc 4.488 1.848
Ammonia (as N) 586.500 257.800
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(i) Platinum Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of platinum precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693.200 304.700
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(j) Palladium Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of palladium precipitated
Copper 4.480 2.135
Cyanide (total) 0.700 0.280
Zinc 3.570 1.470
Ammonia (as N) 466.600 205.100
15
-------
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(k) Other Platinum Group Metals Precipitation and
Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of other platinum group metals
precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693.200 304.700
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(1) Spent Solution from PGC Salt Production
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold contained in PGC product
Copper 1.152 0.549
Cyanide (total) 0.180 0.072
Zinc 0.918 0.378
Ammonia (as N) 120.000 52.740
BAT MASS LIMITATIONS FOR THE SECONDARY PRECIOUS METALS
SUBCATEGORY
(m) Equipment and Floor Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
16
-------
4. NSPS are proposed based on the performance achiev-
able by the application of chemical precipitation,
sedimentation, and multimedia filtration (lime,
settle, and filter) technology, and in-process flow
reduction control methods, 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 SECONDARY PRECIOUS METALS SUBCATEGORY
(a) Furnace Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
incinerated or smelted
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0. 000
Total suspended 0.000 0.000
solids
pH Within the range of 7.5 to 10.0
at all times
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(b) Raw Material Granulation
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals in the granulated
raw material
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
Total suspended 0.000 0.000
solids
pH Witnin the range of 7.5 to 10.0
at all times
17
-------
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(c) Spent Plating Solutions
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/liter of spent plating solution used as a
raw material
Copper
Cyanide (total)
Zinc
Ammonia (as N)
Total suspended
solids
pH
1.280
0.200
1.020
133.300
15.000
0.610
0.080
0.420
58.600
12.000
Within the range of 7.5 to 10.0
at all times
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(d) Spent Cyanide Stripping Solutions
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/troy ounce of gold produced by
cyanide stripping
Copper
Cyanide (total)
Zinc
Ammonia (as N)
Total suspended
solids
pH
1.408
0.220
1.122
146.600
16.500
0.671
0.088
0.462
64.460
13.200
Within the range of 7.5 to 10.0
at all times
18
-------
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(e) Refinery Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc . 1.020 0.420
Ammonia (as N) 133.300 58.600
Total suspended 15.000 12.000
solids
pH Within the range of 7.5 to 1 0. 0
at all times
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(f) Gold Solvent Extraction Raffinate and Wash Water
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by solvent extraction
Copper 0.806 0.384
Cyanide (total) 0.126 0.050
Zinc 0.643 0.265
Ammonia (as N) 83.980 36.920
Total suspended 9.450 7.560
solids
pH Within the range of 7.5 to 10.0
at all times
19
-------
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(g) Gold Spent Electrolyte
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by electrolysis
Copper 0.0111 0.0053
Cyanide (total) 0.0017 0.0007
Zinc 0.0089 0.0037
Ammonia (as N) -1.160 0.510
Total suspended 0.131 0.104
solids
pH Within the range of 7.5 to 10.0
at all times
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(h) Gold Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold precipitated
Copper 5.632 2.684
Cyanide (total) 0.880 0.352
Zinc 4.488 1.848
Ammonia (as N) 586.500 257.800
Total suspended 66.000 52.800
solids
pH Within the range of 7.5 to 10.0
at all times
20
-------
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(i) Platinum Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of platinum precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693.200 304.700
Total suspended 78.000 62.400
solids
pH Within the range of 7.5 to 10.0
at all times
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(j) Palladium Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of palladium precipitated
Copper 4.480 2.135
Cyanide (total) 0.700 0.280
Zinc 3.570 1.470
Ammonia (as N) 466.600 205.100
Total suspended 52.500 42.000
solids
pH Within the range of 7.5 to 10.0
at all times
21
-------
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(k) Other Platinum Group Metals Precipitation and
Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce
Copper
Cyanide (total)
Zinc
Ammonia (as N)
Total suspended
solids
pH
of other platinum
precipitated
6.656
1.040
5.304
693.200
78.000
group metals
3.172
0.416
2.184
304.700
62.400
Within the range of 7.5 to 10.
0
at all times
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(1) Spent Solutions from PGC Salt Production
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold contained in PGC product
Copper 1.152 0.549
Cyanide (total) 0.180 0.072
Zinc 0.918 0.378
Ammonia (as N) 120.000 52.740
Total suspended 13.500 10.800
solids
pH Within the range of 7.5 to 10.0
at all times
22
-------
NSPS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(m) Equipment and Floor Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
Total suspended 0.000 0.000
solids
pH Within the range of 7.5 to 10.0
at all times
5. PSES are proposed based on the performance achiev-
able by the application of chemical precipitation,
sedimentation, and multimedia filtration (lime,
settle, and filter) technology, and in-process flow
reduction control methods, 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 SECONDARY PRECIOUS METALS SUBCATEGORY
(a) Furnace Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
incinerated or smelted
Copper 5.760 2.745
Cyanide (total) 0.900 0.360
Zinc 4.590 1.890
Ammonia (as N) 599. 900 263.700
23
-------
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(b) Raw Material Granulation
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals in the granulated
raw material
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(c) Spent Plating Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/liter of spent plating solution used as a
raw material
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc 1.020 0.420
Ammonia (as N) 133.300 58.600
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(d) Spent Cyanide Stripping Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by
cyanide stripping
Copper 1.408 0.671
Cyanide (total) 0.220 0.088
Zinc 1.122 0.462
Ammonia (as H) 146.600 64.460
24
-------
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(e) Refinery Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc 1.020 0.420
Ammonia (as N) 133.300 58.600
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(f) Gold Solvent Extraction Raffinate and Wash Water
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by solvent extraction
Copper 0.806 0.384
Cyanide (total) 0.126 0.050
Zinc 0.643 0.265
Ammonia (as N) 83.980 36.920
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(g) Gold Spent Electrolyte
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by electrolysis
Copper 0.0111 0.0053
Cyanide (total) 0.0017 0.0007
Zinc 0.0089 0.0037
Ammonia (as N) 1.160 0.510
25
-------
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(h) Gold Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold precipitated
Copper 5.632 2.684
Cyanide (total) 0.880 0.352
Zinc 4.488 1.848
Ammonia (as N) 586.500 257.800
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(i) Platinum Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of platinum precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693.200 304.700
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(j) Palladium Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of palladium precipitated
Copper 4.480 2.135
Cyanide (total) 0.700 0.280
Zinc 3.570 1.470
Ammonia (as N) 466.600 205.100
26
-------
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(k) Other Platinum Group Metals Precipitation and
Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of other platinum group metals
precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693.200 304.700
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(1) Spent Solution from PGC Salt Production
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold contained in PGC product
Copper 1.152 0.549
Cyanide (total) 0.180 0.072
Zinc 0.918 0.378
Ammonia (as N) 120.000 52.740
PSES FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(m) Equipment and Floor Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
27
-------
PSNS are proposed based on the performance achiev-
able by the application of chemical precipitation,
sedimentation, and multimedia filtration (lime,
settle, and filter) technology, and in-process flow
reduction control methods, 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 SECONDARY PRECIOUS METALS SUBCATEGORY
(a) Furnace Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
tag/troy ounce of precious metals, including silver,
incinerated or smelted
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 . 0.000
PSNS FOR-THE SECONDARY PRECIOUS METALS SUBCATEGORY
(b) Raw Material Granulation
Pollutant or Maximum for Maximum for
Pollutant Property Any One Pay Monthly Average
mg/troy ounce of precious metals in the granulated
raw material
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
28
-------
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(c) Spent Plating Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/liter of spent plating solution used as a
raw material
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc 1.020 0.420
Ammonia (as N) 133.300 58.600
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(d) Spent Cyanide Stripping Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by
cyanide stripping
Copper 1.408 0.671
Cyanide (total) 0.220 0.088
Zinc 1.122 0.462
Ammonia (as N) 146.600 64.460
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(e) Refinery Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 1.280 0.610
Cyanide (total) 0.200 0.080
Zinc 1.020 0.420
Ammonia (as N) 133.300 58.600
29
-------
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(f) Gold Solvent Extraction Raffinate and Wash Water
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
ing/troy ounce of gold produced by solvent extraction
Copper 0.806 0.384
Cyanide (total) 0.126 0.050
Zinc 0.643 0.265
Ammonia (as N) 83.980 36.920
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(g) Gold Spent Electrolyte
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by electrolysis
Copper 0.0111 0.0053
Cyanide (total) 0.0017 0.0007
Zinc 0.0089 0.0037
Ammonia (as N) 1.160 0.510
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(h) Gold Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold precipitated
Copper 5.632 2.684
Cyanide (total) 0.880 0.352
Zinc 4.488 1.848
Ammonia (as N) 586.500 257.800
30
-------
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(i) Platinum Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of platinum precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693.200 304.700
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(j) Palladium Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of palladium precipitated
Copper 4.480 2.135
Cyanide (total) 0.700 0.280
Zinc 3.570 1.470
Ammonia (as N) 466.600 205.100
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(k) Other Platinum Group Metals Precipitation and
Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of other platinum group metals
precipitated
Copper 6.656 3.172
Cyanide (total) 1.040 0.416
Zinc 5.304 2.184
Ammonia (as N) 693. 200 304.700
31
-------
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(1) Spent Solution from PGC Salt Production
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold contained in PGC product
Copper 1.152 0.549
Cyanide (total) 0.180 0.072
Zinc 0.918 0.378
Ammonia (as N) 120.000 52.740
PSNS FOR THE SECONDARY PRECIOUS METALS SUBCATEGORY
(m) Equipment and Floor Wash
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
7. EPA is not proposing best conventional pollutant
control technology (BCT) at this time.
32
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION III
INDUSTRY PROFILE
This section of the secondary precious metals supplement
describes the raw materials and processes used in refining
secondary precious metals and presents a profile of the secondary
precious metals plants identified in this study. For a discus-
sion of the purpose, authority, and methodology for this study
and a general description of the nonferrous metals category,
refer to Section III of the General Development Document.
DESCRIPTION OF SECONDARY PRECIOUS METALS PRODUCTION
The secondary precious metals industry consists of plants which
recover gold and platinum group metals from recycled materials.
Platinum group metals, also known as PGM, consist of platinum,
palladium, iridium, rhodium, osmium, and ruthenium. The produc-
tion of secondary precious metals can be divided into two stages:
raw material preparation steps and refining steps. Raw material
preparation steps include grinding, crushing, incineration,
smelting, granulation, cyanide stripping, and precipitation of
precious metals from spent plating solutions. Refining steps
include dissolution in either strong acid or base, precipitation,
filtration, recycle, solvent extraction, electrolytic refining,
salt manufacturing, casting, and granulation. The secondary
precious metals production process is presented schematically in
Figure III-1, and described below.
RAW MATERIALS
The principal raw materials used by plants recovering precious
metals are jewelry scrap, dental scrap, optical scrap, electrical
scrap, impure bullion, spent industrial and automotive catalysts,
sweeps, and contaminated or spent electroplating solutions.
Sweeps are usually low-grade precious metal-bearing residue
generated from various raw materials, including floor sweepings
(hence the name), waste treatment sludges and incinerated filter
cakes. The various raw material preparation and refining steps a
plant uses are dictated by the type and composition of raw
materials being processed.
RAW MATERIAL PREPARATION STEPS
Based on the source of raw materials, the raw material prepara-
tion steps can be divided into four basic processes for the
recovery of precious metals: incineration and smelting (pyro-
metallurgical steps), raw material granulation, stripping with
33
-------
cyanide solutions, and recovering precious metals from spent
plating solutions.
Incineration and Smelting
Dental scrap, optical scrap, electrical scrap, and catalysts may
be ground and incinerated in a furnace in order to remove the
carbonaceous material and volatile fraction. The temperature and
rate of burning must be carefully controlled if high efficiency
is to be maintained. Air emissions include vapors from the vola-
tilization and decomposition of carbonaceous scrap contaminants,
as well as combustion gases and dust. The emissions are usually
controlled by afterburners in series with a baghouse or scrubber.
Wet air pollution control techniques result in wastewater dis-
charges. Precious metal-bearing residues may then be fed
directly to the refinery for recovery of pure metals.
Smelting is generally used to produce a copper-based bullion
which can either be sold or further processed to produce a pure
metal. The raw material for smelting may be the precious metal-
bearing residue produced in the incinerator, or it may be
ground-up raw material. Like the incineration furnace, the
smelting furnace may also have emissions which are controlled by
a baghouse or scrubber. The furnace or incinerator scrubber
results in a wastewater discharge.
Raw Material Granulation
Raw material may be granulated with water in order to make it
easier to dissolve in acid in the refinery. Either solid scrap
or incinerated residue may be melted in a furnace and granulated
with water in a similar manner to shot casting. This operation
produces wastewater discharge, consisting of the spent granula-
tion water.
Stripping With Cyanide Solutions
Gold-containing electrical components, strip, or ceramics may be
stripped with sodium or potassium cyanide solutions. The raw
material may be ground-up prior to stripping in order to increase
the exposed surface area. Cyanide attacks the gold which is
exposed on the surface of the metal, but does not recover gold
which is buried beneath a non-precious metal. Stripping with
cyanide has limited application because of the relatively few
types of scrap amenable to the process.
After the gold is stripped away from the base metal, it may be
precipitated from solution with either sodium hydrosulfite or
zinc. An oxidizing agent may be added to destroy the free cya-
nide. The solids, containing precious metals, are separated from
34
-------
the spent cyanide stripping solution by filtration. Filtration
results in a wastewater stream which may be discharged. The
product of cyanide stripping is a sludge containing high precious
metal values which may go on for further processing.
Recovery From Spent Plating Solutions
Precious metals can be recovered from contaminated or spent
electroplating solutions, which are cyanide-based, either by
precipitation with sodium hydrosulfite or zinc, or by electroly-
sis. Electroplaters use cyanide solutions for plating precious
metals onto base metals. The depleted or contaminated solutions
still contain enough precious metal values to make recovery
economical. Either gold, palladium, or rhodium can be recovered
in this manner. The precipitation process for plating solutions
is the same as cyanide stripping. Zinc or sodium hydrosulfite is
added and the precious metals are recovered by filtration. For
electrolytic recovery, the spent plating solution acts as the
electrolyte, and the precious metal is recovered on the cathode.
Wastewater may be generated by the discharge of barren solution
after either precipitation or electrolytic recovery occurs. The
resultant sludge from this process may be routed to the refinery
for further processing.
REFINING STEPS
Refining steps are taken to recover high-purity precious metals
(high-purity generally refers to 99.9 or 99.99 percent pure) from
lower purity raw materials, which may or may not have undergone
raw material preparation steps. The standard hydrometallurgical
process includes dissolution in acid or base, combined with
precipitation and filtration. Other hydrometallurgical refining
steps include solvent extraction and electrolytic refining.
After pure precious metals are produced, they may be further
processed into a potassium cyanide-based salt, cast as bars, or
granulated.
Hydrometallurgical Processing
Jewelry, dental, optical, electrical, and catalyst scrap, along
with sludges generated from spent solutions, containing gold, .
platinum, palladium, and other platinum group metals (PGM), may
be refined using hydrometallurgical processing. The first step
usually consists of dissolving the raw material in aqua regia.
Aqua regia (one part concentrated nitric acid .-three to four parts
concentrated hydrochloric acid) is the only known reagent that
dissolves gold. Nitric acid alone cannot oxidize gold unless the
chloride ion is present to complex the product. The net equation
for dissolving gold in aqua regia can be written:
35
-------
Au(s) + 3N03~ + 4C1~ + 6H30+ -> AuCl^" + 3N02(g) + 9H20
though a variety of nitrogen products are obtained.
After dissolving the raw material, the silver chloride solids are
filtered away, and the gold is precipitated with sulfur dioxide,
ferrous sulfate, or chlorine gas. The filtrate may be sent on
for further recovery of platinum group metals. The platinum
group metals are generally recovered by precipitating them as
platinum and palladium chloride, often done with NlfyCl,
followed by filtration to remove the non-precious metals.
The filter cake (called "red salt") is then dissolved with ammo-
nium hydroxide to separate the platinum (which does not dissolve)
from the palladium. The platinum can then be purified with
various acid dissolutions, precipitations, and filtrations, and
finally thermally reduced to the pure metal. Similarly, palla-
dium can be purified using various alkaline dissolutions, precip-
itations, filtrations, and finally reduced to the metal with a
strong reducing agent. Each of the purification processes may be
repeated via recycle to increase the purity of the refined metal.
After each metal is recovered as either a final product or inter-
mediate, it may be washed with water or an acid or base in order
to remove residual acid or base from it and to further purify it.
The wash water or solution is generally discharged with the pre-
cipitation and filtration water, and is considered as part of the
same waste stream. The various hydrometallurgical processing
steps a plant uses to recover precious metals may occur in any
order. For example, one plant may recover gold prior to pal-
ladium prior to platinum, and another plant may recover platinum
first, then gold, and finally palladium. The order of processing
does not impact the wastewater generation at a refinery.
Based on the composition of the raw material, and the order of
processing, the recovery of each precious metal may result in a
wastewater discharge. There is variability in the types of raw
materials processed within this subcategory; however, the basic
processing steps and wastewaters generated are similar from one
plant to another.
Acid fumes generated in the refinery may be controlled with a wet
scrubber, resulting in a wastewater stream. This scrubber gener-
ally controls the fumes from all the reaction vessels, whether
they are acid-, alkaline-, or cyanide-based. The scrubbing
medium is usually an alkaline solution which neutralizes the acid
fumes.
36
-------
Solvent Extraction
Solvent extraction may be used to refine impure bullion to high
purity gold. Solvent extraction consists of extracting the gold
from an acid solution into the organic phase and subsequently
recovering it. The aqueous solution which originally contained
the dissolved impure bullion may be discharged as a waste stream.
After recovery, the gold may be washed with water and the wash
water may also be discharged. The aqueous raffinate and wash
water may be considered as one waste stream.
Electrolytic Refining
Electrolytic refining is also used as a means of recovering high
purity gold from precious metal-containing bullion, jewelry and
dental scrap. First, the raw material is melted and cast as an
anode. An acidic electrolyte is used, and gold is recovered on
the cathode. In the electrolytic method, a current is passed
between an anode and a cathode which are suspended in the elec-
trolyte. A portion of the electrolyte is periodically discharged
to maintain the purity of the solution.
Further Process ing
Once the gold or platinum group metals have been refined to the
pure state, they may be further processed. Gold may be reacted
with potassium cyanide solution to produce a potassium gold
cyanide salt (generally written KAu(CN)2 or PGC) which is
useful in the electroplating industry. There may be a waste
stream associated with this process, consisting of excess cyanide
solution.
Pure precious metals may either be cast as bars or granulated
using a method similar to shot casting. In either case, the
metal is melted in a furnace. Molten metal may be poured into
molds which may be quenched with water, or it may be poured
directly into a container of water, in which case it will be
granulated. In either case, a waste stream is generated which
may be discharged.
PROCESS WASTEWATER SOURCES
Although a variety of processes are involved in secondary pre-
cious metals production, the process wastewater sources can be
subdivided as follows:
1. Furnace wet air pollution control,
2. Raw material granulation,
3. Spent plating solutions,
4. Spent cyanide stripping solutions,
37
-------
5. Refinery wet air pollution control,
6. Gold solvent extraction raffinate and wash water,
7. Gold spent electrolyte,
8. Gold precipitation and filtration,
9. Platinum precipitation and filtration,
10. Palladium precipitation and filtration,
11. Other platinum group metals precipitation and
filtration,
12. Spent solution from PGC salt production, and
13. Equipment and floor wash.
The sources of these wastewater streams are identified by their
respective numbers in Figure III-1 .
OTHER WASTEWATER SOURCES
There are other waste streams associated with the production of
secondary precious metals. These waste streams include but are
not limited to:
1 . Casting contact cooling water,
2. Final product granulation water,
3. Acid storage area wet air pollution control, and
4. Pump seal water.
These waste streams are not considered as part of this rulemak-
ing. EPA believes that the flows and pollutant loadings associ-
ated 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 the authority of
Section 403(a) of the Clean Water Act.
Casting contact cooling water is not considered as part of this
rulemaking because, although several plants do discharge this
stream, sampling data indicate that this wastewater contains
little or no pollutants and that the pollutant loadings are
insignificant compared with the other waste streams selected.
Sampling data for casting contact cooling water are presented in
Table V-26 (see Section V).
AGE. PRODUCTION, AND PROCESS PROFILE
Forty-eight secondary precious metals plants were identified in
this study. Figure III-2 shows that the plants are concentrated
in the Northeast and California, with plants also located in
Washington, Arizona, Minnesota, Illinois, Ohio, Virginia, and
Florida.
Table III-1 summarizes the relative ages of the secondary pre-
cious metals plants by discharge status. Three plants discharge
38
-------
directly, 29 are indirect dischargers, 10 are zero dischargers,
and six plants have no process wastewater. Most of the plants
began operating within the last 15 years.
Table III-2 shows the production ranges for the 48 secondary pre-
cious metals plants. One-third of the plants that reported pro-
duction data produce less than 10,000 troy ounces of total
precious metals per year. All three of the direct dischargers
produce in excess of 50,000 troy ounces per year, as do 10 of the
indirect dischargers.
Table II1-3 provides a summary of the plants having the various
secondary precious metals processes. The number of plants
generating wastewater from the processes is also shown.
39
-------
O\ O NO! 00
CM — •*
-o
®
1_
o
a
a>
ce.
UJ LU
I 0_
t- >-
CO
< O
_) CO
CL —
Q
O >-
CD
C£ >-
I co H-
— UJ CD
0) Z CO
-O CC CO
— o
(*• 00
CM —
(*- 00
bO CM
oo
in
CN
CM
CM
~
Q) L>
M Q
(0
40
-------
4J
O
2:
0)
4J
O
cxc
01.
T- en
CM
I
H PS
CJO
§°
O
o
o
o
o
o
m
00
00
* *
oo
oo
T-lD
oo
o •
•o
oo
IT) i—
I
i- O
oo
o o
00
,- m
I O
.- o
o o
o «
o
o
o
I
o
I m
^| CM
4J
C
(1)
C
O
o
CO
CXrH
Direct*
ndirect
OJ
O
CO
JJ
O
H
CO
4J
CO
41
-------
CO
r-1
rO
CO
H
H co
*
rl
(U
CO 00 C 4J
4J C O CO
rl C 1-4 .,-1 £
0) CO 4J 4-J 0)
43 r-l rl CO 4-1
B PH O rl CO
d a,
B
CO
M-l 4J
O -n
COv£> CM
00 OO CT> CO
CM^-r-
r- CO
co
00
co
CM »-i-
,— CO
CO
CO
Process
CO
a
0)
4J
CO
o
•r-l
4->
CO
U
CO
Cu
0)
l-i
Oi
CO
I— 1
cO
•H
V4
cu
4J
CO
S
^
cfl
OS
d Smelting (Furnace Air Pollution
c
cO
c
o
••-4
4J
cO
Jj
0)
d
•H
0
c
1— 1
1
anulation
VJ
o
I-l
cO
•r-l
5-1
/-N 0)
t-4 4-»
O CO
% S
4J
C !*
O cfl
O OS
I
Cyanide Solutions
pent Plating Solutions
CO
J3
4J S
•H O
!» ^
fa
00
C t>%
•H V4
a. cu
P->
•H O
M 0
4-1 (U
CO OS
1 1
ometallurgical Processing)
j-i
T3
>,
PS
N-X
CO
a
(U
4J
CO
00
c
•i-4
c
•H
<4-l
(U
OS
ion and Filtration
4-1
CO
4J
•pH
a
•r-l
o
CU
1-1
&4
T3
r-l
O
o
1
i tat ion and Filtration
pitation and Filtration
Group Metals Precipitation and
CVH
•H O
O (U
(U \->
VlCXi
o,
e
S 3
3-H
CTJ
•^ cO
4Jr-l
CflrH
rH CO
OH(XI
1 1
e
3
C
•r-i
•u C
CO O
r-l-r-l
PLI 4-1
CO
r4 14
(U 4-)
JS--I
4J-H
O fa
1
00
C
•r-l
C C
O -^
•<-\ M-l
4-) (U
o os
cfl
r4 O
4J -i-l
>s
r-l
4J O
C VJ
0
r-l
-------
To Atmosphere
Furnace Wet
Air Pollution
Control
Raw Material (Includes
Jewelry Scrap, Dental
Scrap, Optical Scrap,
Electrical Scrap," '
Catalyst Scrap, Impure
Bullion, and Spent
Plating Solutions)
Incineration or
Smelting
Furnace
Intermediate
Product to
Recovery
Sold as
Product
Raw Material
Granulation
J
Granulated
Raw Material
to Refinery
Spent
Plating
Solutions
Precipitation or
Electrolytic
Recovery
Precious Metal
Sludge to
Refinery
Electri-
cal
Scrap
*-
KCN or NaCN
1
Cyanide
Stripping,
Precipitation
Precious Metal
Sludge to
Refinery
Figure III-l
RAW MATERIAL PREPARATION
SECONDARY PRECIOUS METALS PRODUCTION PROCESSES
43
-------
To tUoosphere
H70 or
Caustic '
Solucion
Raw M«eri*l
(May or May Hoc
3*v* Undergone '
?r«p«r«cory SCipt)
POC
1 Salt
Oth«r Platinum
Group M«tals
(Rhodium, Irlaium,
Osniun, Ruthvoium)
Dashed line Indicates
possible recycle or
reuse of £ titrate
Figure III-l (Continued)
REFINING STEPS
SECONDARY PRECIOUS METALS PRODUCTION PROCESSES
44
-------
H
CO
CO
3
H
CO
o
M
O
I
H4 Q
i i t—p
M O
CJ
<1J fxj
?-l CO
bO W
*1~1 jj^.
fn H
CO
55
O
K-1
H
3
O
(J
O
M
CM
t
I
O
W
O
45
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION IV
SUBCATEGORIZATION
As discussed in Section IV of the General Development Document,
the nonferrous metals manufacturing category has been subcatego-
rized to take into account pertinent category characteristics,
manufacturing process variations, wastewater characteristics, and
a number of other factors which affect the ability of the facili-
ties to achieve effluent limitations. This section summarizes
the factors considered during the designation of the secondary
precious metals subcategory and its related subdivisions.
FACTORS CONSIDERED IN SUBCATEGORIZATION
The following factors were evaluated for use in determining
appropriate subcategories for the nonferrous metals industry:
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 secondary precious metals sub-
category. Three factors were particularly important in estab-
lishing these classifications: the type of metal and co-products
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 prod-
ucts, manufacturing processes and raw materials as the principal
factors used for subcategorization is discussed. On the basis of
these factors, the nonferrous metals manufacturing category
(Phase II) was divided into 21 subcategories, one of them being
secondary precious metals.
47
-------
FACTORS CONSIDERED IN SUBDIVIDING THE SECONDARY PRECIOUS METALS
SUBCATEGORY
The factors listed previously were each evaluated when consider-
ing subdivision of the secondary precious metals 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 second-
ary precious metals subcategory is based primarily on the produc-
tion processes used. Within the subcategory, a number of differ-
ent operations are performed, which may or may not have a water
use or discharge, and which may require the establishment of
separate effluent limitations and standards. While secondary
precious metals is still considered a single subcategory, a more
thorough examination of the production processes, water use and
discharge practices, and.pollutant generation rates has illus-
trated the need for limitations and standards based on a specific
set of waste streams. Limitations and standards will be based on
specific flow allowances for the following subdivisions:
1. Furnace wet air pollution control,
2. Raw material granulation,
3. Spent plating solutions,
4. Spent cyanide stripping solutions,
5. Refinery wet air pollution control,
6. Gold solvent extraction raffinate and wash water,
7. Gold spent electrolyte,
8. Gold precipitation and filtration,
9. Platinum precipitation and filtration,
10. Palladium precipitation and filtration,
11. Other platinum group metals precipitation and
filtration,
12. Spent solution from PGC salt production, and
13. Equipment and floor wash.
These subdivisions follow directly from differences within the
various production stages of secondary precious metals: raw
material preparation steps and refining steps. Depending on the
type and composition of raw material, a plant may operate one or
more raw material preparation or refining steps to recover gold,
platinum, palladium, or other platinum group metals from scrap.
Each of these operations may create a need for a subdivision.
Smelting or incinerating a raw material creates the need for the
first subdivision--furnace wet air pollution control. Smelting
or incineration furnaces produce dust and particulate emissions
which need to be controlled prior to venting to the atmosphere.
Other raw material preparation steps which create the need for
subdivisions include raw material granulation, recovering gold or
48
-------
other precious metals from spent plating solutions, and cyanide
stripping of gold from gold-plated scrap. Granulating a raw
material involves melting the raw material in a furnace and
pouring it into a container of water. This granulates the raw
material, and the granulation water may be discharged, thus
creating the need for a subdivision. Spent plating solutions may
be treated with a precipitating agent such as zinc or sodium
thiosulfate in order to precipitate the precious metals. Dis-
charging the depleted solution creates a need for a separate
subdivision. Stripping gold away from scrap with a cyanide
solution and then precipitating the gold from solution creates a
need for the fourth pre-refining subdivision.
Various refining operations create the need for the other nine
subdivisions. Recovering gold by a solvent extraction process or
an electrolytic refining process creates the need for two subdi-
visions: gold solvent extraction raffinate and wash water, and
gold spent electrolyte. The wet chemistry technique of dissolu-
tion and selective precipitation creates the need for four subdi-
visions: gold precipitation and filtration, platinum precipita-
tion and filtration, palladium precipitation and filtration, and
other platinum group metals precipitation and filtration.
Depending on the composition of the raw material being processed,
and the manner in which each metal is recovered, any one or all
of the precious metals may result in the discharge of a
wastewater stream.
Acid fumes generated during dissolution and precipitation pro-
cesses are generally controlled with a wet scrubber, creating
the need for the seventh refining subdivision: refinery wet air
pollution control. Washing the equipment and the floor of the
refinery in order to recover any precious metals from spills and
leaks creates a need for the equipment and floor wash subdivi-
sion. Finally, manufacturing gold into a PGC salt product by
reacting it with potassium cyanide solution creates a need for
the last subdivision: spent solution from PGC salt production.
OTHER FACTORS
The other factors considered in this evaluation either supported
the establishment of the secondary precious metals subcategory
and its subdivisions or were shown to be inappropriate bases for
subcategorization. Air pollution control methods, treatment
costs, nonwater quality aspects, and total energy requirements
are functions of the selected subcategorization factors—raw
materials and production processes. As such, they support the
method of subcategorization wMr.h 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 employ-
ees were also evaluated and determined to be inappropriate for
use as bases for subdivision of nonferrous metals plants.
49
-------
PRODUCTION NORMALIZING PARAMETERS
The effluent limitations and standards developed in this document
establish mass limitations on the discharge of specific pollutant
parameters. To allow these limitations to be applied to plants
with various production capacities, the mass of pollutant dis-
charged must be related to a unit of production. This factor is
known as the production normalizing parameter (PNP). In general,
the actual precious metals production from the respective manu-
facturing process is used as the PNP. This is based on the
principle that the amount of water generated is proportional to
the amount of product made. Therefore, the PNPs for the 13
secondary precious metals subdivisions are as follows:
Subdivision
PNP
Furnace wet air pollu-
tion control
Raw material granulation
3. Spent plating solutions
4. Spent cyanide stripping
solutions
5. Refinery wet air pollution
control
6. Gold solvent extraction
raffinate and wash water
7. Gold spent electrolyte
8. Gold precipitation and
filtration
9. Platinum precipitation
and filtration
10. Palladium precipitation
and filtration
Troy ounces of precious
metals, including silver,
incinerated or smelted
Troy ounces of precious metals
in the granulated raw
material
Liters of spent plating solu-
tions used as a raw material
Troy ounces of gold produced
by cyanide stripping
Troy ounces of precious
metals, including silver,
produced in refinery
Troy ounces of gold produced
by solvent extraction
Troy ounces of gold produced
by electrolysis
Troy ounces of gold precipi-
tated
Troy ounces of platinum pre-
cipitated
Troy ounces of palladium pre-
cipitated
50
-------
Subdivision PNP
11. Other platinum group Troy ounces of other platinum
metals precipitation and group metals precipitated
filtration
12. Spent solution from PGC Troy ounces of gold contained
salt production in PGC product
13. Equipment and floor wash Troy ounces of precious
metals, including silver,
produced in refinery
Other PNPs were considered. The use of production capacity
instead of actual production was eliminated from consideration
because the mass of pollutant produced is more a function of true
production than of installed capacity. The total precious metals
produced in the refinery was eliminated from consideration
because most of the operations generating wastewater in a refin-
ery do so as a function of one metal being produced, rather than
as a function of the total amount of metal produced in a
refinery.
The PNP selected for spent plating solutions is liters of spent
plating solution used as a raw material. The volumetric PNP was
selected rather than a mass-based PNP because a plant cannot
control the concentration of precious metals in the raw material
spent plating solutions. One plant's raw material may be twice
as concentrated as another's in precious metals, and therefore
flow cannot be related to production for this unit operation.
Wastewater discharge flow is directly related to volume of spent
plating solution used as raw material, and not the quantity of
precious metals in the solution.
51
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the secondary precious metals subcategory. Water
use and discharge rates are explained and then summarized in
tables at the end of this section. Data used to characterize the
wastewaters are presented. Finally, the specific source, water
use and discharge flows, and wastewater characteristics for each
separate wastewater source are discussed.
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 information briefly, 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 secondary pre-
cious metals 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 never analyzed for asbestos. There is no reason to expect
that TCDD or asbestos would be present in nonferrous metals
manufacturing wastewater.) A total of five plants were selected
for sampling in the secondary precious metals subcategory. In
general, the samples were analyzed for cyanide and three classes
of pollutants: toxic organic pollutants, toxic metal pollutants,
and criteria pollutants (which includes Doth conventional and
nonconventional pollutants). Cyanide was analyzed for because it
is present in raw materials for this subcategory.
As described in Section IV of this supplement, the secondary pre-
cious metals subcategory has been further split into 13 subdivi-
sions, so that the proposed regulation contains mass discharge
limitations and standards for 13 unit processes discharging pro-
cess 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.
53
-------
The principal wastewater sources in the secondary precious metals
subcategory are:
1. Furnace wet air pollution control,
2. Raw material granulation,
3. Spent plating solutions,
4. Spent cyanide stripping solutions,
5. Refinery wet air pollution control,
6. Gold solvent extraction raffinate and wash water,
7. Gold spent electrolyte,
8. Gold precipitation and filtration,
9. Platinum precipitation and filtration,
10. Palladium precipitation and filtration,
11. Other platinum group metals precipitation and
filtration,
12. Spent solution from PGC salt production, and
13. Equipment and floor wash.
WASTEWATER FLOW RATES
Data supplied by dcp responses were evaluated, and two flow-to-
production ratios were calculated for each stream. The two
ratios, water use and wastewater discharge flow, are differenti-
ated by the flow value used in calculation. Water use is defined
as the volume of water or other fluid required for a given pro-
cess per mass of precious metals product and is therefore based
on the sum of recycle and make-up flows to a given process.
Wastewater flow discharged after preliminary treatment or recycle
(if these are present) is used in calculating the production
normalized flow--the volume of wastewater discharged from a given
process to further treatment, disposal, or discharge per mass of
precious metals produced. Differences between the water use and
wastewater flows associated with a given stream result from recy-
cle, evaporation, and carryover on the product. The production
values used in calculation correspond to tne production normal-
izing parameter, PNP, assigned to each stream, as outlined in
Section IV. As an example, gold precipitation and filtration
wastewater flow is related to gold metal production. As such,
the discharge rate is expressed in liters of filtration waste-
water discharged per troy ounce of gold produced by precipita-
tion.
The production normalized 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-13 at the end of this section. Where appropriate, an
attempt was made to identify factors that could account for
variations in water use. This information is summarized in this
section. A similar analysis of factors affecting the wastewater
54
-------
flows is presented in Sections X, XI, and XII where representa-
tive BAT, NSPS, and pretreatment flows are selected for use in
calculating the effluent limitations and standards.
WASTEWATER CHARACTERIZATION DATA
Data used to characterize the various wastewaters associated with
secondary precious metals production come from two sources--data
collection portfolios and analytical data from field sampling
trips.
DATA COLLECTION PORTFOLIOS
In the data collection portfolios, the secondary precious metals
plants which discharge wastewater were asked to specify the
presence of toxic pollutants in their effluent. Of the 48
secondary precious metals plants, 12 did not respond to this por-
tion of the questionnaire. No plant responding to this portion
of the questionnaire reported that any toxic organic pollutants
were known to be or believed to be present in their wastewater.
The responses for the toxic metals and cyanide are summarized
below:
Believed Present
(Based on Raw Materials and
Pollutant Known Present Process Chemicals Used)
Antimony 0 3
Arsenic 1 5
Beryllium 2 3
Cadmium 7 5
Chromium 9 6
Copper 20 17
Cyanide 10 10
Lead 11 8
Mercury 3 2
Nickel 16 19
Selenium 0 3
Silver 14 18
Thallium 0 2
Zinc 20 15
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from secondary precious metals plants, wastewater
samples were collected at five plants. Diagrams indicating the
sampling sites and contributing production processes are shown in
Figures V-1 through V-5 (at the end of this section).
55
-------
The raw wastewater sampling data for the secondary precious
metals subcategory are presented in Tables V-14 through V-21 (at
the end of this section). Treated and combined wastewater
sampling data are shown in Tables V-22 through V-25. The stream
codes presented in the tables may be used to identify the loca-
tion of each of the samples on the process flow diagrams in
Figures V-1 through V-5. 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
fraction extractable, and volatile organics are generally consid-
ered 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 pesti-
cide fraction is considered not quantifiable a concentrations
equal to or less than 0.005 mg/1.
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 varia-
tion 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 calibra-
tion, 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, nonconven-
tional, and conventional pollutant data reported with a "less
than" sign are considered as detected, but not further quantifi-
able. A value of zero is also used for averaging. If a pollu-
tant 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 not
quantifiable, and consequently were assigned a value of zero in
the calculation of the average.
Finally, appropriate source water concentrations are presented
with the summaries of the sampling data. The method by which
each sample was collected is indicated by number, as follows:
56
-------
1 - One-time grab
2 - Manual composite during intermittent process operation
3 - 8-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since secondary precious metals production involves 13 principal
sources of wastewater and each has potentially different charac-
teristics and flows, the wastewater characteristics and discharge
rates corresponding to each subdivision will be described sepa-
rately. 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.
FURNACE WET AIR POLLUTION CONTROL
Of the secondary precious metals plants with furnaces, smelters,
or incinerators, 16 control off-gas emissions. Five plants use
wet scrubbers, three of these discharging wastewater, as shown in
Table V-1. This table shows the water discharge rates in liters
per troy ounce of precious metals, including silver, processed
through the furnace. Of the five plants using wet scrubbers, two
plants practice 100 percent recycle, one plant practices greater
than 90 percent recycle, and two plants do not recycle this
water.
The Agency sampled the wastewater from two of the three discharg-
ing plants, one of which does not practice recycle and the other
practices greater than 90 percent recycle. The Agency also
sampled the wastewater at another secondary precious metals plant
which did not practice recycle. Furnace wet air pollution con-
trol raw wastewater contains toxic metals, cyanide, and suspended
solids above treatable concentrations, as well as quantifiable
concentrations of phenolics. Raw wastewater sampling data are
presented in Table V-14.
RAW MATERIAL GRANULATION
Raw material may be melted in a furnace and then poured into a
container of standing water in order to granulate it. This
process is similar to shot casting. The purpose of this opera-
tion is to make it easier to dissolve the raw material in the
acid dissolution process. Of the 30 plants which hydrometallur-
gically refine precious metals, three plants granulate the raw
material prior to dissolution. Two plants discharge this
wastewater, as shown in Table V-2. The third plant practices 100
percent recycle of granulation water.
57
-------
The Agency believes the furnace air pollution control wastewater
is similar to raw material granulation water because both are
waste streams associated with the raw material prior to its
entering the refinery. This wastewater is expected to contain
toxic metals, cyanide, and TSS above treatable concentrations, as
well as quantifiable concentrations of phenolics.
SPENT PIATING SOLUTIONS
Spent or contaminated electroplating solutions with a high
precious metal content may be recycled to recover the precious
metals value. After recovering this value, the depleted solution
may be discharged. Twelve plants recover precious metals from
spent plating solutions. Discharge rates for these 12 plants are
presented in Table V-3, in liters of wastewater per liter of raw
material spent plating solution.
The Agency sampled two plants for this waste stream, and the
results are presented in Table V-15. This raw wastewater con-
tains toxic metals, free and complexed cyanide, and TSS above
treatable concentrations.
SPENT CYANIDE STRIPPING SOLUTIONS
Six plants use sodium or potassium cyanide solutions to strip
gold away from electronic scrap and other raw materials. After
precipitating the gold, the spent cyanide solution may be dis-
charged. Six plants use this technique as shown in Table V-4.
Water use and discharge rates are shown in liters per troy ounce
of gold produced by cyanide stripping. Gold production is
measured as the product from the precipitation operation.
The Agency sampled one plant for this waste stream, and the
results are presented in Table V-16. This waste stream contains
toxic metals, free and complexed cyanide, and TSS above treatable
concentrations.
REFINERY WET AIR POLLUTION CONTROL
All of the acid dissolution vessels, alkaline dissolution
vessels, cyanide vessels, and precipitation vessels located in
the refinery are vented to the refinery scrubber. Of the 28
plants using emissions control, 25 discharge wastewater. The
other three plants practice 100 percent recycle. Seventeen of
the 25 discharging plants practice recycle of 90 percent or
greater. Table V-5 shows water discharge rates in liters per
troy ounce of precious metals, including silver, produced ia the
refinery.
58
-------
The Agency sampled the wastewater from four discharging plants,
three of which practice recycle of at least 90 percent. This raw
wastewater contains toxic metals and suspended solids above
treatable concentrations. Raw wastewater sampling data are
presented in Table V-17.
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH WATER
Gold can be extracted from an impure raw material using an
organic solvent and then recovered from the solvent as pure gold.
The raffinate generated by this process can be discharged, and
one plant discharges this waste stream as shown in Table V-6.
After the pure gold is recovered, it is washed with water and
this wash water is also discharged. Although the Agency did not
sample this combined waste stream, it is believed to have similar
characteristics to gold precipitation and filtration wastewater,
because of the similar raw materials and processing steps. It is
not, however, expected to have treatable concentrations of
ammonia. This wastewater should contain toxic metals and TSS
above treatable concentrations.
GOLD SPENT ELECTROLYTE
Three plants use electrolytic refining as a purification step in
secondary gold processing and discharge the spent electrolyte
wastewater associated with this process. Water use and discharge
rates are shown in Table V-7. No samples were taken of this
waste stream, however, the Agency believes it should be similar
to gold precipitation and filtration wastewater because of
similar raw materials except it should not contain treatable
concentrations of ammonia. This wastewater should contain toxic
metals and TSS above treatable concentrations.
GOLD PRECIPITATION AND FILTRATION
Gold may be recovered by dissolving the raw material in strong
acid such as aqua regia, filtering away the silver chloride, and
precipitating the gold with a strong reducing agent such as
chlorine, ferrous sulfate or sulfur dioxide gas. Gold sponge is
recovered by filtering away the wastewater and washing the sponge
with water one or more times to remove residual acid. This
combined filtrate-wash water waste stream may be discharged via a
cementation tank where either zinc or iron is added to recover
additional precious metals, and then to treatment. The 28 plants
with this waste stream are shown in Table V-8.
The Agency sampled this waste stream at four plants, one prior to
cementation, and all four as combined wastewater after cementa-
tion. Only the plant sampled prior to cementation is presented
in Table V-18 to characterize this raw wastewater because of the
59
-------
metallic replacement reactions and commingling of wastewater
taking place in the cementation tank. As shown in Table V-22,
the post-cementation data support the general characterization of
gold precipitation and filtration wastewater data. Both show
high toxic metal concentrations, along with ammonia and TSS above
treatable concentrations. If a plant cements this wastewater
with zinc, the effluent from cementation should contain high zinc
concentrations.
PLATINUM PRECIPITATION AND FILTRATION
Platinum may be recovered by dissolving the raw material in acid,
filtering away the impurities, and precipitating the platinum as
a chloride. The platinum chloride is then separated from the
solution by filtration. The filtrate may be combined with wash
water, and sent via cementation to treatment. Eighteen plants
recover platinum in this manner as shown in Table V-9.
Although the Agency did not sample this wastewater, the platinum
precipitation and filtration wastewater should have similar char-
acteristics to palladium precipitation and filtration wastewater,
based on raw materials and processing steps. The raw wastewater
is expected to contain toxic metals, ammonia, and TSS above
treatable concentrations.
PALLADIUM PRECIPITATION AND FILTRATION
Palladium may be recovered by dissolving the raw material in
strong base, filtering away impurities, precipitating the pal-
ladium as a chloride, and filtering away the solution to produce
a yellow cake. This yellow cake may be reduced with a strong
reducing agent to the pure metal sponge. The filtrate may be
combined with wash water, and sent via cementation to treatment.
Nineteen plants recover palladium in this manner as shown in
Table V-10.
The Agency sampled one of the discharging plants for three pal-
ladium batch discharges, as shown in Table V-19. The raw waste-
water shows toxic metals, ammonia, and TSS above treatable
concentrations.
OTHER PLATINUM GROUP METALS PRECIPITATION AND FILTRATION
Three plants use a wet chemistry process similar to the type used
to recover either platinum or palladium, to recover other plati-
num group metals including rhodium and iridium. All three plants
discharge wastewater as shown in Table V-11.
The Agency believes palladium precipitation and filtration waste-
water should be similar to this waste stream. This wastewater is
60
-------
expected to contain toxic metals, ammonia, and TSS above
treatable concentrations.
SPENT SOLUTION FROM PGC SALT PRODUCTION
Three plants manufacture potassium gold cyanide (PGC) salt from
pure gold and potassium cyanide solution. Excess cyanide solu-
tion may be discharged from this process. Water use and dis-
charge rates are shown in Table V-12.
The Agency sampled one plant for this waste stream, and the
results are presented in Table V-20. Raw wastewater contains
toxic metals, and free and complexed cyanide above treatable
concentrations.
EQUIPMENT AND FLOOR WASH
Three plants reported an equipment and floor wash waste stream.
This waste stream is discharged via cementation, to treatment.
Table V-13 shows water use and discharge rates in liters per troy
ounce of precious metals, including silver, produced in the
refinery. The Agency sampled this waste stream at one plant, and
the data are presented in Table V-21. This wastewater contains
toxic metals, ammonia, and TSS above treatable concentrations.
61
-------
Table V-1
WATER USE AND DISCHARGE RATES FOR
FURNACE WET AIR POLLUTION CONTROL
(liters/troy ounce of precious metals, including silver,
incinerated or smelted)
Production
Production
Plant
Code
1034
1138
1105
1094
1084
1095
1153
1163
1020
1019
1082
1134
1071
1088
1051
1045
Percent Normalized Normalized
Recycle Water Use Discharge Flow
0 116 116
0 27.6 27.6
>90 NR 4.5
1 00 NR 0
100 NR 0
Dry
Dry
Dry
Dry
Dry
Dry
Dry
Dry
Dry
Dry
Dry
NR - Data not reported,
62
-------
Table V-2
WATER USE AND DISCHARGE RATES FOR
RAW MATERIAL GRANULATION
(liters/troy ounce of precious metals
in the granulated raw material)
Plant
Code
1008
1094
1082
Percent
Recycle
0
0
100
Production
Normalized
Water Use
8.67
4.0
Unknown
Production
Normalized
Discharge Flow
8.67
4.0
0
63
-------
Table V-3
WATER USE AND DISCHARGE RATES FOR
SPENT PLATING SOLUTIONS
(liters/liter of raw material spent plating solution)
Production
Production
Plant
Code
1002
1163
1094
1092
1023
1128
1083
1167
1071
1034
1067
1065
Percent
Recycle
0
0
0
0
0
0
0
NR
0
0
0
0
Normalized
Water Use
1 .0
1 .0
1.0
1.0
1.0
1.0
1.0
NR
1.0
1.0
1.0
1.0
Normalized
Discharge Flow
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NR
1.0
1.0
1 .0
1.0
NR - Data not reported,
64
-------
Table V-4
WATER USE AND DISCHARGE RATES FOR
SPENT CYANIDE STRIPPING SOLUTIONS
(liters/troy ounce of gold produced by cyanide stripping)
Plant
Code
1 100
1034
1163
1067
1083
1026
Percent
Recycle
0
0
0
0
0
0
Production
Normalized
Water Use
78.3
7.63
6.04
2.92
1.14
0.631
Production
Normalized
Discharge Flow
78.3
7.63
6.04
2.92
1.14
0.631
65
-------
Table V-5
WATER USE AND DISCHARGE RATES FOR
REFINERY WET AIR POLLUTION CONTROL
(liters/troy ounce of precious metals, including silver,
produced in refinery)
Production
Production
Plant
Code
1100
1117
1029
1020
1051
1147
1065
1067
1091
1071
1105
1080
1115
1069
1008
1164
1083
1104
1138
Percent
Recycle
0
0
0
>90
0
75
0
90
NR
0
>_90
>_90
>90
>90
>90
90
^90
>90
>90
Normalized
Water Use
107
42
32.8
NR
13.2
39.4
6.8
46.4
NR
2.4
NR
NR
NR
NR
NR
7.0
NR
NR
NR
Normalized
Discharge Flow
107
42
32.8
14.2
13.2
9.85
6.8
4.64
3.32
2.4
2.3
1 .75
1 .665
1.41
1.1
0.7
0.67
0.234
0.21
66
-------
Table V-5 (Continued)
WATER USE AND DISCHARGE RATES FOR
REFINERY WET AIR POLLUTION CONTROL
(liters/troy ounce of precious metals, including silver,
produced in refinery)
Production
Production
Plant
Code
1094
1165
1082
1026
1072
1167
1053
1128
1034
Percent
Recycle
>90
>90
99
>90
290
95
100
100
100
Normalized
Water Use
NR
NR
7.2
NR
NR
0.6
NR
NR
NR
Normalized
Discharge Flow
0.19
0.172
0.072
0.06
0.036
0.03
0
0
0
NR - Data not reported.
67
-------
Table V-6
WATER USE AND DISCHARGE RATES FOR
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH WATER
(liters/troy ounce of gold produced by solvent extraction)
Production Production
Plant Percent Normalized Normalized
Code Recycle Water Use Discharge Flow
1094 0 0.63 0.63
68
-------
Table V-7
WATER USE AND DISCHARGE RATES FOR
GOLD SPENT ELECTROLYTE
(liters/troy ounce of gold produced by electrolysis)
Plant
Code
1071
1084
1088
Percent
Recycle
0
0
NR
Production
Normalized
Water Use
0.294
0.0087
NR
Production
Normalized
Discharge Flow
0.294
0.0087
NR
NR - Data not reported.
69
-------
Table V-8
WATER USE AND DISCHARGE RATES FOR
GOLD PRECIPITATION AND FILTRATION WASTEWATER
(liters/troy ounce of gold precipitated)
Production
Production
Plant
Code
1034
1100
1091
1053
1165
1083
1067
1063
1082
1147
1 110
1008
1 138
1065
1117
1153
1026
1020
1069
Percent
Recycle
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
NR
NR
Normalized
Water Use
560.5
404
69.1
24.3
7.98
4.1
3.34
2.65
2.5
1 .86
0.815
0.63
0.341
0.312
0.27
0.144
0.05
NR
NR
Normalized
Discharge Flow
560.5
404
69.1
24.3
7.98
4.1
3.34
2.65
2.5
1.86
0.815
0.63
0.341
0.312
0.27
0.144
0.05
0
0
70
-------
Table V-8 (Continued)
WATER USE AND DISCHARGE RATES FOR
GOLD PRECIPITATION AND FILTRATION WASTEWATER
(liters/troy ounce of gold precipitated)
Production Production
Plant
Code
1018
1 104
1 128
1164
1029
1167
1072
1 115
1071
Percent
Recycle
NR
NR
NR
NR
NR
NR
NR
NR
NR
Normalized
Water Use
NR
NR
NR
NR
NR
NR
NR
NR
NR
Normalized
Discharge Flow
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR - Data not reported.
71
-------
Table V-9
WATER USE AND DISCHARGE RATES FOR
PLATINUM PRECIPITATION AND FILTRATION
(liters/troy ounce of platinum precipitated)
Production
Production
Plant
Code
1020
1082
1069
1105
1147
1051
1018
1063
1072
1115
1 117
1 104
1 156
1 138
1080
1088
1153
1134
Percent
Recycle
0
0
0
0
0
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Normalized
Water Use
354
30.2
10.4
4.5
0.58
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Normalized
Discharge Flow
354
30.2
10.4
4.5
0.58
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR - Data not reported.
72
-------
Table V-10
WATER USE AND DISCHARGE RATES FOR
PALLADIUM PRECIPITATON AND FILTRATION
(liters/troy ounce of palladium precipitated)
Production Production
Plant
Code
1069
1147
1 105
1082
1138
1020
1153
1018
1128
1029
1072
1115
1 117
1 104
1156
1080
1071
1088
1051
Percent
Recycle
0
0
0
0
0
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Normalized
Water Use
15.8
4.58
4.4
3.4
1.53
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Normalized
Discharge Flow
15.8
4.58
4.4
3.4
1.53
0
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR - Data not reported.
73
-------
Table V-11
WATER USE AND DISCHARGE RATES FOR
OTHER PLATINUM GROUP METALS PRECIPITATION AND FILTRATION
(liters/troy ounce of other platinum group metals precipitated)
Plant
Code
1115
1051
1 156
Percent
Recycle
NR
NR
NR
Production
Normalized
Water Use
NR
NR
NR
Production
Normalized
Discharge Flow
NR
NR
NR
NR - Data not reported,
74
-------
Table V-12
WATER USE AND DISCHARGE RATES FOR
SPENT SOLUTION FROM PGC SALT PRODUCTION
(liters/troy ounce of gold contained in PGC product)
Production Production
Plant Percent Normalized Normalized
Code Recycle Water Use Discharge Flow
1100 0 260 260
1034 0 0.90 0.90
1128 NR NR NR
75
-------
Table V-13
WATER USE AND DISCHARGE RATES FOR
EQUIPMENT AND FLOOR WASH
(liters/troy ounce of precious metals, including
silver, produced in refinery)
Plant
Code
1020
1105
1138
Percent
Recycle
0
0
0
Production
Normalized
Water Use
14.2
1 .0
0.97
Production
Normalized
Discharge Flow
14.2
1 .0
0.97
76
-------
CO
C
O
•1-1
•u
CO
o §
25 H
3§
£°
d§
WttJ
CO HW
OW
OnE-l
CO
CO
CM
o a
2525
QQ
a a
522;
QQ
isz;
Q Q
a iz;
QQ
2555
Q
25
Q
Q
25
Q
25
Q
25
Q
25
QO
25 •
O
Q
25
QQ
2525
Q Q
252
Q
25
Q
25
Xi CD
CO O
EH M
O
w
01
r-l -t-
(X U
CO
a
25
Q
25
Q
25
Q
25
Q
25
Q
25
a
25
Q
25
Q
25
QQ
2525
QQ
2525
QQ
2525
QQ
2525
25 25
QQ
2525
Q Q
25 25
QQ
2525
Q Q
25 25
«- CN *-<
CM ,-*- r-
i- eg
oo
OMO
00
oo
oo
ON
oo
oo
00
m
OMO
00
oo
in
Q
25
O
O
4-1
C
CO
4-1
d
r-l
t-l
O
&4
-------
X-S
"^O
(U
3
C
•H
4J
C
O
O
«^
r»-
1
^
W
<-l
43
cd
H
J!3
WOW
§ CX.H
CO
co «<;
>— ^ ._.[ ^>
0 <
.__. h^
0 H<
WWW
Pd ijE
(X,
u
>" O
05 •
cd
Q
1—
>•
cd
Q
d)
U
>j
3
0
CO
0)
r-4 +-
ex, in
oo
o\ in
oo
oo
oo
m
T3
0)
jj
c co
•H C
4J CO
P 42
4J O 4J
c u -
•
O
,—
CU
c
CO
42
4J
V
O
O
r-4
42
O
••-4
M
4J
1
•^
^.
A
*-
«
*—
r—
CO
c
CO
42
U
CO
O
VH
O
r-l
r*
O
X
0)
42
•
CM
i—
CO
G
cd
4J
(U
O
o
T— 1
42
O
•H
""O
1
,_
„
^_
CO
c
CO
42
(U
O
jj
0
r-4
42
O
•H
W
4-1
1
CM
,_
»
,—
OJ
C
CO
42
4-1
cu
O
l-i
0
r~4
42
O
CO
Vi
4J
01
4J
1
CM
•t
CM
•k
t—
A
TM
CU
c
CO
42
(U
0
S_i
o
r-l
42
0
(J
CO
42
4J
0)
x-s
r-l
^
43
4J
CU
e
o
^
o
r-l
43
O
v-x
CO
•r-(
43
(U
43
4-1
OJ
x-v
i— 1
^)
42
4-1
CU
O
5-i
O
r-l
42
O
1
CM
v_x
CO
•!-l
43
oo
78
-------
CO
C
O
•H
4-1
CO
CO
CM
Q Q
S32;
Q Q
a a
o
CM
ge
Q Q
a a
9
55
g
Q
2
Q Q Q Q
Q Q
aa
\/
O
o
•
o
o
i/t
i
i
§
Q
a
>
•-• c
W -H
C >
4-)
C
CO
4J
3
r-l
iH
O
(i,
o
O r-l
^ >>
J3
CO
•u
c
cd
4-1
3
l-l
r-l
O
a<
4J
V
o
)U
0
r-l
XI
CJ
1
CM
(U
c
(U
I—I
CO
J3
4J
X!
a
CO
c
o
M
o
l-l
X!
O
CM
2,4,6-trichloroph(
2
v
?
g
o
s
o
§
o
V
I
-
7
o
H
O
CM
CM
CM
CO
CM
CM
CM
CM
CM
79
-------
Q i-J
o PS
Z H
r4 O
X-N CU O
TO S
0) -
CO H
01 TD
Vi O
4->cj
CO
Q Q
z a
00
zz
Q Q
z z
00
ZZ
O Q
a a
Q Q
z a
Q O
Z S5
00
zz
O Q
Z Z
Q
Z
Q
Z
Q
Z
a
z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q O
z z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
QO
zz
Q Q
z z
Q O
ZZ
0 Q
zz
Q Q
Z Z
Q Q
Z Z
ao
zz
Q Q
Z Z
*- CM
CM
T- CM i— CM
00
m
LO
oo
00
m
m
oo
oo
ao
oo
oo
oo
m
0)
C
3 'O £3 ci) CU cu
C -^ •> O C O< O-
C CO 43 r-l QJ o O
4->OrO 4-14343 rJ M
coo
CO i— T— CM *- »-
r-l
O
C
0
43
a
rH
r*~>
43
4->
Q)
S
•H
rQ
|
,J-
.
CM
-------
CO
e
o
•H
4-)
C
•
co E-i
•— CM i— «—
•-CM
r- CM
»— CM
— CM
••—CM T— »— t— ,_
O-i
e
cO 0)
CU-O
r-l O
•UCJ
co ;
OO
IT)
ON IT)
00
ON ID
00
ON ID
co
a\ ID
00
ON iD
00
ON ID
00
ON ID
00
ON
00
c
*
Po
4J
c
o
u
CO
4->
cO
4-1
o
eu
cu
CO
(-1
-a
Q>
X!
ft.
»H
TJ
1
CM
C
CO
r-l
O
d
rH
(U
X!
4-1
r-l
(U
X!
4J
(U
>s
a
o
M
a
o
CO
•H
O
r-l
O
rH
X!
O
I
CM
•^-x
CO
•H
X>
0)
c
cO
X!
4-1
a;
S
O
X!
4J
0)
O
J-l
o
X!
O
I
CM
^s
CO
•H
X5
0)
T>
•H
M
O
rH
X!
O
0)
c
(U
rH
fc^
X!
4J
CU
e
(U
CO
x:
4-1
(U
e
o
M
o
rH
X!
O
CP
T3
•r-l
r-l
O
rH
X!
CJ
>•>
X!
4J
0)
e
X
o
H
on
oo
en
ON
CM
IT)
ID
81
-------
O Q
z z
Q Q
zz
Q Q
z z
Q Q
zz
Q O
Z Z
Q Q
zz
Q Q
Z Z
00
zz
O Q
Z Z
x-x
-o
01
d
c
•rl
4J
c
o
u
•v^
<
H
3
O
z
M
h4
P-i
IS
•^2
CO
CO
rJ
cn H
cu
r-l
XI
CO
H
cn
3
O
i—i
O
m
«
Pk
i cu
oo
O
Z
Q
Z
Q
Z
Q
Z
QQ
zz
00
Q Q
Z Z
.CN i—
O\
00
Q p3
Z 13
O P=<
o
w
Pollutant
-------
aj
O OS
S3 H
w S3
hJ O
CO
J-l
4J
C
0)
O
c
o
o
O O
5353
QQ
5353
a a
S3 53
00
5353
Q Q
5353
Q Q
S3 S3
00
S3 S3
§
§
o
S3
Q
S3
O Q
• 53
O
Q
S3
QQ
S3 S3
Q
S3
§8
§g
§
gg
§
gi
Q
S3
Q
53
Q
S3
gg
gg
Q Q
53 S3
Q Q
5353
Q
S3
00
S3 S3
§
)
CO H
4J O
CO
'-CM ^- < O
OS <
< S3
O OS
53 a
O fn
o
w
CO
o
09
-------
s
cu
53
4J
C
O
o
0>
r-l
43
cO
H
H
Q rJ
O OS
Z H
"iS
rJ O
04 U
•* U
in
oo
CO
oo
00
00
OO
OO
cr. i
OO
CO
m
4->
C
CO
3
i-H
O
0)
c
o
o
co
40
(3
O
P-4
O
C
o
(-1
o
c
(U
(X
o
Q>
a
a>
40
co
40
p-
X
a>
40
40
cO
r-l
CO
43
40
43
a*
43
40
0)
s
o
CO
S-i
43
40
C
CO
X—v
CO
O
N
C
CU
43
X
o
H
m
vO
00
vO
as
r- CM
84
-------
•o
<
co
<
a.
B a
«d >
CO H
cd cu
m
oo
o fa
o
W
CO
c
•H
•u
4J
C
cd
•u
3
i-4
i— 1
O
o,
O *
l-l
X!
O
0)
c
a;
acenaph
-------
TD
CU
4J
C
O
O
Z H
i-i Z
nJ O
OM O
O
,- O
• •
O O
V
O
z
a
z
Q
z
en
i- O
Q O O
z • •
00
V V
O
z
Q
Z
Q
Z
Q
53
Q
Z
a
z
Q
z
QQ
zz
00
Z5S
QQ
ZZ
Q O
Z S3
Q Q
pa
zz
a a
z z
O
O
CO CO
,-00
000
• • •
oo o
V V \S
o w
fcH
CO
o;
i-i
,0
rt
H
CO
U H-
W W (
ct! 5
O-i
w
SM O
0£
C
«d
/-^»
X!
C(J
v^
O
CM
00
C
9)
VJ
>»
CX
O
I
CO
•k
CM
O
C
(U
CO
00
QJ
C
0)
VJ
00
(U
C
0)
0)
0
j-
O
4J
-------
C1
-( o
OS ^^
^J 23
Q OS
O En
O
M
CO
centrations (mg/1)
c
o
o
CO
>
ctt
a
CM
>-
Q
>
CO
a
J" ON
O T- O
• • •
OOO
CM
O
o
a>
o
oo
o
o
CM
O>
O O
• •
CO O
o o
r- CO
• •
o o
V
CO
o
com
i- OO
o oo
o oo
V VV
CM
o
*- ,-0
O 00
o oo
V VV
CM
o
m »— o
ooo
o o o
W
CO
m T- o
ooo
ooo
x/v
r*.
m i— r-
o o o
ooo
W
CM
in CM m
ooo
ooo
NX
o
OO CO
r- i- O
ooo
N/V
CM r- CM CM ,— CM CMr-CM CM r- CM CM r-CM i— r- «—
CM r-CM
O CT\ in
O OO
CM r-
O
O CO
CM T-
o OM
o co
CM *—
o
o co
CM T-
o O
o oo
CM r-
O ON in
O OO
CM i—
o o\
O CO
CM r-
-------
^0
3
C
1-1
4J
C
o
o
S.X
;£
1
J>
to
en
^-
CO
Q
CM
>
crt
•w
Q
r—
>>
Cf)
Q
(1)
O
r4
rj
O
to
+-
cf r>~cM
*- 00
o o oo
• • • *
O O OO
en V
VO CM
r-
p
CO
4J
v^
,->
r-l
iH
O
O
•i-l
^
O
H
^>
U 1— 1
O J^l
H O
d) >i-4
e P
• •
en >3-
CM CM
r- r-
CO
in
CM
•i-l
CO
CM
r-4
CO
4J
CM
U
C
•H
N
OO
CM
88
-------
O BJ
"-1 Z
•JQ
Oi O
V
c
1-1
4J
C
o
o
CO O
CO HW
H dl2
w
CO
V4
4J
C
a)
o
o
o
CO
>•
CO
a
CM
s a
«o >,
COH
CO
CO
on
•
oo
o
•
o
CO
•
o
OOO
CM «-
OOO
CO
4-1
C
CO
4-1
Q
8
C
CD
00
o
•a
•r-l
o
CO
4J
•••4
C
•r-l
rH
CO
r-l
CO
aluminui
ammonia
barium
c
0
n
o
J3
calcium
§
00
>>
X
o
CO
O
•r-f
8
89
-------
^
cu
j3
C
•H
4J
C
o
o
^>
^»
1
>
cu
r-l
CO
H
<;
H
Q *J
O
O<^/
W»i
25 H
r™t 25
J O
CM CO
< 23
CO O
MC4
CO H W
-3 S3H
H JS
wow
S CMH
CO
co as sg
*™i • * **Z
M-J r" 1 i^
O <3
i— i S
CO E-I <1
W W OS
gs 5
w
0£l ^i
Q a
2: o
O tt<
w
CO
r— T—
X-s
H!^
bt
s
(Q
C
o
4-J
2
4J
C
y
{2
O
CJ
CO
!>.
(0
Q
~3" 00 in CM CM vO
• • • • • f^t
O CM i— -* o in co »— •
0 0 «- O
0 «-
O CM CNin^Nd'O O
CM
CO
a
CO O O OOOOCOO O
vO \S \/ ^^
CM
CO CM
cO
Q
O CO
CU
o
1-4
3
O
CO
O^O O O O CM
ino oo in^~cy\ o in^— mo
OO CM T- O CO CM in — CM r- CM «— CM «— »— «— CM »— CM r-
e
cO cu
Q) *O
VJ O
-UU
CO
o ON o crv o os o c^ in o cy> m o CT> o CT\
O 00 OOO O CO OOO OOO OOO O OO
CM,— CM»- CN ^- CM'— CM'— CM'— CM T-
^-^
T5
(U
•3
C
•H
4J
C
o
u
CO
4-1
C
m
o
o
•
o
T~*
o
o
m
CM
o
m
»—
0
,—
m
4J
cO
4J
O
CM
r-l
O
CM
cO
e
0
1
•f~»
4J
CU
O
O
25
cu
•H 4J
O CO
y o
a;
g
CO
00
S
en
cu
C
bO
cO
B
O
e
CO
o
o
c
cu
OH
90
-------
a
cO
Q
o co
CN i-
O CT>
OOO
CN i-
O ON
O OO
CM ,—
O ON
O CO
CN *-
O ON
O 00
CN T-
O ON
O 00
CN T-
(U
C
•H
4J
C
o
o
O ON
O OO
CN T-
O ON
O CO
CN ^-
4J
C
CO
CO
C
cO
4J
O
CM
CO
4J
C
(U
C
O
o
c
o
(U
4J
cO
Pu
CO
o
O
CO
CD
4J
cO
m
r-l
3
CO
8
H
CO
O
00
5-1
O
i-H
CO
4-1
O
4J
CO
H
CO
O
CO
cO
4J
O
4-)
T3
CO
C
CO
91
-------
o
o
,- r- O CO
in
/^N
r-4
CX
e
^-^
m
C
O
•r^
t '
+™
cO
Vi
i^
C
cu
< z
H C
S o
QJ 0
O
OoS
h*»
Z H
M a
CO! O V \/ 0 r-
dl *-.
in oo H-
0 ^ "*
CM
>•
CO
o
Q CM r- o oo r^ co
V V O
vO
in" C
o
•1-1
V£> 4J
T- *
>
cO
Q
— ° ^ m
v cx
o
w
CO
03 CU
cu
o
14
3
o
CO
CNI ^^^ g
So ^> oooo P-I^VO ^j
• ^.rt '•^
• • • >w
O O T-T- 1—
W S/N/ ^
pJ O CU
/-v 04 CJ 4->
T3 S 4J
CU
0 HvJCS CO H
B
n
CM^_ ^-i-r- CN<-CM CMt-CM aj
c
•H
o wow
x_/ S CX, H 00
CO C
-3- co erf •< -H
t— 3 r-i is e
i O r-l IS w
r-l 065 3 CO
5-i
o o\ ocyiin oo> in oo\in ^
0» 000 000 000 T3
CNr- CM'- CM^- C^1" (j,
4J
£> PU .r4
cO W C1 -0 w
H 5n O ?, « °
os <: S V4 cx
§ 5 -s 5 is 3
g .2 g § r-l « §•
§ il ^ ^ 2 §
§ 3 § 3 o * co
a >, o o w cx *•
•
V4
(U
X!
4J
cu
00
o
4-J
*o
CU
4J
Jj
o
ex
cy
&
s~\
cO
^~s
•
cu
o
c
cu
U
CU
14-1
Vi
cu
JJ
c
•i-4
o
4->
cu
3
•a
TD
(U
CO
•r-t
cO
S-i
4J
•1-1
B
•f-l
r-l
c
0
•1H
4-1
o
cu
4->
cu
0
1
<
92
-------
col
Q
25
Q
25
a
25
a
25
a
21
a
25
a
25
a
2
(=1
25
a
25
a
25
a
25
25
O
25
Q
25
Q
25
Q
25
a
25
Q
25
Q
25
Q
25
Q
25
a
25
a
25
Q
25
Q
25
Q
25
Q
25
Q
25
I
>
0>
§
i
KH
rJ
Oj CO
S 25
vo
VO
Pollutant
Lc Pollutants
acenaphthene
X i-
o
H
acrolein
CM
acrylonitrile
•
on
benzene
•
TJ
carbon tetrachlori
•
vO
chlorobenzene
•
i-*.
o>
C
0*
CO
1 ,2,4-trichloroben:
•
00
hexachlorobenzene
•
o\
1 ,2 -dichloroethane
•
o
0)
C
1,1,1 -trichloroeths
hexachloroe thane
• •
i- CM
O)
C
1 , 1 -dichloroethane
1 ,1 ,2-trichloroetha
• •
en -*
93
-------
cu
C
C
o
H
a
o
z
M
hJ
PLI CO
S Z
< O
CO M
H OS
co o w
r4 hJ H
H CO 3:
w w
§ O H
Z CO
CO r-H <;
OH St
O
as
cO
H
U Pk
03 H
P-i Z
W
>-i fL|
o5 co
Q
Z
o
w
CO
M
CO
4J
C
cu
o
C
o
u
CO
CO
a
CM
CO
CO
Q
CO H
cO 4-> C
^ co
43
4J
0)
E
0
^_(
o
I-l
43
O
CO
•r4
J3
5-i
pj
•P^
>
r-l
^
(*;
4J
CU
O
Vj
0
43
O
1
CM
-------
CO
>
o
Q
2
Q
2
Q
2
Q
2
Q
2
Q
2
Q
2
Q
2
a
2
a
2
a
2
Q
2
Q
2
CM
oc
O
2
2
a
2
Q
2
a
2
a
2
Q
2
Q
2
Q
2
Q
2
O
2
Q
2
co
O
co
Q
Q
2
O
2
a
2
o
c
s
C X!
O -U
o o>
s-x O
Jh4
CO
4J
C
4J
j3
rH
r-l
O
PH
O
rH
XI
O
•H
T3
1
i—
•
1—
JCJ
4J
CU
O
J_l
O
1-1
<-;
CJ
•r-l
T3
1
CO
C
CO
]^
4J
1
CM
0
T—
r-l
O
C
cu
Xl
ex
o
^j
o
rH
XI
0
•H
T£J
1
^J
•k
CM
CU
C
CO
CX
O
>-l
(X
o
1*4
o
rH
f!
O
•H
tJ
1
CM
i—
cu
C
0)
(X
o
fa
(X
o
^
o
pH
X!
0
•r-l
-rj
1
CO
«
r-
r—f
O
c
cu
XI
rH
K*S
X!
4-1
CU
B
•rl
T3
1
^^
,
CM
CU
CU
rj
rH
O
4J
o
Vj
4J
•H
C
T3
1
^>
.
CM
CU
CU
rj
rH
O
4J
O
4J
>rj
CJ
•r-l
T3
1
vO
A
CM
N
CO
i-l
rl
CU
XI
4J
CU
C
cu
CX
VJ
cu
x;
4J
CU
G
0)
XI
P,
cu
X!
4-1
CU
(X
o
i-l
CX
o
CO
rH
>.
C
CU
X!
CX
•H
T3
I
CM
•
i —
CU
c
cu
N
C
cu
Xl
rH
£x,
X!
4J
01
0)
c
cu
XI
4-J
c
cO
r4
0
3
r~f
M-l
C
XJ
CX
o
o
rH
XI
CJ
1
^>
>>
G
cu
JC
CX
o
B
o
Xl
>^-
0
o
X!
CJ
1
CM
<^x
CO
•H
Xl
X
o
H
CM
O r-
ro co
CM
CO
CO
CO
co CO
vo
co
co
oo
CO
co
O r-
CM
95
-------
.
cfl
Cl
Z
o
V
Q
Z
O
z
Q
Z
Q
Z
O
o
z
0
z
Q
z
Q
Z
Q
Z
O
Z
E-i
Q
Of
S
CO
C
O
•H
o
O
c
o
CJ
(1)
o
CO
o
z
o
V
Q
Z
Q
Z
O
z
Q
Z
Q
Z
O
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
O
N/
a
z
a
z
Q
Z
Q
Z
a
z
Q
Z
a
z
a
z
Q
Z
a
z
Q
Z
O
z
Q
Z
a
z
o
z
Q
Z
Q
Z
Q
Z
o
z
Q
Z
Q
Z
a
z
"O
c
c
o
o
m
V—
1
>
CU
r-l
Xi
CO
H
o-t co
S Z
CO M (U
H PS r-l -r-
co 3 w a ai
•
H co DC CO H
W W
§ O E*i
Z CO
CO M
Xl
4J
O
>-i
O
r-l
Xi
O
\o
Q)
c
cu
•I-l
T3
CO
4J
rj
Xi
o
0
r-l
X!
0
cO
X
X!
vO
(U
c
CU
•rl
*O
cO
4-)
c
CU
(X
o
r-l
O
^
o
o
M
O
r-4
X!
cO
X
CU
XJ
vO ^O vO
cu
CU C
cu c cu
C CU N
O r-l C
rl CO CU
O X! Xi
X! 4J O
CX X! rl
O CX 4J
co cO i-i
•H C C
o
H
en
in vo
oo
O T-
cs
m
m
m
96
-------
H
a
o
z
rt
C
<1>
CJ
o
o
CO
{*•
cO
o
CM
co
cO
o
•
o
o
•
o
o
z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
m
CM
O
Q
Z
O
z
Q
Z
O
V
Q
Z
O
z
Q
Z
Q
Z
a
z
m
a
z
o
V
Q
Z
a
z
a
z
Q
Z
Q
Z
Q
Z
O i-
z
o
Q
Z
o
V
Q
Z
o
V
o
•
o
Q
Z
Q
Z
o
z
a
Z
o
z
Q
Z
o
z
CM
O
•
o
Q
Z
0
o
V
Q
Z
o
•
o
V
CJ W W
Z OT
m en M 1— 1 rJ £2
U (X, •<
<0 W pS
rH OS EH
rO D-l Z
CO W
EH >-i OH
Q
Z
O
U
M
C/D
rH H-
(X
W EH
S
cO 01
(0 'O
U 0
4-> O
CO
4J
(3
cO
4J
rj
rH
rH
o
Pu
vO vO vO ^O vO vO
X-N (U r_) .H -H
s o B e
C CO CO CO
••H rH 0) rH i-H
4-> O 5-J >-, >~>
C C 0 43 C
O H -H 5-i 5-i
,3 4-) 4J "O T3 4J 4J
rH -rl «tH | I -H -r-l
rH C (3 -* VO C C
Oil --II
(Xl CM -tf CM >
X
CU
43
rH
>»^
43
4J
0)
1
CM
N^X
CO
•r-l
43
vO
0)
CO
rH
CO
<-!
U
43
CU
rH
r*^
N
c
(U
rH
r*"*
4J
j3
43
vO
4J
O
O
1
(3
•iH
T3
vO
CO
4J
cO
rH
CO
43
4-1
43
a
rH
r*~l
43
d)
•T-(
"U
X
o
H
m
oo
m
o t-
vO vO
CM
CO
vO
vO
m
vO
vO
vO
vO
00
vO
vo
o
r-
97
-------
CO
>
cO
Q
O
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
a
z
o
z
Q
Z
CN
«
B
u
Pi co
a
z
o
u
CO
o
c
o
0)
u
o
CO
a
z
Q
Z
Q
Z
O
z
a
z
a
z
a
z
Q
Z
O
z
Q
Z
Q
Z
Q
Z
a
z
a
z
(U
s Q.
co sx
co H
CO
vO
vO vO vO vO
0)
-p
c
cO
•o
S
c
co
c
cO
t-l
o
cd
CU
c
(U
0)
c
(U
cO co
01
e
o
N
c
(U
T- CM
o
N
c
(U
en
r-.
o
N
c
(U
r—l
4_|
x-v
n^
x_x
o
N
C
(U
iu
c
-------
/—v
-o
D
3
C
•H
( [
C
o
U
m
i
0)
rH
43
CO
H
-i fXi
ttS CO
Q
Z
o
o
H
CO
rH
(X
g
•^>
CO
C
0
4J
cO
•U
C
(1)
O
C
o
o
CO
rV
(0
Q
T—
Q 0 Q Q
»2j • J23 S2
0
\S
>
cO
Q
Q 0 O Q
Z • Z Z
0
N/
,—
>
Q
r—
Q O Q Q
O
\/
(y
o
u
o
CO
Q Q Q Q
Z Z Z Z
V
rH •»-
f^f Q)
Set
»•*
CO H
CO 0)
M O
-P U
CO
^O ^? ^p ^D
X— \
l~!
4J
0)
»"^ O
"O J*j
<1) O
3 , 0»
(3
CO
4J
^J
r—|
rH
O
0<
O 43 rH CU
O 4J ^ T3
v— ' CD j3 «H
O W Jj
CO W Q) O
4J O O rH
C rH Cl C*
CO 43 (U O O
4J 0 C rH
3 cfl cU 43 rH
rH U( 3 Cj ^s
rH 4J rH -H C
O
U
•H • • • •
X in ^o i-v oo
O oo oo oo oo
H
CN
•
m
0
•
i—
ro
o
m o
coo
\/
oO ro
00
OO
OO
\s\s
vO O
pv.
^>
C
o
e
4J
C
CO
•
,-j-
r—
, —
P^ 00
O i- 3"
CM O OO r>^ r- O i—
oo oo oo oo
\S CM
CM CM
mcM o CM o » 6 O
CO U "O rJ
J-i CU cO 43
CO 43 O O
• • • •
in r** oo ON
r— *— *^ ^™
T— 1— * 1—
CM
0
o
\/
0
,-* ^
JJ
C
0)
rH
CO
CO
X
at
43
•r-l
(3
O
43
CJ
99
-------
x-x
•o
01
^
C
4J
c
o
o
m
,— .
i
w
fj hJ E~*
• 0,
oS co
a
53
o
o
w
CO
on
5*
cd
0
/•^
f-l CM
»•»
0£ >•
8 cO
^Q
CO
C
O
•r-l T—
4J
CO >•
l_| (V*
M w
4J Q
C
01
CJ
C
O CU
O 0
v<
o
CO
•
CO H
e
CO 01
V4 O
•U U
CO
4J
C
4J
t
^^
O
d4
O O
• •
o *n
on CM
T»M>
O 0
• •
O r-
•
o
CO U
c
CO .
CM
OOO
OT- Or-
vO t^ ^^ C5
m v
CM CM
CM m oo
O CM OO
o o oo
s/v
r— *—
vO O vOO
p>» r**»
e
V
r-l .r^
- c
^y, a)
O r-l
•^ CO
C co
• •
<(• m
CM CM
00 O
CM O>
• *
0 0
P** r—
csj ON
• •
0 O
m
O CM
*»oo o
CMO CMO
OO i-O
N/ V
CM m
OO r~CM
OO OO
OO OO
oo oo
Vs/ W
^- r-
vO O vOO
r*v r^*
M -H
01 r-l
> r-\
i-l Cfl
•H jC
CO 4J
• •
^o r*»
CM CM
100
-------
x-s
"O
0)
£
C
•H
4J
£
0
U
m
i
< a,
f^CO
o
o
Ed
CO
co r^
>> >± to
•rl f— r— C^O CO CM O\ CO
4-> O T— O CT* • O O O CM T— r- 1-voO QO ON O
•UQ OO OOOOCMCMCM^CTivOOO
C O V O O V
1) (.O O r—
o . -
C ON vO CM
O Q) L/*> V.O ^ CJN ^ OO
C»? O r~ t/1^ v.f\ v/^ c*^ ^J cj^ ^^ ^w
to OO OO O O CM O CM CT> r- CO O
O OO vO O O O CO »* O OO C0 1— O
CO V <— V r-
(U
r-4 -1-
a. at
BPL r- ^_^_^^^r-^_^^-
co H
.
S^
V* O ^O O vO O O O V0O O vOcp vOO O
CO
^^\
•o
(U CO
e c
•i-i co
4-J [ i
4-1 O r-4
CO r-l
CO ^ O
4J (H
3 CO
r-l 4J r-l
rH C CO
O CO C
O( 4J O
r-IO 4J ^
r-4 C (3 4J B nd g -HCU
CJ-HCS 34J coC
O Or-).r43C''-lp-4 0) CO
•H • OcOg-r-iOO cOC C 00
X 00 Cj£3r
-------
<(J
t-*
^d
a
o
S5
r— I
'"N P-l CO
3 COW
n H as
•H CO » W
U-3 T LJ
h-) h-^ C**
C ^3 O **C
0 Hco 3
o H w
Z co
m co M <;
*~ O E-I IS
1 CO ^^
0 PH < PM
ffi CO
Q
O
a
Cd
CO
3
Of
B
co
C
o
•r4
4J
cO
Jj
4J
C
•r-l CO Ci) <1) Vl CX
4J S C VJ CX cO >,
C3co OcxOcoTJ H
CUCO SB •-! 3C
>>C'H cOcfll-i> co ^~s B
(3r-ICU'OC4JC-UC'-H4J CO
OOXO-^-HcOWO-^OlU CO
jsscxco4->u>>suoua -H-
*
]k4
-------
H
2
a
o o
o
C
o
o
CO
CM
!>•
O
CO
O t-
O i-
• *
o o
V
CM
O
O
O
m
oo
OS
oo
o
•
o
V
o
o
o
O CM
00 O O
t- O O
oo
o
V
o
\/
v£>
in
CO
o
0
0
\/
CM
0
o
O
V
o
o
o
o
o
O CO
O CM
-3- CM
O 0
oo
0
o
V
r-
o
o
o
o
CM
O
CM
O
o
o
V
m
o
0
o
0
V
CM
O
0
0
V
m
o
o
0)
CO
H
CU J
SO
,
CO H
cd a)
co
O
O
CM
O
CM CM
O O
r*^ r-»
CM
o
CM
O
CM
o
CM CM
O O
r- r*
CM
o
CM
O
CM
O
r-
CM
O
r--
CM
O
CM
O
CM
O
«-! C
O CO
CU 4J
3
r-t
O
O
X
0
H
f>~,
G
O
s
•H
4J
C
CO
^
r—
O
•H
C
CO
)_l
CO
m
»—
|
H-l
I-l
r— (
^*l
J_|
0)
^P
^^»
T—
e
••-I
s
t3
CO
O
00
»—
4J
O
4->
*^^/
B
j3
•<-l
B
O
i_l
r;
O
O\
T—
(4
cu
ex
ex
o
o
o
CM
CO 0)
4-1 ^%
O 0
,
CM
TD
CO
0)
r-t
CM
CM
B
J-l r-4 -H
^ d~ m
CM CM CM
p
cu
r-l
•H
CO
VO
CM
B
•r-l
r—l
r-l O
cO P
r[ -r^
4J N
r^ oo
CM CM
103
-------
H
a
o
H
cs
w
B
CO
C
O
4->
cd
o
cd
cd
CM
o
o
CM
i- O
o
oo
CN
en
en
«N
CM O
r- O
m
CM
CN
O
V
CM
*- o
in o
o o
V
00
<£> ON
m O
o o
CM
C
o
u
c
o
2
CN
O
CM
O
CM
O
S
B
CN
O
r-
CM
o
CM
O
CM
O
CM
O
CM
O
CM
O
CM
O
CM CM
00
r-. i*»
CN
0
a
r-l Cd
Cd 43
c
o
o
jQ
B
3
•r-t
O
1-1
cd
o
4J
r-4
cd
o
o
C
0
t-l
•H
B
CO
Q)
C
00
cd
nese
cd
00
C
cd
S
B
3
G
cu
^
^^>
rH
O
s
B
3
•H
-o
O
CO
C
•H
4J
B
•H
C
cd
§
•fl
T3
cd
c
cd
B
4J
JJ
104
-------
Q
O O
!-J CD
0
CO
C
O
•H
4-1
CO
S-l
4J
C
CU
O
c
o
o
CO
CO
a
CM
CO
I
CU
CO
H
CO
C/J
as
w
H ft* !5
§ SH
H co
co co <3
o pa
W JZ
p^ ^^
PM >H
O
pjj c^
<«: z
o w
Z OH
OCO
Cd
CO
0)
e a.
CtJ >•
CO H
co cu
C/3
O
O
CM
O
£0
^
r-l
o
ft*
r-l
CO
c
o
•r-l
4->
c
cu
c
o
o
/— ^
CO
4J
•pH
C
3
TJ
^
CO
T3
C
CO
4-)
CO
tu
cx
CU
T3
O
U
CU
a
CU
r-l
a
B
cfl
co
105
-------
J^>,
r_
1
^
CO
r-l
Q
cO
H
-< OS
os w
>
cO
Q
o
QQ QQ QQ QQ QQ CMO QQ
2525 2525 2525 2525 2525 -25 2525
Q Q Q Q Q Q CJ
Z 25 25 25 25 25 25
t-.
>
cO
a
QQ QQ QQ OQ QQ QQ QQ
2525 2525 2525 «25 2525 2525 2525
O
V
(U
o
W4
0
o
CO
QQ QQ QQ QQ QQ QQ QQ
2525 2525 2525 2525 2525 2525 2525
01
p-< -1-
(X (U
S Q.
CO ^
CO H
s
cO <0
CD *O
,J 0
•U> U
r^» -^ r™ r^» *^ ^— F*-*» .^» v— r1*- ch ^— • r^ <^ T—
OOCMOOCSlOOC^oOCMOOCNlOOCSOOCN
t— 00^— QOT— OO^-GO'— OO'— GOT— OO
CO
CO
4J
c
CO 0)
4-1 C
2 co
r-l 4J
-< c
O cO
p 1 ^ i
3
r-<
r-<
o
(U
rj
4J C
X3 *H
(X CO
CO rH
C 0
0) r-l
0 0
CO CO
cu
r-l
•r-l
>J
4J
•T-4
c
o
r-l
K^
V-i
o
cO
H
(3 T3
0) -r-l
N N
C C
cu co
^ ^
CO
TD
•r™l
i-i
o
r-l
f-«
U
CO
4J
CO
4J
c
o
(J
cct
o
a>
C
N
c
CO
o
o
J3
O
o
H
-------
/— X
T>
0)
13
C
4-)
C
O
f-J
r*.
,-.
i
^^
cu
I-I
43
CO
H
^j
H
O
2
i— i
0-1
^*|
^J
CO
CO
<
H
CO
o
o
t— 1
w
OS
p-(
J>4
a!
o
o
o
w
CO
S
H
2
O
gj
O
H W
3 1
cfl
C5
O O O C5 Q O
22 22 2 •
O
V
CN
>-
o
Q Q Q
222
>•
cd
o
Q Q Q Q Q
22 22 2
cu
o
J-l
0
CO
QQ O Q a Q
22 22 22
CU
i— i +•-
Q, 0)
SA
d-
CO 5>>i
CO H
e
co cu
-------
^*
H
j ro H
c h-< J3C
O e-i < (S
OS Cd
<: z
Q M
O W
U OS
w
co
r-H
(X
s
CO
C
0
4J
CO
C
0)
O
O
u
(U
r-l
a
(0
to
g
cO
0)
4-1
CO
cn
co
a
a
"~
Q
rf* T** r**"' >d" T* *
OOCMOOCMOOCMOOCMCOCM
T-OO«— oo *— oo*~ aOi— QO
oj i.
C 0)
CO VJ x!
•^^ X! Vi CO 4J
T3 4J 0) J3 Q)
<1> Q) XI *J
0O 4J 0) rH
C VJ CU /-v ' >,
•HO ^-s r-l C
JJ r-l r-l >, ^|
C XI >> x! >
O 0 X! 4J
O «0 4J CU rH
^ rJ 0) CO O >«,
% G B K X!
CO O X! O
CO CM CU i— 1 o 5-i
4-> • O XI 1 O
P CM V4 O CM r-<
rj 0 v-x N^ J-
i— 1 »— rH CO CO O
O » XI n-t -H I
0-1 i— O Xt Xl CM
O
•H • • • • •
X in vo r~» oo CJN
Or- r- r- r- r-
H
Q Q
z z
Q
Z
Q Q
Z Z
Q Q
Z Z
p** •+
OO CM
r- 00
CO
B
CO
rH
cO
X!
XI
8-
c
o
i-l
o
rH
X!
0
1
CM
•
O
CM
Q Q
Z Z
Q
Z
QO
^>
Q Q
Z Z
r**. ^
OO CM
r- CO
rH
o
c
-------
on
QrJ
O OS
a H
•-i a
01
e
CM
CO
OQ
aa
Q
a
CM
oo
a •
o
CM
O
Q Q
a a
a
Q Q
a a
Q Q
a a
Q Q
a a
O
a
a
a
Q P
a a
CM
Q Q
a a
Q Q
aa
a a
a a
a a
Q Q
a a
QQ
aa
m
00
a •
o
Q Q
a a
Q Q
a a
Q a
a a
a a
a a
Q Q
a a
CO
4J
C
o
CO
H
•< Od
OS W
Q M
a fa
o w
o os
w
CO
cu
e a
CO EH
B
CO
r— CM »~ t—r— '— r— CM »~ t— CM»~
CM *— "~ CM
»- CM
00 CM
*- 00
OO CM 00
T- CO «-
CM
oo
00 CM
T- 00
OO CM
t- oo
OO CM
i- oo
CX3
CM
oo
0
C co
4J
C
CO
•M
rj
r-4
rH
0
o a>
O r(
*-s (J
1
CO
4J
B
CO
u
**
r-l
r-l
O
O-i
0
•r-4
X
o
H
Q
1
o
)_l
o
_J
^^
X!
O
1
a
•
CM
CM
e
S-i
o
o
H
o
ro
CM
O
C
o
o
X!
CJ
•f-l
-a
i
ro
CO
oo
CM
109
-------
Q)
C
•H
4-1
C
o
QJ
ZH
3 ^
CM O
OT O
W H W
H r-JlS
wow
at
a
4-1
c
0)
o
o
u
CO
CN
>
Q Q
Z 55
Q Q
ZZ
Q Q
Z 25
Q Q
Z 23
OQ
Q Q
z a
Q Q
a 2:
Q
25
a
z
Q
Z
a
z
Q Q
ZZ
a a
z z
Q Q
Z Z
O
Z
Q Q
Z Z
Q Q
Z Z
Q O
Z Z
Q Q
z z
QQ
zz
Q Q
z z
Q Q
z z
QQ
zz
Q Q
Z Z
Q a
z z
CM
43
CO
H
0
w
£ «
o$ w
^z
Q M
S3 Pt<
o w
O Oi!
(C CU
<$• r—
CM OO CM
OO »— ' 00
00
CM
CO
(U
c
(U
CO
O
CM
a
o
w
ex
o
O
•r-l
T3
I
CO
CO
CO
o
c
0)
X!
a
•U
0)
B
•!-4
T3
I
CM
CO
(U
g
O
5-1
•U
TJ
I
CM
CO
no
-------
^
3
C
4J
G
O
O
^j
H
Q rJ
O
0 PC!
23 H
M 23
rJ O
CJ
C
O
0
CO
>
cO
><
ctj
a
T—
>,
otf
a
o>
CJ
M
3
0
CO
0)
r-l -1-
cx w
an w
< 23
O r-l
23 fe
O W
O OS
W
CO
0)
VJ O
•PC?
00
o a
23 23
O O
25125
o a
S3 2
o a
53 23
a a
23 2
a a
23 23
a a
55 23
a
23
a
23
a
23
Q
23
a
23
Q
23
a
23
a a
23 23
a a
23 S3
0 O
23 23
a a
2323
a o
23 23
o a
23 23
a a
23 23
a o
23 23
o a
2323
o a
23 23
a a
23 23
a o
2323
a a
23 23
a a
23 23
t- CM r- i- CN
T- ,— *— T-CN<— t— CM •— «— CM *- •— CM •—
00
CO
oo
01
3
C 0)
•H £3
4J OI
C 3
4J
C
CO
4J
3
r_|
O
CL,
O r-l
0 0
^^ 4J
o
CO
4-1
C
cO
4J
*
r-l
O
(Xi
o
•r4
X
O
H
S-i
4-1
•H
C
•r-l
T3
vO
•k
CM
*
vO
CO
N
CB
VJ
TJ
C
(1)
13
I
CM
en
C
ai
N
C
0)
4-1
(U
OO
CO
a
C
-------
QrJ
O §
Z H
*-i S5
a
CO
C
O
1-1
4J
C
CU
u
c
O
O
cd
a Q
z a
Q O
z •
o
V
O Q
ZZ
Z 2
Q Q
5553
00
5555
Q
Z
Q Q
z 25
O
NX
O Q
• 2
O
V
Q
z
Q Q
z z
Q
Z
Q Q
Z Z
a
z
Q
Z
O O
• z
o
V
Q Q
Z Z
Q a
z z
o o
zz
Q O
z •
o
Q Q
ZZ
Q Q
ZZ
Q Q
z z
00
zz
00
zz
CU
3
C
•H
4-1
C
O
o
CO O
r-l »5
CO H W
vJ OH
CO
O W
DnH
co
PS <5
0)
cO
H
0< «
II
Z fe
O W
U QJ
CO
cu
r-t -t-
(X .
co H
cO
CD
»-i
•U
CO
o
a.
t— CM •—
00
CM 00
00 »-
T3
CU
C
O
CO
C
CO
O
a,
cu
c
co
cu
^
X
o
4J
O
o
tH
O
I
CM
CO
CU
a
o
i-l
o
o
r-l
X!
o
•r-l
X
o
H
CO
OO
0.
112
-------
^
—?
o
23 H
M 23
.J O
PH O
< 23
CO O
M OS
CO H W
iJ O E"1
-"
^ OS
OS M
cO
M
4J
C
CD
0
C
0
C^J
CO
CM
>
a
>
cO
a
cu
o
)U
d
o
CO
CU
i— 1 -r-
CX CU
a &
CO H
B
CO OJ
CU "O
Vi O
4J CJ
CO
4J
C
CO
O
OH
QQ
Q Q
23 a
Q Q
2 23
25 23
Q a
23 23
Q Q
23 a
a a
23 23
Q Q
2! 23
O
V
Q Q
2323
Q
23
a a
23 23
a
23
O Q
• 23
O
V
Q
23
Q
23
o a
2323
a a
23 23
QQ
2523
23
O
V
a a
23 23
Q Q
2323
Q O
23 33
Q Q
23 23
Q Q
23 S3
<— CM «— «— CM «— i— CM »—
p«- .3- T- r^
oo CM oo
i- 00 »-
CM
00
OO CM OO
t- OO r-
CM
oo
00 CM 00
t- OO i-
CN
00
OO CM
r- 00
-a
CU
cO
e
o
4-1
.
o
o
0}
X
-------
s
cfl
c
cu
o
c
o
u
CM
CO
cO
00
a •
O
V
Q Q
a a
o a
a a
Q Q
a a
Q Q
a a
a a
o
V
O Q
• a
o
V
Q
a
a
a
Q
a
a
a
o o
a a
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
a a
QQ
a a
Q Q
a a
Q Q
a a
QQ
a a
Q Q
aa
Q Q
a a
Q Q
a a
3
C
4J
C
O
CJ
0)
r-l -I-
OuOl
e a.
05 >^
W H
CM <- *- CM T-
CM
*- CM «— '-CM'— i— CM *— *— CM «—
— OO t— OO <—
CM 00
00 i-
CM
00
3
C
4J
, C
4J
C
cO
4J
rj
r-l
r-l
0
O-i
o
CJ rH
>_x O
C
CO
4J
c
cO
4J
0)
JC«
O-
O
V
o
0
o
H
CM
O
C
(U
J3
a
o
•r-l
c
I
oo
o
c
0)
X!
O.
O
I
st
•,
CM
m
O
CO
cu
V4
o
I
o
I
o
V4
4J
0)
C
•H
e
cO
4J
0)
e
•H
T3
O
CO
O
c
I
a
v£>
cu
c
•r-l
e
CO
C
(U
J3
d.
•H
TD
O
CO
O
i-i
4-)
•H
C
I
a
CM
B
cO
r-l
Ss
cx
o
J-l
Ou
I
C
I
•1-1
T3
O
CO
O
•H
C
I
a
en
114
-------
OC
0
cd
g
o
§
o
cs
cd
Q Q
Z Z
Q Q
Z Z
CO i—
o o
o o
V
QQ
ZZ
CM
o
OQ
• z
0
QQ
ZZ
Q 0
Z •
0
Q
Z
Q a
z z
o
V
OQ
• Z
o
V
o
\/
CO
I— p~
o o
• •
o o
V
Q O
Z Z
o
•
o
00
• •
00
vv
Q
z
a Q
z z
o
V
00
• •
o o
v v
QQ
ZZ
Q Q
Z Z
v£>
CM CM
O O
• •
o o
QQ
ZZ
Q O
Z •
O
V
QQ
ZZ
Q O
Z •
O
\/
,
en H
*— CM *- '—CM'— '—CM'— T— CM *- '-CM'— '-CM'— *— CM '—
0)
co a)
CUTD
M O
4J CJ
en
oo CM oo
»- CO «-
CM
00
oo CM oo
»- co «—
CM 00
00 i-
CM
00
00 CM 00
t- OO »-
CM
00
•o
C
4J 0
C C
4J
C
cd
4-1
j3
r- 1
r-l
0
CM
o ^x Q,
O
CO
4-)
C
cd
4->
d
rH
O
(X,
O
.^J
*^t
x:
o
H
W
o
r-l
X!
0
C
0)
a
^
*>o
0)
4-1
cd
r-i
cd
X!
0)
X!
m
X!
4J
4-)
cd
i-i
cd
X!
4J
X!
N
C
(U
XI
cd
i—i
cd
x:
4-1
x;
a
C
I
00
VO
(U
4->
cd
t—I
cd
X!
4-1
X!
a
4-)
O
O
I
a>
r-l
cd
X!
4-*
X!
(X
X!
4-1
a>
115
-------
-- -I Hgp
r\* rfC-4
J O
OH U
< a
CO O
M as,
co H w
O w
CX.H
CO
(X
s
CO
to
4J
C
cu
o
C
CO
CM
cx
r-H
O
PH
O
i-l
O
H
Ou
r-l
S"-i
X5
0)
e
•H
TD
t
j^
CU
C
CU
o
CO
C
CO
^-\
cO
v_x
o
N
C
cu
XI
CM
CU
C
-------
O OS
a H
*"T* S3
J o
B
cC
01
o
§
o
a a
a a
O Q
2: 2
O Q
25 a
ass
O Q
a a
o o
a a
QQ
aa
Q
a
Q
a
Q
a
a
a
a
a
a
Q Q
a a
Q Q
a a
OQ
aa
Q O
a a
Q Q
a a
Q Q
aa
Q Q
a a
QQ
aa
Q Q
a a
a a
a Q
a a
a a
a a
a a
O Q
aa
C
o
< a
wo
c/> H W
iJ C3 H
O W
0>
r-< -I-
Ok 0)
8 a
co >
WH
i— — T- CM »- '-CM'— <— CM i—
0)
CO
H
O -\
3 cO
C v««x
4-J
C
4J
C
CO
,-j
r-l
r-l
O
cx,
O
O
CO
4J
j3
cO
4J
r-l
r-l
O
Ot
CJ
*X
0
H
0)
C
0)
o
2
4J
C
CO
00
r~>
0)
C
0)
0)
(X
/-v
•r-l
x:
oo
^s
O
N
d
0)
JD
01
(=
0)
w
o
3
r-l
<•*-!
O
00
0)
C
•u
C
CO
C
01
JC
CL
OO
O)
C
Ol
o
CO
J-l
C
CO
x—\
X!
CO*
O
N
0>
CM
00
0)
C
o>
CJ
I
CO
CM
O
C
0)
00
01
C
01
a
OO
117
-------
^J
H
^r
Q »J
O
O OS
a H
•-» a
J O
CO
b
4J
C
-
Q Q
aa
QO
a •
o
v
QQ
aa
Q Q
a a
CM O
COO
• •
00
V
Q
a
Q Q
a a
o
V
o o
• m
o o
V V
a
a
Q
a
Q Q
a a
Q Q
a a
CM
*
CO
00
CO
o
o
•
o
V
CO
o
m
C
0)
O
4J
VO
GO
(U
C
0)
r-l
4J
0)
O
VJ
o
CM 00 CM O OO
00 »- 00 CM r-
(U
g
4J
(U
O
O
O
r-l
•S c
O
H e
CM
OO
OOO CM
CSC- 00
oo
c
•H
>
00
00
4-1
s
C
-------
^
T3
J E3 EH
-j .
CO
Q
o
r- O
00
• •
0 0
NX V
CM
CM
>-
a
o
T- O
0 O
• •
0 0
\S V
T—
>
a
T— 1—
r- 00
O O 0
o o o
V V
CM
(1)
CJ
M
2
0
CO
0
*- T-O
000
ooo
V V V
-
CO H
CM r-CM T-
8
CO n r— o m *— r—
ooo ooo
ooo ooo
V V V \/
CM T— CM i— CM *~ -CM
O 00 CM O 00
CM r~ 00 CM *-
CM 00
O CTi
• •
O O
\/
o
t— 00
• •
0 0
o
p** CO CTs
CO ON CM
O 0 O
CM
m CM m
ooo
OO 0
V
t— T— r— r—
OOO CM
CM'— OO
CO
0)
G
CO
O
PH
c
o
o
CO
•u
C
CO
o
•H
M
O
H
I
(U
e
T3
CO
O
OO
CO
4J
O
4J
I
•r-l
I
U
X!
O
CO
4J
O
o
a
o
CM
CN
119
-------
—
CM
00
O 00
CM T—
CM
00
4J
c
JJ
a
o
0
a*
CO
JJ
C
«
4J
3
r-t
r-1
O
PL,
O
•^
X
c
Q)
CM
CM
>>
V4
V4
(U
6
00
CM
OJ
^<5
O
•r-l
C
•
-------
<
H
^
ii
M 55
-40
<^v Hi CJ
•^ s
2! < a
3 CO 0
C wo!
•••« CO H W
*J r-l 3H
S 3^3
O H r-33
0 M OW
^
*•-.
0,
E
CO
C
O
,_j
4J
CO
^
w
C
OJ
o
c
o
o
00 CM >*
oo
b ° o
CO • •
Q O 0
\/\s
Nl >*•
1 ^^
0
H o
«] BQ .
3| 0
\/
O CM
>• o oo
u PQ • .
3 O O
V
» CM-
J T- OO
i ooo
1 • . .
> 000
3 V VV
01
r-l 4-
cx a
e c
CO >
CO EH
L CM ^ CM T-
ON
ON CO
vo O
vO
m CM
• 9
CM O
ON
oo m co
* • •
'— O CM
0
O r-
«— m o
• • •
O CM O
V
CM <— CM •—
in T—
O O
• •
*- O O O o
V 0 CO \/ v
o «n
CO
ON
m
r- f^ o o vo
V ^- vo ^_
CO V
1 s i 2 -* -
°^ CM V
m -
>
>* on
as w
< a
O rH
Zr_
m
O W
0 OJ
CO
4J
C
CO
4J
3
r-l
rH
O
0,
•a
0)
3
C
,_j
•f^
4J
C
o
o
\-s
CO
•u
C
CO
•u
3
r-l
r-l
O
A4
O
•r-l
X
O
H
1
•H
i— 1
« g
« 'I
• .
Is* OO
CM ^
CO
4J
0
C(
•^
r-
r~
r™
O
Oi
cc
c
o
Nonconventi
c
(U
00
o
V-i
$ e 3
£> c 3 co
% 3 £ -1
•a co 'e o
« 3 ,3 §
« co « §
121
-------
<
LJ
s.
CJJ§
ZH
M a
JO
X-N Ot O
-o S
0) <3 Z
3 CO O
c M »s
•.-i CO H W
1 I T r-i r '
4J (— 1 nJ C"1
c M 3
0 H<
H
H S" PS
PS W
jf{ taM
<; 25
O M
Zr_
l*<
O W
0 OS
W
CO
x-x
r-t
*~»
W
e
'*-'
CO
C
C
•r-
4J
CO
V4
4J
C
~
cO
O
CM
>•
rt
Q
,—
>•
OS
a
>
1 H
3
S (1)
1) T3
^ O
J CJ
0
4.
1
C
4
i
f"
r
P
CM 0% ^ 0
_*_ ^~> C ^1 ^^
5 § « « ^.^
« 5 52 § § v - V0°
r- CM
vO
vo in CM
• • •
u-, o oino o "^ *~ voo
0 2 5^-o o v
v v oo
•» *
vO O
00 Ch
a\ f>cM
• • •
^sssssv-"0"
V 00 O
r-* ON
9£ ^° in o oo in^-ON
So °§ r^ Si 3~ OCOCM
r^r^ rt« l-!r-CO in <1-CM 00 0— 000
5° 53 P;^J- v -"-« w v
CM,- CM'- CM^CM CM r- CM i- CM- CM- CM r- CM r-
§5 §2 g«* §» S2 82 §2 SS^S
CM r— CM *^ ^^ ^^
x-x
T3
0)
3
C
>H
iJ
C
o
8 ~
^ 0
2 §
C
2 •«
3 g
J ^ 1
•* _J *-*
3 o «
j eu ^
3 e
-1 "-1 §
s s «
14 O g»
to
: JQ
boron
calciut
chetnicf
chlori'
cobalt
122
-------
^4
H
^j
Q t ^
Or/,
k*4
t— 1 J2!
•-J O
/-* OH CJ
13 S
oi co 0£ *3j
"- CD r-l 3
i O <
> 1-1 cs
CJ F^ ^fl3
d> W W OS
r-1 OS 5
cO !x
H fx OS
OS W
< 2!
Q M
IS &•*
O W
O OS
w
CO
x^
rH
•^v.
at
B
CO
C
O
•H
4-1
CO
}_l
4-1
C
01
o
c
o
U
01
r— 1
a
B
CO
B
CO
0)
4-1
CO
r
F
(
CO
>
cO
a
CM
;>.
cO
a
t—
^
cO
Q
0)
0
J^
O
CO
•*-
o*
a
H
01
•o
o
CJ
4J
c
CO
4J
3
H
-t
O
^
CM »-
vO O O CM
CO T— O O O T—
• • • • • •
•J" CO O O O -^ & O Q
\S \S V O vO \/
O CM
CM
r-- r~-
vo
• vo r—
oo m
«- T- O 0 ^- cy><|- r~«co oo
w w ^ m ir>r- vv
CM »— CM CM t— CM^— »— r— CM'— CM T— CM »— CM T—
»— fs» ^" T~ r~» ^— h«- ^— r^ >— 1"~- i— r^
O CO O 00 OOO CM O 00 O CO OOO O OO
CM r- CM r- CM<— 00 CM'— CM T- CM^— CM r-
^
TJ
0)
g
C
4-1
c
o
U
CO
4-1
g
CO
4-1
i-l
i— 1
0
J^l
r-l
CO
£J
O
4J g
C 0 a> 3 to o>
Oi 3 co c f 4J
> ••-' 0) 0» -H CO 01
CCO CTJr-l,£-g.u
OCU C04DOCX3CO
CJC OOJ^C CO -H 14-1
COO Cr-fCU OTJ^C
OcO cOOJ-^dO3-H
20 SBa,DuCOCQ4-l
123
-------
T3
cu
u
C
o
u
!•*-
I
CO
£
oos
!SH
MZ;
JO
eu u
i
COf
cO 0)
OJT3
VJ O
4J CO
CO
o
o
•
o
V
o
oo
o
o
o
CM
o
o
•
o
V
CM
O
O
•
o
V
V V
m
V
a\
CM
in
in m
oo
oo
• •
00
w
o
CM
CO
O
o
o
o"
CO
o
o
o
o o
00 T-
00 ^t
m
v
m
CO
m o
oo
» •
00
V V
m
CM
m o
o o
• •
00
V V
^— V
m
oo ^ r^
\/ oo
OS
'OS
o oo
CM T-
O 00
CM r-
O 00
CM T-
O 00
CM *-
O 00
CM T-
O 00
CM T-
CM
OO
25 fyi
O W
O OS
w
co
C
o
CO
C
CO
4J
3
•U
C
CO
4J
r-l
O
CM
r-l
r-H
O
(X,
cO
C
o
1
-*— i
4J
-------
T3
CU
3
C
40
C
O
O
cu
cO
H
01
B
to
C
O
•H
40
cO
C
(U
O
C
o
CO
CO
OJ
cO
cO
CU
r-l -I-
ex cu
s a
co >,
co H
CO CU
cu-o
V-i O
40 o
to
40
c
CO
40
3
O
04
O'-
er! CN
ari
CN o
o -* ao i—
O\ t- r-
oo
vO CTi
O O <— O
O CJH T—
in on co
O aoO
CM T-
CM r- CN
O CO
CN T~
O 00
CN r-
cu
3
C
•H
40
C
O
CO
CO
40
S
40
3
cO
(S
O
•I-I
40
C
CU
c
o
CO
CO
CO
H
CO
"O
o
CO
cu
TD
c
cu
CO
3
co
cO
40
O
40
CO
40
•r-l
§
cO
TJ
C
CO
40
CO
33
ex
intermittent process operation
no
c
•r-l
rW
3
T3
CU
4J
•H
rO CO
cO O
V-i d<
MS
O
CU O
B
•r-l r-l
40 CO
I 3
cu C
OS
i i
•— CN
CU
•o
o
cu
ex
>-,
H
cu
r-l
ex
B
•
v<
0)
ej
40
00
O
4-1
•o
CU
4_)
(-1
o
ex
cu
ttJ
.
cu
o
c
cu
(4
cu
<4-<
iJ
cu
4J
c
•r-l
o
40
cu
3
cu
co
•H
cO
V-i
40
1
*^^
B
r-l
c
o
•H
40
0
CU
40
0)
O
cu
o
c
cu
ID
CU
<4-l
CU
40
C
f^J
•^H
r-l
CO
O
•H
B
0)
r;
CJ
CO
CO
125
-------
QZ
o2
25 H
oc
a
en
cd
cd
in
o
o m o
CM i- *-
• • •
o o o
V
0
o
CM
O
•
o
N/
CM
O
O
o o
0
V
vO
CM
m
•
o
V
O
•
O
CO
o
o
o
V
o
0
o
V
o
»"-
0
o
\s
o
m
o
o
V
0
in
o
o
V
0
m
o
o
V
m
o
o
o
o
V
CM
0
0
o
o
o
CM
O
V
<
0
^_
o
V
o
o
o
V
o
0
o
V
o
o
00
I
0>
cd
H
< M
CO fa
05
CO QW
OH
M CO
O H,
rJ F1
O CM -
01
,-( •»-
(X 0»
e a
ctf !x
CO H
CO •>
o cd c
CX, U O
3 B
r-l —1
r-l 4J
O C
O
•T-l •
x
o
•
T—
CM
-o
cd
o>
i— i
•
CM
CM
^
Jj
rj
O
Vj
0)
e
•
CO
CM
i-l
01
^
O
•H
C
•
-^>
CM
e
3
•r-l
C
0)
r-l
-------
*o
01
4J
QZ
o2
a H
rUF
CO CH
CO Q W
O H 13
O W 125 W
•^ S OH
M CO
OO CO H •<
I O H
< fXi
Q J
S3 O
00
Ed
CO
e
CO
CO
Q
C
O
O
c
o
!S
o
m
00
o
'—
o
m
m
o
V
o
V
o
3
0
o
o
o
O i—
0
o
m
vO ^5
0 0
o
o
o
CO
o
CO r-
o
CM
o
m o
O r-
t- 00
O
V
o
V
CO V
o
in
o
•
o
V
00
CM
O
m
o
•
o
V
o
m
•
00
o
in
o
*
o
V
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CN
CO
CO
CM
acidity
alka
B
3
C
'i-f
s
3
r-l
CO
itrogen
c
CO
•r-l
C
ammo
B
S
•r-l
JJ
CO
43
q
o
J-l
o
x>
e
=J
•f-l
o
r-l
CO
0
oxygen demand (COD
r-l
CO
CJ
•H
B
01
rC
O
01
T3
•H
M
O
r-l
rC
O
4-J
r-l
CO
43
O
0
cu
73
•r-<
M
O
3
i— i
(4-1
iron
a
2
•r-l
CO
O>
C
00
CO
B
QJ
CO
(U
C
CO
00
C
cO
S
127
-------
&
cd
Q
M
Si*
CA
C
O
U
cd
C
0)
o
o
co
rt
o
CO
CM
O
O
O
O
CO
O
NX
O
V
o o
CO
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
OJ
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
CO
CO
CM
cd
4->
o
&*
4J
C
o
CO
CO
4J
C
r-l
r-l
O
CM
C
O
4->
§
^
G
O
O
c
O
z;
a
C W
(U cd
*O £t 8
-O CX 3
>» CO -H
-H O T3
O -C O
saw
0>
cd
M-l
cd
4J
o
o
H,
c
o
cd
0
0
•rl
c
cd
00
^
o
r-l
cd
4-J
o
CO
E-^
CO
•r-l
r— 1
o
CO
r-l
cd
4J
o
4-)
CO
C
cd
3
r-l
r-l
O
P-J
r-l
cd
C
o
S •"•'
3 S 4J
. i r5 *-<
•r-l ? K
T3 -r-l 0)
Cd V4 >
C W C
cd -u O
^ >% o
0>
CO
cd
0)
J-J
00
•o
rt
cd
r-l
•T-l
o
128
-------
T5
01
3
C
4J
C
O
U
00
r-*
1
£>
CO
a
>
ctf
Q
01
0
rj
O
CO
01
r-l -1-
p, n
0 a
CO r*"
CO H
0
CO (U
CU 'O
rl O
4-> U
CO
X™N
-a
(U
^
c
4J
C
o
0
^
CO
4-1
C
4J
C
CO
*J
r-4
r-l
O
PH
cO
4J
3
r-l
I
rH
0
r-l
CO
C
o
•H
4-1
C
0)
^
c
o
CJ
O
vO
•
*-
O
**o
T—
CO
CO
CM
x— \
CO
CO
|H
CO
*o
•r-l
rH
O
CO
T3
0)
T3
C
0)
a
CO
rj
CO
rH
cO
jj
0
4-)
CO
•
as
in
r-.
r-
co
CO
CN
s-*i
CO
4-1
•^
C
t3
p
CO
^
G
cO
4-1
CO
PC
f^
^3
cO
00
O)
s
•iH
^
01
c§
1
*~
a!
*X3
o
CJ
r-l
CX
E
«
CO
•*—
(U
CJ
c
(U
14-1
rl
4-1
C
•«J
•f^
o
4-)
a>
T3
TD
CO
•rl
CO
*"*
4-)
•«J
•^
B
•H
r-l
C
O
•rl
4-1
CJ
0>
4_)
0)
Q
1
-------
0
OC
s
CO
{*
Q
<
CO
ooo
o>"> <<•> 00
CM CM CM
OOO
*,
O
CM
130
-------
cd
H
S
e
CM
00
CM
o
o
o
•
o
V
o
on
o
V
o oo
CM CM CM
OOO
000
OOO CM CM CM
,-»-,- OOO
r-,- T- 000
OOO r-r-r-
o oo
V V\X
ooo
ooo
V V V
ooo
V V V
ooo
ooo
W V
000
0)
C
•r-l
4J
C
O
o
;o«
ai
r-l -t-
a. i)
e a
cd
co
OS
a)
co
-------
H Z
^2
0^3
*z> &
rH £-4
CM CM CM
OOO
OOO
OOO
m m m
ooo i- T-
OOO
V \/V
000
oo
T3
0)
4J
£
O
O
CO Q
CO
0)
cO
H
\&
!w
H
H 03=
W M W
§ HH
w H^
O PL,
os
S§
< M
Q Q
>
CO H
CO 0)
CO
o oo
on on**"*
CS CM CN
ooo
co on en
CM CM CM
ooo
en en co
CM CM CM
OOO
en en co
CM CM CM
OOO
co en en
CM CM CM
000
CO CO CO
CM CM CM
O OO
en coco
CM CM CM
W <3
co Ot
4-1
c
cO
4J
o
PH
CO
4J
CO
4-J
eO
C
O
•H
4J
C
0)
c
o
o
c
o
o
cO
4-)
•H
C
•1-1
I—)
cO
CO
s
3
•r-l
B
cO
C
-------
/— s
T3
0)
d
c
4J
C
0
o
cr>
t_u
1
B cd
--'Q
CO
C
o
•H i—
^j
Cd r^l
h cd
4J Q
C
O
C
o a>
0 0
d
o
CO
0)
r-< •*-
Cu •
co H
B
cd * o
OO r-
m mm
X
0
r-l CU
cd 'O
CJ -H
•rl VJ
B O
C1J r-l
-C JZ
o o
OO -3" OO OO
O O O O r— T^ CTt *-^
CN <*>
00
m CN oo
• • •
0 O -* -l Cd
o y-i -H B
133
-------
CO
2*
< 0
Q 1-4
H
0
C*4
hJ J
^N DM i-)
T3 S fa
cu <;
3 CO Q
C Z Oi
••-4 en < w
4J tJ H
C M l-l S
cj u" S
05 S
<
0 ,J
CJ i-J
w <
CO Pk
rH
M
S
"^
CO
C
O
•H
4J
to
)-l
4J
C
fll
W
O
c
o
CJ
a
r—
e
€
. a
c/
£
c
<
»
4
0
id]
Q|
CM
>
CO
a
.-
>
CO
Q
•
J H
3
6 cu
U 13
-i O
J CJ
0
4.
c
c
4.
1
r"
r"
<
P
coco r-vo r- ->* vo
oo oo T- r- mo oo oo in
VX/ CM VO O O r-
T- O P--
O CM
0
CM
. — . ^.
^— vo ^T
O O -d"
ooo ooo
mmmminin ooo inmin
ooo ooo ooo ooo
OOO OOO ^->3->d- cyi cTi cy> p- r-. r»- ooo
vw vw .— ,— »- m in in \/ w
ooo ooo ooo ooo ooo ooo
COCOCO COCOCO CO CO CO COCOCO CO CO CO COCO^
CMcMCM CVlCMCM CMcMCM CMcMCM CMcMCM CMcMCN
/~\
"O
cu
^
C'
•H
^1
(3
Q
U
*~^
CO
4J
tO
4-1
3
J rH
31
i— H
d/»
O
JA
P-t
-1 <-l
M CO
3 C
M O
•f-4
4J B
f- CU 3 CO
/I I rn f™* -t _1
U) CO W 4-J
> gj (U cti 1)
C C T3 XS | *J
O co A 0j 3 to
O W) >. CO •-» 4-4
C C i-< O T3 r-l C
0 to OX! 0 3 "-"
2 B S P- to w w
134
-------
-o
*l
cO
Q
*
o
in
,
r—
^»
CO
Q
o
V
O O
CO
O
3
O
CO
H)
-1 ,^_
^•n ^^
a a>
CO H
S
cO (U
0) T3
V) O
4-1 O
CO
m m
o o
00
V \/
o o
CO CO
CN CN
s~\
T3
C
o
\^^
CO
4-1
C
cO
4-1
i-«
4-1
C
cO
rj
rH
rH
O
OH
r^
rH
0
a*
rH
cd
C
O
•iH
4-1
C
0 -H
S3 4-1
m m
135
-------
HZ
£2
O^
2 c2
oc
B
u
C
(U
U
c
o
o
c
o
u
0\
I
cu
CO
H
(Xi r-l
22 fe
CO Q
CO <| W
OS
r-1 W
HH
• s
O
U
W
CO
(U
CU
1?
CO H
e
CO V
CUT)
V O
•u u
CO
cO
W
o
O4
O oo
CO COCO
CM CNCN
O OO
CO COCO
CN
-------
o
CM
1
>
01
1— t
rQ
CO
EH
centrations (mg/1)
< z c
HO 0
•
Q
>
CO
O
01
o
M
3
o
CO
1-4 O
i-J OS
f^ | fy j
CO J rH-t-
co cow e a
iJ EH CO >•
,
Vj
(U
43
•
r~-.
T—
B
•r-l
E
*Q
CO
O
*
00
T—
cO
4J
0
4J
S-X
S
•iH
B
O
c*
O
•
cy\
^~
r<
(U
a
P,
0
o
•
o
CM
rH s~\
CO 0)
4-) 0)
O i-J
4J IW
Cl) Q)
*O T3
••H -rf
B B
cO CO
^ t*%
0 0
•
T—
CM
T)
CO
(U
r-l
»
CM
CM
r*%
)_|
rj
O
}j
ai
B
•
CO
CM
r— |
OJ
y
O
•H
fi
^
»5(-
CM
S S
•i-4 M •H
C rH O
r-l rH CO C
OJ -rH 43 .H
CO CO 4-1 N
• • • •
m vo r^ co
CM CM CM CM
137
-------
x-x
TJ
CU
3
C
•H
U
G
O
O
O
CM
1
<(J Jgj
H O
* iJ
as o
* OO
i- 00 «-
• • •
o o o
V
vO
o
00
•
0
o
o
o
o
0
V
CM
•
•tf
^j*
^^
O
•
o
• *
O i-
CO
0
•
0
CM
o
•
o
CO
CM
f""
•
O
V
CM
on CM
r^ o
o o
• «
o o
N/
CO
o
CO
o
co
O
CO
O
CO
O
co
o
CO
o
CO
o
r--
co
o
CO
o
CO
o
CO
o
CO
C
cO
4J
r4
4-1
C
CO
4-1
O
CM
f>
r-4
O
O4
C
o
1
4J
Ol
^
C
O
o
C
o
Z
a
d
c
•H
a
0
r-4
CO
a
3
c
o
a
cO
o
,£>
O
O
C
O
•r-4
a
.^
CO
a)
G
60
a
Ol
CO
Ol
C
cO
00
C
CO
a
c
-------
TJ
0)
3
C
C
O
o
o
CM
I
,n
co
H
< M
Q H
O
O 3
a Q
w O
•J 05
O-i Oi
Q
5 E-1
o z
o w
W CL,
CO CO
ad
e
(T)
CO
Q
CS
CO
CO
Oi
r-^ -t-
(X OI
B a
CO >-
CO H
CO (1)
Q> -X3
r-l O
•P CJ
CO
on
o
jo
CO
M
00
01
a
•H
4J
I
O>
C
O
4J
C
cO
•U
f-4
?
r-l
r-l
O
n.
h*4
c
a
4J
••
»-
"c
04
r^
CO
C
o
•H
JJ
c
0)
^
c
o
o
X-N
CO
•U
•H
C
3
*£3
rJ
CO
TJ
c
CO
4J
CO
W
a
TJ
O
0)
CU
01
r-l
a
E
CO
CO
139
-------
§
en
Q
(X
cd
C
0)
o
c
o
u
o
V
O i~
* •
o o
V
oo
o
o
V
o
\/
m
co o
• •
O T-
CM
T- O
• •
r- O
00
CM
r- CO
• •
O t-
CO
CM
O
o
o
•
o
V
CM
O
o
o
<
CO i-
• •
T- O
V
CM
O i-
CM
00
O CM
V r-
o
V
o
V
in
o
•
o
V
o
•
o
0
o
o
0
0
o
m
0
o
vn
0
o
m
o
o
m
o
0
o
'-
0
CM
O
0
o
o
o
CM
O
*-
O
o
o
o
o
0
»-
o
V
V
V V V
V
N/ \/
V
to
en
o5
03 O
O3
O
O
(A
W
QH
I 03
B &
cd >-
COH
ott 0)
cut)
M O
4JU
02
CO
CM
3
rH
rH
O
rV
>^
f3
O
B
•H
a
cO
X
o
H
O
B
•H
a
CO
^
r-
s
V
O •!
•t-l 1-
C <•
0) t
CO I
cO 4
m r
^ '•
j. y -L i j- uui
dmium
u co
3 O
•«• CO
romium (tota
-C
0
ON
a.
o-
Pu
o
o
o
CM
r-l
cO
o
~^^f
V
"c
cO
^1
o
•
CM
cO
(U
r-l
CM
CM
>-l rH
3 OJ
0 ^1
t-l U
rH 0
rH CO (3
•i-l J£ -i-l
CO -P N
^o ^^ oo
CM CM CM
140
-------
^
•o
3
e
•H
4->
G
O
O
T—
CM
1
^>
1i
^>
EH
^J
Q
O
Z
M
O.
5
CO
CO
(J
^j
EH
M
§
CO
!=>
O
^H|
o
w
CO
.
CO
a
T_
^
CO
Q
•! O*
P(5 W
O
Z
o
o
w
CO
4-1
c
cO
CO
4-)
c
CO
4-)
o
a,
cO
c
o
•iH
4J
c
0)
0
C
O
ON
CM
CM
m
o
*— o
V \£>
CO
O T-
00 V
o
m
o
V
m
m
o
CM
O
\/
CM
*
O
oo
o
o
-l
o
m
•
00
o
V
oo oo
CM CM
CM CM
00
CM
CM
S
CO
-------
S
CO
C
O
4-1
cd
C
d)
o
c
o
CJ
CM
ett
"O
CU
d
c
c
o
o
CM
I
CU
r-4
_Q
Cd
H
O
>J 33
CM cn
T- CO
v r»~
o
•
o
cn
o w
OH
£
a
w
acn
w<3
ao2
(U
O
cn
o
o
o
M
(T)
O
O
CM
CO
•
en
m
m
m
•
o
V
o
•
o
o
o
CM
o
CM
m
o
•
o
V
m
o
•
o
V
m
o
m
o
CM
O
m
o
o o
m m
o o
a.
04 W
25
O
u
CO
73
CU
3
C
4-1
C
o
o
m
o
v
o
V
o
00
en
o
m
o
•
o
V
o
m
*
o
V
00
cs
CM
00
CM
CS
00
CM
CM
00
CM
CM
oo
CM
CM
OO
CM
CM
oo
CM
CM
00
CM
CM
OO
CM
CM
00
CM
CM
00
CM
CM
CO
U
cd
4J
r-l
4J
C
cd
_ J
n^
r-l
0
0,
!->
r-4
O
CM
C
O
. J
•rt
4J
C
CU
C
0
a
c
o
z;
q
T3
J3
>>
O
s
(U
a.
CO
o
ex
B
o
CO
4-)
14-1
CO
C
•r4
4-1
S
•r-l
C
4J
•H
4J
O
O
H
C
O
V-i
O
O
'c
00
o
cd
o
cn
H
CO
TJ
•T-I
r-l
O
CO
cd
O
4->
73
cd
C
cd
•^
5-1
CO
4->
C
cd
4J
o
CM
cd
C
O
•r-l
4-)
G
CU
>
C
o
CO
t>o
S
142
-------
g
CO
CO
Ql
CM
*
CO
O O
00
•
O r-
CM
to
T3
01
4->
C
o
o
CM
I
0)
r-l
rQ
CO
H
CO O-W
rJ OH
< rJ• c/
oi w
a
o
o
w
01
rH +-
ex oi
s oj
co H
CO H
cO 0)
CO "O
rW O
4-» U
CO
00
CM
CM
T3
CO
3
C
•H
4J
C
o
CO
CO
H
CO
CM
CM
4-1
C
4J CO
C 4->
CO 3
4-1 r-l
3 r—
v~ r^
r-l 0
r-4 Cl4
O
(X) r-l
CO
C
O
•H
4->
C
CO
>
c
0
o
CO
TJ
•r-l
i-l
O
CO
TJ
CO
T3
C
CO
CX
CO
3
CO
r-l
CO
4-1
O
4-)
/-%
CO
4J
•1"^
C
3
TJ
}-i
CO
T3
C
CO
4->
CO
•*~/
X
CX
CO
^
00
CO
0
•r-l
4->
I
co
c
o
CO
o
c
CO
r-l
CO
01
4J
c
•H
o
4J
CO
T3
01
CO
•H
CO
0)
U
C
01
r-l
0)
M-l
co
TJ
O
o
0)
Q,
ts
H
O>
rH
CX
e
e
•r-l
r-l
C
O
•r-l
4J
CJ
CO
4J
CO
O
01
4->
c
•r-l
r-l
CO
CJ
•r-f
B
CO
43
O
CO
PQ
143
-------
CM
CM
I
H
Q
O
Z
(-4
JH
£§
CO
co
fa
w
B
O
C
o
o
CO
CO
Q
cs
0)
CU
r-4 •«-
Qb Q)
B CM
CO H
Q
a
z
a
z
a
z
QQ
Z3
QQ
Z53
Q Q
Z53
Q Q
QQ
ZZ
QQ
ZZ
QQ
Z!2
Q Q
55 Z
Q Q
S3Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
QQ Q
ZZ Z
QQ Q
z z z
QQ Q
zz z
Q Q Q
zz z
Q Q Q
ZZ Z
QQ Q
zz z
QQ Q
zz z
.en
cu
r-l
,£>
CO
H
H
CO
§§
h-l h-l
0 H
w <:
Pi H
n . MP
•^^ 4-4
w
05 W
144
-------
H
Q
i
s
CO
C
O
4J
CO
5-i
at
a
a
Q a
a a
P
a
Q
a
QQ
aa
QQ
aa
Q
a
QQ
aa
Q
a
Q
a
Q
a
QQ
aa
Q Q
a a
QQ
aa
Q Q
a a
Q Q Q
a a a
Q Q
a a
QQ Q
aa a
Q Q
a a
Q Q
az
QQ Q
aa a
OQ Q
•a a
o
Q Q
a z;
QQ Q
aa a
Q Q
a a
Q Q Q
a a a
Q Q
a a
QQ Q
aa a
T3
I
CM
145
-------
H
Q
a
«
s
C
o
•H
4-1
CO
4J
C
01
O
en
«
Q
CM
Q
CO
Q
2
Q
a
Q
sz
Q
a
Q
a
Q
a
Q Q
5525
Q Q
£555
Q Q
55 55
00
as
00
ass
Q 0
a z
O
cs
o
o
en
00
O Q
53a
Q Q
a a
O Q
53
C
O
O
CS
CS
I
43
CO
H
w
CO
CO
coH
00
LJ ^»
O H
W <
s
a
o
o
w
JS
w
o
r-l 4-
& &
CO >-
e
CO CN
00 CM
T- 00
m
00
4-1
C
4J
jj
r-l
r-l
O
£•4
C
cO
•O 4-»
-------
(3
O
O
W
CO
fa
Ed
0)
S O.
cfl >
CO H
• CO r— T— <*">
CN
CN
I
CJ H
Ed <
*3
e
CO 0)
O» 73
M O
4J CJ
CO
m f"> CN in (
00 CN . 00
r- 00 r-
CN men CN
CN 00 CN OO CN
OO r- 00 r- OO
OO
CN
CN
OO
OO
CN
00
00
CN
CN
00
(A Ed
3°
g
o
Ed
CO
4J
C
CO
^ \
jj
r-l
r-l
O
PH
T3
O>
C
•rl r-l
4J O
(3 co
O 01
CJ rl
•^ CJ
1
CO
4J
fj
CO
4J
rH
r-l
O
fX(
CJ
•*J
*M
X
o
H
a
}
o
^1
o
r-l
CJ
1
a
CN
CN
e
o
rl
O
r-l
JC!
en
CN
a
o
u
o
1-1
-d
o
I
CN
CN
0)
C
a>
N
c
cu
43
CJ
•l-l
•o
I
CN
CN
cu
C
0)
N
c
cu
J*
o
i-l
o
I
en
vO
CN
0)
G
a>
43
O
M
O
r-l
43
O
•r-l
TJ
I
CN
cu
C
•H
"0
CU
43
O
43
O
•r-l
T3
I
cn
m.
cn
oo
CN
147
-------
PO
cO
Q
W
S
CO
C
O
4J
CO
l-l
C
C
o
o
CX OJ
s CM
CO !
.00
.00
CM
CM
I
CD
CO
H
s
CO 0)
CO "O
Vt O
4-> U
CO
IT| CO CM
00 CM
«— oo
OO
CM
CM
OO
LOCO CM
00 CM
V- OO
lO CO CM
00 CM
t- 00
00
CM
CM
00
LT|f> CM
00 CM
T- 00
OO
CM
00
-------
H
Q
i
CU
O
CJ
H
§
CO
W
co
C
cu
O
C
o
cj
CM
CO
0)
0)
r-l •
3 Q.
CO H
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
z
Q Q
ZZ
QQ
zz
QQ
Q Q
zz
Q Q
ZZ
Q Q
ZZ
Q Q
zz
Q Q
ZZ
Q Q
z z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q Q
zzz
QQ Q
ZZZ
QQ Q
Q Q Q
zzz
Q Q Q
zzz
QQ Q
zzz
QQ Q
zzz
T— CO t— ,_»—,_ ,_ CO i— ,—
• CO »— T— CO
CM
CM
I
CO CM
OOCM
^— 00
l/~» CO CM
OOCM
»— OO
4J
C
CO
4J
3
^
r-l
0
Pt-4
T3
cu
•S C
4-> CU
C S)
O r-l
O 0
N^r* IJ
O
CO
4-)
C
CO
4-1
rj
1-4
1
1^
O
CL,
0
•H
0
H
}_i
4J
•H
C
•H
-o
1
^
CM
.
CO
cu
C
•H
N
CO
C
(U
43
a,
I
CM
CO
cu
C
C
cO
cu
43
4J
CU
C
cu
43
a
(3
CU
a
cu
43
C
cu
43
a
o
s
o
CO
0)
43
4J
0)
O
J-l
Ou
O
CO
•1-1
O
J-i
O
i—l
43
CJ
I
CM
\~s
CO
•H
43
CM
149
-------
en
>•
CM
H
%
XJ
•u
CO
B
CO
B
o
B
O
-------
s
CO
CM
CO
Q
12!
a o
125 a
Q
z
Q
Z
a
z
Q
z
a a
QQ
zz
Q Q
zz
Q Q
3Z
Q Q
Z Z
Q Q
Z Z
o
c
0)
o.
6 CM
CO H
Q Q
Q Q
S55S
QQQ Q Q
Q Q
z z
QQ Q
zz z
a a
zz
QQ Q
zzz
Q Q
z z
QQQ
25Z Z
O Q
• Z
O
QQQ
ZZZ
Q Q
z z
QQQ
ZZZ
t— ,— ,— CO,— ,— OO ,— ,— COi— i~ OO T— i— CO i—
CM
CM
1
^
CD
r-l
,Q
cO
H
CO
3 Z
0 0
U H
Cd «J
OS H
Ed
>• S
OS W
U
CO
tn co CM
oo CM
r- 00
00
CN
oo
00
CN
00
m'
oo
1— 00 ' T-
moo CM
00 CM
00
in co CM
CO CM
t- oo
m'
oo
CM
CM
00
C
4-1
t-l
O
c
•i-4
4J
O
CO
4J
C
cO
0>
C
0
O
(4-4
•-I
o
to
o
o
c
cO
4J
e
o
s
o
•H
-o
o
o
•H
X
o
cO
4J
O
to
o
r-l
X!
O
CO
X
0)
X!
CM
C
0)
•r-l
TJ
CO
CX
O
r-l
O
o
o
w
o
o
CO
X
CO
0>
o
r-l
o
a
o
CO
m
0)
c
(V
r-l
CO
4J
X!
a
(0
c
m
m
-------
H
Q
O
Z
on
CO
Q
r-l CM
e
cO
Q
Q
Z
O
z
Q Q
ZZ
QQ
zz
Q Q
zz
QQ
zz
Q
z
Q Q
ZZ
Q
Z
QQ
ZZ
Q
Z
Q Q
ZZ
Q Q
ZZ
0
sfr
0 Q
A^
o
Q Q
ZZ
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
OQ
• Z
o
QQ Q
zzz
QQ Q
zz z
Q Q Q
zzz
QQ Q
ZZ Z
Q Q Q
zzz
QQ Q
ZZ Z
Q Q Q
zzz
-o
0)
§
•H
4-1
C
O
o
CM
CM
I
rvi
^j 1^4
Qi W
Q
Z
O
w
en
0)
iH +-
O. 0)
§ 5
cO >
e
CO — ,—<
i- CO
r_CO T- r- i
oo
cs
CO
T- CX> t-
CM
00
m co CN
GO CN
t- 00
m co CM
00 CM
r- 00
m co CN
OO CM
i— 00
IT) CO CS
00 01
t- 00
LO CO CM
00 CM
T- 00
0)
C
O
CO
4-J
c
(0
4-J
O
CM
O
rH
O
c
(U
J5
Cu
O
•T-l
C
I
CM
O
C
0)
si
Ou
O
c
O
C
e
•H
T3
O
CO
O
5-1
4J
•r)
C!
Z
CM
co
152
-------
^
*o
*
cd
Q
o
0 0 0 Q Q
• • • a a
000
V V
CN! T— o r>* O ,
CO H
_COr- r-f^r- r- CO r- r- CO T- T- CO r-
e
CO 0)
G
ccj
4->
M
r-l
i— <
O
x_s
T3
(U
c
•U O
o %
X
CD
|-4
r-4
^»
r*
4_)
(J)
r-l 1
O CM
(U CO
jd 1-1
Q^ ,£)
• •
in vo
vO vO
(U
ij
CTS
r- 1
cC
r;
4J
<-{
Ou
r- 1
N
0)
rO
r-l
^
4J
^
^
•
r>»
^-O
(U
4J
ctf
r-l
cd
j2
4J
^^
a.
r-l
fx,
4J
P
J3
I
C
1
•1-1
T)
•
00
V0
CD
•U
CfJ
r-l
ftf
£*
4J
,£j
CX,
rH
rN
4-)
O
O
1
0
1
•rl
T)
•
ON
-------
a
OC
e
0)
c
cu
o
c
o
o
CM
cd
n)
O
CO
QO
CM
00
ir»c«"> CM
00 CM
T- 00
00
CM
CM
00
00
CM
CM
CO
LO
00
CM
CM
OO
OO
CM
CM
00
OO
CM
CM
00
4->
§
4-1
•o
cu
c
o
o
CO
u
c
4J
3
cu
4J
etJ
a
4-1
CU
e
CD
C
cu
o
cd
l-i
C
CO
X-N
CO
v«/
o
N
C
cu
,0
0)
C
s
<4-l
^•\
&
\^
o
c
cu
cu
§
J3
4J
C
CO
1-4
O
£
o
e
>
14
J3
O
cu
a)
X!
4J
X
a
co
e
cu
o
o
H
CN
CO
r-
154
-------
oi
@
C
0*
o
c
o
o
ro
CM
ctf
(U
a
S3
Q
a
z
a
z
Q O
Z Z
QQ
ZZ
zz
aa
zz
zz
aa
zz
OQ
ZZ
a a
z z
a a a
z z z
a a
z z
aa a
zz z
a a
z z
aa a
zz z
a a
z z
a a a
zzz
a a
z z
aa a
zzz
a a
zz
aa a
zzz
a a
z z
aa a
zz z
c
o
o
CO
0)
r-l -I-
CX 0)
IP
CO H
i—CO
• CO »— T— CO
CM
CM
I
01
CO
H
S-s
J-i O
•u u
co
in co CM
OO CM
1- OO
m co CM
00 CM
i— OO
m co CM
00 CM
T- OO
m co CM
OO CM
t— OO
in co CM
00 CM
r~ OO
m co CM
00 CM
r- OO
in co CM
00 CM
»- 00
01
c ^
4-1
C
4J
(3
cO
rj
r-(
r-l
0
O
U
^^
CO
4J
C
cO
4-1
•4
rH
r-l
0
O
'5<
O
H
0)
c
0)
o
CO
X!
4->
fj
cO
00
r«»
a;
C
01
(X
•a
^/
o
N
C
0)
JO
cr>
C
-a
CO
OO
a>
C
01
(X
QO
155
-------
-N CX| Z
"0 S W
(J) MM
O H
o« z
«J Ed
H SH S
OS W
<; o
Q
»— |r»
*&4
o
o
w
w
CO ^_
> Q 0 0
5 Z o o
" V V
x-s
r-ICMl ^ ^
TtJ on QO QO
0 JS ZZ Z • B •
O< Ql O °
1 \/ ^
CO
c
0 ^,
Mr- ^.^ r-
es>] QQ °° °S
SJfl ZZ oo oz
*i Q| \/ v
c
CU
o
go,
°§ ggg §§§ g§§
o
CO
0)
r-l •»-
i- 2| r-^- ^-r-^
B a r-r-r- ^-r-r- 1- »- *-
crj >
CO E-i
*•
e
S -0 inrocN mcOcM ^°°^
iJ3 2 2 * -S 2 S
C/3
x-^
'O
(U
rJ q,
5 g
4J M g
r-i >>. CU
V % £ -*
cow >>
cr) ^-^ CU -C
*J ° m
— | r/* 1 . W
3 CQ H Z
M 4J 0 g
o § ^ g o
* ^ 8 1 |
r-l VI ^ 0
r-l 4J r-l -rl
0 CU 0 V4,
CM *J « U
«
X in ^> ^
o oo «> °o
H
O
-J-
Q CO CM
yz * •
z o -
o vo in
QO r- £?
%
r-l S
1%. .r-l
c n
ti ;i
M C
> cd
• •
00 y
C
O '
•
O C
oco in
i— O O
000
• • *
000
\x \y NX
CM ,— CO
co in co
O 00
CM t-
O
•r-l
g
CO
r-l
CO
•
m
rv
•
D
'—
CM
CM
00
156
-------
H
o
i
«
E
4J
C
O t-
\O »- CM
CO O CO
• • •
O O *--
V
v£>
oo
•
00
0-3-00
• • •
oo co m
CM
00
•
CM
Or- O
• • •
mi— in
CM«- .—
o
in
o
CM
CO
CM
O
•
o
V
o
o
•
o
V
o m o
O in i—
oo CM
o
CM CM O
000
• • «
OOO
VV V
CM
• •
— o
CM
O
o
o o
• •
T- O
CO V
0-d-
CM.—
CM
00
V
CM
o o
,-— o
OOO
OOO
V W
CM
O O
U"> r- O
0 OO
• * *
0 O 0
CO
o o
ire— o
00 O
• • •
OO O
O r^
m r- »-
000
» * *
000
V V
CM
m CM in
OOO
OOO
V
d
c
•1-1
4J
o
o
CO fa
hJ M
B
-------
/-N
T3
At
w
2
c
•rl
4J
c
o
o
x.^
CM
CM
1
>
< S
PS Cd
jf< P T
aiu
z
0
r ^
^/
td
CO
s^.
r-l
OJ
B
CO
C
C
4-
cO
V4
4-1
C
(U
c
o
o
^0
>.
0
CM
>
CO
Q
,
>>
cO
Q
0)
O
rl
3
O
CO
co H
B
CO U
CO
o
»
o
o
o
o
•
o
V
o
o
o
•
o
V
o
•
CM
CMCN T-
oo o
00 O
oo o
oo o
CTn— 00
CJN
• •
O CO
m
o\
oo
CM
•
CM
>tf CO
• •
r- O
CM CM
OCM O
OO O
OO O
• • •
OO O
o
o r^ cs
^•o o
• • •
oo o
r-l
0)
B
O
•r4
C
I
•H
C
CM
158
-------
CQ
° 1 1 1 - s -
?h CMO Si" ^
0 0
•1 o ^-
.8131 n~ "• o
x-s
"O
QJ
3
C
•H
4-)
C
O
0
^.x
CM
CM
1
l
cob*
H CO
4-) Q
C
.
fa r-l ^-
w fa a, oi
•Jw e a
< co >.
Hferf co H
H >z
»*£4 '*C
H
CO
= 2; 3
O O CO (U
MM cj
«H co
Pw 2
Ed
>• S
05 W
< 0
Q
O
O
W
CO
•U
c
CO
4J
3
r-4
r-l
O
Oi
°° ill §8 - |« §1
•^ ^« x^ i ** »i
1 0 3^™ °° 00
1— T—
c^m o
* • •
1 00 Or-
0 0
<>+. oh
^ ^0
CO
OCM r- O O °
*— o o o »— om^f—
OOO r-U~)O ^ ° OO
• • « • » . ••••
000 OCMO C Sj^"0 °° °°
WV \/ cncM'— \/ \/
CM^CO^- CM^CO_ ^_ ^^^ ^^ ^_^_
SS^^ ScS^S SS SS^ 2^ ^^^
CM- 00 CM_ S S* °,2 g« OOOCM
<^s
*O
3
5 ti
•in c
4J *
n ti
0 r2
u i
N-X ^
O
CO *
W r-l C
c a m S
co 3 g oo
a IJ o ?
^ ^ -H ^
si i i,i i ~:
I i 3 § *
'^ - « g 3 S B §
a^ * § o ^ .3 i
^^ - acoco « §
159
-------
<
H
a
z
1-1
x—\ Hi 35
-o S w
(U 1-1 i— i
0 H
-> S
0i M
< 0
P
Z
0
0
W
CO
CO
>. OOO
cd ...
Q in O OOO
v *- in CM o
V O
s~* O
i-i CM m
Ot S» O ,
V4 Cd
4J Q vO
C r-
0)
o
C
o -
CO t-l
S
cd coin coinco coin
Vi O OOO OOO OOO OOO
4JCJ CM*— CM*— CM<— CMr-
CO
X""X
cy
0
C
•H
4J
0
o
o
^ S"
en O
JJ 0
G V— "^
P C
4-> r-4 Cd
C r-l B
cd o O O B
C 1-1 »-( r-l <1)
O cd o cd f^
Z -Q ,O O O
T- O
. «
o m »— o o
O \/ vO O
O r— VO
t— CM
'-
o in o ^"" o
. . • . .
oo m >^ m co o m o
OO T— i— O> CM O
O O P^ oo ON
» «. •
OOvO i—
r*^ in
00
00
1— -^
•k Ik
CM in
o ^o o
ino oo in *— cr>
O O CM r- O CO CM
<^CM OO Or- OOO
r- in N/V \/
CM^- CM^- CM ,— CMr-cOr-
com com com comcocN
ooo ooo Ooo ooo CM
CMr- CM«— CM r- CM i— 00
0) (U
*O T3
•P-l 4J T-l
W r~4 Vl
O cd O C
T-I & 3 O
,fl O r-l VJ
O O <4-i -n
160
-------
CO
o
CM
vO r-
m
O IT)
• •
m o
O
CM
o
*
o
O
O
O
^O CM O OO -*
• • • • .
00 ON
r*-O
CM
O\T-
00
cy> o o
oo o
CMO
CM
CM
00
O O CM IT)
m r- mo T—
<- oo oo o
o
O
oo
O
10
O
oo
ft=
(X
o
CL,
CO
U
C
cd
4-)
cfl
C
O
•i-C
4J
C
(U
i
M
a
0)
CO
0)
C
cd
00
C
ctj
S
S
3
C
,
r-l
O
B
CO
o
•H
r-l
O
c
0)
x:
(X
(U
4J
Ctj
XI
a
CO
o
A
a.
§
•r^
TJ
O
CO
(1)
JJ
cd
n i
*w
t— i
0
CO
C
•r-l
4J
161
-------
x-\
-o
cu
2
G
•r4
4->
G
o
o
\— '
CM
CM
1
>
0)
rH
jQ
CO
H
S
3
CJ>
25
M
JH
cv 2:
S M
<2 3
CO hJ
En
CO &U
r4 M
2*
w a
S£
CO
3Z
O O
M M
UH
W <*
aSH
0< 23
a
KLJ ^—4
^^ tS^4
&> w
C
0)
O
c
o
0
CO
CO
Q
CM
>,
co
^^
^i
cO
O
CU
o
3
0
co
C
O
o
com
ooo
CMi—
com
o oo
co in
o oo
CM T-
co m
o oo
CM T-
com
o oo
CM <-
co in co CM
O 00 CM
CM ,— 00
CO
4J
C
CO
4J
t\ ^-^
C r-l
CO O
4-1 P ' I
jj
<-« r-j
r~4 dJ
O G
PW O
u
c
>
o
0
G
Q
25
S-*i
O
O
H
**-*
C
o
u
CO
O
O
•rJ
C
TO
00
§^|
O
•H
G <-»
CO cO
1 ) 4-J
•H O
4-1 4J
/— V
CO
H_
CO
T3
•H
r-|
O
CO
r-l
CO
O
4J
3
i
•^
^O
cO
C
cO
>
u
CO
G
cO
4->
o
OH
CU
C
O
o
cu
CO
CO
-------
o
o
CM
/-N
T5
•
CO
"~
>
Q
CU
0
jj
O
CO
cu
r-l -i-
CX CU
s &
CO >
CO H
0
cO -" 0
4-> O
CO
co
O "I O
r^ cy> o
lA CO T—
co
<)• r» m
oco o
CO
o
vO
mco oo
C
o
•i-4
4->
cO
u
CU
CU
o
CO
CO
<1J
o
o
O CO
CM »— CO CMT- CO
co m co
o co
CM >-
OOO
CO
4J
•r-l
S
i-l
cu
4-1
C
C 4J
•H -H
M CO
3 O
-o a.
B
(U O
4J O
TD
cu
4J
C
cO
4-J
rH
rH
O
CM
C x-x
o co
0 CO
v- j r,
*. s
CO
4-1
C
4J
3
rH
, 1
r^
o
CM
rH
CC
C
o
._J
•fl
4J
C
0)
>
f3
O
CJ
CO
"O
,r4
i— 1
O
CO
TD
CU
'O
G
CX
CO
CO
rH
CO
4J
O
4-1
XI
CO O cO
00 B C
o ^
0> O S
a^
4J cO 3
i 3 O
TD
I-l
CO
C
cO
4J
CO
a
T- CM CO
TD
o
cu
a
0)
r-l
a
9
CO
cu
4-1
cu
00
o
4-1
cu
4-)
5-i
o
ex
cu
CO
cu
o
C
01
Vj
cu
<4-<
(-1
cu
o
4J
cu
3
-a
cu
CO
•I-l
cO
1-1
4J
C
o
•I-l
4->
CJ
0)
4J
cu
Q
cu
o
C
cu
cu
4-)
C
cO
CJ
•1-1
e
cu
X!
o
163
-------
O H
oc
e
CO
o < < r*» co vo
o o oo o o
V V V V
O O 00*— O O
— t— CM »—
o o o i- CM •* oooooo
o o o o o
r^ CM -3- en m
oooooo
V V W VV
oooooo
v/ V W V
OOOOOO T- CM CM CM CM CO
OOOOOO OOOOOO OOOOOO
m m m m m m
oooooo
OO 00 00
V V
O 00 OOO
V W NX V V
00 OOOO
V V VV
oooooo
WWW
CO
CM
I
CO
co
CO
CX
co H
mmmm'nvo
(U
CO
H
co
CO
o
M
W
a*
CM 2
W
02 H
a w
23 OS
SH
W
CO
e
co
>
C
O
e
c
•
-*
,—
g
CO
M
a)
•H
E
O
oo
164
-------
"O
0)
0
C
•l-f
•u
C
o
CJ
en
CM
1
^
CU
I—I
,Q
cO
H
^J
H
^J
Q d- o
CM i— O
CM
m
\o co o
o
CM
m in in
OO 0
OO 0
V V V
m ^o tn
»— sf Oi
CM CM O
CM CM CM
0 0
o o
CM i—
on on
o o
00
O CM
en on
oo
Of-\
*—-*
en on
in in
oo
oo
w
in m
CM m
T— ^
CM CM
O
000
on -d1 cr»
on on r-
o
OOO
en on o
en on»-
o
O^^ /— *
*v Wi*
o on T-
•*-* CM
m m m
OOO
OOO
V VV
in m vo
o0 1— -^
t-CM CM
CM CM CM
CM CM CM
OOO
OOO
V V V
CM CM CM
OOO
OOO
VV V
CM CM CM
OOO
O^H f~*
\-J SH^
V V V
in in in
OOO
OOO
in in in
CJNCM in
CM CM CM
CM CM CM
OOO
OOO
V V V
CM CM CM
OOO
OOO
V V V
CM CM CM
000
O<""% ^*^
o ^" vO
r*^- N^* en
OOO
o crion
«— en en
r—
OOO
.
"*"-T Ui ^O
CM CM CM
OOO
OOO
V V V
in in m
o> CM in
O T-1-
CM CM CM
OOO
-------
-o
s
C
•l-l
4J
C
o
o
00
CM
1
Q)
l-l
,0
CO
H
^j
H
S
O
z
M
52
s
CO
CO
,J
CO
4J
C
•
Q
CM
O
O
o
T—
>-
cO
Q
TM.
o
o
o
CM
Q
CM
o>
o
o
o
m
o
o
o
m
o
o
o
CM
o
o
in
CM
t-*
CM
^
O
O
o
C*
o
o
o
CO
o
o
o
CM
O
o
in
m
CM
CO
o
o
o
>3f
o
o
0
o
o
CM
O
O
m
00
T—
CM
T— CTt
CM O
0 0
0 0
00 T-
0 O
O 0
oo r*
0 0
0 0
0 O
CM CM
00
Of*\
*— '
Of™^
N>w?
O O
IO VO
T— ^
CM CM
CM CM
^ vo 00 C^ O O O O O
csimcomcos^ V\/N/\/VN/
O^^ r^ /••% g^ /" > ^*i ^^ f^ ^^ ^^ ^^
C« »J *~mJ t<^J \^ \^ "*-^J "WM/ V^B/ 'Sal' Sari' ^V/
OOOOOO OOOOOO
\/ V N/ V V V W V N/ N^ V
m to m loinvo lominmiovo
CJN CM in CO *""
-------
<(l
H
<*»
^*<
t3 *^C
O H
^3 QJ A.
d <: i
C CO
•H CO
4J CO W
c j 3
O , CM CM iT> O
@ cd • • PQ • • PQ
•^Q OO OO
V V W
W
o
4J *~ o OCM o <;
cd >• ID CM O u~> "">
u cd pq .....
•M a o ooo o
C V W V V
CD
C
O vo
cd ^*
CO H
8
cd CD
Q) *XJ ^v <^^ iO OO ^^ *^
4->U CMCMcMCMCMCM
CO
4J
C
cd
4-1
2 co
r^ 4J
•-I C S
O cd 3
A. JJ «*J
3 r-(
r-l r-l
r-l Cd
0 Jfl
P-( 4J
O
•H .
X! r-
O CM
H r-
Of-s e-> <"*> e~*t f*>
V-* '•^ v*^ Wi* ^^^
O O OO O O
CM CM O<— fOt~
^O ^O ^O ^3 ^D ^O
OC3 O C") O Q
^^ Sw^ ^«/ ^•M' \M^
O O OO O O
«d- »— >^- m in vo
00 -*<»•<* st CM
O O OO O O
O O OO O O
OO ^O ^D vO 00 ***—
«- CM CM CM. CM ^-
Oj^s /~\ /— ^ f""S ji"^
t-^ «*-' (_? ^M' W^
O O O O O O
10 m m 10 "i \o
ON CM in oO f ^~
O T- r- r- CM CM
CM CM CM CM CM CM
CO
4J
C
cd
^
^
o
CM
P^
cd
C
o
0 4-1
C C
f4 1)
N >
C
O
o
00 C
CM O
i— 2;
^^ «K ^Q A. .A. j-|^
00 00 T— CM CM -^ V V N/ V N/ V
0% T-
£K ^^ ». ^M -^ — *
O !"*• CM CM T- IT» WN/VN/V
»* *~
00
O «— r- T- t— CM T- CO CO vO »— t—
OWVVt— N/ CM CM CM »* V
00
m
\X N/ \/ N/ \/ ^/ ON ON ON ON ON ON
inmmmmvo mmtomm^o
ON CM m oo T— -d" ONcMinoo'~-> C
4J "r^
^H r-l
"O Cd
,^J ^>
O r-l
cd cd
167
-------
X-s
T3
CU
Jj
C
•I-l
4J
C
o
CJ
CO
CN
1
^
cu
r— 1
,£
c<3
H
Bn4
CO
N.^ / Q
CO
C
O
4->
• , _4
H CD
C
01
o
C
O 0)
u o
rj
o
CO
(U
.-1 -•-
0^( ^)
B &
cO >•
CO H
B
CO Q)
0) -a
VJ O
•u o
CO
x-s
'O
(U
j3
C
•H
4J
C
o
0
»—x
CO
4J
C
4J
-P i-<
C r-l
03 O
4-) P-l
P
r-l Cfl
0 C
P^ O
, -J
*^1
C
(U
C
0
o
C
O
55
O O O O O O
^J T^ ^^ vO 00 OO
i— CN CNCN CN OO
O O OO O O
^D ^«O ^O I""** tO "«^"
CO ^^ C3 CD C^ CO
CN *-r- r-
OO OO 0 0
trt ir\ u^ r»«. vo eft
T- T- r- T- ,- CN
OO OO 00
vN CV| vN O4 v*s vN
OO OO 0 0
m m in *n in ^o
cr> CN moo r— ~4
O *— r-r— CN CN
CN CN CNCN CN CN
B
B
•H
a
0
p-l
CO
in m m m in in
oooooo oooooo
o o o i— mt^ WWN/S/
in m in in m m
oooooo oooooo
T-* pv», {^2 \O **O -^ \/ ^^ N/ >*/ *v^ *^^
^* \45 r*** f**^ r*** \D
o IA in m inm
^^ -_— ^^^-_
r^r^oocriooo N/N/N/N/V
<^ vJD *^ if"} O r*^
» *
r— t—
tj
oooooo oooooo
V V \/ V W
m in in in in vo in vn in m m *o
CTiCNmoO' * CT\CNinOOi d"
O'— ' — r-CMCN O T— r- »— CN^N
CNCNCNCNCNCN CNCNCNCNCNCN
C
00
O
ij
•I-l
G
CO
•H @
C 3
0 -n
B W
B cO
CO X>
OOOOOO
CN CN CN CN CN CN
OOOOOO
CO T— CN CN CM T—
V
OOOOOO
W W V V
oooooo
oooooo
WWW
in in in mm vo
cj\ CN in oo ^— *^
O T- t- ,-CN CN
CN CN CN CNCN CN
C
o
i-l
o
J3
168
-------
/-v
TJ
0)
i-4
rQ
CO
H
-> s
ctf P
• o o oo o o
Q r*- oo r- r-* oo o oooooo
CO CO CO CO CO ~3" O O O O O O
*-~ "^" -3" ^O CM *—
/~v COCM co co m m
i— 1 CM
W >• OOOOOO
^Q (T> 00 l-v OOOOOO
-• OOOOOO
4-) Q vo vo ^o r^» in ^0 o o o o o o
£ CO CO CO OO CO CO O O O O O O
CU CO ^™ CJS CO CM \O
C ^f* vo co in co co
O 4>
CJ 0
b r~^ r*^ r-~ r^ r^- r^
o r*"** r*^ r** p** r^* p^* in in in in in in
CO CO CO CO CO CO CO \S \^ \S \/ \S \/
(U
r-l +-
O. 0)
S O" ^^ ^^ L^^ ^O L^^ ^^ ^Ol L^^ l^^ U^ l^^ ^O
CQ ^>
co H
S
co CM inoo i— -d" o CM m oo »— >d"
J-iO O ^— r- r— CM «M Or- v— ,— CM CM
4->O CMCMCMCMCMCM CMcMCMcMCMCM"
CO
S~^t
TD
~j
C
•H
4J
C
o
^ ^
Q
co o
4J CJ
C ^
cO
4J t3
3 C
4-> r-l CO
C r-4 S
CO O 0)
4J di T3
^ i-4 C
<-4 CO CU
o c oo
ex. 0 ^
•r* X
4-> O
C
S co
C 3 0
O -H •<-)
cj u s
C r-l (U
O cO jz
& 0 o
OOOOOO
o o oo o o
OOOOOO
t~». 00 00 — CO r— r—
^ ^^ \^ \s ^f *s
in in m in in ^o
CTi CM m OO '— >^
O «— T— T- CM CM
CM CM CM CM CM CM
4-J
r-l
CO
o
CJ
169
-------
T3
0)
;3
C
4J
C
o
cj
CO
CM
1
•
Q
r-l CM
~M >-
B ^
CO
C
O
W *~
ct) >-
Vj ctj
4J Q
C
» co
r— CO OO OO 00 ^O
o o oo o o
00'— CM 00
-^ CO ~ m m in vo
ON CM moo r— -^
O'- T-"- CM CM
CM CM CM CM CM CM
00 »— in in m ^o
ONCN in oo r-
-------
•o
CU
f3
C
•l-l
4J
C
o
u,
OO
CM
1
>
r~t
XI
stf
H
i
Q
o
CO
>i
a
o
CM
0)
CJ
t-i
o
rn
m
o
o
\s
0>
r-4 -*-
p, Qj
e a
cO >
co H
o
in o o
o inm
0 00
V VN/
00
o m m
r- 00
V V
o oo
in in m
0 00
V VV
m mm
o oo
o oo
in in in in
s
CO
CM
^•^
*O
CU
•3
C
•r-l
4J
C
o
0
N^
CO
4J
CO
4J
vt
4J
C
CO
4-J
rH
rH
O
PH
,->
r-l
r-l
O
Ok
CO
C
o
C §
CD C
> cu
C TJ
O rO
O >s
C rH
O O
23 e
CM moo
CM CM CM
O 0
m m
0 O
V \/
00
m m
0 O
V V
00
m m
0 0
w
m m
00
0 0
"V V"
m ^o
CM CM
CM CM
o o o o o o
T— vo ^O r— O O
OO OO OO ^" *»0 vO
o o o o o o
O T— ^O C7N «^ CJN O O O
^. CT> OO CM ^ CO OOO
vo \s> r*. r^ cr» r-mr-
oooooo ooo
mmocM vO r^ O O O
cvi oo oo oo oo oo in T— m
oooooo ooo
mCTiO\
r— T~ T—
oooooo
<*<*o>c*cr.c* r>.rv.r-
LO tO tO
intnm"-nnvo mmm
CJNCM m oo r— <(• CJN CM in
O»— T- r- CM CM O T- i—
CMCMcMCNCMCM CMcMCM
(U
f3 - -I-1
J3 CO
•r-l 4-4
73 r-l
O 3
CO M
O
o
o
CO
o
o
o
0
o
o
o
(-2
^
r-
tO
m
CO
CM
00
0 0
00
m co
o o
0 0
o o
CM^-
0 0
0 0
0 O
CM O\
r_
r^.r>.
iO iO
lO v,O
CM CM
CM CM
-------
23
CD O £•»
r— t ^3
Q tt5 t"*
H M
2 §
^^
OH
O
co
CO
ifl
Q
r-l CM
-^
00 >i
ft trt
OQ
CO
C
O
4J *~
CO >l
4J Q
C
MI
CD
0
C
O Q)
O O
O
^ ^
CM r-
OJ CO
O
o% r^
^o m
m
m m
00
00
\s v
m"^
o>-
CM CM
X*X
T3
(3
O
O
C C
0 -^
25 U
vn in in co
o o o m
\/ \/ \/ \/
«^ in o o
vo o m in
V V V
m in in o
o o o m
\/ ^>/ \/ \/
m in m in
oo o o
o o o o
V V V V
m in m ^o
moor- -d-
»— T— CM CM
CM CM CM CM
O O O O O O
mminm m m
t— r- O O O O
t— \/ V \/ \/
o o o o o
in m in m in in
>* o o o o o
CM V N/ V \X VX
O O O O O O
m in in m in m
o o o o oo
WWW
m m m m m m
o o o o o o
o o o o oo
V V W W
m m in m vo \o
CT> CM in oo <~ ~^
O i— t- t— CM CM
CM CM CM CM CM CM
•r-l
c
cd
4J
•r-l
4->
O O O O OO
co oo o o r^ * CM m oo T- ~J-
o i— *— »— CM CM
CM
Q_J
O
H
**-S
O
^
)»i
cd
o
o
•H
C
CO
00
J_l
o
r-l
<0
U
o
iJ
172
-------
«
S
m
o
c
o
u
CM
td
oooooo
in m in in m in
.oooooo
m in m in in in
oooooo
oooooo
oooooo
O i— CM CO -d" vO
OOOOOO
V V V \S V V
o o o o o o
m in in in m m
oooooo
V V V V V V
o o o o o o
in m in in in in
oooooo
oooooo
oooooo
CO CO >*
CO
oooooo
WWW
o o o o o o
in m in in in in
oooooo
WWW
o o o o o o
m m m in in in
oo o o
oo o o
oo o o
r^ oo CM co
coco o- m
oooooo
OO 00 00 00 00 00
CO CO COCO CO CO
oooooo
V W W V
in in m m in in
oooooo
oooooo
WWW
in in in m m m
oooooo
V W V V V
oooooo
WWW
0)
C
•H
4J
C
o
o
cy
<-t -f-
(X 01
e oj
ed f*
CO H
ir> m mm
in m ""> m
in in m m m >>o
CO
CM
I
c
-------
-o
cu
3
C
•r-l
4J
C
O
u
CO
CM
1
^k
CU
rH
j3
CO
H
Q
i— — CM CM -* T-
I«Q **o in CM *— ^^ co co co co co co *— ^d* "^" ~*^ <>j" "^^
N/ •*^J" O^ ^O ^^ CO C^
T- CM «- (^ T- r-
»
m
rrt
CO
Q
T- ,— r-~
in o f"~ oo oo cr» co
CO CM T- CM T— CM OOCJOOOO T— * ^ <}• »cMinoo^~^ cr»cMinoo^— -st
O t— i— *— CM CM O T- ^— t— CM CM O»— »- »— CM CM
CMCMCMCMCMCM CM CM CM CM CM CM CM CM CM CM CM CM
x1^
CO
CO
H
v_x
CO
4J CO
C T)
4J
G
CO
n)
r-l
r-l
O
^J »i~4
4J r-l /-v
3 O CO
r-4 W 4J
r-4 -H
O T3 C
PD cu cu 3
co T3
r-l CO >-^
C r-l -U
O -n 0 UJ
CJ) O 4J CX
CU
4->
•H
CO
O
CX
(3
O
O
^
43 CO
c4-l
V4
cu
4J
c
•H
o
i-J
cu
3
T3
T3
CU
CO
•1-1
cO
S-i
4J
•rl
e
•i-4
i— 1
C
o
•I-l
4-1
O
CU
4->
CU
Q
1
-------
en
&
S
CN
>
CO
C
O
C
0>
O
C
O
O
cu
CJ
O
03
a
z
Q
Z
Q
23
a
z
Q
Z
a
z
Q
Z
Q
Z
Q
Z
a
z
a
z
a
z
Q
Z
a
z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
04
I
cx cu
e oj
eO >-
CO EH
0)
CO
S
cO CU
•H
C
O
J
f^^
>,
CJ
cO
•
CO
cu
£3
CU
N
q
cu
.0
cu
C
*p-4
TJ
•H
N
£3
• cu
43
lortde
43
CJ
CO
J_i
4_)
CU
4->
C
O
43
CO
O
0)
C
CU
N
C
cu
jQ
o
Jj
o
rH
<-;
O
obenzene
r-l
O
rH
43
O
•H
S-i
4J
1
t—
oethane
S-i
o
rH
43
CJ
•H
>_l
f i
1
^_
.
,—
.
i—
CU
C
CO
43
4-)
0)
O
S-i
O
rH
43
O
CO
X
cu
43
cu
C
CO
43
CU
O
43
O
CU
§
43
4J
CU
O
S-i
o
rH
43
CJ
CN
oo
o i-
175
-------
en
V
«
H
e
CO
i-l U 4J
r-l C 1
O Ctj CM
P-l 4J
3 CM
r-l -
r-l i—
O
CU i—
-------
en
0}
a
CM
r^
O
09
C
o
cd
cd
C
0)
o
C
0)
o
o
CO
Q
S3
Q
z
o
z
Q
Q
Z
Q
2!
Q
Z
Q
Z
Q
Z
Q
Z
a
z
Q
Z
a
z
a
z
Q
Z
Q
Z
Q
Z
Q
Z
O
z
Z
a
z
Q
Z
Q
Z
Q
Z
4->
C
O
ex cu
s a
cd ^
co H
I
>
r><
C 43
4-» O 4J
c a cu
cO N— ^ O
4-1 VJ
3 W O
rH 4J rH
rH C 43
o td o
OH -U T-I
J3 "O
rH 1
rH T-
o
OH T—
O
•rH •
X CT\
O CM
H
cu
P
^I
4_>
CU
O
>-l
0
rH
T<-|
CJ
•rH
T3
1
0}
C
r*
4J
I
CN
*
»-
•
O
ro
r-H
O
c
CU
^£3
a
o
v-i
o
rH
O
•rH
T3
1
•-,
43
4J
8
•l-l
*o
1
~f
•I
CN
•
^^
CO
cu
c
cu
rJ
r-H
o
o
r-l
4-1
•rH
C
•r-l
""O
1
»J-
•k
CN
•
m
OO
cu
C
cu
3
rH
O
4-1
O
r-l
4J
•H
C
•H
*o
1
vO
•k
CN
•
vO
CO
43
4J
CU
•
00
oo
0)
43
4J
(U
rH
r*^
c
CU
43
rH
CU C
C cu
cu 43
43 CU
4J O
C }~i
CO C
O 43
3 O
rH 1
• •
CTi O
oo ~a-
VH CU
CO 43
43 4J
4J Q)
rH
rH r*i
^s CX
C 0
CU r-l
43 CX
ex o
CO
rH -rl
r^ O
{3 r-l
01 o
43 rH
CX 43
O 0
0 1
O CN
43 CO
1 T-I
-------
0)
c
4J
O
H
a
CQ
o
23 H
<
cn i
en en
en
en
§|
U hJ
ftj
C^4 ("4
>-i W
05 S
< H
Q -^
23 U
O OS
O H
M
en
m
cO
a
T™^ £xJ
M {*
B a)
CO
C
O
4J
cO ^i
W cO
4J Q
C
(U
o
12
O CO
u o
jj
O
en
CO
(X
en H
B
cO (U
«^
en
4-1
(2
cO
4J
jj
r-l
r-l
O
P-l
a
23
Q
23
^
00
1)
C
X-x j
13 4J
CO CO
3 B
C .X"^.
•H >,
4J X
C 0
0 42
O W
N_/ qj
O
CO 1-1
•u o
C 42
cO O
4J 1
3 *
H
Q
23
Q
23
^
00
CD
•a
•H
K
o
rH
43
O
CO
c
CO
r-l
^
42
4J
(V
S
•
^•T
<^y
Q
23
Q
23
^
00
(U
C
CO
<-;
4J
CO
CO X!
S 4J > O r-l 42
42 B 42 0
4J O O -r^
^-
Q
23
Q
23
<}•
00
CO
c
42
4J
4)
S
0
B
O
U
43
f4
*"O
O
0
r-l
42
O
•
r—
m
a
2!
Q
23
^>
00
0)
C
d)
•rl
-o
CO
4-J
3
43
O
V4
O
r-l
42
O
cO
x
4 (2
O O
r-l VJ
43 0
0 43
cO CX
X O
-------
B
co
C
O
•r-l
4->
cd
G
CD
CJ
C
O
o
en
cd
O
CN
(0
o
a
a
a
o
a
o
a
o
a
Q
a
oo
CM
O
O
CO
O
O
a
CM i-
O O
O O
a
a
a
a
a
Q
a
Q
a
Q
a
a
a
Q
a
Q
a
CM
O
a
a
a
a
Q
a
3
C
•H
4->
C
o
o
.
CO H
CM
I
cd
4J
O
H
(U
c
•r-l
cd
o
s
(X
o
c
I
CM
in
o
G
o
(X
o
c
oo
m
o
c
CD
o
rl
c
TD
^J
•t
CM
•
ON
o
CO
01
o
I
o
I
o
I
vO
o i-
CD
G
i
ex
o
r*N
x:
4J
CD
S
•H
TD
O
CO
O
^
U
•i-l
C
1
a
r*1
C
CD
X!
ex
T>
o
CO
o
^4
4J
•H
c
a
^
ex
1
c
1
•H
T3
O
CO
O
M
4-1
•r-l
G
I
a
o
C
3*1
rt
ex
o
M
o
r-l
X!
O
cd
4J
c
CD
ex
r-4
o
G
CD
r*
ex
01
cd
r-l
cd
X!
ex
X
4J
01
I
CM
CO
CM CO
in
vd
4J
cd
r-l
cd
X!
4J
x;
ex
N
c
CD
4J
x>
MO
I
I
•r-l
T3
0)
cd
r-4
cd
•U
x:
ex
jj
o
o
I
c
I
•r-l
T)
00 ON
CD
4J
4J
X!
ex
!>>
XJ
u
(U
o
r-
179
-------
en
H
5
co
C
O
-U
cd
to
4->
C
CU
o
C
o
U
Q
O
CO
CN
O
o
z
o
z
o
z
Q
Z
Q
Z
Q
Z
O
z
Q
Z
Q
Z
a
z
a
z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
O
Z
a
z
a
z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
Q
Z
cu
C
cu
r-l •»-
a cu
ss
c/> H
cs
I
CU
r-l
X>
cd
H
S
cd cu
CU 13
to O
4J cj
CO
00
-*
00
oo
00 00 OO OO
00 00
OO
00
OQ
CO 00
•u
C
cd
•u
O
PH
(U
C
O
CO
4J
C
cd
O
P-4
U
i-»
X
o
H
CU
4-1
cd
X!
a
r-l
>>
e
cu
cu
o
cd
4J
C
cd
o
N
CU
CM
CU
C
cu
Ou
'cd
o
N
C
cu
CU
C
CU
XI
C
cd
o
N
C
cu
Xi
cu
C
C
cd
o
r-l
o
C
cd
cu
(2
cu
CO
X!
O
cu
C
CU
X!
O<
cd
c
cu
o
cu
cu
o
cd
to
X!
cd
ao
cu
c
cu
t-i
^\
V4
cu
ex
x— \
•r4
XI
oo
N«X
O
C
CU
-0
•
ON
p^
cu
c
cu
J_(
o
£
r-l
«W
•
O
00
^N
cd
\«x
cu
c
cu
^1
X!
pi
cd
c
CU
X!
Ok
•
r—
OO
cu
§
u
CO
)*i
X!
4J
C
cd
X-N
XI
*
cd
v»x
o
M
n
cu
Xi
•H
•o
•
cs
oo
CU
c
cu
Ou
x-s
T3
•
0
1
en
»
CN
*
T—
^-x
O
c
cu
"O
c
•H
•
en
oo
cu
C
cu
to
>>
Ou
•
>3-
00
180
-------
TJ
t\\
r-l
XI
cd
H
•< W
fti S
Q
cd
a
o in
Q Q Q O VO CM CO
CMO O
a>
p
o
CO
CO CO CO
^^ ^^ ?™ i
t»^ W V_^
o a a a oo o
OOO
vvv
o>
f— ( -t—
O- 01
Br»
M.
cd P>>
CO H
^— r— r»
B
cO 01
0) *o
M 0
J-J T3
+•* wx
CO
*^f *xl" >d" "^ ^^ r™" CM
OO 00 OO OO OO r* T~
x-v
0)
C
01
rH
r>1
X!
•J-J
01
x-^ O
0) O
30) rH
C C X!
••H a> 01 o
•U <— ( C v^^
G >> H
0} Jj Ol O
4J O O rH
C rH M Xi >>
cd X! Oi O 0 C
•U O C rH O
3 Ctf 01 X! rH S
rH t-l 3 CJ >-, -r-l
rH W rH -rl C 4J
O 01 O K tH C
CXi 4J 4-1 U > CtJ
O
•rH • • • • «
X m vo r** oo -^*
O 00 00 00 OO i~
H —
cv-,5 '-'-
* CM VO T— T— r—
OO r- O OOO
OOO OOO
vvv
CO CO CO
OOO OOO
OOO OOO
VVV V V V
vd-»— CM «*r- CM
OO r— r- • 00 *"" r—
r— O O r— O O
O -n
*i-* r^t
C rH
CO rl
M Ol
cd Xi
• •
m r*»
r— r—
T— 1
T— T—
OOO
o o
V
m o
• •
0 O
V
,_ ,_
OOO
Or- 0
V V
OOO
000
vvv
•* CM t-
o o o
OOO
OOO
vvv
^- r- CM
00"- T-
r- O O
X-N
r-H
cd
4-)
o
4J
^^
•t^
s
o
J_l
X!
o
*
cr.
, —
1—
181
-------
/~x
T3
0)
3
C
*J
C
O
CO
•*~s
stf-
CM
1
>
. ooo
rt ...
Q 00 O 00
CM V N/V
^1 CM CMCM
>J OO t- O O
| _'o oo
<-" v v
'"I O CM CM CM
{J -^ O r- OOO
Q O CM t— OOO
a I o ^ s/ \/ v
ni
0 r-'- ^ CMCM CM
Li OOO OOO
H . . • • • •
o ooo ooo
^ C\f ?s ^ / *^S ^/ **/
C/5 V V V \/ \/ N^
0)
i— 1 4-
&* oo °o -3" o
CM m CM oo «— o
co O O OOO
CM CM CM
,_ .- ,- OOO
ooo ooo
• . • » • •
ooo ooo
\/ \/ N/
^.,_ CM <*'- CM
oo_ r- oor: T-
T- O O i— O O
CMCM vO r^
oo^. m r»
l-~ OO O O
. . • • •
o*- oo oo
vO
co o cyi
f— • T— » vO •*3"
vo O O O O
. . . • •
oo oo oo
oo
o ^ >— T— in
O 00 r— i— -4" CO CO
vO r- O O OOO
T- O O OOO OOO
OI*^S
w»
in in in
mmm oo oo oo ooo
£r-r^ ooo ooo
ooo ooo °.o.°.
°°'° 555 555
^^ CM -*'- CM £±^ CM
2oo »-oo T-OO
CO
CO
4J
§
4J
3
^
i-t
O
PM
U
•r-
X
O
H
LI
01
O-
P-
O
o
•
o
CM
*—
4J
x.^
>
O
.
CM
*~
T3
CO
5
U
•r-l
C
•
-*
CM
§
3
^4
c:
(U
r-l
0)
CO
•
m
CM
VI
0)
>
rH
•t-l
CO
•
\o
CN
182
-------
X-N
(U
rj
C
•i-l
j»
O
o
*^-
CM
1
J>
(1)
r— I
-0
cd
H
^
EH
^*
Q
PQ
Z EH
rH Z
S CM
CO i
CO CO
EH CM
M 5£
S H Pi]
< EH
0 •
0 cd
^a
CO
C
O
•iH r—
4J
cd ^
VJ Cd
4-) Q
c
0)
o
C
o tf r- CM
OO'- T-
,-0 0
g
3
•iH
r-l
r-l
cd
<-{
4-J
r>!
CM
i —
O r-
O -i"
CO
•I
r~
O
CO O\
• •
O \£>
O O vO
O O if)
o\oo
M M
t-CM
in vn u"i
CM CM CM
^i- CM
OO'— t—
r-O O
o
C
N
00
CM
oo
O >£>
OOi-
00
ON O
OO
O O O
o o o
O O CM
00 00 T—
T-0
r- V
o o
• •
o o
V V
00
CM
. oo
•
. a* CM
m in m
o o o
o o
CM r^
CM O
oo o
o o r»-
OO CO ^O
CM CM
r*. r>» r>. o o o
CM CM CM V V V
OO O
oo o
-------
i— m
r*- o
• •
o o
en on
O ON o o
O i— ON-*
oo
oo
O CM
00
(T> r—
• •
CM O
in ON
i
o
«
,_ oo r-* CM
« • • •
r— O CM CM
CM CM QO
o o
O O
O CM
OOO
m o on
-3- »•£> r-
ON
ooo
• • •
00 O
ON ON ON
o o o
ooo
oo
00
O CM
•t
on
on
ooo
ooo
ooo
O LOt—
CM CMCM
m mm
CM O
i— CM
O COON
N
X
o
ed
0
0)
,£
o
0)
•g
(V
V)
O
s
184
-------
<;
H
<
Q
CO
2 H
r-l 2
"0 £ &,
d co i
c
•H CO CO
[^i . *] rvj
c <; 13
O H CM
3 35
CO
-" W
2r< ^
Q ,
CO
CN
fx,
CO
a
*_
!>~
a
01
o
V-i
o
CO
•t-
QJ
Q.
I-*
>•
H
0)
*O
O
o
4-)
c
cO
4-J
r-l
O
D-i
v£>
T— T— CO \O
CM O CM CN O »— O
• • • • • • •
OO T-CN CMO O O •& *t OO OO
O i— V W OO OO
CN o o m m
CM CO CMi—
in cr\ CM CM
T— o en •>}• o o o
• • « • • # •
OO CM*- CMO OO OO OO
O r— V OO COCO
C*4 O O CT> OO
•t •«
CO i—
a* T- t—
r- co in co
»— OOOOOOCM»— O ^O
o o ^™* in ^— • r— co in o o o o o o o o o o
r- V0 r- CM V OOO OVO
CO *d" O O O — O O »— OO T— OO i — OO OO T— O O *— OO
x-s
T3
3
c
^
o
o
to
e
4J
jH3
f-l
r-l
o
r-l
cO
c
o
4J S 0) S 01
C 3 a> C -U
cu co CO C T3 ,C S 4J
o cu co 42 a, 0 co
OC C 00 >» 03-r-l 4-1
CO 00 C r-l OT3 r-l
OM cO cfl O J3O 3
53 •>-• B B B puco co
185
-------
CQ
T3
3
C
•H
4J
C
o
o
CS
(U
cO
H
O
CO I
co co
K-] W
co
co
02:
05
Pi
to
w
a w
O |Yj
OH
CO
00
cs cs
wT "~ T~
Q do
NX V
^
r-l CS
M >i oo o»
S cO
•So ,-vo
w
C
O
*r4 T—
4-> CS CN CS
4J Q 000
C V NX NX
HI
o
c
o OOO
ooo
•••»•»
r-^ oo cs
30 *-* i— r- T— NXNXNX
* t— CS
OOi — r— OO T— i — OO t— T—
i— O O *— O O t— OO
s~\
o
o
H
v_x
c
o
Vj ^~\
CO CO
0 H
s_^
CJ
•t-l CO
C *^3
CO »H
oO -I
.^1
r-l r-l t3
cO cO cO
v> u C
O O cO
4J -U >
VO CS
00
oo
dd
NX
-*\o
oo
* *
oo
to -^ *^
186
-------
on
O CO
O co
vo m
r-. \o
• •
oo oo
in
«d
V V
00
00
on
O Px
o o
• •
o o
*° «- O O O 00 O
V O O O i-
r-» oo m
cs
t— r— oooooo
V
vO vO
oo cn
T3
00
"O
•H
r— i
o
CO
T3
0)
T1
W
C
01
a,
CO
3
CO
r-J
CO
•U
o
4J
/•"N
CO
4J
•r-l
C
3
T3
L.
w
CO
TJ
C
CO
4J
CO
\^ S
a.
187
I
-------
0
cO
c
.
en H
cu
r-l
43
cd
H
S J
U (x.
&
PM EH
Z
OS S
-------
|cn
Q 0
Z Z
Q Q
Z Z
Q Q
3 25
Q Q
Z 25
Q Q
Z 2!
Q Q
z a
QQ
25 2!
Q Q
ZZ
QQ
ZZ
O Q
• Z
O
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
QQ
ZZ
Q Q
Z Z
Q Q
Z Z
QQ
ZZ
X^v
T3
QI
w
3
c
•H
4J
13
O
U
N» .X
m
CM
i
>
C
cd
Q
Q Q
ZZ
0)
O
rl
3
o
CO
Q Q
zz
•1-
P- 0)
i
CO
S
cd
(U
rl
4->
CO
a
>
H
T- 1-
(U
T3
O
CJ
r«. CM
/-^k
T3
CM
1
,—
.
^_
•k
T—
Q Q
Z Z
Q Q
Z Z
oo vo
r-~cs
• CM
(U
C
cd
43
4->
0)
O
to
O
r-l
43
O
•H
T3
1
^_
«
>—
Q Q
Z Z
Q Q
Z Z
T— 1—
r~ CM
(U
C
cd
43
4J
a>
0
to
O
r-l
43
O
•i-l
to
4-1
1
CM
«.
T—
.
t—
Q Q Q Q
ZZ Z Z
Q a Q Q
z z z z
»— T— T— T—
to
!*•> CM r*« CM
-------
H
Q
O
CJJ
ZH
en
CN
at
6
co
S3
O
4J
(0
cu
o
C
O
O
01
Q Q
Z Z
Q Q
ZZ
QQ
zz
Q Q
z z
Q Q
Z Z
QQ
ZZ
Q Q
53 52
QQ
ZZ
O Q
• Z
O
QQ
zz
Q Q
Z Z
CN CN
O O
00
CNCN
00
• *
00
Q Q
z z
Q Q
Z Z
QQ
Z Z
QQ
ZZ
Q Q
z z
Q Q
Z Z
Q Q
Q Q
Z Z
Q Q
Z Z
Of-
* *
00
Q Q
Z Z
Q O
QQ
zz
Q Q
zz
Q Q
Z Z
00
• *
oo
Q Q
Z Z
QQ
Z Z
QQ
zz
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
zz
cu
a
c
c
o
u
m
CN
i
cu
r-l
43
CO
H
C/l I
CO CO
< rJ
CO
co
U r4
W P-i
PS
(V H
>< W
OS a
CU
r-l -r-
O* 0)
e CL\
CO H
cO d)
CU T)
VJ O
4J O
to
CO
_.t— cn
en
on
cn
CN
I—CN
CN
CN
CN
. CN
W
Ed
CO
to
cu
cu
3 r-l
C ^»
•H C
4J -r-l
C >
•u o
C O r-4
cO x— ' £>•>
4J jrj
3 CO
r-l 4J
r-l C
O cO
p t 4J
3
r-l
O
4J
O
o
t-l
o
r-l
u
1
CN
CU
C
CU
r-l
CO
43
4J
43
O.
cO
C
0
W
o
r-l
O
1
CN
O
(3
CU
43
O
Vj
O
r-l
43
O
•H
Jj
U
1
vO
^T
A
CN
r-l
O
CO
CU
V-i
o
1
€
1
0
Vi
o
r-l
O
1
a
g
)4
O
O
Vj
o
r-l
<-j
0
r-l
O
C
CD
e*
a.
o
Vi
0
r-l
43
O
1
CN
CU
C
£3
c
cu
43
O
to
O
T-4
43
O
•r-l
-o
1
CN
•.
T—
cu
C
(U
N
C
cu
43
O
Vj
0
<-4
43
O
•H
T3
1
cn
«
T—
cu
53
CU
N
C
CU
43
O
O
r-4
43
O
.r-l
"U
1
^j-
•«
r—
o
o
H
O
CN
CN
CN
cn
CN
CN
CN
CN
CN
190
-------
EH
2
CJ
CO
Q Q
aa
Q Q
a a
Q Q
aa
Q Q
QQ
aa
a a
aa
Q Q
aa
O Q
o'55
V
Q Q
2; a
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
aa
Q Q
a a
Q Q
a a
Q Q
a a
QQ
a a
o
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
a a
Q Q
a a
9Q
aa
aa
Q Q
a a
Q Q
a a
Q Q
2 a
Q Q
a a
TJ
§H
co H
on vo T- _ ,_ »_
CM
i
0)
r-H
43
tti
EH
S
cfl
o
i-i
43
O
•H
-a
i
on
en
en
o
C
0)
43
a,
r-H
>s
43
4-1
O
$-1
CM
on
191
-------
Ot
e
oj
on
CN
H
O
o
QQ
QQ
Z Z
Q Q
Q Q
53 13
a o
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
ZZ
Q Q
zz
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
QQ
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
QQ
Q Q
Z Z
Q Q
Z Z
Q Q
Z Z
Q Q
z z
Q Q
Z Z
Q Q
Z Z
Q Q
z z
Q Q
Z Z
o o
oo
oo
oo
V V1
o o
o o
V V
o o
o o
\/ \/
Q Q
zz
Q Q
zz
QQ
ZZ
QQ
ZZ
T3
CU
4-)
C
O
O
CX CU
e CM
CO >
CO H
on ^o *— T-
on
Cn '•O r- r- i— i—
iA
CN
1
h5*
CU
rH
X)
CO
H
CO
OH S
O Z CO CU
H-J ^c d) *^
CJ r4 r-l O
WO, 4J CJ
OS CO
ftt LJ
z
OS S
» CM
w
cu
XI
cu
rH
^*»
c
.
r-l
F**»
p,
o
VJ
PJ
o
CO
•r-l
0
V4
o
l-l
X!
o
1
CM
\-S
CO
•H
Xi
r*-. CM
cu
c
CO
XI
cu
B
r*%
X
o
X!
•u
cu
o
Vj
o
X!
o
1
CM
N-^
CO
•H
Xl
r*~ CM
cu
*o
•H
V-i
o
r—4
X!
O
CU
c
cu
1— 1
r*^
Xl
4-1
cu
B
r-
/->
cu
c
cO
4J
CU
B
O
V4
o
r-l
XI
O
^~s
cu
*0
•r4
V4
O
i— t
XI
o
r-l
>l
X!
4J
CU
B
X
o
H
en
ao
on
en
T- CM
cn
vn
192
-------
«
v^
CO
C
O
•H
4-1
cd
C
cd
X!
4J
cu
0
O
s
o
to
JQ
4->
C
cd
4-)
3
t— I
i— I
O
a,
O CU
0 -0
^ •.-!
CO
4->
C
cd
4-1
3
r— 1
r-l
O
fm
o
•H
X
0
S
O
to
Xt
r-l
>»
X!
4-)
.
o
o
to
O
i—4
X!
O
cd
X
CU
X!
CO
sophorone
m
193
-------
e
CO
CO
QQ
Q Q
23 25
QQ
2523
Q Q
23 23
Q Q
2323
Q Q
2325
QQ
2323
Q Q
23 25
OO O O
* • • •
OO 00
Q
23
QQ
2323
Q Q
23 23
Q Q
23 23
Q Q
23 25
Q Q
55 23
Q Q
23 23
Q Q
23 23
QQ
23 23
Q Q
23 23
QQ
2323
Q Q
23 23
00
* •
O O
V V
QQ
2323
O Q
• 23
O
V
Q Q
232!
Q Q
2323
Q Q
2323
Q Q
23 23
QQ
Q Q
23 23
Q Q
25 23
Q Q
23 23
Q Q
23 23
Q Q
S3 23
Q Q
23 23
0)
(3
4J
C
o
0)
r-l -t-
Pu
-------
QQ
22
00
• •
O O
V
00
• •
00
V
Q Q
2 2
O O
• •
O 0
V V
Q Q
22
0 0
• •
o o
V V
QQ
22
Q Q
2 2
oo
OQ
• 2
O
\/
0 0
* •
0 0
00
* •
00
w
Q Q
2 2
OO
• *
00
V V
QQ
22
O O
• •
O O
V V
QQ
22
Q Q
2 2
CO
22
Q a
«— oo
o o
• •
o o
V
~
Q a
22
OO
• *
oo
oo
00
Q Q
22
Q a
22
00
* •
OO
vv
00
• •
oo
V V
QQ
22
QQ
22
O O Q Q
oo 22:
00 QQ
00 **
Q Q
2 2
Q Q
2 2
.
CO H
CO vO CO vO
CO
CO
CO vo
CO
CO >
CO vO CO
CM
1
J>
(U
r-l
,jQ
CO
H
5 f-1
O 25
r-l
4J
c
o
u
utants
o
•r-l
X
O
H
O
C
CD
x:
ex
o
r<
o
r-l
x:
o
CO
4J
C
0)
V£>
r-l
O
c
0)
X!
a
•hthalate
A
x^N
1— 1
>^
X
(U
X!
t— I
>.
X!
4-)
rC
a
r-l
>^
N
C
0)
x>
rH
rS
jj
3
X)
(U
4-1
phthala
r-l
>,
4-)
3
XJ
c
^
4J
0
O
1
C
1
M-l
T3
:halate
4-1
J2
CX
r-l
r^
x:
4J
(U
•H
T3
thalate
•a
, i
r^
>,
j-1
4-1
CU
e
•r4
t3
hracene
4-1
CO
f N
CO
•^^
O
N
C
a;
rQ
m
oo
vO
vO
O r-
CM
195
-------
Q 0
5555
Q Q
55 55
Q Q
5555
Q Q
55 55
Q Q
5255
QQ
55 55
Q Q
55 55
QQ
5555
Q Q
55 55
Q Q
55 55
Q Q
2 55
Q Q
55 55
Q Q
55 55
Q Q
5555
QQ
55 55
Q Q
55 55
Q Q
55 55
Q Q
55 55
Q Q
5555
Q Q
55 55
Q Q
5555
Q Q
55 55
QQ
55 55
QQ
5555
Q Q
55 55
Q Q
55 55
Q Q
55 55
QQ
55 55
O Q
55 55
QQ
5555
Q Q
55 55
Q Q
5555
Q Q
5555
Q Q
55 55
Q Q
55 55
Q Q
25 55
T3
j
W H
CO VO
en
CO vO
CO
CO vO CO '
CO v£> CO
CN
»
CU
r-l
43
cO
H
(X,
CO <1>
CO T3
r< O
4J O
cn
CN
.
0
r-l
r-l
O
(X,
O
•r
X
o
H
benzo(a)pyrene
CO
CU
c
CU
45
4-1
CO
V4
o
3
rH
M-l
benzo
(1)
§
43
4J
C
cO
W
O
a
M-l
benzo
in
cd
cd
chrysene
vO
acenaphthylene
anthracene
QO
C
CO
C
CU
43
Cu
00
196
-------
Q Q
2525
Q Q
25 25
Q Q
23 25
Q Q
25 25
QO
25 •
O
NX
0 Q
• 25
0
\S
0 Q
• 25
O
V
CM -t
CM r-
00
• •
00
in m
0 0
0 0
* ^
o o
Q Q
2323
Q Q
2325
gg
gg
O
V
9 Q
25 25
Q Q
23 25
CO CM
o o
•J- co
o •-
o o
o o o o
(U
Q Q
25 25
Q Q
25 25
Q Q
23 25
Q Q
2525
Q Q
2525
gg
Q Q
25 25
gg
O
V
gg
O Q
o23
V
Q Q
25 25
25 23 23 23
a-
T- O
• •
O O
CO CO
o o
o o
• •
o o
w
CO VO
o o
• •
o o
m m
o o
o o
• •
o o
0>
r-4 +-
(^ 0)
a a,
CO
a>
B
(0 (U
|
c
CO
4-1
O
m
CO
4J
C
ctf
o
N
C
T3
O
I
C
D
TD
(U
c
0)
4->
0)
o
o
CO
V-4
4J
a>
o
U
cu
e
•r-l
4J
c
•l-«
c
cu
CO
X
o
Hi
CM
CO
CO
00
CO
oo
00
oo
oo
oo
197
-------
H
Q
o
Z H
1-1
ot
«
•at ions (t
Concenti
en
Q
CM
rft
Q
r-»m
oo
mm
00
oo
00
mo
r»> T—
o cs
r^ o
in cr\
O CM
0 0
r- 00
CS t-
i**"** r***
O 0
o o
00
oo
T— r—
O O
O ^O
oo
O\ 00
mm
mm
00
00
p~* m
00
00
on ON
0 0
on m
o o
0 0
00
0 O
0 0
0 0
V V
t— «•*-»
00
00
0 0
0 0
V V
CM m
oo
0 0
O 0
O 0
CM CM
0 0
o o
o o
0 0
0
cso
^^ oo
O CM
00
CSCM
O ON
r^- m
on o
CS CM
o o
0 0
CM CM
OO
o o
oo
V V
cscs
00
00
oo
V V
cs
o
oo
oo
CS CM
00
00
oo
V V
c
•H
4-1
£
O
S PM
cn i
C/3 CO
33
H PM
(U
r-4 -t-
Ou 0)
B &
cO >•
CO H
co NO
m^o
CO
m OT
CM OH
i O &
-cs r-^cs r>.cs t^-cs r~.cs i— cs
OSS
^^
12 Cd
O 05
U H
W
CO
•>
-------
i
o
f H
in
M !5
xv
rH
00
•at ions (B
Concenti
Q
CN
>•
Q
>
Q
(!)
O
}j
jj
O
CO
OO O
O r-
o o
O 0
00
oo
00
CM CM
00
00
00
00
N/V
CM
i- O
O OO
O O
00
00
00
N/ \S
•3- OO
00
o o
o o
0 0
o o
o o
00
o o
oo
oo
co in
o oo r~« ON
00 *~
v*O CO
O O ON ON
o
00
CM O
O 00 OO O
O CM r-
ON
Mi
vO vo COCO
oo -d-
Om
in vO ^O ON O O
-J- CO CM CM OO
^^ r**^ o o
00 ^ oo m «— o
CM OO OO OO OO
ON ON in in
CM CM T- r- r- r~
O O OO CO O O
oo
00
OO^O OOvO OO^O r— r—
CM
> CM r^ CM
CM
CM
•U)
c
2
•3
I-l
rH
o
en
"O
rH 0
rH CO C
•H J3 i-l
00 -P N
• • •
vo r**» oo
CN CM CM
r- 1— ,—
CO
•U
P
cO
1 1
HJ
3
f-l
r-l
o
r-<
cO
c
o
•H
4J
c
0)
>
c
o
o
c
0
2
^,
4J
•r-l
c s
•r-l Jj
r-l .,-1
cO o C
^ r-l O
r-l CO r-l
CO O -H
s
9
•r-l
CO
cu
pj
00
cO
s
CO
o
•H
I-l
o
c
r;
a.
199
-------
i
o
o
SS H
M
-» *^
cO 3
4J r-l
5> ^
r-l O
r-l PH
O
PH rH
CO
C
C
4-
c
cu
^
C
C
cu
CO
cO
cu
w
00
T>
C
CO
r-l
•<-l
o
n-4
t—l
O
CO
TD
CU
T3
C
cu
a
CO
^
CO
r-l
CO
4->
O
4->
/-**
CO
4->
•H
g
0
TD
iJ
CO
'O
C
cO
4J
CO
^~s
33
CX
CO
cu o
4-> CX
^ s
co o
o o
ex
e o
O -r-4
O 4J
cO
j3r-i a
cO * O
H 3 4J
OOC S
ct) cO
cu e
S V4
3 M 3
4J 3 O
I O X!
CU^J I
C i **
OCO CM
I I
,-cn
O
O
cx
>>
H
CU
r-l
!
CO
V4
cu
J3
4J
CU
00
o
4-1
-o
(1)
4J
Vj
o
ex
cu
200
-------
vO
CM
1
J>
-! O
<3 0
H 0
W
S H
a
CO <
ID EH
0 25
rH O
U 0
W
05 O
O-i 25
>-< H
as co
0 0
25
O
o
w
CO
00
e
CO
c
o
•H
4J
CO
4-1
c
<
a
OJ
o
S-i
0
CO
Q)
I—I -t-
p, qj
e a
cd ^-
co H
e
CO CU
-l T3
*">
J_l
3
0
^j
a;
e
^
co
CM
rH
0)
y
O
•r-l
C
^
<^-
CM
e
g
c
0)
r-i
0)
OT
m
CM
c;
5
r-l -r-l
0) rH
> i— 1 O
rH Cti C
•lH J^ .rW
VI J-> N
\o r^ oo
CM CM CM
201
-------
3
c
•r-t
•P
C
O
O
i
25 W
i-i H
£
i
CO H
o
2
o
o
w
CO
e
rt >
U
alkalini
aluminum
•r-l
C
ammonia
barium
boron.
calcium
U
— 1
chemical
cu
-o
•H
S-<
0
r-l
-C
a
cobalt
-------
<(1
H
^
Q
O aS
21 ^-3
1-1 H
~ j <
13 CM ^2
QJ S
3*3 r K
<3 O
C CO 3
•rH """^
4-> CO >-4
O <3 O
O H U
s: H
ys u
CM CO 02
t-i O
CU U U
— ^ i3
J3 ^ O
cO 0-( 2:
H M
>> H
,
cfl
a
N
>^
cd
Q
o o o o
• • • •
OOOcMCJ\OO,
co H
e
CO cu
VJ O
4_) CJ
CO
>3''Cf cu cu cO cu 3 O
Cr* m *-< ca i i i
C ^3 J^ pS 4-1 -r-l
0^,00^3^ c^~i
O 00 >s co T-I U-^ cOcO
C3 C *" H O T? «™4 C 4-J 4J
OcOOX) O3 -ft •!-) O
LD LO
0 0
000*
r- V \/
v^
f -
-------
CO
Q
CN
e
CO
C
O
CO
CO
o
CN
<
H
Q
OS!
cO
03
a
o
c
o
en
m
"O
4)
, — f
-a
cO
H
CM D5
2
<; o
CO Z
t— 1
CO N4
r4 0
H CJ
2 H
CO <
3 H
O 2
M O
U 0
Cd
04 O
CM 2
M
>4 H
04 CO
O O
O
W
CO
CO
r-l -t-
PI gj
B a
cO >•
co H
r— i —
E
cO CU
VJ O
4-> O
CO
0 0
CN CN
CO
CO
H,
co
^J
C
4-1
C
4J
3
r-4
r-l
O
CM
cO
4-1
j3
r-l
r-l
O
CM
r-l
cO
C
o
•r-l
4J
C
cu
>
c
O
CJ
co
-a
•r-1
, — 1
O
co
-o
cu cu
CO T3
CO C
CU 0)
^ O-i
00 co
3
*t3 CO
C
03 i— I
cO
r-l 4J
•H O
O 4J
T
O
CN
, V
CO
4-1
•r-l
C
3
TJ
l_i
CO
T3
C
cO
4-1
CO
**-s
Sfi
CX
cO
00
CU
B
•H
4J
I
CU
o
T3
O
CJ
CU
cx
CU
1
CO
01
o
c
cu
u
cu
VJ
CD
4J
C
a)
T3
T3
CU
CO
CO
6
•r-l
r-H
C
O
•r-l
U
O
CU
4J
CU
Q
204
-------
V
U T)
CD C
,-t flj
O.
Li
01 41
U 1-4
fc. Eb
2 S?
3 P
M Z
CO
w
H
M
CO
cs
CO
1
V 1- O ~*
^ -H -H O
^ •< u w
= 3 u
S Sd g
*.3 o<3
|
Refinery
Wet Air
Pollution
Control
Oold
'recipltati
and
Filtration
Palladium
recipltatic
and
Filtration
I
C
0) ^
e -a o j:
ft. c o m
•H 03 r-i (0
1 fc3
205
-------
m
oo
33
P-t
Z
3
01
'/>
2
ril
s
en
rs
o
* S
0 Q
00 3
•r-l O
•a
I
Furnace I
w
•H
<
4J
QJ
3
C
O
•*•<
jj
3
i— <
O
c-
Control 1
f Refinery |
w
•H
(U
3
C
O
•H
j-i
3
r-<.
i-H
C
&4
Control
0
-1-4
4J
rt en
JJ
c
01
g -C O J=
0. C 0 «
^ to ^ to
3 [u 3
O"
[d
206
-------
Source
Water Tap
in Plant
Spent
Plating
Solutions
Furnace
Wet Air
Pollution
Control
Refinery
Wet Air
Pollution
Control
-0—»
Iron
Cementation
Tank
Vacuum
Pump Seal
Water
Collection
Pit
t
-®-»
Limestone
Pit
-/S?) ^ Discharge
Figure V-3
SAMPLING SITES AT SECONDARY PRECIOUS METALS PLANT C
207
-------
Refinery
Wet Air
Pollution
Control
Iron and
Copper
Cementation
Tanks
Discharge
T
Other
Process
Waste
Streams
I
Solids
Removed
Figure V-4
SAMPLING SITES AT SECONDARY PRECIOUS METALS PLANT D
208
-------
Source Water
Tap in
Administration
Building
/\
704
Spent
Plating
Solution
701
Spent Cyanide
Stripping
Solution
702
Spent Solution
From PGC Pro-
cess, After
Electrolytic
Recovery of
_ Gold
Ion Exchange
for Gold
Recovery
Contract Haul
as Hazardous
Waste
x\
703
Figure V-5
SAMPLING SITES AT SECONDARY PRECIOUS METALS PLANT E
209
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
Section V of this supplement presented data from secondary
precious metals plant sampling visits and subsequent chemical
analyses. This section examines that data and discusses the
selection or exclusion of pollutants for potential limitation.
The legal basis for the exclusion of toxic pollutants under
Paragraph 8(a) of the Settlement Agreement is presented in
Section VI of the General Development Document.
Each pollutant selected for potential limitation is discussed in
Section VI of the General Development Document. That discussion
provides information concerning where the pollutant originates
(i.e., whetfter 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 POTtf
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. Also
described is the analysis performed to select or exclude conven-
tional and nonconventional pollutants for limitation. The treat-
able concentrations used for the toxic metals were the long-term
performance values achievable by chemical precipitation, sedimen-
tation, and filtration. The treatable concentrations used for
the toxic organics were the long-term values achievable by carbon
adsorption (see Section VII of the General Development Document -
Combined Metals Data Base).
CONVENTIONAL AND NONCONVENTIQMAL POLLUTANT PARAMETERS
This study examined samples from the secondary precious metals
subcategory for three conventional pollutant parameters (oil and
grease, total suspended solids, and pH) and one nonconventional
pollutant parameter (ammonia).
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutants and pollutant
parameters selected for limitation in this subcategory are:
211
-------
ammonia
total suspended solids (TSS)
pH
Ammonia was found in 10 of 12 samples analyzed in concentrations
ranging from 0.24 to 5,060 mg/1. Five of the values recorded are
well above the treatable concentration of 32.2 mg/1, attainable
by the available treatment technology. Therefore, ammonia is
selected for limitation in this subcategory.
Oil and grease was analyzed for in 20 samples and was detected
below quantifiable levels 11 times. In only two cases was oil
and grease detected above its treatable concentration of 10 mg/1.
The two treatable values are 14 mg/1 and 37 mg/1 and they are
both for samples of refinery wet air pollution control. However,
five other samples of this waste stream show oil and grease well
below treatability. Because of the small number of sources in
which oil and grease was detected above its treatable concentra-
tion, oil and grease is not selected for limitation in this
subcategory.
Total suspended solids (TSS) concentrations ranging from 0 to
5,600 mg/1 were observed in the 20 samples analyzed for this
study. Nineteen of 20 samples exhibited concentrations above the
concentration attainable by the identified treatment technology
(2.6 mg/1). Furthermore, most of the specific methods for
removing toxic metals do so by precipitation, and the resulting
toxic metals precipitates should not be discharged. Meeting a
limitation on TSS also aids in removal of precipitated toxic
metals. For these reasons, total suspended solids are selected
for limitation in this subcategory.
The pH values observed in 14 of 20 samples were outside the 7.5
to 10.0 range considered desirable for discharge to receiving
waters. Six pH values ranged from 0.1 to 3.4. Six samples
ranged from 5.9 to 9.3. The remaining eight samples ranged from
10.9 to 12.6. Effective removal of toxic metals by chemical
precipitation requires careful control of pH. Therefore, pH is
selected for limitation in this subcategory.
TOXIC POLLUTANTS
The frequency of occurrence of the toxic pollutants in the raw
wastewater samples taken is presented in Table VI-1. These data
provide the basis for the categorization of specific pollutants,
as discussed below. Tabl^ VI-1 is based on the raw wastewater
data from streams 200, 189, 5, 201, 187, 4, 821, 233, 230, 228,
6, 701, 702, and 703 (see Section V). Treatment plant samples
were not considered in the frequency count.
212
-------
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed below were not detected in any
wastewater samples from this subcategory; therefore, they are not
selected for consideration in establishing limitations:
1. acenaphthene
2. acrolein
3. acrylonitrile
5. benzidene
8. 1, 2, 4-trichlorobenzene
9. hexachlorobenzene
12, hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1, 1,2,2-tetrachloroethane
16. chloroethane
17. bis(2-chloromethyl) ether (Deleted)
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether
20. 2-chloronaphthalene
22. parachlorometa cresol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-choroethoxy) methane
45. methyl chlpride (chloromethane)
46. methyl bromide (bromomethane)
49. trichlorofluoromethane (Deleted)
50. dichlorodifluoromethane (Deleted)
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
55. naphthalene
213
-------
56. nitrobenzene
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
67. butyl benzyl phthalate
72. benzo (a)anthracene (1,2-benzanthracene)
73. benzo (a)pyrene (3,4-benzopyrene)
74. 3, 4-benzof luoranthene
75. benzo(k)fluoranthene (1 1,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
78. anthracene
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene (w,e,-o-phenylenepyrene)
84. pyrene
85. tetrachloroethylene
87. trichloroethylene
88. vinyl chloride (chloroethylene)
89. aldrin*
90. dieldrin*
91. chlordane*
92. 4, 4'-DDT*
93. 4,4I-DDE(p,p'DDX)*
94. 4,4'-DDD(p,p'TDE)*
95. a-endosulfan-Alpha*
96. b-endosulfan-Beta*
97. endosulfan sulfate*
98. endrin*
99. endrin aldehyde*
100. heptachlor*
101. heptachlor epoxide*
102. a-BHC-Alpha*
103. b-BHC-Beta*
104. r-BHC (lindane)-Gamma*
105. g-BHC-Delta*
106. PCB-1242 (Arochlor 1242)*
107. PGB-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)*
214
-------
113. toxaphene*
116. asbestos
129. 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin (TCDD)
*We did not analyze for these pollutants in samples of raw
wastewater from this subcategory. These pollutants are not
believed to be present based on the Agency's best engineering
judgement which includes consideration of raw materials and
process operations.
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL QUANTIFICA-
TION LIMIT
The toxic pollutants listed below were never found above their
analytical quantification concentration in any wastewater samples
from this subcategory; therefore, they are not selected for
consideration in establishing limitations.
4. benzene
7. chlorobenzene
10. 1,2-dichloroethane
21. 2,4,6-trichlorophenol
24. 2-chlorophenol
34. 2,4-dimethylphenol
44. methylene chloride (dichloromethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
51. chlorodibroraomethane
54. isophorone
62. N-nitrosodiphenylamine
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
86. toluene
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individually
following the list.
57. 2-nitrophenol
123. mercury
215
-------
2-Nitrophenoi was found in only one sample at its quantification
limit. The reported concentration was 0.01 mg/1, which is also
the treatable concentration. Since the pollutant was not
detected above the concentration attainable by identified
treatment technology, 2-nitrophenol is not considered for
limitation.
Mercury was detected below its quantification limit in ZO out of
24 samples analyzed. The four values reported above the quanti-
fication limit ranged from 0.0003 mg/1 to 0.015 mg/1, which are
all below the concentration attainable by identified treatment
technology, which is 0.036 mg/1. Therefore, mercury is not
considered for limitation.
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The following pollutants were not selected for limitation on tne
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.
6. carbon tetrachloride
11. 1,1,1-trichloroethane
23. chloroform
65. phenol
66. bis(2-ethylhexyl) phthalate
117. beryllium
Although these pollutants were not selected for consideration in
establishing nationwide limitations, it may be appropriate, on a
case-by-case basis, for the local permitter to specify effluent
limitations.
Carbon tetrachloride was detected in only one of 12 samples
analyzed, at a concentration of 0.21 mg/1. The treatability
concentration is 0.01 mg/1 for this pollutant. Since it was not
detected in 11 other samples, the measurement may be regarded as
specific to the site and not characteristic of the subcategory as
a whole. Also, carbon tetrachloride cannot be attributed to
specific materials and processes used in the secondary precious
metals subcategory. Therefore, carbon tetrachloride is not con-
sidered for limitation.
1,1,1-Trichloroethane was detected in only one of 12 samples
analyzed, at a concentration of 0.015 mg/1. The treatabiiity
concentration is 0.01 mg/1 for this pollutant. Since it was not
detected in 11 other samples, the measurement may be regarded as
specific to the site and not characteristic of the subcategory as
a whole. Also, 1,1,1-trichloroethane cannot be attributed to
216
-------
specific materials and processes used in the secondary precious
metals subcategory. Therefore, 1,1,1-trichloroethane is not con-
sidered for limitation.
Chloroform was detected in four of 12 samples above its treatable
concentration of 0.01 mg/1. The four concentrations are ail 0.02
mg/1. All four samples have a lower concentration of chloroform
than the source water at the plant (0.05 mg/1). Chloroform can-
not be attributed to specific materials or processes used in the
subcategory, and very little removal of this pollutant can be
expected with treatment. Therefore, chloroform is not considered
for limitation.
Phenol was detected in only four of 12 samples above its treata-
ble concentration of 0.01 mg/1. The four concentrations are
0.013 mg/1, 0.17 mg/1, 0.45 mg/1, and 0.65 mg/1. The three sam-
ples with concentrations above 0.10 mg/1 were all taken at one
plant which was shut down indefinitely subsequent to being sam-
pled. Since phenol was not detected above its treatable concen-
tration in eight other samples, the measurements may be regarded
as specific to the site and not characteristic of the subcategory
as a whole. Phenol cannot be attributed to specific materials
and processes used in the secondary precious metals subcategory.
Also, because of the relatively low concentrations of phenol in
the raw waste compared with its treatable concentration, very
little removal of phenol can be expected with treatment. There-
fore, phenol is not considered for limitation.
Bis(2-ethylhexyl) phthalate was found above its treatable concen-
tration of 0.01 mg/1 in six of 12 samples. The concentrations
ranged from 0.02 mg/1 to 0.1 mg/1. This pollutant is not associ-
ated with specific processes used in the secondary precious
metals subcategory, but is commonly used as a plasticizer in
laboratory and field sampling equipment. Since the presence of
this pollutant may be attributed to sample contamination, bis(2-
ethylhexyl) phthalate is not considered for limitation.
Beryllium was found in only one out of 24 samples analyzed above
its treatable concentration of 0.20 mg/1. The sample had a con-
centration of 0.46 mg/1. Since it was not found above its treat-
able concentration in 23 other samples, the measurement may be
regarded as site-specific and not characteristic of the subcate-
gory as a whole. Although beryllium may be part of a raw mate-
rial, such as jewelry scrap, used in the secondary precious
metals industry, all the wastewater samples analyzed from plants
which process these raw materials showed beryllium present below
treatable concentrations. Therefore, beryllium is not considered
for limitation.
217
-------
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for further con-
sideration in establishing limitations and standards for this
subcategory. The toxic pollutants selected for further consid-
eration for limitation are each discussed following the list.
11 4. 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 its treatable concentration (0.47
mg/1) in seven of 24 samples. The quantifiable concentrations
ranged from 0.19 mg/1 to 5.2 mg/1. Since antimony was present in
concentrations exceeding the concentrations achievable by identi-
fied treatment technology, it is selected for consideration for
limitation.
Arsenic was detected above its treatable concentration (0.34
mg/1) in four of 24 samples. The quantifiable concentrations
ranged from 0.025 mg/1 to 2.4 mg/1. Since arsenic was present in
concentrations exceeding the concentrations achievable by identi-
fied treatment technology, it is selected for consideration for
limitation.
Cadmium was detected above its treatable concentration (0.049
mg/1) in 12 of 24 samples. The quantifiable concentrations
ranged from 0.0029 mg/1 to 7.6 mg/1. Since cadmium was present
in concentrations exceeding the concentrations achievable by
identified treatment technology, it is selected for consideration
for limitation.
Chromium was detected above its treatable concentration (0.07
mg/1) in 15 of 24 samples. The quantifiable concentrations
ranged from 0.012 mg/1 to 22 mg/1. Since chromium was present in
concentrations exceeding the concentrations achievable by identi-
fied treatment technology, it is selected for consideration for
limitation.
218
-------
Copper was detected above its treatable concentration (0.39 mg/1)
in 15 of 23 samples. The quantifiable concentrations ranged from
0.016 mg/1 to 5,000 mg/1. Since copper was present in concentra-
tions exceeding the concentrations achievable by identified
treatment technology, it is selected for consideration for
limitation.
Cyanide (total) was detected above its treatable concentration
(0.047 mg/1) in 17 of 24 samples. The quantifiable concentra-
tions ranged from 0.09 mg/1 to 9,897 mg/1. Since cyanide is used
as a raw material, and was present in concentrations exceeding
the concentrations achievable by identified treatment technology,
it is selected for consideration for limitation.
Lead was detected above its treatable concentration (0.08 mg/1)
in 17 of 24 samples. The quantifiable concentrations ranged from
0.02 mg/1 to 0.7 mg/1. Since lead was present in concentrations
exceeding the concentrations achievable by identified treatment
technology, it is selected for consideration for limitation.
Nickel was detected above its treatable concentration (0.22 mg/1)
in 17 of 24 samples. The quantifiable concentrations ranged from
0.008 mg/1 to 890 rag/1. Since nickel was present in concentra-
tions exceeding the concentrations achievable by identified
treatment technology, it is selected for consideration for
limitation.
Selenium was detected above its treatable concentration (0.20
mg/1) in three of 24 samples. The quantifiable concentrations
ranged from 0.019 mg/1 to 120 mg/1. Since selenium was present
in concentrations exceeding the concentrations achievable by
identified treatment technology, it is selected for consideration
for limitation.
Silver was detected above its treatable concentration (0.07 mg/1)
in 14 of 24 samples. The quantifiable concentrations ranged from
0.05 mg/1 to 26 mg/1. Since silver was present in concentrations
exceeding the concentrations achievable by identified treatment
technology, it is selected for consideration for limitation.
Thallium was detected above its treatable concentration (0.34
mg/1) in four of 22 samples. The quantifiable concentrations
ranged from 0.82 mg/1 to 1.2 mg/1. Since thallium was present in
concentrations exceeding the concentrations achievable by identi-
fied treatment technology, it is selected for consideration for
limitation.
219
-------
Zinc was detected above its treatable concentration (0.23 mg/1)
in 18 of 23 samples. The quantifiable concentrations ranged from
0.11 mg/1 to 10,000 mg/1. Since zinc is used in the cementation
process, and was present in concentrations exceeding the concen-
trations achievable by identified treatment technology, it is
selected for consideration for limitation.
220
-------
CO
H
i
i—i
>
H OS
z=> o
J O
o
O CQ
M CD
X CO
o as
'-
-------
uc
1 sis
o
£-3
4-1
C
o
u
H
53
H 05
:=> o
h4 O
i-4 W
O H
P* • Q
O 25
55 O
W O
»ZD Ed
ex en
Pd
05
OOOC5Ot3OOOOOOC3C5Oe3OC5C3OOOOC5CSOC5C3OOOOOC5C5
OOOOOOOOOOOOOOOOOOOOOOOOOOCJOOOOOOOO
ooooooooooooooooooooooooooooooooooo
QooooooooooooooooooooooooooooSooooo
^-
OJ y
Ci U4 -5 Co o
O T3 ^ U U
ss^ss
S^ 2-S-g
O XT O > x a,
u u
'•r?^
222
-------
c/3
T3
3
C
•r-4
4J
C
O
u
v«/
1
1— 1
^>
cu
t— 1
CO
H
H OS
3/—,
(_/
^ W
0 H
04 <;
CJ
o «
X CO
O OS
H CO W
t-J E~^
fa -l
g
•C+
U-l
°8'8
U — J M
0) £,>
g flT— »4
*£ S W
t|j
° i'S
l-i § N
m
*e ^1
J w-§
(1) C8 ^
^ tJ J3
rt i» r" s^
•^3 i; & ^^
cd c o ^N
« y jj^v
ai c of
VJ 0 B
HO ^5-
!»•• OJ C>J Csl C*4 CM C»4 C*J CM CM CM CM CM CM CM u"v CMCMOO OOOOOOOOOOOO
CMCMCMCVICMCMCMCMCMCMCMCMCMcMCMeMCMCM:*-* "*c?];?in;?ij3I'*;5'~J?[?ycM
vOvO^OvOvOvO^O^O*OvOvfivOvOvO*O\O>OvO-*'-3'O^OOOO— OOC5OOOC5OOOOC5
O OS
>< Q
U Z
z o
w o
o w
CX CO
w
03
fa
oooooooooooooooooogo
ooSoooo5oooooooooo.~o
) tvl (NC
>o o<
i in o o
' O .— CNJ O t/>
i O O O — O
C3OOOOOC3OOOOC5OOOOC3C5OC5—
223
-------
301
o
0) U C
"H3'
2 $ cu2
oj o —J ''
as-§
i 3\ in
o
U C
•5$ s
3£ S
CU O -
u 3 CO
CU O CU IJ
es ,-s —i jj
a) .Q
as eg
CO
CU
3
•o
i
•o -^ v^
5
4)
r-l
43
cC
H
OLLUTANTS
TEGORY
P-I <
u
O CQ
M»—j
»— '
X CO
O OS
H cow
J H
fa i
O Di
^^
X^
0 Z
Z 0
Pd O
5 w
cy co
w
OS
fa
3§
iw
O tr
J
u —
i v
U-l
0 §
SI
§!
T3
*
N
1
'•§
o o o
O O OJ
S CM f
i"S
U- 0) CsJ
5! ? >r
•S t»H
c •*
5 ^
3 2
"SI
CO 0
w o
H O
§
i _>
Analytical
laitlClcati
d-
^s
— 0 «
^•N
J3
§S
ui
•^-i
O vO
OOJp
s
mcentratli
/mo/TWa1)
^
'
s
i o_ q
f ^--'
C/5
£
CO
•o
CU a)
CO T)
SC
CU
u a.
aC co
•a co §
e «
3 5
C
a
J I
jj a.
6 S
^ —<
S -i
"S tS
-i C
jj O
a
CO
5
£
CO
s, a
JJ O
s -jj
~> ca
•u u
-1 y
^ s
s g
J 8
^ 11
a •-;
•rf J3
JJ CO
x JJ
,-1 CO
a)
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters from secondary pre-
cious metals plants. This section summarizes the description of
these wastewaters and indicates the level of treatment which is
currently practiced by plants in the secondary precious metals
subcategory 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 prin-
ciples 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 being applied to each of the
sources generating wastewater in this subcategory. As discussed
in Section V, wastewater associated with the secondary precious
metals subcategory is characterized by the presence of the toxic
metal pollutants, free and complexed cyanide, ammonia, and sus-
pended solids. The raw (untreated) wastewater data for specific
sources as well as combined waste streams are presented 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. Twenty-four plants in this
subcategory currently have combined wastewater treatment systems,
20 have chemical precipitation and sedimentation, and one of
these has chemical precipitation, sedimentation and pressure
filtration. One plant currently strips ammonia with air, and
eight plants currently treat for cyanide. Seven of the eight use
alkaline oxidation, and one plant precipitates cyanide with
ferrous sulfate. Three options have been selected for considera-
tion for BPT, BAT, NSPS, and pretreatment in this subcategory,
based on combined treatment of these compatible waste streams.
FURNACE WET AIR POLLUTION CONTROL
Air emission sources in secondary precious metals furnace opera-
tions include incinerator and smelting furnaces. Sixteen second-
ary precious metals producers control air emissions, using
various methods. These are:
225
-------
1. Dry baghouse - 11 plants, and
2. Wet scrubber - five plants.
Toxic organics, metals, cyanide, and suspended solids are present
at treatable concentrations in the wastewater produced by furnace
wet air pollution control. Two plants producing this wastewater
practice complete recycle. One practices partial recycle (>_90
percent). Two practice no recycle. Treatment methods used are:
1. iSlo treatment - one plant, and
2. Chemical precipitation and sedimentation - two plants.
RAW MATERIAL GRANULATION
Two of three plants reporting this waste stream discharge it.
The two plants do not practice recycle or treatment of this waste
stream. The non-discharging plant completely recycles this
water.
SPENT PLATING SOLUTIONS
Spent or contaminated cyanide solutions from electroplating shops
may have the precious metal values recovered by a precipitation
or electrolytic process. The waste stream is characterized by
treatable concentrations of toxic organics and metals, free and
complexed cyanide, and TSS. Treatment methods for this waste-
water consist of:
1. Total cyanide precipitation using ferrous sulfate -
one plant,
2. Free cyanide destruction using alkaline oxidation -
six plants,
3. Chemical precipitation and sedimentation - one plant,
and
4. Contractor disposal - four plants.
Four plants that have cyanide pretreatment also have chemical
precipitation and sedimentation end-of-pipe treatment. Ttie plant
which uses ferrous sulfate also uses alkaline oxidation for
cyanide treatment.
SPENT CYANIDE STRIPPING SOLUTIONS
Six plants use potassium or sodium cyanide solution to strip gold
away from scrap. Four plants employ contractor disposal methods
to achieve zero discharge of pp^nt stripping solution. This
wastewater contains toxic metals, free and complexed cyanide, and
TSS above treatable concentrations. One of the two discharging
plants destroys the free cyanide with chlorine gas (alkaline
226
-------
oxidation). The other plant destroys the free and complexed
cyanide with ferrous suifate, and then practices chemical
precipitation and sedimentation.
REFINERY WET AIR POLLUTION CONTROL
Scrubbers are used at 28 plants to control fumes from precipita-
tion and filtration processes. This wastewater contains treata-
ble concentrations of toxic metals, chloride, suifate, and
suspended solids. Twenty plants discharge this wastewater, five
of which practice no recycle, and 15 of which practice recycle of
75 percent or more. Eight plants do not discnarge this waste-
water. Three of these plants practice 100 percent recycle, and
five of them have this wastewater disposed of by a contractor.
At the 20 discharging plants, scrubber water is commonly combined
with other process wastewater and treated in a central treatment
facility. Treatment methods used are:
1. Chemical precipitation and sedimentation - seven plants;
2. Chemical precipitation, sedimentation, and filtration -
one plant; and
3. No treatment - 12 plants.
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH WATER
One plant recovers gold by a solvent extraction process, and
generates a raffinate waste stream and a wash water waste stream.
Toxic metals and TSS are expected to be found at treatable levels
in the raffinate and wash water. This waste stream is not
recycled. Treatment before discharge consists of neutralization
with caustic, but no solids are removed.
GOLD SPENT ELECTROLYTE
Wastewater discharges from electrolytic refining consist of spent
electrolyte solution. Of the three plants practicing electro-
lytic refining, one discharges wastewater. This wastewater is
expected to contain treatable concentrations of toxic metals,
ammonia, and TSS. This waste stream is not recycled. The one
discharging plant practices chemical precipitation and sedimen-
tation of the spent electrolyte prior to discharge. The other
two plants are zero discharge by means of contractor disposal.
227
-------
GOLD PRECIPITATION AND FILTRATION
Nineteen of 28 plants who produce gold by dissolving gold-
containing raw material in acid and then selectively precipitat-
ing it from solution discharge this waste stream. This waste-
water contains toxic metals, ammonia and TSS above treatable
concentrations. No plants reported recycling this waste stream
although two plants reported reuse of the waste stream. Treat-
ment methods for this wastewater consist of:
1. Chemical precipitation and sedimentation - 10 plants;
2. Chemical precipitation, sedimentation, and filtration -
one plant;
3. Contractor disposal - seven plants;
4. One hundred percent reuse - two plants; and
5. No treatment - eight plants.
PLATINUM PRECIPITATION AND FILTRATION
Fourteen of 18 plants who produce platinum by a dissolution and
selective precipitation process discharge tnis waste stream.
This wastewater is expected to contain toxic metals, ammonia, and
TSS above treatable concentrations. No plants reported recycling
this waste stream. Treatment methods for this wastewater consist
of:
1. Chemical precipitation and sedimentation - 10 plants
(one with ammonia air stripping);
2. Chemical precipitation, sedimentation, and filtration -
one plant;
3. No treatment - three plants; and
4. Contractor disposal - four plants.
PALLADIUM PRECIPITATION AND FILTRATION
Fourteen of 19 plants who produce palladium by a dissolution and
selective precipitation process discharge this waste stream.
This wastewater should contain toxic metals, ammonia, and TSS
above treatable concentrations. No plants reported recycling
this waste stream. Treatment methods for this wastewater consist
of:
1. Chemical precipitation and sedimentation - nine plants
(one with ammonia air stripping);
2. Chemical precipitation, sedimentation, and filtration -
one plant;
3. No treatment - four plants;
4. One hundred percent reuse - one plant; and
5. Contractor disposal - four plants.
228
-------
OTHER PLATINUM GROUP METALS PRECIPITATION AND FILTRATION
Two of three plants using a wet chemistry technique to produce
platinum group metals such as rhodium and iridium discharge this
waste stream. This waste stream is expected to contain toxic
metals, ammonia and TSS. Treatment methods for this wastewater
consist of:
1. Chemical precipitation and sedimentation - one plant,
2. No treatment - one plant, and
3. Contractor disposal - one plant.
SPENT SOLUTION FROM PGC SALT PRODUCTION
Two of three plants producing PGC salt from pure gold and
potassium cyanide solution discharge excess cyanide solution.
The two dischargers chlorinate the wastewater to destroy free
cyanide, and one practices chemical precipitation and sedimenta-
tion. The non-discharging plant achieves this status by
contractor disposal. The untreated wastewater contains toxic
metals, free and complexed cyanide, and TSS aoove treatable
concentrations.
EQUIPMENT AND FLOOR WASH
Three plants reported an equipment and floor wash waste stream
and two of these plants discharge it. This wastewater contains
toxic metals, ammonia, and TSS above treatable concentrations.
No plants reported recycling this waste stream. Both discharging
plants practice chemical precipitation and sedimentation. One of
the two plants air strips ammonia. The nondischarging plant uses
contractor disposal to achieve this status.
CONTROL AND TREATMENT OPTIONS CONSIDERED
Based on an examination of the wastewater sampling data, three
control and treatment technologies that effectively control the
pollutants found in secondary precious metals wastewaters were
selected for evaluation. These technology options are discussed
below.
OPTION A
Option A for the secondary precious metals subcategory requires
treatment technologies to reduce pollutant mass. The Option A
treatment scheme consists of ammonia steam stripping preliminary
treatment applied to the combined stream of gold precipitation
and filtration, platinum precipitation and filtration, palladium
precipitation and filtration, other platinum group metal precipi-
tation and filtration, and equipment and floor wash water; and
229
-------
cyanide precipitation preliminary treatment applied to the com-
bined stream of spent plating solution, spent cyanide stripping
solution, and spent solutions from PGC salt production. Prelimi-
nary treatment is followed by chemical precipitation and sedimen-
tation (lime and settle) treatment applied to the combined stream
of steam stripper effluent, cyanide precipitation effluent, and
the combined stream of all other wastewater. Chemical precipita-
tion is used to remove metals by the addition of lime or caustic
followed by gravity sedimentation. Suspended solids are also
removed by the process.
OPTION B
Option B for the secondary precious metals subcategory consists
of ammonia steam stripping, cyanide precipitation, chemical
precipitation, and sedimentation technology considered in Option
A plus control technologies to reduce the discharge of wastewater
volume. Water recycle of furnace and refinery scrubber water are
the principal control mechanisms for flow reduction.
OPTION C
Option G for the secondary precious metals subcategory consists
of the ammonia steam stripping, cyanide precipitation, in-process
flow reduction, and chemical precipitation and sedimentation
technology considered in Option B plus multimedia filtration
technology added at the end of the Option B treatment scheme.
Multimedia filtration is used to remove suspended solids, includ-
ing precipitates of metals, beyond the concentration attainable
by gravity sedimentation. The filter suggested is of the
gravity, mixed media type, although other forms of filters such
as rapid sand filters or pressure filters would perform satis-
factorily. 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.
230
-------
SECONDARY PRECIOUS METALS SUBCATEGORY
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
secondary precious metals subcategory and a description of the
treatment options and subcategory-specific assumptions used to
develop these estimates. Together with the estimated pollutant
reduction performance presented in Sections IX, X, XI, and XII of
this supplement, these cost estimates provide a basis for evalu-
ating 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 addi-
tion, this section addresses nonwater quality environmental
impacts of wastewater treatment and control alternatives, includ-
ing air pollution, solid wastes, and energy requirements, which
are specific to the secondary precious metals suocategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, three treatment options have been
developed for existing secondary precious metals sources. The
treatment schemes for each option are summarized below and
schematically presented in Figures X-1 through X-3.
OPTION A
Option A consists of ammonia steam stripping and cyanide pre-
cipitation preliminary treatment (where required), and chemical
precipitation and sedimentation end-of-pipe technology.
OPTION B
Option B consists of in-process flow reduction measures, ammonia
steam stripping and cyanide precipitation preliminary treatment
(where required), and chemical precipitation and sedimentation
end-of-pipe technology. The in-process flow reduction measures
consists of the recycle of furnace scrubber water and refinery
scrubber water through holding tanks.
OPTION C
Option C requires the in-process flow reduction measures of
Option B, ammonia steam stripping and cyanide precipitation
preliminary treatment, and end-of-pipe treatment technology
consisting of chemical precipitation, sedimentation, and multi-
media filtration.
231
-------
COST METHODOLOGY
A detailed discussion of the methodology used to develop the com-
pliance costs is presented in Section VIII of the General Devel-
opment Document. Plant-by-plant compliance costs have been
estimated for the nonferrous metals manufacturing category and
are presented in the administrative record supporting this regu-
lation. The costs developed for the proposed regulation are pre-
sented in Tables VIII-1 and VIII-2 for the direct and indirect
dischargers, respectively.
Each of the general assumptions used to develop compliance costs
is presented in Section VIII of the General Development Document.
Each subcategory contains a unique set of waste streams requiring
certain subcategory-specific assumptions to develop compliance
costs. The major assumptions specific to the secondary precious
metals subcategory are discussed briefly below.
(1) For overlap plants (i.e., secondary precious metals -
secondary silver or secondary precious metals -
secondary tungsten plants), costs and removal
estimates are apportioned on a flow-weighted basis.
The total flow used for flow-weighting costs includes
recycled floor wash water, whereas the total flow used
for flow-weighting removals does not include floor
wash water.
(2) A flow allowance for floor washing is assumed for each
plant on the basis of 1.0 liter per troy ounce of
precious metals, including silver, produced in the
refinery. The flow allowance is based on the rates
reported by the three plants supplying information
about this stream. Table V-13 shows water use rates
of 14.2, 1.0, and 0.97 liters per troy ounce. The
highest rate was omitted because it is more than 10
times the next highest rate. The flow allowance was
based on the average of the two lower rates.
(3) Floor wash water is obtained by recycling wastewater
treated by chemical precipitation and sedimentation
for all options. The recycle ratio is equal to the
flow of floor wash water divided by the total flow to
treatment.
(4) If a plant has a precipitation and filtration
operation for platinum, palladium, other platinum
group metals (PGM), or silver (from photographic raw
materials), we assume floor wash water requires
ammonia stripping to meet the proposed ammonia
limitations.
232
-------
(5) All sludge produced from chemical precipitation is
nonhazardous. All sludge produced from cyanide
precipitation is hazardous, per RCRA regulations.
(6) All precipitation and filtration wastewater (gold,
platinum, palladium, or other PGM) are assumed to
undergo cementation prior to entering waste treatment.
Zinc cementation is assumed unless iron cementation is
specifically noted as in-place. Costs for installing
and operating a cementation system are not included in
the cost estimates because cementation is not consid-
ered a wastewater treatment operation. Only the zinc
or iron raw waste values are changed by operating a
cementation process. The revised raw waste values
impact a plant's waste treatment cost.
(7) Ammonia stripping costs for plants having less than 50
liters per hour of water requiring stripping are based
on air stripping via agitation-aeration in the batch
chemical precipitation tank instead of steam strip-
ping. These costs include a blower, sparger and hood.
NONVJATER QUALITY ASPECTS
A general discussion of the nonwater quality aspects of the con-
trol 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 secondary
precious metals subcategory, including energy requirements, solid
waste and air pollution are discussed below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for the three options
considered are estimated at 5.11 x 106 kUTh/yr, 5.12 x 106
kWh/yr, and 5.19 x 10° ktfh/yr for Options A, B, and C, respec-
tively. Option B energy requirements are similar to those for
Option A. Because less water is being treated, energy costs for
lime and settle treatment are less; however, recycle equipment
such as holding tanks and pumps require additional energy, off-
setting the energy savings. Option C, which includes filtration,
is estimated to increase energy consumption over Option B by
approximately 1 percent. Option C represents roughly 8 percent
of a typical plant's electrical energy usage. It is therefore
concluded that the energy requirements of the treatment options
considered will not have a significant impact on total plant
energy consumption.
233
-------
SOLID WASTE
Sludge generated in the secondary precious metals subcategory is
due to the precipitation of metal hydroxides and cyanide using
lime and other chemicals. Sludges associated with the secondary
precious metals subcategory will necessarily contain quantities
of toxic metal pollutants. Wastes generated by secondary metal
industries can be regulated as hazardous. However, the Agency
examined the solid wastes that would be generated at secondary
nonferrous metals manufacturing plants by the suggested treatment
technologies and believes they are not hazardous wastes under the
Agency's regulations implementing Section 3001 of the Resource
Conservation and Recovery Act. The one exception to this is
solid wastes generated by cyanide precipitation. These sludges
are expected to be hazardous and this judgment was included in
this study. None of the non-cyanide wastes are listed specifi-
cally as hazardous. Nor are they likely to exhibit a character-
istic of hazardous waste. This judgment is made based on the
recommended technology of lime precipitation, sedimentation, and
filtration. By the addition of a small excess of lime during
treatment, similar sludges, specifically toxic metal bearing
sludges, generated by other industries such as the iron and steel
industry passed the Extraction Procedure (EP) toxicity test. See
40 CFR §261.24. Thus, the Agency believes that the wastewater
sludges will similarly not be EP toxic if the recommended
technology is applied.
Although it is the Agency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 GFR §262.11).
If these wastes identified should be or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's gener-
ator 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
regulation^ require transporters of hazardous waste to comply
with the manifest system to assure that the wastes are delivered
to a permitted facility. See 40 CFR §263.20 [45 FR 33151 (May
19, 1980), as amended at 45 FR 86973 (December 31, 1980)J.
234
-------
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464 [46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982)].
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open dump-
ing standards, implementing §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.
The Agency estimates that the proposed tfPT regulation for
secondary precious metals manufacturing facilities will generate
306 metric tons of solid wastes (wet basis) in 1982 as a result
of wastewater treatment. Proposed BAT will not significantly
increase sludge generation, however proposed PSES will add 1,450
metric tons of solid waste per year.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of ammonia steam strip-
ping, cyanide precipitation, chemical precipitation, sedimenta-
tion, and multimedia filtration. These technologies transfer
pollutants to solid waste and are not likely to transfer
pollutants to air.
At seven secondary precious metals plants, streams with treatable
concentrations of ammonia having flows less than 50 1/hr were
treated with air stripping for design and cost determination.
None of the waste streams were air pollution control streams.
The air stripping is accomplished by aeration and agitation in
the chemical precipitation batch tank, which includes a ventila-
tion hood. Air stripping is not a model treatment technology
because it simply transfers the ammonia from one medium to
another, whereas steam stripping allows for ammonia recovery, and
if desired, reuse. Air stripping was used in costing instead of
steam stripping because at such low flow, continuous operation of
steam stri'ppers is not possible. Therefore, the treatable
concentration for ammonia would be difficult to attain. The
Agency does not believe that under these circumstances (low flow,
non-air pollution control streams) that air stripping will create
an air quality problem.
235
-------
Table VIII-1
COST OF COMPLIANCE FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY
DIRECT DISCHARGERS
The costs for this subcategory cannot be presented here because
the data on which they are based have been claimed to be
confidential.
236
-------
Table VIII-2
COST OF COMPLIANCE FOR THE SECONDARY
PRECIOUS METALS SUBCATEGORY
INDIRECT DISCHARGERS
(March, 1982 Dollars)
Total Required Total
Option Capital Cost Annual Cost
A 1,392,000 950,000
B 1,325,000 928,000
C 1,419,000 984,000
237
-------
SECONDARY PRECIOUS METALS 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)(a)(A). BPT reflects
the existing performance by plants of various sizes, ages, and
manufacturing processes within the secondary precious metals
subcategory, as well as the established performance of the
recommended BPT systems. Particular consideration is given to
the treatment already in place at plants within the data base.
The factors considered in identifying BPT include the total cost
of applying the technology in relation to the effluent reduction
benefits from such application, the age of equipment and facili-
ties involved, the manufacturing processes employed, 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. 1176)).BPT focuses on end-of-pipe treatment rather
than process changes or internal controls, except where such
practices are common within the subcategory.
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 sam-
pled and the wastewaters analyzed. In making technical assess-
ments of data, reviewing manufacturing processes, and assessing
wastewater treatment technology options, both indirect and direct
dischargers have been considered as a single group. An examina-
tion of plants and processes did not indicate any process differ-
ences based on the type of discharge, whether it be direct or
indirect.
239
-------
As explained in Section IV, the secondary precious metals subcat-
egory has been subdivided into 13 potential wastewater sources.
Since the water use, discharge rates, and pollutant characteris-
tics of each of these wastewaters is potentially unique, effluent
limitations will be developed for each of the 13 subdivisions.
For each of the subdivisions, a specific approach was followed
for the development of BPT mass limitations. The first require-
ment 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 deter-
mined for each waste stream which could then be related to the
flow from the process to determine a production normalized flow.
Selection of the PNP for each process element is discussed in
Section IV. Each plant within the subcategory was then analyzed
to determine (1) which subdivisions were present, (2) the spe-
cific flow rates generated for each subdivision, and (3) the
specific production normalized flows for each subdivision. This
analysis is discussed in detail in Section V. Nonprocess waste-
waters such as rainfall runoff and noncontact cooling water are
not considered in the analysis.
Production normalized flows were then analyzed to determine the
flow to be used as part of the basis for BPT mass limitations.
The selected flow (sometimes referred to as the BPT regulatory
flow or BPT discharge rate) reflects the water use controls which
are common practices within the category. The BPT regulatory
flow is based on the average of all applicable data. Plants with
normalized flows above the average may have to implement some
method of flow reduction to achieve the BPT limitations.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the BPT
level of treatment technology. Section VII discusses the various
control and treatment technologies which are currently in place
for each wastewater source. In most cases, the current control
and treatment technologies consist of chemical precipitation and
sedimentation (lime and settle) technology and a combination of
reuse and recycle to reduce flow. Ammonia steam stripping is
applied to streams with treatable concentrations of ammonia.
Cyanide precipitation is applied to streams with treatable
concentrations of free and complexed 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 troy ounce of
production - mg/T.O.) were calculated by multiplying the BPT
regulatory flow (1/T.O.) by the concentration achievable by the
240
-------
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 waste-
water sources which are found at particular plants. Accordingly,
all the wastewater generated within a plant may be combined for
treatment in a single or common treatment system, but the efflu-
ent limitations for these combined wastewaters are based on the
various wastewater sources which actually contribute to the com-
bined flow. This method accounts for the variety of combinations
of wastewater sources and production processes which may be found
at secondary precious metals plants.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/T.O.) is a linic
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow and effluent concentration
achievable by the treatment technology and summed to derive an
appropriate limitation for each plant.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal estimates,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollution control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed BPT. See vJeyerhaeuser
Company v. Costle, 590 F.2d 1011 (D.G. Cir. 1978).
The methodology for calculating pollutant removal estimates and
plant compliance costs is discussed in Section X. Tables X-2 and
XI1-1 show the estimated pollutant removals for each treatment
option for direct and indirect dischargers. Compliance costs are
presented in Tables X-3 and XII-2.
BPT OPTION SELECTION
The technology basis for the BPT limitations is Option A, chemi-
cal precipitation and sedimentation technology to remove metals
241
-------
and solids from combined wastewaters and to control pH, ammonia
steam stripping to remove ammonia, and cyanide precipitation to
remove free and complexed cyanide. Chemical precipitation and
sedimentation technology is already in-place at 20 of the plants
in the subcategory including all three direct dischargers. One
plant has cyanide precipitation in-place. The technology bases
for steam stripping and cyanide precipitation are discussed
below. The pollutants specifically proposed for regulation at
BPT are copper, cyanide, zinc, ammonia, TSS, and pH.
Implementation of the proposed BPT limitations will remove annu-
ally an estimated 34,570 kg of toxic pollutants (which include
6.3 kg of cyanide), 490 kg of ammonia, and 11,200 kg of TSS.
The compliance costs for this subcategory are not presented here
because the data on which they are based have been claimed to be
confidential. The Agency has determined that the benefits
justify the costs for this subcategory.
More stringent technology options were not selected for BPT since
they require in-process changes or end-of-pipe technologies less
widely practiced in the subcategory, and, therefore, are more
appropriately considered under BAT.
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 manufac-
turing category provide a valid measure of this technology's per-
formance 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.
242
-------
The Agency has verified the proposed steam stripping performance
values using steam stripping data collected at a primary zir-
conium and hafnium plant which has raw ammonia levels as high as
any in the nonferrous metals manufacturing category. Data col-
lected by the plant represent almost two years of daily opera-
tions, and support the long-term mean used to establish treatment
effectiveness.
Cyanide precipitation is demonstated in the secondary precious
metals subcategory at one plant. Cyanide precipitation technol-
ogy is required for the secondary precious metals subcategory
because existing treatment within the subcategory does not effec-
tively remove cyanide. Most secondary precious metals plant use
alkaline oxidation to destroy free cyanide, but do not effec-
tively remove complexed cyanide. Cyanide precipitation is
directed at control of free and complexed cyanides in waste
streams within the secondary precious metals subcategory. This
subcategory collectively discharges approximately 557 kg/yr of
cyanide. The achievable performance is transferred from three
well-operated coil coating plants in the coil coating category,
and are contained within the public record supporting this docu-
ment. The Agency believes this technology, and the achievable
concentration limits, are transferable to the secondary precious
metals subcategory because raw wastewater cyanide concentrations
(prior to dilution with waste streams without cyanide) are of the
same order of magnitude in both categories. Further, no pollu-
tants were identified in secondary precious metals wastewater
that would interfere with the operation or performance of this
technology.
Several discharging plants within the secondary precious metals
subcategory use chlorine gas or hypochlorite solution to oxidize
cyanide in their wastewater. EPA considered chemical oxidation
using chlorine. Although the chlorine oxidation process can be
used effectively for wastewater containing predominantly free
cyanides and easily oxidizable cyanide complexes, the Agency
determined that precipitation with ferrous sulfate is more cost-
effective than chlorine oxidation for the removal of iron-cyanide
complexes which may be found in tne secondary precious metals
wastewater.
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
from analysis of the dcp. The discharge rate is used with tne
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 13 wastewater sources are discussed below and
243
-------
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 pro-
duction normalizing parameters, or PNPs , are also listed in Table
IX-1.
Section V of this supplement further describes the discharge flow
rates and presents the water use and discharge flow rates for
each plant by subdivision.
FURNACE WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate for furnace wet air pollution
control is 71.8 liters per troy ounce of precious metals, includ-
ing silver, incinerated or smelted, based on zero percent
recycle. This rate is allocated only for plants practicing wet
air pollution control for the furnace. Five plants reported this
wastewater, two of whom practice 100 percent recycle (plants 1094
and 1084). The BPT rate is based on the average water use rate
of two of the three remaining plants. Plant 1105 was omitted
because its water use rate was not reported, and its recycle rate
was not quantified precisely enough to back-calculate a water use
rate. The BPT rate is the average of 116 and 27.6 liters per
troy ounce. The distribution of wastewater rates for this waste
stream is presented in Section V (Table V-1).
RAW MATERIAL GRANULATION
The BPT wastewater discharge rate for raw material granulation is
0 liters per troy ounce of precious metals in the granulated raw
material. Of the 30 plants which use a dissolution and selective
precipitation process to recover precious metals, only three
plants reported using water to granulate the raw material. Of
the three, one plant practices 100 percent recycle. EPA proposes
zero discharge of pollutants from this waste stream, and solicits
comments. The two reasons for proposing zero discharge are that
27 plants are able to use a dissolution and selective precipita-
tion process and do not need to granulate their raw material with
water, and that one of the three plants that does use water does
not discharge it by means of 100 percent recycle. The discharge
rates for this waste stream are shown in Table V-2.
SPENT PLATING SOLUTIONS
The BPT wastewater discharge rate for spent plating solutions is
1.0 liter per liter of spent plating solution raw material. This
rate is applicable to those plants which recover gold and other
precious metals from spent or contaminated electroplaters solu-
tions which they receive as a raw material. The discharge rate
244
-------
is given in terms of volume of raw material because EPA believes
plants cannot control the concentration of precious metals in
this raw material, and should be allowed to discharge the entire
volume of solution coming into the plant, after recovering tne
precious metals. Only the volume of raw material solution should
be allowed to be discharged, and this is why a discharge rate of
1.0 liter per liter was chosen. The 12 plants with this subdivi-
sion are shown in Table V-3.
SPENT CYANIDE STRIPPING SOLUTIONS
The BPT wastewater discharge rate for spent cyanide stripping
solutions is 1.1 liters per troy ounce of gold recovered by
cyanide stripping. This rate applies to plants which recover
gold by stripping it away from a raw material, like electronic
scrap, with a cyanide-based solution, and then recovering the
gold from this solution. This rate is based on the rate reported
by the lower of the two discharging plants (1.1 liters per troy
ounce and 78.3 liters per troy ounce). The 78.3 liters per troy
ounce rate was not used in the calculation of the BPT flow rate
because the other four plants with this waste stream (but who do
not discharge it), all report wastewater generation rates less
than one-tenth of 78.3 liters per troy ounce. This can be seen
in Table V-4. The Agency believes 1.1 liters per troy ounce is
an achievable discharge rate, and solicits comments on this
selection.
EPA is also considering a BPT wastewater discharge rate of 3.7
liters per troy ounce for this waste stream. This rate is based
on the average of the lower five of the six rates reported for
this stream. Plant 1100 was omitted because of its excessive
water use. At promulgation, EPA will select a discharge rate
(1.1 or 3.7 liters per troy ounce) based on a variety of factors,
including public comments.
REFINERY WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate for refinery wet air pollution
control is 21.0 liters per troy ounce of precious metals, includ-
ing silver, produced in the refinery, based on zero percent
recycle. This rate is allocated only for plants practicing wet
air pollution control for acid or cyanide fumes in the refinery.
Twenty-eight plants reported tnis waste stream, five of which
practice zero percent recycle and discharge the wastewater (107,
42, 32.8, 6.8, and 2.4 liters per troy ounce). The BPT rate is
hased on the average of the lower four of these five dischargers.
The highest flow rate (107 liters per troy ounce) was omitted
from the BPT rate calculation because tnere is no reason to
believe this much water is needed for this operation in light of
rates from the other plants. Table V-5 shows the distribution of
245
-------
water use and discharge rates for refinery wet air pollution
control.
EPA is also considering a BPT wastewater discharge rate for
refinery wet air pollution control of 19.8 liters per troy ounce
of precious metals, including silver, produced in the refinery,
based on zero percent recycle. This rate is based on an average
water use calculation. Again excluding the highest water use
rate (107 liters per troy ounce) and the plants who did not
precisely quantify their recycle rates, the average water use
rate is 19.8 liters per troy ounce (average of 46.4, 42, 39.4,
32.8, 13.2, 7.2, 7.0, 6.8, 2.4, and 0.6 liters per troy ounce).
At promulgation, EPA will select a discharge rate (21.0 or 19.8
liters per troy ounce) based on a variety of factors, including
public comments.
GOLD SOLVENT EXTRACTION RAFFINATE AND WASH WATER
The BPT wastewater discharge rate for gold solvent extraction
raffinate and wash water is 0.63 liters per troy ounce of gold
recovered by solvent extraction. This discharge rate is allo-
cated only to plants which refine gold by a solvent extraction
process. The discharge rate is based on the rate reported by the
only plant with this process (0.63 liters per troy ounce), as
shown in Table V-6.
GOLD SPENT ELECTROLYTE
The BPT wastewater discharge rate for gold spent electrolyte is
0.0087 liters per troy ounce of gold recovered by electrolysis.
This rate only applies to plants which refine gold by electroly-
sis. The discharge rate is based on the lower of the two rates
reported for this waste stream (0.0087 liters per troy ounce), as
shown in Table V-7. The other flow rate (0.294 liters per troy
ounce) is more than 10 times higher than the selected BPT rate.
GOLD PRECIPITATION AND FILTRATION
The BPT wastewater discharge rate for gold precipitation and
filtration is 4.4 liters per troy ounce of gold precipitated.
This rate only applies to plants which refine gold by dissolving
gold-containing raw material in acid, and then recovering gold by
precipitation. Of the 28 plants using this process, nine plants
supplied insufficient information to calculate discharge rates,
two plants report 100 percent reuse of this water, and six plants
do not discharge this waste stream by means of contract hauling
(these plants have water use rates of 560.5, 69.1, 3.34, 0.815,
0.63, and 0.05 liters per troy ounce). The BPT discharge rate is
based on the average water use rate of 10 of the 11 discharging
plants (24.3, 7.98, 4.1, 2.65, 2.5, 1.86, 0.341, 0.312, 0.27, and
246
-------
0.144 liters per troy ounce). The plant reporting 404 liters per
troy ounces rate was not considered in the average because this
water use rate is almost 10 times that of the next highest plant.
Eight of the discharging plants meet the riPT rate. Water use and
discharge rates are presented in Table V-8.
EPA is also considering a BPT wastewater discharge rate for gold
precipitation and filtration of 3.5 liters per troy ounce of gold
precipitated. This rate is based on the average of the water use
rates reported, excluding the three plants with excessive flows
(plants 1034, 1100, and 1091). At promulgation, EPA will select
a discharge rate (4.4 or 3.5 liters per troy ounce) based on a
variety of factors, including public comments.
PLATINUM PRECIPITATION AND FILTRATION
The BPT wastewater discharge rate for platinum precipitation and
filtration is 5.2 liters per troy ounce of platinum precipitated.
This rate only applies to plants which refine platinum by dis-
solving it in acid or base, and recover it by precipitation. Of
the 18 plants using this process, 13 supplied insufficient infor-
mation to calculate discharge rates. Five plants reported
sufficient data (354, 30.2, 10.4, 4.5, and 0.58 liters per troy
ounce). Table V-9 presents the water use and discharge rates for
this waste stream. The BPT discharge rate is based on the
average of the three lowest water use rates. The 354 and 30.2
liters per troy ounce water use rates were omitted from the
average because there is no reason to believe this much water is
needed for this operation in light of the rates from the other
plants.
PALLADIUM PRECIPITATION AND FILTRATION
The BPT wastewater discharge rate for palladium precipitation and
filtration is 3.5 liters per troy ounce of palladium precipi-
tated. This rate only applies to plants which refine palladium
by dissolving it in acid or base, and then recovering it by
precipitation. Of the 19 plants using this process, 14 reported
insufficient data to calculate a water use rate. The BPT dis-
charge rate is based on the average of four of the five plants
reporting sufficient water use data. The highest flow (15.8
liters per troy ounce) was omitted because there is no reason to
believe this much water is needed for this operation. The water
use rates averaged are 4.58, 4.4, 3.4, and 1.53 liters per troy
ounce. These discharge rates are presented in Table V-10.
247
-------
OTHER PLATINUM GROUP METALS PRECIPITATION AND FILTRATION
The BPT wastewater discharge rate for other platinum group metals
(rhodium, iridium, osmium, and ruthenium) precipitation and fil-
tration is 5.2 liters per troy ounce of platinum group metals
precipitated. This rate only applies to plants which refine
these metals by dissolving them in either acid or base, and then
precipitating them. Three plants use this process and none
reported sufficient information to calculate water use or dis-
charge rates. This is shown in Table V-11. The BPT discharge
rate is therefore based on the platinum precipitation and
filtration BPT discharge rate derived from Table V-9. These two
subdivisions are expected to have similar flows because all five
metals (platinum, rhodium, iridium, osmium, and ruthenium) are
part of the platinum group, and should all be refined in a
similar manner.
SPENT SOLUTION FROM PGC SALT PRODUCTION
The BPT wastewater discharge rate for spent solution from the PGC
salt production process is 0.9 liters per troy ounce of gold
contained in PGC product. This rate applies only to plants which
manufacture a potassium gold cyanide salt product by reacting
pure gold with potassium cyanide solution. There are three
plants reporting this process, as shown in Table V-12. The
reported water use rates are 260 liters per troy ounce and 0.9
liters per troy ounce. The third plant provided insufficient
data to calculate a water use rate. The plant reporting 260
liters per troy ounce explained that part of that water is used
in a scrubber above the reaction vessel, and the two flow rates
(discharging excess solution and scrubber liquor) could not be
separated. It is likely that most of that plant's water dis-
charge is due to the scrubber. The plant reporting 0.9 liters
per troy ounce confirmed that its water discharge was due
entirely to the excess reaction solution. Because the data from
the plant reporting 260 liters per troy ounce could not be
apportioned between scrubber liquor and spent solution, the BPT
wastewater discharge is based upon 0.9 liters per troy ounce.
EQUIPMENT AND FLOOR WASH
The BPT wastewater discharge rate for equipment and floor wash is
0 liters per troy ounce of precious metals, including silver,
produced in the refinery. The BPT discharge rate is based on
recycle of treated effluent for use as raw water for equipment
and floor wash. In precious metals refineries, EPA realizes
there is a possibility of accidental leaks and spills which may
contain precious metals and silver, and need to be recovered by
washing the equipment and the floor. We believe that wastewater
treatment plant effluent can be recycled for this purpose,
248
-------
increasing the capacity of treatment but not the actual amount of
water discharged.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain pol-
lutant parameters for limitation. This examination and evalu-
ation was presented in Section VI. Six pollutants are selected
for limitation under BPT and are listed below:
120. copper
121. cyanide
128. zinc
ammonia (as N)
total suspended solids (TSS)
pH
EFFLUENT LIMITATIONS
The concentrations achievable by application of the proposed BPT
treatment are explained in Section VII of the General Development
Document and summarized there in Table VII-19. The achievable
treatment concentrations (both one-day maximum and monthly aver-
age 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 troy ounce of
product represent tne BPT effluent limitations and are presented
in Table IX-2 for each individual waste stream.
249
-------
I
X
0)
EH1
H
U
O
cn
en
H
cn
O
H-1
CJ
cu
O
p
cn
w
as
H
as
O
en
H
e>
05
Q
OS
•a
H
a
H
en
£
CQ
arameter
QJ
OC
C
•r-l
N
•H
rH
cO
E
VJ
O
•z;
C
o
4-1
O
3
"O
o
VJ
OH
M
co
rH
4J
cu
B
CO
3
O
•r-4
O
cu
Vj
cx
'JH
0
CO
cu
o
c
o
>.
O
VJ
H
VJ CU
0) O
cx c
3
W O
CU r*">
4-J O
~H A-l
DO
•
r—
r^>
VJ
o
cu
4-1
cO
VJ
cu
c
•H
o
c
•H
*
VJ
cu
>
rH
• rJ
co
00
c
•H -o
-a cu
3 ^
-H H
O cu
c e
•rJ CO
CU
4J
•rJ
CQ
rH
cO
4J
CU
s
CO —1
3 co
O -H
•H VJ
o cu
0) 4J
VJ cO
cxs
U-l £:
O cO
Vj
CO
cu -a
a cu
C 4J
3 cO
O rH
3
>, fj
O cO
Vj VJ
H 00
O
utions used
—4
O
CO
00
•rJ
4-1
CO
—1
CXrH
cO
4-) -H
c i"j
CU CU
CX4J
CO CO
s
'4-4
O £
cO
CO VJ
y^
CU cO
4J
•H CO
-4 CO
Jj
cu
4J VJ
•rJ CU
— 1 4J
•r-t
O —1
T-^
CU
cx
cx
•r-t
VJ
4_)
co
T~J
rH
O
00
'-M
O
CO
CU
o
c
3
o
!>>
O
H
r—
•
r—
CO
rH
cO
4_>
CU
S
CO
3
0
'r-l
0
cu
Vj
CX
M-l
o
to
CU
O
£J
3
O
>^
O
Vj
H
0
n
r—
CM
00
c
TJ
jj
-H
O
c
0
^
VJ
cu
c
•rJ
'-M
CU
VJ
c
•rJ
T3
CU
O VJ
3 cu
-o >
0 -H
VJ -H
CX CO
-Q
T5
cu
o
'O
0
VJ
cx
-o
rH C
o o
OO'H
4J
<4-l 0
O cO
J_4
CO 4-1
CU X
o cu
c
3 4J
o c
cu
r*"l S>
O-H
VJ O
EH co
ro
vO
*
O
T3
CU
o
3
-o
O
VJ
cx
T-J
rH
o
00
H-l
o
co
CO -H
CU CQ
o >>
C <"* ™>
3 0
O Vj
u
r*^ O
o cu
VJ rH
EH cu
oO
O
o
*
o
"O
CU
CO
• rJ
cx
•H
o
cu
VJ
cx
TD
rH
o
00
'4-4
O
CO
CU
O
q
o
r*S
O
VJ
H
^d1
«
~i
O
VJ
H
CM
«
i-O
c
o
o
c
o
o
cx
VJ
cO
CU
cu
o
cO
c
VJ
3
C
0
•H
4-1
CO
rH
3
C
CO
%j
00
rH
CO
•rJ
J_l
CU
4J
CO
B
!?
cO
05
co
C
O
•H
4J
^
rH
O
co
00
C
•rJ
4-1
CO
rH
cx
4J
c
cu
cx
en
CO
C
O
•H
4-1
3
1
•~i
O
co
00
C
•H
a
CX
•H
V-i
4J
CO
CU
"O
•r-l
C
cO
£>•>
O
4-1
C
cu
cx
cn
o
VJ
JJ
c
o
o
c
o
• H
4-)
3
— 1
— 1
o
cx
VJ
•rJ
cO
4J
cu
u
r*1
l_l
cu
c
•rJ
MH
cu
T3
CU
4J
cO
4-1
•H
CX
•H
o
cu
VJ
cx
e
•rJ
•a
CO
CO
cx
CO
CU
O
c
3
O
O
VJ
H
cu
u
CO
c
•H
'-W
'-W
CO
u
c
0
•H
4J
0
cO
VJ
4->
'yd
CU
4_>
PJ
CU
^>
— -j
O
CO
13
— 1
O
o
i_i
cu
4-J
CO
|5
rj
co
cO
T3
C
cO
CU
4-1
r*%
rH
0
VJ
4J
O
cu
rH
CU
4J
C
cu
cx
co
T3
rH
O
CJJ
c
o
•H
4J
cO
VJ
4J
rH
• H
M-J
13
C
cO
C
O
•rJ
4-1
CO
4-J
•H
CX
•H
o
CU
Vj
cx
TJ
rH
O
CJ
1
CO
VJ
4J
rH
•H
M-l
•^••j
C
cO
C
0
• H
4J
CO
4J
•H
CX
•r-t
O
0)
VJ
ex
B
3
C
•rJ
[ 1 f-J
cO O
rH -H
CM 4-1
1
CO
Vj
4J
-H
• H
'-M
13
0
cO
C
O
•rJ
4J
cO
4J
-H
CX
•H
o
CU
VJ
Q.
e
3
•H
-o
CO
,—1
rH
CO
fX,
£2
O
-rJ
4J
250
-------
-o
(U
d
•r-l
4J
C
o
o
X
OS
o
o
w
H
O
CO
CO
H
W
CO
o
M
O
OJ
o
z
o
u
w
CO
Ed
oj
O
rO CO
CO W
H H
w
o
5C
O
CO
W
H
H
CO
H
O-i
OC
e
•H
N
cO
e
o
25
c
o
o
-o
o
S-i CD
0) O
cxe
co O
jj o
ex
o
00
e
c
••-I
4J
CX
4J 4J
O cfl
O CX
•H
CO O
0) (V
O VJ
C CX
O CO
r-l
O 4J
-o
0)
4-1
c
o
o
o
00
O 4.)
o
eo d
0) T3
o o
C rJ
^ Cu
o
CJ
o
H
CM
o\
o
a
0)
q
01
- $-1
CO
•-< C
CO •!-<
4J
a; -a
e a»
o
CO 3
O O
•r-l J-J
o ex
0)
CO CO
a;
o oo
C C
d-r-i
O T3
o a
O
a
0)
tx
CO
1
cO
(U
Vj
4J
CO
(-(
(U
4J
CO
J3
(U
4->
CO
Cfl
^
i 1
CO
4J
0)
e
C
o
4-1
r— 1
CO
CJ
]^ I
x:
co
cO
£5
CX-l
d
o
}_4
00
s
d
c
•r-l
4J
CO
r-l
CX
J-l
OJ
X!
4J
0
.u
CO
jj
4J
r-l
• r-l
l|_|
T3
C
CO
p«
0
4J
CO
4J
•r-l
B
0
Jj
M-i
c
0
•r-l
4->
d
r-l
O
CD
jj
C
-------
Table IX-2
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(a) Furnace Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
incinerated or smelted
Copper 136.400 71.800
Cyanide (total) 20.820 8.616
Zinc 104.800 43.800
Ammonia (as N) 9,571.000 4,207.000
Total suspended 2,944.000 1,400.000
solids
pH Within the range of 7.5 to 10.0
at ail times
(b) Raw Material Granulation
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metal in the granulated
raw material
Copper 0.000 0.000
Cyanide (total) 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
Total suspended 0.000 0.000
solids
pH Within the range of 7.5 to 10.0
at all times
252
-------
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(c) Spent Plating Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/liter of spent plating solution used as a
raw material
Copper 1.900 1.000
Cyanide (total) 0.290 0.120
Zinc 1.460 0.610
Ammonia (as N) 133.300 58.600
Total suspended 41.000 19.500
solids
pH Within the range of 7.5 to 10.0
at all times
(d) Spent Cyanide Stripping Solutions
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by
cyanide stripping
Copper 2.090 1.100
Cyanide (total) 0.319 0.132
Zinc 1.606 0.671
Ammonia (as N) 146.600 64.460
Total suspended 45.100 21.450
solids
pH Within the range of 7.5 to 10.0
at all times
253
-------
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(e) Refinery Wet Air Pollution Control
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper 39.900 21.000
Cyanide (total) 6.090 2.520
Zinc 30.660 12.810
Ammonia (as N) 2,799.000 1,231.000
Total suspended 861.000 409.500
solids
pH Within the range of 7.5 to 10.0
at all times
(f) Gold Solvent Extraction Raffinate and Wash Water
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold produced by solvent extraction
Copper 1.197 0.630
Cyanide (total) 0.183 0.076
Zinc 0.920 0.384
Ammonia (as N) 83.980 36.920
Total suspended 25.830 12.290
solids
pH Within the range of 7.5 to 10.0
at all times
254
-------
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(g) Gold Spent Electrolyte
Pollutant or Maximum for Maximum for
Pollut an t Property Any One Day Monthly Average
mg/troy ounce of gold produced by electrolysis
Copper 0.017 0.009
Cyanide (total) 0.003 0.001
Zinc 0.013 0.005
Ammonia (as N) 1.160 0.510
Total suspended 0.357 0.170
solids
pH Within the range of 7.5 to 10.0
at all times
(h) Gold Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold precipitated
Copper 8.360 4.400
Cyanide (total) 1.276 0.528
Zinc 6.424 2.684
Ammonia (as N) 586.500 257.800
Total suspended 180.400 85.800
solids
pH Within the range of 7.5 to 10.0
at all times
255
-------
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(i) Platinum Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/troy ounce of platinum precipitated
Copper 9.880 5.200
Cyanide (total) 1.508 0.624
Zinc 7.592 3.172
Ammonia (as N) 693.200 304.700
Total suspended 213.200 101.400
solids
pH Within the range of 7.5 to 10.0
at all times
(j) Palladium Precipitation and Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of palladium precipitated
Copper 6.650 3.500
Cyanide (total) 1.015 0.420
Zinc 5.110 2.135
Ammonia (as N) 466.600 205.100
Total suspended 143.500 68.250
solids
pH Within the range of 7.5 to 10.0
at all times
256
-------
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(k) Other Platinum Group Metals Precipitation and
Filtration
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/troy ounce of other platinum group metals
precipitated
Copper 9.880 5.200
Cyanide (total) 1.508 0.624
Zinc 7.592 3.172
Ammonia (as N) 693.200 304.700
Total suspended 213.200 101.400
solids
pH Within the range of 7.5 to 10.0
at all times
(1) Spent Solution from PGC Salt Production
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/troy ounce of gold contained in PGC product
Copper ' 1.710 0.900
Cyanide (total) 0.261 0.108
Zinc 1.314 0.549
Ammonia (as N) 120.000 52.740
Total suspended 36.900 17.550
solids
pH Within the range of 7.5 to 10.0
at all times
257
-------
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY PRECIOUS METALS SUBCATEGORY
(m) Equipment and Floor Wash
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/troy ounce of precious metals, including silver,
produced in refinery
Copper
Cyanide (total)
Zinc
Ammonia (as N)
Total suspended
solids
pH
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Within the range of 7.5 to 10.0
at ail times
258
-------
I
X
t-4
01
ac
c
0
4J
(B
-U
•H
•O
c
CO
e
o
•H
a.
o
M
D-
£
to
Q-
C
O
•H
w
iH
£
c
c
0
1-1
a.
a
a>
D-
E
3
-o
ct)
,_!
CO
0.
tf
tn c
4-1 n)
a; h
iH
O. -H
O
O C
cfl
E
3 C
C 0
•H -H
>— 1 i~t
a. »H
i- -H
J= 0)
tn
CO
0
o
c
c
a.
3
cr
oS
O
O
w
H
<
O
CQ
O
CO
CO
Cd
S
CO
^
O
(—1
O
w
OS
Oi
>-<
oi
|