CHARACTERIZATION OF OIL SHALE MINE WATERS
CENTRAL PICEANCE BASIN, COLORADO
by
K. E. Kelly
J. 0. Dederick
Kaman Tempo
Denver, Colorado 80222
Contract No. EPA 68-03-2449
Project Officer
Edward R. Bates
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI", OHIO 45268
MAY, 1984
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NOTICE
This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of trade
names or commercial products does not constitute endorsement or recommenda-
tion for use.
ii
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FORWARD
When energy and material resources are extracted, processed,
converted and used, the related pollution impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used.
The Industrial Environmental Research Laboratory-Cincinnati
(lERL-Ci) assists in developing and demonstrating new and
improved methodologies that will, meet these needs both
efficiently and economically.
This report provides data characterizing oil shale mine
waters from the central part of the Piceance Basin in western
Colorado and assesses the effectivness of retention ponds to
treat these waters. The results should assist developers and
permit writers in selecting appropriate controls for,the handling
'of excess mine waters.
David G. Stephan, Director
Industrial Environmental Research Laboratory
Cincinnati
i i i
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ABSTRACT'
A study was conducted to 'character!ze the oil shale mine
waters in the Piceance Basin. The study sites were Federal
Prototype Lease Tracts C-a and C-b, located in the central por-
tion of the basin. The objective was to collect water quality
data in order to characterize the mine waters and to assess the
effectiveness of treatment systems located at these facilities.
These treatment systems involve in-series retention ponds. In
addition, the effectiveness 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 constituents. This suite included total suspended solids
(TSS) and total dissolved solids (TDS), 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 an assessment of the
effectiveness of using a flocculent and sulfuric acid for the
treatment of excess waters encountered during aotive mining on
Tract C-b. The flocculent was added to reduce : the suspended
solids concentrations during periods of active mining and the
acid was used to reduce the somewhat 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.
Fluccuations in some constituents may have been due to such
phenomena as pH changes, aeration, evaporation, and oxidation-.
reduction changes associated with the transformation of the
groundwater from an underground (aquifer) environment to a sur-
face (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 .negligible difference unless
chemicals are added . The addition of the flocculent in the
Tract C-b pond system during periods of active mining was very
effective in reducing the suspended sediment concentrations. In
addition, the sulfuric acid treatment reduced the, pH at Tract C-
b. Concerning the general water quality, such as the trace
elements, cations and anions, and other pertinent constituents,
there was not a significant increase or decrease due to the
chemical additives. In addition, the effectiveness of the one-
pond and two-pond systems are very similar upon comparison.
-iv-
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CONTENTS-:
Forward iii
Abstract iv
Contents v
Figures vi
Tables vii
Acknowledgments viii
Section . Pagi
1 Introduction and Background 1
Purpose and Objective of Study 1
Location and Description of Study Area 1
Overview of Tract C-a and C-b 17
Development Activities
2 Study Approach 22
Constituents Selected for Analysis 22
Sample Collection Points 22
Sampling and Analytical Procedures 25
3 Data Discussion 27
Water Quality Data for Tract C-a 27
and C-b
Conclusions 40
4 Quality Assurance Programs 42
Field Sampling Program Quality Control 42
Laboratories Quality Assurance Programs 46
References 49
Appendix
A Analytical and Field Data for the 51
Sampling Sites on Tract C-a
8 Analytical and Field Data for the 64
Sampling Sites on Tract C-b
_ v -
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FIGURES
Dumber Page.
1 Location of Tracts C-a and C-b ' 2
Study Area in the Piceance Basin
2 Geologic Section of the Piceance Basin 3
Along a North-South Line Between
Tracts C-a and C-b
3 Concentration of Dissolved Solids in 5
the Lower Aquifer, May-September 1973
4 Trilinear Diagram of Water Quality Data 12
for the Upper and Lower Aquifers,
Tract C-a
5 Trilinear Diagram Presenting Groundwater 13
Quality Data for Tract C-b
6 Concentration of Dissolved Solids in the 14
Upper Aquifer, May-September 1973
7 Trilinear Diagram for the Geffrey Pond 29
Inflow, Tract C-a
8 Trilinear Diagram for West Retention Pond 30
Inflow, Tract C-a
9 Trilinear Diagram for West Retention Pond 31
Outflow, Tract C-a
10 Trilinear Diagram for the Pond A Inflow, 35
Tract C-b
11 Trilinear Diagram for the Pond B Outflow, 36
Tract C-b
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TABLES
Number P age
1 Lower and Upper Aquifer Baseline Water 7
Quality Data on Tract C-a
2 . Lower Aquifer Baseline Water Quality 10
Data Collected on Tract C-b
3 Upper Aquifer Baseline Water Quality 15
Data Collected on Tract C-b
4 Surface Water Baseline Water Quality 18
Data for Water Year 1975
5 List of Constituents/Methods Selected 23
for Chemical Analysis
6 Tract C-a Water Quality Data 28
7 Comparison of Tract C-a Groundwater . 33
Baseline Data and Federal Drinking
Water Standards With Holding Pond Data
Collected During This Study
8 Tract C-b Water Quality Data '; 37
9 Comparison of Tract C-b Groundwater 39
Baseline Data, Surface Water Baseline
Data, and Federal Drinking Water
Quality Standards With Holding Pond
Data Collected During This Study
10 U.S. EPA Recommended Sample Preservatives, 43
Volume Requirements, Containers, and
Holding Times
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ACKNOWLEDGMENTS
Dr. Guenton C. Slawson, Jr. was a principal initial
contributor to the report. Dr. Slawson's involvement with the
report ceased when he joined the Rio Blanco Oil Shale Company as
Manager of Environmental Affairs. His continued support toward
the study after joining Rio Blanco Oil Shale Cornpany is greatly
appreciated.
In addition, Kaman Tempo would like to acknowledge the
support and cooperative interaction of Mr. E.B. Baker, as well as
others, of Cathedral Bluffs Shale Oil Company.
- vi11 -
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CHAPTER 1
INTRODUCTION -AND BACKGROUND
PURPOSE AND OBJECTIVE OF STUDY :
The objective of this study was to provide a detailed
characterization of the mine water and assess the treatment
systems used on Federal Prototype Le-ase Tracts C-a and C-b,
located in the Piceance Basin, Colorado. , These data were
collected to assist other' oil shale developers and permit writers
in selecting appropriate controls for the handling of excess mine
waters. The treatment facilities at both sites consisted of two
in-series retention ponds. To characterize these facilities,
samples were collected for determining the quality of water
derived from mine pumpage and aquifer dewatering activities
previous to treatment, as well as the treated water derived from
the outflow of the in-series retention ponds. Presently, the
treated water is disposed of by reinjection into the groundwater
system, utilized for on-site activities, or discharged to surface
water systems. The data collection procedures, results, and
quality assurance programs are discussed in Chapters 2, 3, and 4,
respectively.
LOCATION AND DESCRIPTION OF STUDY AREA
Lease Tracts C-a and C-b are located in the Piceance Basin
of Rio Blanco County, Colorado (Figure 1). The ^climate of the
Piceance Basin is considered to be semiarid montane. The average
annual precipitation in the central portion of the basin is
generally on the order of 12 inches, most of which occurs as
snowfall. High summer temperatures coupled with low humidity
create a high evaporation rate.
The Piceance Basin is drained by two perennial streams,
Yellow Creek and Piceance Creek, both of which are tributary to
the White River. The White River flows into the Green River,
which is a tributary to the Colorado River. The base flow of
Yellow and Piceance Creeks is provided by numerous springs
throughout the basin. :
The regional stratigraphy of the basin is comprised of the
following Eocene units, in ascending order: Wasatch Formation,
Green River Formation, and the Uinta Formation. In addition, the
Green River Formation is comprised of the following members, in
ascending order: Douglas Creek, Garden Gulch, Anvil Points, and
Parachute Creek. The oil shale to be mined is located in the
Mahogany Zone of the Parachute Creek member. A generalized
geologic cross-section through the Piceance Basin is shown in
Figure 2.
The area contains two important bedrock aquifer systems:
the Upper Aquifer and the Lower Aquifer. The Lower Aquifer
occurs in the Parachute Creek Member below the ,Mahogany Zone.
The Upper Aquifer is located in the upper Parachute Creek Member
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and the Uinta Formation above the Mahogany Zone. The Mahogany
Zone acts as a leaky aquitard between the Upper and Lower
Aquifers.
Recharge for the Upper Aquifer dominately occurs along the
rim of the Piceance Basin where the Green River Formation
outcrops, although downward infiltration of snow melt probably
also contributes. The downward potential difference between the
Upper Aquifer and Lower Aquifer indicates that most ' of the
recharge for the Lower Aquifer occurs as leakage through the
Mahogany Zone from the Upper Aquifer. The water in both aquifers
flows toward the center of the basin and, in some locations,
discharges into Piceance and Yellow Creeks.
In regard to water use within the Piceance Basin, there is
no extensive use of water from the bedrock aquifers beneath
Tracts C-a and C-b. This is probably due to groundwater quality
and depth considerations, as well as the availability of surface
water sources. In addition, there is rather limited
agricultural, livestock, industrial, and municipal development in
the area.
The agricultural development which does occur within the
basin consists of 5100 acres of irrigated hay an:d pastureland.
The irrigation water for these activities is derived domi-nately
from the Piceance Creek watershed during the months of April and
May. In addition to the irrigated acreage in the Piceance Creek
watershed, approximately 200 acres of irrigated land are present
in the Yellow Creek watershed. This land is irrigated with water
derived from Yellow Creek.
The existing water quality within the basin will be
discussed separately as Upper Aquifer, Lower Aquifer, and surface
water. The major source of baseline water quality data are the
Tract C-a and C-b operators due to the environmental monitoring
requirements associated with the Federal leases. Additional
sources of baseline data, particularly for surface water,
includes the Bureau of Land Management (B.L.M.) and the U.S.
Geological Survey (U.S.G.S.).
Lower Aquifer
The total dissolved solids (TDS) content for Lower Aquifer
water ranges from about 500 milligrams per liter (mg/1) to nearly
40,000 mg/1 (Figure 3), with the average 9400 mg/1. Using the
classification developed by Robinove, et al. (1958), this water
is classified as moderately saline, although it can be briney in
some locations. Obviously, these high salinity values render the
Lower Aquifer unsuitable for many uses in many locations
throughout the basin. :
The water is of fairly pure sodium-bicarbonate type, with
chloride as the only other major ion. Calcium and magnesium are
very low, partly because of the minerals dissolved are sodium
salts, dominatly nacholite. Chloride is significant because of
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EXPLANATION
• WELL
1000 LINE OF EQUAL DISSOLVED-SOLIDS CONCENTRATION
Interval, in milligrams per litre, is variable
108°
Base from US Geological Survey
State base map, 1969
0
10 15 KILOMETRES
Figure 3. Concentration of dissolved solids in the Lower Aquifer,
May-September 1973 (Weeks et al., 1974).
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the presence of -significant quantities of halite in the aquifer.
Trace elements in the aquifer which can attain rather high
concentrations include barium, boron, fluoride, and lithium. For
instance, even in regions of lower salinity, the fluoride content
is over 10 mg/1 , with extremes as high as 60 mg/1 common. In the
high-salinity region, barium concentrations of 13 mg/1, boron
concentrations of 120 mg/1, and lithium concentrations of 6 mg/1
have been measure. Baseline water quality values for an
extensive suite of constituents measured for samples collected
from the Lower Aquifer on Tracts C-a and C-b are shown in Tables
1 and 2, respectively. This data has been tabulated to show the
minimum, maximum, and mean, as well as the standard deviation for
the period of collection. In addition, Figures 4 and 5 are
trilinear diagrams for the Upper Aquifer and Lower Aquifer
baseline data .on Tract C-a and C-b, respectively. These diagrams
provide a useful means for characterizing the groundwater quality
data.
Aquifer ;
The Upper Aquifer water quality does not exhibit the extreme
salinities or trace element concentrations of the Lower Aquifer.
The water- quality for the Upper Aquifer in the basin does show an
increase in total dissolved solids from 350 mg/1 near the
recharge areas to over 2000 mg/1 in the basin center (Figure 6).
However, this increase in TDS is not accompanied by high trace
element concentrations. The water is of a similar type to that
of the Lower Aquifer, with a sodium-bicarbonate, character and
moderately chloride. However, unlike the Lower Aquifer, fluoride
and other trace elements have very low concentrations. Baseline
water quality data for the Upper Aquifer collected on Tracts C-a
and C-b are shown in Tables 1 and 3, respectively. This data has
been tabulated to show the minimum, maximum, mean, and standard
deviation for the period of collection.
Surface Water
As previously mentioned, Yellow and Piceance Creeks are the
primary surface waters in Piceance Basin. The location of Tracts
C-a and C-b in relation,to these creeks are shown in Figure 1.
Baseline water quality data for four U.S.6.S. stations located
along Piceance Creek and a tributary to -Yellow Creek are
presented in Table 4. These data represent the October, 1974 to
September, 1975, water year. The description•of the U.S.G.S.
stations are as follows:
U.S.G.S. STATION LOCATION
09306007 Piceance Creek below Rio
Blanco, Colorado; in SE1/4,
SE1/4, Sec. 32, T2S, R96W,
above Tract C-b.
09306061 Piceance Creek above Hunter
Creek, in SE1/4, NE1/2,
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LEGEND
° LOWER AQUIFER
• UPPER AQUIFER
Figure 4. Trilinear diagram of water quality data for Upper and Lower
Aquifers, Tract C-a (data from RBOSP, 1977).
12
-------
TRACT C-B
« UPPER AQUIFER
9 LOWER AQUIFER
° SEEPS AND SPRINGS
• ALLUVIAL WELLS
Figure 5. Trilinear diagram presenting groundwater quality data for
Tract C-b (data from C-b Shale Oil Venture, 1977).
13
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EXPLANATION
• WELL
<»» SPRING
• - 507 - LINE OF EQUAL DISSOLVED-SOLIDS CONCENTRATION
Interval 500 milligrams per litre
108 •
40°
Bue from US. Geological Survey
State base map, 1969
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Figure 6. Concentration of dissolved solids in the Upper Aquifer,
May-September 1973 (Weeks et al., 1974).
14
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Sec. 27, T2S, R97W, below
Tract C-b.
09306235 Corral Gulch near Rangely,
Colorado in SE1/4, NW1/4,
Sec.5, T2S, R99VI, a trib-
utary to Yellow Creek above
Tract C-a.
09306242 Corral Gulch near Rangely,
Colorado in SE1/4, NW1/4,
Sec. 25, T1S, R99W, a
tributary to Yellow Creek
below Tract C-a.
The total dissolved solids concentration for Yellow Creek in
the area of Tract C-a ranges from 664 to 1140 mg/1, with an
average of 735 mg/1 upstream from Tract C-a and 851 mg/1
downstream from Tract C-a. The major cations of the baseline
water quality for Yellow Creek consist of sodium, calcium, and
magnesium, whereas the major anion is bicarbonate. There are not
any trace elements present which obtain appreciable values. In
general, the water quality of Yellow Creek can be characterized
as magnesium-calcium-sodium bicarbonate type, very, similar to the
type found in the Upper Aquifer, which provides, base flow to
Yellow Creek. In addition, the water quality of Yellow Creek
degrades downstream, as indicated by the increase in total
di ssolved solids.
The baseline water quality for Piceance Creek is very
similar to Yellow Creek. Total dissolved solids range in
concentration from 502 to 1050 mg/1, with an average of 698 mg/1
upstream from Tract C-b and an average of 893 mg/1 downstream
from Tract C-b. The major cations of Piceance Creek consist of
sodium, calcium, arid magnesium; whereas the dominant anion is
bicarbonate. In regard to trace elements, none are very
important. The water quality of Piceance Creek1 is also very
similar to the Upper Aquifer water quality. In addition, there
is a general degradation of water quality in1 a downstream
direction, as indicated by the increase in total dissolved solids
from an average of 698 mg/1 to 893 mg/1.
OVERVIEW OF TRACT C-A AND C-B DEVELOPMENT ACTIVITIES
Kaman Tempo's sampling activities occurred between
September, 1981 and March, 1983. The specific dates for each
sampling effort were September, 1981; May, June, September, and
November, 1982; and January and March, 1983. To better
understand and interpret the analytical data, the activities of
the operators for Tracts C-b and C-a will be discussed below.
Tract C-b
The principal activities associated with the development of
Tract C-b during the sampling project were the continuation and
17
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completion of three major shafts. In addition, the water
management program to treat and dispose of waters Associated with
the mine dewatering activities was expanded. This program
consists of pumping the excess mine water derived from the
dewatering of two of the shafts into two retention ponds (i.e.,,
Ponds A and B) which are in-series. The retention ponds outflow
water is then discharged to Piceance Creek, . reinjected into the
groundwater system, or utilized for on-site sprinkler irrigation.
These activities did not vary over the duration of the sampling
project.
The mining activities associated with the development of
Tract C-b were rather sporatic during the project. For instance,
mining activities were not very active during the first half of
1982, and virtually non-existent after September, 1982. However,
activities were fairly brisk during 1981.
Tract C-a
At the end of 1981, Rio Blanco Oil Shale Company (RBOSC)
nearly completed the 4-1/2 year development program designed to
determine the technical, economical, and environmental viability
of the modified in-situ (MIS) recovery process. This program
resulted in the ignition of Retort 1 on June, 1981. Retort 1
burned through December of 1981, at which time it was shut-in and
is presently cooling down. Due to the retort activities, aquifer
and surface water quality data collected after June of 1981, are
not considered to represent baseline conditions (RJ30SC, 1983).
The next phase of development was intended to determine the
viability of Lurgi surface retorting activities. This
demonstration was temporarily suspended on August 1, 1982.
The dewatering operations during the initial sampling effort
(September, 1981) consisted of two upgradient dewatering wells
and mine sumps. In November of 1981, the use of the dewatering
wells was discontinued, although pumping from the mine sumps
continued to dewater the mine. The water from the dewatering
operations is treated by two retention ponds which are in-series.
The treated water is then reinjected into the Upper Aquifer.
There are no surface discharges. In addition, water derived from
the Retort 1 burn is pumped to another treatment system
consisting of non-discharging evaporation ponds and, therefore,
was not sampled during this project. ,
21
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CHAPTER 2
STUDY APPROACH ;
CONSTITUENTS SELECTED FOR ANALYSIS
To best characterize the water derived from the mine and
dewatering activities, as well as the treated water, a fairly
extensive suite of constituents was selected for analysis. Many
of these constituents have also been identified as potential
pollutants from studies conducted on the chemical
characterization of simulated and observed in-situ oil shale
process water (e.g., Fox et al., 1978; Slawson, -1979; Pfeffer,
1974; Stuber and Leenheer, 1978; LBL, 1978).
The constituents selected for analysis during this study are
shown in Table 5. In addition, the methods of analysis for each
constituent are also shown in Table 5. This suite of
constituents was divided into a comprehensive group and an
abbreviated group. Analysis for the abbreviated group was
conducted during the months of September, 1981; September, 1982;
and November, 1982. Analysis for the comprehensive group of
constituents, which also included analysis for the abbreviated
group, was conducted during the months of May, 1982; July, 1982;
January, 1983; and March, 1983. The analytical and field data
collected during this study for Tract C-a and C-b are presented
in Appendices A and B, respectively.
SAMPLE COLLECTION POINTS
An overview of the development activities on both Tracts C-a
and C-b was previously discussed in Chapter 1. This section
identifies the sample collection points on each tract, as well as
discusses the mine dewatering and water treatment activities. '.
Tract C-a
The water from the mine on Tract C-a is pumped from levels
within the mine and the mine shaft to the Jeffrey Pond, which is
the primary retention pond. After preliminary treatment in the
Jeffrey Pond, the water is discharged to the West Retention Pond
for secondary treatment. The West Retention Pond is in-series
with the Jeffrey Pond. The treated water derived from the West
Retention Pond is then reinjected into the Upper Aquifer. :
The sampling points on Tract C-a consisted of three
locations: (1) the mine outflow into the Jeffrey Pond, (2) the
Jeffrey Pond outflow into the West Retention Pond, and (3) the
West Retention Pond outflow. This approach allowed the
evaluation of the total treatment system. For example, sampling
both the inflow and outflow of the primary retention pond (i.e.,
Jeffrey Pond) provides an indication of the effectiveness of a
single retention pond. In addition, sampling the outflow of the
secondary pond (i.e., West Retention Pond) demonstrates the
effectiveness of the treatment system as a whole. '.
22
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TABLE 5 ' .'•
LIST OF CONSTITUENTS/METHODS1 SELECTED FOR CHEMICAL ANALYSIS
Abbreviated Analysis
CONSTITUENTMethod
CONSTITUENT
Method
pH Field-
Temperature Field
Conductivity Field
Dissolved Oxygen Field
Ammonia 350.3
Arsenic2 301A.VII
Bicarbonate 310.1
Boron 212.3
Carbonate 310.1
Calcium2 301A.II
Chloride 325.3
Fluoride 340.2
Iron2 301A.II
Magnesium 242.1
Mercury 245.1
Molybdenum 246.1
Nitrate 352.1
Nitrogen 351.1
Potassium 258.1
Selenium 270.3
Silica 370.1
Silver 272.1
Sodium ---3
Sulfate 375.3
V an ad i urn ___ 3
Dissolved Organic Carbon .--7
Total Dissolved Solids 160.1
Total Volatile Solids 160.4
Total Suspended Solids 160.2
Total Solids 160.3
Settleable Matter 160.5
Bari urn
Beryllium
Cadmi urn2
Chromi unr
Cobalt2
Copper2
Cyan i de
Fractionated DOC
Lead2
Lithium
Manganese
Nickel2
Orthophosphorus
Phenols
Phosphorus
Silver2
Strontium EPA
Sulfide
Thallium
Thiosulfate
Tin
Titanium
Tub i di ty
Uranium EPA
Zinc
208. 1
210.1-
301A.III
301A.III
219.1
301A.II
355.2
USGS
Report4
301A.II
AA8
243. 1
301A.II
365.1
420.2
365.4
301A.II
Report 5
376.1
279,2
NSM9
282. 1
283.1
180.1 '
Report6
301A.II
(continued)
23
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TABLE 5
(continued)
11 methods are from U.S. EPA, 1979. Methods of Chemical
Analysis of Water and Wastes, EPA-600/4-79-620; unless
otherwise denoted.
2Methods from American Public Health Association, 1976. Standard
Methods for the Examination of Water and Waste Water. 14th
Ed.
3Method from U.S. EPA, The Inductively Coupled Plasma Optical
Emission Spectrometric Method (Method 200.7).
^Analyzed according to method stated in: U.S. Geolog. Survey,
1979. Analytical Method for Dissolved Organic Carbon
Fractionation. USGS/WRI-79-4.
5 :
Analyzed according to method stated in: U.S. Environmental
Protection Agency, 1975. Interim Radiochemical Methodology
for Drinking Water. EPA-600/7-760-093.
Analyzed according to method stated in: U.S. Environmental
Protection Agency, 1979. Radiometric Method for the
Determination of Uranium in Water. EPA-600A7-79-093.
Analyzed on a Coulmetric Carbon Analyzer.
o
Analyzed with Atomic Absorption.
g
No standard method.
24
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Iract C-b :
As with the treatment facilities on Tract C-a, the Tract C-b
facilities consist of two retention ponds which are in-seri.es.
The water from the mine production and service shafts dewatering
operations are pumped into the primary retention pond (i.e., Pond
A). After retention in Pond A, the water is treated with
sulfuric acid and a magnifloc cationic flocculent to lower the pH
and settle the suspended solids, respectively. This water then
flows into Pond B via gravity for additional retention. The acid
and flocculent treatment was discontinued in September, 1982,
when the mining activities terminated. After this date, chem-
icals were not used in the treatment. The treated waters were
then subject to one of the following modes of disposal: (1)
discharge to Piceance Creek, (2) on-site sprinkler irrigation, or
(3) reinjection into the Upper Aquifer.
The sampling points on Tracts C-b consisted of two
locations: (1) the inflow into Pond A, which is water derived
from the dewatering of the shafts previous to treatment and (2)
the treated water discharge from Pond B. The discharge from Pond
A was not sampled since the effectiveness of treatment with a
single pond was evaluated on Tract C-a. By sampling the inflow
and outflow of the entire treatment system on Tract C-b,
comprehensive analytical data for the effectiveness of the
treatment system as a whole were collected.
SAMPLING AND ANALYTICAL PROCEDURES
Grab samples were collected in the field from the dis-
charging water at the various sample collection points previously
discussed. Immediately upon sample collection, the following
constituents were measured in'the field with portable instru-
ments: pH, specific conductance, dissolved oxygen, and temper-
ature. Samples which were sent to the laboratory for analysis
and required filtering were also filtered in the field through a
standard .45 micron (ym) membrane filter with a Skougstand
filter apparatus. A Gilman stainless steel filtering apparatus
was used to filter dissolved organic carbon samples through a .45
ym silver membrane filter. After filtration, the samples were
preserved and cooled with ice according to U.S. EPA (1979a)
recommended procedures and placed in ice chest for shipment. The
samples were shipped via commercial bus to both the Colorado
State University (CSU) laboratory in Fort Collins, Colorado and
CORE laboratories in Denver, Colorado. Every shipment during the
course of the study was received within 24 hours by the lab-
oratories, except for the samples collected July 20, 1982, whic.h
did not arrive at the CSU laboratory until 36 hours after collec-
tion.
Th.e analytical laboratories performed the analyses of the
selected constituents in Table 5. These constituents were
analyzed according to the methods presented in Table 5. The
quality assurance program for the analytical laboratories, as
25
-------
well as the field sampling, is presented in Chapter 4. It should
be noted that values for ammonia and nitrate reflect abrupt
changes that are not characteristic of historical trends.
Therefore, the data on ammonia and nitrate are suspect.
26
-------
CHAPTER 3
DATA DISCUSSION
The results of the sampling program are discussed in this
chapter. The effects of changes in operational procedures on th.e
water quality trends at each sampling point are also discussed.
The data for each tract is discussed separately under each
section below.
WATER QUALITY DATA FOR TRACT C-A and C-B
Tract C-a :
As previously discussed in Chapter 2, there were three
sampling points on Tract C-a. These included the mine inflow
into the primary retention pond (i.e., Jeffrey Pond), the inflow
to the secondary retention pond (i.e., West Retention Pond) from
the primary retention pond, and the outflow of the secondary
retention pond. The data collected during this sampling effort
are shown in Appendix A. In addition, the following statistics
have been summarized on the major constituents and are presented
in Table 6: number of samples, mean, high, low, and standard
deviation. In addition to the data presented in Table 6,
trilinear diagrams were prepared to characterize the water
quality at each sampling point over the duration of the project.
The trilinear diagrams for the Jeffrey Pond, inflow, West
Retention Pond inflow, and West Retention Pond outflow are shown
in Figures 7, 8 „ and 9, respectively.
Inspection of the trilinear diagrams for all three of the
sampling points indicates that the quality can be classified as a
non-dominant type water. The major cations and anions consist
of: magnesium, sodium, sulfate, and bicarbonate. The
percentages of total anion or cation concentration for each
constituent at each sampling point over the duration of the
project were:
Sampling Point
Jeffrey Pond
Inf1ow
West Retention
Pond Inflow
West Retention
Pond Outflow
Magnes ium Sodi urn Bicarbon ate Sulfate
39.0% 49.4% 50.9% 46.7%
39.4% 48.6% 50.4% • 47.0%
39.2% 48.7% 50.5% 46.8%
The operational procedures on Tract C-a did change during
the course of the study. In November of 1981, the Upper Aquifer
dewatering system was discontinued. Previous to this period,
dewatering wells 6S-D6U and 6S-D8U were used for this activity.
The water derived from these wells was discharged into the
Jeffrey Pond. In addition, the water from the mine sumps was
also discharged into the Jeffrey Pond. This composite water was
then treated in the two ponds and reinjected into the Upper
27
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Aquifer. After the discontinuation of the dewatering wells in
November of 1981, the dewatering of the mine via sumps continued
throughout the duration of the project.
In regard to water quality trends at each sampling point,
none were observed over the course of the study. In fact,
inspection of the trilinear 'diagrams for each sampling point
(i.e., Figures 7, 8, and 9) indicates that the analytical data
are very consistent. The analytical data for all of the sampling
dates are very similar for each sampling point, and consequently,
result in very good grouping of points on the trilinear diagram.
In addition, a variation in the water quality was not observed
after the discontinuation of the dewatering ^program. This
indicates that the quality of water derived from the mine sumps
is very similar to the quality, of water derived from the once
operating Upper Aquifer dewatering program. Comparison of the
trilinear diagrams for the data collected during this study
correlates quite nicely with the Upper Aquifer data presented in
Figure 4, a trilinear diagram of the water quality baseline data
for the Upper and Lower Aquifers on Tract C-a. Therefore, it is
reasonable to assume that water derived from the dewatering
activities on Tract C-a is predominately from the Upper Aquifer.
i
The changes in water quality between the three sampling
points is somewhat variable. A comparison between the untreated
water flowing into Jeffrey Pond with the treated water flowing
out of the West Retention Pond shows an increase in concentration
of many constituents. For example, the mean .values of the
following constituents show slight increases when the data
collected for the Jeffrey Pond inflow is compared with the data
of the West Retention Pond outflow (see Table 6): boron,
carbonate, calcium, dissolved oxygen, iron, magnesium,
molybdenum, potassium, total solids, and total dissolved solids.
None of these increases are very significant and can probably be
related to pH changes, aeration, evaporation, and reduction
oxidation changes associated with the transformation of the
groundwater from an underground environment to a sur'face
environment, as well as the associated retention time in th.e
ponds. In addition, some of the changes may be attributable to
laboratory variations.
Groundwater quality data for Tract C-a are available for
both the Upper and Lower Aquifers. These data, as wel1-a.s the
data collected during this study to characterize the treatment
system, are presented in Table 7. In addition, corresponding
Federal Drinking Water Quality Standards are also included in
Table 7. It should be noted that this comparison is not meant to
imply that the discharges from the treatment system should meet
these standards, these are only included for reference purposes.
Comparison of the water quality data collected from the
outflow of the West Retention Pond with the baseline groundwater
quality, data indicates that several constituents exceed baseline
conditions upon discharge from the West Retention Pond. Specific
water quality constituents in which the mean values exceed the
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mean values for baseline conditions in some or all instances
include carbonate, flouride, magnesium, and pH. However, it is
evident from reviewing Table 7, that these increases over
baseline conditions are minimal and, consequently, do not
constitutesignificant increases.
Tract C-b '-
There were two sampling points on Tract C-b. These points
consisted of (1) The inflow to the primary retention pond (i.e.,
Pond A) and (2) The outflow of the secondary retention pond
(i.e.. Pond B). The data collected on Tract C-b during the
sampling period are presented in Appendix B.
In addition, the following statistics have been summarized
for the major constituents and are presented in Table 8: number
of samples, mean, high, low, and standard deviation. In order to
characterize the water quality, trilinear diagrams were prepared
for both the inflow to Pond A and the outflow of Pond B. These
diagrams are presented in Figures 10 and 11, respectively. ;
The trilinear diagrams presented in Figures 10 and 11,
indicate that the dominant cation and anion present in the water
sodium and bicarbonate, respectively. The average percentages of
total -anion or cation concentration for each constituent at each
sampling point over the duration of the project were:
Samp ling Point Sodi urn B icarbonat-e
Pond A Inflow 96.8% 90.356
Pond B Outflow 96.9% 88.3%.
Therefore, the water of the Tract C-b system is classified as a
sodium-bicarbonate type.
In regard to water quality trends at each sampling point,
none were observed during the sampling program (Table 8). The
sampling dates plotted'on the trilinear diagrams (Figures 1-0 and
11) for the sampling points show a very good grouping of data
points. However, a small deviation is noted for Sample 1, which
represents the sample collected during acid .and flocculent
treatment. In general, the remaining data points indicate that
there is very little variability in the water quality. In regard
to Tract C-b operational procedures, the dewatering of the
production and service shafts continued throughout the sampling
period without variation.
The trilinear diagrams for the data collected on Tract C-b
during this sampling program correlates fairly well with the
Lower Aquifer data presented in Figure 5, a trilinear diagram of
the baseline water quality data for the Upper and Lower Aquifers
on Tract C-b. This indicates the water from Jthe dewatering
activities is- primarily derived from Lower Aq'uifer sources.
However, the stratigraphic interval from which the dewatering
occurs is located in the zone designated as Upper Aquifer. One
explanation for this discrepancy may be that the dewatering
34
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37
-------
activities have reversed the gradient between the Upper 'and Lower
Aquifers to such an extent, that the Lower Aquifer is recharging
the Upper Aquifer through the semi-permeable Mahogany zone.
A comparison of the inflow and the outflow of the Tract C-b
treatment system indicated no significant changes except for
reductions in total suspended solids and pH when flocculent and
sulfuric acid were added. (see Table 8). This relationship is
true for the samples collected during the period of chemical
treatment (i.e., flocculent and sulfuric acid) and the periods
without chemical treatment. Once again, this aspect is probably
due to the exposure of the groundwaters to atmospheric con-
ditions. The fact that many of the constituents increased
slightly after residence in the retention ponds Vindicates that
this type of treatment method may not be totally effective for
groundwaters.
Baseline water quality information is also available for
Tract C-b. These data include locations above and below Tract C-
b on Piceance Creek, as well as groundwater data for both the
Upper and Lower Aquifers. This information is included in Table
9. In addition, both the quality data for the treatment system
on Tract C-b collected during this study and the Federal Drinking
Water Standards are also included in Table' 9. '••
An inspection of Table 9 indicates that the mean values for
some constituents in the discharge from Pond B exceeded, in some
cases, the mean values in the Upper Aquifer baseline groundwater
quality concentrations. These constituents include bicarbonate,
carbonate, conductivity, flouride, molybdenum, (except during
sulferic acid and flocculent treatment) nitrate, potassium, TDS1,
and sodium. However, these increases were fairly minimal and,
therefore, not large enough to insinuate significant degradation
in the quality of groundwater derived from Tract C-b.
The mean values of the following constituents upon discharge
from Pond B exceeded baseline conditions for the mean values
along Piceance Creek at the site below Tract C-b (see Table 9):
ammonia, bicarbonate, boron, carbonate, conductivity, dissolved
oxygen (lower concentration), TDS, temperature, sodium, alkalin-
ity, and pH. One obvious reason for the elevated values of the
above constituents relative to the baseline conditions of
Piceance Creek is the fact that the water discharged from Pond B
is derived entirely from the groundwater system, which is of
poorer quality than Piceance Creek.
38
-------
oo
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^ ^'^^"•Saiaj
nj
39
-------
CONCLUSIONS
This discussion is divided into two sections. The first
section addresses the effectiveness, of a one-pond or two-pond
system without chemical treatment (i.e., flocculent and sulfuric
acid). The second section presents conclusions concerning the
effectiveness of adding a flocculent to decrease total suspended
solids concentrations and adding sulfuric acid to decrease the pH
in the treatment system. It should be noted that the discussions
of the respective pond systems with respect to water quality data
and the resultant changes are presented using mean values of
respective water quality constituents.
Effect i veness of System Without Chemi cal Treatment
The one-pond system addressed here consisted of the West
Retention Pond on Tract C-a. With respect to Jeffrey Pond, it
was not included as part of the assessment due to its extremely
small size and corresponding short retention time. It was felt
that even though the water passed through Jeffrey Pond before it
entered the West Retention Pond, the holding time was so small
that effects on water quality were believed to be negligible
compared to the West Retention Pond.
The overall quality remained essentially unchanged as the
water passes through the West Retention Pond. The decrease in
total suspended solids concentrations from 6.3 -mg/1 to below
detection limits is not significant.
The two-pond system assessed during this study is located on
Tract ' C-b and consisted of the primary retention pond (Pond A)
and the secondary retention pond (Pond B), which are in-series.
Samples were collected for the inflow to Pond A and the outflow
from Pond B on six occassions. In addition, one sample was
collected when flocculent and sulfuric acid were added, as dis-
cussed below. Similar to the one-pond system, fluctuations for
most of the water quality constituents were insignificantly small
(less than 10%). Total suspended solids concentrations remained
unchanged (less than 10 mg/1). Concentrations of other con-
stituents varied slightly but not significantly. In summary, the
general water quality did not improve nor was it degraded, after
treatment in the two ponds (without chemical treatment).
Treatment with F1occulent and Sulfuric Ac i d
A magnifloc cationic flocculent designed to precipitate out
suspended solids concentrations was added to the two-pond system
on Tract C-b. This was done at a time when mining activities
were occurring and large increases in total suspended solids were
expected to be observed in the two ponds.
Water quality samples were taken on September 16, 1981 at
the inflow to Pond A and the outflow from Pond B to assess the
effectiveness of the flocculent. The concentration of suspended
40
-------
solids at the inflow to the system was found to be 565 mg/1, with
the concentration reduced to 6.0 mg/1 at the outflow of the
system. These data clearly indicate the effectiveness of the
flocculent, as the suspended solids concentration was reduced by
about 99%. At the, same time, the silica concentration increased
(from 23 mg/1 to 35 mg/1) and the total dissolved solids concen-
tration increased (from 1,354 mg/1 to 1,517 mg/1). However,
these increases did not significantly degrade the water quality,.
At the same time as the flocculent was added (during mining
activities), 'sulfuric acid was also added in order to reduce th.e
pH of the water be.fore it was discharged from the two-pond
system. The water sampled at the inflow point had a pH of 9.2,
compared to a value of 7.8 at the outflow point, which reflects
the addition of sulfuric acid. At the same time, alkalinity was
reduced from 1147 mg/1 to 926 mg/1 (a decrease of 19%), while
acidity remained stable at <5 mg/1. The one apparent effect of
adding sulferic acid was an increase in sulfate from 186 mg/1 to
311 mg/1 (an increase of 77%). However-, this increase in sulfate
did not seriously degrade the water quality.
The overall conclusion regarding the effectiveness of the
one- and two-pond systems is the same. The wate:r quality con-
stituents analyzed for in this study were not appreciably
affected by the respective pond systems. With respect to the
addition of flocculent and sulfuric acid, both additives appear
to adequately treat specific constituents. The flocculent was
very effective in reducing suspended solids concentrations and
the sulfuric acid reduced the pH. These changes occurred without
significant degradations of the general water quality.
41
-------
CHAPTER 4
QUALITY ASSURANCE PROGRAMS
FIELD SAMPLING PROGRAM QUALITY CONTROL
Grab samples were collected in 5-gallon carboys at each of
the sampling points. Previous to sample collection, the carboys
were thoroughly rinsed with a deionized water to prevent cross-
contamination. In addition, samples were collected as close tp
the discharge point as possible in an effort to obtain
representative samples. Immediately upon sample collection, the
following constituents were measured with portable instruments:
pH, temperature, dissolved oxygen, and specific conductance. In
order to obtain accurate measurements the samples were analyzed
for a period of at least 20 minutes, which allowed the
instruments to equilibrate. In addition, all of the instruments
were calibrated previous to sample measurement. The instruments
were thoroughly cleaned with deionized water after each sample.
Samples which required filtering were filtered with high
purity nitrogen in a Skougstad-type filter apparatus. This
apparatus is' composed of a polyethylene material and can be
pressurized to force the sample through a 0.45 micron filter into
the sample container. The dissolved organic carbon samples were
filtered with a stainless steel apparatus through a 0.45 micron
silver membrane filter to prevent the introductio,n of organics.
Previous to the introduction of another sample into the filtering
units, the units were disassembled and thoroughly decontaminated
with deionized water. In addition, a new filter was installed
into each unit previous to the filtration of another sample.
Following filtration, preservatives were added to the
sample, if necessary. In addition, the samples were placed in
ice chests and cooled to 4 degrees Celsius with ice. The U.S.
EPA (1979a) recommended procedures were utilized for sample
preservation. In addition, the U.S. EPA recommended sample
volume requirements, containers, and holding times were used as
guidelines during this study. All of these aspects are shown in
Table 10.
Samples were shipped from Rifle, Colorado to the Colorado
State University laboratory in Fort Collins and Core laboratories
in Denver. Commercial buslines were used for these sample
shipments due to the overnight services provided by these
buslines. This arrangement worked very well throughout the
duration of the project and, in every case except one, the sam-
ples were received by the laboratory within 18 hours of the
sampling effort. The exception was during the July 20., 1982,
sampling effort in which the samples were not received by the
Colorado State University laboratory until 36 hours after the
samples were collected.
42
-------
TABLE 1O
U.S. EPA RECOMMENDED SAMPLE PRESERVATIVES,
VOLUME REQUIREMENTS, CONTAINERS, AND HOLDING TIMES
(U.S. EPA. 1979)1
Constituent
RESIDUE
Filterable
Non-
Filterable
Total
Volatile
Settleable"
Matter
Turbidity
METALS
Dissolved
Suspended
Total
Mercury
Dissolved
Total
Req.
(ml)
100
100
100
100
1000
100
200
200
100
100
100
2
Container Preservative
P, G Cool, 4°C
P, G Cool, 4°C
P, G Cool, 4°C
P, G Cool, 4°C
P, • G None Req.
P, G Cool, 4°
P, G HN03 to pH<2
Cool, 4°C
P, G HNO3 to pH<2
P, G HNO3 to pH<2
P, G HN03 to PH<2
Holding
Time
-
7 Days
7 Days
7 Days
7 Days
24 Hrs.
7 Days
6 Mos . ( 4 }
6 Mos . ( 4 5
6 Mos . ( 4 }
38 Days
(Glass )
13 Days
(Hard
Plastic)
38 Days
(Glass)
13 Days
(Hard
Plastic)
(continued)
43
-------
Constituent
INORGANICS ,
Non-Metallic
Acidity
Alkalinity
Bromide
Chloride
Cyanides
Fluoride
Nitrogen
Ammonia
Nitrate
Phosphorus
Ortho-
phosphate,
Dissolved
Total
Silica
Sulfate
Sulfide
Vol.
Req.
(ml)
100
100
100
50
500
300
400
100
50
50
50
50
500
TABLE 1O
(Continued)
2
Container Preservative
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P, G
P only
P, G
P, G
None Req.
Cool, 4°C
Cool, 4°C
None Req.
Cool, 4°C
NaOH to pH 12
None Req.
Cool, 4°C
H2SO. to pH<2
Cool, 4°C
Cool, 4°C
Cool, 4°C
H-SO. to pH<2
Cool, 4°C
Cool, 4°C
2 ml. zinc
acetate
Holding
Time^
24 Hrs.
24 Hrs.
24 Hrs.
7 Days
24 Hrs.
7 Days
24 Hrs.
24 Hrs.
.
24 Hrs.
24 Hrs.
7 Days
7 Days
24 Hrs.
Organic carbon 25
P, G
Cool, 4 C
H2S04 or
HC1 to pH<2
(6)
24 Hrs.
(continued)
44
-------
TABLE 1O
(continued)
1. More specific instructions for preservation and
sampling are found with each procedure as detailed in
this manual. A general discussion on sampling water
and industrial wastewater may be found in &STM,
Part 31, p. 72-82 (1976) Method D-3370. '
2. Plastic (P) or Glass (G) . For metals, polyethylene
with a polypropylene cap (no liner) is preferred.
3. It should be pointed out that holding times listed
above are recommended for properly preserved samples
based on currently available data. It is recognized
that for some sample types, extension of , these times
may be possible while for other types, these times may
be too long. Where shipping regulations present the
use of the proper preservation technique or the holding
time is is exceeded, such as the case of a 24-hour
composite, the final reported data for these samples
should indicate the specific variance.
4. Where HNO, cannot be used because of shipping
restriction's, the sample may be initially preserved by
icing and immediately shipped to the laboratory. Upon
receipt in the laboratory, the sample must;be acidified
to a pH<2 with HNO, (normally 3 ml. 1:1 HNC>3/liter
is sufficient). At the time of analysis, the sample
container should be thoroughly rinsed with 1:1 HNO,
and the washings added to the sample (volume correction
may be required).
5. Data obtained from National Enforcement Investigations
Center-Denver, Colorado, support a .four-week holding
time for this parameter in Sewerage Systems.
(SIC 4952).
45
-------
LABORATORIES QUALITY ASSURANCE PROGRAMS
Two laboratories were utilized during this sampling project.
They consisted of the University of Colorado laboratory and CORE
laboratories. The quality assurance programs for each will be
individually discussed below.
CORE Laboratories
I. Instrument Quality Control
A. Calibrations and Standardizations
(1) Instruments are checked daily for
temperature consistency, weighing
accuracy, etc. prior to sample
introduction to assure proper
operation.
(2) Detection limits and linear working
range data are verified by using
sample blanks, standards, standard
additions, sample spiking, etc.
B. Service
Instruments receive periodic servicing to
assure proper functioning within specif-
ications. Special care is taken to insure
precise and accurate operation of all
analytical balances, being the initial
source of laboratory accuracy. Files
are maintained on all major analytipal
.instruments to document servicing.
II. Laboratory Supplies and Reagents
A. Water
(1) Tap water - used as a preliminary
wash for glassware daily.
(2) Deionized water - obtained by
passing through Cation-Anion ion
exchange columns. This water meets
all specifications set forth by the
U.S. Environmental Protection Agency.
B. Reagents - all A.C.S./analytical grade
C. Solvents - all A.C.S./analytical grade ;
D. Volumetric Glassware - all glassware •
used for this purpose meets Class A
requirements as set forth by the National '
Bureau of Standards. This glassware
includes volumetric flasks and pipets
•which are always used for standard
preparation and measurement of sample
volumes, as well as for other purposes.
III. Internal Quality Control/Precision and Accuracy
To assure that data be both precise and accurate,
duplicate samples, spiked samples, and internal
unknowns are run on a routine basis within the Aurora
46
-------
Lab, as well as within the entire CORE laboratories
network for comparative purposes.
In addition, the data base is evaluated on CORE'S
computer system prior to report finalization for
statistically known correlations. These correlations
include sodium conductivity, anion/cation balances,
cation/anion sums, total dissolved solids, maximum oil
and grease, maximum BOD, and nitrogen relationships.
Ultimately, a data base which has had individual
data point pairs compared against themselves,
individual sample inter-relationships compared against
themselves and sample interrelationships compared
against other samples within the same area or project
wi11 be provi ded.
.This detailed procedure performed .on a continuing
basis results in water quality data that is both
precise and accurate.
IV. Sample Tracking
Sample bottles with the appropriate preservatives
added . are supplied by the .laboratory for use in the
field. Records are maintained which indicate bottle
groupings, client name, client location, and total
bottles shipped. This information is then cross-
referenced upon sample receipt.
V. Analysis Reporting
Raw data is handled a single time when entered
into the in-house PDP-11 computer for calculation,
storage, and reporting. The data base analyses
previously mentioned is then performed !and appropriate
analyses are re-checked and re-entered into the
computer. Subsequent data manipulation, i.e.,
additional reports, transfer of data base to client
computers, storage, etc. are handled electronically to
insure integrity of the data.
Colorado State University
Colorado State University laboratory has a quality con-
trol program in the following areas: sample preservation,
sample analysis, and data handling. These programs are per-
formed according to the criteria of the U.S. EPA (1979b).
Each of these items are discussed further below.
The sample analysis quality control involves the use of
blanks and duplicates. For example, both a blank and dup-
licate sample are analyzed per sample set. In addition, a
standard curve consisting of four or more values is estab-
lished and compared to the analytical results. The sample
47
-------
analysis quality control also involves analyzing the U.S.
EPA Reference Standard and biannual participation in the
U.S.. EPA performance study.
In regard to the data handling, records are kept of the
correlation coefficient, slope, and the intercept of the
standard curve. These records are used to insure linearity
and acceptability of standards. In addition, quality con-
trol charts are kept to provide criteria for, accepting data1.
Kaman Tempo Qua!ity Control
Kaman Tempo also performed internal quality control
measures for the data received by the laboratories. These
measures consisted of calculating the cation-anion balance
for the data set and the evaluation of general water quality
trends at each sampling point. The ions utilized for the
cat ion/an ion balance calculation consisted of calcium, mag-
nesium, sodium, potassium, carbonate, bicarbonate, sulfate,
and chloride. The data was considered to be fairly accurate
if the difference between the cations and anions did not
exceed ten percent.
These quality control measures resulted in identifying
some potential problems with the analytical data received
from the Colorado State University laboratory. For instance.
some data sets had a cation-anion balance off by as much as
45 percent. However, by the time the data , was received^
many of the constituents were beyond the recommended holding
periods and, therefore, a reanalysis would probably not have
resulted in more accurate data.
An additional problem associated with the Colorado State
University data were the analytical results for some fairly
volatile constituents. For example, ammonia and nitrate are
very inconsistent and, in some cases, reflect very abrupt
increases which are not characteristic with historic trends.
48
-------
REFERENCES CITED
American Public Health Association, 1975. Stndard Methods for
the Examination of Water and Wastewater, 14th Edition,
1193p.
C-b Shale Oil Venture, 1977. Environmental Baseline Program,
November 1974 - October 1976. Final Report.
Fox, J.P., D.S. Farrier, and R.E. Paulsen, 1978. Chemical
characterization and analytical considerations .for an in-
situ oil shale process water. LETC/RI -78/7, Laramie Energy
Technology Center.
Hem, J.D., 1971. Study and Interpretation of the Chemical
Characteristics of Natural Water. U.S. Geol. Survey Water-
Supply Paper 1473, 363 p.
Lawrence Berkley Labs (LBL), 1978. Diffuse source effects on in-
situ oil shale development on water quality. Draft report.
McKee, J.E., and H.W. Wolf, 1963. Water Quality Criteria:
California State Water Quality Control Board'. Publication
3-A, 548p.
Pfeffer, P.M., 1974. Pollution Problems and Research Needs for
an Oil Shale Industry. Environmental Development on Water
Quality. Draft Report. :
Rio Blanco Oil Shale Company, 1977. Final Environmental Baseline
Report for Tract C-a and Vicinity. Volume 2.
Rio Blanco Oil Shale Company, 1983. Scope of Work, Lease
Suspension Period, Environmental Monitoring Program.
Submitted to Area Oil Shale Office.
Slawson, 6.C., Jr. (ed .), 1979. Groundwater Quality Monitoring
and Western Oil Shale Development: Identification and
Priority Ranking of Potential Pollution Sources, EPA-600/7-
79-023, U.S., Environmental Protection Agency.
Sla.wson, G.C., Jr. (ed.), 1980. Monitoring Groundwater Qualitys
Th-e Impact of In-Situ Oil Shale Retoring. EPA-600/7-80-132:,
U.S. Environmental Protection Agency.
Stuber, H.A., and J.A. Leenheer, 1978. Fractionation of Organic
Solutes in Oil Shale Wastes for Sorption Studies on
Processed Shale. U.S. Geol. Survey, paper presented at ACS
Fuel Sciences Division Symposium.
U.S. Environmental Protection Agency, 1979(a). Methods for
Chemical Analysis of Water and Wastes. EPA-600/4-79-020,
Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio.
49
-------
U.S. Environmental Protection Agency, 1979(b). Handbook for
Analytical Quality Control in Water and Wastewater
Laboratories. EPA-600/4-79-019.
U.S. Geological Survey, 1977. Water Resources Data for Colorado
Water Year, 1975, Volume 2. Colorado .River Basin. Water
Resources Division, Report No. USGS/WRD/HD-77/005.
Weeks, J.B., 6.H. Lewesley, F.A. Welder, and G.J. Saulnier, Jr.
1974. Simulated Effects of Oil Shale Development on the
Hydrology of Piceance Basin, Colorado. U.S. Geological
Survey Professional Paper 908.
50
-------
APPENDIX A
ANALYTICAL AND FIELD DATA FOR THE SAMPLING SITES ON TRACT-C-a
51
-------
TABLE A-l: ANALYTICAL AND FIELD DATA FOR THE MINE INFLOW TO JEFFREY POND
Constituents*
ABBREVIATED MONITORING
Ammonia (NH,-N)
Arsenic
Bicarbonate
Carbonate
Calcium
Chloride
Fluoride
Iron
Magnesium
Mercury (ug/1)
.Molybdenum
Nitrate (N03-N)
Potassium
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity (As CaCOj)
Alkalinity (As CaCOj)
9/17/81
0.11
<0.01
532
<1
36
'8.34
1.71
0.06
83
<0.3
<0.1
<0.1
0.35
<0.01
23
200
430
<0.5
<5
469
5/27/82
.28
<0.005
548
5.1
32
7.9
1.1
.017
78.9
<.001
<0.05
.09
.8
<.02
11
190
388
5.6
458
Sampling Date
7/20/82 9/23/82 11/17/82
.467
<.003
577
6.06
44.1
8.23
1.51
.15
77.1
<.001
<.05
<1.0
.531
.<.002
" 12.3
191
343
5.25
483
.333
.003
527
7.59
46.3
8.52
1.4
1.00
95
<-001
<.03
<1.0
1.26
<.002
174
438
<0.1
3.51
445
<.005
599
9.09
48.7
7.74
1.2
<.01
77.5
.052
.245
.666
<.002
12.7
193
414
3.79
506
1/7/83
.354
<.005
- 554
9.44
32.6
7.89
1.32
.085
76.2
.001
<.03
.231
.615
<.01
12.1
195
400
<.005
3.13
470
3/9/83
.253
<.005
548
3.02
31.9
7.89
1.21
<.01
72.8
<.001
.107
2.02
.136
<.01
12.0
195
400
<.U05
9.45
454
*In mg/1, unless otherwise indicated.
52
-------
TABLE A-l (Continued)
Constituents*
Conductivity (field,
ijmhos/cm)
DOC -
pH (field, units)
Dissolved Oxygen
(field, ppm)
Boron
Fractionated OOC
-Hydrophobics (Total)
-Bases
• -Acids
-Neutral
-Hydrophilics (Total)
-Bases
-Acids
-Neutrals
Residues
-TDS •
-TS.S
-Total Solids
-Total Volatile
-Settleable Matter
Temperature (field, °C)
9/17/81
2250
3.1
9.2
3
0.41
1.5
0.2
1.1
0.2
2.4
0.7
1.6
0.1
1033
<4
1036
226
<0.1
14
5/27/82
1400
4.7
8.35
3.2
.21
3.6
0.0
0.2
3.4
1.1
0.0
• 1.1
0.0
992
<4
992
.
-------
TABLE A-l (Continued)
Constituents* 9/17/81
COMPREHENSIVE MONITORING*
Aluminum
Barium
.Beryl! ium
Cadmium
Chromium
Cobalt
Copper
Cyanide
Lead
Lithium
Manganese
Nickel
Phenols
Phosphorus
-Ortho
-Total
Silver
Strontium
Sulfide
Thallium
Thiosulfate
Tin
5/27/82
<.02
.083
<.0005
<.001
<.005
-------
TABLE A-l (Continued)
Constituents*
Titanium
Zinc
Turbidity
Uranium-234 (pci/1)
Uranium-235 (pci/1)
Uranium-238 (pci/1)
9/17/81 5/27/82
<0.5
.005
.6
1.3 ± 1.1
.2 ± 0.5
0.9 ± 1.0
Sampling Date
7/20/82 9/23/82 11/17/82
<.05
.007
4.5
0.3
0.0
0.3
.122
7.5
± .3
± .2
± .3
1/7/83 3/9/83
: .075 .033
*In rng/1, unless otherwise indicated.
55
-------
TABLE A-2: ANALYTICAL AND FIELD DATA FOR THE JEFFREY POND DISCHARGE INTO THE WEST
RETENTION POND.
Constituents*
ABBREVIATED MONITORING
Ammonia (NHj-N)
Arsenic
Bicarbonate
Carbonate
Calcium
Chloride
Fluoride
Iron
Magnesium
Mercury (vig/1)
Molybdenum
Nitrate (NOj-N)
Potassium
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity (As CaCOj)
Alkalinity (As CaCOj)
9/17/81
0.10
<0.01
531
1.08
, 37
9.47
1.70
0.05
83
<0.3
<0.1
0.1
0.36
<0.01
22
190
382
<0.5
<5
474
5/27/82
.11
<.005
540
5.7
31
8.1
1.2
.026
79.4
<.001
<0.05
.008
.9
<.02
11
187
392
4.9
452
Sampling Date
7/20/82 9/23/82 11/17/82
.317
.003
546
11.4
44.1
7.90
1.22
.049
78.1
<.001
<.OS
<1.0
.369
<.002
10.9
197
345
2.52
467
.238
<-003
523
8.01
47.5
8.94
1.43
.59
98.9
<.001
<.03
<1.0
1.24
<.003
170
427
<0.1
3.28
442
<.005
525
10.5
63.5
8.67
1.28
.282
84
.038
.245
.817
<.002
12.7
196
441
2.53
448
.1/7/83
.306
<.005
533
7.21
32.4
7.58
' 1.21
" .164
74.1
• <.001
<.03
.219
.636
<.01
11.9
198
412
<-005
3.78
449
3/9/83
.243
<.005
548
5.76
31.7
8.14
1.31
.124
76.5
<-001
.3
8.59
1.02
<.01
'10.9
192
364
<.005
4.99
459
*In mg/1, unless otherwise indicated.
56
-------
TABLE A-2 (Continued)
Constituents*
Conductivity (field,
pmhos/cm)
DOC
pH (field, units)
Dissolved Oxygen
(field, ppm)
Boron
Fractionated DOC
-Hydrophobics (Total)
-Bases
-Acids
-Neutral
-Hydrophilics (Total)
-Bases
-Acids
-Neutrals
Residues
-TDS
-TSS
-Total Solids
-Total Volatile
-Settleable Hatter
Temperature (field, °C)
9/17/81
1425
3.9
8.2
7.0
.39
1.5
0.2
1.1
0.2
2.4
0.7
1.6
0.1
1053
<4
1054
214
<0.1
15.5
5/27/82
1400
3.2
8.35
7.4
.22
2.4
0.0
0.9
1.5
1.3
0.2
1.1
0.0
988
4
1016
N/M
<1
16
Sampling Date
7/20/82 9/23/82
1400 1510
<3' 4.0
8.96 7.0
8.5 6.2
.8 <3.0
1.8
0.1
1.2
0.6
2.2
0.0
1.5
0.7
1018 1188
6 10
1061 1244
235 230
.3 <0.1
23 16
11/17/82
1400
4.0
8.7
5.9
.15
1220
<4
1228
252
<0.1
10
1/7/83
1390
3.6
7.8
5.9
1.5
0.0
1.2
0.3
2.1
1.1
0.7
0.3
1446
,<4
1446
74
<.l
10
3/9/83
1510
3
7.45
6.2
.183
1023
5
1028
184
<.l
11
*In mg/1, unless otherwise indicated.
57
-------
TABLE A-2 (Continued)
Constituents* 9/17/81
COMPREHENSIVE MONITORING*
Aluminum
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Cyanide
Lead
Lithium
Manganese
Nickel
Phenols
Phosphorus
-Ortho
-Total
Silver
Strontium
Sulfide
Thallium
Thiosulfate
Tin
5/27/82
<.02
.081
<.0005
<.001
<.005
<.005
<.001
<0.005
<.01
.091
<.002
<.005
<.005
<.01
.4
<.001
8.2
<.l
<.005
5
<.05
Sampling Date
7/20/82 9/23/82 11/17/82
.06
1.05
<.005
.005
<.005
<.005
<.001
<.01
.077
<.002
<.001
<.4
<.05
<.001
8.5
<1.0 .042
<1.0
<.01
.005 <.004
.024
<.05
<.005
<0.5
<.01
.074
.042 .056
<.05 .01
<.05
<.4
.141
<.001
9.19 7.16
<.l
<.05
<0.01
1/7/83
.175
.074
.493
<.004
<.05
N.05
<.005
<.l
<.025
.085
.007
<.01
<.05
<.0l'
.144
<.01
8.31
.06
1 .012
<.05
3/9/83
.242
.069
<.0005
<.004
<.05
' <.05
<.005
<.l
<.025
.085
<.005
. <.01
.257
.299
<,01
7.24
.004
*In mg/1, unless otherwise indicated.
58
-------
TABLE A-2 (Continued)
Constituents*
Titanium
Zinc
Turbidity
Uranium-234 (pci/1)
Uraniura-235 (pci/1)
Uranium-238 (pci/1)
Sampling Date
9/17/81 5/27/82 7/20/82 9/23/82 11/17/82
<-5 -<.05
.009 .032 .077
1.4 3.2 4.9
.1 ± .4 0.4 ± 0.4
0 ± .1 0.0 ± 0.1
1.4 ± 1.5 0.3 ± 0.3
1/7/83 3/9/83
.062 .026
:"
*In rag/1, unless otherwise indicated.
59
-------
TABLE A-3: ANALYTICAL AND FIELD DATA FOR THE WEST RETENTION POND DISCHARGE.
Constituents*
ABBREVIATED MONITORING
Ammonia (NH,-N)
Arsenic
Bicarbonate
Carbonate
Calcium
Chloride
Fluoride
Iron
Magnesium
Mercury (vg/1)
Molybdenum
Nitrate (NO-j-N)
Potassium
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity (As CaCOj)
Alkalinity (As CaCOj)
9/17/81
0.22
<0.01
535
<1
37
9.47
1.25
0.26
83
<0.3
<0.1
0.2
0.36
<0.01
20
190
348
<0.5
<5
469
5/27/82
.16
<.005
541
6.8
32
8.0
1.2
.018
77.4
<-001
<.05
.05
.7
<.02
11
194
391
4.1
455
Sampling Date
7/20/82 9/23/82 11/17/82
.424
<.003
558
5.99
44.5
7.8
1.2
.069
77.5
<.001
<.05
<1.0
.466
<.002
11.6
194
350
4.96
467
.163
<.003
368
5.58
47.5
5.73
1.11
.283
100.9
<.001
<.03
<1.0
1.34
<.002
177
302
<0.1
2.33
311
<.005
524
10.4
62
8.56
1.26
.44
84.6
.24
.769
.858
<.002
12.8
195
449
2.53
447
1/7/83
, : .317
<.005
,- 553
10.1
34.6
8.02
1.32
.644
73.1
<-001
<.03
.516
.632
<.01
11.7
198
398
! <.005
2.92
470
3/9/G3
.185
<.005
1541
6.09
32.4
8.14
1.31
<.01
78.7
<.002
.232
.407
1.49
<,01
11.1
198
402
<.005
4.6
454
*In mg/1, unless otherwise indicated.
60
-------
TABLE A-3 (Continued)
Constituents*
Conductivity (field,
umhos/cm)
DOC
pH .(field, units)
Dissolved Oxygen
(field, ppm)
Boron
Fractionated DOC
-Hydrophobics (Total)
-Bases
-Acids
-Neutral
-Hydrophilics (Total)
-Bases
-Acids
-Neutrals
Residues
-TDS
-TSS
-Total Solids
-Total Volatile
-Settleable Matter
Temperature (field, »C)
9/17/81
1475
3.3
8.1
8.0
.37
1.6
0.0
1.1
0.5
1.7
0.2
1.4
0.1
1003
4
1007
205
<0.1
15
5/27/82
1400
3.7
8.4
6.6
.21
2.0
0.0
0.9
1.1
1.2
0.1
1.1
0.0
1390
<4
1395
<1
16
Samp!
7/20/82
1400
3
8.9
6.4
.9
980
<4
1023
225
<1
20
ing Date
9/23/82
1400
3.8
6.9
3.9
<3
1.5
0.0
1.0
0.5
2.3
0.1
1.7
0.5
1198
<4
1193
207
<.l
16
11/17/82
1420
3
7.9
4.2
.16
1250
<4
1254
236
<0.1
10
1/7/83
1450
4.6
8.1
5.8
.175
1.6
0.0
1.0
0.6
2.0
0.6
1.1
0.2
1392
<4
1392
86
.<.!
9.5
3/9/83
1320
2
7.6
5.6
.173
1028
<4
1028
162
<.!
11
*In ing/1, unless otherwise indicated.
61
-------
TABLE A-3 (Continued)
Constituents* 9/17/81
COMPREHENSIVE MONITORING*
Aluminum
Barium
Beryllium
Cadmi urn
Chromium
Cobalt
Copper
Cyanide
Lead
Lithium
Manganese
Nickel
Phenols
Phosphorus
-Ortho
-Total
Silver
Strontium
Sulfide
Thallium
Thiosulfate
Tin
5/27/82
.04
.082
<.0005
<.001
<.005
<.005
<.001
<0.005
<.01
.09
<.002
<.005
<.005
<.01
.4
<.001
8.4
<.l
<.005
<5
<.05
Sampling Date
7/20/82 9/23/82 11/17/82
.27
1.05
<.0005
<.005
<.005
<.005
<.001
<.01
.077
<.002
<.001
<.4
<.05
<.001
7.2
<1.0 .089
<1.0
<.01
.005 <.004
.024
<.05
<.005
<0.5
<.01
.079
.042 .063
<.05 .01
<.05
<.4
.087
<.001
9.19 7.49
<.l
<.05
<0.01
1/7/83
] .158
.075
1.103
<.004
<-05
<.05
.021
<.l
.025
.085
.022
<.01
<.05
<.01
.166
<.01
8.1
.06
.011
<.05
3/9/83
.115
.07
.946
<.004
<-05
<.05
<.005
8.72
.025
.079
<.OOS
<:.01
<.01
.379
<.01
7.14
.005
*In mg/1, unless otherwise indicated.
62
-------
TABLE A-3 (Continued)
Constituents*
Titanium
Zinc
Turbidity
Uranium-234 (pci/1)
Uranium-235 (pci/1)
Uranium-238 (pci/1)
9/17/81 5/27/82
<.5
. 006
1.2
.5 ± .9
0 ± .1
.5 ± .9
Sampling Date
7/20/82 9/23/82 11/17/82
<.05
.007 : ..068
1.7 5.2
0.2 ± 0.2
0.0 ± 0.1
0.3 ± 0.3
1/7/83 3/9/83
.08 .013
*In mg/1, unless otherwise indicated.
63
-------
APPENDIX B
ANALYTICAL AND FIELD DATA FOR THE SAMPLING SITES ON TRACT C-b
64
-------
TABLE B-l:- ANALYTICAL AND FIELD DATA FOR THE MINE DISCHARGE TO POND A.
Constituents*
ABBREVIATED MONITORING
Ammonia (NH3-N)
Arsenic
Bicarbonate
Carbonate
Calcium
Chloride
Fluoride
Iron
Magnesium
Mercury (yg/1 )
Molybdenum
Nitrate (N03-N)
Potassium
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity (As CaCOj)
Alkalinity (As CaC03)
9/16/81
.90
<.01
1135
10.8
7.30
8.34
15.3
.08
4.40
<.3
<.l
1.2
4.3
<.01
23
540
176
<.5
< 5
1147
5/27/82
.24
< .005
1245
28.6
7.0 '
• 7.2
19.2
.063
4.0
<.001
<.05
4.0
2.9
.02
6.7
530
16.8
5.2
1068
Sampling Date
7/20/82 9/23/82 11/17/82
.688
<.003
1300
46.1
4.78
6.61
19.8
.210
5.38
<.001
.14
1.2
2.29
<.002
7.3
578
13.6
3.57
1140
.208
.003
896
24.1
5.5
5.79
17.0
<.l
4.31
<.001
<.03
1.34
1.81
<.002 -
391
10.9
<.l
3.24
775
<.005
1190
53.3
6.08
7.47
11.1
<.01
5.0
.125
3.12
1.65
<.002
7.23
525
22.6
2.63
1065
1/7/83
.342
<.005
-1320
46.9
5.62
7.4
18.9
-.079
4.52
<.001
<.03
4.12
1.92
<.01
7.06
551
14.6
<.005
3.63
1160
3/9/B3
.396
<,005
1350
33.2
5.52
8.14
19.04
.026
3.S
<.001
.883
3.91
4.67
-:.01
6. 1C
545
17
<.005
5.3
1160
*In mg/1, unless otherwise indicated.
65
-------
TABLE 8-1 (Continued)
Constituents*
Conductivity (field,
umhos/cm)
DOC
pH (field, units)
Dissolved Oxygen
(field, ppm)
Boron
Fractionated DOC
-Hydrophobics (Total )
-Bases
-Acids
-Neutral
-Hydrophilics (Total)
-Bases
-Acids
-Neutrals
Residues
-TDS
-TSS
-Total Solids
-Total Volatile
-Settleable Matter (ral/1)
Temperature (field, °C)
•• - •
9/16/81
2275
4.7
9.2
4.0
.86
3.9
0.2
0.9
2.8
0.8
0.2
0.3
0.3
1354
565
1919
320
4.5
13
Sampling Date
5/27/82 7/20/82 9/23/82 11/17/82
2430 2500 1620 1925
3.0 <3 2.8 5
8-4 8.8 8.6 8.2
4-3 5.7 5.4 4.3
•87 -77 <3 .756
2-2 1.8
0.0 o.l
0-8 0.6
1-3 ' 1.2
0.8 o.9
o.i o.o
0-4 0.6
0-3 0.3
1280 1312 912 1361
8 <4 <4 <4
1296 1424 958 1372
194 117 88
<1 <.i 1
21 23.5 22 16
1/7/83 .
2100
4.3 ,
8
4.6
.739
2.3
o.i t
1.0
1.2
2.0
0.9
0.6
.0.5
1380
<4
1380
172
< 1
16
3/9/H3
2100
<2
(5.3
4.0
.73U
1366
6
1372
136
<
17
— •
*In mg/1, unless otherwise indicated.
66
-------
TABLE 8-1 (Continued)
Constituents* 9/16/81
COMPREHENSIVE MONITORING*
Aluminum
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Cyanide
Lead
Lithium
Manganese
Nickel
Phenols
-Ortho
-Total
Silver
Strontium
Sulfide
Thai! ium
Thiosulfate
Tin
5/27/82
.1
.92
<.0005
<.001
<.005
<.005
<.001
<.005
<.01
.043
<.002
<.005
<.005
<.01
.8
<.001
2.0
<.l
<.005
< 5
<.05
Sampling Date
7/20/82 9/23/82 11/17/82
.31
1.05
<.0005
.016 <
<.005
<.OOS
.001 <
<.01
.028
.063
<.001
<.4
.34
.001 <
1.1
<1 .036
1.05
<.01
.005 .004
<.02
<.05
.005
<.05
<.01
.062
.004 .65
<.05 .01
<.05
<.4 <.01
.043
.001
1.73 1.15
< .1
<.05
<.01
1/7/83
.181
.742
.647
<.004
<.05
<.OS
.119
<.l
.025
.04
.007
<.01
<.5
.244
<.01
1.31
.06
.026
<.05
3/9/C3
.414
.751
4.24
<.004
<.05
<.QS
<.005
<.l
<.C25
.037
<.005
<.01
.212
l.OS
<.01
1.P4
.QCS
"In Kig/1, unless otherwise indicated.
67
-------
TABLE B-l (Continued)
Constituents*
Ti tanium
Zinc
Turbidity (NTU)
Uranium-234 (pci/1)
Uranium-235 (pci/1)
Uranium-238. (pci/1)
9/16/81 5/27/82
<.5
.007
2.8
1.6 ± 1.4
0.0 ± .1
2.3 ± 1.9
Sampling Date
7/20/82 9/23/82 11/17/82
"=•5
.007 .001
.8 1.9
0.0 ± .2
0.0 ± .3
0.4 ± .5
1/7/83 3/9/H3
.02 .001
*In mg/1, unless otherwise indicated.
68
-------
TABLE B-2: ANALYTICAL AND FIELD DATA FOR THE DISCHARGE OF POND B.
Constituents*
ABBREVIATED MONITORING
Ammonia (NH3-N)
Arsenic
Bicarbonate
Carbonate
Calcium
Chloride
Fluoride
Iron
Magnesium
Mercury (mg/1)
Molybdenum
Nitrate (NO-j-N)
Potassium
Selenium
Silica
Sodium
Sulfate
Vanadium
Acidity (As CaC03)
Alkalinity (As CaCOj)
9/16/81
1.33
<-01
1069
<1.0
6.50
8.12
15.10
.05
4.60
<.3
<.l
1.5
4.1
<.01
35
540
311
<.5
<5
926
5/28/82
.28
<.005
1295
25.9
10
7.2
19,7
.048
5.7
<.001
<.05
2.45
2.7
<.02
6.6
550
50.3
6.2
1104
Sampling Date
7/20/82 9/23/82 11/17/82
.326
<.003'
1210
48.2
4.78
6.09
18.2
.311
4.64
<.001
.11
<1.0
2.2
<.002
7.5
541
16.2
<.l
2.97
1070
.346
.004
1359
45.7
5.99
6.13
18.7
<.l
4.07
<.001
<.03
< 1.0
2.56
<.002
578
5.98
3.94
1190
<.005
1274
47.5
5.67
7.25
12.2
<.01
3.94
.063
5.82
1.66
<.002
5.61
522
14.4
3.36
1124
1/7/83
.342
<.005
-1287
63.2
5.43
6.98
18.1
.126,
4.61
.002
<.03
2.5
1.7
<.01
6.75
555
15.7
<.005
2.6
1160
3/9/83
.372
' <.005
1340
38.6
6.04
8.14
19.23
.065
4.13
.002
.804
12.1
4.94
<.01
5.98
545
17.5
<.005
4.5
1160
*In mg/1, unless otherwise indicated.
69
-------
TABLE B-2 (Continued)
Constituents*
Conductivity (field,
umhos/cm)
DOC
pH (field, units)
Dissolved Oxygen
(field, ppm)
Boron
Fractionated DOC
-Hydrophobics (Total)
-Bases
-Acids
-Neutral
-Hydrophilics (Total)
-Bases
-Acids
-Neutrals
Residues
•-TDS
-TSS
-Total Solids
-Total Volatile
-•Settleable Matter
Temperature (field, °C)
9/16/81
2200
3.9
7.8
9 ,
.79
2.1
0.3
1.7
0.2
1.5
0.1
1.0
0.3
1517
6
1523
297
<.l
15.5
5/28/82
2000
3.7
8.5
7.0
.990
3.0
0.1
1.1
1.8
0.7
0.2
0.3
0.3
1390
<4
1395
N/M
<1
20
Sampling Date
7/20/82 9/23/82 11/17/82
2100
<3
9.2
6.3
.83
1206
<4
1342
244
<.l
23
2500 2150
3.6 2
8.5 9.0
4.3 4.5
<3 .648
2.3
0.1
1.2
1.0
1.3
0.1
0.6
0.7
1380 1354
5 <4
1439 1358
125 120
<.l <.l
22 15
1/7/83
2100
4.2
8.2
4.7
.718
3.0
0.1
- 1..1
1.9
1.2
0.5
0.0
:o.7
1398
<4
1398
180
<.l
13
3/9/83
2050
6
8.3
5.1
.736
1352
<4
1356
96
<.l
12
"In mg/1, unless otherwise indicated.
70
-------
TABLE B-2 (Continued)
Constituents* 9/16/81
COMPREHENSIVE MONITORING*
Al umi num
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Cyanide
Lead
Lithium
Manganese
Nickel
Phenols
Phosphorus
-Ortho
-Total
Silver
Strontium
Sulfide
Thallium
Thiosulfate
Tin
5/28/82
.2
.83
<.0005
<.001
<.005
<.005
.002
<.005
<.01
.042
<.002
<.005
. <.005
<.01
1.0
<.001
1.8
<.l
<.005
<5
<.05
Sampling Date
7/20/82 9/23/82 11/17/82
.3
1.34
<.0005
<.005
<.005
<.005
<.001
.04
.028
.012
<.001
<.4
<.05
<.001
1.0
<1 <.02
1.34
<.01
.008 <.004
<.02
.<.05
<.005
<.05
<.01
.056
.004 1.47
<.05 .01
<.OS
<-4
.224
<.001
1.73 .977
<.l
<.OS
<.01
1/7/83
.235
.735
.166
<.004
<.05
<.05
<.005
<.l
<.025
.043
<.005
<.01
<.05
<.01
.202
<.01
1.29
.06
.033
<.5
3/9/83
.586
.748
6.35
<.004
<.OS
<.05
<.005
1.06
<.025
.037
<.005
<.01
.166
1.03
<.01
1.76
.026
*In mg/1, unless otherwise indicated.
71
-------
TABLE B-2 (Continued)
Constituents*
Titanium
Zinc
Turbidity
Uranium-234 (pci/1)
Uranium-235 (pci/1)
Uranium-238 (pci/1)
9/16/81 5/28/82
<.05
.008
1.2
.5 ± .9
0.0 i .1
.5 t .9
Sampling Date
7/20/82 9/23/82 11/17/82
<.5
.013 .007
1.9 1.2
0.0 ± .2
0.0 ± .2
0.1 ± .2
1/7/83 . 3/9/83
.02 .007
*In rag/1, unless otherwise indicated.
72
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
2.
4. TITLE AND SUBTITLE
Characterization of Oil Shale Mine Waters,
Central Piceance Basin, Colorado
7. AUTHOR(S)
K. E. Kelly
J. D. Dedrick
9. PERFORMING ORGANIZATION NAME AN
Kaman Tempo
600 South Cherry Street
Denver, Colorado 80222
D ADDRESS
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
US EPA
Cincinnati, Ohio 45268
3. RECIPIENT'S ACCESSION NO.
5' 'larch ?A7§4
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
N104 Multimedia Energy
1 1 . CONTRACT/GRANT NO.
Contract 68-03-2449
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A study was conducted to characterize the oil shale mine waters in the
Piceance Basin. The study sites were 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 characterize the mine waters and to assess the effective-
ness of treatment systems located at these facilities. These treatment systems
involve in-series retention ponds . :
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 negligible difference unless chemicals are added. The addition of the ;
flocculent during periods of active mining was very effective in reducing the
suspended sediment concentrations. In addition, sulfuric acid treatment reduced
the pH. — - - .- - -
Concerning the general water quality, such as the trace elements, cations :
,__and anions, and other pertinent constituents, there was not a significant increase
or decrease due to the chemical additives. In addition, the effectiveness of the
one-pond and two-pond systems are very similiar. '.
17.
2 DESCRIPTORS
Synthetic Fuels
Oil Shale
Minewaters
Wastewater treatment
18 DISTRIBUTION STATEMENT
'
jxexease unlimited
KEY WORDS AND DOCUMENT ANALYSIS
b. IDENTIFIERS/OPEN ENDED TERMS
Colorado
Mining
Piceance
19. SECURITY CLASS /This Reoor!)
|
20. SECURITY CLASS ,This page I
c. COSATI Held/Group
68D
05C
21. NO. OF PAGES :
22. PRICE
EPA FOTTT 2220 —I (Rev. 4 — 77) PREVIOUS EDITION is OBSOLETE
-------
PROJECT SUMMARY ;
CHARACTERIZATION OF OIL SHALE MINE WATERS
CENTRAL PICEANCE' BASIN, COLORADO
by
KEVIN E. KELLY AND JIM D. DEDERICK
A study was conducted to characterize the oil shale mine
waters in the Piceance Basin. The study 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 characterize the mine waters and to assess the
effectiveness of the treatment systems located at these
facilities. These treatment systems involve in-series retention
ponds. Additionally, the effectiveness 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 (TDS), 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 flocculent and sulfuric acid for the
treatment of excess waters encountered during active mining on
Tract C-b. The flocculent was added to reduce the suspended
solids concentrations and the acid was used to reduce the
somewhat 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 associated
with the transformation of the groundwater 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 flocculent 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.
-------
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 developers and permit writers in
selecting 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 treatment. 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 rei-njection into the groundwater
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 utilized 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 (Geffrey Pond), rthe outflow of
the primary retention pond into the secondary retention pond
-------
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(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, sulfuric acid and a magnifloc catibnic flocculent
were added to the ponds in order to treat the pH and total
suspended solids (TSS), respectively. This sampling strategy
assessed the effectiveness of treatment consisting of two ponds
which are in series. In addition, the samp!ing .program allowed
for an evaluation of chemical treatment (i.e., flocculent and
suIf uric acid).
The following constituents were measured 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. EPA
(1979) recommended procedures. The samples were then shipped to
the laboratories located at the Colorado State University in Fort
Collins, Colorado, and Core Laboratories 'in Denver, Colorado. In
-------
mbstjcases, the U.S. EPA (1979) recommended holding times were
observed. The holding times for a few constituents of the
samples collected on July, 1982 were exceeded. 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 collected 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 comprehensive group of
constituents, which included the abbreviaxed 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 (e.g., Fox et al., 1978; Slawson, 1979;
Pfeffer, 1974, Stuber and Leenheer, 1978; LBL, 1978).
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
6
-------
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Acidity
Alkal inity
Ammon i a
Arsenic
Bicarbonate
Boron
Carbonate
Calcium
Chlori de
Conductivity
Dissolved Org
Alumi num
Bar i um
Beryl 1 i um
Cadmi um
Chromium
Cobalt
Copper
Cyan i de
Fractionated
DOC
LIST
0
0
0
0
0
0
0
0
0
an ic
0
0
0
0
0
0
0
0
OF PARAMETERS FOR
AND COMPREHENSIVE
ABBREVIATE
Dissolved Oxygen
Fluori de
Iron
Magnes i um
Mercury
Molybdenum
Nitrate
PH
Potassi um
•
Carbon (DOC)
COMPREHENSI
Lead
Lithium
Manganese
Nickel
Phosphorus
(total and ortho
Silver
Strontium
Sulf ide
A
D
VE
)
TABLE 1
ABBREVIATED
ANALYSIS
o
o
0
0
0
0
0
0
0
0
0
0
Residues
(Total, total
dissolved,
total , suspended,
settleable,
and volatile)
Silica
Sodium
Sulfate
Temperature
Thallium
Thiosulfate
Tin
Titani urn
Turbidity
Urani urn
(234, 235,
Vanadi urn
Zinc
238)
NOTE: Comprehensive list includes all parameters in the
abbreviated list.
-------
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the mine water data, the analytical results were compared to
groundwater 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 comparisons
for the Tract C-a and C-b data are presented in Tables 4 and. 5,
respecti vely.
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pond system and reinjecting all of the treated water back into
the groundwater system. Concerning the effectiveness of th:e
treatment of the mine waters, the following constituents were
found to generally exceed baseline groundwater conditions:
carbonate, calcium, conductivity, fluoride, magnesium, nitrate,
TDS, sulfate, and pH. However, the increase in these
constituents above groundwater baseline conditions- were small.
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 groundwater analyzed to determin-e
baseline water quality conditions. Therefore, this aspect may
not be a problem if the water is reinjected.
In regard to the Tract C-b in-series two pond treatment
system, the following constituents in the discharge exceeded
baseline groundwater quality concentrations: bicarbonate.,
carbonate, conductivity, fluoride, molybdenum, nitrate,
potassium, TDS, silica, sodium, and pH. However, none of the
increases were very great. In addition, during periods of active
10
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mining on Tract C-b, flocculent 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, bicarbonate, 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 groundwater quality, which is considered
poor. Furthermore, 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
i
changes associated with the transformation of the groundwater
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 attributable to laboratory procedures.
13
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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/1
to below detection limits is not significant. The two-pon'd
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
flocculent and sulfuric acid was effective in reducing total
suspended solids by nearly 99% and adjusting pH to desired value.
14
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