EPA
United States
Environmental Protection
Agency
Office of
Research and
Development
Industrial Environmental Research
Laboratory
Cincinnati, Ohio 45268
EPA-600/7-77-067
June 1977
PALEOENVIRONMENT OF COAL
AND ITS RELATION TO
DRAINAGE QUALITY
Interagency
Energy-Environment
Research and Development
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
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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)
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This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
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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
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essary environmental data and control technology. Investigations include analy-
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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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EPA-600/7-77-067
June 1977
PALEOENVIRONMENT OF COAL AND ITS
RELATION TO DRAINAGE QUALITY
by
Frank T. Caruccio, John C. Perm, John Home
Gwendelyn Geldel and Bruce Baganz
University of South Carolina
Columbia, South Carolina 29208
Grant No. R-802597-02
Project Officer
Elmore C. Grim
Resource Extraction and Handling Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory - Cincinnati, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
ii
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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our environment
and even on our health often require that new and increasingly more
efficient pollution control methods be used. The Industrial Environ-
mental Research Laboratory-Cincinnati (lERL-Ci) assists in developing
and demonstrating new and improved methodologies that will meet these
needs both efficiently and economically.
Reported here are the results of a study to develop a method
whereby the quality of drainage expected from a mine located in a
specific strati graphic horizen can be approximated. Consequently, the
data provided by this method can be utilized in the decision making
process concerned with the economic benefits of resource extraction
versus the degree of anticipated stream pollution and the cost of
reclamation. This research will be of interest to both the mining
industry and state and federal agencies associated with coal extraction.
For further information contact the Extraction Technology Branch of the
Resource Extraction and Handling Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii
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ABSTRACT
The acid production potential of a coal was related to the coal's paleo-
environment (environment of deposition) as interpreted from the overlying
strata. .Within a triangular area between Hazard, Ashland and Grayson in the
Appalachian coal field of eastern Kentucky, excellent rock exposures were af-
forded by a newly constructed highway system. The coals and associated strata
were mapped to determine their paleoenvironment and characterized as either
back-barrier, lower delta plain or upper delta plain.
Coals were sampled from various paleoenvironments and analyzed for sulfur
content and distribution of pyrite types (reactive versus stable). The varia-
bility in the total sulfur contents of coal samples of uniformly distributed
and geologically split seams was greater than expected. In the microscopic
examination of coals, samples collected from the back-barrier, lower delta
plain sequence contained a relatively higher percentage of reactive framboidal
pyrite than the samples collected from seams within strata of upper delta
plain. Both environments produced coals of similar total sulfur contents and
both contained varying percentages of framboidal pyrite. Although reactive
pyrite was present in seams of both paleoenvironments, a differing water chem-
istry caused acid mine drainage to be associated with the back-barrier, lower
delta plain strata and never with the upper delta plain strata.
Water samples were collected from springs and seeps from the locales from
which the coal samples were obtained and analyzed for pH, conductivity, sul-
fate, acidity and hardness. High sulfate-highly acidic, low buffered seeps,
when present, flowed from strata of lower delta plain and some transitional
sequences. High sulfate-neutral, highly buffered drainages emanated from
strata of the upper delta plain. The presence of sulfate in water collected
from all paleoenvironments indicates the presence of reactive pyrite in the
sections, substantiating the results of the microscopic analyses.
For the area studied in eastern Kentucky, strata producing acidic drain-
ages are characterized as having pyrite in the framboidal form and a paucity
of a natural water buffering capacity. These rocks are associated with lower
delta plain-back barrier sequences. On the other hand, strata which produce
low to high sulfate-neutral drainages have relatively lower percentages of
framboidal pyrite and are associated with highly buffered alkaline-water sys-
tems of alluvial-upper delta plain sequences.
This study showed that the.pyrite distribution and, more importantly, the
water chemistry producing acidic or neutral drainages, were correlative with
the paleoenvironment of the coals and associated strata. Thus, it appears
that mapping coals within the context of their paleoenvironment provides a
tool that can be used to approximate the quality of drainage that can be ex-
pected from a proposed mining operation.
iv
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CONTENTS
Abstract iy
Figures vif
Tables x
I. Summary and Conclusions 1
Background 1
Methodology 2
Results . 3
II. Introduction
The Occurrence of Acid Mine Drainage 5
Background of the Problem 5
Factors Affecting Mine Drainage Quality .... 6
The Association of Acid Mine Drainage with
the Deposit!onal Environment (Paleoenvironment)
of Coal and Strata 9
Previous Studies 9
Prediction of Acid Mine Drainage
Pollution Problems 10
Definition of and Criteria for Recognition
of Various Paleoenvironments 11
Hypothesis to be Tested 17
III. Method of Study and Data Procurement 18
Area of Study 18
Coals 18
Method of Mapping 18
Method of Sampling and Depicting Data 20
Analyses 21
Water Chemistry of Coal Seeps 24
IV. Data and Interpretations 30
Variability of Total Sulfur Content of Coal 30
Variability Within Seams of Varying
Paleoenvironments 30
Variability Within a Uniform Seam ....... 33
Variability Within a Split Coal Seam 44
Laboratory Precision of Analyses 44
Limits of Interpretation 44
Occurrence of Framboidal Pyrite 46
Types of Pyrite 46
Method of Identification and Calculation
of Percentages of Reactive Pyrite 54
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Comparison of Framboidal Pyrite
Contents of Various Paleoenvironments 58
Leaching Tests 62
Sample Selection 62
Method of Study 62
Results 64
Aqueous Geochemistry 66
pH and Conductivity Trends Across
Varying Paleoenvironments 66
Regional Water Quality Characteristics 68
Conclusions 71
References , 73
Appendices
A-l. Total Sulfur and Pyrite Type Percentages of
Coal Samples 78
A-2. Pyritic Sulfur and Framboidal Pyrite Percentages
Calculated From Total Sulfur Contents . 89
B. Chemical Analyses of Water Samples Collected From
Eastern Kentucky in the Area of Study 102
vi
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FIGURES
Number Page
1 Diagrammatic representation of the carboniferous
rocks and their depositional environments between
Ashland and Olive Hill, Kentucky 12
2 Location map of geologic cross-sections 19
3 Flow sheet for sample preparation and analysis 23
4 Geologic cross-section of Princess coals along 1-64
near Rush, Kentucky 32
5 Geologic cross-section of the Princess Five coal along
Kentucky 60 south of Meads, Kentucky 34
6 Geologic cross-section of the Princess Five coal along
Kentucky 60 north of Meads, Kentucky 35
7 Geologic cross-section along 1-64 near Grayson, Kentucky .... 36
8 Geologic cross-section along 1-64 near Olive Hill, Kentucky . . 37
9a Geologic cross-section along Daniel Boone Parkway near
Hazard, Kentucky (western half) 40
9b Geologic cross-section along Daniel Boone Parkway near
Hazard, Kentucky (eastern half) 41
10 Total sulfur contents of third-column samples of the
Princess Seven coal collected one inch (2.54cm) apart 42
11 Total sulfur contents of quarter-column samples collected
at PR5K/7 43
12 Photomicrograph of tracheids replaced by pyrite
(Sample PR7K/2-L 1/3) 47
13 Photomicrograph of fusinite encapsulating massive
pyrite (Sample PR7K/2-L 1/2) 47
14 Photomicrograph of plant cells replaced by pyrite
(Sample TCK3/1-M 1/3) 48
vii
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FIGURES (continued)
Number Page
15 Photomicrograph of massive pyrite grains within
plant material (Sample TCK/4-L 11") 48
16 Photomicrograph of pyrite crystals disseminated
within a coal (Sample P.R7K/2-M 1/3E) 49
17 Photomicrograph of pyrite crystals clustering along
layers (Sample PR7K/2-M 1/3E) 49
18 Photomicrograph of pyrite crystals within spherical
agglomerations (Sample below Hindman 9, Hazard,
Kentucky area) 50
19 Photomicrograph of pyrite within cleats (fractures)
in coal (Sample PR7K/2-T 1/3W) 52
20 Photomicrograph of pyrite filling fractures in coal
(Sample TCK/9-CH) 52
21 Photomicrograph of framboidal pyrite (Sample below
Hindman 9, Hazard, Kentucky area) 53
22 Photomicrograph of spheres of framboidal pyrite
(Sample H,indman 9 coal, Hazard, Kentucky area) 55
23A Photomicrograph of clusters of framboidal pyrite
along layers, at 300X (Sample TCK/2-L 1/2) . 56
23B Photomicrograph of clusters of framboidal pyrite
along layers, at 600X (Sample TCK/2-L 1/2) 56
24 Photomicrograph of framboidal pyrite scattered throughout
the coal (Sample PR7K/2-L 1/3W) 57
25 Distribution of framboidal pyrite and total pyrite
for coals collected from the Hazard area and grouped
into paleoenvironments 59
26 Distribution of framboidal pyrite and total pyrite
for coals collected from the 1-64 road cuts and
grouped into paleoenvironments 60
27 Geologic cross-section of carboniferous rocks between
Pine Ridge and Vicco, Kentucky showing locations of
samples used in the leaching study 63
viii
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FIGURES (continued)
Number Page
28 Plot of cumulative acidities per 100 grams of
samples of varying paleoenvironments 65
29 Conductivities and pH of water samples collected
along 1-64, eastern Kentucky 67
30 Conductivities of water samples from various
pal eoenvi ronments - » 69
31 Sulfate content (mg/1) of water samples from
various pal eoenvi ronments 70
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TABLES
Number Page
1 Criteria for Recognizing Depositional Environments ........ 16
2 Explanation of Coal Identification Codes and the
Paleoenvironments Represented by the Samples
Collected for This Study 22
3 Total Sulfur Percentages of Samples Collected from
the Princess Seven Coal 31
4 Total Sulfur Contents of Third-Column Samples of
the Princess Seven Coal Collected One Inch (2.54cm)
Apart at PR7K/2 39
5 Total Sulfur Contents of Quarter-Column Samples of
the Princess Five Coal Collected at PR5K/7 39
6 Description of Samples Used in the Leaching Study 62
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SECTION I
SUMMARY AND CONCLUSIONS
BACKGROUND
Iron disulfides (FeSa) occurring either as marcasite or pyrite in the
coal and associated strata are exposed to the atmosphere during mining pro-
cesses and readily oxidize to a series of hydrous iron sulfates. These sul-
fate compounds are soluble in water and produce mine drainages that commonly
have a pH in the range of 2, contain acidities that range from 400-2000 mg/1
(as CaC03), iron concentrations of 50-500 mg/1 {as ferrous iron), and sulfate
contents in the range of 500-12,000 mg/1 (as SO;;).
It, has been shown by Caruccio (1968) that in coal mines of the Allegheny
Group of Pennsylvania the degree of acidity is a function of (1) the calcium
carbonate content of the strata (which produces a neutralizing medium), (2)
the pH of the ground waters before mining (which controls the occurrence of
the various types of "iron bacteria" that catalyze the acid producing chemi-
cal reaction), and (3) the mode of occurrence of the iron disulfide.
Iron disulfide occurs in coal strata as euhedral grains, coarse grained
(greater than 25 microns) masses which replaced the original plant matter,
coarse grained platy masses occupying joints in the strata, and framboidal py-
rite. The latter occurs as clusters of spherical agglomerates comprised of
0.25 micron grains of iron disulfide and are finely disseminated throughout
the coal and associated strata. Of these basic types of pyrite, it is only
the last one, the framboidal type, that decomposes rapidly enough to produce
severe acid mine drainage (Caruccio, 1970). The other types of iron disulfide
decompose at relatively slower rates; the amount of acidity produced is gen-
erally low and can be neutralized by minor amounts of alkalinity produced by
the calcium carbonate found in the rocks. Strata containing large amounts of
"sulfur" occurring as framboidal iron disulfide will produce more acid than
strata containing equal amounts of "sulfur" composed of coarse grained non-
framboidal iron disulfide. Consequently, the severity of acid mine drainage
pollution from coal mines is, in part, a function of the amount of framboidal
iron disulfide in the rock sequence that is exposed to the atmosphere by the
mining process.
The occurrence of the framboidal iron disulfide within a particular rock
unit is correlative with the paleoenvironment of the stratum; i.e., the con-
ditions under which the rock was deposited control the formation, deposition
and occurrence of the framboidal iron disulfide. This association (framboidal
pyrite related to certain paleoenvironments) is the key to identifying coal
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strata which when mined, will produce acid mine drainage pollution.
Contemporaneously with Caruccio's work, Perm and his associates (Perm et
al., 1959), Perm and Williams (1962, 1964, 1965), Perm et al. (1967), Perm and
Cavaroc (1968), and Perm (1975) were engaged in an extensive program of recog-
nizing and mapping environments of coal deposition in the Appalachian coal
field from Pennsylvania to Alabama. By comparing ancient coal bearing rocks
to modern depositional analogues, a set of criteria has been developed for
recognizing environments which range from alluvial plains through upper delta
plain and lower delta plains grading into a tidally influenced back barriers
and beach barriers. Applying these criteria to Caruccio's Pennsylvania data,
the coals and associated rocks rich in framboidal pyrite would be recognizable
as back barrier and lower delta plain deposits and strata with relatively less
framboidal pyrite would be associated with upper delta and alluvial plain set-
tings.
Because many Appalachian coal beds are known to represent several differ-
ent environments in different places, and because others can be recognized as
belonging to at least two environments, a criterion appears to be available
for predicting the occurrence of framboidal pyrite without costly and time
consuming analytical procedures. Strata and coals of varying paleoenviron-
ments could be mapped (in both vertical and horizontal distributions) and .
zones rich in framboidal pyrite delineated. Having constructed these maps,
areas can be identified that would, in advance of the active mining stage, de-
lineate mines that would create major and minor environmental impacts from
acid mine drainage pollution.
METHODOLOGY
A triangular area within the Appalachian coal field of eastern Kentucky
(between Hazard, Ashland and Grayson) was selected for study because of the
excellent rock exposures afforded by the newly constructed highway system.
From these exposures, paleoenvironmental profiles were constructed and samples
of coals of the various depositional environments of coals could be sampled.
Samples of coals collected along the Daniel Boone Parkway in the Hazard area
and along 1-64 in the Ashland-Grayson area were processed and analyzed for to-
tal sulfur. Representative sample splits were polished and examined by re-
flected light microscopy to ascertain the proportion of framboidal pyrite oc-
curring in the sample.
Some of the samples were used in a laboratory experiment that was de-
signed to test the acid production potential of coals from various paleoenvi-
ronments. Selected samples of coals were crushed to uniform sizes to stand-
ardize the surface area between samples. The samples were weighed and placed
in plastic chambers where humidified air continuously passed over the samples.
Periodically the samples were flushed with de-ionized water, the effluent vol-
ume recorded and hot acidity determinations were made on an aliquot of leach-
ate. Acidity values were then adjusted to a common base and expressed as mil-
ligrams of hydrogen produced per 100 grams of sample. Cumulative acidity gen-
erated by each sample over a time period was then calculated and related to
the acid production potential of coals representative of a particular
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paleoenvironment.
In a field geochemical survey, water samples were collected from springs
and seeps emanating from the coal faces from which the coal samples were col-
lected. Because the quality of ground water reflects the overall geochemistry
of the strata and samples a larger geologic regime, the analyses of specific
chemical quality parameters would serve to corroborate the data obtained from
the sulfur analyses and the pyrite morphology distribution studies.
RESULTS
The field survey that was designed to test the variability of total sul-
fur occurring in channel and column samples of coal seams showed that the per-
centages of total sulfur contents varied to a greater degree than was expect-
ed. Sulfur percentages varied greatly between column and channel samples col-
lected from coals that were uniformally distributed over great distances as
well as those that were stratigraphically split.
Pyritic sulfur contents were calculated from total sulfur contents of in-
dividual samples. These data were adjusted to give an average value for the
total seam. When values of seams were plotted within groups of coals of simi-
lar paleoenvironments, patterns emerged that showed framboidal pyrite to be
associated with back barrier and lower delta plain sequences. Samples that
were collected from seams within strata of upper delta plain were also noted
to have a variety of pyrite types, including framboidal pyrite. A Chi Square
test and one way analysis of variance test both showed that there were signi-
ficant differences between the framboidal content of the marine-brackish water
and fresh water paleoenvironments, the former having a greater proportion
than the latter. Additionally, a significant difference in the total sulfur
contents was noted between the samples collected along the 1-64 (Ashland-
Grayson) area and the ones from the Hazard area, the former having a greater
total sulfur content than the latter.
The results of the leaching test showed that samples collected from the
back barrier-lower delta plain sequences produced abundant quantities of acid-
ity, whereas those from the upper delta plain did not. Fortuitously, acid
producing samples used in the leaching test had higher pyritic sulfur contents
than the neutral samples which had a paucity of sulfur. As a result, the lack
of acid production could be attributable to the lack of pyrite and not direct-
ly related to the absence or presence of framboidal pyrite. This possibility
precluded a strong correlation between acid production potential and paleoen-
vironment.
The ground water seeps that were collected from strata exposed in the
highway cuts and mine faces were analyzed for pH, conductivity, acidity, hard-
ness and sulfate. High sulfate-highly acidic seeps, when present, occurred in
strata of lower delta plain and some transitional sequences. On the other
hand, high sulfate-neutral drainages emanated from strata in the upper delta
plain dequence. The fact that high sulfate drainages flow from both types of
strata suggests that reactive framboidal pyrite is present in strata of both
paleoenvironments, but, as indicated previously from the results of the
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microscopic analysis, with relatively smaller percentages of the reactive py-
rite occurring in the upper delta plain sections, and relatively greater per-
centages of framboidal pyrite in the lower delta plain-back barrier sequences.
Field studies showed that within a regional framework, the natural wa-
ters of strata of a lower delta plain-transitional paleoenvironment do not
have sufficient buffering capacity to offset the acidity produced. Converse-
ly, the waters of strata of an upper delta plain paleoenvironment contain suf-
ficient alkalinity to offset and neutralize the minor amounts of acidity pro-
duced by the smaller percentages of framboidal pyrite present.
For the area studied in eastern Kentucky, strata which produce acidic
drainages are characterized as having most of the pyrite in the framboidal
form and a paucity of a natural water buffering capacity and are associated
with lower delta plain-back barrier sequences. On the other hand, strata
which produce low to high sulfate-neutral drainages also contain framboidal
pyrite but are associated with highly buffered alkaline-water systems in allu-
vial-upper delta plain sequences. Thus, the distribution of framboidal py-
rite, in combination with the concentration of alkalinity of natural waters,
determines the quality of drainage from various strata. This study showed
that both of these parameters were identified and correlated with the paleoen-
vironment of the coals. It appears, therefore, that mapping coals in the con-
text of their depositional environments provides a tool that can be used to
approximate the quality of drainage that can be expected from a mine sited in
a particular strati graphic horizon.
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SECTION II
INTRODUCTION
THE OCCURRENCE OF ACID MINE DRAINAGE
Background of the Problem
The coal resources of the United States will undoubtedly play a major
role in the future energy policy of this country. Various mining techniques
available for the extraction of this energy resource from the ground dis-
rupt the natural system and place various degrees of stress on the environ-
ment. In some cases, the mining process disrupts undisturbed rock strata and
in addition to the physical disruption of the natural system, generates chem-
ical imbalances which impose tremendous stresses on natural aqueous systems.
The problem most prevalent and associated with coal mining in the bituminous
coal fields of the eastern United States and one that has a major Impact on the
environment is the generation of acid mine drainage. One of the objectives
in this study was to identify strata which have a high acid production capa-
bility and accordingly, predict the occurrence of acid mine drainage in ad-
vance of mining.
Acid mine drainage is, as the name implies, an extremely acidic, iron
sulfate rich drainage that forms under natural conditions when certain coal
seams are mined. When coal is mined, the iron disulfides, occurring either
as marcasite or pyrite, which are commonly associated with the coal and
overlying strata, are exposed to the atmosphere and oxidize in the presence
of humidity and oxygen to form soluble hydrous iron sul fates. Subsequent
natural water movement dissolves these compounds which chemically react to
produce a highly acidic drainage with attendant high concentrations of iron
and sulfate. Although this process is generally accepted as the mechanism
by which acid mine drainage is formed, the exact chemical reactions are not
fully understood.
Chemical reactions explaining the oxidation of the iron disulfide and
the generation of acidity are given by the following equations:
FeS2(s) + 7/2 02 + H20 = Fe++ + 2SO= + 2H+ (1)
Fe""" + %02 + H+ = Fe+++ + ^0 (2)
Fe"1"*"1" + 3H20 = Fe(OH)3(s) + 3H+ (3)
FeS2(s) + 14Fe+++ + 8H20 = ISFe^ + 2SO* + 16H+ (4)
Singer and Stumm (1968)
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On the surface of a weathered coal mine face, yellow and white crusts
commonly occur along certain horizons within the strata. These white and
yellow salts are the oxidation products of the pyrlte and are the crystal-
lized products of equation 1. Some of the products have been identified as
melanterite (white crystals of ferrous sulfate), coplapite (yellow crystals
of ferric sulfate), halotrichite (white crystals of iron or magnesium sul-
fate), and alunogenite (white crystals of aluminum sulfate) (Lorenz, 1962).
The ferrous iron generated 1n the reaction described in equation 1 can
be further oxidized to the ferric state 1n accord with equation 3 and gener-
ate additional amounts of acidity. It has been estimated by Stumm and Lee
(1960) that a large part of the acidity generated in acid mine drainage pro-
duction arises from the oxidation of ferrous Iron to ferric iron. The fer-
rous and ferric hydroxides associated with the chemical reaction in equation
3 impart the red and yellow-orange color that is characteristic of acid mine
drainage. The precipitated iron hydroxide is the "yellow boy" that is com-
monly observed in streams and coal mine areas.
Factors Affecting Mine Drainage Quality
Acidity (Sulfur as iron disulfide)
Sulfur in coa.1 can occur as organic sulfur, pyritic sulfur or sulfate
sulfur. Organic sulfur is that component which is incorporated in the plant
structure and is organically bound within the coal. In general, the organic
component is not chemically reactive. Sulfate sulfur usually represents the
water soluble weathering products of the disulfides and 1n most cases con-
stitutes a very small percentage of the total sulfur measured in a section.
Pyritic sulfur 1s that sulfur which is found in the disulfide phase usually
as either marcasite or pyrite.
Studies by Mansfield and Spackman (1965) have shown that variations in
the total sulfur contents of coal samples collected from the bituminous coal
field of western Pennsylvania reflect variations in pyritic sulfur contents.
In their study the organic sulfur content of a particular coal seam remained
relatively constant from the top to the bottom of the seam. Although the
values of organic sulfur varied from 0.5 to 2% between seams, variations in
total sulfur content expressed variations in pyritic sulfur content within
each seam.
In comparing two areas in central Pennsylvania, Caruccio (1968) showed
that the occurrence of acid mine drainage produced in the strip mine areas
could not be related to the sulfur content of the coals and overlying strata.
The two areas in Pennsylvania, one containing strip mines that produced acid,
while the other containing mines with non-acid drainages, had strata with
total sulfur contents which varied and overlapped and whose values were ap-
parently similar. Microscopic examination of polished samples of coal and
rock strata collected from the non-acid producing area showed them to con-
tain abundant amounts of pyrite as well as total sulfur percentages that
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were similar to the samples from the acid producing area.
In a combination of studies, selected samples of coal and rock were
placed in leaching chambers and periodically flushed with distilled water.
The quality of the leachate collected from each sample was analyzed and the
degree of acidity produced by each sample ascertained. Representative splits
of the samples used in the leaching chambers were analyzed for sulfur con-
tents and equal portions cast in polished pellets for microscopic examina-
tion. Caruccio (1968, 1969) found that the pyrite morphology was signifi-
cantly different between the samples that produced acid and those that did
not, even though the total sulfur contents were similar.
In addition, there was a significant variation in the pyrite morphology
between samples from the two areas of study. In samples from the non-acid
producing area the pyrite commonly had a massive form and appeared to be sec-
ondary in origin. Most of the grains were greater than 400 microns and com-
monly had a morphology that suggested that the pyrite had replaced plant
structures and occupied joints in the coal. In samples from the acid produc-
ing area, however, a major portion of the pyrite occurred as clusters of
spheres measuring approximately 25 microns in diameter. Each of the spheres
was an agglomeration of minute crystals of pyrite approximately 0.25 microns
in-diameter that collectively had a globular morphology. Gray, Shapiro and
Coe (1963) called attention to this type of pyrite occurring in the Pitts-
burgh seam of Pennsylvania, which is called framboidal pyrite.
In terms of reactivity, Caruccio showed that framboidal pyrite is much
more reactive and less stable than the massive secondary pyrite (1969, 1973).
Samples containing framboidal pyrite when left in the lab were noted to
readily decompose to produce the salt crusts that appear on the surface of
the coals and which are products of the oxidation process. On the other
hand, coarse grained particles of pyrite were noted to remain shiny and
brassy for indefinite periods of time and did not show appreciable signs of
weathering. Subsequent studies by Caruccio (1970) showed that the percen-
tage of framboidal pyrite within samples of similar permeabilities, multi-
plied by the total pyrite content of that sample can be used as a measure of
the acid producing potential of that particular sample. In this manner,
samples could have high amounts of pyritic sulfur but if occurring as massive
coarse grained secondary types will tend to remain stable and not produce
acid. In contrast* if framboidal pyrite were to be present then it is ex-
pected to readily decompose and produce acid. On this premise, and in view
of the natural limits of alkalinity imposed by the carbonate-bicarbonate ge-
ochemical reactions, the occurrence of acid mine drainage can be directly
related to the occurrence of framboidal pyrite within a coal seam and asso-
ciated strata.
Alkalinity (Calcareous material)
The preceeding discussions show that the amount of acidity produced is
a function of and dependent upon the amount of iron disulfide that is avail-
able for decomposition in the presence of oxygen and ferric ion (Smith and
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Shumate, 1970). Given a fixed amount of oxygen and ferric ion it then fol-
lows that coals and strata containing high amounts of framboidal pyrite will
produce highly acidic mine drainages. However, Caruccio and Parizek (1967)
and Caruccio (1968, 1969) have shown that the degree of acidity is also a
function of the calcium content of the strata (which has the potential of
generating an alkaline, highly buffered and potentially neutralizing drain-
age), and the pH of the ground water before mining takes place (which con-
trols the occurrence of the various types of iron bacteria that catalyze the
acid producing chemical reaction). With regard to the latter, it has been
shown that certain types of iron bacteria can oxidize the soluble iron from
the divalent to the trivalent state, thereby further hydrolyzing the iron
with an accompanying increased acidity (Anon., 1971).
Each of the factors mentioned above plays a major role in determining
the quality of mine drainage that can be expected when a particular stratum
is disturbed. In turn, the occurrence of these factors has been related to
the depositional environment (paleoenvironment) of the coal and accompanying
strata (Caruccio, 1968). In so doing, an association has been established
between the paleoenvironment of the coal and the gross quality of drainage
that can be expected from that seam.
Within a particular strip mine, numerous strata of varying paleoenviron-
ments are uncovered by the mining process and the quality of the drainage
emanating from that mine will be a blend of all the different chemistries
produced by each rock type. Smith and his associates (1974) have developed
a technique that evaluates the acid-base account of various overburden mate-
rials which can be used for selected material placement. Their technique is
useful in the planning of overburden management through the identification of
alkaline and acid producing strata. The present study, however, was re-
stricted to and examined in detail the association between the occurrence of
various modes of pyrite and the paleoenvironment of the coal as identified
by the overlying rock types.
Of the hydrogeochemical factors controlling the quality of mine drain-
age, calcium carbonate occurring in the strata overlying a coal can generate
moderate amounts of alkalinity. At a certain partial pressure of carbon di-
oxide occurring within the infiltrating waters that come in contact with the
calcareous materials in the ground water regime, the amount of alkalinity
(which is a function of the partial pressure of carbon dioxide) is limited by
the solubility of the carbonate phase at a particular pH value. Within broad
ranges and the geochemical limits of the carbonate solubility, the neutraliz-
ing capability of water passing over calcareous materials in the rocks over-
lying a particular coal has a maximum potential. Consequently, although the
alkalinity produced within the ground waters has the potential to neutralize
the acid mine drainage, the overall neutralizing effect is limited by the
maximum alkalinity that can be possibly generated within the geochemical sys-
tems of the overburden material.
In the areas of the bituminous coal field of Pennsylvania which are
overlain by calcareous glacial drift, alkalinities of infiltrating waters
were measured as high as 450 milligrams per liter (as HCO^) (Caruccio, 1968).
-------
In some nonglaciated areas where the Allegheny and Pottsville formations crop
out, the limited calcareous content of the rocks yields ground waters with
alkalinities averaging around 75 to 150 mg/1 (as HCOp» which can effective-
ly neutralize 1 to 2 mg/1 acidity as H+ or 100 to 200 mg/1 acidity as CaC03.
Given the limited amount of alkalinity that can be possibly generated in the
stratigraphic section, the acidic quality of the mine drainage will be deter-
mined by the amount of acidity that is produced. If the acidity is less than
the available alkalinity, the drainage will be neutral; if it is greater,
the drainage will be acidic.
The pH of the ground water before the mining phase also reflects the oc-
currence of calcium carbonate in the overlying strata. In the absence of
calcareous material within a stratigraphic section the pH of the natural
ground water can be expected to be less than 5.5. Within this slightly acid-
ic range the iron bacteria which catalyze the acid mine drainage reaction are
noted to thrive and .can effectively increase the amount of acidity produced.
On the other hand, in the presence of calcareous material in the section, the
ground waters can be expected to be alkaline which preclude the occurrence of
acid producing bacteria and in some cases is conducive to the viability of
bacteria that produce basic substances (Anon., 1971).
THE ASSOCIATION OF ACID MINE DRAINAGE WITH THE DEPOSITIONAL
ENVIRONMENT (PALEOENVIRONMENT) OF COAL AND STRATA
Previous Studies
The occurrence of sulfurous materials in the stratigraphic section of
western Pennsylvania has been outlined in a general way by Williams (1960)
and Williams and Keith (1963). Williams (1960) documented a change of pale-
oenvironments within the Allegheny Group of upper Pennsylvanian age in the
bituminous coal field of western Pennsylvania. He showed that the rocks and
the coals at the base of the Allegheny Group contained fossils which were
characteristic of a marine brackish water paleoenvironment. In general, the
paleoenvironment of the rocks became more continental and fresh water toward
the upper part of the Allegheny Group. Work by Ferm and Williams (I960)
showed that the basal rocks that were deposited in a brackish water environ-
ment become more marine toward the western part of Pennsylvania.
Mansfield and Spackman (1965) traced the variation in the petrography
and the composition of the coals in the lower part of the Allegheny Group
(Lower Kittenning, Lower Clarion) up through the coals into the upper part
of the Allegheny Group (Freeport seams) across western Pennsylvania. With
the exception of one sample in the Lower Freeport coal, the coals, when
viewed on a regional scale, became more sulfurous as the environment of depo-
sition became more marine.
Williams and Keith (1963) statistically related the distribution of sul-
fur in coals to the occurrence of the marine roof rocks. By comparing the
coals in the lower and the upper part of the Allegheny Group, they showed
that coals capped by marine roof rocks had a greater sulfur content than the
-------
coals capped by non-marine roof rocks.
Because the amount of acidity was thought to vary directly with the py-
rite content of the coals and associated strata, it would be expected that
mines extracting coals from strata of a marine-brackish water paleoenviron-
ment should produce more acid than those mines mining coals associated with
strata of a fresh water paleoenvironment. However, although the strata be-
come more sulfurous (reflecting increases in iron disulfide), it has been
shown in the first part of this report that it is the type of iron disulfide
and not the amount which is the critical factor in predicting the occurrence
of acid mine drainage. Strata containing large amounts of "sulfur" occurring
as framboidal pyrite will produce more acid than the strata containing equal
amounts of "sulfur" composed of coarse grained non-framboidal iron disulfide.
Consequently, the association of framboidal pyrite with certain paleoenviron-
ments is the key to identifying coal strata which will produce acid mine
drainage pollution when mined. According to this hypothesis, coals from the
lower part of the Allegheny Group of western Pennsylvania, which are overlain
by strata of marine or brackish water paleoenvironments, should be rich in
framboidal pyrite and would explain the major occurrence of acid mine drain-
age in this area. On the other hand, coals in the upper part of the strati-
graphic sequence, which are overlain by strata of non-marine paleoenviron-
ments, should have a paucity of framboidal pyrite and should produce drain-
ages which should be neutral or slightly alkaline.
Prediction of Acid Mine Drainage Pollution Problems
Perm and his associates (Perm et al., 1959; Perm and Williams, 1962,
1964, 1965; Perm et al., 1967; Perm and Cavaroc, 1968; and Perm, 1975)
have been engaged in an extensive geologic mapping program of recognizing
and mapping the depositional environments of coal deposits found in the
Appalachian coal field from Pennsylvania to Alabama. By comparing the char-
acteristics of the ancient coal-bearing rocks to present day environments of
deposition, a set of criteria has been developed which can distinguish and
recognize various paleoenyironments in the Carboniferous rocks. These envi-
ronments range from alluvial plains through upper delta plains and lower del-
ta plains grading into back and beach barriers which are tidally influenced.
(Detailed definitions and criteria for recognition will follow). Interpret-
ing Caruccio's data of western Pennsylvania in light of Perm's paleoenviron-
mental reconstructions reveals that the coals and associated rocks rich in
framboidal pyrite are associated with the beach and tidally influenced back
barriers and lower delta plain deposits. In contrast, rocks and coals with
a paucity of framboidal pyrite are recognized as the upper delta plain and
alluvial plain sequence. In addition, where Caruccio's samples represent
environments ranging from lower to upper delta plains within a particular
coal bed distributed across a broad geographic range, a significant varia-
tion in the proportion of framboidal pyrite is observable.
Consequently, because many Appalachian coal beds are known to represent
several different paleoenvironments in different places and because other
seams can be recognized as belonging to at least two environments, a
10
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criterion appears to be available for predicting the aerial distribution of
framboidal pyrite without costly and time consuming analytical procedures.
If the differing environments of coal deposition can be readily recognized
and shown on maps, then a predictive model explaining and delineating the
occurrence of framboidal pyrite will be readily available. Strata represent-
ing varying paleoenvironments could be mapped (both vertically and horizon-
tally) and zones in framboidal pyrite could accordingly be predicted.
Definition of and Criteria for Recognition of Various Paleoenvironments
The identification of various paleoenvironments in the Carboniferous
stratigraphic section is based on the present day recognition of various
counterparts in active deltas. This is exemplified by a diagrammatic repre-
sentation of the various components of an active delta as shown in Figure 1.
For further reference, the diagram also shows the paleoenvironments and
stratigraphic position of the various coals used in this study.
The principal criteria for the delineation of depositional environments
are readily distinguished in the coal-bearing portion of the Carboniferous
of eastern Kentucky and will form the basis for the following discussions.
In this study, these criteria were used to identify the paleoenvironments of
the strata containing the coals that were sampled.
The lower delta plain deposits of eastern Kentucky have been described
by Baganz and others (1975). These deposits are dominated by thick coarsen-
ing upward sequences of shale and siltstone. They range in thickness from
50 to 180 feet (15 to 55 meters) and in lateral extent from 5 to 70 miles
(8 to 110 kilometers). Recent counterparts of these sequences are forming
in inte'rdistributary bays and prodeltas of modern lower delta plains.
In the lower portion of these bayfill sequences, dark gray to black
clay shales are dominant with irregularly distributed limestone and siderite
common; while in the upper part of these sequences, rippling and other cur-
rent related structures are common, reflecting the increasing energy of the
shallower water as the bay fills with sediment. Where the bays filled suffi-
ciently to form a surface upon which plants can root, coals formed, whereas
burrowed sideritic sandstones occurred where the bays did not completely
fill, thus permitting organisms to rework the subaqueous surface.
This general coarsening upward pattern of interdistributary bays is
frequently broken by tonques of coarse-grain detritus introduced by crevasse
splays. Chemically precipitated iron carbonate commonly occurs in persist-
ent bands or as large carbonate concretions up to 3 feet in diameter (1
meter) along bedding surfaces. These secondary siderite concretions
formed and lithified early as the enclosing shales and siltstones were com-
pacted around them.
The bayfill sequences commonly contain marine and/or brackish water
fossils and burrow structures. They are usually most abundant in the basal
clay shales but also may occur throughout the sequence.
11
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CO
OFFSHORE
BARS AND
ISLANDS
Figure 1. Diagrammatic representation of the carboniferous rocks and their depositional environments
between Ashland and Olive Hill, Kentucky.
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Overlying and laterally equivalent to the bayfill sequences are lithic
greywacke sandstone bodies one to three miles wide (1.5 - 5 kilometers) and
50 to 90 feet thick (15 - 25 meters). Recent counterparts of these depos-
its are forming at the mouths of distributaries in modern lower delta plains.
These distributary mouth bar sandstones are widest at the base and have gra-
dational lower and lateral contacts. Grain size increases upward in the se-
quence and toward the center of the bar. Persistent graded beds are common
on the flanks of the bars as are rippled surfaces (oscillation and current),
whereas multi-directional festoon cross-beds are prevalent in the central
portion of the bar. In this area of the bar, there is little lateral con-
tinuity of beds due to multiple scouring by flood currents. Slumps and flow
rolls are associated with the flanks and front of the mouth bar where the
sediment interface steepened beyond the angle of repose. Fossils and burrow
structures are generally absent within the bar deposits, but where subaerial
levees are constructed protecting the interdistributary areas from the rapid
influx of detrital sediments, organisms return and burrow the flanks of the
bar.
Distributary channels in the lower delta plain are characterized by two
types of sedimentary fill: active and abandoned. Since channels in the
lower delta plain are straight and exhibit little tendency to migrate later-
ally, except where they are deflected by underlying mouth bars, active chan-
nel fill deposits containing point bar accretion beds are not common. Where
present, these deposits consist of sandy sequences up to 60 feet thick
(18 meters) and 1000 feet wide (300 meters) which grade from coarse to fine
upward with trough cross-beds in the lower part and ripple drift in the up-
per portion. The basal contact, which is scoured along an undulating or wavy
surface, often truncates the underlying distributary mouth bar and bay de-
posits. Commonly pebble lag conglomerates occur at the base of the channel
deposits as do coal spars which represent compressed pieces of wood or bark.
Due to the rapid abandonment of distributaries, fine-grained clay plugs
are the predominant type of channel fill in the eastern Kentucky Carbonifer-
ous lower delta plain deposits. These abandoned fills are most often com-
posed of clay shales and organic debris which settled from suspension in the
ponded water of the abandoned distributary. In some cases, thick accumula-
tions of coal-forming organic matter fill these holes. The clay shales are
commonly root penetrated or burrowed. The only coarse-grained sediments oc-
curring in the abandoned channels are thin rippled and small scale cross-
bedded sands and silts which probably were deposited during floods or at
sites near the distributary cut-off.
In the eastern Kentucky Carboniferous lower delta plain, levees are
thin and poorly developed, the largest being about 5 feet thick (1.5 meters)
and 500 feet wide (150 meters). Levees consist of poorly sorted, irregular-
ly bedded, partially rooted, siltstones and sandstones. These beds have a
pronounced dip (about 10 degrees) away from the associated channel. Coal
beds, other than those associated with abandoned fills, are widespread but
relatively thin.
13
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In contrast to the thick fine-grained bayfill sequences of the lower
delta plain deposits, the eastern Kentucky Carboniferous upper delta plain-
fluvial deposits are dominated by linear, lenticular bodies of sandstone
which, in cross-section, are 50'to 80*thick (15 to 25 meters) and 1 to 7
miles wide (1.5 to 11 kilometers). These sandstone bodies have a scoured
base, sharply truncating the surface upon which they lie, but in the upper
portion, they laterally intertongue with gray shales, siltstones and coal
beds. The mineralogy of the sandstones vary from lithic greywackes to
arkoses, and the grain sizes are predominantly medium to coarse grained.
Over the scoured base, the grain size diminishes upward in these sandstone
sequences with abundant pebble lags and coal spar in the lower portions.
Bedding in these sandstone bodies varies from massive beds with thick festoon
cross-beds in the lower part which merge upward into point bar accretion beds
(average dip of 17 degrees) containing smaller scale festoon cross-beds that
are overlain by partially rooted sandstones and siltstones with climbing rip-
ples. These characteristics, in addition to the lateral relationships, sug-
gest a high energy channel flanked by swamps, small ponds, and lakes. The
upward widening cross-sectional shape of the sandstone bodies and the point
bar accretion beds indicate that meandering was important in the development
of these deposits. These sandstone bodies have an en echelon arrangement
suggesting episodes of lateral jumping of channels into adjoining backswamps.
Backswamp deposits consist of sequences, from the bottom up, of seat
earth, coal, shale with abundant plant fossils and rare freshwater pelecy-
pods, siltstone, sandstone, seat earth, and coal. The sandstone portion
thickens laterally and merges with the major sandstone bodies. Thin 5 to
15 feet thick (1.5 to 4.5 meters) upward-coarsening sequences are typical
deposits of open-water bodies, probably shallow ponds or lakes. The lateral
extent of these deposits is only 1 to 5 miles (1.5 to 8 kilometers).
Levee deposits consist of poorly sorted, irregularly bedded sandstones
and siltstones that are extensively rooted. They are thickest up to 25
feet thick (8 meters) near active channels and decrease in grain size and
thickness away from the channels. The levee deposits also have a prominent
dip (up to 10 degrees) away from the channel. Coals in the upper delta
plain-fluvial deposits, locally, may be thick up to 32 feet (10 meters)
but are laterally discontinuous (sometimes pinching out within 500 feet).
Lying between strata representing the lower and upper delta plain de-
posits of the eastern Kentucky Carboniferous is a transitional zone of rocks
that exhibits characteristics of both the lower and upper delta plain se-
auences. The fine-grained bayfill sequences are thinner 5 to 25 feet thick
(1.5 to 7.5 meters) than those of the lower delta plain, but they do con-
tain marine to brackish faunas. Unlike the thin bayfill sequences of the
upper delta plain they are extensively burrowed. Channel deposits exhibit
features of lateral migration such as point bar accretion beds similar to
the channels of the upper delta plain, but these transitional delta plain
channels are finer grained than those of the upper delta plain. The levees
associated with these channels are thicker 5 to 15 feet (1,5 to 4.5 meters)
and more extensively root penetrated than those of the lower delta plain.
Thin 5 to 15 feet (1.5 to 4.5 meters) splay sandstone are common in these
14
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deposits but are less numerous than in the lower delta plain yet more abun-
dant than in the upper delta plain. Coals of the transitional delta plain
are more laterally continuous than those of the upper delta plain and thicker
than those of the lower delta plain.
The final major depositional setting of coal formation in the Carbonif-
erous of eastern Kentucky is the lagoonal-back-barrier environment. The
characteristics of this setting have been described by Home, et al. (1974).
The principal components of this environment are sequences of organic-rich
dark gray shales and siltstones which are directly overlain by thin,laterally
discontinuous coals or burrowed sideritic zones. These lagoonal-bayfills se-
quences coarsen upward, are extensively burrowed, and often contain marine to
brackish faunas. Seaward, they intertongue with orthoquartzitic sandstones
of barrier origin, whereas in a landward direction, they intertongue with
subgraywacke sandstone of fluvio-deltaic origin. They are thick units 25 to
80 feet thick (7.5 to 24 meters) and similar to those of the lower delta
plain, but are not as laterally continuous 3 to 15 miles (5 to 25 kilome-
ters)
The intertonguing of the orthoquartzitic sandstones with the dark gray
lagoonal bayfills is of three general types. First, long sheets of rippled
or burrowed orthoquartzite dip gently (2 to 12 degrees) in a landward direc-
tion. Similar features to these are observed in modern barrier washovers in-
to open water lagoons. The second type consists of wedge-shaped bodies that
extend nearly horizontally in a landward direction for up to three miles (5
kilometers). Near the main body of orthoquarzite, they are up to 20 feet
thick (6 meters) but rapidly thin and continue as nearly horizontal thin
sheets 2 to 3 feet thick (1 meter). In the thicker portions of the ortho-
quartzites, bedding is predominantly planar to festoon cross-beds with am-
plitudes of 18 to 24 inches (45 to 60 centimeters) and a landward direction
of dip. Similar features to these have been observed in flood tidal deltas
in modern lagoons.
The third type of orthoquartzite intertonguing with the dark shales is
tidal channel deposits that scour up to 40 feet (12 meters). These deposits
may be associated with the inclined sheet sands or the wedge-shaped bodies,
or they occur as solitary isolated units. Associated levees are either ab-
sent or inconspicuous. Near the main sandstone bodies, the orthoquartzites
contain bimodal festoon cross-bedding, and grain size decreases upward. How-
ever, not all channels are filled with sandstone; most are filled with dark
gray shales, siltstone, coal, or slump blocks.
The criteria for recognizing the various paleoenvironments as outlined
above are summarized in Table 1 in their relative order of occurrence in or-
der to facilitate a comparison of the various components.
15
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DEPOSITIONAL ENVIRONMENTS
CRITERIA FOR RECOGNITION
I. Coarsening upward
A. Shale and SI Us tone
sequences
1. Greater than 50 feet
2. 5 to 25 feet
B. Sandstone sequences
1. Greater than 50 feet
2. 5 to 25 feet
II. Channel Deposits
A. Fine grained abandoned
fill
1. Clay and silt
2. Organic debris
B. Active sandstone fill
1. Fine grained
2. Medium and coarse
grained
3. Pebble lags
4. Coal spar
III. Contacts
A. Abrupt (scour)
B. Gradatlonal
IV. Bedding
A. Cross beds «
1. Ripples
2. Ripple drift
3. Festoon cross beds
4. Graded beds
5. Point bar accretion
6. Irregular bedding
V. Levee Deposits
VI. Mineralogy of sandstones
A. Lithic greywacke
B. Orthoquortzltes
VII. Fossils
A. Marine
B. Brackish
C. Fresh
0. Burrow structures
FLUVIAL AND
UPPER DELTA
PLAIN
C-R
H
C-R
R-N
N
R
R
R
R
A
C
A
A
A
A
C-R
A
C
C-A
A
R
A
A
A
A
N
_N
R
C-R
R
TRANSITIONAL
LOWER DELTA
PLAIN
C
R-H
C-A
R-C
N
R-C
C-R
C-R
C-R
C
C
C-R
A
A
A
C
A
C-A
C
A-C
R
C
C
A-C
A
N
R-C
C
R-C
C
LOWER DELTA
PLAIN
A
C-A
C-A
C-A
C-A
C-A
A-C
A-C
A-C
C-R
C-R
R
C
C
C
C-A
A
A
C-R
C-A
C-A
R-N
R-C
R-C
A-C
N-R
C-A
C
R-N
A
BACK-BARRIER
C-A
C-A,
C-A
C
R
C
C
C
C-R
C-R
C-R
R
C-R
C-R
C
C
A-C
A
R-C
C
R-C
R-N
R-C
R
R
A-C
A-C
C-R
N
A
BARRIER
R-C
R-C
R-C
C-A
C-A
C
R-C
R-C
R
C
C
C-R
R-C
R-C
C-A
C
A-C
A
R-C
C-A
R-C
R-tl
R-C
N
R
A
A-C
C-R
N
A
KEY: A - Abundant, C - Common, R - Rare, N - Not Present
TABLE 1. CRITERIA FOR RECOGNIZING DEPOSITIONAL ENVIRONMENTS.
16
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HYPOTHESIS TO BE TESTED
Because of the association of framboidal pyrite with acid mine drainage
and the association of framboidal pyrite with coals of strata of a particular
paleoenvironment, the hypothesis which was postulated and tested in this
study was concerned with predicting the occurrence of framboidal pyrite in
the coal through the recognition of the depositional environment of the
strata. If this hypothesis were true, stratigraphic sections can be mapped
in advance of mining that would:
1) Identify the potential of acid mine drainage pollution associated
with various coal seams.
2) For surface mined areas characterize strata which can be used for
surface dressing as a substrate for vegetation in reclaiming the backfilled
surface and those that will be potential acid producers and should be deeply
buried and hydrologically isolated from the surface environment.
3) Identify coal seams by limits of high and low sulfur content and de-
termine whether or not the high sulfur coals can be cleansed to produce low
sulfur fuels. This is based upon the assumption that framboidal pyrite is
fine grained and evenly disseminated within the coal and cannot be effective-
ly separated from the coal by flotation processes. The fine grained pyrite
is incorporated within the coal and floats off with the coal. On the other
hand, coarse grained pyrite occurring as discrete particles readily affords
a density variation within the coal particles and can be fractionated by
flotation processes to produce a low sulfur coal.
To test whether an association exists between the paleoenvironment of a
coal and the occurrence of framboidal pyrite, an area within the Appalachian
coal field of eastern Kentucky was selected for study because of the excel-
lent rock exposures afforded by the newly constructed interstate highway
system. From these exposures, paleoenvironmental maps could be constructed
and the environment of deposition of the coal readily identified. Having
done so, samples of coals representing various paleoenvironments would be
collected, processed and microscopically examined to determine the occurrence
of framboidal pyrite.
As a further check on the validity of the data, water samples were col-
lected from springs and seeps emanating from the coal faces from which the
coal samples were collected. The quality of ground water reflects the over-
all geochemistry of the strata and the analyses of specific chemical parame-
ters, reflecting particular geochemical reactions, would be used to comple-
ment the results of the microscopic study.
17
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SECTION III
METHOD OF STUDY AND DATA PROCUREMENT
AREA OF STUDY
Within a rough triangle formed by Olive Hill, Ashland and Louisa of the
Appalachian basin of eastern Kentucky, an extensive interstate road building
program had been actively taking place in the years 1971-1974. Because of
the fertile farmland which occurs in the valley portion of that part of the
state and because of the State's intent to preserve these agricultural areas,
the new interstate highway system was projected and constructed through the
mountainous areas. In so doing, extensive bedrock exposures were created and
gave rise to spectacular road cuts, which in some cases averaged between 300-
450 feet (100-150 meters) high and sometimes as much as a mile long (1.6 ki-
lometers). These road cuts afforded excellent mapping control by which rocks
and strata could be identified and paleoenvironment depositional features re-
constructed. (See Figure 2).
In addition to the excellent exposures created by the newly constructed
highway system in eastern Kentucky, the area was also chosen in anticipation
of the future mining of the eastern Kentucky coal field. Most of the mapping
information obtained in this study would also lend itself to future coal ex-
ploration programs and enhance coal mining and coal extraction from that part
of the state.
The road cuts and exposures created by the highway construction pres-
ented the mapper with a three dimensional view by which to enhance his paleo-
environmental reconstructions. Sufficient opportunity to document the depo-
sitional environment of the coal and the overlying strata which were afforded
by the road cut benches also lent themselves and provided an excellent mech-
anism by which to sample the coals. In most cases, the benches were created
along the coal seams and consequently facilitated the sampling program.
COALS
Method of Mapping
As a first step in mapping the strata on the large highway exposures,
sequential overlapping photographs were taken of the outcrops to produce a
composite photo mosaic of the exposures. Subsequently, a sufficient number
of vertical sections were measured to encompass the lateral variability of
the lithologies. Using the photo mosaics and measured sections, detailed
18
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jvASHLAND
tTJUNTINGTON
SCALE
KILOMETERS
dzpiBtzz:
0 10 20 30 40 50
Figure 2. Location map of geologic cross-sections.
19
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diagrams of the outcrops were prepared on graph paper. The outcrop diagrams
were then generalized and replotted to a vertical scale of 1:240 and a hori-
zontal scale of 1:6000 to show correlations and lithologic variations on a
more regional scale along the trend of the direction of the highways.
Method of Sampling and Depicting Data
After the outcrop diagrams were generalized and replotted along the
highway trends, the paleoenvironment of each strati graphic interval was as-
certained using the criteria previously specified. At this stage of the re-
construction, the depositional environment of various strata and coals con-
tained within the stratigraphic sequence could be identified. This guided
the field sampling to selected areas where coals representative of particular
paleoenvironments could be collected. . Within each coal seam, sampling sites
were randomly located at stations that were accessible, relatively dry, and
where the coals appeared to be least weathered.
At each sampling location, the coal seam was examined to determine the
degree of weathering. Badly weathered areas were avoided. In most cases
relatively fresh samples could be collected by selecting appropriate loca-
tions along the coal seam. Thick coal seams were collected by column sam-
pling the various physically different layers within the seams; i.e., blocky
horizons, platy layers, massive, etc. If the seam was less than 12 inches
(30.5 centimeters), then the entire seam was channel sampled. In selected
areas where the coal seam was fresh and readily accessible, five stations
approximately 75 feet (22.8 meters) apart were established, and samples were
collected from various intervals to evaluate the lateral and vertical varia-
tions of sulfur content.
Before the start of the collection, the coal seam was dressed by using
a shovel and pick to clear away the weathered surface. The thickness of the
coal seam led the collector to either channel sample the entire seam or de-
lineate various horizons for column sampling. Where pyrite rich layers were
noted, special attention was paid to collecting samples and separate samples
of pyrite concentrate were collected.
The samples collected from the coal face were bagged in plastic Zip-loc
bags, labeled and shipped to the laboratory in South Carolina for analyses.
All samples collected in the field were labeled by a code that identified the
coal seam, the state in which the sample was collected and a specific site
identification number that appears on the cross sections contained in this
report.
The code has either three or four components separated by a slash which
can be interpreted as follows:
The letter immediately preceeding the slash is either a K or an 0 de-
picting whether the sample was collected in Kentucky or Ohio, respectively.
Preceeding the K or the 0 is the identification code of the coal seam
20
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by explanations that appear in Table 2.
Following the slash is the collection site number which corresponds to
the location on the cross section depicting the data. In some cases, a let-
ter and/or number follows the site location number to show that multiple sam-
ples of the seam were collected at that sampling site.
On the cross section, below the code, appear the coal intervals that
were sampled; "T" indicating Top, "M" for Middle, "L" for Lower, and "CH" for
Channel Samples of the entire seam. At the bottom of each sample code the
total sulfur percentage of that sample is shown. Because of the large num-
bers of samples that were collected, processed and analyzed, it was inevita-
ble that some samples were lost. In this event, either the sample code is
deleted or the analyses omitted from the station tag.
To complement the total sulfur analyses, many samples that were repre-
sentative of the various paleoenyironments were selected for pellet fabrica-
tion for the microscopic identification of framboidal pyrite. During the
course of examination, other varieties of pyrite were noted and the percen-
tages of each were determined with a grid network that scanned the entire
surface of the polished pellet. In addition, photomicrographs were taken of
pellets characterizing features indigenous to the various paleoenvironments.
These results will be discussed in the following section.
A summary of all samples collected and their codes, percentage sulfur
and where applicable, percentages of various forms of pyrite, appear in
Appendix A of this report. However, in order to facilitate the presentation,
selected data representative of patterns and trends observed will be used as
the basis for discussion.
Analyses
Samples collected in the field were stored and transported to the labo-
ratory in plastic Zip-loc bags that afforded an airtight seal which inhibited
oxidation. The samples upon being unpacked, and in preparation for analyses,
were hand cleaned to remove mud and other debris that was inadvertently col-
lected with the sample. When the analysist was assured that all surface con-
tamination was removed, the sample was crushed and processed according to the
flow pattern illustrated in Figure 3. After the field sample was hand
cleaned, it was crushed by a Chipmunk Jaw Crusher to pass 4 mm. The crushed
sample was then riffled into two equal portions; one portion was sealed in a
can under a nitrogen atmosphere. Nitrogen is injected throughout the crushed
sample prior to sealing to prevent oxidation of the sample and preserve it
for future studies. The sealed can is then clearly identified and stored in
the coal repository at the University of South Carolina. The other riffled
portion of the sample, which was to be used for the analyses, was further
riffled into one portion which was to be used for the total sulfur analysis
on the LECO and an equally representative portion which would be used for the
fabrication of pellets.
21
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TABLE 2. EXPLANATION OF COAL IDENTIFICATION CODES AND THE
REPRESENTED BY THE SAMPLES COLLECTED FOR THIS
Coal
Tom Cooper
Fire Clay
Lower Francis
Upper Francis
Lower Haddix
Middle Haddix
Upper Haddix
Hazard Six
Hazard Seven
Hindman Nine
Below Hindman Nine
Princess Five
Princess Five
Princess Seven
Princess Seven
Wolf Creek
Identification
Code
TCK
FCK
LFRK
UFRK
LHAK
MHAK
UHAK
HZ6K
HZ7K
HI9K
BHI9K
PR5K
PR50
PR7K
PR70
WCK
Area of
Collection
Olive Hill, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Daniel Boone Parkway
Hazard, Kentucky
Along 1-64 near
Rush, Kentucky
Ironton, Ohio
Along 1-64 near
Rush, Kentucky
Ironton, Ohio
Along 1-64 near
Rush, Kentucky
PALEOENVIRONMENTS
STUDY
Paleoenvironment
Represented
Lower Delta Plain
Upper Delta Plain
Transition
Transition
Upper Delta Plain
Upper Delta Plain
Upper Delta Plain
Upper Delta Plain
Transition
Lower Delta Plain
Lower Delta Plain
Transition
Transition
Upper Delta Plain
Upper Delta Plain
Back Barrier
22
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Field Sample
I
Hand cleaned
Crushed in Chipmunk
to pass 4 mm
Sealed in can
with Nitrogen
Stored in Coal
Repository
Sample used for Analyses
I
Coffee Mill
Mikropul
Pulverized to
Pass 250 microns
Fabrication of
Pellets
Buehler
Polishing Stages
Total Sulfur
Analysis/LECO Reflected Light
Microscopy
Figure 3. Flow sheet for sample preparation and analysis.
23
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The samples selected for the total sulfur analysis were pulverized using
a Mikro-Pul pulverizer to pass a 250 micron sieve, air dried and stored in
glass vials. During the analyses for total sulfur, a representative portion
of the sample was withdrawn by rolling the jar and randomly collecting small
increments of the pulverized sample to make up a 50 or 100 mg sample. The
weighed sample was transferred to a porcelain crucible, augmented by a tin
and iron accelerator and magnesium oxide flux, covered and ignited by a LECO
induction furnace which converted the sulfur contained in the sample to sul-
fur dioxide. During this process the sample is covered by a purified oxygen
gas flow which enhances burning and entrains the sulfur dioxide into a titra-
tion assembly which is color-metrically titrated to a particular end point by
a starch-iodate reaction. The amount of titrant required to reach the end
point is adjusted for blank corrections and an "F" factor and measures the
percentage of total sulfur content of the ignited sample on a weight per
weight basis.
The portion of the sample selected for microscopic examination was
passed through a coffee mill grinder to pass a 2 mm sieve. The relatively
large sample was further riffled to obtain a 10-15 gram portion which was
air dried and stored in a glass jar in preparation for pellet fabrication.
The sample was poured into a steel mold 3 inches (7.62cm) and exactly 1 inch
(2.54cm) in diameter and stopped with a rubber plug. The sample was then
covered with a low viscosity APCO 823 epoxy resin, stirred, cured, labeled
and subsequently extruded by a hydraulic press. The pellets were mounted in
Buehler sample holders and polished on a series of Buehler polishing wheels
until a final polish utilizing a 0.05 micron alumina grit was achieved. The
polished pellet surface can then be examined by an ore reflected light micro-
scope to a magnification of 300X and the various pyrite morphologies readily
identified. The microscope used in this study also had the capability of
taking photo-micrographs of selected samples. When certain features, charac-
teristic of particular samples were identified, appropriate photographs were
taken and are included in this report.
Water Chemistry of Coal Seeps
Purpose
A major concern in this study was the rock-water quality interactions,
in particular the effect that the aquifer composition and the occurrence of
framboidal pyrite has on water quality. Samples of coal that were collected
for analyses and used to approximate the occurrence and distribution of
framboidal pyrite represent a small portion of the total coal seam under
study. Efforts were made to collect representative portions of the seam
from randomly located sample sites. When compared to the total volume of
coal making up the coal seam, the sample volume is a small percentage of the
total coal population.
Water seeps emanating from each coal, passed through the overlying
strata, moved vertically into the coal seam and encountered the seat earth
underlying the coal. This clayey layer inhibits the vertical migration of
24
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water and generally causes ground water to move laterally along the coal seam
bed until the water emerges from the coal face. During the water's flow
through the geological regime, the water must pass along joints and fractures
and contact a variety of chemical constituents, including the framboidal py-
rlte.
Because the water reflects the gross chemical composition of the coal
over a larger area, samples of water seeps emanating from coal faces were
collected and chemically analyzed to complement the results obtained from the
microscopic examination of the coal samples. In so doing, the results ob-
tained from the microscopic examination of the pellets can be interpreted in
conjunction with the water chemistry analyses to have a broader base and one of
regional significance.
Sample Collection
During the summer of 1975, water samples were collected from the areas
from whence the various coal samples were collected. In so doing, water sam-
ples were collected from strata of the various paleoenvironments which could
be used to evaluate the geochemistry of the water regime. At each location
where the coals were sampled, the coal face was chiseled away with a hand
pick until a water flow was encountered. In most cases, a slow, steady flow
couTd be obtained and by the proper manipulation of a plastic straw, in jux-
taposition with a sample bottle, a sufficient volume of water could be sam-
pled for chemical analyses. Only 1n one or two cases did an insufficient
flow preclude sample collection. Of the 48 coal sample locales, 46 had a
sufficient water flow that was collected and subsequently analyzed. Each
sample was analyzed for specific chemical parameters indicative of a partic-
ular chemical reaction and readily related to the geochemistry of the
strata. The quality of the drainage could be used to relate pyrite stabil-
ity or reactivity with the paleoenvironment of the strata. These data will
further lend themselves to the interpretation of the results obtained from
the microscopic analyses. The specific parameters measured and the reason
for choosing them are outlined below.
Chemical Parameters Measured
The pH, although not a quantitative measure of acidity, reflects the
degree of acidity or alkalinity that could be expected from the sample.
Within broad limits the chemical character of the sample could be quickly
determined and related to the geochemistry of the strata. To insure that no
subsequent changes in pH would occur due to changes in temperature, dissolu-
tion of gases, etc., all pH measurements were made in the field at the col-
lection site using a portable Photovolt pH meter. Prior to measurement, the
meter and electrode were calibrated using the appropriate buffer.
25
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Conductivity
Within broad estimates, the electrical properties of a solution reflect
the ionic strength of that solution. Thus the conductivity of the water
sample can be related to the total dissolved solid content of the water sam-
ple, and in a way approximates the chemical activity taking place within the
aquifer or coal seam through which the ground water flows. Conductivities of
samples were measured within a 12-hour period from time of collection using a
portable Universal Interloc conductivity meter which was calibrated and stan-
dardized against a known conductivity standard solution. The conductivity
measurements were also used to confirm the concentration of the total chemi-
cal species that were to be measured by conventional wet methods and to rap-
idly reconnoiter an area for water quality expectations.
Units of conductivity are commonly expressed as "micromhos per centime-
ter at T° C." Inasmuch as the definition of specific conductance already
specifies .the dimensions of a cube to which the specific conductivity meas-
urements apply, the length in the unit is not necessary and may be omitted
in practice (Hem, 1970). Accordingly, in this report the units of specific
conductance may be expressed as micromhos.
Acidity and Sulfate
The acidity of acidic drainages is assumed to develop principally from
the hydrolysis of the oxidation products of pyrite. As outlined in the be-
ginning of the report, the iron disulfide readily oxidizes to produce a fer-
rous sulfate compound which is readily soluble in water and hydro!izes to
produce acidity and attendant amounts of sulfate. Accordingly, the measure
of the acidity of water flowing from a seam can be related to the amount of
reactive pyrite that could be expected to be found in that particular coal
seam. These data- coupled with the percentages of framboidal pyrite found in
the seam, as noted to occur in the polished pellets, should give a total
picture of the water quality that could be expected from a coal seam of a
particular paleoenvironment.
The method of measuring acidity presented a problem, not because of an-
alytical technique, but because of theoretical considerations concerning the
definition of acidity. Many workers, in determining acidities, commonly
titrate a water sample with a standard alkali solution to two endpoints, one
at pH 4.5 which is defined as the "mineral acidity," and a second endpoint
at pH 8.2, referred to as the carbon dioxide acidity (Sawyer, 1960).
Titrating a sample to these endpoints is meaningful if all the acidity
is in the "free acid" form, that is, existing as sulfuric acid. However, if
the acidity is in major part due to hydrolysis, which in fact is the case in
acid mine drainage, then the acidity determined depends largely on the rate
of hydrolysis and the oxidation state of the metal (Hem, 1970). To get a
true picture of the total amount of acidity present in a sample, hydrolysis
and the oxidation of the metals must be driven to completion before the sam-
ple is titrated. This is accomplished by boiling the sample before
26
-------
titration. In so doing, the dissolved carbon dioxide is driven off with the
loss of carbon dioxide acidity, whereupon titration with a standard alkali
gives the acidity due only to iron hydrolysis and free sulfuric acid, which
is precisely the parameter of interest.
Generally, the endpoint is taken as 8.2 (phenol phthalein). Titration
curves were determined for some samples collected in this study having vary-
ing degrees of acidities. In all cases an inflection point (which determined
the endpoint of a titration) occurred near pH 8.3 which suggests this to be
the proper endpoint.
Hot acidities were determined in a laboratory after boiling the sample
for two minutes. This insured the complete oxidation and hydrolysis of the
iron compounds and expelled the carbonic acid acidity. The sample was cooled
to room temperature and titrated with a 0.0248N sodium hydroxide 'solution to a
pH 8.3 endpoint which was potentiometrically determined (Rainwater and
Thatcher, 1960).
The specific equations explaining the oxidation of pyrite and the genera-
tion of acidity were listed previously. The general equations governing the
nature of the chemical reactions are repeated below to illustrate the rela-
tionship between acidity and sulfate and how sulfate anion concentrations can
be used to substantiate the presence of reactive pyrite.
The oxidation of pyrite can be written,
FeS2 + H20 + 3^02 = FeS04 + H2SO^ (5)
The ferrous sulfate that is formed as an oxidation product may be oxi-
dized further to ferric sulfate and dissolved in water as in equation (6).
Fe2(S(M3^ 2Fe+++ + 3SOij (6)
The iron can hydrolyze as in equation (7)
3H20 ^Fe(OH)3 + 3H+ (7)
to form acidity and the iron hydroxides. The ferric iron formed during the
acid-generating reactions further reacts with the available pyrite to form ad
ditional acidity, ferrous and sulfate ions as in equation (4).
From these reactions, it can be seen that the sulfate content is in part
stoichiometrically related to the acidity. The relationship, however, is not
linear because although the sulfate and iron arise from a common source, the
acidity generated is a function of the oxidation state of the iron. However,
within broad limits of acidity values, determined by the oxidation state of
the iron, the acidity produced can be correlated with the sulfate content of
water samples (Caruccio, 1968).
27
-------
Because the acidity generated is a function of the oxidation state of
the iron, it may be possible to have a sample whose acidity content increases
with time as the iron is gradually oxidized. As a result, the solubility of
the iron will decrease and unless the sample has a very low pH, the iron will
precipitate out of solution. Inasmuch as the solubility of iron is pH-Eh de-
pendent and the samples collected were exposed to atmospheric conditions
prior to collection, determinations of iron content of the water samples were
not performed. The delicate balance between ferrous-ferric ratios, pH-Eh re-
lationships and the solubility of iron coupled with the rapid oxidation of
ground water as it encounters a diffusion zone upon emerging from the rock or
coal face, suggest that any interpretation of iron solubility data would in
fact be tenuous. For these reasons, iron concentrations were not measured.
The sulfate content, however, remains constant assuming no significant
dilution has taken place and the significance of sulfate measurements is ob-
vious. The sulfate anion is the tracer of acid mine drainage and its pres-
ence can be used to approximate the degree of acidity present or that was
present before neutralization took place. By analyzing the sulfate and acid-
ity content of acid mine drainage from various sources, and plotting concen-
trations of sulfate against acidity, a range of acidity can be interpolated
for a particular value of sulfate concentration. An assumption is made that
all of the sulfate in the sample arises from the oxidation of pyrite. The
lack of anhydrite or gypsum layers in the strata substantiates this assump-
tion.
Precipitation of the sulfate ion is possible in the presence of high
calcium waters. A water sample originally acid may be neutralized by cal-
cium-bicarbonate rich waters, but because of calcium sulfate precipitation
will contain a low sulfate content. An incorrect conclusion can be reached,
namely, the sample never was affected by acid mine drainage. Calculations
using sulfate and calcium concentrations °f water samples analyzed in this
study and solubility products for gypsum and anhydrite indicate that levels
of sulfate concentration indicative of acid mine drainage contamination are
possible even though precipitation takes place. Taking the least soluble
phase of calcium sulfate, it was calculated that 1475 mg/1 of sulfate anion
would still remain in solution if precipitation occurred. Hence, the occur-
rence of pyrite decomposition can be interpreted through the presence of
significant concentrations of sulfate anion.
Sulfate concentrations were analyzed by a modified barium chloranilate
method outlined in Standard Methods for Chemical Analyses of Water and
Wastes, 1971. The chloranilate ion is released in the presence of an acid
buffer and develops a wine color that is proportional to. the amount of sul-
fate ion present. The intensity of the color of the filtrate is colorimet-
rically measured on a B & L Spec-20 meter and related to a standard curve.
To preclude cation interferences the samples were processed through ion ex-
change columns for ion removal before adding the reagent.
As noted previously, the decomposition of pyrite produces abundant a-
mounts of sulfate, in addition to iron and acidity. In the absence of abun-
dant amounts of either gypsum or anhydrite in the strata, it could be
28
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assumed that the primary source of sulfate in the water samples is the de-
composition of reactive pyrite. As such, sulfate contents are an excellent
measure of the degree of reactive pyrite present in the section.
Hardness
Hardness is a measure of the inability of a water sample to produce suds
in the presence of soap and is generally attributed to the occurrence and a-
bundance of divalent cations. In water samples collected for this study, the
hardness reflects the presence and degree of occurrence of calcium, magnesium
and iron. Water samples were analyzed for total hardness which grouped all
divalent cations into one measurement. Selected cations were not specifical-
ly analyzed.
By examining the hardness data in conjunction with the acidity and pH
data, the dominance of a particular cation could be accurately deduced. If,
for example, a high hardness content of the water appears coupled with a high
acidity and low pH, one can assume that the primary cation contributing to
hardness is soluble iron. If, on the other hand, hardness is present in sam-
ples with a low acidity and high pH, it can be correctly assumed that the
dominant divalent cation is calcium or magnesium.
Hardness determinations were made in the laboratory by the complexio-
metric EDTA method as outlined in Standard Methods (1971).
Interpretation of Water Quality Data
The exact nature of the geochemical system of the coal seam and over-
lying strata from which the water sample was collected can be quickly ascer-
tained if sulfate data are related to and examined in conjunction with hard-
ness, acidity and pH. If, for example, a sample has high sulfate, hardness
and acidity content, coupled with a low pH, it could be readily assumed that
that particular stratigraphic section is generating acid mine drainage and
contains abundant amounts of reactive pyrite. If, on the other hand, the
sample contains low sulfate concentrations coupled with high hardness, low
acidity and high pH, it could be assumed that the water flowed through
strata containing calcareous material and a paucity of reactive pyrite. Fi-
nally, if a sample has high sulfate, high hardness, low acidity and high pH,
it could be assumed that the geochemical system is such that acidity is
being generated by reactive pyrite, but is subsequently neutralized by the
alkalinity produced by calcareous material present in the section.
Thus, by noting the interrelationships between pH, conductivity, acid-
ity, hardness and sulfate, the interrelationships and combinations thereof
between reactive pyrite (generating acidity) and calcareous material (gener-
ating alkalinity) can be effectively determined. These data, used to com-
plement the results obtained from the examination of the polished pellets,
will be used in further discussions of this report. The wet chemical anal-
yses of water samples collected in the field are shown in Appendix B.
29
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SECTION IV
DATA AND INTERPRETATIONS
VARIABILITY OF TOTAL SULFUR CONTENT OF COAL
Variability Within Seams of Varying Paleoenvironments
To ascertain the degree of variability of total sulfur content that
could be expected within coal seams of varying environments, the Princess
Seven, Princess Five and Tom Cooper seams were selected for a detailed study;
the former two were chosen as representative of the alluvial-upper delta
plain environments, the latter representative of the back barrier environ-
ment. At specific locations within each coal seam sampling networks that ex-
tended vertically and laterally were designed to evaluate the total sulfur
variation that could be expected within the seam.
Within the Princess Seven coal seam, three sampling techniques were used
to collect samples within a 6000 feet (2000 m) distance. At station PR7K/1,
five column samples from the top to the bottom of the seam were collected and
analyzed for total sulfur content. At location PR7K/2 the seam was sampled
by halves and thirds at three sample stations located 1 inch (2.54 cm) apart
from each other. Finally, at sample site PR7K/3, two channel samples of the
entire coal were collected at stations one foot (30 cm) apart. The total
sulfur contents of these samples appear in Table 3 and clearly show the
marked vertical and lateral variation that could be expected in the total
sulfur contents within a particular coal seam. See also Figure 4.
At station PR7K/1 the sulfur content varied from a low 1.31% in the bot-
tom 5 inches (12.7 cm) horizon to a high of 6.54% in the 8 to 12 inch
(20-30 cm) interval at the top.
At site PR7K/2 the central station had a sulfur content averaging 3.4%
at the top half and a 1.26% at the bottom half of the seam. Stations 1 inch
to the east and to the west of the central station at this locale had a high
sulfur content occurring in the lower third of the seam and a low sulfur con-
tent occurring at the upper third of the seam; these data will be used in
following sections and are included here to exemplify the points now being
considered. At PR7K/3, channel samples taken at two locations had abnormally
high sulfur contents, averaging between 6-7% total sulfur. These data point
out that the total sulfur content can vary from as low as 1.1% to as high as
7.34% within a coal seam of one paleoenvironment.
From this preliminary study two observations regarding sulfur distribu-
tion are noteworthy. First, at the site PR7K/2, where samples were collected
30
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TABLE 3, TOTAL SULFUR PERCENTAGES OF SAMPLES COLLECTED FROM THE PRINCESS
SEVEN COAL
Code
PR7K/1A
PR7K/1B
PR7K/1C
PR7K/1D
PR7K/1E
PR7K/2
PR7K/2
PR7K/2
PR7K/2-W
PR7K/2-W
PR7K/2-W
PR7K/2-E
PR7K/2-E
PR7K/2-E
PR7K/3
PR7K/3
Interval Sampled Percentage Sulfur Remarks
Top 8" (20 cm)
8" - 12" (20 - 30 cm)
12" - 22" (30 - 56 cm)
22" - 29" (56 - 74 cm)
Bottom 29" - 34" (74-86 cm)
T 1/3
M 1/3
L 1/3
T 1/3
M 1/3
L 1/3
T 1/3
M 1/3
L 1/3
CH (1) 5" (13 cm)
CH (2)
2.38%
6.54%
1.93%
1.76%
1.31%
3.46%
3.33%
1.26%
1.13%
1.78%
4.13%
1.78%
1.44%
4.48%
6.63%
7.34%
Within
one seam
at one
location
Samples
PR7K/2, PR7K/2-W
and PR7K/2-W
were collected
one inch (2.54 cm)
apart
Channel sample
Channel sample
31
-------
w
PH7K/:
T 3
3.*6IS
PK7K/2
T I/;
PR7K/2
L 1/2
1.26X5
PP. 12
T. JW
1. IS
PF /2
M 3V
PK K/2
L /3U
4. KS
• ' "' .
I I/IE
1. 18**
PR7K/2
H 1/3E
1.44ZS
PR 7 i/ :
L 1/3F
4.48iS
PR7K/?
PR7K/2
TE
'PRINCESS NO. e
'B7R/1C
-93SS
THTK/1D
1.76IS
PR>K/1-1
f t"
2. MIS
PF^K/J-1
T 2/*
3.SOIS
P*5K 3-1
T 2/
1.27 5
PR5K 3-1
L 3/
2.45 S
PRiK/3-1
L J'j"
1. 711'-
ytff./ 3~z
Stllcif led
2.27SS
PIiK/3-2
at
LjUS
KINCESS.NO. 7
jPdlNCESS NO. 6
OJ
FNJ
PR5K/7
i,os:s
PR5K/7
I I/- 1
^,i:«
t 2/4 1
3.98*5
'RjK/7
L 3/» 1
&.J9IS
PR5K/7
L 1/i 1
l.«IS
PH5K/7
L fc/4
3.2*15
PRiH/7
T I/- 2
4. 09X5
PR5K/7
t 2/fc 2
J..52S5
L 3/4 2
4 . d6tS
PRSK/7
PK5K/7
T 1/4 3
5.2ST5
PR5K/7
T 2/4 1
S.20tS
PR5K/7
L 3/4 3
4.77IS
PKSK/7
4,72XS
PR5K/7
T 1/4 4
PB5K/7
T 2/4 *
7.1 (US
L 3/4 4
3.04ZS
PH'JK/7
PRSK/7
t 1/4 •>
3.67IS
PRSK/7
I 2/4 5
3. 4 IIS
PR5K/7
L 3/4 5
2.29ZS
pmr/7
3 . 2 315
SCALE
AND SIUSTONE
[_J BLACK SHALE
IrH LIMESTONE
^ SIMRITE
B
flH ROOTS
PRSK/ID
CH 6"ch
1.19IS
PRSK/1C
l"CHl"ehk
1.76XS
Figure 4. Geologic cross-section of Princess coals along 1-64 near Rush, Kentucky.
-------
from three locattons within a 4 inch (10 cm) interval, there was no consis-
tent pattern that could be used to predict whether high sulfur horizons will
occur in either the top or the bottom of the seam. Second, the two channel
samples collected at PR7K/3 contained total sulfur contents that exceeded the
total sulfur contents of the individual samples which were parts of the seam
that were collected at PR7K/1 or PR7K/2. Within these latter sample loca-
tions high sulfur contents were not found. Had channel samples of the coal
seam been taken at PR7K/1 and PR7K/2, the high sulfur content layers of each
of these separate samples would have been diluted by the lower sulfur hori-
zons to produce a composite sample whose total sulfur content would have been
even lower than the two channel samples. However, the total sulfur analyses
of the channel samples collected at the location showed that this was not the
case and underscores the horizontal variability that could be expected along
a seam.
Samples of coal were also collected from PR7K/5, PR7K/6 and PR7K/7 and
analyzed for total sulfur content (Results appear in Appendix A). The re-
sults are summarized as follows:
Sample Percentage Sulfur
PR7K/5 0.36-0.73%
PR7K/6 1.61-3.5%
PR7K/7 2.06-5.63%
On a regional basis, these data further illustrate the lack of correlation
between the paleoenvirontnent and total sulfur percentages within the coal.
A cursory examination of the analyses of samples collected from the
Princess Five (Figures 5-7) and the Tom Cooper (Figure 8) coals, representa-
tive of differing paleoenvironments, again shows a large variation in total
sulfur content. Within the Princess Five coal seam (an upper delta plain
coal), the total sulfur content varied from 1.2% to a high of 15%;
whereas the Tom Cooper coal seam (a back barrier coal) had total sulfur con-
tents which varied from 1.9% to 5.9%. These results showed that a tremendous
variability in total sulfur content exists within coals of varying paleoenvi-
ronments and that a poor correlation exists between the total sulfur content
of a coal and its depositional environment.
Variability Within a Uniform Seam
To test the vertical variability that could be expected within a coal
seam, column samples were collected from several locations in different seams.
The distribution of sulfur within the Princess Seven at PR7K/7 is summarized
as follows:
33
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US 60
MEADS - SOUTH
Siltttoi"
(ihm bedded)
~; Bidding Plane
PR5K/13
T 1" A'. No
5.78%S
PR5K/13
Nodule
2.15%S
PR5K/13
Nodule
4.01%S
PR5K/13
6" B. No.
2.12%S
PR5K/13
6-ll"BN
2.42%S
PR5K/13
Silicified
4.22%S
SoulK
Figure 5. Geologic cross-section of the Princess Five coal along Kentucky 60 south of Meads, Kentucky.
-------
PR5K/12 PR5K/12 PR5K/12
T V T 9-13" T 16-20"
1.79ZS 2.18ZS 1.732S
PR5K/12 PR5K/12 PR5K/12
T 4-9" T 13-16" Pyrite
1.8A%S O.A2ZS
US 60
MEADS - NORTH
North
a: -• - Vanporl Marine Zone
(•1 • —Mile Branch
Sooth
„ ^^•••••••••••••••M
fi&£^i--.'fc.*rVir'^roli ... _ • [ «B V ^I~~** . "^ ^- '--7.-!^-.—T.•.-,^'L ''• --.I, ^~~—•~~m^-~f ~,'T
Prmcim '5
So nd Jlone
(line grained)
T Sillltone
. (thin bedded)
; Silly SnoU
: Cloy Stiole
S.licified Coal
Cool
] Sea) Rock, Cloy
I '-,- i| Ironstone
Sider»fe Nodulei
Bed dmg Planes
Calcareout BracKiopodi
A Phosphotic Brochiopods
Burrows
Feel
Figure 6. Geologic cross-section of the Princess Five coal along Kentucky 60
north of Meads, Kentucky.
35
-------
w
CJ
KEND8ICK
SHALES
TOM COOPER COAL
PRINCESS NO. S
MAIN B1OCK ODE
PRINCESS NO 4
PRINCESS NO 3
FWECLAY-WHITES80RG COALS ?
SCALE
LEGEND
| | SANDSTONE
p^ SHALE AND SUTSTONE
Q BLACK SHALE
fTT] LIMESTONE
SIDERITE
Figure 7. Geologic cross-section along 1-64 near Grayson, Kentucky.
-------
FIRE CLAY COAL ZONE
TCK4 TCK4 TCK4 TCK4 TCK4
CH T 3" M 3" LM 3" L 11"
5 192S 3.60ZS 3.243:5 3.87%S 4.84%S
00
^>
LEGEND
TCK5/1
T 1/3
3.5«s
TCK5/1
M 3/4
2.75%S
TCK5/1
I. 1/3
TCK5/2 TCKi/2
3.45ZS 3.14ZS
TCK5/2 TCK5/2
T 4/4
3.55%S 2.47ZS
TCK5/3 TCK5/3
L 1/3
1.96ZS
TCK5/3
M 1/3
1..90ZS
TCK5/4 TCK5/4
T 1/3 L 1/3
4.34*5 3.1AIS
TCK5/4
M 1/3
1.972S
SCALE
SANDSTONE
ORTHOQUARTZITE
| RED AND GREEN SHALE
SHALE AND SILTSTONE
COAL AND UNDERCLAY
CALCAREOUS CONCRETIONS
SIDERITE
20
10
METERS
0
1 2
KILOMETERS
TCK/7
MT 1-4
3.39%S
TCK/7
MT 4-7
3.68JS
Figure 8. Geologic cross-section along 1-64 near Olive Hill, Kentucky.
-------
Location PR7K/7 Interval Sampled (Top to bottom) Percentage Sulfur
7
13
20
28
36
Top 7" (18 cm)
13"
20"
28"
36"
41"
[18-33 cm)
33-51 cm)
51-71 cm)
71-91 cm)
91-104 cm)
5.
2.
2.
3.
63%
13%
06%
99%
2.56%
4.5 -
12.5 -
18
22.5 -
25.75 -
28.75 -
Bottom
Top 4.5" (11.4 cm)
12.5" (11.4-31.8 cm)
18"
22.5"
25.75"
28.75"
31.75"
31.8-45.7 cm
45.7-57.2 cm
57.2-65.4 cm
65.4-73.02 cm)
73.02-80.6 cm)
31.75 - 36.5" (80.6-92.7 cm)
Similar vertical variations in sulfur can also be seen in the Hazard
coal seam. The analyses of samples collected at location HZ6K/19 are shown
in the following summary (See also Figure 9).
Location HZ6K/19 Interval Sampled (Top to bottom) Percentage Sulfur
0.55%
0.65%
0.59%
0.58%
0.71%
0.61%
1.86%
0.54%
The examples cited above substantiate the trends and results that were
found during the other phases of this study, that is - the vertical varia-
tions in total sulfur content within coal seams are greater than was previ-
ously suspected.
To ascertain the degree of horizontal variation of total sulfur content
within a coal seam, three channel samples approximately 25 feet (7.6 m) were
collected from the Princess Five coal at PR5K/10. These channel samples were
analyzed for total sulfur content and had the following values: 3.06%, 4.14%
and 3.74%. Although the variation was not as great as that found previously,
it is apparent that the total sulfur content of channel samples within one
coal seam can vary at stations along the seam.
To further evaluate the variation of sulfur content, three stations were
located along the coal seam approximately one inch (2.54 cm) apart (PR7K/2,
PR7K/2E and PR7K/2W). The data collected from the experiments at PR7K/2 and
which appear in Table 3, are recombined and shown in Table 4.
38
-------
TABLE 4. TOTAL SULFUR CONTENTS OF THIRD-COLUMN SAMPLES OF THE PRINCESS SEVEN
COAL COLLECTED ONE INCH (2.54 cm) APART AT PR7K/2
PR7K/2U PR7K/2 PR7K/2E
Top Third of Seam
Middle Third of Seam
Bottom Third of Seam
1.13%
1.78%
4.13%
3.46%
3.33%
1.26%
1.78%
1.44%
4.48%
In addition, these results are plotted in Figure 10 which succinctly demon-
strates the degree of lateral and vertical variability of total sulfur con-
tents that could be expected within a coal seam.
In a final attempt to establish the vertical and horizontal variation
that could be expected, an intricate sampling plan was designed along the
Princess Five coal seam at station PR5K/7. At this locale, five stations
numbered 1 through 5 were located about 20 to 80 feet (6.23 m) apart. The
coal thickness varied from 6 to 9 inches (15-23 cm) and in spite of a rela-
tively thin seam, which would have lent itself to a complete channel sample,
one-quarter column samples were collected at each location (Figure 4). The
results of the total sulfur analyses of the samples are shown in Table 5 and
Figure 11, and further support the contention that large horizontal and ver-
tical variations in total sulfur contents exist in a coal seam.
TABLE 5. TOTAL SULFUR CONTENTS OF QUARTER-COLUMN SAMPLES OF THE PRINCESS
FIVE COAL COLLECTED AT PR5K/7
Station PR5K/7-1 PR5K/7-2 PR5K/7-3 PR5K/7-4 PR5K/7-5
Coal 7"(18 cm) 6"(15 cm) 6"(15 cm) 9"(23 cm) 7"(18 cm)
Thickness
Distance
Between Stations 35 ft(ll m) 20 ft(6 m) 20 ft(6 m) 80 ft(24 m)
Sulfur Content
Top Quarter 6.42% 4.09% 5.25% — 3.67%
Upper Quarter 3.98% 4.52% 5.26% 7.10% 3.41%
Lower Quarter 5.59% 4.86% 4.77% 3.04% 2.29%
Bottom Quarter 1.99% 4.25% 4.72% 5.38% 3.23%
39
-------
r o-^-1
a. jus
j.;:;s
•• .
I 0-4"
t.JOIS
T i-7VFB
i.asis
LFRX/IA-:
J.;7;s
LFHK/iA-3
0.6« IS
.
B 0-4"
'.Bits
Figure 9a Geologic cross-section along Daniel Boone Parkway near
Hazard, Kentucky (western half).
40
-------
SCALE
SHAIE AND SIUSTONE
] BIACK SMAIE
SIDERITE
fff ROOTS
Figure 9b. Geologic cross-section along Daniel Boone Parkway near
Hazard, Kentucky (eastern half).
41
-------
PR7K/2-W
PR7K/2
PR7K/2-E
ro
T5W-.
M3W-
L3W
~ i /tin —
\
\ \
ox T 2 —
X
X
X ]
II L5
1
1
1 1
,* MsE-
s
f
G>' ir
i i L 3 1
I i
**r
o
X
1
24 24 2
%s %s %s
1
4
Figure 10. Total sulfur contents of third-column samples of the Princess Seven coal collected one
inch (2.54cm) apart.
-------
CO
PR5K/7(1) PR5K/7(2) PR5K/7(3) PR5K/7(4)
AVG S% - 4.75 AVG S% =4.43 AVG S% = 4.99 AVG 3% = 5.17
PR5K/7(5)
AVG 5% = 3.15
1
T4-i
9
rl-
3
L_
4-
1
u-
O 0
s \
s' \
s \
O 0
^ \
^x \
x 1
^.o ©
•*• '
^ 1
O 0
III 111
246 246
s% s%
0 0
i ,
0 06
l ^* /
/ ' /
/ •* /
O Q" 0
' s^ \
1 N \
O "0 0
246 246 246
S% S% S%
AVERAGE OF 5 LOCALITIES = 4.50%
CHANNEL SAMPLE = 4.05 %
Figure 11. Total sulfur contents of quarter-column samples collected at PR5K/7.
-------
Variability Within a Split Coal Seam
Up to this point, the fact has been established that the total sulfur
content within a coal seam has a tremendous variation in a vertical and hori-
zontal spatial dimension of a coal seam of a uniform geology. To ascertain
the variability of sulfur content within a split seam, an experiment was de-
signed at station PR5K/1, where the Princess Five coal seam was observed to
split into five different seams over a distance of approximately 100 feet
(33 m). At this location channel samples of each split were collected and
analyzed for total sulfur contents. The results of this study are summarized
as follows:
Location PR5K/1 Split Sampled (Top to bottom) Percentage Sulfur
Top Split PR5K/1A 7.75%
PR5K/1B Split; Top-Half 15.6%
PR5K/1B Split; Bottom-Half 4.5%
PR5K/1C 1.8%
PR5K/1D 1.2%
Bottom Split PR5K/1E 1.3%
This detailed sampling plan further demonstrated that the sulfur content
varied not only within uniform coal seams but within splitting coal seams as
well.
Laboratory Precision of Analyses
To test the precision of the laboratory analyses, the LECO Automatic
Sulfur Titrator was used to analyze a series of coal samples whose total sul-
fur contents ranged from 0.5% to 5.5%. Selected samples having sulfur con-
tents in the low and high range were chosen for replicate analysis and ana-
lyzed five to seven times. Within the low sulfur content coals (on the order
of 0.6% sulfur), the analytical procedures had a variation of 0.03% sulfur.
Analyses of samples with high sulfur content (on the order of 5.5% sulfur)
had a variation of 0.1% sulfur.
These studies showed that the precision of the laboratory facilities was
acceptable and that the sulfur variability within the coal was the dominant
source of error. To reduce analytical error and to insure reproducibility,
samples analyzed for total sulfur were staggered so that every other sample
was analyzed twice. In addition, the LECO instrument was continually cali-
brated at the beginning of each analytical period to obtain a correct F fac-
tor for those sets of analyses. In this manner, trends in the analyses could
be quickly ascertained and anonymous results readily identified.
Limits of Interpretation
In summary, based on the above experimental designs, it was apparent
that sampling problems existed because of the heterogeneous nature of the
44
-------
coal. One source of error occurs because the coal seams have a physical
characteristic whereby degrees of friability are associated with low and high
sulfur horizons. Coal seams usually are a mixture of blocky stratified hori-
zons which are interbedded with laminated friable layers. The studies above
showed the sulfur content to differ between the blocky and friable layers.
In attempts to collect either column or channel samples of coal seams, the
physical nature of the coal caused the blocky layers to be more abundantly
sampled than the friable ones. It was noted, for example, that in channel
sampling a coal, the blocky fragment commonly fell off the coal face in rela-
tively large portions; whereas the laminated boney layers had to be chiseled
away from the coal face to obtain equal portions. The former tended to con-
tribute more to the sample, while the latter made up less of the total vol-
ume. As a result, the blocky layers within the coal tended to overshadow the
laminated friable layers and accordingly dominated the sample analysis. How-
ever, in this study attempts were made and care taken to insure that equal
volumes of coal were collected from each horizon.
In future studies, it is suggested that coal be sampled with the aid of
a mechanical device that would withdraw uniform volumes of material through-
out the entire seam. It would be possible, for example, to channel sample
the entire seam with an auger or corer to prevent the physical segregation of
the blocky material from the laminated material.
Within each coal seam, micro-environments are known to be interbedded
throughout the seam. In this study, coal seams identified and chosen for
sampling were at locations where the paleoenvironment of the overlying strata
was overwhelmingly of one type. Areas of questionable or mixed paleoenviron-
ments were not sampled. Even with these field precautions, it is readily ap-
parent that micro-paleoenvironments exist within the seams and there is no
known way of accurately identifying each micro-horizon within each coal. The
variations in sulfur contents expressed above may be due to these uncertain-
ties.
In this study, and guided by detailed field mapping, samples were col-
ected from coals that were best identified as being representative of parti-
cular paleoenvironments. The following conclusions are drawn from data that
were obtained within the limits of the mapping technique and are cognizant of
the variations in sulfur contents that are known to exist within the coal
seams. Until a sampling plan is designed that can adequately sample the het-
erogeneous nature of the coal and a technique devised to identify the micro-
paleoenvironments in the coal seam, the conclusions of this study must neces-
sarily be constrained within these limits.
45
-------
OCCURRENCE OF FRAMBOIDAL PYRITE
Types of Pyrite
A variety of pyrite morphologies exists within a coal seam which can be
related to either the early phase of the formation of coal (pyrite being de-
posited contemporaneously with the peat) or emplaced subsequent to the coal-
ification of the peat (pyrite being mobilized and subsequently deposited
within a solid coal seam as secondary pyrite). Gray, et al. (1963) described
the morphologies and occurrence of the pyrite forms within the Pittsburgh
coal seam and how they relate to the effectiveness of coal cleaning proc-
esses. In a study by the Ohio State University Research Foundation (1970),
Stiles proposed a classification of pyritic material in coals within two main
categories: primary pyrite and secondary pyrite. Within the primary pyrite
category, sulfur balls, finely disseminated pyrite and primary replacement
pyrite are included. The latter category includes secondary replacement and
fracture filling pyrite. In the present study, pyrite morphologies have been
grouped into five categories which are characterized as 1) primary massive,
2) plant replacement pyrite, 3) primary euhedral pyrite, 4) secondary cleat
(joint) coats, and 5) framboidal pyrite. Each of these types of pyrites was
noted to occur in the coal samples examined with an ore light reflecting mi-
croscope. Of the five categories mentioned, the framboidal pyrite is most
reactive, readily oxidizes and is primarily responsible for the generation
of acid mine drainage.
In the first two categories, the primary massive and plant replacement
pyrite are commonly 150 to 600 microns in size. In most cases, the pyrite
retains the cellular structure of the material that the pyrite emplaced and
can be readily identified with a microscope. Examples of the primary mas-
sive, plant replacement pyrite are illustrated in Figures 12-15. In Figure
12, vessel walls (tracheids) have been replaced by pyrite and the morphology
of the containing unit can be readily identified. Figure 13 shows a mass of
fusinite (ancient charcoal) encapsulating massive coarse grained pyrite.
Figures 14 and 15 illustrate how coarse grained pyrite has replaced existing
cell structures within the coal. These primary pyrite features frequently
occur within coals and do not appear to have been compressed. In contrast,
the layers of coal adjacent to these pyrite replacement features appear com-
pressed and compacted; whereas the pyritic features show no visible signs
of compression. These relationships suggest that these massive pyrite par-
ticles were emplaced syngenetically with the deposition of peat and are con-
sidered as primary in origin; that is, forming at the time the peat is de-
posited.
A third category of pyrite includes primary euhedral pyrite, which, too,
is noted to occur within coal seams and is surrounded by layers of coal that
were compressed. These crystals, or euhedra, of pyrite are commonly shaped
as either cubes or dipyramids and are 0.5 microns to 2 microns in size. In-
dividual crystals may occur as discrete grains widely disseminated within a
coal (Figure 16), clustering along layers (Figure 17), or within spherical
agglomerations (Figure 18), which are collectively called framboidal pyrite.
4fi
-------
Photomicrograph of tracheids replaced by pyrite.
(Sample PR7K/2-L 1/3)
Figure 13. Photomicrograph of fusinite encapsulating massive pyrite.
(Sample PR7K/2-L 1/2)
47
-------
Figure 14. Photomicrograph of plant cells replaced by pyrite.
(Sample TCK3/1-M 1/3)
Figure 15. Photomicrograph of massive pyrite grains within plant material
(Sample TCK/4-L 11")
48
-------
Figure 16. Photomicrograph of pyrite crystals disseminated within a coal
(Sample PR7K/2-M 1/3E)
Figure 17. Photomicrograph of pyrite crystals clustering along layers,
(Sample PR7K/2-M 1/3E)
49
-------
en
O
Figure 18. Photomicrograph of pyrite crystals within spherical agglomerations.
(Sample below Hindman 9, Hazard, Kentucky area)
-------
The microscopic examination of numerous polished pellets for this study
showed euhedral crystals to occur both as disseminated particles and agglom-
erations forming the spheres of framboidal particles as well. In cases where
the euhedral pyrite agglomerated and formed framboidal pyrite, the individual
particle sizes never exceeded 1 to 2 microns.
The fourth type of pyrite classification used in this study includes the
secondary cleat (fracture) coats. Figures 19 and 20 show how layers of pyrite
coat the joints contained within the coal. It is readily apparent that this
type of pyrite could not have been formed prior to the formation of joints
within the coal and had to be mobilized and emplaced as a secondary feature
subsequent to the coalification and diagenesis of the coal.
The fifth category of pyrite type used in this study, and the one that
is most important, is the framboidal pyrite. The word "framboidal" comes
from the French word meaning strawberries and describes the basic morphology
that the framboidal pyrite has (Figure 21).
The origin and nature of framboidal pyrite has been the subject of many
studies including those by Berner (1971), Richard (1970) and most recently,
Javor and Mountjoy (1976). The similarities in morphologies that exist be-
tween the framboidal pyrite and microbial organisms have led some to suggest
.that framboidal pyrite has a microbial origin (Love, 1957; Love and Amstutz,
1966) and some to identify microbial species (Javor and Mountjoy, 1976).
Most authors agree that framboidal pyrite formation takes place within the
realm of a strongly reducing, iron rich, hydrogen sulfide emanating environ-
ment, whether it be in the skeletal remains containing cellular membranes or
in an environment with an extraneous source of hydrogen sulfide that bubbles
into the iron rich solutions. Whatever the mechanism, a distinct relation-
ship exists between the occurrence of framboidal pyrite and strongly-reducing
organic rich environments.
Some interesting data regarding the formation of framboidal pyrite e-
merged from a recent investigation into the failure of culturing crabs in
shallow marine farms fabricated from abandoned rice fields in the marshlands
of South Carolina. The rice patties in this area have been abandoned for ap-
proximately 30-50 years during which time the fresh water barrier was
breached and salt water encroached upon the field. During this 30-year in-
terval the abandoned rice patties remained idle and were subjected to alter-
nating fresh water-salt water flushing which eventually caused a brackish en-
vironment. In the recent past, during the futile attempts to flush out the
brackish water and reinstill a salt water environment, for the purpose of
harvesting marine shellfish, a strongly acidic, high sulfate-high iron pool
of water was formed. Investigations by Czyscinski (1975) showed that the
substrate underlying the abandoned rice pattie contained large amounts of
framboidal pyrite which apparently formed during the past 30 years. In the
attempts to redevelop a marine environment, the inflowing oxygenated waters
oxidized the pyrite, produced acid mine drainage and killed the marine organ-
isms. Interestingly, this study showed that the formation of framboidal py-
rite can occur in short periods of time.
51
-------
Figure 19. Photomicrograph of pyrite within cleats (fractures) in coal
(Sample PR7K/2-T 1/3W)
Figure 20. Photomicrograph of pyrite filling fractures in coal
(Sample TCK/9-CH)
52
-------
Figure 21. Photomicrograph of framboidal pyrite.
(Sample below Hindman 9, Hazard, Kentucky area)
53
-------
Within the Carboniferous rocks, Caruccio (1968) showed that framboidal
pyrite is the pyrite type that is the least stable and is primarily responsi-
ble for the production of acid mine drainage associated with coal mines.
Framboidal pyrite can occur as spheres of crystals as illustrated in Figure
22, finely disseminated particles clustered along layers as in Figures 23A and
23B, or as scattered grains finely disseminated throughout the coal seam as
shown in Figure 24.
One of the objectives of this study was to relate the occurrence of fram-
boidal pyrite to coals of a particular paleoenvironment. The paleoenvironment
was documented by the detailed mapping of the overlying strata, whereas the
coal was the repository for the variety of pyrite types. In the course of ex-
amining numerous samples of coal seams from differing paleoenvironments for
this study, each of the aforementioned types of pyrite was noted to occur
throughout the sections. The nature of the coal simplified sample prepara-
tion and pyrite morphology identification. We readily acknowledge the fact
that pyrite occurs throughout the strata of the geologic column as well as
the coals. However, coals were used exclusively in this study because of
their relatively higher sulfur contents which increased the pyritic sulfur
content and facilitated the evaluation of the occurrence of framboidal pyrite.
Method of Identification and Calculation of Percentages of Reactive Pyrite
Samples of coal collected and analyzed for total sulfur were subriffled
into portions that were cast in epoxy pellets and finely polished for the mi-
croscopic examination of the various pyrite morphologies. Thus, the samples
used in this phase of the study were split from and complement the samples
used in the total sulfur analysis. Using these data, estimates of pyritic
sulfur contents could be obtained and percentages of reactive pyrite could be
ascertained.
The polished pellets were examined with an oil immersion light-reflect-
ing ore microscope with a total magnification of 300X. Lower magnifications
did not provide sufficient resolution to successfully identify the various
morphologies. On the other hand, increasing the magnification beyond 300X
led to a time consuming pellet scan as well as severe eye strain. For opti-
mum viewing, with a large field for rapid scanning yet sufficient magnifica-
tion for pyrite identification, it was found that 300X using a 10X ocular and
25X objective, coupled with a 1.2 internal magnifying index, gave the best
possible results.
Each pellet was leveled onto a glass slide which was mounted in a stage
micrometer. This permitted the sample to be scanned with overlapping paral-
lel sweeps so that the entire surface of the pellet was observed. During
these scans the area occupied by the various types of pyrite was noted and
recorded. Upon completion of the scan of the entire pellet, the various per-
centages of the different types of pyrite were obtained to within 5% incre-
ments. These percentages of the various types of pyrite noted to occur in
each coal seam and the percentage sulfur data of each sample are listed in
Appendix A.
54
-------
Figure 22. Photomicrograph of spheres of framboidal pyrite.
(Sample Hindman 9 coal, Hazard, Kentucky area)
55
-------
Figure 23A. (300X)
Figure 23B. (600X)
Figures 23A and 23B. Photomicrographs of clusters of framboidal pyrite
along layers; A at 300X, B at 600X (Sample TCK/2-L 1/2).
56
-------
Figure 24. Photomicrograph of framboidal pyrite scattered throughout the coal
(Sample PR7K/2-L 1/3W)
-------
Given the premise that the framboidal pyrite is the most reactive of the
pyrlte types, coupled with the assumption that variations of total sulfur
contents reflect variations in pyritic sulfur contents of the samples, the
.percentage of reactive pyrite occurring within each sample can be calculated.
Ah empirical relationship between total sulfur and pyritic sulfur was
derived by Leighton and Tomlinson (1960, in Given, 1969) which can be used to
obtain the pyritic sulfur content of the sample. The relationship is ex-
pressed by:
spyritic ' 0-78 Stotal - °-49 (8)
Using this equation, the total sulfur contents of the samples can be used to
calculate the pyrite content of the samples.
Most of the samples collected for this study were column samples, and
the sulfur analyses show the sulfur content of that particular interval of
the seam. The intent of this study was to compare seams of various paleoen-
vironments and accordingly all of the sulfur data were weighted by the sample
interval thickness to get an average sulfur content for the entire seam.
These data appear in Appendix A-2.
The average sulfur content for the seams were then used in equation (8)
to calculate the pyritic sulfur content of the seam (Appendix A-2).
Subsequently, the relative percentages of the various, pyrite types were
weighted by the sample interval thickness to obtain the average framboidal py-
rite content of the jwhole seam. To obtain the absolute percentages of fram-
boidal pyrite, the pyrite content of the seam was multiplied by the relative
percentage of framboidal pyrite. This gave the percentage of framboidal py-
rite occurring 1n the coal seam (Appendix A-2).
Comparison of Framboidal Pyrite Contents of Coals of Various Paleoenvironments
In reviewing the data, 1t became readily apparent that the total and py-
ritic sulfur contents of samples collected from the Hazard, Kentucky area were
markedly higher than those collected from the road cut sections along Kentucky
Interstate 64 between Grayson and Ashland, Kentucky. This suggested that
there were significant differences in the sulfur contents of samples from var-
ying geographic areas. Thus, to make a valid comparison between coals of dif-
ferent paleoenvlronments, the comparison must be made between coals collected
1n a common geographic location.
Based on these considerations, the samples common to the Hazard-Daniel
Boone Parkway area of Kentucky were separated from those collected along the
1-64 Grayson-Ashland sites. The framboidal and total pyrite percentages of
each seam, as calculated and shown in Appendix A-2, are plotted for those sam-
ples from the Hazard area (Figure 25) and for those samples from the 1-64
area (Figure 26). There is no Importance to the order in which the individual
samples are arranged along the vertical axis, in Figure 25 the Hazard Six and
Haddix coals represent the upper delta plain sequence; the Hazard Seyen and
58
-------
tn
10
UPPER
DELTA
PLAIN
TRANSITION
LOWER DELTA
PLAIN
HADDIX COALS
HAZARD SIX COALS
;.v::y.v.v:::.::::r::::.v.-.::. FRANCIS COALS
•»•••""•- HAZARD SEVEN COALS
HINDMAN NINE COALS EXPLANATION
Framboidal Pyrite
Non-framboidal Pyrite
i
2
i
3
i
4
I
5
Percentage Pyrite
Figure 25. Distribution of framboidal pyrite and total pyrite for coals collected from ttie Hazard
area and grouped into paleoenvironments.
-------
CTi
O
UPPER
DELTA
PLAIN
TRANSITION
LOWER
DELTA
PLAIN
WOLF CREEK COAL
PRINCESS SEVEN COALS
PRINCESS
FIVE
COALS
TOM
COOPER
COALS
EXPLANATION
Framboidal Pyrlte
Non-framboidal Pyrlte
Percentage Pyrlte
Figure 26. Distribution of framboidal pyrite and total pyrite for coals collected from the 1-64
road cuts and grouped into paleoenvironments.
-------
the Francis coals represent the transitional paleoenvironment, and the Hind-
man coals, the lower delta plain. In Figure 26, from top to bottom the
Princess Seven coals represent the upper delta plain, the Princess Five coals
the transitional, and the Tom Cooper and Wolf Creek coals represent the lower
delta plain paleoenvironment.
Comparing these two figures, it becomes readily apparent that a signif-
icant difference in total and framboidal pyrite content exists between coals
of similar paleoenvironments collected from different geographic areas. The
coals representative of a particular paleoenvironment collected from one geo-
graphic area were not the same as those from the other area. For example, in
the Hazard area the Haddix and Hazard Six coals were representative of an up-
per delta plain environment, whereas in the 1-64 areas the Princess Seven .coals
were chosen to be representative of a similar paleoenvironment. Thus, in or-
der to compare coals of various paleoenvironments, the results obtained from
the 1-64 sites were used in preference to those of the Hazard area; .a larger
number of samples being a major consideration in choosing these data.
The histograms plotted in Figure 26 show that framboidal pyrite is found
in coals of all paleoenvironments and is not restricted to the marine-transi-
tional environments as had been supposed. However, it appears that fram-
boidal pyrite is more prevalent in the marine-transitional facies than the
upper delta plain facies.
This hypothesis was tested using a Chi Square test which showed that
there was a significant difference in the percentage of framboidal pyrite in
the upper delta plain coals when compared to the transitional lower delta
plain coals (at the 90% level).
A one-way analysis of variance, coupled with Bartlett's test, showed
that there was no significant difference when the upper delta plain coals and
the lower delta plain coals were compared to the transitional ones, but that
there was a significant difference (at the 95% level) when the upper delta
plain coals were compared to the lower delta plain coals. Inasmuch as the
transitional environment is a blend of the extreme environments, it is to be
expected that the coals from all three environments would be similar when
compared to the "median" environment. However, it is significant that the
lower delta plain coals contain more framboidal pyrite than the upper delta
plain coals.
In view of the variability of total sulfur content that occurs within
coals, it becomes apparent that a similar variability also exists within the
distribution of framboidal pyrite. Quite possibly these reflect variations
of micro-paleoenvironments within one coal seam. In general, though, greater
percentages of framboidal pyrite, combined with a greater percentage of py-
ritic sulfur, occur in lower delta plain sequences when compared to the upper
delta plain-alluvial sequences.
Within the limits of interpretations constrained by the variability of
the total sulfur contents that was previously noted, a positive relationship
exists between the occurrence of framboidal pyrite in lower delta plain se-
quences and a relative paucity of framboidal pyrite in the upper delta plain
61
-------
sequences.
LEACHING TESTS
The hypothesis outlined above basically relates the occurrence of fram-
boidal pyrite to the depositional environment of the strata. In so doing,
the occurrence of reactive pyrite can be approximated and predicted. Inas-
much as one of the major objectives of the study was to predict the occur-
rence of acid mine drainage, a study was designed to test a group of coal
seams from varying paleo-depositional environments to ascertain the degree of
acid production that could be expected from each coal. For this purpose, a
series of leaching tests was designed to test the amount of acid each coal
would produce.
Sample Selection
Within the area of eastern Kentucky, five coals of varying paleoenviron-
ments were identified and chosen for the leaching tests. The coal samples
selected for the leaching study were collected from the Hazard area in east-
ern Kentucky and represent various depositional environments (Figure 27).
The information pertinent to these samples is contained in Table 6.
TABLE 6. DESCRIPTION OF SAMPLES USED IN THE LEACHING STUDY
Sample
Name of Seam
Paleoenvironment Total Sulfur Content
A
B
C
D
E
F
G
H
Grassy #2
Grassy #1
Upper Whitesburg
Hazard #4, Top 12"
Hazard #4, Mid 12"
Fireclay
Fireclay
Fireclay
Back barrier
Back barrier
Lower delta plain
Upper delta plain
Upper delta plain
Lower delta plain
Lower delta plain
Transitional
5.72%
4.90%
2.14%
0.61%
0.61%
0.61%
0.53%
0.43%
Method of Study
The eight samples that were collected and which were representative of
the various paleoenvironments were split from the channeled field samples,
crushed, sieved to a uniform size (2-4 mm), weighed and placed in plastic
chambers which were continuously flushed with humidified air. At selected
intervals, two to three times a week, the samples were covered with deionized
water and drained. The volume of the effluent was measured and recorded and
hot acidity determinations were made on an aliquot of leachate. Acidity val-
ues thus obtained could be converted readily to milligrams of acidity
62
-------
co
Figure 27. Geologic cross-section of carboniferous rocks between Pine Ridge and Vicco, Kentucky
showing locations of samples used in the leaching study.
-------
produced per volume of leachate. In turn, the amount of acidity could be ad-
justed to a common base and expressed as milligrams of acidity produced per
100 grams of sample. Cumulative acidity generated for each sample over a
particular time period was then calculated and cumulative acidities graph-
ically plotted to depict rates of acid production for each sample.
Results
Figure 28 shows the results of the leaching tests over a 25 day time pe-
riod. The coal samples that were collected from the back barrier paleoenvi-
ronments produced more acid than the samples collected from the other deposi-
tional environments. Samples collected from the upper delta plain had low
sulfur contents and did not produce appreciable amounts of acidity.
The leachates produced in this study were also analyzed for sulfate.
The degree of sulfate present would reflect oxidized pyrite and approximate
the percentage of reactive pyrite (framboidal) contained in the sample. On
an average, the sulfate concentrations for the back barrier samples, samples
A and B, were 1200 mg/1 and 1300 mg/1, respectively. For sample C (lower
delta plain), the sulfate concentration was 25 mg/1, while the remaining sam-
ples, which did contain small percentages of pyritic sulfur, had negligible
amounts. On the assumption that sulfate anion is produced primarily from the
decomposition of iron disulfide, it could be stated that samples A and B con-
tain reactive pyrite, sample C contains minor amounts of reactive pyrite,
while all others contain pyrite in a stable form which is not readily decom-
posing.
The results of the leaching tests, however, have limited application.
The samples chosen for the study were selected to represent various paleoen-
vironments and it was hoped that the acid production potential of coal could
be related to the paleoenvironment. The leaching tests did show that greater
acidity was produced by the back barrier coals than by the upper delta plain
coals, but this relationship can also be explained by the fact that the for-
mer have more total pyrite than the latter.
Another possibility exists that back barrier coals have higher sulfur
contents than upper delta plain coals and consequently produce more acid.
But as the sulfur variability studies showed, total sulfur contents and, for
that matter, framboidal pyrite contents, vary across paleoenvironments, and
only in general terms can it be stated that the back barrier samples are more
sulfurous than upper delta plain coals. The probability exists that the back
barrier samples used in the leaching tests were collected from high sulfur
seams with gradations in between. Thus, in the leaching tests, the associa-
tion of acid production with back barrier coals and lack of it with upper del-
ta plain coals may be an artifact of sampling and not truly representative of
acid production potential of varigus paleoenvironments. Inasmuch as these
samples represent a small part of the total outcrop, it is quite probable,
and in view of the variability in coal quality that can be expected, that an in-
adequate sampling program led to the fortuitous selection of upper delta
plain coal samples which were exceptionally low in sulfur.
64
-------
5.0
Grotty
Sample D- Upper Delta Plain Hazard #4
Sample E - Upper Delta Plain Hazard #4
Sample F- Lower Delta Plain Fireday
Sample G- Lower Delta Plain Fireday
Sample H- Transitional Zone Fireday
1 2 3 4 & 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Up. WhHuburg
Figure 28. Plot of cumulative acidities per 100 grams of samples of
varying paleoenvironments.
65
-------
In this study, however, a strong correlation was shown to exist between
the occurrence of reactive pyrite in the sample and sulfate anion in the
leachate. This relationship plays an extremely important role in interpret-
ing the aqueous geochemical data which will be discussed further in the fol-
lowing sections.
AQUEOUS GEOCHEMISTRY
The ultimate quality of a mine drainage will be a combination of complex
geochemical interactions of different ions from a variety of sources. It has
been shown that the source of acidity, iron and sulfate in mine drainage is
readily related to the occurrence and decomposition of framboidal pyrite. On
the other hand, calcareous material found within a hydrogeologic environment
presents the geochemical system with a natural buffering capacity. Ground
water flowing within a geologic section, and contacting either or both of
these geochemical effects, will pick up specific chemical species that re-
flect either of these reactions or combinations thereof.
This section discusses the importance of considering the ground water
chemistry in predicting the quality of mine drainage that might be produced
from a strati graphic section. It has been shown that reactive framboidal py-
rite occurs across, strata of varying paleoenvironments, albeit in greater
preponderance within coals associated with strata of lower delta plain-back
barrier paleoenvironments. The leaching tests further showed that coals of a
particular paleoenvironment were not only higher in sulfur but produced acid
mine drainage as well. Both of these considerations neglect the natural a-
queous geochemistry which will have a profound effect on the ultimate quality
of mine drainage that is produced. The importance of considering the buffer-
ing effects of the natural system was best exemplified by a study by Biesecker
and George (1966) who showed that streams degraded by acid mine drainage were
ameliorated as they flowed into a more calcareous terrain.
pH and Conductivity Trends Across Varying Paleoenvironments
Along Kentucky Interstate 1-64 from Ashland to Olive Hill, a transition
of paleoenvironments exists from an upper delta plain in the east to a lower
delta plain to the west, where near Olive Hill the stratigraphy becomes more
calcareous. Along this transition of paleoenvironments from Ashland to Olive
Hill, a series of water seeps, small springs and streams adjacent to the high-
way occur and drain each of the various paleoenvironments. Along this pro-
file, numerous opportunities exist to sample across paleoenvironments to com-
pare water quality characteristics.
In a preliminary study, water samples were collected from seeps emanat-
ing from the Princess Seven and the Tom Cooper coal seams which are represen-
tative of strata of upper delta plain and lower delta plain, respectively,
and analyzed for field pH and specific conductance. These data are plotted
in Figure 29. In general, the water samples collected from the upper delta
plain sequence have higher pH and conductivity values than samples collected
from the lower delta plain sequence. These data reflect the occurrence of
66
-------
7-
6-
4-
A A CONDUCTIVITIES
o 0 PH
PRINCESS SEVEN
TOM COOPER
1200
1000
800 >.
^
>
H-
600
-------
calcareous material in the upper delta plain strata which affords this water
regime with a natural buffering capacity. This is further substantiated by
the higher conductivities of water samples collected from this area. The
pH's and conductivities of samples collected along the lower delta plain se-
quence are significantly lower than those found in the upper delta plain se-
quence, and the field data illustrate a gradual decline in these geochemical
parameters in transgressing from one sequence to another.
The results of this preliminary study encouraged a more detailed region-
al investigation. Subsequently, water samples were collected from stations
where the coal samples used in this study were previously gathered to relate
water quality characteristics to the existing data. The following summarizes
the results of the regional survey of the water quality analyses.
Regional Water Quality Characteristics
All locations from whence coal samples were collected were revisited
during the month of June 1975. At most of the locations, water samples were
collected and analyzed for field pH, conductivity, acidity, hardness and sul-
fate concentrations. The results of these analyses are summarized in Appen-
dix B. In the following discussion, the sulfate, acidity, conductivity and
pH values of water samples collected from the lower delta plain will be con-
trasted with those collected from the upper delta plain.
A perusal of the data in Appendix B shows that the pH of water samples
from strata of lower delta plain paleoenvironments have low pH's which re-
flect lack of a natural buffering capacity within the section. In contrast,
the pH of the upper delta plain samples show neutral and slightly alkaline
trends. These trends basically corroborate the trends established from the
preliminary survey along Interstate 64.
The conductivity data from Appendix B are grouped by various paleoenvi-
ronments and plotted in Figure 30. The acid mine drainages that were sampled
during the survey are plotted at the top of the diagram for comparison. In-
terestingly, higher conductivities are noted for water samples collected from
the upper delta plain sequence than those emanating from the lower delta
plain sequence. This water quality trend, high conductivity and high pH,
again suggests the presence of calcareous material. Obviously, alkalinity
measurements would have more directly substantiated this premise, but because
of .the sampling difficulty and the inability to run alkalinity analyses with-
in twelve hours (thereby precluding valid results), these analyses were not
performed.
The sulfate values of the water samples shown in Appendix B were simi-
larly plotted, grouping samples into lower delta plain and upper delt^pl-ain
categories. In Figure 31, sulfate concentrations are plotted versus the pa-
leoenvironment of the seam from which the water sample was collected. The
values of acid drainages collected from the area are included for reference.
Again, another interesting trend is observed. Sulfate produced primarily by
the decomposition of the sulfide is readily abundant in water samples collect-
ed from the upper delta plain sequence. Because there are almost three times
68
-------
AMD
FRESH
WATER
TRANS.
MARINE
800
1600
2400
3200
Figure 30. Conductivities of water samples from various paleoenvironments
(units are in ximhos/cm)
69
-------
AMD
FRESH
WATER
TRANS.
3963
MARINE
800
1600
2400
3200
Figure 31. Sulfate content (mg/1) of water samples from various
paleoenvironments.
70
-------
as many samples collected from the upper delta plain sequence as there are
from the lower delta plain sequence, a sample bias may be introduced which
may affect the interpretations. The fact remains, however, that significant
amounts of sulfate are found in water samples emanating from the upper delta
plain rocks. This fact readily substantiates the data presented in Figures
25 and 26, which showed significant percentages of reactive pyrite to occur
within coals from the upper delta plain paleoenvironments. The quality of
ground water emanating from these coals further suggests that framboidal py-
rite is present on a regional scale, as indicated by the significantly high
sulfate concentrations of the water samples collected. Equivalent amounts of
sulfate are also noted to occur in samples collected from the transitional
and lower delta plain strata, which again substantiate the data derived from
the microscopic examination of the pellets.
The analyses of water samples gathered on the regional basis represented
to a greater degree the chemical composition and sulfur distribution within
the coal seam. These water quality data, coupled with the data obtained from
the microscopic examination of coal samples, substantiate the conclusion that
framboidal pyrite is present in upper delta plain strata but not to the de-
gree as noted to occur in the lower delta plain sequence. The fact that no
acid is associated with the occurrence of framboidal pyrite in the calcareous
rich strata underscores the importance of considering the ground water chem-
istry in attempts to ascertain drainage quality characteristics.
CONCLUSIONS
1. In view of the variability of the total sulfur contents that was
demonstrated to occur within uniform and geologically varying coal seams, any
interpretations of the data, and conclusions derived therefrom, must be cog-
nizant of this variability. The distribution of framboidal pyrite, as ascer-
tained by the microscopic examination of the polished pellets, has been shown
to be relatively abundant in seams of the lower delta plain paleoenvironments
and also present in significant concentrations in coals of upper delta plain
sequences. Statistical testing of regional trends, and within the limits of
variation that can be expected to occur naturally, show that framboidal py-
rite can be expected to be most prevalent in lower delta plain coals.
2. The leaching tests> which attempted to relate the occurrence of acid
mine drainage to coals of varying paleoenvironments, were quite possibly in-
fluenced by the inherent natural variability. Fortuitously, the samples of
upper delta plain coals had lower sulfur contents than those of the lower
delta plain. Consequently, the strong correlation between acid mine drainage
production and back barrier-lower delta plain coals and lack of acidity with
upper delta plain coals may be an artifact of high and low sulfur coals and
not related to paleoenvironment. The production of acidity from coals of a
lower delta plain environment, however, can be correlated with the presence
of framboidal pyrite as determined by the microscopic examination of the pol-
ished pellets. The lack of acid mine drainage from'coals of upper delta
plain used in the leaching tests may be due to the use of low sulfur coals
with a paucity of framboidal pyrite. However, the leaching tests did show
that sulfate anion concentrations can be used to identify the absence or
71
-------
presence of weathered pyrite.
3. On a regional basis, a significant amount of sulfate was present in
water samples collected from the upper delta plain paleoenvironment as well as
those collected from the transitional and lower delta plain strata. The pres-
ence of sulfate anion is correlative with the occurrence of reactive pyrite,
which substantiates the results of the reflected light microscopy.
4. The presence of sulfate in water samples collected from the upper
delta plain sequence showed framboidal pyrite to be present in the Princess
Seven, the Hazard Six and the Fireclay coal seams. Yet, in the majority of
cases, these drainages were not acid, although they had high specific conduc-
tances. In this area, pyrite is decomposing to produce moderate amounts of
acidity and sulfate anion. Within other parts of the flow regime, however,
water in contact with calcareous material generates sufficient concentrations
of alkalinity to effectively neutralize the acidity produced, thereby yielding
drainages that are characteristically neutral, high sulfate and have a high
specific conductance.
5. In comparison, the drainages from strata of lower delta plain paleo-
environments have lower specific conductances and pH's, although high sulfate
concentrations. These data indicate that the natural waters have a very low
buffering capacity, as expressed by the low conductivities and pH, and conse-
quently the decomposition of the framboidal pyrite found within these sections
effectively generates significant amounts of acidity which in the absence of
any buffering capacity generates acidic drainages.
In summary, it is the occurrence of framboidal pyrite coupled with the
geochemistry of the natural waters which ultimately controls the quality of
drainage that could be.expected. Both have been related to coals and strata
of varying paleoenvironments.
72
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76
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APPENDIX A
TABLE A-l TOTAL SULFUR AND PYRITE TYPE PERCENTAGES OF COAL SAMPLES
TABLE A-2 PYRITIC SULFUR AND FRAMBOIDAL PYRITE PERCENTAGES CALCULATED
FROM TOTAL SULFUR CONTENTS
77
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TABLE A-l. TOTAL SULFUR AND PYRITE TYPE PERCENTAGES OF COAL SAMPLES
Percentage Pyrite Types
Sample
1 Seam Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
i/>
4->
«
O
<_)
4->
1C
0)
0
Plant
Replacement
Massive
Cooper samples collected along 1-64 near Olive Hill, Kentucky
TCK/1 CH 3.86 70 15
TCK/2
TCK/2
TCK/3-1
TCK/3-1
TCK/3-1
TCK/4
TCK/4
TCK/4
TCK/4
TCK/4
TCK/5-1
TCK/5-1
TCK/5-1
TCK/5-2
TCK/5-2
TCK/5-2
TCK/5-3
TCK/5-3
TCK/5-3
TCK/5-4
TCK/5-4
TCK/5-4
T 1/2
L 1/2
T 1/3
M 1/3
L 1/3
CH
T 7.5cm
M 7.5cm
LM 7.5cm
L 28 cm
T 1/3
M 1/3
L 1/3
T 1/3
M 1/3
L 1/3
T 1/3
M 1/3
L 1/3
T 1/3
M 1/3
L 1/3
4.94
4.57
5.96
3.33
5.19
3.60
3.24
3.87
4.84
3.54
2.75
3.55
3.14
2.47
1.90
1.96
4.34
1.97
3.14
TCK/6
CH
1.96
TCK/7
TCK/7
TCK/7
TCK/7
U 2.5cm
L 5 cm
MT 2- 10cm
MT 10-18 cm
6.45
2.48
3.70
4.17
50
40
95
85
55
95
40
45
20
60
70
40
60
40
95
15
15
20
25
35
_
5
25
5
45
45
10
40
30
50
40
50
5
80
60
70
TCK/9
7.5 cm
6.02
95
10
15
25
25
5
10
20
15
10
70
10
10
5
25
10
60 40
5
10
80
78
-------
TABLE A-l (continued)
Sample
Coal Seam Code
Interval Sulfur
Sampled Content
Percentage Pyrite Types
& .p*1
«— 4-> C
.d -O 4J +J «J •!-
E 0> « C i—
J- 3 i— i— OJ JO
U_ LU 0 CL Q£ £
Princess Five samples collected along 1-64 near Rush, Kentucky
PR5K/1A
PR5K/1B
PR5K/1B
PR5K/1C
PR5K/1D
PR5K/1E
PR5K/2
PR5K/2
PR5K/2
PR5K/2
PR5K/3-1
PR5K/3-1
PR5K/3-1
PR5K/3-1
PR5K/3-2
PR5K/3-2
PR5K/4
PR5K/4
PR5K/4
PR5K/6
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
CH 7.75
T 15 cm 7.21
L 15 cm 4.81
11 cm 1.88
CH 1 5 cm 1.19
CH 7.5cm 1.26
T 1/3 1.96
M 1/3 1.62
L 1/3 1.30
Silicified only 3.90
T 5 cm 2.99
T 2/4 3.39
L 3/4 2.45
B 9 cm 1.73
Silicified 2.27
CH 2.38
Silicified 0.78
T 1/2 2.29
L 1/2 1.93
CH 2.94
CH 4.05
T 1/4 (1) 6.42
T 2/4 (1) 3.98
L 3/4 1) 6.59
L 1/4 (1) 1.99
T 1/4 (2) 4.09
T 2/4 (2) 4.52
L 3/4 (2) 4.86
L 1/4 (2) 4.25
35 20 - 45
10 15 - 75
20 60 - 20
15 5 - 80
10 10 - 80
15 10 - - 75
70 5 - 25
10 10 - 80
5 - 95
70 15 - - 15
50 30 - 20
30 30 - 10 30
80 15 - 5
95 5 -
60 20 - 20
70 10 - 10 10
50 20 - 30
79
-------
TABLE A-l (continued)
Percentage Pyrite Types
Coal Seam
Sample
Code
Princess Five samples
Princess
Princess
Ashland
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
PR5K/7
Five samples
PR5K/9
PR5K/9
Five samples
, Kentucky
PR5K/10
PR5K/10
PR5K/10
Interval Sulfur
Sampled Content
collected along
T 1/4
T 2/4
L 3/4
L 1/4
T 1/4
T 2/4
L 3/4
L 1/4
T 1/4
T 2/4
L 3/4
L 1/4
(3)
(3)
(3)
(3)
(4)
(4)
(4)
(4)
(5)
5)
(5)
(5)
collected along
T 1/2
L 1/2
collected along
CH-A
CH-B
CH-C
CO 4->
<— 4-> C
(O ro a.
S- 3 i— i— V
u. uj o a. on
Massive
1-64 near Rush, Kentucky (cont'd.)
5.
5.
4.
4.
_
7.
3.
5.
3.
3.
2.
3.
25
20
77
72
10
04
38
67
41
29
23
60 30 - 10
50 40 - -
40 30 - 10
40 5 - 25
80 15 - -
50. 50
80 15 - -
65 30 -
75 15 - -
60 30 - -
_
10
20
30
5
-
5
5
10
10
1-64 near Grayson, Kentucky
6.
3.
U.
3.
4.
3.
01
30
60
50
40
50
S. 23 near junction 1725, west of
06
14
74
15 10 - -
75
PR5K/11 CH
3.18
50 10
40
Princess Five samples collected along U.S. 60 Meads-North and South, Kentucky
PR5K/12
PR5K/12
PR5K/12
PR5K/12
PR5K/12
T 10 cm
10-23 cm
23-33 cm
33-41 cm
B 41-51 cm
1.79
1.84
2.18
0.42
1.73
25
100
75
80
-------
TABLE A-l (continued)
Percentage Pyrite-Types
Coal Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
to
4->
<0
O
O
4->
(0
-------
TABLE A-l (continued)
Percentage Pyrite Types
Coal Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
i/>
4->
03
o
o
-(->
5 cm
0.56
0.53
0.392
-
0.360
0.41
0.73
0.71
5*
5*
95
95
95
- No pyrite -
- No pyrite -
- No pyrite -
Princess Seven samples collected along 13th Street from Boy Scout Road towards
Ashland, Kentucky
PR7K/6 T 0-19 cm 3.50
PR7K/6 19-44.5 cm 1.61
PR7K/6 B 44.5-80 cm 1.87
35
20
20
10
20
20
55
60
60
*Paucity of pyrite
82
-------
TABLE A-l (continued)
Percentage Pyrite types
Coal Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
in
-P
ro
O
o
•P
10
-------
TABLE A-l (continued)
Percentage Pyrite Types
Coal Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
o
o
Lower, Middle and Upper Haddix samples collected along Daniel Boone Parkway
near Hazard, Kentucky (cont'd.)
UHAK/1 T 0-7.5 cm 1.41
UHAK/1 7.5-14.5 cm 0.61
4 cm plant shale
UHAK/1 18.5-23.5 cm 1.19
UHAK/1 23.5-29 cm 0.98
UHAK/1 B 29-33 cm 0.84
70
40
75
80
15
10
20
15
15
65
10
20
10
10
20
10
5
20
UHAK/18 T 0-6.4 cm
UHAK/18 6.4-13.3 cm 1.41
UHAK/18 B 13.3-21 cm 1.18
80
80
15
10
5
10
Hindman Nine and Below Hindman Nine samples collected along Daniel Boone Pky.
near Hazard, Kentucky
- No pyrite -
- No pyrite -
- No pyrite -
- No pyrite -
- No pyrite -
HI9K/14
HI9K/14
HI9K/14
HI9K/14
HI9K/14
HI9K/14
HI9K/14
HI9K/14
T 0-11.4 cm
11.4-25.4 cm
25. 4-40. 6. cm
40.6-51 cm
51-66 cm
66-81 cm
81-91.5 cm
B91. 5-101. 5cm
0.46
0.50
0.36
0.26
0.52
0.52
0.41
0.47
BHI9K/5
T 0-15 cm
BHI9K/22 T 0-28 cm
3.63
1.56
85*
30*
10
- No pyrite -
65. 15
85 10
5
70
20
*Paucity of pyrite
84
-------
TABLE A-l (continued)
Percentage Pyrite Types
Sample
Coal Seam Code
Interval Sulfur
Sampled Content
rd
-o >—
•r- (O
0 S-
JO XJ
£ o>
«} .C
S- 3
U. UJ
Cleat Coats
Plant
Replacement
Massive
Upper and Lower Francis samples collected along Daniel Boone Parkway near
Hazard, Kentucky
UFRK/4B T 0-14 cm 7.4
UFRK/4B 14-25.5 cm 11.19
UFRK/4B 25.5-32 cm 4.65
UFRK/4B 32- 42.5 cm 5.54
UFRK/4B
UFRK/13B
UFRK/13B
UFRK/13B
LFRK/4A
LFRK/4A
LFRK/4A
LFRK/4A
LFRK/4A1
LFRK/4A1
LFRK/4A2
LFRK/4A2
LFRK/4A2
LFRK/4A2
LFRK/13A
LFRK/13A
LFRK/13A
Clay spli
LFRK/13A
LFRK/13A
LFRK/13A
LFRK/13A
LFRK/13A
B 42.5-53 cm
T 0-13
13-20
20-35
T 0-5
5-15
15-32
B 32-46
T 0-13
13-29
T 0-10
10-19
19-27
B 27-37
T 0-18
18-28
28-33
t
48-52
52-62
62-74
74-88
88-100
cm
cm
.5 cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
cm
5.
0.
0.
0.
9.
5.
-
3.
8.
3.
5.
4.
3.
2.
0.
0.
0.
0.
0.
0.
-
-
51
73
83
72
98
39
17
33
72
30
88
27
81
40
55
43
66
66
54
90
85
90*
20 60
30 40
60 15
50 10
— _
90*. -
- Paucity
95 5
- Paucity
- Paucity
-
10
15
10
15
20
25
30
- .100*
-
of pyrite
-
of pyrite
of pyrite
- 100*
_
-
-
5
10
-
10
.:
10
-
-
-
-
LFRK/13A B 100-113 cm 0.35
- Paucity of pyrite
*Paucity of pyrite
85
-------
TABLE A-l (continued)
Percentage Pyrite Types
Coal Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
in
+->
<0
-------
TABLE A-l (continued)
Percentage Pyrite Types
Coal Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
-(->
-------
TABLE A-l (continued)
Percentage Pyrite Types
Coal
Seam
Sample
Code
Interval
Sampled
Sulfur
Content
Framboidal
Euhedral
00
+J
to
o
cj
•4->
to
-------
TABLE A-2. PYRITIC SULFUR AND FRAMBOIDAL PYRITf PERCENTAGES CALCULATED FROM TOTAL SULFUR CONTENTS
Sample Weight Sulfur
Pyritic
Wt. Sulfur Avg. S Sulfur
Weighted Framboidal
Relative Pyrite
Framboidal Content of
00
Coal Seam Code
Tom Cooper (Collected
TCK/1 CH
TCK/2
TCK/2
TCK/3-1
TCK/3-1
TCK/4 CH
TCK/4
TCK/4
TCK/4
TCK/4
TCK/5-1
TCK/5-1
TCK/5-2
TCK/5-2
TCK/5-2
TCK/5-3
TCK/5-3
TCK/5-4
TCK/5-4
TCK/5-4
Factor
along
-
2
2
3
3
-
7.5
7.5
7.5
28
3
3
3
3
3
3
3
3
3
3
Content z
1-64 near Olive
3.86%
4.94%
4.57%
5.96%
3.33%
5.19%
3.60%
3.24%
3.87%
4.84%
3.54%
2.75%
3.55%
3. 14%
2.47%
1.90%
1.96%
4.34%
1.97%
3.14%
Wt. Factor of Seam
Hill, Kentucky)
3.86
19.02
27.87
-
215.85
50.5
18.87
27.48
11.58
6
28.35
3.86%
4.76%
4.645%
5.19%
4.27%
3.145%
3.05%
1.93%
3.15%
(Calc.)
2.52%
3.22%
3.13%
3.56%
2.84%
1.96%
1.89%
1.02%
1.97%
Pyrite Content
70%
45%
90%
55%
50%
65%
50%
67%
56%
Seam
1.76%
1.45%
2.82%
1.95%
1.42%
1.28%
0.95%
0.68%
1.10%
(continued)
-------
TABLE A-2 (continued)
Coal Seam
Tom Cooper
Sample
Code
(continued)
TCK/6 CH
TCK/7
TCK/7
TCK/7
TCK/7
Weight
Factor
-
2.5
5
8
8
Sulfur I Wt. Sulfur Avg. S
Content £ Wt. Factor of Seam
1.96% - 1.96%
6.45% 91.485 3.89%
2.48% 23.5
3.70%
4.17%
Weighted Framboidal
Pyritic Relative Pyrite
Sulfur Framboidal Content of
(Calc. ) Pyrite Content Seam
1.04% 60% 0.62%
2.54% 95% 2.42
UD
O
TCK/9 CH
Princess Five (Collected along
6.02%
1-64 near Rush, Kentucky)
6.02%
4.21%
PR5K/3-2 CH -
2.38%
88.92
2.38%
1.37%
(continued)
10%
0.42%
PR5K/1A CH -
PR5K/1B 15
PR5K/1B 15
PR5K/1C CH -
PR5K/1D CH -
PR5K/1E CH -
PR5K/2 3
PR5K/2 3
P 5K/2 3
PR5K/3-1 5
PR5K/3-1 10
PR5K/3-1 10
PR5K/3-1 9
7.75%
7.21%
4.81%
1.88%
1.19%
1.26%
1.96%
1.62%
1.30%
2.99%
3.39%
2.45%
1.73%
180.3
30 :
14.64
9
88.92
34
7.75%
6.01%
6.01%
1.88%
1.19%
1.26%
1.62%
2.62%
5.56%
4.19%
4.19%
0.98%
0.44%
0.49%
0.77%
1.55%
No
35%
35%
10%
20%
No
1%
50%
Sample
1.47%
1.47%
0.098%
0.09%
Sample
0.01%
0.78%
No Sample
-------
TABLE A-2 (continued)
Sample Weight
Coal Seam Code Factor
Princess Five (continued)
PR5K/4 2
PR5K/4 2
PR5K/6 CH -
PR5K/7 CH -
PR5K/7 (1) 4
PR5K/7 (1) 4
PR5K/7 (1) 4
PR5K/7 (1) 4
PR5K/7 (2) 1
PR5K/7 (2) 1
PR5K/7 (2) 1
PR5K/7 (2) 1
PR5K/7 (3) 1
PR5K/7 (3) 1
PR5K/7 (3) 1
PR5K/7 (3) 1
PR5K/7 (4) 1
PR5K/7 (4) 1
PR5K/7 (4) 1
Sulfur E Wt. Sulfur
Content E Wt. Factor
2.29% 8.44
1.93% 4
2.94%
4.05%
6.42% 75.92
3.98% 16
6.59%
1.99%
4.09% 17.72
4.52% ~T~
4.86%
4.25%
5.25% 19.94
5.20% 4
4.77%
4.72%
7.10% 15.52
3.04% 3
5.38%
Avg. S
of Seam
2.11%
2.94%
4.05%
4.75%
4.43%
4.99%
5.17%
Pyritic
Sulfur
(Calc.)
1.16%
1.80%
2.67%
3.07%
2.97%
3.40
3.54%
Weighted Framboidal
Relative Pyrite
Framboidal Content of
Pyrite Content Seam
38%
No
53%
69%
50%
63%
0.44%
Sample
1.63%
2.05%
1.70%
2.23%
(continued)
-------
TABLE A-2 (continued)
Weighted Framboidal
Coal Seam
Princess
Princess
Princess
Princess
Sample Weight Sulfur z Wt. Sulfur
Code Factor Content z Wt. Factor
Five (continued)
PR5K/7 (5) 1 3.67% 12.60
PR5K/7 (5) 1 3.41% 4
PR5K/7 (5) 1 2.29%
PR5K/7 (5) 1 3.23%
Avg. S
of Seam
3.15%
Pyriti
Sulfur
(Calc.
1.97%
c Relative Pyrite
Framboidal Content of
) Pyrite Content Seam
67% 1.32%
Five (Collected along 1-64 near Grayson, Kentucky)
PR5K/9 1 6.01% 9.31
PR5K/9 1 3.30% 2
Five (Collected along US 23 near Junction 1725
PR5K/10 CH-A - 3.06%
PR5K/10 CH-B - 4.14%
PR5K/10 CH-C - 3.74%
PR5K/11 CH 3.18%
Five (Collected along US 60 - Meads - North and
PR5K/12 10 1.79% 84.28
PR5K/12 13 1.84% 51
PR5K/12 10 2.18%
PR5K/12 8 0.42%
PR5K/12 10 1.73%
4.66%
, west of
3.06%
4.14%
3.74%
3.18%
3.15%
Ashland,
1.90%
2.74%
2.43%
1.99%
55% 1.73%
Kentucky)
No Sample
15% 0.41%
No Sample
50% 0.99%
South, Kentucky)
1.65%
0.80%
12% 0.10%
(continued)
-------
TABLE A-2 (continued)
10
oo
Coal Seam
Princess
Princess
Princess
Sample Weight
Code Factor
Five (continued)
PR5K/13 2.5
PR5K/13 10
PR5K/13 15
PR5K/13 13
PR5K/13 15
Five (Collected along
PR50/1 10
PR50/1 13
PR50/1 15
PR50/1 13
PR50/2 CH
PR50/3 CH
Seven (Collected along
PR7K/1 10
PR7K/1 10.5
PR7K/1 25.5
PR7K/1 17.5
PR7K/1 12.5
PR7K/2 1
PR7K/2 1
PR7K/2 1
Sulfur z Wt. Sulfur Avg. S
Content z Wt. Factor of Seam
5.78% 135.36 2.44%
2.15% 55.5
2.12%
2. .42%
2.41%
US 52 at Ironton, Ohio)
0.84% 46.08 0.90%
0.90% 51
0.90%
0.96%
2.43% - 2.43%
2.75% - 2.75%
1-64 near Rush, Kentucky)
2.38% 188.86 2.49%
6.54% 76
1.93%
1.76%
1.31%
3.46% 8.05 2.68%
3.33% 3
1.26%
Pyritic
Sulfur
(Calc.)
1.41%
0.21%
1.41%
1.66%
1.45%
1.60%
Weighted Framboidal
Relative Pyrite
Framboidal Content of
Pyrite Content Seam
44% 0.62%
No Sample
No Sample
No Sample
42% 0.61%
13% 0.21%
(continued)
-------
TABLE A-2 (continued)
Weighted Framboidal
Sample Weight
Coal Seam Code Factor
Princess
Princess
Seven (continued)
PR7K/2W 1
PR7K/2W 1
PR7K/2W 1
PR7K/2E 1
PR7K/2E 1
PR7K/2E 1
Seven (Collected along
PR7K/3 CH-1 -
PR7K/3 CH-2 -
Sulfur
Content
1.13%
1.78%
4.13%
1.78%
1.44%
4.48%
Z Wt. Sul
fur Avg. S
E Wt. Factor of Seam
7.54
3
7.70
3
2.34%
2.57%
Pyritic
Sulfur
(Calc.)
1.34%
1.52%
Relative Pyrite
Framboidal Content of
Pyrite Content Seam
38% 0.51%
33% 0.50%
1-64 between Rush and Grayson, Kentucky)
6.63%
7.34%
PR7K/4 Not Sampled - Too
Princess
Seven (Collected 0.32
PR7K/5 23
PR7K/5 15
PR7K/5 23
PR7K/5 18
PR7K/5 15
PR7K/5 30
PR7K/5 26
PR7K/5 15
km west of
0.56%
0.53%
0.39%
0.36%
0.41%
0.73%
0.71%
-
-
Badly
Overpass
67.13
147
6.63%
7.34%
Weathered
3 and 1-64 on road
0.45%
4.68%
5.24%
65% 3.04%
50% 2.62%
which paralleles 1-64)
Paucity
Of Pyrite
(continued)
-------
TABLE A-2 (continued)
Weighted Framboidal
Pyritic Relative Pyrite
Sample Weight Sulfur I
Coal Seam Code Factor Content z
Princess Seven (Collected along 13th Street
PR7K/6 19 3.50%
PR7K/6 25.5 1.61%
PR7K/6 35.5 1.87%
PR7K/7 18 5.63%
PR7K/7 15 2.13%
PR7K/7 18 2.06%
PR7K/7 20 3.99%
PR7K/7 20.5 2.23%
vo PR7K/7 12.5 2.56%
tn
Princess Seven (Collected along US 52, 2.9
PR70/1A CH - 0.65%
PR70/1B CH - 0.97%
Wolf Creek (Collected along 1-64 near Olive
WCK/1 1 3.38%
WCK/1 1 2.51%
Wt. Sulfur Avg. S
Wt. Factor of Seam
Sulfur
(Calc.)
from Boy Scout Road towards Ashland
173.94 2.17%
80
327.885 3.15%
104
km east of Ironton, Ohio
0.65%
0.97%
Hill, Kentucky)
5.89 2.94%
1.20%
1.97%
bridge)
Paucity
0.26%
1.80%
Framboidal Content of
Pyrite Content Seam
, Kentucky)
23% 0.28%
18% 0.35%
Of Pyrite
10% 0.03%
52% 0.94%
Lower, Middle, Upper Haddix (Collected along Daniel Boone Parkway near Hazard, Kentucky)
LHAK/1 CH - 0.61% - 0.61% Paucity Of Pyrite
MHAK/1 7.5 0.66% 20.11 0.68% Paucity Of Pyrite
(continued)
-------
TABLE A-2 (continued)
Coal Seam
Sample
Code
Weight Sulfur z Wt. Sulfur Avg. S
Factor Content I Wt. Factor of Seam
Weighted Framboidal
Pyritic Relative Pyrite
Sulfur Framboidal Content of
(Calc.) Pyrite Content Seam
Lower, Middle, Upper Haddix (continued)
10
MHAK/1
MHAK/1
MHAK/9
MHAK/9
MHAK/18
MHAK/18
MHAK/18
MHAK/18
UHAK/1
UHAK/1
UHAK/1
UHAK/1
UHAK/1
UHAK/18
UHAK/18
UHAK/18
8
14
7.5
7.5
4.5
14.5
13.5
6.5
7.5
7
5
5.5
4
6.4
6.9
7.7
0.67%
0.70%
0.26%
0.26%
2.29%
0.67%
0.70%
0.61%
1.41%
0.61%
1.19%
0.98%
0.84%
_
1.41%
1.18%
20.11
29.5
3.90
TF~
33.435
39
31.025
29
18.815
14.6
0.68%
0.26%
0.86%
1.07%
Paucity Of Pyrite
Paucity Of Pyrite
0.18%
0.35%
40%
57%
0.07%
0.20%
1.29%
0.52%
80%
0.41%
Hindman Nine and Below Hindman Nine (Collected along Daniel Boone Parkway near Hazard, Kentucky)
45.025 0.44% Paucity Of Pyrite
HI9K/14
HI9K/14
HI9K/14
HI9K/14
HI9K/14
11.4
14
15.2
10.4
15
0.46%
0.50%
0.36%
0.26%
0.52%
101.5
(continued)
-------
TABLE A-2 (continued)
Weighted Framboidal
Coal Seam
Sample Weight
Code Factor
Hindman Nine and Below Hindman
Upper and
HI9K/14 15
HI9K/14 10.5
HI9K/14 10
BHI9K/5 CH -
BHI9K/22 CH -
UFRK/4B 14
UFRK/4B 11.5
UFRK/4B 6.5
UFRK/4B 10.5
UFRK/4B 10.5
Sulfur
Content
z Wt. Sulfur
l Wt. Factor
Avg. S
of Seam
Pyritic Relative Pyrite
Sulfur Framboidal Content of
(Calc.) Pyrite Content Seam
Nine (continued)
0.52%
0.41%
0.47%
3.63%
1.56%
7.4%
11.19%
4.65%
5.54%
5.51%
Lower Francis (Collected along
UFRK/13B 13
UFRK/13B 7
UFRK/13B 15.5
LFRK/4A 5
LFRK/4A 10
LFRK/4A 17
LFRK/4A 14
LFRK/4A1 13
LFRK/4A1 16
0.73%
0.83%
0.72%
9.98%
5.39%
3.17%
8.33%
3.72%
45.025
101.5
-
-
378.535
53
Daniel Boone
26.46
3575"
148.18
29
167.81
29
0.44%
3.63%
1.56%
7.14%
Parkway near
0.75%
5.11%
5.79%
2.34%
0.73%
5.08%
Hazard,
0.10%
3.50%
4.03%
Paucity Of Pyrite
65%
85%
No Sample
Kentucky)
77%
46%
No Sample
1.52%
0.62%
0.07%
1.61%
(continued)
-------
TABLE A-2 (continued)
CO
Coal Seam
Upper and
Hazard Six
Sample
Code
Weight
Factor
Weighted Framboidal
Pyritic Relative Pyrite
Sulfur E Wt. Sulfur Avq. S Sulfur Framboidal Content of
Content E Wt. Factor of Seam (Calc.) Pyrite Content Seam
Lower Francis (continued)
LFRK/4A2 10 5.30% 151.18 4.09% 2.70% No Sample
LFRK/4A2 9
LFRK/4A2 8
LFRK/4A2 10
LFRK/13A 18
LFRK/13A 10
LFRK/13A 5
LFRK/13A 4
LFRK/13A 10
LFRK/13A 12
LFRK/13A 14
LFRK/13A 12
LFRK/13A 13
LFRK/21A 7.5
LFRK/21A 7
LFRK/21A 9.5
LFRK/21A 7
LFRK/21A 10
(Collected along
HZ6K/2 5
HZ6K/2 15
HZ6K/2 5
HZ6K/2 3
HZ6K/2 8
4.88% 37
3.27%
2.81%
0.40% 35.12 0.49% Paucity Of Pyrite
0.55% 72
0.43%
0.66%
0.66%
0.54%
0.35%
154.06 4.60% 3.10% No Sample
5.01% 33.5
4.42%
5.40%
3.92%
Daniel Boone Parkway near Hazard, Kentucky)
0.61% 53.52 0.58% Paucity Of Pyrite
0.48% 93
0.56%
0.64%
0.47%
(continued)
-------
TABLE A-2 (continued)
vo
10
Sample
Coal Seam Code
Hazard Six (continued)
HZ6K/2
HZ6K/2
HZ6K/2
HZ6K/2
HZ6K/2
HZ6K/10
HZ6K/10
HZ6K/10
HZ6K/10
HZ6K/10
HZ6K/10
HZ6K/10
HZ6K/12
HZ6K/12
HZ6K/12
HZ6K/12
HZ6K/12
HZ6K/12
HZ6K/12
HZ6K/12
HZ6K/19
HZ6K/19
HZ6K/19
HZ6K/19
HZ6K/19
Weight
Factor
9
14
14
10
10
16.5
6.5
10
15
15.5
11.5
23
11
19
14
14
12
8
9
6
11
21
14
11
8
Weighted Framboidal
Pyritic Relative Pyrite
Sulfur E Wt. Sulfur Avg. S Sulfur Framboidal Content of
Content E Wt. Factor of Seam (Calc.) Pyrite Content Seam
0.65% 53.52 0.58% Paucity Of Pyrite
0.58% 93
0.53%
0.67%
0.67%
5.78% 152.83 1.56% 0.73% 51% 0.37%
0.56% 98
0.57%
0.61%
1.06%
0.66%
0.65%
0.94% 65.85 0.89% 0.20% 33% 0.07%
74
0.50%
0.57%
0.49%
1.47%
1.71%
1.25%
0.55% 66.26 0.71% 0.06% 9% 0.001%
0.65% 93
0.59%
0.58%
0.71%
(continued)
-------
TABLE A-2 (continued)
o
o
Coal Seam
Hazard Six
Sample
Code
(continued)
HZ6K/19
HZ6K/19
HZ6K/19
Weight
Factor
8
8
12
Hazard Seven (Collected along
HZ7K/3
HZ7K/3
HZ7K/3
10
8
11
HZ7K/3 15.5
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/3
HZ7K/11
HZ7K/11
HZ7K/11
8.5
13
9
10
12
12
10
14
13
14
14
10
12
17
18
11
10
Weighted Framboidal
Pyritic Relative Pyrite
Sulfur z Wt. Sulfur Avg. S Sulfur Framboidal Content of
Content l Wt. Factor of Seam (Calc.) Pyrite Content Seam
0.61% 66.26 0.71% 0.06% 9% 0.001%
1.86% 93
0.54%
Daniel Boone Parkway near Hazard, Kentucky)
1.31% 122.625 0.55% Paucity Of Pyrite
1.62% 221
0.84%
0.65%
0.56%
0.65%
0.48%
0.43%
0.49%
0.46%
0.44%
0.48%
0.47%
0.52%
0.40%
0.49%
0.34%
0.47%
0.54% 63.66 0.53% Paucity Of Pyrite
0.50% 120
0.56%
(continued)
-------
TABLE A-2 (continued)
Coal Seam
Sample
Code
Weight
Factor
Sulfur
Content
£
I
Wt.
Wt.
Sulfur
Factor
Avg. S
of Seam
Pyri ti c
Sulfur
(Calc.)
Weighted
Relative
Framboidal
Pyrite Content
Framboidal
Pyri te
Content, of
Seam
Hazard Seven (continued)
0.53% 63.66 0.53%
0.60% 120
0.56%
0.55%
0.39%"
o HZ7K/20 in 1.75% 97.94 0.82%
1.73% 120
1.56%
0.59%
0.64%
0.68%
0.28%
0.53%
0.49%
0.60%
0.61%
Fireclay (Collected along Daniel Boone Parkway near Hazard, Kentucky)
0.26%
HZ7K/11
HZ7K/11
HZ7K/11
HZ7K/11
HZ7K/11
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
HZ7K/20
23
14
13
18
13
10
8
11
12
15
10
14
9
13
8
10
Paucity Of Pyrite
0.15%
75%
0.10%
FCK/7
FCK/7
19
6.5
0.03%
0.95%
Paucity Of Pyrite
-------
APPENDIX B
CHEMICAL ANALYSES OF WATER SAMPLES COLLECTED FROM
EASTERN KENTUCKY IN THE AREA OF STUDY
102
-------
APPENDIX B. CHEMICAL ANALYSES OF WATER SAMPLES COLLECTED FROM EASTERN KENTUCKY IN THE AREA OF STUDY.
o
CO
Sample
Date
Collected
Date
Analyzed
Field Conductivity
pH (ymhos/cm)
Acidity
(mg/1 as CaC03)
Hardness
(mg/1 as CaC03)
Sulfate
(mg/1 as S0=)
Water Samples Collected From Lower Delta Plain Paleoenvironments
LFRK/4A1 (middle)
LFRK/4A2
LFRK/4A
(overlying SS)
UFRK/13B
HI9K/14
(underlying coal )
TCK/5
(shale over coal )
TCK/5 (coal)
TCK/7
(water puddle)
6/14/75
6/13/75
6/13/75
6/13/75
6/13/75
6/17/75
6/17/75
6/17/75
6/15/75
6/15/75
6/15/75
6/15/75
6/15/75
6/18/75
6/18/75
6/18/75
2.8
2.85
7.10
8.5
8.1
7.1
5.2
6.9
2450
1400
150
no
340
371
509
455
730
442
0.0
0.0
0.0
0.0
0.0
0.0
1010
387
64
30
340
217
115
253
1825
900
0
<30
88
306
375
100
TCK 6/17/75
(0.2m west of TCK/3)
6/18/75 2.85
1280
385
Water Samples Collected From Transitional Paleoenvironments
PR5K/5 (1) 6/17/75 6/18/75 6.55 707
0.0
409
344
612.5
303
(continued)
-------
APPENDIX B (continued)
Sample
•later Samples Collected
PR5K/4
(stream/fish)
PR5K/4
PR5K/4 (turbid)
PR5K/1C
PR5K/1D
PR5K/9
PR5K/11
PR5K/13
PR5K/2 (1)T=16 C
PR5K/2 (2)
PR5K/7
PR5K/8
Date
Collected
Date
Analyzed
Field Conductivity
pH (umnos/cm)
Acidity
(mg/1 as CaC03)
Hardness
(mg/1 as CaC03)
Sulfate
(mg/1 as S0=)
From Transitional Paleoenvironments (cont'd.)
6/17/75
6/17/75
6/17/75
6/16/75
6/16/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/17/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
7/7/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
7.85
6.02
6.18
6.98
6.45
7.25
6.64
6.78
2.88
6.28
685
395
369
mo
212
520
883
689
2680
1050
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1038
0.0
410
142
584
582
in
871
115
250
253
1170
604
325
419
887.5
1481
75
225
456
650
3963
1000
(continued)
-------
APPENDIX B (continued)
Sample
o
en
Date Date Field Conductivity Acidity Hardness Sulfate
Collected Analyzed pH (pmhos/cm) (mg/1 as CaC03) (mg/1 as CaC03) (mg/1 as SO*)
Water Samples Collected
FCK/15
FCK/16
FCK/23
FCK/24
HZ6K/12 (1)
HZ6K/12 (2)
HZ6K/12 (3)
HZ6K/19
(SS over rider)
HZ6K/19 (1)
(underlying leader coal
HZ6K/19 (2)
HZ6K/2
HZ6K/2 (gully)
From Upper Delta Plain Paleoenvironments
6/12/75
6/12/75
6/12/75
6/13/75
6/13/75
6/13/75
6/13/75
6/13/75
6/13/75
6/13/75
6/13/75
6/13/75
6/12/75
6/12/75
6/12/75
6/15/75
6/15/75
6/15/75
6/15/75
6/15/75
6/15/75
6/15/75
6/15/75
6/15/75
8.15
6.5
7.8
7.89
7.7
3.8
6.55
8.0
6.45
3.6
8.1
5.6
750
1310
225
350
470
650
475
1100
910
840
1300
750
0.0
9.6
0.0
0.0
0.0
24
0.0
0.0
0.0
72
0.0
0.0
385
805
123
306
175
272
200
594
479
411
399
373
300
1169
19
131
125
444
131
525
481
450
631
435
(continued)
-------
APPENDIX B (continued)
o
en
Sample
Date
Collected
Date
Analyzed
Field Conductivity
pH (ymhos/cm)
Water Samples Collected From Upper Delta Plain Environments (cont'd.]
HZ6K/2
(underlying rider)
HZ6K/10
UHAK/1
MHAK/1 (shale)
PR7K/2
PR7K/3 (turbid)
PR7K/5 (1)
PR7K/5 (2)
(turbid)
PR70/1
PR7K/1
6/13/75
6/13/75
6/13/75
6/13/75
6/17/75
6/17/75
6/18/75
6/18/75
6/18/75
6/18/75
6/15/75
6/15/75
6/15/75
6/15/75
6/18/75
6/18/75
6/18/75
6/18/75
6/18/75
7/7/75
7.8
7.05
7.15
8.2
7.65
3.57
7.00
7.02
6.85
1825
215
1450
1350
770
182
690
720
1160
1120
Acidity
(mg/1 as CaCO )
1
0.0
0.0
0.0
0.0
0.0
34
0.0
0.0
0.0
Hardness
(mg/1 as CaCO )
1112
116
836
383
298
11
354
284
661
416
Sulfate
(mg/1 as SO;)
2463
106
2875
663
156
0
581
609
1525
763
Samples of Particular Drainages Within the Study Area But Not Representative of a Paleoenvironment
6/14/75 6/15/75 2.7 2250 1178 675
AMD on route 3N near
Prestonsburg, KY
3000
(continued)
-------
APPENDIX B (continued)
Date Date Field Conductivity Acidity Hardness Sulfate
Sample Collected Analyzed pH (umhos/cm) (mg/1 as CaC03) (mg/1 as CaC03) (mg/1 as SO^
Samples of Particular Drainages Within the Study Area But Not Representative of a Paleoenvironment (cont'd.)
White drainage from 6/14/75 6/15/75 6.4 1450 0.0 809 975
deep mine (Rt. 23)
Red drainage (near 6/14/75 6/15/75 7.9 1485 0.0 810 650
Pikeville-Rt. 23)
Red and white drainage 6/14/75 6/15/75 5.35 1500 111 810 1300
(near Pikeville-Rt.23)
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-77-067
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Paleoenvironment of Coal and Its Relation to Drainage
Quality
5. REPORT DATE
June 1977 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Frank T. Caruccio, John C. Perm, John Home,
Gwendelyn Geidel and Bruce Ba'ganz
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Department of Geology
University of South Carolina
Columbia, South Carolina 29208
10. PROGRAM ELEMENT NO.
EHE 623
11. CONTRACT/GRANT NO.
R-802597-02
12. SPONSORING AGENCY NAME AND ADPRESS
Industrial Environmental Research Laboratory - Cin., OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final Report 8/1/73 to 7/31y
75
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The acid production potential of a coql was related to its paleoenvironment
(environment of deposition) as interpreted from the overlying strata. Within the
Appalachian coal field of easterp Kentucky, coals and associated strata were charac-
terized as'either back-barrier, lower delta plain or upper delta plain. Samples from
various paleoenvirqnments were analyzed for sulfur content and pyrite types (reactive
versus stable). Samples from the back-barrier, lower delta plain sequence had a rela-
tively higher percentage of reactive pyrite than the seams within strata of upper del-
ta plain. Both environments produced coals of similar total sulfur contents and
both contained varying percentages of framboidal pyrite. Although reactive pyrite
was present in seams of both paleoenvironments, a differing natural water chemistry
caused acid mine drainage to be associated with the back-barrier, lower delta plain
strata and never with the upper delta plain strata.
This study showed that the.pyrite distribution and, more importantly, the water
chemistry producing acidic or neutral drainages, were correlative with the paleoenvi-
ronment of the coals and associated strata.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/GlOUp
Coal
Drainage
Mines (excavations)
Sulfur
Pyrite
Paleoenvironment
Appalachian Coal Field
Eastern Kentucky
Framboidal Pyrite
Reactive Pyrite
13/B
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
118
20. SECURITY CLASS (THIt page)
22. PRICE
EPA Form 2220-1 (9-73)
108 ^ U'S- COVERNMENT PRINTING OFFICE: 1977-757-056/5639 Region No. 5-11
-------
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Office of Research and Development
Technical Information Staff
Cincinnati, Ohio 45268
POSTAGE AND FEES PAID
U S ENVIRONMENTAL PROTECTSON AGENCY
EPA-335
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