geochemistry of trace metals and pb isotopes of sediments from the lowermost xiangjiang river, hunan...
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ORIGINAL ARTICLE
Geochemistry of trace metals and Pb isotopes of sedimentsfrom the lowermost Xiangjiang River, Hunan Province(P. R. China): implications on sources of trace metals
Bo Peng • Xiaoya Tang • Changxun Yu •
Changyin Tan • Chunyan Yin • Guang Yang •
Qian Liu • Kesu Yang • Xianglin Tu
Received: 7 May 2010 / Accepted: 9 February 2011 / Published online: 24 February 2011
� Springer-Verlag 2011
Abstract This paper reports a geochemical study of trace
metals and Pb isotopes of sediments from the lowermost
Xiangjiang River, Hunan province (P. R. China). Trace
metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn,
Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using
ICP-MS, and Pb isotopes of the bulk sediments were
measured by MC-ICP-MS. The results show that trace
metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and
Tl are enriched in the sediments. Among these metals, Cd,
Bi and Sn are extremely highly enriched (EF values [40),
metals Zn, Sn, Sb and Pb significantly highly
(5 \ EF \ 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl
moderately highly (2 \ EF \ 5) enriched in the river
sediments. All these metals, however, are moderately
enriched in the lake sediments. Geochemical results of
trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes
suggest that metals in the river sediments are of multi-
sources, including both natural and anthropogenic sources.
Metals of the natural sources might be contributed mostly
from weathering of the Indosinian granites (GR) and Pal-
aeozoic sandstones (PL), and metals of anthropogenic
sources were contributed from Pb–Zn ore deposits dis-
tributed in upper river areas. Metals in the lake sediments
consist of the anthropogenic proportions, which were
contributed from automobile exhausts and coal dusts. Thus,
heavy-metal contamination for the river sediments is
attributed to the exploitation and utilization (e.g., mining,
smelting, and refining) of Pb–Zn ore mineral resources in
the upper river areas, and this for the lake sediments was
caused by automobile exhausts and coal combustion.
Metals Bi, Cd, Pb, Sn and Sb have anthropogenic propor-
tion of higher than 90%, with natural contribution less than
10%. Metals Mn and Zn consist of anthropogenic propor-
tion of 60–85%, with natural proportion higher than 15%.
Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropo-
genic proportion of 30–70%, with natural contribution
higher than 30%. Metals Ba, V and Mo might be contrib-
uted mostly from natural process.
Keywords Heavy-metal contamination � Trace metal �Pb isotope � Anthropogenic metal � Sediments �The Xiangjiang River
Introduction
Xiangjiang River is the major watershed of Hunan prov-
ince (China), it covers one-third of the province’s land. The
province is famous for her abundant ore mineral resources
(Qian et al. 2005), and a remarkable array of ore deposits
such as Pb, Zn, Cu, Mo, Sn and REE has been found and
exploited in the upper river areas (Tong 2005). Industrial
activities such as mining, smelting and refining were
popularized in the area since mid 1980s (Tong 2005). Thus,
the river has become one of the rivers that are most seri-
ously contaminated by heavy metals in the country (Li
et al. 1986; Zhai 1986; Qian and Li 1988; Zhang and Zhao
1996; Qian et al. 2005; Yao et al. 2006a). Sediments
B. Peng (&) � X. Tang � C. Yu � C. Tan � C. Yin � G. Yang �Q. Liu � K. Yang
Faculty of Resource and Environment Science,
Hunan Normal University, Changsha 410081, China
e-mail: [email protected]
B. Peng
School of Earth and Environment, The University of Western
Australia, Crawley, WA 6009, Australia
X. Tu
Guangzhou Institute of Geochemistry,
Chinese Academy of Science, Guangzhou 510640, China
123
Environ Earth Sci (2011) 64:1455–1473
DOI 10.1007/s12665-011-0969-0
deposited in the river are also contaminated by heavy
metals including Cd, Hg, Cu, As and Pb (Mao et al. 1981;
Zhang et al. 1983; Zhai 1986; Zhang and Zhao 1996; Qian
et al. 2005; Yao et al. 2006a). Heavy-metal contamination
of the sediments has therefore been investigated by many
researchers in the past, and most of these previous studies
have dealt with the distribution patterns and occurrence of
metals in the sediments (Mao et al. 1981; Zhang et al.
1983; Chen and Zhang 1986; Zhai 1986; Zhang and Zhao
1996), the possible impact of the contaminated sediments
to water, soils and vegetables (Qian et al. 2005; Guo et al.
2008), and the potential sources of metals in the sediments
(Zhai 1986; Qian and Li 1988; Tong 2005). However, the
systematical study on geochemistry of trace metals and Pb
isotopes of the sediments is rare.
Lead of unpolluted sediments is generally derived from
weathered rocks, in which the Pb isotopic composition
evolved with time reflecting the U/Pb and Th/Pb of parent
rock (Hansmann and Koppel 2000). Thus, the rock-derived
(natural) Pb in sediments is characterized by radiogenic Pb
due to supply of Pb from radioactive decay of 238U, 235U,
and 232Th (Mukal et al. 1993; Erel et al. 1997; Hansmann
and Koppel 2000), which (206Pb/204Pb, 207Pb/204Pb and208Pb/204Pb) are not modified by the formation of second-
ary mineral phases (Harlavan et al. 1998) and not frac-
tionated during transportation and deposition (Bollhofer
and Rosman 2002), whereas anthropogenic Pb is generally
derived from sulfide ore deposits and is released to envi-
ronment by combustion of gasoline and as a by-product of
industrial activities such as mining and smelting (Erel et al.
1997; Mukal et al. 1993; Bollhofer and Rosman 2002;
Zhang et al. 2008). As Pb ores are geochemical anomalies
characterized by very low U/Pb and Th/Pb ratios compared
to ordinary rocks, and their Pb isotopic composition
remained constant since their formation (Hansmann and
Koppel 2000), the anthropogenic Pb is significantly char-
acterized by age-dependent isotopic compositions which
are generally unradiogenic (Erel et al. 1997), and distinctly
different from the rock-derived Pb (Erel et al. 1997;
Hansmann and Koppel 2000; Zhang et al. 2008). Thus, the
Pb isotope is a powerful tool for scientists to trace metal
source in environment, which has been widely used to
identify the sources of metals in sediments (Millot et al.
2004; Choi et al. 2007; Cicchella et al. 2008; Zhang et al.
2008; Lee et al. 2008; Bur et al. 2009).
Although many researchers attributed heavy metal con-
tamination of the river sediments to industrial activities
popularized in the upper river areas (Zhai 1986; Chen and
Zhang 1986; Zhang and Zhao 1996; Yao et al. 2006a), there
are almost no data that can support their results because it is
difficult to distinguish the metal sources based on metal
concentrations alone (Roussiez et al. 2005). Metal source is a
fundamental parameter that controls the chemical and
physical properties of sediments, and the extent and time-
scale of material transport to water courses (Stutter et al.
2009). Because trace metals themselves can shine lights on
their sources (Vital and Stattegger 2000; Yang et al. 2006;
Sensarma et al. 2008; Singh 2009, 2010), and Pb isotopes are
able to offer direct evidence on sources of metal Pb (Mukal
et al. 1993; Church et al. 1999; Millot et al. 2004; Zhang et al.
2008), the present work takes a geochemical study on both
trace metals and Pb isotopes of the river sediments. The
purpose of the study is to make a geochemical constrain on
metal source, so as to better understand the geochemical
process of heavy-metal contamination.
Materials and analytical methods
The study area and sampling
This study focused on sediments of the lowermost
Xiangjiang River. The river follows northward from vast
areas of the Hunan province, and the bedrocks of it mostly
include the Indosinian granites (GR), the Palaeozoci
limestone (PL), the Palaeozoci sandstones (HS), the
Mesozoic red sandstones, and the Quaternary sediments, as
shown in Fig. 1. The climatic conditions are subtropically
humid with high precipitation (annual precipitation is
1,500 mm) and medium daily temperature exceeds 10�C
(Zhang and Zhao 1996; Guo et al. 2008). Water of the river
is slightly basic with pH values from 7.6 to 7.7 (Guo et al.
2008). Such climatic conditions are favorable for rock
weathering.
Sediments were sampled at different places of the
lowermost river: the Wanhe village, Xiangying town,
Quyuan village, and Qingshan village. The former three
sites are located in the river channel and the latter in the
Dongting Lake. In order to get samples of different rock
properties of the sediments, sediment cores at above places
were drilled using an organic glass tube with diameter of
75 mm and length of 120 cm. The tube was cleaned using
5% HCl and then de-ionized water before vertically pushed
into the sediments. Sediment cores from the above sam-
pling sites were named as WH, XY, QN, and QS core,
respectively, as shown in Fig. 1. Length of the sediments
cores is 84, 78, 40, and 45 cm, respectively. Based on color
and roughly silty contents, the WH and XY cores were
separated into two layers (Fig. 2): the upper light brownish
silty layer (samples W1–W20 for WH core, and X39–X17
for XY core) and the lower dark muddy layer (W21–W43
for WH core, and X16–X1 for XY core). The upper layer
sediments consist of silt, clay minerals, mica, and minor
sands and organic matters. The lower layer generally clay
minerals and organic maters. The color and silty compo-
sition of the QN (Q1–Q20) and QS (S1–S23) core
1456 Environ Earth Sci (2011) 64:1455–1473
123
sediments (photos omitted) are similar to that of the lower
dark muddy layer of both the WH and XY cores. Sediment
samples were collected by sub-sampling the sediment cores
at an interval of 2 cm from top to bottom or vice versa, and
were collected using clear plastic seal bags. Sampling was
done in November 2007.
Sample treatments and geochemical analysis
Samples were dried under room temperature in laboratory.
The dried samples were sieved at first to remove small
pieces of macrophytes, and then powdered. 50 g powders
were then ground and sieved to -200 mesh size (\75 lm)
using an agate mortar and Nylon sieve, and homogenized.
50.00 mg powders were first baked at 700�C to destroy
organic matters, and then digested using a mixed acid
solution of HNO3 ? HF in a disposable platinum crucible.
Then the dissolved samples were diluted using 2% HNO3
for analysis. Trace metals were measured using a Perkin-
Elan 6000 ICP-MS machine at the Key Laboratory of
Isotopic Geochemistry, Chinese Academy of Science.
Several USGS and Chinese soil and basalt standard refer-
ences, such as GSS-5, GSS-7, GXR-6 (soil) and BHVO-2,
BCR-2 (basalt) were repeatedly measured with samples to
monitor the quality of ICP-MS measurements, and the
results were generally within the range of ±7% of certified
values. Analytical precision for trace metals is better than
5% (Liu et al. 1996).
Pb isotopic ratios (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb,208Pb/206Pb and 207Pb/206Pb) of bulk sediments from the
XY and QS cores were measured using a multi-collector
ICP-MS (Nu Plasma) machine at the State Key Lab of
Environmental Geochemistry, Chinese Academy of Sci-
ence. Powdered samples were digested using a mixed acid
solution of HF ? HClO4 ? HNO3. The digestion solution
was diluted to a final Pb concentration of ca. 2 ng/ml with
2% high-purity HNO3. Pure Pb fractions were collected by
an anion exchange resin Dowex-1X8. Addition of Tl spike
to each sample was used for mass bias correction using the205Tl/203Tl value of 2.3875. Accuracy was checked by
running the US NIST Standard Reference Material 981
(n = 20) which gives values of 16.9405 ± 0.001,
15.4963 ± 0.0008, 36.7219 ± 0.003, 2.1677 ± 0.00008,
and 0.914750 ± 0.0002 (1r) for 206Pb/204Pb, 207Pb/204Pb,208Pb/204Pb, 208Pb/206Pb, and 207Pb/206Pb, respectively.
The precision (1r) was 0.05% for 206Pb/204Pb, 0.04% for207Pb/204Pb, 0.1% for 208Pb/204Pb, 0.002% for 208Pb/206Pb
and 0.001% for 207Pb/206Pb.
Results
Trace metals
Analyzing results of 23 trace metals are reported in
Table 1. These trace metals include alkali metal Ba,
Fig. 1 General geological map (Zhang et al. 1987) showing bedrocks
of the Xiangjiang River (a) and location of the study area showing
sites of sediment cores (b). 1, The Quaternary sediments; 2, the
Mesozoic red sandstones; 3, the Palaeozoci limestone (PL); 4, the
Hunan sandstones (HS); 5, the Indosinian granites (GR); 6, the
Dongting Lake
Environ Earth Sci (2011) 64:1455–1473 1457
123
transition metals Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd,
Th, U, Zr, Hf, Nb and Ta, A-group metals Sn, Sb, Pb
and Tl, and rare earth La. It is seen that concentrations of
most metals in the river sediments are considerably
variable. For example, the notorious pollutants Cd has
concentrations ranging from 1.95 to 23.5 mg/kg, with
average of 5.89 mg/kg (coefficient variation, CV = 0.95)
in the upper layer sediments, and ranging 18.5 to
71.3 mg/kg, with average of 39.0 mg/kg (CV = 0.49) in
the lower layer sediments of the WH core. Among these
trace metals, metals Bi, Sc, V, Cr, Mn, Co, Tl, Th and U
generally show wider variations of concentrations in the
river (WH, XY and QN) sediments (CV [ 11.0%) than
in lake (QS) sediments (CV \ 9%). It is also noted that
trace metals Zr, Hf, Nb and Ta generally display minor
variations of concentrations in all the sediments, with CV
mostly less than 15%.
Concentrations of trace metals Bi, Sc, V, Cr, Mn, Co,
Ni, Cu, Zn, Mo, Cd, Pb and Th are significantly increased
from the upper to the lower layer sediments in the WH and
XY cores (Table 1). Moreover, concentrations of these
trace metals are increased from the upper-river WH sedi-
ments through the XY to the down-river QN sediments. For
example, the average concentrations of metal Bi are
3.71 mg/kg in upper- and 4.29 mg/kg in lower-layer sedi-
ments of the WH core, they are increased up to 8.29 mg/kg
in upper- and 7.75 mg/kg in lower-layer sediments of the
XY core, and up to 16.6 mg/kg in the QN core sediments
(Table 1). However, concentrations of all trace metals are
significantly decreased from the river sediments to the lake
Fig. 2 Photos of WH and XY cores showing rock properties of sediment cores and subsample locations
1458 Environ Earth Sci (2011) 64:1455–1473
123
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1.3
70
22
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6.1
80
21
5.4
6.4
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CV
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0.1
80
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0.1
60
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0.1
30
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0.1
70
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0.1
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0.2
00
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0.1
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30
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0.1
40
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0.1
3
Environ Earth Sci (2011) 64:1455–1473 1459
123
Ta
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Met
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Ba
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.26
0.2
90
.33
0.2
40
.59
0.1
90
.25
0.2
90
.31
0.1
40
.51
0.1
80
.11
0.8
10
.19
0.2
80
.33
0.1
20
.09
0.2
0
QN
core
Q1
61
1.4
15
.60
20
.46
14
6.6
97
.95
35
86.6
27
.26
69
.12
83
.94
60
8.8
3.2
75
20
.74
62
.57
13
.12
23
.21
.859
30
.84
9.0
80
22
8.3
6.9
46
21
.18
2.4
61
56
.32
Q2
61
9.2
16
.28
20
.93
17
9.4
11
6.8
49
06.2
28
.34
10
1.9
96
.54
63
7.2
4.0
61
20
.35
50
.89
35
.81
22
7.2
1.8
50
31
.24
9.5
59
22
3.8
7.1
06
21
.42
.471
65
.39
1460 Environ Earth Sci (2011) 64:1455–1473
123
Ta
ble
1co
nti
nu
ed
Met
als
Ba
Bi
Sc
VC
rM
nC
oN
iC
uZ
nM
oC
dS
nS
bP
bT
lT
hU
Zr
Hf
Nb
Ta
La
Q3
61
7.3
19
.46
20
.44
20
0.5
13
4.5
63
91
31
.09
11
51
02
.96
92
.54
.13
02
2.9
95
9.0
21
7.1
32
60
.61
.811
31
.74
9.5
65
22
9.8
7.3
22
2.4
42
.573
69
.86
Q4
57
3.5
31
.86
20
.95
18
3.5
13
4.2
55
82.5
28
.89
7.6
31
32
.49
17
.64
.87
52
9.6
68
7.3
72
3.0
33
57
.91
.917
29
.35
9.3
92
16
.96
.882
21
.76
2.7
04
75
.94
Q6
59
7.8
27
.10
20
.05
15
1.6
11
9.9
40
71
27
.88
72
.68
11
4.3
10
41
3.3
02
36
.62
82
.95
22
.27
35
3.1
1.8
73
29
.46
8.8
19
22
1.3
7.0
42
1.0
52
.566
68
.52
Q8
59
7.6
16
.20
18
.56
13
8.9
10
7.4
33
17.2
27
.57
3.3
79
7.5
77
87
.62
.90
63
0.6
25
8.2
91
3.7
92
27
.51
.749
28
.86
8.2
46
21
7.4
6.6
88
21
.28
2.4
52
62
.34
Q9
57
6.4
13
.07
21
.22
16
3.7
11
7.4
39
41
29
.73
77
.98
11
1.9
92
7.6
3.0
45
36
.71
65
.96
16
.29
25
1.6
1.8
27
27
.32
8.3
72
21
7.0
6.5
28
19
.39
2.3
64
64
.87
Q1
16
02
.91
7.1
81
9.6
31
35
.21
25
.93
11
3.2
29
.89
67
.42
10
7.5
96
7.5
2.3
74
44
.19
90
.14
11
.97
20
2.0
1.6
92
25
.72
7.1
11
22
4.0
6.9
15
20
.51
2.5
78
64
.29
Q1
35
77
.49
.90
01
8.7
21
34
.01
23
.23
47
3.1
27
.76
6.6
79
0.4
39
65
.22
.25
74
4.4
84
6.4
51
4.3
11
83
.21
.611
24
.87
6.8
78
24
0.7
7.5
24
19
.69
2.4
28
59
.08
Q1
45
58
.81
0.5
72
0.6
81
63
.61
38
.84
30
7.2
27
.05
86
.07
96
.59
86
2.4
2.7
77
39
.25
45
.68
23
.28
18
7.1
1.6
64
26
.81
8.3
23
24
6.5
7.3
69
20
.34
2.3
73
56
.78
Q1
65
89
.41
3.8
32
0.3
21
48
.01
47
.73
38
8.7
27
.75
69
.91
04
.41
13
4.6
2.2
81
59
.80
59
.27
10
.60
23
0.4
1.6
49
26
.89
7.7
06
25
0.9
7.9
07
20
.25
2.4
23
60
.96
Q1
96
08
.01
2.9
32
0.4
71
51
.91
28
.73
67
9.9
27
.10
83
.69
10
8.8
11
65
.33
.29
57
3.2
95
0.3
71
3.8
62
80
.31
.757
27
.98
8.1
85
22
4.5
7.0
67
19
.85
2.3
97
59
.38
Q2
06
26
.21
2.9
42
0.0
51
39
.71
32
.62
60
32
7.7
81
01
.41
01
.51
07
62
.43
66
4.8
84
7.1
91
3.5
12
45
.61
.795
26
.84
7.5
72
24
6.4
7.4
93
19
.95
2.3
78
60
.06
Av
erag
e5
96
.61
6.6
92
0.1
91
56
.61
25
.04
02
7.7
28
.30
83
.29
10
3.7
90
6.4
3.1
50
40
.28
62
.01
17
.61
24
8.4
1.7
70
28
.30
8.3
70
22
9.8
7.1
40
20
.70
2.4
70
60
.77
CV
0.0
40
.38
0.0
50
.14
0.1
10
.28
0.0
40
.21
0.1
10
.16
0.2
70
.37
0.2
30
.46
0.2
10
.06
0.0
70
.12
0.0
60
.05
0.0
50
.04
0.0
9
QS
core
QS
15
12
.20
.91
41
4.7
61
12
.51
12
.21
01
4.8
19
.49
62
.41
54
.26
14
4.6
5.0
72
0.9
99
8.2
03
1.7
25
52
.64
0.7
54
14
.04
3.1
97
24
5.3
6.7
86
18
.52
1.4
75
40
.01
QS
35
73
.80
.97
11
6.6
61
26
.99
0.7
51
07
3.6
20
.38
49
.51
55
.87
15
5.8
0.8
56
1.0
46
9.7
28
8.1
28
60
.66
0.8
75
15
.33
3.3
29
23
2.8
6.6
29
18
.75
1.5
77
44
.13
QS
45
87
.60
.95
01
7.6
41
24
.89
0.0
19
61
.11
9.7
44
8.2
25
1.1
91
52
.10
.86
40
.92
79
.29
42
.043
56
.88
0.9
21
17
.00
3.7
33
24
3.4
7.0
51
8.2
61
.541
47
.23
QS
55
91
.20
.92
41
8.1
91
34
.99
8.5
91
10
9.5
21
.77
58
.19
56
.36
16
8.1
0.9
09
1.0
74
8.9
07
2.2
76
59
.39
0.8
83
16
.66
3.9
16
24
4.5
7.0
32
19
.63
1.5
77
46
.65
QS
75
43
.20
.73
11
6.5
81
26
.09
0.6
11
08
7.3
21
.89
53
.29
61
.51
17
2.1
0.8
80
1.2
04
7.2
06
1.5
09
60
.89
0.6
97
14
.42
3.2
41
25
1.1
6.9
77
19
.71
1.5
27
45
.25
QS
96
12
.60
.83
61
9.7
21
49
.61
06
.41
31
3.1
24
.67
59
.23
77
.81
21
1.1
1.1
64
1.2
52
8.8
88
2.1
26
88
.23
0.8
12
15
.66
3.6
05
22
5.9
6.2
27
21
.25
1.6
29
49
.38
QS
11
64
1.4
0.8
43
19
.44
15
0.6
10
5.8
13
01.0
24
.66
0.7
87
5.0
12
09
.71
.08
81
.21
78
.56
54
.38
6.8
20
.783
14
.93
3.4
62
21
8.4
5.9
77
20
.22
1.5
54
45
.59
QS
13
60
4.0
1.0
75
18
.65
14
1.7
10
2.2
13
65.1
23
.35
7.7
76
7.5
71
90
.71
.11
51
.25
48
.22
41
.954
69
.85
0.7
81
16
.25
3.6
57
25
3.7
7.1
61
20
.33
1.5
81
49
.2
QS
15
56
2.6
0.7
36
16
.31
12
7.0
92
.97
12
18.3
20
.84
10
35
7.4
11
71
.60
.91
61
.19
17
.46
22
.322
63
.21
0.7
43
13
.85
3.2
49
25
4.6
6.8
65
18
.71
1.4
52
43
.61
QS
17
55
4.3
0.8
53
16
.66
12
7.9
93
.93
11
37.9
21
.47
51
.33
58
.18
16
7.9
0.8
67
1.1
17
8.5
85
2.5
36
2.4
00
.787
15
.58
3.4
28
25
9.7
7.3
19
18
.70
1.5
76
46
.31
QS
19
61
1.2
0.9
33
18
.85
13
8.9
10
2.7
13
07.7
22
.65
6.8
66
0.9
91
78
.61
.01
91
.17
19
.05
22
.481
63
.25
0.8
65
16
.63
3.6
52
24
1.7
6.8
48
19
.02
1.5
26
46
.6
QS
20
58
0.6
0.8
79
17
.62
12
7.5
98
.47
11
96.7
20
.75
52
.57
56
.17
16
4.5
1.2
66
1.3
65
8.8
48
3.0
37
56
.27
0.8
53
15
.74
3.4
91
24
4.3
6.8
71
8.8
81
.515
46
.07
QS
21
57
1.7
0.9
53
17
.40
12
3.9
97
.93
12
51.9
21
.02
51
.15
54
.55
16
3.6
0.9
14
1.4
96
9.5
81
4.9
40
55
.59
0.8
43
16
.00
3.6
06
24
4.7
6.8
51
18
.97
1.5
67
45
.27
QS
22
57
5.6
0.9
97
16
.25
11
5.1
87
.81
10
54.5
19
.23
46
.03
49
.28
15
3.4
0.8
32
1.3
78
10
.88
5.2
82
53
.65
0.8
89
16
.86
3.6
22
64
.57
.415
18
.77
1.6
14
45
.85
QS
23
56
2.1
0.9
02
16
.38
12
1.6
92
.70
11
59
20
.16
14
55
1.8
41
50
.60
.93
51
.37
49
.35
72
.661
54
.45
0.8
93
16
.82
3.6
11
25
2.3
7.2
56
18
.34
1.5
26
44
.38
Av
erag
e5
67
.41
.12
81
6.7
51
25
.79
4.9
81
14
9.7
20
.96
61
.75
57
.75
16
8.9
1.2
47
1.2
43
9.2
78
3.1
81
63
.98
0.8
42
15
.61
3.5
10
24
5.3
6.9
00
18
.79
1.5
45
45
.17
CV
0.0
60
.22
0.0
90
.09
0.0
80
.10
0.0
90
.43
0.1
50
.12
0.8
50
.13
0.1
10
.56
0.1
70
.08
0.0
60
.06
0.0
40
.06
0.0
50
.03
0.0
5
BV
a5
54
.10
.30
6.8
09
74
44
50
10
.32
1.2
20
.08
3.3
1.6
50
.33
2.5
1.1
02
3.3
0.6
01
4.8
3.6
27
07
.11
90
.9
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rep
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var
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each
aver
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val
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the
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(Li
etal
.1
98
6)
Environ Earth Sci (2011) 64:1455–1473 1461
123
(QS) sediments. For example, from WH through XY and
QN to QS core, the average concentrations of Bi decreased
from the above values to 1.13 mg/kg. That is to say that the
concentrations of trace metals display a significant spatial
variation from upper river to down-river sediments, and
then to the lake sediments.
Ratios of metal pairs Nb/Ta, Zr/Hf, Th/Sc, Co/Th, Cr/
Th, Zr/Sc and La/Sc are summarized in Table 2. Ratios Nb/
Ta and Zr/Hf are relatively constant in river sediments,
varying around 8.4 and 33.3, with CV mostly less than 0.08
and 0.05, respectively (Table 2). Other metal ratios are
generally variable in the river sediments, for example, from
the upper WH ? lower WH ? upper XY ? lower XY
layer sediments to QN core sediments, average ratios of
Th/Sc vary from 1.91, 1.53, 2.34, 3.05 to 1.40, with CV
mostly higher than 0.10. For the lake (QS) sediments, ratios
of Nb/Ta, Zr/Hf and La/Sc are minor variable, with CV less
than 0.08. But others are also variable, with CV higher than
0.11 (Table 2). Zr/Hf ratios of the river sediments (average
33.6, n = 72) are equal to that of the lake sediments
(average 35.6, n = 15), and the average Zr/Hf ratio of all the
sediments (35.5, n = 87) seems to be similar to that of the
east China upper continental crust (EUCC, 36.7, Gao et al.
1999). Other metal ratios do not display such signatures.
Pb isotopes
Pb isotopic compositions of bulk sediments from the XY
and QS cores are reported in Table 3. Pb isotopic ratios206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, 208Pb/206Pb and207Pb/206Pb vary in minor variations, ranging in 18.509–
18.680, 15.687–15.728, 38.774–38.959, 2.085–2.097 and
0.841–0.848, with average of 18.585, 15.711, 38.874,
2.0917 and 0.8453, respectively, for the XY (river) sedi-
ments; and 18.511–18.646, 15.674–15.692, 38.671–38.852,
2.084–2.095 and 0.842–0.849, with average of 18.572,
15.685, 38.778, 2.0881 and 0.8445, respectively, for the QS
(lake) sediments. It is seen that Pb isotopic ratios of the
river (XY) sediments are generally higher than that of the
lake (QS) sediments, as shown by their average values
(Table 3). Compared to the Pb isotopic composition of
galena from Pb–Zn ore deposits (GAS) distributed in
southern Hunan province (Zhu 1995; Liu et al. 2001; Yao
et al. 2006b) and from Pb–Zn ore deposits (GAE) distrib-
uted in eastern Hunan province (Liu et al. 2001), Pb iso-
topic ratios 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb of the
river and lake sediments (Table 3) are distinctly higher,
and they are also higher than that of the Palaeozoic lime-
stone (Tao et al. 2001) and of the automobile exhausts (Zhu
et al. 2001), suggesting Pb isotopic compositions of the
sediments are more radiogenic than the galena of Pb–Zn
ore deposits, the Palaeozoic limestone and the automobile
Table 2 Ratios of some trace metal pairs for the sediments from the
lowermost Xiangjiang River
Ratio Nb/Ta Zr/Hf Th/Sc Co/Th Cr/Th Zr/Sc La/Sc
WH core—upper layer
W1 7.99 32.97 2.45 0.68 3.01 37.05 5.92
W2 8.42 33.08 2.23 0.76 3.65 40.55 4.87
W3 6.92 32.87 2.08 0.78 2.98 31.21 4.23
W4 8.46 32.80 1.67 0.79 3.95 19.74 3.57
W5 9.04 32.96 2.05 0.65 3.20 18.87 3.82
W6 8.82 35.27 1.97 0.90 3.47 36.35 4.77
W7 7.28 33.81 1.69 0.91 4.05 41.64 4.61
W9 8.15 34.79 2.35 0.78 3.26 41.24 5.85
W11 8.55 31.43 2.28 0.77 3.45 32.34 5.26
W13 8.82 32.05 1.81 0.79 3.70 27.55 4.63
W14 9.45 34.88 1.64 0.79 4.08 29.23 4.02
W16 9.17 33.89 1.65 0.79 3.78 23.86 4.07
W18 8.59 33.60 1.71 0.77 4.23 20.78 4.03
W19 8.92 33.28 1.56 0.95 5.12 22.91 4.09
W20 8.14 32.44 1.49 1.28 5.32 18.07 3.57
Average 8.45 33.34 1.91 0.83 3.82 29.43 4.49
CV 0.08 0.03 0.16 0.18 0.18 0.29 0.17
WH core—lower layer
W22 8.33 33.96 1.60 1.22 5.42 19.80 3.77
W24 8.23 34.15 1.46 1.16 6.25 16.36 3.45
W25 7.31 32.14 1.56 1.01 5.83 17.43 3.45
W26 8.46 34.06 1.35 1.13 6.67 14.56 3.34
W27 8.14 33.95 1.40 1.39 6.86 14.43 3.39
W29 8.18 33.61 1.47 1.99 6.15 15.92 3.53
W30 8.33 33.95 1.62 1.06 5.83 15.57 3.55
W31 8.61 33.62 1.54 1.03 6.44 14.96 3.57
W33 8.35 34.36 1.38 0.97 6.79 13.30 3.09
W35 9.14 33.09 1.29 1.00 5.47 12.59 2.83
W37 8.91 34.76 1.38 1.00 5.84 11.95 3.19
W39 8.62 34.44 1.63 0.85 4.78 12.12 3.19
W40 8.49 32.87 1.82 0.89 4.60 14.51 3.46
W41 8.13 33.15 1.69 0.85 4.96 16.29 3.33
W43 8.46 33.14 1.70 0.89 5.24 16.67 3.63
Average 8.38 33.68 1.53 1.10 5.81 15.10 3.39
CV 0.05 0.02 0.10 0.26 0.12 0.14 0.07
XY core—upper layer
XY38 7.44 32.19 2.59 0.64 3.51 87.52 5.10
XY37 6.79 36.81 3.38 0.45 2.24 103.37 6.76
XY36 2.32 33.70 4.60 0.38 1.92 52.07 6.79
XY35 6.49 31.99 4.27 0.36 2.17 37.47 7.54
XY34 7.50 34.52 1.88 0.64 3.32 10.22 3.50
XY32 8.00 31.33 1.91 0.70 4.15 21.46 3.71
XY31 8.62 33.79 2.17 0.58 3.29 36.44 4.37
XY30 8.29 35.89 5.24 0.26 1.55 101.93 7.72
XY28 8.10 35.28 3.36 0.41 3.13 70.88 5.67
XY27 8.44 32.88 2.24 0.57 3.24 23.33 4.22
1462 Environ Earth Sci (2011) 64:1455–1473
123
exhausts. It is noted that sediments probably have similar206Pb/204Pb, 207Pb/204Pb ratios to the Indosinian granites
(Tong 1986; Zhu 1995), but distinctly have higher208Pb/204Pb ratios (average of 38.874 for XY and 38.778
for QS sediments) than the Indosinian granites (average
38.733, Tong 1986; Zhu 1995), suggesting that sedi-
ments are significantly enriched with the thorium radio-
genic Pb.
Discussions
Trace metal enrichment
It is important to estimate the enrichment and contamina-
tion degree of metals in sediments because some metals
such as Sc, Cd, Pb, Tl, Th and U are toxic (Lee et al. 1988;
Peng et al. 2004; N’guessan et al. 2009), and the enrich-
ment factor (EF) developed by Chester and Stoner (1973)
and recommended by IAEA (1992) is commonly applied to
such estimation. The EF value can be calculated by the
following equation:
EF ¼ X=Mð Þsample
.X=Mð Þbackground; ð1Þ
where (X/M)sample is ratio of an evaluated metal X to a
reference element M in sediment samples; (X/M)background
is ratio of background values of relative metals. The key
for the EF calculation using Eq. 1 is to determine a refer-
ence (index) element and the background values of the
metals.
The reference element selected for calculation must be
natural origin, which must meet the requirements: (1) it
must be conservative during weathering, and river transport
and sorting, (2) it must be immobile and not submitted to
Table 2 continued
Ratio Nb/Ta Zr/Hf Th/Sc Co/Th Cr/Th Zr/Sc La/Sc
XY25 9.25 34.31 1.56 0.83 4.74 16.96 3.28
XY24 8.92 33.51 1.69 0.75 4.01 18.84 3.39
XY23 9.05 34.06 1.40 0.86 5.12 13.31 2.90
XY22 9.65 34.05 1.45 0.80 4.48 11.17 3.10
XY20 9.43 33.94 1.26 0.82 5.29 9.32 2.88
XY19 9.50 35.03 1.42 0.77 4.30 10.61 3.08
XY18 6.84 33.83 1.73 0.68 3.95 19.85 3.57
XY17 9.01 33.17 0.80 1.52 8.85 16.12 3.12
Average 8.04 33.89 2.34 0.68 3.95 35.41 4.41
CV 0.21 0.04 0.53 0.41 0.42 0.90 0.38
XY core—lower layer
XY13 9.55 35.94 1.22 0.97 6.74 12.95 2.91
XY11 8.23 30.85 16.20 0.08 0.45 75.31 7.66
XY10 9.69 34.78 1.37 0.89 5.62 20.93 3.10
XY8 9.78 37.50 1.38 0.94 5.61 20.08 3.30
XY6 9.50 34.73 1.52 0.84 4.77 27.33 3.63
XY4 9.62 34.59 1.38 0.84 5.51 12.41 3.00
XY2 9.53 35.93 1.34 0.83 5.79 10.84 2.90
XY1 9.25 35.42 1.41 0.76 4.77 12.12 2.95
Average 9.36 34.96 3.05 0.78 4.85 23.71 3.63
CV 0.05 0.05 1.52 0.32 0.35 0.80 0.40
QN core
Q1 9.31 34.42 1.44 0.76 4.64 11.55 3.05
Q2 8.61 32.87 1.51 0.88 3.18 11.16 3.20
Q3 8.66 31.49 1.49 0.91 3.74 10.69 3.34
Q4 8.72 31.39 1.55 0.98 4.24 11.24 3.72
Q6 8.05 31.52 1.40 0.98 4.57 10.35 3.27
Q8 8.20 31.43 1.47 0.95 4.07 11.04 3.11
Q9 8.68 32.51 1.55 0.95 3.72 11.71 3.50
Q11 8.20 33.24 1.29 1.09 4.30 10.23 3.03
Q13 7.96 32.39 1.31 1.16 4.90 11.41 3.01
Q14 8.11 31.99 1.33 1.11 4.95 12.86 3.03
Q16 8.57 33.45 1.30 1.01 5.18 11.92 2.95
Q18 8.36 31.73 1.32 1.03 5.49 12.35 2.92
Q19 8.28 31.77 1.37 0.97 4.60 10.97 2.93
Q20 8.39 32.88 1.34 1.04 4.94 12.29 3.03
Average 8.44 32.36 1.40 0.99 4.47 11.41 3.15
CV 0.04 0.03 0.01 0.09 0.15 0.08 0.07
QS core
QS1 12.56 36.15 0.95 1.39 7.99 16.62 2.71
QS3 11.89 35.12 0.92 1.33 5.92 13.97 2.65
QS4 11.85 34.52 0.96 1.16 5.29 13.80 2.68
QS5 12.45 34.77 0.92 1.31 5.92 13.44 2.56
QS7 12.91 35.99 0.87 1.52 6.28 15.14 2.73
QS9 13.04 36.28 0.79 1.58 6.79 11.46 2.50
QS11 13.01 36.54 0.77 1.65 7.09 11.23 2.35
QS13 12.86 35.43 0.87 1.43 6.29 13.60 2.64
QS15 12.89 37.09 0.85 1.50 6.71 15.61 2.67
Table 2 continued
Ratio Nb/Ta Zr/Hf Th/Sc Co/Th Cr/Th Zr/Sc La/Sc
QS17 11.87 35.48 0.94 1.38 6.03 15.59 2.78
QS19 12.46 35.29 0.88 1.36 6.18 12.82 2.47
QS20 12.46 35.56 0.89 1.32 6.26 13.86 2.61
QS21 12.11 35.72 0.92 1.31 6.12 14.06 2.60
QS22 11.63 35.67 1.04 1.14 5.21 16.28 2.82
QS23 12.02 34.77 1.03 1.20 5.51 15.40 2.71
Average 12.17 35.57 0.99 1.345 6.10 15.86 2.835
CV 0.04 0.02 0.12 0.11 0.12 0.15 0.08
EUCCa 16.22 36.72 0.60 1.90 8.94 12.53 2.32
SYZb 63.33 30.37 0.95 1.37 6.61 18.92 3.08
CV coefficient variationa East-China upper continental crust after Gao et al. (1999)b Background values of Sediments of the Yangtze River after Yan
et al. (1997)
Environ Earth Sci (2011) 64:1455–1473 1463
123
Table 3 Pb isotopic ratios of the XY and QS core sediments from the Xiangjiang River and average Pb isotopic ratios of reference materials
Sample 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb 208Pb/206Pb 207Pb/206Pb 206Pb/207Pba 208Pb/207Pba
XY core
X1 18.6801 15.7141 38.953 2.08521 0.84122 1.1888 2.4789
X2 18.6206 15.7089 38.905 2.08940 0.84363 1.1854 2.4766
X4 18.5738 15.7031 38.868 2.09266 0.84543 1.1828 2.4752
X6 18.5550 15.6988 38.847 2.09359 0.84606 1.1819 2.4745
X8 18.5710 15.7080 38.877 2.09347 0.84582 1.1823 2.4750
X9 18.5489 15.7026 38.848 2.09435 0.84653 1.1813 2.4740
X10 18.5422 15.7000 38.836 2.09450 0.84672 1.1810 2.4736
X11 18.5028 15.6865 38.774 2.09557 0.84781 1.1795 2.4718
X13 18.6198 15.7141 38.882 2.08821 0.84395 1.1849 2.4743
X14 18.6090 15.7058 38.868 2.08867 0.84400 1.1849 2.4748
X15 18.5633 15.6926 38.834 2.09198 0.84537 1.1829 2.4747
X17 18.5844 15.7151 38.869 2.09148 0.84559 1.1826 2.4734
X18 18.5558 15.7092 38.863 2.09435 0.84658 1.1812 2.4739
X19 18.6060 15.7184 38.900 2.09073 0.84483 1.1837 2.4748
X20 18.6216 15.7254 38.914 2.08975 0.84447 1.1842 2.4746
X21 18.6246 15.7279 38.926 2.09003 0.84448 1.1842 2.4750
X23 18.6110 15.7254 38.915 2.09094 0.84493 1.1835 2.4747
X24 18.6034 15.7218 38.905 2.09130 0.84510 1.1833 2.4746
X25 18.5952 15.7216 38.905 2.09202 0.84542 1.1828 2.4746
X27 18.5183 15.7066 38.845 2.09766 0.84817 1.1790 2.4732
X28 18.5172 15.7057 38.833 2.09713 0.84814 1.1790 2.4725
X30 18.6172 15.7145 38.89 2.08893 0.84408 1.1847 2.4748
X31 18.5991 15.7106 38.866 2.08967 0.84471 1.1839 2.4738
X32 18.5415 15.7045 38.837 2.09454 0.84700 1.1807 2.4730
X34 18.5094 15.7001 38.811 2.09687 0.84822 1.1789 2.4720
X35 18.5147 15.7005 38.818 2.0966 0.84798 1.1792 2.4724
X36 18.5550 15.7083 38.848 2.09367 0.84659 1.1812 2.4731
X37 18.6562 15.7218 38.902 2.08514 0.84269 1.1867 2.4744
X38 18.6469 15.7176 38.928 2.08765 0.84292 1.1864 2.4767
X39 18.6802 15.7253 38.959 2.08558 0.84179 1.1879 2.4775
Average 18.5848 15.7105 38.8742 2.09172 0.84534 1.1830 2.4744
CV 0.06 0.06 0.04 0.16 0.26
QS core
QS1 18.6247 15.6882 38.814 2.08401 0.84233 1.1872 2.4741
QS3 18.5972 15.6872 38.802 2.08645 0.84352 1.1855 2.4735
QS4 18.6044 15.6844 38.814 2.08626 0.84305 1.1862 2.4747
QS5 18.5868 15.6846 38.798 2.08741 0.84385 1.1850 2.4736
QS7 18.5583 15.6834 38.764 2.08879 0.84509 1.1833 2.4717
QS9 18.5107 15.6788 38.707 2.09104 0.84701 1.1806 2.4688
QS11 18.4572 15.6742 38.671 2.09513 0.84921 1.1776 2.4672
QS13 18.5206 15.6815 38.732 2.09127 0.84671 1.1811 2.4699
QS15 18.5252 15.6815 38.737 2.09108 0.84650 1.1813 2.4702
QS17 18.5476 15.6833 38.764 2.08995 0.84556 1.1826 2.4717
QS19 18.5747 15.6841 38.779 2.08773 0.84438 1.1843 2.4725
QS20 18.5986 15.6871 38.804 2.08642 0.84346 1.1856 2.4736
QS21 18.6076 15.6877 38.812 2.08582 0.84307 1.1861 2.4740
QS22 18.6455 15.6915 38.852 2.08374 0.84159 1.1883 2.4760
1464 Environ Earth Sci (2011) 64:1455–1473
123
geochemical processes such as reduction/oxidation,
adsorption/desorption, and diagenetic processes that may
alter its concentration, and (3) it must be highly insoluble
(Peng et al. 2004; Stutter et al. 2009). Many researches
have notified that trace elements Sc, Co, Cr, Cs, Th, Zr, Hf,
Nb, and Ta were immobile during weathering, transporta-
tion and deposition (Nesbitt and Markovics 1997; Peng
et al. 2004; Das et al. 2008; Bur et al. 2009), and were
frequently selected to be the reference elements for EF
calculation (Zhang et al. 2008; Bur et al. 2009; N’guessan
et al. 2009). In this case study, concentrations of trace
elements Zr, Hf and Nb vary relatively in minor variations
(CV \ 0.30; Table 1), suggesting that these metals in the
sediments might be conservative. Plots of concentrations of
Zr versus Hf display a very good linear relationship
(r2 = 0.99) with Zr/Hf ratio of 35.5 (Fig. 3a). This may
suggest that elements Zr and Hf were not fractionated
during weathering, transportation and deposition, and they
may be hosted in residual fraction of the sediments.
Moreover, Zr/Hf ratios of the sediments are similar to that
of the EUCC (Gao et al. 1999), the Palaeozoic limestone
(PL, Yan et al. 1997), and Hunan sandstone (HS, Bai et al.
2007) as shown in Fig. 3a, suggesting Zr and Hf in the
sediments may be of lithological source. Thus, Zr is
selected as a reference element (choice of element Hf
renders the same results) for EF calculation.
Many researchers (Zhang et al. 1983; Li et al. 1986;
Qian and Li 1988; Tong 2005) have investigated the
background values of many elements for sediments of the
Xiangjiang River. Among the published background val-
ues, these suggested by Zhang et al. (1983) and Qian and
Li (1988) did not include elements as more as possible, so
they were not selected as background values in this study.
Background values of elements suggested by Tong (2005)
are also not referenced because they are generally higher
than many other background values, and even much higher
than the background values of elements of the China soils
(Yan et al. 1997). Thus, the background values (Table 1)
suggested by Li et al. (1986) were referenced in this study
because (1) they were suggested by analyzing sediment
samples of 330; (2) they have included trace metals as
more as possible; and more importantly, (3) they are
comparable to the background values of elements of the
China soils (Yan et al. 1997).
The EF is a useful index to reflect the status of envi-
ronmental contamination. It can also be used to identify
the metals produced by natural (weathering) processes
from these by anthropogenic activities (Sutherland 2000;
Zhang and Liu 2002; Zhang et al. 2008; and references
therein). Sutherland (2000) divide the contamination into
different degrees based on EF values, i.e., EF B 2 sug-
gests deficiency to minimal enrichment, EF = 2–5
moderate enrichment, EF = 5–20 significant enrichment,
EF = 20–40 very high enrichment, and EF [ 40 extremely
high enrichment. Zhang and Liu (2002) recommended
using EF = 1.5 as an assessment criterion, i.e., metal with
EF values between 0.5 and 1.5 are believed to be entirely
from natural weathering processes, these with EF values
greater than 1.5 are thought to be anthropogenic source.
Complementing with the criteria suggested by Sutherland
(2000), here we use EF = 2.0 an assessment criterion to
identify the anthropogenic metals (EF [ 2) from metals
produced by natural (weathering) process (EF \ 2).
Then the EF values of heavy metals Ba, Bi, Sc, V, Cr,
Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th and U were
calculated, and the results are summarized in Fig. 4. It
Table 3 continued
Sample 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb 208Pb/206Pb 207Pb/206Pb 206Pb/207Pba 208Pb/207Pba
QS23 18.6141 15.6894 38.823 2.08566 0.84288 1.1864 2.4745
Average 18.5715 15.6845 38.778 2.08805 0.84455 1.1841 2.4724
CV 0.003 0.0020 0.001 0.001 0.002
GASb 18.5078 15.6665 38.8304 2.09806 0.84648 1.1814 2.4786
GAEc 18.3361 15.6517 38.7308 2.11227 0.85360 1.1715 2.4745
GRd 18.7758 15.6945 38.7328 2.06291 0.83589 1.1963 2.4679
PLe 18.1602 15.6136 38.2760 2.10769 0.85977 1.1631 2.4515
AEf 18.0967 15.5770 37.7403 2.08549 0.86077 1.1618 2.4228
a 206Pb/207Pb and 208Pb/207Pb are calculated by using corresponding measured ratiosb Galena from Pb–Zn ore deposits distributed in Southern Hunan after Zhu (1995), Liu et al. (2001) and Yao et al. (2006b)c Galena from Pb–Zn ore deposits distributed in eastern Hunan after Liu et al. (2001)d Granite rocks of the Indosinian period in Hunan after Tong (1986) and Zhu (1995)e The Palaeozoic limestone after Tao et al. (2001)f Automobile exhaust after Zhu et al. (2001)
Environ Earth Sci (2011) 64:1455–1473 1465
123
shows that the enrichment degrees of different metals are
varied from each other, and from different sediment cores.
According to the assessment criterion suggested by Suth-
erland (2000), the notorious Cd is extremely highly enri-
ched in the WH and QN sediments (average EF [ 78).
Metal Bi is extremely highly enriched in the QN sediments
(EF = 61), and very highly enriched in the WH (average
EF = 23) and XY (average EF = 27). Sn is very highly
enriched in the QN (average EF = 27) sediments. Other
metals including Zn, Sn, Sb, Pb, Sc, Cr, Mn, Co, Ni, Cu
and Tl are highly and moderately enriched in the river
(WH, XY and QN) sediments (Fig. 4a–c, e). For the lake
(QS) sediments, however, most metals such as Bi, Sc, Cr,
Mn, Co, Ni, Cu, Zn, Cd, Sn, Sb and Pb are moderately
(2 \ EF \ 5) enriched (Fig. 4d). Therefore, heavy metals
that may be potential pollutants generally include Cd, Bi,
Fig. 3 Plots of Zr versus Hf (a), Th/Sc versus Zr/Sc (b), Cr/Th versus
Sc/Th (c), Co/Th versus Sc/Th (d), and Th/Co versus Cr/Th (e). GRthe Indosinian granites (Tong 1986; Zhu 1995; Shi et al. 2007);
EUCC East China upper continental crust (Gao et al. 1999); PL the
Palaeozoic limestone (Yan et al. 1997); HS Hunan sandstone (Bai
et al. 2007)
1466 Environ Earth Sci (2011) 64:1455–1473
123
Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl. These
significantly enriched metals (EF [ 2) in the sediments
may have additional portions derived from non-crustal
materials, and major proportion of them may be contrib-
uted from anthropogenic activities, while other metals (Ba,
V, Mo, Th, U, Zr, Hf and Ta) that have EF values less than
2 may be contributed mostly from natural/lithological
(weathering) process.
It is then concluded that sediments of the Lowermost
Xianjiang River may be contaminated by heavy metals Cd,
Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl, and most
of these metals may be of anthropogenic sources.
Fig. 4 Enrichment factor (EF) for heavy metals in WH (a), XY (b),
QN (c) and QS (d), and the average values (e) of river sediments
(WH, XY and QN). For enrichment degree, see the text. Box of the
plots extend from the lower quartile (25%) to the upper quartile
(75%), covering the median (line) and the mean (black dot) values.
Circle and star point above and below the box represent 90th and 10th
percentiles. Vertical bars represent the error
Environ Earth Sci (2011) 64:1455–1473 1467
123
Source implication from trace metals
Trace elements Th, Sc, Co, Cr, Zr, Hf, Nb and REE have
short residence time in water and therefore are almost
quantitatively transferred into sediments (Singh 2010).
Concentrations of these trace metals, and their ratios such
as Th/Sc, Co/Th, La/Sc, Zr/Hf and Cr/Th are sensitive to
the nature of sediment source (Vital and Stattegger 2000;
Yang et al. 2006; Sensarma et al. 2008; Singh 2009, 2010).
Among these element ratios, the Th/Sc ratio is a sensitive
index of the bulk composition of the provenance, and Zr/Sc
ratio is a useful index of zircon enrichment (Vital and
Stattegger 2000 and references therein). Plot of Th/Sc
versus Zr/Sc can evaluate the role of heavy mineral con-
centration during sedimentary sorting (Vital and Stattegger
2000). Enrichment of zircon (high Zr/Sc ratio) can be
observed in a few sediment samples but to a lesser extent in
most samples (Fig. 3b), indicating sedimentary sorting and
recycling. The Zr/Hf ratios of the sediments (average 35.5)
are similar to that of the EUCC (35.8, Gao et al. 1999).
This indicates that the heavy minerals (e.g., zircon), the
major container for Zr and Hf, are well mixed during
sorting and deposition. Moreover, the Cr/Th is significantly
correlated to Sc/Th (r2 = 0.68), and plots of Cr/Th versus
Sc/Th plot (Fig. 3c) fall almost in the field that are located
between end-members of mafic and felsic rocks. This
suggests that the sediments may result from extensively
mixing of different rock sources (Vital and Stattegger
2000).
Because Th and REE are typically more concentrated in
granitic rocks, and Sc, Cr and Co enriched in basic rocks,
the ratios and plots between Co/Th versus Sc/Th, Th/Co
versus Cr/Th can help us to distinguish between the mafic
and felsic source of sediments (Singh 2009, 2010; Yang
et al. 2006). Plots of ratios Sc/Th versus Co/Th, and Cr/Th
versus Th/Co fall in a field that locates between EUCC and
granite (Fig. 3d, e), indicating that sediments were derived
from the mixing of granitic components (GR, Tong 1986;
Zhu 1995; Shi et al. 2007) and other fractionated crust
rocks probably including the Palaeozoic sandstones (Bai
et al. 2007), negligible contribution from mafic rocks.
Ferromagnesian elements Fe, Cr, Ni are enriched in
mafic and ultramafic rocks and elevated abundances of
them in sediments may indicate the addition of compo-
nents derived from mafic lithologies (Sensarma et al. 2008
and references therein). However, the abundances of Cr
(\150 mg/kg) and Ni (\75 mg/kg) are relatively lower,
and the Cr/Ni ratios are higher ([2.18 for WH and XY,
and [1.8 for QN and QS sediments). Concentrations of
metals Cr, Ni and Co are not correlated to metals Fe and
Mn. Thus, the mafic lithologies did not contribute sig-
nificantly to the sediments, further supporting the above
conclusion.
Therefore, natural contributors of trace metals to the
river sediments may include mostly the products from
weathering of the Indosinian granites (GR), and the Pal-
aeozoci sandstones (HS), but not the mafic rocks and the
Palaeozoic limestones.
Source implication from Pb isotopes
In order to trace in detail the sources of metal Pb, ratios of208Pb/207Pb to 206Pb/207Pb are plotted in Fig. 5, in which
the galena (GAS) from Pb–Zn ore deposits distributed in
southern Hunan province (Zhu 1995; Liu et al. 2001; Yao
et al. 2006b), the galena (GAE) from Pb–Zn ore deposits
distributed in eastern Hunan province (Liu et al. 2001), the
bedrocks of the Indosinian granite rocks (GR, Tong 1986;
Zhu 1995; Shi et al. 2007) and Paleozoic limestone (PL,
Tao et al. 2001), and the automobile exhausts (AE, Zhu
et al. 2001) are included for comparison. Plots of the
sediments fall within the field of GAS plots, suggesting
Pb–Zn ores may be a major contributor of metal Pb to the
sediments. Also, plots of the sediments are very close to the
GAE, and to the GR, but are distantly far from the PL and
AE. This suggests that lead in the sediments might be
related to and/or contributed from the Pb–Zn ore deposits
distributed in eastern Hunan (GAE, Liu et al. 2001) and the
GR (Tong 1986; Zhu 1995), but with less contribution from
the Palaeozoci limestone (Tao et al. 2001) and automobile
exhausts (Zhu et al. 2001).
Because automobile exhausts (gasoline) may not be the
major contributor of Pb for the river sediments (Fig. 5a),
we plotted 206Pb/207Pb to 1/EF (N’guessan et al. 2009)
instead of 1/[Pb] (Roussiez et al. 2005; Zhang et al. 2008)
to determine the mixture of various potential Pb sources. It
is seen that 206Pb/207Pb is not correlated to 1/EF for the XY
(river) sediments (Fig. 5b), which displays similar feature
to the sediments of the Yangtze River (Zhang et al. 2008).
Such patterns of Pb isotopes to EF values suggest that
metal Pb in the XY sediments may come from many dif-
ferent sources with different 206Pb/207Pb ratios and Pb
concentrations. Such multi-sources of Pb may include
major Pb contributed from the Pb–Zn ores (GAS) distrib-
uted in the upper river areas (Zhu 1995; Liu et al. 2001;
Yao et al. 2006b) and Pb–Zn ore deposits/mines (GAE) in
eastern Hunan (Liu et al. 2001), and Pb from the Indosinian
granitic rocks (Tong 1986; Zhu 1995; Shi et al. 2007)
probably through weathering. Pb from GAS and GAE
consist of the anthropogenic portion of metal Pb in the
sediments, and they might be concentrated through dis-
persion of Pb emitted from mining, smelting, and refining,
etc. in the watershed. Pb from the granite rocks and Pal-
aeozoic sandstones consist of the natural proportion of
metal Pb in the sediments, which might be mostly depos-
ited from weathering products of such bedrocks.
1468 Environ Earth Sci (2011) 64:1455–1473
123
For the lake (QS) sediments, 206Pb/207Pb ratios are
significantly correlated to 1/EF (r2 = 0.71, Fig. 5c). This
indicates some source differences between the lake (QS)
and river (XY) sediments, and Pb in the lake sediments
may consist mostly of the anthropogenic Pb with minor
Pb of natural source. The Pb isotopic composition
(206Pb/207Pb ratio) of anthropogenic Pb can be determined
using the correlations of 206Pb/207Pb to 1/EF (Fig. 5c).
When 1/EF tends to zero, it gives a 206Pb/207Pb value of
1.168, which is very similar to the average 206Pb/207Pb
ratio of the automobile exhausts (1.162, Zhu et al. 2001),
and to the coal dust of south-China coal (1.164, Mukal
et al. 1993; Zhang et al. 2008). Thus, the anthropogenic
Pb in the lake sediments may be composed of two end-
member Pb: lead from automobile exhausts and from coal
combustion.
Geochemical process of heavy metal contamination
Concentrations of Pb in the sediments are positively
correlated to many other trace metals (Table 4) such as
Bi (0.89), Sc (0.52), V (0.57), Cr (0.63), Mn (0.77), Co
(0.56), Cu (0.82), Mo (0.72), Cd (0.52), Sn (0.63), Sb
(0.54), Tl (0.89), and U (0.78). Such correlation may
suggest that these trace metals have similar sources to
metal Pb. Therefore, based on source implications from
geochemistry of trace metals and Pb isotope, it is suggested
that trace metals in the river sediments were of various
sources, which can be grouped into the natural and
anthropogenic sources. The natural sources mostly include
metals produced from weathering granitic rocks and the
palaeozoic sandstones distributed in upper-river areas. The
anthropogenic proportions of heavy metals were mostly
contributed from the Pb–Zn ore deposits distributed in both
southern (GAS) and eastern (GAE) Hunan province. Thus,
the heavy-metal contamination for the river sediments is
attributed to exploitation and utilization (e.g., mining,
smelting, and refining) of Pb–Zn ore mineral resources in
the upper river areas. However, heavy metals in the lake
sediments were two end-member sources, which consist of
mostly the anthropogenic metals contributed from auto-
mobile exhausts and coal combustion.
Fig. 5 Plots of 206Pb/207Pb versus 208Pb/207Pb (a), and 206Pb/207Pb
versus 1/EF for XY (b) and QS (c) sediments. GR—granitic rocks
distributed in the river area, data from Tong (1986) and Zhu (1995);
GAS—galena minerals from southern Hunan Pb–Zn ore deposits
(Zhu 1995; Liu et al. 2001; Yao et al. 2006b); GAE—galena minerals
from eastern Hunan Pb–Zn ore deposits (Liu et al. 2001); PL—the
Palaeozoic limestone (Tao et al. 2001); AE—automobile exhausts
(gasoline) (Zhu et al. 2001)
Environ Earth Sci (2011) 64:1455–1473 1469
123
Ta
ble
4C
orr
elat
ion
coef
fici
ent
amo
ng
con
cen
trat
ion
so
ftr
ace
met
als
of
the
sed
imen
tsfr
om
the
low
erm
ost
Xia
ng
jian
gR
iver
Ba
Bi
Sc
VC
rM
nC
oN
iC
uZ
nM
oC
dS
nS
bP
bT
lT
hU
Zr
Hf
Nb
Ta
Ba
1.0
0
Bi
0.3
6*
1.0
0
Sc
0.9
5*
0.4
6*
1.0
0
V0
.91
*0
.52
*0
.96
*1
.00
Cr
0.7
4*
0.5
1*
0.8
0*
0.8
3*
1.0
0
Mn
0.5
5*
0.8
1*
0.6
3*
0.7
5*
0.6
1*
1.0
0
Co
0.8
2*
0.5
2*
0.8
4*
0.8
9*
0.7
9*
0.7
7*
1.0
0
Ni
0.4
9*
0.3
20
.56
*0
.58
*0
.46
*0
.48
0.5
3*
1.0
0
Cu
0.7
2*
0.7
9*
0.8
0*
0.8
2*
0.8
1*
0.7
7*
0.8
2*
0.5
0*
1.0
0
Zn
0.4
6*
0.7
7*
0.5
3*
0.5
8*
0.7
2*
0.7
6*
0.7
3*
0.3
90
.85
*1
.00
Mo
0.5
0*
0.7
5*
0.6
0*
0.6
5*
0.5
4*
0.7
8*
0.5
7*
0.4
40
.70
*0
.57
*1
.00
Cd
0.3
00
.48
*0
.33
0.4
00
.56
*0
.58
*0
.63
*0
.31
0.5
9*
0.8
7*
0.3
41
.00
Sn
0.2
30
.68
*0
.29
0.3
20
.25
0.6
4*
0.3
50
.21
0.5
0*
0.5
8*
0.5
5*
0.4
01
.00
Sb
0.1
90
.59
*0
.21
0.2
90
.21
0.5
8*
0.3
20
.18
0.3
90
.46
0.5
0*
0.3
30
.44
1.0
0
Pb
0.4
7*
0.8
9*
0.5
2*
0.5
7*
0.6
3*
0.7
7*
0.5
6*
0.3
10
.82
*0
.80
*0
.72
*0
.52
*0
.63
*0
.54
*1
.00
Tl
0.3
20
.82
*0
.40
0.4
20
.52
*0
.69
*0
.37
0.2
30
.65
*0
.69
*0
.69
*0
.41
*0
.64
*0
.55
*0
.89
*1
.00
Th
-0
.10
0.5
1*
0.0
20
.02
0.0
80
.22
-0
.02
0.0
80
.26
0.2
70
.26
0.1
20
.25
0.2
40
.35
0.3
81
.00
U0
.25
0.8
5*
0.3
70
.42
0.4
80
.70
*0
.42
*0
.29
0.6
6*
0.7
0*
0.6
6*
0.4
60
.59
*0
.61
*0
.78
*0
.81
*0
.70
*1
.00
Zr
-0
.45
*-
0.1
3-
0.4
3-
0.4
4-
0.3
5-
0.3
2-
0.4
7-
0.1
4-
0.2
6-
0.2
4-
0.2
1-
0.2
10
.13
-0
.05
-0
.18
-0
.10
0.3
30
.14
1.0
0
Hf
-0
.47
*-
0.0
7-
0.4
5-
0.4
5-
0.3
7-
0.2
8-
0.4
7-
0.1
6-
0.2
5-
0.2
0-
0.1
9-
0.1
80
.15
0.0
0-
0.1
4-
0.0
60
.39
0.2
00
.99
*1
.00
Nb
0.8
1*
0.4
3*
0.8
8*
0.8
4*
0.6
8*
0.5
2*
0.6
6*
0.6
6*
0.7
0*
0.4
20
.56
*0
.19
0.2
70
.22
0.4
60
.38
0.1
30
.41
-0
.20
-0
.23
1.0
0
Ta
-0
.08
0.2
70
.01
0.0
30
.08
0.2
20
.03
0.4
80
.12
0.2
40
.17
0.1
90
.23
0.2
60
.24
0.3
20
.18
0.2
8-
0.0
10
.01
0.3
11
.00
*C
orr
elat
ion
issi
gn
ifica
nt
atth
e0
.01
lev
el2
-tai
led
1470 Environ Earth Sci (2011) 64:1455–1473
123
Anthropogenic contribution of trace metals
It is important to estimate the proportions of anthropogenic
metals in sediments both for assessment of heavy-metal
contamination and for environmental protection for the
watershed. The proportion (%) of anthropogenic contribu-
tion of metals can be estimated on the base of EF values for
the bulk sediments, and the following equation (Bur et al.
2009; N’guessan et al. 2009) can be applied to calculation:
%Xanthropogenic¼ X½ �sediment� Zr½ �sediment� X=Zr½ �background
� �.
X½ �sediment ð2Þ
where X is the concentration of considered metal and Zr is
the reference element selected for EF calculation. Because
concentrations of metals in the bulk sediments vary errat-
ically, the average %Xanthropogenic value of each metal is
summarized for each sediment core (Table 5). It is seen
that metal Bi, Cd, Pb, Sn and Sb have anthropogenic pro-
portion of 91–98, 90–99, 78–92, 86–96 and 78–94% for
river sediments, respectively. That is to say that these
metals have anthropogenic proportion higher than 90%,
and natural proportion less than 10%. Metals Mn and Zn
have anthropogenic contributions of 58–83 and 69–85%,
respectively, and the natural contribution higher than 15%.
Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta generally have
anthropogenic proportion around 30–70%, and have much
higher natural proportions ([30%). Metals Ba, V and Mo
have negative %Xanthropogenic values in WH and XY sedi-
ments but positive %Xanthropogenic values in QN and QS
sediments, indicating that these metals are contributed
mostly from natural process such as weathering of granitic
rocks (Table 5).
Conclusions
The study of geochemistry of trace metals and Pb isotopes
of the sediments from the lowermost Xiangjiang River
resulted in the following:
(1) Heavy metals including Cd, Bi, Sn, Sc, Cr, Mn, Co,
Ni, Cu, Zn, Sb, Pb and Tl are generally enriched in
sediments distributed in the lowermost Xiangjiang
River. Metals Cd, Bi and to some extent Sn are
extremely highly, metals Zn, Sn, Sb and Pb signif-
icantly, and Sc, Cr, Mn, Co, Ni, Cu and Tl moderately
enriched in the river sediments. All these metals are
moderately enriched in the lake sediments.
(2) Trace metals in the river sediments were of multi-
sources, including both natural and anthropogenic
sources. The natural sources include metals produced
from weathering of granitic rocks and the Palaeozoic
sandstones distributed in upper-river areas. The
anthropogenic sources of metals were from Pb–Zn
ore deposits distributed in southern and eastern Hunan
province. Metals in the lake sediments were mostly
anthropogenic sources, including automobile exhausts
and coal combustion, with minor contribution from
natural process.
(3) Heavy-metal contamination for the river sediments is
attributed to the exploitation and utilization (e.g.,
mining, smelting, and refining) of Pb–Zn ore mineral
resources in the upper river areas, and this for the lake
sediments was caused by automobile exhausts and
coal combustion.
(4) Metals Bi, Cd, Pb, Sn and Sb in the sediments consist
of anthropogenic proportion of higher than 90%, with
natural contribution less than 10%. Metals Mn and Zn
have anthropogenic proportion around 60–85%, with
natural proportion higher than 15%. Metals Sc, Cr,
Co, Cu, Tl, Th, U and Ta have anthropogenic
proportion around 30–70%, with natural contribution
higher than 30%. Metals Ba, V and Mo may be
contributed mostly from natural process (e.g., weath-
ering of granitic rocks).
Acknowledgments This study was financially supported by NSFC
(41073095, 40572172) of China and by a scientific research fund
(07A309) of Hunan Provincial Education Department. We
Table 5 Average proportions (%) of anthropogenic metals in the
sediments of the Xiangjiang River
Core WH XY QN QS
Ba -8.98 -42.3 19.4 12.7
Bi 92.1 94.1 91.3 69.4
Sc 44.3 26.3 66.2 64.3
V -30.7 -78.6 27.3 9.73
Cr 52.4 38.5 64.8 58.8
Mn 71.3 58.8 83.5 64.7
Co 46.0 16.6 64.0 56.1
Ni 41.7 20.0 72.1 67.0
Cu 59.6 53.8 77.4 68.7
Zn 73.3 69.7 85.3 54.9
Mo -21.5 -43.5 48.9 -48.4
Cd 97.8 90.2 92.1 74.7
Sn 90.0 86.1 89.5 74.1
Sb 86.6 78.9 87.3 61.0
Pb 81.9 78.2 85.1 65.5
Tl 56.0 50.9 66.0 33.6
Th 30.9 33.3 51.2 14.2
U 39.5 32.7 58.4 6.85
Hf 11.8 9.45 14.2 6.32
Ta 55.4 48.3 64.0 47.2
Environ Earth Sci (2011) 64:1455–1473 1471
123
acknowledge the help and an analyzing fund (Grant SKLEG6031) for
Pb isotope from the State Key Laboratory of Environmental Geo-
chemistry, Chinese Academy of Science.
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