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Original article

Release of heavy metals during
weathering of the Lower Cambrian
Black Shales in western Hunan,
China
Bo Peng Æ Zhaoliang Song Æ Xiangling Tu Æ Meilian Xiao Æ Fucheng Wu Æ Huanzhe Lv

Abstract Weathering of heavy metal enriched black
shales may be one of the most important sources of
environmental contamination in areas where black
shales are distributed. Heavy metal release during
weathering of the Lower Cambrian Black Shales
(LCBS) in western Hunan, China, was investigated
using traditional geochemical methods and the ICPMS analytical technique. Concentrations of 16 heavy
metals, 8 trace elements and P were measured for
samples from selected weathering profiles at the
Taiping vanadium ore mine (TP), the Matian
phosphorous ore mine (MT), and Taojiang stonecoal mine (TJ). The results show that the bedrock at
these three profiles is enriched with Sc, V, Cr, Co, Ni,
Cu, Zn, Pb, Th, U, Mo, Cd, Sb, Tl, and P. Based on
mass-balance calculation, the percentages of heavy
metals released (in % loss) relative to immobile
element Nb were estimated. The results show
significant rates of release during weathering of: V,
Cr, Co, Ni, Cu, Zn, U, Mo, Cd, Sn, Sb, and Tl for the
TP profile; Sc, Cr, Mn, Co, Ni, Cu, Zn, Pb, Th, Cd,
and Sn for the MT profile; and Sc, Mn, Co, Ni, Zn,
Th, Cd, Sn, and Tl for the TJ profile. Among these
heavy metals, Co, Ni, Zn, Cd, and Sn show very
similar features of release from each of the three
weathering profiles. The heavy metals released

Received: 30 September 2003 / Accepted: 5 January 2004
Published online: 24 February 2004 
Springer-Verlag 2004
B. Peng (&) Æ F. Wu Æ H. Lv
Faculty of Natural Resource and Environmental Sciences,
Hunan Normal University, 410081 Changsha, China
E-mail: pengbo@hunnu.edu.cn
Tel.: +86-731-8912652
Fax: +86-731-8872119
Z. Song Æ X. Tu
Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, 510640 Guangzhou, China
M. Xiao
The 3rd Xiangya Hospital, Central-South University,
410013 Changsha, China

during weathering may affect the environment
(especially topsoil and surface waters) and are
possibly related to an observed high incidence of
endemic diseases in the area.
Keywords Heavy metals Æ Weathering Æ
Release Æ The Lower Cambrian Black Shales Æ
Western Hunan Æ China

Introduction
Black shales are of great ecological significance due to the
high concentration of heavy metals that are released during weathering. Heavy metals constitute one of the most
insidious and dangerous pollutions known to humans
(Akpan and others 2002) because they are toxic (e.g. carcinogenic), non-biodegradable, and may enter the global
ecobiological cycle (Nurnberg 1984; Lakhan and others
2002). In the past, heavy metal contamination in aquatic
environments and agriculture topsoils has been attributed
to industrial wastes (Huy and others 2003), mining
extractions (Marszalek and Wasik 2000; Dogan 2002), and
pollution from traffic vehicles (Fakayode and Olu-Owolabi
2003). Only a few studies have focused on the possibility of
heavy metal contamination from rock weathering,
especially black shale weathering. Human activities, such
as mining and road construction in developing countries,
have accelerated rock weathering physically and chemically. Weathering of heavy metal enriched black shales
may be one of the most important sources of environmental contamination in areas where black shales are
distributed.
It has been recognized that the incidence of cancer and
many other diseases is higher in western Hunan than in
other parts of the province. Environmental geologists
(e.g. Tong 1990; Li 1991) have suggested that these diseases, referred to as endemics, are possibly related to the
geological environment, and especially to the mining
activities popularized in the area since 1980. In a comparison of the geological distribution of black shales and
the geographical incidence of the endemics in Hunan, the
authors noticed that the prevalence of endemics seems to

DOI 10.1007/s00254-004-0974-7 Environmental Geology (2004) 45:1137–1147

1137

Original article

be higher where black shales are abundant. There are
many other factors that may impact on the endemics, but
environmental contamination by heavy metals emitted
from ore extractions and rock weathering is suggested to
be one of the most serious.
The mobility of major and trace elements related to
chemical changes during weathering has been documented by many researchers (Nesbitt 1979; Chesworth
and others 1981; Voicu and Bardoux 2002). Although
the mobility of Re, platinum group elements and organic
matter during black shale weathering has been studied
(Petsch and others 2000; Peucker-Ehrenbrink and
Hannigan 2000; Jaffe and others 2002), there is a paucity
of research on the release of potentially toxic heavy
metals (Nora and others 2002; Coveney and Tao 2001;
Loukola-Ruskeeniemi and others 2003). In this study,
the authors investigated the issue using examples from
the Lower Cambrian Black Shales (LCBS) of western
Hunan, China. It is not possible at this time to document clearly the relationship between the high incidence
of endemics in western Hunan province and heavy metal
contamination by release from black shale weathering.
However, understanding the heavy metal release during
LCBS weathering has set a basis for further study on the

pathology of endemics, and this constituted the major
purpose of the study.

Materials and methods
LCBS weathering profiles were selected at three different
open-pit faces for surveying and sampling in this study.
The profiles are the Taiping (TP) profile at Taiping
vanadium ore mine, 50 km southeast of Anhua county
town; the Matian (MT) profile at Matian phosphorous ore
mine, 10 km west of Nixiang county town; and the Taojiang (TJ) profile at a stone-coal mine, 20 km south of
Taojiang county town. The profile locations and LCBS
distribution in western Hunan are shown in Fig. 1. The
climatic conditions in the study area are favorable for
chemical weathering, with annual average minimum and
maximum temperatures of 16 and 30 C, respectively, and
average annual rainfall of approximately 1.6 m.
The bedrock of the profiles is carbonaceous black shales of
the Lower Cambrian, which can be distinguished in the
field by fresh surfaces with no oxidized minerals. The
degree of weathering can be classified into ‘‘incipient’’,

Fig. 1
Geological sketch of the locations
of profiles and samples. TP, and
MT represent the Taiping, and
Matian weathering profile,
respectively; see Table 1 for
sample description; the distribution map is a diagrammatic
sketch

1138

Environmental Geology (2004) 45:1137–1147

TH0

TH2, TH1

TH4

>1.0

1.6

MT0

MT1, MT2

1.2
MT6, MT5, MT4

1.1
1.0+1.0+0.8
MT3

B1

B10, B11

1.0

0.35
B6

0.5+1.2+1.3

0.3
B4
B7

B9

1.0+1.0

1.5

1.5

>1.0
Bedrock

Characteristics

Discoloration, losse and texture disappeared
Sulfide oxidized, and color washed-out, hardness and texture completely changed
Sulfide oxidized, color washed-out, hardness
and texture start to change
Sulfide oxidized, color changed, but hardness
and texture not changed
Sulfide oxidized, color and hardness and texture not changed
Carbonaceous black shales
Incipient

where X is the heavy metal of interest, Nb is a reference
element in the sample, and the Weathered and Bedrock are
the values of weathered LCBS and the corresponding
bedrock. If EF1, the heavy metal of interest, X , was at

Weak

ð1Þ

Moderate

EF ¼ ðX=NbÞWeathered =ðX=NbÞBedrock

Degree of
weathering

The concentrations of 16 heavy metals, some trace elements, and P, were obtained in fresh and weathered LCBS
for the three profiles. The data are compared to average
black shales in Tables 2, 3, 4. The selected weathering
profiles are less than 15 m in length along strike, and the
lithology of unweathered (fresh) LCBS are similar. Samples
from the fresh bedrock are representative of the original
(unweathered/fresh) LCBS from corresponding profiles.
Compared to average black shales (Mason and Moore
1982), fresh LCBS in these areas show a pronounced
enrichment in Sc, V, Cr, Co, Ni, Cu, Zn, Pb, Th, U, Mo, Cd,
Sb, Tl, and P. This observation agrees well with many
previous studies (Fan 1973, 1983; Sun 1986; Coveney and
Chen 1991).
Assessment of heavy metal concentration in weathered
LCBS samples from three profiles was carried out by the
enrichment factor (EF; IAEA-TCS-4, 1992):

Table 1
Description of weathering profiles and samples

Distribution of heavy metals

Soil
Intense

Thickness
(m)

Results and discussion

0.8
1.2

TP

Sample

Thickness
(m)

MT

Sample

Thickness (m)

TJ

Sample

‘‘weak’’, ‘‘moderate’’, ‘‘intense’’ and ‘‘topsoil’’ (or ‘‘complete weathering’’) on the basis of color, hardness, loss of
texture and discoloration of organic matter and sulfides.
The weathering characteristics of the three profiles are
summarized in Table 1. About 1.5 kg samples of fresh and
weathered rocks with different weathering degrees were
taken from each profile in October 2001. For the TP profile, six samples were selected from a number of samples
taken from an open-pit face at Taiping vanadium ore
mine. Sample locations on each profile are shown in Fig. 1
(TP and MT), and Fig. 2 (photograph).
Six soil and seven surface water samples were also
collected from places near the TJ profile at Taojiang
stone-coal mine. Each one-liter water sample was collected
from surface water flowing through the exposed LCBS
about two weeks after rain. The samples, collected in clean
plastic bottles, were analyzed using an ICP-MS immediately after collection.
Rock and soil samples were powdered in an Alceramic
shatter box after drying at 120 C for 3 h. All analytical
data were reported on a dry sediment basis. About 50 mg
of powder from each sample was dissolved using HF +
HNO3 solution in a disposable platinum crucible so as to
oxide the organic matter. The dissolved sample was then
diluted using 2% HNO3, and a large number of elements
were analyzed at a wide range of concentrations with high
accuracy using an Elan6000 ICP-MS machine at Guangzhou Institute of Geochemistry, Chinese Academy of Science. (Note that only heavy metals and some trace
elements are included in this paper.)

TH3
TH7, TH6, TH5

Original article

Environmental Geology (2004) 45:1137–1147

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Original article

Fig. 2
A photograph of the TJ weathering profile and sample location. The
profile trends north–south, and the photograph was taken eastward

a background level, whereas EF>1, means that the heavy
metal of interest could be enriched, and EF<1, depleted.
All EF values of the weathered LCBS from three profiles are
shown in Tables 5, 6, 7. It can be seen that most heavy
metals are pronouncedly redistributed across the three

Table 2
Heavy metal and trace element concentrationsa (ppm) of weathered and unweathered LCBS from the TP profile compared with average
shales (AS)
Site

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
P
Nb/Ta
Zr/Rb
Th/U
(Zr+Rb)/Sr
Ga/Ge
a

B1

B10

B11

B6

B9

B7

B4

6.801 (5.8)
1951.7 (4.2)
152.5 (4.2)
25.0 (3.4)
30.51 (5.8)
316.1 (3.6)
306.7 (3.8)
867.6 (4.7)
34.85 (5.4)
4.77 (6.7)
95.55 (3.0)
176.6 (4.4)
11.09 (11.2)
6.545 (9)
94.27 (17.3)
5.306 (4.1)
7.822 (3.6)
1.07 (8.9)
40.95 (3.9)
89.18 (6.0)
147.7 (3.9)
7.269 (1.7)
0.463 (5.7)
4.334 (1.6)
1332.3 (3.8)
15.69
3.61
0.05
2.12
7.31

15.3 (3)
12329.6 (1.5)
1193.4 (2.3)
20.25 (1.6)
11.23 (2.5)
206.6 (1.1)
303.9 (2.1)
103.9 (2.9)
147.9 (1)
13.43 (2.5)
97.38 (1.7)
106.9 (1.3)
2.33 (4.3)
10.94 (1.9)
128.5 (18.1)
3.37 (1.3)
28.79 (2.2)
6.584 (4)
111.4 (1.2)
163.1 (2.7)
123.2 (1.4)
13.25 (2.8)
1.268 (3)
4.057 (3)
2612.4 (3.7)
10.45
1.10
0.14
1.44
4.37

11.05 (3.8)
3063.4 (2.7)
188.7 (3.9)
18.0 (2.5)
36.98 (4.5)
176.9 (1.5)
291.4 (3.2)
71.57 (2.8)
59.96 (4.1)
8.0 (2.4)
35.49 (3)
82.78 (1.9)
0.695 (4.9)
5.251 (6.5)
178.5 (11.4)
3.575 (2.4)
10.69 (3.8)
1.169 (2.6)
71.03 (2.5)
67.23 (3.2)
137.3 (2.6)
11.66 (3.3)
0.913 (2.2)
3.326 (5.6)
511.1 (2.9)
12.77
1.93
0.23
3.10
9.14

12.84 (2.5)
753.2 (1.9)
79.61 (2.8)
11.8 (2.3)
8.608 (2.5)
23.68 (3.4)
33.66 (1.6)
16.09 (9.3)
21.79 (2.9)
11.23 (3)
13.35 (1.7)
40.29 (2.6)
0.06 (17.4)
11.21 (1)
154.2 (4)
2.52 (1.8)
20.22 (1.9)
1.849 (2.6)
134.2 (3.4)
12.59 (3.8)
123.6 (2.7)
15.34 (3)
1.343 (4)
3.921 (2.1)
62.46 (11.9)
11.42
0.92
0.84
20.48
10.94

19.11 (1.4)
3095.4 (1.9)
901.2 (1.6)
79.82 (1.8)
6.439 3.3)
10.43 (2.4)
105.5 (2.9)
122.3 (2.1)
407.0 (2)
10.68 (3.4)
38.47 (2.8)
139.8 (1.9)
1.955 (6)
3.0 (2.5)
95.7 (1.5)
7.349 (1)
13.42 (2.8)
3.646 (1)
81.85 (2)
519.3 (4)
125.2 (3.6)
16.23 (0.6)
1.331 (5)
3.772 (2)
13720.3 (1.9)
12.19
1.53
0.28
0.40
3.68

13.21 (2.6)
108.9 (2.4)
59.92 (4)
658.3 (3)
44.56 (4.2)
109.8 (4.6)
95.22 (2.5)
52.84 (4.3)
34.04 (1.7)
10.98 (3.2)
9.682 (1.8)
19.39 (2.9)
0.244 (7.4)
6.80 8 (2.5)
68.97 (3.2)
1.579 (3)
15.41 (2.7)
1.28 (6)
105.0 (7.5)
8.533 (4.9)
75.12 (1.2)
9.138 (2.6)
0.948 (3.6)
2.094 (2.3)
867.0 (1.2)
9.64
0.72
1.13
21.11
12.04

17.26 (3.4)
99.75 (3.4)
85.19 (2.5)
603.0 (2)
48.75 (3.5)
24.78 (2.3)
52.7 (2.8)
73.08 (2.3)
15.75 (2)
20.46 (1.9)
3.62 (3.1)
1.374 (5.5)
1.459 (5.8)
9.359 (3)
39.3 (1.5)
1.046 (3.9)
24.11 (2.2)
1.788 (3.9)
191.1 (2)
16.01 (2.3)
94.78 (1.6)
14.04 (2.3)
1.419 (4.4)
2.536 (3.4)
182.8 (7)
9.89
0.50
5.65
17.86
13.48

Average value of 7 analyzing results with deviation in percentage listed in parantheses
After Mason and Moore (1982)

b

1140

ASb

TP profile

Environmental Geology (2004) 45:1137–1147

13
130
90
850
19
68
45
95
20
12
3.7
2.6
0.3
6.0
1.5
1.0
19
1.6
140
300
160
11
0.8
2.8
700
13.75
0.08
1.4
1
11.88

Original article

Table 3
Heavy metal and trace element concentrationsa (ppm) of weathered and unweathered LCBS from the MT profile compared with average shales
(AS)
Site

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
P
Nb/Ta
Zr/Rb
Th/U
(Zr+Rb)/Sr
Ga/Ge
a

TP profile
MT0

MT1

MT2

MT3

MT4

MT5

MT6

58.64 (3)
343.9 (3.2)
217.7 (3.1)
120.2 (1.9)
32.37 (2.8)
52.64 (2.3)
182.6 (3.6)
69.21 (4.7)
184.1 (2.1)
54.65 (3.2)
16.8 (2.7)
2.316 (6)
0.451 (14)
24.26 (3.4)
7.374 (6.3)
0.451 (3.5)
44.89 (3.4)
2.726 (3.7)
54.44 (3.4)
96.5 (3.7)
358.3 (5.3)
30.81 (2.4)
3.01 (3.5)
9.989 (2.2)
997.9 (1.8)
10.24
6.58
3.25
4.28
16.47

15.09 (2.9)
223.7 (2.8)
86.46 (2.2)
19.21 (1.9)
4.934 (4)
28.7 (1.4)
22.13 (2.8)
16.04 (11.3)
38.45 (2.8)
22.5 (1.7)
13.8 (2.3)
13.815 (2.6)
0.04 (1.5)
12. 468 (4.2)
7.942 (5.5)
2.063 (1.9)
18.98 (2.8)
1.591 (3.2)
129.2 (1.3)
260.9 (2.5)
127.2 (12.7)
17.5 (1.4)
1.55 (5)
4.038 (2.8)
999.99 (2.8)
13.75
0.08
1.4
1
11.88

14.57 (2.4)
200.4 (1.7)
86.97 (3.9)
14.97 (2.1)
5.729 (2.4)
22.88 (3.3)
39.75 (3.3)
9.261 (9.1)
48.72 (1.8)
22.76 (3.8)
22.25 (2.5)
17.31 (1.6)
0.027 (2.8)
10.680 (4.5)
7.713 (3.4)
2.092 (3)
22.62 (2.7)
1.588 (5.9)
126.3 (2.9)
113.0 (5.5)
125.6 (1.5)
17.04 (3.9)
1.521 (3.8)
3.301 (4.5)
546.4 (3.1)
11.20
0.99
1.02
2.23
14.24

16.55 (3.8)
193.2 (2.5)
83.83 (3.4)
13.95 (1.5)
2.161 (4.2)
17.95 (3.3)
21.57 (3.2)
10.64 (15.9)
23.28 (2)
19.36 (4.2)
21.71 (2.4)
17.9 (3.1)
0.021 (2.3)
8.323 (1.5)
9.817 (5.2)
1.235 (3.9)
19.36 (2.9)
1.578 (4.5)
111.8(2.8)
124.1 (3.5)
90.63 (1.5)
13.79 (3.9)
1.211 (4.2)
2.724 (2)
1,849.1 (3.2)
11.39
0.81
0.89
1.63
12.27

14.29 (3.1)
208.0 (2.4)
100.2 (14.8)
11.96 (1.6)
2.828 (5.2)
11.32 (4.9)
38.92 (2.9)
12.28 (5.9)
38.73 (3.3)
20.87 (4.1)
18.04 (1.8)
16.38 (2.5)
0.035 (3.8)
10.04 (2.5)
7.809 (4.3)
1.094 (2.6)
21.13 (1.4)
1.992 (3)
101.8 (2.6)
101.2 (3.2)
112.2 (1.5)
15.55 (2.9)
1.38 (3.6)
3.26 (5.5)
1,334.2 (4.9)
11.27
1.1
1.16
2.11
10.61

23.98 (2.1)
251.8 (1.5)
130.8 (3.1)
21.47 (1.9)
4.262 (4)
24.53 (4.2)
68.34 (2.8)
36.41 (6)
6.989 (3)
29.67 (4.2)
12.13 (1.4)
4.746 (4)
0.017 (7.8)
13.220 (5.3)
7.161 (2.6)
1.607 (2.2)
23.92 (1.4)
2.349 (4.4)
140.6 (3.2)
125.0 (3.2)
136.0 (1.3)
20.680 (1.9)
1.742 (0.8)
3.678 (3.1)
658.0 (4.6)
11.87
0.97
2.45
2.21
10.18

28.38 (3.3)
182.7 (4.2)
97.08 (3.3)
15.66 (4.9)
1.966 (4)
17.75 (4.8)
75.74 (2.9)
12.23 (18)
18.01 (4.6)
23.78 (3.3)
15.63 (4.3)
7.095 (4.2)
0.077 (6.4)
9.048 (4)
5.891 (8)
1.253 (5.2)
19.84 (3.2)
2.061(3)
112.7 (3.4)
68.23 (2.4)
90.85 (1.3)
15.51 (2.2)
1.303 (3.2)
2.642 (4.6)
2,312.6 (4.9)
11.93
0.81
1.52
2.98
9.63

Average value of 7 analyzing results with deviation in percentage listed in parantheses

weathering profiles except Sc and Th for the TP profile, V
and U for the MT profile, and Sc for the TJ profile (Table 7,
with EF values around 1). This element redistribution
leads to metals being either enriched or depleted in
weathered LCBS. For the TP profile (Table 5), heavy metal
redistribution is characterized by depletion of Co, Ni, Cu,
Zn, U, Mo, Cd, Sn, Sb, and Tl in weathered samples, with
Ni, Zn, U, Cd, and Tl strongly depleted. Heavy metal
redistribution along the MT profile (Table 6) is characterized by enrichment and depletion. The enriched metals
include Mo (EF>3), Sb (EF>1.4), and Tl (EF>4.8), and the
distinctly depleted metals are Sc, Cr, Mn, Co, Ni, Cu, Zn,
Pb, Th, Cd, and Sn, among which the EF values of Cu, Zn,
Pb, and Cd, are less than 0.5. The metal redistribution
along the TJ profile (Table 7) is also characterized by
enrichment and depletion. Heavy metals V, Cr, Cu, Pb, U,
Mo, and Sb, are enriched in weathered samples (EF values
of these metals are higher than 2 with the highest up to 19
for V), while Mn, Co, Ni, Zn, Th, Cd, Sn, and Tl are pronouncedly depleted (EF values of Co, Ni, Zn, and Cd are
less than 0.5).
The redistribution of trace elements across the three
profiles is very complicated. The EF values of elements Ga,
Ge, Rb, Sr, Zr, and Hf vary considerably, and the ratios of
Zr/Rb, (Zr+Rb)/Sr, and Ga/Ge (Tables 2, 3, 4) change in
wide ranges. However, compared to other trace elements,

elements Nb and Ta show relatively less mobility and are
possibly not redistributed during weathering. Nb/Ta ratios
of all analyzed samples are constantly around 11 for the TP
and MT profiles (Tables 2 ,3), and 14 for the TJ profile
(Table 4). Meanwhile, the EF values of Ta are relatively
constant around 1.4, 0.9, and 0.8, for the TP (Table 5), MT
(Table 6), and TJ profiles (Table 7), respectively. Nb and
Ta were therefore chosen as reference elements for mass
balance calculations. Redistribution of P is also distinct
across the three profiles, with EF values varying considerably.
It is clear that metals Co, Ni, Zn, and Cd are consistently
depleted in all weathered LCBS samples from the three
profiles. There are no linear relationships for concentrations of Co vs. Ni, and Cd vs. Zn, indicating that the
behaviors of these metals during weathering are probably
controlled by or related to different phases.
Heavy metal release
Heavy metal release during weathering of LCBS can be
estimated through mass-balance calculations. The percentage of metals released during weathering (% loss) can
be calculated relative to the mass of an immobile index
element, assuming that the total inventory of the index
element on each weathering profile does not change

Environmental Geology (2004) 45:1137–1147

1141

Original article

Table 4
Heavy metal and trace element concentrationsa (ppm) of weathered and unweathered LCBS from the TJ profile compared with average shales
(AS)
Site

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
P
Nb/Ta
Zr/Rb
Th/U
(Zr+Rb)/Sr
Ga/Ge
a

TJ profile
TH0

TH1

TH2

TH3

TH4

TH5

TH6

TH7

16.15 (3.6)
761.3 (3.8)
94.31 (4.7)
456.9 (3.3)
29.49 (4.3)
168.1 (4.1)
151.9 (3.8)
397.2 (3.9)
39.9 (3.8)
25.7 (5.7)
26.7 (2.4)
28.79 (2.1)
3.244 (3)
10.406 (2)
11.424 (5)
2.182 (4)
23.56 (3.1)
1.362 (3)
200.3 (1.7)
102.1 (3)
95.67 (3)
17.99 (2.8)
1.697 (4)
2.882 (3)
655.4 (6)
10.60
0.48
0.96
2.90
17.30

5.987 (3)
3879.0 (4.6)
322.6 (2.3)
25.79 (4)
4.294 (5)
7.288 (4)
256.9 (3.3)
4.669 (5)
51.26 (3)
4.268 (2)
40.23 (2)
29.23 (1.4)
0.139 (11)
2.372 (4)
24.2 (4.4)
0.684 (4)
11.6 (4.5)
1.4 (5.6)
39.05 (3.9)
20.35 (4.9)
74.09 (4)
5.395 (3)
0.288 (5)
1.819 (4)
650.1 (7.9)
18.73
0.53
0.11
5.56
8.29

5.243 (2)
1059.7 (2.6)
96.9 (3.5)
60.42 (2.4)
0.607 (8)
2.962 (5)
189.4 (3.6)
11.46 (5.9)
49.04 (3.1)
5.227 (2)
131.8 (2.4)
20.25 (3.4)
0.224 (10)
2.347 (6.2)
31.72 (64.4)
0.345 (7.5)
7.982 (2.2)
1.309 (4.2)
28.45 (4)
24.47 (3.7)
172.7 (3.5)
8.847 (2.6)
0.362 (6.4)
4.545 (3.2)
463.7 (3.9)
24.44
6.07
0.04
8.22
6.10

11.09 (4)
8659.9 (1.4)
643.6 (6.1)
11.6 (1.7)
0.764 (4)
1.315 (2)
414.0 (3.9)
29.5 (5.4)
78.0 (3)
7.449 (3)
62.73 (2)
39.84 (2.2)
0.172 (6)
3.696 (4)
73.29 (3.9)
1.223 (3)
18.57 (2.3)
1.405 (3)
73.61 (1.7)
154.9 (1.3)
161.7 (2.7)
10.75 (2)
0.735 (5)
3.714 (3)
1410.4 (3.3)
14.63
2.20
0.12
1.52
13.22

16.38 (4)
18180.7 (1.5)
2064.9 (3.8)
119.4 (2)
5.942 (4)
8.148 (3)
121.5 (2.5)
31.85 (7.3)
110.0 (2.7)
22.78 (3.4)
57.75 (3.3)
66.16 (1.4)
0.365 (5)
12.78 (2.6)
200.15 (9.8)
2.868 (4)
31.76 (2)
1.411 (3)
176.2 (2)
32.22 (2.4)
219.2 (1.2)
22.42 (2.7)
2.061 (4)
5.689 (3)
750.2 (4.9)
10.88
1.24
0.39
12.27
22.51

10.02 (3.6)
1544.1 (1.8)
389.7 (3.8)
275.1 (2.4)
13.73 (3)
57.03 (2.9)
784.2 (3.8)
130.3 (3.8)
55.16 (3.9)
9.11 (2.2)
63.18 (2.3)
84.39 (2)
0.182 (6)
6.509 (3)
144.07 (3.3)
0.692 (2)
11.28 (2)
1.332 (4)
56.16 (2)
169.1 (2.5)
167.2 (2.5)
12.24 (1.4)
0.848 (3)
4.165 (5)
3355.4 (3.9)
14.43
2.98
0.14
1.32
8.47

29.73 (3.6)
3513.1 (3.1)
487.8 (4.7)
155.9 (3.6)
11.69 (5)
142.0 (4.8)
329.1 (5.1)
80.51 (5.9)
51.98 (3.7)
17.05 (4)
270.1 (3.4)
95.85 (1.7)
0.612 (7)
9.446 (4)
353.76 (11)
1.449 (6)
24.82 (4.2)
1.71 (4)
107.8 (3.5)
49.9 (5)
320.9 (1.1)
12.94 (3.8)
1.393 (4)
8.127 (2)
12636 (3)
9.29
2.98
0.06
8.59
14.51

11.58 (2.9)
2855.7 (2.3)
334.1 (3.5)
357.3 (2.4)
8.147 (2)
30.73 (3.9)
92.01 (0.8)
66.91 (4.8)
59.5 (2.2)
14.73 (3.3)
48.09 (3)
37.53 (2.9)
0.558 (8)
7.758 (4)
85.870 (2)
1.136 (5)
17.63 (2.1)
1.403 (3)
95.15 (1.9)
74.44 (2.2)
124.3 (2.1)
17.41 (2.5)
1.459 (1)
2.975 (4)
916.9 (3.7)
11.93
1.31
0.31
2.95
12.57

Average value of 7 analyzing results with deviation in percentage listed in parentheses

Table 5
Enrichment factor (EF) of heavy
metals and trace elements in
weathered samples from the TP
profile

1142

Site

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
P

Environmental Geology (2004) 45:1137–1147

TP profile
B10

B11

B6

B9

B7

B4

1.23
3.47
4.29
0.44
0.20
0.36
0.54
0.07
2.33
1.54
0.56
0.33
0.12
0.92
0.75
0.35
2.02
3.38
1.49
1.00
0.46
1.00
1.50
0.51
1.08

1.01
0.98
0.77
0.45
0.76
0.35
0.59
0.05
1.07
1.05
0.23
0.29
0.04
0.50
1.18
0.42
0.85
0.68
1.08
0.47
0.58
1.00
1.23
0.48
0.24

0.89
0.18
0.25
0.22
0.13
0.04
0.05
0.01
0.30
1.12
0.07
0.11
0.00
0.81
0.78
0.23
1.22
0.82
1.55
0.07
0.40
1.00
1.37
0.43
0.02

1.26
0.71
2.65
1.43
0.09
0.01
0.15
0.06
5.23
1.00
0.18
0.35
0.08
0.21
0.45
0.62
0.77
1.53
0.90
2.61
0.38
1.00
1.29
0.39
4.61

1.55
0.04
0.31
20.95
1.16
0.28
0.25
0.05
0.78
1.83
0.08
0.09
0.02
0.83
0.58
0.24
1.57
0.95
2.04
0.08
0.40
1.00
1.63
0.38
0.52

1.31
0.03
0.29
12.49
0.83
0.04
0.09
0.04
0.23
2.22
0.02
0.00
0.07
0.74
0.22
0.10
1.60
0.87
2.42
0.09
0.33
1.00
1.59
0.30
0.07

Original article

Table 6
Enrichment factor (EF) of heavy
metals and trace elements in
weathered samples from the MT
profile

Table 7
Enrichment factor (EF) of heavy
metals and trace elements in
weathered samples from the TJ
profile

Site

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
P

MT profile
MT1

MT2

MT3

MT4

MT5

MT6

0.45
1.15
0.70
0.28
0.27
0.96
0.21
0.41
0.37
0.72
1.45
10.50
0.02
0.90
1.90
8.05
0.74
1.03
4.18
4.76
0.63
1.00
0.91
0.71
1.77

0.45
1.05
0.72
0.23
0.32
0.79
0.39
0.24
0.48
0.75
2.39
13.51
0.11
0.80
1.89
8.39
0.91
1.05
4.19
2.12
0.63
1.00
0.91
0.60
0.99

0.63
1.26
0.86
0.26
0.15
0.76
0.26
0.34
0.28
0.79
2.89
17.27
0.10
0.77
2.97
6.12
0.96
1.29
4.59
2.87
0.57
1.00
0.90
0.61
4.14

0.48
1.20
0.91
0.20
0.17
0.43
0.42
0.35
0.42
0.76
2.13
14.01
0.15
0.82
2.10
4.81
0.93
1.45
3.71
2.08
0.62
1.00
0.91
0.65
2.65

0.61
1.09
0.90
0.27
0.20
0.69
0.56
0.78
0.06
0.81
1.08
3.05
0.06
0.81
1.45
5.31
0.79
1.28
3.85
1.93
0.57
1.00
0.86
0.55
0.98

0.96
1.06
0.89
0.26
0.12
0.67
0.82
0.35
0.19
0.86
1.85
6.09
0.34
0.74
1.59
5.52
0.88
1.50
4.11
1.40
0.50
1.00
0.86
0.53
4.60

Site

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
P

TJ profile
TH1

TH2

TH3

TH4

TH5

TH6

TH7

1.23
16.99
11.41
0.19
0.49
0.14
5.64
0.04
4.28
0.55
5.02
3.39
0.14
0.76
7.06
0.99
1.65
3.43
0.65
0.66
2.58
1.00
0.57
2.10
3.31

0.66
2.83
2.09
0.27
0.04
0.04
2.54
0.06
2.50
0.41
10.04
1.43
0.14
0.48
5.65
0.32
0.69
1.95
0.29
0.49
3.67
1.00
0.43
3.21
1.44

1.15
19.04
11.42
0.04
0.04
0.01
4.56
0.12
3.27
0.49
3.93
2.32
0.09
0.59
10.74
0.94
1.32
1.73
0.62
2.54
2.83
1.00
0.72
2.16
3.60

0.81
19.16
17.57
0.21
0.16
0.04
0.64
0.06
2.21
0.71
1.74
1.84
0.09
0.99
14.06
1.05
1.08
0.83
0.71
0.25
1.84
1.00
0.97
1.58
0.92

0.91
2.98
6.07
0.88
0.68
0.50
7.24
0.48
2.03
0.52
3.48
4.31
0.08
0.92
18.54
0.65
0.71
1.44
0.41
2.43
2.57
1.00
0.73
2.12
7.52

2.56
6.42
7.19
0.47
0.55
1.17
3.01
0.28
1.81
0.92
14.06
4.63
0.26
1.26
43.05
0.92
1.47
1.75
0.75
0.68
4.66
1.00
1.14
3.92
26.80

0.74
3.88
3.66
0.81
0.29
0.19
0.63
0.17
1.54
0.59
1.86
1.35
0.18
0.77
7.77
0.54
0.78
1.06
0.49
0.75
1.34
1.00
0.89
1.06
1.45

through time and that the index element has not been
redistributed within the weathering profile. The mass
fraction of element j lost/released from a weathered LCBS
(in % loss) relative to the mass of j originally present
(represented by fresh bedrock) is calculated from the following equation (Nesbitt 1979; Middelburg and others
1988; Nesbitt and Wilson 1992; Kurtz and others 2000):

% Loss ¼ ðCj; w=Cj; p  Ci; p=Ci; w  1Þ  100

ð2Þ

where C represents the concentration of any element in
any of the analyzed samples, the subscript j refers to the
selected element for calculation, the subscript i refers to
the immobile element chosen for calculation, and the
subscripts w and p refer to the weathered and the parent

Environmental Geology (2004) 45:1137–1147

1143

Original article

Fig. 3
Plot of Nb vs. Ta concentrations for weathered and unweathered
LCBS samples from the three profiles

strongly leached during weathering; and (2) Nb/Ta ratios
of all weathered samples are close to the Nb/Ta ratio
(13.75) of average black shales (Fig. 3). Nb/Ta remains
constant in both weathered and unweathered LCBS samples across the three profiles, which strongly implies that
neither element was mobile during weathering. The authors consider Nb as the immobile index element in these
discussions of heavy metal release during LCBS weathering, although normalizing to Ta produces nearly identical results.
The results for heavy metal release from weathered LCBS
(in % loss) are shown in Table 8 and Fig. 4. It is clear that
metals strongly leached out from weathered LCBS include
V, Cr, Co, Ni, Cu, Zn, U, Mo, Cd, Sn, Sb and Tl for the TP
profile; Sc, Cr, Mn, Co, Ni, Cu, Zn, Pb, Th, Cd and Sn for
the MT profile; and Sc, Mn, Co, Ni, Zn, Th, Cd, Sn and Tl
for the TJ profile. In summary, heavy metals show a different behavior for different weathering profiles. For
example, metals Sc and Th are enriched in the TP profile,
but are pronouncedly released from LCBS samples across
the MT and TJ profiles. Meanwhile, V, U, and Mo are
flushed from the TP profile, but remain and are enriched
across both the MT and TJ profiles. Heavy metals Co, Ni,
Zn, Cd and Sn show features of being released from LCBS
in all three profiles during weathering. This result agrees
with the EF value comparison.
The release percentage (% loss) of heavy metals from
samples across the three profiles is summarized in Table 8.
If the mass ( M) of outcropped LCBS can be estimated, and
the average concentration ( C i ) of heavy metal, i , in the
outcropped LCBS is known, then the amount ( DM i ) of
released heavy metal can be estimated using the following
equation:

material (bedrock in this study), respectively. The calculation result is either positive or negative, which represents
the gain or loss relative to the corresponding bedrock
(parent material), respectively.
In previous studies, Ti was traditionally considered to be
an immobile index element for the mass-balance calculation (Nesbitt 1979; Middelburg and others 1988; Nesbitt
and Wilson 1992). In recent years, Nb, Ta, and Ir have
been commonly regarded as immobile index elements for
the calculation because of their low aqueous solubility
(Kurtz and others 2000; Jaffe and others 2002). These data
(Tables 2, 3, 4) show that (1) Nb and Ta in most weathered
and weathered/leached samples from the three profiles are
more strongly enriched over the corresponding parent
DMi ¼ M  Ci  ð% LossÞ
ð3Þ
rock (bedrock) concentrations than other trace elements,
compared to the corresponding values of average black
Among the 16 heavy metals, Co, Ni, Zn and Cd have the
shales (Tables 2, 3, 4), indicating that neither element was highest values of (% loss) across the three weathering

Table 8
Summary on heavy metal release (in % loss) based on mass-balance calculation applied to the three profiles, the original data are listed in
Table 2
Profile

TP profile
Range of % loss

Sc
V
Cr
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl

MT profile

Average of % loss

+
)2.15)97.35
)22.86)75.26
)54.56)77.63
)17.27)90.55
)64.14)98.52
)40.77)94.80
)93.43)99.12
)22.30)76.60
+
)44.09)98.04
)64.55)99.60
)88.47)99.74
)8.3)79.47
)22.49)78.42
)37.97)89.79

+
)61.15
)59.49
)62.70
)59.74
)82.09
)72.04
)95.31
)56.43
+
)80.95
)80.36
)94.62
)33.26
)44.49
)67.46

(5)
(4)
(3)
(5)
(6)
(6)
(6)
(3)
(6)
(6)
(6)
(6)
(5)
(6)

Range of % loss

Average of % loss

Range of % loss

Average of % loss

)3.86)55.08
+
)8.8)30.08
)71.86)80.29
)68.49)87.94
)4.0)57.39
)17.60)78.66
)21.62)75.81
)52.15)94.34
)13.56)27.52
+
+
)66.08–)100.56
)9.52)25.91
+
+

)40.23 (6)
+
)17.09 (6)
)75.2 (6)
)79.54 (6)
)28.37 (6)
)55.42 (6)
)58.67 (6)
)70.01 (6)
)21.68 (6)
+
+
)87.57 (6)
)19.33 (6)
+
+

)8.8)33.99
+
+
)11.5)95.75
)31.57)95.81
)50.14)98.69
)35.82)37.41
)51.78)96.08
+
)7.77)58.64
+
+
)73.77)91.97
)1.45)52.38
+
)0.97)67.85

)21.83 (4)
+
+
)58.92 (7)
)67.81 (7)
)84.67 (7)
)36.62 (2)
)82.51 (7)
+
)40.0 (7)
+
+
)85.93 (7)
)24.9 (6)
+
)27.35 (6)

+ represents metal gain; number in () is the sample numbers used for average calculation

1144

Environmental Geology (2004) 45:1137–1147

TJ profile

Original article

Fig. 4
Comparison of the relative losses of heavy
metals (% loss) from samples from the three
weathering profiles. For details see text

profiles. It can be estimated that the amounts of lost Co,
Ni, Zn and Cd from 1 kg LCBS at the TP profile are 18.2 g,
259.2 g, 826.9 g, and 10.5 g, respectively, using the concentration of these metals in bedrock for the C i values in
Eq. (3). Other possible released heavy metals include Sc,
Cr, Mn, Cu, Th, Sn and Tl. If the released metals are
completely transferred into the environment (soil and/or
surface water system), heavy metal pollution by black
shale weathering is very serious.

Possible environmental effects
Weathering and erosion of geological formations result in
direct input of heavy metals to environments, with the
possibility of environmental contamination. Generally, the
most direct effect of rock weathering is on the compositions of soils and surface waters. To test the possibility of
environmental effects from weathering of LCBS, some soil
and surface water samples were also included in this study.
Concentrations of heavy metals in soil and surface water

Environmental Geology (2004) 45:1137–1147

1145

Original article

Table 9
Concentrationa (lg/g) of heavy
metals and trace elements in
farmland soils near the TJ profile
compared with ACS (Average
China Soils)

Sample
V
Cr
Mn
Co
Cu
Zn
Pb
Th
U
Mo
Cd
Tl
As
Se
Hg
Rb
Sr

S1

S2

S3

S4

S5

S6

ACSb

164.9
137.6
>
110.5
337.1
560.9
276.2
13.93
4.589
15.889
1.050
1.370
2.915
0.075
0.029
85.38
818.9

248.9
162.6
>
157.0
367.1
403.1
337.3
29.70
8.008
22.471
1.044
2.078
6.863
0.089
0.033
130.82
704.3

116.2
115.6
>
64.3
209.1
306.6
175.7
14.60
3.892
8.250
0.697
0.911
1.314
0.054
0.036
93.83
516.8

126.1
183.7
383.04
7.965
39.47
90.77
28.59
12.77
4.144
4.532
0.192
2.253
0.361
0.057
0.036
74.37
49.86

85.67
332.2
69.597
4.623
202.03
149.3
44.36
22.89
3.522
7.997
0.157
6.039
4.791
0.096
0.024
252.4
26.16

79.09
140.5
30.869
2.166
20.96
37.99
16.82
6.88
1.423
0.505
0.046
3.2
3.328
0.039
0.04
143.8
15.64

82.4
61.0
583
12.7
22.6
74.22
26.0
0.097
11.2
0.290
0.065
-

- represents no data
a
Average value of 7 analyzing results with deviation in percentage less than10%
b
After Zhang (1994)

Table 10
Concentrationa (lg/L) of heavy
metal and trace elements in
surface water compared with
WAW (world surface water)
after GERM

Sample
Sc
V
Cr
Fe
Mn
Co
Ni
Cu
Zn
Pb
Th
U
Mo
Cd
Sn
Sb
Tl
Bi
As
Se
Ga
Ge
Rb
Sr
Zr
Nb
Ta
Hf
a

TJ1

TJ2

TJ3

TJ4

TJ5

TJ6

TJ7

WAWb

2.523
0.156
8.446
47.34
2.249
0.056
2.817
1.182
10.43
0.051
<0.01
<0.01
1.636
0.026
<0.01
<0.01
0.02
0.035
0.194
0.122
0.019
0.028
4.161
9.769
0.024
<0.01
0.004
0.001

1.477
0.401
2.739
29.22
0.342
0.022
0.372
0.427
2.784
0.07
<0.01
<0.01
0.081
0.021
<0.01
<0.01
0.026
<0.01
0.013
0.129
1.86
0.023
0.556
15.94
0.042
<0.01
0.003
0.002

1.202
0.126
3.952
19.34
3.097
0.036
2.739
0.653
11.44
0.088
<0.01
<0.01
0.014
0.09
<0.01
<0.01
0.033
<0.01
0.091
0.118
0.335
0.029
1.352
14.77
0.027
<0.01
0.003
0.001

1.425
0.16
4.561
66.20
7.385
0.024
0.97
0.23
3.457
0.041
<0.01
<0.01
0.037
0.022
<0.01
<0.01
0.021
<0.01
0.189
0.1
0.234
0.035
2.78
13.31
0.017
<0.01
0.002
0.001

0.858
2.161
7.054
22.00
2.149
0.057
4.172
6.069
17.07
0.078
<0.01
0.3
0.77
3.407
<0.01
<0.01
0.071
<0.01
0.048
0.204
1.842
0.025
1.457
77.32
0.009
<0.01
0.003
0.001

1.159
0.653
3.865
33.91
14.58
0.408
1.069
1.112
2.601
0.106
<0.01
0.085
0.088
0.104
<0.01
<0.01
0.061
<0.01
0.005
0.248
2.382
0.026
0.834
13.48
0.071
<0.01
0.003
0.002

2.169
0.158
7.936
24.92
5.065
0.025
0.784
0.109
2.619
0.061
<0.01
<0.01
<0.01
0.036
<0.01
<0.01
0.019
<0.01
0.006
0.107
0.982
0.023
2.238
21.44
0.015
<0.01
0.003
0.001

4·10)4
1
0.268
0.009
0.034
0.007
0.146
0.034
0.006
0.0136
0.7
3.2
11
3·10)4
0.001
0.2
0.011
0.02
0.1
0.025
0.015
5·10)4
124
7.4·106
1
0.01
0.025
0.008

Average value of 7 analyzing results with deviation in percentage less than10%
WAW in ug/kg from database on web set: http://www.earthref.org

b

samples obtained from near the TJ weathering profile are
listed in Tables 9 and 10. Compared to average Chinese
soils (Zhang 1994), the soil samples show pronounced
enrichments of V, Cr, Co, Cu, Zn, Pb, Cd and Tl (Table 9).
Concentrations of Sc, Cr, Fe, Mn Co, Ni, Cu, Zn, Pb and Cd
in surface water (Table 10) near the TJ profile are higher
than world average surface waters (Quinby-Hunt and
Turkekian 1983). There are no detailed data on background values of heavy metal contents in soils and surface
water of the adjacent reference areas in western Hunan.
1146

Environmental Geology (2004) 45:1137–1147

If the above comparison is reasonable, the concentrations
of heavy metals in soils and surface waters near the LCBS
weathering profiles are enough to cause heavy metal
contamination in the area. There is no direct evidence that
the enriched heavy metals in soils and surface water came
from the weathering of the LCBS at the TJ profile, but it is
not ambiguous that the enriched heavy metals in soils and
surface waters near the TJ profile overlap these with a
region of high percentage of release (% loss) during the
weathering of the LCBS in the area (Fig. 4). According to

Original article

the standard of average Chinese soils (Zhang 1994) and
world average surface water (Table 10), soils and surface
waters near the TJ profile are seriously contaminated by
heavy metals. Because there is no industrial waste near the
TJ profile, and the soil samples are not from agriculture,
the authors deduce that the contamination is probably
caused through enrichment of these metals from the
weathering of the LCBS. It is therefore considered quite
possible that the weathering of LCBS is a source of environmental contamination in the area.
Residents in western Hunan have suffered endemics for
many years. If these endemics are related to environmental
pollution of heavy metal contamination, the released heavy
metals from the weathering of the LCBS in the area may be
one of the major causes. Although it might be very difficult
to define the relationship between endemics and LCBS
weathering, the discovery of higher concentrations of
heavy metals in soil and surface water due to LCBS
weathering may significantly influence the future direction
of the pathological study of endemics.
Acknowledgements This study was subsidized by the Bureau of
Science and Technology of Hunan province—the Young Scientists Research Project, grant number 01JZY2102, and by the National Scientific Committee of China—grant number 40002021.
Britta Munch at the Geological Institute, University of Copenhagen, Denmark, significantly improved the graphic design of
some figures in manuscript. The authors wish to thank Dr Graeme Beardsmore at Monash University, Australia, for improving
the English language of the manuscript.

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