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 ICP-
MS 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 stone-
coal 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 dur-
ing 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. car-
cinogenic), 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 chemi-
cally. Weathering of heavy metal enriched black shales
may be one of the most important sources of environ-
mental 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 dis-
eases, 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 com-
parison 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 docu-
mented 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 docu-
ment 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
1138 Environmental Geology (2004) 45:1137–1147
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 Tao-
jiang (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 distribu-
tion map is a diagrammatic
sketch
 Original article

‘‘weak’’, ‘‘moderate’’, ‘‘intense’’ and ‘‘topsoil’’ (or ‘‘com-

TH7, TH6, TH5

plete weathering’’) on the basis of color, hardness, loss of

TH2, TH1
Sample
texture and discoloration of organic matter and sulfides.

TH4
TH3

TH0
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

TJ
taken from each profile in October 2001. For the TP pro-

Thickness (m)
file, six samples were selected from a number of samples

1.0+1.0+0.8
taken from an open-pit face at Taiping vanadium ore

>1.0
1.2
1.1

1.6
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

MT6, MT5, MT4

from surface water flowing through the exposed LCBS

MT1, MT2
Sample

MT3

MT0
about two weeks after rain. The samples, collected in clean
plastic bottles, were analyzed using an ICP-MS immedi-
ately after collection.
Rock and soil samples were powdered in an Alceramic

MT
shatter box after drying at 120 C for 3 h. All analytical
data were reported on a dry sediment basis. About 50 mg

0.5+1.2+1.3
Thickness
of powder from each sample was dissolved using HF +

0.35
(m)

0.3

1.0
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 Guangz-
hou Institute of Geochemistry, Chinese Academy of Sci-

B10, B11
Sample

ence. (Note that only heavy metals and some trace

B4
B7

B9

B6

B1
elements are included in this paper.)
TP

Results and discussion

Thickness

1.0+1.0

>1.0
(m)

0.8
1.2

1.5

1.5

Distribution of heavy metals

The concentrations of 16 heavy metals, some trace ele-

ments, and P, were obtained in fresh and weathered LCBS
Sulfide oxidized, and color washed-out, hard-

Sulfide oxidized, color changed, but hardness

Sulfide oxidized, color and hardness and tex-

for the three profiles. The data are compared to average

Sulfide oxidized, color washed-out, hardness
Discoloration, losse and texture disappeared

black shales in Tables 2, 3, 4. The selected weathering

ness and texture completely changed

profiles are less than 15 m in length along strike, and the

and texture start to change

Carbonaceous black shales

lithology of unweathered (fresh) LCBS are similar. Samples

and texture not changed

from the fresh bedrock are representative of the original

ture not changed
Characteristics

(unweathered/fresh) LCBS from corresponding profiles.

Description of weathering profiles and samples

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):
EF ¼ ðX=NbÞWeathered =ðX=NbÞBedrock ð1Þ
Table 1

where X is the heavy metal of interest, Nb is a reference

weathering
Degree of

Moderate

Incipient

element in the sample, and the Weathered and Bedrock are

Bedrock
Intense

Weak

the values of weathered LCBS and the corresponding

Soil

bedrock. If EF
1, the heavy metal of interest, X , was at

Environmental Geology (2004) 45:1137–1147 1139

 Original article

Fig. 2 a background level, whereas EF>1, means that the heavy

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

B1 B10 B11 B6 B9 B7 B4

Sc 6.801 (5.8) 15.3 (3) 11.05 (3.8) 12.84 (2.5) 19.11 (1.4) 13.21 (2.6) 17.26 (3.4) 13
V 1951.7 (4.2) 12329.6 (1.5) 3063.4 (2.7) 753.2 (1.9) 3095.4 (1.9) 108.9 (2.4) 99.75 (3.4) 130
Cr 152.5 (4.2) 1193.4 (2.3) 188.7 (3.9) 79.61 (2.8) 901.2 (1.6) 59.92 (4) 85.19 (2.5) 90
Mn 25.0 (3.4) 20.25 (1.6) 18.0 (2.5) 11.8 (2.3) 79.82 (1.8) 658.3 (3) 603.0 (2) 850
Co 30.51 (5.8) 11.23 (2.5) 36.98 (4.5) 8.608 (2.5) 6.439 3.3) 44.56 (4.2) 48.75 (3.5) 19
Ni 316.1 (3.6) 206.6 (1.1) 176.9 (1.5) 23.68 (3.4) 10.43 (2.4) 109.8 (4.6) 24.78 (2.3) 68
Cu 306.7 (3.8) 303.9 (2.1) 291.4 (3.2) 33.66 (1.6) 105.5 (2.9) 95.22 (2.5) 52.7 (2.8) 45
Zn 867.6 (4.7) 103.9 (2.9) 71.57 (2.8) 16.09 (9.3) 122.3 (2.1) 52.84 (4.3) 73.08 (2.3) 95
Pb 34.85 (5.4) 147.9 (1) 59.96 (4.1) 21.79 (2.9) 407.0 (2) 34.04 (1.7) 15.75 (2) 20
Th 4.77 (6.7) 13.43 (2.5) 8.0 (2.4) 11.23 (3) 10.68 (3.4) 10.98 (3.2) 20.46 (1.9) 12
U 95.55 (3.0) 97.38 (1.7) 35.49 (3) 13.35 (1.7) 38.47 (2.8) 9.682 (1.8) 3.62 (3.1) 3.7
Mo 176.6 (4.4) 106.9 (1.3) 82.78 (1.9) 40.29 (2.6) 139.8 (1.9) 19.39 (2.9) 1.374 (5.5) 2.6
Cd 11.09 (11.2) 2.33 (4.3) 0.695 (4.9) 0.06 (17.4) 1.955 (6) 0.244 (7.4) 1.459 (5.8) 0.3
Sn 6.545 (9) 10.94 (1.9) 5.251 (6.5) 11.21 (1) 3.0 (2.5) 6.80 8 (2.5) 9.359 (3) 6.0
Sb 94.27 (17.3) 128.5 (18.1) 178.5 (11.4) 154.2 (4) 95.7 (1.5) 68.97 (3.2) 39.3 (1.5) 1.5
Tl 5.306 (4.1) 3.37 (1.3) 3.575 (2.4) 2.52 (1.8) 7.349 (1) 1.579 (3) 1.046 (3.9) 1.0
Ga 7.822 (3.6) 28.79 (2.2) 10.69 (3.8) 20.22 (1.9) 13.42 (2.8) 15.41 (2.7) 24.11 (2.2) 19
Ge 1.07 (8.9) 6.584 (4) 1.169 (2.6) 1.849 (2.6) 3.646 (1) 1.28 (6) 1.788 (3.9) 1.6
Rb 40.95 (3.9) 111.4 (1.2) 71.03 (2.5) 134.2 (3.4) 81.85 (2) 105.0 (7.5) 191.1 (2) 140
Sr 89.18 (6.0) 163.1 (2.7) 67.23 (3.2) 12.59 (3.8) 519.3 (4) 8.533 (4.9) 16.01 (2.3) 300
Zr 147.7 (3.9) 123.2 (1.4) 137.3 (2.6) 123.6 (2.7) 125.2 (3.6) 75.12 (1.2) 94.78 (1.6) 160
Nb 7.269 (1.7) 13.25 (2.8) 11.66 (3.3) 15.34 (3) 16.23 (0.6) 9.138 (2.6) 14.04 (2.3) 11
Ta 0.463 (5.7) 1.268 (3) 0.913 (2.2) 1.343 (4) 1.331 (5) 0.948 (3.6) 1.419 (4.4) 0.8
Hf 4.334 (1.6) 4.057 (3) 3.326 (5.6) 3.921 (2.1) 3.772 (2) 2.094 (2.3) 2.536 (3.4) 2.8
P 1332.3 (3.8) 2612.4 (3.7) 511.1 (2.9) 62.46 (11.9) 13720.3 (1.9) 867.0 (1.2) 182.8 (7) 700
Nb/Ta 15.69 10.45 12.77 11.42 12.19 9.64 9.89 13.75
Zr/Rb 3.61 1.10 1.93 0.92 1.53 0.72 0.50 0.08
Th/U 0.05 0.14 0.23 0.84 0.28 1.13 5.65 1.4
(Zr+Rb)/Sr 2.12 1.44 3.10 20.48 0.40 21.11 17.86 1
Ga/Ge 7.31 4.37 9.14 10.94 3.68 12.04 13.48 11.88
a
Average value of 7 analyzing results with deviation in percentage listed in parantheses
b
After Mason and Moore (1982)

1140 Environmental Geology (2004) 45:1137–1147

 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 TP profile

MT0 MT1 MT2 MT3 MT4 MT5 MT6

Sc 58.64 (3) 15.09 (2.9) 14.57 (2.4) 16.55 (3.8) 14.29 (3.1) 23.98 (2.1) 28.38 (3.3)
V 343.9 (3.2) 223.7 (2.8) 200.4 (1.7) 193.2 (2.5) 208.0 (2.4) 251.8 (1.5) 182.7 (4.2)
Cr 217.7 (3.1) 86.46 (2.2) 86.97 (3.9) 83.83 (3.4) 100.2 (14.8) 130.8 (3.1) 97.08 (3.3)
Mn 120.2 (1.9) 19.21 (1.9) 14.97 (2.1) 13.95 (1.5) 11.96 (1.6) 21.47 (1.9) 15.66 (4.9)
Co 32.37 (2.8) 4.934 (4) 5.729 (2.4) 2.161 (4.2) 2.828 (5.2) 4.262 (4) 1.966 (4)
Ni 52.64 (2.3) 28.7 (1.4) 22.88 (3.3) 17.95 (3.3) 11.32 (4.9) 24.53 (4.2) 17.75 (4.8)
Cu 182.6 (3.6) 22.13 (2.8) 39.75 (3.3) 21.57 (3.2) 38.92 (2.9) 68.34 (2.8) 75.74 (2.9)
Zn 69.21 (4.7) 16.04 (11.3) 9.261 (9.1) 10.64 (15.9) 12.28 (5.9) 36.41 (6) 12.23 (18)
Pb 184.1 (2.1) 38.45 (2.8) 48.72 (1.8) 23.28 (2) 38.73 (3.3) 6.989 (3) 18.01 (4.6)
Th 54.65 (3.2) 22.5 (1.7) 22.76 (3.8) 19.36 (4.2) 20.87 (4.1) 29.67 (4.2) 23.78 (3.3)
U 16.8 (2.7) 13.8 (2.3) 22.25 (2.5) 21.71 (2.4) 18.04 (1.8) 12.13 (1.4) 15.63 (4.3)
Mo 2.316 (6) 13.815 (2.6) 17.31 (1.6) 17.9 (3.1) 16.38 (2.5) 4.746 (4) 7.095 (4.2)
Cd 0.451 (14) 0.04 (1.5) 0.027 (2.8) 0.021 (2.3) 0.035 (3.8) 0.017 (7.8) 0.077 (6.4)
Sn 24.26 (3.4) 12. 468 (4.2) 10.680 (4.5) 8.323 (1.5) 10.04 (2.5) 13.220 (5.3) 9.048 (4)
Sb 7.374 (6.3) 7.942 (5.5) 7.713 (3.4) 9.817 (5.2) 7.809 (4.3) 7.161 (2.6) 5.891 (8)
Tl 0.451 (3.5) 2.063 (1.9) 2.092 (3) 1.235 (3.9) 1.094 (2.6) 1.607 (2.2) 1.253 (5.2)
Ga 44.89 (3.4) 18.98 (2.8) 22.62 (2.7) 19.36 (2.9) 21.13 (1.4) 23.92 (1.4) 19.84 (3.2)
Ge 2.726 (3.7) 1.591 (3.2) 1.588 (5.9) 1.578 (4.5) 1.992 (3) 2.349 (4.4) 2.061(3)
Rb 54.44 (3.4) 129.2 (1.3) 126.3 (2.9) 111.8(2.8) 101.8 (2.6) 140.6 (3.2) 112.7 (3.4)
Sr 96.5 (3.7) 260.9 (2.5) 113.0 (5.5) 124.1 (3.5) 101.2 (3.2) 125.0 (3.2) 68.23 (2.4)
Zr 358.3 (5.3) 127.2 (12.7) 125.6 (1.5) 90.63 (1.5) 112.2 (1.5) 136.0 (1.3) 90.85 (1.3)
Nb 30.81 (2.4) 17.5 (1.4) 17.04 (3.9) 13.79 (3.9) 15.55 (2.9) 20.680 (1.9) 15.51 (2.2)
Ta 3.01 (3.5) 1.55 (5) 1.521 (3.8) 1.211 (4.2) 1.38 (3.6) 1.742 (0.8) 1.303 (3.2)
Hf 9.989 (2.2) 4.038 (2.8) 3.301 (4.5) 2.724 (2) 3.26 (5.5) 3.678 (3.1) 2.642 (4.6)
P 997.9 (1.8) 999.99 (2.8) 546.4 (3.1) 1,849.1 (3.2) 1,334.2 (4.9) 658.0 (4.6) 2,312.6 (4.9)
Nb/Ta 10.24 13.75 11.20 11.39 11.27 11.87 11.93
Zr/Rb 6.58 0.08 0.99 0.81 1.1 0.97 0.81
Th/U 3.25 1.4 1.02 0.89 1.16 2.45 1.52
(Zr+Rb)/Sr 4.28 1 2.23 1.63 2.11 2.21 2.98
Ga/Ge 16.47 11.88 14.24 12.27 10.61 10.18 9.63
a
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 charac-
terized 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 pro-
nouncedly 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 consid-
erably.
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 concentra-
tions 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 per-
centage 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 TJ profile

TH0 TH1 TH2 TH3 TH4 TH5 TH6 TH7

Sc 16.15 (3.6) 5.987 (3) 5.243 (2) 11.09 (4) 16.38 (4) 10.02 (3.6) 29.73 (3.6) 11.58 (2.9)
V 761.3 (3.8) 3879.0 (4.6) 1059.7 (2.6) 8659.9 (1.4) 18180.7 (1.5) 1544.1 (1.8) 3513.1 (3.1) 2855.7 (2.3)
Cr 94.31 (4.7) 322.6 (2.3) 96.9 (3.5) 643.6 (6.1) 2064.9 (3.8) 389.7 (3.8) 487.8 (4.7) 334.1 (3.5)
Mn 456.9 (3.3) 25.79 (4) 60.42 (2.4) 11.6 (1.7) 119.4 (2) 275.1 (2.4) 155.9 (3.6) 357.3 (2.4)
Co 29.49 (4.3) 4.294 (5) 0.607 (8) 0.764 (4) 5.942 (4) 13.73 (3) 11.69 (5) 8.147 (2)
Ni 168.1 (4.1) 7.288 (4) 2.962 (5) 1.315 (2) 8.148 (3) 57.03 (2.9) 142.0 (4.8) 30.73 (3.9)
Cu 151.9 (3.8) 256.9 (3.3) 189.4 (3.6) 414.0 (3.9) 121.5 (2.5) 784.2 (3.8) 329.1 (5.1) 92.01 (0.8)
Zn 397.2 (3.9) 4.669 (5) 11.46 (5.9) 29.5 (5.4) 31.85 (7.3) 130.3 (3.8) 80.51 (5.9) 66.91 (4.8)
Pb 39.9 (3.8) 51.26 (3) 49.04 (3.1) 78.0 (3) 110.0 (2.7) 55.16 (3.9) 51.98 (3.7) 59.5 (2.2)
Th 25.7 (5.7) 4.268 (2) 5.227 (2) 7.449 (3) 22.78 (3.4) 9.11 (2.2) 17.05 (4) 14.73 (3.3)
U 26.7 (2.4) 40.23 (2) 131.8 (2.4) 62.73 (2) 57.75 (3.3) 63.18 (2.3) 270.1 (3.4) 48.09 (3)
Mo 28.79 (2.1) 29.23 (1.4) 20.25 (3.4) 39.84 (2.2) 66.16 (1.4) 84.39 (2) 95.85 (1.7) 37.53 (2.9)
Cd 3.244 (3) 0.139 (11) 0.224 (10) 0.172 (6) 0.365 (5) 0.182 (6) 0.612 (7) 0.558 (8)
Sn 10.406 (2) 2.372 (4) 2.347 (6.2) 3.696 (4) 12.78 (2.6) 6.509 (3) 9.446 (4) 7.758 (4)
Sb 11.424 (5) 24.2 (4.4) 31.72 (64.4) 73.29 (3.9) 200.15 (9.8) 144.07 (3.3) 353.76 (11) 85.870 (2)
Tl 2.182 (4) 0.684 (4) 0.345 (7.5) 1.223 (3) 2.868 (4) 0.692 (2) 1.449 (6) 1.136 (5)
Ga 23.56 (3.1) 11.6 (4.5) 7.982 (2.2) 18.57 (2.3) 31.76 (2) 11.28 (2) 24.82 (4.2) 17.63 (2.1)
Ge 1.362 (3) 1.4 (5.6) 1.309 (4.2) 1.405 (3) 1.411 (3) 1.332 (4) 1.71 (4) 1.403 (3)
Rb 200.3 (1.7) 39.05 (3.9) 28.45 (4) 73.61 (1.7) 176.2 (2) 56.16 (2) 107.8 (3.5) 95.15 (1.9)
Sr 102.1 (3) 20.35 (4.9) 24.47 (3.7) 154.9 (1.3) 32.22 (2.4) 169.1 (2.5) 49.9 (5) 74.44 (2.2)
Zr 95.67 (3) 74.09 (4) 172.7 (3.5) 161.7 (2.7) 219.2 (1.2) 167.2 (2.5) 320.9 (1.1) 124.3 (2.1)
Nb 17.99 (2.8) 5.395 (3) 8.847 (2.6) 10.75 (2) 22.42 (2.7) 12.24 (1.4) 12.94 (3.8) 17.41 (2.5)
Ta 1.697 (4) 0.288 (5) 0.362 (6.4) 0.735 (5) 2.061 (4) 0.848 (3) 1.393 (4) 1.459 (1)
Hf 2.882 (3) 1.819 (4) 4.545 (3.2) 3.714 (3) 5.689 (3) 4.165 (5) 8.127 (2) 2.975 (4)
P 655.4 (6) 650.1 (7.9) 463.7 (3.9) 1410.4 (3.3) 750.2 (4.9) 3355.4 (3.9) 12636 (3) 916.9 (3.7)
Nb/Ta 10.60 18.73 24.44 14.63 10.88 14.43 9.29 11.93
Zr/Rb 0.48 0.53 6.07 2.20 1.24 2.98 2.98 1.31
Th/U 0.96 0.11 0.04 0.12 0.39 0.14 0.06 0.31
(Zr+Rb)/Sr 2.90 5.56 8.22 1.52 12.27 1.32 8.59 2.95
Ga/Ge 17.30 8.29 6.10 13.22 22.51 8.47 14.51 12.57
a
Average value of 7 analyzing results with deviation in percentage listed in parentheses

Table 5
Enrichment factor (EF) of heavy Site TP profile
metals and trace elements in
weathered samples from the TP B10 B11 B6 B9 B7 B4
profile
Sc 1.23 1.01 0.89 1.26 1.55 1.31
V 3.47 0.98 0.18 0.71 0.04 0.03
Cr 4.29 0.77 0.25 2.65 0.31 0.29
Mn 0.44 0.45 0.22 1.43 20.95 12.49
Co 0.20 0.76 0.13 0.09 1.16 0.83
Ni 0.36 0.35 0.04 0.01 0.28 0.04
Cu 0.54 0.59 0.05 0.15 0.25 0.09
Zn 0.07 0.05 0.01 0.06 0.05 0.04
Pb 2.33 1.07 0.30 5.23 0.78 0.23
Th 1.54 1.05 1.12 1.00 1.83 2.22
U 0.56 0.23 0.07 0.18 0.08 0.02
Mo 0.33 0.29 0.11 0.35 0.09 0.00
Cd 0.12 0.04 0.00 0.08 0.02 0.07
Sn 0.92 0.50 0.81 0.21 0.83 0.74
Sb 0.75 1.18 0.78 0.45 0.58 0.22
Tl 0.35 0.42 0.23 0.62 0.24 0.10
Ga 2.02 0.85 1.22 0.77 1.57 1.60
Ge 3.38 0.68 0.82 1.53 0.95 0.87
Rb 1.49 1.08 1.55 0.90 2.04 2.42
Sr 1.00 0.47 0.07 2.61 0.08 0.09
Zr 0.46 0.58 0.40 0.38 0.40 0.33
Nb 1.00 1.00 1.00 1.00 1.00 1.00
Ta 1.50 1.23 1.37 1.29 1.63 1.59
Hf 0.51 0.48 0.43 0.39 0.38 0.30
P 1.08 0.24 0.02 4.61 0.52 0.07

1142 Environmental Geology (2004) 45:1137–1147

 Original article

Table 6
Enrichment factor (EF) of heavy Site MT profile
metals and trace elements in
weathered samples from the MT MT1 MT2 MT3 MT4 MT5 MT6
profile
Sc 0.45 0.45 0.63 0.48 0.61 0.96
V 1.15 1.05 1.26 1.20 1.09 1.06
Cr 0.70 0.72 0.86 0.91 0.90 0.89
Mn 0.28 0.23 0.26 0.20 0.27 0.26
Co 0.27 0.32 0.15 0.17 0.20 0.12
Ni 0.96 0.79 0.76 0.43 0.69 0.67
Cu 0.21 0.39 0.26 0.42 0.56 0.82
Zn 0.41 0.24 0.34 0.35 0.78 0.35
Pb 0.37 0.48 0.28 0.42 0.06 0.19
Th 0.72 0.75 0.79 0.76 0.81 0.86
U 1.45 2.39 2.89 2.13 1.08 1.85
Mo 10.50 13.51 17.27 14.01 3.05 6.09
Cd 0.02 0.11 0.10 0.15 0.06 0.34
Sn 0.90 0.80 0.77 0.82 0.81 0.74
Sb 1.90 1.89 2.97 2.10 1.45 1.59
Tl 8.05 8.39 6.12 4.81 5.31 5.52
Ga 0.74 0.91 0.96 0.93 0.79 0.88
Ge 1.03 1.05 1.29 1.45 1.28 1.50
Rb 4.18 4.19 4.59 3.71 3.85 4.11
Sr 4.76 2.12 2.87 2.08 1.93 1.40
Zr 0.63 0.63 0.57 0.62 0.57 0.50
Nb 1.00 1.00 1.00 1.00 1.00 1.00
Ta 0.91 0.91 0.90 0.91 0.86 0.86
Hf 0.71 0.60 0.61 0.65 0.55 0.53
P 1.77 0.99 4.14 2.65 0.98 4.60

Table 7
Enrichment factor (EF) of heavy Site TJ profile
metals and trace elements in
weathered samples from the TJ TH1 TH2 TH3 TH4 TH5 TH6 TH7
profile
Sc 1.23 0.66 1.15 0.81 0.91 2.56 0.74
V 16.99 2.83 19.04 19.16 2.98 6.42 3.88
Cr 11.41 2.09 11.42 17.57 6.07 7.19 3.66
Mn 0.19 0.27 0.04 0.21 0.88 0.47 0.81
Co 0.49 0.04 0.04 0.16 0.68 0.55 0.29
Ni 0.14 0.04 0.01 0.04 0.50 1.17 0.19
Cu 5.64 2.54 4.56 0.64 7.24 3.01 0.63
Zn 0.04 0.06 0.12 0.06 0.48 0.28 0.17
Pb 4.28 2.50 3.27 2.21 2.03 1.81 1.54
Th 0.55 0.41 0.49 0.71 0.52 0.92 0.59
U 5.02 10.04 3.93 1.74 3.48 14.06 1.86
Mo 3.39 1.43 2.32 1.84 4.31 4.63 1.35
Cd 0.14 0.14 0.09 0.09 0.08 0.26 0.18
Sn 0.76 0.48 0.59 0.99 0.92 1.26 0.77
Sb 7.06 5.65 10.74 14.06 18.54 43.05 7.77
Tl 0.99 0.32 0.94 1.05 0.65 0.92 0.54
Ga 1.65 0.69 1.32 1.08 0.71 1.47 0.78
Ge 3.43 1.95 1.73 0.83 1.44 1.75 1.06
Rb 0.65 0.29 0.62 0.71 0.41 0.75 0.49
Sr 0.66 0.49 2.54 0.25 2.43 0.68 0.75
Zr 2.58 3.67 2.83 1.84 2.57 4.66 1.34
Nb 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Ta 0.57 0.43 0.72 0.97 0.73 1.14 0.89
Hf 2.10 3.21 2.16 1.58 2.12 3.92 1.06
P 3.31 1.44 3.60 0.92 7.52 26.80 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 fol-
lowing 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

strongly leached during weathering; and (2) Nb/Ta ratios

Fig. 3
Plot of Nb vs. Ta concentrations for weathered and unweathered
LCBS samples from the three profiles
material (bedrock in this study), respectively. The calcu-
lation 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 calcula-
tion (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
rock (bedrock) concentrations than other trace elements,
compared to the corresponding values of average black
shales (Tables 2, 3, 4), indicating that neither element was highest values of (% loss) across the three weathering
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 sam-
ples across the three profiles, which strongly implies that
neither element was mobile during weathering. The au-
thors consider Nb as the immobile index element in these
discussions of heavy metal release during LCBS weath-
ering, although normalizing to Ta produces nearly iden-
tical 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 dif-
ferent 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:
DMi ¼ M  Ci  ð% LossÞ ð3Þ
Among the 16 heavy metals, Co, Ni, Zn and Cd have the

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 MT profile TJ profile

Range of % loss Average of % loss Range of % loss Average of % loss Range of % loss Average of % loss

Sc + + )3.86)55.08 )40.23 (6) )8.8)33.99 )21.83 (4)

V )2.15)97.35 )61.15 (5) + + + +
Cr )22.86)75.26 )59.49 (4) )8.8)30.08 )17.09 (6) + +
Mn )54.56)77.63 )62.70 (3) )71.86)80.29 )75.2 (6) )11.5)95.75 )58.92 (7)
Co )17.27)90.55 )59.74 (5) )68.49)87.94 )79.54 (6) )31.57)95.81 )67.81 (7)
Ni )64.14)98.52 )82.09 (6) )4.0)57.39 )28.37 (6) )50.14)98.69 )84.67 (7)
Cu )40.77)94.80 )72.04 (6) )17.60)78.66 )55.42 (6) )35.82)37.41 )36.62 (2)
Zn )93.43)99.12 )95.31 (6) )21.62)75.81 )58.67 (6) )51.78)96.08 )82.51 (7)
Pb )22.30)76.60 )56.43 (3) )52.15)94.34 )70.01 (6) + +
Th + + )13.56)27.52 )21.68 (6) )7.77)58.64 )40.0 (7)
U )44.09)98.04 )80.95 (6) + + + +
Mo )64.55)99.60 )80.36 (6) + + + +
Cd )88.47)99.74 )94.62 (6) )66.08–)100.56 )87.57 (6) )73.77)91.97 )85.93 (7)
Sn )8.3)79.47 )33.26 (6) )9.52)25.91 )19.33 (6) )1.45)52.38 )24.9 (6)
Sb )22.49)78.42 )44.49 (5) + + + +
Tl )37.97)89.79 )67.46 (6) + + )0.97)67.85 )27.35 (6)

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

1144 Environmental Geology (2004) 45:1137–1147


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 con-
centration 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.
Original article
Fig. 4
Comparison of the relative losses of heavy
metals (% loss) from samples from the three
weathering profiles. For details see text
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 composi-
tions 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 Sample S1 S2 S3 S4 S5 S6 ACSb
metals and trace elements in
farmland soils near the TJ profile V 164.9 248.9 116.2 126.1 85.67 79.09 82.4
compared with ACS (Average Cr 137.6 162.6 115.6 183.7 332.2 140.5 61.0
China Soils) Mn > > > 383.04 69.597 30.869 583
Co 110.5 157.0 64.3 7.965 4.623 2.166 12.7
Cu 337.1 367.1 209.1 39.47 202.03 20.96 22.6
Zn 560.9 403.1 306.6 90.77 149.3 37.99 74.22
Pb 276.2 337.3 175.7 28.59 44.36 16.82 26.0
Th 13.93 29.70 14.60 12.77 22.89 6.88 -
U 4.589 8.008 3.892 4.144 3.522 1.423 -
Mo 15.889 22.471 8.250 4.532 7.997 0.505 -
Cd 1.050 1.044 0.697 0.192 0.157 0.046 0.097
Tl 1.370 2.078 0.911 2.253 6.039 3.2 -
As 2.915 6.863 1.314 0.361 4.791 3.328 11.2
Se 0.075 0.089 0.054 0.057 0.096 0.039 0.290
Hg 0.029 0.033 0.036 0.036 0.024 0.04 0.065
Rb 85.38 130.82 93.83 74.37 252.4 143.8 -
Sr 818.9 704.3 516.8 49.86 26.16 15.64 -

- 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 Sample TJ1 TJ2 TJ3 TJ4 TJ5 TJ6 TJ7 WAWb
metal and trace elements in
surface water compared with Sc 2.523 1.477 1.202 1.425 0.858 1.159 2.169 4·10)4
WAW (world surface water) V 0.156 0.401 0.126 0.16 2.161 0.653 0.158 1
after GERM Cr 8.446 2.739 3.952 4.561 7.054 3.865 7.936 0.268
Fe 47.34 29.22 19.34 66.20 22.00 33.91 24.92 0.009
Mn 2.249 0.342 3.097 7.385 2.149 14.58 5.065 0.034
Co 0.056 0.022 0.036 0.024 0.057 0.408 0.025 0.007
Ni 2.817 0.372 2.739 0.97 4.172 1.069 0.784 0.146
Cu 1.182 0.427 0.653 0.23 6.069 1.112 0.109 0.034
Zn 10.43 2.784 11.44 3.457 17.07 2.601 2.619 0.006
Pb 0.051 0.07 0.088 0.041 0.078 0.106 0.061 0.0136
Th <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.7
U <0.01 <0.01 <0.01 <0.01 0.3 0.085 <0.01 3.2
Mo 1.636 0.081 0.014 0.037 0.77 0.088 <0.01 11
Cd 0.026 0.021 0.09 0.022 3.407 0.104 0.036 3·10)4
Sn <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.001
Sb <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.2
Tl 0.02 0.026 0.033 0.021 0.071 0.061 0.019 0.011
Bi 0.035 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.02
As 0.194 0.013 0.091 0.189 0.048 0.005 0.006 0.1
Se 0.122 0.129 0.118 0.1 0.204 0.248 0.107 0.025
Ga 0.019 1.86 0.335 0.234 1.842 2.382 0.982 0.015
Ge 0.028 0.023 0.029 0.035 0.025 0.026 0.023 5·10)4
Rb 4.161 0.556 1.352 2.78 1.457 0.834 2.238 124
Sr 9.769 15.94 14.77 13.31 77.32 13.48 21.44 7.4·106
Zr 0.024 0.042 0.027 0.017 0.009 0.071 0.015 1
Nb <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.01
Ta 0.004 0.003 0.003 0.002 0.003 0.003 0.003 0.025
Hf 0.001 0.002 0.001 0.001 0.001 0.002 0.001 0.008
a
Average value of 7 analyzing results with deviation in percentage less than10%
b
WAW in ug/kg from database on web set: http://www.earthref.org

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 back-
ground values of heavy metal contents in soils and surface
water of the adjacent reference areas in western Hunan.
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

1146 Environmental Geology (2004) 45:1137–1147


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 envi-
ronmental 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 Scien-
tists Research Project, grant number 01JZY2102, and by the Na-
tional Scientific Committee of China—grant number 40002021.
Britta Munch at the Geological Institute, University of Copen-
hagen, Denmark, significantly improved the graphic design of
some figures in manuscript. The authors wish to thank Dr Gra-
eme Beardsmore at Monash University, Australia, for improving
the English language of the manuscript.
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