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Energy & Fuels 1999, 13, 728-738

Organosulfur Compounds in Sulfur-Rich Ras a Coal

Jaap S. Sinninghe Damste,*,, Curt M. White, John B. Green,| and
Jan W. de Leeuw,
Department of Geochemistry, Institute of Earth Sciences, Utrecht University, P.O. Box 80021,
3508 TA Utrecht, The Netherlands, Department of Marine Biogeochemistry and Toxicology,
Netherlands Institute for Sea Research, P.O. Box 59, 1790 AB Den Burg, Texel,
The Netherlands, Federal Energy Technology Center, P.O. Box 10940,
Pittsburgh, Pennsylvania 15236, and BDM Petroleum Technologies, P.O. Box 2543,
Bartlesville, Oklahoma 74005
Received November 2, 1998. Revised Manuscript Received February 11, 1999

The organosulfur compounds in the extract and pyrolysate of the unusually organic sulfurrich (11.4 wt %) Upper Palaeocene Rasa coal have been identified by gas chromatography-highresolution mass spectrometry. The major organosulfur compounds (OSC) present in the extract
are alkylated benzo[b]- and dibenzothiophenes and in the pyrolysates alkylated thiophenes and
benzo[b]thiophenes. In addition, a large suite of sulfur-containing polyaromatics were identified,
which sometimes contain more than one sulfur atom per molecule. The degree of alkylation of
many homologous series was found to maximize at either three, four, or five alkyl carbons. The
dominance of polyaromatic sulfur compounds is consistent with the relatively mature stage of
the coal (Ro 0.7%), and their abundance at this rank indicates that the initial peat must have
been extremely organic sulfur-rich (atomic Sorg/C ratio 0.15). This together with the very low
abundance of lignin-derived components in the coal pyrolysate indicates that Rasa coal should
not be considered a typical coal. Nevertheless, our results represent a starting point that can be
used as a guide for analysis of other coals.

Introduction
The characterization of organically bound sulfur in
fossil fuels has been and still is a major topic of interest,
both from the point of view of environmental concerns
with respect to the application of sulfur-rich fossil fuels
as well as for its geochemical significance.1-5 The
concentration of organically bound sulfur in fossil fuels
is often relatively low, which makes it difficult to
determine the structures of organosulfur compounds
(OSC) in low-molecular-weight fractions or pyrolysates
of high-molecular-weight fractions due to the high
concentrations of non-sulfur compounds. One way to
overcome this problem is to study end-members, i.e.,
samples which contain much higher concentrations of
organically bound sulfur than average. An example of
this approach is the study of the Rozel Point oil, a crude
oil which contains ca. 7.5 wt % organic sulfur.6 The very
* To whom correspondence should be addressed. damste@nioz.nl.
Utrecht University.
Netherlands Institute for Sea Research.
Federal Energy Technology Center.
| BDM Petroleum Technologies.
(1) Stock, L. M.; Wolny, R.; Bal, B. Energy Fuels 1989, 3, 651-661.
(2) Sinninghe Damste, J. S.; de Leeuw, J. W. Org. Geochem. 1990,
16, 1077-1101.
(3) Orr, W. L.; Sinninghe Damste, J. S. ACS Symp. Ser. 1990, 429,
2-29.
(4) Sinninghe Damste, J. S.; de Leeuw, J. W. Fuel Process. Technol.
1992, 30, 109-178.
(5) Vairavamurty, M. A.; Orr, W. L.; Manowitz, B. ACS Symp. Ser.
1995, 612, 1-14.
(6) Sinninghe Damste, J. S.; de Leeuw, J. W.; Kock-van Dalen, A.
C.; de Zeeuw, M. A.; de Lange, F.; Rijpstra, W. I. C.; Schenck, P. A.
Geochim. Cosmochim Acta 1987, 51, 2369-2391.

high amount of sulfur in this oil made it possible to

identify ca. 1000 novel OSC, unidentified previously.
Subsequently, these compounds were also identified in
less sulfur-rich samples.2 Since the knowledge about
organically bound sulfur on a molecular level in coal is
relatively scant,1,4 the success of this end-member
approach prompted us to study the OSC of a very
organic sulfur-rich coal. Rasa coal, which contains 11.4
wt % organic sulfur,7 was considered to be an excellent
choice in this respect.
The Upper Palaeocene Rasa coal is from Istria (Slovenia). It is a high-volatile bituminous coal with a mean
vitrinite reflectance (R0) of 0.68% (ref 7). The dominating
maceral is vitrinite with some exinite or liptinite and
very little inertinite.7 Elemental composition data are
listed in Table 1 and reveal the unusually high amount
of sulfur, dominated by organic sulfur.7 The aromaticity,
as determined by solid-state NMR, of 65% (ref 7) is in
agreement with the data of Kreulen8 who reported that
59% of the carbon of this coal is aromatic. Several
workers have determined the organic sulfur speciation
in Rasa coal. Kavcic9 reported that ca. 75% of the sulfur
was thiophenic and 25% reacted with methyliodide and
was thus considered to be non-thiophenic. Ignasiak et
al.10 determined that ca. one-third of the organic sulfur
in Rasa coal is present in sulfide linkages using two
(7) White, C. M.; Douglas, L. J.; Anderson, R. R.; Schmidt, C. E.;
Gray, R. J. ACS Symp. Ser. 1990, 429, 261-286.
(8) Kreulen, D. J. W. Fuel 1952, 31, 462-467.
(9) Kavcic, R. Bull. Sci. Yugosl. 1954, 48, 5809.
(10) Ignasiak, B. S.; Fryer, J. F.; Jadernik, P. Fuel 1978, 578-584.

10.1021/ef980236c CCC: $18.00 1999 American Chemical Society

Published on Web 03/31/1999

Organosulfur Compounds in Sulfur-Rich Ras a Coal

Energy & Fuels, Vol. 13, No. 3, 1999 729

Table 1. Elemental Composition (daf) of Ras a Coal and Its Solvent Extracta

whole coal
coal extract
a

C
(wt %)

H
(wt %)

O
(wt %)

N
(wt %)

Stot
(wt %)

Sorg
(wt %)

Ssulf
(wt %)

Spyr
(wt %)

H/C

80.23
78.42

5.21
5.80

1.54
3.58

1.23
1.66

11.79
10.98

11.44
10.98

0.02
0.00

0.33
0.00

0.78
0.89

atomic ratios
O/C
Sorg/C
0.014
0.034

0.053
0.053

N/C
0.013
0.018

Data from ref 7.

independent techniques. More recent studies using

X-ray absorption near-edge structure (XANES) spectroscopy and X-ray photoelectron spectroscopy (XPS)11-13
established that the Rasa coal contains 70 mol %
thiophenic sulfur and 30 mol % sulfide sulfur, in
agreement with a high-pressure temperature-programmed reduction study.14 Oxidation of this coal
followed by subsequent determination of organic sulfur
forms by XANES and XPS led to the speculation that
about one-half of the so-called sulfide sulfur is actually
thiol or disulfide sulfur.15 These latter findings are at
variance with an earlier study,10 reporting chemical
tests which ruled out the presence of thiols in Rasa coal.
Brown et al.13 postulated that the 30% sulfide sulfur is
mainly composed of aryl sulfides. This has been the
subject of discussion16,17 since it was shown that upon
pyrolysis Rasa coal evolves a significant fraction of its
sulfur as hydrogen sulfide at relatively low temperatures,18-19 which is difficult to rationalize as originating
from aryl sulfides.
Few investigations have been performed to characterize organically bound sulfur in Rasa coal on a molecular
level. White et al.7 have reported molecular formulas of
OSC in a solvent extract of the Rasa coal using lowvoltage, high-resolution mass spectrometry (LVHRMS).
Many families of OSC were detected, some of which
contained more than one sulfur atom per molecule, but
no exact structures could be determined. The degree of
alkylation of these families of OSC was found to
maximize at three, four, or five alkyl carbons. In the
current study, the OSC of the Rasa coal were determined in both the extract and in the pyrolysate of the
residue after extraction. This latter aspect is important
since the residue contains ca. 75% of the total organic
sulfur of the whole coal.
Experimental Section
Extraction and Fractionation. The ground coal (142.9
g) was mixed with an equal amount of Celite and extracted
for 5 days in a Soxhlet apparatus using the pyridine/toluene
azeotrope (22:78), which has a boiling point of 110 C. The
extract was filtered through a 10 m Teflon filter. The filtrate
was subjected to rotary evaporation to remove bulk solvent,
(11) Keleman, S. R.; George, G. N.; Gorbaty, M. L. Fuel 1990, 69,
939
(12) Gorbaty, M. L.; George, G. N.; Keleman, S. R. Fuel 1990, 69,
945.
(13) Brown, J. R.; Kasrai, M.; Bancroft, G. M.; Tan, K. H.; Chen ,
J-.M. Fuel 1992, 71, 649-653.
(14) Mitchell, S. C.; Snape, C. E.; Garcia, R.; Ismail, K.; Bartle, K.
D. Fuel 1994, 73, 1159-1166.
(15) Gorbaty, M. L.; George, G. N.; Keleman, S. R. Fuel 1990, 69,
1065-1067.
(16) Calkins, W. H.; Gorbaty, M. L.; Keleman, S. R. Fuel 1993, 72,
900.
(17) Brown, J. R.; Kasrai, M.; Bancroft, G. M.; Tan, K. H.; Chen,
J-.M. Fuel 1993, 72, 900-901
(18) Keleman, S. R.; Gorbaty, M. L.; George, G. N.; Kwiatek, P. J.;
Sansone, M. Fuel 1991, 70, 396.
(19) Calkins, W. H.; Torres-Ordonez, R. J.; Jung, B.; Gorbaty, M.
L.; George, G. N.; Keleman, S. R. Energy Fuels 1992, 6, 411-413.

followed by further evaporation of solvent using a gentle

stream of nitrogen over the warmed (50 C) extract. Subsequently, the extract was placed in a vacuum oven at 50 C
until the extract reached nearly constant weight (yield 26.5
wt %). The residue of the extraction was also dried in a vacuum
oven. The extract was dissolved in a mixture of THF/benzene/
ethanol (4.5:4.5:1), and an insoluble fraction precipitated (31
wt %). A neutral fraction was isolated (11 wt %) using
nonaqueous ion-exchange liquid chromatography.20 The initial
THF/benzene/ethanol-soluble portion was passed through a
pair of anion and cation columns (70 1.5 cm). Material
eluting through these columns was recovered via rotary
evaporation under nitrogen and subsequently redissolved in
a mixture (3:1) of cyclohexane/benzene. This cyclohexane/
benzene solution was subsequently passed through a fresh pair
of anion and cation columns of the same dimensions, which
had been preequilibrated with this same solvent mixture.
Material eluting from this second pair of columns constituted
the neutral fraction (11 wt % of the extract). Strong acid, strong
base, weak acid, and weak base fractions were subsequently
recovered under nitrogen from the respective ion-exchange
resins as described elsewhere;20 however, these materials were
not analyzed further in this work. Both nonaqueous ionexchange separations were carried out at 40 C to improve
sample solubility.
The whole neutral fraction was fractionated into saturated
hydrocarbon (1 wt % of neutrals) and neutral aromatic (82
wt % of neutrals) fractions using a combination of chargetransfer and adsorption HPLC techniques. Approximately 1
g of whole neutrals was dissolved into a 7:3 mixture of
dichloromethane/hexane, filtered (3 wt % insoluble residue
recovered), and charged onto a column (30 2.5 cm) packed
with 2,4-dinitroanilinopropyl silica (DNAP).21-22 Saturates
plus 1-ring aromatics were collected by eluting the column
with 5 vol % dichloromethane in hexane in the forward
direction until the detectors (UV and RI) indicated the onset
for elution of g2-ring aromatics. The balance of the g2-ring
aromatics were recovered via backflushing with 7:3 dichloromethane/hexane. The evaporated saturate/1-ring aromatic
fraction was subsequently redissolved in hexane and reseparated on silica (30 2.5 cm dimensions, hexane eluent) to
obtain the final saturated hydrocarbon fraction. The recovered
l-ring aromatics from the silica separation were combined with
the g2-ring aromatic fraction from the DNAP column to obtain
the final neutral-aromatic fraction. Approximately 14 wt % of
the initial neutrals was lost in the course of the work,
presumably due to incomplete elution from the DNAP column.
Both HPLC separations were carried out at 50 C, largely in
an attempt to improve sample solubility. Solvent removal was
carried out under a nitrogen atmosphere to reduce degradation.
Curie Point Pyrolysis Gas Chromatography. The whole
coal and coal fractions were thermally degraded using a Curie
point pyrolyzer and ferromagnetic wires with a Curie temperature of 610 C. In addition, thermal extracts were generated
using ferromagnetic wires with a Curie temperature of 358
(20) Green, J. B.; Hoff, R. J.; Woodward, P. W.; Stevens, L. L. Fuel
1984, 63, 1290-1301.
(21) Grizzle, P. L.; Thomson, J. S. Anal. Chem. 1982, 54, 10711078.
(22) Thomson, J. S.; Reynolds, J. W. Anal. Chem. 1984, 56, 24342441.

730 Energy & Fuels, Vol. 13, No. 3, 1999

C. At this temperature, no significant cleavage of carboncarbon bonds occurs and only low-molecular-weight compounds
are released from the sample investigated. The whole coal,
extracted coal, and total extract were applied to the ferromagnetic wire by pressing the samples on the wire.23 The aromatic
fraction was analyzed by applying a few droplets of a solution
of the fraction in dichloromethane to the wire using a syringe
and evaporating the solvent. The pyrolyzer was mounted on
the injection port of a Varian 3700 gas chromatograph. Online separation of the flash pyrolysate was accomplished by
using a fused silica capillary column (25 m 0.32 mm i.d.)
coated with CP Sil-5 CB (film thickness 0.40 m). The oven of
the gas chromatograph was temperature programmed from 0
C, using a cryogenic unit, to 300 C at 3 C min-1. The oven
was first held at 0 C for 5 min and finally at 300 C for 15
min. Helium was used as the carrier gas. Pyrolysis products
were detected by simultaneous flame ionization detection (FID)
and sulfur-selective flame photometric detection (FPD) using
a stream splitter at the end of the capillary column.
Curie Point Pyrolysis Gas Chromatography-Mass
Spectrometry. The Curie point pyrolyser (FOM-3LX) was
directly connected to a gas chromatograph (Hewlett-Packard
5840) in tandem with a magnetic sector mass spectrometer
(VG-70S) by direct insertion of the capillary column into the
ion source. Gas chromatographic separation was performed as
described above. The mass spectrometer was set at an ionizing
voltage of 70 eV and operated at a cycle time of 1.8 s over the
mass range m/z 40-800 at a resolution of 1000. Data acquisition was started 1 min after pyrolysis.
Pyrolysis gas chromatography-high-resolution mass spectrometry (Py-GC-HRMS) was performed on a Hewlett-Packard 5890 gas chromatograph, also equipped with a Curie point
FOM-3LX pyrolyser, interfaced to a VG Autospec Ultima Q
mass spectrometer operated at 70 eV with a mass range m/z
120-400 and a cycle time of 2.2 s (resolution 6000). Gas
chromatographic separation was performed as described above.
Helium was used as the carrier gas.

Results

Sinninghe Damste et al.

Figure 1. Partial (0-90 min) FID (a) and FPD (b) chromatograms of the thermal extract of the whole Rasa coal generated
by flash evaporation (358 C, 10 s). The letters and numerals
refer to Tables 2 and 3, respectively. Filled circles indicate
n-alkanes. Italic numerals indicate the total number of carbon
atoms. The FID chromatogram is normalized on 2-methylnaphthalene (compound R) and the FPD chromatogram on 2,3dimethylbenzo[b]thiophene.

Whole Coal Thermal Extract. Figure 1 shows the

FID and FPD chromatograms of the thermal extract of
the untreated Rasa coal. These were obtained by flash
evaporation of the whole coal at 358 C for 10 s.
Compounds were identified by mass spectrometry. Letters and numbers in Figure 1 refer to identified compounds listed in Tables 2 and 3, respectively. The FID
trace (Figure 1a) is dominated by aromatic hydrocarbons
(i.e., alkylated benzenes and naphthalenes) and, to a
lesser extent, aliphatic hydrocarbons (i.e. n-alkanes,
branched and isoprenoid hydrocarbons). Sulfur compounds are also present and are dominated by alkylbenzo[b]thiophenes and, to a lesser extent, alkyldibenzothiophenes. Their distribution is exemplified by the
FPD trace (Figure 1b). It should be noted, however, that
the FPD has a quadratic response, which leads to an
optical overestimation of the abundance of the dominant
compounds (in this case the C2 alkylated benzo[b]thiophenes).
At 358 C, low-molecular-weight components rapidly
volatilize from the coal while no cleavage of C-C bonds
occurs,24 except for low-energy rearrangement processes
such as, for example, the generation of prist-1-ene.24

Weaker bonds, such as S-S and C-S bonds, can be

(partially) broken at these conditions25 and partly
explain the presence of relatively high amounts of
hydrogen sulfide (i.e., the gas peak in the FPD trace),
which is formed from decomposition of organic (poly)sulfide moieties and, perhaps, pyrite. The presence of
organic polysulfide moieties in the coal matrix is deemed
unlikely, however, since they are preferentially lost
during the earliest stages of thermal maturation (i.e.,
at R0 ) 0.3-0.4).26 The Rasa coal is significantly more
mature. The thermal extract of the solvent-extracted
coal (see below), apart from hydrogen sulfide, did not
contain any OSC, indicating, indeed, that all C2+
components present in the thermal extract are indeed
solvent extractable and do not originate from C-C or
C-S bond cleavage in the macromolecular matrix of the
coal.
GC-MS was used to study the distribution of compound classes in the thermal extract in more detail. The
mass chromatogram of m/z 57 (Figure 2) reveals that,
apart from straight-chain acyclic hydrocarbons, the
thermal extract contains quite abundant C8-C20 regular
isoprenoid hydrocarbons. It is noteworthy that the
isoprenoid C20 hydrocarbon (phytane) is more abundant

(23) Venema, A.; Veurink, J. J. Anal. Appl. Pyrol. 1985, 7, 207213.

(24) Crisp, P. T.; Ellis, J.; de Leeuw, J. W.; Schenck, P. A. Anal.
Chem. 1986, 58, 258-261.

(25) Sinninghe Damste, J. S.; Eglinton, T. I.; Rijpstra, W. I. C.; de

Leeuw, J. W. ACS Symp. Ser. 1990, 429, 486-528.
(26) Koopmans, M. P.; de Leeuw, J. W.; Lewan, M. D.; Sinninghe
Damste, J. S. Org. Geochem. 1996, 25, 391-426.

Organosulfur Compounds in Sulfur-Rich Ras a Coal

Energy & Fuels, Vol. 13, No. 3, 1999 731

Table 2. Non-sulfur Compounds Identified in Thermal Extracts and Flash Pyrolysatesa

A
B
C
D
E
F
G
H
I
J
K
L
M
a

benzene
methylcyclohexane
toluene
2-methylheptane
2,6-dimethylheptane
ethylbenzene
m- and p-xylene
o-xylene
2,6-dimethyloctane
1,2,4-trimethylbenzene
phenol
2,6-dimethylnonane
o-methylphenol

N
O
P
Q
R
S
T
U
V
W
X
Y

m- and p-methylphenol
C2-alkylphenols
naphthalene
2,6-dimethylundecane
2-methylnaphthalene
1-methylnaphthalene
C2-alkylnaphthalenes
cadalene (1-isopropyl-4,7-dimethylnaphthalene)
norpristane (2,6,10-trimethylpentadecane)
pristane (2,6,10,14-tetramethylpentadecane)
prist-1-ene
phytane (2,6,10,14-tetramethylhexadecane)

Letters refer to compounds in Figures 1, 6, 7, and 9.

Table 3. Sulfur Compounds Identified in Thermal Extracts and Flash Pyrolysates
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26

hydrogen sulfide
thiophene
2-methylthiophene
3-methylthiophene
2-ethylthiophene
2,5-dimethylthiophene
3-ethylthiophene
2,4-dimethylthiophene
2,3-dimethylthiophene
3,4-dimethylthiophene
2-propylthiophene
2-ethyl-5-methylthiophene
2-ethyl-4-methylthiophene
ethylmethylthiophene
2,3,5-trimethylthiophene
2,3,4-trimethylthiophene
3-isopropyl-2-methylthiophene
2-methyl-5-propylthiophene
2,5-diethylthiophene
unknown sulfur compound
2-butylthiophene
2-ethyl-3,5-dimethylthiophene
ethyldimethylthiophene
5-ethyl-2,3-dimethylthiophene
ethyldimethylthiophene
ethyldimethylthiophene

27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52

Figure 2. Mass chromatogram of m/z 57 of the thermal

extract of the whole Rasa coal generated by flash evaporation
(358 C, 10 s). n-Alkanes are indicated by filled circles, and
their total number of carbon atoms are denoted by italic
numerals. Regular isoprenoid alkanes are indicated by i-,
followed by a numeral, indicating the total number of carbon
atoms.

than its C19 counterpart (pristane) since, in general, coal

extracts are characterized by high pristane/phytane
ratios of 5-10 (ref 27).

2,3,4,5-tetramethylthiophene
C5-thiophene
2-ethyl-5-propylthiophene
C5-thiophene
2-butyl-5-methylthiophene
2-pentylthiophene dimethyl-5-and 2,3-propylthiophene
2-ethyl-3,4,5-trimethylthiophene
benzo[b]thiophene
C1-benzo[b]thiophenes
7-methylbenzo[b]thiophene
2-methylbenzo[b]thiophene
5- and 8-methylbenzo[b]thiophene
4- and 3-methylbenzo[b]thiophene
C2-benzo[b]thiophenes
2- and 4-ethylbenzo[b]thiophene
2,6-dimethylbenzo[b]thiophene
2,4-dimethylbenzo[b]thiophene
2,3-dimethylbenzo[b]thiophene
C3-benzo[b]thiophenes
C4-benzo[b]thiophenes
dibenzothiophene
C1-dibenzothiophenes
4-methyldibenzothiophene
2- and 3-methyldibenzothiophene
1-methyldibenzothiophene
C2-dibenzothiophenes

The distribution pattern of the most abundant compound class of OSC (Figure 1b), the alkylbenzo[b]thiophenes (I; see Appendix), is exemplified by a summed,
accurate mass chromatogram of m/z 134 + 147 + 148
+ 161 + 162 + 175 + 176 + 189 + 190 (Figure 3a). Since
these ions are the major ions in the mass spectra of
benzo[b]thiophene and its C1-C4 alkylated derivatives,
this summed mass chromatogram provides a quantitative representation of the abundance of these compounds in the thermal extract of the Rasa coal. An
accurate mass chromatogram was used to eliminate
contributions from other compounds with mass spectra
containing the same nominal masses but accurate
masses outside the mass window used (see caption of
Figure 3). The distribution pattern of the alkylbenzo[b]thiophenes is very complex, as expected from the
large number of theoretically possible isomers for C0C4 alkylated benzo[b]thiophenes (i.e., 224 isomers). The
C2- and, to a lesser extent, C3-alkylbenzo[b]thiophenes
dominate in the thermal extract. Specific isomers were
identified by coelution with authentic standards when
available. The major C2-isomer is tentatively identified
as 2,3-dimethylbenzo[b]thiophene. Py-GC-HRMS
provided circumstantial evidence for their identification
as alkylbenzo[b]thiophenes (Table 4). These results
(27) Powell, T. G.; McKirdy, D. M. Nature 1973, 243, 37-39.

732 Energy & Fuels, Vol. 13, No. 3, 1999

Figure 3. Partial, summed, accurate (mass window 0.02

dalton) mass chromatogram of m/z 134.02 + 147.03 + 148.04
+ 161.04 + 162.05 + 175.06 + 176.07 + 189.07 + 190.08
revealing the distribution of benzo[b]thiophene and its C1-C4
alkylated derivatives in (a) the thermal extract of the whole
Rasa coal and (b) the flash pyrolysate (610 C) of the solvent
extracted Rasa coal. Numbers refer to compounds listed in
Table 3.

confirm the findings of White et al.,7 who suggested the

presence of C1-C6 alkylated benzo[b]thiophenes on the
basis of low-voltage, high-resolution mass spectrometry
(LVHRMS) analysis of the solvent extract of the Rasa
coal.
The presence of alkylated dibenzothiophenes (IIa) in
the solvent extract of the Rasa coal7 was also confirmed
by our results. Figure 4 shows accurate mass chromatograms of m/z 184, 198, 212, 226, and 240, revealing the
distribution patterns of dibenzothiophene and its C1C4 alkylated derivatives and, possibly, C0-C4 alkylated
naphthothiophenes (IIb). These latter components probably represent the smaller peaks in the mass chromatogram shown in Figure 4b. The three major peaks
represent the four possible C1 methyldibenzothiophenes
(of which two coelute). The other remaining smaller, not
labeled peaks thus must represent other components
with the same molecular formulas. Again, the clusters
of isomers become increasingly more complex with
increasing number of alkyl carbons (Figure 4). Py-GCHRMS confirmed their elemental composition (Table 4).
Mass chromatography of m/z 234 + n14 (n ) 0-3)
revealed the presence of benzonaphthothiophenes (IIIa),
thienophenanthrenes (IIIb), thienoanthracenes (IIIc),
and C1-C3 alkylated derivatives. Their elemental compositions were confirmed by GC-HRMS (Table 4).
White et al.7 also suggested the presence of these
components in the Rasa coal extract. The mass chromatogram of the parent components (m/z 234) already
revealed the presence of at least four peaks, which can
be explained since 18 isomers are theoretically possible.
The clusters of higher homologues are accordingly
complex. Less complicated are the mass chromatograms

Sinninghe Damste et al.

(m/z 208 + n14, n ) 1-3) of another group of monosulfur

components with four rings, the phenanthro[4,5-bcd]thiophenes (IV) also proposed to be present in the Rasa
coal extract.7 Their elemental compositions were confirmed by GC-HRMS (Table 4). The mass chromatogram of the parent component shows only one peak.
Various series of OSC containing two sulfur atoms
per molecule were also tentatively identified. Small
amounts of thienothiophenes (VIa and VIb) and
bithiophenes (VIIa and VIIb) and their alkyl homologues were detected, and their elemental compositions
were confirmed by GC-HRMS. A series of thienobenzo[b]thiophenes (e.g., VIIIa) was also detected by mass
chromatography and GC-HRMS (Table 4). Figure 5
shows accurate mass chromatograms of m/z 240, 254,
and 268. These chromatograms probably reveal the
distribution of thienodibenzothiophenes (e.g., IXa) or
thienonaphthothiophenes (e.g., IXb) with elemental
composition C14H8S2 + nCH2 as confirmed by Py-GCHRMS (Table 4). White et al.7 identified a homologous
series with the same elemental composition in the
extract of the Rasa coal by LVHRMS analysis and
suggested alkylthiophenanthro[4,5-bcd]thiophenes as
possible stuctures. Since the mass spectra of the components revealed in Figure 5 showed significant doublecharged molecular ions (which is not expected in mass
spectra of the compound type proposed by White et al.7),
thienobenzothiophenes or thienonaphthothiophenes seem
more logical since these components belong to the family
of polycyclic aromatic hydrocarbons (PAH) which are
known to produce substantial double-charged ions upon
electron impact ionization.28 The presence of at least
four components in the trace of the parent of the class
of components (Figure 5a) is to be expected since nine
theoretically possible isomers exist.
Whole Coal Pyrolysate. Figure 6 shows the FID and
FPD chromatograms of the flash pyrolysate of the
untreated coal using a ferromagnetic wire with a Curie
temperature of 610 C. The pyrolysate obtained contains, in addition to compounds which are present as
such and simply evaporate, components which result
from thermal breakdown of the macromolecular fraction
of the coal. The pyrolysate contains the same components as the thermal extract (i.e., aliphatic and aromatic
hydrocarbons, benzo[b]- and dibenzothiophenes) and in
addition a number of other compounds (e.g., n-alk-1enes, prist-1-ene, alkylphenols, alkylthiophenes), which
results in an even more complicated FID chromatogram
(e.g., cf. Figures 1a and 6a). These latter compounds
must be pyrolysis products, but the presence of compounds in the thermal extract does not exclude the
possibility that a significant amount of a compound in
the pyrolysate is due to thermal degradation of the
macromolecular matrix. This hypothesis is confirmed
by changes in the composition of the products which are
both present in the thermal extract as well as in the
pyrolysate (e.g., cf. compounds B and C in Figures 1a
and 6a). Sulfur compounds are somewhat more dominant in the pyrolysate compared to the thermal extract.
More importantly, the distribution of the sulfur compounds has changed considerably (cf. Figures 1b and
6b). In addition to the alkylated benzo[b]thiophenes and
(28) Lee, M. L.; Novotny, M. V.; Bartle, K. D. Analytical Chemistry
of Polycyclic Aromatic Compounds; Academic: London, 1981; 440 pp.

Organosulfur Compounds in Sulfur-Rich Ras a Coal

Energy & Fuels, Vol. 13, No. 3, 1999 733

Table 4. HRMS of Organosulfur Compounds in Ras a Coal Thermal Extract

no. of alkyl
carbons

mol
formula

0
1
2
3
4

C8H6S
C9H8S
C10H10S
C11H12S
C12H14S

0
1
2
3
4

C12H8S
C13H10S
C14H12S
C15H14S
C16H16S

0
1
2
3

measured
mol weighta

calcd
mol weight

Benzo[b]thiophenes (I)
134.0185
134.0190
148.0349
148.0347
162.0495
162.0503
176.0652
176.0660
190.0804
190.0816
Dibenzothiophenes (IIa) and Naphthothiophenes (e.g., IIb)
184.0349
184.0347
198.0486
198.0470
212.0649
212.0660
226.0808
226.0816
240.0964
240.0973

M
(mDa)

min no. of
isomersb

0.5
0.2
0.8
0.8
1.2

1
4
10
20
30

0.2
-1.6
1.1
0.8
0.9

2
7
25
40
60

Benzonaphthothiophenes (e.g., IIIa), Thienophenanthrenes (e.g., IIIb), and Thienoanthracenes (e.g., IIIc)
C16H10S
234.0504
234.0503
-0.1
C17H12S
248.0655
248.0660
0.5
C18H14S
262.0810
262.0816
0.6
C19H16S
276.0964
276.0973
0.9

4
8
25
40

0
1
2
3

Phenanthro[4,5-bcd]thiophenes (IVa) and Thienoacenaphthenes (e.g., IVb)

C14H8S
208.0337
208.0347
1.0
C15H10S
222.0496
222.0503
0.7
236.0644
236.0660
1.6
C16H12S
C17H14S
250.0795
250.0783
2.1

0
1
2
3
4

C14H10S
C14H12S
C14H14S
C14H16S
C14H18S

Phenylbenzothiophenes (e.g., V)
210.0504
210.0503
224.0655
224.0660
238.0812
238.0816
252.0970
252.0972
266.1121
266.1129

0.1
0.5
0.4
0.2
0.8

1
5
20
40
80

0
1
2

C6H4S2
C7H6S2
C8H8S2

Thienothiophenes (VIa and VIb)

139.9733
139.9754
153.9894
153.9911
168.0035
168.0067

2.1
1.7
3.2

2
3
5

0
1

C8H6S2
C9H8S2

Bithiophenes (VIIa and VIIb)

165.9908
165.9911
180.0058
180.0067

0.3
0.9

1
8

0
1
2
3
4
5
6

C10H6S2
C11H8S2
C12H10S2
C13H12S2
C14H14S2
C15H16S2
C16H18S2

Thienobenzo[b]thiophenes(e.g., VIII)
189.9905
189.9911
204.0046
204.0067
218.0199
218.0224
232.0396
232.0380
246.0528
246.0537
260.0683
260.0693
274.0845
274.0850

0.6
2.1
2.5
-1.6
0.9
1.0
0.5

5
15
20
20
30
50
80

0
1
2

Thienodibenzothiophenes (e.g., IXa) or Thienonaphthothiophenes (e.g., IXb)

C14H8S2
240.0069
240.0067
-0.2
C15H10S2
254.0201
254.0224
2.3
C16H12S2
268.0404
268.0380
-2.4

4
12
35

1
8
16
40

a Weighted average over all chromatographic peaks with a mass window of 200 ppm. b As determined by the number of peaks in specific
mass chromatograms (e.g., Figures 3-5).

dibenzothiophenes identified in the thermal extract,

alkylthiophenes are quite important components in the
flash pyrolysate. Furthermore, the distribution of the
alkylbenzo[b]thiophenes is changed. 2-Methylbenzo[b]thiophene is the most dominant benzothiophene in the
pyrolysate, while an unspecified C2-alkylated benzo[b]thiophene is the most abundant benzo[b]thiophene in
the thermal extract (Figure 3).
Extracted Coal Pyrolysate. The FID and FPD
chromatograms of the flash pyrolysate of extracted
coal using a ferromagnetic wire with a Curie temperature of 610 C are shown in Figure 7. The pyrolysate
contains the same suite of compounds present in the
pyrolysate of the whole coal (cf. Figures 6a and 7a). The
two major peaks labeled with an asterisk in the first
part of the FID chromatogram are due to residues of
solvents used to extract the coal. The residues were

incompletely removed by drying the extracted coal.

The FID chromatogram (not shown) of the thermal
extract (358 C) of the extracted coal only revealed the
presence of these two peaks, indicating that the extraction with pyridine/toluene has been extensive, as expected from the high extract yield (26.5 wt %). This
experiment confirms that the compounds present in
the thermal extract of the nonextracted, whole coal
(Figure 1a) are only formed by thermal evaporation and
not by C-C bond cleavage. The FPD chromatogram
(Figure 7b) reveals the distribution of the sulfur compounds in the pyrolysate, which is dominated by the
same compounds as the flash pyrolysate of the whole
coal, although the alkylthiophenes are more abundant
than in the pyrolysate of the whole coal (cf. Figures 6b
and 7b). This can be explained by the fact that the
pyrolysate of the whole coal also contains a contribution

734 Energy & Fuels, Vol. 13, No. 3, 1999

Figure 4. Partial, accurate (mass window 0.02 dalton) mass

chromatograms of m/z (a) 184.05, (b) 198.05, (c) 212.06, (d)
226.07, and (e) 240.10 revealing the distribution of dibenzothiophene and naphthothiophenes and their C1-C4 alkylated
derivatives in the thermal extract of the whole Rasa coal
generated by flash evaporation. Numbers refer to compounds
listed in Table 3.

Sinninghe Damste et al.

Figure 6. Partial (0-90 min) FID (a) and FPD (b) chromatograms of the flash pyrolysate (610 C, 10 s) of the whole Rasa
coal. For peak labeling, see the caption of Figure 1. n-Alk-1enes are indicated with filled squares. The FID chromatogram
is normalized on toluene (compound C) and the FPD chromatogram on 2-methylbenzo[b]thiophene (compound 37).

Figure 5. Partial, accurate (mass window 0.02 dalton) mass

chromatograms of m/z (a) 240.00, (b) 254.02, and (c) 268.04
revealing the distribution of thienyldibenzothiophenes (e.g.,
IXa) and thienylnaphthothiophenes (e.g., IXb) and their C1C2 alkylated derivatives in the thermal extract of the whole
Rasa coal generated by flash evaporation.

The distribution of the C0-C5 alkylthiophenes is

shown by a summed accurate mass chromatogram of
m/z 84 + 97 + 98 + 111 + 112 + 125 + 126 + 139 +
140 + 153 + 154 (Figure 8). Since these m/z values are
the dominant peaks in the mass spectra of the alkylthiophenes, this summed mass chromatogram provides a
quantitative representation of the alkylthiophene distribution. The alkylthiophenes were identified by comparison with data reported previously.29
An accurate summed mass chromatogram of m/z 134
+ 147 + 148 + 161 + 162 + 175 + 176 + 189 + 190
(Figure 3b) shows the distribution of the C0-C4 alkylated benzo[b]thiophenes exclusively generated by thermal breakdown of the macromolecular network. Comparison with the distribution of these compounds in the
thermal extract (cf. Figures 3a and 3b) confirms the
observation from the flash pyrolysis experiment with
the whole coal that 2-methylbenzo[b]thiophene is mainly
generated by pyrolysis. Furthermore, significant changes
in the abundance of specific isomers in the C2 and C3
cluster can be noted. Interpretation of these differences
is, however, hampered by the incomplete identification
of isomers.
GC-HRMS of the flash pyrolysate of the solvent
extracted coal confirmed the presence of the same OSC
as in the solvent extract (cf. Table 4).
Solvent Extract. To compare the results of the
solvent-extract of the coal with those obtained for the

from free alkylbenzo[b]thiophenes but not from alkylthiophenes (Figure 1b).

(29) Sinninghe Damste, J. S.; Kock-van Dalen, A. C.; de Leeuw, J.

W.; Schenck, P. A. J. Chromatogr. 1988, 435, 435-452.

Organosulfur Compounds in Sulfur-Rich Ras a Coal

Figure 7. Partial (0-90 min) FID (a) and FPD (b) chromatograms of the flash pyrolysate (610 C, 10 s) of the solvent
extracted Rasa coal. For peak labeling, see the caption of
Figure 1. n-Alk-1-enes are indicated with filled squares. The
FID chromatogram is normalized on the peak consisting of mand p-xylene and 2,5-dimethylthiophene (compounds G and
6) and the FPD chromatogram on 2,5-dimethylthiophene
(compound 6). Peaks denoted by asterisks in the FID chromatogram indicate residues of solvents used for extraction of
the coal.

Figure 8. Partial, summed, accurate (mass window 0.02

dalton) mass chromatogram of m/z 84.00 + 97.01 + 98.02 +
111.03 + 112.03 + 125.04 + 126.05 + 139.05 + 140.06 +
153.07 + 154.08 revealing the distribution of thiophene and
its C1-C5 alkylated derivatives in the flash pyrolysate (610
C, 10 s) of the solvent extracted Rasa coal. Numbers refer to
compounds listed in Table 3.

whole coal and extracted coal, the coal extract was

analyzed in a similar manner. Figure 9 shows the FID
and FPD chromatograms of the thermal extract of the
coal extract generated using a ferromagnetic wire with

Energy & Fuels, Vol. 13, No. 3, 1999 735

Figure 9. Partial (0-90 min) FID (a) and FPD (b) chromatograms of the thermal extract of the solvent extract of the Rasa
coal generated by flash evaporation (358 C, 10 s). For peak
labeling, see the caption of Figure 1. The FID chromatogram
is normalized on the most abundant C2-alkylnaphthalene
eluting in the cluster of peaks denoted by T + 40 and the FPD
chromatogram on the most abundant C2-benzo[b]thiophene
(2,3-dimethylbenzo[b]thiophene). Peaks denoted by asterisks
in the FID chromatogram indicate residues of solvents used
for extraction of the coal.

a Curie temperature of 358 C. The FID trace is

dominated by alkylated naphthalenes, alkylated benzo[b]thiophenes, alkylated dibenzothiophenes, and alkylated phenanthrenes. In comparison with the thermal
extract of the whole coal (Figure 1a), the loss of lowmolecular-weight components is apparent. This is probably due to the prolonged time (300 h) in a vacuum at
elevated temperature (50 C) to remove the solvents
from the extract, which is assumed to have led to
extensive losses of low-molecular-weight components.
The FPD chromatogram (Figure 9b) shows the distribution of sulfur compounds. In comparison with the
thermal extract, an enrichment of the alkylated dibenzothiophenes relative to the alkylated benzothiophenes
can be observed, which is also most probably due to
evaporative losses during sample workup. The composition of the flash pyrolysate (610 C) of the solvent
extract of the Rasa coal is very similar to that of the
thermal extract of the solvent extract, indicating that
the solvent extract does not contain significant amounts
of high-molecular-weight material from which pyrolysis
products can be generated. For example, the FPD
chromatogram (not shown) contains only traces of
alkylthiophenes (cf. Figure 6b) and is still dominated
by a 2,3-dimethylbenzo[b]thiophene instead of 2-methylbenzo[b]thiophene.

736 Energy & Fuels, Vol. 13, No. 3, 1999

Sinninghe Damste et al.

Figure 11. Gas chromatogram of the saturated hydrocarbon fraction of the solvent extract of the Rasa coal. Filled
circles denote n-alkanes with italic numerals indicating their
total number of carbon atoms. Key: a ) pristane, b ) phytane,
c ) 17R-trinorhopane, d ) 17R,21(H)-30-norhophane, e )
17R,21(H)-hopane.

Figure 10. Partial (0-90 min) FID (a) and FPD (b) chromatogram of the thermal extract of the aromatic fraction of
the solvent extract of the Rasa coal generated by flash
evaporation (358 C, 10 s). For peak labeling, see the caption
of Figure 1. The FID and FPD chromatograms are normalized
on dibenzothiophene (compound 47).

Saturated Hydrocarbon and Neutral Aromatic

Fractions. The thermal extract of the neutral aromatic
fraction of the solvent extract of the Rasa coal is shown
in Figure 10. It reveals a further loss of lower-molecularweight compounds since alkylated dibenzothiophenes
dominate over alkylated benzo[b]thiophenes, whereas
this is the opposite in the thermal extract of the whole
coal. Both compound classes are expected to be present
in the neutral aromatic fraction. Gas chromatography
and gas chromatography-mass spectrometry of the
saturated hydrocarbon fraction confirmed this further
loss of volatile compounds: the FID chromatogram
(Figure 11) contains no compounds <C17, although such
hydrocarbons are present in the thermal extract of the
whole coal (Figures 1a and 2). We conclude that
compounds with a boiling point <300 C have been lost
during workup procedures. The major compounds in the
gas chromatogram of the saturated hydrocarbon fraction
are a series of n-alkanes, a series of hopanes, and the
isoprenoid hydrocarbons, pristane and phytane.
Discussion
Extractable OSC. The results reported on the OSC
present in extractable form in the Rasa coal have
confirmed, in most cases, the structures suggested to
be present on the basis of LVHRMS of the extract.7
Components with thiol or alkylsulfide functionalities
suggested to be present7 were not encountered, in line
with the authors comment that these structures are

particularly suspicious. In some cases, alternative

structures have been proposed. In these cases, the sulfur
atom is part of an aromatic ring system, as in the case
of the major OSC present in the Rasa coal extract (i.e.,
alkylated benzo[b]- and dibenzothiophenes). A significant advantage of our analytical approach compared
with direct LVHRMS analysis of the solvent extract7 is
the possibility to identify different structural isomers
of OSC with the same elemental composition (and thus
with the same molecular formulas) using mass chromatography. This demonstrated how complicated these
distributions can be (e.g., Figures 3-5). For all series
of OSC, an increase in the number of structural isomers
with increasing degree of alkylation is observed (Table
4). Although the relative intensities of individual isomers generally decrease with increasing degree of
alkylation (e.g., Figures 3-5), the increasing number
of isomers are in line with the conclusion of White et
al.7 that the degree of alkylation of many homologous
series was found to maximize at either three, four, or
five alkyl carbons.
In addition to the well-known4 alkylated benzo[b]thiophenes and dibenzothiophenes, the GC-HRMS
approach also enabled the tentative identification in
small quantities of OSC possessing more aromatic rings
(e.g., III-V) and OSC containing more than one sulfur
atom (VI-IX). The first additional group of OSC had
been encountered before in sulfur-rich coals.30-32 As
discussed in detail elsewhere,4 full identification of these
compounds is nearly impossible. White et al.7 and
Winans and Neill33 provided some evidence using
LVHRMS for the presence of OSC containing two sulfur
atoms in extracts and pyrolysates, respectively, in
sulfur-rich coals. Our data (Table 4) confirm that such
OSC are indeed present in Rasa coal. Their detection
was possible only by the fact that Rasa coal is very
organic sulfur-rich.
(30) White, C. M.; Douglas, L. J.; Perry, M. B.; Schmidt, C. E. Energy
Fuels 1987, 1, 222-226.
(31) White, C. M.; Lee, M. L. Geochim. Cosmochim. Acta 1980, 44,
1825-1832.
(32) Nishioka, M. Energy Fuels 1988, 2, 214-129.
(33) Winans, R. E.; Neill, P. H. ACS Symp. Ser. 1990, 429, 249260.

Organosulfur Compounds in Sulfur-Rich Ras a Coal

Our data imply that alkylated benzo[b]thiophenes are

the most important extractable OSC in Rasa coal
(Figure 1b). This seems to contradict the results of
White et al.,7 which suggest that benzo[b]thiophenes are
minor OSC relative to more condensed polycyclic aromatic thiophenes. This apparent discrepancy may be
explained by (i) losses of lower molecular weight components during sample processing (clearly revealed by
a comparison of Figures 1 and 7), (ii) relatively large
differences in ionization yield at low voltage for the
different families of polycyclic aromatic thiophenes, and
(iii) discrimination of relatively low-volatile polycyclic
aromatic thiophenes in the interface between the flash
pyrolysis unit and the GC capillary in the Py-GC-MS
mode. This latter possibility seems, however, unlikely
in view of the presence of higher n-alkanes (Figure 2)
with a similar boiling point.
Macromolecularly Bound OSC. Our results demonstrate that the pyridine/toluene extraction of the coal
removed a large part of the extractable organic matter,
as expected from the high yield (26.5%). This enabled a
detailed study of the OSC present in the macromolecular network of the coal since no interference from free
components is apparent. Flash pyrolysis released alkylthiophenes and alkylbenzo[b]thiophenes as major OSC
(Figure 7b). It should be realized, however, that sulfide
linkages upon thermal breakdown generate mainly H2S
and that only small amounts of cyclic organic sulfides
are generated.4 Since H2S can also be generated from
pyrite, the ratio of [H2S]/[alkylated thiophenes] does not
provide a solid basis for estimation of the sulfur speciation in macromolecules. This can only be done after
complete removal of pyrite.34
In general the composition of the pyrolysate of the
extracted coal is quite similar to that of the extract. This
may be readily explained by the fact that the coal is
already in an advanced stage of maturation (oil window), resulting in a substantial production of extractable organic matter from the thermal degradation of
macromolecular organic matter. Such processes are
occurring relatively early if the macromolecular organic
matter contains high levels of organic sulfur.26,35-36 A
significant difference between the OSC present in the
pyrolysate of the extracted coal and the solvent extract
is the absence of the low-molecular-weight thiophenes
in the extract. This may be caused by the volatility of
these thiophenes, leading to losses during sample
workup. The thermal extract of the whole coal (Figure
1), however, also reveals the absence of thiophenes in a
free form, whereas other volatile products are clearly
present. This would indicate that they indeed are absent
in the extract. Alternatively, it has been suggested that
alkyl thiophenes may be formed, at least in part, by
rearrangement processes of (poly)sulfide moieties.37
Indeed, recent experiments using microsealed vessel
pyrolysis38 indicated that alkylthiophenes in pyrolysates
of kerogen (the insoluble organic matter in sediments
(34) Eglinton, T. I.; Irvine, J. E.; Vairavamurthy, A.; Zhou, W.;
Manowitz, B. Org. Geochem. 1993, 22, 781-799.
(35) Orr, W. L. Org. Geochem. 1986, 10, 499-516.
(36) Koopmans, M. P.; Rijpstra, W. I. C.; de Leeuw, J. W.; Lewan,
M. D.; Sinninghe Damste, J. S. Org. Geochem. 1998, 28, 503-521.
(37) Tomic, J.; Behar, F.; Vandenbroucke, M.; Tang, Y. Org.
Geochem. 1995, 23, 647-660.
(38) Sinninghe Damste, J. S.; Kohnen, M. E. L.; Horsfield, B. Org.
Geochem. 1998, 29, 1891-1903.

Energy & Fuels, Vol. 13, No. 3, 1999 737

and sedimentary rocks), at least in part, result from

thermal degradation of multiple (poly)sulfide bound
short-chain (C5-C7) carbon skeletons, probably originating from natural sulfurization of carbohydrates.39
Upon natural maturation (low temperatures, long reaction times), it is unlikely that these moieties produce
low-molecular-weight thiophenes as they do upon pyrolysis. This may explain the absence of these thiophenes
in the Rasa coal extract
The distribution of the OSC in the extracted coal
pyrolysate is not very different from those in pyrolysates
of kerogens25,40-43 and coals.4,42-48 The major difference
is that the alkylbenzo[b]thiophenes are more abundant
relative to the alkylthiophenes than in most other
samples studied. This is probably related to the more
mature character of the Rasa coal. Eglinton et al.42 have
clearly demonstrated that with increasing maturity, the
relative abundance of alkylbenzo[b]thiophenes increases
in flash pyrolysates of kerogens and coals. In fact, the
OSC distribution in the Rasa coal pyrolysate is comparable to that in a pyrolysate of a Mahakam coal of
similar rank (i.e., vitrinite reflectance 0.65%).42 These
results seem to indicate that observations on OSC in a
high- sulfur coal can be extrapolated to other coals. The
notable difference is, however, that in the Rasa coal
pyrolysate the OSC are dominant components, whereas
there are only traces of these OSC in the Mahakam
pyrolysate.42 This is directly related to the organic sulfur
content and atomic Sorg/C ratio: high in the Rasa coal
(Table 1) and relatively low in the Mahakam coal.4 Since
it is well-known that organic sulfur is lost relatively
early during thermal maturation,26,35 this must indicate
that the original sulfur content of the immature Rasa
coal must have been exceedingly high. Artificial maturation of a sulfur-rich immature (Ro ) 0.25%) kerogen
using hydrous pyrolysis has indicated a drop in the
atomic Sorg/C ratio of a factor 3 in the kerogen heated
for 3 days at 325 C relative to its initial value.49
Although it is always difficult to extrapolate artificial
maturation to natural maturation, this maturation
stage is comparable to that of Rasa coal since the
bituminite reflectance is 0.59%, the aromaticity is 0.67,
the atomic H/C ratio of the kerogen is 0.80, and ca. 80%
of the organic sulfur was thiophenic, all quite comparable to those of Rasa coal. A similar drop in the atomic
Sorg/C ratio has been observed in natural maturity
sets.42 This would indicate that the initial atomic Sorg/C
(39) Sinninghe Damste, J. S.; Kok, M.; Koster, J.; Schouten, S. Earth
Planet. Sci. Lett. 1998, 164, 7-13.
(40) Sinninghe Damste, J. S.; Eglinton, T. I.; de Leeuw, J. W.;
Schenck, P. A. Geochim. Cosmochim Acta 1989, 53, 873-889.
(41) Eglinton, T. I.; Sinninghe Damste, J. S.; Kohnen, M. E. L.; de
Leeuw, J. W. Fuel 1990, 69, 1394-1404.
(42) Eglinton, T. I.; Sinninghe Damste, J. S.; Kohnen, M. E. L.; de
Leeuw, J. W.; Larter, S. R.; Patience, R. L. ACS Symp. Ser. 1990, 429,
529-565.
(43) Eglinton, T. I.; Sinninghe Damste, J. S.; Pool, W.; de Leeuw, J.
W.; Eijkel, G.; Boon, J. J. Geochim. Cosmochim. Acta 1992, 56, 15451560.
(44) Boudou, J. P.; Boule`ge, J.; Malechaux, L.; Nip, M.; de Leeuw,
J. W.; Boon, J. J. Fuel 1987, 66, 1558-1569.
(45) Calkins, W. H. Energy Fuels 1987, 1, 59-64.
(46) Bakel, A. J.; Philp, R. P.; Galvez-Sinibaldi, A. ACS Symp. Ser.
1990, 429, 326-344.
(47) Sinninghe Damste, J. S.; de las Heras F. X. C.; de Leeuw, J.
W. J. Chromatogr. 1992, 607, 361-376.
(48) Hartgers, W. A.; Sinninghe Damste, J. S.; de Leeuw, J. W.; Ling,
Y.; Dyrkacz, G. R. Energy Fuels 1994, 8, 1055-1067.
(49) Nelson, B. C.; Eglinton, T. I.; Seewald, J. S.; Vairavamurthy,
M. A.; Miknis, F. P. ACS Symp. Ser. 1995, 612, 138-166.

738 Energy & Fuels, Vol. 13, No. 3, 1999

ratio would have been 3(0.053) ) 0.16, corresponding

to an initial organic sulfur content of ca.15%, one of the
highest values known for sulfur-rich kerogens3 and
unprecedented for coals, lignites, and peats. This actually raises the question of whether Rasa coal should be
considered a typical coal.
Is Ras a Coal a Typical Coal? A coal is defined as a
chemically and physically modified compact stratified
mass of debris of plants, derived mainly, though not
exclusively, from vegetation growing on land.50 Other
definitions mention that coal is derived from plants but
do not require the plants to be terrestrial. Since the
major biopolymers of terrestrial higher plant are lignin
and cellulose, coals generally have a high content of
oxygen. The very low amount of oxygen in Rasa coal
(Table 1) is very unusual for a coal but is consistent with
the very low abundance of phenol and alkylated phenols
in the flash pyrolysates, typical pyrolysis products of
diagenetically transformed lignin.51 Although it is known
that these phenols are lost from pyrolysates of coals or
vitrinites with increasing coalification,52-53 these components are still the major products of coals with a rank
similar to Rasa coal (Ro ) ca. 0.70%). If the Rasa coal
is plotted on a van Krevelen diagram,54 its position on
the graph indicates that it is a mature Type I or II
kerogen. The almost complete absence of lignin and
cellulose (or their diagenetic products) in Rasa coal is
also consistent with microscopic examination, which
showed very little evidence of cell structure.7 Therefore,
there is no evidence to indicate that the organic matter
is predominantly derived from terrestrial higher plants,
indicating that Rasa coal is certainly not a typical coal.
Corroborating evidence for this conclusion is that (i) the
pristane/phytane ratio of Rasa coal is <1 (Figure 2)
whereas it is generally >5 for coals;55 (ii) the absence
of higher plant biomarkers (although cadalene was
detected); (iii) the distributions of the alkylated alkylthiophenes (Figure 8) and alkylbenzenes (not shown)
in the flash pyrolysate are not typical of a coal;43-44,56
and (iv) the anomalous high level of organic sulfur (see
above). Therefore, we must conclude that in fact Rasa
coal should not be considered a typical coal. Other
marine deposits have a similar high organic sulfur and
organic matter content, e.g., the Kimmeridge Blackstone
(50) Francis, W. Coal, Its Formation and Composition; Edward
Arnold: London, 1961; p 806.
(51) Hatcher, P. G.; Clifford, D. J. Org. Geochem. 1997, 27, 251274.
(52) Senftle, J. T.; Larter, S. R.; Bromley, B. W.; Brown, J. H. Org.
Geochem. 1986, 9, 345-350.
(53) Veld, H.; de Leeuw, J. W.; Sinninghe Damste, J. S.; Fermont,
W. J. J. ACS Symp. Ser. 1994, 570, 149-160.
(54) Tissot, B. P.; Welte, D. H. Petroleum Formation and Occurrence,
2nd ed.; Springer: Heidelberg, 1984; 699 pp.
(55) Powell, T. Nature 1988, 333, 604.
(56) Hartgers, W. A.; Sinninghe Damste, J. S.; de Leeuw, J. W.
Geochim. Cosmochim. Acta 1994, 58, 1759-1775.

Sinninghe Damste et al.

Band (TOC ) 52%, ash content ) 20%, atomic Sorg/C )

0.05 (refs 42,57)) formed in an euxinic shelf environment
with a low supply of detrital matter. Although this
marine black shale is not considered a coal, it is in fact
quite comparable to Rasa coal.
This poses the question of whether Rasa coal can be
used as a model for sulfur-rich coals as done in many
studies,4,7,10-19 including this one. On one hand, it has
been shown that analogies exist in the way organic
sulfur behaves upon maturation between kerogen and
coal.4 On the other hand, it will make quite a difference
whether the organic matter derives predominantly from
marine or freshwater algae or from terrestrial higher
plants. The question is difficult to answer at present.
At a minimum, our results represent a starting point
that can be used as a guide for analysis of other coals.

Acknowledgment. The authors thank M. EckertMaksic for provision of the Rasa coal sample, F. McCown for Soxhlet extractions, and Dr. W. Pool and M.
Dekker for assistance with mass spectral analyses. This
study was partly supported by a PIONIER grant to
J.S.S.D. from The Netherlands Organization for Scientific Research (NWO), NIOZ Contribution No. 3229.
EF980236C
(57) van Kaam-Peters, H. M. E.; Schouten, S.; Koster, J.; Sinninghe
Damste, J. S. Geochim. Cosmochim. Acta, 1998.