Chemosphere 90 (2013) 2381–2387

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Chemosphere
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Spatial distribution of organochlorine pesticides (OCPs) and effect of soil characters:

A case study of a pesticide producing factory
Congcong Zhao a, HuiJun Xie b,⇑, Jian Zhang a, Jingtao Xu a, Shuang Liang a
a
School of Environmental Science and Engineering, Shandong University, Jinan 250100, China
b
Environment Research Institute, Shandong University, Jinan 250100, China

h i g h l i g h t s

" We examined the spatial distribution of OCPs in a pesticide producing factory.

" DDTs and HCHs shared the same migration pattern and dominant impact factor.
" Organic matter appeared to be the main impact factor on the investigated OCPs.
" Total phosphorous showed significantly positive effect on ENDO concentration.

a r t i c l e i n f o a b s t r a c t

Article history: The distribution and concentration of some organochlorine pesticides (OCPs) in the soil around a pesti-
Received 4 May 2012 cide factory in Zibo, China, were examined, including dichlorodiphenyltrichloroethane (DDT) and its
Received in revised form 24 August 2012 metabolites, isomers of hexachlorocyclohexane (HCH) and endosulfan (ENDO). The results showed that
Accepted 17 October 2012
the OCPs concentrations were extraordinary high in this region. The concentrations of DDTs, HCHs,
Available online 16 November 2012
and ENDO were measured in the range of 0.775–226.711, 0.248–42.838, and 0.081–1.644 mg kg1,
respectively. DDT and its isomers were identified to be the dominate contaminants in most of the sam-
Keywords:
pling sites. In the vertical direction, the distribution pattern of the total OCPs was in order of DDTs, HCHs,
OCPs
Spatial distribution
and ENDO in the 0–20 cm, but in 20–40 and 40–60 cm the trends were unobvious. Although no recent
Soil characters input occurred in most areas, the residues of OCPs remained in deep soil due to their persistence. Unlike
Pesticide factory ENDO, DDTs and HCHs appeared to have the similar property in terms of not only the migration pattern
in soil, but also the relationship to the same dominant impact factor (i.e. organic matter). DDTs and HCHs
were affected positively by the organic matter, whereas ENDO was affected negatively. Due to the inter-
relationship among various impact factors, the spatial distribution of pesticides in the soil was considered
to be a combined result.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Organochlorine pesticides (OCPs) have been widely used in
agriculture due to its efficiency in controlling the pests, diseases,
and increasing food production. However, most organochlorine
pesticides are persistent organic pollutants (POPs) that can accu-
mulate in the food chain and consequently impair animal and hu-
man health (Ahmed Azmi et al., 2006; Pilar et al., 2009; Zimmer
et al., 2011). Although some OCPs can be adsorbed and degraded
in soil to some extent (Semple et al., 2003), most of them remained
due to their low vapor pressure and resistance to photo-oxidation
(Dimond and Owen, 1996). Consequently, even the production and
application of many OCPs, e.g. aldrin, DDT, HCB and HCHs, have
⇑ Corresponding author. Tel.: +86 531 8836 1185.
E-mail address: xiehuij@sdu.edu.cn (H. Xie).
been banned or restricted since the 1980s, their residues or metab-
olites are still present in various environments, including but not
limited to, both city and countryside (Kim and Smith, 2001; Zhu
et al., 2005) area, and the sediments of European high altitude
mountain lakes (Grimalt et al., 2004).
The distribution of OCPs in soil is affected by many factors, espe-
cially the microbiological, physical, and chemical properties of the
soil. For instance, the distribution of p,p0 -DDT, b-HCH and c-HCH
is positively affected by humus but negatively affected by soil pH
and density (Škrbić and Ðurišić-Mladenović, 2007). Moreover, pes-
ticide contamination is expected to be more serious particularly in
the soil around or in pesticide producing factory, which as a result,
appears to be a more representative sample for studying the effect
of soil characters on OCPs distribution. As a huge pesticide producer,
China is facing severe OCPs contamination problem, especially the
areas around the pesticide producing factories with a long history.

0045-6535/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2012.10.029
2382 C. Zhao et al. / Chemosphere 90 (2013) 2381–2387
Despite the importance of OCPs contamination, the concentra-
tion and distribution of OCPs in the soil around pesticide producing
factory have not been seriously investigated to date. Abhilash and
Singh (2008) reported an extreme high concentration of total HCH
isomers, ranging from 53 to 99 mg kg1, in a small scale pesticide
producing factory of North India. However, the concentration and
distribution of other OCPs were not examined.
The aims of this work were to study the horizontal and vertical
distribution profiles of OCPs in the soil around a pesticide factory.
Besides HCH isomers, DDT, DDD and DDE, and a-endosulfan and
b-endosulfan were under investigation for a more complete evalua-
tion of OCPs contamination. Research efforts were focused on the ef-
fect of important soil properties on OCPs distribution, including soil
water content, pH, organic matters, total nitrogen, and phosphors.
2. Material and methods
2.1. Soil sampling
The factory is located in Zibo, Shandong province, China. The
layout of eight sampling sites is shown in Fig. 1. Four of them were
50, 100, 200, 400 m away from the DDTs, HCHs, and ENDO produc-
ing plants, named G50, G100, G200, G400, respectively. The four
sites were chosen for the gradient experiment. Two sites (CYA
and OME) were chosen near the organophosphorus pesticide pro-
duction area. The other two sites (GRA and BLA) were in the resi-
dential area about 2000 m away from the factory. At each site,
soil samples were taken from three different layers with the depth
of 0–20, 20–40, and 40–60 cm from the surface, labeled as D-1, D-
2, and D-3, respectively. For each layer, five individual soil cores
with equal amounts were taken up from a delimitation of 3 square
meters and homogenized to obtain a representative sample. The
soil samples were placed in polyethylene plastic bags and trans-
ported to the laboratory in a chilled insulating box. They were then
air dried under through a 2 mm pore size sieve, and stored at
20 °C until analysis.
2.2. OCPs extraction and analysis
2.2.1. Extraction and cleanup
The OCPs were extracted following the Soxhlet extraction meth-
od (Grimalt et al., 2004). Air-dried soil of 5 g underwent Soxhlet
extraction for 24 h using hexane: dichloromethane (4:1, v/v) as
Fig. 1. Map of sampling sites. The shadow part represents the pesticide factory (scale: 1:5000).
extracting solvent (ASE 300, Dionex, USA). In order to improve
extraction efficiency, anhydrous sodium sulfate (5 g) and activated
copper (1 g) were mixed with the soil samples to remove water and
sulfur containing compounds. Before the extraction, samples were
spiked with PCB 209 as surrogate standards. All extracts were con-
centrated under rotary vacuum evaporator system (800, China) to
1 mL, and subsequently cleaned with a Florisil solid phase extrac-
tion (SPE) cartridge (1 g, 6 mL, Supelco, USA) filled with anhydrous
sodium sulfate (2 g). The OCPs were eluted with 40 mL of hexane:
dichloromethane (9:1, v/v), and then concentrated to near-dryness
by rotary vacuum evaporation and reconstituted in hexane (1 mL)
for GC analysis.
2.2.2. GC-conditions
The determination of OCPs was performed using a Shimadzu
2014 gas chromatograph equipped with a Ni63 electron capture
detector and RTX-5 column (30 m  0.25 mm i.d., film thickness:
0.25 lm). Nitrogen (99.99% purity) was used as carrier gas at
1.00 mL min1. The injector and detector temperature were main-
tained at 260 and 300 °C, respectively. The column temperature
was programmed as follows: initial temperature 100 °C held for
2 min, increased to 170 °C at 25 °C min1, then a ramp at
2 °C min1 to 225 °C with the temperature retained for 2 min,
and then to 290 °C at 10 °C min1, maintained for 8 min. 1 lL of
the sample was injected in the splitless mode.
2.3. Soil characters analysis
Soil characters were rigorously examined including moisture
content, pH, organic carbon, total nitrogen, and phosphorous.
Moisture content was measured according to the national standard
(GB 7172-1987, China). Soil pH was measured in water with the
soil to water ratio of 1:2.5 (w/v). Organic carbon was determined
by dichromate oxidation and titrated with ferrous ammonium sul-
fate (Walkley and Black, 1934), followed by converting to soil or-
ganic matter content using the Van Bemmelen factor 1.724.
Available nitrogen was digested by sodium hydroxide and titrated
by boric acid (Singh and Singh, 2005). Olsen-P was extracted with
0.5 M NaHCO 3 and determined calorimetrically according to
Murphy and Riley (1962).
 C. Zhao et al. / Chemosphere 90 (2013) 2381–2387
2.4. Quality control and statistical analysis
Glasswares were thoroughly washed with acetones and then
soaked in 5% K2Cr2O4 sulfuric acid solution overnight. Before use,
they were cleaned with distilled water and further purged with
acetone and hexane. The measured OCPs included four HCH iso-
mers, three DDT homologues and endosulfan isomers (Supelco,
USA). Calibration was made ever since the gas chromatograph
was restarted. For each OCP, the correlation coefficients (r) of cal-
ibration curves were all higher than 0.9996. The certified reference
materials, SRM 1944 (New York/New Jersey Waterway Sediments)
were used to validate the analytical method. The results of OCPs
were in good agreement with the certified value, with a recovery
rate of 108.40%, 117.18% and 83.01% for p,p0 -DDT, p,p0 -DDD, p,p0 -
DDE respectively. Unavailable OCPs in reference material were
not detected. Samples (n = 5) were extracted and measured in
duplicate to evaluate the reproducibility of the overall method,
and the relative standard deviation (RSD) of duplicate samples
was in the range of 5.71–14.02%. The measurement of all the other
samples was repeated twice, and the RSD was below 12%. Anhy-
drous sodium sulfate as method blanks (n = 5) was extracted under
the same procedure as for the samples and no contaminants of
organochlorine pesticides were found, which proved no contami-
nants during the sample handling. The procedure was checked
for recovery efficiencies by analyzing uncontaminated soil (n = 5)
spiked with OCPs standard, and recoveries varied from
72.09 ± 6.11% to 121.43 ± 8.09%. PCB 209 as a recovery surrogate
was added prior to extraction (Yang et al., 2010a). The majority
of the surrogate recoveries was higher than 80%, and remained
basically consistent over time. Consequently, no adjustment was
made on the data since majority of these recoveries were high
(Bozlaker et al., 2009).
The influence of soil characters on OCPs residuals was subjected
to the analysis of principal component analysis (PCA), by using
SPSS 13.0 and Canoco for windows 4.5.
3. Results and discussion
3.1. Overall profiles of OCPs in soil
3.1.1. Total OCPs levels
Data analysis revealed the presence of DDTs, HCHs, and ENDO
in all samples with the concentrations measured in the following
ranges, 0.775–226.711, 0.248–42.838, and 0.081–1.644 mg kg1
of soil, respectively. Although the grade of concentration is consis-
tent with that reported by Yang et al. (2010b) studying the soil
samples taken from a former organochlorine pesticide producing
plant in China, the concentration of DDTs measured in the present
work appeared to be much higher. DDTs was apparently the dom-
inant OCPs in our case. In particular, the concentration of DDTs
turned out to be thousands of time higher than ENDO at some
points. This was understandable since DDTs was once the major
products of the factory for a decade, while the manufacture of
ENDO lasted merely several months.
3.1.2. Distribution in gradient sampling experiment
3D distribution of OCPs (Fig. 2) showed that all the OCPs waved
forward in soil. DDTs and HCHs exhibited the same migration pat-
tern with the highest concentration detected in G100. In contrast,
the highest concentration of ENDO was detected in G200. It ap-
peared that ENDO moved faster than DDTs and HCHs, though its
production initiated around 20 years later. It was noteworthy that
the highest OCPs concentrations were not present at G50, which
meant that the site nearest to the production plant was not most
heavily polluted. This interesting phenomenon might be partially
2383
explained by the soil–air exchange effect. The newly used pesticide
might have stronger deposition from air to soil, whereas the heav-
ily used area might undergo net volatilization (Wong et al., 2010).
After long-term application, the OCPs at G50 might go through the
volatilization rather than deposition. Nevertheless, it should be
noted that the migration and distribution of OCPs in soil is an ex-
tremely complex process affected by many factors, such as the
physicochemical properties of other contaminants, soil properties,
historical use, the vicinity to the source, and the meteorological
conditions (RůŽičková et al., 2008). The results are more site-
specific and further efforts were required accordingly.
In the vertical direction, the distribution pattern concentration
of OCPs was measured to be in order of DDTs, HCHs and ENDO
in D-1. In contrast, no trends could be found in D-2 and D-3, which
probably due to the difference in production volume and degrada-
tion pattern. Although the production of the investigated OCPs
ceased around 20 years ago, their concentrations with a grade of
mg kg1 were measurable in all soil layers, even D-3. Our results
clearly showed the persistence of OCPs residues in not only the
surface but also deep soil layer despite a long term degradation
and absorption.
3.1.3. Distribution and proportion of HCHs, ENDO and DDTs Isomers in
soil
3.1.3.1. DDTs. The percentages of DDTs concentration were shown
in Fig. 3a. The proportions of DDT and its isomers were found to be
in order of DDT > DDD > DDE in most cases. DDD is the anaerobic
degradation products of DDT, so the degradation of DDT to DDD
is expected to increase with depth (Huang et al., 2001), which is
clearly because the oxygen decreases with the depth (Kozlowski,
1985). This appears to be true for half of the sampling points.
DDE is a less toxic product of DDT under aerobic conditions, and
could be an intermediate product further converted into DDD.
According to Fig. 3a, the proportion of p,p0 -DDD and p,p0 -DDE were
measured in the range of 0.2–0.51, 0.03–0.46, respectively. p,p0 -
DDD tended to have a higher fraction than p,p0 -DDE, probably be-
cause that oxygen entered soil largely by diffusion and gradually
declined with the depth (Kozlowski, 1985). As shown in Table 1,
the ratios between each DDT isomers were found to be in the order
of DDD/DDE > DDD/DDT > DDE/DDT, which suggests that conver-
sation from DDT to DDD was the main degradation pathway.
Technical DDT contains 65–80% of p,p0 -DDT and some other
impurities. The fraction of p,p0 -DDT compounds can thus be used
as an parameter for the assessment of DDT input (Bozlaker et al.,
2009). The high fraction of p,p0 -DDT indicates recent use, whereas
the low one suggests the dominance of residues. The fractions of
p,p0 -DDT in our study were found to be in a wide range of 14–
0.77%, implying a complete degradation and no recent use in this
area. Another parameter for assessing the application time of
DDT is the ratio of DDT/(DDD + DDE) with the reference value of
1.0 (Zhang et al., 2001, 2006). The smaller value means longer
application time of DDTs. As shown in Table 1, the mean value of
this ratio was basically around 1.0, which indicates that DDTs were
mainly residues in most samples. However, ratios higher than 1.0
were found in G100, G400 (D-3), CYA (D-1, D-2), and OME (D-3),
which could be explained by the emission of DDT in previous
application (Kim et al., 2007) or further soil–air exchange. DDE is
more volatile so can be more easily released from the soil than
DDT. There is a model to calculate the DDE emission according to
former research in Alabama and for each year 200–600 kg p,p0 -
DDE is released from agricultural soils (Harner et al., 2001). Be-
sides, research in southwestern USA has discovered that poor
metabolite capability could cause the high proportion of parent
DDT, and according to this research, metal content and field capac-
ity is linked to the microbial transformation process of DDT to DDE
2384 C. Zhao et al. / Chemosphere 90 (2013) 2381–2387

Fig. 2. 3D spatial distribution maps of ENDO (a), HCHs (b), and DDTs (c). Color scales represent the total concentration of each OCP (mg kg1 dry weight soil).

and DDD (Hitch and Day, 1992). Further research efforts and more 3.1.3.2. HCHs. Four HCH isomers, i.e. a-HCH, b-HCH, c-HCH, and d-
evidences are, therefore, needed for more convincible conclusions. HCH, were all detected in the soil with the concentration measured
 C. Zhao et al. / Chemosphere 90 (2013) 2381–2387
Fig. 3. Composition of isomers in each investigated OCPs. (a) DDTs (DDT, DDD,
DDE), (b) HCHs (a-HCH, b-HCH, c-HCH, and d-HCH), and (c) ENDO (a-endosulfan
and b-endosulfan).
to be in the range of 0.058–3.470, 0.156–37.154, 0.010–1.287, and
0.008–1.523 mg kg1, respectively. Accordingly, the relative pro-
portion of each isomer in total HCHs was calculated to be 1.93–
64.83%, 30.78–96.48%, 0.69–6.98% and 0.90–15.90%, respectively.
2385
The concentrations of HCHs isomers were relatively low in
G400, especially D-2, which was probably because degradation
and leaching. G100 exhibited the highest concentration of a, b
and c-HCH in D-2, but d-HCH in D-1. In general, the concentration
of the four HCH isomers decreased with increasing distance and
depth, which proved their migration and transformation.
There are many ways to assess the application time and con-
tamination source of HCH. Technical HCH is a mixture product of
a-HCH (67%), b-HCH (10%), c-HCH (15%), and d-HCH (8%). Among
the four isomers, b-HCH is the most persistent and easily accumu-
lated one in soil for the presence of chlorines in equatorial posi-
tions (Li, 1999), lowest vapor pressure, and the isomerization
from a-HCH or c-HCH via a-HCH (Willett et al., 1998; Walker
et al., 1999). The accumulation of b-HCH (30.78–96.48% of total
HCHs) in our study suggested that HCH productions had been
stopped for many years.
Besides technical HCH, c-HCH or Lindane is also a kind of pes-
ticide product. The value of a-HCH/c-HCH would be between 5
and 7 for technical HCH, and would also be approximately zero
for Lindane (Lee et al., 2001). Because c-HCH is less stable than
a-HCH and could isomerize to a-HCH, the ratio would increase
gradually after application. In our study, most of the ratios were
found to be between 1 and 5, which implies that the residues of
HCHs mainly originated from Lindane and were as attributed to
historical input. However, the ratio was 25.65 in D-1 of G400,
which was most likely originated from technical HCH rather than
recent use. Furthermore, in D-1 the mean percentages of four iso-
mers were in order of b, a, c and d-HCH, which was consistent with
the data, reported in soil samples by Yang et al. (2009) and also
proved the historical contamination sources of HCH.
3.1.3.3. Endo. The mean level of endosulfan isomers was relatively
low in most samples. The concentration of a-endosulfan and b-
endosulfan was measured to be in the range of 0.012–0.054 and
0.035–0.762 mg kg1, respectively. According to Fig. 3, b-endosul-
fan was the dominant isomers accounting for 83.53–96.31% of total
ENDO. This may be attributed to the slow degradation of b-endo-
sulfan (Lee et al., 2006; Kumar et al., 2008). Previous studies have
shown that a-endosulfan can be more readily biodegraded by
microbial species than b-endosulfan (Kwon et al., 2002; Siddique
et al., 2003). However, it was noteworthy that b-endosulfan was
not the dominated fraction of ENDO (merely 43.30%) in D-2 of
G100. This implied that the fast degradation of a-endosulfan was
not always the case. It appeared that some microbes (e.g. fungi)
(Goswami et al., 2009), might prefer b-endosulfan, resulting in its
fast degradation. Commercial technical grade endosulfan is the
mixture of a and b isomers with the ratio of 7:3. Our results thus
indicate no recent production or application of ENDO occurred in
this area.
3.2. Effect of soil characters on OCPs
The correlations among various soil characters and OCPs were
also studied (Fig. 4). The angles between the arrows indicated
the correlations between different soil characters and OCPs. The
correlation value was decided by perpendicular projection of one
arrow-tip onto the line overlaying the other arrow. As illustrated
in Fig. 4, organic matter appeared to be the main impact factor
(p < 0.05) on the investigated OCPs. It had positive influence on
DDTs and HCHs, negatively affected on ENDO on the contrary.
The Kow (octanol/water partition coefficient) value is commonly
used to indicate the chemical distribution in the environment. Lar-
ger values means stronger tends to be in an organic or non-polar
environment. The value for these OCPs are higher than 3.5, so they
tends to accumulate in soil or living organisms containing organic
matter. It has been widely reported that the organic matters in soil
2386 C. Zhao et al. / Chemosphere 90 (2013) 2381–2387
Table 1
Summary of ratios values.
Depth DDT/(DDD + DDE)a DDD/DDE
Mean value 0–20 1.09 2.51
20–40 0.97 2.99
40–60 1.27 3.18
Minimum value 0–20 0.45 0.51
20–40 0.39 0.88
40–60 0.20 0.74
Maximum value 0–20 2.67 4.82
20–40 2.19 10.13
40–60 3.34 9.80
Reference value 1 –
a
DDT, DDD, and DDE here refers to p,p0 -DDT, p,p0 -DDD, and p,p0 -DDE, respectively.
Fig. 4. Correlation diagram between OCPs and impacting factors.
were the main sorbent to pesticides for its hydrophobicity. It was
proved that pesticides were more phytotoxic in the soil having
low content of organic matters (Wauchope et al., 2002). Further-
more, organic matters themselves are a kind of energy resource
and nutrient substrates which could facilitate microbial degrada-
tion of OCPs in soil (Tian et al., 2010).
Another interesting finding was the different responses of vari-
ous OCPs to total phosphorous and pH. In our study, total phospho-
rous showed significantly positive effect on ENDO concentration
(p < 0.05), but no correlation with the concentration of DDTs and
HCHs. Phosphorous is one of the essential nutrition of plants and
microbes and reported to be more important than nitrogen for
the optimal microbial growth in soil (Zheng et al., 2009). Besides
organic matter, pH was another important factor and had positive
impact on DDTs and HCHs, but negative effect on ENDO (p < 0.05).
pH is a well known regulator controlling the physicochemical pro-
cess and microbial growth in soil. Awasthi et al. (2000) observed
that endosulfan was not detectable at acidic pH but increased
gradually to an optimal activity at pH 8.5. In our experiment, the
average level of soil pH was 8.18, and at some sampling point
the value was just around 8.5.
No effect was found of moisture content and total nitrogen on
the investigated OCPs. Demoling et al. (2007) also reported that
nitrogen alone was not a significant limitation factor for soil
bacteria.
The difference among the impact factors of DDTs, HCHs and
ENDO was probably due to the different characteristics of these
pesticides and microbes. As illustrated in Fig. 4, a significant corre-
lation was found between DDTs and HCHs (p < 0.05), however no
relationship existed with ENDO. This implies that DDTs and HCHs
may have the similar properties distinguished different from those
of ENDO. The difference in the polarity of OCPs was consistent with
the inference. Though they all have relatively high Kow value, DDT
is twice the value of ENDO. Nevertheless, it should be noted that
the above discussed soil characters are not independent but some-
times interrelated with each other. For instance, water can be an
excellent competitor for any soil surface site, and pH could affect
DDD/DDT DDE/DDT a-HCH/c-HCH
0.78 0.54 5.31
1.07 0.76 3.65
0.98 0.72 3.11
0.31 0.06 1.84
0.36 0.06 1.40
0.25 0.05 0.87
1.33 1.46 25.65
3.35 2.53 7.03
3.00 1.91 5.34
– – 5–7 or 0
other the electric charge and ionic strength of soil (Clausen and
Fabricius, 2002; Kumar and Philip, 2006).
4. Conclusions
The present study clearly showed that most of the surroundings
area of the investigated pesticide factory was seriously contami-
nated by OCPs, especially DDTs with the highest concentration of
226.711 mg kg1. As to each kind of pesticide, p,p0 -DDT, b-HCHs
and b-endosulfan were the dominant substances in this area. The
study revealed that DDTs and HCHs followed the same migration
pattern which was completely different from that of ENDO.
Although produced later in this factory, ENDO showed a faster
migration in soil. In general, the vertical concentration of OCPs
was measured to be in order of DDTs > HCHs > ENDO. In addition,
PCA results between soil characters and OCPs concentrations
indicated that organic matter was the dominant factor showing
positive effect on DDTs and HCHs but negatively affecting ENDO.
ENDO concentration was also significantly affected by total
phosphorous, and DDTs and HCHs were related to pH. Total
nitrogen and water content had little effect on OCPs concentration.
The related indicators proved no recent input of OCPs. Nevertheless,
the contamination should not be ignored and proper measures are
urgently needed to prevent OCPs entering into the food chain or
other environmental medium.
Acknowledgments
We gratefully acknowledge financial support by the National
Science Foundation of China (NSFC, Project No. 21007032), Inde-
pendent Innovation Foundation of Shandong University (IIFSDU,
No. 2009TS025), Natural Science Foundation for Distinguished
Young Scholars of Shandong province (JQ201216).
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