Mining Science and Technology (China) 21 (2011) 469–476

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Mining Science and Technology (China)

journal homepage: www.elsevier.com/locate/mstc

Distribution characteristic and geological significance of rare earth elements

in Lopingian mudstone of Permian, Panxian county, Guizhou province
Shao Yubao a,b,⇑, Guo Yinghai a,b, Qin Yong a,b, Shen Yulin a,b, Tian Li c
a
School of Resource and Geoscience, China University of Mining & Technology, Xuzhou 221008, China
b
Key Laboratory of CBM Resource and Reservoir Generating Process, China Ministry of Education, Xuzhou 221008, China
c
159 Geological Brigade, Guizhou Bureau of Coal Geology, Liupanshui 553500, China

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

Article history: In order to discuss the geochemical characteristic of REEs (rare earth elements) and their geological appli-
Received 12 December 2010 cation, we measured the contents of rare earth elements, trace elements and minerals of 29 Lopingian
Received in revised form 9 January 2011 (Late Permian) mudstone samples in Panxian county, carrying out ICP-MS and XRD analysis. The results
Accepted 27 January 2011
show that the amount of REEs (185.56–729.46  10 6) is high. The ratios of w(LREE)/w(HREE) (6.84–
Available online 30 June 2011
13.86) and w(La)N/w(Yb)N (1.01–3.02) show clear differentiation of LREEs and HREEs. RREE has a signif-
icantly or critically positive correlation with lithophile elements Th, Nb, Ta, Ti, Ga, Sc, Cs, Zr, Hf, Sr, Be and
Keywords:
chalcophile element Zn, a critically negative correlation with siderophile element Fe and a slightly posi-
Rare earth element
Provenance
tive correlation with illite, illite smectite mixed layers and siderite. REEs originate mainly from terrige-
Sequence boundary nous minerals, in an inorganic phase. Source rocks of our samples consist of Emeishan basalt and a
P
Lopingian small part of sedimentary rocks, as suggested by the distribution patterns of REEs and w( REE)–
Panxian county w(La)/w(Yb) diagram. Moreover, abnormal surfaces near the sequence boundaries (SB2, SB3, SB4) are
P
related with the boundaries, identified by geochemical characteristics of the REEs, such as REE,
⁄
w(LREE)/w(HREE), Eu/Eu and Ceanom.
Ó 2011 Published by Elsevier B.V. on behalf of China University of Mining & Technology.

1. Introduction REEs in Lopingian mudstone of Panxian county, we analyzed the

provenances and occurrence of REEs and discussed the relationship
The immobility of REEs (rare earth elements) leads them to be between the sequence boundaries and variation in the vertical con-
mostly preserved in-situ, not subject to sedimentation, weather- tent in geochemical characteristics of REEs near the boundaries.
ing, transportation, deposition and diagenesis. Their distribution This provides a theoretical basis for dividing the sequence stratig-
patterns are free from the effect of these secondary processes. raphy in REEs from a geochemical point of view.
Therefore scientists regard REEs as important symbols of source
rock characteristics, largely effective in the study of crustal compo-
2. Geological setting
nents [1–3]. In recent years, their application has spread widely in
such areas as the determination of sediment provenance, analysis
Panxian county is located in Liupanshui city, Guizhou province.
of ancient tectonic settings, the study of evolution of ancient cli-
During the Lopingian (Late Permian), this area was in the western
mate and environments, genetic relationships between mineraliza-
Liupanshui fault depression within the northern Guizhou uplift of
tion and volcanic activity [1–8]. Research into the occurrence of
the Yangtze continental block [16]. Our research shows that the
REEs may enhance the understanding of provenances. Research
Lopingian coal measures of our study area consists of coal-bearing
methodology includes direct and indirect methods, using mathe-
clastic rocks and limestone, while under the delta a lagoon tidal flat
matical statistics (indirect method) due to its briefness, agility
and restricted subtidal facies are present. The small rises and falls
and universal application [9–12]. The principal geochemical meth-
in relative sea levels may have resulted in widespread transgres-
ods to identify the sequence boundary are clay mineralogy,
sion and regression processes, on the background of gentle ancient
cement, geochemical trace elements and organic geochemistry
slopes and low rates of deposition. Therefore, thin marine marker
[13–15]. All the same, little is known about geochemical methods
beds and coal seams were deposited with a wide planar distribu-
in studying REEs. Given our study of geochemical characteristics of
tion [17]. These marker beds have favorable isochronism and sup-
ply an excellent basis for regional stratigraphic correlation.
⇑ Corresponding author. Tel.: +86 15895210705. Although there have been a series of sequence stratigraphic
E-mail address: yubshao@163.com (Y. Shao). studies of Lopingian in Guizhou province, so far most studies have

1674-5264/$ - see front matter Ó 2011 Published by Elsevier B.V. on behalf of China University of Mining & Technology.
doi:10.1016/j.mstc.2011.06.002
470 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476
focused on carbonate formation of platform margins or inter-
platform basins in mid-eastern Guizhou [18–23]. There is an ab-
sence of a detailed stratigraphic framework of western Guizhou, gi-
ven the background of clastic rock marine-terrigenous facies [17].
This brings about problems when investigating the sequence
stratigraphic framework in the Yangtze platform. In these cases,
we recognized five types of third-order sequence boundaries
(SB1, SB2, SB3, SB4, SB5), four third-order sequences (SQ1, SQ2,
SQ3, SQ4) and constructed a regional sequence stratigraphic
framework (Fig. 1), with a number of features such as biostratigra-
phy and chronostratigraphy data, vertical well sedimentary se-
quences, log responses and geochemical characteristics of wells
in the study area. SB1 is a regional tectonic unconformity and cor-
responds to the first episode of the Dongwu resolution. The SB2
and SB4 sequence boundaries are as follows: a regional regression
unconformity (transition from lagoon tidal flat to delta) and a re-
gional transgression unconformity (transition from delta to lagoon
tidal flat and restricted subtidal facies) and stand for surfaces with
drastic changes in facies. SB3 is an exposure unconformity, with
characteristic of paleosol layers. SB5 is the boundary between the
Triassic and Lopingian of Permian and defines a drowning uncon-
formity or surface with an abrupt large-scale transgression in var-
ious locations.
Fig. 1. Sequence stratigraphic framework of Lopingian in Panxian county.
3. Samples and analytical methods
We used continuous sampling of the Lopingian mudstone in our
research area and collected twenty nine samples from stably and
well developed mudstone layers on the sequence boundaries or
from nearby. The high anomaly of natural gamma-ray (GR) curves
and the lithological features provided a convenient way of con-
trasting or identifying the mudstone layers. We took a sample from
each mudstone layer, which were mostly gray-black and gray
mudstone (Fig. 1). Furthermore, symbols such as P1, P2, P3, stand
for the separate well numbers. The samples P1-1 to P1-4, P2-1 to
P2-4, P3-1 to P3-2 lie in Changxing formation (stratigraphic unit
of the Changhsingian) and the samples P1-5 to P1-9, P2-5 to P2-
10, P3-3 to P3-10 were found in the Longtan formation (strati-
graphic unit of the Wuchiapingian). Analyses by inductively cou-
pled plasma mass spectroscopy (ICP-MS) of REEs and trace
elements from the samples were carried out in the Geological
Experiment Research Institute of the China University of Mining
and Technology. Tables 1 and 2 list the concentrations of twenty
eight REEs and fourteen trace elements of the samples. Analytical
errors were estimated to be less than 10% for most of the elements.
Quantitative mineralogical analyses of nineteen samples were per-
formed on a D/Max-3B powder X-ray diffraction (XRD) instrument
 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476 471

Table 1
REEs contents and associated geochemical parameters.

Sample no. REEs content (10–6) REEs parameter

P
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu REE L/H (La/ Eu/ Ce/ Ceanom
Yb)N Eu⁄ Ce⁄
P1-1 98.72 189.30 23.11 84.80 15.18 4.41 16.57 3.21 19.44 3.75 10.39 1.44 8.71 1.33 480.36 6.41 1.10 1.22 0.86 0.05
P1-2 85.07 169.30 21.38 84.86 15.91 4.20 14.35 2.27 11.94 2.18 5.58 0.76 4.36 0.66 422.83 9.04 1.89 1.22 0.86 0.05
P1-3 36.55 72.32 9.58 38.55 7.11 1.57 6.32 0.99 5.25 1.01 2.87 0.40 2.65 0.39 185.56 8.33 1.34 1.03 0.84 0.07
P1-4 77.24 160.30 20.14 79.71 15.36 4.09 13.77 2.22 11.81 2.16 5.77 0.80 4.90 0.74 399.00 8.46 1.53 1.23 0.89 0.04
P1-5 97.76 201.30 24.88 96.02 17.59 5.01 16.32 2.55 12.63 2.22 5.82 0.76 4.47 0.64 487.96 9.75 2.12 1.30 0.89 0.04
P1-6 52.51 104.30 14.17 55.16 11.70 3.36 11.97 2.12 10.46 1.68 4.30 0.58 3.64 0.53 276.48 6.84 1.40 1.25 0.83 0.06
P1-7 73.93 149.50 19.08 75.55 14.90 4.23 13.44 2.14 11.07 2.01 5.39 0.75 4.38 0.68 377.05 8.46 1.64 1.31 0.87 0.05
P1-8 91.08 181.50 22.25 84.88 14.81 3.50 13.33 2.15 11.46 2.14 5.85 0.80 4.75 0.72 439.22 9.66 1.86 1.09 0.88 0.04
P1-9 153.1 309.00 35.98 133.40 24.26 5.86 22.20 3.52 18.78 3.49 9.49 1.33 7.91 1.14 729.46 9.75 1.88 1.11 0.91 0.03
P2-1 74.03 154.9 18.75 72.96 13.61 3.38 12.52 2.08 11.21 2.04 5.74 0.79 4.84 0.73 377.57 8.45 1.48 1.14 0.91 0.03
P2-2 62.00 125.5 15.44 59.8 10.69 2.78 9.71 1.62 8.77 1.58 4.37 0.58 3.42 0.52 306.77 9.04 1.76 1.20 0.88 0.04
P2-3 72.07 137.8 16.89 62.64 10.61 2.73 9.89 1.66 9.26 1.78 4.81 0.68 4.10 0.62 335.53 9.23 1.70 1.17 0.86 0.05
P2-4 79.82 164.0 19.69 75.19 13.74 3.80 12.65 2.05 11.13 2.04 5.46 0.71 4.48 0.65 395.42 9.09 1.73 1.27 0.90 0.03
P2-5 86.36 174.8 21.32 82.69 16.03 4.28 14.09 2.08 10.43 1.85 4.99 0.67 4.10 0.61 424.30 9.93 2.04 1.25 0.89 0.04
P2-6 67.91 141.0 16.76 63.23 10.57 2.57 8.99 1.56 9.49 1.83 5.27 0.75 4.51 0.67 335.10 9.13 1.46 1.16 0.91 0.03
P2-7 98.93 208.3 24.2 91.72 16.07 3.79 13.93 2.27 12.05 2.26 6.18 0.86 5.12 0.73 486.42 10.21 1.87 1.11 0.93 0.02
P2-8 81.71 164.4 20.18 78.97 14.18 3.56 12.33 1.95 10.29 1.81 4.94 0.69 4.09 0.60 399.70 9.89 1.94 1.18 0.88 0.05
P2-9 77.14 150.0 17.08 57.91 10.08 2.07 12.16 2.20 11.32 1.96 5.08 0.75 4.73 0.69 353.16 8.08 1.58 0.82 0.90 0.03
P2-10 74.19 152.1 19.15 75.46 14.94 3.81 13.62 2.16 11.52 2.09 5.73 0.79 4.77 0.72 381.05 8.21 1.51 1.17 0.88 0.04
P3-1 62.59 127.7 15.68 59.18 10.08 2.35 9.44 1.58 8.73 1.66 4.40 0.62 3.72 0.54 308.27 9.05 1.63 1.06 0.89 0.04
P3-2 59.87 120.3 14.62 54.92 9.332 2.43 8.63 1.38 7.44 1.40 3.98 0.54 3.18 0.48 288.49 9.68 1.82 1.19 0.89 0.04
P3-3 78.21 164.4 20.38 81.01 15.06 3.73 13.19 1.99 10.40 1.90 5.11 0.67 4.17 0.59 400.81 9.54 1.82 1.16 0.90 0.04
P3-4 64.7 135.9 17.03 68.57 13.93 3.58 12.91 1.98 10.44 1.94 5.09 0.71 4.22 0.63 341.64 8.01 1.49 1.17 0.89 0.04
P3-5 123.2 243.1 26.62 91.91 14.65 2.98 12.98 1.90 9.76 1.76 4.66 0.65 3.95 0.58 538.70 13.86 3.02 0.95 0.92 0.02
P3-6 99.78 215.9 25.84 104.1 19.28 4.17 13.77 1.93 10.21 1.89 5.23 0.71 4.27 0.61 507.71 12.14 2.26 1.12 0.93 0.02
P3-7 78.34 161.7 20.21 82.85 16.41 3.93 12.36 1.79 9.34 1.83 4.60 0.66 3.86 0.56 398.43 10.39 1.97 1.21 0.89 0.05
P3-8 71.48 143.3 17.6 69.72 13.34 3.86 12.55 1.90 10.32 1.95 5.43 0.76 4.80 0.68 357.69 8.32 1.44 1.31 0.88 0.05
P3-9 74.42 154.2 19.09 75.52 14.57 3.29 11.08 1.92 10.83 2.05 5.52 0.76 4.72 0.70 378.67 9.07 1.53 1.14 0.89 0.04
P3-10 50.81 103.6 13.32 53.88 10.61 2.56 9.51 1.52 8.57 1.62 4.52 0.65 3.86 0.57 265.60 7.62 1.28 1.12 0.87 0.05
NASC [24] 32 73 7.9 33 5.70 1.24 5.2 0.85 5.8 1.04 3.40 0.50 3.10 0.48 173.21 7.50 1.00 1.00 1.00 0
Emeishan 37.17 86.29 9.76 46.46 10.08 3.02 9.10 1.27 6.53 1.13 2.53 0.21 1.41 0.21 215.17 8.61 2.55 1.38 0.99 –0.02
basalt [25]
Sea [26] 3.40 1.20 0.64 2.80 0.45 0.13 0.70 0.14 0.191 0.22 0.87 0.17 0.82 0.15 11.88 2.64 0.40 1.02 0.18 –0.78
P ⁄ 0.5
Note: REE = LREE+HREE; L/H = LREE/HREE, LREE = La + Ce + Pr + Nd + Sm + Eu; HREE=Gd + Tb + Dy + Ho + Er + Tm + Yb + Lu; Eu/Eu = EuN/(SmN  GdN) ; Ce/Ce⁄ = CeN/
(LaN  PrN)0.5; Ceanom = lg[3CeN/(2LaN + NdN)]; and subscript N stands for NASC-normalized value.

using a Ni-filtered Cu-Ka radiation and a scintillation detector, fol-
lowing Chinese Standard GB 5225-86. Diffraction patterns were
registered in a 2h interval 3°–65° with a step size of 0.02°. Table
3 presents the mineral contents of the samples.
4. Geochemical characteristics of REE mudstone samples
P age) show an anoxic environment. The Eu/Eu⁄ ratios were 0.82–
The total REE contents ( REE) of each of the twenty nine mud-
stone samples varied considerably, ranging from 185.56 to
729.46  10 6 (except for Y, Table 1). The weighted mean value
is 392.38  10 6, much higher than that of the North American
Shale Composite (NASC) (173.21  10 6), of the Emeishan basalt
(215.17  10 6) and the average of seawater (11.88  10 6), sug-
gesting that the REEs are obviously well concentrated in our sam-
ples [24–26]. The LREE/HREE ratios vary from 6.84 to 13.86 with an
average of 9.16, slightly higher than that of Emeishan basalt (8.61),
the NASC average (7.50) and the average of seawater (2.64), indi-
cating that the samples are enriched in LREEs. For our samples,
the REEs contents were normalized by NASC. The associated geo-
chemical parameters and distribution patterns of the REEs are pre-
sented in Table 1 and Fig. 3a–c). The (La/Yb)N ratios range from
1.01 to 3.02 and their average, 1.73, is much higher than that of
NASC (1.00) and average of the sea (0.40), but lower than that of
Emeishan basalt (2.55), indicating a comparatively large differenti-
ation between LREEs and HREEs or a relative enrichment of LREEs
compared to NASC and seawater. The slightly negative Ce anomaly
(Ce/Ce⁄ ratios ranging from 0.83 to 0.93) suggests that all samples
are affected by seawater and deposited in a weak reduction-weak
oxidation environment, which agrees with the background of mar-
ine-terrestrial transitional facies. Elderfield et al. define Ceanom in
order to signify the Ce anomaly [27]. When based on NASC-nor-
malized values, Ceanom < 0.10 expresses a negative Ce anomaly
and Ceanom > 0.10 shows positive Ce anomaly, suggesting, in turn,
oxidizing conditions and anoxic conditions. Therefore the Ceanom
values of the samples (ranging from 0.07 to 0.02, 0.04 on aver-
1.31, showing a range of negative Eu anomalies to positive Eu
anomalies. The average Eu/Eu⁄ ratio (1.16) was slightly higher than
that of NASC (1.00) and the average of seawater (1.02), but lower
than that of Emeishan basalt (1.38).
5. Results and discussion
5.1. Occurrence of REEs
5.1.1. Correlation analysis
We present the contents of trace elements that have statistical
P
significance with REE and their associated correlation coeffi-
cients in Table 2. There is a significantly or critical positive correla-
P
tion between Th, Nb, Ta, Ti, Ga, Sc, Cs, Zr, Hf, Sr, Be, Zn and REE
P
and a critical negative correlation between Fe and REE. Most of
these elements are lithophile elements, suggesting that REEs are
mainly from terrigenous clastic minerals and partially originate
P
in small amounts from marine sources. Additionally, REE has a
slightly positive correlation with illite, illite smectite mixed layers
and siderite and negative but barely statiscally significant correla-
472 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476

Table 2
6 P
Contents (10 ) of fourteen trace elements and correlation coefficients for trace elements with REE.

Sample no. Th Hf Ga Zr Nb Ta Zn Sc Cs Ti Sr Be Fe U
P1-1 19.4 72.77 44.1 2776 94.03 6.24 143.1 47.58 3.73 33590 689.4 4.709 40390 11.05
P1-2 12.16 46.09 37.69 1805 75.98 4.79 168.9 31.21 2.92 33620 526.5 3.641 56230 3.171
P1-3 7.272 16.03 13.98 602.2 19.47 1.57 76.87 9.117 1.24 7755 209.7 1.834 112000 8.286
P1-4 13.23 42.80 33.81 1597 63.18 4.27 208.6 29.88 1.49 24610 449.7 2.866 115700 3.658
P1-5 16.82 52.24 45.02 1953 94.6 6.31 194.4 38.5 2.76 34940 412.8 4.261 50120 4.242
P1-6 19.09 60.00 44.03 2036 117.3 7.70 66.07 38.95 1.71 35830 454.7 6.288 34370 2.981
P1-7 12.14 38.26 32.65 1495 62.18 3.97 235.5 28.69 0.97 23670 332.2 2.878 170200 3.397
P1-8 14.41 42.21 35.42 1631 72.72 5.05 191.9 28.51 2.01 19940 380.3 3.567 107600 3.427
P1-9 18.18 73.31 49.53 2996 185.9 7.57 345.4 27.94 1.51 24520 471.9 4.635 62860 5.457
P2-1 14.63 27.97 30.19 1141 59.22 4.29 241.3 23.71 1.72 20170 371.5 3.143 138700 3.036
P2-2 11.9 22.93 25.04 879.8 47.36 3.31 217.6 21.98 1.58 19700 405.9 2.911 147300 2.771
P2-3 13.69 24.77 27.34 911.9 49.35 3.41 200.2 21.42 2.10 15760 718.6 3.155 99730 2.796
P2-4 14.85 28.67 31.92 1101 63.12 4.49 248.5 26.68 2.15 22720 576.8 3.247 113400 3.478
P2-5 12.86 26.51 33.28 1081 71.55 4.87 296.5 27.63 2.16 24310 318.3 3.22 108600 2.978
P2-6 14.32 25.95 25.58 1081 59.38 4.04 229.4 20.3 1.95 19360 356.8 2.807 145000 7.963
P2-7 17.97 31.36 34.62 1274 67.95 4.70 275.7 24.66 3.79 20440 639.3 3.297 40640 4.428
P2-8 12.82 28.03 34.07 1133 72.36 4.87 185.8 27.55 1.61 26230 293.8 3.718 150700 4.909
P2-9 16.17 32.35 43.41 1383 99.6 6.32 102.4 29.2 2.63 29090 355.7 5.164 29500 3.952
P2-10 11.45 27.49 29.77 1097 64.83 4.33 203.3 26.68 1.16 21410 252.6 2.941 152000 3.675
P3-1 10.96 26.30 23.98 1170 43.6 4.40 151.1 20.63 1.31 22060 311.9 2.514 137900 4.714
P3-2 11.08 20.00 22.55 809.5 39.01 3.67 130.3 18.5 1.36 16410 381.1 2.71 107400 3.293
P3-3 10.37 19.14 25.44 720.8 46.53 4.19 197.8 26.32 1.60 26770 586.8 3.296 98370 2.414
P3-4 10.24 21.27 23.64 925.1 38.89 3.86 164.2 18.49 1.36 18630 397.3 2.946 153600 4.101
P3-5 17.23 34.78 47.12 1595 84.48 7.94 112.8 31.05 3.15 39870 1211 4.62 16940 3.691
P3-6 16.47 42.08 37.4 1773 85.23 8.62 163.4 28.66 3.49 27320 1140 3.943 62390 3.823
P3-7 13.63 36.63 34.28 1594 80.64 8.06 176.9 26.24 2.91 27530 834.5 3.375 75510 3.689
P3-8 12.32 28.12 28.48 1233 49.3 4.97 175.8 26.1 1.36 23840 408.1 2.967 156900 8.576
P3-9 18.24 45.10 41.06 1843 91.1 9.55 196.2 24.74 2.55 28850 638.9 4.665 60200 8.342
P3-10 8.80 18.96 19.89 774.6 32.86 3.03 198.3 17.05 1.23 17490 386.1 2.282 65770 3.974
Correlation coefficient 0.62** 0.64** 0.74** 0.71** 0.75** 0.57** 0.52** 0.51** 0.47** 0.49** 0.46* 0.40* –0.38* 0
*
Numbers indicate values > the critical correlation coefficient at the 95% significance level.
**
Numbers indicate values > the significant correlation coefficient at the 99% significance level.

Table 3
P
Contents (%) of minerals in nineteen samples and correlation coefficients for minerals with REE.

Sample no. Montmo- Illite smectite mixed Illite Kaolinite Chlorite Quartz Feldspar Calcite Dolomite Siderite Pyrite Plaster
rillonite layers
P1-2 1.7 6.8 60 13.8 2.1 7.5 4.6 0.2 / 1.2 0.3 /
P1-3 3.6 12.6 17.8 16.3 1.7 25.8 1.9 / / / 18.0 /
P1-5 4.5 9.4 44.2 25.1 1.5 6.2 5.5 / / 1.7 / /
P1-6 2.5 8.3 64.6 13.9 1.9 4.2 2.8 0.3 / / / /
P1-7 2.4 7.8 6.1 56.5 2.3 10.8 7.9 / 0.3 2.9 1.2 /
P1-8 4.7 16.3 21.3 31.1 4.4 9.1 4.5 / / / 7.1 /
P2-2 4.6 17.6 31.7 20.5 / 8.5 2.6 0.6 10.3 0.3 4.9 /
P2-3 4.3 16.2 26.6 28.3 / 7.2 6.8 / 9.2 / 2.8 /
P2-5 3.4 10.3 39.4 20.3 2.1 10.5 7.1 / 4.7 0.6 3.2 /
P2-6 3.7 9.6 37.8 18.9 / 14.4 7.5 / / 1.2 7.7 /
P2-7 2.4 13.1 38.1 17.2 / 8.2 1.6 / 3.8 / 15.9 /
P2-9 2.1 12.5 66.4 12.3 / 4.5 2.1 / / / / /
P2-10 2.6 14.3 23.8 38.5 / 8.6 7.6 / 0.6 1.4 2.8 /
P3-1 6.2 11.8 3.5 32.5 3.1 16.6 12.8 / / 0.3 14.4 0.5
P3-2 6.7 11.6 2.8 37.5 5.8 15.3 12.3 0.6 4.1 / 4.3 /
P3-4 12.3 42.6 31.3 10.4 1.8 3.1 2.7 0.3 / / 0.5 0.3
P3-6 6.1 34.5 25.7 11.6 2.1 7.8 7.2 / / 1.3 2.7 0.4
P3-8 3.2 21.9 3.5 46.5 2.2 7.2 6.3 / / 4.7 1.9 /
P3-9 6.5 36.2 33.2 6.8 1.6 5.5 4.6 / / / 3.6 2.7
Correlation 0.09 0.14 0.20 0.06 0.06 0.52** 0.02 0.37* 0.11 0.22 0.26 0.05
coefficient
*
Numbers indicate values > the critical correlation coefficient at the 95% significance level.
**
Numbers indicate values > the significant correlation coefficient at the 99% significance level.

P
tion with kaolinite, montmorillonite, chlorite, quartz, calcite, dolo- condition. A negative correlation between REE and pyrite implies
mite and pyrite, and no correlation with feldspar and plaster. There that a strongly reducing condition mitigates the enrichment of
were no REE minerals and REE-containing minerals in our samples REEs and there is a presence of an organic phase within the con-
(Table 3), suggesting that the chief mode of occurrence of REEs is centration of REEs. The major minerals (illite and illite smectite
an inorganic phase. A positive correlation between siderite and mixed layers) and authigenic trace minerals (plaster) are positively
P P
REE, gives an indication of a weak reducing condition. In general, correlated with REE. The existence of these minerals signifies
the formation of siderite requires a relatively weak hydrodynamic that the alkaline, medium condition benefits the enrichment of
 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476 473

5.2. Provenance analysis of Lopingian mudstones

Among the indicators of sedimentary source regions, the distri-

Fig. 2. R-cluster analysis group structure of partial elements of mudstone.
REEs, due to the presence of a mass of K+, Na+, Mg2+ ions and the
alkaline environment of seawater, that are beneficial for the trans-
formation from kaolinite to illite and montmorillonite [28].
Although the correlation between illite and the illite smectite
P
mixed layers and REE is slightly positive, these minerals play
an important role in the concentration of REEs, owing to their ex-
tremely high contents.
bution pattern of REEs is the most reliable indicator [29]. The dis-
tribution patterns of REEs of entire samples are basically similar to
those of Emeishan basalt and NASC, but differ greatly from those of
seawater, pointing to the consistent provenance of REEs in differ-
ent layers of mudstone (Fig. 3a–c). The samples were largely found
in alkaline basalt areas, partly in granite areas and in sedimentary
P
rocks and alkaline basalt intersection areas as seen in the REE vs
La/Yb diagram (Fig. 3d) and concur with the inference of the corre-
lation analysis that REEs originate mainly from terrigenous clastic
minerals. In the early stage of Late Permian, the Dongwu resolution
caused extensive Emeishan basalt eruption of western Guizhou
[16]. If the parent rock is granite, the sedimentary rock will mostly
have a negative Eu anomaly and if the source rock is basalt, there
will be no Eu anomaly in sedimentary rock in most cases [29].
The Eu/Eu⁄ ratio of Emeishan basalt (1.38) is higher than the aver-
age Eu/Eu⁄ ratio of 1.16, suggesting the same inference that the
parent rock is basalt.
5.3. Application of REE parameters in the recognition of sequence
boundaries

5.1.2. Cluster analysis
P
Fig. 2 shows the R-cluster analysis between REE and the trace
P
elements which are clearly related to REE, such as Th, Nb, Ta, Ti,
Ga, Sc, Cs, Zr, Hf, Zn, Sr, Be and Fe. The lithophile elements Zr, Hf,
Ga, Nb, Th, Be, Ta, REEs, Sc and Ti are grouped together, above
the 0.646 correlation coefficient at 95% confidence level. These ele-
ments are related to rock-forming and clay minerals, providing
ample evidence for the inference that REEs of our samples are
mainly from terrigenous clastic minerals.
5.1.3. Occurrence of REEs
The correlation and cluster analyses between elements (REEs
and trace elements) and minerals show that REEs are mainly con-
centrated in clay minerals (illite and illite smectite mixed layers)
and siderite in an inorganic phase.
Through our analyses of REEs in mudstone layers on the se-
quence boundaries and nearby, we obtained the variation in verti-
cal content of the geochemical characteristics of REEs (Fig. 4) and
ascertain the abnormal surface characteristics of REEs, such as
P
REE, w(L/H), (La/Yb)N, Eu/Eu⁄ and Ceanom, agreeing, to some de-
gree, with the sequence boundaries (SB2, SB3, SB4). On this basis,
the rationality of the sequence division is confirmed. It is generally
considered that sequence boundaries are characterized by their
unconformity or corresponding conformity and is an episodic
product or an product acquired during sea-level changes [30].
The variations of REE characteristics are closely related to terres-
trial substances and Eh values (redox potential), as well as the pH
values of the medium. And the level deposits or sea-level changes
will inevitably lead to significant alteration of continental
substance provision, Eh and pH values. Combined with mineral

P1-1 P1-2 P1-3

(a) 10 P1-4 P1-5 P1-6 (b) 10 P2-1
P2-4
P2-2
P2-5
P2-3
P2-6
Samples (NASC)

Samples (NASC)

1 1

0.1 0.1
P2-7 P2-8 P2-9
P1-7 P1-8 P1-9
P2-10 Emeishan basalt Sea
Emeishan basalt Sea
0.01 0.01
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

P3-1 P3-2 P3-3

(c) 10 P3-4 P3-5 P3-6
Samples (NASC)

0.1

P3-7 P3-8 P3-9

P3-10 Emeishan basalt Sea
0.01
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

P
Fig. 3. REE distribution patterns of Lopingian mudstone (a–c) and REE vs La/Yb diagram (d, after Allegre et al. [36]).
474 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476

characteristics of partial samples (Table 3), we elucidated the con-

sistency between geological setting of surface variation in the char-
acteristics of REEs and the features of sequence boundaries,
because changes in the content of minerals may designate a shift
P
in media environments and REE. Furthermore, where the se-
quence boundaries had no mudstone, we will investigated the
characteristics of REEs of mudstone near the boundaries.

(1) SB2 (a region regression unconformity): the REE characteris-

(2) SB3 (an exposure unconformity, formed by weathering and
Fig. 4. Vertical content variations of geochemical characteristics of REEs.
tics of the Pan 2 well recorded an environmental mutation.
P
The values of REE, w(L/H), (La/Yb)N and Eu/Eu⁄ below the
boundary were reduced, in which the reduction of Eu/Eu⁄
is apparent, pointing to a rise of sea levels. These coincide
with the content reduction of kaolinite, quartz, feldspar
P
and the increasing content of illite. The rapid rise of REE,
⁄
w(L/H), (La/Yb)N and Eu/Eu and the reduction in Ceanom
indicate a sudden decrease in the sea level in P2-7 above
SB2. The increments of Eu/Eu⁄ ratios and the values debase-
ment of Ceanom suggests that the supply of terrigenous clast
grows and that the reducing conditions decrease from P1-8
P
to P1-7 of the Pan 1 well. The decline in values of REE,
w(L/H), (La/Yb)N from P1-8 to P1-7 may be related to the
pH of the medium. In other words, the infiltration and leach-
ing of an acid solution in argillaceous siltstone above P1-7
may lead to the decline in the values of REE parameters, as
verified by the variations in the content of clay minerals
(kaolinite, illite, illite smectite mixed layers). The changes
of REE parameters and the contents of minerals from P3-9
to P3-8 of the Pan 3 well are similar to those of the Pan 1
well. Moreover, the minerals of P3-9 include plaster, which
is immediate evidence for transgression [31]. The reason is
that the formation of plaster begins only when the thickness
of Ca2+, SO24 ions reaches saturation under the medium of
saline sea [31].
leaching of kaolinite mudstone and identified by a high
P
anomaly natural GR curve): the values of REE, w(L/H),
(La/Yb)N, Ceanom are all relatively low, even reaching almost
minimum. In addition, the Eu/Eu⁄ ratios display positive Eu
anomaly in P1-6 on SB3 of the Pan 1 well, suggesting low
enrichment of REEs and LREEs, a weakly reducing-weakly
oxidizing condition and a relatively abundant supply of ter-
rigenous clast. The low contents of marine elements Zn, Fe
suggest that the marine effects are weak. Furthermore, the
major mineral is illite (64.6%). From these features, we
determine that the sample P1-6 is paleosol. Generally, in tor-
rid zones, large precipitation, longtime weathering and
leaching easily lead to the loss of REEs and a reduction of
w(L/H) in kaolinite of the soil [32]. It shows that Guizhou
had a tropical-subtropical climate during Late Permian
[33–34]. Based on the geochemical characteristics and fea-
tures of minerals in P1-5, a new round of transgression
exists and its infiltration caused the transformation from
kaolinite to illite, montmorillonite, illite smectite mixed lay-
ers of P1-6. The anomaly of a natural GR curve is mostly
related to the rock forming element K and the radioactive
elements Th and U [35]. The sample concentrates Th and
illite (K<2(Al,Fe,Mg)4(Si,Al)8O20(OH)4
nH2O, enriching K+
ions), leading to a high anomaly of the natural GR curve.
The gradually rise of water levels and enhancement of
P
reduction conditions create the concentrations of REE,
w(L/H), (La/Yb)N in P1-5 above SB3. This explains why the
weakly reducing conditions and the relatively weak alkaline
medium conditions are favorable to the enrichment of REEs.
 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476
The past rises in sea levels have provided ample time for the
concentration of LREEs, because LREEs are easily absorbed
by clay minerals and are enriched in suspended matter
[32]. The Eu/Eu⁄ ratios increase continuously while, in con-
trast, the contents of pyrite and the values of Ceanom
decrease constantly from P2-7 to P2-5 below SB3 of the
Pan 2 well, indicating an increasing oxidizing condition
and a decline in sea level. In the Pan 3 well, the values of
P
REE, w(L/H), (La/Yb)N rose and those of Ceanom increased
rapidly. In contrast, the Eu/Eu⁄ ratios decreased considerably
from P3-7 on SB3 to P3-6, P3-5 above the boundary, suggest-
ing an ancient exposed surface and a new round of
transgressions above the interface. This shows that the
responses of the Pan 3 well are more obvious than those of
the Pan 1 well.
(3) SB4 (a regional transgression unconformity, characterized
P
by marine marker bed 4): the values of REE, w(L/H), (La/
Yb)N, Eu/Eu⁄ and Ceanom of P1-3 located 0.25 m above SB4
of the Pan 1 well, are relatively low, showing that the sea
level was high, since these parameters of the sea are very
P
poor [26]. In the Pan 2 well, the values of REE and w(L/
H) decreased and those of (La/Yb)N, Eu/Eu⁄ and Ceanom
increased from the bottom to the top of SB4, implying a
gradual enhancement of reducing conditions and the exis-
tence of transgression near the boundary. The variation in
the content of illite, pyrite, kaolinite and feldspar prove this
P Sci Front 2009;16(6):325–36 (In Chinese).
result. In contrast, the values of REE in the Pan 3 well
increased slightly, while those of w(L/H), (La/Yb)N, Eu/Eu⁄
declined by a small margin, showing a slow increase in sea
levels, matching the content features of illite, pyrite, kaolin-
ite and plaster.
6. Conclusions
P elements in coal. In: Swaine DJ, Goodarzi F, editors. Environmental aspects of
(1) The results of our study show that REE is high. The ratios
of w(LREE)/w(HREE) and w(La)N/w(Yb)N indicate a clear dif-
ferentiation between LREEs and HREEs. The distribution pat-
terns of REEs illustrate enrichment of LREEs. The Eu/Eu⁄
ratios range from 0.82 to 1.31, suggesting a negative Eu
anomaly to a positive Eu anomaly. The Ce/Ce⁄ ratios vary
from 0.83 to 0.93 (slightly negative Ce anomaly). The Ceanom
values (ranging from 0.07 to 0.02) imply a weakly reducing
media environment.
(2) RREE is significantly or critically positively correlated with
the lithophile elements Th, Nb, Ta, Ti, Ga, Sc, Cs, Zr, Hf, Sr,
Be and the chalcophile element Zn, critically negatively cor-
related with the siderophile element Fe and slightly posi-
tively correlated with illite, illite smectite mixed layers and
siderite. The mudstone samples show an absence of REE
minerals and REE-containing minerals, indicating that REEs
originate largely from terrigenous minerals and for a small
amount from marine sources. REEs are concentrated in illite,
illite smectite mixed layers and siderite in an absorbed state,
confirmed by the results of our cluster analysis. Under mar-
ine-terrigenous facies, the weakly reducing conditions and
relatively weak alkaline medium conditions, large amounts
of illite and illite smectite mixed layers are the major rea-
sons benefiting the enrichment of REEs in the Lopingian
mudstone. Source rocks of our samples consist largely of
Emeishan basalt and a small amount of sedimentary rocks,
as suggested by the distribution patterns of REEs and
P facies in southern Guizhou and their chronostratigraphic correlation.
w( REE)–w(La)/w(Yb) diagram.
P
(3) The abnormal surfaces of REE characteristics, such as REE,
⁄
w(L/H), (La/Yb)N, Eu/Eu and Ceanom, agree, to some degree,
with sequence boundaries (SB2, SB3, SB4) in mudstone layers
on the sequence boundaries and nearby. Combined with
475
mineral characteristics of partial samples close to the abnor-
mal surfaces, we have elucidated the consistency between
the geological setting of sudden variable surfaces on REE
characteristics and features of sequence boundaries. Due to
the complexity and multiplicity of REEs, our methodology
can serve as an auxiliary sign to discern sequence boundaries.
Acknowledgments
This study is supported by the Key Program of the National Nat-
ural Science Foundation of China (No. 40730422). We are grateful
to the anonymous reviewers for their valuable comments on the
manuscript.
References
[1] Bhatia MR. Rare earth element geochemistry of Australian Paleozoic
graywackes and mudrocks: provenance and tectonic control. Sed Geol
1985;45(1/2):97–113.
[2] Bhatia MR, Crook KAW. Trace element characteristics of graywackes and
tectonic setting discrimination of sedimentary basins. Contrib Mineral Petrol
1986;92(2):181–93.
[3] McLennan SM, Taylor SR. Sedimentary rocks and crustal evolution: tectonic
setting and secular trends. J Geol 1991;99(1):1–21.
[4] Condie KC. Another look at rare earth elements in shales. Geochim Cosmochim
Acta 1991;55:2527–31.
[5] Li LX, Li HM, Wang DH, Zhang CQ. Trace element and REE geochemistry and its
metallogenic significance for Cu–Zn deposits in the Tongbai area, Henan. Earth
[6] Li SJ, Xiao KH, Wo YJ, Long SX, Cai LG. REE geochemical characteristics and their
geological signification in Silurian, west of Hunan province and north of
Guizhou province. Geoscience 2008;22(2):273–80 (In Chinese).
[7] Taylor SR, McLennan SM. The Continental Crust: its Composition and
Evolution. Oxford: Blackwel; 1985.
[8] Zhang HC, Zhang WX, Chang FQ, Yang LQ, Lei GL, Yang MS, Pu Y, Lei YB.
Geochemical variation of rare earth elements in Lacustrine sediments: in a case
of Beiqiaodi section in Qaidam Basin. Sci Chin Earth Sci 2009;39(8):1160–8
(In Chinese).
[9] Finkelman RB. Modes of occurrence of environmentally-sensitive trace
trace elements in coal. Dordrecht: Kluwer Academic Publishers; 1995. p. 24–50.
[10] Li DH, Tang YG, Chen K, Deng T, Cheng FP, Liu D. Concentration, distribution,
and occurrence of REEs in coals from Chongqing, Southwest China. J Chin Univ
Min Technol 2005;15(3):227–32.
[11] Wang WF, Qin Y, Song DY. Geochemical features of hazardous elements and
cleaning potential of coal from Xinzhouyao Coal Mine. J Chin Univer Min
Technol 2002;31(3):281–4 (In Chinese).
[12] Wang WF, Qin Y, Song DY, Sang SX, Jiang B, Zhu YM, Fu XH. Element
geochemistry and washing–cleaning potential of the No. 11 coal seam from
the Antaibao mining district, China. Sci Chin Earth Sci 2005;35(10):963–72 (In
Chinese).
[13] Ji YL, Hu SM, Zhang SW. Mineralogical and geochemical methods in study of
sedimentary sequence boundary. J Tongji Univ 2003;32(4):455–60 (In
Chinese).
[14] Zhang LQ, Luo XR, He DF, Liu LJ, Jia JD. Sequence boundaries of the lower
Cretaceous, Southern Junggar Basin. Acta Sedimentol Sinica
2004;22(4):636–42 (In Chinese).
[15] Zhao JQ, Ji YL, Zhang SW. Application of geochemical methods in the
recognition of High-Resolution sequence boundary. Oil Gas Geol
2003;24(3):264–8 (In Chinese).
[16] Xu BB, He MD. Guizhou Coal Geology. Xuzhou: China University of Mining and
Technology Press; 2003 (In Chinese).
[17] Wang HZ, Shi XY, Wang XL. Sequence Stratigraphy of
China. Guangdong: Guangdong Science and Technology Publishing House
Press; 2000 (In Chinese).
[18] Chen HD, Wang CS, Liu WJ, Tan JX. Permian sequence stratigraphy and basin
evolution in south of China. Acta Sedimentol Sinica 1999;17(4):529–35 (In
Chinese).
[19] Deng HY, Shou JF. Sequence characteristics of Permian in southern China. Mar
Pet Geol 1999;4(2):9–15 (In Chinese).
[20] Mei MX, Zheng KB, Chu HM, Deng J, Li H. Sequence stratigraphic framework
and palaeogeographical evolution of the Permian of Dian-Qian-Gui Basin and
its adjacent areas. J Palaeogeogr 2004;6(4):401–18 (In Chinese).
[21] Shi XY, Mei SL, Sun Y, Li B, Sun KQ. Permian sequence successions of slope
Geoscience 1999;13(1):1–10 (In Chinese).
[22] Wang CS, Li XH, Chen HD, Tan JX. Permian sea-level changes and rising-falling
events in south China. Acta Sedimentol Sinica 1999;17(4):536–41 (In Chinese).
[23] Wang LT, Lu YB, Zhao SJ, Luo JH. Lithofacies Palaeogeography and
Mineralization of Permian in Southern China. Beijing: Geological Publishing
House; 1994. p. 1–138 (In Chinese).
476 Y. Shao et al. / Mining Science and Technology (China) 21 (2011) 469–476
[24] Haskin LA, Haskin MA, Frey FA, Wilderman TR. Relative and absolute
terrestrial abundances of the rare earths. In: Ahrens LH, editor. Origin and
distribution of the elements. Oxford: Pergamon; 1968. p. 889–912.
[25] Mao DM, Zhang QH, An SR. Emeishan Basalts in Western Guizhou Province and
its Mineral. Guiyang: Guizhou Science and Technology Press; 1992. p. 24 (In
Chinese).
[26] Zhao YY, Wang JS, Qin ZY, Chen YW, Wang XJ, Wu MQ. Rare earth elements in
marine sedimentary of continental shelf, China. Acta Sedimentol Sinica
1990;8(1):37 (In Chinese).
[27] Elderfield H, Greaves MJ. The rare earth elements in seawater. Nature
1982;296(18):214–9.
[28] Zeng YF, Xia WJ. Sedimentary Petrology. Beijing: Geological Publishing House;
1989 (In Chinese).
[29] Liu YJ, Cao LM. Elements Geochemistry. Science Press: Beijing; 1984. p. 324–
343 (In Chinese).
[30] van Wagoner JC, Posamentier HW, Mitchum RM. An overview of the
fundamentals of sequence stratigraphy and definitions. In: Wilgus CK,
Hastings BS, StKendall CG, Posamentier HW, Ross CA, van Wagoner JC,
editors. Sealevel changes: an integrated approach. Tulsa: Society
of Economic Paleontologists and Mineralogists Special Publication; 1988. p.
39–45.
[31] Liu HJ, Sang SX, Shi J. Comparative Sedimentology of Coal-forming
environments: in a case of tidal-flat and peat mangrove. Xuzhou: China
University of Mining and Technology Press; 1997 (In Chinese).
[32] Wang ZG, Yu XY, Zhao ZH. Rare Earth Element Geochemistry. Beijing: Science
Press; 1989 (In Chinese).
[33] Guo YY. Paleoclimate of late Permian, western Guizhou. Coal Geol Chin
1990;2(3):18–20 (In Chinese).
[34] Nan JY, Ye JL, Wang ZM, Zhou DQ. Geochemistry of paleoclimate and paleo-
ocean environment during Permian-Triassic in Guizhou Province. Acta
Mineralogica Sinica 1998;18(2):239–49 (In Chinese).
[35] Li Q. The Radioactive Anomaly in the Deep Strata and its Impacts on Source
Rocks’ Evolvement in Southwest Ordos Basin. Xian: Northwestern University;
2007 (In Chinese).
[36] Allegre CJ, Minster JF. Quantitative models of trace element behavior in
magmatic processes. Earth Planet Sci Lett 1978;38:1–25.