DoE
United States
Department of Energy
Division of Environmental
Control Technology
Washington DC 20545
LA-8275-PR
EPA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-81-073
April 1981
Trace Element
Characterization
of Coal Wastes -
Fourth 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 Research 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
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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DoE LA-8275-PR
EPA-600/7-81-073
April 1981
UC-90I
Trace Element Characterization
of Coal Wastes -
Fourth Annual Progress Report
October 1,1978 - September 30,1979
by
J. M. Williams, J. P. Bertino,* M. M. Jones,
P. Wagner, P. L Wanek, L E. Wangen,
and E. M. Wewerka
Los Alamos National 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. INE825
EPA Project Officer: David A. Kirchgessner
Industrial Environmental
Research Laboratory
Research Triangle Park, NC 27711
DoE Project Officer: Cnarles Grua
Division of Environmental
Control Technology
Washington, DC 20545
'Consultant. I079 Mansion Ridge Road, Santa Fe, NM 8750I.
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 2
CHART OF WORK TASKS 6
TASK PROGRESS REPORT 7
I. TASK I: ENVIRONMENTAL CONTROL TECHNOLOGY FOR TRACE ELEMENTS
IN THE DRAINAGE FROM (HIGH-SULFUR) COAL PREPARATION WASTES . . 7
A. Waste Disposal 7
B. Altering the Waste 11
C. Moderating the Disposal Site with Abaters 18
D. Treating the Waste Effluent 29
E. Combined Pretreatment and Codisposal 30
F. Economics of Pollution Controls for Coal
Preparation-Combustion Scenarios 36
II. TASK II: IDENTIFY TRACE ELEMENTS OF ENVIRONMENTAL CONCERN IN
(LOW-SULFUR) COAL PREPARATION WASTE FROM THE
APPALACHIAN BASIN 39
A. Mineralogy and Cleaning Behavior 39
B. Trace Elements and Their Locations in the
Waste Structure 42
C. Trace Element Leachability 50
D. Assessing the Pollution Potential 58
III. TASK III: LEVEL I BIOASSAY OF (HIGH-SULFUR) COAL CLEANING
WASTES AND WASTE LEACHATES 64
A. Health Effects 64
B. Ecological Effects 66
C. Summary 68
MISCELLANEOUS 69
I. WASTE COLLECTION SUMMARY 69
II. DEVELOPMENT OF ASSESSMENT METHODS 72
A. Batch Leaching, LASL, ASTM, EPA, and RCRA 72
B. Column (Dynamic) Leaching 75
C. Visual Presentation of Statistical Results 78
D. Pollutant Attenuation and Movement Through Soils 78
E. Spark Source Mass Spectrometry (SSMS) Analyses 87
F. "Standard" Coal Waste Leachate 87
PERSONNEL 90
BIBLIOGRAPHY 91
v
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APPENDIX A
CONTENTS (Continued)
EFFECTS OF TEMPERATURE AND ADDITIVES ON SULFUR
RETENTION AND AQUEOUS TRACE ELEMENT RELEASES
FROM CALCINED COAL WASTE 92
I. CALCINING PROCEDURE '.'.'..... 92
II. CARBONATE TREATMENT 92
III. AQUEOUS LEACHING 92
APPENDIX B MORTARS FROM FINE COAL PREPARATION WASTE 95
I. CEMENT CYLINDER PRODUCTION 95
II. CYLINDRICAL SPECIMENS 95
III. LEACHING 95
APPENDIX C LIME/LIMESTONE TREATMENT OF COAL WASTE 98
I. MIXING PROCEDURE 98
II. LEACHING 98
APPENDIX D ATTENUATION OF SEVERAL TRACE ELEMENTS IN A
COAL WASTE LEACHATE BY SOLID MATERIALS -
SUCCESSIVE INCREMENT METHOD 104
APPENDIX E ATTENUATION OF SEVERAL TRACE ELEMENTS IN A
COAL WASTE LEACHATE BY SOLID MATERIALS -
BATCH METHOD USING DILUTED LEACHATE 107
APPENDIX F EFFECT OF pH ON TRACE ELEMENT LEVELS IN
COAL WASTE LEACHATES 117
APPENDIX G LIME/LIMESTONE/COAL WASTE SLURRIES -
AN ATTRACTIVE ROUTE TO COAL WASTE DISPOSAL 119
I. PREPARING THE LIME/LIMESTONE/
COAL WASTE SLURRIES 119
II. DUMPING THE SLURRIES INTO DISPOSAL BOXES .... 119
III. RAIN-DRY WEATHERING CYCLES (IN PROGRESS) .... 119
IV. DISPOSAL BOX DISMANTLEMENT AND SOLID WASTE
EVALUATION (IN PROGRESS) 122
APPENDIX H TRACE ELEMENT AND MINERAL ANALYSES AND
CORRELATIONS FOR A LOW-SULFUR APPALACHIAN
COAL PREPARATION PLANT 123
APPENDIX I BATCH LEACHINGS OF LOW-SULFUR APPALACHIAN COAL
PREPARATION WASTE FROM PLANT G 128
APPENDIX J COLUMN LEACHINGS OF LOW-SULFUR APPALACHIAN COAL
PREPARATION WASTE FROM PLANT G 130
VI
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CONTENTS (Concluded)
APPENDIX K BIOASSAY RESULTS 138
I. FRESHWATER-ALGAE 138
II. MUTAGENESIS (AMES) 143
III. RABBIT ALVEOLAR MACROPHAGE (RAM) 143
IV. HUMAN LUNG FIBROBLAST (WI-38) 144
V. CLONAL TOXICITY (CHO) 145
VI. QUANTAL RODENT TOXICITY 146
APPENDIX L pH-CONTROLLED LEACHING OF COAL WASTE,
FLY ASH, AND SOIL 147
APPENDIX M ATTENUATION OF SEVERAL TRACE ELEMENTS IN A
COAL-WASTE LEACHATE PASSED THROUGH
COLUMNS OF SOILS 151
APPENDIX N SPARK SOURCE MASS SPECTROMETRY SAMPLE
PREPARATION AND ANALYSIS 153
APPENDIX 0 RAINWATER FLOW THROUGH A COAL WASTE DUMP 155
vii
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ILLUSTRATIONS
Figure
1 Schematics for several coal waste, burial
scenarios. 8
2 Particle sintering of calcined coal
preparation waste. 11
3 Sulfur retention as a function of calcination
temperature and Ca/S molar ratio. 12
4 Sulfur retention as a function of temperature
at Ca/S = 1.5. 13
5 Effect of physical proximity on the retention
of sulfur during coal waste calcining with
dry-mixed carbonate. 14
6 Leachate pH for coal waste calcined at various
temperatures. 15
7 The pH, iron, and manganese levels in leachates
from coal wastes slurry treated with alkaline
agents. 19
8 Relative amount of natural sorbent needed' to
attenuate coal waste acidity as a function
of the carbonate level in the sorbent. 22
9 Relative amount of natural sorbent needed to
attenuate coal waste acidity as functions of the
carbonate level and particle size of the sorbent. 23
10 The pH of 0.14M sulfuric acid solutions treated
with natural sorbents having different
carbonate contents. 24
11 Trace element concentrations in coal waste
leachate at various pH values. 31
12 Stages in laboratory demonstration of lime/
limestone/coal waste disposal method. 32
13 Leachate pH from lime/limestone/coal-waste
mixes weathered weekly in open disposal boxes. 33
Vlll
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ILLUSTRATIONS (Continued)
Figure Page
14 Conductivity of leachates from lime/
limestone/coal-waste mixes weathered
weekly in open disposal boxes. 34
15 Total iron levels in leachates from lime/
limestone/coal-waste mixes weathered weekly
in open disposal boxes. 35
16 Particle size distributions of high-sulfur
and low-sulfur coal wastes. 40
17 Photomicrographs of the float/sink fractions
from a low-sulfur, Appalachian coal waste. 41
18 Particle density distributions of high-sulfur
and low-sulfur coal wastes. 42
19 Trace-element, correlation-coefficient
clusters for all coal and refuse samples
collected from Plant G. 45
20 Major element associations in Plant G,
Appalachian coal waste. 46
21 SEM photographs of selected particles
observed in a low-sulfur coal preparation
waste. 47
22 The pH and trace element levels as a function
of leach time during the batch leachings of a
low-sulfur, Appalachian coal waste. 51
23 Relationships between the percentages of
trace elements released from high-sulfur
and low-sulfur coal preparation wastes. 54
24 The pH-controlled release of elements into
coal waste leachates. 55
25 Leachate pH, total dissolved solids, and
potassium and iron levels for column
leachings of Plant G coal preparation waste. 56
26 Elemental associations from the column leaching
data of a low-sulfur coal waste. 57
IX
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ILLUSTRATIONS (Continued)
Figure Page
27 Elemental associations from the column leaching data
of a high-sulfur coal waste. 59
28 Discharge severity for column leachates of several
coal wastes. 61
29 Discharge severity for batch leachates of several
coal wastes. 62
30 The pH influence on the leachability of iron from an
eastern fly ash. 73
31 The pH influence on the leachability of iron from an
Illinois soil. 74
32 Ferrous ion attenuation by Kentucky coal seam No. 11
overburden as a function of the direction of leachate
flow at comparable flow rates. 77
33 Trace element attenuation by increasing amounts of a
soil acting on a coal waste leachate. 80
34 The pH of effluent from coal waste leachate-solid mixtures
(2:1) as a function of the same solids in 2:1 mixtures
with 0.14M H2S04. 81
35 Trace element and pH levels of leachates from successive
batch equilibrations with sorbents. 82
36 Manganese levels in effluents from soils treated with coal
waste leachate as a function of influent Fe++ levels. 83
37 Trace element and pH levels of effluents from a column
packed with an unweathered, calcareous till. 85
38 Trace element and pH levels of effluents from a column
packed with a weathered Loess soil. 86
B-l The pH of leachates in contact with mortar cylinders
from fine aggregate coal waste. 96
x
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ILLUSTRATIONS (Concluded)
Figure Page
E-l Trace elements in effluents attenuated by sorbents. Ill
H-l Trace-element, correlation-coefficient clusters for
sized fractions of the average coal preparation waste
from Plant G. 127
H-2 Trace-element, correlation-coefficient clusters for float/
sink fractions of the average coal preparation waste from
Plant G. 127
J-l Total dissolved solids, pH, and trace element levels for
column leachings of Plant G, coal preparation waste. 134
L-l The pH influence on the leachability of iron from an
Illinois Basin coal waste. 150
XI
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TABLES
Table
I
II
III
WASTE CONTROL APPROACHES
SOME ISSUES TO BE CONSIDERED WHEN ADDRESSING CONTROL
TECHNOLOGIES FOR TRACE ELEMENTS IN COAL REFUSE DRAINAGE
EFFECTS OF CALCINING CONDITIONS ON AQUEOUS TRACE ELEMENT
RELEASES FROM CALCINED COAL WASTES
Page
9
10
16
IV STRUCTURAL STABILITY AND LEACHATE pH FOR MORTARS FROM
FINE COAL PREPARATION WASTE 17
V CALCIUM CARBONATE TREATMENTS OF COAL WASTE 18
VI DISCHARGE SEVERITY FOR CALCIUM CARBONATE TREATMENT OF
COAL WASTES 20
VII SORBENTS TESTED FOR THEIR ABILITY TO ATTENUATE COAL
WASTE ACIDITY 21
VIII SORBENTS RATED FOR THEIR ABILITY TO ATTENUATE COAL
WASTE ACIDITY 25
IX ATTENUATION OF TRACE ELEMENTS IN COAL WASTE LEACHATES
BY FUELS AND PROCESS WASTES 27
X
ATTENUATION OF TRACE ELEMENTS IN COAL WASTE LEACHATES
BY SOILS AND CLAYS
28
XI
TRACE ELEMENT ATTENUATION BY SORBENTS CAPABLE OF
CONTROLLING COAL WASTE ACIDITY
29
XII COSTS OF VARIOUS OPTIONS FOR CONTROLLING POLLUTION
FROM COAL CLEANING WASTES
XIII SULFUR LEVELS AND CLEANING YIELDS FOR THREE
ILLINOIS BASIN COAL CLEANING PLANTS
XIV COMBINED CONTROL TECHNOLOGY COSTS TO MEET WATER
QUALITY STANDARDS AT THE CLEANING PLANT AND STACK
EMISSION STANDARDS AT THE POWER PLANT
XV MINERAL COMPOSITIONS OF HIGH-SULFUR AND LOW-SULFUR
COAL WASTES
XVI COMPARISON OF TRACE ELEMENT LEVELS IN LOW-SULFUR COAL
WASTES WITH THOSE IN HIGH-SULFUR COAL WASTES
36
37
38
39
43
xii
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TABLES (Continued)
Table
XVII MINERAL LOCATIONS OF TRACE ELEMENTS IN A LOW-SULFUR
APPALACHIAN COAL WASTE
XVIII PERCENTAGES OF TRACE ELEMENTS LEACHED FROM SOME
COAL WASTES
XIX A RATING OF THE TRACE ELEMENTS OF CONCERN IN
APPALACHIAN LOW-SULFUR AND ILLINOIS BASIN HIGH-SULFUR
COAL PREPARATION WASTES
XX QUANTITATIVE SUMMARY OF HEALTH EFFECTS TESTS FOR A
COAL WASTE AND ITS LEACHATE
XXI TRACE ELEMENT CONCENTRATIONS AND DISCHARGE SEVERITY
FOR LEACHATES GIVING EC5Q IN CLONAL TOXICITY TEST
XXII QUANTITATIVE SUMMARY OF ECOLOGICAL EFFECTS TESTS FOR A
COAL WASTE AND ITS LEACHATE
XXIII TRACE ELEMENT CONCENTRATIONS AND DISCHARGE SEVERITY FOR
LEACHATES GIVING TLM5Q IN DAPHNIA MAGNA TOXICITY TEST
XXIV QUALITATIVE RESULTS OF LEVEL I BIOASSAY OF REFUSE
AND REFUSE LEACHATES
XXV RECORD OF COAL-PREPARATION PLANT SAMPLINGS
XXVI INFORMATION ON PREPARATION PLANT G
XXVII INFORMATION ON PREPARATION PLANT I
XXVIII INFORMATION ON PREPARATION PLANT K
XXIX INFORMATION ON PREPARATION PLANT M
XXX RECIPE FOR SYNTHETIC, HIGH-SULFUR COAL WASTE LEACHATE
A-l SULFUR RETENTION UPON CALCINING TREATED AND UNTREATED
COAL WASTE
A-II TRACE ELEMENT CONCENTRATIONS IN LEACHATES FROM CALCINED
COAL WASTES
50
52
63
65
66
67
67
68
69
70
70
71
71
88
93
94
xiii
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TABLES (Continued)
Table Page
B-I TRACE ELEMENT RELEASES FROM CEMENT/COAL WASTE CYLINDERS 97
C-I SUMMARY OF COAL WASTE-ALKALINE AGENT SLURRY EXPERIMENTS 99
C-II TRACE ELEMENT LEVELS IN LEACHATES FROM COAL WASTE
SLURRIED WITH LIME WHICH WAS THEN NEUTRALIZED WITH
CARBON DIOXIDE 100
C-III TRACE ELEMENT LEVELS IN LEACHATES FROM A COAL WASTE
SLURRIED WITH FINE-PARTICULATE CALCIUM CARBONATE 101
C-IV TRACE ELEMENT LEVELS IN LEACHATES FROM A COAL WASTE
SLURRIED WITH LIME FOLLOWED BY CALCIUM CARBONATE 102
C-V TRACE ELEMENT LEVELS IN LEACHATES FROM A COAL WASTE
SLURRIED WITH A GROUND LIMESTONE 103
D-l SOLID SORBENTS USED IN SUCCESSIVE INCREMENT, BATCH
EXPERIMENTS 105
D-II TRACE ELEMENT ATTENUATIONS BY SUCCESSIVE TREATMENTS
WITH SOILS AND ALKALINE SOLIDS 106
E-I SOLID SORBENTS USED IN DILUTED LEACHATE, BATCH
EXPERIMENTS 108
E-II TRACE ELEMENT ATTENUATIONS OF VARIABLY CONCENTRATED
LEACHATES BY SOILS AND ALKALINE SOLIDS 109
F-I TRACE ELEMENT LEVELS AS A FUNCTION OF THE pH OF A
COAL WASTE LEACH 118
G-I LIME/LIMESTONE/COAL WASTE SLURRIES 120
G-II pH OF EFFLUENTS FROM WEATHERED BOXES OF SLURRY-TREATED
COAL WASTE 121
G-III TOTAL IRON IN EFFLUENTS FROM WEATHERED BOXES OF
SLURRY-TREATED COAL WASTE 121
G-IV CONDUCTIVITY OF EFFLUENTS FROM WEATHERED BOXES OF
SLURRY-TREATED COAL WASTE 122
xiv
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TABLES (Continued)
Table Page
H-I SUMMARY OF PLANT G COAL AND REFUSE SAMPLES 123
H-II TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE
MATERIALS FOR APPALACHIAN PLANT G SAMPLES 124
H-III TRACE ELEMENT CONTENT OF SIZED WASTE MATERIALS FOR
APPALACHIAN PLANT G SAMPLES 125
H-IV TRACE ELEMENT CONTENT OF FLOAT/SINK-SEPARATED WASTE
FROM APPALACHIAN PLANT G 126
I-I TRACE ELEMENT LEVELS FROM THE BATCH LEACHINGS OF
LOW-SULFUR, PLANT G COAL WASTE 128
I-II DISCHARGE SEVERITY OF BATCH LEACHATES FROM LOW-SULFUR
AND HIGH-SULFUR COAL WASTES 129
J-I COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-23) 131
J-II COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-24) 132
J-III COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-25) 133
J-IV COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-26) 133
J-V DISCHARGE SEVERITY OF COLUMN LEACHATES FROM LOW-SULFUR
AND HIGH-SULFUR COAL WASTES 137
K-I TRACE ELEMENT LEVELS IN LEACHATE USED FOR ALGAL TEST 139
K-II RESULTS FOR SENSITIVITY OF FATHEAD MINNOWS TO COAL
WASTE LEACHATE 141
K-III RESULTS FOR SENSITIVITY OF DAPHNIA MAGNA TO COAL
WASTE LEACHATE 142
K-IV RESULTS OF RABBIT ALVEOLAR MACROPHAGE (RAM) TEST ON A
COAL WASTE AND ITS LEACHATE 143
xv
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TABLES (Concluded)
Table Page
K-V RESULTS OF HUMAN LUNG FIBROBLAST (WI-38) TEST ON A
COAL WASTE AND ITS LEACHATE 144
K-VI RESULTS OF CLONAL TOXICITY (CHO) TEST FOR COAL WASTE
LEACHATE 145
K-VII RESULTS OF CLONAL TOXICITY (CHO) TEST FOR COAL WASTE
SOLID 146
L-I LEACHING SOLUTION COMPOSITIONS FOR pH-CONTROLLED
LEACHING 147
L-II EFFECT OF ACIDITY ON THE LEACHING OF EASTERN FLY ASH 148
L-III EFFECT OF ACIDITY ON THE LEACHING OF AN ILLINOIS SOIL 148
L-IV EFFECT OF ACIDITY ON THE LEACHING OF AN ILLINOIS BASIN
COAL WASTE 149
M-I ATTENUATION OF TRACE ELEMENTS IN A COAL WASTE LEACHATE
BY A COLUMN OF UNWEATHERED, CALCAREOUS SOIL 151
M-II ATTENUATION OF TRACE ELEMENTS IN A COAL WASTE LEACHATE
BY A COLUMN OF WEATHERED AND LEACHED SOIL 152
N-I TRACE ELEMENT LEVELS IN NBS 1632 COAL BY SPARK SOURCE
MASS SPECTROMETRY 154
xvi
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TRACE ELEMENT CHARACTERIZATION OF COAL WASTES
FOURTH ANNUAL PROGRESS REPORT
October 1, 1978 - September 30, 1979
by
J. M. Williams, J. P. Bertino, M. M. Jones, P. Wagner,
P. L. Wanek, L. E. Wangen, and E. M. Wewerka
ABSTRACT
In the past year we continued our assessment studies of
low-sulfur coal wastes from the Appalachian Region. These
included mineralogical and trace elemental analyses on these
materials and studies of their weathering and leaching behav-
ior. Although the concentrations of the acid-forming minerals
(pyrite and marcasite) were very low, leachates were quite acid
(pH <_ 3) with concomitant trace element (Al, Mn, Fe, Ni, Cu)
concentration elevation. As part of the overall assessment of
the degree of environmental concern associated with acidic coal
waste drainages, bioassay studies were performed. These
revealed that coal wastes and their leachates are toxic to
fresh water algae, fathead minnows, and one species of fresh-
water flea.
Our laboratory experiments to identify control options for
the coal wastes and their drainages have been focused on pre-
disposal and codisposal treatments of the waste, with techni-
cal and economic evaluations being performed on the most prom-
ising options. One of the most promising control methods is
pretreatment of the waste with a lime/limestone mixture; this
produces a waste with no acid-forming tendencies for times up
to several months, during which time it may be possible to
dispose of the treated waste in a nonreactive environment. The
cost of this option is comparable to that of the commonly used
lime neutralization of the acid drainage. Other experiments
have investigated, in considerable detail, the economic and
environmental advantages and disadvantages of codisposing the
wastes with 37 naturally occurring soils and industrial wastes.
These methods look promising only under certain conditions, but
are in general an order of magnitude less effective than
existing controls or the lime/limestone disposal method.
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EXECUTIVE SUMMARY
This section summarizes some of the technical highlights, evalu-
ations, and recommendations from the ongoing research program at the Los
Alamos Scientific Laboratory (LASL) on the assessment of acid and trace
element contamination of aqueous drainages from coals and coal cleaning
wastes and from laboratory investigations of environmental controls
germane to these problems. Our research has identified the trace
-elements that are released in concentrations of environmental concern
during the leaching and weathering of coal refuse materials from the
Illinois Basin and from the Appalachian region. In this report we also
include the results of our bioassay evaluations on some of these high-
sulfur coal waste leachates. We have established general strategies for
the control of these acid and trace element releases and are performing
laboratory research to identify the most promising environmental control
technologies. These strategies fall into three general categories:
refuse treatment prior to disposal, disposal of the refuse in a manner
that prevents the release of aqueous contaminants from a refuse dump, and
treatment of the contaminated drainages after escape from the refuse
pile. The details of these and related research comprise this report of
our FY 1979 programmatic accomplishments.
The mineral wastes from coal mining and preparation constitute a
potentially major environmental problem. More than 3 billion tons of
these refuse materials have accumulated in the U.S., and the current
waste production is adding to this at a rate in excess of 100 million
tons each year. The number of coal waste dumps is estimated to be
between 3000 and 5000; half of these pose some type of health, environ-
mental, or safety problem. Structural weaknesses in coal refuse banks
have led to landslides in West Virginia and in Wales, both incurring
considerable loss of human life. In addition, there are some 300 burning
refuse piles that contribute strongly to the potentially serious air
pollution problems of the coal-utilizing areas of the central and eastern
U.S. There is also growing awareness and concern about environmental and
ecological effects resulting from the trace elements present in acid
drainages from coal preparation wastes and surface and underground water-
ways into which the coal waste leachates drain.
Although it has been known for some time that the drainages from
coal wastes may be highly contaminated with trace elements, until just a
few years ago little was known about the quantities of undesirable trace
elements released into the environment from this source. Since the
development of appropriate environmental control technologies for human
protection requires quantitative assessment of the extent and severity of
the problem, LASL's research, which is supported by the Department of
Energy (DOE) and the Environmental Protection Agency (EPA), has included
such an assessment program as an integral part of the laboratory invest-
igations of viable environmental controls for the contaminated drainages
from coal preparation wastes. Overall, the major objectives of LASL's
research program are
-------
- Assessment of the nature and magnitude of trace elements in
the effluents from coals and coal preparation wastes,
- Experimental identification of the chemistry of the trace
constituents of environmental concern,
- Identification and experimental verification of effective
environmental control strategies to control the release
of potentially hazardous trace elements, and
- Analysis of the tradeoffs associated with the different
control technologies and recommendations for required
pollution control or for necessary RD and D programs.
The table on p. 5 is a summary of the trace elements we have identified
in leachates from coal preparation wastes and their degree of environ-
mental impact.
During the past year the program included the specific tasks of
performing a Level-1 bioassay of coal wastes and coal waste leachates and
identifying trace elements of environmental concern in low-sulfur coal
preparation wastes from the Appalachian region. The results of the
bioassay studies revealed that both the coal wastes and their leachates
produce cytotoxic effects and that the leachates are toxic to freshwater
algae, fathead minnows, and a freshwater flea (Daphnia). The work on the
low-sulfur coal preparation wastes from the Appalachian region has begun
to show similarities, in acid-forming character and in leached trace
element types, with those of the Illinois Basin.
The research reported here represents a continuation of the studies
begun in FY 1976 to establish a firm foundation for subsequent efforts.
In the initial period we did the appropriate literature searches, devel-
oped laboratory and analytical techniques, collected coals and coal waste
samples from several parts of the country, and initiated laboratory
studies on the stated objectives. The technical highlights, conclusions,
and recommendations resulting from these efforts to date, with detailed
emphasis on the accomplishments during the period October 1, 1978 through
September 30, 1979, are described briefly in this summary and in detail
in the Task Progress Description and in the appendixes.
During the past year the emphasis of our assessment studies centered
on low-sulfur (<10%) refuse from a coal preparation plant in the Appala-
chian region. We performed extensive mineralogical and trace elemental
analyses on these materials, and we subjected these mineral wastes to
experiments designed to evaluate their weathering and leaching behavior
in a coal refuse pile. We then performed trace element analyses on the
leachates to quantify the level of pollution caused by the solubilized
trace elements. Despite the low concentrations of the acid-forming.
minerals (pyrite and marcasite), leachates from these waste materials
were quite acid with pH values of 3 or lower observed in the dynamic
column leachates, and pH values of about 4 in the shaker, batch leach-
ates. These data, when viewed in the context of our past observations
that the concentrations of trace elements released by a coal waste are
related to the acid-generating tendency of that waste, demonstrate that
even low-sulfur wastes have the potential of acting as sources of trace
elements in amounts that are of potential environmental concern. These
experiments are discussed in detail in the Task Progress section of this
report.
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Our research in environmental control technology for coal prepara-
tion wastes has followed the basic strategy wherein the wastes are
- Treated to make a nonpolluting solid waste,
- Disposed of in a manner to prevent the release of
trace elements, and
- Disposed of in a conventional manner, and the drainages
treated to remove the trace element contaminants.
Perhaps the most attractive technical solution to the disposal of
coal preparation wastes is conversion to a nonpolluting solid. Last
year, we reported experimental evidence that calcining converts coal
preparation wastes to a nearly neutral, nonpolluting mass. We also
reported, however, that the high-sulfur wastes lose 20 - 25% of their
weight during calcining and that this is largely due to the release of
nearly all (>95%) of the sulfur (as sulfur oxides). Loss of bromine,
cadmium, molybdenum, and lead was also observed. Employing technology
used in fluidized bed combustion, we have run a number of sulfur-
retention experiments in which calcium carbonate has been admixed with
ground coal waste before calcining. We found that the sulfur retention
is roughly proportional to the added carbonate for all temperatures
between 600 and 1000°C, with the maximum sulfur retention (79%) occurring
at 800°C. While calcining is clearly an excellent disposal strategy, our
economic analysis indicates that this technology is the most expensive
option that we have examined.
The second strategem in our control studies assumes that the solid
wastes may be disposed of in a manner that prevents the release of trace
elements of environmental concern. One method we tried was to slurry the
waste with a mixture of lime and limestone. The result was a waste with
leachate having a neutral pH and essentially total containment of trace
elements. Economically, this treatment was competitive with the most
economic control -- effluent lime neutralization; however, the long-term
effectiveness of the lime/limestone slurry method is still being investi-
gated in the laboratory and remains a question at this time.
Last year we reported on our initial efforts to locate materials
other than lime and limestone that might be codisposed with the coal
preparation wastes to produce a nonreleasing system. Our research has
broadened to include not only soils with an acid neutralizing ability,
but also commonly available natural or industrial materials that appear
to have the capability of removing trace elements by a sorbing mechanism.
Thus far we have included 37 codisposal agents, among them a variety of
calcareous and weathered soils, clays, scrubber sludges, ashes and
specialized materials like peat. In general, these materials were at
least an order of magnitude less effective than lime in elevating the
leachate pH values and attenuating the trace element concentrations. At
this stage in our investigations, we can say that this approach (i.e.,
use of a sludge to codispose of a coal waste also solves the sludge
removal problem) shows considerable promise, but it is clear that the
economics are less attractive than the lime/limestone slurry treatment or
the effluent alkaline neutralization.
-------
Our third step in the environmental control strategy for high-sulfur
coal preparation wastes involves treatment of the leachates. We reported
details on a number of water treatment methods last year. Because they
tre.at only a small portion of the potential polluting capacity of the
waste, economics and effectiveness are the strong points of these meth-
ods. Several, such as reverse osmosis and ion exchange, only concentrate
the pollutants and must also include another treatment step.
Alkaline neutralization, which incorporates acidity control, is the
best nondestructive control technology that we have found for handling
the trace element pollution in coal-preparation wastes. Alkaline neu-
tralization with lime is a state-of-the-art method. Alkaline neutraliza-
tion is a logical method to use because of its effectiveness, economy,
and ease of implementation by nontechnical personnel. Indeed, effluent
treatment by alkaline neutralization is the only control technology that
has been used to any large extent by the coal industry.
It is clear from our research that similarities and differences
exist in the drainages from the coal waste piles in Appalachia and the
Illinois Basin. Identification of similarities has the potential of
allowing us to generalize environmental controls; recognition of differ-
ences will tell us the limits of generic controls. Further research on
leachate contamination from more extensive sampling in coal production
regions, on generic controls applied to the coal wastes from these
regions and their leachates, and on statistical evaluation of these
controls and their economic and field-implementation tradeoffs is needed
in order that the completed work have a high degree of reliability and
not need to be redone for future integrated studies. The impending
extensive increase in the use of coal for synthetic fuels, from all the
coal regions in the nation, will require assessment and identification of
environmental controls far in excess of that which has already been done.
A substantial part of our effort will be directed to laboratory
research that bears directly on these problem areas.
EVALUATION OF POLLUTING POTENTIAL
OF TRACE ELEMENTS IN COAL PREPARATION WASTES3
Elements of concern under acid or neutral conditions:
Ni, Mn
Elements of concern under acidic (pH<4) condtions:
Al, Cd, Fe, Zn
Elements of concern only under highly acidic (pH < 2.5) conditions:
As, Be, Co, Cu, Pb, Se
aBased on EPA health and ecology MATEs data from column leachates.
-------
CHART OF WORK TASKS FOR FY 1979
TRACE ELEMENT CHARACTERIZATION AND REMOVAL/RECOVERY
FROM COAL AND COAL WASTES
TASK 1
ENVIRONMENTAL CONTROL TECHNOLOGY
FOR TRACE ELEMENTS IN THE DRAINAGE
FROM HIGH SULFUR COAL PREPARATION
WASTES
1.1 ASSESS TECHNOLOGY TO
IMMOBILIZE OR REMOVE TOXIC
TRACE ELEMENTS FROM REFUSE
MATERIALS
1.2 ASSESS TECHNOLOGY TO RETAIN
TRACE ELEMENTS CONTAMINA-
TION WITHIN REFUSE DISPOSAL
SITES
TASK 2
IDENTIFY TRACE ELEMENTS OF ENVIRON-
MENTAL CONCERN IN HIGH SULFUR COAL
PREPARATION WASTES FROM THE
APPALACHIAN REGION
TASK 3
LEVEL I BIOASSAY OF COAL WASTES
AND WASTE LEACHATES.
2.1 ASSESS TRACE ELEMENT
STRUCTURE AND MINERALOGY
IN REPRESENTATIVE REFUSE
SAMPLES
2.2 DETERMINE ENVIRONMENTAL
BEHAVIOR OF THE TRACE
ELEMENTS IN REFUSE
SAMPLES
1.3 ASSESS CONTROL TECHNOLOGY
FOR CONTAMINATED REFUSE
DRAINAGE
-------
TASK PROGRESS REPORT
The work plan for FY79 called for efforts to be expended in three
areas. These areas were designed to 1) determine the nature and magni-
tude of any problems of environmental concern resulting from trace ele-
ment release from coal preparation wastes (Task III); 2) evaluate the
extent and cause of problematic areas (Task II); and 3) perform the
research necessary to develop suitable environmental controls (Task I).
In the past 3 yr of the project, Tasks I and II have received the major
fraction of the effort. Task III was included this year to substantiate,
with biological evidence, the concerns that had already been identified
based on chemical evidence. We have also extended our study to include a
wider range of coal types. Because our research shows that the pollu-
ting potential of coal preparation wastes is of environmental concern,
our effort has continued to be concentrated into finding viable technical
and economical control methods. Following the described waste disposal
strategies, we have identified and evaluated a variety of control
technologies.
I. TASK I: ENVIRONMENTAL CONTROL TECHNOLOGY FOR TRACE ELEMENTS IN
THE DRAINAGE FROM (HIGH-SULFUR) COAL PREPARATION WASTES
One of the primary reasons for studying the releases of trace ele-
ments from high-sulfur coal preparation wastes is to provide necessary
information about the nature and magnitude of this form of pollution to
plan and develop environmental control strategies for coal refuse dumps
and disposal areas. The research done in the early years of the pro-
gram has provided us with a broad base of information and understanding
that we have used in our environmental control activities. This task
describes the work done in this area. Also included in our discussion
are economic and physical aspects of the various controls investigated,
and we have kept in mind potential impacts on solid waste disposal of the
Resource Conservation and Recovery Act (RCRA).
A. Waste Disposal
The ultimate waste disposal scheme is one that blends the waste into
the environment with no detrimental effects. Because burial restricts
wind and air access, water flow, and temperature fluctuations, it also
restricts pollutant movement and is a possibility that should be con-
sidered. The major problem with the burial of coal refuse is that, in
many parts of the country (especially where most of the acid-generating
coal is mined), it is difficult to identify underground burial sites
where ground or surface water will not eventually intrude into the area.
This intruding water can dissolve latent pollutants, allowing them to get
into general water systems. The possibility that this influxing water
can be acidic, as the result of acid mine drainage or acid rains, may
compound the problem when disposing of coal wastes in the coal mining
terrains of the East and Midwest.
-------
Burial sites for coal refuse are often located in hollows or val-
leys, where the wastes are compacted into layers, covered with topsoil
and revegetated. Increasingly, these waste materials are also being
deposited into depleted strip mines, and the possibility of disposal in
underground mines is being explored. Schematics of these methods are
presented in Fig. 1. It appears that both near-surface and strip or deep
mine burial of coal wastes will require measures to prevent or minimize
pollution of ground water. There are certain natural mechanisms that may
help to keep such contamination within acceptable limits, however. These
include sorption processes in rocks and soils, precipitation, coprecipi-
tation, dilution and dispersion of contaminants by the natural water
system, and biological activity. The effectiveness and magnitude of
treatment offered by these or other natural mechanisms depend on the
geological and hydrological conditions at a specific site. In many cases
the degree of buffering, attenuation, and dilution by aquifers is not
NEAR-SURFACE BURIAL OF COAL REFUSE- X
NEAR-SURTAX BURIAL OF COAL REFUSE -H
TOPSOIL
ING
COAL REFUSE BURIAL IN STRIPMINE
COAL REFUSE BURIAL IN DEEP MINE
//'//'/'//,' '/////
A/PRECIPITATION///
AQUIFERC
ion.
coal uicute.,
-------
known. In these cases, it would be difficult to predict reliably how
much natural attenuation of trace elements or other contaminants would
occur. It seems advisable, however, to let nature help. Wastes could be
placed under temporarily nonpolluting conditions that would allow time
for natural assimilation of the waste into the environment.
The high-sulfur coal preparation wastes have significant trace-
element polluting potential, resulting from pyrite oxidation. We have
found damp, oxidizing conditions to be the worst of all. Disposed of in
an untreated state, the waste must be isolated and any effluent must be
treated. Such containment is sometimes feasible over the short term but
impractical to guarantee over the long term. The widespread pollution
from acid mine drainage (AMD) is an excellent example of the difficulties
that can arise. Attempts to control AMD have met with limited success,
and long-term solutions seem lacking or prohibitively expensive. Placing
coal refuse under similar conditions in deep mines could create new
problems or aggravate an old one. Polluted drainage could continue for a
long time (see Appendix 0 for time calculation) . In addition to air and
water intrusions, near-surface and strip-mine sites are subject to ero-
sion by wind and floods. Sites designed to completely contain or channel
the pollutants may also be subject to earthquakes, tremors, roots of
trees and other plants, and burrowing animals. All these work to under-
mine burial scenarios based entirely on containment and subsequent treat-
ment by conventional means.
Ideal waste disposal sites would contain the pollutants completely,
release them at environmentally acceptable rates, or deliver them for
treatment at some collectible point. This is the crux of our waste
control philosophy: address the waste first, the disposal site next, and
the polluted discharges last. This approach is depicted in Table I.
While methods designed to treat the waste and make it innocuous are most
effective, other factors (e.g., economic positions) may favor other
control measures. For these reasons, our research efforts have mainly
been directed at the technical feasibility of various control methods.
Numerous questions may arise for the various options considered. Some of
the more recurrent questions are listed in Table II.
TABLE I
WASTE CONTROL APPROACHES
Approach
Waste
Disposal Method
Leachate
Disposal Method Leachate
Comment
Nonpolluting
\J Nonpolluting
Polluting
Clean Minimal environmental impact
Clean Compliance red tape
V Polluted Perpetual, elusive pollution
-------
TABLE II
SOME ISSUES TO BE CONSIDERED WHEN ADDRESSING CONTROL TECHNOLOGIES
FOR TRACE ELEMENTS IN COAL REFUSE DRAINAGE
• Effectiveness for treating or preventing the type and quantity of trace element contamina-
tion expected for refuse dump drainage
• Effectiveness of method for treating widely varying volumes of contaminated drainage
• Mechanism of process; what makes it work?
• Specific or general trace element removal
• Restrictions or shortcomings of method
• Time required to set up technique
• Special skills or training necessary to operate method
• Necessity for frequent or extensive maintenance or replacement
• Present state of development
• Current use; where and for what?
• Does expertise with the method now exist? Where and with whom?
• Expendable materials requirements; availability and transportation requirements
• Probable reliability
• Feasibility for use in coal industry
• Long and short term use implications; economic, technical, and environmental
• Potential for mineral or metal recovery
• Necessity of additional feasibility or assessment studies
• Capital equipment needs and costs
• Operating equipment needs and costs
• Comparative or absolute economics
10
-------
B. Altering the Waste
One good technical solution to the disposal of a hazardous, pol-
luting waste is the conversion of this waste to a nonpolluting one.
Last year, we reported experimental evidence that calcining converts
high-sulfur coal preparation wastes to nearly neutral and nonpolluting
systems. This is achieved with only moderate change, some sintering, in
the outward appearance of the wastes (see Fig. 2). We also reported,
however, that the waste loses 20 - 25% of its weight during calcining and
that this is largely due to the release of nearly all (>95%) of the
sulfur (as sulfur oxides). Bromine, cadmium, molybdenum, and lead were
also observed to be lost. Treating the effluent gases from calcining
would be akin to flue gas desulfurization (FGD) at a power plant. In the
following paragraphs, we describe experiments to retain the sulfur in the
calcined waste and present a discussion of the leaching behavior of such
a calcined waste.
Employing technology used in fluidized bed combustion, we have run a
number of experiments in which calcium carbonate has been admixed with
ground coal waste before calcining (see Appendix A). Because solid/solid
and solid/gas reactions are occurring, the method can give varying
degrees of sulfur retention, depending on the concentrations and physical
nature of the components and the temperature of the calcining. Sulfur
retention is roughly proportional to the added carbonate (as measured by
the Ca/S ratio)! for all temperatures between 600 and 1000°C (see
Fig. 3). The exact proportionality, however, is temperature related
with the maximum retention corresponding to 800°C (see Fig. 4).* This
F/uj. 2.
9($ calc-ined coal pfLqpaAntion
tAt a Ca/S = 1 ratio, 12 grams of calcium carbonate are added to 30 grams
of waste.
*Dry mixing of powdered ferric oxide and granular sodium chloride addi-
tive did not improve sulfur retention.
1 I
-------
0.5 1.0 1.5
Ca/S MOLAR RATIO
2.0
a.
g. 3.
and Ca/S
12
-------
80
70-
Q
UJ
60-
LJ
tr
££
50
40
C/5
30
600 800
TEMPERATURE (°C)
1000
. 4.
a.
Ca./S * 7.5
temperature corresponds to the disappearance of the XKD lines that iden-
tify the clay components (third annual report, LA-7831-PR, p. 9). Above
this temperature, the sulfur-containing species begin to release sulfur
dioxide and revert to the more stable oxide. At 1100°C, practically no
sulfur (<0.1%) is retained.
Smaller particles of waste and calcium carbonate combine to give
more contact area and, hence, higher sulfur retention than do larger
particles containing the same amounts of the sulfur and carbonate react-
ants (see Fig. 5).| Increasing the contact area by reducing the size of
either component improves the S retention (compare the half-shaded square
with the open squares of Fig. 5). More dramatic improvement results when
the components are slurry mixed (compare the solid and half-shaded
squares of Fig. 5).
Based on these findings, large quantities of coal wastes would have
to be handled in the treatment process and also be ground to fine parti-
cle sizes if most of the sulfur were to be retained in the waste mass
tVolumes occupied by 1 gram of material are 0.8 cc for -10+32 mesh
waste and limestone, 1.2 cc for -20 mesh waste, and 3.0 cc for AR
calcium carbonate.
13
-------
80
70
Q
UJ
2
ill 60
IT
tr
50
40
30
i
-20 MESH
COMPONENTS
I
-10+32 MESH
COMPONENTS
7
LEGEND
., SQUARES-10+32 MESH WASTE
// CIRCLES-20 MESH WASTE
III,
0
Ca/S MOLAR RATIO
f-ig. 5.
pky^-ical. ptioxMnLty on the. nztantijon. ofi i,vJL^(jJi dutu.n.Q coal
w-uth dny-mtmd caA-bonoute.. (-115 m&,h CaCO? iue.d Jin Ak&d&d
m-bcing ^on AoLid
during calcining. Under the best experimental conditions used, 20% of
the sulfur is off gassed. If calcining is to be employed, the best
procedure seems to be to concentrate the sulfur-control effort entirely
in the off-gas area by employing FGD technology.
Calcined coal preparation wastes form nearly neutral leachates which
increase slightly in alkalinity as the calcining temperature increases
(see Fig. 6). Likewise, the release of trace elements is dramaticallv
14
-------
-H-
8
I
Q.
20 600 800 1000
CALCINING TEMP (°C)
f^Q. 6.
Leackatz. pH fan. coat waAte. c.cULcJin
-------
TABLE III
EFFECTS OF CALCINING CONDITIONS ON AQUEOUS TRACE ELEMENT
RELEASES FROM CALCINED COAL WASTESa
remp(°C)b
Control
600
800
1000
PH Controlled
Leachate6
Ecological
MATE Values
Ca/Sc Leachate"
0 Water
0 Water
0 Water
1.0
0 Water
0 0.4M H2S04
Water + Lime"
-
pH TDS(%)
2.9 O.(i3
6.6 0.38
6.9 0.33
12.4 0.34
8.0 0.17
2.9 0.5
8.1
-
Al Ca
100 550
<0.8 (ill)
0.38 5(iO
().(! i>00
(),.( -100
88 580
<0,l 500
1 16
Cd F
0.008 14
0.005 0.5
0.0008
0.0000
0.0002 1
<0.0()08 40
<0.009 10
0.001
Fe
600
<0.()5
0.5
0.05
<0.03
25
2.2r
0.25
Mn Na
5.8 76
4.2 73
3.2
0.03
0.03 12
1.2 30
0.3
0.1
Zn
2.8
0.35
0.43
0.11
0.05
3.8
<0.02
0.1
'Element values in rag/I
'Calcined in muffle furnace for 2h.
"Calcium to sulfur molar ratio for added calcium carbonate
4«n leach, 4 mi, leachate per gram waste,
J>Pen to air, magnetically stirred.
rorn Table F-I on alkaline neutralization of coal
waste leachates.
ferrous cation accounts for nearly all the iron present.
-------
Forming cement blocks from the waste is a method of altering the
waste which does not require the expensive on-site furnaces, etc.,
required by the calcining process. To evaluate the potential of this
technique, we have prepared small (2.5-cm-high by 3-cm-diam) cylinders
using fine (-20 mesh) coal waste as the aggregate (see Appendix B) . The
mixes for these cylinders were prepared as variations on the ASTM formula
for mortars, i.e., one part portland cement, one-half part hydrated lime,
and three parts fine aggregate (see Table IV). Even though the cylinders
were small, they began to spall as the aggregate level was increased
above the norm. At high aggregate loading (1 cement:1/2 lime:12 aggre-
gate) and lower loadings without lime (1:0:6), the cylinders rapidly
disintegrated when placed in water. For structural integrity to be
maintained, the coal-waste concrete blocks will need to be richer in
cement and lime.
Leachates in contact with the coal-waste cement cylinders were
initially quite alkaline (see Table IV). The pH values dropped as fresh
water was brought into contact with the solid. After five water changes,
the pH values were down to 9 and leveling off. Trace element levels at
this point were well below levels of concern (see Appendix B) . As with
the calcining method, the major effect here is probably pH control. One
of the leached specimens (1:1/2:6) spalled but still gave acceptable
leaching behavior; higher loading of waste materials will be possible if
lower structural requirements are acceptable.
Waste alterations could provide an excellent way to dispose of coal
preparation wastes. Removal of the acid-generating components via
calcining appears to be an excellent predisposal treatment for coal prep-
aration wastes in order to release potentially hazardous levels of trace
elements. Our analysis reveals, however, that calcining is an expensive
option.
TABLE IV
STRUCTURAL STABILITY AND LEACHATE pH FOR MORTARS
FROM FINE COAL PREPARATION WASTE
Leachate pH
Mix* Structural Stability Initial 5th Rainc
1:1/2:3 Sound; sand control13 11.5 9.0
1:1/2:3 Like sand control 11.5 9.0
1:1/2:6 Some cracking on drying 11.5 8.9
1:0:6 Disintegrated within 1 minute in water
1:1/2:12 Disintegrated within 1 hour in water
BVolume parts of portland cement:hydrated lime:-20 mesh waste."
"Sand used instead of waste.
"Each rain of 250 m& was in contact with
cylinder for several days to weeks.
17
-------
C. Moderating the Disposal Site with Abators
The second option in our control strategy uses the approach that a
hazardous, polluting waste can be placed in a disposal site in such a way
that it will release pollutants at an acceptable level. Coal production
for energy produces several large-volume waste problems. Large acreages
of overburden are disturbed; acidic coal preparation wastes are produced;
and fly ash, bottom ash, and sludges from flue gas scrubbers are gener-
ated. Each poses a disposal problem of its own. Conceivably, two or
more of these problems can be handled together to create a single waste
with more desirable characteristics. (This may be practical where mine
mouth plants are operated.) Our objective here has been to evaluate ways
that coal preparation waste can be codisposed to produce acceptable
leachates and ways other coal production and utilization wastes can be
used in achieving a symbiotic codisposal scheme.
In our third annual report (LA-7831-PR), we related our partially
successful efforts to dry-mix coarse (-3/8-in.)limestone with acidic coal
preparation waste and pass the leachate through crushed (0.84-mm) lime-
stone. By using hydrated lime slurries, however, acceptable leachate
levels of trace elements could be obtained, but the pH levels were diffi-
cult to control and often were very high. We have continued this series
of experiments to determine whether fine-particle limestone slurries
could give acceptable leachates with regard to both trace element and
acidity levels.
Calcium carbonate was added to acidic coal-preparation waste in four
ways. A short tabulation is given in Table V. (Full descriptions and
results appear in Appendix C.) In CTWT-11-6, the calcium carbonate was
produced by converting most of the unneutralized lime to CaCC- with car-
bon dioxide. In CTWT-11-8, some of the acid present was neutralized by
TABLE V
CALCIUM CARBONATE TREATMENTS OF COAL WASTE2
Sample
No.
Neutralizing Agent
Additive
Size
___ Type of Initial
(%) Mixing pH
CTWT-11-6 Ca(OH)2 + C02 -100 mesh 5.0 Slurry
CTWT-11-7 CaC03 -100 mesh 6.7 Slurry
CTWT-11-8 Ca(OH)2 +
CaCO3
CTWT-11-9 Limestone
-100 mesh 1.5 Slurry
-100 mesh 4.0
-20 mesh 6.0 Slurry
7.4
6.9
6.2
6.4
"-3/8 inch Plant B average coal waste.
18
-------
first adding lime, then adding the calcium carbonate. The first three
treatments have comparable acid neutralizing equivalences, while
CTWT-11-9 has less.
Two of the four slurry-effected calcium carbonate treatments pro-
duced coal wastes which gave acceptable leachates. The other two were
close (see Fig. 7). Even after exposing to air to induce oxidation, the
fine-particle calcium carbonate treatment (CTWT-11-7) continued to pro-
duce leachates with pH values of 6 to 9. The others were less effective
but returned to acceptability with a water flow. The main solids load of
the leachates was calcium sulfate. Trace element concentrations (except
for fluorine) dropped as increasing amounts of leachate passed through
the treated waste. (See Fig. 7 for Fe and Mn. Other elements are
LEGEND
a = CTWT11-6
° = CTWT11-7
« = CTWT11-8
« = CTWT11-9
20
JO 4O 5-0
VOLUME (Liters)
60
7-0
00 X) 2O
—T—
30
—1—
4O
LEGEM)
a = CTWT11-6
o = CTWTfl-7
4 = CTWT11-8
o = CTWT11-9
50
6O
80
oo
(Liters)
30 40 50
VOLUtvE (Liters)
pH, -cAon, a.nct manganese.
wJth aJLkaLinn age.n&>.
7.
-in £&ac.kat&> {^fiom coat waAt&>
19
-------
reported in Appendix C.) Forced oxidation elevated the trace element
level. Ecological discharge severity factors7'5' for the initial leachates
from each treatment show acceptable levels for all trace elements except
iron and nickel, and these were acceptable when the treatment raised the
pH level to 1 (see Table VI).
Adding a neutralizing agent to coal-preparation waste materials
during disposal can be effective in moderating the trace element dis-
charges. Combined with soil attenuation (see below and the section on
"Pollutant Attenuation and Movement through Soils"), this technique could
provide an orderly assimilation of coal waste into the environment with-
out dump liners, addition of sorbents, neutralizing soils, etc. Slurry-
ing of fine particulates with neutralizing agents is needed. Excess
agent needs to be added to handle further oxidation encountered during
delays in burying the waste. A short "soak" or aeration time (several
days at pH > 1) before burying would allow oxidation of ferrous ions to
ferric ions and eliminate the last bit of soluble iron. High pH values
are not necessary, but a little excess lime would shorten this "soak"
time. Indeed, these experiments have been quite encouraging.
TABLE VI
DISCHARGE SEVERITY FOR CALCIUM CARBONATE
TREATMENT OF COAL WASTES3
Treatment Number
Parameter CTWT-11-8 CTWT-11-9 CTWT-11-7 CTWT-11-6
pH
Al
Ca
Cd
Co
Cr
Cu
F
Fe
K
Mn
Na
Ni
Zn
6.2
6.4
6.9
7.4
<0.005
0.4
0.06
0.06
<0.00002
<0.02
0.0004
5.2
0.003
0.6
0.0001
2.4
0.04
<0.005
0.4
0.02
0.02
<0.00004
<0.02
0.0004
2.4
0.002
0.2
0.00008
0.9
0.01
<0.005
0.4
0.03
0.001
<0.00002
<0.02
0.0005
0.6
0.004
0.2
0.0002
0.8
0.006
<0.005
0.6
0.02
0.005
<0.00002
0.02
0.0008
0.2
0.003
0.007
0.00009
0.3
0.007
Discharge severity = Concentration in ppm/100/MATE in ppm.
-These include a 100-fold "environmental" dilution of the leachate.
20
-------
In our third annual report (LA-7831-PR), we reported initial efforts
to locate materials other than lime and limestone that might be codis-
posed with coal preparation waste to produce an acceptable waste system.
We .have now broadened our search to a wider sampling of possible sor-
bents. Special precautions have also been taken to evaluate oxygen-
sensitive ferrous ions. Up to six successive batch encounters between a
leachate and a new portion of sorbent have been run to quantify the
attenuating power of the materials. These efforts have much broader
application than just codisposal, however. The data generated also
reflect migratory behavior through these materials (see the section on
"Pollutant Attenuation and Movement through Soils") and thus indicate the
suitability of an area as a coal-waste disposal site.
A major requirement of a sorbent for coal-waste codisposal is its
ability to handle the acid generated. Natural and process waste sorbents
show a wide range of effectiveness. Most of the 22 materials listed in
Table VII have acid-attenuating capability. Under test conditions
TABLE VII
SORBENTS TESTED FOR THEIR ABILITY
TO ATTENUATE COAL WASTE ACIDITY
Sample No.a Material
1 Alluvial Soil
2 Organic Soil
3 Glacial Till
4 KYS-12 Overburden
5 KY S-ll Overburden
6 Glacial Till
7 Loess Soil
8 Glacial Till
16 Loess Soil
19 Loess Soil
20 Montmorillonite
21 Kaolinite
2!) Feat
26 Western Coal
27 AR Calcium Carbonate
28 Quarry Limestone
29 Limestone Scrubber Sludge
liO Kconomizer Ash
:il Precipitator Ash
;« FGI) Scrubber Sludge
U4 KSP Ash
Hydrated Lime
"These numbers correspond to those used in other
tables and graphs in this section.
21
-------
designed to emphasize soil attenuation of acid and trace metals, many
sorbents are within a factor of 2 of being as effective as powdered
calcium carbonate. All other things being equal, it is reasonable to
assume the carbonate content of the soils would be the major factor in
their ability to neutralize the acidity of coal waste leachates. How-
ever, Fig. 8 suggests that other mechanisms are operational as only a
fraction of the stoichiometric amount of carbonate is utilized, and this
fraction varies considerably from one soil to another. Soils containing
little carbonate perform almost as well as calcium carbonate does.
Almost none of the soils do as well as they could if they used all of
their carbonate.
Carbonate utilization by the soils appears in part to be related to
particle size at all carbonate levels. Identifying the sorbents with
similar-mass median particle sizes, we find two groups that explain much
of the vertical scatter (see Fig. 9). Thus, at any given percentage of
carbonate, about twice as much -100 mesh soil is required to neutralize
the same quantity of coal waste leachate as that neutralized by a -200
mesh soil. We have noted a similar particle size effect in previous
column attenuation experiments with limestone. This effect apparently
results from deactivating the calcium carbonate by coating the particle
'16
'28
'27
(AR CaC03)
I 5 10
LEVEL OF CARBONATE IN MATERAL (%!
*AR = ANALYTICAL REAGENT
50
100
fctg. 8.
Relative, amount ofi natuAat AoSibe.nt needed to attenuate, doal waAte.
OA a. fiunct-ion ofi the. c-onbonate. JieveJi Jin. the.
22
-------
CO
O 20
o
o
O
<
p
LJ
>
Ld
cr
LU
Q
UJ
LD
10
0.5
"V
o\
\
\
LEGEND
-200 MESH
- 100 MESH
\
\
\0
\
\
(-100 MESH)
O
(-200 MESH)
0.5 I 5 10 50
LEVEL OF CARBONATE IN MATERAL (%)
100
F-tg. 9.
Relative, (mount oft natuAaJL &on.be.nt ne.e.de.d to attenuate. coo£ wcu>te.
cu> ^u.nction^ o& the. daA.bon.ate. leveL and poAtlcJte. A^ze. o the.
surfaces with layers of Fe(OH)_ and/or CaSO, . Such an explanation is
consistent with the approximate two-fold decrease in carbonate required
to neutralize coal waste leachate acidity in going from -100 mesh
(149-(Jm) to -200 mesh (74-|Jm) soil particle size. Spherical particles of
74-pm diameter have twice as much surface area per unit mass as 149 -|Jm
spherical particles. We expect that the neutralizing efficiency of
calcareous materials will continue to decrease as the particle size
increases. Thus it is important to classify potential sorbents as to
their effectiveness at the same particle size or under the actual phys-
ical conditions to be used in the field.
The poor neutralizing power at high carbonate levels is a conse-
quence of using an experiment designed to evaluate trace-element atten-
uation at a high solids-to-leachate ratio also as an experiment to deter-
mine acid neutralizing stoichiometry. Calcium carbonate, being a weak
base, forms a buffer at a pH value around 6 in the presence of a strong
acid, such as H-SO,. As long as the acid added is less than the stoi-
chiometric amount of calcium carbonate, addition of more carbonate will
not greatly alter this pH. However, when this leachate is equilibrated
with new soil, a small change in pH to 7 is effected, and the end point
is achieved. This is quite different from lime, a strong base, which is
highly soluble and gives high pH values when over-neutralizing an acid.
23
-------
This buffering capacity of calcium carbonate is apparent from our experi-
mental data plotted in Fig. 10, where a sulfuric acid solution with total
acidity comparable to the coal waste leachate, but without its chemical
constituents, is agitated with soil at a 2:1 liquid-to-soil ratio. About
1.7% carbonate is needed in the soil to neutralize the 0.14M IiLSO,. This
amount of carbonate is stoichiometrically equivalent to the amount of
sulfuric acid present. Adding more than the stoichiometric amount of
soil or calcium carbonate material in the first equilibration will result
in unused or wasted base and will cause the material to be underestimated
in its neutralizing ability. For analytical reagent (AR) CaCO this
amounts to a 36-fold lower rating. The effect of equilibrating nearly
equal quantities of materials with coal waste leachate is to level the
7
i I
J I i i i i
I 10 100
CARBONATE LEVEL IN MATERIAL (%)
Thu pH ofi 0.1 4M
having di
. TO.
con£&n&>.
wi£k natuSiaZ
o &, 2:7
24
-------
calcareous materials with more than the stoichiometric amount of calcium
carbonate into a poorly differentiated group.*
If we wish to compare the capability of the various sorbents to
attenuate contaminant levels in coal waste leachates, we must adjust our
results for carbonate content above the stoichiometric amount required to
neutralize a given quantity of acidity and for particle size differences.
Normalizing the coal waste leachate sorbent data for these variables, we
have generated a semiquantitative rating of the ability of the tested
sorbents to control acidity (see Table VIII). In general, most sorbents
TABLE VIII
SORBENTS RATED FOR THEIR ABILITY
TO ATTENUATE COAL WASTE ACIDITY
Weight per Equivalent (tons lime)
Material Sample No. Adjusted* As-measured"
Hydrated Lime 1 1
ARCaCO,, 28 2 50
Quarry Limestone 27 2 100
Limestone SS 29 4 80
Glacial Till 6 6 60
Organic Soil 2 10 50
Loess Soil 7 14 150
Glacial Till 3 18 150
FGDSS 33 22 350
KYS-11 Overburden 5 30 80
Alluvial Soil 1 50 80
EC Ash 30 60 60
KY S-12 Overburden 4 60 300
Precipitator Ash 31 80 80
Kaolinite 21 80 80
Montmorillonite 20 100 100
Loess Soil 16 150 800
ESP Ash 34 250 250
Glacial Till 8 300 300
Western Coal 26 900 900
Loess Soil 19 >600 >600
Peat 25 °° »
"Adjusted for particle size and "underestimation";
see text.
"From Appendixes D, E, and F.
*Researchers who want to devise a single-equilibration, batch experiment
to evaluate soils, especially for attenuating power and transport poten-
tial, should note that quantities of pollutants in relation to available
soil sites may be more important than the ratio of the liquid to the
solid. Column schemes may be more appropriate than batch ones. For
acid neutralizing ability, a titration method seems the best character-
ization tool. In any case, the importance of various parameters, such
as physical size, needs to be understood to properly evaluate and apply
laboratory results.
25
-------
are at least a factor of 10 poorer than lime. Since many of the natural
sorbents, such as limestone and overburden materials, are unlikely to be
crushed below -3/4-in. in field codisposal use, their ratings should
probably be at least another order of magnitude poorer. Scrubber sludges
and fly ashes, being process wastes and crushed finely, would not have a
similar reduction due to size.
The ability to attenuate trace elements released by the coal prepa-
ration waste is another important requirement of a sorbent. Qualitative
evaluations of the abilities of numerous sorbents to control 13 elements
of interest released by coal wastes are given in Tables IX and X. (In
most cases these evaluations are based on three to five equilibrations of
the leachate with fresh sorbent. See Appendixes D and E for details and
elemental levels.) Sorbent attenuation of trace elements is roughly
related to the sorbent"s ability to attenuate acidity. Thus, those
sorbents unable to handle the acidity are likewise unable to handle the
trace elements. Notable exceptions to this rule are the natural (humic)
species, peat, and subbituminous (NM) coal. In our experiments, sorbents
with l/300th the neutralizing strength of hydrated lime were able to
handle the acidity. More importantly, all soils showed some attenuation
of nearly all the elements studied.
Differences among the tested sorbents as to their abilities to
control trace elements when the acidity is controlled (pH > 7) are not
easily recognized. More noticeable are the differing responses of the
trace elements, regardless of sorbent. Four groupings are needed to
describe attenuating behavior from excellent to poor (see Table XI).
Iron (ferric state) and aluminum are very pH-sensitive and well attenu-
ated. Iron (ferric) is even attenuated better than pH in every case. At
the other extreme are manganese and calcium, which show poor attenuation
by any sorbent. Lack of calcium attenuation is not surprising, since
calcium carbonate is being dissolved to neutralize the acidity. Man-
ganese is different and variable. Normally it is not attenuated well,
but occasionally it is attenuated excellently and, often with soils, is
even released in greater quantities than have already been released by
the coal waste! (An explanation for the releases is given in the section
on "Pollutant Attenuation and Movement through Soils.") The best manga-
nese attenuation occurred at high alkalinity (pH > 11) and high cation
exchange capacity (e.g., montmorillonite with a value of 115 - see Table
IX). Acidity control (pH) is by far the dominant means of controlling
trace elements by codisposed sorbents. Coprecipitation of less pH-
sensitive elements is possible. Individual sorbents do appear to have
differing, second-order abilities to attenuate elements, but the second-
order effects are not readily seen for most materials. The excellent
attenuation of Ni, As, and Fe++ by peat, which only raises the pH to 4.0,
is a good example. Manganese attenuation by montmorillonite is another.
All sorbents with any neutralizing capacity and complexing ability have
some attenuating ability.
Codisposing sorbents with coal preparation wastes to moderate the
dump is attractive. Except where large volumes of the sorbent are
already being moved (e.g., fly ash and overburden), transporting the
sorbent may be prohibitive. Extensive mixing of such large quantities
will be tedious, if not impractical.
26
-------
TABLE IX
ATTENUATION OF TRACE ELEMENTS IN COAL WASTE LEACHATES
BY FUELS AND PROCESS WASTES
Material Parameters
Material
Peat
NM Coal
ProcessResidue
CaCO,
Quarry Limestone
FGD Sludge
Coal Ash-Economizer
Coal Ash-Precipitator
AMD Treatment Sludge
KC,D Sludge
Coal Ash-Precipitator
Coal Ash-Bottom
Coal Ash-Slag
Coal Ash-Bottom
Sample
No
25
26
27
28
29
30
31
32
33
34
35
36
Carbonate"
(%)
2.2
1.6
60
60
30
1.7
1.2
51.9
25.4
0.6
(1.5
(1.12
(1.30
CEC"
pH1 lmeq/10()g>
5.4 4H.3
7.0 5.3
7.4
7.5
7.3 2.7
12.3 3.2
11.2 3.0
7.7 II.H
H.ll 5 1
11.4 3.11
H.I O.H
4.2 0.2
12.3 I.I
Clay" OM'
(%l (%l pH
21.2 46.11 FK
H.I 17.0 GG
EEEE
EEEE
6.3 3.7 EEEE
11.4 0.5 EEEE
!.."> 0.3 EEEE
.1.1 0.4 EEEE
5.(l 2.3 EEEE
(1.6 EEEE
1.0 0.4 EEEE
II.H 0.3 FF
FK
Fe
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
P
KK
Al
EEEE
GG
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
KK
P
Zn Ni
EEEE
GG
EEEE EEEE
EEEE
EEEE EEEE
EEEE
EEEE EEEE
GG EEEE
GG
GG
GG FK
P P
P
Degree of Attenuation"
Co As Fe(ll) Cr
EEEE EEEE
EEEE EEEE
GG EEEE GG
EEEE GG
EEEE EEEE GG
GG EEEE
GG FK 1
GG GG
GG EEEE
GG EEEE
FK GG
P GG
P 1
K Cd Cu
GG
GG
EEEE GG GG
GG
GG KK KK
GG
GG GG KK
FK 1 GG
GG
GG
P KK 1
1 1 1'
1
Mn
1
KK
EEEE
EEEE
KK
EEEE
EEEE
GG
P
1
1
1
1
Ca
1
1
1
•EEEE = >100x Reduction
GG = 10-lOOx Reduction
KF = :i-ll)x Reduction
P = (>.5-3x Reduction
o = >2x Increase
"Carbonate by Rapid Titration
cpH on Filtrate from Solid-Water Equilibration
"Cation Exchange Capacity by Ammonium Acetale Sal
eClay by Pipet Sedimentation
'Organic Matter by Walkley-Black Method
K>
-------
TABLE X
ATTENUATION OF TRACE ELEMENTS IN COAL WASTE LEACHATES
BY SOILS AND CLAYS
Soil
11 Alluvium
11 Organic
11 Glacial Till
Ky S12 Overburden
Ky Sll Overburden
11 Glacial Till
11 Loess
II G acial Till
11 G acial Till
11 G acial Till
11 G acial Till
11 G acial Till
II Loess
11 Loess
11 Alluvium
11 Loess
11 Loess
Ala Soil
11 Loess
Clay
Montmorillonite
11 Kaolinite
Montmorillonite
Illite
Kaolinite
Sample
No
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Carbonate"
(%)
1.6
6.8
7.1
1.4
:i.8
15.1
8.:i
(I.MI)
7.7
l:t.4
9.2
8.6
5.8
0.72
0.24
0.48
0
0.45
0.54
0.48
0.66
2.4
0
Material Parameters
CEC" ClaV OM'
pH' imi.(|/l(l(l|!l (%l l°o>
8.:l 211.1 47.7 0.7
H.I ;|[|..| MH.ii 7.:l
7.9 14 5 28. (i 0.1
7.8 7 5 9.5 :i.2
76 98 0 :l 2
8.2 9 I 1:1.5 0 4
8.2 8 8 9.5 ().:l
7.9 28.0 17.0 O.:l
8.5 14 :l 2:1.0 0.2
8.2 7.7 16.1 0.9
8.2 9 li 15 4 0.2
8.2 H 9 20 4 0.9
8.1 11 li 12.5 0.4
7.6 U 4 55 4 O.:l
7.7 25.1 :12.1 0.6
4.8 24.1 22.0 1.5
5.6 27 9 :I5 9 0.5
4.0 20 5 44.7 O.:l
8.0 0.8 108 0.2
7.7 115.2
8.2 21.4 O.:l
7.9 i;:l.5 0.2
8.1 41.4 0.8
4.3 2 1 0.1
pH
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
GG
FF
FF
FF
FF
EEEE
EEEE
EEEE
EEEE
FF
Fe
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
GG
FF
EEEE
EEEE
EEEE
EEEE
GG
Al
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
GG
FF
P
P
P
EEEE
EEEE
FF
GG
P
Zn
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
EEEE
GG
V
V
1-
EEEE
EEEE
GG
FF
Ni
EEEE
EEEE
GG
GG
EEEE
EEEE
EEEE
GG
GG
GG
GG
GG
GG
FF
P
P
I
1
EEEE
EEEE
GG
GG
P
Degree
Co
EEEE
EEEE
EEEE
EEEE
GG
GG
GG
GG
GG
GG
FF
FF
FF
P
P
GG
GG
GG
GG
P
of Attenuation"
As Ke(ll)
EEEE
EEEE
EEEE EEEE
EEEE EEEE
EEEE EEEK
GG
GG
GG
GG GG
FF FF
EEEE
EEEE
Cr
GG
GG
GG
GG
GG
GG
GG
GG
GG
GG
1
GG
GG
GG
GG
GG
GG
FF
K Cd Cu Mn C'a
EEEE EEEE (id FF 1
KEEE GG GG FF
(id
GG
dd
(id GG GG GG 1
GG GG GG FF 1
EEEE FF FF
FF dd dd P
FK dd FF 1
KF GG FF 1
KF dd KK 1
KF GG KK 1
i KF P 1
II II
KK
PI II
III 1
1 1 1
GG GG GG EEEE 1
GG GG FF GG u
GG FK FK dd Kr
P GG GG GG
1 1
•EEEE = >100x Reduction
GG = 10-lOOx Reduction
FF = 3-10x Reduction
P = 0.5-3x Reduction
o = >2x Increase
"Carbonate by Rapid Titration
cpH on Filtrate from Solid-Water Equilibration
"Cation Exchange Capacity by Ammonium Acetate
Sat.
•Clay by Pipet Sedimentation
'Organic Matter by Walkley-Black Method
-------
TABLE XI
TRACE ELEMENT ATTENUATION BY SORBENTS
CAPABLE OF CONTROLLING COAL WASTE ACIDITY
Attenuation Elements
Excellent Fe+++, Al, (Zn)
Good to excellent Zn, Ni, Co, As, Fe++
Fair to good Cr, F, Cd, Cu
Poor Mn, Ca
D. Treating the Waste Effluent
The third option in our environmental control strategy is the col-
lection and treatment of the polluted water that is discharged from the
disposal site. Having a polluted effluent in hand makes it amenable to a
variety of proven water treatment methods. We reported details on a
number of these in our third annual report (LA-7831-PR). A partial
listing includes
Alkaline Neutralization
Reverse Osmosis
Biological Treatment
Freezing and Distillation
Ion Exchange
Chelation and Precipitation
Sorption on Solids.
Because the methods treat only a small portion of the potential polluting
capacity of the waste, their strong points are economics (especially for
alkaline neutralization) and effectiveness. (See the section on "Econ-
omics of Pollution Controls for Coal Preparation-Combustion Scenarios.")
Several, such as reverse osmosis and ion exchange, only concentrate the
pollutants, however, and must also include another step, such as alkaline
neutralization. Based on effectiveness, economics, and ease of implemen-
tation, alkaline neutralization appears to be the most favorable environ-
mental control for effluent treatment.
Alkaline neutralization with lime is a state-of-the-art method.
Examining the list of natural and waste materials in Table VIII, we find
that only limestone (calcium carbonate) is likely to compete with lime in
a mechanical device. Even here, extensive research and development has
shown that the inability of limestone to achieve high pH values (>7)
29
-------
severely limits the oxidation rate of ferrous ion and precipitation of
manganese and hence the usefulness of limestone by itself (see R. C.
Wilmoth, "Combination Limestone-Lime Neutralization of Ferrous Iron Acid
Mine Drainage," EPA-600/2-78-002, Jan 1978). Lime-limestone appears to
work but becomes less applicable as the ferrous iron content increases
(ibid.)- This statement was made for solutions with 200-500 ppm of Fe++.
Coal waste effluents from the more acid-producing wastes may contain iron
levels of 3000-15000 ppm of which most is Fe++- Only a high-lime-
content neutralization process appears suited for these coal waste
effluents.
A careful evaluation of how well and at which pH values lime
cleanses coal-waste effluents of trace elements is needed to determine
optimum neutralization treatments. Reliable data are also needed to
determine how well these systems are described by computer codes, which
give thermodynamic treatments of aqueous, ionic solutions. We have
conducted a series of experiments in which a highly contaminated coal
waste leachate was neutralized with lime and filtered under argon.
(Experimental details and results are given in Appendix F). All 14
elements studied, except calcium and, to some extent, fluorine (not
shown) are pH sensitive (see Fig. 11). Trivalent ions (ferric and
aluminum) are well- known to be quite sensitive to pH changes at high
acidity and behave accordingly. The attenuation of arsenic and chromium
(not shown) at such high acidities is somewhat surprising. Cadmium,
cobalt, copper, nickel (shown), and zinc exhibit similar behavior as a
group and are greatly reduced by the time pH 7 is reached. The reason
for the well-known problem of attenuating ferrous and manganese ions
below pH 8 is clearly evident.
The best control technology for handling the trace element pollution
in coal-preparation waste drainages is acidity control. 'Once the pollu-
tion occurs, pH adjustments are effective if the effluent can be col-
lected. Given a choice, however, prevention would seem a better overall
alternative.
E. Combined Pretreatment and Codisposal
An extensive experiment designed to demonstrate this disposal method
is described in Appendix G. Briefly, a highly acidic, Illinois Basin
coal waste was mixed in plastic 55-gal. barrels with wet slurries con-
taining lime in amounts from 0.17% to 3.3% of the waste by weight (see
Fig. 12A). In one case, 1.1% limestone in a slurry was mixed in after
0.33% lime had been used. These slurries were screened to remove excess
water (see Fig. 12B) and then placed in specially designed disposal boxes
(see Fig. 12C). Six boxes of each of the six lime/limestone/waste mixes
were then placed in a pattern to await rain and dry weathering cycles
(see Fig. 12D).
Simulated weathering cycles consisted of Monday (i.e., once a week)
"rains" of 0.75 in, the equivalent of 39 in./yr. These rains drained
through the treated wastes and were collected after a 24-h percolation
period. Analyses for pH, iron species, and conductivity were done imme-
diately. Sample aliquots were acidified and stored for trace element
analyses.
30
-------
DETECTION LIMIT
10
nJtmtnt conc.e.n&L&tionA in coat
OA.QOYI.}
Fig. 11.
tza.c.ka£(>, at VOA^OLU, pH
31
-------
Slurry mixing
B
Slurry screening
REFUSE SLURfiv
c
Disposal Box
D
Box matrix for weathering
U .n
m&tlwd.
12.
-------
All the neutralizing agent levels used (0.17% and up) were able to
elevate the initial pH of the coal waste leachates above 5 (see Fig. 13).
X
a.
V
A
0
O
LEGEND
0.17% LIME
0.33% LIME -
0.53% LIME
1.1% LIME
3.3% LIME
0.33% LIME +'
1.1% CaCO,
0
4 6 8 10
TIME (WEEKS)
12
13.
Lvi open
The two highest lime levels made the waste leachates very alkaline
(pH >11), while the lime/limestone treatment gave a moderate pH of 7.6.
The leachate pH values for all the lime-treated wastes except that with
the highest lime content dropped rapidly. The high salt loads in the
leachates from the 1.1% and 3.3% lime treatments at the 3-week mark
compared to those of the lime/limestone treatment (see Fig. 14) suggest
that part of this drop resulted from washing the lime out of the lime/
waste systems. The lime/limestone/waste system maintained constant pH
and conductivity levels for the entire 3 months monitored.
33
-------
20
10
O
ID
O
z
O
o
UJ
>
I-
_
UJ
a:
—I—I—I—I—
LEGEND
=3 0.17% LIME
XO.33% LIME
A 0.53% LIME
0 1.1% LIME
-O 3.3% LIME
• 0.33% LIME
l.l%CaC03
T r
4 6 8 10
TIME (WEEKS)
12
Conductivity o^ Jteac.kat&>
-in. open dJi&pa&at
JUjnzftAm&>£oyi£fc.oa£~M(L(>te. nvbuu*
Reduced alkalinity and pyrite oxidation combine to lower the pH and
release iron when low levels of lime are present (see Fig. 15). Again
the equivalent lime/limestone/waste system maintained constant pH and
conductivity levels for the entire 3 months monitored.
The lime/limestone/waste system of disposal looks very good so far.
It is stable for at least 3 months under some of the worst conditions
(damp, open to air, and in a thin 3-1/2-in. layer) that are likely to
occur in a coal waste dump. This should allow a disposer to add new
layers of waste or soil on top. As the pile grows the interior will
become oxygen deficient. Reductive conditions, enhanced by residual
coal, will return, and the oxidized pyrite should ultimately return to
pyrite.
34
-------
10'
CL
a.
I- I05
Z
UJ
li.
li.
UJ
^ 10
o
a:
r
/
LEGEND
I — 0.17% LIME _
/ V 0.33% LIME
' A 0.53% LIME
/ 0 1-1% LIME
/ O 3.3% LIME
0.33% LIME+
U%CdC03 -\
r
I
2 4 6 8 10 12
TIME (WEEKS)
TotaJi JUwn Lw
-------
F. Economics of Pollution Controls for Coal Preparation-Combustion
Scenarios
The economics of 10 alternative methods for preventing or treating
trace element releases from coal preparation wastes have been calculated
and combined with the cost of meeting pollution standards at power
plants. Details about the included controls and how the economics were
determined were reported in LASL document LA-8039-MS, "Costs of Coal and
Electric Power Production - The Impact of Environmental Control Tech-
nologies for Coal Cleaning Plants," by E. F. Thode, J. M. Williams, E. M.
Wewerka, and P. Wagner (1979), and in Annual Report No. 3 of this series.
The brief summary presented here covers the cost of each control method
singly and combined with FGD control cost at the power plant and
accounts for the compositions and volumes of wastes generated by real
plants whose depth of cleaning vary widely.
Costs of 10 control technologies for three Illinois Basin preparation
plants cleaning high-sulfur coals are presented in Table XII. The high-
cost methods involve either extensive treatment of the waste (calcining)
TABLE XII
COSTS OF VARIOUS OPTIONS FOR CONTROLLING POLLUTION
FROM COAL CLEANING WASTES""
Process Plant A Plant B Plant C
Calcining - Conventional FGD 8.30 3.40 9.89
Codisposal with Fly Ash 5.84 2.62 7.71
Codisposal with Fly Ash- 3.90 1.75 5.15
modified with limestone
Calcining-Lime/Limestone 3.36 1.39 3.99
Recycle System
Codisposal with Alkaline Soil 1.27 0.57 1.69
Direct Addition of Lime to Pile0 1.01 0.45 1.33
Lime-Limestone Slurry Coating 0.50 0.22 0.44
Effluent - Ion Exchange 0.38+d
Effluent - Reverse Osmosis 0.26+d
Effluent - Lime 0.13 0.42 0.066
"Actual plants; non-process
in plant figures.
b$/ton of product coal, March 1978 time base.
°Labor cost not included.
dCost to dispose of sludge not included.
36
-------
or hauling low alkaline content fly ash. The intermediate cost methods
utilize lime or locally available alkaline soils in treating the waste.
The low-cost methods treat the effluent from the waste pile. The differ-
ences in the costs among the noneffluent treatment methods from plant to
plant are related to the amount of waste produced by each plant and the
amount of sulfur in the waste. An inspection of Table XIII shows that
Plant B produces about one-third as much waste as Plants A and C per ton
of clean coal and that the waste from Plant C has the highest sulfur
content. The effluent treatment processes reflect the differing
responses of the wastes to weathering. Plant B weathers more rapidly and
produces such a concentrated leachate that we have determined that efflu-
ent treatment for it is not the cheapest process.
TABLE XIII
SULFUR LEVELS AND CLEANING YIELDS
FOR THREE ILLINOIS BASIN COAL CLEANING PLANTS
Plant
Plant Parameter A B
Sulfur in Raw Coal (%) 3.7 3.9 5.2
Sulfur in Clean Coal (%) 2.8 2.8 3.6
Ash in Raw Coal (%) 30.0 18.8 29.0
Sulfur in Waste (%) 9.8 13.9 15.7
Cleaning Plant Yield (%) 68 87 72
Tons waste/ton clean coal 0.47 0.15 0.39
Tons clean coal/ton waste 2.1 6.7 2.6
The overall impact of coal usage controls, determined by adding the
costs related to stack emissions cleanup at the electric power plant, is
seen in Table XIV. For high-sulfur coals of the type discussed here, the
stack controls cost in the range of $8.50 - $9.50 per ton of clean coal
in FY-1978 dollars. Coal preparation waste controls will add less than
10% to costs with the cheaper methods and 100% or more with the more
costly ones. Estimates based on 1979 prices suggest that this will add
$0.002 - $0.004/kWh or less for the less expensive control methods for
coal preparation wastes. The cost of producing electricity by coal-fired
plants would seemingly be little affected by using an inexpensive control
method for mitigating the effects of coal-cleaning waste on the
environment.
37
-------
TABLE XIV
COMBINED CONTROL TECHNOLOGY COSTS TO MEET
WATER QUALITY STANDARDS AT THE CLEANING PLANT3
AND STACK EMISSION STANDARDS AT THE POWER PLANT
Cost of Cleaning Option & FGD, $/tonb
Process
Calcining -
Codisposal
Codisposal
Conventional FGD
with
with
Fly
Fly
Ash
Ash-
Plant A
16.
14,
,86
,40
12.46
Plant B
12,
11,
10
.20
.43
.55
Plant
19
17
14
.24
.06
.50
C
modified with limestone
Calcining - Lime/Limestone
Recycle System
Codisposal with Alkaline Soil
Direct Addition of Lime to Pilec
Lime/Limestone Slurry Coating
Effluent - Ion Exchange
Effluent - Reverse Osmosis
Effluent - Lime
11.93
"Actual plants; non-process,
b$/ton of coal burned, time base, March 1978.
cLabor cost not included.
dCost to dispose of sludge not included.
10.19 13.34
9.84
9.58
9.06
8.69
9.38
9.25
9.03
9.23
11.04
10.68
9.79
9.73+d
9.61+d
9.41
38
-------
II. TASK II: IDENTIFY TRACE ELEMENTS OF ENVIRONMENTAL CONCERN IN (LOW-
SULFUR) COAL PREPARATION WASTE FROM THE APPALACHIAN BASIN
New samples have been collected from the Appalachian region (see
Plants I and K in the section on "Waste Collection Summary"). Their
evaluation has begun and will be reported next year. Complete evalua-
tions of the low-sulfur coal waste begun last year are reported here.
A. Mineralogy and Cleaning Behavior
Low-sulfur, Appalachian coal waste differs from high-sulfur, Illi-
nois Basin coal waste in several ways. (Data for comparison can be found
for low-sulfur wastes in Appendix H and for high-sulfur wastes in the
second annual report, LA-7360-PR.) The most obvious difference is the
absence of pyrite (iron sulfide), corresponding to the low-sulfur content
in the Appalachian coal waste studied here (see Table XV). This can
readily be seen. Other minerals are comparable by x-ray analysis, but
this technique accounted for only 61% of the material. Since the low-
temperature ash (LTA) value is 80%, about 20% of the sample must be
microcrystalline or amorphous material. Correcting the observed mineral
values to approximate the LTA value (parenthetical values in Table XV)!
probably gives a more reasonable measure of the mineral contents. (The
mineral matter in the high-sulfur waste was completely accounted for
without any correction.) Thus the low-sulfur waste contains around 40%
more quartz and 25% more clays (aluminosilicates). About 25% of each of
these will show up in microcrystalline or amorphous states. Only a small
amount of calcite, desirable for alkalinity control, is present.
TABLE XV
MINERAL COMPOSITIONS OF HIGH-SULFUR AND LOW-SULFUR COAL WASTESa
Density Low-Sulfur High-Sulfur
Mineral (g/cc) Appalachian Illinois Basin
Quartz 2.59-2.66 22.(29)b 21
Dlite 2.7-3.0 19.(25) 14
Kaolinite 2.60-2.63 11.(14) 12
'Clays' 6.(8) 11
Gypsum 2.32 l.(2) 2
Calcite 2.71 l.(D 2
Pyrite/Marcasite 4.95-5.17 <1.(
-------
The low-sulfur coal studied here was initially crushed by the prep-
aration plant to 0 by 6 in. , as were the Illinois Basin coals. The size
distribution, however, was quite different (see Fig. 16). Large parti-
cles or chunks were more prominent in the high-sulfur coal wastes,
whereas small particles were the norm in the low-sulfur coal waste.
Although some of the differences could be attributed to the crushing
machinery, a more plausible answer lies in the differences in mineral
crushability. Thus, two modes should occur (as they do) in the particle
size diagram: one for hard-to-crush particles (large) and one for
friable particles (small). Cleat and overburden materials, together with
the coal, would provide the large, starting lumps. Cleat pyrite and
"rocks" would resist crushing and give higher proportions of weight to
the large particles. Clays (especially dry ones) and coal would crush
more easily and give higher proportions of weight to the smaller parti-
cles. (Some large particles of coal are likely because of the block
cleaving of coal.) Since the density separation of two particles of
similar density improves as the size of the two particles increases (our
observation of raw coal buoyance), high-sulfur coals should be much more
easily reduced in ash content than low-sulfur coals of similar mineral
content.
Photomicrographs of the different density fractions for the low-
sulfur coal waste are shown in Fig. 17. The particle density distribu-
tion of these fractions differs considerably from those of high-sulfur
wastes (see Fig. 18). The lack of much high-density (> 2.97-g/cc) mate-
rial in the low-sulfur waste is not unexpected, as little pyrite or other
40
30
o:
20
o
10
0
LOW SULFUR (G)
HIGH SULFUR (ABC)
mean* <]
1 "^(ID) <2 >2
SIZE FRACTION (in.)
F-ig. 76,
ofi h£gk~Au£fiuJi and low-AiitfiuA coat
i. -m one. d^Mtn&^on and <1 Jin. Jin alt otkeA
40
-------
FLOAT 2.15 g/ml
SINK 2.16-2.48 g/ml
E >- , ' - V „•
*'• •'"• 4-
'X» , ^'V '• % /'•
+>&Jyi .-«;••.,. :e,. , v ? •-'.
«»' -/V' " "
^
>j|,i ^
ii
-------
40
30 -
O
H
o
<
cc
10
0
LOW SULFUR (G\
O
<2.I5
<2.48
>2.I5
<2.97
>2.48
>2.98
DENSITY FRACTION(g/cm3)
Pa/uticte,
IB.
and
heavy-density mineral was found by x-ray analysis. The real surprise
comes in the low-density (< 2.15-g/cc) fraction. Most nonsulfide coal
waste minerals have densities between 2.5 and 2.97 g/cc (see Table XV).
Some swelling of the expandable clays by incorporation of the organic
solvent probably accounts for much of the material in the lighter
2.15-2.48-g/cc fraction. The low-density fraction, on the other hand, is
mostly coal but contains half the levels of silicon, aluminum, and
potassium as does the 2.15-2.48-g/cc fraction. Because few alumino-
silicate particles are found by optical microscopy in the lightest
fraction (see Fig. 17), the mineral components must be distributed
throughout the coal particles. Cleaning these coal chunks would require
extensive comminution.
B.
Trace Elements and Their Locations in the Waste Structure
An important consideration in the design of control technology is
the mineralogical location of the various metals that can be released.
Metals in chemically immobile, inert, and unreactive minerals such as
feldspars should cause no problems. On the other hand, those associated
with active materials, such as pyrites and carbonates (which neutralize
the acid generated by the pyrites) should be mobile.
Nearly all the elemental concentrations in the low-sulfur coal waste
studied here are within a factor of 2 of those for corresponding elements
in the high-sulfur wastes reported in a previous annual report (see Table
XVI). Those concentrations higher in the low-sulfur waste should be
42
-------
TABLE XVI
COMPARISON OF TRACE ELEMENT LEVELS IN LOW-SULFUR COAL WASTES
WITH THOSE IN HIGH-SULFUR COAL WASTES
Element
Li
Sh
K
MK
Ti
Cr
HI
Al
V
Th
Si
Sc
Cs
v
A
La
Cu
On
7r
Tii
I)y
Lu
VI)
(V
Ku
He
(VI
Ni
H
Na
Sm
K
HI)
r
y
7,n
)'l)
Mn
Co
As
Ke
Cii
s
}'
Lo-sulfur
120
•> •>
20000
f)4()(>
6500
9:1
5.1
92000
110
15
200000
16
8.8
'Kl(K)
• Ji/V !\ >
49
48
20
i:(0
1.1
5.6
0.4
2.8
79
1.:)
2.5
().:!:!
49
,V)
i:i()()
T).:i
oTO
i:io
4.2
19
(59
•)•>
97
11
18
20000
1400
7100
1 50
Hi-Sulfur
40
I..1*
12000
2HOO
4200
64
:i.5
65000
79
11
150000
12
6.9
•)O(U\
l)£\l\l
42
42
18
120
1
5.4
0.4
2.9
85
1.4
2.8
().:!9
58
(58
1(500
6.8
750
180
5.9
27
120
44
190
25
57
94000
19000
110000
154(50
Ratio Major
Lo/Hi-Sulfur Element Groupings
3
1.7
1.7
1.6
1.5
1.4
1.4
1.4
1.4
1.4
l.:5
i.;5
1.15
1.2
I.I
1.1
1.1
1.1
Lithophiles
1.0
1.0
1.0
0.9
0.9
0.9
0.8
0.8
0.8
0.8
0.8
0.8
0.7
0.7
0.7
0.6
0.5
0.5
0.4
().:5
0.2
0.07
0.06
0.04
Rare Earths/Miscellaneous
Chalcophiles ,,
Calcite/Pyrile/Apatile ^
43
-------
related to clays and quartz (lithophiles) . Those higher in the high-
sulfur waste should be related to sulfides (chalcophiles). Calcium,
sulfur, and phosphorous, interestingly, are much lower in the low-sulfur
waste. Pyrite and calcite are measurably lower (see preceding section),
whereas apatite is not measurable but should be lower than in the high-
sulfur waste. To define better the element and mineral relationships, we
have used both statistical analyses of chemical and mineral data and
scanning electron microscopy (SEM) analyses of mounted powder specimens.
Statistical analyses proved effective with high-sulfur wastes
(second annual report, LA-7360-PR) . In general, such analyses only give
one behavioral pattern per element and require some physical separation
of the various mineral species followed by accurate (±5%) chemical anal-
yses. We used the three methods here which proved successful earlier.
The first method takes advantage of the separation made at the prepara-
tion plant during the coal cleaning process. The input coal and output
coal and waste streams provide a reasonably sharp separation of the
mineral and coal components based on density differences. The second
method is based on particle size separations before laboratory crushing
and assumes that some particles, such as cleat pyrite, will resist
crushing and, therefore, show up as large chunks. The third separation
method is based on mineral density differences as used in conventional
float/sink procedures. Our float/sink technique utilizes very small
particles and many tedious separations in order to achieve the cleanest
separation possible. Analytical data for these samples are given in
Appendix H. A discussion of the mineral and size fractionation in the
separation schemes was given in the preceding section.
Fig. 19 is a visual representation of the statistical analysis of
the chemical data for the coal and waste samples as collected at the
low-sulfur coal cleaning plant. (See the section on "Visual Presentation
of Statistical Results" for information on how to achieve this display.)
The elements fall into two well-defined groups: the smaller group has
only nitrogen (N), sulfur (S), calcium (Ca), and cobalt (Co), while the
other has everything else. Elements in the smaller group correlate
inversely with the LTA and are more concentrated in the coal portion of
the plant streams. Nitrogen appears to be the best indicator for the
coal component. The major sulfur component is coal associated, although
inspection of the original sample data shows that sulfur becomes concen-
trated in the fine waste stream in contrast to nitrogen. This implies
that a second type of sulfur occurrence exists in the fine particles.
Mineral sulfides would be a logical explanation for this.
Statistical treatment of the chemical data for samples produced by
the particle sizing method also produce two groupings (see Appendix H).
Neither was as distinct as the groupings described above. Arsenic (As),
iron (Fe), copper (Cu), lead (Pb), and perhaps gallium (Ga) are found to
be associated with sulfur. These elements occur in higher concentrations
in the very small (<-20-mesh) and very large (>2-in) particles than in
the midrange sizes. (A plausible explanation might be the occurrence of
microscopic and massive forms of pyrite.) The remaining elements fall
into a weakly defined group containing phosphorous (P), aluminum (Al),
and silicon (Si). Of particular note are the presences of manganese
(Mn), cobalt (Co), uranium (U), zinc (Zn), nickel (Ni), and possibly
cadmium (Cd) in this, the clay group.
44
-------
•
a
a
a
a
H
s
•
1 . U
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
1 n
t. 79.
co
-------
Statistical
Treatment
Plant
Scparat inn
Si/cd
Waste
Float '
Sink
Kesldui'ss
K\ alual ion
Element Groupings^
I
N.S.(Ta) (f^)
X.S.^Ta)
VS. (fa)
Coal/
Carhnnates
II
As, FejOu,
Pb.(Ga)
S.As.Fe,
Cu.Pb
Sultide?
111
IV
V
VI
Others
Others
Mn.Zn.Ni.
Hl.Zr/Q)
Oxides/Carbonates
(Sull'ides)
Ce,Th,U,Dy,Y,
Ku.Yb.Lu^B.Rb,
("r,Ti,P,(Ca\
Oxides/Phosphates
UCs.Sc.Al.
Si.KjNa.Mg.
F,(Sn)
Clays/Quartz
Cl.Tb.Cd.Be.
V.Ta.(ro) tf\a\
Quest ionahle.
hut mineral
' Rased on statistical treatments presented in the text.
tCirrlesarmmd an element indicate uncertainty:
also possible multiple mineral assignment.
'Some assignments based on previous two "treatments
zJLmz.Yit
20.
Vt&wt G,
doat wo4-£e.*
The bulk of the low-sulfur waste material (Plant G) is composed of
silica, aluminosilicates , potassium aluminosilicates , and coal. A photo-
graphic abridgment of the many particles studied is given in Fig. 21.
Some, but not all, of the circular iron sulfide particles in Frame 3a
include manganese, copper, zinc, and perhaps magnesium. These circular
inclusions occur at cracks and contain aluminum and silicon as well. The
rare earth elements identified in the particles in Frame 4 were cerium
(Ce), lanthanum (La), and neodymium (Nd) . No calcium was found. The
copper sulfide particle in Frame 5 contains some zinc and iron. The
aluminosilicate region in Frame 7 contains iron and manganese. In addi-
tion to these particles, massive and framboidal pyrite areas were
observed. Some of the framboidal areas were backfilled with iron sulfide
containing arsenic. Carbonate particles were composed mainly of calcium,
magnesium, and perhaps aluminum with some manganese and iron. Iron,
titanium, and zirconium oxide particles were common. Some silica parti-
cles contained high levels of iron and zirconium. Barium sulfate parti-
cles were also prevalent. In general, this waste contained a wide vari-
ety of accessory minerals in a predominantly aluminosilicate matrix
The corroborative statistical and microprobe data have allowed us to
generate a list of the locations where the elements in this low-sulfur
waste reside (see Table XVII). Those elements assigned to clay may
actually reside as nonaluminosilicates interspersed throughout the clay.
Also, many of the sulfide minerals are buried in or surrounded by clay
matrices. For a comparison with the element locations in high-sulfur,
Illinois Basin wastes, the reader is referred to a similar table in the
second annual report (LA-7360-PR, p. 26). Trace element location informa-
tion is also obtained from leaching behavior.
46
-------
Fxcg. 27. (Page* 48 and 49}
SEM photograph* o^ A£le.cte.d pasuticldA ob^eAvnd /en a low-AulAuA. coal
F-tcune 1: GypAwm paJvticti (A).
FJiame. 2: Ckalcopytute. (A), 4-ctcco. (B), coal (C), and a KhlSi.-typz clay
nuxtuAe (V).
Flame. 3: Mat,A^vc-type py^Ltc (A) w-itk KkiS^-type. clay (B) attacked.
3A: CXACCI£OA. xtAon Aul^-Lde. lnclLU,^ion& (A) -en mci4-6xlue--:tt/pe py^ute,
poJitidLn. (B) o^ F/r.cme 3.
4: Ro/r.e. eoA^fi pko&pkate. paA^tLclu (A) ioc£Ji KA£S^-^t/pe c£at/ (B).
MS-L-typz. clay (C) oXio pA.e4en^:.
ritcma. 5: CoppeA Aul^de. pa/utidu (A).
Tsiame. 6: 2-Lnc Aul^de.-clay particle, (A).
Tn.cm
-------
-p-
CO
50,im
20pm
-------
Sum
lOum
1C
-------
TABLE XVII
MINERAL LOCATIONS OF TRACE ELEMENTS
IN A LOW-SULFUR, APPALACHIAN COAL WASTE
ELEMENT RESIDENCE IN WASTE
Li Clay
Be Clay
B Clay
N Coal
F Clay
Na Clay
Mg Clay, carbonate
Al Clay, carbonate, iron sulfide
Si Clay, silica, iron sulfide
P Phosphates (in clay)
S Coal, sulfides, sulfates
f ] r>9<7
K Clay
Ca Clay, sulfate, carbonate
Sc Clay
Ti Oxide (in clay)
V ?? (possibly with iron oxide)
Cr Clay (with Al)
Mn Sulfide, carbonate, clay
Fe Clay, sulfide, carbonate, oxide
Co 7':1 (possibly as sulfide)
Ni Sulfide
Cu Sulfide (w/wo iron)
Zn Sulfide
Oa Mineral phase
ELEMENT RESIDENCE IN WASTE
Ge
As
Rb
Y
Zr
Mo
Cd
Sn
Sb
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Pb
Th
U
999
Sulfide
Clay
Clay
Oxide (in clay)
Sulfide
Sulfide
Clay
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Phosphate
Oxide (in clay)
Clay
Sulfide
Clay (possibly as phosphate)
Clay (possibly as phosphate)
C. Trace Element Leachability
The behavior of low-sulfur coal preparation waste under the influ-
ence of leaching and weathering is the primary concern from the environ-
mental point of view. To determine this behavior we have subjected
composite samples from Plant G of the Appalachian region to both batch
and column leaching tests. Portions of these experiments were reported
in the third annual report (LA-7831-PR). Complete results are tabulated
and plotted in Appendixes I and J of this report.
The trace element leaching behavior of the low-sulfur waste with
time, when equilibrated with water in the, presence of air, is shown in
Fig. 22. A general lack of any strong time dependence over the study
period (42 days) is readily apparent for most elements, although small
increases in the levels of some elements over those in the initial
(10-min) period were found by the 5th day. (The behaviors of Cr and Cu
are clearly kinetically controlled.) A growing, upward trend for Al, Cr,
Co, Cu, Fe, Mn,and Zn does seem apparent and corresponds to the increase
observed in the acidity (drop in pH). This probably signals slow sulfide
oxidation.
50
-------
1000
UJ
o>
Q
UJ
I
O
<
UJ
UJ
UJ
_l
z
UJ
UJ
_J
UJ
10
Mg
Cr(ppb)
Al
10 20 30
LEACH TIME (days)
40
Ug. 22.
Tkz pH and fiace. ntme.nt L cu> a function oft leach time, dusting the.
batch £eachA,ngA ofi a Low-i^ijJL^vJi, hppa&achijan.coal.
51
-------
The most surprising result from the leachings is the low pH values
of the leachates. The initial value was 3.9. After rising quickly to
4.3, the pH was still falling when it reached 3.0 at the experiment
terminus. This low pH level was unexpected for the small amount of
pyrite present. The low iron values would suggest that not much pyrite
was oxidized. The polluting parts of the waste may not "generate" much
pollution, but what little is generated cannot be abated by the rest.
This is not entirely surprising, since this waste started with little
calcium, and the most readily identifiable calcium mineral was gypsum,
although the presence of some calcite was identified by x-ray mineralogy
(see Table XV).
The most highly leachable elements, as measured by the percentage of
the total available, are Ca, Co, Cd, Ni, Zn, and Mn. This suite is the
same as was found for the high-sulfur coal wastes. A comparison of the
percentages leached in 1 day for the 14 elements in common between Plant
G (low sulfur) and Plant B (high sulfur) is given in Table XVIII. Gener-
ally, the percentages leached are lower for the low-sulfur coal waste.
Fe, Al, and Cr have much lower leachabilities for the low-sulfur coal
waste. The prevalent view seems to be that high-sulfur wastes give
high-iron leachates, and that low-sulfur wastes give low-iron leachates,
but the situation is more complicated than this.
TABLE XVIII
PERCENTAGES OF TRACE ELEMENTS LEACHED
FROM SOME COAL WASTES3
% Leached Ratio
Element Low Sulfur" High Sulfur0 Hi/Lo Sulfur
Ca 60 55 0.9
Co 14 100 7
Cd 9 32 4
Ni 8 41 5
Zn 7 23 3
Mn 7 16 2
Mg 5 92
Cu 2 14 7
Na 1.5 1.1 0.7
K 0.6 0.3 0.5
F 0.4
Fe 0.08 5.7 70
Al 0.03 1.4 50
Cr 0.01 0.6 60
al day shaker leach of 50g of -20 mesh waste with
250-ml water; room temperature, open vessel.
"Plant G.
cPlant B.
52
-------
In Fig. 23 we have plotted the percentages of each element leached
from the low-sulfur waste versus those from the high-sulfur waste. (The
solid diagonal lines indicate the magnitude of the difference in leacha-
billty between the two sets of data.) Immediately recognizable is the
clustering of the elements into monovalent, divalent, and trivalent groups
(marked by dashed lines). The low solubilities for the monovalent
cations deny the existence of appreciable simple salts in the waste and
suggest that these elements are bound tightly in aluminosilicate struc-
tures. (Simple salts such as sodium chloride would have been removed, if
they were ever present, by the washing process.) The dramatic difference
in the behavior of the trivalent species* suggests that leachate acidity
might be dictating their leaching response. Plots of the element levels
in the leachates for the three Illinois Basin plants and the Appalachian
plant show that the aluminum and iron levels change enormously with small
changes in pH (see Fig. 24). The divalent elements show less sensi-
tivity, although manganese increases with increasing acidities at low pH.
The pH-associated behavior of potassium is not explained.
Since the comparisons of element leachabilities for the high-sulfur
and low-sulfur coal wastes were made using data corresponding to pH 2.2
and pH 4.3 (indicated by the arrows at the bottom of Fig. 24), the high-
sulfur waste is much worse than the low-sulfur waste. Comparing the
low-sulfur coal waste with the high-sulfur waste from Plant A (pH 7.3),
however, will show that the low-sulfur waste is worse. Over the short
term (at least 8 wk), the leaching behavior is not dependent on the
amount of pyrite in the coal but rather on the ability of the waste to
control acidity. Natural or induced alkalinity is the critical
parameter.
The batch or equilibrium experiments yielded results emphasizing
constant interaction between the solid waste and the same unreplaced
leachate. Column leaching experiments emphasize the interaction of a
continuously changing leachate with the waste, accentuate the dissolution
of readily soluble materials, and on occasion, illuminate the chromato-
graphic behavior of transportable species through the solid being leached
(see also the section on "Column (Dynamic) Leaching"). By draining the
column, aerating the waste, and then reestablishing water flow, soluble
species from oxidatively sensitive components are easily seen as they
concentrate in the first few increments of leachate that pass through the
column. Subjecting coal wastes to dynamic leaching experiments should
provide additional insight into their leaching behavior and provide
information about the discharge levels expected.
Column leaching experiments utilizing the low-sulfur Appalachian
coal waste are described in Appendix J, where trace element levels in the
leachate increments are tabulated and plotted. Plots of pH, total dis-
solved solids, potassium, and iron levels at various effluent volumes are
also given in Fig. 25. The initial leachates from each column are more
acidic (pH 2.9) than the 10-minute leachates from the batch studies (pH
4.3). This probably arises from a combination of a flow that is too fast
(0.5 m£/h - see the section on "Column (Dynamic) Leaching" for a discus-
sion of flow rates) and the presence of leachable material at the exit
*Iron apparently is oxidized readily from the ferrous to ferric state in
the open vessels when the pH is above 2.
53
-------
100
00
Q <
UJ ^
!=F UJ
UJ
I- h-
-z. tr>
UJ <
UJ <
o
CJ
10
O.I
0.01
O.I
10
100
ELEMENT LEACHED FROM A HIGH -SULFUR
COAL WASTE GENERATING pH2.2 IN ONE DAY(%)
g. 23.
between ^e peAcen^age* o^ ;ftace
pfinpaA.atA.on
54
-------
10 -
LEACHATE
Pig. 24.
The. pti~c.on&ioiJL2jd. fi&t, (PJLantt, A,
B, and C have. kLgh-AiLtfiuA. uxut&>; VLavit G hot, tow-AutfiuA. watte.; ?La,Yvt A
ha* > 1 % catc^tn pnu, tnt.}
55
-------
00 15
-
3.0 4 5 6.0 7.5
VOLUME (liters)
LEGEND
o = GL-23
° = GL-24
« = GL-25
« = GL-26
105
120
1.5
3.0 4.5 6.0 7.5
VOLUME (liters)
LEGEND
= GL-23
= GL-24
=GL-25
=GL-26
12.0
O-
0.0 15 30 4.5 6.0 7.5 9.0 10.5 120
VOLUME (liters)
LEGEND
= =GL-23
°=Gl-24
a=GL-25
«=GL-26
3.0 4.5 6.0 7.5 9.0 10.5 12.0
VOLUME (liters)
fig. 25.
Le.adh.ate. pH, total dlt>t>olve.d Aottfa, and potaAAlum and Ifion le.velA fan. column
le.ac.hA,YiQ& o\ ?la.nt G coal pfie.pojwitA.OYi watte..
boundary. Both would minimize leachate interaction with the acid neu-
tralizers in the waters.* The pH values level off at 3.9, which is near
the 1-day batch experiment pH value. Trace element concentrations in
these leachates are discussed in the next section in relationship to
pollution assessment.
Dissolved solids load in the column leachates is not particularly
high (< 0.5 percent) and drops exponentially as the volumes of the leach-
ates increase. Similar behavior is observed for all 14 elements measured
(Al, Ca, Cd, Co, Cr, Cu, F, Fe, K, Mg, Mn, Na, Ni, and Zn), as illus-
trated by potassium and iron in Fig. 25. This is consistent with
*Column leaching of Plan A waste really demonstrated this behavior. Ini-
tial leachate pH was around 2.9 for the column and 7.1 - 7,8 for the
entire batch time period (10 min to 56 davs1 - Second Annual Report (LA-
7360-PR).
56
-------
exponential elution (dilution) of nonregenerative species. Regenerative
species are present, however, as demonstrated by the drops in pH (down to
3.2) and increase in element levels after column airing and resumption of
leaching (see the level increases after the "Air Regeneration" lines of
Fig. 25). They are simply not regenerated under the experimental
conditions.
Like the batch leaching data, the column leaching data also contain
information about the locations of the elements in the waste. Figure 26
shows the column leaching behavior of the low-sulfur coal waste. Element
leaching behavior along the horizontal axis is defined by the amount of
the element in the initial leachate fraction relative to its level in the
waste, i.e., pseudo percentage-leached parameter. Leaching behavior
along the vertical axis is defined by the level of the element in the
initial fraction relative to its level in the first fraction collected
after airing. Three general clusters appear. As with the batch experi-
ments, these clusters contain only common or isovalent species. The
horizontal axis indicates that only the divalent species have significant
SMALL AMOUNT OF
VERY SOLUBLE PHASE
OR
pH SENSITIVE PHASE
PHASES SIMILAR
VERY SMALL AMOUNT
OF SOLUBLE PHASE
INITIAL = 2.9
REGENERATED =3.2
MODERATE AMOUNT
OF ELEMENT SOLUBLE
ALMOST ALL OF
ELEMENT INSOLUBLE
I NIT LEACH ]/[ WASTE]
3,000
g. 26.
-------
solubility. The fluorine position suggests the possibility of fluoro-
aluminosilicates, although fluorophosphates are possible and more common.
The vertical scale shows that the trivalent species had a greater amount
of a soluble phase present at the beginning of the leaching than after
the "air-regeneration" of the column. The divalent elements show less
difference, and the monovalent elements show almost none. The higher pH
(3.2) in the regenerated case than was initially encountered (2.9) could
explain the difference (see the pH-dependency in Fig. 11). Alterna-
tively, the lower initial pH could indicate that more oxidation had
occurred before the beginning of the leaching than during the "air-
regeneration" step. In either case, the oxidation step points to at
least two phases (locations) for each of these "oxidatively sensitive"
elements.
Figure 27 is a similar presentation of the column leaching data for
the high-sulfur coal waste from Plant B. The general alignment is simi-
lar except for the trivalent cluster. Cr and Al have moved to a higher
initial solubility. This is probably reflective of the higher acidity
for this waste. Even more noteworthy is the behavior of iron. In this
case, iron is more closely aligned with the divalent elements than the
trivalent ones. This coincides with a major change in the occurrence of
iron. Here iron resides predominantly in pyrite (ferrous or divalent
state), whereas in the low-sulfur waste it occurs mainly with the clays
(most likely in the ferric or trivalent state). Alternatively, the shift
might simply reflect the pH-sensitivity of iron noted earlier (Fig. 11).
Another cluster contains rare earth elements and uranium and reflects
phosphate behavior. The "regeneration" behavior for fluorine is unavail-
able, but its initial leachate value would place it in line with this
cluster, suggesting the existence of fluorophosphates.
Much of the foregoing is speculative, but we also think that it is
quite plausible. This discourse points out that generalizations can be
made about the leaching behaviors of coal preparation wastes. Every coal
waste situation is not unique, and the variables are not limitless.
Acidity appears most important; both the ability of a waste to produce
acid and its ability to neutralize the acid are critical. And last, a
coal preparation waste is not bad just because it is a high-sulfur one.
D. Assessing the Pollution Potential
Quantitative knowledge about the existence and extent of the pollut-
ing capabilities of a waste is needed to evaluate whether control meas-
ures are needed. Once need has been established, this knowledge is also
needed to define the types, magnitudes, and efficiencies of the control
techniques that must be used to remedy the problems. Such information
has been gathered for the trace elements of concern for coal preparation
wastes in the Illinois Basin. Of the 69 elements studied, 12 were found
to be released from these wastes in potentially hazardous quantities
(E. M. Wewerka, J. M. Williams, and P. Wagner, "The Use of Multimedia
Environmental Goals to Evaluate Potentially Hazardous Trace Elements in
the Drainage from High-Sulfur Coal Preparation Wastes," in preparation).
Preliminary assessment results for the low-sulfur Appalachian coal waste
were reported in the third annual report of this project (LA-7831-PR). A
more complete evaluation of the pollution potential of these wastes is
reported here.
58
-------
i i i i i i
SMALL AMOUNT OF
VERY SOLUBLE PHASE
OR
pH SENSITIVE PHASE
PRIMARY AND
SECONDARY
PHASES SIMILAR
OR PRIMARY
SWAMPS
SECONDARY
VERY SMALL AMOUNT
OF SOLUBLE PHASE
INITIAL =1.6
REGENERATED =2.3
MODERATE AMOUNT
OF ELEMENT SOLUBLE
ALMOST ALL OF
ELEMENT INSOLUBLE
100
1000
[INIT LEACH]/[WASTE] xio4
10,000
fig. 11.
the. column tracking data ofi a hj
coal uxute..
Ul
-------
Both batch and column leaching experiments can be used to evaluate
pollution potential. Because they are thought to represent the real
world better, column leachates have been favored and used in the past.
The problem has been which ratio of liquid to waste should be used. For
practical purposes, we have chosen the 100-m£ increment taken after
400 m£ of water have passed through 1 kg of waste. These leachates seem
to correspond reasonably well with field samples (E. M. Wewerka, J. M.
Williams, and P. Wagner, "The Use of Multimedia Environmental Goals to
Evaluate Potentially Hazardous Trace Elements in the Drainage from High-
Sulfur Coal Preparation Wastes," in preparation). For comparison we have
chosen the 1-day-batch leachings in which the leachate-to-waste ratio is
5:1, but whose element-release data are reported in micrograms of element
released per gram of waste leached. The EPA MEG/MATE system has been
used to evaluate the element toxicity. Ecology MATE values have been
chosen as representative of the most critical toxicity (see Task III on
Bioassay). A dilution factor of 100 has been applied to all the leachate
levels to simulate environmental dilution. Hazard factors reflect the
ratio of the adjusted leachate level to the toxicity level (MATE).
Values approaching or exceeding 1 are cause for concern. Hazard factors
for 11 elements in column and batch leachates for wastes from the low-
sulfur Appalachian plant and the three Illinois Basin plants are reported
in Appendixes I and J, and are plotted in Figs. 28 and 29 as functions of
the leachate pH. The most remarkable feature of these plots is the
consistency in the behavior of the elements, regardless of their origin.
Thus, elements that are hazardous in one waste are generally hazardous in
another. Almost all elements also show a decrease in "hazardousness" as
pH increases. Manganese, calcium, and potassium are notable exceptions.
Aluminum and iron exhibit the strongest response to pH changes. These
two elements are the most toxic in coal wastes that, generate low pH
values (< 2) but are also two of the least worrisome for wastes pro-
ducing little acidity (pH > 6). Manganese and nickel are the only con-
sistently worrisome elements.
Rating the elements in terms of their environmental impact and waste
association is a tricky business. Indeed, our choice of the column
leachates to test and our assumption of a 100-fold environmental dilution
factor introduce about a 1000-fold reduction in the element levels that
can be released. Without this reduction, most of the 69 elements that we
have studied would be hazardous in one coal waste or another. Fortun-
ately, the "hazardousness" ordering of the elements remains relatively
constant. Thus, if a waste does not have the big offenders, it does not
have the little ones either.'
Based on our observation that the elements released by a coal waste
are related to the acid-generating tendency of that waste, we have rated
69 elements with respect to their pollution potential. The ratings for
high-sulfur Illinois Basin and low-sulfur Appalachian coal wastes are
given in Table XIX. We believe that this evaluation has general applica-
bility to all neutral and acid-generating coal wastes. Further work is
needed to verify this opinion.
60
-------
100
CO
LJ
I
o
10
o
o
LT
O
b i
or
LJ
LU
CO
LJ
O
OL
<
O
cn
o o.l
0.01
0.001
X-Mn
\
\N.
\
WORRY LINE
1.5 2.0 2.5 3.0 3.5
PH
fig. 23.
Ae.v&u£y ^on column l.t>ac.hateA oft
at 2:5 £e.a.c.kat&:w
-------
0.001
Vc.haA.g
-------
TABLE XIX
A RATING OF THE TRACE ELEMENTS OF CONCERN IN
APPALACHIAN LOW-SULFUR AND ILLINOIS BASIN HIGH-SULFUR
COAL PREPARATION WASTES"
Elements (2) of concern under acid or neutral conditions:
Ni, Mn
Elements (4) of concern under acidic (pH<4) conditions:
Al, Cd, Fe, Zn
Elements (6) of concern only under highly acidic (pH<2.5) conditions:
As, Be, Co, Cu, Pb, Se
Elements (36) not particularly hazardous under acid or neutral conditions:
Ag, B, Ba, Bi, Ca, Ce, Cr, Cs, Dy, F, Ga, Ge, Hf,
K, La, Li, Mg, Mo, Na, Nb, Pr, Rb, Rh, Sb, Sc, Sm,
Sr, Ta, Te, Th, Ti, Tl, U, V, Y, Zr
Elements (21) with neither an ecology nor a health MATE value listed. (All,except S and P, oc-
cur at very low levels and are unlikely to be hazardous)":
Au, Br, Er, Eu, Gd, Ho, I, Ir, Lu, Nd, Os, P, Pd, Pt, Ru, S, Sn, Tb, Tin, W, Yb
aBased on EPA health and ecology MATEs and column leachates.
"Sulfur would probably fall under the 'highly acidic' category, while P would probably not be par-
ticularly hazardous even then.
63
-------
III. TASK III: LEVEL I BIOASSAY OF (HIGH-SULFUR) COAL CLEANING WASTES
AND WASTE LEACHATES
Toxicological characterizations of high-sulfur Illinois Basin coal
waste leachates were performed on leachates that had been diluted 100-
fold. Under these conditions 12 elements were shown to be of potential
environmental concern. The samples chosen for study were Illinois Basin
Plant C average solid waste (#18A) and its shaker-formed leachate. The
chemical analyses for the waste are reported in our second annual report
(LA-7360-PR), and an abbreviated list of elements and their concentra-
tions for the leachate is reported in Appendix K under the "FRESHWATER
ALGAE" heading.
A. Health Effects
The tests chosen to evaluate the damage the coal waste leachates
could cause to higher animals and humans were listed in the document
EPA-600/7-77-043 [K. M. Duke, M. E. Davis, and A. J. Dennis, "IERL-RTP
Procedures Manual: Level I Environmental Assessment, Biological Test for
Pilot Plants" (April 1977)]- The specific sections used were 3.3.1
(Mutagenesis or AMES test), 3.3.2.1 (Rabbit Alveolar Macrophage or RAM),
3.3.2.2 (Human Lung Fibroblast or WI-38), 3.3.2.3 (Clonal Toxicity or
CHO), and 3.3.3 (Quantal Rodent Toxicity). Each of these tests was run
at LASL by personnel in our Life Sciences Division (LS Division). Their
results and observations are included in Appendix K. A quantitative
summary of their findings is given in Table XX.
The Quantal Rodent Toxicity and AMES tests were negative for both
leachate and solid waste. In the Quantal test, this means that the
leachate can be ingested (drunk) undiluted in moderate quantities (cor-
responding to 700 m£ for a 150-lb human) without short-term problems.
In the mutagenesis test, this means that each of the four Salmonella
strains tested produces as many revertants with the waste component pres-
ent as without the waste component. A revertant is a genetic reversal
of a mutant back to its normal form, as measured by a change in ability
of the strain to metabolize certain nutrients.
The cytotoxicity (RAM, WI-38 and CHO) tests demonstrated that the
waste materials can cause health degradation on the cellular level. The
test sensitivity was CHO>RAM>WI-38, with only a factor-of-4 spread
from CHO to WI-38 for the leachate. The more sensitive CHO test shows
that the leachate is still toxic (50 percent reduction in activity) when
diluted 1 part to 32. When this diluted solution is evaluated in terms
of the constituent health MATE values (see Table XXI), Fe, Mn, and Ni are
the only elements with potentially hazardous levels. At this level only
iron, with a hazard factor of 11, would be singled out. Iron, apparently
the trace element of primary concern, appears to be tolerable from a
health standpoint at levels (15 ppm) above that set by EPA (3.5 ppm) for
waste effluents.
The solid sample causes more (60 - 300x) degradation than the liquid
samples in the cytotoxicity tests. Little of this difference seems to be
related to the trace element content that the solid would release. We do
not have a satisfactory explanation for this.
64
-------
TABLE XX
QUANTITATIVE SUMMARY OF HEALTH EFFECTS TESTS
FOR A COAL WASTE AND ITS LEACHATE3
Test
Mutagenesis (AMES)
Leachate
Solid Waste
Rabbit Alveolar Macrophage (RAM)
Leachate
Human Lung Fibroblast (WI-38)
Leachate
Solid Waste
Clonal Toxicity (CHO)
Leachate (1 day)d
Leachate (1 week)d
Solid Waste (lday)d
Solid Waste (lweek)d
Quantal Rodent Toxicity
Leachate
Solid Waste
LC50)LD50, orEC50(%)b
Test# 20hourc 24hourc 40 hourc 48 hour0
3.3.1
3.3.2.1
3.3.2.2
3.3.2.3
7.5
3.3.3
-Negative-
-Negative-
11
0.18
4.5
4.5
0.0125
•>10m,e/kg
— >10g/kg'
3.1
4.5
0.0125
aLEACHATE is CTWT-1012; Iron concentration is 5460 ppm;
SOLID WASTE is Plant C waste #18A.
bLC50: Concentration of test material which causes mortality
in 50% of test organisms.
LD50: Dose of test material administered which causes
mortality in 50% of test organisms.
EC50: Concentration of test material which causes immobility
in 50% of test organisms.
cHours after inoculation.
dColony growth time before inoculation.
65
-------
TABLE XXI
TRACE ELEMENT CONCENTRATIONS AND DISCHARGE SEVERITY
'50
FOR LEACHATES GIVING EC50 aIN CLONAL TOXICITY TESTb
1.5
0.25
0.23
0.75
80
0.05
38
240
0.25
25
800
5
Total
113
2
1.6
0.2
0.2
0.2
0.09
0.07
0.06
0.03
0.02
0.01
118
Element Concentration Mate Discharge
(ppm) (ppm) Severity
Ke 170
Mn 0.50
Ni 0.38
Co 0.18
Al 17
Cd 0.01
F :U
Ca 17
Cr 0.016
7.r\ 0.75
Na 19
Cu 0.05
''EC-,,: Concentration of test material which causes immobility
in 50'7r of test organisms.
''Leachate CTWT-1012 diluted 1 part to 32.
B. Ecological Effects
The tests chosen to evaluate whether the coal waste materials could
degrade the ecological systems were those under section 3.4 of EPA-600/
7-77-043. The specific tests were 3.4.1 (freshwater algae) and 3.4.2
(both fathead minnows and Daphnia magna). The algae tests were run at
LASL in the LS Division, and the minnow and Daphnia tests were run by the
LFE Environmental Analysis Laboratories of Richmond, California. The
results are reported in Appendix K. Only leachate was tested. A summary
of the levels at which 50% immobility or death occurs is given in
Table XXII.
Algae and small aquatic life are sensitive to coal waste leachate.
In general, these systems are a factor of 10 more sensitive than the
health-related systems discussed above. (This difference is well-known
and reflected by the MATE values EPA has given to many elements; e.g., Fe
has a health MATE of 2.5 and an ecology MATE of 0.25; Mn, on the other
hand, has values of 0.25 and 0.1, respectively, while Al has values of 80
and 1.) The lower limit for the algal test was not established and thus
cannot be related directly to the values for the fishes. Of the two
aquatic animals, however, Daphnia magna is several times more sensitive.
A quantitative assessment of the trace metal concentrations which
give these results can be made with EPA ecology MATE values. Using the
concentration for TLM96 (total lethal median, or that concentration of
test solution in which 50% of the test animals die or, in the case of
Daphnia, are inactive within 96 h of being exposed to the test solution)
for the more sensitive Daphnia magna, hazard factors above 1 are found
for only iron and nickel (see Table XXIII). At a safe concentration,
66
-------
TABLE XXII
QUANTITATIVE SUMMARY OF ECOLOGICAL EFFECTS TESTS
FOR A COAL WASTE AND ITS LEACHATE3
Test
EPA
Test#
TLM50b or EC5,,C
for Leachale (%)c
Freshwater Algae 3.4.1 <0.75
Fathead Minnows 3.4.2 0.45
Daphnia magna 3.4.2 0.17
Leachate CTWT-1012 used.
TLMSO: Total lethal median; concentration of test material
which causes mortality in 50% of test organisms
within defined test period.
CECSO: Concentration of test material which causes immobility
in 50% of test organisms.
dFor example, 0.75% CTWT-1012 in test media.
TABLE XXIII
TRACE ELEMENT CONCENTRATIONS AND DISCHARGE SEVERITY
FOR LEACHATES3 GIVING TLM50b IN
Daphnia magna TOXICITY TEST
Element
Concentration
(ppm)
MATE Discharge
(ppm) Severity
Fe
Ni
Al
Cu
Cd
Zn
Mn
Ca
Co
Or
K
8.7
0.02
0.88
0.026
0.0005
0.038
0.026
0.86
0.009
0.001
0.027
0.25
0.01
1
0.05
0.001
0.1
0.1
16
0.25
0.25
23
Total
Hazard
35
2
0.88
0.52
0.5
0.38
0.26
0.05
0.04
0.003
0.001
39
"Leachate CTWT-1012 dilution 1620 parts to 1 million.
''TLM,,,.: Total lethal median; concentration of test material
which causes mortality of iiO'.'ii of test organisms
after 96 hours exposure to test material.
67
-------
l/10th as strong as this, iron would still be above 1 at 3.5, suggesting
that the MATE value for Fe may be a little low but again certainly not
by much. Ruling out pH effects [the controls and test units were near
the same values (6.2 - 6.7)1, iron seems to be the main problem in the
leachate.
C. Summary
Coal preparation wastes and their leachates are toxic but not
excessively so under acute testing conditions. A qualitative evaluation
of the Level I Bioassay tests is given in Table XXIV. Ecological systems
represented by fathead minnows and Daphnia magna are an order of magni-
tude more sensitive than the most sensitive health system (CHO). The
ecological systems test an organism's ability to survive when completely
surrounded by the pollutant. The health systems measure the degradation
of higher order, more diverse systems by a pollutant. In the most highly
developed animals (rodents), coal preparation waste leachate was not
found to be acutely toxic. Long-term or chronic toxicity is not known.
The high acidity (low pH) of the leachates was found to be toxic,
but even when the acidity was neutralized, the leachates remained toxic.
The active trace elements have been identified by EPA MATE values to be
iron (Fe), nickel (Ni), and manganese (Mn), in that order. The original
leachate contained 5500-ppm iron and needed to be diluted 1 part to 600
just to reach a concentration where 50 percent of the Dapnia magna could
survive. A l-to-6000 dilution, giving 1 ppm of iron, was acceptable for
the most sensitive bioassay test run. From our study, future Level I
bioassay testing of coal and coal waste leachates can be limited to the
more sensitive ecological tests (fathead minnows and Daphnia magna).
TABLE XXIV
QUALITATIVE RESULTS OF
LEVEL I BIOASSAY OF REFUSE AND REFUSE LEACHATES
Test Solid Leachate
Quantal Rodent Toxicity Neg Neg
Mutagenicity (Ames) Neg Neg
Cytotoxicity
Rabbit Alveolar Macrophage (RAM) Pos Pos
Human Lung Fibroblast (WI-38) Pos Pos
Clonal Toxicity (CHO) Pos Pos
Freshwater Algae Pos
Freshwater Fish (Fathead Minnows) Pos
Daphnia Pos
68
-------
MISCELLANEOUS
I. WASTE COLLECTION SUMMARY
Since the project's inception, samples have been collected from coal
preparation plants as the need evolved. A brief log of samplings is
presented in Table XXV. Samples collected from plants for more extensive
TABLE XXV
RECORD OF COAL-PREPARATION PLANT SAMPLINGS
location
Sulfur Level
Date Sampled
Total Weight (Ibs)
Feed Coal
Coal Waste
Coal Waste Drainage
Product Coal
Plant
A
B
c
E
M
N
High
11/75
2000
y
V
j
High
11/75
2000
V/
V
V
High
11/75
2000
V
V
^
High
6/76
2000
v7
V
V
High
10/78
:«) ooo
V
High
4/78
(500 gal)
v7
H
City
High
X
G
I
K
Low
6/76
2000
v/
v"
V
High
5/79
1500
v/
v'
V
High
5/79
1500
v7
\/
\/
D
Low
1 1/75
:)()()
V
V
studies are in the 1500- to 2000-lb range. The 300-lb sampling of Plant
D was exploratory. Generally the volumes of feed coal, clean coal, and
waste have been comparable. The samples were usually collected from
moving belts, although one waste sample had to be collected from a waste
pile as the waste was being dumped, and a product-coal sample was col-
lected from a just filled rail car. Shovelfuls were normally taken every
10 - 15 min. Plastic-lined, 10- to 12-gal. cardboard barrels were filled
every 1 - 2 h. These were sealed and transported by truck or air back to
the laboratory, where they were prepared further (see first and second
annual reports, LA-6835-PR and LA-7360-PR). Some oxidation problems have
been encountered. Sealing under nitrogen and storage at 4°C might have
been helpful but were not tried. Plants A, B, C, and D were described
in the first annual report. Information about Plants G, I, and K is
given in Tables XXVI to XXVIII.
A large waste sample was collected from Plant M at the end of 1978
to provide a source for scaled-up disposal testing. This sample was
scooped up by a front-end loader as it was dumped, fresh out of the
plant, and poured into 55-gal. drums. Air-tight lids were then placed on
the drums. Because of the nature of the ultimate use of this sample, no
liners were used in the barrels. The drums were placed on a truck and
shipped back to the laboratory for testing. Information about Plant M is
given in Table XXIX.
A large sample of high-sulfur, acid mine, coal waste drainage was
also secured for control technology studies. This sample was collected
in 55-gal., plastic-lined drums and shipped by truck to the laboratory.
This sample had little ferrous content, as oxidation had been extensive,
69
-------
TABLE XXVI
INFORMATION ON PREPARATION PLANT G
Date Sampled: 6/211/76
Lot-atiim. Eastern Kentucky
Coal Seams: Coalburg and Stockton
Cleaning Kquipment: 0 x (i in. rotary breaker
] -I x (i in. to hi'avy density media (- 1 ' 'I feedt
Oxl -I in. to Deister tables (~ I '2 feed)
Feed Kale: 1000-1200 ton/h
Product Coal: Whitish in appearance
0.88 % Sulfur (company data)
10 % Ash
Haw coal after crushing
Cleaned and dried coal
Refuse (fine and coarse)
Streams clear of yellow-boy, but muddy
TABLE XXVII
INFORMATION ON PREPARATION PLANT I
Dale Sampled: 5/1/79 for 4 hours
Location. Western Pennsylvania
Coal Seams: Purchased coal that is blended
Old piles and seconds
Deep mines - Lower Kittanning
Strip mines - Upper Kittanning
- Lower Freeport
Feed cortl properties: Company data March,1979
Moisture (%)
Ash (%,dry)
Sulfur (%,dryl
Htu
% Float
CleaninK Kqui|)menl: -'-]/4 in. rotary breaker
Cvclones
-15/4 in. clean coal
Feed Rale: 500 ton/h
Snm|)i('d: Kiuv coal before Im-nker 1 x l.'t^al
Cli'LHH-tl iind dried I x l.'i jial
HeCuwe and breaker rt-jt-i-t I x l.'i tral
Waste disnnsal; Convevared; thin-layered in shallow valley;
clav-lined with drainage ditches;
effluent collected and treated with
mine water al lime plant.
".mix i:>00 ft pile. 20 I'l liitfh.
I 'ncovered without evidence of intermittent coxcr
70
-------
TABLE XXVIII
INFORMATION ON PREPARATION PLANT K
Date Sampled:
Location:
Coal Seams:
5/3/79 1'or 3 hours
Western Pennsylvania
Purchased coal that is blended
Upper and lower Kittanning
Upper and lower Freeport
Cleaning Equipment: -5 in. crusher
1 cell, Jeft'ery jig
-2 in. clean coal
-3/8 in. bypass
Feed Rate: 150 ton/h
Sampled: Raw coal (5 x ,'i H)
Raw coal "clean" coal (.') H x 0)
Clean coal (2 x :! H)
Refuse (."> x 0)
(it) 40 fine coarse split
Observations: pH adjusted in washing water with soda ash
Waste Disposal: Trucked back to strip mine
-1 x
•1 x
-1 X
TABLE XXIX
INFORMATION ON PREPARATION PLANT M
Date Sampled:
Location:
Coal Seams:
Cleaning Equipment:
Feed Rate:
Sampled:
Waste Disposal:
11/15/78 for 6 hours
Western Kentucky
Kentucky 9 and 11
-6 in.crusher
McNallyjig
500 ton/h
Refuse (K x 0)
Steel drums sealed and shipped back
to Los Alamos by truck
Graded pile in elevated area.
Waste dumped in 3 ft-high piles and spread
in 6 in. layers. Pile uncovered.
:tO x .
71
-------
and was quite dilute, as it was collected in the spring during high water
flow.
II. DEVELOPMENT OF ASSESSMENT METHODS
Control technology researches at LASL are being addressed in several
areas related to energy production. As a consequence, we have been
investigating a number of areas that have general significance to the
ultimate understanding, measurement, and control of pollution from coal
preparation waste. In the next few sections we present several of these
multiprogrammatic efforts.
A. Batch Leaching, LASL, ASTM, EPA, and RCRA
A major problem in relating real life water pollution to laboratory
simulations is deciding just what to simulate. The overall problem is
depicted in the following diagram; the main concern was to release water
that is environmentally safe. From a management point of view, however,
knowledge of which parameters are responsible for the release and control
of the pollutants is desired.
WATER
SOURCE
(A)
WASTE
DUMP
(B)
SOIL (OR)
WATER
TREATMENT
(C)
WATER
RELEASED
(D)
For several years we have conducted our own leaching tests in a
manner now employed in the ASTM Method A leaching test. While we believe
this gives a fair representation of the waste behavior, some questions
have always remained: how important is the leaching medium in deter-
mining the trace element levels leached from a waste, and can we use this
knowledge to build a better dump? To address these issues we have run
several series of leaching tests. One set of tests studied the release
of trace elements under a wide range of acidities using highly buffered
extractants. This set included pH values from 1.4 to 9.7 and included a
high-sulfur coal preparation waste; an eastern fly ash; and an Illinois,
kaolinite-type soil. The experimental descriptions and results are given
in Appendix L. A second set of tests studied the attenuation of trace
metals already in solution by pH adjustments. The details of this set
are reported in Appendix F and are discussed further in connection with
waste effluent treatment under the Task I section.
Highly buffered leaching media of different acidities can give
significantly different leachabilities for trace metals in solid mate-
rials. This is clearly illustrated by Figs. 30 and 31, where the amounts
of iron leached from an eastern fly ash and an Illinois soil are shown to
be sensitive to pH outside the range pH 5 to pH 8. In these two cases,
the test needed little acetic acid to reach pH 5, and the leaching
behavior was similar to that found for the water control. Using highly
buffered acetic acid as described in the ASTM method B, however, gave
greatly different results for the two materials. This behavior for
acetic acid is very different from that of the phosphate and sulfate
72
-------
I ' I '
LEGEND
• LASL BUFFERS
D WATER ONLY
A ASTM-HOAC
O EPA-EXTRACTION
PROCEDURE
EPA .PERMITTED
••••••••••••••••••••<
UPPER LIMIT
0.01 -
Tke. pH i.nfilu.&nc.e. on tkn
so.
ofi -Oion. fiiom an
cu,h.
73
-------
100
E
CL
CL
UJ
o
<
UJ
10
O
O
O.I
0.01
LEGEND
• LASL BUFFERS _
D WATER ONLY
A ASTM - HOAC
O EPA-EXTRACTION
PROCEDURE
EPA PERMITTED
UPBER"UMIT""
D
-^^
D
I
1
2468
PH
10
FoJUL.
74
-------
buffers. Organic chelation might be important. At any rate, the acetic
acid buffer gives a different picture, and cases where much acetic acid
is needed to lower the pH should be viewed cautiously.
The concentrations of many trace elements drop as the pH of the
leaching medium increases, and low values are achieved near pH 8. (This
can be seen for the 13 trace elements leached from a high-sulfur coal
waste in Appendix L, Table L-IV). At pH values much higher than 8, a few
trace elements such as Mo are released at levels that could be cause for
concern. From an environmental viewpoint, a dump should be kept around
pH 8 to maintain the lowest overall release of trace metals.
What is happening under the various leaching conditions is not
completely understood. At low pH, the metals are certainly leached and
remain in solution. At higher pH values, the metals may not be leached
at all, or they may be leached and then reprecipitate. Thus, when the pH
is raised on a coal waste leachate by adding lime, the metal concentra-
tions behave in the same manner as the buffered leachates (compare
Fig. 11 with Fig. L-l for iron, and Table F-I with Table L-IV for some
others).
Whether or not a metal is leached and reprecipitated or never
leached at all may not seem significant, but the mechanism is important
to a waste control technology designed to reestablish the previously
existing environment. For example, iron and sulfur could be leached from
pyrite and then redeposited as ferric oxide and calcium sulfate. When
placed in a closed dump, the iron will be converted to the more soluble
ferrous state as reducing conditions develop. If the sulfate is reduced
to sulfide and the iron and sulfur have not migrated away, pyrit.e forma-
tion should occur in time. In any case considerable reorganization must
occur to return these materials to their former state, namely pyrite.
If, on the other hand, iron and sulfur are not oxidized and leached, they
may already be in their most likely final states and extensive chemical
reorganization will not be encountered as the pile reverts to its "ori-
ginal", reductive environment. These comments emphasize the importance
of minimizing the weathering of natural wastes, such as coal waste, and
rapidly returning the dump environment to the original geologic
conditions.
B. Column (Dynamic) Leaching
The manner in which a leachate flows through a column can affect the
levels of trace metals in the effluent. Chemical reactions are con-
trolled not only by the interaction between two species, but also by the
diffusion or transport rate of these species to and from the reaction
site. Understanding transport phenomena is particularly important in
evaluating data from studies of pollutant attenuation inside and outside
waste dumps. A simple illustration of the flow problem is shown on the
next page.
Leachate movement is determined by the difference between the inlet
force and outlet force on the leachate and the size of the channels (D)
between the soil (or waste) particles. These channels may be large
cracks or fissures at one extreme and small capillaries, as illustrated
in the soil particles, at the other. Water flow in the cracks will be
fast; flow in the capillaries will be slow. The size of the channels
will be determined, among other things, by the plasticity of the soil
75
-------
FORCE OF GRAVITY + OVERBURDEN SOIL
4
OUT
particles and by the pressure exerted by gravity and the soil or overburden.
For example, clays are deformable when wet and will generally compact,
resulting in small channels and low flow rates.
Pollutant movement is determined by the flow of the leachate and the
various available chemical reactions. Elements with very facile reac-
tions available, such as those of ferric and aluminum cations with water
at pH values above 4, should be less sensitive to leachate flow rates
than those having only slower mechanisms available. Ferrous cations, for
example, are not readily attenuated by "neutral" water and must find
cation exchange sites on the soil particles to be attenuated. (See the
section on "Pollutant Attenuation and Movement Through Soils" for possi-
ble Fe++-Mn interactions in soils.) As the water flow slows, these
reactions can be accomplished more easily.
Over the past 4 years, we have run a number of column experiments.
For convenience we have used up-flow at 0.5 m£/min in 4.6-cm-diameter
tubes. This seemed like a good compromise for the column leaching of
coal waste. Recently, however, we noticed that, in soil attenuation
experiments, rapid flow (1 to 5 m£/min) of leachate to prewet the soil
gave little attenuation of some elements which had previously been atten-
uated in equilibrium studies. This increased our concern about con-
ducting meaningful flow experiments. Consequently, as part of our
efforts to evaluate the transport of trace elements through soils, we
have begun to evaluate the influence of flow parameters on leaching
results. Preliminary results for up-flow versus down-flow through
several soils are presented here. Further experiments are planned and
will be reported as they develop.
A simulated coal-waste leachate (see the section on "Standard Coal
Waste Leachate") was diluted with distilled water to provide an influent
leachate with a pH of 2.7, a Fe++ concentration around 450 |Jg/m£, and a
Fe+++ concentration around 250 |Jg/m£. Glass columns (4.6-cm I.D. by
20-cm high) were packed with about 150 g of subsoil or overburden mate-
rial to a bulk density of about 1 g/cm3. Columns were evacuated and then
slowly filled with leachate solution by allowing leachate to displace air
in void spaces in the evacuated columns under gravity flow. A leachate
76
-------
pressure drop of 20 in. of water was maintained in the downward-flow
columns. Flow rates for the gravity flows varied, depending on permea-
bility of the packed columns. Flow rates of columns operating with
upward-flow under pump control were between 1.2 and 5.0 m£/h, at constant
head. Eluent was collected continuously, and periodic aliquots were
taken for immediate determination of pH, Fe++ and total Fe.
The first soil used was Kentucky coal seam No. 11 overburden with a
cation exchange capacity of 0.098 meq/g. Ferrous ion concentration in
the effluent relative to the influent is given in Fig. 32. Down-flow
resulted in more attenuation than up-flow. The first signs of Fe++ were
23% higher, and at C/C0 = 0.5, the Fe++ was 18% higher. The Fe++ atten-
uated by the soil column with down-flow at C/C0 = 0.5 was 0.096 meq/g of
soil, in good agreement with cation exchange capacity of the soil.
U=UPFLOW
D = DOWN FLOW
0 246 8 10 12 14 16 18 20
VOLUME ELUENT/MASS SOIL (ml/g)
-------
In summarizing our current understanding of column attenuation, we
would say that down-flow approaches equilibrium conditions better than
up-flow, and that l-m£/h flow is the maximum advisable for soil columns
with a cross-sectional area around 15-20 cm2. If up-flow is used, atten-
uation results are likely to be lower by 10 - 25%.
C. Visual Presentation of Statistical Results
For several years, we have presented our clustered data in graphical
form. In addition to this black-and-white form, we have used a colored
display for talks and for easier inspection. We believe this method of
presenting the data is useful and have now made it available in a report.
The report is available from NTIS or LASL as LASL document LA-7943-MS,
entitled, "SORTNGO: A Program to Sort Matrices and Produce Graphics."
This document presents a discussion of the method and lists the computer
programs needed to carry out the operation.
D. Pollutant Attenuation and Movement Through Soils
As an adjunct to our studies on the ability of solid materials to
attenuate trace elements (see the section on "Moderating the Disposal
Site with Abaters"), we included efforts to evaluate the movement of
trace elements through the solids. Although extensive, these efforts are
still preliminary and only designed to pave the way for more sophisti-
cated experiments. The methods used were 1) batch experiments in which
more and more dilute solutions of an original leachate were equili-
brated with different aliquots of soil (see Appendix E), 2) batch experi-
ments in which leachate previously equilibrated with a soil was repeat-
edly equilibrated with new aliquots of soil (see Appendix D), and 3)
column experiments in which leachate was passed through a soil and the
effluent monitored (see Appendix M). Comments about the results of each
will be followed by a brief, generalized discussion.
Approximating trace element transport through soils by equilibrating
increasingly more dilute original leachate with aliquots of soil has
several advantages, of which the ease of conducting the experiment is
probably foremost. Large quantities of leachate can be used at each
step. Atmospheric control is also possible, allowing oxygen-sensitive
species, such as Fe++, to be determined.* A major disadvantage of this
method is its failure to account for previous attenuation, or lack of it.
This is particularly critical when significant pH changes occur. The
behavior of manganese (described below) is a good example. In spite of
this problem, this method does give a quick assessment of how some ele-
ments are attenuated as leachate passes from one unit of soil to the
next.
^Columns do this well too, but batch methods which require repeated use
of the same leachate give too many chances for error, especially when
the pH changes to a range in which oxidation is very rapid (see the
successive equilibration method).
78
-------
Results for Al, Fe++ and Mn under this dilution-equilibrium method
represent the major behavioral types and are given in Fig. 33. (Results
and plots of these, plus As, F, Fe+++, and Ni, are given in Appendix E
for 10 solids.) The solids used in Fig. 33 are noted in the legends:
QLS is a quarry limestone; S-ll is a calcareous subsoil just above
Kentucky coal seam No. 11; LOESS is a weathered, Illinois subsoil (OKAW);
and TILL is an unweathered, calcareous, glacial till from Illinois. The
C/CQ values represent the amount of attenuation at each equilibration.
Attenuating abilities of the soils were discussed in the section on
"Moderating the Disposal Site with Abaters."
As the leachates became more dilute, the pH of the effluent rose.
The final pH approximated that for the water-solid equilibrium (4.8 for
LOESS and 7.5 - 7.9 for the others). This rise in pH was generally
accompanied by a decrease in trace element content in the effluent (as
illustrated by LOESS versus others for Al in Fig. 33 at a "solids-to-
leachate" ratio of 0.5). Fe++ showed less pH-dependence (compare LOESS
and TILL), but showed good attenuation as the leachate contacted more and
more solid. Some ion exchange was likely, although some oxidation of
Fe++ to Fe+++ may have occurred in spite of our efforts to prevent it.
This behavior was typical of most of the ions (As, F, Fe+++, and Ni).
Manganese behaved like Fe++ in the presence of the limestone tested (also
in the presence of EC and ESP power plant ashes), but its behavior in the
soils was dramatically different. In these, Mn was released in 5- to
30-fold greater quantities than were present in the influent. We think
that the soils contained Mn which was somehow released by components in
the leachate, since pure water released little Mn from the soils. If
this continued release of Mn is due to acid neutralization by manganese-
containing minerals, then batch leaching experiments in which previously
equilibrated effluent is used could be conducted for the next equilibra-
tion to clarify the situation.
Conducting attenuation experiments by equilibrating previously
attenuated leachate with new solid has the main advantage of incorpora-
ting differential attenuation. Thus pH-sensitive ions such as A1+++ and
Fe+++ will generally be attenuated quickly and not enter too strongly
into later equilibrations. Major disadvantages to this method are
rapidly diminishing quantities of leachate, which limit analyses, and
multiple handlings of the same leachate, which increase the chances for
oxidation.
We have conducted a series of such attenuation experiments with 11
solid materials, using a 5100-ppm iron (mainly Fe++) leachate. Most of
these solids were weathered and unweathered soils that covered a range of
types (alluvial, glacial till, loess, and organic, plus some standard
clays and limestone). A list of the materials, some of their properties,
and the trace element levels for Al, As, Ca, Cd, Co, Cr, Cu, F, Fe, Mn,
Ni, and Zn in the effluents are given in Appendix D. In addition to
treatment with leachate, each solid was also leached with water and 0.14M
sulfuric acid (equivalent to the total acidity of the leachate) to pro-
vide information about the ability of the solids to contribute trace
elements and control pH. An evaluation of the ability of the sulfuric
acid solution to reflect the pH effects on the solids is given by Fig.
34. Sulfuric acid tends to overstate this pH effect at low pH values.
This would be due to the incomplete oxidation of the Fe++ in the coal-
waste leachate, which accounts for much of the acidity in the coal-waste
leachate.
-------
LEGEND
3 = QLS
3 =5-11
<. = LOESS
• = TILL
10 20 3.0 40 50 60 70 80
Solid to Learhcli" r a• io
\
LEGEND
J = OLS
> = LOESS
• » TILL
Experimental Dilution Effect
Detection I imit
0.0 1.0 20 30 40 5.0 60 70 80
Solid to Leachate Ratio
\
LEGEND
J =-- OLS
i- LOESS
> = TILL
Detection Limit
00 1.0 2.0 3.0 4.0 50 ^6.0 70 80
Solid to Leachate Ratio
LEGEND
= QLS
• S-11
=LOESS
= TILL
0.0 10 2-0 3.0 40 50 60 70 80
Solid to Leachate Ratio
0.0 1.0 2.0 3.0 4,0 5.0 6.0 7.0 8.0
Solid to Leachate Ratio
00 10 20 30 40 50 60 70 80
Solid to Leachate Ratio
T-tace &temnn£ attenuation by -L
uxute.
o = S-11
- =LOESS
» « TILL
De t ec ti on Limit
0.0 1.0 2.0 3.0 4,0 50 60 7.0 80
Solid to Leochate Ratio
33.
amounts o& a i>o
-------
8
PH 0.14m H2S04
Kg. 34.
The pH Oj$ e^£uen£ ^om coo£ w/Oxi^i
function ofi the. borne. &oLidf> -en 2:7 mtxtutiu w-Ltk 0.14M
(2:7
a.
Major trace element behaviors are represented by the Fe and Mn
results shown in Fig. 35. Most metals behaved like Fe and dropped
rapidly as the leachate came in contact with more and more solid
material. The effect appears to be mainly pH-related. If the pH was low
(around 3), little attenuation was observed, even for Al. In the pres-
ence of non-soil solids, Mn also behaved this way, as illustrated by its
attenuation by CaC03 in Fig. 35. When the coal-waste leachate interacted
with the soils, copious quantities of Mn were released. In some cases,
400 - 500-ppm levels of Mn were found in the effluents! As the leachate
passed through much larger amounts of soil, however, Mn did become atten-
uated. Calcium showed little tendency to be attenuated and normally
showed a slightly higher level in the effluent than was present in the
influent.
The behavior of Mn in the soils for the two types of batch attenua-
tion experiments was similar and surprising. Obviously, Mn was being
released by the soil, but how? Our first thought was that it was being
released from a carbonate during the neutralization of the influent acid.
Leaching the soils with sulfuric acid proved this not to be a major
factor (see Fig. 35). Then we noticed that the level of Mn in the efflu-
ent was related to the influent level of Fe++ (see Fig. 36). It seemed
likely that Fe++ was ion exchanging with Mn++, but observing that most of
the really high Mn values occurred with weathered soils suggested that Mn
release from amorphous Mn02 might be important. Electrochemically this
is possible.
81
-------
D ALLUVIAL WEATHERED SOIL
O LOESS UNWEATHERED SOIL
X LOESS WEATHERED SOIL
AMONTMORILLONITE CLAY
OCQ co3
0.0 1.0 2.0 H2S04 H20
SOIL'LEACHATE RATIO (g/ml)
I03
I02
Si
CJl
E
10
1.0
O.I
00
D ALLUVIAL WEATHERED SOIL:
O LOESS UNWEATHERED SQL !
X LOESS WEATHERED SOIL
A MONTMORILLONITE CLAY
0 CoC03
xo
A
1.0
2.0X>YT
H2S04 H20
SOIL: LEACHATE RATIO (g/mO
„ 10
1.0
O.I
0.01
Q ALLUVIAL WEATHERED SOIL
o LOESS UNWEATHERED SOIL
x LOESS WEATHERED SOIL
A MONTMORILLONITE CLAY
0 Co Co,
!f-\A—A—A
V—
MONTMORILLON
Co CO,
OnoxA
0.0 1.0 2.0 H2S04 H20
SOIL^ LEACHATE RATIO (g/ml)
T>z.a.c.e. ntwe.nt and pH
with t>ofibnnti> .
Pig. 35.
batch.
82
-------
500
400
—x WEATHERED GLACIAL TILL —•UNWEATHERED LOESS
- — WEATHERED LOESS (OKAW) —-WEATHERED -
"° WEAKLY WEATHERED LOESS ALLUVIAL
-^UNWEATHERED ILL TILL —• UNWEATHERED KY
-AUNWEATHERED GLACIAL TILL SEAM II
-*MONTMORILLONITE ^\~* UNWEATHERED KY
I--VWEAKLY ^ \ SEAM 12
WEATHERED
ORGAN 1C
0
0 1000 2000 3000
H
4000
5000 6000
Fe
INFLUENT
(ppm)
LnuzLb -01 e.^£ae.n£6
cu> a. function ofi
-------
The experiments reported here are first efforts; they point out some
parameters which can affect the execution of the experiment, and they
give some information about the behavior of several trace elements.
Columns were packed with fine-grained soils (an unweathered, calcareous
till and a weathered loess soil). Concentrated, coal-waste leachate
(4000 ppm Fe++) was passed slowly down through them. Trace element
levels and pH values were monitored and are tabulated in Appendix M.
The results for the unweathered, calcareous till (Fig. 37) corres-
pond well with those observed in the batch experiments for similar mate-
rials. As long as the pH was high, Al and Fe+++ were well attenuated, so
well, in fact, that the column became plugged at a leachate:soil ratio of
6:1. Bivalent ions were attenuated but quickly broke through under the
high influx. Ca passed through and Mn was released in small constant
quantities by the soil.
The results for the weathered loess soil (Fig. 38) also agreed with
the batch results but added several additional features. The pH was
lower at all effluent volumes since there was less neutralizing agent
present than in the till above. Initially, Al and Fe+++ precipitated in
the soil. As the pH dropped, the deposited Al began to dissolve and move
further through the soil, as did the soluble aluminum originally present
in the soil. Added together these dissolved Al species formed a front
(or wave) which slowly moved through the soil. Even the less pH-sensi-
tive Fe++ and Ni++ ions showed this wave phenomenon. Column overload
probably identified a phenomenon that might not easily surface otherwise.
Ca was generally independent of the conditions. Mn, however, was
released in large concentrations early and eventually decreased to levels
approximating those of the influent. Some of the Fe++ attenuation may be
related to this. (Recall the discussion about Mn release in the batch
experiments above.)
The most apparent problem with this set of experiments is column
overload. Because of this, the high soil-to-leachate ratio phenomena are
obscured by the time that sufficient effluent has been collected. One
remedy is the placement of a small quantity of concentrated leachate on
the soil at the inlet and the use of distilled water to transport it as
is common in chromatographic columns. Another is the use of a continuous
stream of more dilute leachate. The latter is probably closer to real
life. Using lower influx concentrations should permit ready evaluations
of the amounts of soils needed to reduce the less pH-sensitive trace
elements to acceptable levels.
Trace element transport through soils is variable and affected by
many parameters. An experiment designed to evaluate these might be
simple, but is more likely to include several perturbations. It is clear
that complex interactions are occurring and that overloading the soil
will quickly eliminate information about the ultimate ability of a soil
to reduce pollutants to acceptable levels. Overloading may accentuate
phenomena such as wave fronts, however. Simulating systems too simply
may ignore or not identify some phenomena, such as that found for Mn in
the experiments above. Batch equilibrium experiments do give results
which can be related to column experiments. Redox conditions are impor-
tant and eluent streams should be protected. In short, transport
behavior can be measured, and soils do attenuate trace elements. Knowing
84
-------
o
o
\
o i
0.5
pH OF INFLUENT LEACHATE 2.0
pH OF SOIL/WATER MIXTURE 8.2
(PLUGGED COLUMNM
O
O
\
O
0
Al,
Fe'
Fe
TOTAL A
Q g p o
100 200 300
EFFLUENT VOLUME (ml)
F-tg. 37.
T/uice eleinejtt and pH IwzJU* o£ e.Ulu.e.nt& Atom a zolumn pac.ked wljtk an
85
-------
pH OF SOIL/WATER MIXTURE 5.6
pH OF INFLUENT LEACHATE 2.0
o
o
\
o
0.4
0
100 200 300
EFFLUENT VOLUME (ml)
e/emeitt and pH £eve&i
. 3S.
a. column packed wJitk a
86
-------
how well and how fast could give a waste disposer valuable, maybe price-
less, flexibility and allow him to operate when technical or economic
restrictions were otherwise prohibitive.
E. Spark Source Mass Spectrometry (SSMS) Analyses
SSMS is an attractive technique for semiquantitative analysis of
coal and coal-related solid and liquid samples for all elements [J. W.
Hamersma, S. L. Reynolds, and R. F. Maldalona, "IERL-RTP Procedures
Manual: Level I Environmental Assessment," EPA-600/2-78-160a (June
1976)]. In conjunction with the MEG/MATE system of analysis [J. G.
Cleland and G. L. Kingston, "Multimedia Environmental Goals for Environ-
mental Assessment," EPA-600/7-77-136a,b (November 1977)], an effective
diagnostic is to locate sources of possible trace element contamination
(E. M. Wewerka, J. M. Williams and P. Wagner, "The Use of Multimedia
Environmental Goals to Evaluate Potentially Hazardous Trace Elements in
the Drainage from High-Sulfur Coal Preparataion Wastes," in preparation).
The technique can be made quantitative for specific elements by incor-
porating isotope-dilution techniques at the expense of increased analysis
time. Without isotope-dilution, the reliability is about a factor of 3
for most trace elements. In certain cases, the reliability is not even
this good [E. D. Estis, F. Smith, and D. E. Wagoner, "Level I Environ-
mental Assessmental Performance Evaluation," EPA-600/7-79-032 (1979)].
We initiated the use of spark source mass spectrometry in 1979. A
chemical treatment has been developed to destroy organic material that
otherwise interferes over the whole atomic mass region and above 200 amu.
A major effort is underway to establish sensitivity factors for about 70
elements at selected operating conditions to attain improved reliability.
The more quantitative measurement technique of line-density photometry
coupled with emulsion calibration is being used, rather than the "disap-
pearing line" technique. Appendix N presents early results and the
technique used for an analysis of NBS SRM 1632 coal. This and other
reference materials, interlaboratory exchange samples, and routine sam-
ples will be analyzed in the future, using more reliable sensitivity
factors.
F. "Standard" Coal Waste Leachate
Over the years we have leached a number of high-sulfur coal waste
materials. When confronted with evaluating control technologies for
cleaning up these leachates, we leached large quantities of waste mate-
rials to give us samples that represented real world models. This pro-
cess was slow, as large quantities had to be shaken and filtered. The
filters readily clogged, which made a tedious mess. To remedy this
problem, we have formulated an artificial leachate for future use where
high-sulfur coal-waste leachates are needed.
The recipe representing a slightly weathered leachate in which the
ferrous:ferric ratio is 2:1 is given in Table XXX. The Fe2(S04)3 is
dissolved in 6 £ of Milli-Q water, the Na2S04 is dissolved in 2 £ of
water, and each is added to a 12-gal. carboy. The last 12 compounds
(from CdS04 to H2S04) are dissolved in 500 m£ of water. The NaF and
Na3P04 are dissolved in water together and acidified with the acid solu-
tion above. The MgS04 is dissolved in several liters of water and added
87
-------
TABLE XXX
RECIPE FOR SYNTHETIC, HIGH-SULFUR COAL WASTE LEACHATE
Formula
FeS04-7H20
Fe2(S04),-xH20|72%|
CaCO,
A12(S04)3-18H20
MgS04
Na3PO4-12H20
NaF
Na2S04
Cr2(S04),-15H20
CdS04
CoCl2
CuS04
MnS04-4H20
MoO,
NiS04
H3As04
K2S04
Na2B40,-10H20
ZnS04
PbS04
H2S04|96%|
S0=4
Cl-
Namea
Ferrous Sulfate
Ferric Sulfate
Calcium Carbonate
Aluminum Sulfate
Magnesium Sulfate
Sodium Phosphate Tribasic
Sodium Fluoride
Sodium Sulfate
Chromic Sulfate
Cadmium Sulfate
Cobaltous Chloride
Cupric Sulfate
Manganous Sulfate
Molybdenum Oxide
Nickelous Sulfate
Arsenic Acid
Potassium Sulfate
Sodium Borate
Zinc Sulfate
Lead Sulfate
cone. Sulfuric Acid
Sodium Ion
Sulfate Ion
Chloride Ion
Weight in 40l(g)
876
438
49.9
267
15.9
17.2
11.6
34.0
0.102
0.0036
1.62
0.0148
2.44
0.0180
3.04
0.182
2.50
0.812
4.75
0.0029
68.6
Trace Metal
ppm mole/^b
4400
2200
500
540
80
39
131
0.40
0.049
12
0.15
22
0.30
29
3.0
28
2.3
27
0.05
520
18 800
12
7.88 X 10-2
3.94 X 10~2
1.25 X 10-'
2.00 X 10-
3.30 X 10-'
1.25 X 10-"
6.90 X 10-3
(5.98 X 10-')
7.70 X 10-
4.32 X 10-'
1.70 X 10-
2.32 X 10-
4.04 X 10-
3.12 X 10-
4.91 X 10-
1.98 X 10-"
7.17 X 10-
2.13 X 10-
4.13 X 10-
2.39 X 10-'
(1.68 X 10-2)
2.27 X 1()-2
1.96 X K)-1
3.40 X 10-
•Trace metal underlined; Milli-Q water used.
bValue in parentheses is molar concentration of
compound used.
88
-------
to this acid mixture, which is then added to the carboy. (Heating and
stirring may be required before adding it to the carboy, if a precipitate
forms.) The Cr2(S04)3 is dissolved in 1 £ of boiling water and added to
the carboy. The FeS04 is dissolved under argon or nitrogen in 6 £ of
water. The carboy is purged with inert gas, and the FeS04 solution is
added. The A12(S04)3 is dissolved in 2 £ of water and added to the
carboy. Finally, the CaC03 is added to the carboy as a water slurry, and
the remainder of the water (to make up 40 £) is added. The carboy is
swirled to mix, and the liquid is stored under inert gas to preserve it.
To simulate a leachate which has had little weathering, the amount
of ferric ions is drastically reduced. To keep the acidity constant, the
H2S04 content is increased. Using the following amounts in place of
those in Table XXX will produce a leachate in which the ferrous ions
account for 95 percent of the iron ions. More water is used to dissolve
the ferrous sulfate. Again the solution must be protected from air.
Metal
Formula Compound g/40^ Level (ppm)
FeS04 Ferrous sulfate 1248 6270
Fe2(S04)3-xH20[72%] Ferric sulfate 65.7 330
H2S04 [96%] cone. Sulfuric acid 137.3
SO4 Sulfate ions 18500
89
-------
PERSONNEL
A large number of LASL personnel besides the authors participated in
the programmatic effort during the year. Their work and contributions
are gratefully acknowledged.
Administrative Advisors: R. D. Baker, W. J. Maraman, R. J. Bard,
R. C. Feber, P. Wagner, and E. M. Wewerka
Analytical Chemistry Advisors: G. R. Waterbury and M. E. Bunker
Atomic Absorption Spectrophotometry and Wet Chemistry: E. J. Cokal,
L. E. Thorn, and E. S. Gladney
Level I Bioassay: L. M. Holland, B. Barnhart, V. H. Kollman,
A. Stroud, S. Wang, and J. S. Wilson
Neutron Activation Analyses: W. K. Hensley and M. E. Bunker
Optical and SEM Microscopy: R. D. Reiswig and L. S. Levinson
Spectrochemical Analysis: 0. R. Simi, J. V. Pena, and D. W. Steinhaus
Spark Source Mass Spectroscopy: J. E. Rein, R. M. Abernathy, S. F.
Marsh, C. F. Hammond, and J. E. Alarid
Statistical Evaluation: R. J. Beckman
X-ray Diffraction: R. B. Roof and J. A. O'Rourke
90
-------
BIBLIOGRAPHY
1. J. G. Cleland and G. L. Kingsbury, "Multimedia Environmental Goals
for Environmental Assessment," EPA-600/7-77-136a,b (November 1977).
2. K. M. Duke, M. E. Davis, and A. J. Dennis, "IERL-RTP Procedures
Manual: Level I Environmental Assessment, Biological Test for
Pilot Plants" EPA-600/7-77-043 (April 1977).
3. E. D. Estis, F. Smith, and D. E. Wagoner, "Level I Environmental
Assessment Performance Evaluation," EPA-600/7-79-032 (1979).
4. J. W. Hamersma, S. L. Reynolds, and R. F. Maldalona, "IERL-RTP
Procedures Manual: Level I Environmental Assessment," EPA-600/ 2-
78-160a (June 1976).
5. E. F. Thode, J. M. Williams, E. M. Wewerka, and P. Wagner, "Costs
of Coal and Electric Power Production - The Impact of Environmental
Control Technologies for Coal Cleaning Plants," Los Alamos Scienti-
fic Laboratory report LA-8039-MS (October 1979).
6. E. M. Wewerka and J. M. Williams, "Trace Element Characterization
of Coal Wastes -- First Annual Report," July 1, 1975-June 30, 1976,
Los Alamos Scientific Laboratory report LA-6835-PR (also EPA-600/
7-78-028) (March 1978).
7- E. M. Wewerka, J. M. Williams, N. E. Vanderborgh, A. W. Harmon, P.
Wagner, P. L. Wanek, and J. D. Olsen, "Trace Element Characteriza-
tion of Coal Wastes -- Second Annual Report," October 1, 1976-
September 30, 1977, Los Alamos Scientific Laboratory report LA-
7360-PR (also EPA-600/7-78-028a) (July 1978).
8. E. M. Wewerka, J. M. Williams, L. E. Wangen, J. P. Bertino, P. L.
Wanek, J. D. Olsen, E. F. Thode, and P. Wagner, "Trace Element
Characterization of Coal Wastes -- Third Annual Progress Report,"
October 1, 1977 to September 30, 1978, Los Alamos Scientific Labora-
tory report LA-7831-PR (also EPA-600/7-79-144) (June 1979).
9. E. M. Wewerka, J. M. Williams, and P- Wagner, "The Use of Multimedia
Environmental Goals to Evaluate Potentially Hazardous Trace Elements
in the Drainage from High-Sulfur Coal Preparation Wastes," in
preparation.
10. J. M. Williams, "SORTNGO: A Program to Sort Matrices and Produce
Graphics," Los Alamos Scientific Laboratory report LA-7943-MS
(November 1979).
11. R. C. Wilmoth, "Combination Limestone-Lime Neutralization of Ferrous
Iron Acid Mine Drainage," EPA-600/2-78-002 (January 1978).
91
-------
APPENDIX A
EFFECTS OF TEMPERATURE AND ADDITIVES ON SULFUR RETENTION
AND AQUEOUS TRACE ELEMENT RELEASES FROM CALCINED COAL WASTE
I. CALCINING PROCEDURE*
Prepared mixtures were placed in a porcelain dish and heated (nor-
mally for 2 h) in a muffle furnace preheated to the desired temperature.
The calcined products usually sintered above 800°C, but were friable.
Samples were ground for leaching and analyses. Mixtures calcined and
their sulfur-retention values are given in Table A-I.
II. CARBONATE TREATMENT
A. Dry Mixing
Ground (-20 mesh or -10+32 mesh), Plant C, average coal waste was
tumbled together for 1 hour with powdered (-115 mesh) AR grade calcium
carbonate or pulverized (-10+32 mesh) Jemez limestone. If additives,
such as powdered (-115 mesh) ferric oxide and granular (-35 mesh) sodium
chloride, were used, they were blended at the same time.
B. Slurry Mixing
Similar to above except that a creamy paste of calcium carbonate was
slurried with the waste in a porcelain dish. The paste was dried over-
night on a steam bath. Without being disturbed, the mass was calcined.
III. AQUEOUS LEACHING
Calcined waste (20 - 25 g and free flowing) was leached for 48 h
with distilled water (1 waste:4 water) in a beaker. In several cases,
dilute sulfuric acid solutions were used as leaching agents. Agitation
was provided by a magnetic stirring bar and motor. The leachates were
separated by vacuum filtration through Whatman #2 paper. Filtration
through #42 paper produced the leachate that was analyzed for trace
elements. Trace element levels in the leachates are reported in Table
A-II.
"Another procedure in which 3/8 in or 3/8 x 0 waste was burned in flowing
air for 6 h in a quartz tube heated to 800-850°C is reported on p. 8 of
our third annual report (LA-7831-PR). Levels of elements retained and
trace elements leached from columns of burned waste are reported there
also.
92
-------
TABLE A-I
SULFUR RETENTION UPON CALCINING TREATED AND UNTREATED COAL
WASTE
Temp Time Size Wt CaCO3 Ca/S Sulfur Retained
CALNo. (°C) (h) (mesh) (g) Source' Additive" (mole/mole) in Waste (%)
29
13,14
19.20
30
31
24
59
25
36
26
27
46
58
32
33
51
60
55
56
34
35
45
47
52
61
53
38
54
66
67
68
69
37
48
62
39
49
63
40
41
50
1100 2 -20 25 AR
1000 2 -20 50
25 AR
30
30
900 2 -20 25 AR
30 " 8%NaCl
4 " 25
30
6 " 25
12 " 25
2 " 30
2 " 30
800 2 -20 30 AR
30
30 " 4% Fe203
30 " 4%NaCl
-10+32 30
30 " (Slurry)
-20 30
30
30
30
30 " 4%Fea(),
30 " 4%NaCl
-10+32 30 Jemez
-20 30 AR
-10+32 30 .lemez
30
30
30
30
600 2 -20 30 AR
30 " 4°oFe203
30 " 4°0 Nad
30
30 " 4°o Fe2()3
30 " 4% Nad
30
30
30
0.5
0
0.5
1.0
1.5
0,5
11
11
"
"
1.0
1.5
0.25
0.5
11
11
"
0.75
1.0
"
"
1.5
"
2.0
"
2,5
0.5
11
1.0
1.25
1.5
<0.1
2.2
22
32
33
32
19
44
29
44
38
50
64
32
53
49
32
42
57
71
79
64
67
68
50
43
74
48
52
54
53
60
44
37
45
55
52
58
53
68
69
"AR = AR grade CaC(\ powder:
.Jerne7. = _10+;i2 mesh-lemez. NM limestone.
"Percentage based on CaCO, level.
93
-------
TABLE A-II
TRACE ELEMENT CONCENTRATIONS IN LEACHATES FROM CALCINED COAL
WASTES'1
Temp(°C) Time(h) Particle Size" Ca/Sc Leachate"
Control
Control
600
800
900
1000
-20
-10+32
-20
-20
-20
-20
-10+32
-20
0
0
0
1.0
0.5
0
0
0
0
0
Water
Water
Water
Water
Water
Water
0.02M H,S04
0.04M H2SO,
pH
2.9
3.2
6.6
6.9
7.0
7.0
12.4
10.5
8.0
7.9
8.3
4.0
2.9
TDS(%)
0.63
0.51
0.38
0.33
0.36
0.35
0.34
1.6
0.17
0.17
0.11
0.4
0.5
Al
100
48
<0.8
0.38
0.45
0.4
0.6
0.3
0.4
<0.4
<0.3
5
88
Ca
550
360
610
560
580
570
900
820
400
400
240
620
580
Cd
0.06
<0.0003
0.005
0.0008
0.0008
0.0008
<0.0002
0.0006
0.0002
0.0003
0.023
<0.008
<0.008
Co
2.8
1.3
0.1
0.25
0.23
0.24
0.03
0.06
<0.01
<0.01
<0.03
0.04
0.05
Cr
0.068
0.060
<0.0003
0.025
0.025
0.019
0.016
<0.013
0.001
0.003
<0.03
<0.03
<0.04
Cu
0.10
0.20
0.18
0.14
0.16
0.15
0.21
0.30
0.01
0.01
0.14
0.13
0.20
F
14
0.5
1
1
5.5
40
Fe
600
520
<0.05
0.5
0.13
0.32
0.05
0.09
<0.03
<0.03
0.05
13
25
K
14
7
9.3
9.5
15
25
Mn
5.8
5.0
4.2
3.2
2.9
3.0
0.03
0.06
0.03
0.03
<0.03
0.90
1.2
Na
76
73
12
12
15
30
Ni
4.8
4.2
0.08
0.3
0.25
0.28
0.13
0.13
0.01
0.01
<0.03
0.15
0.15
Zn
2.8
1.8
0.35
0.43
0.48
0.46
0.11
0.17
0.05
0.08
0.15
4.0
3.8
"Element values in ppm.
bValues are meshes.
cCalcium-to-sulfur molar ratio.
d48h leach, 4 ml leachate per gram of waste.
-------
APPENDIX B
MORTARS FROM FINE COAL PREPARATION WASTE
I. CEMENT CYLINDER PRODUCTION
Formulas were dry mixed, treated with water until workable, and
poured into 3.2-cm Silastic molds. Setup occurred overnight to give a
damp, scratchable cylinder. Curing in Los Alamos air (normally 10%
humidity) continued after the cylinders were removed from the mold until
they were leached. Controls used: -10 mesh river sand. Test samples
used: -20 mesh, Plant C, high-sulfur, coal waste. Cylinders were nor-
mally 1 in high.
II. CYLINDRICAL SPECIMENS
Sample No.
CM-4
CM-fi
CM -
-------
0 = CONTROL
o =1=3 MIX
=h6MIX
10 15 20
TIME (DAYS)
FxLg. B-7.
The pH 0^ le.acha£eA -in contact w-tt.k moittvi
coal, wtutz. (le.ac.hate. change.d
eac^i pH dtiop.
96
-------
TABLE B-I
TRACE ELEMENT RELEASES FROM CEMENT/COAL WASTE CYLINDERS"
Parameter CM-7 CM-13
Waste Mass (cc) 60 18
Leachate Vol (ml) 250 250
Length of Leach (days) 128.b 120.c
pH (initial) 12.2 11.3
pH (final) 11.2 9.0
Al
As
Ca
Cd
Co
Cr
Cu
Fe
Mn
Ni
Zn
"Elemental concentrations in ppm, except Cd, which
is inppb.
"Four 250-m& leaches in the first 55 days.
Trace element results are for the fifth leachate, which
was in contact with cylinder for 73 days.
Tour 250-mS, leaches in the first 44 days.
Trace element results are for the fifth leachate.
0.10
5
250
<0.05
0.02
0.008
0.10
0.05
0.05
0.04
0.05
0.13
3
1
<0.05
0.01
<0.004
0.08
0.03
<0.008
0.01
0.04
97
-------
APPENDIX C
LIME/LIMESTONE TREATMENT OF COAL WASTE
The first experiments in this series were reported in the third
annual report. They included the dry-mixing series designated GL-12 to
GL-17 (Appendix C, LA-7831-PR) and the slurry-mixing series marked
CTWT-11-1 to CTWT-11-5 (Appendix D, LA-7831-PR). The experiments here,
CTWT-11-6 to CTWT-11-9, are extensions of the CTWT, slurry-mixing series.
Salient items are presented in Table C-I for the entire series.
I. MIXING PROCEDURE
Average coal preparation waste (-3/8 in) from Plant B was added to a
2-S, beaker containing a slurry of neutralizing agent (see CTWT-11-6 to
CTWT-11-9 in Table C-I) with hand stirring for 1/2 h. In several cases
the slurry was allowed to soak. In one, carbon dioxide was bubbled in
until the mixture was neutral. Drying was accomplished with Los Alamos'
10% humidity with a forced air oven at 60°C. The friable mass was passed
through a -3/8-in jaw crusher to return it to the original waste size.
II. LEACHING
The treated waste was packed in a 4.6-cm I.D. by 40-cm-long glass
column containing a glass wool plug at the bottom. Distilled water was
passed upward through the column at 0.5m£/min. Leaching was halted after
approximately 8 i. The columns were drained and aired for 20 days.
Leaching was then resumed. Trace element data are reported in Tables
C-II to C-V.
98
-------
TABLE C-I
SUMMARY OF COAL WASTE-ALKALINE AGENT SLURRY EXPERIMENTS3
NEUTRALIZING AGENT
ADDITIVE
None
Limestone
Limestone
Limestone
Limestone
None
Ca(OH)2
Ca(OH)2
Ca(OH)2
Ca(OH)s
Ca(OH)2
CaCOs
Ca(OH)2 +
CaCO,
Limestone
SIZE
-
-3/8 in.
-3/8 in.
-3/8 in.
-20 mesh
-
-100 mesh
-100 mesh
-100 mesh
-100 mesh
- 100 mesh
-100 mesh
-100 mesh
-100 mesh
-20 mesh
(%)"
0.0
16.9
17.0
17.6
16.9
0.0
0.5
1.5
3.0
10.0
5.0
6.7
1.5
4.0
6.0
TYPE OF
MIXING
-
Dry
Dry
Dry
Dry
-
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
Slurry
EFFLUENT pH
COMMENTS
Control
Evenly mixed
Placed at water inlet
Placed at water outlet
Placed at water outlet
Control; wetted; 24h @ 60°C
l/2hmix;24h@60°C
l/2h mix; 24h ® 60°C
l/2hmix;24h@60°C
l/2hmix;24h@60°C
l/2h mix + CO2 for 3 days;
24h @ 60°C
l/2h mix; soak for 3 days;
24h@60°C
l/2h mix of lime; then
l/2h mix CaCO,;
24h®60°C
24hsoak;24h@60°C
INITIAL
1.3
2.5
1.5
2.4
3.5
1.8
2.1
2.6
6.6
13.0
7.4
6.9
6.2
6.4
AFTER AIRING
1.7
3.2
3.6
-
-
2.2
2.2
2.3
2.8
10.7
5.8
7.3
3.8
4.6
DAYS
AIRING"
28"
28"
28"
-
-
14"
14"
14"
14"
14d
20"
20"
20«
20"
EFFLUENT Fe (ppm)
INITIAL
15000
8100
10400
10700
7800
13200
10750
2820
120
<0.1
5
15
130
60
AFTER AIRING
7600
940
1400
-
—
700
1020
1980
700
<0.1
23
0.7
210
100
SAMPLE
NO.
GL-12
GL-14
GL-15
GL-16
GL-17
CTWT-11-1
CTWT-11-2
CTWT-11-3
'CTWT-11-4
CTWT-11-5
CTWT-11-6
CTWT-11-7
CTWT-11-8
CTWT-11-9
" 1500 grams of combined material leached in GL series and
CTWT-11-1 to 11-5; 500 grams of material used in
CTWT-11-6 to 11-9; -3/8" waste used in all cases.
b Based on waste.
c Leaching stopped after x liters of leachate;
column drained and air circulated through column.
" Air started after ~4 liters; first 3 days with dry air,
then remainder with H2O saturated air.
" Air started after ~8 liters; first week with dry air,
then remainder with H20 saturated air.
-------
TABLE C-II
TRACE ELEMENT LEVELS IN LEACHATES FROM COAL WASTE SLURRIED
WITH LIME WHICH WAS THEN NEUTRALIZED WITH CARBON DIOXIDEa
Sample No. 1 2 4 11 17 ,'51b 33 34
Vol (I)
pH
TDS (%)
F
Na
Al
K
Ca
Cr (nx/l)
Mn
Fe
Co
Ni
Cu
/n
Cd (wit)
0.100
7.4
0.84
0.3
7
<0,5
7
900
<0,5
0.7
5
0.13
0.3
0.1
0.07
2
0.201
7.2
0.63
0.4
6
<0,5
8
870
1
0,5
2
0.12
0.2
0.1
0.07
1
0.697
7.9
0,34
0.3
2,5
<0,5
4
630
<0,5
0.2
0.4
0.06
0.2
<0.1
0.03
0.4
2.309
7.7
0.27
0.3
1
<0,5
2
540
<0.5
0.1
<0.3
0.05
0.1
<0.1
0.01
0.2
3,326
7.7
0.22
0.4
1
<0,5
1
480
<0,5
0.07
<0,3
<0.05
<0.07
<0.1
<().()!
0,3
8.826
5.8
0.29
0,3
5
<0,5
6
560
<0,5
1,5
23
0.4
0.7
<0.1
0,3
2
9.002
6.4
0.27
0.4
2
<0,5
4
470
<0,5
1.4
17
0,3
0,5
<0.1
0.2
1
9.107
6.9
0.21
0.2
2
<0.5
4
400
<0.5
0.8
5
0.25
0.4
<0.1
0.1
0.6
"Values in pg/mi unless otherwise noted.
"After column "air-regenerated"
100
-------
TABLE C-III
TRACE ELEMENT LEVELS IN LEACHATES FROM A COAL WASTE SLURRIED
WITH FINE-PARTICULATE CALCIUM CARBONATE11
12 18 31b 34
VJO.Alli/**-' A 1 V.
Vol (Jfc)
pH
TDS (%)
F
Na
Al
i<
I\
Ca
Cr (tig/ 1)
Mn
FP
1 C
Co
Ni
Cu
Zn
Cd (Mg/.«)
0.101
6.9
0.38
0.2
14
<0.5
10
650
<0.5
2
15
0.3
0.8
<0.1
0.06
3
0.155
7.5
0.39
0.2
12
<0.5
8
620
<0.5
2
12
0.3
0.8
<0.1
0.06
2
0.641
7.1
0.37
0.05
5
<0.5
5
610
<0.5
0.4
<0.3
0.1
0.3
<0.1
<0.01
<0.05
2.298
7.5
0.23
0.15
1.5
<0.5
2
540
<0.5
0.09
<0.3
0.05
0.07
<0.1
0.03
0.1
4.622
7.7
0.18
0.19
1
<0.5
1
370
<0.5
<0.05
<0.3
<0.05
<0.07
/A 1
-------
TABLE C-IV
TRACE ELEMENT LEVELS IN LEACHATES FROM A COAL WASTE SLURRIED
WITH LIME FOLLOWED BY CALCIUM CARBONATE3
Sample No. 1 2 4 11 17 25" 26 27 28
Vol(£)
pH
TDS (%)
F
Na
Al
K
Ca
Cr (fig/I)
Mn
Fe
Co
Ni
Cu
Zn
Cd Ug/*)
0.088
6.2
0.45
0.14
11
<0.5
7
600
<0.5
6
130
1.4
2.4
<0.1
0.4
6
0.174
6.3
0.23
0.14
10
<0.5
6
590
<0.5
5
155
1.2
2.0
<0.1
0.4
5
0.689
6.4
0.37
0.16
4
<0.5
5
650
<0.5
2
64
0.2
0.6
<0.1
0.1
0.7
2.327
7.1
0.32
0.18
1.5
<0.5
2
610
<0.5
0.2
1
0.05
0.1
<0.1
0.02
0.2
3.953
7.3
0.24
0.29
1
<0.5
2
570
<0.5
0.2
<0.3
<0.05
0.08
<0.1
0.02
0.2
8.237
3.8
0.41
0.30
6
5
7
570
<0.5
1
210
1
1.5
0.1
0.6
13
8.325
4.2
0.40
0.26
5
4
6
550
<0.5
0.8
190
0.8
1.3
0.1
0.3
11
8.413
4.4
0.33
0.21
4
2
6
510
<0.5
0.7
170
0.6
1
0.1
0.2
7
8.508
4.9
0.29
0.17
4
0.9
5
480
<0.5
0.5
120
0.5
0.8
<0.1
0.2
15
"Elemental concentrations in ng/mt, unless noted.
"Column drained and aired for 20 days; then leaching
resumed.
102
-------
TABLE C-V
TRACE ELEMENT LEVELS IN LEACHATES FROM A COAL WASTE SLURRIED
WITH A GROUND LIMESTONE a
Sample No. 1 5 14 15 31b 33 34
Vol (I)
pH
TDS (%)
F
Na
Al
K
Ca
Cr (ng/£)
Mn
Fe
Co
Ni
Cu
Zn
Cd (ne/l)
0.208
6.4
0.14
0.15
6
<0.5
4
610
1
2
60
0.4
0.9
<0.1
0.1
2
0.538
6.4
0.30
0.16
4
<0.5
3
590
<0.5
1
27
0.2
0.4
<0.1
0.06
0.8
2.218
7.2
0.20
0.18
2
<0.5
2
420
6
0.2
1.
<0.05
0.08
<0.1
0.04
2
5.308
7.8
0.35
0.20
1
<0.5
1
290
<0.5
0.1
0.6
<0.05
<0.07
<0.1
0.01
0.05
8.422
4.6
0.28
0.18
22
<0.5
6
620
<0.5
1
100
0.6
1
<0.1
0.07
6
8.598
5.4
0.25
0.14
4
<0.5
5
580
0.5
0.7
50
0.3
0.8
<0.1
0.19
7
8.675
6.2
0.24
0.15
3
<0.5
4
470
1
0.6
19
0.2
0.6
<0.1
0.04
2
"Elemental concentrations in ^/mi, unless noted.
"Column drained and aired for 20 days; then leaching
resumed.
103
-------
APPENDIX D
ATTENUATION OF SEVERAL TRACE ELEMENTS IN A COAL WASTE
LEACHATE BY SOLID MATERIALS -
SUCCESSIVE INCREMENT METHOD
A 2:1 weight ratio of leachate (CTWT-1012; see the section on
"Freshwater Algae" in Appendix K for trace element data) solids was
shaken overnight at ninety 3-1/2-in. strokes per minute. (A list of the
solids, along with several of their properties, is given in Table D-I).
This slurry was vacuum-filtered through Whatman 42 paper and then
gravity-filtered through Whatman 42 paper. Where initial filtration was
not possible because of clogging, high speed (15000 rpm) centrifugation
was substituted for the vacuum filtration. Part of the resultant fil-
trate was taken for analyses, and the remainder was diluted to a volume
sufficient to continue and equilibrated with fresh solid material in a
2:1 ratio. Up to six successive equilibration cycles were performed in
this manner for each solid material. Control equilibrations were per-
formed with distilled water and 0.136M H2S04 (equivalent in total acidity
of the initial coal refuse leachate).
The analytical results for pH and trace element contents of the
filtrates are given in Table D-II.
104
-------
TABLE D-I
SOLID SORBENTS USED IN SUCCESSIVE INCREMENT, BATCH EXPERIMENTS
Material
Comment
Cation
Exchange
Carbonate0 Capacity6
(%) (meq/lOOg)
Organic
Clayc Matterd Number of
(%) (%) pHe Equilibrations
Alluvial
Soil
Glacial
Till Soil
Glacial
Till Soil
Loess
Soil
Loess
Soil
Organic
Soil
Kaolinite
Clay
Montmorillonite
Clay
Precipitator
Ash
Scrubber
Sludge
Calcium
Carbonate
Weathered 1.65 26.1 48 0.7 7.8
Partly Calcareous
Unweathered 15.1 9.1 13.5 0.4 7.6
Calcareous
Weathered 0.3 28.0 17.0 0.3 7.3
Leached
Weakly Weathered 0.45 9.8 10.8 0.2 7.3
Leached
Unweathered 8.3 8.8 9.5 0.3 7.6
Calcareous
Weakly Weathered 6.8 30.3 38.6 7.3 7.6
Calcareous
0.48 21.4 0.3 8.2
0.54 115 0 7.7
Highly 1.2 3.0 1.5 0.3 11.2
Alkaline
Limestone 30.0 2.7 6.3 3.7 8.1
Scrubber
Reagent 60.0 7.4
Grade
3
6
4
3
5
3
6
6
6
4
6
'Carbonate by rapid titration method.
"('ation exchange capacity by ammonium acetate extraction
following sodium acetate saturation.
c('lay by pipet sedimentation.
d()rganic matter by Walkley-Black procedure.
epH ol'water-soil filtrate after equilibration for 16 h.
105
-------
TABLE D-II
TRACE ELEMENT ATTENUATIONS BY SUCCESSIVE TREATMENTS
WITH SOILS AND ALKALINE SOLIDSa
0 UM H.SO.
H,0
Weak! vWsai he-red H,0
H,0
Uachaie
0 UM H,SO,
\\eakk VVenlhered H,0
0 UM H,SO,
H.O
0 UM H,SO.
H,O
H
"
1
u
li
fi
0
li
It
4
:i
0
<,
7
2
0
,
4
0
fi
6
fi
9
4
R
0
1
fi
(1
a
'!
0
0
fl
fi
fi
J
1
5
H
1
4
11
H
0
11
7
1
H
4
" 1
•1 1
S I
-4
" H
H II
1
14
F Al
«" '"' '
1 H 7M S
7fl 170 5
S2, HiO 9
24 54<«> 5
Ofi
o:is MJ-, i
Mi ^ri ''
< i 1 --HI
10
10
fid
HI
ri
40
80
7(1
40
20
fin
10
20
40
40
4,
10
20
10
90
20
10
00
20
10
70
OO
flO
RO
80
SO
24
1(1
90
100
SO
90
10
12
no
00
so
70
•90
.10
70
rfXI
70
60
7(1
20
20
iff)
6U
10
40
60
2(1
70
70
90
•W
40
lil)
OS7
<0 01
<0,02
<(1 01
09.S
<0,01
<(l ll'i
<(! 11,1
«i o:<
<(1 Oli
<0 02
<0(ll
<0(ll
<
•\\ 2K'HI
21 n J". 1
1 I M "Jl < OS <
ir, :. <0 002
fl 001 H <0001
1,5 <00.1 (1 1 <0009
0.11 <0002
,S < MKt 'I
-------
APPENDIX E
ATTENUATION OF SEVERAL TRACE ELEMENTS IN A COAL WASTE
LEACHATE BY SOLID MATERIALS -
BATCH METHOD USING DILUTED LEACHATE
Coal refuse leachate (CTWT-1012, iron concentration around 5000 ppm)
was equilibrated with subsurface solids and quarry limestone which were
collected from the Illinois Basin in November 1978. In addition, four
Widow's Creek Power Plant solid effluents, Gallup coal, and a commercial
peat were tested. A list of the materials and some of their properties
is given in Table E-I.
Different dilutions of the original leachate rather than the fil-
trate from a previous equilibration were equilibrated overnight with
fresh solid. (This gives better control of oxidation and allows some
assessment of Fe++ attenuation, but does not account for previous dif-
ferential attenuation.) All leachate/solid mixtures were purged about 5
minutes with argon, sealed and shaken overnight. Filtering was performed
in a polyethylene chamber containing nitrogen. Filtrates were purged
with nitrogen or argon gas, sealed, and stored after filtration in pre-
paration for determining Fe++. Oxidation of Fe++ to Fe+++ was greatly
retarded by these precautions. Filtrate pH, Fe++, and total Fe measure-
ments were taken as soon as practical after filtration.
Analytical data for pH and trace elements are given in Table E-II.
Plots of eluent concentration and effluent-to-influent ratios (C/C ) for
solids-to-original leachate used are given in Fig. E-l.
107
-------
TABLE E-I
SOLID SORBENTS USED IN DILUTED LEACHATE, BATCH EXPERIMENTS
Material
Titratable
Carbonate (%)a
Cation
Exchange
Capacity" Clay0
Peat
Bottom Ash
2.2
0.3
48.3
4.1
21.2
0
Organic
Matterd pHe
Limestone
Illinois Quarry
Overburden,
Kentucky Seam 11
Overburden,
Kentucky Seam 12
Loess Subsoil
Glacial Till
Western Coal
Economizer Ash
Precipitator Ash
FGD Scrubber
Sludge
3.8
1.4
0.48
7.1
1.6
1.7
0.6
25.4
9.8
7.5
24.1
14.5
5.3
3.2
3.0
5.4
3.2
9.5 3.2
22.0 1.5
28.6 0.1
8.4 17.0
0.4 0.5
0 0.6
5.9 2.3
7.5
7.6
7.8
4.8
7.9
7.0
12.3
11.4
8.0
46.0
0
5.4
8.0
"Carbonate by rapid titration method.
"Cation exchange capacity by ammonium acetate extraction
following sodium acetate saturation.
cClay by pipet sedimentation.
dWalkley-Black method for organic matter.
"pH of water-soil filtrate following 16h equilibration.
108
-------
TABLE E-II
TRACE ELEMENT ATTENUATIONS OF VARIABLY CONCENTRATED
LEACHATES BY SOILS AND ALKALINE SOLIDSa
ATTENUATING
MATERIAL
Leachate
Limestone
Overburden
Kentucky
Seam 1 1
Overburden
Kentucky
Seam 12
Loess
Subsoil
Glanal
Till
RUN LEACHATE/SOLID
COMMENT
Undiluted
From
Illinois
Quarry
Calcareous
Slightly
Organic
Calcareous
Slightly
Organic
Weathered
Leached
Acid
Calcareous
I'nweathered
NUMBER
NA
Water
1
2
3
4
Water
1
9
3
4
Water
1
2
:i
4
Water
1
•2
n
4
Water
1
0
;)
4
RATIO
NA
2.0
2
0.71
0.40
0.20
2.0
20
0.71
0 4(1
0.20
20
2.0
0 40
(I 20
0.06
2.0
2.0
0.71
0 40
0.20
2.0
20
1.0
0.40
0.20
pH
2.0
7.5
6.3
7.1
8.0
8.0
7 6
6.0
6.7
7.2
8 1
7.8
4.5
6.5
7 6
8.0
4.8
29
3 4
3.7
4.9
7.9
6.3
7 0
7.8
8.2
Fe(II)
4680
<0.02
3640
96
17.6
<0.02
<0 02
2980
246
61
<0.02
<0 02
3880
419
3.3
<0.02
<() 02
2980
561
150
6 7
<0.02
970
72
<().():)
<0 02
C/C.
NA
NA
0.78
0.059
0.019
NA
0.64
0.15
0 (Xi5
NA
0.83
I) 45
0.1X17
NA
0 64
034
0.160
0.015
NA
0 21
0031
Fe(IH)
260
<0.02
40
6
<0.02
<002
<0.02
80
11
0
<0.02
<0.02
80
0.0
0.9
<0.02
<0.02
140
4
1
0 2
<0 02
30
7
0.4
<0.02
C/C.
NA
NA
0.15
0.066
NA
0.31
0.12
NA
0.31
0.056
NA
0.54
0 044
0.019
0.012
NA
0.12
0.054
0.008
F
127
0 7
6.6
3.9
2.2
1.2
1.3
28.8
4.9
3.4
28
0.9
93.6
1.8
1.5
0.9
<0.2
105
28.3
1 1 .3
3.3
1 6
5.3
2.2
1.5
1.6
C/C,
NA
NA
5.05
0.061
0.09
0.09
NA
0.22
0.11
0.41
0.21
NA
0 70
007
0.11
0.24
NA
0.82
0.63
0.47
025
NA
0.04
0.03
0.06
0.12
Al
570
<0.2
1.0
<0.2
<0.2
<0.2
<0.2
5.4
<0.2
<0.2
<0.2
<0.2
136
<0.2
<0 2
<0 2
2.2
566
110
35
7.6
07
1.6
<0.2
<02
<0.2
C/C
NA
NA
0.001
NA
0.07
NA
0.23
NA
0.99
055
0.35
0 14
NA
0002
Mn
15.3
<0.01
12.7
0.44
0.09
0.03
8.4
68.4
35.6
23.9
13.4
0.99
36.8
14.0
7.9
270
0.21
324
184
108
51.2
0.03
227
146
65.6
17.8
C/C
NA
NA
0.&3
0.08
0.03
0.02
NA
4.47
6.64
~ 73
8.37
NA
2.40
4.53
4.93
6.00
NA
21.17
34.32
34.95
32.00
NA
148.3
19.08
21.22
11.12
Ni
11.6
<0.02
8.76
0.24
0.07
0.02
0.18
9.91
1.02
0.48
0.26
<0.02
11.1
092
0.18
0.02
<0.02
11.2
4.06
2.06
0.91
<0.02
3.22
0.52
0.16
0.03
C/C
NA
NA
0.75
0.05
0.03
001
NA
0.85
0 25
0.23
0.24
NA
0.95
0.44
0.16
0.05
NA
0.96
1.00
1.00
0.85
NA
027
0.08
0.07
0.02
As
09
<0.(X)1
0.022
<0.(»01
0.001
0.002
«).(XK
0.015
0.002
<0 002
0.(X)2
<0 003
0.05
<0.(X)2
<0.003
<() 1X13
0.1X15
0.22
0 018
0.011
0.009
<0.(XI1
0 (X)5
<0.(X>6
0.1X14
0.(X)6
C/C.
NA
NA
0.02
(I 007
0.02
NA
0.01
O.IX16
0.02
NA
06H
NA
(1.24
0 05
0 07
0 12
NA
0.1X15
(1 02
008
"Element concentrations in
-------
TABLE E-II
TRACE ELEMENT ATTENUATIONS OF VARIABLY CONCENTRATED
LEACHATES BY SOILS AND ALKALINE SOLIDS3 (CONCLUDED)
ATTENUATING
MATERIAL COMMENT
Western Alkaline
dial
Krnnnmizer HighK
Ash Alkaline
Prenpitatnr HifihK
Ash Alkaline
F(H) Limestone
S( rubber Process
Sludge
Peat ~>" °'°
Organic1
('(intent
Bnttnm Alkaline
Ash
RUN LEACHATE/SOLID
NUMBER
Water
1
•)
3
4
Water
1
2
3
4
Water
2
:i
4
Water
1
2
3
4
Water
1
1
3
4
Water
1
RATIO
."i 0
2 1)
11.71
0 41)
(1 20
5 (}
2 (I
1 1)
1) 411
t) 20
5 I)
2.0
(1 71
(1 4(1
(1 20
fid
2 I)
0 40
0 20
ll.Ofi
S 0
2 0
071
0 40
0 20
fi.O
O..i
pH
7 (I
:i 7
3 8
4 2
5 1
12:i
4 3
11.0
12:1
12 1
11 4
4 1
4 H
fi.fi
II 7
K I)
fi.O
fi.fi
7..'!
7 H
f) 4
4.1
4 fi
4 fi
4 8
H.O
3.2
Fe(II)
<() 02
:i7:to
fi'22
8fi 4
(1 fi2
<0.02
3fi.3(>
<0 02
<(] 03
<0.02
<() 02
4210
1 19H
K4 4
<0.02
<0.02
3120
2.~ifi
17 K
<0 02
<0.02
HMX)
IOK
1 4 .5
0.2
<0.02
4210
C/C,
NA
0 8(1
o 38
0.092
0 001
NA
0 78
NA
0.90
o 7:1
(1.119(1
NA
Ofi7
0 274
o 0:19
NA
0.21
O.Ofifi
O.Olfi
0.004
NA
0.90
Fe(III)
<0 02
70
fi
2.5
(1 Ofi
<(] (12
80
<() 02
<0.03
<(! 02
<(> 02
fill
:t2
(
<0.02
<0(I2
120
4
O.fi
<0.02
<(l 02
90
2 (1
0
0.3
<002
90
C/C,
NA
0.27
(1.066
0 048
0 «)4
NA
o.:ll
NA
0.19
0 35
NA
0.46
0.077
o 038
NA
o 35
0 022
0.019
NA
0 35
F
09
109
:« 4
11.3
1 1
0.7
5.7
17.0
4.0
2.6
100
12H
3.5
6.5
2.:i
2 lj
12.2
4.5
4.5
5 8
(1 1
28
2.4
1 :i
1.1
0.2
111
C/C,
NA
0 8f)
0 75
0 47
0 08
NA
0.04
0.26
0.16
0.2(1
NA
1 (K)
0(12
0.27
0 17
NA
0.09
0.19
3.48
1 54
NA
0.22
0 Ofi
0.05
0.08
NA
0.87
Al
0.2
548
120
18.9
0.7
0 1
2.2
5.3
«).2
<02
1.7
388
08
i :t
<0.2
0 1
4 a
«>.2
«).2
«).2
0.1
:17
1.:!
0.6
0.2
2.6
541
C/C,
NA
0.96
0.60
o.ia
001
NA
0.003
001
NA
0.68
0004
001
NA
o.ooa
NA
006
0.006
0006
o.ixn
NA
0.94
Mn
<0.01
149
5 4
2.80
0.38
<0.01
27.2
<0.02
<0.02
<0.01
<0.01
23.4
9.6
4.28
<001
002
167
4.04
1 70
021
<0.01
21.4
8.6
5.2
2.24
<0.01
16.6
C/C,
NA
097
1.00
0.91
0.23
NA
1 77
1.52
1 79
1.3R
NA
1.09
1 30
1 06
046
NA
1.39
1.60
1.68
1 40
NA
1 08
Ni
0.03
10.7
3.27
1.38
0 02
0 04
997
<0 02
<0.02
<0 02
0.02
11.7
349
0.02
<0.02
0.02
896
0.86
022
«) 02
0.01
1.59
0 12
0.03
<0.02
0.01
9.8
C/C,
NA
0.92
0.80
0.67
0.01
NA
0.85
1 (XI
0 8;i
0.009
NA
0.77
041
0.20
NA
0 13
0 02
0.01
NA
084
As
0 19
0 05
<() (XII
<0.(XI5
<0.024
O.Olfi
0 (X)7
0 1X18
0 14
0.031
0.013
0.90
0019
0.010
0 010
0.024
0.012
0(X)9
0(X)9
0.1X18
(1 30
C/C0 '
0.21
003
0 05
0.10
o i:,
0.09
0 09
1 23
0 02
0 07
0.13
0.92
0.01
0.02
0.06
0 10
0 33
•Element concentrations in uf/ml.
-------
Deter.tinn I imit
LEGEND
o = OLS
« = LOESS
« = TILL
0.0 10 2.0 3.0 40 5.0 60 70 80
Solid to Leachate Ratio
a.
a
t_
v_
\
^
H
LEGEND
o = QLS
o=S-1l
« = LOESS
<> = TILL
°Tfc._
Detention 1 imit
2.0 3.0 4.0 50 6.0 70
Solid to Leachate Ratio
LEGEND
«= LOESS
= = TILL
Detect!on Limit
\
2.0 3.0 4.0 5.0 6.0
Solid to Leachate Ratio
o-
o-
E'
a.
< "~|
„
o-
T°:
\ «-.
\ """~De"te'c'tibrr-L-imit
*"\ -•-.
LEGEND
o = QLS
' = LOESS
» = TILL
^<—^
10 0.0 1.0 2.0 3.0 4.0 5.0
O-
-
o2:
o
\ .
u
1
"-.
'o;
LEGEND
o = OLS
i. = LOESS
° = TILL
',
'.
k-"" *^
a ^-^^De t ec ti on Ljrfn it
\<-^' ^^-^^
6.0 7.0 80 * 0.0 1.0 2.0 3.0 40 5.0 60 70 8
Solid to Leochate Ratio Solid to Leachate Ratio
T
§TO:
u.
o-
o-
\ ""-,
\ --....
\^^~-^!~~ —- - """"•-
\_^>^^ '*
LEGEND
o = OLS
o = S-11
- = LOESS
o = TILL
"o-
o
O-
o— :
U ~-
^. -
0
o-
LEGEND
o = OLS
- = LOESS
° = TILL
« —
t^;.....
/ ~-'^--i.-...
^ / •—.
"^^w - Detection Limit
0.0 VO 2.0 3.0 4.0 50 6.0 70 80
Solid to Leachote Ratio
0.0 1.0 2.0 3.0 4.0 5,0 60 70 80
Solid to Leachate Ratio
TVia.ee element -in.
E-l.
cuttznuated. by
Ill
-------
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Solid to Leachate Ratio
o°
LEGEND
o=OLS
o-S-11
• -LOESS
« . TILL
2.0 3.0 4.0 5.0 6.0
Solid to Leochate Ratio
LEGEND
n-QLS
» = LOESS
= = TILL
DetectioiVxLimi
imit
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7 0 8.0
Solid to Leachate Ratio
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 80
Solid to Leachate Ratio
E-,
«= LOESS
• - TILL.
00 10 20 3.0 4.0 5.0 60 ^0 80
Solid to Leachate Ratio
= =5-11
»= LOESS
> = TILL
Detection Limit
0.0 1.0 2.0 3.0 4.0 50 6.0 7.0 6.0
Solid to Leachate Ratio
LEGEND
3 = OLS
a =5-11
»=LOESS
• = TILL
20 3.0 4.0 5.0 6.0 70 80
Solid to Leachate Ratio
LEGEND
= -OLS
= = 5-11
«= LOESS
• = TILL
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Solid to Leachate Ratio
l. E~7
112
Tia.ce.
ui
aXtamattd by
-------
s.
Dpf pr ti nn I im it
LEGEND
3 = WST COAL
J = EC ASH
> =ESP ASH
• = PEAT
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Solid to Leachate Ratio
2.0 3.0 4.0 5.0 6.0 70 8.0
Solid to Leachate Ratio
0.0 1.0 2.0 3.0 4.0 5.0 60 7.0 80
Solid to Leachate Ratio
7
O-
LEGEND
i= WST COA,
> =EC ASH
i =ESP ASH
> = PEAT
0.0 1.0 2.0 3.0 4.0 5.0 6.0 70 80
Solid to Leochate Ratio
o
u
\7
"O-
'o-
LEGEND
3 = WST COAL
> = EC ASH
• = ESP ASH
> = PEAT
Detection Limit
00 1.0 20 3.0 40 50 60 70 80
Solid to Leachate Ratio
LEGEND
= WST COAL
= EC ASH
= ESP ASH
= PEAT
I imit
0.0 1.0 2.0 3,0 4.0 5.0 6.0 7.0 80
Solid to Leachate Ratio
LEGEND
o = WST COAL
o =EC ASH
" =ESP ASH
° =PEAT
Detection Limit
0.0 10 2.0 3.0 40 5.0 60 70 60
Solid to Leachate Ratio
aj. E-J [contd] .
e.Ulu.e.n&, cutte.nuate.d by
113
-------
00 1.0 20 3.0 4.0 50 6.0 7.0 8.0
Solid to Leachate Ratio
LEGEND
= = WST COAL
= = EC ASH
» = ESP ASH
• = PEAT
t5e~t-eiti.on Limit
0.0 1.0 20 3.0 4.0 5.0 60 70 8.0
Solid to Leochate Ratio
LEGEND
i = WST COAL
i = EC ASH
> = ESP ASH
> = PEAT
Detection Limit
0.0 10 2.0 30 40 50 60 70 80
Solid to Leachate Ratio
00 1.0 2-0 30 4.0 50 60 70 80
Solid to Leachate Ratio
00 1.0 20 3.0 40 50 60 70 80
Solid to Leachate Ratio
0.0 1.0 20 30 4.0 50 6.0 70 80
Solid to Leachate Ratio
00 1.0 20 30 40 50 60 70 80
Solid to Leachote Ratio
0.0 1.0 20 30 4.0 50 60 70 80
Solid to Leachate Ratio
114
F/tg. E-7 (c.ontd) .
Tiace. element -in e.^lu.e.yitA cuttznuicut&d. by
-------
Q. "
LEGEND
n = S-11
o = FGD SS
Detection Limi
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leochote Rotio
LEGEND
= S-11
= FGD ss
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leochote Ratio
LEGEND
o = S-11
° = FGD SS
Detection Lir
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leachate Ratio
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20 C
Solid to Leochate Ratio
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leachate Ratio
LEGEND
J = 5-11
J = FGD SS
Detection Limit
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leochate Ratio
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leachate Ratio
LEGEND
3 = S-11
i = FGD SS
Detection Limit
0.0 2.5 5.0 7.5 \0.0 12.5 15.0 175 20.C
Solid to Leachate Ratio
cg. E-7 (contd) .
-n
by
115
-------
Dpi pr ti nn I irr
LEGEND
o = 5-11
° = FGD 55
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20,C
Solid to Leochote Rotio
CLO-
LEGEND
o = S-ll
o = FGD SS
Detection I imil
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leochate Ratio
LEGEND
o = S-11
° = FGD SS
Detection Limit
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leochate Ratio
LEGEND
3 = S-ll
J = FGD SS
Detection Limit
0.0 2.5 5.0 7 5 10.0 12.5 15.0 17.5 20.C
Solid to Leochote Rotio
LEGEND
= 5-11
= FGD SS
Detection Limit
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leachote Ratio
0.0 2.5 50 7.5 10.0 125 150 17.5 20.C
Solid to Leochate Ratio
LEGEND
o = S-11
° = FGD SS
Detection Limit
25 5.0 7.5 10.0 12.5 15.0 17.5 20.C
Solid to Leachate Ratio
116
Beg. E-7 (aon&f).
T/iace. e£e/nm£6 -in e^&ieitti attenuated by Aosibe.ntt>.
-------
APPENDIX F
EFFECT OF pH ON TRACE ELEMENT LEVELS IN COAL WASTE LEACHATES
Coal waste leachate CTWT-1012. which had been stored for many months
under argon, was metered out (50 m£) into 125-m£ Erlenmeyer flasks which
were purged with argon and stoppered. Varying amounts of hydrated lime,
Ca(OH)2, were added to each flask to raise the pH. The flasks were
purged with argon, resealed, and stirred with magnetic stirrers for 24 h.
After equilibrating, the slurries were vacuum filtered under argon
through 0.45-|Jm Millipore disks. The filtrates were tested for pH, Fe++
and Fe+++, and then acidified for further elemental analyses. These
results are posted in Table F-I. Plots of most of the elements are given
in Fig. 11 in the section on "Treating the Waste Effluent."
117
-------
CO
TABLE F-I
TRACE ELEMENT LEVELS AS A FUNCTION OF THE pH OF A COAL WASTE
LEACHa
CTWT-17 LIME(g)" pH
Al
As
Ca
Cd
Co
Cr
Cu
Fe
Fe+
Fe+
Mn
Mo
Ni
Zn
0
1
2
3
4
5
0.16
0.35
0.43
0.50
0.60
2.25
2.73
5.82
6.49
8.09
10.18
370
370
.46
<.l
<.l
1.1
.41
.14
<.01
<.006
<.003
<.003
350
540
430
450
500
490
.21
.23
.08
<.003
<.003
<.009
3.5
3.7
2.8
.5
<.02
<.02
.43
.28
<.01
<.01
<.01
<.04
.09
.11
.01
<.01
<.01
<.01
81
86
2.0
4.2
10.
12.
3310
1960
1350
620
2.2
<.02
1680
1800
1350
620
2.2
<0.02
1630
160
<0.02
<0.02
<0.02
<0.02
9.9
10.1
10.8
8.1
0.3
<.02
<.l 7.5
<.l 7.7
<.l 3.8
Cl .5
<.l <.02
<.4 <.02
16
17
3
.5
<.02
<.02
"CTWT-1012 leachate used; argon atmosphere throughout
experiment.
"Grams ofhydrated lime slurried in 25 m.£ water
and added to 50 mi, of leachate.
-------
APPENDIX G
LIME/LIMESTONE/COAL WASTE SLURRIES -
AN ATTRACTIVE ROUTE TO COAL WASTE DISPOSAL
I. PREPARING THE LIME/LIMESTONE/COAL WASTE SLURRIES
Three 55-gal. drums of Plant M, high-sulfur, Illinois-Basin coal
preparation waste were crushed to minus 3/8 in. without prior drying.
Scoops of material from each barrel were placed, in sequence, into six
empty barrels fitted with plastic liners until 250 Ibs of material were
present in each barrel. To each barrel, 30 £ of deionized water were
added and the barrel tumbled for 5 min at 15 rpm. After the barrels had
stood for several days, the excess water (approximately 8 £) was siphoned
off and analyzed for acidity. The leachates had pH values from 2.8 to
2.9 and were 0.045 molar in acid. To each barrel was added a slurry
(generally 38 to 50% solids) of lime. This slurry was blended into the
waste slurry by tumbling the barrel at 15 rpm for 2 minutes. In one
case, limestone was later added and blended. (Each mixture sat for 4 to
9 days as other barrels were being prepared and used.) After settling,
excess water was siphoned off, and the slurry was poured into a muslin
filter in a 90- by 150- by 25-cm polyethlyene tub and spread out evenly
to allow further water drainage. The slurry was then ready for use. A
listing of the lime and limestone levels and pH values for each slurry is
given in Table G-I.
II. DUMPING THE SLURRIES INTO DISPOSAL BOXES
The drained lime/limestone/waste slurries were portioned out into
several groups. The first six portions (1/10 barrel each) were placed in
molded plastic pans which had previously been fitted with Tygon drains
covered with glass wool that, in turn, was covered with sand (see Fig.
12c in the text). The plastic, scale-up boxes were then placed in a
6-column by 6-row grid for weathering by raining and drying cycles.
The remainder of each barrel was divided into numerous 600-g and
4000-g units. These portions were sealed in polyethylene bags from which
the air had been excluded by rolling them up like toothpaste tubes before
sealing. These portions have been sealed as wet, oxygen-deficient
controls.
III. RAIN-DRY WEATHERING CYCLES (IN PROGRESS)
The weathering cycles start with Monday morning "rain showers" of
1650 m£ of deionized water (equivalent of 39 in/yr), with the drains
stoppered. On Tuesday the drains are opened and the leachates allowed to
drain out. (This overnight soaking increases the water-to-waste con-
tact.) These leachates are monitored weekly for pH, conductivity, volume
of flow, and ferric and ferrous ion levels. (Results for the first 9
weeks are given in Tables G-II to G-IV.) Samples are retained for trace
element levels, to be measured at a later time. The drained boxes of
lime/limestone/waste are then allowed to dry until the next Monday, when
the cycle is started again.
119
-------
TABLE G-I
LIME/LIMESTONE/COAL WASTE SLURRIES3
pH"
Barrel # Additive Amount (g) Level (%)b Water(l)c Immediate" Steeped (days)1
1 Lime" 192 0.17 20.5 6.3 5.6(9)
2 Lime 377 0.33h 20.6 11.0 6.5(9)
3 Lime 599 0.53 21.8 8.6(7)
4 Lime 1276 1.12 25.6 12.6 11.0(9)
5 Lime 3784 3.33 30.2 12.1(6)
6' Lime+ 314 0.35 21.0 7.6(4)
CaC03J 982 1.08
•113.5 kg (250 Ib) waste/barrel.
bBased on waste.
cln final slurry.
"Slurry + extra deionized water; allowed to settle;
electrode placed in liquid only.
"Immediately after lime slurry added and mixed.
'Slurries allowed to settle before siphoning
off most of the excess water.
g-325 mesh hydrated lime.
hAmount of lime needed to neutralize acid
in slurry exactly; based on base titration of
hydrogen peroxide-treated leachate.
'Only 90.8 kg (200 Ib) used.
J-8() mesh precipitated limestone.
120
-------
TABLE G-II
pH OF EFFLUENTS FROM WEATHERED BOXES OF SLURRY-TREATED
COAL WASTE3
Time
(weeks)
0
3
6
9
12
Lime (%)
0.17
5.6
2.4
2.2
2.0
1.8
0.33
6.5
2.5
2.2
2.0
1.9
0.53
8.6
3.8
2.4
2.0
1.9
1.1
11.0
2.2
4.2
3.0
2.8
3.3
12.1
11.7
11.5
9.6
7.6
Lime (%)
Limestone
0.35 + 1
7.6
7.4
7.3
7.5
7.4
"Values are pH units.
TABLE G-III
TOTAL IRON IN EFFLUENTS FROM WEATHERED BOXES OF SLURRY-TREATED
COAL WASTEa
Time
(weeks)
3
6
9
12
0.17
3700
8500
14000
12000
0.33
1600
10000
13000
10000
Lime (%)
0.53
3.9
3600
14000
23000
1.1
1.4
0.8
3.9
4-50
3.3
0.3
<0.01
0.1-0.3
0.1-0.9
Lime (%)
Limestone
0.35 + 1
<0.01
<0.01
0.01
0.05
"Values in ppm.
121
-------
TABLE G-IV
CONDUCTIVITY OF EFFLUENTS FROM WEATHERED BOXES OF SLURRY-
TREATED COAL WASTE3
Lime (%)
Time Lime (%) Limestone
(weeks) 0.17 0.33 0.53 1.1 3.3 0.35+1
1.3
1.2
1.1
1.2
3
6
9
12
4.4
6.3
8.5
10.6
3.3
5.9
7.9
10.1
1.2
4.4
8.3
10.6
5.1
1.3
1.5
3.0
2.7
1.6
1.4
1.4
"Values in grams KC1 per liter equivalents.
IV. DISPOSAL BOX DISMANTLEMENT AND SOLID WASTE EVALUATION (IN PROGRESS)
Plans also call for dismantling a box from each lime/limestone/
waste level at various times to permit an evaluation of the depth of
degradation. The scheduled periods are 1 week, 1 month, 3 months, 6
months, 1 year, and 2 years. Each dismantled box will produce one frac-
tion in which 2.5 cm is skimmed off half of the top and another in which
a vertical third of the layer between this and the sand layer is removed.
These fractions will be sealed in polyethylene bags for later analyses.
The boxes for the first week have been spread out and allowed to dry. At
various times, fractions from these will be separated and "rained" upon.
This will provide an evaluation of the influence of air oxidation in the
absence of rain water.
122
-------
APPENDIX H
TRACE ELEMENT AND MINERAL ANALYSES AND
CORRELATIONS FOR A LOW-SULFUR APPALACHIAN COAL
PREPARATION PLANT
Procedures for sizing are discussed in the first annual report
(LA-6835-PR). Float/sink procedures are described in the second annual
report (LA-7360-PR). Statistical correlation treatment is discussed in
the section on "Visual Presentation of Statistical Results" in this
report. Tables H-I through H-IV and Figs. H-l and H-2 give specific data
on waste from Plant G coal preparation.
TABLE H-I
SUMMARY OF PLANT G COAL AND REFUSE SAMPLES
Identity Sample Wt (kg) % of Whole
Feed Coal A 38 47 100
Feed Coal B 39 45 100
Coarse Gob A 40 60 100
Coarse Gob B 41 61 100
Fine Gob 42 43 100
Average Gob:Sized 40A 100
-20 mesh 40G 8.9
2in. 40F 17-0
Average Gob:Float/Sink 40A 100
Float<2.15g/ml F18F 31.0
Float < 2.48, Sink > 2.15 F18E 31.0
Float < 2.97, Sink > 2.48 F18C 37.7
Sink > 2.97 F18A 0.3
123
-------
TABLE H-II
TRACE ELEMENT AND MINERAL CONTENT OF COAL WASTE MATERIALS
FOR APPALACHIAN PLANT G SAMPLES
36
40
m
IDE' TITY
LUCALL
DATE OPTNU
PCT |-:20
PCT LTA
PCT ORIGNL
SIZE, KG
ChhS ANAL
NITROGEN
SULFUR
MlhEHALOGY
KAOL1N1TE
ILLllb.
QUARTZ
PYRITE:
CALCITt;
MIXED cm
GYPSUM
SAMPLE
SLEMEIiT
(2)
LI PPM H 4
PF PP" F A
P PPf>¥ L !i
F PPK (! <°
Nf PCT H A
[•Y, PCT H A
AL PCT H A
SI PCT R 0
P PPK fi 0
CL PPl- h N
K PCT H A
CA PCT H A
SC PPM [• r:
TI PCT R N
V PPM fi M
CR PP1- H A
MN PPM H A
Ft' PCT H /i
CO PPM R N
NI PPM L E
ca PPM i; A
ZN PPM H A
uA PPM h i.'
obi PPM L n
Ao PPt\ h i'v
RB PPK ,t 14
1 PPli L L
Zh PPM L i
y/o PPK L L,
CL) pp;-. li A
o:\ PPK L L
Sb Ppli h N
Co PP;; R N
LA PP" R ii
Cb, PPH H N
SM PPM R N
KU PP.: h N
TP Ppy r, N
DY PP^ R N
YP PP^ R N
LU PPK H N
HF PPN P N
TA ppf' R 1,
\ PPM R M
PC PP*1 H A
TH ppr- i; c
U PPM f 0
ftlD COAL A
PLANT G
06/23/76
5.49
46.78
100.00
46.30
.60
.72
38
RAW FA3IS
61 .00
2.20
^2.00
^'10.00
.06
.27
5.03
10.24
10.00
329.00
.99
. T-i
8.83
.34
75.20
58.00
51.15
1.07
13.00
32.00
36.00
43.00
8.90
-5.00
tj.15
126.00
15.00
69.00
-5.00
.20
-5.00
1.00
3.99
27.50
41.10
2. 10
.bu
^.64
.2^
2.05
21 .00
7. 19
2.71
FCD COAL f-
PLANT 0
06/23/76
5.41
40.45
100.00
44.60
.bo
.69
39
RAW BASIS
&1 .00
2.70
46.00
300.00
.05
.23
4.26
9.58
90.00
305.00
.83
.10
8.94
.36
67.10
47.00
42. 10
.90
12.00
33.00
31 .00
33.00
10.90
-4.00
5.99
b3.50
12.00
78.00
-4.00
. 10
-4.00
1 .07
4.46
23.90
40.40
?.97
3.66
1.69
.21
2.88
15.00
?.13
2.55
OOP A CCliS
PLANT G
06/23/76
4.54
84.82
100.00
59.70
.20
.60
11.18
1Q.03
23.87
-1.00
1.03
7.47
1.52
40
RAW PASIS
119.00
3.00
55.00
600.00
.17
.52
9.56
20.20
160.00
2.07
.12
15.80
116|00
67.00
93.90
1 .89
9.00
00
43.00
22^20
-o.OO
14.20
121.00
21.00
160.00
-o.OO
.20
-8.00
9.22
58.30
74.50
6.09
1.13
.86
5.82
2.83
.59
5.73
1.46
22.00
15.60
4.32
cor. B CURS
PLANT G
06/23/76
4.60
81.52
100.00
60.60
.42
.64
11.34
19.61
19.76
-1.00
.49
3.49
1.58
41
RAW BASIS
132.00
2.60
56.00
560.00
. 11
.57
9.25
20.45
150.00
2.05
.15
17.20
.67
116.00
104.00
96.75
2.05
11.00
46.00
53.00
69.00
19.30
-8.00
20.30
134.00
19.00
130.00
-8.00
.40
-8.00
2.95
9.58
52.40
05.80
5.50
1,
1.
5.
2.
.50
56
.46
.56
4.o2
1.14
20.00
15.80
4.40
KN GOB
PLANT G
06/23/76
20.14
73.35
100.00
42.oC
.46
.Ob
11.16
19.46
21.31
-1.00
1.92
6.29
.7o
42
HAW BASIS
.00
.60
1 14.
1 ,
52.00
550.00
.12
.52
8.38
20.10
150.00
1.99
.14
14.60
.56
109.00
oO.OO
99.50
2.10
14.00
45.00
47.00
65.00
17.00
-o.OO
1o.60
141.00
10.00
99.00
-8.00
.40
-0.00
1.52
7.52
33.00
76.50
4.34
14
94
13
00
13
4.76
73
.33
27.00
13.90
184
5.
3.
1,
124
-------
TABLE H-III
TRACE ELEMENT CONTENT OF SIZED WASTE MATERIALS
FOR APPALACHIAN PLANT G SAMPLES
SAMPLE
40G
IDENTITY
LOCALE
DATE OETND
PCT LTA
PCT ORIGNL
-20
PLANT G
06/23/76
87.5.3
8.69
40B
-1/4
PLANT G
06/23/7b
82.59
27.49
40C
-1
PLANT G
06/23/76
83.69
3L51
40U
40r
-1D
PLANT G
06/23/76
35.62
7.87
PLANT G
06/23/76
81.27
7.22
+2
PLAM u
06/23/76
t6.96
17.03
CHUS ANAL
NITROGEN
SULFUR
.45
1.22
.42
.62
.38
.57
.36
.42
.45
.31
SAMPLE
ELEMENT
40G
40P
40C
(2)
RAW BASIS
LI
bt
B
(•'
KG
AL
SI
P
CL
K
CA
SC
TI
V
CR
MN
FE
CO
NI
CU
ZN
GA
jF
AS
RF
Y
ZK
MO
CU
SN
sr
cs
LA
cc
SM
EU
TF
PPM
PPM
fPh
PPM
PCI
PCT
PCT
PCT
PPM
PPh
PCT
PCT
PPM
PCT
PPP
PPM
PPK
PCT
PPM
PPM
PPM
PPN!
fff.
PPM
PPt'
PPN
PPM
PPM
PPM
PPK
PPM
PPM
PPM
PPi-
PPH
PPM
ff^r.
PPM
h
H
L
h
ri
h
H
h
H
H
H
H
R
R
R
H
H
H
R
L
H
H
R
L
u
H
L
L
L
H
L
H
H
fc
R
h
ft
H
A
A
t.
0
A
A
A
0
0
N
A
A
N
N
N
A
A
A
N
L
A
A
N'
£
N
N
L
E
t
A
E
iv
H
N
I-1
r.
1-J
N
110
2
52
540
a
18
140
82
1
15
110
63
90
2
9
42
68
71
21
-9
20
97
22
170
-9
-9
1
7
'*3
81
3
.00
.50
.00
.00
.12
.49
.43
. 14
.00
.90
.87
.63
.60
.53
.00
.00
.60
.34
.00
.00
.00
.00
.60
.00
.40
.00
.00
.00
.00
.40
.00
.70
.32
.oO
.60
.76
.33
It Pr-h
Li/ i'fi.
i r rVi'
T/> fpf
i. m.
pr. PPK
Tii PPM
U PPil
n h
h h,
H C.
R 0
H C
4.43
'..'15
.bu
33.00
14. 10
3.82
RAW BASIS
121.00
2.60
56.00
600.00
.17
.59
9.10
19.60
150.00
96.40
2.15
.14
16.20
.60
124.00
84.00
105.00
2.14
9.00
58.00
42.00
87.00
.70
.00
14. 10
109.00
22.00
170.00
-0.00
1<
.40
-8.00
10.10
62!60
4.76
1.23
4. Y f
2.40
.94
10.00
14.70
3.86
RAW BASIS
123.00
2.70
54.00
590.00
.12
.58
10.02
19.50
140.00
2.Ob
.16
17.20
.68
122.00
92.00
101.00
1.92
7.00
5?.00
39.00
79.00
21 .90
-8.00
12.90
134.00
19.00
130.00
-o.OO
.20
-8.00
2.46
7.62
ri2.?0
92.50
6.29
1.44
1.35
40D
RAW L'ASIb
40t;
"! . P'J
1 .26
.39
24.00
15.70
4.23
130.00
3.20
b4.00
640.00
10.23
20.20
170.00
2.31
.16
17.10
.64
124.00
86.00
110.50
2.01
11 .00
58.00
51.00
82.00
21.10
-9.03
7.36
174.00
21.00
100.00
-9.00
.20
-9.00
9.61
52. 10
£•9.30
5.2b
1.58
1.12
5 . Hi'
4 . i'l
.53
5.L7
<:l . 32
3.78
29.00
15.00
4.80
RAW BASIS
142.00
2.20
54.00
560.00
.12
.54
9.43
18.61
150.00
2.00
.22
19.20
.72
127.00
95.00
.55
.47
.00
.00
1.
54.00
67.00
21 .10
-b.OO
5.44
136.00
21.00
190.00
-8.00
.90
-o.OO
11 .20
r>5.i;J
95.60
5.49
1.5b
1 .32
o?5
i.to
28.00
10.40
4.59
117.00
2.20
50.00
o20.00
.13
.oO
9.44
21 .b5
1bO.00
2.17
.11
1o.90
.69
119.00
03.00
120.00
2.22
15.00
52.00
31.00
82.
21
.00
.80
-9.00
15.60
165.00
23.OU
100.00
-9.00
.40
-9.00
.o4
3,so
59.90
94.00
o.17
1 .60
b . 0 /'
1.37
26. Oj
16.40
5.05
125
-------
TABLE H-IV
TRACE ELEMENT CONTENT OF FLOAT/SINK-SEPARATED WASTE
FROM APPALACHIAN PLANT G
SA>'PLi'
F18C
F18E
m
lothim
LOCALE
PCT OH1GNL
CHMS ANAL
Nl'lRCGbh
SULtUh
SAMPLE
40A SK/TPb
PLANT ;":
.32
35.70
F18A
ELFYilNT RAl- TASI?
(21
LI
FT
P
r
N f
VG
AL
SI
P
CL
-v
CA
.SC
TI
V
CK
V"i
r t.
CO
M
Cu
k,i.
uA
ub
Ao
hb
i
k-h
K<
tJ
Si,
SP
CS
LA,
i'^ L
S' '
t l]
IT
ul
if
Lb
i!F
PI
I>
Ppr
PP''
PP(-
PPM
PCT
PCT
PCT
PCT
PPI-:
i'PC
PCT
PCT
ppv
PCT
ppu
PPM
PPK
PCT
PPM
PPM
FtT.
PPM
f Pi,
PPK
pp^
pp^
rPi ,
PP;-;
PPr
pp;-,
pf ;••
PPM
Pf V
ppr
PPi*1
PPr
PP!'
ppr.
PP'-'
ppr
ppy
ppr
PP:-
ppM
i-i
P
L
h
H
H
d
R
R
;,
|,
H
h
P
P
P,
11
H
h
L
li
h
ii
L
n
n
L
L
L
h
L
R
H
K
R
H
j<
R
H
H
H
h
H
K
a
A
h
L
A
A
A
0
0
f.
A
f;
h
V
A
A
A
l,
t.
fi
A
h
D
li
1,
L
ii
E
A
b
fi
N
ti
N
Iv
i.
!»'
N
r,'
[,
!\'
A
0
1 1
-10
94
1
2
62
11
140
8d
'^70
31
16
50
270
240
-
-30
1200
-20
29
750
5o
-100
-10
c
2
2tf 10
67
4
1
2
1
17
IbO
b
.40
.00
.no
.03
. 14
4 3
.68
.00
.2"
.0-
20
'.44
.00
.00
.00
. 10
.00
.00
.00
.00
.50
.00
.00
.00
.00
.00
.00
.00
.00
. 7^
. 10
.00
. 10
.28
.21
.42
.30
.33
S^
.'50
.00
.04
40A SK/DBK
PLANT G
37.73
.14
.20
F18C
RAW PASIS
125.00
3.10
98.00
300.00
.18
.70
11.21
23.94
190.00
60.00
2.76
.16
19.70
.67
130.00
91 .00
159.00
2.47
12.20
24.00
39.00
05.00
27.00
-30.uo
14.30
236.OJ
27.00
200.00
-10.00
.40
-10.00
-1 .00
5.84
49.40
121.00
8.09
1 .47
.67
4.50
3.86
" .54
4.57
22.00
18.10
40A SK/DBE
PLANT G
30.90
.28
.56
RAW PASIS
133.00
3.30
70.00
680.00
.14
1o!o6
21.18
150.00
250.00
2.08
.37
17.50
.66
120.00
100.00
93.50
1.83
13.80
52.00
44.00
126.00
30.70
-30.00
15.60
188.00
28.00
220.00
-9.00
.50
-9.00.
-1 .00
5.74
51 .00
104.00
6.25
1.23
.65
2.90
?.90
.49
4.28
34.00
17.10
2.
41 ,
40A FVD13E
PLANT G
31.04
.70
.65
F18F
RAV, PASIS
94.00
.50
.00
320.00
.06
.22
5.50
10.61
100.00
160.00
.90
.02
11.60
220.'00
74.00
30.00
.86
16.00
35.00
59.00
37.00
-.50
-20.00
-1.00
4a.yo
21 .00
150.00
-7.00
.30
-7.00
-1.00
4.67
30.90
44 .40
4.56
.80
-.10
.62
.37
.12
2.32
39.00
1.15
tOO'iNvJTt'3
126
(1) PLUo OK nlNUS INUlCATtS SlZt GfihATtH Oh Lb.33 THAl-l Sli.li GlvtM.
IvUMbLho 6 Oh LAhuEK Artt' Ktiili olZbS, O'ir.EhS AHc lii INCtibo
(2) LclltRb llsUlCATb HUlu SAMPLc, WAS PRbPAHLU ANU Al-iALi'ZbU
L =
RAV,
LOV<
TbHPbRATUHb ASH
HIGH Tt.MPb'hATURE ASH
fi= I-.LUTRGN AoriVATION ANALYSIS
.'.= ATONIC AbSCRPTJOIJ
E= EMISSION SPbCTHOSCOPi
0= OTtiE«
-------
I
D
0
B
coa£
H-l.
£
P£a.nt G.
•
a
a
a
;
3
®
.
1 . U
n R
n K
0.4
0.2
0.0
-0.2
-0.4
Oc
. D
n R
1 n
f-ig. H-2.
j ($xcx.eKU
of, the. average coaJL ptepaAatton wcu>t
-------
APPENDIX I
BATCH LEACHINGS OF LOW-SULFUR, APPALACHIAN
COAL PREPARATION WASTE FROM PLANT G
The experimental procedures for these leachings are those reported
in Appendix H of the second annual report (LA-7360-PR, p. 116). The waste
samples leached were composites of the originally collected, coarse waste
samples reported in Appendix H that had been ground to less than 20 mesh.
The leachings of 50 g waste with 250 mJi of water were conducted at room
temperature with the system open to the air. Shaking was performed with
ninety 3-1/2-in. strokes/min. The element levels in the leachates are
reported in Table I-I below. Ecology discharge severity is given in
Table I-II.
TABLE I-I
TRACE ELEMENT LEVELS FROM THE BATCH LEACHINGS OF
LOW-SULFUR, PLANT G COAL WASTE3
Sample No.
Time (Days) 0.01 1 4 16 42
pH
TDS (%)
F
Na
Mg
Al
K
Ca
Cr (/ig/kg)
Mn
Fe
Co
Ni
Cu
Zn
3.9
0.10
1.4
18
240
29
90
580
49
6
15
1.5
3
3
4
4.3
0.13
2.0
20
250
25
130
810
7
7
16
1.5
4
1
5
4.3
0.09
2.3
29
270
28
135
850
9
8
16
2
4
1
6
4.1
0.10
2.6
25
260
40
170
840
7
8
11
2
5
2
7
3.0
0.23
3.1
29
320
280
165
960
300
12
31
3
6
6
15
Cd (jug/kg) 30 31 27 46 25
"Values in /ig/g unless otherwise noted.
128
-------
TABLE MI
DISCHARGE SEVERITY OF BATCH LEACHATES FROM
LOW-SULFUR AND HIGH-SULFUR COAL WASTES3
Plant
Element
Ni
Mn
Fe
Zn
Ca
Cd
Al
Cu
Co
K
Cr
Gb
4
0.7
0.6
0.5
0.5
0.3
0.2
0.2
0.06
0.06
0.0003
Ac
7
2
<0.004
0.06
2
0.07
0.01
<0.02
0.1
0.02
0.0002
Cd
10
2
70
0.7
0.9
1
1
0.01
0.4
0.04
0.006
Be
30
3
400
5
0.5
2
10
0.3
0.8
0.004
0.03
"Based on jig of element leached per
gram of waste in one day.
"One day batch values in this Appendix.
cGL-22-l.
dSGL-5-6.
"GL-21-1.
129
-------
APPENDIX J
COLUMN LEACHINGS OF LOW-SULFUR APPALACHIAN
COAL PREPARATION WASTE FROM PLANT G
Experiment procedures are given in Appendix I of the second annual
report (LA-7360-PR, p. 117). Composite material of the coarse waste
collected from the plant was crushed to less than 3/8 in., and 500 g was
used in each of four columns, 4.6-cm I.D. Upward flow of water was at
0.5 m£/min.
For two samples (GL-23 and GL-24), the flow of water was stopped
after approximately 3 H had passed through, and the columns were drained
and aired. Intermittently, these aired columns were moistened during a
2-wk period to simulate the wet and dry periods encountered by a refuse
pile. At the end of the 2-wk period water flow was resumed as before
until a total of 10 S, of water had passed through the column.
Element levels, pH, and total dissolved solids at various eluent
volumes are given in Tables J-I to J-IV. Plots of these values are given
in Fig. J-I. Ecology discharge severity is given in Table J-V.
130
-------
TABLE J-I
COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-23)a
Sample No.
11
16
20
21
22
24
27
8 Values in MS/m-0 unless otherwise noted.
b After column "air-regenerated"
32
Vol (£)
pH
TDS (%)
F
Na
Mg
Al
K
Ca
Cr (jug/4)
Mn
Fe
Co
Ni
Cu
Zn
Cd (/ig/i)
0.092
2.9
0.47
1.6
16
260
83
28
410
100
9
49
2
4
5
7
41
0.177
3.0
0.45
1.5
14
230
73
26
390
96
8
44
2
3
4
6
27
0.435
3.1
0.28
0.8
6.3
140
32
18
300
34
4
23
0.8
2
2
4
16
0.789
3.2
0.14
0.4
2.4
61
13
13
170
13
2
10
0.4
0.8
0.9
2
7
1.445
3.5
0.06
0.2
1
16
2.5
8
70
5
0.5
3.6
0.15
0.3
0.3
0.5
2.5
2.489
3.8
0.02
0.13
0.7
3.3
3
4
18
4
0.1
0.9
<0.05
<0.06
0.2
0.1
1.6
3.403
3.9
0.01
0.11
0.7
1.7
2
4
9
1
0.07
0.1
<0.05
<0.06
<0.1
0.08
0.7
3.746
3.5
0.06
0.20
3.7
16
<0.5
19
74
1
0.4
0.9
0.25
0.4
0.6
0.9
2.4
3.829
3.5
0.04
0.19
2.9
12
<0.5
11
58
1
0.4
0.6
0.2
0.3
0.3
0.7
3.0
4.017
3.6
0.01
0.13
1.7
5.6
0.5
8
24
1
0.2
0.4
<0.05
0.1
0.2
0.3
1
4.853
3.9
<0.01
0.11
0.6
1.6
<0.5
4
7
1
0.05
0.3
0.06
<().()6
<0.1
0.08
0.4
5.815
3.9
0.01
0.11
0.5
1.1
<0.5
3
5
1
<0.05
<().!
<0.05
<0.06
<().!
0.05
0.3
u>
-------
u>
TABLE J II
COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-24)a
Sample No.
11
15
18
19'
21
23
26
30
31
Vol (&)
pH
TDS (%)
F
Na
Mg
Al
K
Ca
Cr (ng/l)
Mn
Fe
Co
Ni
Cu
Zn
Cd (fj.g/H)
0.208
3.0
0.43
1.1
14
220
68
25
380
92
8
45
1.5
3
4
6
21
0.450
3.2
0.20
0.6
5.8
110
24
18
240
22
3
18
0.7
2
2
3
8
0.784
3.4
0.10
0.33
2.5
53
10
12
160
9
1
9
0.4
0.7
0.8
1
6
1.081
3.4
0.07
0.24
1.7
34
6
11
120
4
0.8
7
0.3
0.5
0.5
1
5
1.483
3.5
0.03
0.15
1.0
19
2
7
62
4
0.4
4
0.15
0.3
0.3
0.4
2
2.483
3.8
<0.01
0.06
0.7
3.2
1
5
20
3
0.1
0.9
<0.05
0.07
<0.1
0.1
0.5
3.127
3.9
0.01
0.06
0.7
1.7
1
4
10
4
0.05
0.5
<0.05
<0.06
<0.1
0.09
0.1
3.443
3.2
0.02
0.11
2.3
11
<0.5
9
38
5
0.3
1
0.15
0.3
0.3
0.4
2
3.610
3.4
0.02
0.11
2.1
11
<0.5
9
40
3
0.3
1
0.15
0.3
0.3
0.5
2
4.035
3.6
<0.01
0.10
1.1
3.9
<0.5
6
16
<1
0.1
0.3
0.05
0.1
0.1
0.2
0.8
4.675
3.8
<0.01
0.07
0.7
1.6
<0.5
5
7
1.6
<0.05
0.3
<0.05
<0.06
<0.1
0.1
0.5
5.393
3.8
<0.01
0.06
0.6
1.3
<0.5
4
5
1.9
<0.05
0.2
<0.05
<0.06
<0.1
0.09
0.8
7.065
3.9
<0.01
0.05
0.6
1.1
<0.5
3
4
<1
<0.05
0.1
<0.05
<0.06
<0.1
0.08
0.7
"Values in ng/m& unless otherwise noted.
bAfter column "air-regenerated"
-------
TABLE J-III
COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-25)a
Sample No.
14
20
24
Vol (I)
pH
TDS (%)
F
Na
Mg
Al
K
Ca
Cr (ng/t)
Mn
Fe
Co
Ni
Cu
Zn
Cd (ne/i)
0.239
2.9
0.49
1.3
15
240
100
26
230
110
9
59
2
4
5
7
30
0.320
3.0
0.33
1.0
8.6
150
62
20
190
80
5
37
1
2
3
5
19
0.570
3.1
0.19
0.6
4.1
91
25
16
140
30
3
18
0.6
1
2
2
9
0.869
3.2
0.09
0.4
2.0
44
11
12
84
12
1
10
0.3
0.6
0.7
1
5
1.334
3.5
0.03
0.1
1.0
15
3
8
42
2
0.5
4.3
0.2
0.25
0.3
0.5
2
2.395
3.7
<0.01
0.08
0.9
3.6
<0.6
5
12
0.8
0.1
1.2
<0.05
0.06
0.1
0.15
1
3.466
3.9
<0.01
0.06
0.7
1.6
<0.5
4
6
0.6
<0.05
0.6
<0.05
<0.06
<0.1
0.09
0.5
6.039
4.0
<0.01
0.06
0.7
1.1
<0.5
3
4
1.1
0.08
0.7
<0.05
<0.06
<0.1
0.06
0.3
"Values in Mg/m.0 unless otherwise noted.
TABLE J-IV
COMPOSITION OF LEACHATE FROM A COLUMN LEACHING OF
PLANT G COAL WASTE (GL-26)a
Sample No.
14
19
"Values in nz/ml unless otherwise noted.
23
Vol (I)
pH
TDS (%)
F
Na
Mg
Al
K
Ca
Cr Mi)
Mn
Fe
Co
Ni
Cu
Zn
Cd (nzlt)
0.086
2.9
0.56
1.6
19
270
120
25
250
170
14
52
2
4
5
9
40
0.174
3.0
0.44
1.1
15
210
87
23
220
100
9
40
2
3
4
7
32
0.827
3.3
0.08
0.2
1.7
35
8
10
74
6
1
6.7
0.2
0.5
0.6
1
11
1.393
3.5
0.02
0.1
0.8
11
1.6
7
38
0.5
0.3
3
0.07
0.2
0.2
0.4
2
2.471
3.8
<0.01
0.06
0.7
2.9
<0.5
4
12
<0.5
0.06
1
<0.05
<0.06
<0.1
0.1
0.5
3.499
3.9
<0.01
0.06
0.7
1.6
<0.5
4
7
0.4
<0.05
0.6
<0.05
<0.06
<0.1
0.1
0.4
6.085
4.0
<0.01
0.06
0.7
0.8
<0.5
3
3
0.9
<0.05
0.4
<0.05
<0.06
<0.1
0.05
0.3
133
-------
I ,n
Q.KJ-
3.0 4.5 6.0 7.5
VOLUME (liters)
LEGEND
= GL-23
=GL-24
=GL-25
=GL-26
3.0 4.5 6.0 7.5 9.0
VOLUME (liters)
12.0
3.0 4.5 6.0 7.5
VOLUME (liters)
4 5 6.0 7.5
VOLUME (liters)
LEGEND
= GL-23
=GL-24
=GL-25
=GL-26
45 60 7.5
VOLUME (liters)
O
O
3.0 4.5 6.0 7.5
VOLUME (liters)
LEGEND
° = GL-23
o=GL-24
«= GL-25
o =GL-26
9.0
10.5
12.0
3-1.
Total, dib&ohxid Aotidb, pH, and tna.ce. &£e.m&nt L&veJU,
G, coat pniipasuition watte..
column
134
-------
Q.
a
o-
0.0 1.5
LEGEND
°=GL-23
°=GL-24
« =GL-25
« =GL-26
3.0 4.5 6.0 7.5 9.0
VOLUME (liters)
12.0
LEGEND
= GL-23
= GL-24
=GL-25
= GL-26
3.0 4.5 6.0 7.5 9.0
VOLUME (liters)
E
a
a
0.0
1.5
3.0
4.5 6.0 7.5
VOLUME (liters)
LEGEND
o = GL-23
o =GL-24
A = GL-25
o =GL-26
9.0
0.0 1.5
3.0 4.5 6.0 7.5 9.0
VOLUME (liters)
Q.
a
o.o
1.5
4.5 6.0 7.5
VOLUME (liters)
10.5
12.0
£
a.
0.0 1.5
I
3.0
—I
4.5
LEGEND
a=GL-23
o =GL-24
«=GL-25
« =GL-26
6.0
VOLUME (liters)
FxLg.
Total dAA&ol\xtd i^oUA^, pH, and
oft Plant G, coal p^epamtton
J-J
c.olmn
135
-------
=GL-24
« = CL-25
» = GL-26
30 45 6.0 7.5 9.0
VOLUME (liters)
10.5 12.0
E"
Q.
3.0 4.5 6.0 7.5
VOLUME (liters)
9.0 10.5
LEGEND
° = GL-23
o = GL-24
3.0 4.5 6.0 7.5 9.0
VOLUME (liters)
10.5 12.0
E
Q.
o
LEGEND
= GL-23
= GL-24
=GL-25
=GL-26
3.0 4.5 - 60 7.5 9.0
VOLUME (liters)
10.5 12.1
Fig. 3-1
Total dLf>4olve.d AotLdb, pH, and
o{ Plant G, coat ptie.paAatA.on
leveJU,
column
136
-------
TABLE J-V
DISCHARGE SEVERITY OF COLUMN LEACHATES FROM
LOW-SULFUR AND HIGH-SULFUR COAL WASTESa>f
Plant
Element Gb A° Cd Be
Fe 4 80 90 500
Ni 3 10 20 50
Mn 0.8 3 2 4
Al
Cu
Zn
Ca
Cd
0.8
0.8
0.6
0.4
0.3
0.8
0.2
0.8
0.4
0.5
0.4
0.2
0.8
0.3
1
10
2
6
0.4
3
Co 0.08 0.3 0.5 1
K 0.01 0.02 0.04 0.01
Cr 0.004 0.001 0.03 0.02
"Based on element values at 2:5 leachate:waste ratio
Discharge Severity = leachate concentration/100/MATE value.
"Average of GL-23-2,GL-24-l,GL-25-l and GL-26-2
data used.
°GL-19-2 data used.
dAverage of GL-8-2 and GL-8-3 used.
"Average of GL-20-1 and GL-20-3 used.
'Health MATE used.
137
-------
APPENDIX K
BIOASSAY RESULTS
LEVEL I BIOASSAY RESULTS
FOR A COAL WASTE AND ITS LEACHATEa'b
Section Test EPA# Performed by
1 Freshwater Algae ^.4.1 LASL
2 Fathead Minnows ^.4.2 LFE EAL, Richmond, CA
:{ Daphnia magna ^.4.2 LFE EAL, Richmond, CA
Mutagenesis (AMES) :U.l LASL
Rabbit Alveolar Macrophage (RAM) ;i.:i.2.1 LASL
Human Lung Fibroblast (WI-38) IU.2.2 LASL
7 ClonalToxicity(CHO) IU.2.:* LASL
8 Quanta! Rodent Toxicity :!..'!.:! LASL
'Composition of (TWT-1012, called LEACHATE,
under Freshwater Algae section.
bSolid waste used, called (iOB, was Plant C, average, waste
#1HA: (JL-21-1 is its 1 day leachate at 5 mi water/g
waste.
I. FRESHWATER ALGAE
(V. Kollman, LASL)
Algal growth assays were based upon the principle of limiting nutri-
ent supply to the growing organism. Growth of a specific alga was
limited by the required nutrient which was present in shortest supply.
The ecological effect studies using coal waste leachate were designed to
determine biological responses to changes in macro- and micro-nutrients
supplied by the waste material. Growth response was determined by adding
a selected alga or various types of algae to the test water and measuring
their growth at scheduled intervals. The test water was evaluated in its
discharged concentration and in numerous dilutions combined with the
appropriate minimal growth medium. Dilutions were used when the con-
centrated test solution was found to be toxic or greatly inhibitory to
the test algae.
138
-------
Seven types of algae -- three green species and four blue-green
species -- and two types of diatoms were used as test organisms in these
preliminary studies. S_._ capricornutum, C_._ vulgaris, C^ pyrenoidosa, and
the diatoms Cyclotella sp. and P^ tricornutum were grown using cool white
fluorescent lamps with an illumination intensity of 400 ft-candles. M^
aeruginosa, A^ flos-aquae, A^ nidulans, and S_^ maxima were grown using
200 ft-candles. The temperature was maintained at 25°C and the cells
were kept in suspension by oscillation of the cultures at 110 cpm.
The test organisms were transferred from agar slants to 30 m£ of
sterile, minimal Ecological Nutrient Medium (ENM) and grown for 7 days in
a nutrient-stressed condition. Only 7-day cultures were used for inocu-
lation of coal waste leachate samples, since these cultures were already
in a stressed condition following their long-term exposure to a growth on
minimal medium.
Nutrient-stressed organisms were cultured on various concentrations
of coal-waste leachate. The diluted culture solutions were made by
adding Ecological Nutrient Medium to the aqueous contaminant (see Table
K-I). One set of test organisms was cultured on a medium in which the
waste leachate was added at levels down to 0.75% of the medium. No
TABLE K-I
TRACE ELEMENT LEVELS IN LEACHATE USED FOR ALGAL TEST
Leachate concentration Diluted Leachate
Element Original Diluted + Algal Medium
1.65
9.2 40
8.30 24.1
0.26 0.68
8.10 22.7
0.01 0.04
0.24 0.79
81.9 226
0.09 0.28
0.18 0.52
0.02 0.06
0.36 1.12
0.005 0.017
F
Na
Al
K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
Cd
pH
TDS (%)
110
610
553
17
540
0.52
16
5460
5.9
12
1.6
24
0.31
1.87
2.56
"Values in ng/ml unless otherwise noted.
139
-------
subsequent adjustment was made in the acidity (pH was 3 or less). All of
these organisms died within 12 h after inoculation. Therefore, the EC
was < 0.75%. A second set of test organisms was grown on coal leachate/
ENM with the pH adjusted to 7.5. At concentrations up to 3% coal waste
leachate and 97% ENM (pH 7.5), both green algae and blue-green algae grew
at rates similar to those for the controls which were maintained on ENM
only. Diatoms were not successfully cultured on either the ENM control
or ENM plus coal-waste leachate. At concentrations of coal-waste leach-
ate greater than 3%, the blue-green algae did not retain their viability;
however, at concentrations up to and including 100% coal-waste leachate,
the green alga Chlorella pyrenoidosa did retain a certain viability.
Only at 50% or greater amounts of coal leachate was there significant
loss of viability. At 50% coal-waste leachate and 50% ENM, 38% of the
cells died. At 100% coal-waste leachate, 62% of the cells died. At
concentrations of coal-waste leachate which were 10% or greater, there
was no visible growth or increase in number of cells of C^ pyrenoidosa.
This may be due, in part, to the decrease in light transmission at the
higher concentrations of coal-waste leachate. The order of adaptability
and viability of the algae to the contaminant was green algae > blue-
green algae > diatoms.
At concentrations of coal waste leachate between 0.75% and 3%, the
algae grew at nearly normal rates. Under these conditions it can be
expected that the growing organisms biologically metabolized or physi-
cally fixed some of the inorganic chemicals present in the contaminant.
The tests chosen to evaluate whether the coal waste materials could
degrade the ecological systems were those under section 3.4 of EPA-600/
7-77-043. The specific tests were 3.4.1 (freshwater algae) and 3.4.2
(both fathead minnows and Daphnia magna. The minnow and Daphnia tests
were run by the Environmental Analysis Laboratories of LFE, Richmond, CA.
The results are reported in Tables K-II and K-III. Only leachate was
tested.
The tests chosen to evaluate the damage the coal waste leachates
could cause to higher animals and humans were listed in the document
EPA-600/7-77-043 [K. M. Duke, M. E. Davis, and A. J. Dennis, "IERL-RTP
Procedures Manual: Level I Environmental Assessment, Biological Test for
Pilot Plants" (April 1977)]. The specific sections used were 3.3.1
(Mutagenesis or AMES test), 3.3.2.1 (Rabbit Alveolar Macrophage or RAM),
3.3.2.2 (Human Lung Fibroblast or WI-38), 3.3.2.3 (Clonal Toxicity or
CHO) , and 3.3.3 (Quantal Rodent Toxicity). Each of these tests was run
at LASL by personnel in our Life Sciences Division (LS-Division). Their
results and observations are included in Tables K-IV through K-VII.
140
-------
TABLE K-II
RESULTS FOR SENSITIVITY OF FATHEAD MINNOWS TO COAL WASTE
LEACHATE
LFE I-:NVIRONME\TAL ANA LYSIS LABORATORIES
2030 Wright Avenue
Richmond, CA 94804
STATIC BIOASSAY REPORT
Company: i^ds Alamos Scientific- ]g.b
Date & Time Sampled:
Control 1
Control 2
Percent
Sample
7,500 pom
4,500 ppm
3 , 500 ppm
2,500 ppm
1,500 ppm
1,000 ppm
6.3
6.3
I
pH
5.5
5.4
5.5
5.6
5.9
6.0
9.8
9.8
litial
D.O.
9.9
9.8
9.9
9.9
9.9
9.8
16.2
16.2
Temp.
16.2
16.2
16.2
16.2
16.2
16.2
pH
10.2
10.4
24 hoi
D.O.
10.2
9.8
9.8
9.8
9.8
9.7
17
17
oca
Temp.
17
17
17
17
17
17
Sampl
Date B
10
10
Surv.
0
6
8
9
10
10
3 Identification: CTWT - 1012
teceived: 2/27/79 Date Started: 3/6/79
pH
9.8
10.0
48
D.O.
10.0
10.2
10.0
10.1
10.0
17
16
tours
Temp.
17.0
17.0
17.0
17.0
16.5
10
in
Surv.
6
8
7
10
8
pH
LO.O
10.0
72
D.O.
9.7
9.6
9.6
9.8
9.8
16.0
15.4
ours
Temp.
17.0
16.2
16.0
16.0
16.0
LFE No. : 979-1-1
96 hr
10
10
Surv.
6
8
7
8
8
6.8
6.7
PH
5.7
6.0
6.7
7.0
7.0
TLM
9.8
9.8
9
D.O.
9.5
9.4
9.6
9.4
9.7
4,500 ppTi
17.9
16.9
B hours
Temp.
17.8
17.8
17.7
17.7
17.6
10
10 ,
i
Surv.l
1
5
8
7
8
8
Species: Fathead Minnow
Min. Length: 3.7 cm
Max. Length: 5.0 em
Ave. Length:- 4.5 cm
Min. Weight: 0.6 gm
Max. Weight: 1.9 gm
Ave. Weight: 1.2 gm
TLMj,4 4,900 ppm TLM4g 4,900 ppm
4,900 ppm TLM96 4-500PP
Vol. Test Soln.. 10 liters
Tank Depth: 28 em
Type aeration: filtered air
No. of fish/cone.: 10 ea.
Acclimatization: 7 days @ 18°C
Mortality In Accl. tank: <1 %
Holding tank salinity: 0 ppt @ 20°C
141
-------
TABLE K-III
RESULTS FOR SENSITIVITY OF Daphnia magna
TO COAL WASTE LEACHATE
LFE ENVIRONMENTAL ANALYSIS LABORATORIES Paphni.
Company: U.C. Los Alamos Sample IdentificatioiCTWT-
Date Received; 2-27-79 Date Started: 4-20-79 Report Checked: M. Clavti
magna BIOASSAY REI'ORT
1012 TFE W.005300-0815
Report Date; Apr-M 27 H7IJ
LFE No. 979-1-1 _
96 hr
1620
Cone.
or
Z
Control 1A
IB
1C
Sontjcol 2A
2B
2C
lOO ppm A
B
C
'25 ppm A
B
C
1275 ppmA
B
C
2275ppm A
B
C
4125 ppmA
B
C
7500 ppmA
B
C
Initial
#
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
pH
6.1
6.1
6.1
6.3
6.3
6.3
6.5
6.5
6.5
6.4
6.4
6.4
6.3
6.3
6.3
6.0
6.0
6.0
5.6
5.6
5.6
4.8
4.8
4.8
Temp.
•c
_17.0
17.0
17.0
16.5
16.5
16.5
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
AIK.
g/1
36
36
32
26
20
16
10
1.2
Hard.
mg/1
60
46
53
63
64
67
64
81
* Alkalinity. Hardness: (mg/1 C«CO3>
24 hours
Surv.
10
10
10
10
10
10
10
9
10
9
10
10
10
9
9
5
6
3
2
1
3
0
0
1
pH
6.2
6.2
6.2
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.5
6.4
6.4
6.4
6.2
6.2
6.2
5.5
5.5
5.5
4.7
4.7
4.7
Temp.
°c
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
EC50 22(1(1
48 hours
Surv.
10
10
10
10
10
10
10
9
10
9
10
10
9
8
8
1
3
0
1
0
0
pH
6.3
6.3
6.3
6.5
6.5
6.5
6.6
6.6
6.6
6.6
6.6
6.6
6.5
6.5
6.5
6.3
6.3
6.3
5.4
5.4
5.4
1
0
4.7
Temp.
•c
16.0
16.0
16.0
16.0
16.0
16.0
_16_J1_
16.0
16.0
16.0
16.0
16.0
16.0
16.0
16.0
16.0
JJLJL
16.0
_16_J1_
16.0
16.0
16.0
EciO 1710
72 hours
Surv.
10
10
10
10
10
10
10
9
10
9
10
10
9
8
8
0
1
0
pH
6.1
6.3
6.3
6.6
6.6
6.6
6.7
6.7
6.7
6.6
6.6
6.6
6.5
6.5
6.5
6.4
6.4
5.4
l
EC50 1630
Temp.
•c
17.0
17.0
17. 0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0-
17.0
17.0-
96 hours
Surv.
10
10
10
10
10
10
10
9
10
9
9
10
9
8
8
0
EC50
PH
6.3
6.3
6.3
6.6
6. f,
6.6
6.7
6.7
6.7
6.6
6.6
6.6
6.5
6.5
6.5
6.5
162(1
Temp.
•c
17. (L
17. n
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
17.0
AIK.
mg/1
38
37
30
26
19
10
2 9
lard.
.g/1
57
57
63
57
59
76
87
84
142
-------
II. MUTAGENESIS (AMES)
(B. Barnhart and S. Wang, LASL)
Negative responses were obtained with and without S-9 activation for
both coal-waste leachate (LEACHATE) and solid coal waste (GOB). The
number of spontaneous revertants/plate was within acceptable limits for
the test strains used.
Spontaneous
Strain Revertants/plate
TA-98 >50 ± 25
TA-100 >150 ± 75
TA-1535 >20 ± 10
TA-1537 >15 ± 10
III. RABBIT ALVEOLAR MACROPHAGE (RAM)
(L. M. Holland and J. Wilson, LASL)
TABLE K-IV
RESULTS OF RABBIT ALVEOLAR MACROPHAGE (RAM) TEST
ON A COAL WASTE AND ITS LEACHATE
Dose"
(mi/mi)
0
0.006
0.02
0.06
0.2
0.6
Viability
(%)
92
77,75
74,57
71,40
3
Too few cells
0.075(Est) 50
"pH adjusted to 7.3-7.6;
precipitate formed;
CTWT-1012 used.
143
-------
IV. HUMAN LUNG FIBROBLAST (WI-38)
(A. Stroud, LASL)
TABLE K-V
RESULTS OF HUMAN LUNG FIBROBLAST (WI-38) TEST
ON A COAL WASTE AND ITS LEACHATE
Leachate Gob
Dose (ml/ml)* Surviving (%) Dose (mg/m.£)a Surviving (%)
0 100 0 100
0.01 94.5 0.05 83.2
0.02 84.8 0.10 80.9
0.03 82.5 0.50 77.2
0.04 76.7 1.0 60.8
O.ll(Est) 50 1.84(Est) 50
"Dose applied 20 hours after incubation; 40 hour total
test period. 5 mi, total size; CTWT-1012 used.
Observations
Leachate test samples were significantly different from controls,
except at the low (0.01 m£/m£) dose.
Gob (waste) test samples were similar to one another but were dif-
ferent from the control. Cells were more sensitive to the gob than they
were to the leachate.
144
-------
V. CLONAL TOXICITY (CHO)
(A. Stroud, LASL)
TABLE K-VI
RESULTS OF CLONAL TOXICITY (CHO) TEST FOR COAL WASTE LEACHATE
Surviving Fraction (%)
Dose"
(ml/mi)
0
0.0025
0.0125
0.025
0.05
20-hour Inoculation"
24 Hourc
100
79.6
65.4
0.02
48 Hourc
100
65.3
57.9
0.02
1-week Inoculation b
24 Hour*
100
94.7
85.5
85.8
48 Hourc
100
99.4
90.7
88.6
"Total media was 4 ml; CTWT-1012 used.
"Time after incubation before inoculation.
"Duration of treatment.
Observation
Colonies became detached and were floating around in the media in
the higher dose samples.
145
-------
TABLE K-VII
RESULTS OF CLONAL TOXICITY (CHO) TEST FOR COAL WASTE SOLID
Surviving Fraction (%)
Dose" 20-hour Inoculation11 1-week Inoculation"
(mg/mi.) 24 Hour0 48 Hour0 24 Hour0 48 Hour0
0 100 100 100 100
0.05 79.6 72.6 91 90.7
0.10 68.3 60.2 91.2 92.4
0.50 15.0 11.1 87.3 86.7
1.0 3.5 1.7 81.6 83.5
5.0 2.2 1.3
"Total media was 5 nuB; gob (#18A) prepared
as suspension in 0.85% NaCl solution.
'Time after incubation before inoculation.
°Duration of treatment.
VI. QUANTA! RODENT TOXICITY
(J. Wilson, LASL)
Tests using the quantal method established the acute, in vivo,
toxicity of a coal-waste leachate (LEACHATE) and coal waste TCOB)as
having an LD5Q greater than 10 g/kg. This test used male and female rats
given one acute intragastric dose of 10 g or 10 mS, per kg body weight
followed by 2 weeks of observation. There were no gross les'ions at
sacrifice.
146
-------
APPENDIX L
pH-CONTROLLED LEACHING OF COAL WASTE,
FLY ASH, AND SOIL
The following procedures were followed: 50-g portions of Plant B
waste (24A, ground to -20 mesh) were placed in 500-m£ Erlenmeyer flasks
equipped with ground glass stoppers. The leaching solutions were pre-
pared according to the descriptions given in Table L-I. Each 200 m£ of
leaching solution was added to the flasks and the pH adjusted with 0. IN
sodium hydroxide. The flasks were purged with argon, capped, sealed with
Parafilm, and placed on a reciprocating shaker. The flask contents were
mixed with ninety 3-1/2-in.strokes per min for 48 h with one interruption
at the 24-h point to adjust the pH and repurge. At the end of the leach
period, the contents of the flasks were vacuum filtered under argon
through Whatman #42 paper and refiltered through 0.45 pm Millipore
filters. The filtrate was analyzed for pH and trace element concentra-
tions. The results are posted in Tables L-II to L-IV. Plots are pre-
sented in Figs. 30 and 31 of the text and Fig. L-l.
TABLE L-I
LEACHING SOLUTION COMPOSITIONS FOR pH-CONTROLLED LEACHING*
CTWT-18 Buffer Soln" !NNaOH(m^)c
20 (+ 3°)
15 (+ 4C)
20(+60C)
20 (+ 3°)
33 (+ lc)
20 (+ 10C)
Additive
1
2
3
4
5
6
7
8
20m£ofA
20 m^ofB
200m£ofC
20m£ofD
20m£ofD
20m^ofD
20m£ofE
12.4gNH2OH-HCl
20m^of30%H202
"Deionized water to give 200 ml.
"Buffer A: 0.5M H2S04 and 0.5M Na2S04
B: 0.5M H3PO4 and 0.5M NaH2P04
C: 4.9g HOAc + 3.7g NaOAc in 1 liter water (ASTM method B)
D: 0.5M NaH2P04 and 0.5M Na2HPO4
E: 0.5M NaHCOa and 0.5M Na2C03
cThis NaOH was added as the leaching progressed to control pH.
147
-------
TABLE L-II
EFFECT OF ACIDITY ON THE LEACHING OF EASTERN FLY ASHS
Buffer Comment pH Ca Fe
la HsI'O."
h
2a H2SO,
h
;ta H,PO.
h
4a HOAc
h
iia HOAc TEPC
h
6a Control
h
7a H,0,°
h
Ha NaH,PO,
h
9a \H,HP(),
h
2.04
2.06
2.82
3.14
3.81
3.91
4.55
4.56
5.00
5.00
5.20
5.43
5.47
5.56
6.76
6.76
9.72
9.73
510
580
430
425
450
410
320
320
52
49
260
310
235
230
14.8
14.8
7.2
7.2
400
380
120
120
0.20
0.06
1.38
1.49
0.03
0.03
0.02
0.01
0.01
0.01
0.01
0.01
0.32
0.32
•From AS'I'M, Phase I, leaching round robin; run in duplicate.
"Kxtra acid to lower pH.
'Original. KI'A.TKI' leaching test.
dAdded to nxidi/.e ferrous to ferric.
TABLE L-III
EFFECT OF ACIDITY ON THE LEACHING OF AN ILLINOIS SOIL3
# Buffer Comment pH Ca Fe
la H,S(),
h
:ia H.O,"
h
4a HOAc
h
fia HOAc TEP"
I)
Ha Control
h
7a \!iH2PO,
h
Ka \H,HP(), 9.51
I)
"From ASTM. 1'hase I. leaching round robin; run in duplicate.
bAdt!ed in oxidi/e ferrous to ferric (note Ca reduction, too).
'Original. Kl'A. TKP leaching test.
1.77
1.88
2.00
2.06
3.85
5.40
4.54
4.55
5.00
5.00
5.62
5.72
6.62
6.64
6.8
9.57
280
290
220
190
4.3
4.2
58
68
0.69
0.92
2.93
1.52
16.0
16.4
0.20
6.6
220
220
360
310
0.62
0.50
0.01
0.02
0.10
2.10
0.06
1.42
0.33
0.16
0.60
148
-------
TABLE L-IV
EFFECT OF ACIDITY ON THE LEACHING OF AN ILLINOIS BASIN COAL WASTE3
CTWT-18 BUFFER COMMENT pH" AI
As
Ca
Cd
Co
Cr
Cu
Fec
Mn
Mo
Ni
Zn
1
2
3
4
5
6
7
8
H2S04
—
H,PO.
HOAc
NaHsP04
NaH2P04
NaH2P04
Na2HP04
Control
NH2OH
H202
1.39
1.91
2.94
4.45
4.51
5.95
6.24
8.98
240
220
29
32
.6
<.2
<.2
<.2
1.7
.9
1.2
.09
.69
.7
.28
.01
170
150
120
120
90
12
13
7
.02
.02
.02
.02
.012
.003
<.003
<.003
3.7
3.6
3.3
3.1
.6
<.01
.1
<.01
.19
.16
.09
.01
<.01
<.01
<.01
<.01
.2
.02
.01
.02
.02
<.01
<.01
<.01
4.6
5.7
.8
1.7
.7
.6
.3
2.2
2740
2430 d
1360
1480
8
17
3
.4
6.7
6.7
5.7
6.0
1.2
.09
.1
<.02
.1
.1
<.l
<.l
<.l
.4
.6
1.2
6.1
5.9
5.9
5.6
2.4
.06
.6
<.02
10
10
6
7
.2
.04
.03
.01
"50 g waste (Plant B, -20 mesh) leached with 200-260 mi
of solution; argon atmosphere used. Data normalized to 250 mi.
Tinal pH value before filtering.
cApproximately all Fe+z.
"2400 ppm Fe+2 and 30 ppm Fe+s
-------
P —1
O •=?
Q
S
r
cr Tt
Q
O
b
IV)
TJ
X
00
ro
IRON IN LEACHATE (ppm)
o
o
o
o
o
DETECTION LIMIT O
I I
-------
APPENDIX M
ATTENUATION OF SEVERAL TRACE ELEMENTS IN A COAL-WASTE
LEACHATE PASSED THROUGH COLUMNS OF SOILS
Two Illinois soils were selected for a preliminary column atten-
uation study. The soils selected were a noncalcareous, weathered loess
(No. 20 in Table XIV of the third annual report) and an unweathered,
calcareous till (No. 110 in Table XIC of the third annual report). The
leachate was CTWT-1012, which is a highly contaminated coal refuse
leachate. The experiment was performed under an argon atmosphere to
prevent air oxidation of iron from ferrous to ferric. Approximately 55 g
of each soil (less than 100 mesh) was placed in a glass column, and
leachate was passed downward through the column under a head of about
3-4 in. Flow was around 1 mJi/h. The pH, Fe++ and total Fe were
monitored for column influent and effluent. Ferric iron was calculated
as the difference between total and ferrous iron and has a very large
error. Selected effluent aliquots were further analyzed for the elements
Al, Ca, Mn and Ni. Results of this experiment are tabulated in Tables
M-I and M-II. Plots can be found in Figs. 37 and 38 of the text.
TABLE M-I
ATTENUATION OF TRACE ELEMENTS IN A COAL WASTE LEACHATE
BY A COLUMN OF UNWEATHERED, CALCAREOUS SOIL11
Sample
Original
Leachate
1
3
4
5
6
7
8
9
10
Effluent
Volume(ml) pH
0 2.0
28
106
160
195
226
255
285
310
320
Al
560
±20
Ca
500
±50
Mn
14.2
±0.5
Fe+2
4000
±300
Fe+3
700
±200
FeT
4700
±200
Ni
12.6
±0.3
6.2
5.5
6.0
-
5.7
6.1
6.0
4.4
3.7
4.1
27.2
5.1
1.0
5.9
4.8
7.2
8.0
550
500
400
450
450
450
550
550
23.2
22.8
23.0
25.2
22.6
22.2
26.3
23.5
1800
4100
4200
-
4300
4000
4600
3600
100
100
0
-
0
0
0
100
1900
4200
4200
4400
4300
4000
4600
3700
6.5
11.9
11.7
13.1
11.8
11.9
13.2
11.9
"Soil properties: pH-8.2; CO3 - 13.4%;
clay - 16.1%; ("EC1 7.7 meq/lOOg; organic matter - 0.91%.
151
-------
TABLE M-II
ATTENUATION OF TRACE ELEMENTS IN A COAL WASTE LEACHATE
BY A COLUMN OF WEATHERED AND LEACHED SOILa
Effluent
Sample Volume (ml)
Original
Leachate
1
2
3
4
5
6
7
8
9
10
11
0
a
17.5
54
93
134
191
251
272
343
387
430
476
pH
2.0
_
3.9
3.5
3.1
2.4
2.2
2.1
2.1
2.2
2.2
2.0
Al
560
±20
430
570
920
1170
750
730
710
640
640
690
690
Ca
520
±50
500
720
510
640
530
530
540
510
510
560
580
Mn
14.2
±0.5
120
215
62
38
19
18.0
18.3
16.5
16.6
18.9
17.6
Fe+2
4000
±300
1800
1900
3800
5000
5200
5100
4200
4900
3700
4700
4600
Fe+3
700
±200
300
300
200
500
500
100
700
400
500
200
600
PgTOTAL
4700
±200
2100
2200
4000
5500
5700
5200
4900
5300
4200
4900
5200
Ni
12.6
±0.3
8.0
11.6
13.0
18.3
14.0
13.8
14.3
13.3
12.8
15.1
14.6
"Soil properties: pH - 5.6; CO3 - 0.0%;
clay - 35.9%; CEC - 27.9 meq/lOOg; organic matter - 0.47%.
152
-------
APPENDIX N
SPARK SOURCE MASS SPECTROMETRY SAMPLE PREPARATION AND ANALYSIS
(R. M. Abernathy, C. F. Hammond, J. E. Alarid,
S. F. Marsh, and J. E. Rein), LASL
Multielemental, quantitative analysis of coal materials by spark
source mass spectrometry (SSMS) requires chemical pretreatment of the
sample to destroy remaining organic components, which produce charged
ions over the entire atomic mass region. A two-step dissolution treat-
ment has been developed that completely eliminates organic components and
ensures a homogeneous distribution of sample elements and the added
internal standard(s). The dissolution consists of igniting pulverized
samples in air at 500°C for 4 h and dissolving the ash completely in an
acid mixture using a LASL-developed, Teflon-container, metal-shell
apparatus (now manufactured by the Parr Instrument Company). The acid
mixture is 6 volumes 12M HC1, 1 volume 15.6M HNO 1 volume 29M HF, and 2
volumes water. Dissolution of 100 mg of coal asn in 5 m£ acid mixture is
accomplished in 12 hours at 200°C. The solution of the ash and a
measured portion of the internal standard solution are added to 150 mg of
graphite (spectroscopic grade) in a polyfluorinated plastic container.
The mixture is dried and ground with a mortar. Ethanol is added and the
mixture is again dried, homogenized in a Wig-L-Bug mixer, and pressed
into an electrode.
For the initial analyses, an erbium internal standard and photoplate
detection were used. A major effort is under way to establish more
accurate sensitivity factors for about 70 elements and to develop a
procedure in which different internal standard elements will be used at
low, medium, and high mass regions. Current results for NBS 1632 coal
are listed in Table N-I.
153
-------
TABLE N-I
TRACE ELEMENT LEVELS IN NBS 1632 COAL
BY SPARK SOURCE MASS SPECTROMETRY*
Element Literature b LASLC
Element
Literature11 LASLC
Ag
Al
As
Au
B
Ba
Be
Bi
Br
Ca
Cd
Ce
Cl
Co
Cr
Cs
Cu
Dy
Er
Eu
F
Fe
Ga
Gd
Ge
Hf
Hg
Ho
I
Ir
K
La
Li
Lu
Mg
Mn
(<0.1) d
18500 f
5.9 d
50 *
352 f
(1.5) d
0.4 «
8*
4300 f
0.19 d
19.5 '
890 f
5.9 f
20.2 d
1.4 f
18 d
2"
0.7 B
0.33 f
500."
8700 d
8.5 h
1 g
1 g
0.96 f
0.12d
1 g
2s
2800'
10.7 r
60 g
<0.3 g
2000 '
40 d
0.1
3900
<0.01
4
220
0.05
1600
0.2
16
250
(1600.) J
15
0.06
70
1
0.9
0.7
3500
2
6
0.7
4
0.4
0.2 e
0.3
5600
9
30
0.4
570
25
Mo
Na
Nb
Nd
Ni
P
Pb
Pd
Pr
Pt
Rb
Rh
Ru
S
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Tb
Te
Th
Ti
Tl
Tm
U
V
w
Y
Yb
Zn
Zr
3.4 h
414 f
11 *
6*
15 d
71'
30 d
2"
21 f
14300 '
3.9 f
3.7 f
2.9 d
(32000.) d
1.7 f
2"
161 f
0.24 f
0.4 *
«0.1) d
3.2 f
1100 f
0.59 d
0.2 *
1.4 d
35 d
<1«
7*
<1"
37 d
45 h
1
450
1
8
30
80
20
20
2
<0.1
19
0.1
0.01
30 e
5
2
2
4
95
2
0.3
1
2800
0.3
0.5
0.4
20
5
0.4
15
15
aElemental concentrations are in ppm.
b"Best" of a number of sources.
C0thers: AA and NAA data; SSMS: spark source mass
spectroscopy.
dNBS values; those in parentheses are not certified.
"Volatile; some or extensive loss during dissolution
expected.
fOndov et al. Analytical Chemistry
47, 1102(1975).
154
^Private communication from Commercial Testing and
Engineering Co.
"Klein et al. Environmental
Science and Technology 9, 973 (1975).
'LASL (LA-6835-PR, 1st Annual Report).
JContaminated during sample preparation?
-------
APPENDIX 0
RAINWATER FLOW THROUGH A COAL WASTE DUMP
The bulk density of high-sulfur coal preparation waste is approx-
imately 125 lb/ft3. A 30-ft high pile of this waste would occupy an area
326 ft square or 100,000 ft2. In a location receiving 30 in.of rain per
year, 42 m£ of water per kilogram of waste would enter the pile if 100%
percolation is allowed. Laboratory column leaching shows that 2 £ of
water are needed to wash the pollutants from each kilogram of the waste.
Without the intrusion of groundwater, 48 years would be required to purge
the pile if the waste did not generate further pollutants and if all the
rain percolated through the waste. Rainwater runoff and evaporation and
waste oxidation would increase the time, while groundwater recharge would
reduce it.
155
-------
TECHNICAL REPORT DATA
(Please read Instructions an the reverse before completing/
. REPORT NO.
EPA-600/7-81-073
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE Trace Element Characterization of
Coal Wastes: Fourth Annual Progress Report
6. REPORT DATE
April 1981
6. PERFORMING ORGANIZATION CODE
7 AUTHORIS) J.M.Williams, J. P. Bertino, M.M.Jones,
P.Wagner, P.L.Wanek, L.E.Wangen, and
E.M.wewerka
3. PERFORMING ORGANIZATION REPORT NO.
LA-8275-PR
9. PERFORMING OROANIZATION NAME AND ADDRESS
Los Alamos Scientific Laboratory
University of California
Los Alamos , New Mexico 87545
10. PROGRAI
INE825
11. CONTRACT/GRANT NO.
IAG-D5-E681
)2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
)3. TYPE OF REPORT AND PERIOD COVERED
Final; 10/78-9/79
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES iERL.RTp project officer is David A. Kirchgessner, Mail Drop
61, 919/541-4021. EPA-600/7-79-144 and EPA-600/7-78-028 and -028a are the three
previous progress reports.
I?. ABSTRACT ". " .,
The report describes progress during the year of a trace element character
ization of coal wastes. Assessments continued of low-sulfur coal wastes from the
Appalachian Region, including mineralogical and trace element analyses of the
materials, and studies of their weathering and leaching behavior. Although the acid-
forming mineral (pyrite and marcasite) concentrations were very low, leachates
were quite acid (pH < or = 3) with concomitant trace element (Al, Mn, Fe, Ni, Cu)
concentration elevation. Bioassays, part of the overall assessment of the degree of
environmental concern associated with acidic coal waste drainage, revealed that
coal wastes and their leachates are toxic to freshwater algae, fathead minnows, and
a species of freshwater flea. Experiments to identify control options for coal wastes
and their drainage have focused on predisposal and co-disposal waste treatment,
with technical and economic evaluations of the most promising options. One of the
most promising is waste pretreatment with a lime/limestone mixture, producing a
waste with no acid-forming tendencies for up to several months, during which time
it may be possible to dispose of the treated waste in a nonreactive environment. The
cost of this option compares to that of the commonly used lime neutralization of
acid drainage.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Pollution
Coal
Waste Treatment
Properties
Analyzing
Chemical Analysis
Weathering
Leaching
Bioassay
Toxicity
Calcium Oxides
Calcium Carbonates
Pollution Control
Stationary Sources
Coal Wastes
Characterization
Trace Elements
13B
08G
14G
14B
07D
07A
06A
06T
07B
3. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS /This Report)
Unclassified
21. NO. OF PAGES
172
20. SECURITY CLASS (This page)
Unclassified
EPA Form 2220-1 (1-71)
156
S. GOVERNMENT
OFFIC6M 961 -0-7 77-02 2/94
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