Fresenius J Anal Chem (2001) 370 : 6063

Springer-Verlag 2001

O R I G I N A L PA P E R

Grayna Gryglewicz Stanisaw Gryglewicz

Determination of elemental sulfur in coal

by gas chromatography mass spectrometry

Received: 20 November 2000 / Revised: 29 January 2001 / Accepted: 1 February 2001

Abstract A method for the determination of S0 in coal

based on the extraction with cyclohexane with subsequent
quantitative analysis of elemental sulfur in the extract by
GC/MS is described. The quantity of elemental sulfur was
determined in four coal samples with different distribution of sulfur forms. The effect of solvent and extraction
time on the efficiency of sulfur removal was studied. The
elemental sulfur extracted from coal occurred in the form
of S6, S7 and S8. Calibration solutions were prepared from
freshly recrystalized elemental sulfur. It was found that
the injection temperature has a crucial influence on the
m/z 64 ion chromatogram.

Introduction
The determination of the various sulfur forms in coal is
among the most important analytical parameters used to
characterize coal. It is generally assumed that sulfur in
coal occurs as pyritic sulfur, sulfate sulfur and organic
sulfur. The fourth sulfur form which has been detected,
i.e., elemental sulfur S0, is considered to be artificial. Duran et al. [1] and Stock et al. [2] showed that pristine coal
samples are free from elemental sulfur and concluded that
elemental sulfur is not a natural constituent of coal but
rather a product of atmospheric oxidation of pyrite or bacteriological action. Elemental sulfur can be formed when
coal is exposed to air, for example, during coal storage.
Weathered coals can contain a significant amount of elemental sulfur, even up to 0.3 wt% [3]. However, relatively
fresh coals are characterized by a few tens to a few hundreds mg/kg S0 [4].
There are some consequences when the coal studied
contains elemental sulfur. This is connected to the fact

G. Gryglewicz S. Gryglewicz ()

Institute of Chemistry and Technology of Petroleum and Coal,
Wrocaw University of Technology,
ul. Gdaska 7/9, 50-344 Wrocaw, Poland
e-mail: gryglewicz@nafta1.nw.pwr.wroc.pl

that the ISO methods [5] as well as ASTM methods [6]

for sulfur forms analysis assume that three sulfur forms
are present in coal. Thus, there are only the standard analytical procedures for determining the pyritic, sulfatic and
organic sulfur. The latter form is determined in an indirect
way, i.e., by subtracting the sum of pyritic and sulfatic
sulfur from the total sulfur. If elemental sulfur is present
in the coal, it is included in the so-called organic sulfur.
As a result, an overestimation of the organic sulfur content takes place. A potential source of interference in the
determination of sulfur forms is even more serious for
coals which have been chemically altered [7] or microbiologically desulfurized [8]. Moreover, in the case of organic sulfur compounds (OSC) identification when the
examined coal is subjected to a procedure involving elevated temperatures, the presence of elemental sulfur generates the uncertainties in the evaluation of the results. For
example, it was found that elemental sulfur reacts with
methanol [9] and isopropanol [10] under supercritical
conditions leading to the formation of artefacts OSC which
do not occur in the initial coal.
Since the elemental sulfur can not be considered by
standards there have been several attempts to determine
quantitatively the elemental sulfur in coal and coal derived materials. Most of them involve chromatographic
techniques. Generally, the procedures for the determination of elemental sulfur in coal and environmental samples comprise the extraction of elemental sulfur with a
solvent and subsequently, its quantification. For the latter
purpose Duran et al. [1] used gas chromatography coupled with a Hall electrolytic conductivity detector with a
high selectivity for sulfur. They examined the coal samples from the Illinois Basin Coal Sample Program (ICB)
and the Argonne Premium Coal Sample Program (APCS).
High performance liquid chromatography (HPLC) was
applied by Buchanan et al. [11] for determining the elemental sulfur in the tetrachloroethene extract obtained
from both ICB and APCS coals. Another technique was
used by Louie et al. [12], i.e., supercritical fluid extraction
(SFE), using CO2/10% methanol, with quantification by
gas chromatography interfaced with atomic emission de-

61
Table 1 Coal samples

Table 2 Sulfur forms analysis, wt% (dry)

Sample

Type

Carbon
wt% (daf)a

Total sulfur
wt% (dry)b

Sample

Pyritic
sulfur

Sulfatic
sulfur

Organic
sulfur

Bechatw
Siersza
1 Maj
Szczygowice

lignite
sub A
mvb
refuse

61.5
76.1
87.5
85.3

8.50
3.00
4.30
1.81

Bechatw
Siersza
1 Maj
Szczygowice

4.08
2.42
2.36
0.10

0.59
0.14
0.27
1.44

3.83
0.44
1.67
0.27

a dry
b dry

ash free basis

basis

tection (GC/AED). Comparing to the methods based on

conventional liquid solvent extraction SFE gives quantitative elemental sulfur removal in a shorter time.
The aim of this work was to elaborate the method for
the quantitative determination of elemental sulfur in coal
by gas chromatography mass spectrometry (GC/MS).

Experimental
Materials
Three Polish coals of different rank from lignite to medium
volatile bituminous coal were selected for this investigation. The
studied coal samples were not protected from exposure to the air.
Additionally, the refuse from beneficiation of Szczygowice coal
was a subject of our interest. The latter sample enriched in pyrite
has been remained in a contact with air for many years. The list of
the samples is given in Table 1.
All solvents used in this work were analyzed by GC/MS and
found to be free of elemental sulfur contamination prior to their
use.
Sample preparation
The external standard for the sulfur GC response was prepared using freshly recrystallized sulfur from cyclohexane. To evaluate the
reapeatibility, a calibration curve was made for two series of standard solution. The A and B series were prepared from the solution
containing 10 mg and 10.4 mg of sulfur in 50 mL cyclohexane, respectively. The initial standard solution was diluted in cyclohexane to desired concentration.
Extraction
A 2 g sample (particle size < 60 m) was extracted in a Soxhlet apparatus for 1, 2 and 6 h. 90 mL of a solvent was used for the extraction of elemental sulfur. The obtained extract was transferred
to a volumetric flask and diluted to 100 mL using the same solvent.
Analysis
Sulfur form analysis of coal was performed according to ISO Standards. Pyritic sulfur was determined indirectly via the pyritic iron
and the sulfatic sulfur was determined directly in the hydrochloric
acid extract obtained prior to the nitric acid extraction for the determination of pyritic sulfur. The Eschka method was used to determine the total sulfur content. The organic sulfur was calculated
by subtraction of the inorganic sulfur from the total sulfur.
A Hewlett-Packard HP 6890 gas chromatograph coupled with
HP 5973 mass detector was used for quantitative determining the
elemental sulfur extracted from coal samples. An HP-5 capillary

column (30 m 0.25 mm I.D., 0.25 m film thickness,

Crosslinked 5% PH ME Siloxane) was used with He of 0.6 mL
min1 as the carrier gas. To get an optimum response from the
GC/MS analysis for elemental sulfur, several combination of GC
parameter settings were tested. Extracts and standards were analyzed using 5 m injection at a split of 1 : 10. The mass spectrometer was set at an ionizing voltage of 70 eV.

Results and discussion

The results of ISO forms of sulfur analysis are given in
Table 2. The coal samples selected for this study contain a
total sulfur in the range of 1.818.50 wt%. They are characterized by different distribution of sulfur forms. For the
refuse from Szczygowice coal the sulfatic sulfur has the
highest contribution which confirms that this sample was
exposed to the atmosphere for a long time. The pyritic
sulfur predominates in the other coal samples.
Solvent selection
A number of solvents were tested to choose the solvent
with the highest S0 extractability. Table 3 presents the results obtained for Szczygowice refuse which was extracted for 6 h. The response of the GC/MS to S8 was used
to quantify the elemental sulfur. The quantity of sulfur extracted is expressed as a percentage of the mass of coal
sample subjected to extraction. Cyclohexane, ethanol and
tetrachloroethene were found to give the highest effectiveness in the extraction of elemental sulfur. The extraction with cyclohexane yielded 0.111 wt% of elemental
sulfur. The comparable quantity of S0, i.e., 0.105 and
0.098 wt%, was obtained for tetrachloroethene and ethanol,
respectively. Cyclohexane and tetrachloroethene are
used for the extraction of elemental sulfur in the following
part.
Table 3 Effect of the kind of
solvent on the elemental sulfur
content of Szczygowice refuse
measured

Solvent

Elemental
sulfur, wt%

Acetone
Cyclohexane
Ethanol
Hexane
Methanol
Tetrachloroethene
Tetrahydrofurane
Toluene

0.060
0.111
0.098
0.059
0.055
0.105
0.026
0.056

62
Table 4 Effect of extraction time on the elemental sulfur content
of Szczygowice refuse measured
Time
h

Elemental sulfur
wt%

Cyclohexane

1
3
6
10

0.093
0.067
0.111
0.108

1
3
6
10

0.024
0.076
0.105
0.044

Tetrachloroethene

3.62

S6

S8

7.32
S7

Response

Solvent

15.12

15.11

Extraction conditions
The effect of extraction time on the quantity of the S0 extracted using cyclohexane and tetrachloroethene was studied. The area under S8 peak was used to quantify the elemental sulfur extracted. As given in Table 4, the quantity
of S0 extracted increases with time reaching a maximum,
i.e., 0.111 wt% for cyclohexane and 0.105 wt% for tetrachloroethene, after 6 h of the process. However, a prolongation of extraction process to 10 h results in lowering the
S0 content in the tetrachloroehene extract, from 0.105 to
0.044 wt% whereas for cyclohexane, the value remains
the same. This indicates that for the S0 extraction, cyclohexane is more suitable than tetrachloroethene. The latter
has a higher boiling point, thus, the extraction process is
carried out at higher temperature compared with cyclohexane (121.3 vs 80.7 C). Moreover, Buchanan et al. [9]
reported that long Soxhlet extraction times with tetrachloroethene lead to elemental sulfur loss due to reaction
between elemental sulfur and the coal matrix. The results
obtained here indicate that at the boiling temperature of
cyclohexane, an uptake of elemental sulfur by the coal
does not occur at reflux for 10 h. No difference in the
S6 : S7 : S8 ratio vs extraction time was observed. This
suggests that all the allotropic sulfur forms detected are
extracted with the same kinetics.
Conditions of GC/MS analysis
A several parameter sets were tested to optimize the conditions of chromatographic analysis for determining the
elemental sulfur. It was found that an optimum GC-MS
response is observed when both the injection and column
temperatures are the same, 180 C. Figure 1 a shows an
example of a mass chromatogram of m/z 64 for the standard solution of elemental sulfur in cyclohexane. It can be
seen that upon injecting the S0 standard, three peaks were
detected which are attributed to the allotropic forms of
sulfur, i.e., S6, S7 and S8. However, their relative proportion varies with the change of the inlet temperature as
shown in Table 5. An increase of injection temperature,
from 180C to 270C resulted in a change of S8 : S7 : S6
proportion from 6.4 : 1 : 2.5 to 1.6 : 1 : 1.9. Mass spectra

S8

3.61

S6

7.30
S7
Retention time, min

Fig. 1 Mass chromatogram of m/z 64 of a, standard solution of elemental sulfur in cyclohexane; b, cyclohexane extract from
Szczygowice refuse
Table 5 Effect of inlet temperature on the proportion of allotropic
forms determined by GC/MS, %
Inlet temperature, C

S6

S7

S8

180
210
240
270

25.6
29.4
36.6
42.0

10.1
15.6
19.4
22.0

64.3
55.0
44.0
36.0

for S6, S7 and S8 indicate that these species undergo fragmentation mainly to m/z 64. Thus, a mass ion of m/z 64
was monitored to quantify the elemental sulfur.
The established GC parameters setting are an optimal.
Due to low volatility of sulfur, the column temperature
below 180C was too low. When the oven temperature
was higher than 180C, inseparable signals for S6, S7 and
S8 were obtained. Probably, this is connected with a dynamic secondary dissociation of sulfur molecules which
takes place in the column. A visible effect of this phenomena is the raising background observed.
The quantity of elemental sulfur extracted from coal
was determined on the base of the calibration curve prepared for standard solution of elemental sulfur in cyclohexane. Figure 2 shows the calibration curve expressed as
the S8 peak area of the m/z 64 ion vs sulfur concentration
for two standard series indicating high repeatability of MS
response. For A and B series, the correlation coefficient of
0.9998 and 0.9987 was obtained, respectively. Moreover,
this Figure shows the calibration curves expressed as the
S7 and S6 peak areas of the m/z 64 ion vs sulfur concen-

63
Table 7 Sulfur forms analysis including elemental sulfur, wt%
(dry)

Fig. 2 Calibration curve determined on the base of: +, S8 for A

standard serie; , S8; , S7 and , S6 for B standard serie
Table 6 Elemental sulfur content determined on the base of calibration curve for different allotropic forms of sulfur, wt% (dry)
Sample

S6

S7

S8

S6+ S7+S8

Bechatw
Siersza
1 Maj
Szczygowice

0.100
0.009
0.126
0.104

0.082
0.017
0.128
0.132

0.071
0.021
0.094
0.111

0.092
0.019
0.121
0.145

Sample

Total
sulfur

Pyritic
sulfur

Sulfatic Elemental Organic

sulfur sulfur
sulfur

Bechatw
Siersza
1 Maj
Szczygowice

8.50
3.00
4.30
1.81

4.08
2.42
2.36
0.10

0.59
0.14
0.27
1.44

0.09
0.02
0.12
0.14

3.74
0.42
1.55
0.13

duplicate measurements of elemental sulfur in coal was

< 7%.
Finally, the results for sulfur forms analysis of the coal
studied including the elemental sulfur are summarized in
Table 7. Generally, the contribution of elemental sulfur in
the total sulfur of coal studied reaches a few percent. This
implies an overestimation of organic sulfur when analysis
of sulfur forms is performed without determination of elemental sulfur.

Conclusions
Extraction with cyclohexane combined with quantitative
analysis of the extracted elemental sulfur by GC/MS is
proposed as a promising method for the determination of
elemental sulfur in coal and related materials. It was
found that the sulfur extracted from coal occurs in three
allotropic forms, i.e., S8, S7 and S6. To quantify the elemental sulfur, the S6 + S7 + S8 signal of the m/z 64 ion was
used. The response of the GC-MS to allotropic forms of
sulfur is dependent upon the injection temperature. With
increasing injection temperature from 180 C to 270 C, a
decrease of the S8 signal followed by an increased response to both S6 and S7 was observed.

Fig. 3 Calibration curve determined on the base of the sum (S6 +

S7 + S8)

tration for the B standard, which are characterized by very

high correlation coefficient, 0.9995 and 1.0000.
Determination of elemental sulfur content in coal
A typical mass chromatogram of m/z 64 ion for the cyclohexane extract of the coal is given in Fig. 1 b. Table 6 presents the amount of elemental sulfur determined on the
base of the m/z 64 peak area, separately for S6, S7 and S8 .
It can be seen that there are some differences between the
values of elemental sulfur determination for different allotropic forms. Thus, to calculate the elemental sulfur
content in coal, the calibration curve expressed as the sum
of the m/z 64 ion area for S6, S7 and S8 was taken (Fig. 3).
For this calibration curve a correlation coefficient of
0.9995 was obtained. Relative standard deviations of

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