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Journal of Asian Earth Sciences 21 (2002) 167–174

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The background concentrations of 13 soil trace elements and their


relationships to parent materials and vegetation in Xizang (Tibet), China
Xiaoping P. Zhang, Wei Deng, Xueming M. Yang*
Northeast Institute of Geography and Agricultural Ecology, The Academy of Sciences of China, Changchun 130021, People’s Republic of China
Received 9 July 2001; revised 15 February 2002; accepted 11 March 2002

Abstract
The background concentrations of 13 soil trace elements, copper (Cu), lead (Pb), zinc (Zn), cadmium (Cd), nickel (Ni), chromium (Cr),
mercury (Hg), arsenic (As), selenium (Se), cobalt (Co), vanadium (V), manganese (Mn), and fluorine (F), from approximately 205 pedons in
Tibet, China are reported here for the first time. The 13 trace element concentrations follow an approximately log– normal distribution. While
the mean concentrations of Hg and Se are lower and As is higher than the average concentration for all of China, concentrations of the other
trace elements are similar to the national average. Trace element concentrations are related to vegetation and human activity also played a
notable role on the contents of trace elements in Tibet. The parent material relationship for all 13 soil trace element concentrations follows the
pattern: shale . sandstone ø igneous rock ø limestone . alluvial sediment . glacial deposits . lake sediments; while for vegetation and
human activity the concentration pattern is farmland ¼ shrub . forests . meadow . prairie . marsh and others. The soil trace element
concentrations on the Tibetan Plateau are related primarily to the parent material, but were also affected by vegetation and human activity.
q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Trace element; Soil; Parent material; Vegetation; Xizang; Tibet

1. Introduction monitoring the impacts of human activity on the quality soil


chemicals.
The trace element concentrations of soil are essential in Tibet, also called ‘the third pole in the world’, is one of the
maintaining environmental quality and soil micronutrients. least polluted areas on earth today; hence, it is an ideal area to
A deficit or excess of these elements can cause serious study the background concentrations of trace elements. In the
problems for plant growth and animal and/or human health past half-century, Chinese scientists have conducted many
(Tiller, 1989; Fergusson, 1990). The concentrations of trace pioneering studies regarding the geology, topography, soils,
elements in virgin soil depend mainly upon the bedrock type vegetation, salty lakes, and meteorology in the Tibetan
from which the soil parent material was derived and upon Plateau. A series of reports regarding the scientific expedition
which the pedo-genetic processes were carried out (Miti- have been published in Chinese (The Scientific Expedition to
chell, 1974). The more developed a soil, the less may be the Qing-zang Plateau, 1979, 1982, 1983, 1984, 1985, 1988a,b,c).
influence of the parent materials on trace elements. To our knowledge, however, only a few studies on trace
Although the impacts of human interference are generally element concentrations in Tibetan soils have been reported,
of secondary importance to soil trace element concen- including fluorine (F) (Zhang, 1998), mercury (Hg) (Zhang
trations, awareness of the adverse impacts of human and Zhu, 1994a), and selenium (Se) (Zhang and Zhu, 1994b).
activities on trace element concentrations in the environ- The data presented in this report are summarized from the first
ment has grown strongly since the 1970s (Dudas and systematic study of the background concentrations of trace
Pawluk, 1977; Nriagu, 1990). Determination of the back- elements in Tibetan soils, which is a part of larger project to
ground soil trace element concentrations is crucial for determine the background concentrations of soil trace
elements in all China for future use in monitoring and
* Corresponding author. Address: Greenhouse and Processing Crops
evaluating environmental changes. The specific objectives of
Research Centre, Agriculture and Agri-Food Canada, 2585 Highway 20, E.,
Harrow, Ont., Canada N0R 1G0. Tel.: þ1-519-738-2251x539; fax: þ 1-
the present paper are to illustrate the background concen-
519-738-2929. trations of 13 soil trace elements and their relationships to
E-mail address: yangx@em.agr.ca (X.M. Yang). parent materials and vegetation type in Tibet, China.
1367-9120/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 6 7 - 9 1 2 0 ( 0 2 ) 0 0 0 2 6 - 3
168 X.P. Zhang et al. / Journal of Asian Earth Sciences 21 (2002) 167–174

Fig. 1. Study area and sampling locations in Tibet.

2. Materials and methods 2.2. Sample collection

2.1. Study area Two hundred and five samples from surface soils (A
horizon) and 156 samples from subsurface soils (B and/or C
The Xizang (Tibet) Autonomous Region (268520 – horizon) were collected from 205 pedons in the Tibetan
368320 N; 788240 –998060 E; Fig. 1) is located in southwestern Plateau (Fig. 1). The soil samples were air-dried, ground in
China and occupies an area of 120 £ 104 km2, which an agate mortar and passed through a 2-mm sieve, then
accounts for one-eighth of the nation’s territory. The analyzed for particle size, pH, and organic matter content.
Tibetan Plateau is characterized by an average elevation For the determination of trace elements, soil samples were
of 4000-m with various topographic features. Tibet is not further ground with the agate mortar and passed through a
only unique in geology, but also unique in landscape, 100-mesh sieve.
climate, hydrology, biology, and soils. All of these factors
make the Tibetan Plateau a very special region on Earth. 2.3. Chemical analyses and quality control
With the exception of glacier and ice fields, sediments of
the Quaternary Period cover all of the Tibetan Plateau. Soil The concentrations of 13 trace elements considered to be
parent materials vary, consisting of mainly residue deposits of high environmental importance were determined, specifi-
of different rocks, glacial deposits, and other sediments of cally copper (Cu), lead (Pb), zinc (Zn), cadmium (Cd),
the Quaternary Period. The climate in Tibet is variable, with nickel (Ni), chromium (Cr), mercury (Hg), arsenic (As),
precipitation ranging from 50 to 3000 mm and mean annual selenium (Se), cobalt (Co), vanadium (V), manganese (Mn),
air temperature ranging from 0 to 20 8C. Various vegetation and fluorine (F). The analyses were conducted at the
types exist in Tibet such as subtropical forest, temperate Northwest Soil and Water Conservation Research Institute
forest, shrub, grassland, meadow and prairie, and cold of the Academy of Sciences of China in accordance with the
desert. Soil samples were collected beneath coniferous standard methodology (including quality control) developed
forest, broad-leaf forest, coniferous-broad leaf mixture, by the Environmental Monitoring Center of China (1990).
alpine prairie, alpine meadow, alpine shrub, alpine farm- Cd, Pb, Zn, Cu and Ni were analyzed by an atomic
land, alpine marshland and other uncategorized vegetation absorption spectrophotometer. Hg was analyzed by a cold
types. Soils in Tibet are seldom seen in other parts of the vapor technique after digestion with nitric acid– perchloric
world (The Scientific Expedition to Qing-zang Plateau, acid– sulfuric acid. The elements As, Cr, Mn, V and Co
1985). The relationships among soil types and trace were analyzed by neutron activation analysis using HPGE
elements will be reported elsewhere. ORTEC’s Gammavisione, a spectroscopy software for
X.P. Zhang et al. / Journal of Asian Earth Sciences 21 (2002) 167–174 169

Fig. 2. Range of concentrations for 13 trace elements in surface and subsurface soils in Tibet (expressed in 5th/95th percentiles). The dotted line inside the plot
box is the mean line. The ‘ þ ’ inside the small square is the mean for all China.

germanium detector gamma-ray analysis. Selenium was accumulation of Hg in soils (Tao, 1995; Mermut et al.,
measured by a fluorescence spectrophotometer. Alkali 1996). Soils in an environment that is exposed to industrial
melting and an ion selective electrode method were used wastes via dust, irrigation water, and/or precipitation are
to determine F. likely to be enriched in certain trace elements. Obviously,
To gain reliable and comparable data, more than 30% of agricultural and industry are less intensive in Tibet than in
the samples were analyzed in duplicate, especially for other parts of China. Therefore, the lower levels of Hg and
elements with extremely low concentration or with poor Se in Tibet soils may reflect less human impact. Conse-
analytical accuracy, such as Cd, Se, F, and Hg. Environ- quently, Hg and Se may serve as indices for monitoring
mental standard soil samples supplied by the Environmental anthropogenic pollution of soil in the Tibetan Plateau.
Monitoring Center of China were used to control the The trace elements in Tibetan soils were probably
accuracy of determination throughout the analysis. inherited from the soil parent materials because the soils
Although statistical distributions of the trace element are young with little weathering or anthropogenic impacts.
concentrations were frequently skewed, we presented the Understanding those relations can help determine the
data using arithmetic means and without any data behavior of these elements in an ecosystem and perhaps
transformation to avoid introducing additional uncertainty. even help predict and/or monitor the concentrations of some
R-type factor analysis of trace elements and soil properties elements in soils. A simple correlation between trace
was performed using the SAS software package (SAS element concentration and selected soil properties are
Institute, 1996). shown in Table 1. Mercury shows no relation to any other
trace element or any selected soil property in Tibetan soils.
In contrast, significant correlations exist between Hg and Se,
3. Results and discussion Co, Mn, or pH in the eastern alluvial plain of China where
intensive agriculture exploits the soils (Wang and Chen,
3.1. Total concentrations of 13 trace elements and 1998). Ni and Cr were strongly correlated both with each
relationships among them other and Co in Tibetan soils. Arsenic was positively
correlated with Pb, Zn, and Cd, which may not be surprising
The concentration ranges and mean values for all 13 since they exhibit similar geochemical behavior with regard
trace elements in Tibetan soils are shown in Fig. 2, along to the internal growth of the crystal lattice and the formation
with the rational mean values. Except for Hg of rocks (Liu, 1987). The element Pb coexists closely with
(0.026 mg kg21) and Se (0.15 mg kg21), the mean concen- Zn in the internal growth of a crystal lattice (Mitichell,
trations were remarkably less than the averages (0.065 and 1974). The element Cd often replaces Zn in soil because of
0.29 mg kg21) for the whole nation, and As (18.7 mg kg21) their analogous nature and because Zn combines with As to
had an obviously higher mean concentration than the form sulfur-containing mineral salts (Liu, 1987).
average for the whole country (11.2 mg kg21). Other Certain trace elements correlate with some soil proper-
elements were similar to or slightly above the national ties. Close relationships between clay content and many
averages. The concentrations of soil trace elements in trace elements have been found in other studies (Dunn and
subsurface soils follow the same pattern as that in the Irvine, 1993; Mermut et al., 1996). Adriano (1986) and
surface soils. The low level of Hg in Tibetan soils indirectly Wang and Chen (1994) attribute the relationships to the high
supports the argument that the long-term use of chemical affinities of trace elements to clay minerals. However, in this
fertilizer and pesticides in agricultural land might lead to an study the clay showed significant positive correlation to
170 X.P. Zhang et al. / Journal of Asian Earth Sciences 21 (2002) 167–174

Table 1
Correlation matrix for trace elements and partial correlation matrix between trace element and selected properties of A horizon soils in the Tibetan Plateau
ðn ¼ 205Þ

Cu Pb Zn Cd Ni Cr Hg As Se Co V Mn F

Cu þ þþþ þþþ nsa ns ns ns þþþ þþþ þþþ þþþ þþþ


Pb þþþ þþþ ns ns ns þþ þþþ þþþ þþþ þþþ þþþ
Zn þþþ ns ns ns þþþ þþþ þþþ þþþ þþþ þþþ
Cd ns ns ns þþ ns þ þ ns ns
Ni þþþ ns ns ns þþþ ns þþ ns
Cr ns ns ns þþþ ns ns ns
Hg ns ns ns ns ns ns
As ns ns ns ns ns
Se þþþ þþþ þþ ns
Co þþþ þþþ þþþ
V þþþ þþþ
Mn þþþ
F
SOC ns þþþ ns ns ns ns ns 22 þþþ ns ns þþþ þþ
PH ns 222 ns ns ns ns ns þþþ 222 ns 222 222 222
Sand 22 ns ns ns ns 222 ns 2 222 222 22 222 ns
Clay ns ns ns ns ns ns ns þþ ns þþ ns ns ns

þ , þþ, and þþþ denote positive correlation significant at p , 0.10, ,0.05, and ,0.01 level, respectively. 2, 22, and 222 denote the negative
correlation significant at p , 0.10, ,0.05, and ,0.01 level, respectively.
a
ns: not significant ( p , 0.10). Sand $ 0.01-mm particle and clay , 0.001-mm particle.

only As and Co. On the other hand, sand was negatively elements in Tibetan soils is probably due to weak soil
correlated with Cu, Cr, As, Se, Co, V, Mn, and F. Organic development.
matter has a marked affinity to trace elements to form Since soil pH controls the substitution of ions inside the
organo-mineral complexes (Aoyama, 1982). However, such crystal lattice and acidic leaching of elements, one might
correlation only occurred for Se, Pb, and Mn in this study. expect positive correlations between pH and some trace
Weak correlation between soil organic matter and trace element species (Jenkins and Jones, 1979). In Tibetan soils,
however, pH showed negative correlations with Pb, Se, V,
Mn, and F, while Wang and Chen (1998) found pH to be
positively correlated to these elements in the soils of eastern
China. Since low soil pH is associated with strong leaching
of some elements, the relatively high pH in Tibetan soils
(The Scientific Expedition to Qing-zang Plateau, 1985)
could explain the weak correlation between pH and trace
elements.
Factor analysis is a powerful tool for identifying
relationships that are not readily evident from simple
correlation analysis. The result of R-mode factor analysis
(205 surface soil samples) shows that, after varimax
rotation, the first three principal factors contribute 46, 30,
and 18% of the variances, respectively (Fig. 3). Ni, Cr and
Co are found in positive to factor 1, which reflects the close
relationship among these three ferrofamily transition
elements. They have similar geochemical behavior, mainly
expressed by strong substitution for each other (Mitichell,
1974). A similar pattern of natural abundance and
correlation of these three elements was found in the crust
of the Earth (Liu, 1987).
The pH value, and clay, Hg, and As concentrations are in
the positive direction of factor 3, which to some extent
Fig. 3. Plot of loading on the principal factors (F1, F2 and F3 referring to
principal factors 1, 2, and 3, respectively). a ¼ Cu, b ¼ Pb, c ¼ Zn,
represents the special relationships of Hg and As to these
d ¼ Cd, e ¼ Ni, f ¼ Cr, g ¼ Hg, h ¼ As, i ¼ Se, j ¼ Co, k ¼ V, l ¼ Mn, two soil properties. This demonstrates that Hg and As were
m ¼ F, n ¼ CO, o ¼ pH, and p ¼ clay. not only closely associated in mineral formation, but also
X.P. Zhang et al. / Journal of Asian Earth Sciences 21 (2002) 167–174 171

Table 2
Concentrations of 13 soil trace elements over different parent materials in the Tibet Plateau (sample number in parentheses)

Igneous rocks Sandstone Shale Limestone Glacial deposit Alluvial sediment Lake deposit
(47) (58) (28) (14) (5) (44) (9)
(mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil)

Cu 18.3 21.9 28.7 31.8 18.6 22.7 16.9


Pb 30.0 28.5 31.3 30.2 33.4 26.5 26.4
Zn 67.9 75.8 88.8 74.7 76.9 69.1 63.5
Cd 0.078 0.073 0.083 0.098 0.067 0.083 0.075
Hg 0.028 0.025 0.030 0.028 0.020 0.022 0.018
Ni 27.5 32.9 41.4 29.2 22.1 33.0 28.5
Cr 63.8 80.5 100.8 66.0 60.9 78.8 77.5
Co 10.4 11.9 15.9 12.1 7.6 10.9 8.8
V 71.5 81.3 83.2 73.2 72.6 70.8 62.9
Mn 607.9 640.1 795.9 656.0 518.0 612.0 401.0
F 591.4 544.8 609.5 508.0 528.0 486.0 389.0
As 14.7 19.5 20.0 18.6 20.5 20.8 20.0
Se 0.141 0.133 0.215 0.155 0.144 0.142 0.154
Total 1550 1595 1843 1514 1363 1474 1103

similar in geochemical behavior; that is, both have a ments. Based on absolute concentrations, the 13 trace
tendency to associate with fine particles (Aoyama, 1982; elements may be divided into five groups: Mn, F . Cr, V,
Adriano, 1986). Moreover, this tendency would be more Zn . Pb, Ni . Cu, As, Co . Se, Cd, Hg. This grouping of
notable with increasing soil acidity. trace element relative abundance in Tibetan soils corre-
All other factors embrace their association to the factor 2 sponds to the relative abundance of trace elements in the
and cannot yet be explained. Overall, the factor analysis crust of the earth (Liu, 1987). However, the high
indicates that while the relationships among trace elements concentration of some elements, such as Ni and Cr, did
in Tibetan soils were mainly inherited from the parent not occur in soils derived from alkaline rock (both elements
materials, soil-forming processes also played a significant . 1000 mg kg21) parent materials (Liu, 1987).
role. Differences in trace element concentrations between
surface and subsurface soil horizons may reflect the impact
3.2. Trace elements and parent materials of pedo-genesis on the original trace element distributions.
Table 3 lists the ratios of trace element concentration
The concentrations of 13 soil trace elements from between the A and C horizons. Assuming ^ 0.10 as a
different parent materials in the Tibetan Plateau followed criterion for redistribution of an element, the ratio of , 0.90
the pattern: shale . sandstone ø igneous rocks ø may be regarded as element leaching from the surface soils
limestone . alluvial sediment . glacial deposits . lake and the ratio of . 1.10 as accumulation of the element in the
sediments (Table 2). Small amounts of trace elements in surface horizon. Based on this criterion, all elements display
soils derived from alluvial, glacial, and lake sediments may some kind of redistribution and the extents of redistribution
indicate leaching loss of trace elements in wet environ- vary with parent material types. It appears that igneous rock

Table 3
Ratio of soil trace element concentrations for A/C horizons over different parent materials in the Tibet Plateau

Igneous rocks Sandstone Shale Limestone Glacial deposit Alluvial sediment Lake deposit

Cu 0.93 0.97 0.81 1.05 0.76 0.83 0.96


Pb 1.02 0.99 0.92 1.10 0.91 1.00 0.91
Zn 0.99 1.04 0.90 1.09 1.04 1.01 0.99
Cd 1.04 1.01 1.08 1.09 1.04 1.00 1.01
Hg 1.21 1.28 0.98 1.00 0.65 1.33 0.79
Ni 1.02 0.90 0.82 0.99 0.65 0.91 1.02
Cr 1.21 0.98 0.89 1.00 0.70 1.08 1.04
Co 0.99 0.91 0.87 1.13 0.66 0.97 1.03
V 1.07 1.01 0.92 1.12 0.73 1.02 0.83
Mn 1.13 1.05 1.13 1.23 0.86 1.04 1.09
F 0.97 1.03 1.03 1.10 0.84 1.16 1.01
As 1.22 1.11 1.07 0.97 0.74 1.01 0.90
Se 1.15 1.00 0.94 1.12 0.69 1.20 1.11
172
Table 4
Concentrations of soil trace elements under different vegetation types in the Tibet Plateau (sample number in parentheses)

Coniferous forest Broad leaf forest Coniferous-broad mixture Alpine prairie Alpine meadow Alpine shrub Alpine farmland Alpine marshland Others
(17) (4) (12) (73) (58) (25) (6) (4) (6)
(mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil) (mg kg21 soil)

Cu 18.2 15.8 21.3 20.2 21.5 30.8 36.0 15.6 18.7


Pb 30.7 29.7 31.1 26.8 30.6 32.4 25.5 23.7 23.7
Zn 80.5 84.6 67.4 68.6 74.8 84.6 78.7 66.3 67.3
Cd 0.079 0.075 0.076 0.086 0.074 0.074 0.099 0.089 0.069
Hg 0.047 0.057 0.044 0.019 0.023 0.024 0.040 0.015 0.022
Ni 26.2 28.0 25.6 34.4 29.8 36.2 45.5 26.8 33.0

X.P. Zhang et al. / Journal of Asian Earth Sciences 21 (2002) 167–174


Cr 57.1 59.8 52.8 85.2 79.5 79.4 78.6 84.9 64.9
Co 11.7 11.5 10.3 10.6 11.4 16.1 16.6 7.35 8.84
V 78.7 65.9 73.8 69.0 80.1 84.9 116.0 49.3 61.7
Mn 875 951 665 517 620 806 914 375 458
F 602 617 687 467 572 625 527 389 413
As 13.3 12.2 10.9 21.2 18.7 19.9 24.5 18.6 14.6
Se 0.165 0.130 0.189 0.117 0.154 0.210 0.185 0.156 0.114
Total 1793 1875 1645 1320 1538 1815 1862 1056 1163

Table 5
Ratio of soil trace element concentrations for A/C horizons under different vegetation type in the Tibetan Plateau

Coniferous forest Broad leaf forest Coniferous-broad mixture Alpine prairie Alpine meadow Alpine shrub Alpine farmland Alpine marshland Others

Cu 0.94 1.58 0.52 0.96 0.87 0.96 1.12 1.08 1.09


Pb 0.84 1.13 1.11 0.97 1.01 0.90 1.09 1.08 1.23
Zn 0.98 1.15 0.84 1.03 0.94 1.04 1.11 0.94 1.08
Cd 1.19 1.47 1.23 0.99 0.97 1.03 1.23 1.10 0.93
Hg 0.97 2.91 1.64 0.94 1.05 0.96 1.68 0.74 1.31
Ni 0.72 1.49 1.00 0.93 0.89 0.92 1.37 1.29 0.99
Cr 0.91 1.92 0.97 1.02 1.02 1.06 1.16 0.97 0.91
Co 0.73 1.46 0.80 0.98 0.89 0.92 1.20 1.05 1.04
V 0.88 1.11 0.90 1.01 0.99 1.03 1.20 0.94 1.02
Mn 1.36 2.00 1.18 1.00 1.03 1.10 1.14 1.60 1.11
F 0.90 0.95 0.94 1.09 0.96 1.04 1.08 0.87 1.19
As 1.04 1.76 1.00 1.12 1.04 1.13 0.80 0.80 1.45
Se 0.94 1.52 0.96 1.03 1.01 1.04 1.81 1.25 0.99
Mean 0.95 1.57 1.01 1.01 0.97 1.01 1.23 1.05 1.10
X.P. Zhang et al. / Journal of Asian Earth Sciences 21 (2002) 167–174 173

and limestone favored the surface accumulation of elements 4. Conclusions


while shale and other Quaternary deposits favored the
leaching of elements from the surface. For the glacial In Tibet soils, the Hg and Se concentrations were lower
deposits, 10 out of 13 elements were depleted from the than the national average and the As concentration was
surface. Of the 91 A/C ratios, 53 (58%) showed no changes, higher than the national average. The concentrations of the
18 (20%) indicated enrichment and 20 (22%) showed other trace elements in Tibetan soils were within the ranges
depletion, respectively. The elements, Se, Mn, and Hg were of those reported for the rest of China. While the trace
enriched in three out of seven parent materials, while Cu and element species and concentrations in Tibetan soils were
Ni were depleted at the same frequency. These results mainly inherited from the soil parent materials, soil-forming
indicate that pedo-genetic processes were active in Tibetan processes and human activity also played a notable role.
soils, although where physical weathering was obviously
the dominant process.
Acknowledgments
3.3. Trace elements and types of vegetation
We greatly acknowledge contributions from Cheng Jian-
Vegetation is a well-known key factor governing soil- ao, Tian Junliang, Wang Dasheng, Wang Hengjun, Yu
forming processes. Under certain climatic conditions, Zhicheng, Zhang Guoshu, Zeng Cheng, Li Xianhua, Liu
vegetation influences the status of trace elements by Puling, Xie Yongsheng, and Wang Qicun for field sampling
affecting their release, migration, transformation, and and lab analyses. We would also like to thank Drs W.D.
transportation. In the Tibetan Plateau, nine types of Reynolds and Kevin Burke who helped to improve greatly
vegetation exist, namely: coniferous forest, broad-leaf the quality of this manuscript.
forest, mixture of coniferous forest and broad-leaf forest,
alpine prairie, alpine meadow, alpine shrub, farmland,
alpine marsh, and others. Crop soils (dry farmland) were the
richest in trace elements, where the contents of Cu, Cd, Ni, References
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