ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-7 5-00 2
EVALUATION
NPDES PERMIT LIMITATIONS
FOR
HOMESTAKE MINING COMPANY
AND
LEAD-DEADWOOD	SA
NO.
NATIONAL FIELD INVESTIGATIONS CENTER-DENVER
DENVER. COLORADO
i «¦ \
mj

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ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EVALUATION OF PROPOSED
NPDES PERMIT LIMITATIONS
FOR
HOMESTAKE MINING COMPANY
AND
LEAD-DEADWOOD SANITARY DISTRICT
NO. 1
NATIONAL FIELD INVESTIGATIONS CENTER-DENVER
DENVER, COLORADO
FEBRUARY 1S75

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CONTENTS
Page
INTRODUCTION 		1
CONCLUSIONS 		3
RECOMMENDATIONS		5
RESULTS AND DISCUSSIONS		6
BIOASSAY TESTS		6
FISH SURVIVAL STUDIES 		15
REFERENCES 		19
APPENDIX 		20
INVESTIGATION METHODS 		20
EPA REGIONAL REQUEST FOR
BIOASSAY STUDY		23
LIST OF TABLES
1	Effluent Limitations in NPDES Permits. . .	7
2	Bioassay Data - Homestake Mining Co.
Simulated Effluent		8
O
3	Bioassay Data - Homestake Mining Co.
Plus Municipal, Simulated Effluent. .	10
4	Bioassay Data - Homestake Mining Co.
"Slime Plant" Effluent		12
5	Bioassay Data - Homestake Mining Co.
"Sand Plant" Effluent		14
6	Fish Survival and Stream Quality Data. . .	17
FIGURE
1 The 48-Hour Lethal Concentrations of
Three Heavy Metals for Rainbow Trout . . 16

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INTRODUCTION
1
In September 1971 NFIC-D and Regions VII and VIII prepared the docu-
ment "Pollution Affecting Water Quality of the Cheyenne River System in
Western South Dakota." The document, including its conclusions and
recommendations, became the U. S. Government presentation at an Enforce-
ment Conference held in Rapid City, S. Dak., October 19-22, 1971. A
major portion of the document specifically addressed pollution from the
Homestake Mining Company waste discharges. Recommendations of the EPA
document and ti-e Confer*es (state and federal pollution abatement of-
ficials) included the construction and operation by the Homestake Mining
Company of treatment facilities to reduce cyanide, mercury, arsenic and
tailings solids pollution.
Since the 1971 Conference, the Homestake Mining Company has pro-
posed several treatment alternatives, including the discharging of
liquid wastes into a proposed Lead-Deadwood Wastewater treatment fa-
cility. The ^M-Hill Consulting Company of Seattle, Wash, is presently
studying the problem and designing treatment facilities for the Lead-
Deadwood Sanitary District No. 1.
On November 14, 1974, the EPA held a public hearing in South Dakota,
in accordance with Section 101 (e) of PL 92-500. Information exchanged
at the hearing will be considered before issuance of the NPDES permits
to the Homestake Mining Company and the Lead-Deadwood Sanitary District
No. 1. At the hearing, the EPA proposed effluent limitations to which
the Homestake Mining Company objected. The industry objected to some of

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2
the limitations they felt were too stringent. As part of the Hearing Record,
it was agreed that the EPA would determine effluent limitations and
monitoring requirements based on the review of industry information
presented to the Agency within 20 days (by Dec. 4, 1974) and, if neces-
sary, based on a limited field or laboratory study of the industry
wastes and receiving water.
On November 21, 1974, the EPA Regional Administrator requested (see
Appendix) that the NFIC-D conduct the studies necessary to accomplish the
following objectives:
1.	Determine the toxicity of the 1977 effluent conditions
as proposed in the NPDES permits to Homestake Mining Company
and Lead-Deadwood Sanitary District No. 1.
2.	Determine the suitability of background and receiving waters
of Whitewood Creek and diverted Spearfish Creek for support
of a coldwater fishery.
As a result of this request, NFIC-D performed the necessary investigations
from January 8-24, 1975. This report describes the studies conducted,
presents findings and conclusions, and provides recommendations relative
to the NPDES permit limitations.

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3
CONCLUSIONS
1.	The bioassays of the simulated waste of the Homestake Mining
Company and the Lead-Deadwood Sanitary District No. 1 demonstrated that
both effluents are potentially toxic to the degree that test fish were
killed in 96 hours or less (acute toxicity). The results of these
bioassays indicated that the proposed 1977 permit limitations for cyanide
are not adequate. Acute toxicity occurred with cyanide concentrations
of approximately 0.07 mg/1, three times greater than the proposed permit
limitations, "ne proposed limitations cannot be expected to assure the
survival and reproduction necessary to maintain a permanent coldwater
fishery. Chronic exposure to cyanide concentrations of 0.2 mg/1 has
been shown to produce abnormal behavior in coldwater fishes.
2.	The combined Homestake Mining Company and Lead-Deadwood Sani-
tary District No. 1 waste was considerably more toxic than the Homestake
Mining Company simulated waste alone. The increased toxicity of this
waste was attributed to the complexing of cyanide and chlorine to form
highly toxic cyanogen chloride.
3.	Both the "slime plant" and the "sand plant" effluents were
acutely toxic at approximately the same cyanide concentrations as the
simulated wastes. An effective concentration that killed 50 percent of
the test fish (EC50) in the "slime plant" discharge test was determined
to be a 0.07 percent concentration of effluent containing 0.07 mg/1 total
cyanide. No EC50 was estimated for the "sand plant" discharge; however
acute toxicity was observed at a 0.8 percent effluent concentration.

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4
4.	Analyses of bioassay results and supporting chemical data led
to the conclusion that cyanide was the principal toxic agent. In all
tests, fish kills were associated with total cyanide concentrations from
0.07 to 0.11 mg/1.
5.	There was no indication that either heavy metals or un-ionized
ammonia, at the levels specified in the 1977 permit, contributed to the
toxicity of the waters tested. In fact, copper and iron limitations in
the proposed 1977 permit are lower than the concentrations of these metals
detected in Whitewood Creek, upstream from Gold Run, which supports a per-
manent coldwater fishery.
6.	In situ exposure of rainbow trout demonstrated that the quality
of Whitewood Creek upstream from the Gold Run confluence, its tributaries
(Strawberry Creek and Grizzly Creek) and diverted Spearfish Creek were
sufficient to support a coldwater fishery. Whitewood Creek downstream
from the Gold Run discharge was extremely toxic to rainbow trout; all
test fish died in less than 15 minutes of exposure. However, if the con-
centrations of pollutants discharged to Whitewood Creek at Gold Run were
reduced to acceptable levels, Whitewood Creek downstream from this point
could support a coldwater fishery.

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5
RECOMMENDATIONS
To improve the water quality of Whitewood Creek sufficiently to
establish a coldwater fishery and assure the protection of aquatic
biota, the following recommendations are made for the Homestake Mining
Company and the Lead-Deadwood Sanitary District No. 1 discharges:
1.	Total cyanide concentrations shall not exceed 0.005 mg/1 (1/20
EC50). In the absence of analytical procedures having detection limits
in this range, total cyanide concentrations shall be limited to the
presently detectable limit of 0.02 mg/1.
2.	To prevent the formation of cyanogen chloride, effluents con-
taining cyanide shall not be combined with wastewaters containing resi-
dual chlorine.
3.	Heavy metal concentrations as proposed in permits No. SD0000043
and No. SD0020796 shall be implemented in the final NPDES permits.
4.	Total ammonia and residual chlorine levels shall be adopted in
the final NPDES permits as stated in the proposed limitations, providing
recommendations 1 through 3 of this document have been met.

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6
RESULTS AND DISCUSSION
BIOASSAY TESTS
Continuous flow bioassays were conducted during the survey to
determine if the proposed effluent limitations are adequate to protect
the aquatic life of the receiving waters. Two bioassays employed simu-
lated wastes representing the Homestake Mining Company and the combined
effluents of the Homestake Mining Company plus the Lead-Deadwood Sani-
tary District No. 1. The chemical components and concentrations used
were based on the 1977 effluent limitations in NPDES permits SD0000043
and SD0020796 prepared by EPA Region VIII (Table 1). Two components,
iron and copper, were found to exist in the receiving water (Whitewood
Creek upstream from the Gold Run Creek confluence) at concentrations
greater than those of the permit limitations (Table 2).
To assure that the simulated wastes actually represented the chemi-
cal characteristics of the Homestake Mining Company effluent, two addi-
tional bioassays were conducted using plant discharges diluted with
process water to chemical concentrations similar to those of the simu-
lated wastes.
The Homestake Mining Company simulated waste was shown to be acutely
toxic. It killed test fish within 96 hours at concentrations of cyanide
and heavy metals four times that of the permit limitations (Table 2).
At this level (0.09 mg/l-CN), within the first 24 hours of exposure,
some test fish displayed signs of sublethal toxification (i.e., general
loss of equilibrium and erratic swimming patterns). Within 72 hours,
ten percent mortality had occurred among the fish (Table 2). No additional
mortalities were observed during the 96-hour test. Insufficient mortalities

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7
Table 1
Effluent Limitations in NPDES Permits
July 1, 1977
Effluent	Homestake	Homestake
Characteristic	No. SD-0000043	Plus Municipal
(mg/1)	No. SD-0020796
(mg/1)
Ammonia (as N)

0.6
Total Residual Chloride

0.02
Total Iron
0.2
0.3
Free Cyanide
0.005
0.008
Total Cyanide
0.02
0.03
Total Arsenic
0.1
0.16
Total Cadmium
0.003
0.005
Total Chromium
0.05
0.08
Total Copper
0.02
0.03
Total Lead
0.05
0.08
Dissolved Lead
0.015
0.022
Total Mercury
0.0002
0.0003
Total Nickel
0.2
0.31
Total Silver
0.0002
0.0003
Total Zinc
0.04
0.06

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Table 2
o Bloassay Oata^
Homestake Mining Company, Simulated Effluent
Lead, South Dakota - January 11-15. 1975
Parameter
4x^
3x
2x
X
0.5x
0.25x
Control
(Receiving water).
pH (Units)
7.9
7.9
7.8
7.85
7.8
7.8
7.7
DO
7.1
6.65
7.25
7.35
7.45
7.5
7.25
Temperature (°C)
12.6

12.6



13.1
Specific Conductance
495

522



522
(umho/^.Ti)







Total Alkalinity
252

196



149
Total Hardness
253

198



155
Total Iron
0.24
0. 8
0.12
0.06
0.03
0 015
3.1
Total Cyanide
(0.8)
(0 6)
(0.4)
(0.2)
(0.1)
(0.05)

0.10
0.075
0.05
0.025
0.012
0.006
<0 02

(0 08)
(0.06)
(0 04)
(0.02)
(0.01)
(0 005)

Total Arsenic
0.36
0.27
0.18
0.09
0.045
0.022
<0.100

(0.4)
(0.1)
(0.2)
(0.1)
(0.05)
(0 025)

Total Cadmium
0 005
0. )U4
0.0025
0.001
0.0005
0 0002
<0.002
Total Chromium
(0.012)
(0.009)
(0.006)
(0.003)
(0.0015)
(0 0007)

0 04
0.03
0.02
0.01
0.005
0 0025
<0.01
Total Copper
(0 20)
(0 15)
(0 10)
(0.05)
(0.025)
(0 0125)

0.079
0.059
0.040
0 020
0 010
0 005
0.044
Total Lead
(0 08)
(0.06)
(0.04)
(0 02)
(0 01)
(0 005)

<0 02
<0 02
<0.02
<0.02
<0.02
<0 02
<0.02
Dissolved Lead
(0 20)
(0.15)
(0.10)
(0 05)
(0.025)
(0 0125)

<0 02
<0.02
<0.02
<0 02
<0 02
<0 02
<0.02
Total Mercury
(0.06)
(0 J45)
(0.030)
(0 015)
(0.0075)
(0 0038)

0 0002
0.0002
0 0001
0 00005
0.000025
0 000012
0.0003
Total Nickel
(0 0008)
(0.0006)
(0.0004)
(0.0002)
•(0.0001)
(0 00005)

0 86
0.64
0.43
0 22
i 11
0.05
<0.01
Total Silver
(0.8)
(0 6)
(0.4)
(0.2)
vl.l)
(O 05)

<0 004
<0.004
<0.004
<0.004
<0.004
<0.004
<0.004

(0 0008)
(0.0006)
(0.0004)
(0 0002)
(0.0001)
(0 00005)

Total Z1nc
0 081
0.063
0 042
0.021
0 on
0.005
0.036

(0.16)
(0.12)
(0.08)
(0.04)
(0.02)
(O 01)

X Survival







at 24 hours
100
100
100
100
^00
100
100
at 48 hours
100
100
100
100
100
100
100
at 72 hours
90
100
100
100
100
100
100
at 96 hours
90
100
100
100
100
100
100
«7 Avg. values In mg/1. Data as analyzed; concentrations In parentheses based on permit limitations.
b/ X represents proposed 1977 effluent limitations.
oo

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9
precluded an estimation of a 96-hour EC50^ for this simulated waste.
The combined Homestake Mining Company and the District No. 1 simu-
lated waste was more toxic than the Homestake Mining Company simulated
waste alone. All test fish died in the undiluted simulated waste (four
times limitation) during the first 48 hours of exposure. Forty percent
mortality occurred at the 75 percent level (three times effluent permit
limitations) within 96 hours (Table 3). A 96-hour EC50 for the undiluted
simulated waste was estimated to be a 78 percent concentration, repre-
senting a level about three times the permit limitations.
Supporting chemical data showed the Homestake Mining Company
simulated waste and the combined Homestake and District No. 1 simulated
wastes contained cyanide concentrations of 0.10 mg/1 (Table 3). It has
been demonstrated that free cyanide (Cn + HCN) becomes acutely toxic to
trout in the range of 0.05-0.10 mg/1 (1,2). The combined simulated
wastes differed in composition from the Homestake Mining Company simu-
lated waste only by the addition of chlorine and ammonia at levels of
0.08 mg/1 and 2.4 mg/1 (total ammonia-N), respectively. At the test
temperature and pH (12°C and 7.7), insufficient un-ionized ammonia was
available to be acutely toxic to fish (3). Therefore, it is probable
that the increase in toxicity of the combined waste was primarily the
result of chlorine addition. Field testing failed to establish the
presence of any free chlorine in the combined simulate, precluding the
possibility that chlorine was the toxic agent. However, chlorine com-
plexes readily form with cyanide to produce cyanogen chloride, which has
1/ "96-hour EC50" is an abbreviation referring to the effective concentration
of contaminant required to kill the 50 percentile in a group of
test animals during a 96-hour exposure. The 50 percentile is
selected in toxicity tests because it represents the average animal.

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Table 3
Bloassay Data^/
Homestake Mining Company Plus Municipal, Simulated Effluent
Lead, South Dakota - January 11-15, 1975
Parameter

3x
2x
X
O.Sx
0.25x
Control
(Receiving water)
pH (Units)
7.8
7.8
7.7
7.8
7.7
7.7
7.6
DO
8.2
7.6
7.6
7.9
• 8.0
7.8
7.3
Temperature (°C)
11.0
10.5
12.0
11.0
11.0
11.0
12.5
Specific Conductance
517

505



519
(umho/cm)







Total Alkalinity
246

196



148
Total Hardness
247

198



155
fcimonia (as N)
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
(2.4)
(1.8)
(1.2)
(0.6)
(0.3)
(0.2)

Total Residual Chlorine
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01

(0.08)
(0 06)
(0.04)
(0.02)
(0.01)
(0.005)

Total Iron
<0 1
<0.08
<0.05
<0.02
<0 01
<0.005
3.1

(1.2)
(0.9)
(0.6)
(0.3)
(0 2)
(0.1)

Total Cyanide
0.1
0.08
0 05
0.02
0 01
0.005
<0.02.
(0.12)
(0.09)
(0.06)
(0.03)
(0.02)
(0 01)

Total Arsenic
0.39
0.30
0 20
0.10
0.05
0 02
<0.1

(0.64)
(0 48)
(0.32)
(0.16)
(0 08)
(0 04)

Total Cadmium
0.007
0 005
0.004
0.002
0 001
0 0005
<0.002

(0 02)
(0 02)
(0.01)
(0.005)
(0.002)
(0.001)

Total Chromium
<0 02
<0.02
<0.01
<0.005
<0 002
<0.001
<0.01

(0 32)
(0.24)
(0.16)
(0 08)
(0 04)
(0 02)

Total Copper
0 087
0.065
0.044
0.022
0 011
0.006
0.044
(0 12)
(0 09)
(0.06)
(0 03)
(0 02)
(0 01)

Total Lead
<0 02
<0.02
<0 02
<0 02
<0 02
<0 02
<0.02

(0 32)
(0 24)
(0 16)
(0.08)
(0.04)
(0 02)

Dissolved Lead
<0 02
<0.02
<0.02
<0 02
<0.02
<0 02
<0.02

(0 088)
(0.066)
(0 044)
(0.022)
(0 011)
(0 006)

Total Mercury
0.0003
0.0002
0.0002
0.0001
0.00005
0 00002
0.0003
(0 0012)
(0 0009)
(0.0006)
(0 0003)
(0.0002)
(0.0001)

Total Nickel
1 0
0.8
0.5
0.2
0.1
0 05
<0.01
Total Silver
(1.2)
(0.9)
(0 62)
(0.31)
(0.2)
(0.1)
<0 004
<0.004
<0.004
<0.004
<0.004
<0.004
<0.004
Total Zinc
(0 0012)
(0.0009) .
(0.0006)
(0.0003)
(0 0002)
(0 0001)
0.076
0.057
0.038
0 019
0.010
0.005
0.036

(0 24)
(0.18)
(0.12)
(0.06)
(0.03)
(0.02)
X Survival







at 24 hours
90
100
100
100
100
100
100
at 48 hours
0
80
100
100
100
100
100
at 72 hours

60
100
100
100
100
100
at 96 hours

60
100
100
100
100
100
®7 Avg. values in mg/1. bata as analyzed; concentrations in parentheses based on permit limitations.
6/ X represents proposed 1977 limitations.
O

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11
been demonstrated to be more toxic to rainbow trout than cyanide alone
(4). Qualitative testing was positive for the presence of cyanogen
chloride; thus, it appears that the increased toxicity of the combined
simulated waste was due to the formation of this compound. Heavy metals
were not found in concentrations which were acutely toxic to fish (Table 3).
While no mortalities occurred in either simulated waste at the
proposed limitation level, it does not appear that these limitations are
adequate, particularly in regard to cyanide and chlorine concentrations.
The bioassays indicated that both simulated wastes are acutely toxic at
levels three to four times the permit limitations. This is a small
margin in light of the fact that safe levels for long-term survival and
reproduction of fish are calculated using application factors of 1/20 to
1/100 of the acutely toxic level (EC50). Little study has been made of
the chronic effects of cyanide on coldwater fishes; however, there is
evidence that chronic exposure to cyanide levels of less than .02 mg/1
produces abnormal behavior (1).
The bioassays of the actual Homestake Mining Company effluents were
accomplished using wastewater collected at 1) the "slime plant" sluice
inside the plant proper, and 2) the "sand plant" sluice at the head of
the sand dam. Water was collected daily in sufficient quantities to
operate the diluter system. Both effluents were settled for approxi-
mately two hours and the supernatant was siphoned. All bioassays were
conducted using presettled, filtered supernatant.
The "slime plant" effluent was extremely toxic, and 100 percent
mortality was observed at concentrations as low as 0.1 percent (0.10
mg/1 cyanide) during the 96-hour test (Table 4). An EC50 for this
discharge was estimated to be a 0.070 percent concentration of the

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Table 4
Bloassay Data^
Homestake Mining Company "SUme PI ant" Effluent
Lead, South Dakota - January 17-21, 1975
Parameter


Effluent
Concentrations

Control
(Receiving Water)
0.2%
0.15%
0.1%
0.05%
0.025%
0.0125%
PH (units)
7.8
7.9
7.8
7.8
7.8
7.8
7.8
Dissolved Oxygen
8.9
9.0
9.0
8.8
8.6
8.6
8.4
Temperature (°C)
12.0
12.0
12.0
12.0
12.0
12.0
12.2
Specific Conductance
496
461
520
530
540
545
554
( mho/cm)







Total Alkalinity
251

194



138
Total Hardness
251

197



146
Total Iron
0.12
0.09
0.06
0.03
0.02
0.01
3.1
Total Cyanide
0.21
0.16
0.10
0.05
0.02
0.01
<0.02
Total Arsenic
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Total Cadmium
<0.002
<0.002
<0.002
<0.002
<0.002
<0.002
<0.002
Total Chromium
<0.01
<0.008
<0.005
<0.002
<0.001
<0.0005
<0.01
Total Copper
0.016
0.012
0.008
0.004
0.002
0.001
0.044
Total Lead
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
Dissolved Lead
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
<0.02
Total Mercury
<0.0002
<0.0002
<0.0001
<0.00005
<0.00002
<0.00001
<0.0003
Total Nickel
<0.01
<0.008
<0.005
<0.002
<0.001
<0.0005
<0.01
Total Silver
<0.004
<0.004
<0.004
<0.004
<0.004
<0.004
<0.004
Total Zinc
0.008
0.006
0.004
0.002
0.001
0.0005
0.036
Survival







at 24 hours
0
0
100
100
100
100
100
48 hours


0
100
100
100
100
72 hours



100
100
100
100
96 hours



100
100
100
100
a/Avg. values in mg/1.
ro

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13
effluent. Supporting chemical data (Table 4) showed this level to
contain a consistent cyanide concentration of 0.07 mg/1 which is acutely
toxic to trout. No other single component was found in sufficient
quantity to be acutely toxic.
The "sand plant" discharge was not as toxic as the "slime plant"
effluent. Mortalities were observed only at the 0.8 percent level and
occurred within the first 48 hours of the test. At this concentration,
100 percent of the test fish died (Table 5). Chemical data indicated
that the cyanide concentration in this discharge was variable (0.04 to
0.11 mg/1 CN). The initial cyanide concentration of 0.11 mg/1 (at the
0.8 percent level) declined sharply after the first 24 hours. This
accounts for the initial mortality observed in the highest concentration
with no subsequent death occurring in the bioassay. Consequently, it
was not practical to estimate an EC50 value for this effluent on the
basis of these studies.
In general, the four bioassays indicated cyanide or a cyanide
-complex (cyanogen chloride) was the principal toxic agent. In all
cases, fish mortality was associated with total cyanide levels ranging
from 0.07 to 0.11 mg/1. Although heavy metals were common to all waters
tested and chlorine was a known addition to the combined simulated
waste, the possibility of either being the prime toxic agent has been
rejected for the following reasons:
1. Heavy metals were not detected at levels generally known to be
acutely toxic to fish (Tables 2 to 5) (5)(6). Hard water (greater
than 120 mg/l-CaC0,) decreases the toxicity of most heavy metals
(Fig. 1)(7)(8). Tne acute (48-hour) toxicity of copper,
for instance, decreases approximately 350 percent with a

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Table 5
Bioassay Data^
Homestake Mining Company "Sand Plant" Effluent
Lead, South Dakota - January 17-21, 1975
Parameter		Effluent Concentrations		Control

0.8*
0.6X
0.42
0.2X
0.1X
0.05X
(Receiving Water)
pH (Units)
7 8
7.8
7.8
7.8
7.8
7.8
7.7
Dissolved Oxygen
8.8
h.8
8.8
B.8
8.8
8.7
8.6
Temperature f°C)
11.0
11.2
11.4
11.0
11.3
11.2
12.2
Specific Conductance
469
510
508
515
535
530
552
(umho/cm)




Total Alkalinity
250

198



143
Total Hardness
256

200



151
Total Iron
<0.10
<0.08
<0.05
<0.02
<0.01
<0 005
3.1
Total Cyanide
0.07
C .05
0.04
0.02
0.01
0.005
<0.02
Total Arsenic
<0 1
<0.1 •
<0.1
<0.1
<0.1
<0 1
<0.1
Total Cadmium
<0.002
<0.002
<0.001
<0.0005
<0.0002
<0.0001
<0.002
Total Chromium
<0 01
<0.008
<0.005
<0.002
<0 001
<0 0005
<0 01 •
Total Copper
0.018
0.014
0 009
0.004
0.002
0.001
0.044
Total Lead
<0 02
<0.02
<0 02
<0 02
<0 02
<0 02
<0 02
Dissolvcd Lead
<0 02
<0.02
<0.02
<0.02
<0 02
<0.02
<0 02
Total Mercury
<0.0005
<0.0004
<0.0002
<0.0001
<0.00005
<0 00002
0 0003
Total Nickel
<0 01
<0.01
<0 01
<0.01
<0.01
<0.01
<0 01
Total Silver
<0 004
<0.004
<0.004
<0.004
<0.004
<0.004
<0.004
Total Zinc
0.025
0.019
0.012
0 006
0.003
0.002
0.036
1 Survival







at 24 hours
100
100
100
100
100
100
100
at 48 hours
0
100
100
100
100
100
100
at 72 hours

100
100
100
100
100
100
at 96 hours

100
100
100
100
100
100
«7 Avg. values 1n mg/1. Data as analyzed; concentrations In parentheses based on permit limitations.
of X represents proposed 1977 effluent limitations.

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15
corresponding increase in water hardness from 50 to 200 mg/1.
The total hardness of all test waters (ranging from 146 to
256 mg/1) was in excess of 120 mg/l-CaC03 (Fig. 1).
2.	Field testing did not reveal the presence of free chlorine in
the combined simulated waste.
3.	The physical appearance and behavioral characteristics of
stricken fish were indicative of cyanide poisoning. Early signs
of stress were exhibited by erratic whirling swimming, followed
by a gradual loss of equilibrium. Death was preceded by violent
convulsions ending in extreme longitudinal torsion of the body
(approaching 90°). Gills of dead fish were widely flared and
dark pink in color. These are not symptoms associated with
either heavy metal or chlorine poisoning in fish but are common-
ly associated with cyanide poisoning.
FISH SURVIVAL STUDIES
To determine the suitability of background and receiving waters of
Whitewood Creek and diverted Spearfish Creek for support of a coldwater
fishery, young-of-the-year rainbow trout were exposed in situ at six
sites (Table 6).
All fish survived the five-day exposure at five sites and showed no
signs of stress or abnormalities during the five-day exposure and observa-
tion period. At Whitewood Creek downstream from Gold Run, all the fish
underwent immediate stress when placed in the stream and died within 15
minutes after exposure.
These exposure tests indicated that the quality of Whitewood Creek
and its principal tributaries in all reaches upstream of Gold Run was
satisfactory to support a coldwater fishery. Field studies (9) have
demonstrated that coldwater fishes (Brook trout and Longnose dace)
survive and reproduce in stretches of Whitewood Creek 50 to 100 yards

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16
Total llardncis. mg/l asCaCoj
Figure 1. The 48-Hour Lethal Concentrations of Three Heavy Metals for
Rainbow Trout (Salmo gairdneri). (Similar Relationships
Exist for Other Species of Fish.) (7,8)

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Table 6
Fish Survival and Stream Quality Data^
Lead, South Dakota - January 11-15, 1975

Spearflsh
Hearst Ditch
Whitewood Ck.
Whitewood Ck.
Grizzly Ck.
Strawberry Ck.
Parameter
Diversion
Whitewood Ck.
Upstream of
Downstream of
Near
Tributary to

(Englewood)
Diversion
Gold Run
Gold Run
Whitewood Ck.
Grizzly Ck.
Temperature
3.0
0.1
0.2
5.0
0.4
0.6
(°C)
(1.0-5.0)
(0.0-1.0)
(0.0-1.0)
(1.0-8.0)
(0.0-2.0)
(0.0-2.0)
pH (Units)
7.6
7.6
7.2
8.6
6.9
7.3"
(7.2-7.9)
(7.0-7.8)
(6.3-7.7)
(8.3-8.9)
(6.4-7.4)
(6.9-7.6)
DO (mg/1)
11.0
11.5
11.7
>10^
11.1
11.3
(9.5-11.9)
(11.0-11.9)
(10.7-12.2)

(10.2-12.2)
(10.4-11.9)
% Survival



„ /


at 24 hours
100
100
100
o
100
100
at 48 hours
100
100
100

100
100
at 72 hours
100
100
100

100
100
at 96 hours
100
100
100

100
100
at 120 hours
100
100
100

100
100
a/ Avg. values.
B/ DO probe and analyzer used.
c/ All fish died within 15 minutes after exposure.

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18
upstream of Gold Run. It is, therefore, evident that Whitewood Creek
downstream from Gold Run can support a coldwater fishery if the pollutants
presently discharged into Gold Run were reduced to acceptable levels.

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19
REFERENCES
1.	Broderius, Steven. 1974. Affidavit on the Determination, Chemistry
and Toxicity of Cyanides. Dept. of Entomology, Fisheries and Wildlife,
University of Minnesota, St. Paul, Minn. 73 p.
2.	Herbert, D. W. M. and J. C. Merkews. 1952. The Toxicity of Potassium
Cyanide to Trout. J. Exper. Biol. 29:632-649.
3.	Tressel, R. P. 1972. The Percent Un-ionized Ammonia in Aqueous
Ammonia Solutions at Different pH Levels and Temperatures. J. Fish.
Res. Bd. Can. 29(10):1505-1507.
4.	Allen, L. A., N. Blezard, and A. B. Wheatland. 1948. Formation of
Cyanogen Chloride During Chlorination on Certain Liquids. Toxicity
of Such Liquids to Fish. Jour, of Hyg. 46:184-193.
5.	McKee, J. E. and H. W. Wolf, eds. 1963. Water Quality Criteria,
2nd Ed. Cal. State Water Qual. Control Bd., Sacramento, 548 p.
6.	Water Quality Criteria - 1972. 1973. Rpt. of the Committee on
Water Quality Criteria. Envir. Studies Bd. Nat. Acad of Sci. Nat.
Acad of Engineering, p. 177-191.
7.	Brown, V. M. 1968. The Calculation of the Acute Toxicity of Mixtures
of Poisons to Rainbow Trout, Water Res. 2(10):723-733.
8.	Lloyd, R. 1960. Toxicity of Zinc Sulfate to Rainbow Trout. Ann.
Appl. Biol. 48:84-94.
9.	Report on Pollution Affecting Water Quality of the Cheyenne River
System Western South Dakota. 1971. Environ. Protect. Agy.,
Off. of Enforcement, Div. of Field Investigations-Denver Ctr.;
Regions VII and VIII.
10.	Standard Methods for the Examination of Water and Sewage. 1971.
13th ed., Amer. Pub. Health Assoc., New York, N.Y., 874 p.

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APPENDIX
INVESTIGATION METHODS
AND
EPA REGIONAL REQUEST FOR
BIOASSAY STUDY

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20
APPENDIX
INVESTIGATION METHODS
FISH SURVIVAL STUDIES
Young-of-the-year rainbow trout used in fish survival studies av-
eraged 51 mm (38-64 mm) [2.0 in; 1.5-2.5 in] in total length and 1.5 g
(1.1-1.7 g) [0.053 oz; 0.039-0.060 oz] in weight. These trout were
obtained from the McNenny National Fish Hatchery, Spearfish, S. Dak.
The fish were exposed in situ at all sites except at the Spearfish
Diversion-Englewood, where water was pumped through ^ stainless steel
tank in which fish were exposed. The exposure period at all sites was
five days.
Temperature, pH, and dissolved oxygen were recorded daily at all
sites. In addition, hardness, alkalinity, iron, arsenic, cadmium,
chromium, copper, mercury, nickel, silver, zinc, lead (total and dis-
solved) and total cyanide were analyzed from Whitewood Creek samples
collected upstream of Gold Run.
BIOASSAY METHODS
All 96-hour bioassays were done according to standarized methods
(10) using a continuous flow proportional diluter providing a series of
six dilutions of effluent and a 100 percent dilution water control.
Dilution water (receiving water) for all bioassays was obtained
from Whitewood Creek 0.5 km (0.3 mi) upstream from the Gold Run discharge.
This creek is the receiving water of the Homestake Mining Company effluent
and the proposed Lead-Deadwood Sanitary District No. 1 discharge. The
chemical quality of this water is shown in text Tables 2 thru 5. "Make-
up" water was obtained from the Spearfish diversion, which is the process
water for the Homestake Mining Company.

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21
Test waters for Homestake Mining Company bioassays were obtained from
the "slime plant" sluice inside the plant and the "sand plant" sluice at
the head of the sand dam. These discharges were "grab sampled" daily
during times of plant operation. Both samples were settled for approxi-
mately two hours, then siphoned through glass wool to remove particulate
matter. Only the supernatant was used in the bioassays.
Test water for the simulated bioassays was prepared fresh daily
from stock chemical concentrates prepared with the reagent grade chemi-
cals listed as follows: ammonium nitrate (NH^NO^); calcium hypochlorite
[Ca(CI0)2*2 H2O]; ferrous chloride (FeCl2'4 H^O); sodium cyanide (NaCN);
cupric nitrate [Cu(N03)2]; sodium arsenate (NaAs02); cadmium nitrate
[Cd(N03)2'4 H20]; lead nitrate [Pb(N03)2]; mercurous nitrate (HgN03'H20);
nickel nitrate [Ni(N03)2"6 H20]; silver nitrate (AgNC>3); and zinc acetate
[Zn(C2H302)2"2 H20]. Concentrations were calculated so that the diluter
system delivered 4x, 3x, 2x, x, .05x, .025x, where x represents those
concentration limits defined by the 1977 NPDES permits (text Table 1).
The test organism used in all bioassays was young-of-the-year
rainbow trout obtained from the McNenny National Fish Hatchery, Spearfish,
S. Dak. These fish averaged 51 mm (2.0 in) in total length and 1.5 g
(0.053 oz) in weight.
All test chambers were of glass construction having an 8 liter cap-
city. All concentrations were done in duplicate by exposing ten fish in
each of the fourteen chambers. The minimum volumetric turnover for any
chamber was seven times in twenty-four hours.

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22
Test water was monitored daily for pH, temperature, dissolved
oxygen, specific conductance, total alkalinity and total hardness.
Water for the simulated waste of Lead-Deadwood Sanitary District No. 1
was also tested for free chlorine and total ammonia (NH^ + NH^). One
test chamber in each series was continuously monitored for temperature
fluctuation with a recording thermocouple.
All continuous flow bioassays were 96 hours long. Mortalities were
recorded at 24 hour intervals. EC50 values were estimated using a
straight line graphical interpolation method (10).

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Ufa \
szy
(•
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION VIII
I860 LINCOLN STREET
DENVER. COLORADO 0O2O3
November 21, 1974
Ref: 8E
MBDRANDUM
23
TO:	Thomas P. Gallagher, Director
National Field Investigations Center-Denver
FROM: Regional Administrator
SUBJECT: Bioassay on Hemestake Mining Lease
I request your services for performing a bioassay on Homestake
Mining Company, Lead, South Dakota.
Since it is required in South Dakota's Water Quality Standards that
bioassay be used to determine the allowable discharge of uiispecific
toxic materials, this analysis is necessary. It would be appreciated
that the analysis be done as soon as possible, however, considering the
time element, at least by the end of January.
If further information involving the exact analysis is required,
please contact Rich Andrews, the individual who is responsible for
this permit. He can be reached at 837-4901.
We appreciate your help in this matter.
cc: Keith Schwab
Rich Andrews
Charles Murray

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