DoE
United States
Department of Energy
Division of Environmental
Control Technology
Washington,DC 20545
LA-7360-PR
PA
US Environmental Protection Agency
Office of Research and Development
Industrial Environmental
Research Laboratory
Research Triangle Park, NC 2771 1
EPA-600/7-78-028a
July 1978
Trace Element
Characterization
of Coal Wastes -
Second Annual
Progress Report
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Researcn and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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DoE LA-7360-PR
EPA-600/7-78-028a
July 1978
UC-90i
Trace Element Characterization
of Coal Wastes -
Second Annual Progress Report
October 1, 1976-September 30, 1977
by
E. M. Wewerka, J. M. Williams, N. E. Vanderborgh,
A. W. Harmon, P. Wagner, P. L. Wanek, and J. D. Olsen
Los Alamos Scientific Laboratory
University of California
Los Alamos, New Mexico 87545
An Affirmative Action/Equal Opportunity Employer
EPA/DoE Interagency Agreement No. IAG-D5-E681
Program Element No. EHE623A
EPA Project Officer: David A. Kirchgessner
Industrial Environmental
Research Laboratory
Research Triangle Park, NC 27711
DoE Project Officer: Charles Grua
Division of Environmental
Control Technology
Washington, DC 20545
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
and
U.S. DEPARTMENT OF ENERGY
Division of Environmental Control Technology
Washington, DC 20545
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CONTENTS
ABSTRACT 1
EXECUTIVE SUMMARY 1
SUMMARY OF TASK PROGRESS 5
TASK PROGRESS DESCRIPTION 7
Task 1 7
Task 2 27
Task 3 48
Task 4 54
PERSONNEL 70
APPENDIX A. Standard Procedure for X-Ray Mineralogical Analysis
of Coal and Waste Materials 71
APPENDIX B. Summary of LASL Coal and Refuse Sample Analyses 73
APPENDIX C. Summary of LASL Sized-Coal Refuse Sample Analyses 87
APPENDIX D. Summary of LASL Float/Sink Analyses 95
APPENDIX E. Graphic Display of Clustered Trace Element/Mineral
Correlation Coefficients for Coal Preparation Wastes
from Three Illinois Basin Coal Cleaning Plants 107
APPENDIX F. Procedure for Multistage Float/Sink Separation of
Coal Preparation Wastes 114
APPENDIX G. Sample Preparation Procedure for Microprobe Analysis
of Coal and Refuse Materials 116
APPENDIX H. Procedure for Static/Equilibrium Leaching of Coal or
Waste Materials 116
APPENDIX I. Experimental Procedure for Column Leaching Studies of
Coal and Coal Refuse 117
APPENDIX J. Description of Static Leaching Experiments with Refuse
from Illinois Basin Cleaning Plants A, B, and C 118
IV
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APPENDIX K. Description of Static Leaching Experiments with Refuse
from Illinois Basin Cleaning Plant B 123
APPENDIX L. Description of Continuous Leaching Studies of
Illinois Basin Coal Refuse 127
APPENDIX M. Description of Static Leaching Experiments with Coal
from Illinois Basin Cleaning Plant E 135
APPENDIX N. Description of Continuous Leaching Studies of Coal
from Illinois Basin Cleaning Plant E 139
TABLES
I. Two-Theta Band Positions and Relative Peak
Intensities of XRD Mineral Standards 9
II. Major Minerals in Refuse from Illinois Basin
Coal Preparation Plants A, B, and C 10
III. Trace Element Composition of Refuse from Illinois
Basin Coal Preparation Plant A 11
IV. Trace Element Composition of Refuse from Illinois
Basin Coal Preparation Plant B 13
V. Trace Element Composition of Refuse from Illinois
Basin Coal Preparation Plant C 15
VI. Statistical Correlation of Trace Element-Mineral
Associations in Illinois Basin Coal Refuse Plant A 20
VII. Statistical Correlation of Trace Element-Mineral
Associations in Illinois Basin Coal Refuse Plant B 20
VIII. Statistical Correlation of Trace Element-Mineral
Associations in Illinois Basin Coal Refuse - Plant C 20
IX. Descriptions of Features on Photomicrographic Map 23
X. Trace Element-Mineral Associations from Microprobe Analysis
of Illinois Basin Coal Refuse from Plants A and B : 24
XI. Ion Microprobe Observation of Trace Elements Associated
with Clay Minerals in Illinois Basin Coal Refuse 25
XII. Ion Microprobe Observation of Trace Elements Associated
with Pyrite and Marcasite in Illinois Basin Coal Refuse 25
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XIII. Ion Microprobe Observation of Trace Elements Associated
with Carbonates in Illinois Basin Coal Refuse 25
XIV. Ion Microprobe Observation of Trace Elements Associated
with Quartz in Illinois Basin Coal Refuse 25
XV. Summary of Trace Element-Mineral Associations in Refuse
from Three Illinois Basin Coal Preparation Plants 26
XVI. Description of Static Leaching Experiments with
Refuse from Illinois Basin Cleaning Plants A, B, and C 28
XVII. Elemental Composition of Leachates from Static
Leaching Experiments with Plant A Illinois Basin
Coal Refuse 31
XVIII. Elemental Composition of Leachates from Static
Leaching Experiments with Plant B Illinois
Basin Coal Refuse 31
XIX. Elemental Composition of Leachates from Static
Leaching Experiments with Plant C Illinois
Basin Coal Refuse 32
XX. Release Percentages of Elements During Static
Leaching Experiments with Plant A Illinois
Basin Coal Refuse 32
XXI. Release Percentages of Elements During Static
Leaching Experiments with Plant B Illinois
Basin Coal Refuse 33
XXII. Release Percentages of Elements During Static
Leaching Experiments with Plant C Illinois
Basin Coal Refuse " 33
XXIII. Experimental Conditions Used in Static/
Equilibrium Leaching Study of Illinois Basin
Coal Refuse 35
XXIV. Static/Equilibrium Leaching of Illinois Basin
Coal Waste 37
XXV. Static/Equilibrium Leaching of Illinois Basin
Coal Waste 37
XXVI. Static/Equilibrium Leaching of Illinois Basin
Coal Waste 38
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XXVII. Static/Equilibrium Leaching of Illinois Basin
Coal Waste 38
XXVIII. Static/Equilibrium Leaching of Illinois Basin
Coal Waste 39
XXIX. Static/Equilibrium Leaching of Illinois Basin
Coal Waste 39
XXX. Description of Continuous Leaching Studies
of Illinois Basin Coal Refuse 40
XXXI. Elemental Composition of Leachates from
Continuous Leaching Experiments with Plant A
Illinois Basin Coal Refuse 43
XXXII. Elemental Composition of Leachates from
Continuous Leaching Experiments with Plant B
Illinois Basin Coal Refuse 44
XXXIII. Elemental Composition of Leachates from
Continuous Leaching Experiments with Plant C
Illinois Basin Coal Refuse 44
XXXIV. Environmental Activity Factors from Continuous
Leaching Experiments with Plant A Illinois
Basin Coal Refuse 45
XXXV. Environmental Activity Factors from Continuous
Leaching Experiments with Plant B Illinois
Basin Coal Refuse 46
XXXVI. Environmental Activity Factors from Continuous
Leaching Experiments with Plant C Illinois
Basin Coal Refuse 46
XXXVII. Elements Highly Associated with Labile Minerals
in Illinois Basin Coal Refuse 49
XXXVIII. Trace Elements of Environmental Concern as
Delineated by Static and Dynamic Leaching Studies
of Illinois Basin Coal Refuse 50
XXXIX. Trace Elements of Environmental Concern in
Illinois Basin Coal Refuse 51
XL. Trace Element Concentration Ranges for
Experimental Leachates and Field Samples of
Drainage Produced by Illinois Basin Coal Refuse 52
vu
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XLI. Trace Element Composition of Raw Coal from
Illinois Basin Coal Preparation Plant E 55
XLII. Experimental Conditions used in Static/Equilibrium
Leaching Study of Illinois Basin Coal 56
XLIII. Static/Equilibrium Leaching of Illinois
Basin Coal 58
XLIV. Static/Equilibrium Leaching of Illinois
Basin Coal 58
XLV. Static/Equilibrium Leaching of Illinois
Basin Coal 59
XLVI. Static/Equilibrium Leaching of Illinois
Basin Coal 59
XLVII. Static/Equilibrium Leaching of Illinois
Basin Coal 60
XLVIII. Static/Equilibrium Leaching of Illinois
Basin Coal 60
IL. Static/Equilibrium Leaching of Illinois
Basin Coal 60
L. Environmental Activity Factors from Continuous
Leaching Experiment with Plant E Illinois Basin Coal 66
LI. Elemental Composition of Leachates from Static
Leaching Experiment with Plant E Illinois Basin Coal 67
LII. Release Percentages of Elements During Static
Leaching Experiment with Plant E Illinois Basin Coal 68
LIII. Elemental Composition of Leachates from Continuous
Leaching Experiment with Plant E Illinois Basin Coal 68
LIV. Environmental Activity Factors from Continuous
Leaching Experiment with Plant E Illinois Basin Coal 69
LV. Trace Elements of Environmental Concern in
Illinois Basin Plant E Coal 69
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FIGURES
1. Trace element correlation coefficients for
sized refuse fractions from cleaning Plant B 18
2. Photomicrograph of -20 mesh refuse 21
3. Leachate pH and TDS as a function of time from
static leaching experiments with refuse from three coal
cleaning plants 29
4. The relationship between pH and TDS for leachates
from static leaching experiments with coal refuse 30
5. Leachate pH values and TDS from the static/equilibrium
leaching study of coal refuse 36
6. Total dissolved salts and pH values for
uninterrupted dynamic leaching experiments with
refuse from cleaning plants A, B, and C 41
7. The concentrations of iron, aluminum, and cobalt as
a function of leachate volume during the continuous leaching
of refuse from cleaning plant B 42
8. The effect of discontinuous flow on leachate pH
values for a column leaching experiment 47
9. The behavior of leachate salt content when flow
is interrupted in a column leaching experiment 48
10. Leachate pH as a function of experimental variables
for leaching study of Illinois Basin coal 57
11. Leachate pH from a continuous leaching experiment
with Illinois Basin coal 62
12. TDS as a function of leachate volume for a
continuous leaching experiment with Illinois Basin coal 62
13. The effect of interrupted flow on leachate pH
for Illinois Basin coal 63
14. The effect of discontinuous flow on leachate solids
content for Illinois Basin coal 64
IX
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15. Liquid chromatogram of organic contaminants in
coal leachate obtained by passing 10 ml of leachate through
a 4-mm-i.d. by 30-cm Bondapak C-18 column followed by elution
with a linear gradient progressing from pure water to pure
acetonitrile at a flow rate of 2.0 ml/min 65
E-l. Trace element correlation coefficients for all coal and
refuse samples collected from cleaning Plant A 109
E-2. Trace element correlation coefficients for sized
refuse fractions from cleaning Plant A (samples 25b-f) 109
E-3. Trace element correlation coefficients for float/sink
fractions of average refuse from cleaning Plant A (sample FlO) 110
E-4. Trace element correlation coefficients for all coal
and refuse samples collected from cleaning Plant B 110
E-5. Trace element correlation coefficients for sized refuse
fractions from cleaning Plant B (samples 24b-f) Ill
E-6. Trace element correlation coefficients for float/sink
fractions of average refuse from cleaning Plant B (sample F13) Ill
E-7. Trace element correlation coefficients for float/sink
fractions of —1/4-in. refuse from cleaning Plant B (sample F3) 112
E-8. Trace element correlation coefficients for float/sink
fractions of +2-in. refuse from cleaning Plant B (sample F4) 112
E-9. Trace element correlation coefficients for all coal and
refuse samples collected from cleaning Plant C 113
E-10. Trace element correlation coefficients for sized refuse
fractions from cleaning Plant C (sample 18b-f) 113
E-ll. Trace element correlation coefficients for float/sink
fractions of average refuse from cleaning Plant C (sample Fll) 114
F-l. Schematic for multistage float/sink technique 115
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TRACE ELEMENT CHARACTERIZATION OF COAL WASTES
SECOND ANNUAL REPORT
by
E. M. Wewerka, J. M. Williams, N. E. Vanderborgh,
A. W. Harmon, P. Wagner, P. L. Wanek, and J. D. Olsen
ABSTRACT
Early in FY 77, we completed the analyses of the trace elements and major
minerals in bulk refuse and coal samples from the Illinois Basin. This ac-
tivity was followed at midyear by studies to elucidate the structural
relationships and associations among the trace elements in these materials.
Concurrent with these efforts, and continuing throughout most of the year,
we conducted several series of weathering and leaching experiments to
define the environmental behavior of the trace elements in the refuse and
coal samples under various environmental conditions. These investigations
resulted in the identification of the trace elements of most environmental
concern in typical Illinois Basin refuse and coal. During the latter part of
the year, we began to investigate methods to control the trace element con-
tamination of refuse and coal drainage.
EXECUTIVE SUMMARY
This section summarizes some of the technical highlights, evaluations, and recommendations
from a Los Alamos Scientific Laboratory (LASL) study of trace element contamination of
drainage from coals and coal cleaning wastes. This research has identified those trace elements
that are released in hazardous amounts during the weathering and leaching of high-sulfur coal
refuse from the Illinois Basin. Control technology strategies to address this problem are discus-
sed. A comprehensive appraisal of the FY 77 programmatic accomplishments is contained in the
main body of the report.
The mineral wastes from coal preparation and mine development constitute a major en-
vironmental problem. More than 3 billion tons of these materials have accumulated in the U.S.,
and the current annual rate of waste production of 100 million tons per year is expected to double
within a decade. The total number of coal waste dumps is estimated to be between 3000 and 5000,
of which half pose some type of health, environmental, or safety problem. Structural weaknesses
in coal refuse banks have led to tragic landslides such as those at Buffalo Creek, West Virginia,
and Aberfan, Wales, and the approximately 300 burning waste banks are a major source of air
pollution. In addition to these problems, there is growing concern about environmental effects
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from the trace elements present in the highly mineralized acid drainage from coal refuse dumps
that affect many thousands of miles of streams and waterways.
Although it has been established that the drainage from coal refuse dumps is often highly con-
taminated with trace or inorganic elements, little is known about the quantities of undesirable
elements released into the environment from this source. Development of the necessary control
technologies for human and environmental protection requires quantitative evaluation of the ex-
tent and severity of the problem. LASL has been directed by the Department of Energy (DOE)
and the Environmental Protection Agency (EPA) to assess the nature and magnitude of trace ele-
ments in the effluents from coal preparation wastes (and to a limited extent raw coals), and to
identify the technology necessary to control this form of environmental pollution.
The principle objectives of the LASL research program are
• to assess the nature and magnitude of trace elements in the effluents from coals and coal
preparation wastes,
• to identify experimentally the chemistry of the trace constituents of environmental concern
with the aim of delineating potential removal/recovery systems, and
• to recommend required pollution control technology or necessary RD and D programs.
The researches reported here represent a continuation of the studies begun in FY 76 to es-
tablish a firm foundation for subsequent efforts. In this initial period we did the appropriate
literature search, developed laboratory and analytical techniques, collected coals and coal waste
samples from several parts of the country, and started work on the stated objectives. The follow-
ing sections summarize the technical highlights, conclusions, and recommendations resulting
from this effort to date.
To understand why coals and coal preparation wastes release trace elements (trace elements
here are defined as all elements except carbon, hydrogen, sulfur, and oxygen) in the amounts that
they do, we have studied the levels and occurrences of these elements in samples of high-sulfur
coal cleaning wastes from the Illinois Basin.
Our Illinois Basin refuse samples were composed of clay minerals (illite, kaolinite, and other
more complex clays), quartz, pyrite, and marcasite. Interspersed throughout the mineral network
were a variety of minor minerals and residual coal. The relative magnitudes of the major minerals
constituting these refuse materials did not vary greatly from sample to sample.
Elementally, we found these refuse materials to be very complex. We have identified the
presence of some 55 elements in most of the refuse samples and undoubtedly there are more. The
most abundant of these elements, iron, aluminum, and silicon, compose the structures of the ma-
jor mineral systems. The minor elements are present as constituents of minor minerals, compo-
nents of the residual coal, or substituents in the major mineral lattices.
Our studies of refuse structure and mineralogy delineated the great potential of these materials
to release harmful quantities of trace elements. A large number of elements that are generally
considered to be environmentally sensitive are present in these refuse materials in significant
quantities (>30 /xg/g)- Included among these are fluorine, aluminum, manganese, iron, cobalt,
nickel, copper, zinc, arsenic, and lead. Although the relative amounts of some of these compo-
nents are seemingly small, the absolute quantities that are available in a large or active waste
dump could cause grave consequences in the surrounding environment if they were to be released
and concentrated by natural processes.
Static and dynamic leaching experiments were performed to evaluate the trace element
behavior of Illinois Basin coal wastes under simulated weathering conditions. These experiments
were done to provide information needed to predict quantitatively the trace element levels in the
drainage from coal refuse dumps or disposal areas and to identify those elements of environmen-
tal concern.
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Perhaps the single most important characteristic of the high-sulfur refuse materials during
aqueous leaching is their pronounced tendency to rapidly produce acidic leachates. This is due to
the oxidative degradation of the pyrite and marcasite present in the refuse. Acid formation is par-
tially attenuated by calcite or other neutralizing species in the refuse, but the leachates from the
Illinois Basin refuse samples that we studied nearly always had pH values in the range of 2 to 4.
These acid leachates are very efficient in dissolving or degrading many of the mineral compo-
nents of the refuse, thus releasing the trace or minor elements associated with them.
Two types of trace element teachabilities were observed. Because of their abundance in the
refuse some elements (such as iron, aluminum, calcium, magnesium) are released in relatively
high absolute quantities. Other, less abundant elements (for example, nickel, cobalt, zinc, cop-
per) are leached in a high proportion to the total of each present, although this may not be a large
amount in the absolute sense. The first group is highly concentrated in the leachates, the second
is highly leachable from the refuse.
Experiments designed to simulate intermittent leaching of high-sulfur coal waste piles were
also conducted. These studies revealed that as a result of the rather continuous oxidation of
pyrite (and acid formation), intermittently leached refuse dumps pose a far greater pollution
threat than those wastes that are always in contact with water or otherwise isolated from air.
The experimental data on trace element leachability that we generated as a result of our
simulated weathering and leaching studies were compared with similar data for actual refuse
dump drainage from diverse points in the Illinois Basin. The high level of agreement between the
two sets of results indicates convincingly that the laboratory leaching tests realistically simulate
refuse dump conditions.
The aqueous leachates from the high-sulfur coal and refuse from the Illinois Basin contain a
vast array of potentially harmful trace elements. Several toxic elements are consistently present
at levels (>10 ng/m&) that could cause environmental or ecological problems in refuse disposal
areas unless some form of effluent control or clean up is exercised. A few other elements, though
not present in the refuse leachates in high quantities, have inherently high leachabilities or are
associated with labile mineral species, and thus have a significant potential to contaminate
refuse drainage under some circumstances.
By assessing our experimental data and using available information on trace element tox-
icology, we have identified nine elements that have the greatest potential to contaminate
drainage or runoff from Illinois Basin coal preparation wastes. These elements appear in the fol-
lowing table along with the criteria by which they were chosen. All of the elements listed in the
table are recognized toxicants to plants or animals in quantities comparable to those present in
the refuse or refuse leachates. These are the priority elements that should receive the greatest
emphasis in subsequent work on environmental control technology.
Despite the thoroughness of the laboratory investigations, it is important when considering the
list of elements of environmental concern to bear in mind that almost any designated level of
trace elements in a refuse drainage system is somewhat arbitrary from an environmental view-
point, since the actual harm that toxic elements can cause is a function of the efficiency of ac-
cumulation into the surrounding ecosystem. This may depend on factors not directly related to
the waste pile, such as volume and dilution of the drainage, and the ability of plants, animals,
and soils in the area to concentrate specific toxic elements. Accordingly, the emphasis in our work
has been directed at understanding the chemistry and environmental behavior of the trace ele-
ments in coal refuse materials to allow us to arrive at technically sound recommendations for
those instances where environmental control will prove necessary.
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TRACE ELEMENTS OF MOST ENVIRONMENTAL CONCERN
IN HIGH-SULFUR ILLINOIS BASIN COAL REFUSE
Labile Mineral HighLeachate High Inherent
Element Association* Concentration" Leachabilityc
F x
Al x
Mn xxx
Fe x x x
Co xx
Ni xx
Cu xx
Zn xx
Cd x
"Associated with labile minerals (pyrite, marcasite,or calcite) in
the refuse samples.
"Consistently present in refuse leachates in concentrations ex-
ceeding 10 [
"Consistently leached in amounts exceeding 10 wt% of the total
present in the refuse.
Several of the principal conclusions from our work carry implications concerning environmen-
tal control strategies.
One of the main implications concerns the importance of pH in determining the levels of trace
element contamination in refuse drainage. Throughout our studies, under all conditions of static
and dynamic leaching, an inverse relationship prevailed between pH and the amounts of ele-
ments leached from the refuse samples. Thus, at low pH (2 to 3), worrisome quantities of trace
elements were leached from all of the samples studied; whereas, in those systems where the
leachate was more nearly neutral (pH from 5 to 7), trace element teachability and the capability
of the leachates to solubilize contaminants were minimized. Therefore, preventing the formation
of acids in refuse dumps, or neutralizing the acid drainage as it is formed, should prove effective
in controlling trace element releases into the environment.
A related observation from our work concerns the ease with which many of the elements that
we have designated as being of environmental concern can be removed from the refuse materials
simply by leaching them with aqueous acids. Our environmental studies with Illinois Basin
refuse revealed that substantial percentages of the total manganese, cobalt, nickel, zinc, and cad-
mium available in the refuse materials can be removed by short-term leaching with dilute sul-
furic acid. This suggests that many of the environmentally harmful elements in high-sulfur refuse
could be removed before disposal by treating the crushed refuse with a dilute acid, and isolating
the easily removable elements in the ensuing leachates. This process looks even more attractive
when it is considered that the necessary acid could be generated in situ by treating the refuse sul-
fide constituents with water and air.
Finally, it is quite important to keep in mind, when considering regional control of water pollu-
tion from coal waste dumps, that high-sulfur waste materials, which are only intermittently
leached by water, generally pose a far greater pollution threat than those that are continuously
being leached. Therefore the highest priority and greatest emphasis in pollution abatement
programs should be given to those disposal sites that are frequently, but not continuously, in con-
tact with surface or ground water.
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It is evident from our studies, and from the available information about actual refuse dump
drainage, that further research is needed to identify or assess suitable control technology to pre-
vent environmental degradation by the release of acid and trace elements from some Illinois
Basin coal cleaning wastes. Control technology will be necessary both for newly produced coal
wastes and for existing refuse dumps. Among the options for preventing the release of trace ele-
ments from new refuse materials are immobilization or removal of the elements in question by
physical or chemical treatment; reduction of air and water passage through refuse dumps by
grading and compacting the refuse as it is disposed, or by the use of sealing agents; prevention of
acid build-up in refuse dumps by the addition of neutralizing agents; and, burial of refuse to
isolate it from the environment. Methods to treat contaminated drainage from existing refuse
dumps include alkaline neutralization, ion exchange, reverse osmosis, and the application of
selected adsorbents. A substantial part of our future effort in this program will be directed at
identifying the most effective of these options for preventing or controlling trace elements con-
tamination of Illinois Basin coal refuse drainage. Also, to broaden the scope of our work, we will
include studies of refuse from the Appalachian and Western coal regions. This investigation will
define the potential of the trace elements in these wastes to cause environmental problems, and
identify necessary environmental control technology for these materials.
SUMMARY OF TASK PROGRESS
The major objectives of this research program are to assess the potential for environmental pol-
lution from trace or minor elements that are released in the drainages from coal preparation
wastes and stored coals, and to identify suitable environmental control measures, if necessary.
This report describes technical accomplishments in each of the main research areas of the
program for the period October 1, 1976, to September 30, 1977.
The research activities in this program are broken down into major tasks and subtasks, as
listed in the Task Breakdown Chart.
TASK BREAKDOWN
TRACE ELEMENTS CHARACTERIZATION AND REMOVAL/RECOVERY
TASK I
TASK 2
TASK 3
TASK 4
ASSESS THETRACE
ELEMENTS AND MINERALS
IN COAL PHKFARAT1ON
WASTES
1.1 IDENTIFY TRACE
ELEMENTS AND
MINERALS IN
WASTES
1.2 DETERMINE RELA-
TIONSHIPS AMONG
TRACE ELEMENTS
AND MINERALS
1.3 ESTABLISH MINER-
ALOGY, MORPHOLOGY,
AND CHEMISTRY OF
TRACE ELEMENTS
DETKKM1NBTHK
ENVIRONMENTAL BEHAVIOR
OF TRACE ELEMENTS IN
COAL WASTES
2.1 STUDY WEATHERING
AMU LEACHING OK
TRACE ELEMENTS
IN WASTES
2.2 MODELTHK
ENVIRONMENTAL
BEHAVIOR OF
WASTES
IUENT1KYT11ACE ELEMENTS
OK CONCERN IN WASTES
AND RECOMMEND POLLUTION
CONTROLTECHNOLOGY
:i.l IDENT1KYTRACK
ELEMENTS OF
ENVIRONMENTAL
CONCERN IN REFUSE
RECOMMEND
TECHNOLOGY KOK
CONTROLLING TRACE
ELEMENT CONTAM-
INATION
ASSBSS ENVIRONMENTAL
CONTAM1N AT1ON FROM TRACE
ELEMENTS AND ORGANICS
IN STORED COALS
4.1 DETEKM1NETHE
TRACK ELEMENTS/
ORGANIC CPUS IN
I.KACHATES KROM
STORED COALS
•1.2 OBTAIN TRACE
COMPONENTS RE-
LEASE RATES FROM
COALS
4.:l ASSESS THE POTEN-
TIAL FOK ENVIRON-
MENTAL CONTAMINA-
TION FROM STORED
COALS
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The objective of Task 1 was to provide an assessment of the identities, structures, and
chemistries of the trace elements and minerals in samples of high-sulfur, coal preparation wastes.
Accordingly, we completed extensive quantitative analyses of the elemental and mineral com-
positions of more than 60 refuse samples collected from three coal cleaning plants in the Illinois
Basin. These waste materials were found to be composed mainly of clay minerals (illite,
kaolinite, and mixed-layer varieties) pyrite, marcasite, and quartz. Smaller amounts of calcite
and gypsum were also identified in some of the refuse samples.
The elements present in greatest abundance (usually greater than 1000 /ug/g refuse) in the Il-
linois Basin refuse materials are silicon, aluminum, iron, sodium, potassium, calcium, and
magnesium, which are components of the major mineral species. Phosphorus, fluorine, and
titanium are also present in significant quantities in these refuse samples. Among the trace ele-
ments identified in these wastes, several are present in environmentally disturbing quantities, in-
cluding manganese, cobalt, nickel, copper, zinc, arsenic, selenium, cadmium, and lead.
Also in Task 1, we conducted an extensive investigation of the structural relationships and as-
sociations among the trace elements and major minerals in the Illinois Basin refuse samples. We
established structural relationships both by statistical correlation of chemical and physical data,
and by direct observation of refuse structure with electron and ion microprobes. The most
notable result from the investigation concerned the mineral associations of many of the trace ele-
ments that we identified as being highly leachable from the refuse samples and, therefore, of en-
vironmental concern. We found that such typical sulfide-forming elements as cobalt, nickel, cop-
per, zinc, and cadmium were not associated with the major pyritic fractions, but rather were con-
stituents of, or embedded in, the refuse clay fractions.
Our efforts in Task 2 were directed at determining the environmental behavior of the trace ele-
ments in Illinois Basin refuse samples during weathering and leaching. Both static and dynamic
testing were conducted to determine the trace element leachabilities of the various waste sam-
ples. In general, the trace elements leached in highest quantities from these samples were iron,
aluminum, calcium, magnesium, and sodium, which are constituents of the major refuse
minerals. Several elements, while not present in the leachates in large amounts, were nonetheless
found to be very easily removed from the refuse materials during aqueous leaching. This group
included cobalt, nickel, zinc, cadmium, and manganese.
The highest degree of trace element leachability occurred in waste samples that produced the
most highly acidic leachates. Therefore, the largest reductions in the quantities of trace elements
released from Illinois Basin wastes were accomplished by keeping the pH of the leachates approx-
imately 7 or higher. Lesser, but significant reductions in acid formation were achieved by increas1-
ing the sizes of the refuse particles, reducing the temperature of the system, and limiting the ac-
cess of air.
One of the objectives of Task 3 was to interpret the information and experimental results ob-
tained in the study, and to identify from them the most environmentally worrisome trace ele-
ments in typical Illinois Basin coal preparation wastes. Based on our studies of refuse mineralogy
and environmental behavior, we identified fluorine, aluminum, manganese, iron, cobalt, nickel,
copper, zinc, and cadmium as being the elements of most concern in cleaning wastes from the Il-
linois Basin. These elements were chosen because they are often toxic in aqueous systems or soils,
and because they are present in the refuse materials in a highly leachable state, or are associated
with a labile mineral component of the refuse structure.
Also in Task 3, we began to evaluate several techniques to control acidity and trace elements in
the drainage or runoff from coal refuse dumps. Initially, we are considering ^uch methods as
alkaline neutralization, ion exchange, reverse osmosis,, and flash distillation, which are being
used or tested for control of acid drainage from coal mines and refuse dumps. Results from these
experiments will be reported during FY 78.
-------
Finally, in Task 4, we investigated the potential for environmental contamination from the
trace elements and organic compounds that are released during the weathering and leaching of
stored coals. We made extensive use of static and dynamic leaching tests to investigate the en-
vironmental behavior of samples of a high-sulfur Illinois Basin coal. The types and quantities of
trace elements released from the coal during aqueous leaching are nearly identical to those
released from the Illinois Basin cleaning wastes. Iron, aluminum, manganese, cobalt, nickel,
zinc, copper, and cadmium were identified as the trace elements most likely to cause en-
vironmental problems in the drainages from this type of coal.
The levels of organic contaminants in the coal leachates were determined to be in the range 5 to
50 ppm. A preliminary mass-spectral analysis of this material suggests that it is composed main-
ly of aliphatic and alicyclic compounds that often contain nitrogen, oxygen, and sulfur functional
groups. No direct evidence was obtained for the presence of aromatic or phenolic components in
the organic fractions of the coal leachates.
TASK PROGRESS DESCRIPTION
TASK 1—ASSESS THE STRUCTURE AND CHEMISTRY OF TRACE ELEMENTS
AND MINERALS IN COAL CLEANING WASTES
The purpose of this task was to provide a comprehensive assessment of the identities, struc-
tures, and chemistry of the trace elements and minerals in refuse and coal samples collected from
several coal preparation plants in the Illinois Basin. This information was used to support work
throughout the year on trace element environmental behavior and removal/recovery technology.
Subtask 1.1—Identify the Trace Elements and Major Minerals in Bulk Waste Materials
During FY 77, we completed the quantitative analysis of the mineral compositions of refuse
samples collected from three Illinois Basin coal cleaning plants, where they were produced from
the physical cleaning of several of the major types of high-sulfur coals. Descriptions and details of
the origins of these samples appear in our FY 76 annual report (EPA-600/7 -78-028). Accurate in-
formation on the mineral compositions of the refuse materials is necessary to establish trace
element/mineral correlations, and to understand behavior of the elements during weathering and
leaching.
The mineral compositions of the bulk Illinois Basin refuse samples were determined by x-ray
diffraction according to the procedure detailed in Appendix A. A series of pure mineral standards
was used to calibrate the x-ray diffractometer and calibration curves were constructed for each of
the standards to relate diffractometer response (x-ray peak height) to mineral concentrations.
These calibration plots (shown in Progress Report No. 5, LA-6933-PR) are relatively linear over
the range of concentrations likely to be encountered. Exceptions to this are pyrite and marcasite,
whose calibration curves deviated considerably from linearity above concentrations of 30 wt%.
This behavior, we think, is due either to background fluorescence of the iron in these materials, or
to particle orientation effects in the sample holder. Both the pyrite and marcasite calibration
curves were straightened by using an internal standard and applying the following equation.
-------
FeS?(corr)
PH
Al203(FeS absent)
Al 0 (FeS in sample)
where PH = peak height.
With the exception of calcite, calibration curves were constructed for at least two x-ray bands
for each mineral component. This was done to increase the precision of the mineralogical
analyses of the coal and waste samples. Many variables, including sample composition, prepara-
tion procedure, orientation effects, and band overlapping, can affect the intensities and exact
positions of the individual x-ray bands, making quantitative analyses based only on a single band
for each mineral somewhat tenuous. A compilation of the positions and relative intensities of the
26 bands that we used to characterize the various coal-related minerals is given in Table I. In
general, these values compare well with similar data from the literature.
The quantitative mineralogical analyses of approximately 45 refuse samples or fractions
therefrom were completed by the XRD technique. The results of these voluminous analyses are
reported in their entirety in Appendixes B, C, and D. A summation of these results is given in
Table II, which lists the average major mineral compositions of the refuse samples collected from
each of the three Illinois Basin preparation plants. These data are based on a minimum of three
replicate analyses of each sample. The refuse analyses were done on the as-received material, so
only about 80 to 95% of the total was identifiable by the XRD method. The remaining or un-
analyzed part of the samples represents residual coal, amorphous mineral matter, and minor
mineral species in undetectable amounts.
As is usual for Illinois Basin coals, these refuse samples are composed mainly of clay minerals:
illite, kaolinite, and other more complex clays. Quartz, pyrite, and marcasite account for most of
the remaining material. Lesser amounts of calcite and gypsum were also identified in some of the
samples. The XRD analyses show that variations do occur in the mineral compositions of the
refuse materials from the various plants. For example, the total amount of analyzable pyrite and
marcasite in the refuse from Plant A averages about 22 wt%, whereas the iron sulfide contents of
the Plants B and C refuse were 26 and 30 wt%. Such variation in refuse composition results from
geological differences in the character of the mine floor and roof material and of the coal seams
supplying the feed coal, and are not unexpected. The relative magnitude of each mineral species
or class, however, appears to be fairly fixed. The clay minerals are always predominant relative to
the amounts of quartz, pyrite, and marcasite, and these in turn do not vary greatly relative to
each other. The exception is calcite, which was found in widely varying amounts in these refuse
samples.
Also during FY 77, we completed an extensive analysis of the elemental compositions of the
refuse samples collected from the Illinois Basin cleaning plants. These analyses established the
levels of the various toxic trace elements in the refuse materials, thus revealing the overall poten-
tial of trace element contamination of water.
A description of the analytical methods and techniques used for refuse elemental analyses is
given in our FY 76 annual report. Neutron activation analysis (NAA) was used extensively
because the refuse materials can be analyzed directly with a minimum of sample preparation,
and the concentrations of many elements can be determined simultaneously. Trace elements not
readily determined by NAA were analyzed with atomic absorption spectrophotometry, optical
emission spectroscopy, or wet chemical methods.
In all, the trace elements in more than 70 refuse samples or increments were analyzed during
the year. In each case the concentrations of up to 55 elements were determined. The results of
these analyses appear along with the refuse mineral data in Appendixes B, C and D. Listings of
the averages, extremes in elemental compositions, and relative standard deviations (RSD) for the
-------
TABLE I
TWO-THETA BAND POSITIONS AND RELATIVE PEAK INTENSITIES OF XRD MINERAL
STANDARDS
Mineral
Alumina
Calcite
Gypsum
111ite
Kaolinite
Magnesium Oxide
Marcasite
Montmorillonite
Pyrite
Quartz
26 Band
(Degrees)
43.4
30.0
12.1
29.4
8.9
20.0
26.8
12.4
20.2
24.9
43.0
33.4
52.2
5.8
20.2
33.1
40.7
56.2
20.8
26.7
Relative
Intensity3
1.1
4.4
3.0
2.2
0.30
0.15
0.24
1.3
0.31
1.0
2,8
1.1
0.48
0.90
0.22
1.4
0,55
1.0
0.66
3.6
Based on the 26.7° 29 band of quartz having an intensity of 3.6.
DGlycolated.
refuse samples collected from each of the three Illinois Basin coal preparation plants appear in
Tables III through V. These values, we feel, are representative of the elemental compositions of
the major types of high-sulfur coal cleaning wastes now produced in the Illinois Basin.
The elements present in greatest abundance in these refuse materials make up the structures of
the major minerals, namely, silicon, sulfur, aluminum, iron, sodium, potassium, calcium, and
-------
TABLE II
MAJOR MINERALS IN REFUSE FROM ILLINOIS BASIN COAL PREPARATION PLANTS A, B, AND C
Plant A Plant B Plant C
Mineral Average - Wt. % Average - Wt. % Average - Wt. %
Kaolinite
Illite
Other clays
Pyrite
Marcasite
Quartz
Calcite
Gypsum
Other
15
14
7
14
8
22
6
3
11
-7
11
17
15
11
17
0
1
21
14
16
8
21
9
23
1
1
7
-------
TABLE III
TRACE ELEMENT COMPOSITION OF REFUSE FROM ILLINOIS BASIN
COAL PREPARATION PLANT Aa
Element
Li
B
F
Na(%)
Mg(%)
Cl
Ca(%)
Sc
V
Cr
Mn
Fe(%)
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Low
36
54
400
0.10
0.34
6.5
13.14
1100
6.6
20
1.04
2.41
11.2
0.42
72
52
234
6.2
18
37
51
74
16
3.9
50
6.5
High
59
70
733
0.12
0.51
7.4
16.4
3300
10.8
37
1.33
6.31
13.4
0.50
87
70
419
9.4
20
50
55
93
23
7.6
65
11
Mean
51
62
630
0.11
0.41
7.0
14.32
2340
9.1
30
1.15
4.06
12.2
0.46
78
60
301
8.0
19
44
52
83
19
5.1
56
9.3
9
7
137
0.01
0.07
0.4
1.4
792
1.7
9
0.12
1.54
1.0
0.03
6
8
76
1.3
1
5
2
9
3
0.6
7
1.9
RSD
0.18
0.11
0.22
0.09
0.17
0.06
0.10
0.34
0.19
0.30
0.10
0.38
0.08
0.07
0.08
0.13
0.25
0.16
0.05
0.11
0.04
0.11
0.16
0.13
0.12
0.20
11
-------
TABLE III (Cont.)
Element
Y
Zr
Mo
Cd
Sn
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
Pb
Th
U
Low
30
130
8.1
0.16
< 8
1.4
4.5
41
83
6.8
1.3
5.8
2.4
0.4
3.0
< 1
38
11.5
4.6
High
40
160
16-
0.30
< 9
1.5
7-1
49
100
8.1
1.7
7.3
3.7
0.5
3.7
3
60
13.2
8.2
Mean
35
150
12.2
0.24
< 9
1.5
6.2
45
92
7.4
1.6
6.4
3.1
0.4
3.4
1
49
12.2
6.8
Sigma
5
14
3
0.06
-
0.1
1
3
7
0.5
0.2
0.6
0.5
0.06
0.3
-
8
0.8
1.3
Av.
RSD
0.14
0.09
0.02
0.25
-
0.07
0.02
0.07
0.08
0.07
0.12
0.09
0.16
0.15
0.09
-
0.16
0.06
0.19
0.14
o
Analyses include samples No. 10, 11, 12, 25, and-28.
Elemental compositions reported as Ug/g of refuse unless otherwise noted.
/-»
Relative standard deviation.
12
-------
Element
TABLE IV
TRACE ELEMENT COMPOSITION OF REFUSE FROM ILLINOIS BASIN
COAL PREPARATION PLANT Ba
Low
High
Mean
Li
Be
B
F
Na(%)
Mg(%)
Al(%)
Si(%)
s(%)
Cl
K(%)
Ca(%)
Sc
Ti(%)
V
Cr
Mn
Fe(%)
Co
Ni
Cu
Zn
Ge
As
Se
Br
Rb
47
2.4
63
346
0.07
.21
4.94
12.90
11.4
42
1.07
0.09
11
0.33
78
56
130
9.3
25
68
32.4
117
- < 8
64
4.8
2
81
58
3.1
65
410
0.09
.31
5.29
14.60
14.7
76
1.21
0.13
13
0.36
95
72
160
12.8
35
73
38.8
197
< 8
130
8
2
110
52
2.8
64
374
0.08
.26
5.09
13.57
13.5
57
1.12
0.11
12
0.35
86
62
144
11
30
71
35.4
149
< 8
94
6.2
2
96
6
0.4
1
33
0.01
0.05
0.2
0.9
1.8
17
0.08
0.02
1
0.02
9
9
15
1.8
5
3
3
42
-
33
1.6
-
15
0.11
0.14
0.02
0.09
0.12
0.19
0.04
0.07
0.13
0.30
0.07
0.18
0.08
0.06
0.10
0.14
0.10
0.16
0.17
0.04
0.08
0.28
-
0.35
0.26
-
0.16
13
-------
TABLE IV (Cont.)
Element
Y
Zr
Mo
Ag
Cd
Sn
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
Pb
Th
U
Low
15
80
47
0.4
0.35
< 8
1.1
5.8
31
61
4.8
1
4.3
2.5
0.37
2.4
0.8
31
8.4
2.7
High
21
100
57
0.6
0.5
< 8
1.7
7.1
41
88
7
1.4
4.4
4.4
0.47
3.7
1.1
36
11
2.7
Mean
17.7
87
52
0.5
0.4
< 8
1.4
6.6
37
73
5.9
1.2
4.4
3.2
0.41
3.1
0.9
34
9.5
2.7
Sigma
3.1
11
5
0.1
0.08
-
0.3
0.7
6
14
1.1
0.2
0.1
1.0
0.06
0.7
0.2
3
1.3
-
Av.
RSDC
0.18
0.13
0.10
0.20
0.20
-
0.21
0.11
0.16
0.19
0.19
0.17
0.02
0.31
0.15
0.22
0.22
0.09
0.14
-
0.15
cL
Analyses include samples 17, 23, and 24.
Elemental compositions reported as yg/g of refuse unless otherwise noted.
Q
Relative standard deviation.
14
-------
TABLE V
TRACE ELEMENT COMPOSITION OF REFUSE FROM ILLINOIS BASIN
COAL PREPARATION PLANT Ca
Element
Low
High
Mean
Sif
RSD
Li
B
F
Na(%)
Mg(%)
Al(%)
Si(%)
P
S(%)
Cl
K(%)
C«a(%)
Sc
Ti(%)
V
Cr
Mn
Fe(%)
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Rb
7
68
936
0.26
0.22
6.10
15.06
2700
4.9
86
0.99
1.02
10.4
0.40
62
60
101
6.6
21
41
27
57
14
4.2
18
6.5
210
ii —
22
87
1670
0.37
0.40
8.70
17.40
7300
15.1
170
1.64
1.71
12.4
0.54
85
80
162
10.2
32
80
44
228
21
6.4
26
9.6
300
14.8
79
1257
0.30
0.32
7.36
16.21
4580
11.6
109
1.39
1.44
11.2
0.46
73
69
132
9.2
27
59
39
125
17
5.4
22
8.3
258
5.5
7
345
0.04
0.07
1.11
1.06
1979
2.7
36
0.26
0.26
0.9
0.05
10
9
24
1.6
5
18
7
70
3
0.9
3
1.4
33
0.37
0.09
0.27
0.13
0.22
0.15
0.06
0.43
0.23
0.33
0.19
0.18
0.08
0.11
0.14
0.13
0.18
0.17
0.19
0.30
0.18
0.56
0.18
0.17
0.14
0.17
0.13
15
-------
TABLE V (Cont.)
Elementb
Y
Zr
Mo
Cd
Sn
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
Pb
Th
U
Low
24
120
8.1
0.51
< 8
0.9
6.7
39
76
6.1
1.4
4.7
1.8
0.3
3.3
0.9
33
10.0
5.7
High
32
130
14.0
1.50
< 9
1.3
9.1
56
100
8.8
1.6
6.3
3.7
0.4
4.6
1.2
59
13.8
12.9
Mean
28
126
12.4
1.12
< 9
1.1
8.0
45
89
7.2
1.5
5.4
2.4
0.4
3.9
1.0
50
12.1
8.3
Sigma
3
5
2.5
0.37
-
0.2
1.0
7
10
1.0
0.1
0.7
0.8
0.1
0.5
0.2
10
1.7
3.1
Av.
RSDC
0.11
0.04
0.20
0.33
-
0.18
0.12
0.16
0.11
0.14
0.06
0.13
0.33
0.15
0.13
0.20
0.20
0.14
0.37
0.19
aAnalyses include samples 18, 19, 20, 21,and 22.
Elemental compositions reported as yg/g refuse unless otherwise noted.
Relative standard deviation.
16
-------
magnesium. Phosphorus and titanium, not components of the major minerals per se, are also pre-
sent in significant quantities. Among the less abundant elements present in environmentally dis-
turbing concentrations are manganese, cobalt, nickel, copper, zinc, arsenic, selenium, yttrium,
cadmium, and lead. Later in this report, we will present experimental evidence that several of
these elements are indeed released into the aqueous environment in worrisome quantities by
refuse dump weathering and leaching.
Subtask 1.2—Determine the Structural Relationships and Associations Among Trace Ele-
ments and Major Minerals in Coal Wastes
During the year we conducted research designed to clarify some of the physical associations or
relationships among the trace elements and major minerals in the Illinois Basin refuse materials.
Two basic approaches were used to achieve this end: statistical correlations and direct observa-
tion. In the first, we used specially designed computer programs to statistically correlate
similarities in behavior among the various trace elements and minerals when the refuse samples
were subjected to chemical or physical processes. The second approach to understanding the
trace element mineralogy of the coal refuse samples involved direct observation of the elemental
composition of the microstructures of these materials with electron and ion microprobes and
scanning electron microscopes (SEM). The information gained in this subtask was used as a
basis for interpreting and understanding the release behavior of trace elements during refuse
weathering and leaching.
The behavior correlation method was applied to various samples of refuse collected from each
of the three Illinois Basin cleaning plants and to refuse fractions that had been separated on the
basis of particle size or density. We expected that trace elements intimately associated with one
another in the bulk refuse structure would be nearly identically distributed among the various
refuse fractions.
We used the statistical method to relate trace element and mineral data. To quantify the
relationships among the various elements in the refuse fractions, we used a computer program to
calculate Pearson's correlation coefficients for each of the elements studied (see Statistical
Package for Social Sciences, Second Ed., by Nie et al., published by McGraw-Hill Book Co., New
York, 1975, for details of the calculations). These coefficients range on a scale from +1 among ele-
ments present in exactly the same relative amounts in each of the waste fractions to -1 for ele-
ments that exhibit exactly inverse behaviors. Intermediate values of the coefficients among ele-
ments indicate, of course, varying degrees of similarities or differences in the manner in which the
elements are distributed in the waste fractions.
To make any sense of this massive volume of correlation coefficients, however, data must be ar-
ranged into groups of elements having similar coefficients. This was accomplished by using
sorting methods to cluster the data in conjunction with computer graphic techniques (see Appen-
dix E).
An example of the output from such manipulations is shown in Fig. 1 for the sized refuse sam-
ples from Plant B. This chart presents both the values for the correlation coefficients among the
various elements, and the clusters or groupings of elements according to these values. The
relationships among the elements and such experimental parameters as low-temperature ash
(LTA), high-temperature ash (HTA), and the various mineral phases are also included. The
values of the correlation coefficients among the elements are denoted by various shadings in-
dicated by the key at the right of the figure. The highly positive coefficients are designated by a
black background with varying degrees of white superimposed, and the more highly negative
coefficients by a basic white background with black superimposed. The correlation coefficients in
17
-------
•
a
a
G
E
IS
0.8
0.6
0.4
0.2
0.0
-0.2
-0 4
-0 6
-0.8
Fig. 1.
Trace element correlation coefficients for sized refuse fractions from cleaning plant B (sam-
ples 24b-f).
the range of about —0.7 to +0.7 are less meaningful in terms of interpreting trace element as-
sociations, and are left blank.
The clustering or grouping of elements or entities with like correlation coefficients is apparent
from Fig. 1. Clusters of elements with highly positive correlation coefficients (> 0.7) signifying a
high degree of mutual association in the sized refuse samples, are positioned along the upper left
to lower right diagonal of the figure. The clusters of highly negative correlation coefficients, which
almost certainly indicates that these elements are not associated in the refuse material, appear in
this example along the lower and right edges of the chart.
This method of displaying the correlation data allows a rapid, visual interpretation of associa-
tions based on similarities or differences in elemental behavior to be made. For example, in Fig.
1, three distinct groupings of elements that are highly associated with one another can be defined.
The largest of these, located near the center of the chart and encompassing the minerals and ele-
ments from beryllium through cobalt, includes silicon, aluminum, and most of the other silicate-
forming or lithophile elements. In the lower right and the upper left of the graph are two smaller
highly associated groupings; one contains iron and sulfur and several other sulfide-forming or
chalcophile elements, and the other contains carbon, hydrogen, and nitrogen, which normally are
organically associated elements.
For two or more elements to be structurally associated or related in the refuse sample, they
must consistently behave alike when the refuse samples are subjected to various types of tran-
sformations. It is possible in any single event that factors other than a common structural origin
(such as sample inhomogeneity) could cause some of the elements to behave in an apparently
similar manner. Therefore, structural relationships among the refuse components based on
similarities in behavior can be established only after they have been substantiated in a number of
different ways.
18
-------
Accordingly, we have calculated and grouped the correlation coefficients for the as-collected
coal and refuse fractions from cleaning plants A, B, and C, and for refuse fractions from these
three plants that had been separated both according to density and particle sizes.* Descriptions
of the samples involved and the trace element and mineral analyses for these samples appear in
Appendixes B, C, and D, and the cluster plots of the correlation coefficients appear in Appendix
E.
To aid in the interpretation of the rather massive amount of data in Appendix E, we have con-
densed the information from the trace element-mineral correlations for each coal preparation
plant and have presented it here as Tables VI, VII, and VIII. The tables contain only the group-
ings of elements and minerals for each plant that were highly correlated (R > 0.7) in all the sam-
ples studied. We must emphasize that these data reveal only the groups of trace elements and
minerals that reside together in the refuse samples in a physical or spatial sense. This informa-
tion does not provide the basis for defining the chemical or mineralogical state of the various ele-
ments.
The data presented in Tables VI, VII, and VIII largely reflect anticipated differences among
the various mineral phases in the refuse from each plant. The clay and quartz fractions contain
mainly the lithophile or silicate-forming elements such as aluminum, silicon, sodium, and potas-
sium, and many of the rare earth elements. The iron sulfides (pyrite and marcasite), surprisingly,
were relatively free of trace constituents. Only molybdenum was highly associated with the
pyritic fractions of the refuse from all plants, and arsenic and selenium were allied with pyrite or
marcasite in one or two plants. Similarly, calcium and manganese were the only elements con-
sistently present in the calcite fraction of Plant A. Interestingly, in Plant C, we also delineated a
small grouping or cluster of elements including phosphorous, which we have tentatively iden-
tified as representing apatite or fluorapatite. Uranium was the only element, other than calcium,
fluorine, and phosphorus, highly associated with this mineral type. Finally, in addition to the in-
organic components, we differentiated a cluster of elements in each refuse type that were at-
tributable to the coal fractions. Carbon, hydrogen, and nitrogen were strongly linked to the car-
bonaceous matter in each refuse sample, and chlorine, in addition, was associated with the coal
fractions of Plant C refuse.
In addition to the above, a glance at Appendix E will reveal that there are many other elements
that we could not associate with any identifiable mineral phase by statistical means. Con-
spicuous among these are several chalcophile elements, such as cobalt, nickel, copper, and zinc,
which are most likely to be present in the refuse as sulfide minerals, and might have been ex-
pected to correlate strongly with the iron and sulfur group. Our inability to determine the struc-
tural origins of such elements is possibly a reflection of areas that cannot be differentiated on the
basis of float/sink separation or particle size segregation. This could be a circumstance where an
element is a constituent of a very minor or highly dispersed mineral phase, or where an element
occurs simultaneously as a component of two or more mineral species.
The second method that we used to gather detail about the elemental and mineral associations
in the Illinois Basin refuse samples involved direct microstructural observation with the electron
and ion microprobes. For this study, which included refuse from Plants A and B, we used
powdered samples that were mounted in epoxy rather than the as-collected materials. This al-
lowed us to examine the structures of a large number of representative mineral phases while
keeping the total number of analytical samples to a minimum. The procedure for preparing the
samples for microprobe analysis is given in Appendix G.
The goal of our work with the probes was to conduct a survey of the elemental compositions of
representative examples of each of the major refuse minerals, to provide useful information on
*The procedure used to separate the refuse samples according to particle sizes appears in our FY 76 annual report (EPA-
600/7-78-028). The analytical scheme for separating the refuse materials on the basis of density is presented as Appendix
F in this report.
19
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TABLE VI
STATISTICAL CORRELATION OF TRACE ELEMENT-MINERAL ASSOCIATIONS
IN ILLINOIS BASIN COAL REFUSE - PLANT A
Mineral Class Associated lUcmerUis'
Clays/Quartz Na, A], Si, K, So, Ti, V, Cr, Ga, Y, La, Ce,
Sin, Eu, l)y, Yb, Lu, Ilf, Th
Pyrite/Marc as tie S, Fe, Mo
Calcite Ca, Mn
Coal H, C, N
a Data from cluster analyses of elements having correlation
coefficients (R) >0.7 in all instances studied.
TABLE VU
STATISTICAL CORRELATION OF TRACE ELEMENT-MINERAL ASSOCIATIONS
IN ILLINOIS BASIN COAL REFUSE - PLANT B
MIneral Class Associated Elements
Clays/Ouartz Li, F, Na, Mg, Al, Si, K, Sc, TI, V, Y, Zr, Cs,
La, Ce, Sm, Dy, Yb, Lu, Hf, Th, U
I'yrite/Marcasite S, Fe, As, Se, Mo
Coal H, C, N
a Data from cluster analyses of elements having correlation
coefficients (R) >0.7 In all instances studied.
TABLE VIII
STATISTICAL CORRELATION OF TRACE ELEMENT - MINERAL ASSOCIATIONS
IN ILLINOIS BASIN COAL REFUSE - PLANT C
Mineral Class Associated Elements'3
Clays/Quartz Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Ga, Rb, Cs, La,
Ce, Sm, Eu, Dy, Yb, Lu, Hf, Th
PyriCe/Marcasite S, Fe, As, Mo
Apatites F, P, Ca, U
Coal u, C, N, Cl
a Data from cluster analyses of elements having correlation
coefficients (R) >0.7 in all instances studied.
20
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Fig. 2.
Photomicrograph of —20-mesh refuse.
trace-element mineralogy, and to point out which elements were most likely to be associated with
labile mineral systems.
Figure 2 is a photomicrograph of one of the Illinois Basin refuse samples that we studied with
the microprobes. Although several samples of this kind were examined with the probes, the
procedure for this particular one is typical. This analytical sample was prepared from powdered
refuse (-20 mesh) that had been mounted in epoxy and polished (and in some areas etched) to
reveal the structural detail of the waste material. The various mineral particles or areas that we
examined microstructurally in the sample are denoted in Fig. 2 by a numbered bar or arrow. A
-------
brief description of each numbered area is given in Table IX. Table IX and Fig. 2 show that many
examples of each predominant mineral species in the refuse material were considered. The infor-
mation gathered from the microprobe analyses of several samples of Illinois Basin refuse similar
to that shown in Fig. 2 is summarized in Table X. The terms "abundant" and "occasional" in
Table X reflect the relative frequency with which each element was observed in conjunction with
the major minerals. The microprobe study revealed, not surprisingly, that the refuse constituents
are very finely divided. Thus, areas thought to be relatively pure mineral phases when examined
by optical microscopy were shown to be quite impure and heterogeneous when scrutinized by
microprobe techniques. It is this fine-grained inhomogeneity which accounts for the varied and
often unexpected elemental constituents found in some of the major mineral phases. The clay
and coal fractions particularly contain numerous impurities in the form of inclusions and ex-
traneous particles.
Several minor minerals were also detected in the refuse samples. Particles presumed from the
elemental analyses to be rutile (Ti02) and zircon (Zr02) were frequently observed in the clay frac-
tions. The occurrence of considerable rutile is not surprising because the titanium content of
these wastes is fairly high (0.4 wt%). What are thought to be particles of apatite and fluorapatite
were also observed with the probes as constituents of the clay phases. Interestingly, the
microprobe analyses of these phosphate minerals showed them to be a source of uranium,
thorium, and many of the rare earth elements. Phosphorous also is present in these wastes in
relatively high concentrations (~0.3 wt%).
As was also the case for the statistical analyses of trace element-mineral relationships
described earlier, during these microprobe studies we were unable to determine the residences of
such chalcophile elements as cobalt, nickel, zinc, and copper in the refuse samples considered.
This difficulty suggests that these elements are present either as submicron mineral grains or as
very dilute polymorphic substituents of the identifiable mineral phases.
The results from the microprobe analyses complement the statistical investigations described
earlier. The statistical analyses of refuse trace elements, which are based on much larger and
hence more representative samples of the total refuse composition, lack the sensitivity to detect
minor mineral phases. Conversely, the microprobe analyses, while limited to a relatively small
area of each sample, are much more adept at determining elemental distributions on a
microstructural scale.
Subtask 1.3—Establish the Mineralogy, Morphology, and Chemistry of Selected Trace Ele-
ments in Coal Refuse
The major concern of this subtask was to gather additional details about the structure and
chemistry of a selected group of trace elements that we judged to be of most environmental con-
cern in the Illinois Basin refuse. This information was needed both to better understand the en-
vironmental releases of these elements, and, eventually, to aid in choosing suitable environmen-
tal control technology. Therefore, we began at midyear to focus on identifying the mineral
residences and elemental associations of 13 trace elements (beryllium, aluminum, manganese,
iron, cobalt, nickel, copper, zinc, arsenic, selenium, molybdenum, cadmium, and thallium) that
had been delineated on the basis of preliminary laboratory leaching studies as being the most en-
vironmentally troublesome in the Illinois Basin waste materials. Most of these elements were ex-
pected to be present in the refuse in the form of sulfides, and nearly all had been shown by our
early environmental studies to be highly leachable from the refuse under typical waste dump con-
ditions.
Based on earlier experiences, we decided that the most rewarding technique for these analyses
was the ion microprobe. The statistical studies were useful only to provide information about the
22
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TABLE IX
DESCRIPTIONS OF FEATURES ON PHOTOMICROGRAFHIC MAP
Area No.
2
3
5
6
7
8
9
10
11
12
13
15
16
17
18
Description Area No.
Pyrite - massive, dense 19
Quartz - pyrite adhering 20
Pyrite - massive, dense 21
Pyrite - framboid 22
Pyrite - framboids and small massive 23
Quartz - pyrite inclusion 2k
Quartz - pyrite inclusion 25
Pyrite - framboids 26
Clay/qfrartz 27
Pyrite - dense 28
Quartz 29
Coal 30
Coal 31
Pyrite - massive, dense 32
Pyrite - massive, porous 33
Clay/quartz/coal 3>k
Pyrite - dendritic 35
36
Description
Pyrite - massive, jSorous
Quartz
Quartz
Pyrite - massive, porous
Pyrite - massive, porous
Pyrite - framboid
Coal
Clay
Clay
Quartz/coal
Pyrite - massive, dense
Pyrite - massive, porous
Pyrite - massive, dense
Pyrite - small massive
Pyrite - small massive
Pyrite - framboids
Clay
Clay
Map is shown in Fig. 2.
-------
TABLE X
TRACE ELEMENT - MINERAL ASSOCIATIONS FROM MICROPROBE ANALYSIS
OF ILLINOIS BASIN COAL REFUSE FROM PLANTS A AND B
Mineral
Abundant Elements
Occasional Elements
Iron Sulfides
Clays
Quartz
Oxides
Carbonates
Phosphates
Coal
K, Mg,
Ca, Fe, Ti
Fe, Ti, Zr, 0
Ca, Y, F
S, 0
TI, Mn, As, Cu
Li, Rb, Sr, Ba, Cl, Ta,
Zr, Ce, La, Nd
Li, Be, Na, Mg, Al, K,
Ca, Fe, Ta
Mn, V, Cr
None
La, Ce, Pr, Nd, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tm,
Th, U, Ba
Li, Na, Mg, Si, Al, K, Ca,
Ti, Fe, V, Cr, Mn, Y, La,
Ce, Nd, Sm, Eu, Cl
elemental constituents of the major mineral systems, and the electron microprobe, although
more highly developed than the ion microprobe method, is limited in sensitivity for most ele-
ments to the range of about 100 Mg/g- The ion microprobe, on the other hand, is usually sensitive
to elemental concentration near 1 /ig/g, but interferences among the many elements in the refuse
samples had limited the practical usefulness of this technique. Fortunately, we were able to over-
come this limitation by using a commercially available computer program to erase mathe-
matically some of the most bothersome interferences from the ion probe spectrum. This routine,
called peak stripping, enabled us to gain new insight into the sources and associations of many of
the elements.
The results from the ion microprobe analyses of about 50 separate areas in samples of refuse
from both plants A and B are given in Tables XI, XII, XIII, and XIV. There is broad agreement
between the information displayed in these tables and the trace element/mineral associations
identified in the earlier studies. In addition, though, new information was obtained. Foremost
was the discovery that several of the chalcophile elements (cobalt, nickel, copper, and zinc) are
physically associated with the refuse clay minerals rather than with the iron sulfide systems,
where they might have been expected to reside. It is unlikely that these elements are present as
parts of the clay mineral structures, but they probably are constituents of separate micromineral
phases entrapped within the clay grains.
24
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TABLE XI
ION MICROPROBE OBSERVATION OF TRACE ELEMENTS
ASSOCIATED WITH CLAY MINERALS IN ILLINOIS BASIN COAL REFUSE
Associated in More Than
75% of Areas Studied
Lithophile Elements:
Na, K, Ca, Mg, Ti,
Li, B, F, Cr, Mn, Cs,
Ta, U, Ba, Rb, Sr, C
Chalcophile Elements:
Fe, Co, Ni, Cu, Zn
Observed Occasionally
Nb, Cl, Zr, La, Nd, Ce
TABLE XII
ION MICROPROBE OBSERVATION OF TRACE ELEMENTS
ASSOCIATED WITH PYRITE AND MARCASITE IN ILLINOIS BASIN COAL REFUSE
Associated in More Than
75% of Areas Studied
Clay Impurities
(Al, Si, 0, Ma, K, Ca, Mg, Ti)
Observed Occasionally
Li, C, F, Cr; Cu, Mo,
TI, As, Mn, Se, Hg
TABLE XIII
ION MICROPROBE OBSERVATION OF TRACE ELEMENTS
ASSOCIATED WITH CARBONATES IN ILLINOIS BASIN COAL REFUSI
Associated in More Than
73% of Areas Studied
Observed Occasionally
Clay Impurities
(Al', Si, Na, K)
Mn, Sr, F
Li, Fe
TABLE XIV
ION MICROPROBE OBSERVATION OF TRACE ELEMENTS
ASSOCIATED WITH QUARTZ IN ILLINOIS BASIN COAL REFUSE
Associated in More Than
75% of Areas Studied
Clay Impurities
(Al, Na, K, Ca, Mg)
Occasionallv Observed
Ti, V, Cr, Fe, Co, Si,
Li, Be, Ta
25
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A second observation of note from the ion microprobe studies is that the clay minerals are ap-
parently ubiquitous throughout the refuse structure. Evidences of clay minerals (aluminum,
silicon, sodium, potassium, and oxygen) were found in intimate association with every mineral
phase studied, including what appeared to be relatively pure pyrite crystals. (This latter observa-
tion was substantiated by SEM studies of pyrite framboids that showed what appeared to be
lamellar veins of clay dispersed among the individual pyrite crystals.)
A third important observation from the ion microprobe study is the fact that most of the ele-
ments of initial environmental concern that we could identify in the refuse materials reside in the
clay minerals. Included among these elements are aluminum, manganese, iron, cobalt, nickel,
copper, and zinc. Because of the structural complexity of the clay mineral regions and the ex-
treme dilution of many of the toxic trace elements within the clay areas, the chance of rapidly
learning very much about the details of the mechanisms governing the aqueous leaching of these
elements is quite poor.
As an aid to the assimilation of the rather voluminous amount of information that we have as-
sembled from the statistical and microprobe investigations of Illinois Basin coal refuse, we have
attempted to summarize all the data into Table XV. It must be remembered in using the table,
however, that there are some very distinct differences in the elemental distributions among the
various refuse types studied, and that the information in the table represents only a guide for the
likely residences of the trace or minor elements in the refuse samples considered. More accurate
information concerning the mineralogical associations for specific elements may be obtained
from the data in the foregoing text and the pertinent appendixes.
TABLE XV
SUMMARY OF TRACE ELEMENT - MINERAL ASSOCIATIONS IN REFUSE
FROM THREE ILLINOIS BASIN COAL PREPARATION PLANTS
Element Mineral Association
H coal
Li clays
Be quartz
B clays
C coal/carbonates
N coal
F phosphates/carbonates
Na clays
Mg carbonates/clays
Al clays
Si quartz/clays
F phosphates
S pyrite/marcasite/gypsum
Cl coal/clays
K clays
Ca carbonates/clays/gypsum/phosphates
Sc clays
Ti clays/oxides
V clays/quartz
Cr clays
Mn clays/carbonates/pyrite/marcasite
Fe pyrite/marcasite/clays/carbonates
Element
Mineral Association
Co
Ni
Cu
Zn
Ga
As
Se
Br
Rb
Y
Zr
Mo
Cd
Cs
Ba
Rare earths
Hf
Ta
Hg
Tl
Th
U
clays
clays
clays/pyrite/marcasite
clays
clays
pyrite/marcasite
pyrite/marcasite
coal
clays
phosphates/clays
oxides/clays
pyrite/marcasite
clays
clays
clays/phosphates
phosphates/clays
clays
clays
pyrite/marcasite
pyrite/marcasite
phosphates/clays
phosphates/clays
26
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TASK 2—DETERMINE THE ENVIRONMENTAL BEHAVIOR OF
TRACE ELEMENTS IN COAL PREPARATION WASTES
The objective of this task was to develop an understanding of the environmental behavior of
the trace elements in Illinois Basin coal preparation wastes when they are subjected to conditions
encountered during waste dump weathering and leaching. This information was essential in
delineating the elements of environmental concern in these wastes.
Subtask 2.1—Laboratory Studies of the Weathering and Leaching of Trace Elements in
Coal Wastes
During FY 77, we completed a substantial number of leaching experiments designed to
evaluate the environmental behavior of trace elements in samples of refuse collected from three
Illinois Basin coal cleaning facilities. Some of these studies were conducted under static or quasi-
equilibrium conditions, wherein a known quantity of waste material was allowed to equilibrate
with a constant volume of aqueous leachate. Agitation of the sample mixture was provided to
promote faster interaction and equilibration between leachates and waste materials. The main
advantage of the static/equilibrium experiments was that they were easy to set up and results
were quickly obtained; therefore, such studies were ideally suited to rapidly scope the system
response to various environmental parameters. A description of the apparatus and experimental
procedure for the static/equilibrium leaching method appears in Appendix H.
In addition to the static experiments, we conducted a number of investigations to determine
the release behavior of the trace elements in Illinois Basin refuse samples when in contact with
flowing leachates. In these experiments, crushed refuse (~1500 g) was packed into a 70-cm-long
by 4.6-cm-diam glass column and the leachate, in contrast to the static experiments, was con-
tinuously metered through the column. The details of the experimental setup and procedures for
the column leaching studies are given in Appendix I. Although these continuous flow experiments
were much more difficult and time-consuming, they do represent the actual environmental con-
ditions encountered in refuse dumps much more closely than the static systems. Therefore, we
used the static experiments mainly to rapidly scope elemental behavior and the effects of certain
variables on refuse/leachate systems. The continuous flow studies served to relate more
realistically our laboratory work to a full-scale waste dump.
A composite or average refuse sample from each of the three Illinois Basin coal cleaning plants
was used in our initial static leaching experiments. Table XVI is a description of the samples and
a listing of their experimental variables. Since the refuse materials from these three plants repre-
sent a reasonably broad range of trace element and mineral compositions (see Tables II through
V), this series of leaching experiments was suited for determining the overall relationships among
refuse bulk mineralogy and trace element releases during aqueous leaching.
For these static experiments, we used refuse samples crushed to -20 mesh to more closely
equalize the particle sizes and surface areas of each sample. Each refuse sample (50 g) was
agitated with distilled water (250 ml) in an open system for times varying from 1 to 56 days. At
the completion of each experiment, the leachates were separated from the residues by vacuum
filtration and analyzed. The analytical results, including data on leachate pH, solids contents,
and trace element compositions, are reported in Appendix J.
The measured values for leachate pH and total dissolved solids (TDS) at the termination of
each experiment are plotted in Fig. 3. These parameters reflect some striking differences in the
leaching behavior of each of the three refuse types. With regard to pH, the leachates from Plant B
27
-------
TABLE XVI
Leachate No.
Plant A
3
A
DESCRIPTION OF STATIC LEACHING EXPERIMENTS WITH REFUSE
FROM ILLINOIS BASIN CLEANING PLANTS A, B, AND C
Experiments No. GL-22, SGL-5, and GL-21
Refuse Size
-20 mesh
-20 mesh
-20 mesh
-20 mesh
22
22
22
22
Air
open
open
open
open
Time (Days)
1
7
28
56
Plant B 6
12
18
22
-20 mesh
-20 mesh
-20 mesh
-20 mesh
22
22
22
22
open
open
open
open
1
7
28
56
Plant C
1
2
3
-20 mesh
-20 mesh
-20 mesh
22
22
22
open
open
open
1
7
28
An average of refuse samples 12, 25, and 28 was used in this study.
An average of refuse samples 17, 23, and 24 was used in this investigation.
"An average refuse material consisting of sample numbers 18 through 22 was
used in this study.
refuse almost immediately became acidic and remained so throughout the duration of the experi-
ment; whereas leachates in contact with Plant A refuse remained essentially neutral throughout
the test. Refuse from Plant C exhibited an intermediate acid generating potential. These
characteristics undoubtedly reflect differences in the balance between refuse acid-forming con-
stituents (iron sulfides) and basic substances (carbonates). Plant B refuse has a lot of pyrite and
marcasite, but contains only negligible amounts of calcite (Table II), which explains its very
marked tendency to produce highly acidic leachates. Refuse from Plant A also contains substan-
tial amounts of pyritic minerals, but in addition, apparently contains enough calcite to balance
acid formation throughout the experiment. Plant C refuse contains pyrite and marcasite in quan-
tities similar to those found in Plant A and B refuse, but has much less calcite in its structure
than Plant A. The small amount of calcite is soon consumed and the leachate becomes more like
28
-------
10
20 30 40
TIME (days)
50
Fig. 3.
Leachate pH and TDS as a function of time from static leaching experiments with refuse
from three coal cleaning plants.
that associated with Plant B refuse. The relationship between leachate pH and TDS for the static
leachates from the three refuse samples is shown in Fig. 4. In general, where leachate pH is low,
TDS values tend to be high, and vice versa. The more highly acidic leachates associated with
Plant B refuse were observed to contain from about 1 to more than 5 wt% of dissolved solids
depending on the leach duration. By contrast the essentially neutral leachates produced by Plant
A refuse were never observed to contain more than 0.4 wt% TDS.
The trace element levels in the various leachates produced during this static leaching study are
reported in Appendix J. For the most part, the elements present in the highest concentrations in
these leachates (iron, aluminum, calcium, magnesium, and sodium) are the main constituents of
the major mineral systems in the refuse. Indeed, the high levels of these trace elements detected
in the aqueous leachates from each of the three refuse types indicate that most of the compo-
nents of the mineral matrixes of the refuse have been affected, though not always extensively.
To help assimilate the vast quantity of trace element data contained in Appendix J, we have
tabulated the information for 1 day of leaching into groups according to concentration ranges in
Tables XVII through XIX. These tables reflect two important points that may have been dif-
ficult to ascertain from the total appendix. First, there is a continuing trend to produce far more
highly contaminated solutions when leachate acidity is high. Leaching of refuse from cleaning
29
-------
6 —
-9
£ 5
Q
O 4
to ^
Q
UJ
O
to
t/}
O
0
T
B PLANT A
® PLANT B
A. PLANT C
4 5
pH
Fig. 4.
The relationship between pH and TDS for leachates from static leaching experiments with
coal refuse.
Plants B and C for 1 day produced acidic leachates that removed aluminum, calcium, iron,
sodium, magnesium, potassium, manganese, cobalt, nickel, and zinc from the refuse in excess of
10 jtg/g of refuse involved. By comparison, the neutral leachates produced by Plant A refuse
removed only four elements in excess of 10 /ug/g of refuse (calcium, magnesium, potassium, and
manganese). The second important observation from these tables concerns the relatively high
concentrations of certain environmentally harmful trace elements in the leachates, particularly
those associated with the acid refuse samples. Concentrations in excess of 10 /xg/g aluminum,
iron, manganese, cobalt, nickel, and zinc were observed in the leachates from one or more of the
refuse samples. As will be discussed under Task 3, all of these elements are thought to be toxic to
certain plants or animals in aqueous systems or soils at levels comparable to those observed in our
experimental leachates.
Tables XX through XXII show the 1-day static leaching data as they reflect the percentages of
the total of each element available in the refuse leached from the various waste samples. These
tables are intended to reveal the elements that are inherently the most labile from the refuse
samples during environmental weathering. Here we obtain a slightly different picture of refuse
teachability. The overall solubility of the clay minerals and the iron sulfides is relatively low for
all three refuse types, because 10% or less of the total aluminum and iron is leached from the
samples. (The hydroxides of these ions would be insoluble at pH = 7, but soluble at the pH = 2.2
encountered with Plant B leachate.) Several elements, however, including cobalt, nickel,
calcium, zinc, cadmium, magnesium, and manganese, frequently exceed 10% leachability (par-
ticularly in the acidic leachates), and are, therefore, environmentally active. Again, several of
30
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TABLE XVII
ELEMENTAL COMPOSITION OF LEACHATES FROM STATIC LEACHING EXPERIMENTS
WITH PLANT A ILLINOIS BASIN COAL REFUSE3
Experiment No. GL-22
Leachate Concentration,
Ug/g Refuse Element
> 500 Ca
100-500 Mg
10-100 K, Mn *
< 10
Na, Al, Sc, V, Cr, Fe, Co, Ni,
Cu, Zti, Ga, As, Br, Rb, Ag, Cd,
Sb, Cs, La, Ce, Sm, Eu, Dy, Yb,
Lu, Hf, Ta, W, Hg, Pb, Th, U
* Of environmental concern (see Task III).
Conditions: -20 mesh refuse, 1 day, room temperature, unlimited air.
bpH - 7.1.
TABLE XVIII
ELEMENTAL COMPOSITION OF LEACHATES FROM STATIC LEACHING EXPERIMENTS
WITH PLANT B ILLINOIS BASIN COAL REFUSE
Experiment No. SGL-53
Leachate Concentration,
Ug/g Refuse Element
> 500 Ca, Fe*
100-500 Mg, Al
10-100 Na, Mn , Co , Ni , Zn
< 10 K, V, Cr, Cu, Cd, Dy, Pb
Of environmental concern. (See Task III.)
Conditions: -20 mesh refuse, 1 day, room temperature, unlimited air.
bpH = 2.2.
31
-------
TABLE XIX
ELEMENTAL COMPOSITION OF LEACHATES FROM STATIC LEACHING EXPERIMENTS
WITH PLANT C ILLINOIS BASIN COAL REFUSE ,
Experiment No. GL-21a
Leachate Concentration
Ug/g Refuse Element
> 500 Na, Ca, Fe*
100-500 Mg, Al
10-100 K, Mn*, Co*, Ni
< 10 Sc, V, Cr, Cu, Zn, Ga, As, Br,
Rb, Ag, Cd, Sb, Cs, La, Ce, Sin,
Eu, Dy, Yb, Lu, Hf, Ta, W, Hg,
Pb, Th, U
*
Of environmental concern (see Task III).
Conditions: -20 mesh refuse, 1 day, unlimited air, room temperature.
V = 3.5.
TABLE XX
RELEASE PERCENTAGES OF ELEMENTS DURING STATIC LEACHING EXPERIMENTS
WITH PLANT A ILLINOIS BASIN COAL REFUSE
Experiment No. GL-22a
Percent Leached of
Original in Refuse Element
> 25
10-25 Co*, Ni*
1-10 Mg, Ca, Mn, Cd
< 1 Na, Al, K, Sc, V, Cr, Fe, Cu,
Zn, As, Sb, La, Ce, Sm, Eu, Dy,
Hf, Pb, Th, U
*
Of environmental concern (see Task III). •
Conditions: -20 mesh.refuse, 1 day, room temperature, unlimited air.
bpH = 7.1.
-------
TABLE XXI
RELEASE PERCENTAGES OF ELEMENTS DURING STATIC LEACHING EXPERIMENTS
WITH PLANT B ILLINOIS BASIN COAL REFUSE
Experiment No. SGL-5a
Percent Leached of
Original in Refuse Element
* * * *
> 25 Ca, Co , Ni , Zn , Cd
10-25 Mg, Mn*, Dy
1-10 Na, Al, V, Cr, Fe, Cu, Pb
< 1 K
Of environmental concern (see Task III).
Conditions: -20 mesh refuse, 1 day, room temperature, unlimited air.
bpH = 2.2.
TABLE XXII
RELEASE PERCENTAGES OF ELEMENTS DURING STATIC LEACHING EXPERIMENTS
WITH PLANT C ILLINOIS BASIN COAL REFUSE
Experiment No. GL-21a
Percent Leached of
Original in Refuseb Element
> 25 Na, Co*
10-25 Ca, Mn , Ni , Cd
1-10 Mg, Sc, Fe, Zn, Ce, Sm,
Eu, Dy, Yb, Lu, U, Pb
< 1 K, Al, V, Cr, Cu, Ga,
As, La, Ce, Th
Of environmental concern (see Task III).
Conditions: -20 mesh refuse, 1 day, room temperature, unlimited air.
bpH - 3-5.
33
-------
these elements are known, under some circumstances, to be harmful in aqueous systems. These
observations of trace element leachability demonstrate potential environmental problems that
may be caused by refuse dump leaching, and they also suggest possible economical recovery of
certain trace constituents.
Additional static leaching experiments (only on Plant B refuse) were run during the year. They
were designed to explore the effects of temperature, refuse particle size, and the availability of air
on trace element releases during refuse leaching. The experimental conditions used in this
leaching study are presented in Table XXIII.
The effects of the experimental variables on leachate pH for the Plant B refuse samples are
shown in Fig. 5. All of the leachate pH values, whether for long or short leach times, are quite low.
The variables with the most pronounced effect on solution pH are temperature and air
availability. Lower leachate pH values are observed for the experiments conducted at 75°C than
for those done at ambient temperature. Also the pH values of the leachates from the experiments
conducted in open vessels with unlimited access to air are, except for short reaction times, con-
sistently lower than those in closed vessels. Smaller particle sizes give leachates with lower pH
values, but size appears less important than temperature or air content. It must be remembered,
however, that many waste piles contain particle sizes much larger than those used here.
The TDS values of the leachates from these experiments are also reported in Fig. 5. Not unex-
pectedly, they follow a pattern nearly inverse to that of leachate pH. Where the pH is relatively
low, the TDS in the leachates tend to be high and vice versa. An important point to note is the
very high amounts of dissolved materials in all the leachate samples. After only 10 min of contact
with the crushed refuse, the aqueous solutions already contain in excess of 0.38 wt% of extraneous
material. These values can increase to as much as 5 wt% of TDS after 56 days of leaching time.
This is a vivid demonstration of the ability of aqueous acids (acid mine drainage) to dissolve and
alter the structure of coal mineral matter.
Before continuing to the other results from these experiments some observations should be
made concerning the apparent influences of the various experimental parameters on leachate pH
and TDS. To put these observations in perspective, however, it is necessary to realize that the
major contributor to solution acidity in the refuse-leachate mixture is the oxidation of pyrite
(marcasite) in the presence of air and water to form ferrous sulfate and sulfuric acid. In ab-
breviated form this reaction is written as
FeS2 + 7/2 02 + H2 | FeS04 + H2S04
Consider first the effects of oxygen or air content on the pH and TDS of the leachate. In nearly
all instances, the pH of the mixtures with free access to air were lower and TDS higher than those
contained in air-deficient systems. This can be attributed to the fact that oxygen is a necessary
reactant in the acid-formation step. If enough oxygen is available, the generation of sulfuric acid
would be expected to continue throughout the leaching period. We believe that the fact that the
pH curves, even for the air-rich systems, flatten out with time rather than continue to decrease
reflects the development of a bisulfate buffer system (pKa = 1.3) in the leachate rather than a
cessation of acid production.
The observation that the effects of refuse surface area were minimal also leads to an interesting
possibility. This behavior is characteristic of heterogenous reactions in which the rate-
determining step is a diffusion rather than a chemical process. If so, the rate-limiting step for
acid formation and solids dissolution in our system involves either the diffusion of reactants to
the refuse surface or products away from the surface. This proposition is substantiated by the
observance of a rather small temperature effect for pH development. Diffusion-controlled proces-
ses generally have relatively low activation energies, although the small temperature dependence
34
-------
TABLE XXIII
EXPERIMENTAL CONDITIONS USED IN STATIC/EQUILIBRIUM LEACHING STUDY OF
ILLINOIS BASIN COAL &EFUSE
TIME
ATMOSPHERE 'a'
TEMPERATURE, °C
GOB SAMPLE
-20 mesh
-3/8 in.
10 MIN.
S
22
x(b:
X
1 DAY
S
22
X
X
0
22
X
X
0
75
X
X
7 DAYS
S
22
X
X
0
22
X
X
0
75
X
X
28 DAYS
S
22
X
X
0
22
X
X
0
75
X
X
56 DAYS
0
22
X
X
(a) S = sealed vessel, 0 = open vessel.
(b) The combination of variables studied is designated by an x.
-------
I 1 1 1 1 1
CLOSED SYMBOLS=-20 MESH WASTE
a RT LIMITED AIR OPEN SYMBOLS = 3/8 WASTE
o RT OPEN TO AIR
- A 75»C OPEN TO AIR
20 30 40
LEACH TIME (days)
Fig. 5.
Leachate pH values and TDS from static/equilibrium leaching study of coal refuse.
of our system could be partly due to the reduced solubility of oxygen in the leachate at high
temperatures.
The trace element data collected from this series of static leaching experiments on Plant B
refuse are presented in Appendix K. To illustrate the effects of the_experimentaljarameters on
certain trace element releases during refuse leaching we have calculated the release percentages
based on the total amounts of those elements available in the refuse samples. This information is
presented in Tables XXIV through XXIX.
An inspection of the data in Tables XXIV through XXIX reveals some very interesting facts.
Several elements, including iron, calcium, manganese, cobalt, nickel, zinc, and cadmium, are
consistently leached in high percentages from the refuse samples under all of the experimental
conditions studied. These labile elements (except calcium) share at least one common trait: ther-
modynamically, all should exhibit a marked tendency to be present in the refuse sulfide
minerals. The remaining elements in the tables, aluminum, sodium, potassium, magnesium,
chromium, and lead, are much less leachable than the above elements under the experimental
conditions. The copper percentages are very erratic. We strongly suspect that copper is
sometimes complexing with some other agent in the system.
The experimental variables, particle size, availability of air, and temperature, have only
moderate influence over the elemental compositions of the leachates. In most cases, greater
amounts of the elements studied are solubilized from the — 20-mesh refuse than the cor-
responding -3/8-in. material (compare Tables XXIV and XXV, XXVIII and XXIX), although
refuse particle size has a less notable effect when air is limited (Tables XXVI and XXVII). Also,
36
-------
TABLE XXIV
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL WASTE
CONDITIONS: -20 MESH; 22°C, UNLIMITED AIR
Elements Leached (% available in waste)
Leaching
Time (days)
10 rain.
1
7
28
56
Leaching
TJme.(days)
10 mln.
1
7
28
56
Fe Al Na K Mg Ca Cr Mn Co Nl Cu Zn Cd Pb
9.0 1.9 1.3 0.07 12 90 1.0 21 70 46 3 11 50 3
9.0 1.8 1.0 0.05 11 84 0.4 22 65 44 3 53 68 2
26 2.1 0.20 0.00 11 89 1.1 27 68 50 21 76 76 2
46 2.2 0.10 0.01 12 90 1.2 32 70 54 36 100 82 3
TABLE XXV
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL WASTE
CONDITIONS: -3/8 IN., 22°C, UNLIMITED AIR
Elements Leached (X available In waste)
Fe Al Na K Mg Ca Cr Mn Co Nl Cu Zn Ce Pb
6 0.8 0.9 0.27 8.2 62 0.4 15 50 33 7 26 32 2
8 0.6 0.9 0.17 8.6 76 0.5 18 68 39 7 34 40 2
20 1.2 1.0 - 10.0 59 0.8 32 66 47 28 44 47 2
37 1.7 1.1 0.01 11.5 100 1.0 42 78 60 48 51 58 2
-------
TABLE XXVI
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL WASTE
CONDITIONS: -20 MESH, 22°C, LIMITM. AIR
Elements Leached (% available In waste)
Leaching
Time (days)
10 mln.
1
7
28
Fe
6.7
7.5
8.3
10.0
Al
1.5
1.6
1.7
1.9
Na
0.9
0.5
1.5
3.1
K MR
0.29 10
0.11 10
0.64 10
1.82 11
Ca
64
75
82
87
Cr
0.95
1.0
0.9
1.0
Mn
17
19
20
21
Co
56
61
59
60
Mi
40
41
39
40
Cu
3.5
1.2
0.1
0.3
Zii
33
35
41
49
Cd
37
42
42
45
Vb
4
11
2
4
Leaching
TIme(day9)
10 mln.
1
7
28
3.0
5.4
7.1
10.2
TABLE XXVII
STATIC/EQUILIBRIUM LKACliING OF ILLINOIS BASIN COAL WASTE
CONDITIONS: -3/8 IN., 22°C, LIMITED A1K
ElemcnLs Leached (% available in waste)
Al
0.78
1.04
0.94
1.07
Na
0.7
0.9
0.9
2.8
K. Mg
0.28 7.4
0 . 34 9.3
0.31 9.6
].12 9.5
Ca
50
70
66
60
Cr
0.
0.
0.
0.
3
5
6
7
Mil
14
17
20
17
Co
42
61
66
63
Ni Cu
30 9.6
42 11.7
41 2.5
36 0.3
Zn
22
33
39
57
Cd
29
37
40
37
Pb
6
3
2
10
-------
TABLE XXVI11
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL WASTE
CONDITIONS: -20 MESH, 75°C, UNLIMITED AIR
Elements Leached (% available Jn waste)
Leaching
Tlme(days)
10 mJ.n
1
7
28
Fe
-
11
21
30
Al
-
1.8
3.2
5.8
Na
-
2.0
3.5
6.1
K Mg
-
0.10 11
0.15 15
2.77 20
Ca
-
90
89
94
Cr
-
0.8
2.1
3.7
Mn
-
22
27
32
Co
-
59
55
57
Nl Cu
-
41 0.5
44 1.7
49 0.5
Zn
-
48
69
96
Cd
-
74
74
82
PI
2
3
2
Leach Lng
Time (days)
10 iidn.
1
7
28
TABLE XXIX
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL HASTE
CONDITIONS: -3/8 IN., 75°C, UNLIMITED AIR
Elements Leached (% available in waste)
Al
Na
Ca
Cr
Mn
8 0.9 0.9 0.29 9
12 1.8 1.8 0.50 13
18 4.1 3.5 0.64 18
71 0.7
95 1.1
100 2.9
Co
Nl Cu
Zn
Cd
19 62 38 4.3 34 37 3
24 60 46 3.1 46 45 4
37 71 54 7.6 56 53 1
-------
limitation of air to the system reduces the solvating power of the leachates (compare Tables
XXIV and XXVI, XXV and XXVII), probably by limiting the acid-forming reactions of pyrite
and marcasite. And finally, temperature effects can be seen by comparing the data in Tables
XXIV and XXVIII, and XXV and XXIX. Here the results are mixed. Some elements
(aluminum, sodium, potassium, and chromium) appear to be more highly leachable at elevated
temperature, but most are not affected. This is not an implausible result for the complex kinetic
system represented by the refuse leachate mixture.
From our observations of trace element behavior during the static aqueous leaching of Illinois
Basin coal refuse, a reduction in both the absolute amounts and percentages of trace elements
released from the refuse materials during aqueous leaching under conditions simulating the en-
vironmental circumstances in refuse dumps can be obtained by (1) increasing the particle sizes of
the crushed refuse to give minimum surface area, (2) reducing the temperature of the system, and
(3) limiting access of air to the refuse dump.
With the information from the static/equilibrium leaching studies of the Illinois Basin refuse
samples as a guide, we began at midyear, to investigate the leaching behavior of these refuse
materials under more dynamic conditions. Water was passed through packed columns of crushed
refuse to simulate (more closely than the static studies) aqueous leaching under refuse dump con-
ditions. Table XXX is a listing of the experiments for this series. The trace element analyses for
the leachates from these experiments are tabulated in Appendix L.
TABLE XXX
DESCRIPTION OF CONTINUOUS LEACHING STUDIES
OF ILLINOIS BASIN COAL REFUSE3
Plant
A
Experiment No.
GL-19
GL-7
GL-3
GL-9
GL-10
GL-20
Refuse Used
12, 25, 28
17, 23, 24
17, 23, 24
17, 23, 24
17, 23, 24
18,19,20,21,22
Leachata Flow Pattern
Uninterrupted
Uninterrupted
Uninterrupted
Interrupted at 2.7 i for 1 day
and at 8.7 i for 7 days
Interrupted at 2.7 i for 1 day
and at 8.7 I for 7 days
Uninterrupted
HThese experiments were conducted at ambient temperature with 1.5 kg of refuse
material crushed to -3/8 in. and packed into a 70-cm-long by 4.6-cm-diam glass
column. Laachate (distilled water) flow rate was maintained at 0.5 tni/min.
Refuse sample studied was an average of the listed fractions.
40
-------
Two types of flowing or dynamic leaching experiments were completed with the Illinois Basin
refuse samples. In the first we used a continuous leachate flow (30 ml/h) for the duration of the
experiment (GL 19, 7, 8, and 20). This condition simulates water continuously passing through
the refuse dump, such as for refuse that has been deposited into a swamp or waterway, or where
the refuse has been used to impound a slurry pond or as a reservoir dam. In the second type of
dynamic leaching experiment, leachate flow was periodically interrupted and a stream of air was
blown through the column before flow was restarted (GL 9 and 10). This is more typical of the ac-
tual environmental condition of a majority of the waste dumps, where water from rain or some
other source only periodically comes in contact with the refuse mass.
The data for pH and total salt content of the leachates collected from the uninterrupted
leaching experiments are plotted in Fig. 6. The trends in leachate pH and TDS throughout the
experiment are readily apparent. The leachate pH values are initially low and as a greater
volume of leachate flows through the refuse column, pH begins to rise and level off. Apparently,
LEACHATE VOLUME (liters)
Fig. 6.
Total dissolved salts and pH values for uninterrupted dynamic leaching experiments with
refuse from cleaning plants A, B, and C.
41
-------
this occurs because the acid-forming reactions of pyrite and marcasite are slow relative to the
flow of fresh leachate into the system. Alternatively, the trend to increasing pH values may be
due to delayed buffering of the leachate acid content by some refuse component. The salt con-
tents of the refuse leachates are tied directly to the pH of the system. Initially, at low pH, the
leachates contain relatively high dissolved salt contents. As the pH begins to rise and level off,
the leachate salt values begin a corresponding decrease and leveling. This relationship between
the level of dissolved solids in the leachates and pH is analogous to that observed under static/e-
quilibrium conditions.
The pH and TDS curves in Fig. 6 reflect the compositional differences in the three refuse types.
Plant A, which contains the highest abundance of calcite, also exhibits by far the steepest rise in
pH values (and corresponding drop in TDS content) as the experiment progresses. Cleaning
Plants B and C contain relatively little calcite; therefore, the leachate increments from these two
refuse types remain relatively acidic throughout the experiment. Interestingly, even the modest
decreases in leachate acidity as a function of leachate volume displayed by the Plants B and C
refuse result in rather substantial drops in TDS levels.
Trace element behavior during the continuous leaching of the Illinois Basin refuse samples
generally parallels that of the TDS values (Appendix L). Initially, when leachate acidities are
relatively high, the elemental concentrations also tend to be high, but as the leachate pH begins
to increase with increasing effluent volume, the trace element concentrations in the leachates
begin to decrease nearly exponentially. An example of this behavior for aluminum, iron, and
cobalt is given in Fig. 7.
50000
0.
4 6
VOLUME (liters)
10
Fig. 7.
The concentrations of iron, aluminum, and cobalt as a function of leachate volume during
the continuous leaching of refuse from cleaning Plant B.
42
-------
The information on elemental releases collected from the continuous leaching studies shows
rather conclusively that the greatest potential for trace element contamination of refuse dump ef-
fluents occurs during the earliest contact with the refuse material. This occurs very frequently in
nature as rains or seasonal water flows intermittently permeate refuse disposal areas. We have
chosen, therefore, the initial period of leaching in which to assess the nature and magnitude of
the trace element releases from the Illinois Basin refuse during dynamic leaching. To assist in the
endeavor, the ranges of concentration of the trace elements studied in the leachates after about
100 ml of leachate had been passed through the refuse column have been reported in Tables
XXXI through XXXIII. The tables show that many of the same elements that were detected in
high concentrations in the static leachates (for example, iron, magnesium, sodium, calcium, and
aluminum) are also present in high concentrations in the leachates from the dynamic experi-
ments. Among these are many potentially harmful trace elements present in concentrations ex-
ceeding 10 ng/ml of leachate, indicated by an asterisk in the table. Another point of interest
brought out in these tables is that even for refuse from cleaning Plant A, which contains a sub-
stantial amount of an acid neutralizing agent (calcite), there is still a notable group of elements
of environmental concern that are released into the flowing leachates. This, of course, reflects the
fact that even the leachates from Plant A refuse are initially quite acidic under flowing leachate
conditions (Fig. 6).
The elements just discussed are those leached from the refuse samples in relatively high con-
centrations. The amount of each released from the refuse, however, represents only a small part
of the total of that element present in the refuse structure. Environmentally, we are also in-
terested in identifying the trace elements in these refuse materials that are inherently highly
leachable or soluble in flowing leachates. Because they will be easily released into the environ-
ment in a short period of time, these elements present an inordinately large potential to cause en-
vironmental harm even though they may not represent a large proportion of the total refuse struc-
ture.
TABLE XXXI
ELEMENTAL COMPOSITION OF LEACHATES FROM CONTINUOUS LEACHING EXPERIMENTS
WITH PLANT A ILLINOIS BASIN COAL REFUSE
Experiment No. GL-19
Leachate Concentration,
Leachate*3
> 500
100-500
10-100
< 10
Element
Mg, Ca, Fe
Al*
* * * *
Na, K, Mn , Co , Ni , Zn
Sc, V, Cr, Cu, Ga, As,
Br, Rb, Ag, Cd, Sb, Cs, La, Ce,
Sin, Eu, Dy, Yb, Lu, Hf, Ta, W,
Hg, Pb, Th, U
Of environmental concern (see Task III).
Conditions: -3/8-in. refuse, 100 mS- leachate, room temperature.
bpH = 2.9.
43
-------
TABLE XXXII
ELEMENTAL COMPOSITION OF LEACHATES FROM CONTINUOUS LEACHING EXPERIMENTS
WITH PLANT B ILLINOIS BASIN COAL REFUSE
Experiment No. GL-8a
Leachate Concentration
yg/m& Leachate
> 500
100-500
10-100
< 10
Element
Al*, Ca, Fe
Mg
Na, Si, K, Mn , Co , Ni , Zn
Sc, V, Cr, Cu, Ga, As, Br, Rb,
Ag, Cd, Sb, Cs, La, Ce, Sm, Eu,
Dy, Yb, Hf, Ta, W, Hg, Pb, Th, U
Of environmental concern (see Task III).
Conditions: -3/8-in. refuse, 100 m£ leachate, room temperature.
bpH = 1.7.
TABLE XXXIII
ELEMENTAL COMPOSITION OF LEACHATES FROM CONTINUOUS LEACHING EXPERIMENTS
WITH PLANT C ILLINOIS BASIN COAL REFUSE
Experiment No. GL-20a
Leachate Concentration
yg/m£ Leachateb
> 500
Element
Na, Fe , Ca
100-500
10-100
< 10
Mg
e e
Al , K, Mn , Co , Ni , Zn
Sc, V, Cr, Cu, 'Ga,
As, Br, Rb, Ag, Cd, Sb,
Cs, La, Ce, Sm, Eu, Dy, Yb, Lu,
Hf, Ta, W, Hg, Pb, Th, U
b
Of environmental concern (see Task III).
^Conditions: -3/8-in. refuse, 100 m& leachate, room temperature.
PH = 2.4.
44
-------
To provide a measure of the ease with which the trace elements studied are released from the
refuse samples into the flowing leachates, we have coined a term called the "environmental ac-
tivity factor" or EAF. The EAF is the dynamic equivalent of the elemental release percentages
reported in Tables XX through XXII for the static leaching studies. The EAF for any element is
defined by the equation
(leachate concentration in yg/ml)
EAF = -7 5 : : ; V X 100 ,
(refuse concentration in yg/g
where v = 0.1 specifies that the elemental concentration used in the calculation is that in the
leachate after 100 ml (O.I/) has passed through the refuse column. (It is understood that an EAF
calculation can be made at any increment of leachate volume.) The calculated EAF values in ac-
tuality are modified "percentage released" calculations. Hence, the most highly teachable ele-
ments, when the calculation is made, are those exhibiting the highest EAFs. The EAFs for the
elements studied in the 100-ml increments of the continuous leaching studies are presented in
Tables XXXIV through XXXVI. The EAF values in the tables reveal that several elements, such
as cobalt, nickel, cadmium, manganese, and zinc, while not leachable in high absolute quan-
tities, are nonetheless rapidly leached from the refuse, and therefore, are classed as being quite
environmentally active during the early stages of dynamic leaching. As we will discuss later in
this report, these elements are of considerable environmental concern in the Illinois Basin refuse
materials. Interestingly, most of the elements that were found to be highly releasable in the con-
tinuous flow studies are the same elements that were released in high percentages during the
static leaching experiments.
A second type of dynamic leaching experiment conducted during the year was intermittent
flow or discontinuous column leaching, designed to determine the degree to which the acid- and
salt-forming potential of Illlinois Basin refuse is regenerated by halting the flow of leachate
TABLE XXXIV
ENVIRONMENTAL ACTIVITY FACTORS FROM CONTINUOUS LEACHING EXPERIMENTS
WITH PLANT A ILLINOIS BASIN COAL REFUSE
Experiment No. GL-19a
Leachate Environmental
Activity Factor Element
* * *
> 25 Co , Ni , Cd
10-25 Mg, Mn*. Zn*
1-10 Na, Ca, Sc, Fe, Cu, La,
Ce, Sm, Eu, Dy, Yb, Lu, Th, U
< 1 Al, K, V, Cr, Ga, As, Cs,
Hf, Pb
Of environmental concern (see Task III).
Conditions: -3/8-in. refuse, 100 mi leachate, room temperature.
bpH = 2.9.
45
-------
TABLE XXXV
ENVIRONMENTAL ACTIVITY FACTORS FROM CONTINUOUS LEACHING EXPERIMENTS
WITH PLANT B ILLINOIS BASIN COAL REFUSE
Experiment No. GL-8a
Leachate Environmental
Activity Factor"
> 25
10-25
Element
* * * * *
Ca, Sc, Mn , Co , Ni , Zn , Cd
Mg, Fe , Cu , Eu, Dy, Yb, Lu
Th, U
1-10
Na, Al, V, As, La, Ce, Sm
< 1
K, Cr, Pb
Of environmental concern (see Task III).
Conditions: -3/8-in. refuse, lOO'md leachate, room temperature.
V = 1.7-
TABLE XXXVI
ENVIRONMENTAL ACTIVITY FACTORS FROM CONTINUOUS LEACHING EXPERIMENTS
WITH PLANT C ILLINOIS BASIN COAL REFUSE
Experiment No. GL-203
Leachate Environmental
Activity Factor
> 25
Element
10-25
1-10
Na, Sc, Co , Sm, Eu, Dy
Mg, Mn, Ni, Zn, As, Cd, La,
Ce, Yb, Lu, Th, U
< 1
Al, K, Ca, V, Cr, Fe, Cu, Ga,
Cs. Hf, Pb
Of environmental concern (see Task III) .
Conditions: -3/8-in. refuse, 100 mX, leachate, room temperature.
bpH = 2.4.
46
-------
through the refuse bed and allowing the material to equilibrate in air. This condition is very
prevalent in most refuse disposal areas where seasonal variations in precipitation or water flows
cause erratic or only intermittent contact of the refuse dump with surface or ground water.
An example of the trends in leachate pH and salt content for an interrupted column leaching
experiment using Plant B refuse is shown in Figs. 8 and 9. In this instance, leachate flow was in-
terrupted at about 2.7,6 and air was passed through the refuse column for 1 day. Then normal flow
was commenced until a total of about 8.7.0 of leachate had passed through the column and flow
was again interrupted. After passing dry air through the column, this time for 7 days, leachate
flow was again started and continued until the end of the experiment. The dashed vertical lines
on the abscissas of the plots in Figs. 8 and 9 denote the places in the experiment where flow was
stopped and the refuse was dried. After 1 day of refuse drying, there was slight evidence that pH
had begun to again decrease and salt content to increase. A much larger effect in this direction
was noted after 7 days of refuse drying. In this case about 5 to 10% of the original capacity of the
refuse material to produce dissolved salts was regenerated; however, in another column leaching
experiment, where we interrupted leachate flow and passed alternating dry and wet air through
the refuse bed for a period of 3 weeks, we succeeded in regenerating about 35% of the original
potential of the refuse material to contaminate aqueous leachates. These experiments convince
us that under some circumstances in the field, the refuse material will return to a condition ap-
proximating its original chemical state and that subsequent leaching will again result in the
release of large quantities of acid and dissolved salts.
This observation is extremely important because it implies that the capacity of refuse dumps
to contaminate aqueous drainage with acids and trace elements is substantially regenerated each
time there is an opportunity for the dump to thoroughly dry out. This means, strangely enough,
that refuse banks or waste dumps that have only occasional intrusions of water may have far
more potential for contaminating the surrounding environment than do those continually in con-
tact with water.
3.5
3.0
2.0
51 i i i i ii
0.0
5.0 10.0 15.0
VOLUME (liters)
20.0
Fig. 8.
The effect of discontinuous flow on leachate pH values for a column leaching experiment.
47
-------
•t.v
83.0
0
CO 2.0
O
UJ
CO '-°
5
Go
,\j
0
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1 J
-
-I
" I
-\
- \
— \
\ 7 DAYS AIR
; x IDAYAIR „ '.
*b-^ 1 ^^-x
i i i i r<^Tir9~riTTCUi I i I i'T*'r-*O— i— i-L-i-J— i— lni_ i-j ,ij-i-i— 1_ 1-
0 5.0 10.0 15.0 2C
VOLUME (liters)
Fig. 9.
The behavior of leachate salt content when flow is interrupted in a column leaching experi-
ment.
Subtask 2.2—Model the Environmental Behavior of Coal Wastes
During FY 77, we began to investigate the usefulness of thermodynamic models for predicting
the weathering and leaching behavior of coal refuse systems. Unfortunately, we did not progress
in this endeavor as well as originally planned.
For our initial work, we chose a complex equilibrium model developed by Ma and Shipman (Y.
H. Ma and C. W. Shipman, AEChE Journal 18, 299-304, 1972), being used at LASL to model
scale formation from geochemical brines. The original model, as developed by Ma and Shipman,
however, applied only to mineral melts and solid solutions. Therefore, their routine was modified
by LASL scientists to include a solvent, so the behavior of mineral mixtures in aqueous solution
at equilibrium could be modeled. Unfortunately, this modification to the model was not com-
pleted during the year, and we were unable to apply the model to our purpose.
Our intent was to use the modified model to predict the solubilities of the major elements or
minerals in Illinois Basin refuse during static/equilibrium leaching with water. This was to be
done by checking the correspondence between the concentrations of the various species identified
in the experimental leachates with those predicted by the model. We will make this comparison
when the model is satisfactorily modified and debugged.
TASK 3— IDENTIFY TRACE ELEMENTS OF ENVIRONMENTAL CONCERN IN
COAL PREPARATION WASTES AND RECOMMEND POLLUTION-CONTROL TECHNOLOGY
Two main research areas were addressed in this task. One involved compiling and evaluating
the information and experimental results collected during the course of the program, and iden-
tifying the trace elements of environmental concern, in coal preparation wastes from the Illinois
48
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Basin. In the other we began studies to identify and recommend suitable technology to prevent or
control the release of trace elements from the Illinois Basin refuse materials.
Subtask 3.1—Identify the Trace Elements of Environmental Concern in Coal Refuse
One of the main objectives of this program for FY 77 was to identify the trace elements in the
drainage from Illinois Basin coal refuse that have the greatest potential for causing environmen-
tal damage. Much of the focus of our research both on refuse structure and environmental
behavior was directed toward this end.
Two criteria were considered in arriving at a compilation of the environmentally troublesome
elements. First, the element in question must be a known or suspected toxic substance, especially
in aqueous systems. This is a difficult area to assess considering differences in plant and animal
tolerances for the elements under consideration. For the moment, however, we have chosen ele-
ments that are reported to be generally toxic to plants and animals in concentrations comparable
to those available in the coal refuse. (See for example: "Effects of Trace Contaminants From Coal
Combustion," Proceedings of a Workshop, Sponsored by ERDA/DBER, August 2-6, 1976, Knox-
ville, Tennessee, ERDA 77-64; and "Trace Element Emissions: Aspects of Environmental Tox-
icology," Chap. 15 in Trace Elements in Fuel, S. P. Babu, Ed., Advances in Chem Series 141, Am.
Chem. Soc. 1975.) Also, to be included in our list of suspect elements, the element must be
leached in relatively high quantities or be readily released from the refuse material under normal
waste dump conditions. This condition means either that the element is present in the matrix of
a labile or reactive refuse mineral, such as the pyrites, carbonates, or phosphates, or that it has
been shown by experimental studies to reside in the refuse in a highly leachable state. Of the ap-
proximately 55 elements in the Illinois Basin refuse, only a few meet these criteria.
The trace elements listed in Table XXXVII are those in the refuse that we identified in Task 1,
either by statistical studies or direct microprobe analyses, as being present in or highly associated
TABLE XXXVII
ELEMENTS HIGHLY ASSOCIATED WITH LABILE MINERALS IN
ILLINOIS BASIN COAL REFUSE3
Mineral Major Constituents Associated Elements
*
Pyrite/Marcasite Fe, S
* *
Carbonates Ca, Mg, C F, Mn
Phosphates P, Ca
* Of environmental concern.
a Based on data from statistical correlations and
microprobe analyses of selected samples of
Illinois Basin refuse.
49
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with labile or environmentally active mineral phases. The trace elements associated with the iron
sulfide and carbonate constituents will be of concern because these minerals are often present in
the waste in large quantities. Because the phosphate minerals are very minor components in the
Illinois Basin materials, the trace elements associated with this mineral type exert a much less
important influence on the ultimate composition of the waste effluents and are not considered.
The elements that we consider to be potentially harmful in aquatic systems or soils, on the basis
of mineralogy, are shown in Table XXXVII with an asterisk.
The leachabilities of the various refuse elements, as revealed by both static and dynamic
laboratory leaching tests, were discussed in Task 2. In the static studies the trace element com-
positions of the leachates showed a general tendency to increase with time. The trace element
contents of the dynamic leachates were initially observed to be quite high (on par with the
elemental composition of the static leachates), but with continued leaching the contaminant
levels of the dynamic leachates began to fall off in an exponential manner. We did find, however,
that there was a marked tendency for the contaminant levels of the dynamic leachates to remain
relatively high if the refuse samples were subjected to intermittently rather than continuously
flowing leachates. We concluded that the leachabilities of the various refuse elements during the
early stages of either static or dynamic leaching were a reasonable representation of the natural
potential of refuse disposal areas to release toxic inorganic contaminants into associated
waterways.
To identify the most environmentally troublesome trace elements in these refuse samples, we
considered only those elements present in the initial dynamic leachates in amounts exceeding 10
Mg/ml of leachate (10 /ug leached/g of refuse for the static leachates) or that had leachability
percentages or EAFs of 10 or greater. The elements meeting both the toxicity and leachability
criteria were designated with an asterisk in the tables of leachate data reported in Task 2. A
tabulation of these elements is presented in Table XXXVIII.
TABLE XXXVIII
TRACE ELEMENTS OF ENVIRONMENTAL CONCERN AS DELINEATED BY STATIC AND
DYNAMIC LEACHING STUDIES OF ILLINOIS BASIN
COAL REFUSE
Element High Leachate Concentration3 High Leachability
Al x
Mn x x
Fe x x
Co x x
Hi x
Cu x x
Zn x x
Cd
Elements present in initial dynamic leachates in excess of
10 pg/ml of leachate. or in static leachates greater than
10 pg/g of refuse.
Elements having EAF's or percent leachabilities of 10 or
more in initial dynamic or static, leachates.
50
-------
A complete listing of the trace elements of greatest environmental concern in Illinois Basin
refuse as delineated both by our mineralogical and leaching studies, appears in Table XXXIX.
The elements listed will receive our greatest attention in subsequent studies of environmental
control technology for refuse dump drainages and effluents.
Several points concerning our choices of the environmentally troublesome trace elements in the
refuse samples deserve further comment. One concerns the required level of toxic element con-
centration in the leachates before consideration of an element as an environmental concern (10
jug/ml of leachate or 10 ^g/g of refuse, depending on the type of experiment). Many toxic elements
are, of course, harmful in aqueous systems in quantities much less than these; however, to avoid
grossly overstating their real contamination potential, we purposely set our elemental composi-
tion limits at relatively high values. We hope, by this procedure, to have identified those ele-
ments most likely to cause environmental problems in refuse drainage (but certainly not every
harmful element) without putting undue emphasis on the toxicology of specific elements.
An important point to bear in mind is that designating any level of trace element content in the
refuse leachates as "safe" is rather arbitrary from an environmental viewpoint, because the actual
harm that toxic elements in refuse drainage systems can cause is a function of how efficiently
these elements are accumulated into sensitive areas of the surrounding ecosystem. This depends
on a number of factors not directly connected with the refuse dump, including the total volume of
contaminated drainage released from the disposal site, the degree that the contaminated
drainage is diluted and carried away by adjacent waterways, and the ability of soils, plants, or
animals in the area to concentrate specific toxic elements. The research reported here does not
purport to answer these questions, but rather to call attention to those trace elements in the
drainage from Illinois Basin refuse materials that have the greatest potential for causing en-
vironmental damage, and hence, should be given foremost consideration in the planning of effec-
tive environmental control strategies.
Finally, a question may be raised concerning the correspondence between our laboratory data
on trace element releases from various refuse samples and the levels of trace element contamina-
tion in actual refuse dump drainage. Although we have attempted to incorporate generality into
this study by stressing the relationship between refuse composition and environmental behavior,
it is true that only a limited number of refuse samples or leaching conditions were used in our
work. The validity of our data and conclusions is substantiated, however, by the good cor-
respondence between the levels of elemental contaminants observed in our experimental
leachates and a limited group of trace elements identified in actual refuse dump drainage from
TABLE XXXIX
TRACE ELEMENTS OF ENVIRONMENTAL CONCERN IN ILLINOIS BASIN COAL REFUSE
Element
F
Al
KQ
Fe
Co
Ni
Cu
Zn
Cd
Labile Mineral
x
x
Static Leaching Dynamic Leaching
x
X
X
X
X
X
X
X
X
X
X
X
X
X
51
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widely diverse points in the Illinois Basin (Table XL). The high level of agreement between our
results and the available information gathered from analyses of refuse dump drainages indicates
convincingly that the leachates produced in the laboratory do indeed simulate the effluents from
many refuse dumps throughout the Illinois Basin, and reflect the general types and levels of
elemental contaminants that will need to be accommodated by any environmental control
technology.
Subtask 3.2—Recommended Methods and Technology for Controlling Trace Element Con-
tamination
One of the main reasons for studying the releases of trace elements from coal refuse materials
during weathering and leaching is to provide useful information about the nature and seriousness
of this form of contamination for planning and developing environmental control strategies for
coal refuse dumps and disposal areas. Accordingly, the emphasis of our work over the past 2 years
has been directed not only at identifying the trace elements in waste or refuse drainage that are
most likely to cause environmental problems, but also at understanding the chemistry and
behavior of these materials. Several of the principal conclusions from our studies of Illinois Basin
coal preparation wastes carry implications concerning possible control technology methods and
warrant further elaboration and discussion. One concerns the importance of pH in determining
the levels of trace element contamination of refuse drainage. Throughout our studies, under all
TABLE XL
TRACE ELEMENT CONCENTRATION RANGES FOR EXPERIMENTAL LEACHATES AND FIELD SAMPLES OF
DRAINAGE PRODUCED BY ILLINOIS BASIN COAL REFUSE
Experimental Leachates, Refuse Dump Drainage,
Element Ug/mla
Na
Mg
-Al
K
Ca
Mn
Fe
Co
Hi
Cu
Zn
Cd
pH
21
61
8.7
21
130
5.6
610
3.7
5.6
0.3
2.2
- 700
- 369
- 910
- 28
- 532
44
-12000
- 28
- 43
8
- 55
0.02- 0.24
1.7
- 2.9
IS - 270
90 - 285
50 - 440
0.7 - 13
160 350
24 - 120
50 -13500
0.4 - 3.0
1.7 - 8.0
2.2 - 3.6
Data from LASL studies of the initial leachates from dynamic leaching
of selected samples of Illinois Basin coal refuse.
Data from analyses of samples of refuse pile drainage collected from
various locations in the Illinois Basin as reported by Martin, Papers
from First Symposium on Mine and Preparation Plant Disposal "
pp 26-37, 1974.
52
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conditions of static and dynamic leaching, an inverse relationship prevailed between pH and the
amounts of elements leached from the refuse samples. Thus, at low pH (high acidity) worrisome
quantities of toxic elements were leached from all the refuse samples studied; whereas, in those
systems where leachate acidity remained relatively low (pH 5 to 7), trace element teachability
and the capacity of the leachates to solubilize contaminants were minimized. These observations
suggest that preventing the initial formation of acids in refuse dumps, or neutralizing the acid
drainage as it is formed, would be an effective means of controlling trace element releases into the
environment.
Some of the many possibilities for alleviating or controlling acid formation in refuse leachates
that we will investigate in future work include removal or fixation of acid-forming substances
(iron sulfides) before refuse disposal, burying or sealing refuse piles to limit the influx of air and
water, adding neutralizing agents to existing refuse materials, and neutralizing refuse drainage as
it emerges from the disposal site.
Another observation which has implications in the control technology area comes from our
studies of refuse trace element mineralogy. Here we observed that most of the elements identified
as being of environmental concern reside as constituents of, or are embedded in, the refuse clay
fractions. Even such chalcophile elements as cobalt, nickel, copper, zinc, and cadmium, which
might have been expected to be associated with the major sulfide minerals, were found to be
highly concentrated in the predominately clay areas of the refuse samples. The clay minerals
represent a substantial part of the total refuse structure (usually more than 30%), but more im-
portant, the clay constituents are finely divided and intermixed with the other refuse fractions.
Therefore, attempting to remove the clay refuse component, which contains the bulk of the trace
elements that we are concerned with, before disposal (as has been suggested by some), appears to
be highly impractical.
A related observation from our work concerns the ease with which many of the worrisome ele-
ments can be removed from the refuse materials simply by leaching them with aqueous acids.
Our environmental studies with Illinois Basin refuse revealed that substantial percentages of the
total manganese, iron, cobalt, nickel, zinc, and cadmium in the refuse materials can be removed
by short-term leaching with dilute sulfuric acid. This suggests that many of the environmentally
harmful elements in high-sulfur refuse could be removed before disposal by treating the crushed
refuse with a dilute acid, and isolating the easily removable elements in the ensuing leachates.
This process looks even more attractive when it is considered that the necessary acid could be
generated in situ by the proper application of water and air to the refuse pyritic constituents.
This process also will be given careful consideration in our future research.
A last observation from our studies is quite important when considering regional control of
water pollution from coal refuse dumps. Some refuse materials pose a far greater pollution threat
when they are only intermittently in contact with water than when they are continuously being
leached. Therefore, we conclude that the highest priority and greatest emphasis in pollution
abatement programs for coal refuse dumps should be given to those disposal sites that are fre-
quently, but not continuously, in contact with surface or ground water.
We have also begun experiments to evaluate the potential of a number of techniques to control
the acidity and trace element composition of coal refuse drainages. Our initial emphasis in this
study is on techniques such as alkaline neutralization, ion exchange, reverse osmosis, and flash
distillation. Each of these is used in the field, or under consideration, to control acid in the
drainage from coal mines or refuse dumps. (A discussion of AMD control methods was presented
earlier in our literature review of trace elements in coal cleaning wastes, published as EPA report
600/7-76-007, August 1976.) Results from our work with the various environmental control
methods will be reported in the coming year.
53
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TASK 4-ASSESS THE POTENTIAL FOR ENVIRONMENTAL CONTAMINATION
FROM TRACE ELEMENTS AND ORGANIC COMPOUNDS IN THE
EFFLUENTS FROM STORED COALS
The research described in this section was designed to determine the potential for environmen-
tal contamination from the trace elements and organic compounds that are released during the
weathering and leaching of stored coals. The emphasis during FY 77 focused on how the various
environmental conditions encountered during outdoor storage affect the character of the aqueous
discharges from a high-sulfur Illinois Basin coal.
Subtask 4.1—Determine the Identities and Amounts of Inorganic and Major Organic Com-
ponents Released by the Aqueous Leaching of Unwashed Coals Under Simulated Storage
Conditions
The coal used in this study was an unwashed variety that we collected at the input feed of a
coal preparation plant located in the Illinois Basin (cleaning plant E). This high-sulfur coal is
one of the major varieties mined in the basin. The elemental composition of the coal is reported
in Appendix B. A tabulation of the averages and extremes in elemental components for the two
increments of the coal that were collected appears in Table XLI. The bulk mineralogical com-
position of this coal was not determined.
Analogous to the coal refuse studies, we completed a number of coal leaching experiments dur-
ing the year using both the static equilibrium (Appendix H) and the dynamic (Appendix I)
leaching methods. As in the case of the refuse investigation reported earlier in Task 2, we used
the static experiments to determine the effects of pertinent experimental variables on the
elemental composition of the leachates; the dynamic tests provided information on trace ele-
ment releases from the coal under conditions more closely simulating those encountered during
the outdoor storage of coal.
The static leaching studies of this high-sulfur Illinois Basin coal were completed about
midyear. Two coal particle sizes, -3/8 in. and -20 mesh, were included in this study. These were
chosen to determine the influence that coal surface area has on the leaching process. Both wet
(as received) and predried coal samples were incorporated into the study to simulate the effects
of preparation plant drying and long dry spells during coal storage. Distilled water was the
leachate used in all instances. The experiments were conducted either at ambient temperature
(22°C) or at 70°C. The high-temperature studies represent the interior conditions of coal piles
maintained at hyperambient temperature by various heat-producing reactions (mainly the ox-
idation of coal and pyritic materials). Provisions were also made to study coal leaching behavior
under conditions of low oxygen content in sealed vessels and when free access to air is main-
tained with an open reaction vessel. Low oxygen conditions often prevail at the interior of com-
pacted coal heaps, but in poorly compacted piles there is often very good circulation of air.
Finally, the experiments were conducted for a period of 28 days. Samples were removed from the
shaker for analyses after leaching times of 10 min, and 1, 7, 14, and 28 days. These experiments
simulate a variety of leaching conditions, from very mild to those which may prevail in the ex-
treme where the stored coal is nearly continuously in contact with water. A listing of the various
combinations of experimental variables under consideration in this study is given in Table XLII.
The effects of the various experimental parameters on the coal-leachate systems are reflected
by the solution pH values, which were monitored throughout the experiment. The pH values at
54
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TABLE XLI
TRACE ELEMENT COMPOSITION OF RAW COAL FROM ILLINOIS
BASIN COAL PREPARATION PLANT Ea
Element1* Low High Mean
Li
3e
B
F
Na(%)
Mg(%)
Al«)
Si(%)
P
Cl
K(Z)
Ca(%)
Sc
T1(Z>
V
Cr
Mn
Fe(Z)
Co
Nl
Cu
Zn
Ga
Ge
As
Br
Y
Zr
Mo
Cd
Sn
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Pb
Th
U
63
20
62
60
0.03
0.05
1.8
•1.4
260
77
0.23
0.15
4.5
0.08
37
21
42
3.90
13
26
33
22
24
16
29
39
16
0.15
0.79
19
31
2.3
0.7
3.1
1.1
0.2
0.4
11
3.4
2.5
65
22
70
80
0.03
0.06
1.8
2.5
310
123
0.26
0.21
4.8
0.10
50
30
58
4.70
13
42
38
32
43
41
37
55
25
0.21
1.38
22
34
2.5
0.9
3,8
3.1
0.2
1.3 '
11
3.5
2.6
64
21
66
70
0.03
0.06
1.8
2.0
285
100
0.24
0.18
4.7
0.09
43
26
50
4.30
13
34
36
27
6
< 8
34
29
33
47
21
0.18
• < 8
1.08
2.4
21
32
2.4
0.8
3-5
2.1
0.2
0.8
11
3.5
2.6
Analyses included coal samples 36 and 37.
Elemental compositions reported as Ug/g coal unless otherwise noted.
55
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Vl
o\
TABLE XLII
EXPERIMENTAL CONDITIONS USED IN STATIC/EQUILIBRIUM LEACHING STUDY OF
ILLINOIS BASIN COAL
Time
(a)
Atmosphere
Temperature, °C
COAL SAMPLE
-20 mesh, dry
-20 mesh, wet
-3/8 in.
10 min.
S
22
x(b)
X
X
1 Day
S
22
X
X
0
22
X
X
0
75
X
X
7 Days
S
22
X
X
X
0
22
X
X
0
75
X
X
14 Days
S
22
X
X
28 Days
1
S
22
X
X
X
0
22
X
X
o
75
X
X
(a) S = sealed vessel, 0 = open vessel.
(b) The combinations of variables studied are designated by an X.
-------
6.0
5.0
4.0
3.0
2.0
T
SAMPLE/TEMP/AIR
+ -20 MESH DRY RT LIM
0-20 MESH WET RT LIM
n-20 MESH WET RT ATMOS
o -20 MESH WET 75° ATMOS
x-3/8 In. WET RT LIM
•-3/8 In. WET RT ATMOS
• -3/8 in. WET 75° ATMOS
• BLANK RT LIM
x
j i
10 20
LEACHING TIME (days)
30
Fig. 10.
Leachate pH as a function of experimental variables for leaching study of Illinois Basin coal.
the termination of the leaching experiments are illustrated in Fig. 10. Several striking observa-
tions can be made about these data. First, the pH of all of the leachate solutions dropped very
rapidly upon initial contact with the crushed coal. In fact, given some slight variation with time,
most of the change in solution pH occurred within the first 10 min of contact with the coal.
Therefore, there is a very short time dependence connected with the build-up of free hydrogen
ion in the aqueous leachate. Another interesting point is that the temperature of the leaching ex-
periment had little effect on the pH of the solution. The pH values were similar for both the am-
bient and high-temperature conditions. Also, the solution pH was little affected by the particle
size (surface area) of the coal. The two variables having the greatest effect on leachate pH were
whether the coal was dry or wet when it came into initial contact with the water, and whether
there was free or restricted air flow into the leaching zone. In each instance, the pH of the
leachates associated with the predried coal was substantially higher than those in contact with
the wet coals. Likewise, the pH of the leachate solutions are significantly higher for those
coal/leachate mixtures in which the flow of air into the system was severely restricted.
The trace element levels and other pertinent data for the various leachates from the static
leaching studies of the Illinois Basin coal are reported in Appendix M. To clarify the effects of
the experimental variables, we have retabulated the data for several of the more highly leachable
elements and presented them as Tables XLIII through IL. For comparison, the leachate trace
element concentrations are expressed in ng of element released per g of coal leached. Thus, in
considering the leaching experiments, the values reported represent the total mass of a par-
ticular element released per g of coal, regardless of solution volume.
The major observation to be made from the information in Tables XLIII through IL is that the
leachabilities of the 12 elements listed generally increased with time although the data for
several elements are somewhat erratic. In all cases iron was by far the element most abundantly
leached from the coal samples, indicating that much dissolution of pyritic material occurred dur-
ing the leaching treatment. Also, in nearly all instances, calcium (not shown), aluminum, and
57
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TABLE XL III
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL
CONDITIONS: WET COAL, - 3/8 IN., 22°C, LIMITED AIR
Elements Leached (jig/g of coal_)_
Leaching Time (days) Fe
10 min 1820
1 1060
7 2220
14
28 3420
Al Ma K
25 12 1.0
12 23 3.8
28 42 2.9
35 62 21.8
STATIC/EQUILIBRIUM
Mg Cr
30 0.12
30 0.09
45 0.14
50 0.20
TABLE XL IV
Mi\ Co Ni
8 5 10
10 7 12
14 8 14
14 5 .14
Cu Zn Cd
1.4 5.0 0.06
0 . 50 4.9 0.07
0.75 9.1 0.05
<0. 10 5.4 0.05
LEACHING OF ILLINOIS BASIN COAL
CONDITIONS: WET COAL, - 20 MESH, 22°
Leaching Time (days) Fe
10 rain 1270
1 1.090
7 2590
14 2755
28 3150
Elements
Al Na K.
56 24 1.4
50 20 0.6
62 14 0.4
54 14 1.6
94 9 12.5
Leached (ng/g of
Mg Cr
50 0.10
5.5 0.09
55 0.13
55 0.14
55 0.20
C, LIMITED AIR
cnal)
Mn Co Ni
13 7.0 16
16 8.0 J9
18 .11 22
17 10 19
18 10 19
Cu Zn Cd
0.63 7.2 0.05
0.42 9.1 0.06
<0.10 11.6 0.07
<0.10 11.9 0.07
0.20 14.1 0.08
-------
TABLE XLV
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS 1JASIN COAL
CONDITIONS: WET COAL, -3/8 IN., 22°C, UNLIMITED AIR
Elements _l:gaf_Iied_
Leaching Time (days) Fe Al Na K Mg
Cr
o/_c ofl ^ )
Mil
Co
Nl
Cu Ztt
Cd
1
7
14
28
1880
1950
10060
29
25
75
54
32
46
8.
1.
1.
8
2
1
45
30
50
0.
0.
0.
150
140
270
1.0.0
10.0
25.0
7.0
7.0
8.0
12.0
14.0
18.0
0.150 6.56 0.05
0.140 4.12 0.04
0.270 7.19 0.05
TABLE XLVI
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL
CONDITIONS: WI!T COAL, -20 MESH, 22°C, UNLIMITED AIR
Element.s_ Leached _(|J£/j;__of_Sl°;iI)_
Leaching Time (days) >'e Al Na K Mg Cr Mil
Co
Ni
Cu Zn
Cd
1
7
14
28
1100 52 20 1.5 50 0.100 17.0 9.0 17.0 0.100 9.06 0.07
3260 75 4 1.0 45 0.150 17.0 9.0 17.0 0.150 10.9 0.07
16440 155 2 0.8 50 0.230 25.0 12.0 27.0 0.230 21.6 0.11
-------
TABLE XLV]1
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL
CONDITIONS: WET COAL, -3/8 IN., 75°C, LIMITED AIK
ntt^ Leaohed (yig/g of c-.oaJj
Leaching Time (days) Fe Al _N_a_ K Hg Cr Mil Co Hi „ _C"_ z" .._Cd_
1 2480 28 33 5.2 45 0.15 12 7 13 0.31 7.19 0.054
7 3170 50 37 10.6 55 0.19 13 7 13 0.70 6.56 0.054
14
28 5550 160 70 28.7 80 0.26 17 26 15 0.63 8.44 0.07
TABLE XLVII]
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL
CONDITIONS: WET COAL, - 20 MESH, 75°C, LIMITED AIR
Elements l.ear.hed (pg/g of coal)^
Leaching Time (days) Fe Al Na K Mg Cr Mil Co Nl Cu Zn Cd
1 4100 47 27 7.7 55 0.18 20 10 21 0.38 12.2 0.07
7 7500 120 62 36 80 0.23 24 32 24 0.30 19.1 0.09
14
28 10750 410 89 54 95 0.40 22 10 22 1.88 24.7 0.10
TABLE 1L
STATIC/EQUILIBRIUM LEACHING OF ILLINOIS BASIN COAL
CONDITIONS: DRIED COAL, - 20 MESH, 22°C, LIMITED AIR
Elements Leached (ug/g_£|__coa 1)
Leaching Time (days) _Fe_ _AI_ JJa_ K Mg _Cr_ _Mn_ _Co_ Ml Cu Zn Cd
10 mln 23
-------
magnesium were leached in relatively high quantities from the coals. This undoubtedly resulted
from the dissolution of the clay and carbonate minerals. Sodium and potassium were often ob-
served in the leachates in amounts comparable to aluminum and magnesium, but the behavior
of these elements was somewhat erratic perhaps because they tend to form ion-exchange com-
plexes with both the clay and carbon fractions of the coal. Other elements that were consistently
leached from the Illinois Basin coal in appreciable quantities (>10 /ug/g of coal) include
manganese, nickel, zinc, and cobalt.
A few elements, for example iron, aluminum, and chromium, appeared in all instances to be
continuously released from the coals as a function of leaching time, and showed little sign of ap-
proaching an equilibrium condition. Others, like magnesium, were leached to the maximum
relatively quickly. In some cases, some elements (sodium, potassium, and copper) appeared to
decrease in concentration from the leachate as time went on. This phenomenon probably
resulted from the time-dependent adsorption or recombination of the elements with the coal
residues or other parts of the experimental system.
The effects of coal particle size (surface area), system temperature, and oxygen content on the
leachabilities of the observed elements are somewhat variable depending on the element.
Generally, higher elemental concentrations in the leachates were obtained from the smaller coal
particles (compare Tables XLHI and XLIV, XLV and XLVI, XLVII and XLVIII). This il-
lustrates a positive enhancement of mineral solubility by increasing coal surface area. Increasing
the system temperature similarly enhanced the solubility of the various elements in the
leachates (Tables XLIII and XLVII, XLIV and XLVHI). And, other things being equal, the coal-
leachate systems that had unlimited access to air exhibited the greatest degrees of elemental dis-
solution (Tables XLIII and XLV, XLIV and XLVI). The most dramatic effect of all was caused
by drying the coal sample before it was leached (see Tables XLIV and IL). The amounts of iron
and aluminum leached from the predried coal were substantially lower than the amounts
leached from the as-received material, and most other elements were correspondingly lower. We
observed much the same effect from predried coal with regard to leachate pH. We do not have an
explanation for this.
In addition to the static leaching studies, we conducted several leaching experiments with the
Illinois Basin coal using the dynamic column method. These experiments, like those with the
Illinois Basin refuse samples, were conducted according to the procedure outlined in Appendix I.
In contrast to the static leaching experiments, where a constant and single volume of water is
used, these dynamic experiments feature a flowing leachate that is constantly pumped through a
column of crushed coal. The values for leachate pH and TDS, and the trace element composi-
tions of the various dynamic coal leachates are reported in Appendix N.
The trends in leachate pH and TDS for the continuous column leaching studies of crushed Il-
linois Basin coal (CL 7 and 8) are given in Figs. 11 and 12. Initially, the acid generating capacity
of the coal system is quite high, but with increasing leachate volume, pH begins to rise and level
off. The behavior of dissolved solids in the leachate corresponds roughly with the acidity of the
leachate. Initially, at low pH, the leachate contains a relatively high salt content (approaching 4
wt%). As the pH curve begins to rise and flatten with greater leachate volume, the TDS content
drops dramatically and eventually levels off at a relatively low constant value.
The data in Appendix N show that the trace element release patterns for the coal samples dur-
ing continuous leaching are similar to those exhibited by the Illinois Basin refuse samples. In-
itially, at high acidity, elemental concentrations in the dynamic leachates are also high.
However, as acidity drops with continued leaching, trace element concentrations for most ele-
ments also decrease (similar to the TDS behavior shown in Fig. 12) to values 1% or less of the in-
itial concentrations.
61
-------
4.0
i i i i i i i i i i i i i i i i i | i i i i i i i i i | i i i i i i i i
oo cP
LEGEND
o CL-7
D CL-8
I I I i I I i I I i I I I I I I I 1 I I I I I L.I J
5.0 10.0 15.0
VOLUME (liters)
20.0
Fig. 11.
Leachate pH from a continuous leaching experiment with Illinois Basin coal.
(O
o
d
CO 2.0
Q
CO 1.0
o
0.0
1 1 I 1 1 I 1 1 1 I I 1 1 1 1 I 1 1 1 1 1 I I )> 1 1 1 1 1 1 1 1 1 1 1 1 I
1
T
1 LEGEND I
-n o CL-7
I n CL-8
A
:\ :
^ D
- ov
i i i i I^Ma-Ui-i-mi-i-i-i-i-ia-lfvt-i-i-M-i-i-^inLici-i-i-i-i-i-i-u
5.0 10.0 15.0
VOLUME (liters)
200
Fig. 12.
TDS as a function of leachate volume for a continuous leaching experiment with Illinois
Basin coal.
62
-------
To simulate rainy and dry weather cycles, we conducted dynamic leaching studies with the
Illinois Basin coal samples in which we incorporated intermittent flow conditions. In these ex-
periments (results reported in Appendix N) leachate flow was interrupted at several points, air
was passed through the packed coal column for periods of up to 7 days, and flow was again star-
ted. The effects of intermittently leaching the coal sample are shown in Figs. 13 and 14 for ex-
periment CL-5. As we observed earlier for coal refuse systems, these coals also have a substantial
capacity for contaminant regeneration when leachate flow is interrupted and the coal is allowed
to dry. As Figs. 13 and 14 show, particularly vividly after the 7-day column drying period, both
the leachate acidity and solids content tend to rise significantly following a pause in leachate
flow. This is strong evidence that, analogous to the refuse materials studied, Illinois Basin Coals
will remain a high potential source of mineral and trace element contamination regardless of the
age of the coal or storage pile.
Our studies of the Illinois Basin coal leachates also involved assessing their organic composi-
tions. Our objective here was to determine the degree to which drainage from coal storage piles
might be contaminated with organic compounds, and, if possible, to identify these compounds.
Total organic carbon contents (TOC) were determined for several of the leachates from the
static/equilibrium study of the Illinois Basin coal sample. The TOC values for these leachates
ranged from about 5 to 50 ppm. These values are only rough approximations because our
analytical reproducibility was poor, but they do represent typical levels of organic carbon to be
found in the coal leachates.
After determining how much organic material was in the coal leachates, we wanted to identify
the natures of their individual species. It was necessary first to separate these components into
groups or classes and then to subdivide them further into smaller groups or individual species
suitable for identification by mass spectrometry, infrared spectroscopy, or nuclear-magnetic-
resonance spectroscopy. Most of our remaining effort in this area was spent on achieving these
separations with chromatographic techniques.
5.0 10.0 15.0
VOLUME (liters)
20.0
Fig. 13.
The effect of interrupted flow on leachate pH for Illinois Basin coal.
63
-------
IO.O
g 8.0
v>
o
_l 6.0
O
0
> 4.0
O
CO
en
0 2.0
0.0
0
i i i i i i i i i | i i i i i i i i i
3 D
i
3
^
3
rt
:\
E\
^ \ 1 DAY AIR 7 DAYS
\ | 1
: \ ! IA.
- 1 1 i iM i i T"r*b^- t-i^nt-i-ji i r*
i I I I i I i I I | i i i i i I i i i-
—_
'-
i
~
-
I
-
i
2
'-
-
-
—
AIR :
-
(^WV-HfW-LA-i 1 1 1 I 1 1 1 IA±_LI
0 5.0 10.0 15.0 20.0
VOLUME (liters)
Fig. 14.
The effect of discontinuous flow on leachate solids content for Illinois Basin coal.
Isolation and partial separation of the organic contaminants in samples of the coal leachates
was accomplished with a chromatographic method called reverse-phase, gradient-elution, liquid
chromatography. This technique has been widely used to effect separation of organic contami-
nants from drinking water. With this method, the contaminants are removed from the aqueous
solutions by passing the solutions through a nonpolar chromatography column which retains the
organic molecules. Usually a relatively large volume of contaminated water or leachate is passed
through the column (in our work, up to 50 ml) to concentrate the organic impurities in sufficient
quantities for analysis. The organic matter held on the column is then progressively removed by
eluting with mixtures of organic solvents. The separated components or fractions are collected as
they emerge from the chromatography column and prepared for analyses.
A typical liquid chromatogram of the organic constituents removed from a coal leachate (as
described above) is given as Fig. 15. The first very broad peak appearing after the injection point
is composed mainly of compounds containing inorganic elements. Whether these are present in
the form of organometallic complexes or in ionic form is not yet known. The group of smaller
peaks in the middle part of the chromatogram (elution volumes in the range 20 ml to 35 ml) are
polar organic molecules; i.e., oxygen-, nitrogen-, or sulfur-containing compounds. Finally, the
last peaks to elute (at >35 ml of solvent) are the nonpolar organic constituents.
We have completed a small number of mass spectral analyses of several of the organic frac-
tions obtained from the chromatographic separations. Our results are far from conclusive, but
they indicate that most of the organic components in the coal leachates are heteroatom
(nitrogen, sulfur, oxygen) containing aliphatic or alicyclic compounds. No direct evidence of
phenol or other aromatic compounds, however, was obtained from this superficial mass analysis.
64
-------
20 30 40
ELUTION VOLUME (ml)
Fig. 15.
Liquid chromatogram of organic contaminants in coal leachate obtained by passing 10 ml of
leachate through a 4-mm-i.d. by 30-cm Bondapak C-18 column followed by elution with a
linear gradient progressing from pure water to pure acetonitrile at a flow rate of 2.0 ml/rain.
Subtask 4.2—Obtain Data on the Relative Release Rates of Specific Inorganic and Organic
Components From Stored Cells
The purpose of this subtask was to compute or calculate the relative release rates of the
various trace elements and organic contaminants during aqueous leaching of an Illinois Basin
coal sample. This effort was satisfactorily completed for the inorganic leachate contaminants,
but the limited study that we completed on the organic components of the leachates did not
provide sufficient information to make a similar assessment.
Our work on relative release rates of the trace elements in the coal sample concentrated on the
dynamic leaching studies, which are more representative of actual storage pile conditions. In-
itially we plotted leachate elemental concentrations as a function of time and then determined
rate expressions for each element. After inspecting the complex polynomial equations necessary
to describe the trace element leaching data, we concluded that more understandable release data
would result simply by comparing the EAFs (defined in Task 2) for each element in the initial
leachates. A tabulation of the EAFs for the elements studied in the 200-ml increment of one of
65
-------
TABLE L
ENVIRONMENTAL ACTIVITY FACTORS FROM CONTINUOUS LEACHING EXPERIMENT
WITH PLANT E ILLINOIS BASIN COAL
Element
rt
Experiment No. CL-7
EAFb Element
Co
* 74.6 Na 9.7
Ni* 52.9 Yb 9.5
Zn* 48.2 Sc 8.9
Cd* 46.1 U 7.2
Mn* 45.9 Lu 5.0
Ca 20.0 La 2.6
Dy 18.3 Ce 1.8
Cu 16.9 V 1-3
Mg 15.5 Al 0.7
Fe 13.5 Cr 0.6
Sm 11.7 Pb 0.4
Eu 11-3 K 0.2
Th 11-2
* Of environmental concern.
a Conditions: -3/8-in. coal, 200 ml leachate, room temperature.
b pH = 2. 2 .
the dynamic leaching experiments (CL-7) appears in Table L. The EAFs cluster into groups
reflecting relative leachabilities or release rates. Cobalt, as we also observed from the studies of
Illinois Basin refuse, is in a class by itself with regard to ease of removal from the coal during
dynamic leaching. Nickel, zinc, cadmium, and manganese fall into the next group, which have
EAFs in the range of 45 to 55. These elements were similarly leached from the refuse samples
that we studied. Next, in terms of relative leachabilities, is a large group of elements having
EAFs in the range of about 5 through 20. This group includes calcium, magnesium, and iron, as
well as uranium, thorium, and most of the rare earth elements. Finally at the low end of this
leachability scale are aluminum, lead, potassium, and vanadium. This general order of
leachabilities is remarkably close to that observed under similar conditions for the Illinois Basin
refuse samples.
66
-------
Subtask 4.3—Assess the Potential For Environmental Contamination From the Trace Ele-
ments and Organic Matter in the Aqueous Discharges From Stored Coal
The major effort in this subtask involved compiling and interpreting the information obtained
from our studies of the composition and environmental behavior of an Illinois Basin coal. By
assessing our experimental data, we have identified the trace elements in the coal sample most
likely to cause environmental harm when released into the drainage or runoff from coal storage
piles. Although this assessment of potential environmental problems is based on experimental
evidence from only one variety of coal, the general correspondence between its elemental
leachability and the trace element behavior for the Illinois Basin refuse samples that we studied
lends increased weight to the generality of our results for Illinois Basin coals.
The trace elements of most environmental concern in the coal sample were determined by the
same process used in Task 3 for the refuse materials. For reasons outlined in Task 3, we chose in-
itial leachates obtained from both the static and dynamic leaching tests of the coal sample with
which to make our environmental assessment. Without again going into great detail, the criteria
used for choosing the trace elements of concern in the coal or refuse leachates were (1) The ele-
ment had to be generally known to be toxic to specific plants or animals in aqueous systems or
soils in quantities comparable to those present in the coal leachates; (2) The element must have
been present in the initial static or dynamic coal leachates in concentrations greater than 10 /ug/g
of coal or 10 /ug/g of leachate, respectively; and/or (3) The trace elements in question must have
possessed 10% or greater leachability or EAF greater than 10.
The static and dynamic leaching data for the Illinois Basin coal, which were used in our final
deliberations of trace elements of environmental concern, have been condensed from Appendix
N into Tables LI (elemental composition of initial static leachate), LII (release percentages of in-
itial static leachate), LIII (elemental concentration of initial dynamic leachate), and LIV (EAFs
TABLE LI
ELEMENTAL COMPOSITION OF LEACHATES FROM STATIC LEACHING EXPERIMENT
WITH PLANT E ILLINOIS BASIN COAL
Experiment No. SCL - la
Leachate Concentration,
ug/g coal Element
> 500 Ca, Fe*
100 - 500
10 - 100 Na, Mg, Al*. Mn*. Ni*
< 10 K, Sc, V, Cr, Co, Cu, Zn, Ga, As,
Br, Rb, Ag, Cd, Sb, Ce, La, Sm, Eu,
Dy, Yb, Lu, Hf, Ta, W, Hg, Pb, Th, U
* Of environmental concern.
a Conditions: -20 mesh coal, unlimited air, room temperature.
b pH = 3.1.
67
-------
TABLE LII
RELEASE PERCENTAGES OF ELEMENTS DURING STATIC LEACHING EXPERIMENT
WITH PLANT E ILLINOIS BASIN COAL
,a
Experiment No. SCL - 1
% Release of Original
in Coal Element
*****
> 25 Ca, Mn , Co , Ni , Zn , Cd
10 - 25 Sm, Eu, Dy, U
1-10 Na, Mg, Sc, Fe, Yb, Lu, Pb
< 1 Al, K, V, Cr, Cu, As
* Of environmental concern.
a Conditions: - 20 mesh coal, unlimited air, room temperature.
b pH = 3.1.
TABLE LIII
ELEMENTAL COMPOSITION OF LEACHATES FROM CONTINUOUS LEACHING EXPERIMENT
WITH PLANT E ILLINOIS BASIN COAL
Experiment No. CL-73
Leachate Concentration
Leachate Element
> 500 Fe*
100 - 500 Al , Ca
10 - 100 Na, Mg, Mn*, Co*, Ni*, Zn*
10 K, Sc, V, Cr, Cu, Ga, As, Br,
Rb, As, Cd, Sb, Cs, La, Ce,
Sm, Eu, Dy, Yb, Lu, Hf, Ta, W,
Hg, Pb, Th, U
b pH = 2.2.
68
* Of environmental concern.
a Conditions: - 3/8-in. coal, 200 ml leachate, room temperature.
-------
TABLE LIV
ENVIRONMENTAL ACTIVITY FACTORS FROM CONTINUOUS LEACHING EXPERIMENT
WITH PLANT E ILLINOIS BASIN COAL
Experiment No. CL-7a
Leachate Environmental
Activity Factor Element
A * A *
> 25 Mn , Co , Ni , Zn , Cd
10 - 25 Mg, Ca, Fe , Cu , Sm
Eu, Dy, Th
1-10 Na, Sc, V, La, Ce
Yb, Lu, U
< 1 Al, K, Cr, Pb
* Of environmental concern.
a Conditions: - 3/8-in. coal,200 ml leachate, room temperature.
b pH = 2.2.
TABLE LV
TRACE ELEMENTS OF ENVIRONMENTAL CONCERN IN ILLINOIS BASIN PLANT E COAL
Element Static Leaching Dynamic Leaching
Al x x
Mn x x
Fe K x
Co x x
Ni x x
Zn x x
Cd x x
69
-------
of initial dynamic leachate). The elements that meet both the toxicity and leachability require-
ments in these four tables have been identified with an asterisk.
A single listing of the trace elements of greatest environmental concern in the Plant E coal ap-
pears in Table LV. A comparison of the information in this table with similar data in Table
XXXIX for the Illinois Basin refuse samples reveals that a nearly identical set of elements has
been identified as being of most environmental concern in the coal and refuse materials. From
this we conclude that the trace elements in crushed samples of both Illinois Basin coal and coal
refuse behave nearly identically when subjected to similar kinds of weathering and leaching.
Unfortunately, in our brief study, we did not learn a great deal about the identities of the
organic compounds released from the coal sample during aqueous leaching. As we reported
earlier, the total organic content of the coal leachates is on the order of 5 to 50 fig/ml of leachate.
How environmentally harmful this level of organic contaminants may be will depend upon the
nature of the individual constituents. Organic compounds vary widely in their known or suspec-
ted toxicity, carcinogenicity, etc. The question concerning organic contamination of coal
leachates will remain unanswered until a more detailed study of the various contaminants is
completed.
PERSONNEL
A large number of LASL personnel participated in the programmatic effort during the year.
Their work and contributions are gratefully acknowledged.
Administrative Advisors: R. D. Baker, R. J. Bard, and R. C. Feber
Analytical Advisors: G. R. Waterbury and M. E. Bunker
Neutron-Activation Analyses: W. K. Hensley
Atomic Absorption Spectrophotometry and Wet Chemistry:
E. J. Cokal, L. E. Thorn, and W. H. Ashley
Spectrochemical Analyses: 0. R. Simi, J. V. Pena, and D. W. Steinhaus
Electron and Ion Microprobe: W. F. Zelezny, N. E. Elliot,
W. B. Hutchinson, W. 0. Wallace, R. Raymond, and R. C. Gooley
X-ray Diffraction Analyses: R. B. Roof and J. A. O'Rourke
Optical and SEM Microscopy: R. D. Reiswig and L. S. Levinson
Mass Spectrometry: E. D. Loughran
Statistical Evaluation: R. J. Beckman
70
-------
APPENDIX A
STANDARD PROCEDURE FOR X-RAY MINERALOGICAL
ANALYSIS OF COAL AND WASTE MATERIALS
Standard minerals used for calibration were ground to -325 mesh by hand with a mortar and
pestle and were mixed with alumina as the internal standard. (Magnesium oxide was also an ac-
ceptable internal standard, except for reactive minerals like calcite, gypsum, and iron sulfate.)
Glass beads (—325 mesh) were used as diluent for the mineral standards. This provided a means
to measure the x-ray patterns of these materials over a range of concentrations. Typical mixtures
for instrument calibration contained 0.4000 g of alumina (20%) and 1.6000 g of mineral standard
plus diluent. The diluent/mineral mixtures were blended for several minutes on a wigglebug
before analysis.
Coal and waste samples were prepared for analysis by crushing them to —20 mesh. Where the
samples contained substantial amounts of carbon, they were ashed before analysis with a low-
temperature, oxygen plasma (LTA). The -20-mesh materials were further ground to -325
mesh, mixed with alumina (20 wt%), and blended on a wigglebug before analysis.
The powders were placed in the 2.22-cm- (7/8-in.-) diam by 0.15-cm- (1/16-in.-) deep cavity of
a 2.54-cm- (1-in.-) diam aluminum holder and pressed smooth with a glass plate. Before placing
the holder into the x-ray unit, each sample was glycolated for 1-1/2 h by placing it in a vessel con-
taining the saturated vapor from ethoxyethanol (monoethylglycol) at 50°C. After this treatment,
which was done to enhance some of the clay components, each sample was again pressed gently
into the holder with a glass plate and analyzed.
A Norelco-Philips diffractometer equipped with an x-ray generating source was used to
analyze the mineral contents of the powdered samples. The instrument was operated at 40 kV
and 20 mA, using a copper target. The diffractometer was driven at 1 degree/min from 29 = 4
degrees to IB = 60 degrees. The x-ray intensity response of the nonrotating sample was obtained
from a strip chart recorder. Noise levels and peak heights were then determined by visual inspec-
tion.
A computer program was used to determine the percentage of minerals in the coal and refuse
samples. This program employed second-degree equations for each mineral standard. Matrix
and equipment corrections were based on the internal standard. A correction for iron
fluorescence, and an estimate of the error in the mineral percentages based on noise level were
also obtained by computer calibration.
71
-------
APPENDIX B
(1)
SUMMARY OF LASL COAL AND REFUSE SAMPLE ANALYSES
9-30-77
(2)
LOCALE
IDENTITY
PLANT A
A
A
A
A
A
A
A
A
A
A
A
PLANT B
B
B
B
B
B
B
B
B
B
B
B
PLANT C
C
C
C
C
C
C
C
C
PLANT E
E
E
TOTAL
FEED COAL A
FEED COAL B
CLEAN COAL
GOB A-FRESH
GOB B-FRESH
GOB C -FRESH
GOB D-FRESH
GOB E-FRESH
GOB A,C,E AVE
GOB OCCAS LG PC
GOB 1Y TOP 3IN
GOB 1Y 24IN BELO SURF
FEED COAL
PRODUCT COAL-FINE CUT
PRODUCT COAL-COARSE CUT
GOB A FRESH-DUMPED
GOB B FRESH-DUMPED
GOB C FRESH-DUMPED
GOB A,B,C AVE
GOB A TYPE 2
GOB B TYPE 2
DRY STREAM AT 8Y GOB PILE
GOB PILE-8Y AT FOOT
SLURRY POND
FEED COAL A
FEED COAL B
FEED COAL TYPE 2
GOB A COARSE-FRESH
GOB B COARSE-FRESH
GOB C COARSE -FRESH
GOB A,B,C, AVE
GOB FINE-FRESH
GOB VERY FINE-FRESH
FEED COAL A
FEED COAL B
FEED COAL A,B AVE
NUMBER OF SAMPLES = 36
28KG
30KG
6KG
65KG
73KG
71KG
73KG
70KG
20KG
31KG
37KG
30KG
29KG
29KG
47KG
49KG
51KG
61KG
54KG
10KG
16KG
10KG
30KG
34KG
33KG
51KG
59KG
55KG
48KG
24 KG
38KG
41KG
FOOTNOTES
(3)
SIZE
2BKG
30KG
6KG
65KG
73KG
71KG
73KG
70KG
20KG
31KG
37KG
30KG
29KG
29KG
47KG
49KG
51KG
61KG
54KG
10KG
16KG
10KG
30KG
34KG
33KG
51KG
59KG
55KG
48KG
24 KG
38KG
41KG
SAMPLE
13
14
15
25
11
12
10
28
25A
16
8
9
30
31
29
24
17
23
24A
26
27
5
6
4
32
33
35
18
21
22
ISA
20
19
36
37
36A
LTA
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
CRN
ANAL
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
NA
NA
NA
MINE-
RALOGY
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
TRACE
ELEMENTS
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
FLOAT
SINK
NA
NA
NA
NA
NA
NA
NA
NA
YES
NA
NA
NA
NA
NA
NA
NA
NA
NA
YES
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
YES
NA
NA
NA
NA
NA
(1) YES=ANALYSIS DONE, NA=NO ANALYSIS IS TO BE DONE
(2) DESIGNATIONS A,B,C, ETC INDICATE THE ORDER IN WHICH SAMPLES WERE COLLECTED: A, FIRST;
B, SECOND; ETC. Y=AGE OF MATERIALS IN YEARS
(3) SAMPLE WEIGHTS IN KILOGRAMS; SAMPLE PARTICLE SIZE IN MINUS(-) OR PLUS(t) MESH (SAMPLE 7)
AND INCHES (ALL OTHERS); -1 ID INDICATES MINUS 1 INCH IN ONE DIRECTION AND -2 INCHES IN
THE OTHERS
-------
SAMPLE
13
TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE MATERIALS
FOR ILLINOIS BASIN PLANT A SAMPLES
14 15 16
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PC T OR I GN L
SIZE, KG
FED COAL A
PLANT A
11/18/75
7. 00
40. 57
30. 18
100. 00
27. 70
FED COAL B
PLANT A
11/18/75
4. 42
38. 67
29. 44
100. 00
29. 60
CLN COAL
PLANT A
11/18/75
6. 77
18. 49
9. 47
100. 00
6. 00
GOB LRG
PLANT A
1. 67
96. 11
100. 00
19. 70
GOB TP3 1Y
PLANT A
11/18/75
12. 24
85. 20
71.50
100. 00
31. 20
GOB D24 1Y
PLANT A
11/18/75
6. 43
83.90
74. 10
100. 00
37. 40
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
52. 20
4. 02
1.05
3. 11
RAW BASIS
51.00
4. 12
1. 03
4. 27
RAW BASIS
66. 20
5. 36
1. 48
2.84
RAW BASIS
7. 50
. 81
. 12
RAW BASIS
•12.61
1. 42
. 28
6.99
RAW BASIS
13. 55
1. 40
. 28
10. 60
MINERALOGY
RAW BASIS
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASnE
GYPSUM
ROZ EN IT E
ALBITE
8.74
10. 27
11. 77
6. 63
5.55
. 36
RAW BASIS
10. 19
11. 08
6. 37
9. 56
1. 95
RAW BASIS
21. 17
13. 45
21. 16
17. 24
27. 73
1. 67
2.15
.78
RAW BASIS
8. 84
15. 93
27. 77
6. 38
2. 00
11. 75
4.95
8. 25
RAW BASIS
9. 88
15. 46
26. 05
15. 00
1. 26
12. 66
4. 01
-------
SAMPLE
13
14
15
16
ELEMENT
RAW BASIS
(2)
LI PPM
BE PPM
B PPM
F PPM
NA PCT
MG PCT
AL PCT
SI PCT
P PPM
CL PPM
K PCT
CA PCT
SC PPM
TI PCT
V PPM
CR PPM
MN PPM
FE PCT
CO PPM
NI PPM
CU PPM
ZN PPM
GA PPM
GE PPM
AS PPM
SE PPM
BR PPM
RB PPM
t PPM
ZR PPM
MO PPM
AG PPM
CD PPM
SN PPM
SB PPM
CS PPM
LA PPM
CE PPM
SM PPM
EU PPM
TB PPM
DY PPM
ffi PPM
LU PPM
HP PPM
TA PPM
W PPM
HG PPM
PB PPM
TH PPM
U PPM
H A
H A
L E
R 0
H A
H A
H A
R 0
R 0
R N
H A
H A
R N
R N
R N
H A
H A
H A
R N
L E
H A
H A
H N
L E
R N
R N
R N
R N
L E
L E
L E
R N
H A
L E
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
H A
R 0
R 0
53. 00
3.30
73.00
250. 00
.07
.21
2.90
6. 25
330. 00
40. 00
.53
1.55
8.80
. 21
69. 00
40.00
132. 50
2.43
15. 00
34. 00
56. 00
130. 00
14. 00
6.90
30. 00
5.00
. 30
94. 00
15. 00
65.00
10. 00
.20
-5. 00
1.00
3. 20
31. 00
61. 00
5.60
1.10
1.00
4.00
2.80
.39
1.90
.80
.50
20. 00
7.30
3.60
RAW BASIS
32. 00
3. 10
56. 00
300.00
. 05
. 14
3.30
6. 62
680.00
39. 00
. 56
. 55
8. 00
. 21
69. 00
35. 00
75. 00
3. 17
13.00
30. 00
24. 00
4B. 00
15. 00
11.00
20. 00
4. 00
66. 00
14. 00
61. 00
14.00
. 30
-5.00
-1 . 00
4. 20
29. 00
55. 00
4. 60
.90
4. 10
2. 20
. 28
1. 60
21.00
6. 50
3. 80
RAW BASIS
16.00
3. 40
46.00
84.00
.05
1.
1,
135.
69
00
66. 00
. 10
. 15
5. 10
. 08
51. 00
30. 00
31. 50
1.43
9. 00
18. 00
45. 00
220. 00
7. 00
11. 00
10.00
4.00
1. 50
77.00
9. 00
28. 00
8. 00
. 20
-3 . 00
1. 00
30
11.00
23.00
1. 70
2.10
1. 50
. 17
1. 10
11. 00
2. 90
2. 10
RAW BASIS
33.00
53. 00
290. 00
. 10
. 54
6. 70
13. 20
600. 00
1. 42
11.12
9. 90
. 47
47. 00
56. 00
573.50
7. 14
10. 00
24. 00
39. 00
34.00
19. 00
3. 80
23. 00
4. 20
210. 00
39. 00
180. 00
13. 00
. 19
-9. 00
7. 00
40. 00
84. 00
6. 60
1. 30
5. 20
2. 00
. 40
3. 10
27. 00
10. 80
3. 20
RAW BASIS
27. 00
1. 70
63. 00
1140. 00
. 14
. 36
7. 00
16. 30
970.00
1. 45
. 75
9. 10
. 35
72. 00
87. 00
237. 50
6. 84
3. 40
20. 00
16. 00
69. 00
18. 00
-9. 00
16. 00
10. 00
64. 00
18. 00
95. 00
29. 00
1.40
. 10
-9. 00
1. 40
5. 30
46. 00
86.00
4. 70
.99
4. 10
1. 80
. 47
3. 20
.40
6. 00
32. 00
10. 00
9. 80
RAW BASIS
27. 00
1. 30
65. 00
691.00
. 14
. 44
6. 40
15. 80
12. 00
24. 00
1. 30
1.91
10. 00
. 42
72. 00
85. 00
442. 00
8. 91
13. 00
46. 00
34. 00
81.00
20. 00
-8. 00
35. 00
6. 80
100. 00
23. 00
100. 00
35. 00
2. 70
. 50
-8.
2.
5.
. 70
10
39. 00
77. 00
7. 30
1.10
4. 90
2. 30
. 41
3. 10
. 75
36. 00
10. 00
5. 40
-------
SAMPLE
25
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
GOB A
PLANT A
11/18/75
5.91
85.46
78. 70
100. 00
64. 70
TRACE ELEMENT AND MINERAL CONTENT OF COAL HASTE MATERIALS
FOR ILLINOIS BASIN PLANT A SAMPLES
11 12 10 28
GOB B FRSH
PLANT A
11/18/75
6. 09
85. 70
73. 60
100. 00
73. 20
GOB C FRSH
PLANT A
11/18/75
6. 15
80. 78
69. 00
100. 00
70.70
GOB D FRSH
PLANT A
11/18/75
6. 23
84. 87
73.60
100. 00
72. 90
GOB E
PLANT A
11/18/75
6. 17
86. 04
76.70
100. 00
70 . 20
CHNS ANAL
CARBON
HYDROGEN
N IT ROGE N
SULFUR
RAW BASIS
14. 60
1.25
. 31
8.28
RAW BASIS
14.10
1.28
. 31
10. 86
RAW BASIS
17. 30
1. 47
. 39
10.41
RAW BASIS
13.70
1.11
. 30
9.16
RAW BASIS
13. 20
1. 25
. 27
6.62
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
RAW BASIS
13. 74
12. 82
21. 20
14. 49
10. 39
4. 64
9.03
2.60
RAW BASIS
14. 52
12. 12
20. 40
15. 79
5. 22
3.47
13.68
2. 25
RAW BASIS
13. 44
10. 78
18. 24
14.71
2. 38
9. 53
11. 57
2. 22
RAW BASIS
16. 02
15. 36
22. 27
13. 52
1. 36
7. 96
9. 68
1.80
RAW BASIS
15. 36
19. 48
25. 64
12.72
5. 24
6. 39
2. 97
-------
SAMPLE
25
11
ELEMENT
LI PPM
BE PPM
B PPM
F PPM
NA PCT
MG PCT
AL PCT
SI PCT
P PPM
CL PPM
K PCT
CA PCT
SC PPM
TI PCT
V PPM
CR PPM
MN PPM
FE PCT
CO PPM
NI PPM
CU PPM
ZN PPM
GA PPM
GE PPM
AS PPM
SE PPM
BR PPM
RB PPM
Y PPM
ZR PPM
MO PPM
AG PPM
CD PPM
SN PPM
SB PPM
CS PPM
LA PPM
CE PPM
SM PPM
EU PPM
TB PPM
D¥ PPM
YB PPM
LU PPM
HF PPM
TA PPM
W PPM
HG PPM
PB PPM
TH PPM
U PPM
H A
H A
L E
R O
H A
H A
H A
R 0
R O
R N
H A
H A
R N
R N
R N
H A
H A
H A
R N
L E
H A
H A
R N
L E
R N
R N
R N
R N
L E
L E
L E
R N
H A
L E
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
H A
R O
R O
(2)
RAW BASIS
36. 00
67. 00
666. 00
.10
.44
6.90
13. 44
2500. 00
20. 00
1.15
6.31
11. 20
. 42
72. 00
54.00
418.50
7. 20
20. 00
50. 00
51.00
78.00
17. 00
5.10
51. 00
9.20
100. 00
40. 00
160.00
11. 00
.25
-9.00
1.40
6.00
42. 00
83. 00
7.20
1.30
5.80
2.70
. 40
3.00
60. 00
11.60
6.80
RAW BASIS
55. 00
55. 00
400. 00
. 10
. 36
6.50
13. 14
1100. 00
1.05
4.50
11.60
. 44
74.00
57. 00
313.00
9.40
20. 00
43. 00
55. 00
93. 00
17. 00
3.90
65. 00
11.00
130.00
30.00
140. 00
14.00
. 30
-8.00
4.50
41.00
7.60
1.60
6. 20
3.30
. 40
3. 50
-1.00
50. 00
12.00
4.60
12
RAW BASIS
55. 00
64. 00
620. 00
. 10
. 34
6. 90
13.50
2500. 00
1. 04
2. 84
11.60
. 47
78.00
52. 00
235. 00
8. 90
18.00
48.00
51.00
74 . 00
16.00
4. 30
53.00
6. 50
180. 00
39.00
160.00
16.00
. 20
-8. 00
1. 50
6. 80
47. 00
90. 00
7. 50
1. 50
6. 10
3.70
. 40
3. 30
46. 00
11. 50
8. 20
10
RAW BASIS
59. 00
54. 00
733. 00
. 12
. 40
7. 40
15. 14
330k). 00
37. 00
1. 33
2. 41
13. 40
. 50
87.00
70.00
233.50
8. 40
18.00
40.00
52. 00
92.00
23.00
4.80
50. 00
11. 00
220. 00
30.00
130.00
12.00
. 30
-8. 00
1. 50
6. 40
45. 00
100.00
6. 80
1. 70
7. 30
3. 30
. 50
3. 60
3. 00
50. 00
12. 80
7. 40
28
RAW BASIS
51. 00
70. 00
730. 00
. 11
. 51
7. 30
16. 40
2300. 00
32.
1.
4.
13.
.00
19
25
10
. 47
81.00
66. 00
304.00
6. 24
19. 00
37. 00
52. 00
79. 00
22.00
7. 60
60. 00
8.80
250. 00
36. 00
160. 00
8. 10
. 16
-9. 00
7. 10
49. 00
98. 00
8. 10
1. 70
6.60
2. 40
. 50
3. 70
38. 00
13. 20
6. 90
-------
SAMPLE
30
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H2O
PCT LTA
PCT HTA
PCT ORIGNL
SIZE,KG
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
FEED COAL
PLANT B
11/19/75
4.07
28. 25
18. 81
100. 00
38. 00
RAW BASIS
59. 20
4.49
1.25
3.92
0 A fJ D &C T C
KHW DriDlD
4.61
5.82
5.09
5.31
2.48
1.03
TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE MATERIALS
FOR ILLINOIS BASIN PLANT B SAMPLES
31 29 24 17
FN COL PRD
PLANT B
11/19/75
9. 38
24.42
14. 06
100. 00
28.80
RAW BASIS
64.30
4.67
1.33
3.08
RAW BASIS
4. 21
4.-41
3.03
4.85
.58
2. 19
.11
CORS COL P
PLANT B
11/19/75
5. 32
21. 34
10.76
100.00
29. 50
RAW BASIS
66. 40
4. 81
1.34
2.61
RAW BASIS
3.69
3.51
2. 21
4.01
.90
1.46
. 06
GOB A
PLANT B
11/19/75
9. 62
79. 80
64. 20
100. 00
46. 60
RAW BASIS
18. 80
2. 20
.42
14. 30
RAW BASIS
7. 16
10. 40
19. 02
13. 61
18.76
9. 75
1. 10
GOB B
PLANT B
11/19/75
10. 35
77.
61.
. 41
. 30"
100. 00
49. 10
RAW BASIS
21
2
40
30
45
14.70
RAW BASIS
6. 38
12. 77
13.90
19.98
11.94
11. 19
1. 25
23
GOB C
PLANT B
11/19/75
10. 38
79.84
65.20
100. 00
50. 60
RAW BASIS
19.
2.
30
20
. 42
11. 40
RAW BASIS
7. 18
8. 54
18. 56
12. 43
21. 10
11. 09
.94
-------
SAMPLE
ELEMENT
(2)
LI PPM H A
BE PPM H A
B PPM L E
F PPM R O
NA PCT H A
MG PCT H A
AL PCT H A
SI PCT R O
P PPM R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
NI PPM L E
'C(J PPM H A
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L E
AG PPM R N
CD PPM H A
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM HA
TH PPM R O
n POM R n
30
RAW BASIS
19. 00
1.50
53. 00
151 . 00
.03
.09
2.10
3.92
320. 00
120. 00
.40
.05
5.70
. 13
44. 00
27. 00
39. 00
2.57
10. 00
20. 00
11. 60
43. 00
9. 00
3.60
22. 00
2.50
69. 00
8.20
48. 00
6.80
.12
-4.00
1.50
2.90
15. 00
28. 00
2.30
. 50
2.10
1.40
. 14
1 .40
.80
.60
13. 00
3.10
1 1 0
31
RAW BASIS
15. 00
1.
51.
60
00
133. 00
. 03
. 07
. 50
52
1
2
280.00
160. 00
. 30
. 06
4. 50
. 10
40. 00
149.00
107. 50
1.82
9. 00
16. 00
64
00
183.00
8. 00
5. 20
8. 00
3. 00
2.50
45. 00
6.80
43. 00
5. 00
. 08
-3. 00
-1.00
12.00
19. 00
1.60
. 40
1. 40
. 90
. 10
1. 10
. 60
. 60
12.00
2. 50
29
RAW BASIS
8.00
1. 40
58. 00
130.00
. 02
.05
1. 30
1.99
270.00
11.00
. 24
.08
4. 10
. 08
29. 00
30. 00
33. 00
1.
24
17
23
RAW BASIS
. 25
7. 00
9. 50
31. 00
100.00
00
80
00
00
50
20. 00
5. 10
27. 00
3.70
. 13
-4 . 00
-1.00
6. 00
17.00
1. 30
. 30
.40
1. 10
. 10
1. 10
7. 00
2. 20
. 70
52.
2.
64 .
. 00
. 80
. 00
346. 00
. 07
. 21
5. 03
13. 20
42.
1.
13.
00
07
10
00
. 33
78. 00
56. 00
143.50
12. 80
35. 00
73. 00
32. 40
117.00
-8. 00
130. 00
2.
81.
15.
82.
57.
-a'.
1.
7.
43.
88.
7.
00
00
00
00
00
40
35
00
70
10
00
00
00
1. 40
2. 50
. 47
3.70
.94
31. 00
11. 00
•).. 70
RAW BASIS
58. 00
2
63
40
00
366.00
.08
. 24
4. 94
12.90
53. 00
1. 07
. 09
11.00
. 36
85. 00
59. 00
130. 00
10.80
30. 00
73. 00
35. 00
197.00
-8. 00
89. 00
5. 80
2. 00
97. 00
17. 00
80 . 00
53. 00
. 50
. 50
-8. 00
1. 30
5.80
31. 00
61.00
4. 80
1. 00
4. 40
2. 80
. 37
2. 40
.78
36. 00
8. 40
?.. 70
RAW BASIS
47. 00
3. 10
65. 00
410. 00
. 09
. 31
5. 29
14. 60
76.00
1. 21
. 13
12. 00
. 36
95. 00
72.00
159. 50
9. 30
25. 00
68. 00
38. 80
133. 00
-8.
64.
4.
2.
110.
21.
100.
47.
-8.
1.
6.
37.
71.
5.
00
00
80
00
00
00
00
00
60
39
00
10
80
00
00
90
1. 30
4. 30
4. 40
. 38
3. 30
1. 10
34. 00
9. 10
2. 7M
-------
SAMPLE
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
26
GOB A
PLANT B
11/19/75
6.01
88.44
69.50
100.00
60. 90
TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE MATERIALS
FOR ILLINOIS BASIN PLANT B SAMPLES
27 5 6 4
GOB B
PLANT B
11/19/75
4.77
90
71
58
24
100. I
54. :
DRY STM 8Y
PLANT B
11/19/75
7.83
68.58
56.50
100. 00
9. 50
GOB PIL 8Y
PLANT B
11/19/75
7.83
79. 90
67. 40
100. 00
16.30
SLURY POND
PLANT B
11/19/75
22. 10
69.37
58. 10
100. 00
9. 70
7A
GOB/WH -6
PLANT B
11/19/75
1. 60
. 40
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
10. 70
1.37
. 22
21. 40
RAW BASIS
11.00
1.25
. 25
16. 00
RAW BASIS
17.00
2. 12
. 56
3. 95
RAW BASIS
13.70
1. 34
. 31
14. 10
RAW BASIS
22. 54
1. 88
. 47
11. 10
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
RAW BASIS
9.89
12. 43
17. 22
23. 47
6.32
15. 10
4.01
RAW BASIS
9. 80
9.04
21. 47
24. 00
7. 26
16. 95
2.06
RAW BASIS
10.81
9. 64
24.25
1. 50
20.54
RAW BASIS
6. 30
6. 89
15.19
11. 01
13. 75
10. 24
4. 03
RAW BASIS
8.96
9. 39
19. 52
17. 12
5.92
8. 01
2. 08
-------
SAMPLE
26
27
ELEMENT
B
F
NA
LI PPM
BE PPM
PPM
PPM
PCT
MG PCT
AL PCT
SI PCT
P PPM
CL PPM
K PCT
CA PCT
SC PPM
TI PCT
V PPM
CR PPM
MN PPM
FE PCT
CO PPM
NI PPM
CU PPM
ZN PPM
GA PPM
GE PPM
AS PPM
SE PPM
BR PPM
RB PPM
Y PPM
ZR PPM
MO PPM
AG PPM
CD PPM
SN PPM
SB PPM
CS PPM
LA PPM
CE PPM
SM PPM
EU PPM
TB PPM
DY PPM
YB PPM
LU PPM
HP PPM
TA PPM
W PPM
HG PPM
PB PPM
TH PPM
U PPM
H A
H A
L E
R 0
H A
H A
H A
R 0
R O
R N
H A
H A
R N
R N
R N
H A
H A
H A
R N
L E
H A
H A
R N
L E
R N
R N
R N
R N
L E
L E
L E
R N
H A
L E
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
H A
R 0
R 0
(2)
RAW BASIS
18. 00
1.80
85.00
540. 00
.10
.18
5.90
10. 98
1625. 00
30. 00
.97
.92
8.10
. 33
39. 00
41.00
159.00
17. 43
25. 00
71. 00
35.00
103.00
13.
-9.
. 00
.00
30. 00
6.00
250. 00
19.00
110 .00
42. 00
-9
-1
4
33
83
7
.41
90
00
1.60
. 60
5. 20
2.40
. 40
80
40
2.
7.
3.00
48.00
9. 80
2 .40
RAW BASIS
35. 00
1. 80
85. 00
570.00
.06
. 20
6. 60
13. 98
1630.00
20. 00
1.16
. 61
9.90
. 31
38. 00
47. 00
156. 50
12.97
20. 00
61. 00
35.00
72. 00
15.00
-9.00
20.00
5.00
230. 00
18. 00
120.00
40. 00
. 61
-9. 00
-1.00
6. 20
43. 00
96.00
8.10
1. 70
. 70
4. 80
2. 60
. 39
3.90
1. 10
. 60
19. 00
12. 00
2. 80
RAW BASIS
34. 00
1. 60
83.. 00
341.00
. 10
.14
6. 40
15.80
410.00
59.00
.90
.08
6.90
. 41
54. 00
75.00
37. 00
2.84
.94
9. 40
11.00
20.00
16. 00
-7.00
15.00
6. 00
. 86
93 . 00
11. 00
64.00
24.00
1.40
-. 10
-7.00
1. 70
5. 60
45.00
80.00
4. 40
. 78
2. 20
1. 70
. 30
3.90
.60
20. 00
7. 00
2. 60
RAW BASIS
54. 00
.90
80 . 00
790.00
.09
. 14
5.90
15. 20
12.00
1.01
. 45
6. 40
. 40
46. 00
67.00
119. 00
10 . 30
2. 10
13. 00
13.00
27.00
6.60
-8.00
15. 00
5.80
110. 00
12.00
77.00
39.00
5.80
. 10
-8.00
1. 50
3.70
49.00
81 .00
4.60
.79
2. 50
1. 60
. 31
3.40
. 60
22.00
8. 60
4 . 80
RAM BASIS
21.00
1.90
57. 00
400.00
. 06
. 20
5. 30
11. 30
10. 00
57. 00
.89
. 46
7. 40
. 26
61.00
62.00
213. 00
10. 10
21. 00
80. 00
62. 00
197. 00
18. 00
-7. 00
72.00
7. 50
2. 50
150. 00
15. 00
78.00
27. 00
3. 90
. 70
-7. 00
, 40
. 00
2.
4.
25. 00
55. 00
4. 40
.88
3. 30
1. 40
. 27
3. 40
. 44
4. 00
37. 00
7. 90
3. 90
7A
RAW BASIS
.04
39. 00
. 27
3. 80
. 13
22. 00
77.00
6. 40
9. 70
76.00
6. 10
150. 00
2. 20
12. 00
23.00
2. 00
. 35
1. 60
. 70
. 21
.89
. 11
3. 50
1. 60
-------
00
N)
TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE MATERIALS
FOR ILLINOIS BASIN PLANT C SAMPLES
33 34 35 1H
(11
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
RAW COAL A
PLANT C
11/20/75
3.75
29. 98
25. 15
lee. 00
3d. 20
RAW COAL B
PLANT C
11/20/75
3. 59
37. 35
32. 79
188.88
34. 50
CLEAN COAL
PLANT C
11/28/75
4. 06
U. 45
10.61
100. 00
27. 20
COAL TYP 2
PLANT C
11/20/75
3. 92
35. 6B
31 .08
108. 00
32.60
GOB A CORS
PLANT C
11/20/75
3. 26
92.97
BO. 10
100. 00
51. 10
GOB 8 CORS
PLANT C
11/20/75
3. 88
90. 56
76. 30
100. 08
50. 48
GOB C CORS
PLANT C
11/20/75
2.92
91 .85
83. 80
100.00
54. 90
FN GOB
P LANT C
11/20/75
7.92
84. 39
71. 78
100. 00
48. 10
GOB V FINE
11/20/75
79. 80
180. 00
23.70
CHW3 ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
54. 08
4. 18
1.00
6.43
RAW BASIS
49. 10
3. 81
.83
4.05
67.98
5. 24
1.23
3. 55
52. 28
3. 94
1. 01
3. 95
RAW BASIS
7. 20
. 19
10. 31
RAW BASIS
9. 48
1. 05
. 25
15. 13
RAW BASIS
8. 38
1. 37
. 24
12. 14
RAW BASIS
13. 50
1. 55
. 29
12. 81
RAW BASIS
17. 70
1. 41
. 36
7. 93
MINERALOGY
RAW BASIS
KAOLINITE
11,LITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCAS ITE
GYPSUM
ROZENITE
ALBITE
5.04
4.88
5.75
9.81
.74
. 50
3.18
RAW BASIS
7. 83
8.92
11.89
7. 42
. 57
1.15
2.95
. 77
2. 81
3. 57
4.82
.87
. 32
1. 79
4.05
13. 35
6.63
5.87
2.42
. 59
1.78
15. 36
15. 39
24. 01
17.94
1. 31
14. 26
5. 14
14. 12
14.98
28. 02
26. 43
2. 27
11.37
1. 38
RAW BASIS
13. 45
16. 89
24.83
20. 43
6.94
9. 30
RAW BASIS
10. 18
13. 84
22. 56
22. 19
4. 79
8. 62
2. 17
RAW BASIS
10. 47
15. 93
21. 91
14. 77
2.53
8. 78
5.74
. 56
-------
SAMPLE
ELEMENT
(21
LI PPM H A
BE P PM H A
B PPM L E
F PPM R 0
NA PCT H A
MG PCT II A
AL PCT H A
SI PCT R 0
P PPM R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN em H A
Ffi PCT H A
CO PPM R N
HI P PM L E
CU PPM H A
ZN PPM II A
GA PPM H N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
1 PPM L E
ZR PPM I. E
MO PPM L E
AG PPM H N
CO PPM H A
S N P PM L E
SB PPM R N
CS PPM R N
LA P(tl R N
C E P PM R N
SM PPM R N
EU PPM R N
TB PP» R N
DY PPM H N
IB PPM R N
LU P PM R N
HF PPM R N
TA PPM R N
VI PPM R N
IIG PPM R N
PB PPM II A
TH PPM R 0
U PPM R 0
32
RAM BASIS
9. 00
2. 10
68. 00
232. 80
.12
.11
2. 10
5.03
4 90 . 11 6
4ee.ee
.43
.45
5. 30
. 14
34.00
60. 08
118.50
4 . 33
11. 00
21. 00
44. 00
153.00
9. 00
4. 50
9.00
4.00
3.50
100. 00
9.60
54. 00
17. 80
.17
-4.00
1.70
4.00
17.00
33. 80
2.40
. 5B
1.80
1.00
. 20
1. 30
. 30
13. 00
4.30
1.60
18. 00
2. 00
72. 00
340.00
. 17
. 13
3.60
B. 02
615.00
310.00
. SB
. 52
7.80
. 24
41.00
30.00
63. 50
2. 60
17. 00
29. 00
40. 00
200.EH
13. 00
4. 80
10.00
3. 00
3. 00
60. 00
9. 10
50. 110
16. 00
. 09
-4.00
1.00
5. 00
31.00
60.00
4 .80
1. 40
2.90
1.50
. 26
2.90
1. 00
1 .20
18. 00
B. 00
2. 10
13.08
1.70
37. 00
164.00
.04
. 06
I/. 00
2. 29
270.00
490. 00
. 21
. 13
3.80
. 07
30. 00
30. 00
31 . 50
1. 44
7. 00
9. 80
32. 00
160. 00
7. 80
5.28
5.00
4.00
46.00
5. 50
25.00
. 16
-2 .00
13.00
1. 30
. 20
1. 10
.90
. 12
. 60
. 40
. 50
9.00
2. 20
1. 40
14.00
1. 50
62.00
282.00
. 15
. 33
2. B0
6. 90
455.00
450.00
. 79
. 89
6. 88
. 15
100.00
73. 00
267. 00
3. 21
9. 00
26. 00
31 . 00
180.00
13. 00
4. 90
15.00
7.00
4. 50
22.00
10. 00
58. 00
25.00
2. 10
-4 . 00
2. 70
3. 20
20.00
38. 00
3. 20
. 60
. 70
2. 00
1. 30
. 23
1. 50
1. 26
15 00
5. 90
4. 20
18
RAH BASIS
22.00
80 . 00
1580. 00
. 37
33
8. 70
17. 40
5800. 00
90 . 00
1. 52
1. 51
12. 10
. 54
85 . 00
80. 00
124. 50
8. 90
32.00
80 .00
44. 00
228.00
16. 00
6 . 40
23.00
9. 60
260. 00
32. 00
130. 00
13.00
1. 30
-9. 00
1. 20
7.40
56. 00
10 0. 00
8. 80
1. 60
6. 30
1. 90
. 40
3. 80
1. 00
54.00
IS. 50
9. 90
21
RAH BASIS
16.
68.
1670.
6.
15.
00
00
00
26
22
10
20
7300. 00
86.
1.
10.
62.
60.
181.
10.
27.
52.
27.
76.
14.
4.
26.
9.
300
28.
120.
14.
1
-9
1
9
42
97
-)
1
5
2
3
1
56
12
12
00
99
71
60
44
00
00
00
15
00
00
00
00
00
20
.00
50
. 00
00
. 00
. 00
. 10
. B0
. 30
. 00
. 00
. 00
. 00
. 50
. 20
. 50
. 40
. 70
. 20
. 00
. 20
. 90
22
RAW BASIS
13.00
84 . 08
1130. 00
. 32
. 28
8. 30
17.07
4300.00
88.00
1. 30
1.02
10.70
. 4fl
68. Be
64. HO
125. 50
10. 11
31 .01)
75. 08
37. 08
57. 08
15.00
5.00
20.00
7. 00
210. 00
24. 00
120. 00
14. 00
. 51
-9. 00
1. 18
6. 70
47. 00
92.08
6. 90
1. 40
4. 70
2. 20
. 48
4 . 60
. 90
59.00
13.80
7. 40
20
RAW BASIS
7.
78.
936.
e!
15.
2800.
110.
1.
1.
IB.
68.
63.
149.
IB.
21.
45.
41.
160.
21.
6.
IB.
6.
250.
26.
130.
13.
1.
-8.
\
9.
39.
76.
6.
1.
4.
1.
3.
00
00
00
27
36
60
06
00
00
50
42
40
40
00
BB
50
>.«
00
08
00
00
00
20
00
V
00
00
00
08
50
00
90
10
00
08
] 0
40
90
80
30
30
19
RAW BASIS
16. 00
87. 00
970. 00
. 30
. 40
7. 10
16. 34
2780. 00
170, 08
1. 64
1. 53
12. 40
. 46
80 . 00
78.00
161. 50
6. 57
22. 00
41. 00
44. 00
103. 00
20. 00
5. 30
21.00
8.80
270. 80
28. 00
130. 00
8. 18
1 . 20
-8 . 00
1. 28
7. 80
42. 80
81.80
7. 10
1. 40
6. 00
3.70
. 30
4. 00
49. 00
10. 00
5. 70
33.00
10. 80
5. 70
-------
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
P Y RIT E
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE MATERIALS
FOR ILLINOIS BASIN PLANT E SAMPLES
SAMPLE
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE,KG
(1)
36
FED COAL A
PLANT E
06/22/76
5.46
24.73
100. 00
39. 90
37
FED COAL B
PLANT E
06/22/76
4. 42
25. 36
100. 00
43.30
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
5.27
RAW BASIS
5.81
-------
SAMPLE
36
37
ELEMENT
B
F
NA
LI PPM
BE PPM
PPM
PPM
PCT
MG PCT
AL PCT
SI PCT
P PPM
CL PPM
K PCT
CA PCT
SC PPM
TI PCT
V PPM
CR PPM
MM PPM
FE PCT
CO PPM
NI PPM
CU PPM
ZN PPM
GA PPM
GE PPM
AS PPM
SE PPM
BR PPM
RB PPM
Y PPM
ZR PPM
MO PPM
AG P'PM
CD PPM
SN PPM
SB PPM
CS PPM
LA PPM
CE PPM
SM PPM
EU PPM
TB PPM
DY PPM
YB PPM
LU PPM
HF PPM
TA PPM
W PPM
HG PPM
PB PPM
TH PPM
U PPM
H A
H A
L E
R 0
H A
H A
H A
R 0
R 0
R N
H A
H A
R N
R N
R N
H A
H A
H A
R N
L E
H A
H A
R N
L E
R N
R N
R N
R N
L E
L E
L E
R N
H A
L E
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
H A
R O
R 0
(2)
1
1
310
RAW BASIS
65. 00
20. 00
70.00
80. 00
.03
.06
82
40
00
77. 00
.26
.15
4.53
.08
37. 00
30.00
42. 10
3.90
13. 50
42. 00
38. 00
32. 00
-8. 00
24. 20
16. 00
37. 00
55. 00
25. 00
.21
-8.00
. 79
2.37
22. 10
34. 30
2.27
.91
3.10
3.08
.17
.35
11. 00
3. 39
2.47
RAW BASIS
63. 00
22.00
62. 00
60.00
. 03
. 05
1.81
2. 50
260. 00
123.00
. 23
. 21
4.81
. 10
49. 70
21. 00
58. 15
4.70
13.30
26. 00
33. 00
22.00
5.52
-7. 00
43. 00
41. 00
29.00
39. 00
16. 00
. 15
-7.00
1.38
18. 60
30. 50
2.48
. 73
3. 80
1.10
. 24
1. 26
11. 00
3.52
2.64
oo
V/l
FOOTNOTES
(1) PLUS OR MINUS INDICATES SIZE GREATER OR LESS THAN SIZE GIVEN.
NUMBERS 6 OR LARGER ARE MESH SIZES, OTHERS ARE IN INCHES
(2) LETTERS INDICATE HOW SAMPLE WAS PREPARED AND ANALYZED
R= RAW SAMPLE
L= LOW TEMPERATURE ASH
H= HIGH TEMPERATURE ASH
N= NEUTRON ACTIVATION ANALYSIS
A= ATOMIC ABSORPTION
E= EMISSION SPECTROSCOPY
0= OTHER
-------
APPENDIX C
SUMMARY OF LASL SIZED-COAL REFUSE SAMPLE ANALYSES
9-30-77
(1)
(2)
(3)
LOCALE^
PLANT A
A
A
A
A
PLANT B
PLANT C
C
C
C
C
C
C
C
C
C
C
C
C
IDENTITY
GOB A,C,E AVE
GOB A,B,C AVE
GOB A,B,C AVE
GOB FINE-FRESH
GOB VERY FINE-FRESH
SIZE
-1/4
-1
-1 ID
+ 2
-1/4
-1
-1 ID
-2
+2
-1/4
-1
-1 ID
-2
+ 2
-1/4
-1
-1 ID
-2
-1/4
-1
-1 ID
-2
SAMPLE LTA
CHN
ANAL
MINE-
RALOGY
25B
25C
25D
25E
25F
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
24B
24C
24D
24E
24F
18B
18C
18D
18E
18F
20B
20C
20D
20E
19B
19C
19D
19E
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
NA
NA
NA
NA
NA
NA
NA
NA
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
NA
NA
NA
NA
NA
NA
NA
NA
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
NA
NA
NA
NA
NA
NA
NA
NA
TRACE
ELEMENTS
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
NA
NA
NA
NA
NA
NA
NA
NA
FLOAT
SINK
NA
NA
NA
NA
NA
YES
NA
NA
NA
YES
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TOTAL NUMBER OF SAMPLES = 23
FOOTNOTES
(1) YES=ANALYSIS DONE, NA=NO ANALYSIS IS TO BE DONE
(2) DESIGNATIONS A,B,C, ETC INDICATE THE ORDER IN WHICH SAMPLES WERE COLLECTED: A, FIRST;
B, SECOND; ETC. Y=AGE OF MATERIALS IN YEARS
(3) SAMPLE PARTICLE SIZE IN MINUS(-) OR PLUS(+) INCHES; -1 ID INDICATES MINUS 1 INCH IN
ONE DIRECTION AND -2 INCHES IN THE OTHERS
87
-------
00
QO
SAMPLE
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
25B
-1/4
PLANT A
11/18/75
86.27
78. 50
18. 50
TRACE ELEMENT AND MINERAL CONTENT OF SIZED WASTE MATERIALS
FOR ILLINOIS BASIN PLANT A SAMPLES
25C 25D 25E 2 5F
-1
PLANT A
11/18/75
85. 98
74. 30
20. 20
-ID
PLANT A
11/18/75
85.71
73. 10
13. 40
-2
PLANT A
11/18/75
83.08
71. 50
10.90
+ 2
PLANT A
11/18/75
83.85
72. 90
37. 00
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
14. 10
1.53
. 33
6.51
RAW BASIS
14.60
1.70
. 33
7.67
RAW BASIS
14. 20
2. 07
. 34
9.49
RAW BASIS
16.
1.
, 20
. 39
. 28
12.06
RAW BASIS
16.
1
50
76
. 35
10.53
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
RAW BASIS
16. 38
13. 94
26. 56
11. 72
-.01
10. 49
1.60
5.58
RAW BASIS
13. 10
12. 35
23. 28
11. 52
4.76
14.80
6.57
1.20
RAW BASIS
16.72
15. 83
21. 40
17. 63
2. 21
4. 15
6. 34
2. 39
RAW BASIS
11.83
12. 80
19. 21
20.96
9. 69
2.88
8, 26
. 68
RAW BASIS
10. 84
8. 38
15. 20
16.97
18. 59
8. 32
11. 92
-------
SAMPLE
ELEMENT
(2)
LI PPM H A
BE PPM H A
B PPM L E
P PPM R 0
NA PCT H A
MG PCT H A
AL PCT H A
SI PCT R O
P PPM R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
NI PPM L E
CO PPM H A
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L E
AG PPM R N
CD PPM HA
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM H A
TH PPM R O
U PPM R O
25B
RAW BASIS
40. 00
76. 00
750. 00
.11
.41
7.50
16. 60
2100. 00
1.48
2.19
14. 00
.51
85. 00
72.00
227. 50
5.76
19. 00
49. 00
58.00
250.00
21. 00
5.10
68. 00
8.90
240. 00
36. 00
180.00
9.00
.62
-9. 00
1.90
6.10
52. 00
110.00
8.80
1.80
6.70
4.50
.60
4.90
50
53.00
12. 90
7 .80
25C
RAW BASIS
33.00
71.00
960.00
.11
. 43
7. 70
16.65
3100.00
1.37
2.69
13.90
.47
82.00
67. 00
255.00
7.23
21.00
48.00
56.00
114.00
22.00
6. 20
67.00
11.00
320:00
36. 00
150.00
10.00
2. 30
-9.00
2. 20
7. 50
50.00
110.00
8. 90
1.80
7. 10
3.40
. 50
5. 20
1. 00
57. 00
12. 80
2.60
25D
RAW BASIS
40. 00
64.00
700. 00
.12
.37
7. 60
15.94
2500.00
1.25
2.11
12. 70
. 50
85.00
65.00
220. 50
8. 30
22.00
46.00
62.00
400.00
23
7
25E
25F
00
70
79.00
7. 00
240.00
35.00
140.00
12.00
5. 10
-9.00
5.70
50.00
100. 00
9.00
1.80
7. 20
3.60
. 50
3.70
1. 10
56.00
12.60
6.60
RAW BASIS
30.00
59. 00
530.00
. 10
. 41
5. 30
12.55
1800.00
.90
5. 47
8.90
.37
59.00
39.00
334.00
9.95
17.00
38. 00
33.00
57.00
15.00
3.90
59.00
5. 00
250. 00
33. 00
160. 00
15. 00
. 10
5.20
31. 00
59.00
4.80
1. 10
4. 70
2.30
. 40
2. 80
38. 00
7. 70
5.80
RAW BASIS
31.00
56.00
410.00
. 10
. 42
6.00
12. 10
900. 00
.88
6.75
9. 30
.39
57.00
46.00
382 .50
8. 54
19. 00
39.00
40. 00
72.00
17.00
5. 30
30.00
8. 10
160. 00
34.00
160.00,
14. 00
, 10
1.10
3. 20
37. 00
"72.00
5. 60
1. 20
4. 80
2. 10
. 40
2. 20
39. 00
9.80
4. 70
-------
SAMPLE
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
24B
AVE -1/4
PLANT B
11/19/75
86.30
72.30
23. 80
TRACE ELEMENT AND MINERAL CONTENT OF SIZED WASTE MATERIALS
FOR ILLINOIS BASIN PLANT B SAMPLES
24C 24D 24E 24F
AVE -1
PLANT B
11/19/75
78.90
65. 20
30.90
AVE -ID
PLANT B
11/19/75
80. 20
64. 60
12.40
AVE -2
PLANT 3
11/19/75
68.80
49. 80
12. 50
AVE +2
PLANT B
11/19/75
81.30
60. 00
20. 30
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
13. 80
2.00
. 30
8.60
RAW BASIS
20.70
2. 20
. 45
8. 50
RAW BASIS
19.60
2. 20
.43
8. 60
RAW BASIS
27. 60
2. 50
. 56
13. 90
RAW BASIS
17.
1.
. 30
. 70
. 38
24. 40
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
HARCASITE
GYPSUM
ROZENITE
ALBITE
RAW BASIS
9,83
14. 63
20.70
15. 03
33. 26
2.72
1.29
RAW BASIS
8. 69
14. 71
19. 25
14. 57
. 51
25. 65
1. 55
1.83
RAW BASIS
8. 56
20. 70
22. 68
16.20
. 81
12.06
4.81
RAW BASIS
5. 26
9. 84
13. 42
22. 41
. 58
4. 43
12. 34
. 52
RAW BASIS
5. 14
13. 17
19.97
27. 09
17. 23
. 51
-------
SAMPLE
ELEMENT
(2)
LI PPM H A
BE PPM H A
B PPM L E
F PPM R O
NA PCT H A
MG PCT H A
AL PCT H A
SI PCT R 0
P PP'M R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
NI PPM L E
CU PPM H A
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L" E
AG PPM R N
CD PPM H A
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
ED PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM H A
TH PPM R 0
U PPM R O
24B
RAW BASIS
66.00
3.50
67.00
480.00
.10
.34
5.92
17. 10
600. 00
37. 00
1.48
.18
18. 00
. 45
120. 00
84. 00
166.50
9.00
44. 00
110. 00
50. 00
220.00
-9.00
64. 00
5.70
210.00
20. 00
100. 00
46. 00
. 80
50
-9.00
1.70
9.10
50. 00
110.00
8.70
1.80
6.70
3.90
. 56
4 .70
1.20
39.00
14. 00
3.70
24C
RAW BASIS
59.00
2. 80
68. 00
460.00
. 09
. 30
5. 47
14.60
210. 00
39.00
1.22
.12
15. 00
. 41
100. 00
74. 00
134. 00
8.50
34. 00
70.00
39.80
101.00
64. 00
5.70
160.00
20.00
84.00
40. 00
. 40
. 20
-8.00
1.10
7.70
45.00
91.00
7. 40
1. 50
5. 40
3.60
. 51
3. 70
. 98
30.00
12.00
3. 20
24D
RAW BASIS
33. 00
3. 50
65.00
430.00
. 10
. 29
5. 26
15. 90
480. 00
31. 00
1. 40
. 16
12.00
. 42
92.00
71.00
128. 50
9. 50
24.00
70.00
43. 00
87.00
-8. 00
54. 00
120. 00
19. 00
79.00
42. 00
. 60
. 24
-8.00
1. 10
5.90
35. 00
70.00
5.70
1. 20
5. 40
3. 10
. 38
3. 20
. 90
38.00
9. 60
3.10
24E
RAW BAS
36.
2.
57.
450.
.
t
4.
9.
200.
55.
.
f
10.
,
61.
64.
111.
11.
26.
43.
35.
78.
-7.
88.
6.
3.
80.
12.
63.
53.
-7.
1.
4.
25.
55.
4.
3.
2.
3.
1.
IS
00
50
00
00
06
18
12
70
00
00
97
06
00
26
00
00
00
20
00
00
00
00
00
00
60
30
00
00
00
00
70
30
00
20
90
00
00
50
96
20
30
33
20
40
24F
RAW BASIS
, 70
25.
1.
57. 00
232.00
.04
.12
3. 17
8.90
-10. 00
40.00
.71
.09
6. 80
. 21
51. 00
35. 60
108. 00
18. 20
24.00
50. 00
21. 00
45. 00
200.00
7. 40
1. 30
190.00
10. 00
65.00
87. 00
. 40
. 50
-8. 00
1. 10
2. 70
24. 00
50. 00
4. 30
1. 00
30
10
20
20
25 . 00
7.80
2. 00
1. 40
35. 00
5. 10
1. 60
-------
SAMPLE
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
18B
-1/4
PLANT C
11/20/75
79. 60
5. 50
TRACE ELEMENT AND MINERAL CONTENT OF SIZED WASTE MATERIALS
FOR ILLINOIS BASIN PLANT C SAMPLES
18C 18D 18E 18F
-1
PLANT C
11/20/75
79.80
14. 00
-ID
PLANT C
11/20/75
76 . 30
11. 50
-2
PLANT C
11/20/75
77. 90
16 . 00
+ 2
PLANT C
11/20/75
82. 10
53. 00
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
8. 50
1.04
. 25
7.65
RAW BASIS
6.90
.81
. 20
13. 70
RAW BASIS
7. 50
.98
. 26
19.17
RAW BASIS
7. 60
1. 20
. 17
14.11
RAW BASIS
9. 40
1. 32
. 22
10. 72
MINERALOGY
RAW BASIS
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CAICITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
10. 61
18. 29
24. 92
16. 07
16.12
3.89
RAW BASIS
12.98
21. 78
25. 84
21. 75
8. 05
2.71
RAW BASIS
10.77
12.14
18. 22
32.92
6.00
11. 04
1. 10
RAW BASIS
12. 23
18. 12
23. 08
22. 57
7. 43
6. 60
.94
RAW BASIS
15. 89
13. 24
23. 89
18 . 11
16. 49
1. 51
-------
SAMPLE
ELEMENT
(2)
LI PPM H A
BE PPM H A
B PPM L E
F PPM R 0
NA PCT H A
MG PCT H A
AL PCT H A
SI PCT R 0
P PPM R O
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
NI PPM L E
CD PPM H A
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L E
AG PPM R N
CD PPM HA
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HP PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM H A
TH PPM R 0
U PPM R 0
18B
RAW BASIS
12. 00
93. 00
1040. 00
.36
.50
7.60
17. 47
2400. 00
115.00
1.97
.84
14. 10
. 52
85. 00
81.00
131.00
7.60
21. 00
52. 00
44. 00
149. 00
22. 00
4.00
15. 00
3.80
290.00
37. 00
180 . 00
11. 00
.80
-9.00
1.30
9.60
49. 00
93.00
7 .70
1.30
5.90
4.60
. 50
4.30
52.00
12. 80
5.10
18C
RAW BASIS
9. 00
74. 00
950. 00
. 29
. 42
7. 00
16. 74
2400.00
• 90.00
1.69
.61
13.40
. 48
77.00
78. 00
128. 00
11.60
25. 00
53. 00
61. 00
86. 00
16. 00
6.60
19. 00
7. 70
360. 00
24.00
130.00
16. 00
. 35
-9.00
. 90
10. 30
49. 00
95.00
7.20
1. 60
5. 20
3.80
. 50
4. 90
68. 00
12.60
5. 30
18D
RAW BASIS
58.00
1550.00
. 24
.29
6.10
13.88
6600.00
76.00
1.24
1.52
9. 20
.38
60.00
70.00
128. 50
16.20
20.00
48. 00
40.00
99.00
15.00
6. 80
25.00
8.60
1.00
160.00
25.00
130.00
21 . 00
.70
-9.00
1.10
4.50
39. 00
95.00
5.90
1. 10
5.20
2. 40
.30
2. 10
46. 00
9. 60
10.60
18E
18F
RAW BASIS
11. 00
63. 00
1130.00
. 29
. 30
7. 20
15. 83
4600.00
57. 00
1.
1.
37
, 24
10. 40
. 54
73.00
70. 00
139.50
12. 10
29. 00
59. 00
39. 00
79. 00
15.00
-3.00
22.00
5. 60
260. 00
27. 00
130.00
14. 00
. 70
-9. 00
1. 00
6. 00
48. 00
85.00
6. 50
1. 20
5.70
1. 70
. 40
4. 10
68. 00
11. 50
RAW BASIS
25.
76.
1510.
t
.
7.
17.
7500.
170.
1.
1.
10.
.
67.
73.
114.
9.
29.
66.
38.
74.
17.
6.
24.
00
00
00
29
24
80
11
00
00
16
70
00
57
00
00
50
40
00
00
00
00
00
60
00
10. 00
160. 00
34. 00
120. 00
14. 00
10
1.
-9. 00
1. 10
6. 60
52. 00
95.00
7. 30
1. 30
5.70
3. 70
. 40
3. 90
1 . 00
46. 00
13. 10
11. 70
-------
FOOTNOTES
(1) PLUS OR MINUS INDICATES SIZE GREATER OR LESS THAN SIZE GIVEN.
NUMBERS 6 OR LARGER ARE MESH SIZES, OTHERS ARE IN INCHES
(2) LETTERS INDICATE HOW SAMPLE WAS PREPARED AND ANALYZED
R= RAW SAMPLE
!..= LOW TEMPERATURE ASH
H= HIGH TEMPERATURE ASH
N= NEUTRON ACTIVATION ANALYSIS
A= ATOMIC ABSORPTION
E= EMISSION SPECTROSCOPY
O= OTHER
-------
APPENDIX D
(1)
SUMMARY OF LASL FLOAT/SINK ANALYSES
9-30-77
(2)
LOCALE
IDENTITY
PLANT A
A
A
A
A
PLANT B
.B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
PLANT C
C
C
C
C
GOB A
FLOAT
FLOAT
FLOAT
GOB A
FLOAT
FLOAT
FLOAT
GOB A
FLOAT
FLOAT
FLOAT
GOB A
FLOAT
,c
@
@
@
,B
@
@
@
,B
@
@
@
,B
@
,E
2
2
2
,c
2
2
2
,c
2
2
2
,c
2
SUSPENDED
FLOAT
FLOAT
@
@
LTA-GOB
FLOAT
FLOAT
GOB A
FLOAT
FLOAT
FLOAT
@
@
,B
@
@
@
2
2
A
2
2
,c
2
2
2
AVE(#25A)
.15g/ml
.48 SINK
.97 SINK
SINK
AVE(#24A)
.15g/ml
.48 SINK
.97 SINK
SINK
e
@
@
@
@
@
2
2
2
2
2
2
.15
.48
.97
.15
.48
.97
-1/4"(#24B)
.15g/ml
.48 SINK
.97 SINK
SINK
+2"(#24F)
.ISg/ml
@ 2.15
.48 SINK
.97 SINK
SINK
@
@
@
@
@
9
2
2
2
2
2
2
.15
.48
.97
.15
.48
.97
,B,C AVE(#24)
.48g/ml
.97 SINK
SINK
AVE(#18A)
.15g/ml
.48 'SINK
.97 SINK
SINK
@
@
@
@
@
2
2
2
2
2
.48
.97
.15
.48
.97'
SAMPLE
F/S
F/S
F/S
F/S
F/S
F/Y
F/Y
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
F/S
10
10F
10E
IOC
10A
13
13F
13E
13C
13A
3
3F
3E
3C
3A
4
4FF
4FS
4E
4C
4A
16
16D
16C
16A
11
11F
HE
11C
11A
LTA
NA
NA
NA
NA
NA
NA
YES
YES
YES
YES
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
CHN
ANAL
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
MINE-
RALOGY
NA
NA
NA
NA
NA
NA
YES
YES
YES
YES
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
TRACE
ELEMENTS
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
YES
TOTAL NUMBER OF SAMPLES = 24
FOOTNOTES
(1) YES=ANALYSIS DONE, NA=NO ANALYSIS IS TO BE DONE
(2) DESIGNATIONS A,B,C, ETC INDICATE THE ORDER IN WHICH SAMPLES WERE COLLECTED:
A, FIRST; B, SECOND; ETC. Y=AGE OF MATERIALS IN YEARS
95
-------
SAMPLE
F10A
TRACE ELEMENT AND MINERAL CONTENT OF FLOAT-SINK FRACTIONS
OF ILLINOIS-BASIN PLANT A COAL WASTE SAMPLES
F10C F10E F10F
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
25A SK/TBE
PLANT A
18. 90
25A SK/DBM
PLANT A
23.80
25A SK/DBE
PLANT A
44. 10
25A F/DBE
PLANT A
13. 20
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
36. 80
RAW BASIS
2.32
RAW BASIS
4. 75
RAW BASIS
2. 87
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARC AS ITE
GYPSUM
ROZENITE
ALBITE
-------
SAMPLE
F10A
ELEMENT
RAW BASIS
LI PPM
BE PPM
B PPM
F PPM
NA PCT
MG PCT
AL PCT
SI PCT
P PPM
CL PPM
K PCT
CA PCT
SC PPM
TI PCT
V PPM
CR PPM
MN PPM
FE PCT
CO PPM
NI PPM
CU PPM
ZN PPM
GA PPM
GE PPM
AS PPM
SE PPM
BR PPM
RB PPM
Y PPM
ZR PPM
HO PPM
AG PPM
CD PPM
SN PPM
SB PPM
CS PPM
LA PPM
CE PPM
SM PPM
EU PPM
TB PPM
DY PPM
YB PPM
LU PPM
HF PPM
TA PPM
W PPM
HG PPM
PB PPM
TH PPM
U PPM
H A
H A
L E
R 0
H A
H A
H A
R 0
R 0
R N
H A
H A
R N
R N
R N
H A
H A
H A
R N
L E
H A
H A
R N
L E
R N
R N
R N
R N
L E
L E
L E
R N
H A
L E
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
H A
R 0
R 0
(2)
17. 00
2.00
59.00
1000. 00
.03
.10
1.39
2.20
6000.00
.16
3.40
15.00
207.00
36. 00
54.00
220.00
215. 00
-10.00
23. 00
140.00
30. 00
2.60
200.00
F10C
RAW BASIS
108.00
5. 00
68. 00
570.00
. 12
.64
8.70
17. 30
1060.00
716.00
1. 46
6.73
11.80
.38
63.80
86. 00
414.00
3.14
26.50
48.00
63. 00
65.00
-10. 00
46. 20
32. 00
140. 00
30. 00
. 12
-10. 00
3.94
41. 60
79. 10
220.00
4.59
1.36
1.10
5.21
1 04
. 41
2 34
330. 00
11. 30
6. 20
F10E
RAW BASIS
151. 00
31. 00
66. 00
540.00
. 10
. 54
8. 20
15.90
1050.00
104.00
1.
3.
F10F
34
86
12. 20
. 46
10
72.
65.
276.
00
00
5.10
34.70
49. 00
68.00
98.00
-9. 00
129.00
35.00
170.00
27. 00
. 23
-9.00
8.04
44. 80
92.20
63
5. 57
3. 14
. 48
2. 57
79. 00
13. 80
6. 34
RAW BASIS
62. 00
\ 35.00
\ 40.00
150.00
.03
. 16
2.81
2. 30
120.00
. 48
.21
6.45
55.80
40. 00
39. 30
2. 00
41. 10
28. 00
50. 00
74. 00
-4.00
17. 00
63. 00
14. 00
. 12
-4.00
40. 40
53. 40
2. 53
37. 00
5. 90
4.95
-------
SAMPLE
F13A
TRACE ELEMENT AND MINERAL CONTENT OF FLOAT-SINK FRACTIONS
OF ILLINOIS-BASIN PLANT B COAL WASTE SAMPLES
F13C F13E F13F F16A
F16C
F16D
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
- - ~
24A SK/TBE
PLANT B
30. 00
RAW BASIS
37. 30
RAW BASIS
4.20
11. 30
2. 59
65. 11
.95
10. 82
24A SK/DBM
PLANT B
21. 60
RAW BASIS
7. 38
RAW BASIS
10. 64
24. 27
32. 87
14. 25
. 25
2.34
24A SK/DBE 24A F/DBE 24ALTASKTB 24ALTASKBM 24ALTA/FBM
PLANT B PLANT B PLANT B PLANT B PLANT B
32.20 16.20 26.40 72.70 .90
R A W B AS I S RA W B AS I S
4.91 4.19
RAW BASIS RAW BASIS
10.05 8.90
19.64 10.92
22.74 12.00
9.01 8.67
15.18 5.65
5.03 2.12
3.16
-------
SAMPLE
ELEMENT
(2)
LI PPM H A
BE PPM H A
B PPM L E
F PPM R O
NA PCX H A
MG PCT H A
AL PCT H A
SI PCT R 0
P PPM R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM HA
FE PCT H A
CO PPM R N
NI PPM L E
CU PPM HA
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L E
AG PPM R N
CD PPM H A
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM H A
TH PPM R 0
U PPM R 0
F13A
RAW BASIS
19. 00
13. 00
59.00
20. 00
.02
.06
1.43
2.10
180. 00
30. 30
.20
.13
1.98
. 07
11.70
9.50
205. 50
36. 10
28. 50
77.00
95.00
123. 00
-10. 00
202. 00
13. 00
140. 00
13. 00
.80
-10.00
1.67
3.73
. 39
21. 60
. 23
2.65
48.00
2.16
.54
F13C
RAW BASIS
112. 00
14. 00
66.00
420.00
. 09
. 43
9. 00
18. 90
770.00
280. 00
1.90
. 11
14. 30
. 22
79. 10
83. 00
133.00
8.70
37. 10
74. 00
68.00
110. 00
150.00
-10. 00
197.00
27. 00
160.00
21.00
. 25
-10. 00
5 99
42. 60
87. 90
.00
F13E
RAW BASIS
206.00
97
56
70
45
. 32
2.69
. 95
32. 00
12. 20
3. 98
17
73
430
00
00
00
09
. 42
8.80
16.30
460.00
50. 00
1.78
. 29
14.90
.49
73 . 70
76. 00
96.75
5.70
40.90
62. 00
42. 00
104. 00
-9.00
31. 00
150.00
20.00
. 12
-9.00
9.13
27. 50
92 .00
3.70
1.22
5.52
.31
32. 00
14. 70
3.72
F13F
RAW BASIS
79. 00
12. 00
130.00
150. 00
. 03
. 16
3. 60
6. 40
180. 00
78.90
. 68
. 07
6. 17
35. 20
40.00
36. 10
3. 30
38. 50
29. 00
20. 00
42. 00
-6.00
134. 00
16. 00
67.00
13. 00
.06
-6. 00
2.43
36. 20
2. 43
. 57
F16A
RAW BASIS
. 06
60. 60
. 06
8.56
. 27
57.70
189. 00
32. 10
134.00
10. 00
4. 38
1.76
.08
3.38
24. 10
49. 80
2. 46
.81
2. 44
1. 22
. 20
3.79
6. 24
2. 38
F16C
RAW BASIS
. 10
190.00
. 13
14.90
. 42
110. 00
147.00
38. 70
57. 70
172. 00
7. 05
38. 80
88.70
4. 18
1. 22
5. 44
3. 26
. 51
5. 73
1. 89
9. 75
4. 07
F16D
RAW BASIS
.05
180. 00
11. 30
. 37
73.00
58. 00
36. 00
5.11
22. 10
74.80
2. 23
2. 78
.34
6 . 29
2. 66
-------
o
o
SAMPLE
(1)
I DEN TITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
F 3A
24B SK/TBE
PLANT B
5.40
TRACE ELEMENT AND MINERAL CONTENT OF FLOAT-SINK FRACTIONS
OF ILLINOIS-BASIN PLANT B COAL WASTE SAMPLES
F 3E F 3F F 4A
F 3C
24B SK/DBM
PLANT B
37.70
24B SK/DBE
PLANT B
51. 30
24B F/DBE
PLANT B
5. 70
24F SK/TBE
PLANT B
40. 20
F 4C
24F SK/DBM
PLANT B
25. 60
F 4E
24F SK/DBE
PLANT B
5. 20
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
39. 70
RAW BASIS
8.26
RAW BASIS
4. 66
RAW BASIS
2.90
RAW BASIS
42. 50
RAW BASIS
12. 30
RAW BASIS
8. 40
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CADCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
-------
SAMPLE
ELEMENT
P 3A
RAW BASIS
F 3C
F 3E
(2)
LI PPM HA
BE PPM H A
B PPM L E
P PPM R O
NA PCT H A
MG PCT H A
AL PCT H A
SI PCT R O
P PPM R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PW1 R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
NI PPM L E
CU PPM H A
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L E
AG PPM R N
CD PPM H A
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM H A
TH PPM R 0
U PPM R O
31.00
6.00
41. 00
50. 00
.02
.08
2.38
3.80
240. 00
61. 30
.32
.11
3.30
.09
21. 20
20.00
350.50
35.10
51. 40
140. 00
116.00
430.00
19. 80
-10. 00
214. 00
14. 00
120. 00
24. 00
.27
1.60
-10.00
1.80
6 . 78
1.09
. 30
1.18
. 28
1 .84
1.59
25.00
2.93
.89
RAW BASIS
141. 00
33.00
57.00
350.00
. 10
.46
9.
18.
560.
139.
1.
.
15.
.70
10
00
00
99
40
00
. 41
112. 00
79.00
200. 00
8.50
43. 20
100. 00
67.00
198.00
-9. 00
296.00
35. 00
220. 00
23. 00
. 39
-9.00
4.69
47. 90
94. 30
5.82
2. 07
6. 39
. 32
37. 00
13. 40
4. 21
RAW BASIS
169. 00
10. 00
75.00
380.00
. 10
. 43
9. 10
16. 40
500.00
251.00
1.84
. 27
13.70
.56
101.00
77.00
130.00
5.40
46. 40
86. 00
48. 00
150. 00
-8.00
73.60
33. 00
150.00
22. 00
. 30
8. 53
43. 80
73 10
3. 19
1. 29
1.18
4. 95
2.76
. 53
52. 00
11. 30
4. 11
F 3F
RAW BASIS
124.00
11. 00
53. 00
. 05
. 23
4.85
8. 80
250. 00
197.00
.94
.09
8. 57
.06
53.90
52. 00
51. 35
2. 70
41. 00
37. 00
35.00
72.00
-7. 00
21. 00
110. 00
20. 00
.19
-7.00
3.65
25. 10
31. 40
3. 45
F 4A
RAW BASIS
16. 00
6. 00
57. 00
70. 00
.01
.03
.73
1. 90
90. 00
28. 70
. 16
.09
1. 75
4. 98
16. 00
89. 50
35. 50
30. 10
39.
29.
21.
00
29. 00
6. 20
2. 47
-10. 00
11. 00
140. 00
19. 00
. 25
-10. 00
2. 79
.37
. 47
5. 41
65.00
1. 33
.55
F 4C
RAW BASIS
89. 00
6. 00
59. 00
370. 00
. 07
.03
6. 30
18.00
770.00
465.00
1.45
. 23
14. 40
.30
66. 60
61.00
136. 50
12. 50
48. 30
66. 00
33.00
82. 00
-10. 00
70.90
118.00
26. 00
140.00
35. 00
. 17
-10.00
3. 53
65. 60
122.00
7. 77
2. 08
5. 06
3. 32
69. 00
11.70
2. 93
F 4E
RAW BASIS
178. 00
25. 00
66. 00
360. 00
. 08
. 30
6. 60
11. 60
540.00
1020. 00
1. 26
.30
11.00
. 23
61. 00
103.90
9. 70
50. 70
63. 00
33. 00
77.00
-9. 00
92.60
27. 00
120.00
41. 00
. 50
-9. 00
4. 25
40. 90
46. 00
5. 75
1.84
6. 08
60. 00
7. 96
3. 02
-------
o
to
SAMPLE
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
F4FS
24F F/DBE
PLANT B
5.10
TRACE ELEMENT AND MINERAL CONTENT OF FLOAT-SINK FRACTIONS
OF ILLINOIS-BASIN PLANT B COAL WASTE SAMPLES
F4FF
24F F/DBE
PLANT B
23.90
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SULFUR
RAW BASIS
5.28
RAW BASIS
5.80
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
-------
SAMPLE
ELEMENT
(2)
LI PPM H A
BE PPM H A
B PPM L E
P PPM R 0
NA PCT H A
MG PCT H A
AL PCT H A
SI PCT R 0
P PPM R O
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
NI PPM L E
CU PPM HA
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM R N
SE PPM R N
BR PPM R N
RB PPM R N
Y PPM L E
ZR PPM L E
MO PPM L E
AG PPM R N
CD PPM H A
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
TA PPM R N
W PPM R N
HG PPM R N
PB PPM H A
TH PPM R 0
U PPM R O
P4FS
RAW BASIS
61.00
11.00
56.00
80. 00
.04
.17
3.50
4.90
390.00
785.00
.74
.09
6.98
. 32
46. 60
47.00
74.95
5.40
49. 70
36. 08
24. 00
74.00
-4.00
233. 00
16. 00
74. 00
26. 00
.16
-4.00
2.61
25. 30
41. 50
3. 42
.74
57. 00
5.89
2.01
F4FF
RAW BASIS
60. 00
12.00
58. 00
110.00
. 02
. 10
2. 18
2. 10
250. 00
94. 20
. 42
. 09
4. 45
30.00
33. 15
4.50
72.40
26.0.0
16. 00
24.00
-6. 00
14. 00
47.00
7. 20
. 10
-6. 00
25. 30
41.50
25. 00
3.75
1 . 20
-------
SAMPLE
(1)
IDENTITY
IDCALE
DATE OBTND
PCT H20
PCT LTA
PCT HTA
PCT ORIGNL
SIZE, KG
FllA
ISA SK/TBE
PLANT C
17. 60
TRACE ELEMENT AND MINERAL CONTENT OF FLOAT-SINK FRACTIONS
OF ILLINOIS-BASIN PLANT C COAL WASTE SAMPLES
F11C FllE FllF
18A SK/DBM
PLANT C
65. 80
18ft SK/DBE
PLANT C
ISA F/DBE
PLANT C
8. 20
CHNS ANAL
CARBON
HYDROGEN
NITROGEN
SU LFUR
RAW BASIS
33. 60
RAW BASIS
3.90
RAW BASIS
4. 17
RAW BASIS
4. 40
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
SPHALERITE
CALCITE
MIXED CLAY
MARCASITE
GYPSUM
ROZENITE
ALBITE
-------
SAMPLE
F11A
F11C
F11E
FllF
ELEMENT
LI PPM
BE PPM
B PPM
F PPM
NA PCT
MG PCT
AL PCT
SI PCT
P PPM
CL PPM
K PCT
CA PCT
SC PPM
TI PCT
V PPM
CR PPM
MN PPM
FE PCT
CO PPM
MI PPM
CU PPM
ZN PPM
GA PPM
GE PPM
AS PPM
SE PPM
BR PPM
RB PPM
Y PPM
ZR PPM
MO PPM
AG PPM
CD PPM
SN PPM
SB PPM
CS PPM
LA PPM
CE PPM
SM PPM
EU PPM
TB PPM
DY PPM
YB PPM
LU PPM
HF PPM
TA PPM
W PPM
HG PPM
PB PPM
TH PPM
0 PPM
(2)
H A
H A
L E
R 0
H A
H A
H A
R O
R 0
R N
H A
H A
R N
R N
R N
H A
H A
H A
R N
L E
H A
H A
R N
L E
R N
R N
R N
R N
L E
L E
L E
R N
H A
L E
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
R N
H A
R O
R 0
RAW BASIS
86.00
-1.00
80.00
470,00
.08
.06
1.64
RAW BASIS
50
9260.00
121.00
.23
2.73
2.54
.12
10. 00
18.00
98.20
34. 50
29. 10
60. 00
191.00
475.00
-10.00
31.00
120.00
26. 00
6.60
79.00
2.59
25.70
35. 00
2.53
. 70
2. 36
.82
. 22
320.00
3.41
18.50
79
16
99
1300
9
19
4020
256
1
1
12
73
116
120
4
30
51
124.
88,
-10. (
00
00
00
00
37
39
70
40
00
00
77
20
40
54
90
00
00
60
30
00
00
00
128.00
31.00
110.00
25.00
. 35
-10.00
7.30
49. 30
92.00
5.28
2.46
5. 06
3.60
. 42
2.87
1.13
52.00
13.60
11.21
RAW BASIS
140.00
32. 00
100. 00
1100.00
. 34
. 46
8. 90
19.80
2410.00
171.00
1.99
.90
12. 30
. 50
73.90
147.00
118.00
4.50
29.60
60.00
86. 00
116.00
60. 20
-10. 00
141.00
34.00
140.00
27. 00
-10.00
2.80
8. 21
38.80
87. 40
5. 29
1.35
4. 94
2. 09
. 54
4. 22
1.03
30.00
12.40
8. 27
RAW BASIS
28. 00
15.00
00
26
160
07
10
32
10
2
2
450.00
214. 00
.35
. 23
3. 58
25.00
76. 00
32.70
2. 60
40. 30
31.00
28. 00
28. 00
-3.00
10.00
55.00
15 00
1.80
-3.00
2.93
35.60
1.35
. 69
1.20
42.00
5.31
2. 70
O
ui
-------
FOOTNOTES
(1) PLUS OB MINUS INDICATES SIZE GREATER OR LESS THAN SIZE GIVEN.
NUMBERS 6 OR LARGER ARE MESH SIZES, OTHERS ARE IN INCHES
(2) LETTERS INDICATE HOW SAMPLE WAS PREPARED AND ANALYZED
R= RAW SAMPLE
L= LOW TEMPERATURE ASH
H= HIGH TEMPERATURE ASH
N= NEUTRON ACTIVATION ANALYSIS
A= ATOMIC ABSORPTION
E= EMISSION SPECTROSCOPY
0= OTHER
-------
APPENDIX E
GRAPHIC DISPLAY OF CLUSTERED TRACE ELEMENT/MINERAL
CORRELATION COEFFICIENTS FOR COAL PREPARATION WASTES
FROM THREE ILLINOIS BASIN COAL CLEANING PLANTS
This appendix describes the computational and graphics methods used to convert the expan-
sive listings of trace element and mineral data for Illinois Basin coal refuse into a form from
which element-element and element-mineral associations can be recognized more easily. In-
cluded also in this appendix are the graphic results from the application of these methods to data
for the as-collected coal and waste samples, and for refuse samples that had been separated into
fractions on the basis of density or particle size.
As the first step of this computational routine, trace element and mineral data for the various
coal and refuse fractions are evaluated by bivariate correlation analysis. The program for
performing this task was the Pearson's correlation option of the statistical program called SPSS.
A manual is available, titled Statistical Package for the Social Sciences, Second Ed., by Nie et
al., published by McGraw-Hill Book Co., New York, 1975. The data from this treatment are of-
ten tabulated, with the result that extensive visual inspection is necessary to find even pairs of
correlated variables. Finding groups of correlated elements and minerals is even more difficult
by visual inspection. To group the trace elements and minerals into clusters or sets that have
similar correlation coefficients, we have developed a method for sorting the information by
means of three algorithms.
The initial sorting involves selecting variables from the original unsorted group and placing
them in a sorted group. The algorithms used to accomplish this are termed maximum,
minimum, and average. In each of the three algorithms, the two variables with the maximum
correlation are selected and/ placed in the sorted group. Variables are then added one at a time to
the sorted group in the following manner. At the nth step variables in the sorted group are
denoted by Bj, B2, ....Bn. The remaining variables (those not yet sorted) are denoted by A1; A2,
....An_m. Variables are then taken from the A group one at a time, according to the algorithm
chosen. To accomplish this, a statistic Z, (i=l,2...n-m) is calculated. Letting p(A,B) denote
calculated Pearson's correlation coefficient between a variable in group A and one in group B, Zj
is defined as
Z = max [p(A. ,B.) ]
for the maximum algorithm. Thus for any variable (A() in the unsorted group, the maximum
Pearson's correlation coefficient for this variable and any of the variables in the sorted group (B)
is given as Z4. Similarly,
Z± = min [p(A.,B )]
j=l,m J
for the minimum algorithm. For the average algorithm,
m
Z = 1/m Z p(A.,B.)
107
-------
Here, for any variable (A,) in the unsorted group, the average of the Pearson's correlation coef-
ficients for this variable and all of the variables in the sorted group (B) is given as Z,. This set of
Z's is inspected and the maximum value
[Z = max(Z )]
K. , - -L
1=1,n-m
is selected. The variable Ak that corresponds to this Z-value is removed from the unsorted group
(A) and placed in the sorted group (B).
The secondary sorting process takes the variable chosen from the unsorted group and places it
in an orderly manner into the sorted group. The placement is either as the first member of the
sorted group or as the last. To be placed as the first member, the variable must have a higher
average correlation with a designated number (w) of variables in the first half of the sorted group
than with a corresponding number of variables in the second half. If only the outermost variables
at each end of the sorted group are to be considered, then the designated number (w) of variables
is one. Considering two outermost variables, w will equal two. The choice of variables to be con-
sidered can be increased to a maximum of one-half of the number of variables in the sorted
group. The placement of Ak as the first member of the sorted group is thus determined by the
following condition:
where w = min (m/2,w) and w is a preselected integer. If this condition is not met, then AK is
placed as the last member of the sorted group. If w = 0, Ak is always placed as the last member in
the sorted group. After the last variable in the unsorted group has been added to the sorted group,
the sorted group is ready for tabulation.
Because the inspection and interpretation of the voluminous number of correlation coefficients
of even a sorted tabulation is still laborious, we have developed a process by which these data can
be graphically displayed. This is accomplished by assigning a symbol (or a
color, where facilities permit) that corresponds to a range of Pearson's cor-
relation coefficients. Such an assignment is given at the right. Using these
symbols, the relatively nondescript, but sorted, accumulation of correlation
coefficients can be transformed into readily discernible groups which per-
mit easy visual inspection. Such outputs are found in Figs. E-l through fi-
ll.
The computer programming used to accomplish this graphic depiction
was the DISSPLA software product supplied by Integrated Software
Systems Corp., San Diego, California. Hardware output has been succes-
sful with Tektronix 4000 series graphics terminals, and with Stromberg
Carlson Model 4020 microfilm recorder (black and white) and Information
International, Inc., Model FR80 microfilm recorder (black and white and
color) 35-mm film outputs. (For investigators with only alphanumeric-type
terminals, we have demonstrated that proper selection of alphanumeric
characters will give a fairly discernible, but skewed, graphics output
without the need for the special software or hardware units noted above. Further refinements,
such as removing the skew and overstriking could greatly improve this process.)
-a-
o
a
a
B
bit
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 .0
108
-------
1 0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 0
Fig. E-l.
Trace element correlation coefficients for all coal and refuse samples collected from cleaning
Plant A.
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 .0
Fig. E-2.
Trace element correlation coefficients for sized refuse fractions from cleaning Plant A (sam-
ples 25b-f).
109
-------
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 0
Fig. E-3.
Trace element correlation coefficients for float/sink fractions of average refuse from cleaning
Plant A (sample FlO).
1 .0
0.8
0.6
0.4
0.2,
0.0:
-0.2:
-0.4 =
-0 6.
-0.8
-1 0
Fig. E-4.
Trace dement correlation coefficients for all coal and refuse samples collected from cleaning
Plant B.
110
-------
1 .0
0.8
0.6
0/4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 .0
M£. E-5.
Trace element correlation coefficients for sized refuse fractions from cleaning Plant B (sam-
ples 24b-f).
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 .0
Fig. E-6.
Trace element correlation coefficients for float/sink fractions of average refuse from cleaning
Plant B (sample F13).
Ill
-------
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
Fig. E-7.
Trace element correlation coefficients for float/sink fractions of -1/4 -in. refuse from cleaning
Plant B (sample F3).
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2-
-0.4
-0.6
-0.8
-1 .0
Fig. E-8.
Trace element correlation coefficients for float/sink fractions of +2-in. refuse from cleaning
Plant B (sample F4).
112
-------
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 .0
Fig. E-9.
Trace element correlation coefficients for all coal and refuse samples collected from cleaning
Plant C.
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1 .0
Fig. E-10.
Trace element correlation coefficients for sized refuse fractions from cleaning Plant C (sam-
ple 18b-f).
113
-------
a
D
D
B
l;l
1 .0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
Fig. E-ll.
Trace element correlation coefficients for float/sink fractions of average refuse from cleaning
Plant C (sample Fll).
APPENDIX F
PROCEDURE FOR MULTISTAGE FLOAT/SINK SEPARATION
OF COAL PREPARATION WASTES
Step 1: Dibromomethane Float/Sink Separation
Powdered waste material (200 g of -20 mesh) was added to a 2-1 separatory funnel containing
1 i of dibromomethane (DBM). (DBM has a density of 2.48 g/cm3.) After shaking to promote
thorough mixing, the contents were allowed to settle until the float and sink fractions were clearly
separated, generally requiring 15 to 30 min. Then, the sink fraction was drained from the
separatory funnel via the stopcock and filtered with a Buchner funnel equipped with Whitman
#40 paper. The float portion, remaining in the separatory funnel, was resuspended by shaking,
and the settling and separation steps were repeated. This sequence was repeated as many times
as necessary to achieve the desired separation. After the removal of the last sink fraction, the
remaining float material was removed from the funnel and also filtered with the Buchner ap-
paratus. The float and sink fractions were then dried in a vacuum oven at 60°C. This operation
provides two waste fractions, one with a higher density and another with a lower density than
2.48 g/cm3.
114
-------
Step 2: Dibromoethane Float/Sink Separation
The dried float portion from the DBM treatment (waste material with a density less than 2.48
g/cm3) was transferred into another separatory funnel containing 1 & of dibromoethane (DBE),
which has a density of 2.15 g/cm3. A sequence of settling and separation steps, similar to those
described in Step 1, was performed. The dried products represent the waste materials that fall
into the density ranges <2.15 g/cm3 and 2.15 to 2.48 g/cm3.
Step 3: Tetrabromoethane Float/Sink Separation
The sink fraction from the DBM treatment (density >2.5 g/cm3) was separated into two ad-
ditional density fractions by a float/sink treatment with tetrabromoethane (d=2.96 g/cm3). The
steps and work-up procedure for the products were identical to those given in Step 1. The waste
fractions obtained in this step have densities in the range 2.48 to 2.97 g/cm3 and >2.97 g/cm3.
A flow diagram for the entire float/sink process appears in Fig. F-l.
DBM FLOAT
FILTER
DRY
1
TBE FLOAT
Fl LTER
DRY
DBE FLOAT
FILTER
DRY
Fig. F-l.
Schematic for multistage float/sink technique.
115
-------
APPENDIX G
SAMPLE PREPARATION PROCEDURE FOR MICROPROBE ANALYSIS
OF COAL AND REFUSE MATERIALS
After grinding the sample to the desired size (usually -20 mesh), the powder is mounted in the
upper part of a 2.54-cm- (1-in.-) diam by 3.8-cm- (1.5-in.-) long cylinder of epoxy. This is accom-
plished by placing the powder into a small blind hole at the top of the cylinder and filling the
remainder of the hole with epoxy resin. After curing the resin, the surface of the mounted
specimen is ground and polished to expose the powder particles. Special care and nonaqueous
polishing are needed because there is a wide range of hardnesses among the samples. Then, to
improve contrast, the polished surface is etched for about 5 min, using bombardment by 3-kV
H+ ions in a cathode vacuum etcher. Finally, a 100-A gold or carbon film is applied to the etched
surface of the sample.
APPENDIX H
PROCEDURE FOR STATIC/EQUILIBRIUM LEACHING OF
COAL OR WASTE MATERIALS
The crushed coal or waste sample (50 g) was added to 250 ml of leachate (distilled water or
acid) contained in a 500-ml Erlenmeyer flask. The flask was either stoppered or fitted with a
modified stopper that allowed air into the flask while retaining the contents. Heating, when
desired, was provided by a Variac-controlled heating mantle. The completed flask assembly was
inserted into a shaking apparatus that was used to agitate the sample during the experiment. Af-
ter the leach period, the sample was removed from the shaker and the leachate and residue were
separated by vacuum filtration. The pH, dissolved solids, and trace element contents of the
leachates were then determined.
116
-------
APPENDIX I
EXPERIMENTAL PROCEDURE FOR COLUMN LEACHING
STUDIES OF COAL AND COAL REFUSE
Coal or refuse material (1.5 kg), crushed to -3/8 in., was packed into a Pyrex column 70 cm
long by 4.6 cm diam in a vertical position. The leaching column was equipped with a necked-
down inlet at the bottom for introducing the leachates. A side arm located 5 cm below the open
top served as an effluent outlet. Both the upper and lower ends of the coal or refuse bed were
retained in the column with loosely packed glass-wool plugs. An upward or countercurrent
leachate flow was used in most of the experiments to prevent flow blockage from fine sediments
that might settle to the bottom of the column.
The leachate, usually distilled water, was gravity-fed through the packed column from a reser-
voir elevated above the column outlet. Leachate flow rate, normally 0.5 to 1.0 ml/min, was
regulated with a valve located between the reservoir and column inlet. Measurements of leachate
flow and pH were made at the column outlet. Periodically, samples of leachate were collected for
analysis of total solids and trace element composition.
The refuse or coal column was easily dried by stopping the leachate flow, disconnecting the in-
let tubing, and draining the liquid from the sample column through the inlet. Then a dry or
moist air supply was connected to the column inlet and maintained at approximately 10 scf/h.
117
-------
APPENDIX J
Leachate No.
Plant Aa 1
2
3
4
DESCRIPTION OF STATIC LEACHING EXPERIMENTS WITH REFUSE
FROM ILLINOIS BASIN CLEANING PLANTS A, B,AND C
Experiments No. GL-22, SGL-5, and GL-21
Refuse Size T, °C Air
-20 mesh 22 open
-20 mesh 22 open
-20 mesh 22 open
-20 mesh 22 open
Time (Days)
1
7
28
56
Plant B
Plant C
6
12
18
22
2
3
-20 mesh
-20 mesh
-20 mesh
-20 mesh
-20 mesh
-20 mesh
-20 mesh
22
22
22
22
22
22
22
open
open
open
open
open
open
open
1
7
28
56
1
7
28
r*
An average of refuse samples 12, 25, and 28 was used in this study-
An average of refuse samples 17, 23, and 24 was used in this investigation.
An average refuse material consisting of sample numbers 18 through 22 was
used in this study.
118
-------
ANALYSES FROM STATIC LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT A
EXPERIMENT No. GL-22a
Leachate Sample No.
Time (Days)
pH
TDSb
Na
Mg
Al
SiO
K
Ca
Sc
V
Cr(yg/kg)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(yg/kg)
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(yg/kg)
Th
U
JL
1
7.1
0.28
2.4
360
1.0
47
3000
< 0.01
< 0.02
< 5
22.0
< 0.1
3.2
6.9
< 0.01
0.62
< 0.2
< o.ok
0.06
<8
<0.04
6.8
< 0.01
< 0.16
< 2
< 0.32
< 0.08
< 0.02
< 0.01
< 0.12
< 0^01
< 0.08
< 0.2
< 0.04
< i
< 0.08
< 0.01
2
1
7.4
0.27
24
400
1.0
49
2900
< 0.01
< 0.02
< 5
10.3
< 0.1
0.5
1.0
< 0.01
0.52
< 0-2
< o.ok
0.07
< 8
< 0.04
2.0
< 0.2
< 0.16
< 2
< :0.32
< 0.08
< 0.02
< 0.01
< 0.12
< 0.01
< 0.08
< 0.2
< 0.04
< io
< 0.08
< 0.01
3.
28
7-6
0.26
30
470
0.5
57
3100
< 0.01
< 0.02
6
8.9
0.26
0.2
0.6
0.01
0.33
< 0.2
< o.ok
0.03
< 8
< 0.04
1.4
< 0.2
< 0.16
< 2
< 0,32
< 0.08
< 0.02
< 0.01
< 0.12
< 0.01
< 0.08
< 0.2
< 0.04
< ^0
< 0.08
< 0.01
4.
56
7.8
0.28
31
540
< 0.2
38
2900
< 0.01
< 0.02
7
9.7
< 0.1
0.12
0.4
0.05
0.19
< 0.2
< o.ok
0.07
< 8
0.06
0.6
< 0.2
< 0.16
< 2
< 0.32
< 0.08
< 0.02
< 0.01
< 0.12
< 0.01
< 0.08
< 0.2
< 0.04
< W
< 0.08
< 0.01
Elemental concentrations reported as yg/g of refuse unless otherwise indicated.
Total dissolved solids reported as wt. %.
119
-------
ANALYSES FROM STATIC LEACHING OF REFUSE
FROM ILLINOIS BASIN PLANT B
Experiment No. SGL-5a
Leachate Sample No .
6
1
2.2
1.05
12.3
269.9
976
8.4
809
1.38
780
31.5
9500
21.0
32.7
1.6
50.8
190
0.66
1.6
12
7
2.0
1.15
9.8
251.2
938
7.0
759
2.0
1.8
330
32.5
10000
19.6
31.0
1.6
65.3
3.4
<8*
260
<0.2
-------
ANALYSES FROM STATIC LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT C
EXPERIMENT No. GL-21a
Leachate Sample No.
Time (Days)
PH
TDSb
Na
Mg
Al
K
Ca
Sc
V
Cr(ug/kg)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/kg)
Sb
Cs
La -
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(ug/kg)
Th
U
1
1
3.5
0,31
1800
161
124
97
1400
0.12
0.02
160
16.8
1800
9.4
14
0.05
6.9
<0.2
<0.02
0.15
<8
*0.04
100
<0.2
<0.16
0.35
1.61
0.24
0.05
0.25
0.04
0.01
<0.08
<0.2
<0.04
1600
<0.08
0.20
2
7
3.3
0.33
1500
186
80
60
2100
0.11
<0.02
42
20.8
230
10.5
18
0.60
10.6
<0.2
<0.02
<0.04
<8
<0.04
89
<0.2
<0.16
0.46
1.94
0.24
0.05
0.25
<0.12
0.01
<0.08
<0.2
<0.04
2700
0.02
0.13
1
28
1.88
1.81
1500
243
613
15
2800
1.19
0.9
1200
52.8
14000
20.3
39
11.4
39
<0.2
.0.88
<0.04
<8
<0.04
620
<0.2
<0.16
3.41
9.11
13.8
0.25
1.28
0.29
0.05
<0.08
<0.2
<0.04
1800
1.11
3.37
Elemental concentrations reported as yg/g of refuse unless otherwise noted.
Total dissolved solids reported as wt. %.
121
-------
APPENDIX K
DESCRIPTION OF STATIC LEACHING EXPERIMENTS WITH REFUSE
FROM ILLINOIS BASIN CLEANING PLANT Ba
Experiment No. SGL-5
Leachate No.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Refuse Size
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
T. °C
22
22
22
22
22
22
75
75
22
22
22
22
75
75
22
22
22
22
75
75
22
22
Air
limited
limited
limited
limited
open
open
open
open
limited
limited
open
open
open
open
limited
limited
open
open
open
open
open
open
Time (Days)
0.01
0.01
1
1
1
1
1
1
7
7
7
7
7
7
28
28
28
28
28
28
56
56
aAn average of refuse samples 17, 23, and 24 was used in these studies.
123
-------
ANALYSES FROM STATIC LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT B
EXPERIMENT No. SGL-5
Leachate Identification No.
Time (days)
pH
TDSb
Ma
Mg
Al
SiO,
K *
Ca
Sc
V
Cr(yg/kg)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(yg/kg)
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
la
W
Hg
Pb
Th
U
2
0.01
2.4
0.80
9.2
242
817
34.6
628
1.77
0.84
870
27.5
8000
17.9
30.2
1.7
34.8
<0.2
2.99
<0.04
<8
<0.04
150
<0.2
<0.l6
<2
1.28
0.47
0.07
0.31
.0.62
< 0.01
< 0.08
< 0.2
< 0.04
< 1
«, 0.08
< 0.24
3
•r
0.01
2.5
0.38
7.0
169.9
346
31.9
453
1.42
0.37
260
21.0
3300
12.7
21.2
4.9
27.6
<0.2
1.63
0.05
<8
<0.04
110
<0.2
-------
ANALYSES FROM STATIC LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT B (Cont.)
EXPERIMENT No. SGL-5a
Leachate Identification No.
Time (days)
pH
TDSb
Na
Mg
Al
SiO,
K
Ca
Sc
V
Cr(ng/kg)
Mn
Fe
Co
Hi
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/kg)
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
H£
Ta
W
Hg
Pb
Th
U
11
7
2.1
0.83
9.2
198.1
319
19.7
688
1.50
1.43
390
26.0
9100
20.5
27.4
3.5
42.1
<0.2
2.32
"6.04
<8
<0.04
150
<0.2
<0.16
1.82
2.81
0.43
0.11
0.73
<0.12
0.04
<0.08
<0.2
-------
APPENDIX L
DESCRIPTION OF CONTINUOUS LEACHING STUDIES
OF ILLINOIS BASIN COAL REFUSE3
Plant Experiment No. Refuse Used Leachate Flow Pattern
A GL-19 12, 25, 28 Uninterrupted
B GL-7 17, 23, 24 Uninterrupted
GL-8 17, 23, 24 Uninterrupted
GL-9 17, 23, 24 Interrupted at 2.7 £ for 1 day
and at 8.7 £ for 7 days
GL-10 17, 23, 24 Interrupted at 2.7 £ for 1 day
and at 8.7 I for 7 days
C GL-20 18,19,20,21,22 Uninterrupted
These experiments were conducted at ambient temperature with 1.5 kg of refuse
material crushed to -3/8 in and packed into a 70-cm long by 4.6 cm diam. glass
column. Leachate (distilled water) flow rate was maintained at 0.5 mil/min.
Refuse sample studied was an average of the listed fractions.
127
-------
ANALYSES FROM CONTINUOUS LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT A
EXPERIMENT No. GL-193
Leachate Increment No.
Volume (J.)
pH .
TDSb
Na
Mg
Al
K
Ca
Sc
V
CrUlg/S,)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/)l)
Sb
Cs
La
Ce
Sm
£u
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(yg/«.)
Th
U
1
0.1
2.9
2.72
63
650
140
61
610
0.68
0.05
110
52
4100
17
27
4.7
15
<0.05
0.16
0.07
<2
<0.01
150
<0.05
<0.04
0.48
1.66
0.43
0.09
0.32
0.11
0.02
<0.02
<0.05
<0.01
<0.25
120
0.20
0.43
2
0.6
3.3
1.6
29
360
82
37
580
0.19
0.02
30
29
2070
10
14
1.1
7.5
<0.05
0.11
<0.01
<2
<0.01
51
<0.05
<0.04
0.25
0.99
0.27
0.05
0.14
0.07
0.01
<0.02
<0.05
<0.01
<0.25
37
0.08
0.16
4
1.3
4.6
0.7
14
160
2
20
540
0.01
<0.01
30
15
870
4
6.5
< 0.05
3.2
< 0.05
0.05
< 0.01
< 2
< 0.01
11
< 0.05
< 0.04
0.06
0.25
0.04
0.01
0.04
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
< 0.02
0.01
7
2.5
6.0
0,4
3.6
80
< 1
11
600
<0.01
<0.01
30
7
190
0.7
1.7
< 0.05
0.7
< 0.05
0.01
< 0.01
< 2
< 0.01
< 1
< 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
33
< 0.02
< 0.01
12
6.9
6.8
0.1
0.71
13
< 1
3.6
360
< 0.01
< 0.01
30
0.94
5.4
< O.Q5
0.05
< 0.05
0.09
< 0.05
0.01
< 0.01
< 2
< 0.01
< 1
< 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
0.02
9
< 0.02
0.01
13
8.1
7.0
0.1
0.60
10
< 1
8.4
320
<0.01
<0.01
30
0.68
2.4
< 0-05
< 0.05
< 0.05
0.08
< 0.05
< 0.01
0.01
< 2
< 0.01
< 1
< 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
16
< 0.02
< 0.01
19
13.7
7.5
0.06
0.41
4
< 1
1.8
150
< 0.01
< 0.01
30
0.18
0.9
< 0-05
< 0.05
< 0.05
0.04
< 0.05
< 0.01
0.02
< 2
<• 0.01
< 1
< 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
< 5
< 0.02
< 0.01
20
14.2
7.7
0.06
0.38
3
< 1
4.3
140
< 0.01
< 0.01
30
0.17
0.1
< 0-05
< 0.05
< O.Q5
0.03
< 0.05
0.01
< 0.01
< 2
< 0.01
< 1
< 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
< 5
< 0.02
< 0.01
Elemental concentrations reported as ug/m£ unless otherwise noted.
Total dissolved solids reported as wt. %.
-------
Volume (£)
PH
TDSb
Na
Mg
Al
SiO,
K
Ca
Sc
V
Cr(ug/JO
Mn
Fe
Co
Hi
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/i)
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(pg/£)
Th
U
107
ANALYSES FROM CONTINUOUS LEACHING OP REFUSE FROM ILLINOIS BASIN PLANT B
EXPERIMENT No. GL-73
Leachate Increment No.
2
1.2
2.1
1.19
3.0
49
122
29
8
146
•fO.Ol
0.35
53
5.8
1678
3.9
6.4
0.7
10.6
36
0.17
7_
1.6
1.9
2.58
6.4
120
327
106
10
313
0.71
126
14.4
3408
8.6
13.6
• 0.9
26.0
82
0.38
M
3.5
2.3
0.69
2.3
36
87
64
7
129
0.05
0.27
46
4.4
1005
2.5
4.3
< 0.05
8.5
0.36
0.02
28
0.10
0.28
0.09
0.02
0.12
0.02
< 0.01
17
5.3
2.7
0.11
0.43
60
8
15
2
21
0.01
0.06
7.5
0.7
159
0.4
0.63
< 0.07
1.3
0.39
0.04
3.8
0.01
li
10.5
2.8
0.05
0.37
24
1.6
10
2
15
< 0.01
0.01
0.8
0.23
60
0.1
0.24
< 0.08
0.51
1.9
< 0.01
1Z
15.1
3.0
0.03
0.27
11
< 1
10
1
9
0.01
0.4
0.1
26
< 0.05
0.06
< 0.06
0.22
0.7
44
18.3
3.0
0.02
0.23
1
< 1
10
1
6
< 0.01
0.8
0.1
24
< 0.05
0.06
< 0.06
0.17
0.6
53
13
0.02
5.8
0.03
0.2
Elemental concentrations reported as ug/mSl unless otherwise noted.
Total dissolved solids reported as wt. %.
-------
ANALYSES FROM CONTINUOUS LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT
EXPERIMENT No. GL-8a
Leachate Increment No.
Volume (£)
pH
TDSb
Na
Mg
Al
SiO,
K i
Ca
Sc
V
CT(UB/S.)
Mn
Fe
Co
Nl
Cu
Zii
Ga
As
Br
Rb
Ag
Cd(ug/8.)
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(Vg/«.)
Th
U
1.
0.1
1.7
8.1
21
368
910
34
21
532
3.25
1.4
400
44
12000
28
43
8
55
< 0.05
7.13
1.25
<2
<0.01
240
<0.05
<0.04
<0.5
4.59
0.46
0.20
0.69
0.44
0.05
-------
ANALYSES FROM CONTINUOUS LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT B
EXPERIMENT No. GL-9a
Leachate Increment No.
Volume (£)
PH
TDSb
Na
Mg
Al
SiO,
K L
Ca
Sc
V
Cr(ug/£)
Mn
Fe
Co
Nl
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/J>)
Sb
Cs
, La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(pg/8.)
Th
U
2
0.2
1.6
8.4
17
400
1080
140
25
579
3.32
1.69
544
47
12200
31
46
6
73
<0.05
5.45
<0.01
<2
<0.01
160
<0.05
<0.04
1.55
4.34
1.05
0.30
1.38
0.44
0.05
<0.02
<0.05
<0.01
<0.25
410
1.60
0.41
T_
1.2
2.1
1.2
4.6
60
129
101
11
273
0.10
0.56
60
7.1
1720
4
6.6
0.09
43
<0.05
0.72
0.03
<2
<0.01
46
-------
ANALYSES FROM CONTINUOUS LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT B
EXPERIMENT No. GL-103
Leachate Increment Ho.
Volume (£)
PH
TDSb
Na
Mg
Al
SiO,
K l
Ca
Sc
V
CrCvig/fc)
Mn
Fe
Co
Nl
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/«0
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb (pg/i)
Th
U
2
0.3
1.7
6.8
14
353
988
163
24
578
2.2
2.94
506
,-A2
10800
27
41
3
61
<0.05
<0.01
<0.01
<2
<0.01
240
<0.05
<0.04
1.5
2.8
1.1
0.18
1.1
0.3
0.04
<0.02
<0.05
<0.01
<0.25
360
0.9
0.3
3
1.5
1.6
6.9
15
753
946
40
22
971
2.7
2.63
510
41
11100
27
42
8
56
<0.05
<0.01
<0.01
<2
<0.01
240
<0.05
<0.04
1.3
2.7
0.3
0.17
0.9
< 0.03
0.03
< 0.02
< 0.05
< 0.01
< 0.25
280
1.3
0.4
6
2.6
2.6
0.2
5.2
10
10
37
6
98
< 0.01
0.11
8
1.1
286
0.60
1.1
< 0.07
2.0
< 0.05
< 0.01
< 0.01
< 2
< 0.01
5.1
<0.05
<0.04
<0.5
-------
ANALYSES FROM CONTINUOUS LEACHING OF REFUSE FROM ILLINOIS BASIN PLANT C
EXPERIMENT No. GL-203
Leachate Increment No.
Volume (£)
pH
TDSb
Na
Mg
Al
K
Ca
Sc
V
Cr(yg/£)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/A)
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
W
Hg
Th
U
I
0.1
2.4
3.1
3300
290
41
99
610
1.42
0.49
1040
26
2870
17.4
26.4
1.6
1.0
<0.05
0.69
<0.01
3.1
<0.01
1.6.0
<0.05
<0.04
1.16
4.47
0.92
0.16
0.58
0.19
0.03
<0.02
<0.05
0.2
<0.25
130
1.2
0.65
1
0.8
2.6
1.6
1600
140
38
68
440
0.75
0.21
510
14
1570
8.9
13.7
0.44
5
<0.05
0.15
<0.01
<2
<0.01
.72
<0.05
<0.04
0.92
3.72
0.71
0.13
0.35
0.14
0.02
<0.02
<0.05
<0.01
< 0.25
63
0.6
0.41
5.
1.2
2.8
1.2
1030
122
10
61
490
0.16
0.12
150
11
1250
7.2
10.6
< 0.05
5
< 0.05
0.10
0.11
< 2
< 0.01
38
< 0.05
< 0.04
0.62
2.58
0.44
0.09
0.21
0.07
0.01
< 0.02
< 0.05
< 0.01
< 0.25
27
0.1
0.18
8_
3.0
3.5
0.1
63
12
4
17
150
< 0.01
< 0.01
< 10
1
130
0.6
1
< 0.05
0.5
< 0.05
0.04 '
< 0.01
< 2
< 0.01
2
< 0.05
< 0.04
0.02
0.15
0.01
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
<0.25
< 2
<0.02
<0.01
11.
5.4
3.8
0.1
6
0.7
9
110
< 0.01
< 0.01
< 20
0.5
5.6
0.2
0.4
< 0.05.
0.3
< 0.05
0.03
< 0.01
< 2
< 0.01
0.8
< 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
X0.02
< 0.05
< 0.01
< 0.25
< 4
<0.02
<0.01
Elemental concentrations reported as yg/m£ unless otherwise noted.
Total dissolved solids reported as wt. %.
133
-------
APPENDIX M
DESCRIPTION OF STATIC LEACHING EXPERIMENTS WITH
COAL FROM ILLINOIS BASIN CLEANING PLANT E&
Experiment Ho. SCL-1
Time (Days)
0.01
0.01
0.01
1
1
1
1
1
1
7
7
7
7
7
7
7
lU
28
28
28
28
28
28
aAn average of coal samples 36 and 37 was used in these studies,
Wet coal sample uaed unless indicated.
Leachate No.
1/2 b
3
k
5
6
7A
8A
9
10
Il/I2b
13
lU
15
16
17
18 '
19/20
21/22b
23
2k
26
27
28
Refuse Size
-20 mesh
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-3/8 in.
-20 mesh
-20 mesh
-20 mesh
-3/8 in.
-3/8 in.
-20 mesh
-3/8 in.
T.,°C
22
22
22
22
22
75
75
22
22
22
22
22
75
75
22
22
22
22
22
22
75
22
22
Air
Limited
Limited
Limited
Limited
Limited
Open
Open
Open
Open
Limited
Limited
Limited
Open
Open
Open
Open
Limited
Limited
Limited
Limited
Open
Open
Open
3Coal sample dried at 6o°C "before leaching.
135
-------
ANALYSES FROM STATIC LEACHING OF PLANT E ILLINOIS BASIN COAL
EXPERIMENT No. SCL-13
Leachate Increment No.
Time (Days)
pH
TDSb
Na
Mg
Al
K.
Ca
Sc
V
Cr(yg/kg)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/kg)
Sb
Cs
La
Ce
Sro
Eu
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb
Th
U
IC
0.01
5.3
0.06
70
30
<6
20
415
<0.01
<0.07
30
5
21
5
10
<0.01
1.2
<0.2
<0.02
<0.04
<8
<0.04
20
<0.2
<0.16
<2
<0.32
<0.08
<0.05
<0.01
<0.12
<0.01
<0.08
<0.2
<0.04
<1
0.58
<0.08
0.1
lc
0.01
5.4
0.06
70
30
<6
20
415
<0.01
<0.07
35
5
27
5
10
<0.01
1.1
<0.2
<0.02
<0.04
<8
<0.04
20
<0. 2
<0.16
<2
<0.32
-------
ANALYSES FROM STATIC LEACHING OF PLANT E ILLINOIS BASIN COAL (Cortt.)
EXPERIMENT No. SCL-13
Leachate Increment No.
Time (Days)
PH
TDSb
Ha
Mg
Al
K
Ca
Sc
V
Cr(ug/kg)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
•
-------
APPENDIX N
DESCRIPTION OF CONTINUOUS LEACHING STUDIES OF
COAL FROM ILLINOIS BASIN CLEANING PLANT E&'
Experiment No. Leachate Flow Pattern
CL-5 Interrupted at O.^Jl for 1 day
Interrupted at l.Uifor 1 day
Interrupted at 2.2£for 1 day
Interrupted at 3.8£for 2 days
Interrupted at U.S&for 2 days
Interrupted at T.Ufor 7 days
CL-6 Interrupted at 0.8£ for 1 day
Interrupted at 1.3& for 2 days
Interrupted at 2.8& for 1 day
Interrupted at h.8& for 2 days
Interrupted at 7.1& for 2 days
Interrupted at 10.1JI for 6 days
CL-7 Uninterrupted
CL-8 Uninterrupted
a
These experiments were conducted at ambient temperature with 0.95 kg
of coal material crushed to -3/8 in. and packed into a TO-cm-long by
^.6-cm-diam glass column. Leachate (distilled water) flow rate was
maintained at 0.5 ml/min.
An average of coal samples 36 and 37 was used in these studies.
139
-------
ANALYSES FROM CONTINUOUS LEACHING Of ILLINOIS BASIN PLANT E COAL
EXPERIMENT No. CL-5a
Leachate Increment No.
Volume («,)
PH
TDSb
Na
Mg
Al
K
Ca
Sc
V
Cr(ug/!.)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
CddJg/H)
Sb
Cs
La
Ce
Sra
Eu
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb()Jg/£)
Th
U
2+3
0.2
2.2
3.76
25
87
125
0-9
515
0.445
0.58
144
22
5240
9.4
17
4.8
13
0.07
6.64
< 0.01
< 2
< 0.01
70
< 0.05
< 0.04
0.80
1.38
0.35
0.11
0.66
0.20
0.02
< 0.02
< 0.05
< 0.01
< 0.25
15
0.34
0.22
6+7
0.9
2.4
1.45
14
45
59
1
400
0.19
0.40
66
10
2420
4.7
9
2.6
7
<0.05
1.25
< 0.01
< 2
< 0.01
48
< 0.05
< 0.04
0.18
0.35
0.20
0.05
0.43
0.05
0.01
< 0.02
< 0.05
< 0.01
< 0.25
24
0.10
0.09
8+9
1.2
2.6
0.70
6
17
22
2.5
470
0.06
0.18
25
5
940
1.8
4
0.9
3
<0.05
0.25
< 0.01
< 2
< 0.01
23
< 0.05
< 0.04
< 0.5
0.15
0.09
0.02
0.20
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
8
0.04
0.04
13+14
2.1
2.9
0.24
2
4
4
4
305
0.01
0.03
4
1
200
0.4
0.7
0.2
0.5ft
<0.05
0.01
<0.01
<2
<0.01
8
<0.05
<0.04
<0.5
<0.08
0.03
0.01
0.05
<0.03
<0.01
<0.02
<0.05
<0.01
<0.25
9
<0.02
0.01
22+23
4.5
2.8
0.08
9
0.5
1.5
1
81
< 0.01
< 0.01
< 3
0.2
31
0.09
0.1
0.2
0.11
<0.05
< 0.01
0.01
< 2
< 0.01
2
' 0.05
< 0.04
< 0.5
< 0.08
< 0.02
< 0.01
0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
9
< 0.02
< 0.01
29+30
5.2
2.7
0.12
2
0.5
1.5
0.9
92
0.01
0.01
< 3
0.4
100
0.09
0.2
0.2
0.17
<0.05
0.03
< 0.01
< 2
< 0.01
2
0.05
0.04
0.5
0.08
0.02
< 0.01
0.02
c 0.03
' 0.01
< 0.02
< 0.05
< 0.01
< 0.25
2
< 0.02
< 0.01
34+35
7.0
3.2
0.04
2
0. L4
< 0.7
1
14
< 0.01
< 0.01
< 3
0.07
15
< 0.07
< 0.07
0.02
< 0.02
< 0.05
0.02
- < 0.01
< 2
< 0.01
0.5
< 0.05
< 0.04
< 0.5
0.02
< 0.02
s 0.01
< 0.01
' 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
0.7
< 0.02
< 0.01
39+40
8.2
2.2
0.41
2
1
7
0.8
130
0.04
0.08
7
1
640
0.2
0.6
1.6
0.57
< 0.05
0.75
< 0.01
< 2
< 0.01
10
0.03
< 0.04
< 0.5
< 0.5
0.04
0.01
0.10
0.02
' 0.01
< 0.02
< 0.05
< 0.01
< 0.25
< 2
0.04
0.03
44+45
8.6
2.4
0.31
3
1
4
3
110
0.01
0.07
4
0.9
470
0.2
0.4
0.3
0.44
< 0.05
< 0.01
< 0.01
< 2
< 0.01
9
< 0.05
< 0.04
< 0.5
< 0.5
0.02
0.01
0.05
0.03
0.01
0.02
0.05
0.01
0.25
5
< 0.02
0.01
46+47
11.5
3.1
0.02
1
0.07,
< 0.6
0.9
3
<0.01
' 0.01
< 3
0.02
11
< 0.06
< 0.06
< 0.02
< 0.02
< 0.05
< 0.01
< 0.01
< 2
< 0.01
< 0.2
< 0.05
< 0.04
< 0.5
< 0.5
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
< 2
<0.02
< 0.01
aElemental concentration reported as jig/mfc unless otherwise indicated-
Total dissolved solids in wt. %.
-------
ANALYSES FROM CONTINUOUS LEACHING OF ILLINOIS BASIN PLANT E COAL
EXPERIMENT No. CL-63
Leachate Increment No.
Volume («,)
PH
TDSb
Na
Mg
Al
K
Ca
Sc
V
Cr(ng/Jl)
Mn
Fe
Co
N.i
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(yg/J.)
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
H£
Ta
W
Hg
Pb(yg/£)
Th
U
4+5
0.2
2.1
2.50
20
78
113
0.7
480
0.42
0.79
230
70
4830
9
16
5
12
<0.05
"O.Ol
<0.01
<2
<0.01
91
<0.05
<0.04
<0.5
0.68
0.34
0.09
0.72
0.22
0.03
<0.02
<0.05
<0.01
-------
ANALYSES FROM CONTINUOUS LEACHING OF ILLINOIS BASIN PLANT E COAL
EXPERIMENT No. CL-73
Leachate Increment No.
Volume (i)
PH
TDSb
Na
Mg
Al
K
Ca
Sc
V
Cr(ug/£)
Mn
Fe
Co
Nl
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/i)
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb(ug/J.)
Th
U
2+3
0.2
2.2
2.94
29
93
125
5.5
500
0.42
0.58
150
23
5800
10
18
6
13
< 0.05
< 0.01
0.03
< 2
< 0.01
83
< 0.05
< 0.0k
0.54
0.57
0.28
0.09
0.64
0.20
0.01
< 0.02
< 0.05
< O.OJ.
< 0.25
45
0.38
0.18
9+10
0.5
2.3
1.74
16
52
75
0.5
470
0.20
0.32
60
14
3120
5.6
11
2
8
< 0.05
< 0.01
< 0.01
< 2
< 0.01
71
< 0.05
< O.Qlt
< 0.5
0.37
0.30
0.06
0.38
0.10
0.02
< 0.02
< 0.05
< 0.01
< 0.25
13
0.09
0.11
12+13
1.0
2.4
1.02
10
30
38
0.8
420
0.07
0.32
34
8
2430
3.2
6
1
5
< 0.05
< 0.01
< 0.01
< 2
< 0.01
38
< 0.05
< o.ok
0.13
< 0.08
0.16
0.04
0.31
0.05
0.01
< 0.02
< 0.05
< 0.01
< 0.25
15
0.02
0.07
14+15
1.9
2.9
0.21
2
5 >
5
1.5
260
< 0.01
0.04
4
2
260
0.5
1
0.05
0.8
< 0.05
< 0.01
< 0.01
< 2
< 0.01
13
< 0.05
< 0.0k
< 0.5
< 0.08
< 0.02
0.01
0.06
0.01
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
5
< 0.02
< 0.01
17+18
2.5
3.1
0.10
1.5
1.5
1
6
160
<0.01
< 0.01
< 3.5
0.5
70
0.2
0.3
< 0.02
0.2
< 0.05
0.02
< 0.01
< 2
< 0.01
2
< 0.05
< O.Qk
< 0.5
< 0.08
< 0.02
< 0.01
0.01
< 0.03
< 0.01
< 0.02
< 0,05
< 0.01
< 0.25
5
< 0.02
< 0.01
19+20
3.1
3.2
0.07
1
0.8
< 0.7
0.9
135
< 0.01
< 0.01
< 3.5
0.2
37
0.09
0.2
< 0.02
0.1
< 0.05
< 0.01
< 0.01
< 2
< 0.01
1
< 0.05
< 0.0k
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
< 0.03
< 0.01
< 0.02
< 0.05
< 0.01
< 0.25
< 2
< 0.02
< 0.01
32+33
7.0
3.3
0.03
2
0.2
< 0.7
0.75
32
< 0.01
< 0.01
< 3.5
0.1
2
< 0.08
< 0.08
< 0.02
0.03
< 0.05
< 0.01
< 0.01
< 2
< 0.01
1
< 0.05
< O.Olt
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
<0.03
< 0.01
c 0.02
< 0.05
< 0.01
< 0.25
< 2
< 0.02
< 0.01
44+45
10.2
3.6
0.02
2
0.09
< 0.7
0.5
9
< 0.01
< 0.01
< 3.5
0.02
2
< 0.08
< 0.08
< 0.02
< 0.02
< 0.01
< 0.01
< 0.01
< 2
< 0.01
0.3
< 0.05
< 0.0k
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
<0.03
< 0.01
< 0.02
< 0.01
< 0.01
< 0.25
2
< 0.02
< 0.01
56+57
15.0
3.5
0.02
2
0.1
< 0.7
4.5
9
< 0.01
<: 0.01
< 3.5
0.05
0.7
< 0.08
< 0.03
< 0.02
< 0.02
< 0.05
< 0.01
< 0.01
< 2
< 0.01
0.2
< O.OJ
< O.Olt
< 0.5
< 0.08
< 0.02
< 0.01
< 0.01
<0.03
<0.01
<0.02
<0.05
<0.01
<0.?5
5
<0.02
< 0.01
62+63
20.5
3.9
0.02
1
0.07
< 0.7
1
5
-
< 3.5
0.02
2
< 0.08
< 0.08
< 0.02
< 0.02
-
-
-
-
-
1
-
-
-
-
-
-
-
-
-
-
-
-
-
2
-
Elemental concentrations reported as pg/m£ unless otherwise indicated.
Total dissolved solids reported as wt. %.
-------
ANALYSES FROM CONTINUOUS LEACHING OF ILLINOIS BASIN PLANT E COAL
EXPERIMENT No. CL-83
Leachate Increment No.
Volume («,)
pH
TDSb
Na
Mg
Al
K
Ca
Sc
V
CrCwg/JO
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Ag
Cd(ug/H)
Sb
Cs
La
Ce
Sm
Eu
Dy
Yb
Lu
Hf
Ta
W
Hg
Pb (yg/ i)
Th
U
2+3
0.2
2.3
3.87
29
92
126
0.5
460
0.16
0.54
146
25
7160
11
20
5.5
14
< 0.05
< 0.01
< 0.01
< 2
< 0.01
76
< 0.05
< 0.04
< 0.5
< 0.08
0.10
0.04
0.62
0.04
0.01
<0.02
-------
TECHNICAL REPORT DATA
t: readlnuructions on tin: n'l-cm before
I. REPORT NO.
EPA-600/7-78-G28a
4. TITLE AND SUBTITLE
Trace Element Characterization of Coal Wastes--
Second Annual Progress Report
6. PERFORMING ORGANIZATION CODE
7.AUTHOR[S) E. M. Wewerka, J. M. Williams, N. E.
Vanderborgh, A. \V. Harmon, P. Wagner, P. L.
Wanek, and J. D. Olsen
9. PERFORMING ORGANIZATION NAME ANO AODfiESS
Los Alamos Scientific Laboratory
University of California
Los Alamos , New Mexico 87545
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
July 1978
8. PERFORMING ORGANIZATION REPORT MC
LA-73 60-PR
10. PROGRAM ELEMENT NO.
EHE623A
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
11. CONTRACT/GRANT NO
IAG-D5-E681
13 TYPE OF REPCR" ANC PERIOD COVERED
Progress_Rej2ort:J 0/76- 9/77_
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES TERL-RTP project officer is David A. Kirchgessncr . Mall Drop
61, 919/541-2851. EPA-600/7-78-028 is earlier report in this series.
16. ABSTRACT
The report describes the results to date of research to assess the poten-
tial pollution by trace elements discharged from coal storage piles and coal cleaning
wastes. Mineralogic and trace element analyses on raw coal and coal wastes from
three Illinois Basin preparation plants have been completed. Static and dynamic
aqueous leaching studies to determine the release potential of pollutants from coals
and coal cleaning wastes have also been completed. Based on their toxicity and
teachability, the nine trace elements of primary environmental concern are F, Al.
Mn, Fe, Co, Ni, Cu, Zn, and Cd.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Trace Elements
Coal
Coal Dust
Coal Storage
Wastes
Coal Preparation
Leaching
Toxicity
Chemical Analysis
Properties
Pollution Control
Stationary Sources
C har acter ization
b. IDENTIFIERS/OPEN ENDED TERMS
C. COSATI i idci/Gr.T.lp
13B
06A 07D,07A
21D 06T
081
Unlimited
19. SECURITY CLASS /This Rtporlj
Unclassified
21. NO. Ol PAGES
154
20.SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
*U.S. GOVERNMENT PRINTING OFFICE: 1978—777-089/117
144
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