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SUMMARY OF DATA PRESENTED IN THE BACKGROUND
DOCUMENT FOR EFFLUENT LIMITATIONS GUIDELINES AND
u-x STANDARDS - ORE MINING AND DRESSING POINT SOURCE
V CATEGORY
October 1993
U.S. Environmental Protection Agency
Office of Solid Waste
Mining Waste Section
Washington D.C. 20460
US EPA Headquarters Library
Mail code 3404T
1200 Pennsylvania Avenue NW
Washington, DC 20460
20^366-0556
ttlL-
EPA Headquarters Library
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DISCLAIMER
The mention of company or product names is not to be considered an endorsement by
the U.S. Government or by the U.S. Environmental Protection Agency (EPA). Any
opinions, findings, and conclusions expressed are those of the authors and not necessarily
those of the U.S. EPA.
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SUMMARY OF DATA PRESENTED IN THE BACKGROUND DOCUMENT FOR EFFLUENT
LIMITATIONS GUIDELINES AND STANDARDS -
ORE MINING AND DRESSING POINT SOURCE CATEGORY
The Ore Mining and Dressing Category bcludes extraction and beneficiation operations in the hard rock and
mineral mining sectors. These sectors include: Iron, Copper, Lead, Zinc, Gold, Silver, Molybdenum,
Aluminum, Tungsten, Nickel, Vanadium, Mercury, Uranium, Antimony, Titanium, and Platinum. In the
early 1980's, EPA conducted a study of wastewaters generated at ore mining and dressing sites to support
development of national effluent guidelines to be included in NPDES permits issued for these facilities. The
results of this study, including wastewater sampling and analysis data, are presented in the "Development
Document for Effluent Limitations Guidelines and Standards for the Ore Mining and Dressing Point Source
Category," EPA 440/1-82/061, November 1982.
The EPA's Office of Solid Waste has recompiled the data contained in the effluent guideline for possible use
in its effort to develop a rational mining program. Data contained in this report is taken from the effluent
guideline document and does not represent new research. Further, it should be noted that the data
represented has not been reviewed for quality control/quality assurance. The source documents detailing
sampling methodolgies and protocols were not consulted for this review.
In 1982, there were over 500 known major active ore mines and over ISO active ore milling operations in the
U.S. Approximately two-thirds of these mines and mills were existing point source dischargers, the
remainder discharged no process wastewater.
The data presented in the Development Document are divided by sector (or group of sectors) and further
subdivided according to type of operation (mining, milling, etc.). The specific types of operations within each
sector are listed in Attachment 1 (Table IV-1, page 118 of the Development Document).
Data gathering for the ore mining and dressing category was conducted over several years through the
following activities:
(1) Screening and verification sampling and analysis programs
(2) Engineering cost site visits
(3) Supporting data from EPA regional offices
(4) Treatability studies (13 conducted)
(5) Industry self-monitoring sampling
(6) Best Practicable Technology database
(7) Placer study
(8) Titanium sand dredges study
(9) Uranium study
(10) Solid waste study
The parameters analyzed for include:
Organics, see Attachment 2 (All 114 specific organics as listed in Table V-l pages 142-146,
attached)
Total Phenolics, see Attachment 3 (4AAP)1
Metals (13 metals listed in Table V-2 page 147 attached)
1 4AAp - 4 Amino Anti Pyrine, a reagent designation of use in analysis of total phenolics.
1
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Total and dissolved analyses performed
Cyanide (Total analyses only)
Asbestos
Total Fibers
Chrysotile
Conventional Pollutants:
Total suspended solids (TSS)
pH
Non-Conventional Pollutants:
Temperature
Volatile Suspended Solids (VSS)
Chemical Oxygen Demand (COD)
Total Organic Carbon (TOC)
Radium - 226 Total and dissolved
Total Pbenolics (4AAP)
Total Settleable Solids
A narrative description of the results of wastewater characterization for each process is included on pages
155-165 of the Development Document (see Attachment 4). This description provides such information as
pollutants found at elevated levels, potential pollutants found at specific types of plants, and impacts of
treatment technologies. The raw and treated (see narrative discussion, 155 - 165) wastestream pollutant data
are summarized in greater detail for each sector and process category in the attached tables. An index of
the Attachment 4 data included in these tables is as follows:
Category
Reference Pages for
Sampling and Analysis Data
Ore Mining
Data Summary for All Subcategories
Ore Milling
Summary of Reagent Use in Ore Flotation Mills
Iron
Mining - Mine Drainage
Milling - Physical and/or Chemical
Copper /Lead/Zinc/Gold/Silver /Platinum/Molybdenum
Mining - Mine Drainage
Milling - Cyanidation
Milling - Flotation
Milling - Heap/Vat/Dump
Copper/Lead/Zinc/Gold/Silver/Platinum/Molybdenum
Milling - Gravity Sep
Aluminum
Mining - Mine Drainage
166-170
187-192
171
172
173
174
175
176
177
178
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Category
Reference Pages for
Sampling and Analysis Data
Ore Mining
Data Summary for All Subcategories
Tungsten
Milling
Mercury
Milling - Flotation
Uranium
Mining - Mine Drainage
Milling - Arid Location
Titanium
Mining - Mine Drainage
Milling - with Dredge Mining
Vanadium
Mining
Milling Flotation
166-170
179
180
181
182
183
184
185
186
Table 1 provides a list of the applicable standards for many of the contaminants detected in ore processing
wastewater. This Table was included to assist the reader in assessing the levels of specific pollutants
detected in the wastewaters.
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TABLE 1
APPLICABLE STANDARDS FOR CONTAMINANTS DETECTED IN
ORE PROCESSING EFFLUENT
Constituent of Concern
pH
Flouride
Chloride
Sulfate
Cadmium
Barium
Lead
Aluminum (pH 6.5 - 9.0 s.u.)
Asbestos
Turbidity
Nitrate
Sulfide
Chromium
Iron
Manganese
Zinc
Radium
Maximum Allowable Level (in
mg/1 except where noted)
6.5 - 8.5 s.u.
4
250
250
0.010
1.0
0.05
0.05
7 MFL2
1NTU
10
2 ug/1 (criterion continuous
concentration)
0.05
0.3
0.05
5
5pCi/l
Regulation
NSDWR
NPDWR
NSDWR
NSDWR
NPDWR
NPDWR
NPDWR
NSDWR
NPDWR
NPDWR
NPDWR
NSDWR
NPDWR
NSDWR
NSDWR
NSDWR
NPDWR
NPDWR = National Primary Drinking Water Regulations
NSDWR = National Secondary Drinking Water Regulations
MFL = Million Fibers per Liter
NTU = National Turbidity Units
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ATTACHMENT 1
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TABLE IV-1. PROPOSED SUBCATEGORIZATION FOR BAT - ORE MINING AND
DRESSING
SUBCATEGORY
Iron Ore
Copper, Lead, Zinc. Gold,
Silver,
Molybdenum Ores
Aluminum Ore
Tungrten Ore
Nickel Ore
Vanadium Ore*
Mercury Ore
Uranium Ores
Antimony Ores
Titanium Oret
Platinum Ore
SUBDIVISION
Mine Drainage
Mills
Mine Drainage
Milli or Hydro-
metallurgical
Benefication
Mine Drainage
Mine Drainage
Mills
Mine Drainage
Mill
Mine Drainage
Mills
Mine Drainage
Mills
Mine Drainage
Mills, Mines and Mills
or In-Situ Mines
Mine Drainage
Mills
Mine Drainage
Mills
Mills with Dredge
Mining
..Mine Drainage
Ml 1 IS
PROCESS
Physical and/or Chemical Benefictation
Physical Beneficiation Only (Mesabi Range)
Cyanidation or Amalgamation
Heap, Vat, Dump, In-Situ Leaching (Co)
Froth Flotation
Gravity Separation Methods (ind. Dredge, Placer,
or other physical separation methods; Mine
Drainage or mines and mills)
(Physical Processes)
Ore Leaching
Gravity Separation, Froth Flotation, Other
Methods
Flotation Process
*vanadmm extracted from non-radioactive ores
118
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ATTACHMENT 2
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Table V-l
TOXIC ORGANICS
Compound Name
1. *acenaphthene (B)***
2. *acrolein (v)***
3. *acrylonitrile (V)
4. *benzene (V)
5. *benzidene (B)
6. *carbon tetrachloride (tetrachloromethane) (V)
*Chlorinated benzenes (other than dichlorobenzenes)
7. chlorobenzene (V)
8. 1,2,4-trichlorobenzene (B)
9. hexachlorobenzene (B)
*Chlorinatedethanes(including 1,2-dichloroethane,
1,1,1-trichloroethane and hexachloroethane)
10.
11.
12.
13.
14.
15.
16.
(V)
1,2-dichloroethane
1,1,1-trichlorethane
hexachlorethane (B)
1,1-dichloroethane (V)
1,1,2-trichloroethane
(V)
1,1,2 , 2- t etrachloroethane
chloroethane (V)
(V)
(V)
*Chloroalkyl ethers (chloromethyl, chloroethyl and
mixed ethers)
17. bis (chloromethyl) ether (B)
18. bis (2-chloroethyly) ether (B)
19. 2-chloroethyl vinyl ether (mixed) (V)
^Chlorinated naphthalene
20. 2-chloronaphthalene (B)
^Chlorinated phenols (other than those listed elsewhere;
includes trichlorophenols and chlorinated cresols)
21. 2,4,6-trichlorophenol (A)***
22. parachlorometa cresol (A)
23. ^chloroform (trichloromethane)
24. *2-chlorophenol (A)
(V)
142
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Table V-l (Continued)
TOXIC ORGANICS
*Dichlorobenzenes
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
*Dichlorobenzidine
(B)
(B)
(B)
28. 3,3'-dichlorobenzidine (B)
*Dichloroethylenes (1,1-dichloroethylene and
1,2-dichloroethylene)
29. 1,1-dichloroethylene (V)
30. 1,2-trans-dischloroethylene (V)
31. *2,4-dlchlorophenol (A)
*Dichloropropane and dichloropropene
32. 1,2-dichloropropane (V)
33. 1,2-dichloropropylene (1,3-dichloropropene) (V)
34. *2,4-dimenthylphenol (A)
*Dinitrotoluene
35. 2,4-dlnltrotoluene (B)
36. 2,6,-dinitrotoluene (B)
37. *l,2-diphenylhydrazine (B)
38. *ethylbenzene (V)
39. *fluoranthene (B)
*Haloethers (other than those listed elsewhere)
40. 4-chlorophenyl phenyl ether (B)
41. 4-brotnophnyl phenyl ether (B)
42. bis(2-chloroisopropyl) ether (B)
43. bis(2-chloroethoxy) methane (B)
*Halonethanes (other than those listed elsewhere)
44. methylene chloride (dichloromethane) (V)
45. methyl chloride (chloromethane) (V)
46. methyl bromide (bromomethane) (V)
47. bromoform (tribromomethane) (V)
48. dichlorobromomethane (V)
143
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Table V-l (Continued)
TOXIC ORGANICS
49. trichlorofluoromethane (V)
50. dichlorodifluoromethane (V)
51. chlorodibroraomethane (V)
52. *hexachlorobutadiene (B)
53. *hexachlorocyclopentadiene (B)
54. *isophorone (B)
55. *naphthalene (B)
56. *nitrobenzene (B)
*Nitrophenols (including 2,4-dinitrophenol and dinitrocesol)
57. 2-nitrophenol (A)
58. 4-niCrophenol (A)
59. *2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
*Nitrosamines
(A)
(A)
61. N-nitrosodimethylamine (B)
62. N-nitrosodiphenylataine (B)
63. N-nitrosodi-n-propylamine (B)
64. *pentachlorophenol (A)
65. *phenol (A)
*Phthalate esters
66. bis(2-ethylhexyl) phthalate (B)
67. butyl benzyl phthalate (B)
68. di-n-butyl phthalate (B)
69. di-n-octyl phthalate (B)
70. diethyl phthalate (B)
71. dimethyl phthalate (B)
*Polynuclear aromatic hydrocarbons
(B)
72. benzo (a)anthracene (1,2-benzanthracene)
73. benzo (a)pyrene (3,4-benzopyrene) (B)
74. 3,4-benzofluoranthene (B;
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene (B)
77. acenaphthylene (B)
78. anthracene (B)
79. benzo(ghi)perylene (1,12-benzoperylene) (B)
80. fluorene (B)
81. phenathrene (5)
(B)
144
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Table V-l (Continued)
TOXIC ORGANICS
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene) (B)
83. indeno (1,2,3-cd)(2,3,-o-phenylenepyrene) (B)
84. pyrene (B)
85. *tetrachloroethylene (V)
86. *toluene (V)
87. *trichloroethylene (V)
88. *vinyl chloride (chloroethylene) (V)
Pesticides and Metabolites
89. *aldrin (P)
90. *dieldrin (P)
91. *ch'lordane (technical mixture and metabolites) (P)
*DDT and metabolites
92. 4,4'-DDT (P)
93. 4,4'-DDE(p,p1DDX) (P)
94. 4J4'-DDD(p,plTDE) (P)
*endosulfan and metabolites
95. a-endosulfan-Alpha (P)
96. b-endosulfan-Beta (P)
97. endosulfan sulfate (P)
*endrin and metabolites
98. endrin (P)
99. endrin aldehyde (P)
*heptachlor and metabolites
100. heptachlor (P)
101. heptachlor epoxide (P)
*hexachlorocyclohexane (all isomers)
J°2. a-BHC-Alpha (P) (B)
}°3- b-BHC-Beta (P) (V)
J04. r-BHC (lindane)-Gamma (P)
iQ5. g-BHC-Delta (P)
145
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Table V-l (Continued)
TOXIC ORGANICS
*polychlortnated biphenyls (PCB's)
106. PCB-1242 (Arochlor 1242) (P)
107. PCB-1254 (Arochlor 1254) (P)
108. PCB-1221 (Arochlor 1.221.) (P)
109. PCB-1232 (Arochlor 1232) (P)
110. PCB-1248 (Arochlor 1248) (P)
111. PCB-1260 (Arochlor 1260) (P)
112. PCB-1016 (Arochlor 1016) (P)
113. *Toxaphene (P)
114. **2,3,7,8-tctrachlorodibenzo-p-dioxin (TCDD)
^Specific compounds and chemical classes as listed In the
consent degree.
**This compound was specifically listed in the consent degree
***B » analyzed in the base-neutral extraction fraction
V » analyzed in the volatile organic fraction
A « analyzed in the acid extraction fraction
146
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ATTACHMENT 3
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Table V-2
TOXIC METALS, CYANIDE AND ASBESTOS
1. *Antimony (Total)
2. *Arsenic (Total)
3. *Asbestos (Fibrous)
4. *Berylliura (Total)
5. *Cadmium (Total)
6. *Chromium (Total)
7. *Copper (Total)
8. *Cyanide (Total)
9. *Lead (Total)
10. *Mercury (Total)
11. *Nickel (Total)
12. *Seleniun> (Total)
13. *Silver (Total)
14. *Thallium (Total)
15. *Zinc (Total)
*Specific compounds and chemical classes as listed in the
consent degree.
147
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ATTACHMENT 4
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SECTION VI
W ASTEWATER CHARACTER I Z AT I ON
The data base developed during the sampling program described in
Section V is presented in Supplement A and summary tables are
presented and discussed in this section. Also, a summary of
reagent usage at flotation mills, the largest users of mill
process chemicals, is presented to evaluate mill reagents as
potential sources of toxic pollutants. Special circumstances,
such as, the presence of certain toxic pollutants in mine water
as a result of backfilling mines with mill tailings, are
discussed at the end of this section.
SAMPLING PROGRAM RESULTS
The analytical results of the nine sampling programs discussed in
Section V are presented in Supplement A and were entered into a
computerized data base. Using this data base, summary data
tables were generated for the entire category; and each
subcategory, subdivision, and mill process (Tables VI -1 through
Vl-18, which may be found at the end of this section). These
tables include raw and treated wastewater data; and the range of
pollutant concentrations observed is indicated by the mean and
median values, and the 90 percent and maximum values (defined
below) .
All Subcateqories Combined
Table Vl-l summarizes the BAT data base for all .the mines and
mills in all subcategories in the ore mining and dressing point
source category. . As indicated by the table, only 27 of the toxic
organics were detected in the category's treated wastewater.
Organic compounds are not found naturally with metal ores.
Introduction of organics during froth flotation mill processing
is discussed later in this section. Otherwise, the discussion of
toxic organics is left to Section VII, Selection of Pollutant
Parameters .
Toxic metals are naturally associated with metal ores and all of
the 13 toxic metals were found in wastewater from the category.
The concentrations of each metal varied greatly, as expected for
such a diverse category. Cyanide and asbestos, also toxic
Parameters, were observed in many samples and in varied
concentrations.
conventional parameters observed were primarily those
t|gulated by BPT effluent guidelines, that is TSS and pH. The
*5S values are very high in many raw samples because tailings
sampies which typically run in the tens of thousands of mg TSS/1
included in "raw" samples. Effluent TSS values vary, but are
low indicating good solids settling characteristics.
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Values of pH vary, but are often in the alkaline range (7 to 1
This is because several mill processes operate at elevated pH
As indicated by discussions in Section III, pH, TSS, and metals
values are closely allied. The solubility of many metals varies
greatly with pH, and the status of the metals (dissolved v.
solubilized) affects the concentration of TSS. This relationship
is used by the industry for ore beneficiation and for wastewater
treatment.
Nonconventional parameters such as COD, TOC, volatile suspended
solids (VSS), and iron were also analyzed for many samples. The
concentrations of the organic related parameters, COD, TOC, and
VSS, were always low. Any organic compounds added in mill
processes are not indicated by these tests which are designed to
measure relatively large masses of organics (in the mg/1 range at
a minimum). Iron is common in metal ores and the summary table
reflects this.
The entire BAT data set is discussed below by subcategory,
subdivision, and as a mill process or mine drainage, and these
discussions more completely characterize mine/mill wastewaters.
In general it can be noted from Table VI-1 that organic compounds
are not the major concern in this category (a point discussed
thoroughly in Section III), metals are prevalent, pH values are
generally alkaline, and cyanide and asbestos are often present.
Iron Subcategory, M i ne Drainage Subdivision
Table VI-2 summarizes the data for iron mines. Many of the toxic
metals were not detected in the one or two available samples;
arsenic (.005 mg/1) copper (.090 and 120 mg/1), and zinc (.018
and .030 mg/1) are the exceptions. Asbestos fibers, both total
and chrysotile, were detected in relatively small amounts
compared to the rest of the category (see Table VI-1}.
Generally, (comparing Tables VI-1 and VI-2) iron mine water is
characterized by low pollutant levels. This is true of most mine
water and is the reason for separate mine and mill subdivisions.
Iron Subcateqory, Mill Subdivision, Physical and/or Chemical Mill
Processes
As indicated in Table VI-3, several of the toxic metals were
present in the one or two raw samples taken, but most are removed
by existing treatment technologies (sedimentation) and were not
detected in discharge samples. Copper is the least affected by
current treatment methods. Asbestos was detected in relatively
high concentrations in the raw sample (compared to Table VI-1),
and in lower concentrations in the discharged sample. This indi-
cates that current treatment methods are removing a portion of
the asbestos; a conclusion supported by Table VI-3. The COD,
VSS, and TOC (indicators of gross organic pollution) are somewhat
higher than the rest of the industry (compared to Table VI-1)
but they are effectively removed by current technologies. Ir
156
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was detected in one raw sample, as expected for iron mills, but
was below detection in the discharge water. Several toxic
metals, asbestos, TSS, and some npnconventional parameters were
found in the raw wastewater of iron mills, but these parameters
were reduced during treatment and many do not appear in the
discharge water.
Copper/Lead/Zinc/Gold/Silver/Molybdenum
Drainage Subdivision
Subcategory,
Mine
This subcategory includes more mines than any other subcategory
and more samples are available for characterization than for
other subcategories. As shown in Table VI-4, all of the toxic
metals were detected at least four times in sixteen raw samples.
High median concentrations (relative to the other metals
detected) of antimony, arsenic, cadmium, chromium, copper, lead,
nickel, thallium, and zinc are shown in Table VI-4 for raw mine
drainage. In the discharged water, however, the metals
concentrations are lower, with the median values ranging from not
detected to 280 ug/1 (zinc).
Cyanide, asbestos, and phenolics are other toxic parameters
detected in this subdivision. Cyanide is used in the froth flo-
tation process and-backfilling mines with mill tailings can cause
cyanide to pollute the mine water. Asbestos, being a mineral, is
found with many metal ores, although the concentrations reported
in Table VI-4 are relatively low (compared to Table VI-1) and
have a small range for samples taken at many types of mines.
Phenolics were detected at low concentrations.
Copper/Lead/Z i nc/S i1ver/Go1d/Mo1ybdenum
Mill Process
Subcateqorv, Cyanidation
This subdivision was regulated as no discharge of process
wastewater in BPT effluent guidelines, therefore, few samples
were taken in BAT sampling programs and no discharge samples were
taken. It can be seen from Table VI-5 that many toxic para-
meters, including cyanide, were found in high concentrations in
this mill water; thereby supporting the BPT no discharge
requirement.
Copper/Lead/Zinc/Si 1ver/GoId/Molybdenum
Subdivision, Froth Flotation Mill Process
Subcategory,
Mill
There were more samples of this mill process than of any others
because froth flotation is a widely used process with the
potential to generate wastewater polluted with many toxics. As
seen in Table VI-6, all of the toxic metals were detected in raw
mill water. The number of detections ranged from 7 to 78 out of
78 samples and median concentrations ranged from 1.1 ug/1 (mer-
cury) to 63,300 ug/1 (copper). These wide ranges are due to the
variations in. the ore milled at different locations. Generally,
the metals concentrations are in the high range of values
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reported for the category as a whole {Table VI-1). The
discharged concentrations of metals are, generally, one or two
orders of magnitude lower than the raw values. The number of
toxic metals with median concentration over 20 ug/1 are reduced
from ten in raw samples to five in treated samples and, overall,
the concentrations are reduced by existing treatment.
Asbestos, cyanide, and phenolics were also detected in both raw
and discharged samples. Median values for all were above the
respective medians for the whole category (Table VI-1). All were
reduced by the existing treatment systems.
Nonconventional parameters and TSS were generally high (compared
to Table VI-1} and the pH range is great.
Generally, mill water and tailings from this mill process contain
a wider range and higher concentrations of pollutants, including
toxics, than other mill processes or mines in this category. The
various process reagents used in flotation are discussed later in
this section.
Copper/Lead/Z inc/GoId/Si 1ver/Molybdenum Subcateqorv,
Subdivision, Heap/Vat/Dump/In-Situ Leaching
Mill
Very few samples were taken in this mill process because it1
regulated as no discharge of process water in BPT effluent guide-
lines. As can be seen in Table VI-7, the raw wastewater has high
concentration of several parameters, the reason for the no dis-
charge requirement. The one discharged sample reported is
actually treated recycle water which is not discharged.
Copper/Lead/2 i nc/Gold/S i1ver/Molvbdenum
Operations Recoverino Gold
Subcateqorv,
Placer
A study was conducted in 1978 to evaluate current wastewater
handling practices at gold placer mines. Eleven operations, all
located in Alaska, were sampled to determine performance capabil-
ities of existing settling ponds. Only two of the toxic metals
were monitored during the program, arsenic and mercury. Settle-
able solids were also monitored to provide an indication of
treatment pond performance. As can be seen in Table VI-8, the
settleable solids concentrations range from not detected to 500
ml/l/hr. However, many of the different samples are discharges
that had not been treated in settling ponds.
Aluminum Subcateqorv, Mine Dr a inagie Subdivision
As shown in Table VI-9, aluminum mine drainage is low in most
pollutants. The toxic metals present in the discharge are in
relatively low concentrations (compared to Table VI-]) and ar
chromium, copper, mercury, nickel, and zinc. Asbestos
present in moderate concentrations (compared to Table VI-1)
was not affected by the existing treatment methods. Acid
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levels were noted in the raw, but these increased to the alkaline
range (7 pH 14) after pH adjustment.
Tungsten Subcategorv, Mil1 Subdivision
As shown in Table VI-10, 13 of the toxic metals were detected in
the raw wastewater. However, these are reduced during treatment
leaving only seven above 20 ug/1 in the discharge. Of these,
copper, lead, and zinc have high concentrations (compared to the
other discharge metals concentrations).
Asbestos and phenolics were detected in the raw samples; cyanide
was not. The values of asbestos are high relative to the
category as a whole (see Table VI-1 ).. The effluent phenolics are
low relative to the values in Table VI-1.
Mercury Subcateqory, Mill Subdivision
As seen in Table VI-11, the toxic metals are found in high
concentrations in the raw wastewater in this subdivision, as are
asbestos and phenolics. That is why the applicable BPT regula-
tion is no discharge of process wastewater. The discharged
sample in Table VI-11 is actually treated recycle water.
Uraniurn Subcategory, Mine Drainage Subdivision
Uranium mine drainage, is, relative to mill water less polluted.
As seen in Table VI-12, many of the toxic metals were detected,
all but zinc in concentrations less than 65 ug/1. Only six were
detected in the treated samples, none greater than 50 ug/1.
Cyanide was not detected, and phenolics were detected at a low
concentration (10 ug/1). Asbestos was detected in both raw and
treated samples at moderate concentrations (as compared to Table
VI-1-).
Not listed in Table VI-12, but shown in the support data
(Supplement A), are radium 226 concentrations. Uranium ore is
radioactive and radium 226 is a radionuclide always associated
with uranium. It is one of the uranium decay series and has a
half life of 1,620 years. Raw mine water may have several
hundred to a thousand pico-Curies per liter (p Ci/1) of Ra 226,
but existing treatment is capable of reducing this to the BPT
guideline of 10 p Ci/1 (total, .30-day average).
Uranium Subcategory, Mill Subdivision
As seen in Table VI-13, several of the toxic metals are found in
both raw and treated wastewater. Treated wastewater in this
table is actually recycle water. The facilities do - not
discharge. This recycle water is not treated specifically for
metals, and, therefore, little reduction occurs.
-------
Asbestos was found in both influent and effluent
moderate concentrations (as compared to Table Vl-l). Cyanide was
not detected and total phenol (4AAP) were detected at a low con-
centration (10 ug/1). As with mine drainage, mill water may have
several hundred to a thousand p Ci/1 Ra 226. Current treatment
at the single uranium mill discharging is reducing this to 10 p
Ci/1, the BPT limitation.
Titanium Subcateqorv. Mine Subdivision
As can be seen in Table VI-14, the mine water from this
subcategory is relatively clean (relative to Table VI-l). Three
toxic metals (copper, lead, and zinc) were detected at 20 ug/1.
Relative to the category as a whole (Table VI-l), the asbestos
values are low. Total phenolics were detected at 30 ug/1.
Titanium Subcateqorv. Mill Subdivision
As shown in Supplement A (Support Data; Sample Points 1A and 2A,
for Mill 9905), seven toxic metals were detected in the raw
wastewater; all but selenium and lead at concentrations greater
than 200 ug/1. These concentrations were reduced by treatment,
leaving only five detected toxic metals ranging in concentration
from 20 to 100 ug/1.
Asbestos was detected at moderate concentrations (comparec
Table VI-l). Cyanide was not detected and phenolics were
detected at 10 ug/1 in raw and discharged samples.
Titanium Subcateqorv. Mills with Dredge Mining Subdivision
Table VI-l5 summarizes the data for the titanium mills employing
dredge mining.. Ten toxic metals were detected in the raw water,
at concentrations less than or equal to 80 ug/1. In the treated
effluent, six toxic metals were detected. Only zinc was detected
in concentrations greater than 10 ug/1.
COD and TOC concentrations in the raw water were generally
present in higher concentrations than the rest of the category
due to the presence of organic material in some of the ores. The
treatment processes used substantially reduced the concentrations
of both COD and TOC. The TSS concentration of the effluents were
less than 10 mg/1.
Vanadium Subcateqorv. Mine Drainage Subdivision
Table VI-l6 illustrates the character of vanadium mine drainage.
Several toxic metals were present both in the raw and discharged
water. Discharge concentrations greater than 20 ug/1 were
reported for chromium, copper, lead, nickel, and zinc. Cyanide
and total phenolics were not detected. The asbestos values w
low relative to the category as a whole.
-------
Vanadium Supcateqory,. Mi 1:1 Subdivision
As seen in Table'VI-17, many toxic metals were detected in both
the raw and discharged waters from this subdivision. Of the
metals, only mercury was reduced below the detection limit by the
existing treatment system. Cyanide was also reduced below the
detection limit, and no total phenolics were detected in raw or
discharged water.
Antimony Subcategory/ Mill Subdivision
The data for this subcategory are presented in Table VI-18.
There is no discharge of treated wastewater from the single mill
in this subdivision. Relatively high concentrations of antimony
and arsenic are present in the raw and treated wastewater.
Phenolics were not detected in the raw or treated wastewater.
Asbestos was detected in moderate concentrations compared to
Table VI-1. The pH of the impounded water was greater than 12.0.
REAGENT USE IN FLOTATION MILLS
Froth flotation processes use various reagents in the porcess,
and these reagents are discharged with the tailings and mill
process water. Flotation reagents are a possible source of toxic
organics in an industry which, otherwise, has no known source of
toxic organics. Therefore, a survey was conducted to determine
the availability of toxic organics and other toxics in flotation
reagents.
The results of a nationwide survey of sulfide ore flotation mills
indicate that over 547,400 metric tons (602,000 short tons) of
chemical flotation reagents were consumed in 1975 (Reference 1).
Reagent use data supplied by 22 milling operations indicate that
63 different chemical compounds are used directly in sulfide ore
flotation circuits. These reagents are categorized as:
1. pH Modifier (Conditioner, Regulator)Any substance used
to regulate or modify the pH of an ore pulp or flotation
process stream. Examples of the most commonly used
reagents are lime, soda ash (sodium carbonate), caustic
soda (sodium hydroxide), and sulfuric acid.
2. Promoter (Collector)A reagent added to a pulp stream
to bring about adherence between solid particles and
air bubbles in a flotation cell. Examples of the most
common promoters are xanthate and dithiophosphate salts,
as well as saturated hydrocarbons (such as fuel oil).
3. FrotherA substance used in flotation processing to
stabilizeair bubbles, principally by reducing surface
tension. Common frothers are pine oil, cresylic acid,
amyl alcohol, MIBC, and polyglycol methyl ethers.
-------
-
4. ActivatorA substance which, when added to a mineral
pulp, promotes flotation in the presence of a collecting
agent. It may be used to increase the floatability of a
mineral in a froth or to refloat a depressed mineral. A
good example of an activating agent is copper sulfate,
used in the flotation of sphalerite.
5. DepressantA substance which reacts with the particle
surface to render it less prone to stay in the froth,
thus causing it to wet down as a tailing product
(contrary to activator). Examples of depressing agents
most commonly used are cyanide, zinc sulfate, corn
starch, sulfur dioxide, and sodium sulfite.
Table VI-19 summarizes reagent use for copper, lead, zinc,
silver, and molybdenum flotation mills which discharge process
wastewater. Comparing the reagents listed in Table VI-19 to the
list of toxic pollutants given in Section V, only the following
reagents are considered to be potential sources of one or more
toxic pollutants in mill process wastewater: copper, zinc,
chromium, and total phenolics (4AAP).
Copper
Copper sulfate addition to a flotation pulp containing _
(ZnS) is a good example of an activating agent. The cupric ions
replace zinc in the sphalerite lattice to permit better collector
attachment, thus allowing the mineral to be floated with a
xanthate (Reference 2). Copper ammonium chloride functions in
much the same manner and is used at one operation (Mill 3110)
because it is purchased as a waste byproduct from the
manufacturer of electronic circuit boards. Copper sulfate is
highly soluble in water and is added to the flotation circuit in
concentrations as high as 100 mg/1 (as Cu). Residual dissolved
copper in the tailings pulp stream readily forms copper hydroxide
precipitates at the alkaline pH common to most sulfide flotation
systems.
Zinc
The function of zinc sulfate is the depression of sphalerite when
floating galena and copper sulfides (Reference 3), and the
mechanism involved is very similar to that of copper sulfate
described above. Typically, dosage rates of 0.1 to 0.4 kilogram
of zinc sulfate per metric ton (0.2 to 0.8 pound per short ton)
of ore feed are used, often in conjunction with cyanide. These
dosage rates translate to dissolved zinc loads in the flotation
circuit of 5.2 to 65 mg/1 (as Zn). Residual zinc concentrations
from excessive zinc sulfate use are small compared to the total
zinc content of the tailings.
Ifi*
-------
Chromium
Sodium dichromate is used as a flotation reagent at only one of
the 22 flotation mills listed in Table VI-19. it functions as a
depressant for galena in copper/lead separations. Dosages of
this reagent .are relatively small, and long term analyses of
treated effluent have not indicated the presence of chromium in
detectable concentrations.
Cyanide
Sodium cyanide and, to a lesser extent, calcium cyanide have
found widespread application within the industry as strong
depressants for iron sulfides and sphalerite. Cyanide also acts
as a mild depressant for chalcopyrite, enargite, bornite, and
most other sulfide minerals with the exception of galena {Refer-
ence 4). A secondary action of cyanide, in some instances, may
be the cleaning of tarnished mineral surfaces, thereby allowing a
more selective separation of the individual minerals (Reference
5). Typical cyanide reagent dosages range from 0.003 to 0.125
kilogram per metric ton (0.006 to 0.250 pound per short ton) of
ore feed and average 0.029 (0.058). Expressed in terms of water
use, cyanide dosages range from less than 1.0 to 50.4 milligrams
per liter (as sodium cyanide), with an average of about 11.
Sodium cyanide and calcium cyanide flotation reagents are the
sole source of cyanide in flotation mill effluents. Four flota-
tion mills (2122, 3121, 6101, and 6102) have effluent discharge
concentrations of 0.1 mg/1 total cyanide or greater. Mill 6102
is the largest consumer of cyanide in terms of dosage per unit of
ore feed and per unit of flotation circuit water feed. As a
result, Mill 6102 produces a raw discharge with total cyanide
concentrations of 0.2 to 0.4 mg/1. Cyanide dosages used at Mills
2122, 3121, and 6101 are consistent with amounts used throughout
the industry, and, for this reason, reagent use alone does not
appear to be the cause for high cyanide levels. The treatment of
cyanide-bearing wastewater and the chemistry of cyanide in mill
wastewater are discussed in Section VIII of this report.
Phenolic Compounds
"Reco" (sodium dicresyldithiophosphate) is used at Mill 2122 to
promote the flotation of copper sulfide minerals. Reco is
similar to American Cyanamid's AEROFLOAT 31 and 242 promoters,
which are used at Mills 3101, 3104, 3115, 4403, and 9202. These
reagents contain the cresyl group (CH3_.C£H3_.OH), a very close
relative of the toxic substance 2,4-dimethylphenol, which has
been detected in raw mill wastewater samples collected during the
toxic substance screen sampling program at Mills 2122 and 9202.
Mills 3101, 3104, 3115 and 4403 were not selected as sites for
screen and/or verification sampling of organic toxic pollutants
during this program.
163
-------
Cresylic acid is used as a flotation reagent at Mills 2117, 21
and 4403. Xylenols, C2H5_.C6H40H or (CH3J2.C6H3.0H, are the
dominant constituents of commercial cresylic acid's" and include
the toxic pollutant, 2,4-dimethyphenol, which has not been
detected in raw or treated wastewater samples at Mills 2117 and
2121. Mill 4403 was not sampled for the organic toxic
substances. Nitrobenzenes are present in Aero 633, but
nitrobenzene was not detected in wastewater during this program.
However, screening and verification sample data strongly
implicate these phenol-based flotation reagents as the sources of
total phenol (4AAP) in mill process wastewaters. From a
practical standpoint, cresylic acid can be considered as 100
percent phenolic with the relative phenolic content of the other
phenol-containing reagents being considerably less. Phenolic
concentrations of 5.2 mg/1 and 5.0 mg/1 have been detected in the
mill tailing samples at Mill 2117, and treated effluent samples
were found to contain 0.30 mg/1 and 0.36 mg/1 on 2 consecutive
days. The large consumption of cresylic acid at Mill 2117 (0.035
kilogram/metric ton equivalent to 0.070 pound per short ton, of
ore) and the consistency of data substantiate cresylic acid as
being a significant source of phenolic compounds in flotation
mill process effluents.
Phenolic compounds were found to be the most prevalent toxj
organic species detected in the screen samples, but concent
tions did not exceed 0.03 mg/1 except at operations which
known to employ one or more of the phenol based flotation
reagents previously discussed.
SPECIAL PROBLEM AREAS
Backfilling of Mines With Mill Sand Tailings
A review of sample data and historical monitoring data supplied
by the industry indicates the presence of significant
concentrations of cyanide in several mine water discharges.
Further examination revealed that the facilities with cyanide in
mine water backfilled mined-out stopes using mill sand tailings
from flotation circuits which use cyanide compounds as process
reagents.
A variety of undergound mining techniques are used throughout the
mining industry. Typical mining methods include room-and-pillar,
vein (or drift) mining, open stoping, pillar stoping, cut-and-
fill, and panel-and-fill. The selection of method(s) is
dependent on many factors, such as the type and shape of the ore
deposit, the depth of excavations, and the ground conditions.
Cut-and-fill, pillar stoping, and panel-and-fill techniques have
found common application in lead, zinc, and silver mines located
in Colorado, Utah, and the Coeur d'Alene Mining District
Idaho. An inherent feature of these mining methods is
refilling of worked-out and abandoned stopes and other workirf
-------
to prevent subsidence and cave-ins as mining progresses through
the ore body. For many years, waste rock from the mine
exploration crosscuts was used as fill material; however, the
development of hydraulic sandfill procedures has simplified the
backfill operation. In current practice, the coarse (sand)
fraction of the flotation-mill tailings is often segregated from
the tailings pulp stream by hydro-cyclones and pumped into the
mine for backfilling.
Nine mines (Mines 3107, 3113, 3120, 3121, 3130, 4104, 4105, 4401
and 4402) are known to practice hydraulic backfilling with mill
sand tailings. Eight of these nine mills use cyanide either as a
flotation reagent (Mills 3107, 3113, 3121, 3130 and 4401) or as a
leaching agent (Mills 4104, 4105, and 4402). The nature of the
mechanism by which cyanide depresses pyrite and sphalerite is
such that much of the cyanide added to the flotation circuit
associates with the depressed minerals in the tailings and ulti-
mately is leached into mine water during hydraulic backfill.
Mine 3130 is the only facility with a separate mine drainage
treatment system that periodically monitors for cyanide. Efflu-
ent monitoring data (summarized in Section VIII) include cyanide
analyses of five 24-hour composite samples collected during the
period of June 1977 through October 1977, The data indicate that
cyanide concentrations . in the treated mine water did not exceed
0.2 mg/1 total cyanide for mills and mine/mills on a daily basis,
although the monthly average exceeded 0.1 mg/1 on one occasion.
Examination of raw (untreated) mine-water data from Mine 3130
indicates that cyanide is not effectively removed by the treat-
ment system, which consists of lime and flocculant addition,
followed by a series of two sedimentation ponds. This treatment
is not designed for destruction or removal of cyanide and, does
not provide sufficient residence time for natural aeration.
fore, the poor removals observed are not surprising.
Total cyanide concentrations' detected in five mine-water grab
samples collected to support BAT at Mine 3130 were found to range
from 0.04 to 0.16 mg/1. A 24-hour composite mine-water sample
collected at Mine 3107 was found to contain 0.4 mg/1 during
backfill operations.
Mine 4105, located in South Dakota, was visited during the
screening phase of this program. Analysis of mine water for
total cyanide indicated that, for the days when the contractor
sampled, concentrations were less than detectable. During pre-
vious visits to this facility, no cyanide was detected in mine
water samples.
-------
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