International Journal of Coal Geology 82 (2010) 37–44

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International Journal of Coal Geology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / i j c o a l g e o

Solid-state C-13 CP/MAS NMR study of Baganuur coal, Mongolia: Oxygen-loss during
coalification from lignite to subbituminous rank
Bat-Orshikh Erdenetsogt a,c, Insung Lee a,⁎, Sung Keun Lee a, Yoon-Joo Ko b, Delegiin Bat-Erdene c
a
School of Earth and Environmental Sciences, Seoul National University, Seoul 151-747, South Korea
b
National Center for Inter-University Research Facilities, Seoul National University, Seoul 151-742, South Korea
c
Faculty of Earth Sciences, National University of Mongolia, Ulaanbaatar 210646а, Mongolia

a r t i c l e i n f o a b s t r a c t

Article history: The rank of Lower Cretaceous Baganuur coal from Mongolia ranges from lignite to subbituminous coal,
Received 8 October 2009 indicating transition from biochemical to physico-chemical coalification stages. The changes in the chemical
Received in revised form 12 February 2010 structure of coal were studied using solid-state C-13 CP/MAS NMR.
Accepted 21 February 2010
The predominant change during the transition between the two coalification stages was the dramatic
Available online 26 February 2010
decrease in dihydric and/or methoxy phenols. Concurrently, protonated aromatic carbon positioned next to
Keywords:
O-substituted carbon decreased drastically, while C-substituted aromatic carbon increased. These changes
Lignite indicate that O-containing functional group was continuously replaced by C-substituent. In addition, the
NMR amount of carbonyl and oxygenated aliphatic carbons decreased. All these transformations were greatly
Coalification intensified at the beginning of the physico-chemical stage. The results, based on the chemical structure of
Oxygen groups inertinite-rich coal, suggest that during the fusinitization path, small amounts of hydrogen and oxygen
Mongolia remained as H- and OH-substituents of condensed aromatic rings, while other functional groups were
completely destroyed. During the coalification from lignite to subbituminous rank, oxygen is significantly
changed compared with carbon and hydrogen due to the elimination of oxygen-containing functional groups
especially from dihydric phenol, methoxyl, and carbonyl carbon.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction microbial activity ceases when the temperature approaches the

The main proportion of the Mongolian coal reserves is Lower
Cretaceous lignite in eastern Mongolia; the reserves are estimated to
be 7 Gt (Erdenetsogt et al., 2009). The Baganuur deposit, where an
open-pit mine was opened in 1978, has coal reserves of 550 Mt. At
present, the mine produces 3 Mt of coal per year and supplies 40% of
the domestic demand for steam coal. In addition to this utilization,
Mongolia is interested in the liquefaction and gasification possibilities
of the Lower Crataceous lignite reserves in eastern Mongolia.
The transformation of organic matter into peat and coal is com-
monly regarded as a two-step process: the biochemical and physico-
chemical stages of coalification. Biochemical coalification begins with
the accumulation of dead organic matter and ends at the rank of
subbituminous coal. The physico-chemical stage of coalification is
initiated and maintained by deep post-depositional subsidence of the
peat. During the biochemical stage, microorganisms play a major role
in the chemical decomposition of vegetal matter and its conversion
into peat and lignite. In contrast, during physico-chemical coalifica-
tion, temperature and pressure conditions become key factors because
⁎ Corresponding author. Silim-dong San 56-1, Kwanak-gu, Seoul, 151-747, Republic
of Korea. Tel.: + 82 2 880 6730; fax: +82 2 871 3269.
E-mail address: insung@snu.ac.kr (I. Lee).
boiling point of water (Diessel, 1992). Thus, chemical transformation
during biochemical coalification is different from that of physico-
chemical coalification.
Solid-state C-13 NMR, an effective method for characterizing the
chemical structures of coal and its precursor, has been widely used
during the last three decades (VanderHart and Retcofsky, 1976; Zilm
et al., 1981; Wilson et al., 1983; Newman and Davenport, 1986;
Axelson, 1987; Hatcher, 1988; Hatcher et al., 1989a,b; Love et al., 1993;
Maroto-Valer et al., 1998; Freitas et al., 1999; Yoshida et al., 2002;
Almendros et al., 2003). A number of studies on the changes in the
chemical structure of plant matter during coalification have been
published previously (Stout et al., 1988; Hatcher et al., 1989a; Hatcher,
1990; Behar and Hatcher, 1995; Ibarra et al., 1996; Orem et al., 1996).
As a result of these studies, major reactions such as degradation of
cellulose, β-O-4 ether bond cleavage, demethylation, dehydroxylation,
and the aromatization of alkyl chains have been identified. However,
the transformation pathways have not yet been fully understood
(Hatcher and Clifford, 1997).
The rank of Baganuur coal ranges from lignite to subbituminous
coal. This reflects the transition between the biochemical and physico-
chemical coalification stages. In addition, it is expected that the source
of organic matter and the geotectonic conditions for the coals are
similar. The coals are, therefore, suitable for investigating the changes

0166-5162/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2010.02.005
38 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44

in the chemical structure of coal during the transition between the
two stages of the coalification process. The inertinite maceral group in
coal is important, not only for their practical purposes but also for
their geological implications. The amount of inertinite influences
mining dust, combustion, and coking properties, etc. (ICCP, 2001).
Recently, Diessel (2010) proposed that the global variation of
inertinite content in coal depends on the oxygen content of the
Earth's atmosphere. The inertinite content of the Lower Cretaceous
coals in eastern Mongolia is much higher than that of Jurassic coals,
probably due to regional climate changes (Erdenetsogt et al., 2009).
Therefore, an inertinite-rich sample was also studied here.
The purpose of this paper is to examine the changes in the chemical
structure of coals and their relative fractions during the transition from
lignite to subbituminous rank and to chemically characterise inerti-
nite-rich coal. Based on these experimental data, we attempt to
provide structural origins of oxygen-loss during coalification process.
We also note that a detailed study of the chemical structures of
Baganuur coal, which can represent eastern Mongolian lignite, has
practical importance because it could be useful in some aspects of coal
utilization in the future.
2. Geological setting
The Baganuur mine (47°43′N, 108°18′E) is located on the northern
margin of the Choir-Nyalga basin of the Eastern Mongolian coal- and
oil shale-bearing province (Fig. 1). The basin covers an area of
approximately 50,000 sq. km and is divided into several fault-bounded
sub basins (Erdenetsogt et al., 2009). The open-pit mine is situated in a
graben-syncline structure to the north of the Bayansum subbasin. The
NNE–SSW-trending graben-syncline, 3 km wide and 12 km long, is
filled with Cretaceous and Cenozoic deposits (Bat-Erdene, 1998). Coal-
bearing Lower Cretaceous sedimentary rocks consist of the Shinekhu-
dag oil shale-bearing, Khukhteeg coal-bearing and Baruunbayan
sandy-conglomerate formations of the Zuunbayan group (Fig. 1c).
The Shinekhudag oil shale-bearing formation is 250 m thick and is
characterized by conglomerates with sandstone and siltstone. The
lower part of the Khukhteeg coal-bearing formation consists of
sandstone and siltstone with thin coal seams, while the middle and
upper part of the formation consist of sandstone and siltstone
intercalated with thick coal seams. The thickness of the formation is
250 m. The 70 m thick Baruunbayan sandy-conglomerate formation

Fig. 1. (a) Map showing the basins in the Eastern Mongolian coal- and oil shale-bearing province (modified from Erdenetsogt et al., 2009); (b) coal seam map of the Baganuur deposit
with cross section (Bat-Erdene, 1998); (c) generalized stratigraphic column of the coal-bearing Lower Cretaceous Zuunbayan group at the Baganuur deposit.
 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44 39

consists of sandstone with thin layers of siltstone. The formation is numbers of each element were generally obtained based on the aver-
overlain by Cenozoic sand and gravel. age of the elemental numbers in those functional groups. For example,
The Khukhteeg coal-bearing formation contains twenty three coal in the 150–160 ppm region, the main functional groups are aromatic
seams, including the three main seams at the bottom: Seam 2, Seam C–O– and C–OH moieties. Thus, the C number is 1, the O number is
2A and Seam 3. The net thickness of each of the three main seams 1, and the average of H is 0.5. Hence, the estimated average
ranges from 36 m to 98 m, but decreases to the west, northwest and elemental composition of this chemical shift range is COH0.5. The %C,
southwest, where the seams are splitted and become more complex. %H, and %(O+N) were calculated using the following equations:
The Baganuur coals have relatively low ash (14.2 wt.% average) and
sulfur content (0.5 wt.% average). Average moisture and volatile %C = 1200 = D ð1Þ
matter contents are 11.4 wt.% and 44.1 wt.%, respectively. The mean
maximum reflectance value of vitrinite in oil of Seam 2A is 0.4% 1 9 H
(Erdenetsogt et al., 2009). The coal beds formed in a lacustrine-fluvial %H = ∑n p ð2Þ
D i=1 i i
environment with climates ranging from semi-arid to warm temper-
ate (Dill et al., 2004). The time of the peat accumulation is thought to
be Aptian–Albian (Bat-Erdene, 1989), however Dill et al. (2004) 16 9 OþN
%ðO þ NÞ = ∑n pi ð3Þ
identified Berriasian–Barremian palynomorphs. D i=1 i

3. Methods
Six samples of coal were taken from fresh working faces of the
mine. Two samples are from Seam 3, one sample is from Seam 2A, and
two samples are from Seam 2. Additional one sample was chosen from
the inertinite-rich bed of Seam 2A (Table 1).
Samples were ground to pass through a 70 mesh sieve and
pretreated with hydrochloric acid to remove carbonate minerals. The
ultimate analysis (C, H, N, total S, and O) was performed at the
National Center for Inter-University Research Facilities (NCIRF) at
Seoul National University, using EA 1110 and EA 1112 analysers (CE
instruments).
The molecular structures of coal samples were determined using
solid-state C-13 NMR at NCIFR. The experiments were performed
using a Bruker Avance II 500 NMR spectrometer at a carbon frequency
of 125.77 MHz and a proton frequency of 500.12 MHz. Dry, powdered
samples were packed into a 4 mm zirconia rotor with a Kel-F cap. The
{H-1} C-13 CP/MAS spectra were recorded at a spinning speed of
10 KHz using a triple resonance probe. The measurement conditions
were as follows: the contact time was 3 ms, with a recycle delay of 1 s
and a scan number of 5120. The contact time, which provided suitable
peak intensity for semi-quantitative analysis, was chosen based on the
results of variable contact time experiments for sample BN-19. The
spinning speed of 10 KHz was not fast enough to remove the spinning
side bands (SSB), which appeared in the spectra. Thus, we also
collected {H-1} C-13 CP/MAS spectra using Total Suppression of
Sidebands sequence (TOSS), which effectively suppressed SSB (Dixon
et al., 1982). TOSS sequences were recorded at a spinning speed of
5 KHz and spectra were acquired with a 1 ms contact time, 1 s recycle
delay and 10240 scans.
To test the reliability of the NMR data, elemental compositions of
C, H, and (O+N) were estimated from the NMR spectra according to
the method described in Mao et al. (2000). Briefly, based on the
deconvolution of the NMR spectrum, the elemental numbers of C, H,
and O can be estimated from different deconvoluted bands. As
different functional groups can contribute to a given range, the
9 9
D = 16 x ∑ ni
OþN
pi + 1200 + ∑ ni pi
H
ð4Þ
i=1 i=1
H O + N
where, ni and ni are the elemental numbers of H and (O+N),
respectively. The sum of carbon pi is 100 and the atomic weight is 12;
C contributes 1200 in Eq. (1) and Eq. (4). Table 2 lists the ranges and
their average elemental compositions.
In addition, SSB correction is also based on the deconvolution of
the spectra. The bands centered at around 40 ppm, 205 ppm and
220 ppm were assigned to SSB and their areas were excluded from the
calculation of the relative percentages of other bands. Unfortunately,
low field SSB from the resonance at 32 ppm and the high field SSB
from the resonance at 143 ppm were completely overlapped by the
resonances at around 113 ppm and 63 ppm, respectively. Thus, it
should be noted that the relative percentages of the ranges between
90–120 ppm and 60–90 ppm have relatively low accuracy.
There are limitations in the quantitative reliability of CP/MAS
spectra: this technique is intrinsically not quantitative unless the
signal intensity is carefully calibrated with standards where compo-
sition, dipolar coupling constant, relaxation times in a rotating frame,
and molecular structures are well known. Notwithstanding, it has
been shown that the technique can be used to compare intensity
distributions among similar samples.
4. Results and discussion
4.1. Elemental composition of Baganuur coal
During the coalification process, the carbon content increases,
whereas the oxygen content decreases progressively (Smith and
Smith, 2007; Petersen et al., 2008). In contrast, the hydrogen content
remains constant up to the rank of medium volatile bituminous coal of
approximately 80 wt.% of carbon and then decreases up to anthracite
Table 2
Assignments and elemental numbers of different chemical shift ranges.

Range Chemical shift Functional groups Elemental

Table 1 composition
Ultimate analysis data of Baganuur coal.
1 185–220 Ketone, quinine, aldehyde C=O, HC=O COH0.5
Seam # Sample Elemental analysis (wt.%) H/C O/C 2 165–185 Carboxyl, ester, quinone COO, COOH CO1.75H0.5
code 3 135–165 O-substituted aromatic C–O, C–OH COH0.5
N C H S O
4 120–135 Aromatic CH, C CH0.5
Seam 3 BN-19 0.97 66.70 4.70 0.20 27.42 0.84 0.31 5 90–120 Aromatic CH CH
BN-18 1.03 67.56 4.78 0.15 26.49 0.84 0.29 6 60–90 Sacchride, alcohol, ether CHOH, CH2OH, CH2.5O
Seam 2A BN-15 1.22 67.32 4.88 0.23 26.36 0.86 0.29 CH2-O-
BN-8a 0.71 84.28 3.0 0.42 11.6 0.42 0.10 7 50–60 Methoxy, methyne, quaternary CH3O-, CH-NH, CH1.5O0.5
Seam 2 BN-3 1.20 70.37 4.54 0.36 23.53 0.77 0.25 CH, C
BN-1 1.14 71.26 4.39 0.35 22.86 0.73 0.24 8 25–50 Methylene CH2 CH2
a 9 0–25 Methyl CH3 CH3
Inertinite-rich sample.
40 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44
Fig. 2. Plots of atomic H/C versus O/C ratios for Baganuur coal. Boundary between coal
rank is adopted from Suggate (2000). Peat/lignite and lignite/subbituminous rank
boundaries are 0 and 4, respectively. More detailed explanation could be found in
Suggate (2000).
Fig. 3. The solid-state 13C NMR spectra of Baganuur coal; (a) CP/MAS spectra with the chemical shift ranges that correspond to the relative percent of functional groups in Table 2–3;
(b) TOSS spectra with peak labels as ppm.
(Diessel, 1992). Hence, elemental composition and H/C and O/C ratios
can be used as rank parameters.
According to the ultimate analysis results, the coal rank of the
three main seams of the Baganuur increases from the top seam to the
bottom seam (Table 1). The C content of the coals (excluding the
sample BN-8, which is enriched in the inertinite maceral group)
ranges from 66.7 to 71.3 wt.% and increases from Seam 3 (top),
through Seam 2A (middle), to Seam 2 (bottom seam). The O content
ranges from 22.9 to 27.4 wt.% and decreases towards the bottom
seam. The H content varies between 4.4 and 4.9 wt.% and remains
nearly constant. The N content ranges from 0.97 to 1.2 wt.%. Seams 3
and Seam 2A have average H/C and O/C ratios of 0.84 and 0.30, and
0.86 and 0.29, respectively, whereas Seam 2 has H/C and O/C ratios of
0.75 and 0.24, respectively. Fig. 2 shows that the coal rank of Seam 3
and Seam 2A is lignite, whereas that of Seam 3 is at the transition
between lignite and subbituminous coal.
The elemental composition of sample BN-8 is distinct from the
others because of the high content of inertinite. The C content is
significantly higher (C = 84.3 wt.%), whereas O, H and N contents are
very low (Table 1). This is consistent with the elemental composition
of inertinite macerals (ICCP, 2001).
 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44 41

The total sulfur contents of all six samples vary between 0.2 and 1990). A small shoulder at about 152 ppm indicates the presence of
0.4 wt.%, indicating that the Baganuur coals were formed in a monohydric phenol.
freshwater environment. Peaks at 175 and 195 ppm are carboxyl and carbonyl carbons,
respectively (e.g. position j and k in Fig. 4). Taken together, a
comparison of spectra using normal CP/MAS without and with TOSS
4.2. C-13 CP/MAS NMR sequence allowed us to distinguish carbonyl peaks from SSB. The TOSS
spectra of the samples, except BN-8, have small broad peaks at
4.2.1. Peak assignments ∼195 ppm that are resonances from carboxyl carbons. In the CP/MAS
NMR spectra were interpreted based on previous studies of humic spectra of the samples, SSB is clearly centered at around 205 ppm and
soil, insoluble organic matter, cellulose, lignin, peat, coal and coal shoulders at 195 ppm arise from carboxyl carbons. The spectra of the
yields (Wilson et al., 1983; Hatcher, 1988; Newman et al., 1988; BN-8 sample show no resonances from carboxyl carbon.
Hatcher et al., 1989a,b; Hatcher, 1990; Gardinier et al., 2000; Yoshida
et al., 2002; Almendros et al., 2003). The 13C CP/MAS NMR spectra of 4.2.2. Comparison of elemental compositions estimated by NMR and
the coal samples studied here are shown in Fig. 3. The spectra of coals from ultimate analysis
can generally be divided into two main chemical regions: aliphatic Fig. 5a–c shows the %C, %H, and %(O+N) estimated from the
carbons (0–90 ppm) and aromatic carbons (90–220 ppm, including quantification of CP/MAS NMR spectra and those from ultimate
carbonyl/carboxyl and phenolic groups). analysis. The dashed lines represent a 1:1 relationship. The result
In the aliphatic carbon region, a peak of 30–32 ppm originates indicates that the element fraction obtained from NMR spectra is
from methylene carbons in aliphatic chains (e.g., position b in Fig. 4). roughly consistent with the ultimate analysis, except for the H
A small shoulder at ∼14 ppm originates from terminal methyl groups contents from NMR (Fig. 5a). Mao et al. (2000) also noted this
(e.g., position a in Fig. 4). Its low intensity relative to the signal at systematically high H content in the sample estimated using direct
30 ppm supports the presence of long chain aliphatic structures. A polarization NMR data due to the overestimation of the H content of
shoulder at ∼ 55 ppm is assignable to methoxyl carbon (e.g., position c
in Fig. 4). The TOSS spectra of the samples show more intense peaks at
55 ppm. This is possibly due to the absence of interference from SSB
centered at around 40 ppm in the CP/MAS spectra. A peak at 74 ppm is
aliphatic alcohol and ether carbon with contribution from carbohy-
drate carbon (e.g., position d in Fig. 4).
In the aromatic carbon region, peaks at 115 and 125 ppm are
assigned to protonated aromatic carbon. The peak at around 115 ppm
is characteristic of protonated aromatic carbon ortho or para to
aromatic-O carbon (e.g., position e in Fig. 4). The peak at 125 ppm is
protonated aromatic carbon at least two bonds away from an oxygen-
substituted aromatic carbon (e.g., position f in Fig. 4). A peak at ∼144
arises from O-substituted aromatic carbon of the dihydric (or
methoxy) phenols such as catechol (e.g., position h in Fig. 4), because
the adjacent hydroxyls influence each other's chemical shift (Hatcher,
1990). If there is no influence from a hydroxyl in an ortho position, the
normal chemical shift of a monohydric phenolic carbon is at about
153 ppm (e.g., position i in Fig. 4) (Newman et al., 1988; Hatcher,

Fig. 4. Structural model for lignite A (Hatcher, 1990); the circled letters indicate Fig. 5. The comparison of elemental composition from ultimate analysis and NMR
connecting sites (e.g., →); specific sites designated by lower case letters are referred to calculation; (a) hydrogen, %; (b) carbon, %; (c) (O+N), %; and (d) O/C atomic ratio.
in the text. Dashed lines represent a 1:1 relationship.
42 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44
some of the chemical groups in Table 2. Fig. 5b shows that C contents
obtained by CP/MAS NMR are slightly lower than those of the ultimate
analysis data, especially for the samples with lower H/C ratios (b0.8)
and deviation increases with decreasing H/C ratios of the sample
(Table 1). It is well known that some non-protonated carbon cannot
be detected by 13C CP/MAS NMR (Love et al., 1993; Maroto-Valer et al.,
1998) because protons lose magnetization before complete transfer to
non-protonated carbons in the large polyaromatic units. Hence, the
amount of an ‘undetectable’ carbon increases with the decreasing
hydrogen content and/or the increasing condensed aromatic rings. In
contrast, (O+N) contents from NMR are quite consistent with those
from the ultimate analysis (Fig. 5c). In addition, the sum of oxygen
atoms in the oxygen-functional groups (assuming a 1:1 ratio for
atomic O/C ratio) were calculated according to the equation [Eq. (5)]
modified by Yoshida et al. (2002):
%ðO=CÞ = ðC ¼ OÞ + 2ðCOOHÞ + ðAR–OÞ + ðR–OH and=or R–O–RÞ
ð5Þ
where, C=O is carbonyl, COOH is carboxyl, AR–O is aromatic carbon
bound to oxygen, and R–OH and/or R–O–R are aliphatic carbon bound
to alcoholic OH or etheric oxygen.
The plot in Fig. 5d also shows a correlation between the calculated
NMR O/C value in Eq. (5) and the O/C value from the ultimate analysis.
The results suggest that CP/MAS NMR can be effective estimating the
relative distributions of O-substituted carbon in coals as well as other
carbon types in lower rank coal (having a ratio greater than 0.8 H/C). In
addition, our calculation result is similar to that of humic substances
quantification based on 13C direct polarization NMR experiments
reported by Mao et al. (2000), who established the methods used
here to check the reliability of CP/MAS NMR data.
4.3. Implications for the oxygen-loss and structural evolution of coal from
lignite to subbituminous rank and the properties of inertinite-rich coals
According to the ultimate analysis, coal from Seam 2 of Baganuur lost
16% of oxygen and gained 7% of carbon compared with that from Seam 3.
Due to these changes in chemistry, the network structure of coal is
transformed considerably. The main changes, observed in the spectra,
were the disappearance of the resonances from the following:
oxygenated aliphatic carbon at 63 ppm, protonated aromatic carbon
at 115 ppm, oxygen-substituted aromatic carbon at 144 ppm, and
carbonyl carbon at 195 ppm. In addition, the intensity of the resonances
from methoxyl carbon at 55 ppm and oxygenated aliphatic carbon at
74 ppm decreased, while the intensities of the resonances from aliphatic
structures at 30 ppm, protonated aromatic carbon at 125 ppm and
carboxyl carbon at 175 ppm increased or remained the same.
The relative percent of O-substituted aromatic carbon from 135–
165 ppm decreased by ∼25% mainly due to the diminished intensity of
Table 3
13
Relative intensity distribution in solid-state C NMR spectra of Baganuur coal.
Sample Carbonyl/ O-substituted C-substituted and
carboxyl C aromatic C protonated aromatic C
220–165 ppm 165–135 ppm 135–120 ppm
BN-19 100c 100 100
BN-18 97 91 103
BN-15 87 84 101
BN-3 87 82 112
BN-1 73 74 123
BN-8 0 50 241
a
OCH3/R — the number of methoxyl carbons in a ring. It was obtained by normalizing the area for methoxyl carbons (peak at 53 ppm) in CP/MAS NMR spectra to the area for
aromatic carbons (90–165 ppm) and then multiplied by 6 (Hatcher et al., 1989a).
b
O-AR/R — the number of O-substituent in a ring obtained by dividing the peak area for O-substitued aromatic carbons (135–165 ppm) by the area for aromatic carbon (90–
165 ppm) and then multiplied by 6.
c
(100) — intensity changes respect to the peak intensity of BN-19.
the peak at 144 ppm, indicating rapid loss of O-containing functional
groups substituted to aromatic carbon (Table 3). It is also consistent
with the decreased relative percent (by ∼75%) of the peak at 115 ppm
(see Fig. 6c), which is resonance from protonated aromatic carbon
nearby oxygen-substituted aromatic carbon. The loss of dihydric (or
methoxy) phenol at 144 ppm reached 50% of its initial percent that is
much higher than that of phenolic carbon. The elimination of this
catechol-like unit is one of the main alterations during coalification from
lignite to subbituminous rank observed in this study. The result is
consistent with the model for transformation from lignite to subbitu-
minous coal (Hatcher and Clifford, 1997). In addition, the resonance at
125 ppm was apparently shifted to 128 ppm and its relative intensity
increased by ∼20% (see Fig. 6d). Once, the O-containing functional
groups were replaced by hydrogen or a carbon-substituent, the
relative percentage of protonated and/or carbon-substituted carbon
increased. As previously discussed, protonated aromatic carbon gives
a resonance at 125 ppm and carbon-substituted aromatic carbon
leads to a resonance at 130–132 ppm (e.g., g position in Fig.4) (Wilson,
et al., 1983; Freitas et al., 1999). With increasing relative fraction of
C-substituted aromatic carbons, their resonances overlapped with
protonated aromatic carbons and were shifted to a higher chemical
shift. Hatcher et al. (1989a) also proposed a similar transformation
for gymnospermous xylem during the coalification process.
The number of methoxyl and O-substituted aromatic carbons per
ring decreased by ∼20% and ∼25%, respectively (Table 3). During the
biochemical coalification stage, demethylation reaction (methyl group
is removed from OCH3 attached to a ring to produce an OH substituent)
is mostly considered as the dominant reaction mechanism (Hatcher
et al., 1989a; Orem et al., 1996; Hatcher and Clifford, 1997). Our results
indicate that both OCH3 and O-substituted aromatic carbon were
removed concurrently and replaced by H- and/or C-substituents, during
this particular coalification stage. However, some of the OCH3 groups
could transform to OH first (demethylation), and later OH groups were
removed from the aromatic rings by dehydroxylation. In addition, if
OCH3 groups are replaced by OH groups, the relative intensities at
144 ppm, 125 ppm, and 115 ppm would remain about the same,
because the strong O-substitution effects would have been the same
as in the original units (Hatcher, 1988). For Baganuur samples, the
intensities at 115 ppm (from protonated aromatic carbon nearby
oxygen-substituted aromatic carbon) and 144 ppm (from O-substituted
carbon of the dihydric or methoxy phenols) decreased constantly. This
supports the removal of both OCH3 and O-substituent from the aromatic
rings. It is also notable that when an H- or C-substituent replaces one of
the two O-substituents of a ring (e.g., OH groups), phenolic carbons are
formed. Thus, the peak intensity at 153 ppm should increase. But the
relative percentages of phenolic carbon (∼153 ppm) for the samples
decreased slightly and continuously. This could be explained by the
number of oxygen-substituted carbon of aromatic rings. For example,
the number of O-substituted groups per ring of the BN-1, which
Protonated Oxygenated Methoxyl C Aliphatic C OCH3/ O-AR/
aromatic C aliphatic C Ra Rb
120–90 ppm 90–60 ppm 60–50 ppm 50–0 ppm
100 100 100 100 0.56 1.24
81 95 99 107 0.57 1.16
81 96 94 114 0.55 1.10
43 96 87 113 0.50 1.06
25 85 79 117 0.45 0.93
0 0 0 54 0.0 0.37
 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44
Fig. 6. The intensity change of the individual peaks during the transition between
biochemical and physico-chemical coalification: (a) methylene (30 ppm); (b) methoxyl
(55 ppm); (c) protonated aromatic (115 ppm); (d) carbon-substituted plus protonated
aromatic carbons (125 ppm); (e) dihydroxy (or methoxy) phenols (144 ppm); and
(f) carbonyl carbons (195 ppm). The shaded area represents the beginning of the physico-
chemical coalification stage.
has the lowest relative percent of O-substituent among others, in-
dicates that approximately every one of three aromatic rings have two
O-substitutions. Thus, one can say that there were still sufficient
amounts of catehol-like structures remaining, which suppressed the
resonance from phenolic carbons. However, methoxyl and hydroxyl
groups have been removed, continually.
Decreased oxygenated aliphatic carbon (∼ 15 %) are explained by
the β-O-4 ether cleavage and loss of hydroxyl groups from the side-
chains (Buchanan et al., 1997; Hatcher and Clifford, 1997) as well as
the complete removal of all cellulosic material. In addition, those
deoxygenating reactions are more likely responsible for the increased
43
relative intensity of aliphatic carbons. In detail, the relative percent of
methyl groups at 14 ppm remained almost constant (decreased only
by ∼ 4%), while that of methylene increased by 20%. During the β-O-4
ether cleavage and loss of hydroxyl groups from the side-chains,
relative amounts of CH2 should increase in respect to O-containing
original structures.
The relative percentage of carboxyl/carbonyl carbon at 165–
220 ppm decreased by ∼25%. This is mainly due to a decrease in
intensity of carbonyl carbons at 195 ppm. At the later stage of
coalification (at subbituminous rank), carboxyl/carbonyl carbons
completely disappear. Decreased carboxyl/carbonyl carbon contents
are consistent with the results of artificial coalification of fossil wood
and peat carbonization experiments (Behar and Hatcher, 1995; Freitas
et al., 1999) and FTIR studies of the evolution of oxygen group contents
in coals of lignite to subbituminous rank (Ibarra et al., 1996; Petersen
et al., 2008). In addition, the type of organic matter and its bacterial
community played an important role during peat diagenesis. Barkovskii
et al. (2009) found that reed–sedge peat lost more than half of its
ketones during the 4 month experiment.
At the beginning of the physico-chemical coalification stage, the
above-mentioned chemical transformation of the coal structures was
dramatically intensified due to elevated temperatures and pressure
conditions (Fig. 6). The removal of methoxyl and carboxyl functional
groups increased from 5% to 20% and from 10% to 70%, respectively.
The loss of protonated aromatic carbon and catechol-like unit
intensified from 15% to 85% and from 10% to 50%, respectively. The
relative percentage of carbon-substituted aromatic carbon increased
from 5% at the biochemical stage to 25% at the beginning of the
physico-chemical stage. In contrast, the relative amount of methylene
carbon became constant (Fig. 6a). This may indicate that the β-O-4
ether cleavage ceased. Once the β-O-4 ether cleavage declined, a
relative amount of aliphatic carbon content became constant and then
decreased at a later stage of physico-chemical coalification.
The 13C CP/MAS NMR spectrum of sample BN-8 contains SSB
centered at ∼ 40 ppm and 205 ppm. Especially, SSB at 40 ppm is
overlapped with resonance from aliphatic carbon. TOSS spectrum,
therefore, was used for peak assignments. Both TOSS and CP/MAS
NMR spectra show a main resonance at 128 ppm with shoulders at
around 142 ppm and 152 ppm, indicating that the sample consists of
mainly aromatic carbon with few hydrogen and hydroxyl group
attachments. The TOSS spectrum has a broad peak at ∼ 32 ppm with
two small shoulders centered at around 21 ppm and 38 ppm, which
can be assigned to CH2 attached to the aromatic rings (Pan and
Maciel, 1993) and complex aliphatic carbon (Mao et al., 2000),
respectively. In addition, the TOSS spectrum contains a faintly
detectable resonance at 75 ppm, suggesting the presence of oxygen,
nitrogen or possibly sulfur-containing functional groups. However,
this was excluded from the calculation of the relative distribution of
carbon types.
All these NMR data indicate that the BN-8 sample is dominated by
inertinite macerals. It is consistent with previous results on fusinite
concentrations and hand-picked fusinite macerals (Zilm et al., 1981;
Maroto-Valer et al., 1998). Moreover, maceral analysis shows that the
sample consists of more than 80 vol.% of fusinite with minor amounts
of semifusinite and huminite macerals. Fusinite contains fused
aromatic and hydroaromatic rings with minor amounts of OH and
C–O groups (ICCP, 2001). Hence, the main resonance at 128 ppm from
aromatic carbon is due to fusinite and the peaks at 32 ppm and
75 ppm are more likely due to semifisinite and huminite macerals.
The relative percentage of aromatic carbon in BN-8 increased more
than doubled, while the aliphatic carbon content decreased by ∼60%
compared to BN-15, which was sampled from the same coal seam. The
increased carbon (∼ 20%) and decreased H (∼ 40%) content of BN-8 is
largely due to an increase in aromatic ring content and the reduced
amount of aliphatic chains. During fusinitization path, most of the
hydrogen remained as a hydrogen substituent of aromatic rings, while
44 B.-O. Erdenetsogt et al. / International Journal of Coal Geology 82 (2010) 37–44
oxygen survived in hydroxyl groups of phenolic carbons. Other O-
containing groups were completely destroyed.
Overall oxygen-loss of coal from lignite to subbituminous rank is
controlled by the loss of dihydric phenol at 144 ppm, methoxyl group
at 55 ppm, and carbonyl group at 195 ppm. This relative contribution
of each functional groups in lignite to total oxygen-loss during
coalification is generally consistent with the results of recent work by
Petersen et al. (2008) and other previous studies (e.g., Ibarra et al.,
1996; Hatcher and Clifford, 1997). Furthermore, taking into consid-
eration the chemical structure of the BN-8 sample (Fig. 3), the most
resistant oxygen-containing group during coalification is likely to be
hydroxyl group of phenol. The results presented here show structural
origins of changes in chemical composition of Mongolian coal from
Baganuur (particularly a loss of oxygen content in lignite) during
coalification from lignite to subbituminous rank and can be applied to
other lower rank coals.
5. Summary and conclusions
Coal samples from the Lower Cretaceous Baganuur mine in
Mongolia were analysed. The coal rank increases from lignite (Seam
3) to subbituminous coal (Seam 2), indicating the transition from
mainly biochemical to physico-chemical coalification. During the
transition, O-substituents, such as hydroxyl and methoxyl functional
groups, were removed from the aromatic rings concurrently. The
result indicates that at the end of the biochemical coalification
stage, demethylation is no longer a dominant reaction. In addition,
C-substituted aromatic carbon content increased continuously be-
cause of the replacement of O-substituent by carbon. The carboxyl/
carbonyl carbons decreased mainly due to the loss of carbonyl
functional groups. All these changes in the chemical structure of the
coal were intensified at the beginning of the physico-chemical stage.
Furthermore, the relative percentage of CH2 increased in respect to
O-containing original alkyl structures, due to β-O-4 ether cleavage
and loss of hydroxyl groups from the side-chains. However, at the
beginning of the physico-chemical stage, this increase becomes
stable, probably because the β-O-4 ether cleavage ceased. During the
fusinitization path, hydrogen and oxygen survived as H- and OH-
substituents of condensed aromatic rings while other functional
groups were completely destroyed.
Finally, a comparison of ultimate analysis and NMR data shows
that CP/MAS NMR is effective in providing semi-quantitative analysis
(particularly for the calculation of the relative distributions of O-
substituted carbons in coals or other similar organic substances) as
well as the structural evolution during coalification.
Acknowledgments
We gratefully acknowledge Mr. B. Altansukh for his outstanding
field assistance. Special thanks go to Mr.Tsogtbaatar, Chief Geologist of
the Baganuur mine, for giving us access to the mine to collect samples.
The authors acknowledge the constructive comments by anonymous
reviewers, which led to a significant improvement of the paper.
B. Erdenetsogt is supported by the GSFS program and the Brain Korea
21 fund at SNU.
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