Readings and Notes An Introduction to Earth Science

2016

Coal Genesis
John J. Renton

Thomas Repine

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Part of the Geology Commons, and the Natural Resources and Conservation Commons
FIGURE 1. Goal Genesis
TIME ---------
PEAT COAL

Peat Braun Kohle Stein Kohle

German
Rank
Nomencl. Soft Brown Dull Brown Bright Brown
Peat Coal
Coal Coal
U.S. Sub-
Rank Peat BrownCoal Lignite Bituminous Anthracite
Nomencl. Bituminous

Basis for Moisture > 75% Moisture< 75% Moisture > 8-10% Moisture< 8-10%
subdivision dafCarbon < 60% dafCarbon > 60% daf Carbon < TT¾ datCarbon > TT¾
of major FreeCellulose No FreeCellulose Soluble in KOH & Insoluble in KOH &
rank categories HNO, HN0 3

PEATIFICATION COAUFICATION METAMORPHISM

Process of
Humification I I
organic _______ I' Vilrinitization
f Gelilication

i
conversion
Biochemical Geochemical
Vilrinitlzation
Gelification Geliflcation
Opt. pHCond. pH< 4-4.5 -+I pH Rising pH Neutral
(Peatification)
(a) Suga,s }
Starches CO2
Cellulose + Bacteria > CH.
Hemi-Cell NH,
Pectins H20
Protein
(b) Lignin Concentrates

(Humification)
(a) Ugnin Oxidizes • Humic Substances
Humic acids (sol in alk, ptt'd w/min. acids)
Fulvic acids (sol in aik, not ppt'd w/min. acids)
Basic Humins (insol in alk)
changes (�) Formation of organo-metallic complexes
within (Ties up Ca, Fe, Al, Mo etc.)
Peat•
Coal (Getification)
Components {a) Humic acids convert to humins
(Large increasingly aromatic mot)
{b) Functional groups lost-in
particular - COOH • ·H + CO2
(c) Metals rereleased into sol.
for second phase of mineralization
(d) Peptization • Desiccation • Solidification
Gel begins to convert to vitrlnite

(e) Porosity: Perm decreasing

(f) Coal becoming chemically inert

Coal now chemically

inert

Indicated Bacteria Bacteria Conversion of

depth change to cease to peat to coal
Anerobic function below
relationships below 0.5m below 10's m 200-400m

J
,,,

Time of mineral
implacement
SYNGENETIC 5 Cleat
Fmtion. EPIGENETIC
Early late �
Source of Detrital
mineral matter Vegetal CHEMICAL
Chemical
Source of Ground water Ground water Ground water
dissolved ions surface water chemical processes of Weather of minerals
for chemical Decomp9sition ot peatiflcation & exposed on cleat faces.
reactions plant debris, coalification

-
plant inorganlcs
--- SILICATES
-

J
Kaolinite -- - - - -Cleat Kaollnlte - -- - - - _.
,... lllite ]
Major& -- Mixed layer
--
-
minor

-
Chlorite
minerals Quartz
...- CARBONATES
-:
..,.__Calcite Cleat Calcite
Generalized �
---
..,.__ Siderite ,.
range and ..,.__ Dolomite -- Cleat Dolomite- _____ _.,.
time of OISULFIOES r
occurrence
-- Framboids/Euhedral X'L's - - -t>
(Non Dendritic) - Anhedral Pyrite - (Dendritic, Cleat Pyrite
-
..,._ - - - - Marcasite -- - - - - Cleat Marcasite - - - - - __.,..
...- Trace Minerals
�.
COAL GEOLOGY - A SYNOPSIS

INTRODUCTION: Most textbooks classify coal as a sedimentary rock

even though it does not fit the definition of a sedimentary rock.
While a sedimentary rock is a "rock formed from the products of
weathering and erosion", coal forms from the remains of land
plants. In fact, coal doesn't even fit the definition of a rock.
A rock is defined as "mixture of minerals" and minerals are
defined as "natural occurring, solid, inorganic substances •.• "
Coal is composed largely (~90+%) of organic substances (macerals)
which, by definition, are not minerals. If coal must be
classified as a rock, because it forms from a "previously
existing rock by the application of heat, pressure, and
chemically active fluids", it would best fit the definition of a
metamorphic rock. All of this points up the shortcomings of
classification systems. Rather than forcing coal to fit a
classification scheme in which it does not belong, a better
definition is that coal is "a natural-occurring, carbon-rich,
combustible solid found in association with terrestrial
sedimentary rocks."
Plant Sources: Coal forms from the tissues of land plants with
the major contributor being wood that accumulates and is
preserved in wetland environments. Land plants first evolved in
the Devonian and by the end of the period had adapted to most
terrestrial environments. Beginning in the Pennsylvanian, vast
portions of the super-ontinent of Pangea were covered by coal-
forming swamps and bogs, environments that were to be repeated
throughout the remainder of the Paleozoic Era and again in the
Jurassic, Cretaceous, and Tertiary. It was during these times
that the combination of climatic conditions and wetland
environments developed that were conducive to the growth and
preservation of large volumes of wood-rich plants, largely as the
result of tectonic events that placed continental masses in the
proper climatic settings while at the same time producing the
topographic settings under which vast peat-forming environments
could be maintained for long periods of time. Some coals, such as
many of those in the western United states, formed from peat that
accumulated in land-locked basins created by extensional
tectonics while others formed from peat that accumulated in areas
of low topographic relief along the margins of continents where
they were near but, as will be seen later, not chemically
influenced by the chemistry of ocean waters.
The rates at which plant debris accumulates varies greatly
depending on the particular type of plant. From the standpoint of
the accumulation of dry plant matter, for example, the most
prolific plants are cat-tails (Typha) that provide plant debris
at rates from 5 to as much as 15 kg/m2 /yr. The remains of cat-
tails are converted into peat that adds to the surface of the
peat mat at a rate of about 0.5-1.0 mm/yr. In comparison, swamp
fore ts in Florida generate plant debris at a rate of about 2-3
kg/m1/yr with subsequent peat accumulation of about 1-2 mm/yr;

1
the higher rate of peat accumulation reflecting the higher
concentration of woody tissue in the mangrove trees that inhabit
the Florida swamp forests. In temperate and cooler boreal regions
{tundra and taiga), 9n the otherhand, plant accumulation rates
rarely exceed 1 kg/m /yr due to the lack of large wood-rich trees
but because the cooler climates inhibit the activity of the
microbes responsible for plant decay, peat deposits are
widespread.
From these few data, it can be seen that the rate of peat
accumulation depends on factors other than plant productivity. A
simple, and speculative, model relates peat accumulation rates to
mean temperature and annual precipitation. Under temperate
conditions where cooler temperatures and limited rainfall inhibit
microbial activity that would decompose the plant debris, the
rate of accumulation of plant litter increases with 2 increased
precipitation, reaching a maximum of about 1.3 kg/m /yr at a
percipitation level of 2.2 m/yr after which the accumulation rate
decreases with increasing levels of precipitation. Under such
conditions, peat may form, even on non-wetland sloping surfaces
with annual precipitation rates of only 1.5 m/yr. Under tropical
conditions, the rate of litter accumulation increases to a
maximum of about 4 kg/m 2 /yr at an annual precititation of 2.8 m.
Again, increased precipitation results in decreases accumulation.
It is important to note that in tropical regions, except for
basins where water may accumulate, very high rates of
precipitation are required for the accumulation of peat. Studies
have shown that even under suitable wetland conditions, the
increased rate of microbial degredation of the plant litter in
tropical areas requires a minimum of 2 m of annual precipitation
just to maintain a peat mat.
Peat-Accumulating Environments: over the years, much confusion
has been introduced into the literature because of the
terminology applied to peat-forming environments, especially the
over-use of the term swamp. In recent years, the term mire has
been adopted for all freshwater peat-forming environments with
the particular kind of mire being primarily based on the relative
dominance of the two sources of water, rainwater and groundwater.
The importance of the water source lies in the totally different
chemistries of rainwater and groundwater. Rainwater is almost
always acidic because of reactions between atmospheric moisture
and gases such as co 2 and invariably is characterized by very low
ion content. Groundwater, on the other hand, because of the
influx of dissolved solids generated by the chemical weathering
of the surrounding bedrock is typically neutral to alkaline with
relatively high ionic content.
Mires that are totally fed by rainwater are only found in
everwet regions that receive precipitation during 10-11 months of
the year,. such mires are termed ombrotrophic and are referred to
as bogs. Bogs where the vegetation is dominated by trees are
referred to as bog forests. Because of the everwet conditions
that characterize ombrotrophic mires, precipitation always
dominates over evaporation, resulting in high rates of vegetal
growth. The combination of high rates of litter accumulation and

2
reduced microbial activity due to the presence of the acidic
waters, the peat surfaces in ombrotrophic swamps become elevated
above the influence of the groundwater, forming domed peats.
Because the domed peat within ombrotrophic bogs is totally
subjected to percolating, acidic rain water, much of the
inorganic constituents originally present within the plant litter
and subsequently formed peat are removed by dissolution. As a
result, domed peats are the precursors to low-ash, low-sulfur
coals. Many of the raised mires in eastern Europe and in the
temperate regions of North America are of this type with the
vegetation consisting of an upper story of coniferous trees below
which grows a dwarf shrub layer and a ground cover of Spagnum
moss. In the tropics, such forests are dominated by angiosperm
trees. Modern analogs of the peat-forming bog forests that
provided the peat for the Carboniferous coals are those of
Indonesia.
In areas with more seasonal rainfall, i.e., with periods of
wet and dry throughout the year, mires are subjected to a
combination of rainwater and ground water. Such mires are termed
rheotrophic. Because of the increased microbial activity in the
more neutral waters, doming of the peat does not take place and
the peat mat develops dominantly in a lateral direction to form
planar peats with the upper surface of the peat essentially
located at the watertable. Examples of rheotrophic mires are
estuarian and maritime wetlands such as saltwater marshes and
coastal mangrove swamps. In such settings, the high rates of
microbial degredation often precludes the accumulate of peat,
certainly peats that would be precursors to coal. At best, such
environments would give rise to carbonaceous shales. As we will
see, the fundamental difference in the chemistries of neutral to
alkaline groundwater and acidic rain water is responsible for
many of the compositional differences seen in coal, in particular
the quality of coal, i.e. the relative abundance of ash and
sulfur that characterizes the coal and associated rocks.
The term swamp is restricted to rheotrophic wetlands in
which the dry season water table is almost always above the
surface of the underlying sediment. The term swamp forest usually
refers to a tropical or sub-tropical swamp, such as the mangrove
swamps of southern Florida, where trees make up a major portion
of the vegetation. Rheotrophic wetlands located in temperate
areas are usually referred to by the Scandanavian term, carr. It
is important to note that the modern analogs to the "coal-forming
swamps" of the past are in fact not rheotrophic swamp forests but
rather ombrotrophic bog forests.

BASIC PLANT COMPOSITION

As is the case with most living things, water makes up most plant
mass. Typically, the dry weight of combined plant materials is
only about 10% of the original bulk weight with ash (mineral
matter) making up about 10% of the dried plant materials.
Although coal contains the entire suite of plant parts from roots
to leaves, the greatest volume of the coal is composed of the

3
remains of woody tissues. Compared to other plant parts, wood
contains less water with the dry weight of wood being about 50%.
The organic portion of plant debris is composed of a number of
different organic materials including: 1) protoplasm, 2)
chlorophyll, 3) oils, 4) carbohydrates which in turn include a)
starches and b) cellulose, 5) proteins, 6) lignin, 7) epidermis,
8) seed coats, 9) cuticles, 10) spore and pollen exines, 11)
waxes, and 12) resins. The first three materials decompose
rapidly and quickly disappear while the last six are very
resistant and are commonly found in coal in recognizable forms.
From the standpoint of peat formation, the principle peat-forming
components are carbohydrates (10-55%), 2) protein (0.2-18%), and
3) lignin (10-35%).
Carbohydrates are long-chained organic compounds that
include the monosaccharides (simple sugars such as glucose,
C6H 12 o 6 ), and monosaccharide polymers such as starch {the form in
which glucose is stored in plants) and cellulose. Cellulose,
(C 6 H100s)n forms the basic framework of plant cell walls and is
I • • •
the most abundant glucose polymer, containing approximately half
of all the organic carbon in the biosphere. From the standpoint
of coal formation, cellulose is the most important carbohydrate.
Proteins are complex chain structures consisting of at least
50 amino acids. An amino acid is a carboxylic acid with an amino
group (NH 2 ) on the carbon chain. A carboxylic acid is a carbon
chain ending with a carboxyl group, (-COOR).
Lignin consists of an aromatic nucleus (one made from
benzene rings), a side chain with three carbon atoms, hydroxyl
groups (-OH), and methoxyl groups (-OCH 3 ). The lignin content of
the wood ranges from 25 wt% to 30 wt%. Lignin and cellulose are
the primary plant components from which the great volume of coal
forms.

MICROBIAL DEGRADATION

Introduction: The process of coalification begins with microbial

attack on the accumulating plant debris. Aerobic conditions at
the very surface of the mire support the life processes of
microbes including fungi, actinomycetes (microorganisms
resembling both fungi and bacteria), and bacteria, all of which
take part in the biochemical reactions that initiate the
transformation of the cellulose and lignin contained within plant
debris into peat. In order for peat to accumulate, the rate of
plant growth must obviously exceed the rate at which the
microorganisms decompose the plant debris. In order for this to
occur, the decaying plant materials must be transferred into an
environment where microbial activity progressively decreases. The
most effective environment for this to occur is a waterlogged
site (a wetland) with living plants at the surface, dead plants
undergoing decomposition immediately below the surface the serve

4
as a major source of nutrients for the living plants, all
underlain by a mass of decayed plant debris encountering
decreasing rates of biochemical decomposition.
controls on Microbial Activity: Under most (non-wetland) surface
conditions, plant debris is totally decomposed by a combination
of microbial activity and chemical oxidation and is recycled. In
order for a coal-forming peat to accumulate, processes of plant
decay must be inhibited to the point that the rate of litter
accumulation exceeds the rate of litter decay. The major process
that must be affected is microbial degradation.
Microbial activity is largely controlled by: 1) availability
of moisture, 2) temperature, 3) supply of nutrients, and 4) the
acidity/alkalinity of the water. Of the four, moisture is the
main factor. Excessive moisture, such as is present in
waterlogged mires, reduces the overall activity of bacteria to a
minimum by excluding air from the aerobic bacteria while at the
same time allowing the continued growth of plants at the surface
of the mire. As long as the mire is kept wet by either high
levels of precipitation or poor drainage or both, the rate of
decomposition will be depressed relative to the rate of plant
growth and peat will accumulate. Note also that under typical
wetland conditions, chemical oxidation is severly inhibited as
dissolved oxygen reacts with the abundantly available carbon to
form CO2.
Assuming the availability of adequate moisture, the rates of
both plant growth and bacterial activity increase with increasing
temperature, reaching a maximum in warm, humid climes. Plants,
however, are less affected by variations in temperature than are
bacteria with bacterial activity decreasing at a faster rate than
plant growth with decreasing temperature. As a result, while
plant growth will be maintained in cool, temperate climates,
bacterial activity will be reduced to the point that allow the
preservation of increased amounts of plant debris and the
subsequent formation of peat; explaining why modern peat
development is most extensive at latitudes greater than 45°.
Another example of peat accumulation in cool, moist climates is
the fact that the most extensive peat accumulations in Europe are
located along the Atlantic coast where the combined effect of
high rainfall, dense clouds, and cool summers prevail. In
comparison, although plant growth will be maximized in tropical
climates, the accumulation of peat in tropical regions requires
bacterial activity to be reduced to such a level that the rate of
growth greatly exceeds that of decay, a scenario that requires
either the presence of acidic water such as is found in the domed
swamps or the presence of toxic materials generated during the
decomposition process.
The inorganic nutrients required by bacteria and
fungi(potassium, phosphate, and lime) are similar in kind but not
in abundance to those needed by green plants. In general, the
abundance of nutrients in the mire waters is dependent on the
acidity/alkalinity of the water. Acidic water will contain
relatively few nutrients while nutrients are more abundant in
neutral to alkaline waters because of their higher ionic

5
strength. While more extensive plant growth will occur on rich
soils or in water with high mineral contents with the subsequent
generation of increased masses of plant litter, the debris will
be subjected to higher bacterial populations and subsequently
higher rates of bacterial decay than plants debris derived from
plants growing in poor or impoverished soils or in water low in
dissolved solids. As a result, the rate of peat accumulation in
the latter case will be higher.
In mires, the major factor affecting acidity/alkalinity is
the lime content of the water. Where calcium carbonate content is
high, such as where the mire is underlain by carbonate rocks or
where it is influenced by ocean waters, acidity will be
neutralized and the waters will be neutral to alkaline. Examples
are the wetlands of the Everglades underlain by carbonate rocks
and the tidal-influenced mangrove swamps of south Florida. Peat
bogs fed largely by rainwater, on the otherhand, will be acid
because of the low ionic strength and inherent acidity of
rainwater. The microorganisms responsible for the decomposition
of plant debris are highly affected by extremes in both acidity
and alkalinity. Bacteria, for example, are more active near pH7
explaining the high rates of bacterial degredation of plant
debris in tidal-influenced coastal swamps. Fungi, although most
active in mildly acidic conditions, are not very active in
strongly acidic conditions such as those that prevail in areas of
high rainfall. The effect of either high acidity or lime
deficiency is therefore to suppress the rate at which plant
debris is decomposed relative to the rate of both plant growth
and debris accumulation. The result will be an increase in the
rate of peat accumulation.
Changes in Bacterial Acitivity with Depth: During the initial
stages of coalification, the biological-bacterial processes take
place at atmospheric temperature and pressure. Within the peat
layer, the availability of dissolved oxygen decreases with depth
as do the number of aerobic microorganisms until eventually the
biochemical processes affecting the peat are totally driven by
anaerobic bacteria. Because of the ease with which they can be
utilized by the microorganisms, cellulose and its decomposition
products remain the most important sources of carbon for micro-
organisms under both aerobic and anaerobic conditions. Only with
the onset of the more severe conditions that develop at depth
within the peat layer does lignin begin to decompose.
Once the peat layer is buried by sedimentation, usually
fluvial, a major change takes place in the coalification process.
Temperatures begin to rise within the buried peat, largely due to
the geothermal gradient. Eventually, the tem8erature reaches
100°c. Because temperatures in excess of 100 C (the boiling point
of water) for the most part preclude any type of microbial
activity, burial brings the microbiological phase of coal
formation to an end and physical-chemical processes take over as
the driving forces of coalification.
PHYSICAL-CHEMICAL COALIFICATION PROCESSES

6
Introduction: Once microbial activity ceases, continued
coalification becomes the result of the interaction of three
physical parameters, time, pressure, and temperature.
Notwithstanding the important aspect of time, temperature is the
most important with pressure actually inhibiting the
coalification process.
Temperature: After burial, most coalification processes take
place at temperatures between 100 0 C to 200 0 C, the process
commonly being compared to baking in a "slow oven". Although the
temperatures are relatively low, they are able to support
reactions that modify the composition ansd structure of the
organic components of the peat including decarboxylization,
condensation, desiccation, and the various structural
rearrangements that occur during continued coalification.
Once coalification proceeds beyond the lignite stage of coal
rank (we will discuss rank shortly), the chemical and physical
conditions are of such severity that the process must be
considered metamorphic in character. Because organic materials
are far less resistant to heat than are inorganic materials, the
coal materials will undergo major metamorphic changes even though
the rocks that surround them will show no alteration. As
coalification proceeds, the initial base-soluble organic
materials such as humic acids are converted into increasingly
insoluble materials with concurrent structural rearrangements
within the coal mass resulting in an increase in the aromaticity
of the coal molecule. By the time coalification attains the
anthracite stage, the coal molecule is composed entirely of
condensed benzene rings.
PROCESSES OF COALIFICATION

Three processes are involved in the transformation of plant

during the peat-brown-coal stages: 1} peatification, 2)
humification, and 3} gelification.
Peatification: The first step in coalification begins when
bacteria and fungi attack the newly accumulated plant debris by
decomposing the easily hydrolyzable plant components such as the
sugars, starches, cellulose, and proteins. A goodly portion of
these materials decompose under aerobic conditions to carbon
dioxide (CO 2 ), ammonia (NH3), methane (CH 4 ), and water (H2O) which
are either removed in solution or escape into the atmosphere. The
major result of these early coalification processes is the
concentration of the relatively stable lignins and mineral matter
in the peat.
Hwnification: Of all the processes taking place during the
peatification process, humification is probably the most
important. Humification is a slow oxidation process, although it
may be accelerated by the introduction of additional oxygen into
the peat such as during periods of drought when the watertable is
depressed or at sites where oxygenated water is introduced into
the swamp. The process of humification is most severe on and

7
immediately below the peat surface in what is referred to as the
peatigenic layer.
The two major plant tissues that are precursors to coal are
cellulose and lignin. During the rotting of plant tissues, the
linear macro-molecular (aliphatic) structure of cellulose is
rapidly attacked by microorganisms to form glucose which is in
turn used by them as an energy source and to make their bodily
parts. Experiments have shown that in the presence of the
nitrogen provided by the NH 4 generated during mineralization,
cellulose will decompose fifteen times faster than lignin. The
reason why lignin decomposes more slowly than cellulose is
because the combined 3-D aliphatic-aromatic structural units of
lignin are far more resistant to the microbial bond-breaking
processes that easily break the long-chain structures of
cellulose. Once the cellulose fibrils are removed from the cell
walls, the lignin within the cell becomes accessible to oxidative
degradation. Because lignin decomposes much more slowly than
cellulose, with time, it becomes an increasingly more important
material for the formation of the humic substances from which
coal forms.
Oxygen is necessary for the humification of lignin. In the
presence of oxygen and following the removal of the cellulose-
rich cell walls, the first attack on lignin is by wood-destroying
fungi followed by aerobic bacteria, converting the lignin into
humic acids. By definition, humic acids are those organic
materials that are insoluble in acids and organic solvents but
soluble in alkalis. The microbial attack on lignin first removes
the aliphatic side chains from the aromatic ring structures that
serve as its core and then attacks the ring structures
themselves. The smaller molecular units that are subsequently
formed then become the basis for the formation of the humic
acids. As the process continues and the -OH and -COOH groups are
removed from the humic acids, they lose their acidic character
and are converted into humins, the precursors to the vitrinite
macerals (to be discussed shortly).
Gelification: The process of gelification follows humification
and leads to the formation of vitrinite by the sub-bituminous
stage of evolution. Studies indicate that the gelification
process entails bringing the humins into colloidal solution with
the formation of a gel which is subsequently desiccated. Two
types of gelification are recognized, biochemical and
geochemical. Biochemical gelification initiates the process
during the peat and soft brown-coal stages (pre-lignite); the
process being governed by the original materials, the kinds and
abundance of ions available in the interstitial water, the
acidity-alkalinity of the water, and the redox potential of the
system. Geochemical gelification affects the humins once the
materials have attained the boundary between dull and bright hard
brown coal (lignite and sub-bituminous coal). Unlike biochemical
gelification that goes on at atmospheric temperature, geochemical
gelification requires elevated rock temperatures that are
attained only after the peat has undergone a certain amount of
burial. The major change brought about by geochemical

8
gelification is the conversion of the humins into the vitrinite
coal macerals. By the time coalification has progressed to the
bituminous stage, the vitrinites consist of humins that are
totally insoluble in alkalis.
THE COAL MACERALS

Introduction: Macerals are to coal what minerals are to rocks;

they are the microscopic entities of which the organic portion of
coal is made. There are three maceral groups, vitrinite, exinite
(liptinite), and inertinite. Because most modern coal petrography
is performed using reflected light and oil immersion lenses
rather than thin sections and transmitted light, the maceral
types are identified primarily on their relative colors and
degree to which they reflect incident light (brightness).
Vitrinite, for example is usually light to dark gray in
appearance while the exinites are much darker. The inertinites
are the most reflective of light and are therefore the brightest
macerals when viewed under the microscope. In addition to being
very bright, the inertinites are also the hardest of the maceral
types and therefore commonly stand out in relief above the
polished surface of the coal mount. Within the same rank,
vitrinite contains relatively more oxygen, exinite more hydrogen,
and inertinite more carbon. Of the three, exinite contains the
highest concentration of volatile-matter {67 wt%), vitrinite is
intermediate in volatile content (35 wt%), and inertinite has the
lowest volatile content (23 wt%).
Vitrinite

Of the three maceral types, vitrinite is volumetrically the most

abundant and is responsible for the brilliant, black bands seen
in coal. Vitrinite forms primarily from trunks, branches, stems,
leaves, and roots. There are three types of vitrinite: 1)
telinite which forms from the remains of cell walls and in which
the cell structures are visible within the vitrinite, 2)
collinite which is the structureless constituent of vitrinite
formed from preserved cell fillings, and 3) vitrodetrinite which
consists of aggregates of small, irregular-shaped fragments of
vitrinite that cannot be assigned with any assurance to either of
the other two types. Many observations of vitrodetrinite
indicates that the vitrinite components actually formed early in
the degradational history of the peat materials and do not simply
represent fragments of vitrinite that have been formed by the
pressure-crushing of existing vitrinite.
Often the telinite (cell walls) is filled with collinite.
Collinite is considered to be a preserved gel, explaining its
structureless appearance. The name is derived from the Greek word
"kolla" meaning glue; collinite does in fact commonly serve as
the binder or glue with which the other coal components are held
together. In cases where cell structures are difficult to see,
the maceral is simply recorded as vitrinite. Pure telinite is
relatively rare.

9
 Compositionally, vitrinite consists of aromatic nuclei
surrounded by aliphatic groups such as -OH, -COOH, and -CH3. With
increasing rank, the peripheral aliphatic groups are lost and the
aromatic nuclei increase in size.
Exinite

Exinite, also called liptinite, is derived from the remains of

the most chemically resistant plant components, namely, spores,
cuticles, resins, and algae giving rise to the four kinds of
exinite macerals, sporinite, cutinite, resinite, alginite. A
fifth exinite maceral, liptodetrinite is to the exinite maceral
group what vitrodetrinite is to the vitrinite maceral group. As a
result of compositional changes that take place within the
exinite materials during metamorphism, exinite cannot be
microscopically distinguished from vitrinite beyond the upper end
of the low-volatile bituminous rank.
Sporinite consists of the skins of spores and pollen. In most
Paleozoic bituminous coals, sporinite is overwhelmingly the major
maceral of the exinite group. It is estimated that, on the
average, a gram of Carboniferous coal contains 5 million spores.
Spores are easily recognized under reflected light because of
their dark colors. Because spores are invariably compressed by
burial, they are identified by their cross-sectional shape.
Spores are classified based on size as megaspores (>200 microns)
and microspores and on the thickness of the cell wall as either
tenuispores (thin-walled) or crassispores (thick-walled).
Megaspores have been identified with diameters as large as 3 mm.
The composition of sporinite is thought to be similar to that of
vitrinite (aromatic ring structures with aliphatic side chains)
but with fewer condensed rings. When heated, sporinite yields
more gas than the total coal sample and typically generates
exceptionally high tar yields.
cutinite is made up of the highly resistant skin, or cutin, that
covers and protects the surfaces of leaves, needles, shoots,
stalks, and thin stems of plants. It should be noted that some
plants that grow under water do not possess cutin. The widespread
occurrence of cutinite in coal is due to several factors
including the high resistance of cutin to chemical reactions, its
resistance to heat, and the fact that it is not accepted as a
food supply by bacteria and fungi. In Paleozoic bituminous coals,
cutinite is less abundant than sporinite. The characteristic
compositional feature of cutinite is its high hydrogen content(>
50 atomic%).

Resinite includes all the resinous components in coal. Resins,

such as sap, are the products of plant metabolism. With increased
metamorphism, much of the resinite present in lower-rank coals is
converted into vitrinite. Typical of exinites, resinite is
enriched in hydrogen, in fact, studies have shown that resinite

10
contains more hydrogen than sporinites of the same carbon
content.
Preserved algae, or alginite, has the lowest reflectivity and
therefore appears as the darkest bodies under reflected light.
Alginite is not usually found in humic (layered) coals but in
boghead coals where it represents the preserved remains of the
algae Pila and Reinschia.
Liptodetrinite is the catch-all classification for finely divided
particles of exinite that cannot be assigned with reasonable
certainty to any other member of the exinite group.
From the standpoint of coal-utilization, especially the
conversion of coal into gaseous and liquid fuels, the
exinite macerals are the most important. Because exinite is
enriched in hydrogen, it produces the greatest volume of
tars upon heating. The tar yield from spores and cuticles
ranges from 20% to 40% while waxes and resins produce as
much as 80% to 90% tar.
Inertinite

The name derives from the fact that while the vitrinite and
exinite macerals soften during the coking process, the inertinite
macerals are little affected. Compared to exinite, inertinite is
poor in hydrogen and rich in carbon. The inertinite maceral group
consists of fusinite, semi-fusinite, maorinite, miorinite,
solerotinite, and inertodetrinite.

Fusinite and vitrinite forms from the same plant materials.

Although particularly common in bituminous coals, fusinite rarely
exceeds a few percent by volume. Based on the mode of origin,
fusinite is subdivided into pyrofusinite and degradofusinite,
Pyrofusinite is the charred remains of woody tissue that forms by
rapid oxidation during swamp fires while degradofusinite is the
result of slow, chemical oxidation.
Studies of the woody tissues found in modern peat that has
been subjected to swamp fires have shown continuous transitions
from totally carbonized wood (pyrofusinite) to partially charred
wood (semi-fusinite) to unoxidized wood. Comparable transitions
are commonly observed on preserved wood sections within coal with
a wood fragment being converted to fusinite (completely burned
wood) on one end while the other end has been converted to
vitrinite (unburned wood).
Most of the fusinite found in Carboniferous and Permian
coals is degradofusinite that forms during the moldering of peat
by bacteria and fungi at the surface of the peat mat where the
supply of oxygen is at a maximum. Reports have also been made of
wood having been converted to fusinite in karst areas by the
subsurface percolation of oxygen-rich groundwater. Because of the
periodic wetting and desiccation of the peat, little if any of
the original wood structure is preserved.

11
 Fusinite is characterized by high carbon and low hydrogen
contents with both chemical and physical properties showing
little change with increasing rank. It might also be pointed out
that fusinite is the coal component that makes it "dirty".
semifusinite represents an intermediate stage between fusinite
(total carbonization) and telinite (no charring). Most of the
semifusinite in Carboniferous and Permian coals is of the
degrado-semifusinite type.
Macrinite is a more or less amorphous, non-granular groundmass
exhibiting high reflectance. As a maceral, it is relatively rare
and appears mostly in durites and clarodurites (coal lithotypes
that will be discussed below).
Micrinite is characterized by its rounded shape and small
size (~ 1 micron in diameter). Micrinite can occur in all
lithotypes but is especially abundant in durites.
Sclerotinite forms from the sclerotia of fungi (masses of
branched structures within which food is stored). Compared to
Tertiary coals, sclerotinite is relatively rare in Carboniferous
and Permian coals.

COAL TYPES

Coals are classified on their structure and source of origin as

being either humic or sapropelic. Humic coals are layered or
banded coals form from peat that accumulate in swamps with the
peat forming from plant debris by the process of peatification.
Sapropelic coals, on the other hand, are non-stratified coals
that form from a combination of finely divided plant debris,
spores, and algae accumulated in stagnant or standing bodies of
water and are initially converted by the process of
putrefaction. Sapropelic coals include channel coal and boghead
coal, both of which are relatively high in volatiles and
typically dull in appearance. Humic coals are, by far, the more
dominant of the two; sapropelic coals are, in fact, quite rare.
COAL LITHOTYPES

Humic coals: Humic coals are characterized by macroscopic layers

or bands called lithotypes that are identified based on their
degree of brightness and differ compositionally in the relative
abundance of the various maceral. The humic coal lithotypes are
vitrain (bright bands), clarain (semi-bright bands), durain (dull
bands) and fusain (mineral charcoal). Duroclarain and clarodurain
represent the transition between clarain and durain. The coal
lithotypes and their characteristic maceral groups and individual
maceral types are summarized in the following table.

12
LITHOTYPE MACERAL GROUP INDIVIDUAL MACERAL TYPES

VITRAIN Vitrinite(Vt) collinite(cell fillings)

telinite(cell walls)
micrinite
massive(inertinite detritus)
fine(microspore protoplasm)
FUSAIN Inertinite(I) semifusinite
fusinite
sclerotinite(fungal remains)
cutinite(skins of leaves)
resinite(resin bodies, cell
Exinite(E) fillings)
sporinite(spore remains)
alginite (algae, Pila,
Reinschia)
CLARAIN Vt+ E
DUROCLARAIN Vt+ E + I
CLARODURAIN I+ E + Vt
DURAIN I + E

Sapropelic coals: Sapropelic coals are subdivided intotwo

lithotypes, cannel coals and boghead coals with transitions in
between. As previously indicated, a major difference between
humic and sapropelic coals is that humic coals are stratified
(layered) while sapropelic coals are not. Because of their
composition and lack of internal structure, sapropelic coals are
dull, very dense, and very strong. From prehistoric times, for
example, sapropelic coals have been carved into statuary and
jewelry. Even today, cannel coals are used in the production of
"coal art".
Macroscopically, cannel coals and boghead coals are
difficult to distinguish; both being black, dull, exhibiting a
greasy luster and conchoidal fracture. Microscopically, however,
they differ in that cannel coals show micro-stratification,
contain little or no alginite, and are commonly rich in spores.
Boghead coals, on the other hand, are non-stratified and are
composed primarily of alginite.
COAL RANK

Introduction: Rank refers to the degree of coalification or

metamorphism to which the plant material has been subjected and
takes into account all of the chemical and physical changes that
take place within the material. The rank series begins with peat
as the lowest rank coal and ends with meta-anthracite as the
highest rank (see Table below). Metamorphism of coal beyond the
meta-anthracite stage results in the formation of graphite. The
numbers in the table represent estimated averages for the mid-

13
range rank. Note that sub-bituminous A and high-vol bituminous C
ranks are the same. The higher designation was initiated for
sales purposes.

VIT. d.a.f. d.a.f. CAL.

RANK REFL. VOL. CARBON BTU/lb
%Ro MAT.
Peat 0.25 67% 55% 4500

Lignite 0.32 58% 65% 7000

C 0.40 51% 69% 9000

Sub- B 0.45 48% 72% 9900
Bit. A 0.60 45% 75% 12000

Hi- C 0.60 45% 75% 12000

Vol. B 0.72 41% 78% 13000
Bit. A 0.82 35% 82% 14100

Med.
Vol. 1. 3 29% 87% 15500
Bit.

Low
Vol. 1.7 18% 89% 15500
Bit.

Semi-
Anth. 2.1 11% 90% 15500
----------- 2.5 ------ 8% ----- 92% -----------
Anth. 3.2 5% 95% 15500

Meta.
Anth. >4 <2 >95% 15500

During the first stages of coalification, the biological-

bacterial processes dominate and convert plant debris into the
lowest rank coal, peat. By the time the rank has risen to the
lignite stage, conditions of temperature and pressure preclude
the survival of microorganisms and the processes become purely
chemical or physical in nature with most of the energy used to
drive the coalification process being provided by heat. Beyond
the lignite stage, the changes that take place within the coal
are sufficiently severe that the coalification process can
realistically be considered metamorphic in character.

Affect of Depth of Burial: In most cases, the primary factor

driving the metamorphic process is the heat provided via the
geothermal gradient. Studies have shown that in a few isolated
cases, the heat was provided by magmatic sources located below
the basin of accumulation. Overburden pressure, although
responsibly for physical changes such as compaction that take

14
place within the coal, is not responsible for any of the chemical
changes that take place with increasing rank. Recent experiments
conducted under the same temperatures and for the same lengths of
time but under different pressures showed that the degree of
carbonization as measured by reflectance decreased with
increasing pressure. It is very important, however, to note that
carbonization is accelerated by tectonic pressure. Recent work
has definitely shown that coalification from the meta-anthracite
to graphite range requires the conditions brought about by
tectonic deformation where the important agent was the
involvement of tectonic shear.
It is also important to repeat the fact that, except for the
change of anthracite to graphite where temperatures in the range
of 300-350°c (and higher) are involved, the temperatures involved
in the coalification process rarely exceed 200°c. In the
discussions that follow, keep in mind the factor of time. Shallow
burial of peat over long periods of time can produce the same
result as deep burial over short periods of time. It is also
important to note that the entire coalification process from peat
to the beginnings of anthracite has taken place before any
changes in the surrounding sedimentary materials (diagenesis) has
begun.
One of the first studies to document the effect of depth of
burial on coalification was reported in 1963 based on samples
removed from the German Munsterland I borehole in the Saar region
of western Germany, at the time the deepest borehole in Europe.
The maximum temperature measured in the borehole was 209°c at a
depth of 5956 m. The borehole encountered about 100 coal beds and
thin coal bands with the uppermost Carboniferous beds encountered
at 1844 m and the deepest coal being encountered at 3445 m. Data
from the study showed that with increasing depth: a} the d.a.f.
(dry ash free} volatile matter decreased almost linearly from 35%
to about 5%, b) moisture decreased from 4% to 0.8%, c) vitrinite
reflectance increased from slightly more than 1%Ro to almost
4%Ro, d) d.a.f. carbon increased from 80.5% to 90%, and e) a.f.
(ash free) calorific content increased from 7600 kcal/kg to 8700
kcal/kg. Another important discovery from this and other studies
is that the increase in rank with depth of burial is totally
independent of the composition of the coal.
Determination of Rank: Because of the systematic changes in the
various coal parameters with rank, any one of the discussed
parameters could be used to determine rank. The parameter(s) used
depend primarily on the coal rank itself. For coals lower in rank
than medium-volatile bituminous, changes in d.a.f. carbon, d.a.f.
volatile matter, and vitrinite reflectance are not only irregular
but the changes with any incremental change in rank is very
small. As a result, they are not the best rank indicators for
coals below the rank of medium-volatile bituminous. On the other
hand, the a.f. moisture and calorific values for these coals show
marked changes with rank and, as a result, are the best
indicators of rank.

15
 As the rank increases beyond high-volatile bituminous,
moisture and moisture-dependent calorific content change little
with increasing rank. Between 30% and 8% volatile matter (from
medium-volatile bituminous to semi-anthracite coal), volatile
matter and vitrinite reflectance are the best determiners of
rank.
The most common parameter used to determine the rank of
bituminous and anthracite coals is vitrinite reflectance (%Ro), a
measure of the percent of incident light reflected from a
polished coal surface. Once rank has attained the anthracite and
meta-anthracite level, hydrogen content is the best rank
indicator.
compositional/Physical Changes with Increasing Rank: In the hard
brown-coal stage (lignite to sub-bituminous coal), vitrinite
undergoes profound physical changes. Below the rank of lignite,
cell walls and cell contents are readily visible in the stems of
plants. As the coal enters the lignite rank stage, the process of
gelification has resulted in the compaction and homogenization of
the cell tissues leading to the formation of a gel from which the
homogenous vitrinite of bituminous coal forms. As a result of
these combined chemical-physical modifications, the coal changes
from soft, brown, and dull to black, hard, and bright. Water is
expelled as the change takes place, explaining the marked
decrease in moisture content during early coalification. Because
the calorific content of ash-free coal is highly dependent on the
moisture content, the decrease in moisture is accompanied by a
parallel increase in calorific content. During this stage of
coalification, the humic substances lose increasing numbers of -
COOH, -C=O, -OCH3, and -OH groups from their aromatic cores
resulting in the concurrent increase in the aromaticity of the
coal and decrease in the oxygen content.
At approximately 87% carbon and 29% volatile matter (medium-
volatile bituminous), an important change referred to as the
coalification break takes place. By this time, desiccation of the
humic gel formed by the gelification process is near complete.
With increasing rank, the hydrogen-rich methyl (-CH3) groups
associated with the aromatic core are reduced and methane, CH 4 ,
begins to evolve. With the loss of the methyl groups, the
aromatic clusters begin to condense into larger groupings,
further concentrating the aromatic carbon and subsequently
resulting in an increase in the vitrinite reflectance.
The rank stages and a summary of the basic coal characteristics
are listed below:

Rank Stage %d.a.f. volatile vitrinite moisture BTU/lb

carbon matter reflect.
%d.a.f. % %
Meta-anthr.
Anthracite

16
--------------- 91 ------- 8 ------- 2.5 -------------- 15500 --
Semi-anthr
low-vol BC
med-vol BC 87 ------- 29 ------ 1.1 -------------- 15500
high-vol BC
--------------- 77 ------- 42 ------ 0.5 ----- 8-10 --- 12600
sub-bi tum
--------------- 71 ------- 49 ----------------- 25 9900
lignite
-------------------------- 53 ------ 0.3 ------ 35 7200
Brown Coal
--------------- 60 ---------------------------- 75 -------------
Peat
COAL QUALITY

coal quality is determined by the ash and sulfur content of the

coal and is subdivided into high-, medium-, and low-quality. In
general, ash and sulfur contents increase or decrease together.
We will discuss the conditions responsible for the encorporation
of ash and sulfur into coal later. The subdivision of coal into
high-, medium- or low-quality is purely an arbitrary decision.
High-quality coal is any coal whose sulfur content is less than 1
wt% and whose ash content is less than 10 wt%. Experience has
shown that coals with sulfur and ash contents below these limits
can be mined and utilized with little or no environmental impact.
As the ash and sulfur contents increase above these limits,
however, problems involving the generation of acid mine drainage
during mining and of air pollution when the coal is burned become
increasingly troublesome.
Unlike the standards set for high-quality coal, the
specifications separating medium-and low-quality coal is not so
definite but rather depends more on the potential environmental
impact. Generally, medium-quality coals would be those whose
sulfur and ash contents could be reduced by various cleaning
operations to produce an acceptable fuel for a coal-burning power
plant. This would include coals with sulfur contents between 1
wt% and about 3 wt% and ash contents from 10 wt% to about 25-30
wt%. Coals with higher levels of sulfur and ash would be low-
quality and would certainly result in unacceptable environmental
problems both during mining and utilization. It should be noted,
however, that state-of-the-art fluidized bed combustor technology
(to be discussed) allows the burning of fuels of unlimited sulfur
content. In that sense, once fluidized bed combustor facilities
replace all of the older coal burning power plants, there would
no longer be coal quality requirements for coal-fired power
plants.
COAL UTILIZATION

Introduction: Historically, coal has been used for two purposes:

1) coking and 2) the generation of steam. Since the Industrial
Revolution in the mid-1700s, the major use of coal has been the

17
production of steam, first to drive the steam engine, then the
steam turbine. Today, most coal is used to produce electrical
energy via the use of steam turbines.
Coking Coal: Whether a coal qualifies as a coking coal or steam
coal is primarily a function of coal quality. Coke is produced by
roasting the coal and driving off the volatile components leaving
behind a residue composed primarily of carbon. The major use for
coke is the reduction of iron ore (Fe 2 o 3 ) in blast furnaces. The
requirements for a coking coal are very stringent, less than 0.5%
sulfur and 6% ash. Any impurities in a coal used to make coke
could potentially be transferred to the molten iron which, in
turn, would affect the quality of any steel produced from the
iron. As a result, only the highest quality coals can be used.
Although there is no rank requirement for coking coal, bituminous
coal is preferred.
Steam Coal: Until the Environmental Protection Act of 1962, any
coal that did not qualify as a coking coal was considered a steam
coal. The major environmental problem associated with the use of
coal as a fuel for power plants is that during the combustion of
the coal, all of the sulfur is converted into sulfurous gases,
usually indicated as SOx. When released into the atmosphere, the
SOx gases react with water to produce the strong acids, H2SOx,
which are, in turn, partly responsible for much of the acid rain
that affects most of the industrialized countries of the world.
It must be pointed out that a second major source of atmospheric
acids are the HNOx acids produced when NOx gases generated by
internal combustion engines react with moisture in the
atmosphere.
Because of the air pollution problems that arose due to the
widespread burning of coal, especially during the past century,
laws were enacted to limit the amount of SOx gases that could be
produced from coal-fired power plants. Today, us law requires
that coals burned in coal-fired power plants cannot produce more
than 1.2# of sulfur per million BTU of heat generated,
essentially limiting coal burned in power plants, so-called
"compliance coals", to those containing less than 1.2 wt% sulfur.
For reasons that will be discussed, significant variability
in quality exists amongst coal. All coals west of the Mississippi
River, for example, are in compliance with the EPA sulfur limit,
as are coals in the southern Appalachian Coal Basin. The problem
that arises for today's coal industry, however, is that the
sulfur content of many of the coals in the northern Appalachian,
Illinois, and Mid-Continent coal basins are in excess of 1.2 wt%
sulfur. For example, the coal that represents about 25% of the
total coal production in the northern Appalachian Coal Basin, the
Pittsburgh coal, averages about 2.1 wt% sulfur. Before such coals
can be utilized as steam coals, they must be subjected to one or
more procedures designed to reduce the problems related to their
high sulfur contents. To this end, all non-compliance coals are
submitted to coal-cleaning processes. During coal cleaning, the
coal and any associated coal-associated rock is subjected to s
series of gravity-separation processes which are designed to

18
remove coal and rock fragments enriched in the iron disulfide
minerals. The disposal of the reject material, called coal
refuse, unfortunately is one source of another major
environmental problem associated with the coal industry, acid
mine drainage. We will discuss acid mine drainage latero
Another process designed to bring high-sulfur coal into
compliance is blending. Blending is simply the mixing of high-
quality coals with non-compliance coals such that the sulfur
content of the mixture is less than 1.2 wt% sulfur.
Since 1985, all new coal-fired power plants have been
required to incorporate scrubbers. Scrubbers are literally
washing machines within which the gases emerging from the
combustion chamber are washed with water that removes the SOx
gases by dissolution:

Note that the chemical reaction that goes on within the scrubber
is the same as that which is responsible for the generation of
acid rain in the atmosphere; scrubbers simply allow the reaction
to go on within the power facility where the acid can be removed
rather than being produced in the atmosphere where it can
contribute to the acid rain problem.
A relatively recent development to mitigate the sulfur
problem in coal-fired power plants is the use of getters. A
getter is a chemical added to the combustion chamber along with
the coal that reacts with, or "gets", the SOx gases as they form
and removes them as an inert compound. The most common material
used as a getter is limestone. The reaction within the combustion
chamber is quite simple. The limestone is thermally decomposed to
Cao and co 2 • The Cao, in turn, reacts with the SOx gases to
produce caso 4 which is removed with the ash.
The most recent development, and perhaps the technology that
will eventually eliminate coal-fired power plants as sources of
environmental problems, is the fluidized bed oombustor combined
with the use of limestone getters and the downstream use of
scrubbers. The fluidized bed combustor allows total combustion of
the fuel and getter within the combustion chamber and provides
ample time for the getter to react with any SOx gases produced.
This state-of-the-art system is so efficient that there is no
longer any limit on the sulfur content of the fuel burned. In
fact, most fluidized-bed power plants are so-called co-generation
power plants which refers to the fact that they burn a mixture of
coal and refuse. The plant at Morgantown, for example, burns a
mixture of 40% coal and 60% refuse. Some plants use all refuse as
fuel. Within such facilities, the SOx being generated is
constantly monitored with the amount of limestone getter
introduced into the combustion chamber being computer controlled
to that which all but eliminates the arrival of SOx gases at the
exhaust stack.
An additional plus for fluidized power plants is that if the
amount of limestone added to the combustion chamber is in excess
of that needed to react with any generated SOx gases, the ash,

19
referred to as FBC ash, contains a combination of Cao, Ca(OH} 2 ,
and unused caco 3 • The FBC ash has been used with great success as
an AMO ameliorant (to be discussed later). The Cao and Ca(OH) 2
reacting readily with water to immediately form a strong alkaline
solution while the caco 3 dissolves slowly over time to provide a
sustained alkaline production. The initial high levels of
alkalinity can actually inhibit the bacterial production of AMO
until the toxic material can be disposed of in such fashion to
minimize further oxidation. Once buried, the caco 3 content can
provide the lower levels of alkaline generation needed to
maintain the abiotic conditions that would preclude the future
generation of acid within the reclamation structure.
MINERALS IN COAL t ls' k c \ ;\ Q):.v.) ~ ' v '.(

Coal quality is largely determined by the abundance of minerals

contained within the coal. The primary coal minerals are the
silicate minerals clay minerals, including mixed layered clays,
kaolinite and illite, and quartz. As a group, the silicates
comprise 80-90 wt% of all the minerals found in coal. Of the clay
minerals, kaolinite and illite predominate with their relative
abundance reflecting the geochemical conditions that existed
within the original peat-forming swamp. Coals that formed from
peat that accumulated in swamps dominated by acidic water (< pH3)
will be dominated by kaolinite due to the fact that the ions such
as potassium and iron needed to generate illite would have been
removed in solution by the acidic water. With increasing pH,
elements such as the alkali and alkaline earths became more
abundant and consequently, illite becomes the favored clay
mineral. You will remember from previous discussions that acid
conditions prevail in domed swamps where the peat is influenced
by percolating, acidic rain water while planar swamps, because
the peat is more affected by groundwater are more alkaline.
The carbonates and disulfide minerals are second in
abundance with calcite and siderite being the major carbonates
and pyrite dominating over marcasite. Once again, the relative
abundance of the carbonate and disulfide minerals reflects the
geochemistry of the original swamp waters. Coals that formed in
acidic water conditions show a relative dominance of carbonates,
particular siderite. With sulfur removed by the acidic
interstitial waters, any available iron reacts with the
bicarbonate ion to form siderite. Coals that formed from peat
that accumulated under more neutral conditions show carbonates
and disulfides in more equal abundance. Siderite is conspicuous
by its absence ¾n such coals, the iron preferring to react with
the available s - ion. Most important from the environmental
standpoint is the increased abundance of iron disulfides in coal
forming under more neutral conditions of swamp geochemistry. Once
the sulfur content of Appalachian coals exceeds 1 wt%, the
increased sulfur content is due to the formation of the iron
disulfide minerals, mostly pyrite (FeS 2 ). Once pyrite begins to
precipitate, it forms at the exclusion of siderite.

20
 Depending on the coal, a variety of other minerals such as
feldspars, gypsum {CaSO 4 *2H 2O), bassanite (CaSO4*1/2H2O),
anhydrite (caso 4 ), jarosite {KFe3 {SO4)2(OH)6), and ankerite
(Ca(Fe,Mg,Mn) (CO 3 ) 2 ) may be present, almost always in relatively
low abundance.
Most of the mineral matter in coal is fine-grained with
particles measuring less than 20 µmin large dimension. With the
exception of massive occurrences of iron disulfides within the
coal or found as part of cleat mineralization, few mineral
occurrences will exceed 100 µmin large dimension. Although coal
balls, concretions, and nodules of pyrite, calcite, or siderite
can be locally abundant and distributed along persistent layers
within the coal, most such occurrences are relatively rare. Most
of the mineral matter in autocthonous coals is concentrated in
layers, a fact that allows much of the mineral matter to be
removed by coal-cleaning operations.
CLASSIFICATION OF COAL MINERALS

Introduction: Coal minerals can be classified as to: a) origin,

b) time of emplacement, and c) relative abundance.
origin of Coal Minerals: Based on origin, coal minerals can be
classified as either detrital, vegetal, or chemical. A detrital
origin implies that the mineral was derived from a source
external to the peat-forming swamp and was transported as
particulate matter into the swamp by water or wind. For many
years it was a common misconception that most coal minerals, in
particular the clay minerals and quartz, were detrital in origin
having been introduced into the swamp as stream over-bank
deposits during times of flood. Certainly, some such introduction
of detrital sediments takes place as streams break through the
levee and expunge into the adjacent swamp as a crevasse splay or
as distributary streams go overbank during flood events. Studies
have shown, however, that even during major flood events, little
detritus is carried beyond the levee into the swamp. Most quartz
stays within the stream channel and the clay minerals flocculate
from suspension immediately upon encountering the acidic swamp
waters. One need only remember that during the preparation of
clay minerals for x-ray analysis, clay suspensions are
flocculated onto the sample mount surface by the addition of a
mere drop of acetic acid. studies have definitely shown that the
detrital introduction of minerals into a coal-forming swamp is at
best minimal. Although some portion of the minerals in coal could
be of airborne origin, it would be very small in abundance. In
summary, the great volume of minerals in coal are not detrital in
origin but, rather, are of vegetal and authegenic origin.
Vegetal origin: Most of the minerals in coal are, in fact, of
vegetal origin. Think of the ash remaining after the burning of a
log. All plants contain inorganic material with the kinds and
amounts of mineral matter depending on the type of plant, the
particular plant part, the climate, and the bed rock geology of

21
the site upon which the plant grew. Plants draw water throughout
their body structures and use whatever dissolved ions are needed
for their metabolism and continued growth. Upon reaching the
plant extremities, the water is transpired through the leaves
into the atmosphere. Any dissolved ions remaining at the time of
transpiration are disposed of by storage in unused cells,
typically, the dead wood cells that are responsible for the great
volume of most coals.
X-ray diffraction analysis of plant ash generated by the
low-temperature ashing of various types of plant materials have
shown that most of the inorganic material in plants is amorphous
with elemental analyses showing that alumina (Al 2 o3 ) and silica
(Si0 2 ) are the most abundant ingredients. A suite of wood samples
collected by the author from the Snuggedy Swamp along the South
Carolina coast, the Okefenokee Swamp on the Georgia-Florida
border, and the Mississippi Delta showed an average alumina and
silica content of 1.4 and 1.7 wt% (on a dry weight basis)
respectively. These amorphic materials are the source materials
for the subsequent formation of the silicate minerals found in
coal, the clay minerals and quaartz. The same x-ray diffraction
study showed that the only crystalline material found in the
plant ashes was calcium oxalate (CaC 2 0 4 *H 2 0). Calcium oxalate is
a common mineral found in the tissues of sub-tropical and
tropical plants ..
Of the various types of plant parts, wood generally contains
the least amount of ash{< 1-2 wt% on a dry weight basis). By
contrast, bark and leaves contain relatively high amounts of ash
with concentrations of 15-20 wt% (on a dry weight basis) not
being unusual. In addition, in contrast to the material found in
wood, much of the material in bark and leaves was shown by x-ray
diffraction to be crystalline. The most abundant crystalline
material observed in ashes from all of the woody plants that were
samples was calcium oxalate. Crystalline silica was commonly
found in swamp grasses although most of the silica was amorphous.
Although the actual abundance of inorganic materials found
in plants is relatively low, when one considers the enormous
amount of plant debris that accumulates in a coal-forming swamp,
the amount of accumulated inorganic material is impressive and
must be taken into account in any discussion of the origin of
minerals matter in coal. Rather than proposing that the mineral
matter is primarily detrital and derived from sources outside the
swamp, one must explain what happens to most of the mineral
matter provided by the accumulated plant debris. Simple
calculations, for example, indicate quite clearly that in order
to arrive at the ash content of a typical low-ash coal, >90% of
the plant-derived inorganic matter must be removed from the
accumulating peat, let alone any introduced from outside the
swamp. It is estimated that 5.1 tons of plant debris is required
to produce a 1 mm-thick layer of peat over an area of 1 acre.
Assuming a peat-to-coal compaction ratio of 10:1, it would
require nearly 16,000 tons of plant material to produce 1 acre-
foot of coal that would in turn weigh approximately 1800 tons
with.

22
Chemical origin: Minerals of chemical origin are those that
formed from materials once contained in aqueous solution. The
individual minerals may form by direct precipitation from
solution or as the result of a chemical reaction between the
solution and both the inorganic and organic materials present in
the peat or the coal.
A variety of sources exist for dissolved ions. One source,
external to the swamp, is the chemical weathering of rocks in the
surrounding highland. Materials that are taken into solution as
the result of the attack of dissolved carbon dioxide are
transported into the swamp via groundwater of surface water flow.
A second source of dissolved materials is the decomposition of
the plant materials within the swamp itself. Some of the
inorganic materials held within the plant parts, such as calcium
oxalate, are water soluble. Other inorganic plant components,
although insoluble, may undergo dissolution by being attacked
chemically within the swamp. In addition, the decomposition of
the organic plant components that were originally held as part of
the organic molecules by organo-metallic bonds will be released
into solution as the bonds are destroyed. Although such releases
are especially important and dominant during the early
humification and peatification stages of coal formation, they may
actually go on later in the coalification process.
Time of Origin:

Minerals are emplaced in coal throughout its history beginning in

the earliest peat-accumulation stage and continuing up to the
most recent time. There appear to be, however, two major times of
emplacement, syngenetic and epigenetic.
syngenetic Minerals: The syngenetic stage of mineral formation
occurs as long as solutions can move through the peat or coal
mass. Early syngenetic mineral formation occurs during the
peatification stage of coal formation up to the time of peat
burial when the less-resistant plant tissues are being decomposed
by microbial activity and converted into various gases, mostly
CO2 and NH4, and water. The co 2 subsequently reacts with water to
form carbonic acid, one of the most important, and potent, agents
of chemical weathering on Earth. The increase in the acidity of
the water contributes to the increased mobility of many ions,
especially the metals.
As the more soluble plant components undergo dissolution,
cellulose and lignin survive and become concentrated in the peat.
During the initial plant decomposition, the amorphous alumina and
silica, commonly found in woody tissues, are released into the
peat and become the precursors to the silicate minerals that
dominates the mineral matter of most coals, especially the clay
minerals. Although ordered clay minerals are not commonly found
at this early stage, it is not unusual to find chemically
precipitated, crystalline iron disulfides in the form of
framboids and individual euhedral crystals. It would be at this
time that any contribution of detrital materials would be made.

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 After burial of the peat, additional accumulation of
minerals of either vegetal or detrital origin is precluded. The
minerals of the late syngenetic stage are therefore totally
chemical in origin. With burial, the coalification processes of
humification and gelification are initiated. Upon being buried,
the products of peatification, lignin and cellulose, begin to
undergo oxidation and are converted to humic acids by the process
of humification. As we have seen, the process of humification
begins at the surface of the peat and continues at depth within
the accumulating peat mass and after the peat has been completely
buried by overlying sediments. The humic acids subsequently
complex with cations contained in interstitial solutions such as
calcium, aluminum, and iron. The late syngenetic minerals are
formed in part from ions released into solution as the basic
organic molecules undergo decomposition during the process of
humification.
During gelification, the products of humification are
further modified by fundamental structural changes within the
organic material. Various functional groups are lost, carboxylic
acid groups decompose with the formation of co 2 , and the organic
materials are converted into complex organic molecules called
hum.ins. Humins are the precursors to the vitrinite macerals.
During gelification, the organic material becomes increasingly
aromatic in nature as aliphatic functional; groups are lost. At
the same time, elements that were originally held in organo-
metallic complexes are released into solution. As the materials
desiccate with time, the total ionic strength of the remaining
interstitial solutions increases.
With the decomposition of the organic groups, the pH of the
interstitial solutions begins to rise to neutral or alkaline
levels. During this phase of chemical activity, two major groups
of minerals are emplaced, the carbonates and the disulfides. The
decomposition o! the carboxylic acid groups introduces co~ into
solution as co 3 - while, at the same time, calcium ion, Ca+, is
released into solution from disintegrating organic associations.
As the pH rises, the solubility product of the calcite is
exceeded and calcite begins t~ precipitate. Depending on the
availability of magnesium, Mg+, dolomite may form although it is
rarely as abundant as calcite. sj.9-erite will form only if the
activity of the sulfate ion, so 4 , is low. Most carbonate
minerals occur as pore or fracture fillings.
When the interstitial solutions contain significant
concentrations of sulfate ion, the disulfide minerals form. The
sulfate ion is formed by bacterial activity and is subsequently
reduced by the a9aerobic conditions within the buried peat to the
di~ulfide ion, S -, which, in turn, reacts with ferrous iron,
Fe+, to form pyrite, Fes 2 , and to a lesser extent, marcasite.
Most of the disulfides that characterize the high-sulfur coals
(>1-2 wt% S) are emplaced during this phase of mineralization and
occur largely as the more massive morphological occurrences such
as cavity fillings, cement within inertinites, overgrowing
previously formed disulfides, and replacing coal macerals such as
vitrinite and, to a lesser extent, exinite. Framboids and small

24
euhedral crystals continue to form during this phase of
mineralization.
In addition to the carbonates and disulfides, authigenic
kaolinite apparently forms during this time, filling
microfractures that are beginning to develop within the coal. The
microfractures are also the site of a host of trace minerals
found in coal that are emplaced at this time. The late syngenetic
phase of mineralization probably accounts for the greatest
variety of minerals found in coal.
With continued burial, the compaction due to the
increasing weight of the overlying sediments combined with
the continued diagenesis of the humins to form the vitrinite
macerals serves to progressively decrease both the porosity
and permeability within the coal. Eventually, the dimensions
of the pores remaining within the coal are reduced to that
of a molecular sieve. At this point, although the coal
continues to show hydraulic communication throughout, the
hydrated ions from which the coal minerals form are
progressively excluded from entering and moving throughout
the coal mass because of their molecular dimensions. Those
that do find entry find it increasingly difficult to form
crystal lattices in the available space. This restriction on
the entry to and movement of hydrated ions within the coal
mass terminates the syngenetic phase of mineral formation.
Epigenetic Minerals: Once cleat forms, the final, or epigenetic,
phase of mineral implement begins. The development of major
fractures within the coal allows the ready movement of
groundwater bearing mineral-forming ions throughout the coal bed.
By this time, the organic portion of the coal has become
essentially inert and no longer serves as a major contributor of
ions to groundwater nor does it react with groundwater to result
in the formation of minerals. At this point in time, groundwater
becomes the sole source of ions from which the epigenetic
minerals forms. The most common epigenetic minerals are the
carbonates, pyrite, and kaolinite. Of the carbonates, calcite is
the dominant while pyrite is, by far, the dominant disulfide.

PEAT-FORMING ENVIRONMENTS

One of the most significant field trips relative to the

geochemical environment of the peat-forming swamp was led by Bill
Spackman, one of the world's foremost coal petrographers. The
field trip was part of the GSA national meeting in Miami,
Florida. The trip compared the geochemistry of the Okefenokee
Swamp along the Georgia-Florida border and the Everglades of
southern Florida. The Okefenokee Swamp is a fresh water swamp
located behind an ancient barrier island system that completely
isolates it from the Atlantic Ocean. With the exception of a
small amount of limestone bedrock at its southern tip, the swamp
is located entirely on non-carbonate rock materials. As a result,
the swamp waters are acidic with pH values as low as 3 and with

25
very low concentrations of both total dissolved solids and
sulfate ion.
Over most of its extent, the Everglades is a marsh
rather than as swamp, the difference being that a marsh is a
wetland dominated by grasses while a swamp is a wetland
dominated by wood-rich plants, mostly trees. The Everglades
begins as a broad overflow of Lake Okeechobee in central
Florida and flows southward as a very broad, shallow
"channel" to Florida Bay. Because of the underlying
carbonate bedrock, the pH of the water is everywhere near
neutral. In the extreme southern portion of the Everglades,
the marsh changes into a swamp as mangrove trees begin to
dominate over grasses. Along the coast where the swamp is
influenced by marine waters via tides, the waters become
alkaline.
The main objective of Spackman's trip was to compare
the contribution of the plant communities to the peat and to
illustrate the influence of water chemistry on organic
degradation. One of the leading organic geochemists of the
day, Peter Given, had installed some simple and ingenious
experiments in the swamps six months prior to the trip that
were designed to demonstrate the relative rates of
degradation of cellulose depending on water chemistry. The
experiments consisted of wrapping cellulose filters around
plastic rods which were in turn driven into the peat. As the
trip progressed, the experiments were removed for
inspection. The results were dramatic. The experiments
showed that when the water pH was below pH3, microbial
activity was very low and remained low as long as the pH was
below pH5. Above pH5, however, microbial activity increased
markedly and reached a maximum at pH7 where the filters had
been nearly completely consumed. The data clearly indicated
that in order to accumulate enough peat to form a coal, the
peat must accumulate in acidic (<pH3-4)conditions. Swamps
within which the water pH rose above 5 would not accumulate
sufficient peat to be the precursor to a mineable coal. This
was directly in opposition to the reigning "truth" that
coastal swamps were good models of coal-forming peat
environments and that the coal was divided into marine and
fresh-water facies depending on the relative influence of
fresh and marine waters. At the time, the Mississippi Delta
was the "premier" swamp environment with the relative
influence of marine and fresh waters generating what were
designated as lower-, middle-, and upper-delta plain coals.
Aside from the fact that all of the data clearly indicated
that the water chemistry of any swamp that had even the
slightest marine influence would preclude the accumulation
of sufficient peat to form a mineable coal, the areal
dimensions of modern swamps located on delta surfaces were
nowhere near large enough to account for the areal extent of
known mineable coals such as the Pittsburgh coal.
As the result of subsequent research done in this department
in conjunction with the USGS, it became apparent that all

26