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Critical Reviews in Biotechnology, 1 1 (4):347-366 (1991)

Biological Coal Conversions*


B. D. Faison
Chemical Technology Division and Environmental Sciences Division, Oak Ridge
National Laboratory**, P.O. Box 2008, Oak Ridge, Tennessee 37831-6194
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ABSTRACT: The discovery in 1982 that microorganisms can interact with, and presumably modify, the
chemical structure of coal has focused attention on the potential for the use of microbial cultures or isolated
microbial enzymes in coal conversion. Biological processes based on this activity will promote the effective
utilization of low-rank coal, which is poorly suited to direct combustion. Research in this area may also support
the development of improved biological technologies for the cleaning of high-rank coal and/or the treatment of
coal-derived waste.

KEY WORDS: Coal, low-rank coal, coal utilization, coal bioconversion, biological coal conversion.

1. INTRODUCTION under way in other countries, most notably (the


Federal Republic of) Germany, the present re-view
This review will describe current research will focus on domestic initiatives. A number of
into the application of biotechnology to coal uti- papers describing engineering considerations and
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lization. A major goal of the work described here process economics relevant to biological coal
is the development of technologies for the con- conversions have appeared previously. 5-8
version of coals to high-quality liquid or gaseous Coal represents one of the world’s most
fuels, or to chemicals. Coal bioconversion as de- abundant fossil energy resources. It is estimated
fined here differs fundamentally from coal clean- that the world’s coal reserves stand at 153,000
ing (i.e., the removal of inorganic contaminants quads (1 quad = lOI5 Btu), or 71.4% of the world’s
such as sulfur from coal). Substantial research total fossil fuel r e s ~ u r c e sBy.~ compar-ison,
efforts have focused on biological coal desulfur- the world’s crude oil reserves represent 7100
ization, and numerous reviews are available on quads, or 3.3% of its total resources. The energy
that topic. content of the world’s recoverable coal is 91.1 %
A number of laboratories in the U.S., pri- of the total energy content available in oil, gas, and
marily with support from the U.S. Department of coal combined; its carbon content, which is
Energy (DOE) or the Electric Power Research predominantly aromatic carbon, is 93.9% of that
Institute (EPRI), have made contributions in the in the three resources combined. Thus, coal rep-
area of biological coal conversion. Although ac- resents a significant source of fuel or organic
tive research programs on coal bioconversion are chemicals.
In the U. S., increased utilization of coal rep-
* Research supported by Fossil Energy Advanced Re- resents an avenue to greater economic self-reli-
search and Technology Program, managed by the ance. (Note: domestic coal reserves represent
Pitts-burgh Energy Technology Center, U.S.
Department of Energy. 38,000 quads, or 24.8% of the world’s t ~ t a l . ) ~
** Managed by Martin Marietta Energy Systems, Inc., for Indeed, since the oil embargoes of the mid-l970s,
the U.S. Department of Energy under contract DE- the development of technologies for coal utili-
ACO5-840R21400. zation has become a strategic need. In 1987 coal

0738-8551/91/ $so
0 1991 by CRC Press, Inc.

347
supplied 20.1 quads of domestic energy used, or by the action of biological and, to a greater ex-tent,
3 1.1% of that produced domestically and 26.4% geological forces over prolonged periods. I I The
of total domestic energy consumption. The latter early reactions in the coalification process are
figure represents an increase from 17.5% in mostly biochemical (i.e., the microbial deg-
1973, primarily due to coal’s increasing primary radation of polysaccharidic residues contained
usage for electricity generation. One tenth (net) of within biomass to form humins and peat),I2 and
the coal mined in the U.S. is exported. In contrast, may be either aerobic or anaerobic. The presence
42% of the oil consumed here is imported. The of hopanoids, compounds unique to certain bac-
U.S . possesses a 148-yearproven reserve of coal, teria, suggests that coal consists, in part, of fos-
vs. an unproven 30-year supply of petroleum silized microbial residues. l 3 The presence of the
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products (crude, shale, and bitumen). Thus, the fossilized remains of fungal hyphae, sclerotia, and
importance, both actual and potential, of en- spores in some coals further bolsters this view.I4
hanced coal utilization to the U.S. energy econ- The sediment produced by microbial ac-tion,
omy is obvious. under the further influence of heat and ex-treme
The most common coal utilization technol- pressure, is metamorphosed to coal. Ad-jacent
ogy is its direct combustion. A substantial portion inorganic materials, plus water, may also be
of the U.S. supply is, however, unsuitable for use incorporated. The resultant material was de-
in this manner. Although these low-rank coals scribed by Hippo et al. as a “carbonaceous rock”
make up less than one tenth of the nation’s sup- with mineral inclusions.’s These authors, in the
ply, their sheer abundance mandates their future same work, likened coal to a fruitcake. Because of
use. Indeed, one such deposit - the Fort Union the unique paleoenvironment and physical
Field, located in the Dakotas - has been called the conditions involved in coal formation and weath-
largest coal basin on Earth.lo This deposit ering, no two coals obtained from different sites
contains 80% of the U.S. reserve of low-rank coal. are alike. These factors, coupled with the inher-ent
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Another important deposit is the Gulf Coast field, chemical heterogeneity of plant tissue and the
whose borders extend from Texas through varying distribution of mineral elements in soil
Arkansas, Louisiana, Mississippi, Alabama, and microenvironments, explain the observed differ-
Tennessee. Smaller deposits are found in Colo- ences in composition between samples taken from
rado and Alaska. Conventional processes for the adjacent areas within a coal seam. 16.”
utilization of low-rank coals include thermo- The extent of metamorphism of a given coal
chemical liquefaction and gasification, processes is dependent on several factors, including geol-
that require high temperature (as high as 1350°C) ogy, climate, depth of burial, and the time
and pressure (20 to 140 atm). The high capital and elapsed since deposition. ‘ I One may generally
operating costs associated with the use of these distinguish younger coals (i.e., lignites and
processes render them economically unat-tractive subbituminous coal) from the older bituminous
in light of the substrate’s low value. A current and anthracite coals. Lignites (as well as
technological goal is the development of petroleum and natural gas) tend to be less than
alternative processes for the utilization of low- 200 million years old; in contrast, bituminous
rank coals that require milder operating condi- coals may date from 225 to 325 million years
tions. The need for such processes is the driving Coal analysis presents extreme technical
force behind the biological research described dif-ficulties, which have been discussed in de-
here. tail. 1 5 * 1 8 ~ 1 9The following summary reflects the
current state of knowledge regarding coal struc-
ture, with emphasis on those aspects that affect
II. COAL: COMPOSITION AND its bioconversion.
UTILIZATION

A. Genesis B. Organic Components


Coal is formed from decayed plant material Light microscopic examination of coal re-

348
veals the presence of macerals, or distinct bony1 groups (of which 80% is in bridging struc-
organic entities that arise from different plant tures). Organically bound oxygen is distributed in
tissues. These entities include vitrinite, which subbituminous coals in similar proportions.
originates in lignified tissues; liptinite (also All coals contain small amounts of sulfur, a
known as ex-inite or resinite), which originates portion of which is organic. However, the amount
in spores, pol-len, waxes, and other resinous of inorganic sulfur in coal generally equals or
materials; and inertinite, which originates in exceeds the organic sulfur content.’ Sulfur ap-
carbonized wood and other detritus. These pears to be more tightly bound to higher-rank
macerals are agglom-erations of complex coals, suggesting a higher proportion of organi-
macromolecular structures whose relative cally bound materials. l9 Major organic sulfur
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proportions may influence the chemical functionalities in coal include aromatic and ali-
characteristics or biodegradability of coal. U.S. phatic sulfides, disulfides, and thiols and thio-
coals are composed of 50 to 90% vitrinite, 5 to phenes. Quantitative removal of sulfur from coal
30% liptinite, and 5 to 40% inertinite .,’ thus requires the breaking of covalent carbon-
Young or low-rank coals, such as lignites and sulfur bonds.
subbituminous, resemble lignin somewhat in Coals tend to contain nitrogen as well as sul-
structure and composition. 19,2122 Their degree of fur, generally in an inverse relation.19 It may be
aromaticity has been reported to lie in the range of assumed that at least a portion of this nitrogen is
50 to 75%, by conservative estimates. These coals
l9qz3 covalently bound to carbon (e.g., in quinoline or
generally contain one or two fused or con-densed carbazole-like structures). However, little infor-
rings per aromatic moiety, although fused-ring mation exists on the structure of organic nitrogen
systems containing three, four, or more rings are structures within coal.
also present. Specifically, lignites are based
primarily on benzene and naphthalene ring struc- C. Inorganic Component
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tures; subbituminous coals, on naphthalene , an-


thracene, and phenanthrene structures. Lignite High- and low-rank coals contain clays (sil-
contains more three-ring and fewer four-ring icates), quartz (SiO,), calcite (CaCO,), and var-
structures than does subbituminous coal, al-though ious sulfur compounds, among other materiak6
they have similar amounts of one- and two-ring Inorganic sulfur in coal is mainly pyritic, in-
clusters. Hydroaromatic structures are also present. cluding pyrite and/or marcasite (FeS,) .,,, Other
Higher-rank coals, namely, bitu-minous and sulfide compounds, sulfates, and, rarely, ele-
anthracite, approach graphite (“chicken wire”) in mental sulfur may be present. The bulk mineral
structure. Both lower- and higher-rank coals contain phase of coal, although not Covalently bound to
aliphatic structural ele-ments, primarily as the carbon backbone, is intimately associated with
polymethylene bridges be-tween aromatic moieties. the organic component. Pyritic sulfur may be
The aliphatic carbon content of coal is inversely either macroscopic, existing as discrete nodules
proportional to the total carbon content. Bituminous within the organic matrix, or it may be finely
coal may con-tain 30% aliphatic carbon. In addition, dispersed.
all coals contain a presumably low-molecular- The metal content of coals varies according to
weight vol-atile component, which ranges from 53% its paleoenvironment. Low-rank coals have a
in lig-nite through 48% in subbituminous, 38% in fairly high content of ion-exchangeable cations,
bi-tuminous, and 6% in anthracite.,’ which are probably mainly associated with car-
Low-rank coals have a fairly high content of boxyl groups.I9 Iron and aluminum may, how-
oxygen that is covalently incorporated into the ever, be organically bound. Polyvalent ions con-
organic matrix. Approximately 60% of the or-ganic tribute to the structural stability of low-rank coals
oxygen within lignite coals is in either ether or through bridging of ionic residues.
hydroxyl functionalities, 10% of which occurs in
bridging structure^.^^ The balance (40%) of the D. Water
organic oxygen is in ester, carboxyl, and car-
There are five categories of moisture in

349
intrinsically adsorbed water, which is associated was described as early as 1962.25 Since then,
with microcapillaries or micropores; surface-ad- several species of fungi and bacteria have been
sorbed water; capillary water; interparticle water; shown to grow on or transform solid coal (Table
and water that is adherend to the coal surface. The 1). This phenomenon was first documented in the
first three types are considered to be inherent English-language literature in 1982 by Cohen and
moisture and are difficult to remove. Lignite con- Cabrielle,26 who described the activity of Poria
tains 35 to 70%moisture, and subbituminous coal placenta and Coriolus (also known as Po-lyporus
contains 10 to 35% moisture, as mined. l 2 Lignite is or Trametes) versicolor with reference to growth
therefore something of a hydrous gel, presum-ably on lignite. These organisms are highly evolved
due to the moisture that is associated with its many basidiomycetous fungi known to interact with
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polar oxygen functionalities. 2o Bitu-minous and lignified plant tissue. They are brown- and white-
anthracite coals contain less than 10% and less than rot wood-decay fungi, respectively. Cor-
5% moisture, r e s p e c t i ~ e l y . ~ ~ , ~ ~ iolus, which degrades lignin, grew more rapidly
on lignite than did the nonligninolytic Poria. The
E. Utilization as a Fuel substrate for this work was a fairly young (-70
million years old) lignite in which lignified plant
The fuel value of a given coal is determined by remains were clearly visible. Both organisms
its chemical properties, including its degree of produced a dark, water-soluble liquid transfor-
oxidation, its oxygen content, and its moisture
content. The low-rank coals are considered to have TABLE 1
a low fuel value that would not be substan-tially Examples of Organisms Capable
enhanced by cleaning. Low-rank coals were thus of Coal Solubilization
seen as a legitimate target for bioconversion
Organism Ref.
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technology development. Fortunately, these are the


coals most amenable to biological treatment. Fungi
The conversion of low-rank coals to trans- Basidiomycetes (“Higher
portation fuels (i.e., fuel alcohols) or to methane fungi”)
Coriolus versicolor 26
is a desirable goal. Traditional fermentative pro- Phanerochaete 45
cesses may be useful in either application. Pro- chrysosporium
posed intermediates in the biological breakdown Poria placenta 26
of coal (e.g., monoaromatic compounds) are seen Unidentified isolate 28
as valuable commodity chemicals whose large- Fungi
Hyphomycetes (“common
scale production would alleviate the current de-
molds”)
pendence on petrochemicals. The microbiology Acremonium sp. 28
and biochemistry of coal conversion are de- Aspergillus spp. 27,31
scribed in Section 111. Section IV summarizes Cunninghamella sp. 28
potential uses for coal bioproducts. The potential Mucor spp. 27
Paecilomyces spp. 27,31
for the application of organisms or biocatalysts,
Penicillium spp. 27
shown to be effective in the conversion of low- Sporothrix sp. 31
rank coals, in coal cleaning or in the treatment of Yeastlike fungi
coal-derived waste is addressed in Sections V and Candida sp. 27
VI. Actinomycetes
Streptomyces badius 32
S. setonii 50
111. BIOLOGICAL COAL CONVERSION: S. viridosporus 50
FUNDAMENTAL ASPECTS
Eubacteria
Bacilfus sp. 30
Pseudomonas sp. 49
A. Microbiology Other
CP 1 + 2 (bacteriaVfungal 92
The presence of microbial populations in coal consortium)

350
mation product when cultured in direct contact Microbial coal solubilization is seen as a
with coal. po-tential basis for the design of novel coal
Since this early report, a variety of fungal conver-sion processes. This activity will be the
isolates found associated with lignin or with coal focus of the remainder of this section.
in nature or in the laboratory have been shown to
effect a similar transformation (Figures 1 and
2) . The majority of these isolates were first de- 6. Substrate Requirements
scribed by Ward27and Ward and Sanders.28 The
abiIity to solubilize coal is apparently quite wide- Low-rank coals such as lignite are generally
spread among aerobic microorganisms. Activity more susceptible to biosolubilization than are the
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within axenic cultures has been demonstrated in the higher-rank coals. Also the degree to which na-
higher, basidiomycetous fungi; in a number of lower tive coals may be biosolubilized has been re-
fungal genera such as Candidu and Pae-cilomyces; ported to be related more closely to the coal than
in several species of wood-rotting an& or to the microorganism tested. 17.29.30 This suscep-
ligninolytic streptomycetes; and in one mem-ber tibility in low-rank native coals generally paral-
each of the eubacterial genera Bacillus and lels their degree of weathering. 17,31*32Short-term (-
Pseudomonas. 90 d) weathering, however, has no effect on
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FIGURE 1. Fungal coal solubilization in surface culture. (a) Candida sp.


was pregrown on Sabouraud maltose agar for 7 d at 30°C,80% relative
humidity. Lignite particles (3-to 5-mm diameter) were sprinkled on right
side of culture, and culture was reincubated for an additional 7 d under
the original growth conditions. Left side of culture illustrates intact mycelial
mat and undissolvedcoal particles (added immediately before photograph
was taken). (b) Sporothrix sp. was cultured for 7 d as described above;
lignite was added, and culture was reincubated for 3 d.

351
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only.

FIGURE 16
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solubili~ation.’~~~’Acorrelation between the ox- nally, Maka et al.34 described enhanced bioso-
For personal use

ygen content of coal and its susceptibility to bio- lubilization as a result of oxidizing treatments and
solubilization has been noted. 30.32 This correla- poor biosolubility of a coal that had undergone wet
tion may be the basis for the previously cited carbonization (a dehydrative and hydrogen-ative
influence of coal rank. process). Chemical and physical oxidizing
Various substrate pretreatments have been treatments are known to swell coal, exposing more
shown to enhance microbial activity against coal. of the polymer to attack.” Indeed, a gross cor-relation
Pioneering studies by Strandberg and Lewis29and between the rate and extent of coal bio-
by Scott et aL3’suggested that the most effective solubilization, and particle size has been n ~ t e d . ’
treatments were those that increased the oxygen ~These.~~ oxidizing treatments also pro-duce
content and thus, effectively, decreased the rank of oxygen-containing functionalities that may provide
the substrate. Lignites treated with H,O, or 0, initiation sites for subsequent biological reactions .
displayed increased susceptibility to attack by 29,36 However, certain nonoxidizing treatments
organisms previously shown to solubilize natu-rally affected biosolubility as well. Sodium dodecyl
oxidized native coals.29Exposure of lignites or sulfate, an anionic surfactant, enhanced coal
subbituminous coals to 8 N nitric acid for 48 h biosolubilization, as did acidic (Tris), am-photeric
resulted in increased solubilization as well, and was (glycylglycine), and basic (phosphate) buffers at
the most effective treatment tested by these alkaline pH.33.37Extraction with HC1 caused up to
workers. Elsewhere, Stewart et al.33showed that a 50% increase in biosolubility. 1 7 3
mild, oxidizing heat treatment -preincubation in an
air atmosphere for 7 d at 150°C - would enhance
degradation of lignites and even of bi-tuminous coal C. Product Characteristics
by a Penicillium sp. (It is worth-while to note that
the “native” coals described in the preceding The product of microbial action against either
paragraph were autoclaved dry for 15 to 60 min at native or pretreated coal may be generally de-
121OC prior to testing.) Fi- scribed as a heterogeneous, polar, water-soluble,

352
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A
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FIGURE 2. Fungal coal solubilization in submerged culture. faecilomyces sp. was grown in a defined minimal
culture on the right received nitric acid-treated subbituminous coal (3-to 5-mm particles) at the time of
inoculation. Control and experimental cultures were both incubated at 30°C with agitation for 7 d. (A) Side
view; (B) illuminated from below.

353
acidic, polycondensed aromatic material that is of these inhibitory substances can be extracted
oxidized and that may have a fairly high oxygen from solid coal with acetone and/or
content relative to the coal ~ ~ b ~ t r a t e . ~ ~ ,Conversely,~~~ ~ , ~a ~coal,~ fraction~ that is extractable
A high-molecular-weight (30,000 to 300,000 Da) with tetrahydrofuran has been shown to enhance
fraction may be separated by acid precipitation microbial g r o ~ t h . ~It- ~is ’this latter coal com-
of the solubilized material. However, this “po- ponent that may support growth of microorgan-
lymeric” fraction may be in part derived from isms exclusive of polymer breakdown.
the agglomeration or polymerization of smaller An extensive solubilization of coal indicates
fragments that include acidic polyphenols and a true breakdown of the substrate’s polymeric
other carboxylated residues. 39,40 The solubiliza- structure. The mechanism underlying this micro-
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tion products generated by fungal or bacterial bial attack on coal has been much disputed. The
action are similar, although slight differences be- results obtained in various studies of this phe-
tween the products formed by unrelated fungal nomenon are presented below. One or more of
species have been d e ~ c r i b e d . ~ ’ . ~ ~ these mechanisms may be operative in any bio-
solubilization system.
Perhaps the simplest method for achieving
D. Biochemical Mechanism(s) coal solubilization is through the production of
a surfactant, in whose presence largely apolar
The ability of an organism to grow on lignite material would be brought into aqueous suspen-
or other low-rank coal must be distinguished from sion or emulsified without the breaking of co-
coal solubilization per se. Growth on lignite may valent bonds. Tween 80, a nonionic surfactant,
actually occur at the expense of low-molecular- has been shown to solubilize a low-molecular-
weight, water-soluble, and/or volatile com- weight fraction of coal ,47a Biosurfactants may be
pounds incidental to solid coal’s polymeric
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important in the mobilization of low-molecular-


framework. These compounds may include fatty weight nutrients that support microbial growth in
acids and alcohols, which are known to be uti- the absence of solubilization. Biosurfactant pro-
lized by a wide variety of microbial species. duction has been shown to be critical to the mi-
Growth of fungi on volatile hydrocarbons has crobial utilization of low-molecular-weight pe-
also been de~cribed . ~’Nonvolatile nutrients, in- troleum components .48 Coal solubilization by
cluding inorganics, may be dissolved in inter- Pseudomonas sp. has been ascribed, in part, to
particle water or in a surface film of free water. the production of a bio~urfactant .However,~~
Organisms that adhere to solid, apparently dry surfactancy alone may be predicted to achieve
coal particles may be presumed to inhabit these only a limited solubilization of coal due to the
moist areas. The porous structure of low-rank polymer’s extreme molecular size. Indeed, non-
coals provides a particularly large available sur- biological solubilization of coal by surfactants
face area for colonization. Photomicrographs of such as sodium dodecyl sulfate, Tween 80, and
fungi growing on coal (Figure 3) suggest an ex- cety lpyridinium chloride is generally minimal,
tensive hyphal ramification throughout the solid even when the substrate is highly oxidized. 37
particle in both surface and submerged cul- Thus, bond cleavage may be predicted to be an
t u r e ~ .Treatments~~,~~ (such as HNO,, H,O,, and important component of coal-solubilizing activity
0,) that swell the coal structure may be very in cultures.
important in providing access to and/or mobiliz- The role of alkaline catalysis in biological
ing low-molecular-weight components .29 Indeed, coal solubilization has been examined in a num-
the growth of two bacterial species in a coal- ber of laboratories. Strandberg and Lewis noted
water slurry was enhanced by pretreatment of the an increase in medium pH during growth of
coal substrate with H202.42But this treatment Streptomyces setonii 75Vi2 that corresponded
may also have effected the detoxification of with the solubilization of several low-rank
leachable coal components that are inhibitory to The substrate for this work was readily solubi-
growth. Coal has long been known to contain lized in vitro by spent medium. The authors hy-
bacteriostatic s u b ~ t a n c e s . ~At~least-~~a- portion~~ pothesized that coal dissolution was catalyzed by

354
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111
0 1 2
mil I imeters

A
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FIGURE 3. Growth of coal-solubilizing fungi on coal particles. Undissolved


coal par-ticles were removed from (A) surface culture of Candida sp., or (B)
submerged culture of Paecilomyces sp. described above.

355
basic polypeptides or polyamines that were pro- such as phosphate, to solubilize coal at alkaline
duced during growth. The production of such pH may reflect in part their activity in metal
alkaline metabolites by streptomycetes is well ~ h e l a t i o n . Fungi~~.~ are~ known to excrete a va-
known.51It was later shown that organic nitrogen riety of dicarboxylic acids such as oxalate during
compounds (such as those contained in yeast ex- growth and metaboli~rn.~’Indeed, production of citrate
tract) that were already present in the medium were has been directly linked to fungal sorption of metals
involved in this t r a n ~ f o r m a t i o n Thus,.~~~ ~ such as zinc.5s Certain coal-solubilizing fungi are
~ coal solubilization by streptomycetes may pro- known to produce metal-chelating com-p o u n d ~ .
ceed indirectly, via the biological “activation” ~Coal~.~ ’solubilization by C. versicolor has now been
of medium components. However, fungi that were shown to be catalyzed by excreted
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cultured in inorganic salts media (i.e., in the ab- ~ x a l a t e This.~~ behavior may form the basis
sence of organic nitrogen) have been shown to of fungal activity against coal within an acidic
solubilize coal more readily at an alkaline than at medium.
an acidic pH.52 In that work, changes in me-dium The preceding paragraphs describe the ap-parent
pH resulted solely from the accumulation of participation of nonenzymatic materials -
excreted microbial products. Alkaline cata-lysts surfactants, alkali, and chelating agents - in the
that were involved in solubilization would thus, biological solubilization of coal. As stated ear-lier,
necessarily, be of direct microbial origin. The particular attention has been focused on the role of
nonbiological solubilization of low-rank coals by alkaline materials in coal (bio)solubilization.
alkali has now been amply demon-strated. Treatment of oxidized coal with alkali generates
30,32,36.37.53,54 Evidence for the presence of titratable products very similar to those produced in vivo by
base-equivalents within coa130,36*37is.54 streptomycetes or by fungi. 34.36.54 However, the
consistent with the current understanding of the average molecular weight of the biological products
structure of these coals. The mechanism of al- tends to be lower than that of the material produced
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kaline coal solubilization may thus involve the nonbiologi-ally,^^ and in some cases biosolubilized
neutralization and consequent dissolution of pen- coal exhibits spectral characteristics different from
dant acidic groups, present naturally or created by those of the alkali-solubilized natural. 3634 This
oxidizing pretreatments. 36,37s4 There is addi-tional finding supports the Strandberg and Lewis h y p o t
evidence that alkaline extraction of coal effects the h e ~ i s *that~.~ ~alkaline (or other nonenzy-matic)
hydrolysis of esters.53 The biosolu-bility of low- reagents are involved in only the initial steps of
rank coal generally parallels its sol-ubility in polymer breakdown. Low- to interme-diate-
alkali, 17,36 suggesting that alkaline ca-talysis is an molecular-weight products generated in this manner
important component of the biological attack. may support further microbial growth. Indeed, C .
versicolor was shown to utilize a sol-ubilized coal
The demonstration of coal biosolubilization by product obtained by treatment of lignite with alkali
fungi under acidic condition^^*.^^ suggests a role in the presence of a small amount of ~ u r f a c t a n
for nonalkaline catalysts in the microbial activity. tThe.~~ lignite substrate in the latter work had been
Lignite coal is partially soluble in HCl.35 Treatment extracted previously with a benzene:methanol
of coal with this nonoxidizing acid has been shown mixture, which presumably would have removed
to cause the removal of multivalent organic cation^,'^ certain low-molecular-weight, possibly inhibitory
presumably in the absence of ester materials. (Methanol extraction of inhibitory
hydroly~isPretreatment.~~ of coal with acidic metal substances from solid coal was described above.)
chelators such as citrate, ethylenediami-
netetraacetate, and nitriloacetate resulted in an
increase in alkali solubility and, usually, bioso- The role of enzymes in coal solubilization
lubility.” These data are consistent with the in-tegral remains unclear. However, the demonstrated ac-
role of metals in the structural stabilization of low- tivity of wood-decaying fungi and actinomycetes
rank coals, discussed in a previous sec-tion. The against lignites suggests a role for oxidative en-
ability of acidic buffers (i.e., those in which the zymes, similar to those that degrade lignin, in the
buffering ion is negatively charged), solubilization process catalyzed by these or-

356
ganisms. Cohen et al.35 first described the ap-parent cultures of an unidentified basidiomycete.68Model
participation of enzyme catalysts in the compound studies underscore the potential for fungal
solubilization of a highly oxidized lignite by C. breakdown of stable coal products. Cun-
versicolor. Pyne et al.59subsequently associated this ninghamella elegans, a member of a genus that
solubilizing activity with that of syringal-dazine includes a coal-solubilizing organism, exten-sively
oxidase. Coal solubilization in vivo by P . degraded fluoranthene, a coal substructure
chrysosporium was enhanced in the presence of an model Similarly, C. versicolor, a coal solubilizer,
inducer of lignin peroxidase, suggesting a role for has been shown to catalyze the initial oxidation of
that enzyme activity in the solubilization pro- anthra~ene,~’ finding that suggests the potential
cess.60Enzymatic activity was implicated in the for oxidative ring cleavage of soluble products
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solubilization of lignite in vitro by spent medium formed from coal in cultures. Hydrolytic activities
from cultures of Penicillium S P . ~Purified’ com- potentially relevant to coal solubilization, namely,
mercial enzymes, namely, horseradish peroxi-dase etherases and esterases, were also noted in
and fungal laccase, were subsequently shown to cultures of C. versicolor. However, coal
solubilize oxidized coal in vitro when tested in solubilized by Streptomyces sp. was not observed
aqueous or nonaqueous so1vents.m*62Solubil- to undergo further modification
ization under these conditions was presumed to in suggesting that streptomycetes lack the
result from oxidative (peroxidase) or oxygenative relevant enzymes.
(laccase) ring-cleavage reactions. However, hy- Production of coal-solubilizing activity in fungi
drolytic activities may be important in coal so- is regulated in a complex manner similar to that of
lubilization by other organisms. Indeed, a non- the production of lignin-degrading en-zymes. Coal
oxidative enzyme activity has now been shown to solubilization by fungi has been de-scribed as a
depolymerize coal in cultures of an aerobic b a ~ t e secondary metabolic f u n c t i ~ n .It~ ~ . ~ is
For personal use only.

rium.~~ promoted by growth in surface culture, and


It is possible that the enzymes produced by coal- the appearance of activity is associated with the
solubilizing organisms function primarily in vivo in establishment of an aerial mycelium. The ap-
the degradation of nonenzymatically bio-solubilized pearance of solubilizing activity in fungi corre-
material. Proteins (presumably in-cluding those with lates with the formation of asexual
enzymatic activity) have been shown to adsorb to c Normal differentiation processes, including spor-
~ a l ,an~ occurrence,~~ that would be predicted to ulation, are known to be inhibited by submer-gence
cause enzyme denaturation and/or to block binding in both fungi and streptornycete~ .Coal~~.~~
sites. Biosurfactants may cause an initial, minimal solubilization by fungi is suppressed during growth
solubilization of coal but may carry out a more in submerged liquid culture, although
important function in preventing protein adsorption streptomycetes appear to solubilize coal fairly
and thus allowing subsequent enzymatic effectively under submerged condition^.^^ These
degradation. Coal-derived products formed by alkali findings argue for an obligate association in fungi
or by acidic (chelating) reagents may also undergo between differentiation and coal solubilization. The
enzymatic attack. Lig-nin peroxidase obtained from mechanism underlying this association may be
the white-rot fun-gus P . chrysosporium has been simple. The oxidative enzyme(s) implicated in
shown to degrade high-molecular-weight, lignite solubilization by C. versicolor is (are)
(nonbiologically) alkali-solubilized lignite and idiophasic or secondary metabolic and appears after
subbituminous coals in vi-tro.66A pseudomonad cultures differentiate to form ~ p o r e s . ~ ~InJ j ”
isolated from coal was also shown to depolymerize the case of P . chrysosporium, enzymes involved in
an exogenously solubi-lized lignite in vivo, lignin degradation are localized on fungal spores.71
presumably via enzymatic catalysis .67 The slow The enzyme(s) involved in coal solu-bilization by C.
degradation of biologically solubilized coal versicolor may be similarly placed. In that particular
observed in acidic cultures of Paecilomyces sp. 39 system, it may be ar-gued that the coal-solubilizing
may also reflect enzymatic activity against reagents and lig-ninolytic enzymes are identical. In
nonenzymatically generated ma-terial. A similar the absence of information on the ligninolytic
behavior was reported in acidic capabilities of

357
the non-white-rot lower fungi that are also known to incorporated into drilling mud as a chelating
solubilize coal, a similar conclusion may not be agent. l I 3 Biologically treated material may be
drawn. However, the lesser effect of sub-mergence similarly useful in this application.
on coal solubilization by streptomy-cetes, coupled The polyphenolic, polyanionic structure of
with the aforementioned absence of further biosolubilized coal suggests additional, agricul-
degradation of solubilized material, suggests a tural uses. Humins, which may be considered coal
minor role for (spore-associated?) en-zymes in these precursors, act as natural soil conditioners by
bacterial systems. virtue of their ability to fix divalent cations."
Biosolubilized coal has little value with re- Lignite itself is also used in this capacity.'I3 This
spect to its direct use as a fuel. However, it has effect is beneficial when it results in improved
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considerable potential for use in other applica- translocation of metals to plant roots and detri-
tions or as a feedstock for further microbial mental when the metals are tightly bound and thus
modification. unavailable. It may be worthwhile to eval-uate
biosolubilized coal for this application. Al-
ternatively, biosolubilized coal may be used to
IV. BIOLOGICAL COAL CONVERSIONS: immobilize and/or detoxify agrochemicals within
PRODUCT UTILIZATION the soil via sorption. Although these examples
demonstrate potential applications for biosolu-
A. Potential Direct Uses bilized coal in soil environments, this material will
for Biosolubilized Coal probably be more suitable for use in aquatic
systems.
Certain characteristics of biosolubilized coal, Process kinetics and the choice of microbial
as described by Faison et strongly resemble those of catalyst may be important practical considera-tions
in the large-scale production of biosolubil-ized coal
For personal use only.

a product obtained by microbial action on lignin.


The major lignin catabolite produced by for direct applications. Fungi have been shown to
Srrepromyces spp. is a polyphenolic, water-soluble, attack biosolubilized coal in situ, as described in
acid-precipitable polymeric lignin (APPL) .72-75 a previous section. Although there have been no
Perhaps not coincidentally, species that solubilize reports of further breakdown of biosolubilized coal
lignin are also active against low-rank coals. APPLs by streptomycetes, APPLs (the analogous product
have commerical potential as antioxidants, from lignin) are known to be metabolized to varying
surfactants, components of resins or adhesives, degrees by streptomy-cetes in situ, or when
and/or immunoadjuvants.75-78 Bio-solubilized coal incubated with fungal cul-
may ultimately be shown to have similar tures Microbial transformations of bio-
.73*74777,86

commercial potential. A recent report of the solubilized coal may affect characteristics
therapeutic use of lignosulfonate, a water-soluble, important for its direct use. However, there is
partially oxidized, acidic lignin deriva-tive, in the evidence that its further degradation will yield
treatment of human immunodefi- partially oxidized aromatic monomers valuable
ciency virus in ~ i t suggestsr~~ another~ in their own right.
potential biomedical application.
Lignite has been shown to possess consid-
erable ion-exchange and/or sorptive B. Production of Chemicals
Tannins**and tree barkR3exhibit similar behav- from Blosolubilized Coal
ior. The sorptive ability of the latter toward basic
and hydrophobic materials was shown to be en- The apparent release of low-molecular-weight
hanced following oxidative treatment .x4 These re- aromatic metabolites following fungal attack on
sults suggest that biosolubilized coal may be par- biosolubilized coal suggests the preferential
ticularly useful as a commercial ion-exchange cleavage of pol ymethylene bridges w i h n the coal
resin or sorbent. The potential application of these polymer. Phenolic products generated by this ac-
sorptive behaviors in waste treatment is ad- tivity may be industrially useful per se. The po-
dressed in a later section. Lignite is currently tential for production (by Srrepromyces spp.) of

358
similar materials from lignin via APPLs was liquid culture, with production of methane.92Or-
de-scribed e l ~ e w h e r e . ~ ~ * ~ ' ganisms capable of this interaction were obtained
The desired products from coal have intact from a variety of sources, including coal pits,
single-ring systems. It is critical to note, how-ever, sewage sludge, and termite gut. The final reac-
that P . chrysosporiurn, a coal-solubilizing fungus, tions in methanogenesis could be inhibited by
is known to degrade mono- and poly-cyclic addition of 2-bromoethanesulfonic acid or mo-
aromatic compounds related to coal. 87,88 The nensin, with accumulation of ethanol and fatty
metabolic capabilities of coal-solubilizing acids. However, the precise origin of the prod-
organisms may indeed be analogous to those of a ucts, whether from attack on the coal polymer or
Pseudomonas sp. isolated from crude oil that was from leachable materials associated with the pol-
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shown to degrade a variety of single- and fused- ymer, was not determined. Faison and Lewis (un-
ring hydrocarbon^.'^ Thus, there is a dan-ger that published) obtained evidence for the direct an-
biosolubilized coal would be degraded completely aerobic conversion of lignite by Candida, with
to CO, and other low-value products within a production of ethanol and fatty acids. At least a
nonoptimized producing system. The organisms portion of the reduced product was derived from
currently known to solubilize coal, however, are attack on the polymer itself. Similar activity
aerobic. Incubation of biosolubil-ized coal with against subbituminous or higher-rank coals has
anaerobic organisms may yield more desirable, not been detected.
partially reduced, low-molecu-lar-weight In light of current knowledge of the bio-
aliphatic metabolites suitable for use as fuels. chemistry of anaerobic breakdown of aromatic
the prospects for the direct anaerobic coal
bioconversion to low-molecular-weight
C. Production of Fuels compounds in high yield are not favorable. An
initial, nonenzymatic solubilization of coal is
For personal use only.

from Biosolubilized Coal


possible under anaerobic conditions. Oxidative
Coal solubilized under aerobic conditions may enzymes catalyzing intra- or intermolecular ex-
be transformed to useful, hydrogenated products via change of fixed oxygen may be involved, but
a subsequent microbial treatment in the ab-sence of oxygenative activity obviously would not occur.
oxygen. Davison et a1.% demonstrated the apparent Thus, the product of this anaerobic activity may
production of methane from fungally solubilized coal be somewhat less oxidized than that described in
by an anaerobic consortium. Rates of conversion preceding sections andlor of a somewhat higher
within this nonoptimized fermen-tation were low and molecular weight. Further anaerobic metabolism
apparently reflected, in part, the extent to which the of soluble material would depend both on its de-
coal substrate had under-gone aerobic gree of oxidation and on its polyaromaticity. An-
depolymerization. Ackerson et al.91 and Barik et aerobic activity against even monoaromatic com-
al.92have obtained similar results. The latter group pounds requires that the substrate be at least
noted also that biosolubilized coal is a better partially oxidized. Also, in the case of poly-
substrate for anaerobic metabolism than is alkali- phenolic compounds, anaerobic degradability is
solubilized material. The demon-strated inversely related to the complexity of internuclear
methanogenesis from solubilized coal may be ring linkages. Thus, reduced polyaromatic com-
presumed to proceed via the production of partially pounds that are produced by anaerobic solubili-
reduced intermediates, such as fatty al-cohols and zation would be very poorly degraded under an-
fatty acids. Compounds of this type have intrinsic aerobic conditions. (It is worthwhile to note that,
value as fuels (e.g., ethanol, meth-anol) or as under anaerobiosis, initial solubilization as well as
chemical feedstocks. further degradation would be predicted to be
Some preliminary evidence has been gath-ered exquisitely sensitive to the rank of the coal sub-
for the direct solubilization and fermentation of strate.) From a strictly microbiological stand-
lignite by anaerobic consortia in submerged point, a two-stage process for production of fuel
alcohols or methane from low-rank coal - in-

359
corporating aerobic solubilization followed by utilization of higher-rank coals and in the treat-
anaerobic treatment - would have a greater li- ment of coal-derived wastes.
kelihood of success (Figure 4).

V. POTENTIAL APPLICATIONS OF COAL


D. Summary BIOCONVERSION TECHNOLOGY IN COAL
BENEFlClATlON
Biological treatment of low-rank coals may be
a useful approach to their conversion to useful fuels Bituminous and anthracite coals, like the
and chemicals, as described above. Fun-damental lower-rank coals described above, contain var-
knowledge gathered during the course of research ious amounts of sulfur, nitrogen, and heavy met-
in this area suggests, moreover, the applicability of als. Burning of these coals results in the partial
Critical Reviews in Biotechnology Downloaded from informahealthcare.com by University of California San Francisco on 03/20/15

coal-solubilizing cultures in the oxidation of both the carbon structure and the

ORNL DWG 88-882R


For personal use only.

COAL SOLUBlLlZATlON

u
(AER OBIC)

n I

MIXED CULTURE No. 2 r(


SOLUBLIZED
COALPRODUCT \ MIXED CULTURE No. 1
(PRIMARILY BACTERIA) (PRIMARILY BACTERIA)

BIOREACTOR BIOREACTOR
PRODUCTION
OF LIQUID FUELS

METHANOL CH4
ETHANOL (METHANE)

FIGURE 4. Schematic of a two-stage process for the production of fuel chemicals from coal.

360
contaminants, with the release of sulfur and ni- coal itself. Such an attack would presumably oc-
trogen oxides (SO,, NO,) plus heavy metals, cur at the surface, thus necessitating the grinding
among other materials, into the atmosphere. pretreatment described above. However, at worst,
Emissions containing SO, and NO, are a partic- this activity could be integrated into existing mi-
ular problem in that they contribute to acidic crobial coal-cleaning processes, resulting in the
pre-cipitation (‘ ‘acid rain”). Coal combustion development of a dual process for removal of both
prob-ably accounts for over 60% of SO, inorganic and organic sulfur (and perhaps
emissions and 30% of NO, emissions.’ nitrogen). Coal-conversion organisms would be
However, some NO, release associated with predicted to be most active at the interface be-
this practice arises from oxidation of tween organic and inorganic macerals, which is
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atmospheric N, in the combustion chamber. particularly enriched in “immature” nitrogen-and


Because of the low fuel value of low-rank sulfur-containing organic structures.96
coals, current coal beneficiation technologies fo- Successful development of such a process for
cus on sulfur removal from higher-rank (gener- organic sulfurhitrogen removal will hinge on the
ally bituminous) coal exclusively. Physical (flo- use of organisms that specifically cleave carbon-
tation) processes and current biological sulfur or -nitrogen bonds without degrading the
desulfurization processes are primarily effective rest of the carbon polymer and thus decreasing its
in removal of inorganic sulfur only and, more- caloric value. (The latter, unfortunate tend-ency
over, require extensive grinding of the coal as a has been described el~ewhere.’~)Either ge-
pretreatment. Chemical desulfurization processes netically modified fungi” or, potentially, strep-
achieve some removal of both inorganic and or- tomycetes may be required for that task.
ganic sulfur but frequently destroy certain desir- The potential value of coal-solubilizing fungi
able properties of the ~ubstrateThus,.~ there is a for removal of metals from coal is suggested by
need for effective, nondestructive technologies studies of the role of metal chelation in solubil-
For personal use only.

for desulfurization of higher-rank coal. Viable ization, as summarized above. Again, some
precombustion processes for nitrogen or metals grinding of the substrate would be required.
removal also remain to be developed.
There has been very little investigation into the
potential utility of coal-solubilizing organ-isms in VI. POTENTIAL APPLICATIONS OF
the removal of organically bound sulfur or nitrogen COAL BIOCONVERSION
from coal. However, preliminary data indicate that TECHNOLOGY IN THE TREATMENT
fungi of this type may degrade cer-tain organic OF COAL-DERIVED WASTES
sulfur structures of the type found in coal. P .
chrysosporium, a ligninolytic fungus known to Coal mining, storage, transport, and pro-
solubilize coal, has subsequently been found to cessing activities (coke manufacture, coal-tar dis-
degrade thianthrene, a sulfur hetero-cycle.94 tillation, gasification, and liquefaction) generate
Paecilomyces sp., a coal-solubilizing fungus, has significant amounts of coal-derived waste. These
been shown to attack a variety of organic sulfur wastes include particulate matter (coal dust), tar,
compounds representative of coal sludge, and liquids that contain both dissolved and
~ u b ~ t r u c t u rActivitye~.~~ was demonstrated suspended solids. Areas where coal is mined may
against thianthrene; dibenzothiophene, a be highly impacted, and both soil and ad-jacent
heterocyclic reference compound routinely used in ponds formed by accumulated water from natural
coal de-sulfurization research; aromatic sulfides and sources may be contaminated. Conven-tional coal-
di-sulfides; and thiophenol. The microbial attack utilization technologies generate large volumes of
was oxidative and sulfur specific, leading in some contaminated process water. The in-creasing use
cases to loss of the sulfur atom. Paecilomyces also of coal-water slurries as fuels, for transport, or as
degraded quinoline, an organic nitrogen- feed mixtures (e.g., for pressur-ized fluidized-bed
containing heterocyclic There is no information combustion) suggests a grow-ing need for
on the ability of these organisms to attack sulfur methodologies for the treatment of aqueous coal-
and nitrogen contaminants within derived wastes.

361
Coal-processing wastewaters contain mate- knowledge suggests several practical limitations
rials that are toxic, mutagenic, and/or carcino- to its exploitation. This activity has been ascribed
g e n i ~ . ~Compounds~-'~ found in these wastes in- to various organisms known to grow on coal, but,
clude phenols, polyphenols, and polyaromatic as noted above, growth on coal may have no
hydrocarbons. The successful biological treat-ment bearing on transformation of the coal polymer.
of coal-processing wastewaters has been Thus, many of the organisms currently under
demonstrated.1"1,'M-'08 However, traditional bi-ological study may not be appropriate for use in coal pro-
treatments have been shown, in some cases, to be cessing. Microbial coal solubilization, where
effective against only low-molecular-weight (< 1000 demonstrated, yields a polyanionic, sorptive sub-
Da) components of these wastes. 107~108The apparent stance with numerous potential industrial appli-
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ability of coal-solu-bilizing and/or ligninolytic fungi cations. However, a similar product can be gen-
to degrade phe-nolic, polyaromatic materials erated nonbiologically through use of inexpensive
suggests their util-ity in the treatment of such reagents such as alkali.
materials dissolved in aqueous coal wastes. The commercial value of coal-solubilizing
Organisms known to grow at the expense of microorganisms may derive from their ability to
solubilized coal may also have a broad substrate transform soluble coal-derived material to useful
range with respect to low-mo-lecular-weight products. Laboratory studies have provided evi-
polyaromatic components. This behavior was dence for the microbial breakdown of solubilized
demonstrated by the aforemen-tioned Pseudomom coal to low-molecular-weight compounds, po-
isolate from crude oil, which degraded a variety of tentially including valuable fuel and commodity
oxygen-, nitrogen-, or sul-fur-containing chemicals. In practice, judicious choice of the
heterocyclic compounds in addi-tion to their microbial catalyst will permit the targeting of a
homocyclic analogs.89 specific product or product mixture. Processes
Potential applications of biosolubilized coal in incorporating these activities may be designed for
For personal use only.

waste treatment were mentioned above briefly. To the transformation of coal solubilized by either
reiterate, biosolubilized coal may be generally biological or nonbiological means. Coal conver-sion
useful in the removal of charged or, in some cases, may ultimately be achieved through wholly
hydrophobic materials from aqueous sys-tems. The biological means; alternatively, microbial pro-
high concentration and variety of dis-solved metals cessing may serve as a unit operation within an
and organic compounds contained within coal- otherwise nonbiological coal conversion scheme.
processing wastewaters suggest a specific utility for The rapid development of practical coal bio-
this product. It is worthwhile to note that microbial conversion technologies will require a rational
biomass has an intrinsic sorptive capacity as well. approach that incorporates an appreciation of the
Various fungal species have been shown to unique biochemical capabilities and limitations of
accumulate silver, copper, zinc, iron, cadmium, the microorganisms involved. Technological
nickel, and manganese, among other elements. 'O9- advances in this area may contribute to related
'I1 Particulate matter, including elemental sulfur, is fields, specifically coal beneficiation and the
also bound. 11* Cells of coal-solubilizing organisms treatment of coal-derived wastes. Coal biotech-
(especially those with chelating ability) may exhibit nology thus has a potentially major role in shift-
similar or even superior binding activity. Spent ing the U.S. economy toward an increased, ef-
biomass from coal-conversion activities would then ficient utilization of this abundant resource.
have a po-tential utility in metals removal from coal-
pro-cessing wastewaters.
ACKNOWLEDGMENTS

The author thanks S. N. Lewis and C. A.


VII. CONCLUSIONS Woodward for supplying the photographs; J . S .
Taylor and D. J . Weaver for retyping the man-
The phenomenon of biological coal solubil- uscript; and D.R . Quigley, B. H. Davison, and
ization is real. However, current scientific G. W. Strandberg for helpful comments.This

362
manuscript was written by a contractor of the U the Biol. Processing of Coal and Coal-derived
Sub-stances, 1/15, 1989.
.S . government. Accordingly, the U .S . gov-
16. Harris, L. A., Barrett, H. E., and Kopp, 0. C.,
ernment retains a nonexclusive, royalty-free li- Elemental concentrations and their distribution in two
cense to publish or reproduce the published form bituminous coals of different paleoenvironments, Int.
of this contribution, or allow others to do so, for .ICoal. Geol. , 1, 175, 1981.
U.S. government purposes. The research was 17. Ward, B., Quigley, D. R., and Dugan, P. R.,
sponsored by the Fossil Energy Advanced Re- Relationships between natural weathering and
search and Technology Program (Pittsburgh En- lignite biosolubility or alkali solubility, Proc. Inst.
Gas Technol. Conf. Coal, 40, 1988.
ergy Technology Center), U .s. Department of 18. Stock, L. M., Choi, C.-Y., Muntean, J. V., and
Energy, under contract DE-AC05-840R2 1400 Wang, S.-H., Aliphatic structural units of bitumi-
Critical Reviews in Biotechnology Downloaded from informahealthcare.com by University of California San Francisco on 03/20/15

with Martin Marietta Energy Systems, Inc. nous coals, Proc. Electric Power Res. Inst. Symp.
on the Biol. Processing of Coal and Coal-Derived
Substances, 1/37, 1989.
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coals, Resources Conserv. Recycling, 3, 111, 1990.
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