United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S7-84-071 Aug. 1984
&ER& Project Summary
Characterization of Oil Shale
Mine Waters, Central Piceance
Basin, Colorado
Kevin E. Kelly and Jim D. Dederick
A study was conducted to characterize
the oil shale mine waters in the Piceance
Basin. The stu<|y sites were the Federal
Prototype Lease Tracts C-a and C-b,
located in the central portion of the
basin. The objective was to collect
water quality data in order to character-
ize the mine waters and to assess the
effectiveness of the treatment systems
located at these facilities. These treat-
ment systems involve in-series reten-
tion ponds. Additionally, the effective-
ness of a one-pond versus two-pond
system was investigated.
The sources of the water routed
through the retention ponds were water
pumped from the on-site aquifers that
were dewatered during mining activities
and the water pumped directly from the
underground mines. Water samples
were taken from both the inflow and
outflow points for both the Tract C-a and
C-b pond systems and were analyzed
for a fairly detailed suite of selected
water quality parameters. This suite
included total suspended solids (TSS)
and total dissolved solids (IDS), pH, the
major species of cations and anions,
and dissolved trace elements such as
selenium, lead, and arsenic. The inflow
samples were then compared to the
outflow samples to determine changes
in water quality and, therefore, the
effectiveness of the retention ponds.
An additional part to this study was the
assessment of the effectiveness of
using a flocculant and sulfuric acid for
the treatment of excess waters encoun-
tered during active mining on Tract C-b.
The flocculant was added to reduce the
suspended solids concentrations and
the acid was used to reduce the high pH
values.
The water quality changes observed
during this study, when comparing the
inflow waters to the outflow waters of
the respective pond systems, were
found to be generally small. Fluctuations
may have been due to such phenomena
as pH changes, aeration, evaporation,
and oxidation-reduction changes asso-
ciated with the transformation of the
ground water from an underground
(aquifer) environment to a surface
(retention pond) environment. The
retention time, as well as inherent
laboratory technique variations, may
also help explain the small fluctuations.
The overall conclusion with respect to
the effectiveness of the retention pond
systems in maintaining or improving
water quality is that they appear to
make no significant difference unless
chemicals are added. The addition of
the flocculant in the Tract C-b pond
system was effective in reducing the
suspended sediment concentrations.
In addition, the sulfuric acid treatment
effectively reduced the pH values.
Concerning the general water quality,
such as the trace elements, cations and
anions, and other pertinent parameters,
there was no noticeable increase or
decrease.
This Project Summary was developed
by EPA's Industrial Environmental
Research Laboratory, Cincinnati, OH,
to announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).
Introduction
The objective of this study was to
provide a detailed characterization of the
-------
mine waters and treatment systems used
on Federal Prototype Lease Tracts C-a
and C-b, located in the Piceance Basin,
Colorado (Figure 1). These data were
collected to assist other oil shale devel-
opers and to permit writers to select
appropriate controls for the handling of
excess mine waters.
The treatment facilities for the excess
mine waters at both sites consisted of two
in-series retention ponds. To characterize
these facilities, samples were collected
for determining the chemistry of water
derived from mine pumpage and aquifer
dewatering activities previous to treat-
ment. In addition, samples were derived
from the outflow of the in-series retention
ponds to characterize the treatment.
Presently, the treated water is disposed of
by reinjection into the ground-water
system, is utilized for on-site activities, or
is discharged to surface-water systems.
The approach, data collection procedures,
and results are discussed below.
Approach
The procedures for obtaining these
data involved collecting grab samples of
five sampling points. On Tract C-a, the
sample collection included sampling the
mine water inflow into the primary
retention pond (Jeffrey Pond), the outflow
of the primary retention pond into the
secondary retention pond (West Retention
Pond), and the discharge from the
secondary pond previous to disposal. It
was felt that Jeffrey Pond was fairly
inconsequential with respect to the total
treatment system due to the very short
residence time of the mine waters in this
pond. Therefore, the above described
sampling scheme would adequately assess
the effectiveness of treating the excess
mine waters with a one-pond system,
namely the West Retention Pond.
In regard to Tract C-b, samples of
untreated mine water were collected at
the inflow point of the primary retention
pond (Pond A). In addition, samples of the
treated water were collected from the
discharge of the secondary retention
pond (Pond B), which is in series with
Pond A. During periods of active mining
on Tract C-b, sulf uric acid and a magnif loc
cationic flocculant were added to the
ponds in order to treat the pH and total
suspended solids (TSS), respectively. This
sampling strategy assessed the effective-
ness of treatment consisting of two ponds
which are in series. In addition, the
sampling program allowed for an evalua-
tion of chemical treatment (i.e..flocculant
and sulfuric acid).
The following constituents were mea-
sured in the field immediately upon
sample withdrawal: pH, temperature,
conductivity, and dissolved oxygen. The
samples were then filtered (if necessary)
and preserved according to the U.S.
Environmental Protection Agency (EPA)
recommended procedures. The samples
were then shipped to the laboratories
located at the Colorado State University
Lower Colorado
Basin
New Mexico
I Drainage Basin
Boundary
05 JO 15
Scale in Miles
Figure 1. Location of Tracts C-a and C-b study area in Piceance Basin.
2
-------
in Fort Collins, Colorado, and Core
Laboratories in Denver, Colorado. In
most cases, the EPA recommended
holding times were observed. The holding
times for a few constituents of the
samples collected in July, 1982 were ex-
ceeded. However, the analytical results
were generally in agreement with those
for other sampling periods. Exceptions to
this include nitrate and ammonia, which
were higher in concentration than
historic trends. Seven samples were col-
lected at each sample collection point
between September, 1981 and March,
1983.
A fairly detailed suite of constituents
was selected for analysis during this
study. This suite of constituents involved
two groups, an abbreviated group and a
comprehensive group (Table 1). Analysis
for the abbreviated group of constituents
was conducted during the months of
September, 1981; September, 1982; and
November, 1982. Analysis for the com-
prehensive group of constituents, which
included the abbreviated group, was
conducted during the months of May,
1982; July, 1982; January, 1983; and
March, 1983. These constituents were
selected after a review of the baseline
water quality data collected by the Tract
C-a and C-b operators, as well as the
chemical characterization studies of
simulated and observed in-situ oil shale
process waters conducted by various
researchers.
Data Discussion
The analytical results for the data
collected during this study on Tracts C-a
and C-b are presented in Tables 2 and 3,
respectively. In order to provide a
perspective for evaluating the mine water
data, the analytical results were compared
to ground-water and surface-water
baseline data, as well as Federal Drinking
Water Standards. This comparison is not
meant to imply that the discharges
should meet these standards. The com-
parisons for the Tract C-a and C-b data
are presented in Tables 4 and 5, respec-
tively.
The Tract C-a system involved treating
the water in a one-pond system and
reinjecting all of the treated water back
into the ground-water system. Concerning
the effectiveness of the treatment of the
mine waters, the following constituents
were found to generally exceed baseline
ground-water conditions: carbonate,
calcium, conductivity, fluoride, magne-
sium, nitrate, TDS, sulfate, and pH.
However, the increase in these consti-
tuents above ground-water baseline
conditions were small.
Table 1. List of Parameters for Abbreviated and Comprehensive Analysis
Acidity
Alkalinity
Ammonia
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chloride
Conductivity
Dissolved Organic Carbon (DOC)
Aluminum
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Cyanide
Fractionated
DOC
ABBREVIATED
Dissolved Oxygen
Fluoride
Iron
Magnesium
Mercury
Molybdenum
Nitrate
pH
Potassium
COMPREHENSIVE
Lead
Lithium
Manganese
Nickel
Phosphorus
(total and ortho)
Silver
Strontium
Sulfide
Residues
(Total, total
dissolved.
total, suspended,
settleable.
and volatile)
Silica
Sodium
Sulfate
Temperature
Thallium
Thiosulfate
Tin
Titanium
Turbidity
Uranium
(234. 235, 238)
Vanadium
Zinc
NOTE: Comprehensive list includes all parameters in the abbreviated list.
The following constituents exceeded
the Federal Drinking Water Quality
Standards in the discharge from the Tract
C-a system: iron, TDS, sulfate, and pH.
However, these constituents also exceeded
standards in the ground water analyzed
to determine baseline water quality
conditions. Therefore, this aspect may
not be a problem ifthewaterisreinjected.
In regard to the Tract C-b in-series two-
pond treatment system, the following
constituents in the discharge exceeded
baseline ground-water quality concen-
trations: bicarbonate, carbonate, conduc-
tivity, fluoride, molybdenum, nitrate,
potassium, TDS, silica, sodium, and pH.
However, none of the increases were
very great. In addition, during periods of
active mining on Tract C-b, flocculant and
sulfuric acid were added to the system to
settle suspended solids and lower the pH,
previous to the discharge to Piceance
Creek. This treatment was effective and
should be utilized if suspended solids and
pH are areas of concern.
The quality of the discharge from Tract
C-b also exceeded many constituents in
the Federal Drinking Water Standards, as
well as the baseline water quality data for
Piceance Creek. For example, iron, TDS,
and sulfate exceed the Drinking Water
Standards. In addition, ammonia, bicar-
bonate, boron, carbonate, conductivity,
fluoride, iron, molybdenum, nitrate,
potassium, TDS, temperature, silica,
sodium, alkalinity, and pH all exceeded
the baseline water quality conditions of
Piceance Creek. However, all of these
constituents were within reasonable
agreement with baseline ground-water
quality, which is considered poor. Fur-
thermore, the water discharged to
Piceance Creek appears to be adequate
for livestock and irrigation use.
The water quality changes observed in
the data when comparing inflow and
outflow of the treatment systems were
generally insignificant. These changes
can probably be related to pH changes,
aeration, evaporation, and reduction-
oxidation changes associated with the
transformation of the ground water from
an underground environment to a surface
environment, as well as the associated
retention time in the ponds. In addition,
some of the variations may be attributa-
ble to laboratory procedures.
Conclusion
The effectiveness of the treatment
systems with respect to improving water
quality without use of chemicals appeared
to be negligible. For the one-pond
treatment system on Tract C-a, the
overall quality, with the exception of total
suspended solids, remained essentially
unchanged during treatment. The slight
decrease in total suspended solids
concentrations from 6.3 mg/l to below
detection limits is not significant. The
two-pond treatment system on Tract C-b
is very similar in results to the one-pond
system on Tract C-a. The general water
quality did not improve or degrade after
treatment. However, the addition of a
flocculant and sulfuric acid was effective
-------
in reducing total suspended solids by
nearly 99% and adjusting pH to desired
value.
Table 2. Tract C-a Water Quality Data
Constituent*
Inflow to Jeffrey Pond
Number Mean High Low
West Retention Pond Inflow West Retention Pond Outflow
Stnd. Stnd. Stnd.
Dev. Number Mean High Low Dev. Number Mean High Low Dev.
Ammonia
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chloride
Conductivity
f/j mhos/cm)
Dissolved
Organic Carbon
Dissolved Oxygen
Fluoride
Iron
Magnesium
Molybdenum
Nitrate
Potassium
Residues
-Total Dissolved
-Total Suspended
-Total Solids
-Total Volatile
-Settleable Matter
Temperature (°C)
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity
Alkalinity
pH (Units)
6
7
7
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
7
7
7
6
7
7
4
7
7
7
.30
BDL
555
.21
6.33
38.8
8.06
1.590
3.5
4.0
1.35
9.1
80.1
.06
.53
.62
994
BDL
L071
197
BDL
14.3
BDL
13.9
191
402
BDL
5.1
469
7.7
.47
«003)
599
.41
9.09
48.7
8.52
2,250
4.7
6.8
1.71
1.0
95.0
.11
2.02
1.26
1,152
«4)
1,208
226
«1)
19
(<-01)
23
200
430
9.45
506
9.2
.11
527
.12
1.0
32.6
7.74
1,400
<2
3.0
1.1
<01
72.8
<03
<1
.14
614
992
148
11
11
174
343
«005)
3.13
445
7.17
.12
25.3
.10
2.85
7.3
.30
308
1.1
1.3
.21
.36
8.0
.02
.83
.36
175
69
31
2.7
4.5
8.2
31
2.13
20
.77
6
7
7
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
7
7
7
6
7
7
4
7
7
7
.22
BDL
535
.34
7.09
41.0
8.4
1.434
3.5
6.7
1.34
.18
82
.16
1.83
.76
1,134
6.3
1.153
198
BDL
14.5
BDL
13.2
190
342
3.56
456
7.6
.32
K0.003)
548
.80
11.4
63.5
9.47
1.510
4
8.5
1.7
.59
98.9
.3
8.59
1.24
1,446
10
1,446
252
«1)
23
«01)
22
198
441
BDL
4.99
474
9.0
.10
523
.15
1.08
31.0
7.58
1.390
3
5.9
1.2
.03
74.1
<03
0.1
.36
988
<4
1,016
74
10
10.9
170
345
«005)
2.52
442
7.0
.09
9.8
.26
3.43
11.8
.67
53
.46
1.0
.18
.20
8.2
.18
3.78
.33
164
2.6
160
65
4.7
4.4
9.7
137
1.13
11
.7
6
7
7
7
7
7
7
7
7
7
7
7
7
7
5
7
7
7
7
6
7
7
7
5
7
7
4
6
7
7
.24
517
.33
7.5
41.4
7.96
1,409
3.3
5.8
1.24
.29
82.3
.23
.39
.84
1,177
BDL
1,185
187
BDL
13.9
BDL
11.6
192
377
3.57
439
7.6
.42
BDL
558
.9
10.4
62
9.47
1.475
3.8
8.0
1.32
.64
100.9
.24
.77
1.49
1.392
«4)
1,395
225
«D
20
<<0.1)
12.8
198
449
BDL
4.96
470
8.9
.16
«003)
368
.16
<1
32
5.73
1,320
2.0
3.9
1.11
<01
73.1
<01
.05
.36
980
1,007
86
9.5
11.0
177
302
«O05)
2.33
311
6.9
.11
67
.29
2.2
10.8
1.13
49
.8
1.4
.07
.23
9.1
.01
.28
.43
177
170
55
3.9
.7
7.3
48
1.12
57
.6
*ln mg/l. unless otherwise indicated.
BDL = Below Detection Limits, with detection limits in parenthesis.
-------
Table 3. Tract C-b Holding Pond Quality Data Collected During This Study
Suit uric Acid
and Flocculant No Chemical Treatment
Inflow to Outflow from
Constituent* Pond A Pond B
Ammonia
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chloride
Conductivity
(fj mhos/cm)
Dissolved
Organic Carbon
Dissolved Oxygen
Fluoride
Iron
Magnesium
Molybdenum
Nitrate
Potassium
Residues
-Total Dissolved
-Total Suspended
-Total Solids
-Total Volatile
-Settleable Matter
Temperature fC)
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity
Alkalinity
pH {Units)
.90
-------
Table4. Comparison of Tract C-a Ground-Water Baseline Data and Federal Drinking Water Standards with Holding Pond Data Collected During This Study
Baseline Data (Tract C-af
Groundwater
Upper A quifer Lower A quifer
Constituent*
Ammonia
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chloride
Conductivity
ffj mhos/cm/
Dissolved
Organic Carbon
Dissolved Oxygen
Fluoride
Iron
Magnesium
Molybdenum
Nitrate
Potassium
Residues
- Total Dissolved
- Total Suspended
- Total So/ids
-Total Volatile
-Settleab/e Matter
Temperature I°C)
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity
Alkalinity
pH /Units)
Mean
Value
037
001
744
075
098
83.5
16.9
1,702
102
-
0.37
63
593
0.50
-
1,267
-
BDL
328
301.8
474
654
678
High
Value
1.8
004
2,760
4.8
66
260
69
2,610
35
18
180
155
45
2,790
-
.
<0.01
58
1,170
900
-
.
2,343
8.8
Mean
Value
0.35
BDL'
599
1.21
1.25
28.2
19.2
1.258
11 a
6.35
345
382
0.47
976
-
BDL
10.8
284
250
-
558
7 1
High
Value
2.0
<001
2.980
200
84
980
96
3.600
37
32
162
130
-
2.0
3.360
-
<001
32
1,320
600
-
2,540
10.2
Inflow to
Jeffery Pond
Mean
Value
030
BDL
555
021
6.33
38.8
806
1,590
35
4.0
1 35
0 19
80.1
006
053
062
994
BDL
1,071
197
BDL
143
BDL
139
191
402
BDL
5 1
469
77
A
047
<0.003
599
041
9.09
487
8.52
2.250
250
4 7
68
1 71
10
95.0
0 107
2.02
1 26
1.152
<4
1.208
226
<0 1
19
<001
23
200
430
<0005
9.45
506
9.2
Tract C-a Data
West Retention
Pond Inflow
Mean
Value
0.22
BDL
535
034
7.09
41 0
8.4
1,434
35
05
1.34
0.18
82.0
0 16
1 83
076
1.134
63
1.153
198
BDL
145
BDL
132
190
342
BDL
386
456
76
High
Value
032
<0.003
548
080
11 4
635
947
1,510
4
85
1 7
059
989
03
859
1 24
1,446
10
1.446
252
<0 1
23
<0.01
22
198
441
<0005
499
474
9.0
West Retention Federal Drinking Water
Pond Outflow Quality Standards'*
Mean
Value
024
BDL
517
033
75
41 4
7.96
1,409
33
58
1 24
0.29
82.3
023
039
084
1.177
BDL
1.185
187
BDL
139
BDL
11 6
192
377
BDL
357
439
7.6
High Primary2 Secondary3
Value I40CFR Part 141 )(40CFR Part 143)
042
<0.003 05
558
0.90
104
62
9 47 250
1,475
38
8.0
1 32 20 -22s
064 03
1009
0.24
077 10
1 49
1,392
<4
1.395
225
<0 1 001
20
<0.01
128
198
449 250
<0005
496
470
89 65-85
^Values in mg/l unless otherwise indicated.
^Provided as a reference point. Not intended to imply that discharge should meet Drinking Water Standards.
^Federally Enforceable - Federal Register - EPA Water Programs, Wednesday, December 24, 1975 IVol 40, No 248).
3Not Federally Enforceable - Federal Register - EPA Water Programs, Thursday, July 19, 1979 fVol 44, No 140)
"BDL = Below Detection Limit.
'Dependent on Temperature (A verage of maximum daily air temperatures).
^Source Rio Blanco Oil Shale Company. 1977
-------
Table 5. Comparision of Tract C-b Ground Water and Surface Water Baseline Data and Federal Drinking Water Standards with Holding Pond
Data Collected During This Study
Baseline Data - (Tract C-b)
Ground Water'
Upper Aquifer
Constituents*
Ammonia
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chloride
Conductivity
fu mhos/ 'cm)
Dissolved
Organic Carbon
Dissolved Oxygen
Fluoride
Iron
Magnesium
Molybdenum
Nitrate
Potassium
Residues
-Total Dissolved
-Total Suspended
-Total Solids
-Total Volatile
-Settleable Matter
-Temperature I°C)
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity
Alkalinity
pH (Unitsi
Mean
Value
7.9
001
790
14
21
32
26
1,670
10
0.5
42
002
041
22
1,100
0006
17
330
220
0002
86
High
Value
12
006
2.100
18
76
120
510
4.200
190
7
150
0 1
29
11
3.100
003
32
1.200
520
0006
91
Lower Aquifer
Mean
Value
17
002
4.0OO
36
220
14
1,200
7,240
23
21
08
11
004
046
21
6,190
0004
13
2,500
63
oo;
87
High
Value
2OO
OO2
25,000
4OO
2.OOO
220
9, BOO
45.000
175
48
8.0
110
02
34
120
42.OOO
002
38
1 7.0OO
350
9'
93
Surface Water7
Piceance Creek
Above Tract C-b
Mean
Value
.004
2 1
523
0 194
15
689
155
1.099
99
098
007
462
00104
033
37
698
87
OO01
15
1154
161
BDL
432
83
High
Value
013
50
602
029
32
79
24
1.41O
13
1 3
039
56
0016
083
19
762
22
0002
18
150
190
<0003
494
87
'Piceance Creek
Below Tract C-b
Mean
Value
002
2 1
572
0 183
IS
787
135
1,324
97
06
004
659
00097
039
37
893
9 1
0001
17
148
239
0002
472
83
High
Value
009
50
678
0270
39 •
87
16
1,560
160
09
046
820
0014
079
50
1,050
21 1
0002
20
180
330
0006
544
92
Tract C-b Holding Pond Data
No Chemical Treatment
Inflow to
Pond A
Mean
Value
037
BDL'
1,217
77
387
575
7 10
2,113
38
47
175
09
450
38
295
254
1,269
70
1,300
141
< ;
193
BDL
688
520
159
BDL
393
1,061
83
High
Value
069
<0003
1,350
087
533
TOO
814
2.500
50
57
198
021
538
0883
4 12
467
1,380
80
1.424
194
< ;
235
-------
Table 5. (Continued)
Constituents*
Federal Drinking
Water Quality Standards'
Primary2 Secondary*
I40CFR Pan 141) (40CFR Part 143)
Ammonia
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chloride
Conductivity
Ip mhos/cm!
Dissolved
Organic Carbon
Dissolved Oxygen
Fluoride
Iron
Magnesium
Molybdenum
Nitrate
Potassium
Residues
-Total Dissolved
-Total Suspended
-Total Solids
-Total Volatile
-Sett/eab/e Matter
-Temperature f°Cf
Selenium
Silica
Sodium
Su/fate
Vanadium
A cidity
Alkalinity
pH (Units!
05
250
20- 22s
03
K. E Kelly andJ. D. Dederick are with Kaman Tempo. Denver, CO 80222.
Edward R. Bates is the EPA Project Officer (see below).
The complete report, entitled "Characterization of Oil Shale Mine Waters, Central
Piceance Basin, Colorado." (Order No. PB 84-211 283; Cost: $11.50, subject to
change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
001
250
65-85
'Values in mg/l except as noted
1 Provided as a reference point Not intended to imply that discharge should meet Drinking Water Standards
1 Federally Enforceable - Federal Register - EPA Water Programs, Wednesday. December 24. 1975 (Vol 40. No 2481
3 Not Federally Enforceable - Federal Register • EPA Water Programs. Thursday. July 19, 1979 IVol 44. No 140)
' BDL = Below Detection Limit
5 Dependent on Temperature (A verage of maximum daily air temperatures)
6 Source C-b Shale Oil Venture, 1977
7 Source USGS, 1977
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
O tU
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