Springer 2006

Environmental Geochemistry and Health (2006) 28:1926

DOI: 10.1007/s10653-005-9007-z

Distribution and mobility of metals in agricultural soils

near a copper smelter in South China
Ningjing Hu1,2,5, Zeqin Li3, Peng Huang2,4 & Cheng Tao3
1
Soil and Environment Bioremediation Research Center, State Key Laboratory of Soil and Sustainable
Agriculture, Institute of Soil Science, Chinese Academy of Sciences, 210008 Nanjing China
2
Graduate School of the Chinese Academy of Sciences, 100039 Beijing, China
3
Chengdu University of Technology, 610059 Chengdu, China
4
Institute of Oceanology, Chinese Academy of Sciences, 266071 Qingdao, China
5
Author for correspondence (e-mail: hningjing@163.com)

Key words: geoaccumulation index, heavy metals, mobility, speciation

Abstract
The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in
south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were
heavily aected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin.
Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality
criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with
the residual and NH2OH HCl extractable fractions. In contrast, Cd was predominantly associated with the
MgCl2 extractable fraction. A large proportion of Cu was bound to the acidic H2O2 extractable fractions,
while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially
is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which
heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water
extraction using a modication of Tessiers procedure, and the order of mobility was Zn > Cd > Cu > Pb.
Introduction
The problem of contaminated soils is of increasing
concern because of the large number of polluted
sites in existence. Smelting activities impose
harmful, usually irreversible, eects on the terrestrial and aquatic environments (Rybicka 1996).
The processes of smelting and rening can never
approximate to becoming environmental neutral,
but the areas of impact can be ameliorated
(Kwolek 1999; Klukanova & Rapant 1999).
Environmental geochemistry encompasses many
factors that inuence the sources, dispersion and
distribution of elements in the environment, their
pathways into soils, foodstus and water supplies
and their inuence on plant, animal and human
health (Thornton 1993, 1996). The regions where

mining and smelting have been conducted for a

long time are potential candidates for a wide diffusion of pollutant elements in the environment
(Boni et al. 1999), which could enhance the risk of
metal contamination of the food chain.
The contamination arising from smelting activities is a global problem, and how to understand
the processes that control the behavior and impact
of contaminants will be a major challenge to
environmental geochemists for the next decade or
more (Thornton 1996).
Current research has focused on the inuence of
smelting and base mining on heavy metal
contamination and controlling factors in the surface environment and its implications for soils and
plants (Jung & Thornton 1996; Allan 1997; Dinelli
& Tateo 2001).

20

ningjing hu et al.

There has been extensive smelting and industrial

mineral mining activity in China, resulting in
serious impacts on the environment (Sun & Zhang
2001; Teng et al. 2003). At present, although
impacts of smelting and mining activities on the
environment have been studied in some areas,
there has been little research on the environmental
geochemistry of smelted porphyritic copper.
To study the environmental impact of smelting
activities, we selected the Guixi smelting area as a
case study.
Guixi City is situated in south China. The area
has a humid subtropical climate with an annual
average temperature and rainfall of 18.2 C and
1836 mm, respectively. The mild climate favors
agriculture, allowing an annual production of
1015 vegetable crops.
In 1979, the Guixi copper smelting plant was
established and Guixi City became one of the most
important Cu production sites in China. Today,
Guixi copper smelting plant produces around
200,000 tons of Cu and 900,000 tons of sulfuric
acid per year. The atmospheric metal emissions
generated by the smelter and metals in wastewater
have led, through sedimentation and irrigation, to
the contamination of the surrounding soils by Cd,
Pb, Cu and Zn (Guixi Environmental Protection
Bureau 1999; Sun & Zhang 2001). Coupled with
the lack of pollution controls, human activities
associated with these developments have caused
signicant impacts on the local environment
(Guixi Environmental Protection Bureau 1999).
Despite the fact that contamination has long been
known, few studies have been carried out on its
distribution and mobility in the soils.
Chemical speciation plays an inuential role in
mobility and potential bioavailability of heavy
metals in soils. A sequential chemical extraction
method, for example, Tessiers method (Tessier
et al. 1979) and modied Tessiers method (Jiang
et al. 1990) can be used to study the operationally
denable fractions of metals in soil. In order to
assess the degree of contamination and distinguish
between natural and anthropogenic pollution
sources, the index of geoaccumulation has been
used in many studies (Muller 1969, 1979; Teng
et al. 2003).
Thus, the primary objectives of the present
study were to examine heavy metal concentrations
in agricultural soils in a smelting area, (Guixi), to
study the chemical partitioning and the mobility of

pollutants in the soils, and to distinguish between

natural and anthropogenic pollution sources.

Materials and methods

Soil sampling and pretreatment
Surface samples were obtained with a trowel after
removing the top layer in contact with the atmosphere and stored in plastic bags. The samples
were air-dried and, after breaking the agglomerates with a plastic hammer, sieved through a 2-mm
sieve and ground with a ball mill.
Analytical methods
pH
The evaluation of pH was performed according to
the method described by Lun (1999). About 4.0 g of
soil sample (<2 mm) were mixed with 10.0 mL of
deionized water in centrifuge tubes. The mixtures
were shaken for 30 min on a mechanical shaker and
then centrifuged at 3000 rpm for 10 min. The pH of
the supernatants was measured using a pre-calibrated pH meter (Oakton Acron Series).
Sample digestion for total metal determination
The prepared soil samples were analyzed for their
heavy metal concentrations using an acid digestion
method (Lun 1999). About 0.50 g of the soil
samples were weighed and placed in polyethylene
tubes. Concentrated nitric acid (10.0 mL) was
added and left to digest overnight and then 15 mL
concentrated hydrouoric acid and 1.0 mL perchloric acid were added. The mixtures were heated
in an aluminum block at 50 C for 3 h, 150 C for
3 h, 190 C for 4 h until complete dryness. After
the test tubes were cool, 5% (0.8 M) nitric acid
was added and heated at 60 C for 1 h with
occasional mixing. Upon cooling, the mixtures
were decanted into polyethylene tubes and centrifuged at 3500 rpm for 10 min. Cd, Ni, Co, Cr and
Pb concentrations of the solutions were measured
using graphite furnace atomic absorption spectroscopy (GF-AAS, PE5100PC), and the other
metals in the solutions were determined using
ame atomic absorption spectroscopy (F-AAS,
PE5100PC).
All glass- and plastic-ware was soaked in 10%
nitric acid overnight and rinsed thoroughly with

distribution and mobility of metals

deionized water before use. For quality control,
reagent blanks and replicates representing 10 and
20% of the total sample population, respectively,
were incorporated in the analysis to detect contamination and assess precision and bias. The
analytical results showed no signs of contamination and the precision and bias of the analysis were
generally <10%.
Sequential extractions
The prepared soil samples were analyzed for the
chemical partitioning of Cu, Cd, Pb and Zn using a
sequential chemical extraction method (Tessier
et al. 1979; Jiang et al. 1990). The extraction
method operationally denes the metals in six
chemical forms: (1) water extractable fraction
(10 mL); (2) MgCl2 extractable fraction (8 mL,
1 M); (3) NaOAcHOAc extractable fraction
(8 mL, 1 M, pH = 5.0); (4) NH2OH HCl
extractable fraction (20 mL, 0.04 M); (5) NH4OAc
extractable fraction (30% H2O2/3.2 M NH4OAc in
20% HNO3), and (6) residual fraction (HClO4/
HNO3). In general, heavy metals in the MgCl2
extractable and NaOAcHOAc extractable fractions are considered readily and potentially bioavailable, while the NH2OH HCl and NH4OAc
extractable fractions are relatively stable under
normal soil conditions. Heavy metals in the residual fraction are entrapped within the crystal
structures of the minerals and, thus, represent the
least labile fraction. Quality controls similar to
those in the acid digestion method were carried out.
Statistical analysis
In order to investigate elemental associations
among the heavy metals and major elements in the
soils, Pearson correlation and principle component
analysis (PCA) were performed using the SPSS
statistical package version 11.0. In the PCA,

21

Varimax with Kaiser normalization was used as

the rotation method in the analysis.
Results
Heavy metal concentrations
Nine metals, namely Cu, Zn, Cd, Pb, Cr, Fe, Mn,
Ni, and Co, were determined. Table 1 shows the
ranges, means and medians. In accordance with
the Environmental Quality Standard for Soils of
the Chinese National Environmental Protection
Agency, the mean Cd, Cu, and Zn concentrations
of the paddy soils were elevated compared with the
corresponding threshold values of soil quality. In
contrast, the mean Pb, Cr, Ni, and Co concentrations in the paddy soils were generally below the
threshold levels.
Chemical partitioning of Cu, Zn, Pb and Cd
Speciation according to the modied Tessiers
scheme (Tessier et al. 1979; Jiang et al. 1990) was
determined on all samples of the paddy soils.
Figure 1 shows the chemical partitioning of Cu,
Zn, Pb and Cd and Figure 1 shows that a signicant fraction of Cu in the paddy soils was bound
to the acid H2O2 extractable phase, followed by
the MgCl2 extractable phase and NH2OH HCl
extractable fraction. Zn was predominantly associated with the residual fraction and secondarily
with the NH2OH HCl extractable fraction. The
chemical partitioning of Cd in the soils was such
that Cd was predominantly associated with the
MgCl2 extractable fraction (Figure 1), and the
second most important fraction was the water
extractable phase. Pb in the soils was largely
associated with the residual fraction, and secondarily with the NH2OH HCl extractable fraction
(Figure 1).

Table 1. Mean, median, and ranges of total metal concentrations (mg kg)1) in the paddy soils.
Subgroup

(mg kg)1)

Cu

Zn

Cd

Pb

Cr

Ni

Co

Paddy soils (n = 18)

Range
Median
Mean

548.386.7
196.7
209.9
35

430.045.0
81.3
103.8
100

13.10.2
0.6
1.4
0.2

40.010.7
18.8
20.3
35

43.01.5
14.2
16.1
90

18.22.6
4.7
6.1
40

6.60.7
1.0
1.5
N/Ab

Threshold of soil qualitya

a
b

National Environmental Protection Agency of China 1995.

N/A, not available.

22

ningjing hu et al.

Fig. 2. Percentages of extracted fraction in deionised water.

Fig. 1. Chemical fractions of Cu, Zn,Cd and Pb. Pha1, water

extracted fraction; pha2, MgCl2 extracted fraction;
pha3,NaOAcHOAc extracted fraction; pha4, NH2OH HCl;
pha5, acidic H2O2 extracted; pha 6, residual fraction.

Extraction studies were carried out in order to

investigate the mobility of the metals and therefore
their possible release into the environment and
their toxicity. An experiment was carried out by the
modied Tessiers scheme (Tessier et al. 1979; Jiang
et al. 1990) with deionized water in order to evaluate the fraction of metals weakly bound to the
matrix, e.g., present as inorganic soluble salts. The
results may also give a preliminary indication of the
possible release of pollutants by rain, although of
course the laboratory experimental conditions are
dierent from the on-site situation. Moreover, it is
likely that most of the very labile metal fraction has
already been leached over the years. The percentages of metals leached by water and the median and
ranges are reported in Figure 2. As can be seen, the
mean percentage of Cu, Zn, Cd and Pb in the paddy
soils descended in the order: Zn > Cd > Cu > Pb.
Soil pH
The average pH of the paddy soils was 4.64 (range
4.25.0).
Elemental associations
The Pearson correlation coecient matrices
between some major elements and heavy metals
are presented in Table 2. In general, major and
trace elements, except for Cr and Mn, were sig-

nicantly correlated with each other in the paddy

soils. In the PCA, the rst two principal components accounted for 81.6 of the total variance for
the paddy soils. The result of the PCA (Figure 3)
indicates that Cr was dominated by the second
component, and the association of Cr with other
elements was weak. Mn in also exhibited strong
domination by the second component, and the
association of Mn with other elements, except for
Fe, was weak.
Index of geoaccumulation
The index of geoaccumulation (Igeo) can be used to
assess whether or not soils have been contaminated by heavy metals (Muller 1969, 1979):
Igeo log2 CN =1:5BN
where CN is the measured concentration of element N in the soils, and BN is the content of the
element in average shale (Turekian & Wedepohl
1961), either directly measured in texturally
equivalent uncontaminated soils or taken from the
literature. The factor 1.5 is introduced to include
possible dierences in the background values due
to lithological variations.
The Muller Index of Geoaccumulation, Igeo,
indicating the level of contamination found in
various soils, is widely recognized in Europe. Igeo
consists of seven grades ranging from unpolluted
to very seriously polluted (Table 3). Grade 6
indicates a 64-fold enrichment over the background values (Singh et al. 1997).
In our calculation of Igeo, BN is the background
content of the element (The Assessment of

23

distribution and mobility of metals

Table 2. Correlation (Pearson) coecient matrix between metal concentrations in the paddy soils (n = 18).
Cu
Cu
Zn
Cd
Pb
Ni
Co
Fe
Mn
Cr

1
0.639**
0.801**
0.313
0.555*
0.563**
0.229
0.129
)0.045

Zn

Cd

Pb

Ni

Co

Fe

Mn

Cr

1
0.933**
0.572**
0.774**
0.817**
0.679**
0.295
0.003

1
0.532*
0.824**
0.847**
0.631**
0.3
0.014

1
0.723**
0.608**
0.651**
0.239
0.29

1
0.873**
0.819**
0.444*
0.333

1
0.913**
0.685**
0.235

1
0.678*
0.352

1
0.279

*p < 0.05; **p < 0.01.

Table 3. Index of geoaccumulation (Igeo) and contamination

level.
Igeo Igeo class Contamination level
<0 1
01 2
12 3
23 4
34 5
45 6
>5 7

Fig. 3. The component analysis plots of heavy metals and

major elements in the paddy soils.

Environment in Guixi, 1979, Institute of Environmental Science, Beijing Normal University).

The Igeo of Cu, Zn, Cd, Pb, Cr, Ni and Co in
the paddy soils is displayed in Figure 4. According
to the index of geoaccumulation (Igeo) and the
contamination level, the degree of contamination
from strong to weak in the paddy soil is:
Cu > Cd > Zn > Pb, while Cr, Ni and Co were
below pollution levels in the soils.

Uncontaminated
Uncontaminated to moderately contaminated
Moderately polluted
Moderately to highly polluted
Highly polluted
Highly to very highly polluted
Very seriously polluted

nated. Collectively, these ndings suggest that

heavy metals have accumulated in soils due to the
smelting plant.
All heavy metal concentrations were most
enriched in the paddy soils and the residual Cd,
Cu, Pb and Zn in the soils was lower (Figure 1),
strongly suggesting that the paddy soils received a
comparatively high input of anthropogenic heavy
metals, possibly related to irrigation with waste-

Discussion
Heavy metal concentrations in soils
Elevated concentrations of Cu, Cd and Zn were
found in the paddy soils in Guixi (Table 1),
suggesting potential Cu, Cd and Zn contamination
of the soils. Although the mean concentration of
Pb was below the nationwide threshold value,
some soils were found to be moderately contami-

Fig. 4. Box-plot of Igeo for paddy soil.

24

ningjing hu et al.

water from the copper smelting plant. The soil pH

was generally below 5.0, indicating that the soils
were acid. The low pH of the paddy soils (4.64)
compared with that of the agricultural soils might
be due to the SO2 and NOx emitted by the copper
smelting plant.
Rice cultivation in paddy elds generally
requires moderate ooding. Excessive soil water
may enhance leaching and migration of some
readily soluble elements such as Cd and Zn and,
possibly, those in exchangeable and weakly bound
forms through percolating water in soils of low
pH. The low Zn and Cd concentrations in the
paddy soils were most likely attributable to losses
of readily soluble Zn and Cd through leaching and
percolation processes.
Mn oxides play a signicant role in the xation
of Co in soils due to the strong anity of Co and
Mn oxides (Kabata-Pendias & Pendias 1992).
Taylor & McKenzie (1966) reported that a significant fraction of Co (>70% of total soil Co) was
associated with Mn oxide minerals. Table 2 also
shows that the correlation between Mn and Co
was signicant. Therefore the low Co concentration of the paddy soils may be attributed to the
dissolution and subsequent loss of Mn oxides
induced by ooding. The low soil Mn concentration (62.4 mg kg-1) provides additional evidence of
dissolution and leaching of Mn and Co.
Chemical partitioning of Cu, Zn, Pb and Cd
The higher acidic H2O2 extractable Cu fraction is
in agreement with the general nding that Cu
forms the most stable complexes with organic
matter. Cu in the water, MgCl2 and NaOAc
HOAc extractable fractions accounted for <50%
of total soil Cu, representing the readily soluble
and potentially bioavailable Cu fractions. The
results indicate that a small fraction of soil Cu was
relatively stable. Soil Zn in the the water, MgCl2
and
NaOAcHOAc
extractable
fractions
accounted for <12% of total soil Zn. These
results may indicate the inuence of ooding in the
paddy soils, as Zn readily migrates downward in
soil proles (Kabata-Pendias & Pendias 1992;
Wong et al. 2002). The highest level (80%) of soil
Cd in the MgCl2 extractable fraction suggests that
most soil Cd is potentially available for crop
uptake. The higher Cd concentration in rice gives
additional evidence of uptake of soil Cd (Sun &

Zhang 2001). The water extractable soil Pb values

were generally low, accounting for <2% of total
soil Pb. Collectively, the readily soluble and
potentially bioavailable Pb fractions accounted for
<30% of total soil Pb. In comparison, the readily
soluble and potentially bioavailable Pb fractions in
the paddy soils were noticeably larger than those
of natural soils. Moreover, the residual Pb was
lower than that of natural (uncontaminated) soils
(Lu et al. 2003). These dierences indicate that a
greater fraction of Pb in paddy soil might be
attributed to anthropogenic Pb sources.
In general, the elemental content in the nonresidual fraction is relatively high in comparison
with the partitioning of metals in unpolluted soils.
These dierences are particularly apparent, suggesting a greater contribution of anthropogenic
metals. Our ndings are in agreement with the
results of other workers (Li et al. 1995) who have
used Tessiers scheme to fractionate contaminated
soils. The relatively large water and MgCl2
extractable fractions of Cu, Zn, Cd and Pb in the
paddy soils may be due, at least in part, to lower
soil pH.
Mobility of Cu, Zn, Pb and Cd
The results of the water extraction experiment
show that Cu, Zn, Cd and Pb increased in mobility
due to lower soil pH (Jiang & Cheng 1997). The
mobilities of Cu, Zn, Cd and Pb in the paddy soils
descended in the order: Zn>Cd>Cu>Pb, indicating their chemical properties. The mobility of
Zn in soils is high (Liu & Cao 1985), while that of
Pb is weak (Liu & Cao 1985; Yu & Wu 1997).
Elemental associations
The results of the Pearson correlation and PCA
show that elemental association of Cr with other
elements was generally weak in the paddy soils,
indicating that the relationship between Cr and
other elements was insignicant. In contrast, other
heavy metals were generally highly correlated with
each other. The statistical results may indicate that
Cr in the paddy soils had distinct geochemical
behaviors and, possibly, originated from dierent
sources compared with the other elements. In the
PCA, the strong associations among Cu, Zn, Pb
and Cd in the paddy soils may suggest that they
have the same input sources and common geo-

distribution and mobility of metals

chemical characteristics. Their associations with
Fe and Mn in the paddy soils indicate the inuence
of agricultural activities on the soils. Moreover,
the strong inuence of Mn by the rst and second
components in the PCA and the weak association
between Fe and Mn in the paddy soils may suggest
the leaching of Mn in the paddy soils due to the
inuence of ooding. The strong associations
between Ni and Co in the soils may also suggest
that they have the same input sources and common geochemical characteristics.
Index of geoaccumulation
The results of the Box-plot of Igeo show that the
paddy soils were very highly or very seriously
polluted with Cu (Figure 4). Cd was of contamination Grade 16, i.e., uncontaminated or moderately to very highly polluted. Zn was of
contamination Grade 25, i.e., moderately to
highly polluted. Pb was of contamination Grade
12, i.e., uncontaminated to moderately contaminated. On the other hand, Cr, Ni and Co in the
paddy soils were of Grade 1, that is uncontaminated. These results indicate that for Cu, Zn, Cd
and Pb, whose concentrations are heavily aected
by anthrogenic inputs, wastewater, smelting slag
and dust were the contamination sources, while
Ni, Co and Cr were mainly of geochemical origin.
The principal component analysis loading plots of
heavy metals and major elements in the paddy
soils gives additional evidence for this.

Conclusions
The study investigated the distribution of heavy
metals in the paddy soils. Chemical partitioning of
Cu, Zn, Cd and Pb in the soils were also analyzed.
An hypothesis on the origin of each metal, i.e.,
either (mainly) anthropogenic or (mainly) geochemical, was made. The higher concentrations of
Cu, Cd, Zn and Pb are derived mainly from
wastewater, copper smelting slag and dust. The
identied pollutants can be released into the
environment mainly through three pathways,
namely plant uptake, soil ingestion and leaching
into groundwater. Flooding in rice cultivation has
led to the reduction and dissolution of Mn oxides
leading to leaching of Co. Soil Cd and Pb were
predominantly in MgCl2 extractable and residual

25

fractions, respectively. Extraction studies suggest

that the mobility of contaminants was higher than
in unpolluted soils, therefore such contaminants
are potentially more harmful to the environment.
Acknowledgements
We thank the Institute of Geochemistry, Chinese
Academy of Sciences (Project HDH-020208) and
the Program of Creative Engineering of the
Chinese Academy of Sciences, PR China (No.
KZCX3-SW-429) for nancial support.
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