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cn
International Journal of Coal Geology 70 (2007) 184 – 192
www.elsevier.com/locate/ijcoalgeo

The geochemistry of rare earth elements (REE) in acid mine drainage

from the Sitai coal mine, Shanxi Province, North China
Fenghua Zhao a,b,⁎, Zhiyuan Cong c , Hongfu Sun a , Deyi Ren a,b
a
Department of Resource and Earth Science, China University of Mining and Technology. Ding 11# Xueyuan Road,
Haidian District, Beijing 100083, PR China
b
Key Laboratory of Coal Resource, Ministry of Education, P. R. China (Beijing), Ding 11# Xueyuan Road,
Haidian District, Beijing 100083, PR China
c
Institute of Tibetan Plateau Research, Chinese Academy of Sciences, 18 Shuangqing Road,
Haidian District, Beijing 100085, PR China
Received 2 January 2005; accepted 25 January 2006
Available online 25 July 2006

Abstract

In this paper, geochemical characteristics of rare earth elements (REE) in acid mine drainage (AMD) from the Sitai coal mine of
Shanxi Province, North China were investigated by determining concentrations of dissolved REEs and major solutes in the AMD
samples, concentrations of REEs in the AMD precipitate samples and country rock samples (mudstone and coal), and modeling
REEs species in the AMD. The results show that AMD in the Sitai coal mine have high REEs and SO2− 4 concentrations in
comparison with several terrestrial waters worldwide. The REE speciation modeling indicates that sulfate complexes (LnSO+4 , >
60%) and free metal species (Ln3+, 20%–40%) are dominant REEs species in the AMD. AMD of the Sitai coal mine also shows a
middle REE-enriched NASC (North American Shale Composite)-normalized pattern. The authors suggest that both REE sulfates
(LnSO+4 ) in the AMD and country rock of coal measures are possible reasons for middle REE-enriched NASC-normalized pattern
of the Sitai coal mine AMD. Further work on the AMD precipitates is needed to obtain more information on the origin of the
middle REE-enriched NASC-normalized patterns.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Acid mine drainage (AMD); Rare earth elements (REEs); Sitai coal mine; Speciation

1. Introduction of coal and coal-bearing measures, and ore bodies contain-

ing acid-forming metal sulfides such as pyrite (FeS2). The
Acid mine drainage (AMD) occurs worldwide and rep- oxidation of such sulfides exposed to atmospheric O2
resents a serious environmental problem for international during or after mining activities generates acidic waters
mining industries. AMD can occur during the exploitation with high dissolved SO42−, Fe, and heavy metals. The low
pH may cause further dissolution of local country rock and
⁎ Corresponding author. Department of Resource and Earth Science, the leaching of additional metals into water (Tabaksblat,
China University of Mining and Technology. Ding 11# Xueyuan Road, 2002), and thereby adversely impact aquatic life and the
Haidian District, Beijing 100083, PR China. Tel.: +86 10 81613155;
fax: +86 10 62325016.
surrounding vegetation (Gray, 1997; Geller et al., 1998;
E-mail addresses: [email protected], Bell et al., 2001; Cherry et al., 2001). Consequently, the
[email protected] (F. Zhao). behavior of heavy metals in AMD has been exhaustively
0166-5162/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2006.01.009

转载
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F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192 185

Fig. 1. Sampling location map of the study area.

studied (Johnson, 1986; Yu, 1996; Schemel et al., 2000; ically considered to have less toxic effect than heavy
Black and Craw, 2001; Kim and Chon, 2001; Lee et al., metals.
2002). Less research has been focused on the rare earth However, it has been proven that high concentrations
elements (REE) in AMD, possibly because REE are typ- of REE in soil or water may be harmful to human beings

Table 1
Major-ion concentrations in the AMD from the Sitai coal mine (mg/L)
Sample S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-11a Average b
pH 3.62 3.55 3.52 3.56 3.65 3.75 6.76 7.76 3.61
Eh(mv) 568 413 416 409 420 394 192 177 437
F− 0.28 0.37 0.40 0.34 0.99 0.40 0.33 0.63 0.46
Cl− 189 181 167 163 184 160 203 435 174
NO−3 1.74 3.82 4.02 3.81 4.77 4.31 – 34.6 3.75
SO2−
4 2128 1790 1856 1747 1842 1798 911 1296 1860
Na 119 110 106 152 117 115 141 475 120
Ca 242 246 267 246 229 261 181 194 249
Mg 99.2 99.2 90.2 132 97.4 99.2 63.3 119 103
K 37.0 35.3 13.8 13.0 12.0 13.0 15.6 20.6 20.7
Fe 16.2 2.09 3.48 3.62 1.67 1.29 0.16 0.06 4.73
Mn 5.28 3.61 3.55 5.18 3.45 4.02 0.20 0.79 4.18
Al 10.8 7.64 7.64 10.9 7.34 8.66 0.07 0.03 8.83
a
Water sample of the Shili River.
b
Average of S-1 to S-6.
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186 F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192

and animals (Wu et al., 1983; Zhu et al., 1997). REE are discharge program was adopted by the Sitai Coal Au-
widely used to study the geochemical reactions between thority, and 4.0 × 103 m3 of AMD was pumped from deep
and within rocks, groundwater and surface water wells. This AMD is discharged along a small valley, and
(Elderfield et al., 1990; Smedley, 1991; Hall et al., then enters the Shili River (Fig. 1). The AMD pollution is
1995; Johannesson et al., 2000). Therefore, a detailed easily recognized in the field by a red Fe-bearing
investigation of the geochemistry of REEs is important precipitate in the stream channel.
for comprehensive assessment of the potential environ-
mental impacts of AMD. 3. Sampling and methods
AMD is also a serious problem for some Chinese
coal mines; however, limited research has been con- Samples were collected at the Sitai coal mine in Nov-
ducted on the geochemistry of AMD. ember 2002. Seven acidic water samples (S-1, S-2, S-3, S-
In this paper, preliminary results of a study on REE 4, S-5, S-6, S-7) were collected along a small valley at
concentrations, distribution patterns and speciation in about 200 m intervals (Fig. 1). One water sample (S-11)
AMD from the Sitai coal mine, Shanxi Province, North was collected from the Shili River. Redox potential, pH
China are presented. and temperature were measured in the field with portable
instruments that were recalibrated during the sampling
2. Site description programme. Water samples were filtered through 0.45 μm
pore-size membrane and collected into acid-cleaned poly-
The Sitai coal mine is located in the northwestern part of ethylene bottles that were rinsed three times with sample
the Datong Coal Field. The Shili River is the main stream water. The sample bottles were completely filled to elim-
in the studied area and flows from west to east (Fig. 1). inate the headspace. The samples for metal analysis were
The Middle Jurassic Datong Formation is the major immediately acidified to less than pH 2 using high-purity
coal sequence, and primarily consists of sandstones, mud- HNO3; all samples were stored at less than 4 °C until
stones, shales and coal seams. The thickness of coal mea- analyzed.
sures range from 103 m to 224 m. The Datong Formation Concentrations of REE and most of cations in the water
contains 21 coal seams; however, only the No. 8, No. 10 samples were determined using an inductively coupled
and No. 11 coal seams are currently being mined. plasma mass spectrometer (ICP-MS). Internal standards
The Nos. 2 and 3 coal seams were mined underground were used to correct for instrumental drift and matrix
decades ago and AMD comes from the abandoned work- suppression for each sample. The following REE isotopes
ings of these seams. The total amount of AMD is nearly were chosen in order to minimize matrix or polyatomic
3.0 × 105 m3. AMD seeps affect current exploitation of interferences: 139La, 140Ce, 141Pr, 146Nd, 147Sm, 151Eu,
157
Nos. 8 and 11 coal seams below it. Recently, an extensive Gd, 159Tb, 163Dy, 165Ho, 167Er, 169Tm, 173Yb, and

Table 2
The REE concentrations in the acid mine drainage samples from the Sitai coal mine (μg/L)
Sample S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-11a Average b NASC c
La 8.26 6.44 10.4 7.73 6.65 7.15 0.030 0.116 7.77 32.0
Ce 22.0 17.4 18.0 20.4 18.5 19.8 0.130 0.010 19.4 73.0
Pr 3.18 2.60 2.66 2.87 2.61 2.75 0.017 0.004 2.78 7.90
Nd 14.6 11.9 12.7 13.4 12.6 12.7 0.084 0.022 13.0 33.0
Sm 3.36 2.54 2.64 3.60 2.64 3.09 0.017 0.005 2.98 5.70
Eu 1.08 0.77 0.74 0.98 0.84 0.83 0.016 0.016 0.87 1.20
Gd 4.27 3.18 3.50 4.31 3.69 3.70 0.012 0.008 3.78 5.20
Tb 0.77 0.66 0.62 0.81 0.66 0.68 0.005 0.002 0.70 0.85
Dy 4.44 3.75 3.32 4.92 3.96 3.99 0.018 0.012 4.06 5.80
Ho 1.00 0.74 0.73 1.03 0.86 0.83 0.005 0.005 0.87 1.00
Er 2.86 2.03 2.08 3.09 2.29 2.25 0.023 0.008 2.43 3.40
Tm 0.41 0.27 0.29 0.40 0.32 0.32 0.003 0.001 0.34 0.50
Yb 2.21 1.84 1.48 2.65 1.79 1.95 0.027 0.028 1.99 3.10
Lu 0.36 0.25 0.24 0.39 0.32 0.32 0.004 0.005 0.31 0.48
∑REE 68.8 54.4 59.4 66.6 57.7 60.4 0.391 0.242 61.2 173
a
Water sample from the Shili River.
b
Average of S-1 to S-6.
c
North American Shale Composite (μg/g, Taylor and McLennan, 1985).
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F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192 187

Table 3
The REE concentrations in water samples of this work and other locations (μg/L)
Place The Sitai Colour Osamu Odiel Metalliferous Mississippi Zhujiang
Coal mine Lake, Canadaa Utsmi, Brazilb River, Spainc Hills, Italyd River, USAe River, Chinaf
Sample Average Cl-23 GW-58 OR1 BC18 Average Average
pH 3.61 4.7 4.43 3.25 3.10
∑REE 61.21 1.90 1046 42.62 929 0.0418 0.355
La 7.77 0.32 567 13.23 185 0.0039 0.035
Ce 19.35 0.57 124.01 36.16 390 0.0073 0.075
Pr 2.78 0.07 0 45.75 0.0014 0.012
Nd 12.98 0.32 250 19.72 172 0.0073 0.053
Sm 2.98 0.09 28.57 4.85 34.82 0.0021 0.037
Eu 0.87 0.03 7.75 1.09 8.65 0.0007 0.015
Gd 3.78 0.19 22.64 5.78 40.18 0.0036 0.031
Tb 0.70 0.02 0 0.83 5.00 0.0005 0.006
Dy 4.06 0.13 23.24 4.96 23.66 0.0045 0.028
Ho 0.87 0.02 5.28 0.90 4.18 0.0012 0.006
Er 2.43 0.05 12.21 2.20 10.50 0.0041 0.023
Tm 0.34 0.01 0 0.30 1.21 0.0006 0.006
Yb 1.99 0.03 5.54 1.73 7.07 0.0039 0.023
Lu 0.31 0.05 0.52 0.26 0.94 0.0007 0.005
a
Johannesson and Lyons, 1995. bMiekeley et al., 1992. cElbaz-Plulichet and Dupuy, 1999. dProtano and Riccobono, 2002. eHannigan and
Sholkovitz, 2001. fWang et al., 1998.

175
Lu. Isobaric interferences of Ba and light REE oxides means of the Davies approximation because all of the ionic
and hydroxides were corrected during analysis. Detection strengths of the AMD are <0.1 mol/L (Shen et al., 1993).
limits are less than 0.001 mg/L.
Sodium and magnesium in the water samples were 4. Results
determined by Atomic Absorption Spectrometry (AAS).
The anions were determined by ion chromatography Major ion concentrations, pH and Eh for each water
(IC). sample are presented in Table 1. The pH of the AMD
The BST1 and SST1 samples are AMD precipitates water samples (S-1 to S-6) ranges from 3.52 to 3.75, and
collected from underground workings. The SST4 sample Eh values between 394 mV and 568 mV. The dominant
is a channel sediment collected at the AMD outfall shown cation is Ca2+ (229–267 mg/L) in these samples,
in Fig. 1. The coal sample (SST5) was obtained from the followed by Na+ (106–152 mg/L) and Mg2+ (99.2–
No. 3 coal seam. The SST2 and SST3 samples are mud- 132 mg/L). The concentration of SO42− in Sitai coal mine
stones collected from the coal measures. These samples
were digested with high-purity HNO3 and HClO4, and
then analyzed by ICP-MS to determine their REE
contents. X-ray diffraction was employed to examine
the mineral composition of these solid samples.
Speciation calculations were performed with the
PHREEQCI code, a comprehensive aqueous geochemical
modeling code developed by the USGS (Charlton and
Parkurst, 2002). In order to model REE speciation,
PHREEQCI includes stability constants of the REE
sulphates (LnSO4+, where Ln represents any of the
lanthanide series elements), chlorides (LnCl2+), fluorides
(LnF2+), and hydroxide complexes (LnOH2+) calculated
by Millero (1992), and the carbonate complexes (LnCO3+,
Ln(CO3)2−) determined by Lee and Byrne (1993). The REE
phosphate complexes were not considered in this modeling
because of their extremely low concentrations. In this Fig. 2. The speciation of REE in AMD samples from the Sitai coal
study, activity coefficient calculations were performed by mine.
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188 F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192

4.1. REE concentrations in the AMD

The REE concentrations in the AMD samples are listed

in Table 2. Table 3 compares average REE concentrations
(S-1 to S-6) from this study with other published results
(Miekeley et al., 1992; Johannesson and Lyons, 1995;
Wang et al., 1998; Elbaz-Plulichet and Dupuy, 1999;
Hannigan and Sholkovitz, 2001; Protano and Riccobono,
2002). The total concentration of REEs (∑REE) in the
AMD samples range from 54.37 μg/L to 68.80 μg/L (Table
2), which are about two or three orders of magnitude higher
than total REE concentrations in the acidic Colour Lake
(1.90 μg/L, Johannesson and Lyons, 1995), neutral
Zhujiang River (0.355 μg/L, Wang et al., 1998) and Mis-
Fig. 3. The NASC-normalized REE patterns for the Shili River and the sissippi River (0.0418 μg/L, Hannigan and Sholkovitz,
AMD of the Sitai coal mine (S-1 to S-6: AMD, pH = 3.52–3.75; S-7: 2001). However, the total concentrations of REE in AMD
AMD, pH = 6.76; S-11: the Shili River, pH = 7.76).
from the Sitai coal mine are less than those reported for
AMD from Osamu Utsmi (1046 μg/L, Miekeley et al.,
AMD is very high (1742–2128 mg/L) compared to the 1992) and Metalliferous Hills (929 μg/L, Protano and
drinking water upper limit of 250 mg/L (Freeze and Riccobono, 2002), and are similar to those from Odiel
Cherry, 1979). Cl− is also high, whereas concentrations River (42.62 μg/L, Elbaz-Plulichet and Dupuy, 1999). The
of NO3− and F− are relatively low, and PO43− was below REE concentrations of the Shili River and S-7 water
detection limits. High concentrations of SO42− (Table 1) samples (pH =6.76) are 0.242 μg/L and 0.391 μg/L,
are from pyrite oxidation from the coal measures, respectively, which are similar to that of Zhujiang River
whereas Na and Al are from weathering of the alu- (0.355 μg/L, Wang et al., 1998).
mosilicates (e.g. albite). Although Ca and Mg can also be
derived from aluminosilicate it is more likely derived 4.2. Speciation modeling of REE in the AMD
from carbonates. The AMD samples have higher Fe, Al
and Mn concentrations and lower pH than S-7 and the Average results of speciation modeling for the AMD
sample from the Shili River (S-11). samples from the Sitai coal mine are presented in Fig. 2,
Table 4
REE concentrations in AMD sediment and country rock samples from the Sitai coal mine (μg/g)
Sample no. BST1 SST1 SST4 SST2 SST3 SST5
Lithotype AMD precipitate AMD precipitate AMD channel Sediment Mudstone Mudstone Coal
La 47.2 7.74 33.2 30.5 55.4 3.65
Ce 78.3 17.6 70.0 64.2 105 7.02
Pr 9.10 2.08 7.88 7.00 11.2 0.76
Nd 38.8 8.99 31.0 27.4 42.4 3.08
Sm 5.99 1.87 5.37 4.85 6.35 0.51
Eu 1.24 0.58 1.14 1.3 2.31 0.18
Gd 6.72 3.31 6.01 5.68 8.05 0.67
Tb 0.91 0.52 0.72 0.762 1.00 0.12
Dy 5.16 3.04 4.12 4.11 5.57 0.74
Ho 1.13 0.68 0.74 0.798 1.15 0.15
Er 2.97 1.70 2.16 2.18 3.1 0.44
Tm 0.56 0.23 0.34 0.313 0.439 0.07
Yb 3.05 1.28 2.48 2.29 2.8 0.41
Lu 0.57 0.17 0.34 0.314 0.385 0.06
ΣREE 202 49.8 166 152 245 17.9
S/Fe 0.09 0.03 0.06 nd nd nd
BST-1 and SST1 are AMD precipitate samples (mainly goethite) collected from underground workings.
SST4 is a channel sediment sample (quartz, goethite and feldspar) collected at the AMD outfall located on Fig. 1. SST2 and SST3 are mudstone
(kaolinite, quartz, feldspar, calcite) samples collected from the coal measures.
SST5 is a coal sample obtained from No. 3 coal seam. S/Fe: atomic ratio. nd: not detected.
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F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192 189

where the percent abundance of each aqueous REE

species is plotted against REE atomic numbers. Specia-
tion modeling indicates that the REE sulfate complexes
(LnSO4+) are the primary form of dissolved REE, and
always account for more than 60% of the dissolved REE
concentration. Moreover, the partitioning of dissolved
REE into SO42− complexes decrease as atomic number
increases, especially from Eu (Fig. 2). Free metal cations
(Ln3+) are the next most abundant dissolved REE species
and are responsible for between 20% and 40% of the REE
in solution. The partitioning of dissolved REE into free
metal species (Ln 3+ ) increases as atomic number
increases. The proportion of dissolved REE present as
other inorganic complexes such as LnCl2+, LnF2+ and
LnOH2+ is less than 1%. Fig. 5. The NASC-normalized REE patterns for mudstone and coal
samples of coal measures from the Sitai coal mine (SST2 and SST3:
mudstone samples; SST5: coal sample).
4.3. Distribution patterns of REE in the AMD

The normalization of REE concentrations to those in 4.4. Concentrations and distribution patterns of REE in
North American Shale Composite (NASC, Taylor and AMD precipitates and country rock samples
McLennan, 1985) can act as an indicator of REE enrich-
ment. Fig. 3 illustrates the NASC-normalized patterns of Table 4 presents REE concentrations in AMD
the REE concentrations in the AMD samples, a near precipitate samples (BST1 and SST1), an AMD channel
neutral water sample (S-7) from the Sitai coal mine, and sediment sample (SST4), two mudstone samples from the
the Shili River sample (S-11). As can be seen in Fig. 3, the coal measures (SST2 and SST3), and a coal sample
AMD samples display a pronounced convex-up NASC- (SST5). Based on the XRD results, the BST1 and SST1
normalized REE pattern without Ce- or Eu-anomalies. samples consist mainly of goethite; the SST4 sample
Therefore, middle rare earth elements (MREE) are en- consists of quartz, goethite and minor feldspar; the SST2
riched over both light rare earth elements (LREE) and sample is mainly composed of quartz, kaolinite, feldspar,
heavy rare earth elements (HREE) in the AMD samples dolomite, and minor mica; the SST3 sample is mainly
in comparison with NASC. However, the near neutral made up of kaolinite, quartz, feldspar, and minor calcite.
water (S-7) and the Shili River samples (S-11) do not The minerals in the SST5 sample are quartz, kaolinite,
display the MREE enrichment. calcite, dolomite and gypsum. Table 4 shows the total
concentrations of REE in mudstone samples (SST3 and
SST2) and in AMD precipitate samples with the highest
S/Fe atomic ratios for BST1 and SST4.
Fig. 4 shows the NASC-normalized REE patterns for
AMD precipitate samples (BST1, SST1 and SST4); and
Fig. 5 for the country rock samples (SST2 and SST3) and
the coal sample (SST5). As can be seen in Figs. 4 and 5,
most of these solid samples do not demonstrate the typical
characteristic of MREE-enriched NASC-normalized REE
pattern. However, the SST1 sample shows a similar
NASC-normalized REE pattern to that for AMD samples.

5. Discussion

5.1. Enrichment mechanism of REEs in acidic water

Fig. 4. The NASC-normalized REE patterns for AMD precipitate

Previous investigations indicate that pH, and the
samples from the Sitai coal mine (BST1 and SST1: AMD precipitate presence of colloids and complexes play a major role in
samples; SST4: AMD channel sediment sample). controlling REE concentrations in natural waters
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190 F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192

(Sholkovitz, 1995; Protano and Riccobono, 2002; and/or amorphous phases occurs in local rocks by acidic
Tabaksblat, 2002; Astrom and Corin, 2003). Concentra- waters at Colour Lake (Canada), and are the most likely
tions of REE in low-pH waters dominated by SO42− may source of the MREE enrichment in the lake waters. On the
significantly increase because of formation of more stable contrary, many researchers have argued that such a feature
LnSO4+ (Johannesson and Lyons, 1995; Tabaksblat, depends mainly on water chemistry, including the solution
2002). Coagulation and aggregate precipitation of iron pH, and the presence and concentration of complexing
and aluminum colloids may effectively remove REE in ligands, rather than on country rock geology (e.g. see
mine water with increases in pH (Zanker et al., 2003). Moller and Bau, 1993; Sholkovitz, 1995).
In the present study, the concentrations of SO42− In the current study, the average proportions of MREE
appear to control concentrations of REEs in AMD sam- sulfate complexes (70.21%) appear to be higher than those
ples from the Sitai coal mine. Higher concentrations of of LREE sulfate complexes (69.67%) and HREE sulfate
SO42− lead to the formation of stable LnSO4+, thereby complexes (61.99%). The sulfate complex (LnSO4+) is
resulting in higher concentrations of REEs in AMD probably one of the reasons for MREE enrichment in the
samples. The concentrations of Fe, Al, Mn and SO42− in AMD.
AMD samples decrease with increases in pH, implying Although REE in the mudstone and coal samples from
that coagulation and precipitation of Fe–Al–Mn oxide/ the coal measures do not show a typical MREE-enriched
hydroxide colloids occur. It also implies that REE sulfate NASC-normalized REE pattern (Fig. 5), some of the
complexes (LnSO4+) are possibly adsorbed onto the Fe– MREE (Eu, Gd and Tb in the SST2 sample; Eu and Gd in
Al–Mn oxide/hydroxide colloids and then co-precipitate the SST3 sample and, Eu, Gd, Tb, Dy and Ho in the SST5
with them, thereby resulting in the REEs scavenging sample) show higher NASC-normalized concentrations
from AMD samples with the increase in pH, especially than the HREE and most of the LREE. Therefore, country
for the S-7 sample (pH = 6.76). Compared with the AMD rocks (mudstone and coal) of the coal measures possibly
samples (S-1 to S-6), the Shili River sample (S-11, contribute to enrichment of MREE in the AMD from the
pH = 7.76) has a lower concentration of SO42−; conse- Sitai coal mine.
quently, it also has a lower REE concentration. Different AMD precipitate samples demonstrate dif-
REE and SO42− in AMD precipitate samples are from ferent NASC-normalized REE patterns (Fig. 4). Similar
the AMD. Data in Table 4 indicate that concentrations of MREE-enriched NASC-normalized REE patterns of the
REE are higher in the AMD precipitate samples with SST1 sample to that of the Sitai coal mine AMD probably
higher S/Fe atomic ratios than in those with smaller S/Fe imply that REE concentrations of the SST1 sample are
atomic ratios, which also implies that concentrations of partly from pore water within the sample. However, con-
SO42− control concentrations of REE in AMD samples. tribution of AMD precipitates to MREE-enriched NASC-
normalized REE patterns of the Sitai coal mine AMD is still
5.2. Mechanism of MREE enrichment in the AMD unclear based on current data. Further work is needed to
elucidate the contribution of AMD precipitates to MREE-
Similar MREE enrichments to that in AMD from the enriched NASC-normalized REE patterns of the AMD.
Sitai coal mine have been reported for acidic lakes, rivers
affected by AMD and acidic groundwater (Johannesson 6. Conclusions
and Lyons, 1995; Elbaz-Plulichet and Dupuy, 1999;
Serrano et al., 2000). Therefore, the convex-up NASC- When compared with several terrestrial waters, the
normalized REEs pattern of AMD is one characteristic of AMD of the Sitai coal mine have high REEs and SO42−
acidic natural water although Bozau et al. (2004) recently concentrations, and concentrations of SO42− control con-
reported that LREEs in an acidic mine water (Lusatia, centrations of REE in the AMD. The REE speciation
Germany) are enriched. modeling indicates that REE sulfate complexes (LnSO4+, >
However, the processes controlling MREE enrichment 60%) and free metal species (Ln3+, 20%–40%) are the
observed in acidic terrestrial waters are still not well un- dominant REE species in the AMD, while other possible
derstood and it is unclear whether observed distributions inorganic complexes such as LnCl2+ and LnF2+ are neg-
relate to the source or aqueous processes. Hall et al. (1995) ligible. The AMD of the Sitai coal mine also shows a
studied a lake in Newfoundland (Canada), and found that typical MREE-enriched NASC-normalized REE patterns.
the REE distribution pattern is generally similar to that of Both REE sulfate (LnSO4+) in the AMD and country rock
the associated sediments, reflecting the REE patterns of the of the coal measures are possible causes for MREE-
host rocks. Johannesson and Zhou (1999) found that the enriched NASC-normalized REE patterns of the Sitai coal
leaching or dissolution of MREE enriched in the minerals mine AMD.
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F. Zhao et al. / International Journal of Coal Geology 70 (2007) 184–192 191

Acknowledgements Johannesson, K.H., Zhou, X.P., 1999. Origin of middle rare earth
element enrichments in acid waters of a Canadian High Arctic lake.
Geochimica et Cosmochimica Acta 63, 153–165.
The research was funded by the National Natural Johannesson, K.H., Zhou, X., Guo, C., Stetzenbach, K.J., Hodge, V.F.,
Science Foundation of China (No. 40272128 and No. 2000. Origin of rare earth element signatures in groundwaters of
40133010) and Special Foundation for the Authors of circumneutral pH from southern Nevada and eastern California.
Excellent PhD Dissertation of Ministry of Education P. R. Chemical Geology 164, 239–257.
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