RECONNAISSANCE STUDY OF LEACHATE QUALITY FROM
RAW MINED OIL SHALE - LABORATORY COLUMNS
by
David B. McWhorter
Agricultural and Chemical Engineering Department
Colorado State University
Fort Collins, Colorado 80523
Grant No. R806278
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
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f -X
DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory-Cincinnati, U. S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U. S. Environmental Protection
Agency, nor does mention of trade names of commercial products constitute
endorsement of recommendation for use.
ii
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FOREWORD
When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on our
health often require that new and increasingly more efficient pollutional
control methods be used. The Industrial Environmental Research Laboratory -
Cincinnati (IERL - Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these meeds both efficiently and econom-
ically.
This report presents the results of the chemical characterization of
leachates generated from laboratory columns of several unretorted mined oil
shales, unmined shales, and soils. The findings are indicators of the levels
of common and trace species that can be expected to occur in field generated
leachates. For further information contact the Energy Pollution Control
Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
111
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CONTENTS
Foreword ni
Abstract iv
Figures V1
Tables vii
Acknowledgements V111
Section
1. Introduction 1
2. Conclusions 3
3. Recommendations 5
4. Materials 6
Designation and source of samples 6
Particle size analysis 8
Leaching methods 8
Methods of chemical analysis 9
Leaching experiments conducted 9
5. Results 12
Range of concentrations observed 12
Leaching of common species 14
on
Trace elements cv
nr
Bibliography
27
Appendix
v
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ACKNOWLEDGEMENTS
The cooperation of Rio Blanco Oil Shale Company, Occidental Oil Shale
Corporation,Union Oil Company, Colony Development Operation and the US
Bureau of Mines in providing permission to obtain materials and assisting in
their collection is greatly appreciated. We also wish to thank the personnel
from these organizations that have reviewed and commented upon this report.
vi i i
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t.
FIGURES
Number Page
1 Schematic diagram of leaching apparatus 8
2 Leaching characteristics of USBM raw shale 15
3 Leaching characteristics of Colony raw shale 17
4 Leaching characteristics of Colony naturally leached shale . . 18
5 Leaching characteristics of Union naturally retorted shale . . 19
6 Leaching of Boron from raw shale 23
7 Leaching of Fluoride from raw shale 24
8 Leaching of Fluoride from raw shale 25
A-l Particle size distribution for USBM raw shale 28
A-2 Particle size distribution for Colony raw shale 28
A-3 Particle size distribution for C-a composite raw shale .... 29
A-4 Particle size distribution for C-a R-5/Mahogany raw shale ... 29
A-5 Particle size distribution for Union naturally retorted shale . 30
A-6 Particle size distribution for C-b soil 30
A-7 Particle size distribution for Colony naturally leached shale . 31
A-8 Particle size distribution for Colony soil 31
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SECTION 1
INTRODUCTION
The modified in-situ method of oil shale retorting and the various sur-
face methods require that quantities of raw (unretorted) shale be mined from
shafts and drifts that provide access to the retorts. Raw shale is also
mined to provide a void space into which the shale in the retort expands upon
rubblization by blasting. The mined shale will be stored on the ground sur-
face for a period of at least a few years and possibly even permanently. The
placement of the unretorted shale on the surface places it in an environment
with which it is no longer in geochemical equilibrium, and the precipitation
on the pile creates the potential for the release of a variety of chemicals
into percolating waters at elevated levels relative to the base line condi-
tions.
There is no single generally accepted method by which the effect of
solid waste upon the chemistry of percolating waters can be assessed. Most
of the comparative studies of leaching methods have been oriented toward
landfill problems (Lb'wenbach, 1978; Ham et al., 1979). It is not practical
to simulate in the laboratory the wet and dry cycles, the freeze and thaw
sequences, the microbial activity, the aerobic and anaerobic conditions,
temperature fluctuations, and variable residence times that will be expe-
rienced in the field.
Futhermore, the chemical and physical properties of raw mined shale can-
not be expected to be uniform. This natural heterogeneity imposes an addi-
tional constraint on the extrapolation and generalizations of laboratory
results.
This report contains the results of a laboratory based reconnaissance
study of potential water quality problems associated with leachate from sur-
face storage of raw shale. In view of the fact that laboratory tests are
not capable of simulating field conditions, the results of this study must
be viewed only as a general indicator of the water quality that can be ex-
pected in leachates from raw shale. A major purpose of the study was to
investigate whether or not more realistic and comprehensive field tests are
warranted.
Eight different materials were subjected to leaching. Four of the
materials were raw mined shales obtained at different locations in the Colo-
rado oil shale region. The other four materials were samples of shales and
soils that had been exposed to natural leaching processes. The four pre-
viously exposed materials provide a background or baseline that assisted in
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placing the results for the mined shales in an appropriate perspective. No
attempt was made to establish statistical distributions of the concentrations
of the various chemical constituents. Because the laboratory conditions do
not adequately simulate those in the field, rigorous establishment of the
ranges of variation for various confidence intervals was not warranted.
Leaching was conducted by passing de-ionized water through columns of
each material. Both saturated and unsaturated tests were conducted.
Samples of the effluents were collected and subjected to chemical analyses.
The electrical conductivity of the effluent from the columns was measured at
small time intervals by means of a flow-through probe and a data logger.
Grain size analyses were made for each material. The results of these ex-
periments are summarized in the body of the report. All of the data gener-
ated from the chemical analyses are contained in the appendices. Graphical
representations of the grain-size distributions are also included in the
appendices.
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SECTION 2
CONCLUSIONS
Raw mined shales of the type tested in this study can be expected to
result in leachate containing dissolved solids at elevated concentrations
relative to the background. The major contributors to the dissolved solids
content are calcium, magnesium, sodium, bicarbonate, chloride and suTfate.
Using the electrical conductivity (EC) as an indicator of the dissolved
solids concentration, it was found that the dependence of the EC on the
throughput volume could be satisfactorily described by
(\-ct
PV 1 PV > PV
PVm I ' KV - m
where PV is the effluent volume expressed in pore volumes, ECm is the maxi-
mum EC observed and PVm is the corresponding effluent volume. The exponent
a is an indicator of the Teachability; large a representing a more rapid
decline in EC than for small a , other factors being equal. This equation
does not hold at large PV where the EC is approaching a stable value.
The leaching index a for the mined shales ranged between 0.4 and 1.1.
The USBM, Colony, and C-a composite materials exhibited remarkably similar
values of a that ranged between 0.8 and 1.1. The C-a, R-5/Mahogany material
had a leaching index of 0.4-0.5. For the materials tested, the leaching
index did not depend upon whether the test was conducted under saturated or
unsaturated conditions. Futhermore, nearly identical values of a were
obtained for the mined shales on a second leaching cycle following a period
of drainage and aeration.
In contrast to the mined shales, the values of a obtained for the
soils and previously exposed shales on the second leaching cycle were marked-
ly reduced from the values obtained on the first cycle. It is likely that
the readily Teachable precipitates in the previously exposed materials are
TargeTy deposits on the surface of the grains Teft by evaporating waters.
Once the deposits were Teached away in the first cycTe, they couTd not be
readiTy repTaced because Teaching by precipitation over many decades has
removed the source. In the case of the mined shaTes, diffusion of dissolved
soTids and capiTTary fTow from the interior to particTe surfaces during the
drainage/aeration period is proposed as the cause of the observed recovery.
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The concentrations of Al, B, F and Zn were found to be significantly
greater in the leachates from some of the mined shales than in the corre-
sponding samples from the previously exposed materials. The levels of all
other trace elements produced by the mined shales were comparable to those
observed from the soils and previously exposed shales. Elevated concentra-
tions of Al, B, F and Zn were measured in leachates from the USBM raw shale.
The largest values of Al concentration were produced from the unsaturated
leaching tests and the second cycle of saturated leaching. No consistent
relation between Al concentration and the volume of effluent was found.
The largest concentrations of B were also found in the leachates from
the USBM shale columns. A trend toward decreasing concentration of B with
increasing leachate volume was observed for all of the mined shales.
Concentrations of B did not increase significantly during the period of
drainage/aeration.
Fluorine concentrations in the leachates from the mined shales was
generally greater than from the previous exposed materials. Concentrations
of F decreased rapidly with the first pore volume of effluent from the USBM
and C-a R-5/Mahogany mined shales and then approximately stabilized. A
similiar leaching effect for the soils was observed, but the concentration
of F in leachate from the other materials did not decline significantly.
After the concentration was approximately stable, the range of F concen-
trations for the mined shales was 1-25 mg/1. Only the USBM shale yielded F
concentrations consistently greater than 10 mg/1.
The concentration of Zn in the effluent from the USBM shale was con-
sistently greater than for any of the other materials tested. The other
mined shales yielded Zn concentrations comparable to those obtained in the
background materials.
From comparisons of the maximum observed concentrations of various
parameters with drinking water criteria, it is concluded that even the worst
leachate from the columns does not exceed 100 times drinking water standards
for measured parameters. The maximum concentrations of Cr, F, Fe, Hg, Mn,
NO^, Pb, SO^, TDS, and Zn were found to exceed drinking water criteria,
however. After leaching, the minimum concentrations generally fell well
below the standards with the exception of F.
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SECTION 3
RECOMMENDATIONS
It is recommended that the chemical constituents of the leachates
generated under field conditions be determined. The present study indicates
that particular emphasis should be placed upon the total dissolved solids
and the trace elements Al, B, F and Zn, although only B and F were
found at significantly elevated levels in all of the mined shales tested.
There was some indication that Mo concentrations in leachates from the
C-a R-5/Mahogany mined shale are significantly above background values. It
is recommended that this element be given additional study. It is recommended
that the sulfur chemistry be given additional attention. There is a need to
determine the levels of sulfur species other than sulfate in the leachates.
At the present time, little is known about the geochemical and biologi-
cal processes that result in the release of these trace elements to the per-
colating waters. An understanding of these processes would assist in pro-
jecting long term consequences and might suggest methods or practices that
would minimize the degradation of the quality of waters contacting the
materials.
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SECTION 4
MATERIALS AND METHODS
A variety of samples of raw shale and soils was obtained from the
Piceance Basin of Colorado for use in this study. The purpose of extending
the study to selected soil samples was to provide a background and perspec-
tive from which the results on the raw shale can be viewed. A total of eight
different materials were tested; four raw shales, two soils, one sample of
naturally leached outcropping shale, and one sample of naturally retorted
shale from a surface fire of unknown age.
DESIGNATION AND SOURCE OF SAMPLES
Two samples of raw shale were obtained from federal lease tract C-a
with the cooperation of Rio Blanco Oil Shale Company. One of these is a
sample of mixed ore from the R-5 and Mahogany zones and is designated C-a
R-5/Mahogany in the remainder of this report. The second sample from this
site is designated C-a composite and represents a sample of the trimmings
from the service shaft.
A sample of unretorted shale from the Mahogany zone was obtained with
the cooperation of Colony Development Operation from the mine on Parachute
Creek. This sample was extracted from a stock pile of minus 1/2 inch
material that was mined approximately 6 years ago. The sample was collected
from well beneath the surface of the pile but has, undoubtedly, been sub-
jected to some weathering and leaching prior to testing. This sample is
called Colony raw shale throughout the report.
The fourth raw shale sample was obtained from the United States Bureau
of Mines site in Horse Draw. This material is from a drift at 4208 MSL ele-
vation in the saline zone and had been stockpiled outside for approximately
6 weeks.
Soil samples were collected from two locations. The sample designated
Colony soil was obtained in the vicinity of the crusher and stockpile at the
Colony site on Parachute Creek and was scraped directly from the surface.
The second sample was obtained from the B-horizon exposed in a small cut
in Cottonwood Gulch on the C-b federal lease tract. These samples are
designated Colony soil and C-b soil, respectively.
The other two materials tested are designated Colony naturally leached
and Union naturally retorted. The first is talus slope material collected
near the mine on Parachute Creek. This material has been exposed to
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weathering and leaching and is presumed to be in approximate equilibrium with
the surface environment. The material designated as Union naturally retorted
shale is shale that has burned under natural conditions and was obtained near
the portal of Union's mine on Parachute Creek. The age of the burn is unknown
but probably occurred many decades ago.
PARTICLE SIZE ANALYSIS
Quantities of each material sufficient to fill the leaching columns
were separated from the samples collected. These quantities were quartered
and samples were taken for particle size analysis. These samples were pre-
pared for analysis in accordance with the standard method for "Dry Prepara-
tion of Soil Samples for Particle-Size Analysis and Determination of Soil
Constants" (ASTM D421-58). The distribution of particle sizes was deter-
mined in accordance with the standard method for "Particle-Size Analysis of
Soils" (ASTM D422-63).
LEACHING METHODS
Columns constructed of PVC pipe, 15 cm in diameter, were used to contain
the materials during leaching. The columns were capped on the lower end and
an outlet was provided as shown in Figure 1. The effluent was forced to pass
through an electrical conductivity probe that was connected to an automatic
data logger. Below the sample, a layer of glass beads and silica sand was
placed to prevent the movement of fines into the outflow. The length of the
sample was 107 cm.
Two sets of experiments were performed. In one set, the flow through
the columns was controlled so that the sample remained saturated. In the
second set, the flow was controlled so that the major portion of the column
was unsaturated. The inflow to the columns in the saturated flow experi-
ments was controlled by means of a Mariotte siphon placed on a platform whose
position could be adjusted to any desired elevation. A small depth of
ponded water was maintained on the surface of the sample at all times during
the experiments with saturated flow. The elevation of the outflow tube was
adjusted to maintain the desired flow rate.
The inflow to the unsaturated column experiments was provided by means
of positive displacement, constant rate pumps. In these runs, the elevation
of the outflow tube was maintained near the level of the bottom of the sample,
and inflow was provided at a rate per unit area less than the value of satu-
rated hydraulic conductivity. This procedure insured that the pressure of
the water in the column was less than atmospheric everywhere except in the
immediate vicinity of the bottom of the column. The degree of aeration in
the upper portion of the column was not quantified.
With the exception of the soils, the saturated hydraulic conductivities
of the materials were rather large. Therefore, during the saturated runs,
the differences in elevation between the water surface in the columns and
the outflow had to be maintained at a small value to insure reasonable resi-
dence times in the columns. Small changes in the difference in head were
-------
Inflow from
. Mariotte Siphon
Outflow
f .« -
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Probe
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Figure 1. Schematic diagram of leaching apparatus.
8
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thus large relative to the total difference and this caused the inflow rate
to be somewhat variable.
The inflow rate per unit area during the unsaturated runs was maintained
below the value of saturated hydraulic conductivity. The fact that the
hydraulic conductivity was large made it possible to maintain unsaturated
conditions with inflow rates that were substantially greater than those used
in the saturated runs. Therefore, the residence times for the unsaturated
columns were actually less than for the saturated columns. Quantitative
residence times for the unsaturated columns could not be calculated because
the water content (degree of saturation) was not known. However, the resi-
dence times in the unsaturated columns is less than the column length divided
by the inflow rate per unit area.
Effluent was collected from the columns continuously and the cumulative
volume was measured. The electrical conductivity of the effluent was recorded
automatically every two hours. At least daily, the effluent was sampled and
the pH and EC measured. Samples of the effluent were collected periodically
and subjected to a chemical analysis described subsequently. Influent in all
experiments was deionized water.
METHODS OF CHEMICAL ANALYSIS
Chemical analyses were performed at the analytical laboratory in the
Chemistry Department at Colorado State University under the direction of
Dr. Rodney Skogerboe. Table 1 summarizes the methods utilized. The degree
of accuracy decreases from those listed in Table 1 when the concentration
approaches the determination level.
LEACHING EXPERIMENTS CONDUCTED
All of the materials described previously were subjected to saturated
leaching testing and most were also subjected to unsaturated leaching. In
addition, several of the materials were allowed to gravity drain and stand
in an aerated condition for several weeks and were then subjected to saturated
leaching a second time. Funds available for chemical analysis did not permit
a complete chemical analysis in all cases. Table 2 contains a summary of the
tests conducted. In those runs for which a chemical analysis is indicated,
between one and seven samples were analyzed.
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TABLE 1. SUMMARY OF ANALYTICAL METHODS AND LEVELS OF ACCURACY
Constituent
B
. Cd
Be
Mg
Si
Mo
Mn
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Sn
F
Cl
N03
S04
As
Se
Hg
Fe
Li
Zn
HC03
C03
Method
Level of
Accuracy
Eschelle Multi -element Plasma Spectrometer +_ 20%
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Eschelle Single-element Plasma Spectrometer "
Dionex Ion Chromatograph +. 10%
Atomic Absorption-Hydride Gen. "
Atomic Absorption-Cold Vapor "
Atomic Absorption-Flame "
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Calculated "
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SECTION 5
RESULTS
The leaching characteristics of the materials studied are presented in
this section. The results are divided into three categories; the first being
a summary overview of the range of concentrations observed in leachates.
The observations relative to the leaching of the common elements that make
up the majority of the dissolved solids are presented, and finally the re-
sults obtained for selected trace elements are summarized. The chemical
analyses for each individual sample of leachate are tabulated in the appen-
dices.
RANGE OF CONCENTRATIONS OBSERVED
Raw shale disposed above ground in the field will be subjected to a
variety of weathering processes that probably cannot be adequately simulated
in the laboratory. There will be wet and dry cycles, freeze and thaw, micro-
bial activity, periods in which percolation from precipitation is rapid and
others in which the contact time will be great. Superimposed upon this
variability will be the inherent spatial heterogeneity of the geochemical
properties of the'materials placed in the embankment. The concentrations of
various chemical species in leachates is expected to be highly variable.
The results contained in this subsection should be viewed as indicators of
the possible range of concentrations that can be anticipated in field
disposal.
The range of concentration variation observed in leachates from each
material are presented in Table 3. The values in this table were obtained
by searching all data for the maximum and minimum values without regard to
the cumulative volume of throughput, whether the material was saturated or
unsaturated, or the residence time. Thus, this table represents an overview
of the magnitudes observed for each species. In most cases the maximum
values were obtained early in the leaching process and the minimum values
were obtained after several pore volumes of throughput.
As an aid to assessing the significance of the concentrations of
several parameters, drinking water criteria are_also listed in Table 3. The
maximum concentrations of Cr, F, Fe, Hg, Mn, NO , Pb, SO4, TDS, and Zn exceed
their respective recommended maximum drinking water concentrations. The
minimum concentrations obtained after substantial leaching are generally
well below the drinking water criteria. Fluoride is a major exception to
this statement. The ratios of the maximum observed concentration to the re-
spective drinking water standard were calculated. In no case did the ratio
12
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exceed 100. The largest ratio was found to be 64 for Mn in effluent from
USBM raw shale in saturated run number 2. This comparison indicates that
even the worst of the leachates generated from the laboratory columns do not
exceed 100 times drinking water standards for the parameters measured.
The four materials on the right side of the table have all been exposed
to natural leaching. The quality of leachate from these materials is useful
for establishing a perspective in which the leachates from the raw shale can
be viewed. The maximum dissolved solids in the effluent from the raw shales
are significantly greater than in that from the previously exposed materials.
The increased dissolved solids are almost entirely attributable to increases
in Ca, Mg, Na, HC03, Cl and $04 in some combination. In general, the maxi-
mum concentrations of trace elements from the raw shales are low and are not
often substantially greater than the values measured for the previously ex-
posed materials. One exception is B, the maximum concentration of which was
significantly greater in the raw shale leachate (except for C-a R-5/Mahog-
any). The minimum values of B from the raw shales are within the observed
range for the previously exposed materials, indicating the Teachability of
this species. Boron, F, and Al concentrations are discussed further in a
subsequent section.
Calculation of the quantities of anions and cations for the raw shales
showed a substantial deficiency of anions, except for the colony raw shales
for which an acceptable balance on every sample was observed. There are at
least two possibilities that are presently under investigation. First,
there may exist an error in the determination of sulfate. For this reason
sulfate concentrations on individual samples have not been reported. It is
believed that another probable explanation involves the presence of other
sulfur species. For instance, thiosulfate (S2032~) is a common constituent
of oil shale process waters and Wong and Mercer (1979) found that this
species accounted for 7-20 percent of the chemical oxygen demand. A few
spot checks of the COD of the leachates from the raw shale showed values
ranging between 1000 and 1500 mg/1. This is suggestive that substantial
quantities of thiosulfate may be present. Stuber, et al., (1978) analyzed
four process waters from in-situ production operations for various sulfur
species. They found the percentages of total sulfur to range from: 3.9 to
30.2 as sulfate, 34.8 to 55.2 as thiosulfate, 1.0 to 26.3 as thiocyanate,
and <0.3 to 3.5 as tetrathionate. It is not likely that these percentages
can be extrapolated to leachates from raw shale, but the possible presence
of such species seems to warrant investigation.
LEACHING OF COMMON SPECIES
The most convenient indicator of the quantity of the common species
Ca, Mg, Na, Cl, HC03 and $04 in the leachate is the electrical conductivity
(EC) of the solution. A measure of the Teachability of these species is
the rate at which the EC declines with the volume of throughput. Figure 2
shows such a relationship for the USBM raw shale. The two sets of data in
the upper block are those obtained under saturated leaching conditions; the
black circles being the initial run and the open circles being the
14
-------
ir>o
T 1 I I I II IU
Initial Saturated Run
After Aeration
slope =-0-934
r£ = 0-889
slope =-0-977
r* = 0-970
0-1
JOli.
1-0 10-0
Port VWume*
>" I 1i I I I I 11
KX>0
K>0
slope = -0-866
r2 = 0-978
Ui
1-0 K>-0
Port VWumes
100-0
Figure 2. Leaching characteristics of USBM raw shale.
15
-------
resaturated run. The data in the lower block are those obtained by leaching
under partially saturated conditions.
Because the columns were quite permeable and saturated from the top, the
residence time of the first few hundred ml of water was much smaller than
the mean residence time. This short residence time and probable channeling
of flow caused the dissolved solids in the first sample to be less than the
maximum. In the preparation of Figure 2 and similar graphs, only values after
the maximum were used. This tends to laterally shift the straight line in a
rather arbitrary way, but has no affect on the slope of the lines.
The rate of leaching of the common species for the USBM raw shale is
practically the same in all three of the experiments. After the initial
saturated leaching had been completed, the column was allowed to drain and
become aerated for 108 days. Leaching was initiated again and the data indi-
cated by the open circles were obtained. Note that the EC almost completely
recovered to its original value and subsequently declined at almost the same
rate as in the first run. The mean residence time was 46 hours in these
runs. The variation of EC with the volume of throughput during the unsatu-
rated run is, again very similar, even though the residence time during the
unsaturated run was less than one-half the residence time for the saturated
runs.
Similar results were observed for the other raw shales tested. Figure 3
shows the results for the Colony raw shale. Again the leaching character-
istics are practically the same for all three tests. As for the raw shales,
the rate of leaching during saturated and unsaturated tests was about the
same for the four materials that had been exposed to natural leaching.
However, in each of these four cases, the rate of leaching following the
drainage/aeration period was markedly less than during the initial run.
Examples are shown in Figure 4 and 5 for Colony naturally leached and the
Union naturally retorted. Futhermore, the EC did not recover substantially
during the aeration period.
In the case of the previously exposed materials, it is believed that the
large fraction of the readily Teachable materials existed as the result of
long term weathering processes and precipitation of dissolved solids caused
by the evapotranspiration of soil water. When these materials were leached
during the initial run, they were not rapidly replaced. In the raw shales,
the percolating waters of the first run removed the readily Teachable
materials from the surface of the solid particles much as in the case of the
previously exposed materials. However, during the aeration period the Teach-
able materiaTs were repTenished rapidTy to the surfaces, probabTy by diffu-
sion and capiTTary fTow. The movement of dissoTved species to the surfaces
of the particTes was reTativeTy rapid for the raw shaTes because no signi-
ficant leaching on the interior of the particTes had occurred and, thus,
the concentration gradients were very Targe. A simiTar process may stiTT be
operative in the other four naturaTTy Teached materiaTs, but at a much
reduced rate due to the countTess number of such cycTes experienced pre-
viousTy.
16
-------
10-Q
I
I-O
i i
i I I I I 1 L
Initial Saturated Run
After Aeration
slope - -1-076
r2* 0-933
1-0
slope = - MO4
r2 = O-974
i I 8 I I I 11
KX>
i i i
(00-0
lO-Oi
I
' 10
0-1
.Unsaturated
slope =-0-902
>2 = 0-978
1 I I I I ll II i I I i I t i I
I I I I I
0-1
1-0
10-0
100-0
Port Ytotomts
Figure 3. Leaching characteristics of Colony raw shale.
17
-------
10-0
I
13 1-0
Initial Saturated Run
$lopc = -0-815
2 = 0-593
After Aeration
1-0
10-0
Pore Vbfumts
KX>0
10-0
'I 1-0
e
u
UJ
Unsaturated
slope = -0-847
0-986
1-0 10-0
Port Vfelumts
KX)-0
Figure 4. Leaching characteristics of Colony naturally leached
shale.
18
-------
10-0
I
i-o
i
T« 'i i i iiij ri i i i iiij 1i i i i ML
initial Saturated Run
" After Aeration
slope =-0-340 :
r2 «0-960
slope = -0-054
r2=0-966
t I I H
10-0
ii i ii 111
IOO-0
Pore Volumes
10-0
I
e
E
5 i-o
o
u
TI \ I Ml| T 1II I 111) 1 1 I I I I I L
-» Unsaturated
slope = -0-310
V2 = 0-935
i i i i mi
0-
I-O 10-0
Ror« VWumts
IOO-O
Figure 5. Leaching characteristics of Union naturally retorted shale.
19
-------
I. '
All of the EC versus pore volume data were fit satisfactorily with an
equation of the type
> PV>PVm
where ECm is the maximum electrical conductivity observed and PVm is the
corresponding volume of effluent expressed in pore volumes (PV). This equa-
tion does not apply after the EC of the leachate begins to stabilize follow-
ing the removal of the most readily soluble materials. For the USBM, Colony,
and C-a composite raw shales, the exponent a varied between 0.8 and 1.1.
However, for the C-a R-5/Mahogany shale this leaching index was between 0.4
and 0.5. The chemical composition of the leachate from the R-5/Mahogany
shale was also substantially different from that of the other three raw
shales; the total dissolved solids being significantly greater, sodium con-
centrations being disproportionately greater, and a very small quantity of
magnesium being present in the leachate.
TRACE ELEMENTS
The results from the eight materials tested were divided into two
groups; those for the 4 mined shales and those for the 4 materials that have
been exposed to leaching and weathering under natural circumstances. The
maximum concentrations of each trace element that were observed for each
group are presented in Table 4. This presentation assists in gaining an
overview of the degree to which trace element concentrations in leachate
from the mined shales differ from those obtained from materials that might
reasonably be expected to represent background conditions.
In view of the range of values that results entirely from material
variability, variable leaching rates, and analytical error, only the con-
centrations of Al, B, F, Mo, Pb, and Zn in Table 4 are significantly
elevated in the mined shales relative to that in the background materials.
In the case of zinc, only the USBM raw shale produced concentrations in
excess of the maximum observed in the background materials. The elevated
zinc concentrations from the USBM material does not appear to be spurious,
as relatively high concentrations were observed in a number of samples.
The maximum concentration of Mo was observed in the initial sample from
the unsaturated leaching of the C-a R-5/Mahogany material. The subsequent
sample collected at 0.88 PV of effluent contained a much reduced quantity of
Mo but still a relatively high value. The Mo concentration in the initial
sample from the saturated column of R-5/Mahogany material was not obtained
due to analytical difficulties. However, the C-a composite material in both
the saturated and unsaturated experiments showed initial Mo concentrations
that are approximately twice those obtained in the other materials. It is
believed that subsequent leaching studies of raw shale from the C-a site
20
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should include analyses for Mo to verify or disprove the indications of
elevated Mo obtained in this study.
Concentrations of Al in leachate from both saturated runs and the
unsaturated experiment on USBM raw shale were significantly elevated relative
to the background materials. Elevated concentrations in the C-a R-5/Mahogany
leachate were also observed. The greatest concentrations of Al for each
material were found in the leachates from either the aerated columns or the
unsaturated columns. No consistent relationship between the Al concentration
and leachate volume was observed. The average concentration of Al in the
USBM saturated runs was 1.76 mg/1, which compares to 3.71 mg/1 obtained for
the same material by averaging the concentrations from the aerated and
unsaturated experiments. These data suggest that Al is produced into the
water in the greatest quantites when aerated conditions exist.
The concentrations of F and B observed in this study are of the same
order as those measured by others (Runnel!s, et al., 1979). Boron concentra-
tions in the leachates obtained at small throughput volumes from USBM, Colony,
and C-a composite were all substantially greater than the maximum value
observed in the background materials that were tested. Boron concentrations
in leachates from C-a R-5/Mahogany were all less than the maximum value
obtained in the soils and previously exposed materials. The largest con-
centrations of B were consistently measured in leachates from the USBM raw
shale. The other mined shales exhibited B concentrations much less than the
USBM material. A trend toward decreasing concentration of B with increas-
ing leachate volume was observed as shown in Figure 6. Because of the large
differences in concentrations for different materials, the actual concentra-
tions were divided by the maximum observed value so that all data could be
shown conveniently on a single figure. The data in Figure 6 suggest that
the Boron concentrations will be reduced to 10 percent of the maximum value
by approximately 5 PV of continuous leaching. Aeration following the first
leaching did not cause the B concentration to recover significantly.
The maximum concentrations of F were observed in the USBM experiments,
but the F concentrations in the background materials are also relatively
high. In these leaching tests, the concentration of F was generally great-
est in samples obtained at small throughput volumes, although this was not
uniformily true. Figure 7 shows the leaching trend for F from USBM and
R-5/Mahogany materials. These data show a relatively stable concentration
of F of 20-25 mg/1 after an initial reduction from a maximum of 75 mg/1 for
the USBM raw shale. Concentrations of F in leachate from the same column
after 108 days of drainage and aeration did not differ significantly from
the stable values obtained in the first cycle of leaching.
With the exception of the USBM material, the more-or-less stable concen-
trations of F obtained in the mined raw shales were between 1 and 10 mg/1.
(Figure 8). The stable concentrations in both materials from the C-a site
were found to be about equal to that for the soils. The Colony naturally
leached shale and the Colony mined raw shale showed approximately equal F
concentrations over most of the range of leachate volumes (Figure 8), even
though the naturally leached material had previously been subjected to
countless leaching cycles in its natural environment.
22
-------
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o USBM Raw Shale
C-a R-5/Mahogany
4567
Pore Volumes of Leachate
Figure 7. Leaching of F from raw shale. (Saturated columns)
24
-------
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BIBLIOGRAPHY
Ham, R. K., M. A. Anderson, R. Stagmann, and R. Stanforth. 1979. Comparison
of Three Waste Leaching Tests. EPA-600/2-79-071. Municipal Environ-
mental Research Lab, Office of Research and Development, USEPA,
Cincinnati, Ohio.
Lowenbach, W. 1978. Compilation and Evaluation of Leaching Test Methods.
EPA-600/2-78-095. Municipal Environmental Research Lab, Office of
Research and Development, USEPA, Cincinnati, Ohio.
Runnells, D. D., M. Glaze, 0. Saether, and K. G. Stollenwerk. 1979.
Release, Transport, and Fate of Some Potential Pollutants in Water
Associated with Oil Shale. In Trace Elements in Oil Shale, Progress
Report: 1976-1979, Contract No. EY-76-S-02-4017. Department of Energy
by Center for Environmental Sciences, University of Colorado, Boulder,
Colorado.
Stollenwerk, K. G., and D. D. Runnells. 1977. Leachability of Arsenic,
Selenium, Molybdenum, Boron, and Flouride from Retorted Oil Shale.
Proc. Chem. Engr. Congress, AICHE, New York. 2:1023-1030.
Stuber, H. A., J. A. Leenheer, and D. S. Farrier. 1978. Inorganic Sulfur
Species in Waste Waters from IN-SITU Oil Shale Processing. Journal
of Environmental Science Health. A13(9):663-675.
Wong, A. L., and B. W. Mercer. 1979. Contribution of Thiosulfate to COD
and BOD in Oil Shale Process Waste Water. ASTM Symposium on Analysis
of Waters Associated with Alternate Fuel Production. Pittsburgh, PA.
26
-------
APPENDIX
TABULATED CHEMICAL DATA AND GRAIN SIZE DISTRIBUTIONS
27
-------
100
80
1
60
v>
£60
f 40
20
I I I 1 I
OOI
"I
i i i i i
ill
O-l 1-0
Particle Size, mm
IOO
I I MTT
I I I I 111
IOOO
Figure A-2. Particle size distribution for Colony raw shale.
28
-------
too
80-
feo
|40r-
20-
I i I I I
"I
0-01
1-0
Particle Size, mm
10-0
100-0
Figure A-3. Particle size distribution for C-a Composite raw
shale.
100
O-OI
0-1 1-0 10-0
Particle Size, mm
100-0
-Figure A-4. Particle size distribution for C-a R-5/Mahogany
raw shale.
29
-------
0-01
0-1 1-0 10-0
Particle Size, mm
IOOO
Figure A-5. Particle size distribution for Union naturally
retorted shale.
100
I I 1 ITT
II I I I Illl 1t I I Mill i i i i i mi » i i i i m
OOOI OOI 0-1 1-0 10-0
Particle Size, mm
Figure A-6. Particle size distribution for C-b soil.
30
-------
II I I III
I I I I I 11II I I 1 I I I I ll I
I 11
0-01
0-1
10-0
Porficle Size, mm
100-0
Figure A-7. Particle size distribution for Colony naturally
leached shale.
too
I I I I III I 1 1 I I III
8O
60
4O
2O
i i i i 1 1 1 i i i i i 1 1 1 i
0-01
0-1 1-0 10-0
RjrtiGle Size, mm
A-8. Particle size distribution for Colony soil.
31
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