ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 pp.

803–818 803

Rare earth elements in No. 2 coal of Huangling mine,

Huanglong coalfield, China

Cunliang Zhao1,2*, Dujuan Duan2, Yanheng Li2 and Jianya Zhang2

1
China University of Mining and Technology, Beijing 100083
2
Key Laboratory of Resource Exploration Research of Hebei Province; Hebei University of
Engineering, Guangmingnan Street, Handan, Hebei 056038, China
*
Author for corresponding. Email: cunliang909@163.com

(Received 21 May 2011; accepted 2 June 2012)

Abstract
Rare earth elements (REEs) can provide lots of information relevant to the
evolution of source rocks, depositional environment, and epigenetic tectonic
activity. In this study, 14 bench samples (including 11 coals, 1parting, 1roof and
1floor) of the No. 2 coal seam from Huangling Mine, Huanglong Coalfield,
Ordos Basin, China were collected to study the REE geochemistry. The average
concentration of REEs is 44.03 µg/g, and it is lower than those in coals of the
Chinese and world coal. The coals are enriched in light REEs and the LREEs-
HREEs have been highly fractionated, with an average (La/Yb)N of 11.38. The
values of Ce/Ce* are more or less than 1 (with an average 0.92) and indicates
that the anomaly of Ce is very slight. However, the values of Eu/Eu* (with an
average 7.69 of coal) are distinctly higher than reported data of coals. The
extremely high contents of Ba caused the geochemical anomaly of REEs. The
Ba2+ was origin from the barium metallogenic belt in Qinling Old-upland.

Keywords: REE, No. 2 coal, Geochemistry, Huanglong coalfield

1. INTRODUCTION
The lanthanides (from La to Lu), usually called rare earth elements (REE), is a unique
group of elements with similar geochemical properties (McLennan, 1989; Olmez
et al., 1991). From a genetic point of view, the REE abundance can be used to identify
different coal-forming swamp environments and their patterns have a capacity to
provide important information about the nature of sediment source rocks as well as the
REE fractionation mechanism related to coal-forming processes, because their
distributions resulted from the processes associated with peat accumulation and rank
advance, as well as interaction between the organic matter and basinal fluids, sediment
diagenesis, and synsedimentary volcanic inputs (Eskenazy, 1987a; 1987b; Ren, 1996;
Ward, 2002; Zhao, 2002; Yudovich and Ketris, 2002; Dai et al., 2008; Ren et al.,
2006; Zheng et al., 2007). Additionally, REE can be recovered as by-products from
coal deposits with high REE contents. REE-rich coals have been found in many coal
basins over the world (Dai et al., 2008; 2012a; 2012b; Hower et al., 1999; Mardon and
804 Rare earth elements in No. 2 coal of Huangling mine, Huanglong coalfield, China

Hower, 2004; Seredin and Dai, 2012). Among them, the deposits of the Russin Far
East and Southwest China are of typical significance (Seredin, 1996; Zhou et al.,
2000; Dai et al., 2012a). The composition of sediment source rocks of the coal basin
margin is the key factor that controls the geochemistry of REE (Bouska and Pesek,
1999; Dai et al., 2012a; Ren et al., 1999). The depositional environment also plays a
very important role in the accumulation of syngenetic REE (Liu et al., 2004; 2006;
Sun et al., 2010). In addition, the groundwater and hydrothermal fluids generated by
magmatic can influence the REE concentrations (Ren et al., 1999).
The Ordos Basin is a huge coal basin in North China (Liu et al., 1991; Wang, 1996;
Wang and zhang, 1999). Many researchers have study the geochemistry of trace
elements (including the REE) of the coal in this basin (Chen, 2007; Dai et al. 2006;
2008; 2012b; Li, 2005; Wang et al. 2011). However, the study areas are mostly located
in northern Ordos Basin, such as Junger Coalfield, Dongsheng Coalfield and
Daqingshan Coalfield, and the coal seams belong to Permian-Carboniferous. In this
paper, we reported the geochemistry of REE of Jurassic coal in the southern of Ordos
Basin. Some distinct characterizations were found between the northern and southern,
the Permian-Carboniferous and Jurassic coal in Ordos Basin.

2. GEOLOGICAL SETTING
The Huanglong Coalfield is located in Shannxi Province of northern China, covering
the area of north latitude 34°46'~35°05' and east longitude 106°35'~109°15', with an
area of 9324.75 km2 (Fig. 1). The Huangling Mine is located in the northeast of the
coalfield (Fig. 1).

0 30 60 km

W E

Yan’an

Huangling
mine
Jungar coalfield ield
alf
Huang long coalfield co
ng
nglo
Hua

0 1000 km Baoji Xi’an

Figure 1. Location of the Huanglong Coalfield.

ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 805

The coal-bearing stratum in the Huanglong Coalfield is the Jurassic Yan’an

Formation. It was deposited in the lacustrine sedimentary system in the Jurassic period
(Fig. 2). The Yan’an Formation is divided into four sections from the bottom to top.
The fourth section consists of sandstone and mudstone; the third section and the upper
part of the second section mainly consist of dark mudstone and siltstone with a thin
layer of fine sandstone on the top; the bottom part of the second section and the first
section consist of sandstone, shale and coal seam (Fig. 3) (Wang and Zhang, 1999;
Zhong, 2009).
The major coal seam in the Huanglong Coalfield is the No. 2 coal, which is located
in the First section of the Yan’an Formation. Its thickness varies from 0 to 7.39 m with
an average of 1.94 m. The No. 2 coal contains 0 to 2 parting layers. Generally, the
thicker places of the coal seam have more partings. The lithology of the partings
consists mainly of mudstone and carbonaceous mudstone. The roof and the floor are
sandstone and mudstone (He, 2001; Zhong, 2009; Gao et al., 2010).

41°
00 ′ Baotou N

0 60 km

Wuhai
39°
00 ′

Yinchuan

37°
00 ′

Yan an

Huangling

35°
00 ′

Baoji
108° 00 ′
Xi’ an 110° 00′

Fluvial Lacustrine Alluvial Eluvial Fluvial &

lacustrine

Figure 2. Sedimentary facies map of the Jurassic in Ordos basin (Modified from
Wang and Zhang, 1999).
806 Rare earth elements in No. 2 coal of Huangling mine, Huanglong coalfield, China

Sedimentary Thickness
sequence (m)

Anding
25

Upper
70

Zhiluo

Lower
Jurassic

55
Jurassic

4th

10
Middle

35
3rd
Yan′ an

2nd

45
1st

15
jurassic
Lower

Fuxian

20

Shale Mudstone Sandstone Coalseam

Figure 3. Sedimentary sequences in Huangling Mine.

3. SAMPLING AND ANALYTICAL METHODS

3.1. Sampling
A total of 14 bench samples were taken from the face of the mined coal at the
Huangling Mine, Huanglong Coalfield, following the Chinese Standard Method
GB482-1985. These samples include 11 coal bench samples, one parting, one roof and
one floor samples. Each coal bench sample was cut over an area 10-cm wide, 10-cm
deep, and 30-cm thick. All collected samples were immediately stored in plastic bags
to minimize contamination and oxidation.

3.2. X-ray fluorescence spectrometry analysis

The LOI (Loss on ignition) value was determined by weighing the loss of each sample
after heating in the 815 °C muffle for nearly 4 hours. Then, X-ray fluorescence
ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 807

spectrometry(ARL ADVANT’XP+) was used to determine the oxides of major

elements for the coal ash (815 °C), including SiO2, Al2O3, CaO, K2O, Na2O, Fe2O3,
MnO, MgO, TiO2, and P2O5.

3.3. X-ray powder diffraction analysis

The samples were ground to 200 mesh and oven-dried overnight before ashing in a
low-temperature asher. Low temperature ash (LTA) residues were cast into pressed
pellets and analyzed on an automated powder diffractometer. The minerals in the
samples were identified by X-ray powder diffraction, using Ni-filtered Cu-Kα
radiation and a scintillation detector in the Key Laboratory of Resource Exploration
Research of Hebei Province. The diffractometer patterns were recorded over a 2θ
interval of 3 – 70°, with a step size of 0.02°.

3.4. ICP-MS analysis

For the ICP-MS (inductively coupled plasma mass spectrometry) analysis, microwave
digestion about 200 mg sample (40 µm) were weighed into PTFE vessels, 2 ml HF
(50%) + 5 ml HNO3 (65%) + 2 ml H2O2 (30%) were added and microwave digested
1h at a temperature of 210 °C. The vessels were left overnight in a deep freezer to cool
down. Then the digestion liquid was evaporated at 90 °C under vacuum, which took
about 1 h. The residue was then dissolved in 1 ml HCl (32%) + 8 ml deionised
water +1 ml HNO3 (65%). This solution was then transferred into 125 ml FEP bottles
which were filled up to 100 g with deionised water.
REE contents were determined by ICP-MS in the laboratory of Beijing Research
Institute of Uranium Geology and the Key Laboratory of Resource Exploration Research
of Hebei Province. The signal collection of HR ICP-MS lasted 25 s, and the scanned
mass ranges were set at 90 – 120 and 175 – 200 amu to cover the target elements.

4. RESULTS AND DISCUSSION

4.1. Major elements and minerals
4.1.1. Major elements
The concentration of major oxides of the samples is listed in Table 1 Compared with
the Permian-Carboniferous coals of the northern Ordos Basin (Heidaigou Mine,
Haerwusu Mine and Adaohai Mine), the proportions of Al2O3 and TiO2 are less, and
the others, including SiO2, CaO, Fe2O3, K2O, MgO, MnO, Na2O, and P2O5 are more
(Table 1) (Dai et al., 2008; 2012a; 2012b). Especially, the proportion of CaO is
extraordinary high (with an average 2.67%, maximum 12.76%). Although the major
element oxides in coals from the Huangling Mine are dominated by Al2O3 and SiO2,
which are like the common Chinese coals (Table 1), the Al2O3/SiO2 for each bench
sample of the No. 2 coal (0.51 on average) is lower than common values in Chinese
coals (0.71; Dai et al., 2012a). This is very different from the No. 6 coals of Haerwusu
and Heidaigou Mine, Junger Coalfield, northern Ordos Basin, in which the ratios reach
1.44 and 1.31, respectively (Dai et al., 2006; 2008; 2012a). The reason is the
depositional environment of the No. 2 coal seam in the Huangling coal mine was the
lacustrine sedimentary system, and the sediment source are the Qinling Old-upland
 808

Table 1. The major elements content of No. 2 Coal of Huangling Mine (%).

Al2O3/
Samples Al2O3 SiO2 SiO2 CaO Fe2O3 K2O MgO MnO Na2O P2O5 TiO2
HL-roof 22.85 57.36 0.40 0.22 3.46 2.830 1.28 0.039 0.460 0.187 0.89
HL-12 3.47 6.26 0.55 5.35 1.03 0.142 0.14 0.033 0.079 0.024 0.10
HL-11 10.22 18.63 0.55 0.04 1.99 0.242 0.10 0.019 0.191 0.022 0.34
HL-10 1.76 3.25 0.54 2.45 0.45 0.014 0.16 0.012 0.060 0.484 0.05
HL-9 2.26 3.95 0.57 0.52 0.06 0.009 0.01 bdl 0.035 0.411 0.06
HL-8p 7.74 15.22 0.51 3.43 25.41 0.078 0.15 0.272 0.147 0.137 0.28
HL-7 3.54 5.16 0.69 3.19 0.40 0.061 0.12 0.014 0.070 0.209 0.10
HL-6 2.33 3.48 0.67 5.70 0.36 0.027 0.40 0.024 0.073 0.476 0.07
HL-5 2.25 4.02 0.56 0.74 0.14 0.025 0.02 0.001 0.051 0.586 0.08
HL-4 3.12 5.75 0.54 0.48 0.22 0.033 0.02 0.001 0.047 0.284 0.12
HL-3 1.07 2.1 0.51 0.86 0.10 0.019 0.02 0.004 0.042 0.146 0.05
HL-2 1.51 2.4 0.63 12.76 2.51 0.025 1.42 0.084 0.084 0.239 0.04
HL-1 1.64 2.89 0.57 0.78 0.38 0.053 0.05 0.004 0.060 0.207 0.05
HL-floor 14.13 20.82 0.68 0.87 1.09 0.521 0.24 0.009 0.394 0.030 0.27
Av 5.56 10.81 0.51 2.67 2.68 0.291 0.30 0.040 0.128 0.246 0.18
Haerwusu a 8.89 6.19 1.44 1.33 0.56 0.1 <0.01 0.01 0.07 0.1 0.47
Heidaigou b 10.56 8.04 1.31 0.44 0.93 0.21 3.66 0.006 0.01 0.016 0.74
Adaohe c 10.75 9.99 1.08 1.69 0.94 0.027 0.32 0.016 0.028 0.124 0.55
China d 5.98 8.47 0.71 1.23 4.85 0.19 0.22 0.015 0.16 0.092 0.33
World e nd nd nd nd nd nd nd 0.011 nd 0.053 0.133
a
, from Dai et al. (2006); b, from Dai et al. (2008); c, from Dai et al. (2012b); d, from Dai et al. (2012a); e, from Ketris and Yudovich (2009).
Rare earth elements in No. 2 coal of Huangling mine, Huanglong coalfield, China
ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 809

(Wang, 1996; Wang and Zhang, 1999), whereas the No. 6 coal seam of the northern
Ordos Basin was deposited in delta sedimentary system and the Yinshan Old-upland
was the sediment source (Liu et al., 1991).

4.1.2. Minerals
The X-ray diffraction (XRD) results (Fig. 4) reveal that the major minerals within the
coal sample LTAS are calcite, dolomite, quartz, kaolinite, ankerite and witherite
(Figs. 4A and B), while the major minerals are pyrite, polylithionite, clinochlore and
muscovite in the floor and parting samples (Figs. 4 C and D). The abundant carbonate
minerals in the coal including calcite, dolomite and ankerite (Figs. 4A and B) are the
reason for high CaO contents (Table 1). The mineral assemblage is very special,
because the major minerals generally found in coal are clay minerals (mainly
kaolinite), sulfide minerals (mainly pyrite), quartz, and calcite (Ren et al., 2006; Ward,

(a)
150
d = 3.0172
d = 2.8898

d = 2.2718

d = 2.0859

d = 1.9028
d = 1.8682
d = 2.4820
d = 3.3262
d = 3.8245

d = 2.1924
Intensity (Counts)

100 d = 1.7926
d = 1.8138
d = 2.0169

d = 1.6304
d = 2.8204

d = 1.5979
d = 7.0657

d = 3.6844

d = 2.4086
d = 3.5561

d = 2.6948

50

0
05−0586> Calcite −CaCO3

14−0164> Kaoliniite−1A − AI2Si2O5(OH)4

41−0586> Ankerite − Ca(Fe+2, Mg) (CO3)2

36−0426> Dolomite − CaMg (CO3)2

20 30 40 50 60
2−Theta (°)
(b)
d = 3.7136
d = 3.6482
d = 3.5680
d = 3.3430

d = 3.0273
d = 2.9006

d = 2.2784
d = 7.1443

d = 1.9058
d = 1.9356
d = 2.0906
d = 2.6225

d = 1.8682

150
d = 2.4886

d = 2.0112
d = 2.1446
Intensity (Counts)

d = 2.5858
d = 3.8377
d = 4.2511

d = 1.6285

100
d = 4.3508

d = 3.2083

d = 2.6455
d = 4.1722
d = 4.4536

d = 2.3411

d = 1.8167
d = 2.7966

d = 1.6695
d = 2.4110
d = 2.8326

d = 1.4900
d = 2.6943

50

0
05−0378> Witherite −BaCO3

05−0586> Calcite−CaCO3

41−0164> Kaolinite−1A−Al2Si205(OH)4

46−1045> Quartz − SiO2

10 20 30 40 50 60

2−Theta (°)

Figer 4. (Continued)
810 Rare earth elements in No. 2 coal of Huangling mine, Huanglong coalfield, China

(c)

d = 3.3484

d = 2.7135

d = 1.6349
d = 2.4262
300

d = 2.2139
250
Intensity (Counts)

d = 3.1316

d = 1.9157
200

d = 4.2834

d = 3.4103
d = 3.5704
150

d = 4.4853
d = 7.6235

d = 1.4488
d = 3.0685

d = 1.5035
d = 5.4733

d = 3.9875
d = 7.2130

d = 3.4476

d = 2.8783

d = 1.5643

d = 1.2124
d = 3.2406

d = 1.8146
100

d = 1.5428
50

0
42−1340> Pyrite −FeS2
14−0164> Kaolinite−1A− Al2Si2O5(OH)4

46−1045> Quartz− SiO2

33−0311> Gypsum − CaSO4!2H2O

10 20 30 40 50 60 70

2−Theta (°)

(d) d = 1.8193
d = 7.1561

d = 4.2626

d = 3.5760
d = 3.3460

d = 2.4585

200

d = 1.5433
d = 2.2809

d = 2.1283
Intensity (Counts)

d = 1.3761
d = 4.4754

d = 2.5645

150
d = 1.9812

d = 1.3832
d = 1.6728
d = 3.2515
d = 4.3491

d = 2.2382
d = 4.9899

d = 2.7995

d = 1.9961

100

d = 1.2887
d = 1.4537

d = 1.2568
50

0
14−0164> Kaolinite −1A −Al2Si2O5(OH)4
42−1399> Polythionite−1M− K (AIFeLi)(Si3AI)O10(OH)F
07−0042> Muscovite− 3T − (K,Na)(AI,Mg,Fe)2(Si3. 1A10.9)O10(OH)2
29−0701> Clinochlore − 1Mllb − (Mg,Fe)6(Si,Al)4O10(OH)8
46-1045> Quartz − SiO2

20 30 40 50 60 70
2−Theta (°)

Figure 4. X-ray powder diffraction patterns of some typical samples. A: H-2, B: H-6,
C: H-8 and D: H-roof.

2002). Many other minerals are in minor to trace amounts in coals (Goodarzi et al.,
1985; Harvey and Ruch, 1986; Hower et al., 1987; Ward, 1989; 2002; Finkelman,
1993; Querol et al., 1997; Rao and Walsh, 1997; Hower and Robertson, 2003; Sun
et al., 2007; Dai et al., 2012a), but the witherite has been hardly reported. Several
barite and witherite deposits are located in Qinling, which were formed during
Proterozoic era (Wu et al., 2010), so the barium metallogenic belt in Qinling could
supply abundant Ba2+. When the Ba2+-enriched fluids flowed into the coal seam, Ba2+
can combine with CO32– to form the witherite in the organic environment (Habicht and
Canfield, 1997; Goldberg, 2006).

4.2. Geochemistry of REE

It has been reported that rare earth elements in coal are often positively correlated with
ash yield and generally related to minerals, primarily clay minerals and phosphates
ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 811

(Finkelman, 1995; Chou, 1997; Dai et al., 2008). However, rare earth elements may
also be partly associated with the organic matter in coal (Eskenazy, 1987a; 1987b).
There are four main genetic types of high REE accumulation in coals: terrigenous
type, tuffaceous type, infiltrational or meteoric ground water driven type and
hydrothermal type (Seredin and Dai, 2012). Dai et al. (2006; 2008) found that REE are
associated with Al, Ga, Ba and Sr in Junger coalfield and the REE sources are the
bauxite (Benxi Formation) of the weathered surface in the sediment-source region and
the overlying partings.

4.2.1. ∑REE
The concentration of total REEs (from La to Lu) in the Huangling coals varies from
9.31 to 119.00 µg/g and averages 59.10 mg/g (Table 2), observably lower than that
in common Chinese (135.89 mg/g; Dai et al., 2012a), common USA (62.09mg/g;
Finkelman, 1993) and common world coals (68.27 µg/g; Ketris and Yudovich,
2009). It is also lower than that in the No. 6 coal in the Junger Coalfield (193.3
µg/g; Dai et al., 2008). The main mineral in the sediment-source region of No. 6
coal are the bauxites, and REEs were usually enriched within the bauxites (Dai et
al., 2008). The sediment-source region of the No. 2 coal is Qinling Old-upland,
which is mainly composition of granite and metamorphic rock (Wang and Zhang,
1999), the concentration of REE was lower than that in bauxites (Liu and Cao,
1993).

4.2.2. L/H and (La/Yb)N

The ratios of LREEs to HREEs (L/H) in the samples are much greater than 1 (mean
8.59; Table 2), show similar patterns with LREEs enrichment. (La/Yb)N values
(mean 11.38) for the Huangling No. 2 coals indicate that the coals are enriched in
light REE and that the LREE–HREE have been highly fractionated. The small
difference in ionic radii among the REEs could lead to varying ability for
isomorphous replacement in minerals (Taylor and Mclennan, 1985; Liu and Cao,
1993). The ionic radii between of LREEs are very similar with, and leads to Sr- or
Ba-bearing minerals relatively enriched in light REEs (La and Ce). Dai et al. (2008)
reported that the correlation coefficients between REEs and Sr or Ba decreased with
increasing atomic number of the REEs in the coal of Haerwusu Surface Mine. Some
witherite minerals, one kind of Ba-bearing mineral, was found in the samples of
Huangling Mine. So it is concluded that the high concentrations of Ba cause the
enrichment of light REE.
The ratio of LREEs to HREEs (L/H) in the parting is lower than that in the
underlying coal bench. For example, the L/H values of H-P and its underlying coal
bench H-7 are 6.67 and 11.29, respectively (Table 2). The LREEs in the parting are
more prone to leaching by groundwater than the HREEs, leading to low LREE/HREE
ratios in the partings but high LREE/HREE ratios in the underlying coal benches (Liu
and Cao, 1993).
 812

Table 2. Rare earth elements in the sample of No. 2 coalseam from the Huangling Mine. (concentration of REE µg/g; on
whole-coal basis).

(La/ (La/ (Gd/

Sample La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu REE LREE HREE L/H δCe δEu Yb)N Sm)N Lu)N
H-roof 21.41 47.94 5.87 24.91 4.79 1.10 4.31 0.60 3.18 0.60 1.91 0.26 1.86 0.27 119.00 106.02 12.98 8.17 1.01 0.73 7.78 2.81 1.97
H-12 4.86 9.26 1.11 5.08 1.15 0.31 1.20 0.19 1.19 0.24 0.77 0.11 0.76 0.11 26.35 21.77 4.58 4.75 0.92 0.79 4.29 2.66 1.32
H-11 11.03 25.18 2.94 11.90 2.19 0.44 2.01 0.31 1.82 0.38 1.28 0.19 1.36 0.19 61.20 53.67 7.53 7.13 1.04 0.63 5.47 3.17 1.29
H-10 2.81 5.88 0.78 3.85 0.83 0.17 0.78 0.11 0.62 0.13 0.40 0.05 0.38 0.06 16.87 14.33 2.54 5.64 0.94 0.65 4.93 2.14 1.72
H-9 15.23 29.21 3.19 11.92 1.54 0.54 1.59 0.16 0.69 0.13 0.40 0.05 0.36 0.05 65.07 61.64 3.43 17.97 0.96 1.05 28.31 6.21 3.63
H-8p 9.62 21.37 2.58 11.39 2.52 0.58 2.23 0.34 1.88 0.35 1.09 0.15 1.01 0.15 55.26 48.06 7.20 6.67 1.01 0.73 6.42 2.40 1.85
H-7 10.58 20.70 2.33 9.06 1.62 4.56 1.68 0.20 1.02 0.19 0.57 0.08 0.52 0.08 53.19 48.86 4.33 11.29 0.96 8.40 13.80 4.12 2.65
H-6 9.68 15.97 1.78 7.36 1.45 13.97 1.58 0.15 0.77 0.15 0.44 0.06 0.47 0.08 53.93 50.22 3.71 13.52 0.86 28.03 13.79 4.18 2.32
H-5 5.96 11.21 1.42 6.57 1.42 4.17 1.45 0.18 0.97 0.18 0.55 0.07 0.51 0.08 34.75 30.76 3.99 7.70 0.90 8.83 7.95 2.64 2.31
H-4 8.70 16.38 1.90 7.72 1.38 3.28 1.50 0.18 0.95 0.18 0.56 0.08 0.52 0.08 43.39 39.35 4.04 9.74 0.93 6.95 11.18 3.98 2.39
H-3 3.74 6.81 0.88 4.16 0.92 3.85 0.88 0.11 0.59 0.11 0.32 0.04 0.26 0.04 22.71 20.36 2.35 8.66 0.88 12.90 9.60 2.56 2.77
H-2 1.65 3.17 0.38 1.62 0.33 1.21 0.33 0.04 0.21 0.04 0.14 0.02 0.14 0.02 9.31 8.36 0.95 8.80 0.93 11.16 8.06 3.18 1.73
H-1 12.28 18.76 2.03 8.19 1.15 2.13 1.35 0.15 0.81 0.16 0.52 0.07 0.46 0.07 48.13 44.54 3.59 12.40 0.83 5.23 17.83 6.73 2.51
H-floor 10.62 26.12 2.96 12.26 2.26 0.54 2.02 0.28 1.63 0.34 1.13 0.17 1.20 0.17 61.70 54.77 6.93 7.90 1.10 0.76 5.99 2.96 1.46
Av-coal 7.87 14.78 1.70 7.04 1.27 3.15 1.30 0.16 0.88 0.17 0.54 0.07 0.52 0.08 39.54 35.80 3.73 9.59 0.92 7.69 11.38 3.78 2.24
Av-p 13.89 31.81 3.80 16.19 3.19 0.74 2.86 0.41 2.23 0.43 1.38 0.19 1.35 0.20 78.66 69.62 9.04 7.58 1.04 0.74 6.73 2.73 1.76
AV 10.88 23.29 2.75 11.61 2.23 1.95 2.08 0.29 1.55 0.30 0.96 0.13 0.94 0.14 59.10 52.71 6.39 8.59 0.98 4.22 9.06 3.25 2.00
China a 22.5 46.7 6.42 22.3 4.07 0.84 4.65 0.62 3.74 0.96 1.79 0.64 2.08 0.38 117.69 102.83 14.86 6.92 0.59 0.9 7.31 3.48 1.52
World b 11 23 3.5 12 2 0.47 2.7 0.32 2.1 0.54 0.93 0.31 1 0.2 60.07 51.97 8.10 6.42 0.62 0.87 7.43 3.46 1.68
L/H, ratio of LREE Vs. HREE; Eu/Eu* = 2EuN/(SmN + GdN); Ce/Ce* = 2CeN/(LaN + PrN); Av-coal, average content of REE in coal; Av-P, average content of REE in parting, roof and
floor; Av = (Av-coal + Av-p)/2; a, from Dai et al. (2012a); b, from Ketris and Yudovich (2009). The chondrite-normalizing values for the calculations of Eu/Eu*, Ce/Ce*, (La/Yb)N,
(La/Sm) N and (Gd/Lu) N are from Taylor and McLennan (1985).
Rare earth elements in No. 2 coal of Huangling mine, Huanglong coalfield, China
ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 813

4.2.3. Ce/Ce* and Eu/Eu*

The cerium anomaly is expressed as Ce/Ce* whereby Ce concentration is either
depleted or enriched in the samples relative to the other rare earth elements. The values
of Ce/Ce* vary from 0.86 to 1.10 and with an average value of 0.98. Most of them are
more or less 1.00 (Table 2). This means Ce/Ce* shows weakly negative anomaly. The
Ce/Ce* in the parting is higher than that in the underlying bench sample of the No. 2
coal, because cerium is the only rare earth element that can be oxidized to Ce4+ and
precipitated in-situ during the leaching, leading to the generation of Ce-poor leachates
from the parting (Dai et al., 2008; 2012b).
By contrast, the variation of value of Eu/Eu* is abnormally large, from 0.63 to
28.03 and average 4.22 (Table 2). Many researchers have reported that the pattern of
REEs in coal usually shows negative Eu anomaly (Zhao and Tang, 2000). However,
Eu shows strongly positive anomaly in Huangling Coal. This very different with the
pattern of coals of Haerwusu and Heidaigou Mine located in the northern of Ordos
Basin (Dai et al., 2008), common coals of North China and common coals of China
(Zhao and Tang, 2000).
Based on the Eu/Eu* (Table 2) and the chondrite-normalized REE distribution
patterns (Fig. 5), the No. 2 coal seam can be divided vertically into 2 sections:
Section I: Consisted of samples: H-1(Eu/Eu*: 5.23), H-2(Eu/Eu*: 11.16),
H-3(Eu/Eu*: 12.90), H-4(Eu/Eu*: 6.95), H-5(Eu/Eu*: 8.83), H-6(Eu/Eu*: 28.03)
and H-7(Eu/Eu*: 8.40). This kind of pattern shows LREEs enrichment and a
distinct positive Eu anomaly (Fig. 5A). This pattern is similar with submarine
hydrothermal solutions, and the fluids share common characteristics such as very
high temperature (>23°C), high Cl content and pH < 6. (Michard et al., 1983;
Michard, 1989; Campbell et al., 1988; Ding et al., 2000; Yin et al., 2008; Wang
et al., 2010). Wang et al. (2010) reported that the black rocks of Miaowan
Formation (Ordovician-Silurian) in Qinling Mountain were characterized by
slightly negative or positive Ce anomalies (δCe = 0.65~1.02) and distinctly
positive Eu anomalies (with Eu/Eu* mostly higher than 1.54), and black rock
series was formed in a dry, anoxic and shallow sea environment belonging to an
active continental margin, with the participation of some hydrothermal fluids. The
distinctly positive Eu anomalies of Huangling coals are also closely related with
the contents of Ba. Because the ionic radii of Eu2+ is very similar with Ba2+, Eu
can be isomorphous replacement with Ba in minerals, like witherite and barite
(Yin et al., 2008).
Section II: Consisted of samples: H-8p (Eu/Eu*: 0.73), H-9(Eu/Eu*: 1.05),
H-10(Eu/Eu*: 0.65), H-11(Eu/Eu*: 0.63), H-12(Eu/Eu*: 0.79), H-floor (Eu/Eu*:
0.76) and 2–10(Eu/Eu*: 0.73). The patterns of these samples show negative Eu
anomaly (Fig. 5B) and are very similar with patterns of the common coal (Zhao and
Tang, 2000).
It can be found that the parting (H-8p) is the interface of the two sections. The
pyrite is the dominating mineral in Sample H-8p (Fig. 4C). It is very unique because
the pyrite isn’t indentified in the other samples. It may indicate that the sedimentary
environment changed during the parting sedimentation.
814 Rare earth elements in No. 2 coal of Huangling mine, Huanglong coalfield, China

(a)
1000.00

100.00

10.00
H-1
H-2
H-3
1.00 H-4
H-5
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
H-6
H-7
0.10

(b)
100.00

H-9
10.00 H-10
H-11
H-12
H-roof
H-floor
H-8p
1.00
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Figure. 5 Chondrite-normalized rare earth element patterns of samples. A: Section I

and B: Section II.

5. CONCLUSIONS
The average concentration of total REEs (from La to Lu) in the Huangling coals is
59.10 µg/g and lower than that in common Chinese, common USA and common world
coals. It is also lower than that in No. 6 Coal in the Junger Coalfield, northern Ordos
Basin. The high values of L/H and (La/Yb)N for the Huangling No. 2 coals indicate
that the coals are enriched in light REE and that the LREE–HREE have been highly
fractionated.
The variation of value of Eu/Eu* is abnormally large along the No. 2 coal profile.
The No. 2 coal seam can be divided vertically into 2 sections: I with distinct positive
Eu anomaly and II with negative Eu anomaly. The distinct positive Eu anomalies of
Huangling coals are closely related with the contents of Ba. The Ba2+ was originally
from the barium metallogenic belt in Qinling Old-upland.
ENERGY EXPLORATION & EXPLOITATION · Volume 30 · Number 5 · 2012 815

ACKONWLEDGEMENTS
This research was supported by the National Natural Science Foundation of China
(Nos. 41072115 and 51174626) and Natural Science Foundation of Hebei Province
(No. D2012402025).

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