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Pedosphere 22(2): 178–189, 2012

ISSN 1002-0160/CN 32-1315/P


c 2012 Soil Science Society of China
Published by Elsevier B.V. and Science Press

Residues of Organochlorine Pesticides (OCPs) in Agricultural Soils


of Zhangzhou City, China∗1

YANG Dan1,2 , QI Shi-Hua1,2,∗2 , ZHANG Jia-Quan1,2 , TAN Ling-Zhi1,2 , ZHANG Jun-Peng1,2 , ZHANG Yuan1,2 ,
XU Feng1,2 , XING Xin-Li1,2 , HU Ying1,2 , CHEN Wei1,2 , YANG Jun-Hua3 and XU Mei-Hui3
1
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China)
2
School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)
3
Geological Survey of Fujian Province, Fuzhou 350013 (China)
(Received June 30, 2011; revised November 25, 2011)

ABSTRACT
A soil survey was conducted in Zhangzhou City, an important agricultural region in south of the Fujian Province, China.
93 surface soil samples were collected in the paddy fields, vegetable lands, orchards and tea plantations from Zhangzhou
City. An additional soil profile was sampled in a paddy field as previous research had indicated high concentrations of
organochlorine pesticides (OCPs) in the paddy fields. Dichlorodiphenyltrichloroethanes (DDTs) ranged from 0.64–78.07 ng
g−1 dry weight and hexachlorocyclohexanes (HCHs) ranged from 0.72–30.16 ng g−1 dry weight in the surface soil of the
whole study region. Ratios of α-HCH/γ-HCH < 4 and o, p -DDT/p, p -DDT > 1 in all soil samples suggested that lindane
and dicofol were widely applied in this region in the past. Concentrations of HCHs and DDTs in soils from the four land
use types followed the orders: paddy fields > vegetable lands > tea plantations > orchards and tea plantations > orchards
> paddy fields > vegetable lands, respectively. Analyses of the data showed no correlation (r < 0.1) between elevation and
OCPs contents in paddy fields, orchards and vegetable lands, indicated no significantly different features in distribution of
HCHs and DDTs in the soils from low lying plains and mountains and the unsystematic usage of OCPs, and highlighted
the fragmented nature of agricultural production in Zhangzhou, as well as the reemission of OCPs from the soils, where
high OCPs concentrations were found, in Longhai of Zhangzhou. In addition, no obvious relationship between the OCPs
and total organic carbon (TOC) (r < 0.3) was observed in the soil profile. The mean contribution of dicofol in total DDTs
was 66% in the whole Zhangzhou region. The approximate burdens of HCHs and DDTs in the surface layer of 0–20 cm
were 0.44 and 1.55 t, respectively. The storage of both HCHs and DDTs in soil surface layer (0–20 cm) accounts for 40%
burden of the soil layer of 0–50 cm (1.10 t HCHs and 3.87 t DDTs), in which the highest concentrations of OCPs were
observed in soil profile.
Key Words: dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexane (HCHs), landform, land use types, vertical
distribution

Citation: Yang, D., Qi, S. H., Zhang, J. Q., Tan, L. Z., Zhang, J. P., Zhang, Y., Xu, F., Xing, X. L., Hu, Y., Chen, W.,
Yang, J. H. and Xu, M. H. 2012. Residues of organochlorine pesticides (OCPs) in agricultural soils of Zhangzhou City,
China. Pedosphere. 22(2): 178–189.

INTRODUCTION Voogt, 1999). The OCPs, including hexachlorocy-


clohexanes (HCHs), dichlorodiphenyltrichloroethanes
Organochlorine pesticides (OCPs) have caused (DDTs), aldrin, dieldrin, endrin, chlordane, heptachlor
great concern for decades due to their persis- and hexachlorobenzene (HCB), have been linked to
tence in the environment, bioaccumulation through causing cancer, damage to the nervous system, repro-
food chains, and high toxicity to humans and ductive disorders, and disruption of the immune sys-
biota (Dimond and Owen, 1996; Jones and de tem in humans (Rissato et al., 2006). These OCPs are

∗1
Supported by the National Natural Science Foundation of China (No. 41073070), and the Research Fund for the Doctoral
Program of Higher Education of China (No. 20090145110004).
∗2
Corresponding author. E-mail: shihuaqi@cug.edu.cn.
ORGANOCHLORINE PESTICIDES IN AGRICULTURAL SOILS 179

listed in the Stockholm Convention as persistent or- 5–10, 10–20, 20–30, 30–50, 50–70, 70–90, 90–110, 110–
ganic pollutants (POPs) that are to be banned by the 130 and 130–150 cm. The samples were sealed in clean
United Nations Environment Program (UNEP) (Blais polyethylene plastic bags and transported to the labo-
et al., 1998; UNEP, 2001). ratory where they were packed in amber glass bottles
Although the usage of OCPs has been banned in and immediately stored at −4 ◦ C until analysis.
China for more than 20 years, OCPs are still routinely
found in soils, air, waters, foodstuff, sediments and
even in humans (e.g., milk and blood) (Wang et al.,
2005, 2007; Ennaceur et al., 2007; Guo et al., 2008;
Li et al., 2008; Sun et al., 2009, 2010; Xing et al.,
2010). Soil is considered to be an important and po-
tential source of OCPs to other environmental media
and organisms after long-term use of OCPs for the pest
control in the agriculture.
The historical usage of OCPs may affect the OCPs
residuals in the soil. The spatial distribution charac-
teristic of pesticide application for crop protection in
China has been reported as follows: southeast > cen-
tral > northwest (Wang et al., 2005). Fujian Province
is in the southeast of China and Zhangzhou, a large
agricultural region, is located in the south of the
province. Therefore, the application of OCPs on crops
in Zhangzhou maybe considerable and likely to affect
the environment, including soil, water and air. Ad-
ditionally, human health could potentially be harmed
through crops uptake and subsequent accumulation
through the food chain (Ennaceur et al., 2007).
The main objectives of this study were i) to inves-
tigate the levels and distribution patterns of OCPs in Fig. 1 Map of the sampling locations in Zhangzhou City.
the agricultural region of Zhangzhou; ii) to compare
Standard mixtures of α-hexachlorocyclohexane
and assess the impact of four different land use types
(HCH), β-HCH, γ-HCH, δ-HCH, p,p -dichlorodipheny-
(paddy fields, vegetable lands, orchards and tea planta-
ldichloroethylene (DDE), p, p -dichlorodiphenyldichlo-
tions) on the OCPs residues in soil; and iii) to analyze
roethane (DDD), o, p -DDD, and p, p -dichlorodipheny-
the distribution of residual OCPs with elevation and
ltrichloroethane (DDT), as well as 2,4,5,6-tetrachloro-
at different soil depths.
m-xylene (TCMX), decachlorobiphenyl (PCB 209)
MATERIALS AND METHODS and pentachloronitrobenzene (PCNB), were pur-
chased from Ultra Scientific, USA. Dichloromethane
In March 2009, 93 surface soil samples (0–20 cm) (DCM) and n-hexane were obtained from Tedia Co.,
were collected, using a 12 km × 12 km sampling grid USA. Acetone was purchased from Fisher Scientific,
across the whole region of Zhangzhou (located in 116◦ USA. Anhydrous sodium sulphate was obtained from
54 –118◦ 8 E, 23◦ 34 –25◦ 15 N). This is the most im- Sinopharm Medicine Holding Co., Ltd., China. Silica
portant agricultural region in the south of the Fujian gel (75–150 μm) was purchased from Qingdao Haiyang
Province, southeast China (Fig. 1). Samples were taken Chemical Co., China. Before use, the silica gel and
from four different land use types, including paddy anhydrous sodium sulfate were Soxhlet-extracted for
fields, vegetable lands, orchards and tea plantations. 48 h with DCM, and then baked for 16 h at 130 ◦ C
At each site, four subsamples were collected randomly and for 6 h at 600 ◦ C, respectively. The silica gel was
and bulked together to form one composite sample. A then deactivated by purified water (3.0%, w/w) and
single soil profile was collected from a paddy field in stored in a desiccator. All glassware was washed with
the study region. The soil profile was sampled at 0–5, detergent, K2 Cr2 O7 -H2 SO4 solution, tap water and
180 D. YANG et al.

deionized water, and was finally baked at 180 ◦ C for and 300 ◦ C, respectively. A sample of 2 μL was in-
3.5 h to remove trace amounts of organics. jected into the GC-ECD for analysis. Concentrations
A 10 g sample of the soil was spiked with 20 ng of individual target OCPs were quantified according to
of TCMX and PCB 209 as recovery surrogates, and a six-point internal standard calibration curve.
was Soxhlet-extracted for 24 h with dichloromethane. The spiked samples containing internal standard
In the collection flask, activated copper granules were compounds were analysed simultaneously with soil
added to eliminate elemental sulfur. The crude ex- samples. A procedural blank and a replicate sample
tract was concentrated and reduced to 2–3 mL by ro- were run with every set of 12 samples analyzed to check
tary vacuum evaporation, and solvent-exchanged with for contamination from solvents and glassware. The
hexane. An alumina/silica (1:2, v/v) gel column (both limits of detection (LODs) were based on 3:1 S/N ra-
3% deactivated with H2 O) was used to purify the ex- tio. The recoveries of surrogate (standard mixtures)
tract. The extract was then eluted with 30 mL of spiked in soil samples ranged from 70% to 105%. The
dichloromethane/hexane (2:3, v/v) to obtain the OCP relative standard deviation (RSD) was less than 10%.
fraction. The fraction was concentrated to 0.2 mL un- All OCP concentrations were expressed on an air-dried
der a gentle stream of nitrogen. Pentachloronitroben- weight basis. Correlation analysis was performed using
zene (PCNB) was added as an internal standard be- PASW (formerly SPSS) Statistics 18.0.
fore gas chromatograph-electron capture detector (GC-
ECD) analysis. RESULTS AND DISCUSSION
OCPs analysis was conducted using an Agilent OCPs in soils of study region
7890A gas chromatograph equipped with a 63 Ni elec-
tron capture detector (GC-ECD). Separation was per- An overview of the concentrations of OCPs in the
formed using a fused silica capillary column DB-5 (30 surface soil of Zhangzhou is shown in Table I. Concen-
m, 0.32 mm i.d., 0.25 μm film thickness). Nitrogen was trations of DDTs (sum of p, p -DDT, p, p -DDE, p, p -
used as the carrier gas at a constant flow of 2.5 mL DDD and o, p -DDT) ranged from 0.64–78.07 ng g−1
min−1 . The temperature program was as follows: ini- with an average of 3.86 ng g−1 , and HCHs (sum of α-
tial oven temperature was 100 ◦ C (equilibrium time 1 HCH, β-HCH, γ-HCH and δ-HCH) ranged from 0.72–
min), raised to 200 ◦ C at a rate of 4 ◦ C min−1 , then 30.16 ng g−1 with an average of 9.79 ng g−1 . Both
increased to 230 ◦ C at 2 ◦ C min−1 , then finally raised DDTs and HCHs had high detectable ratios, and α-
to 280 ◦ C at 8 ◦ C min−1 and, held for 15 min. The HCH, γ-HCH, δ-HCH and p, p -DDE residues were de-
injector and detector temperatures were set at 290 ◦ C tected in all samples.

TABLE I

Concentrations of organochlorine pesticides (OCPs) in the surface agricultural soil from Zhangzhou

Compounda) Mean Minimum Maximum Detectable rate Rb)


ng g−1 %
α-HCH 0.66±0.41 c)
0.18 2.90 100 0.254
β-HCH 1.27±2.28 NDd) 15.08 92.47 0.251
γ-HCH 1.36±3.18 0.27 28.76 100 0.136
δ-HCH 0.57±0.32 0.17 2.12 100 0.253
p, p -DDD 0.65±1.07 ND 7.23 98.92 0.272
p, p -DDE 2.38±3.68 0.07 26.85 100 0.277
p, p -DDT 3.86±10.13 ND 63.44 98.92 0.144
o, p -DDT 2.91±4.12 ND 39.25 98.92 0.091
HCHs 9.79±4.17 0.72 30.16 0.270
DDTs 3.86±14.76 0.64 78.07 0.249
a)
HCH = hexachlorocyclohexane; DDD = dichlorodiphenyldichloroethane; DDE = dichlorodiphenyldichloroethylene; DDT
= dichlorodiphenyltrichloroethane.
b)
Correlation coefficient between OCPs compound and total organic C.
c)
Mean±standard deviation.
d)
Not detected.
ORGANOCHLORINE PESTICIDES IN AGRICULTURAL SOILS 181

Concentrations of DDTs were higher than those of were mostly taken from paddy fields and vegetable
HCHs (Fig. 2), which is similar to many studies else- lands. Samples from Longhai, Longwen and Zhangpu
where for agricultural regions (Falandysz et al., 2001; regions were mostly from paddy fields and orchards,
Wang et al., 2006; Hao et al., 2008; Jiang et al., 2009; which are mostly distributed in the low lying regions.
Sun et al., 2009). Generally in agricultural soils, the Therefore, the land use types and landform were stud-
half-life of DDT is 4–35 years (average 10–10.5 years), ied further to assess the residues of OCPs in agricul-
whereas the half-lives of γ-HCH and α-HCH are only tural soils of Zhangzhou.
20–50 days and 20 weeks, respectively (Dimond and
OCPs in soils under four land uses
Owen, 1996; Harner et al., 1999). DDTs are therefore
likely to be more persistent and to stay longer in soil as OCP concentrations in soils from paddy fields,
residues. DDT can be dehydrochlorinated to DDE and vegetable lands, orchards and tea plantations are sum-
reductively dechlorinated to DDD. These metabolites marized in Table II. Concentrations of HCHs and
are even more persistent than the parent compound DDTs in soils under four land uses from highest to
(Quensen et al., 1998; Meijer et al., 2001). lowest were in the order: paddy fields > vegetable
Among the HCH isomers, high concentrations of lands > tea plantations > orchards, and tea planta-
β-HCH and δ-HCH indicated historical usage and tions > orchards > paddy fields > vegetable lands,
residues in the study region because their properties respectively. This discrepancy of sequence may be in-
are more stable than those of α-HCH and γ-HCH in the fluenced by the different land use types, which may re-
environment. In comparison to each of the mean va- quire various pesticide regimes to be used and will also
lues, the soil concentrations of the HCH isomers, DDT, have different soil conditions. The different properties
and DDT metabolites varied greatly, which might be of the OCPs could also have an effect. The high solubil-
due to different land use types. ity of HCHs in comparison to DDTs (Loganathan and
Highest concentration of HCHs was found in the Kannan, 1994) may explain why HCHs were found to
Pinghe region, while concentrations of DDTs were have elevated concentrations in paddy fields that were
higher in Longhai, Longwen and Zhangpu regions. The submerged in water.
highly polluted regions were different, which probably It has been widely recognized that technical HCH
due to that the soils were sampled from different land is a mixture of 60%–70% α-HCH, 2%–12% β-HCH,
use types in different regions. Soil samples of Pinghe 10%–15% γ-HCH (ratio of α-HCH/γ-HCH is from 4

Fig. 2 Spatial distribution of (a) hexachlorocyclohexanes (HCHs) and (b) dichlorodiphenyltrichloroethanes (DDTs) in
soils of Zhangzhou, Fujian Province, China.
182 D. YANG et al.

TABLE II

Concentrations and ratios of organochlorine pesticides (OCPs) in the agricultural soils of four land use types in Zhangzhou
Compounda) Paddy field Vegetable land Orchard Tea plantation

Mean±SDb) Range Mean±SD Range Mean±SD Range Mean±SD Range


−1
ng g
α-HCH 0.80±0.52 0.25–2.90 0.59±0.27 0.27–1.48 0.55±0.26 0.18–1.26 0.63±0.25 0.46–0.93
β-HCH 1.24±1.54 NDc) –6.18 1.36±2.64 0.15–12.32 1.06±2.58 ND–15.08 1.43±1.04 0.35–2.42
γ-HCH 0.66±0.43 0.25–2.12 0.53±0.18 0.30–0.93 0.49±0.22 0.17–1.26 0.55±0.13 0.40–0.63
δ-HCH 1.83±4.87 0.36–28.76 1.46±2.34 0.44–10.05 0.93±0.90 0.27–4.42 0.61±0.17 0.41–0.75
p, p -DDD 2.08±1.04 ND–6.14 2.18±0.87 0.01–4.69 4.22±1.23 0.16–39.25 1.74±0.58 0.86–2.48
p, p -DDE 1.97±2.10 0.18–8.99 1.62±1.67 0.22–6.21 3.17±5.30 0.07–26.85 2.99±2.15 0.10–7.74
p, p -DDT 0.73±3.74 ND–5.80 0.67±1.55 0.06–3.40 0.56±2.65 0.01–7.23 0.45±0.20 0.01–1.12
o, p -DDT 2.89±1.28 ND–63.44 2.13±0.99 0.08–6.02 4.66±6.86 0.13–52.27 16.90±5.06 0.01–50.46
α-HCH/γ-HCH 1.25±0.55 0.57–3.54 1.11±0.31 0.63–2.01 1.15±2.04 0.68–2.04 1.16±0.38 0.73–1.48
p, p -(DDD+ 4.75±10.16 ND–59.43 1.79±2.04 0.12–7.79 1.58±1.65 0.06–6.04 39.35±47.59 0.18–117.40
DDE)/p, p -DDT
o, p -DDT/p,p -DDT 6.53±21.39 ND–125.93 2.37±3.75 0.01–16.81 3.20±4.27 0.08–19.75 74.75±100.47 0.02–216.09
HCHs 4.53±5.29 0.98–30.16 3.94±3.93 1.48–16.82 3.03±3.07 0.72–18.30 3.21±1.36 2.08–4.73
DDTs 7.67±12.84 0.64–78.07 6.60±3.49 1.81–15.39 12.61±11.69 1.47–72.97 22.08±30.00 2.23–60.18
a)
HCH = hexachlorocyclohexane; DDD = dichlorodiphenyldichloroethane; DDE = dichlorodiphenyldichloroethylene; DDT
= dichlorodiphenyltrichloroethane; HCHs = sum of α-HCH, β-HCH, γ-HCH and δ-HCH; DDTs = sum of p, p -DDT, p, p -
DDE, p, p -DDD and o, p -DDT.
b)
Standard deviation.
c)
Not detected.

to 7), and other minor isomers, with lindane having greater than those of p, p -DDT in all studied land use
a high ratio of γ-HCH (Iwata et al., 1993). Generally, types, indicating dicofol input over the whole study
the ratio of α-HCH/γ-HCH is used to identify whether region. In tea plantation soils, the DDT levels were
the pollution source is technical HCH or lindane. In significantly higher than in the soils under other three
the present study, the ratios of α-HCH/γ-HCH were all land uses and around 7 times greater than the levels of
less than 4 and varied slightly within these four land total HCHs. The ratio of o, p -DDT/p, p -DDT (Table
use types, showing that lindane was applied widely. II) in tea plantations was at least 11 times greater than
The technical DDTs contains more p, p -DDT that of the other land types, suggesting high pollution
(about 85%) than o, p -DDT (about 15%), while co- levels of dicofol in tea plantations.
mpositions of dicofol are exactly opposite (Qiu et al., In order to know the exact contribution of dico-
2005). The anaerobic conditions in the tea plantations fol in total DDTs, the ratio (o, p -DDT/p, p -DDT) of
and orchards increased DDT degradation, making the technical DDT and dicofol were used to estimate the
values of p, p -DDE/p, p -DDD in these two land use source apportionment of DDTs. FD which stands for
types greater than those of the other two land types. the fraction of DDT from dicofol formulation, was cal-
Mean ratios of p, p -(DDE+DDD)/p, p -DDT in the culated by the ratios of o, p -DDT/p, p -DDT of techni-
four land use types were all more than 1, indicat- cal DDT, dicofol, and result of the present study (Qiu
ing that historical applications of technical DDT were and Zhu, 2010). The soil FD of the four land use types
widespread in agricultural soils in Zhangzhou. How- and the whole study area are given in Table III.
ever, these ratios varied significantly for the four land Principal component analysis (PCA) combined
types, indicating that different land conditions, such as with multiple linear regression analysis (MLRA) was
the degree of soil tillage, permeability and the strength also used to estimate the source apportionment of
of different microbial activities influenced the degrada- DDTs (Larsen and Baker, 2003; Yang et al., 2008). It
tion of DDT in soils. The degradation of DDT in the was found that mean contribution of dicofol-type DDT
tea land was more pronounced than the others. The is 23% to the paddy fields, 26% to the vegetable lands,
concentrations of o, p -DDT were almost equal to or 82% to the orchards, 66% to the tea plantations and
ORGANOCHLORINE PESTICIDES IN AGRICULTURAL SOILS 183

74% to the whole Zhangzhou region (Table III). results to describe the contribution of dicofol in our
The results of these two methods were different, work. The highest contributions of dicofol-type DDT
which is similar to the report of Qiu and Zhu (2010), was found in tea plantations (73%), which meet the
possibly due to that the PCA method is more or supposition on the preceding analysis of DDTs pollu-
less arbitrary and might generate negative values, and tion.
the ratios of o, p-DDT/p, p-DDT were influenced by The concentrations and ratios of OCPs in various
complex factors in their long resident time in the soil. uses of soils reported from other regions of China, as
Therefore, we used the mean value of these two method well as from other countries are listed in Table IV. The

TABLE III

Contribution of dicofol-type dichlorodiphenyltrichloroethane (DDT) to each land use type

Methoda) Contribution of dicofol-type DDT

Paddy field Vegetable land Orchard Tea plantation Zhangzhou region


%
FD 58±39b) 50±32 58±34 79±64 57±31
PCA-MLRA 23 26 82 66 74
Mean 41 38 70 73 66
a)
FD = the fraction of DDT from dicofol formulation; PCA-MLRA = principal component analysis (PCA) combined with
multiple linear regression analysis (MLRA).
b)
Mean±standard deviation.

TABLE IV

Concentrations of organochlorine pesticides (OCPs) in soils of diverse land use types in some other regions

Region Land use HCHsa) DDTsb) α-HCH/ o, p -DDT/ Reference


γ-HCH p, p -DDT
ng g−1
Nantong, China Cotton field - 183.07±171.68c) - 0.64d) Yang et al., 2008
Taihu Lake, China Vegetable lands 21 82c) 1.16d) 0.65d) Gao et al., 2005
Taihu Lake, China Paddy field 28.53±10.77 50.23±28.70c) 1.4d) 1.44d) Wang et al., 2007
Beijing, China Irrigated soils 3.70±0.52 31.27±6.65 0.52e) 0.06 Sun et al., 2009
Shanghai, China Agricultural land 2.41±2.32 21.41±22.43 0.51f) 1.33f) Jiang et al., 2009
Fujian, China Tea land 3.7 8.3 - - Sun et al., 1997
Hong Kong, China Farmland 6.53±0.17 1.85±1.64 6.0 2.25d) Zhang et al., 2006
South Korea Rice growing 5.22 2.93g) - - Kim and Smith, 2001
Corn Belt, USA Agricultural land - 9.63 - 0.38f) Aigner et al., 1998
Southern USA Cotton field 0.30h) 211±343c) 2.66d) 0.21f) Bidleman and Leone,
2004
Southern Ontario, Agricultural land - 18 500i) 0.29d) - Kurt-Karakus et al.,
Canada 2006
Leipzig-Halle, Germany Agricultural land 23.7–173 4.60–10.00g) 0.18e) - Manz et al., 2001
UK Background in 1986 < 0.88h) 0.34 < 0.05 - Meijer et al., 2001
a)
HCHs (hexachlorocyclohexanes) refer to the sum of α-HCH, β-HCH, γ-HCH and δ-HCH.
b)
DDTs (dichlorodiphenyltrichloroethanes) refer to the sum of p, p -DDT, p, p -DDE, p, p -DDD and o, p -DDT.
c)
Sum of p, p -DDT, p, p -DDE, p, p -DDD, o, p -DDT and o, p -DDE; mean±standard deviation.
d)
Calculated by the mean±standard deviation of each HCH isomers or DDT metabolite.
e)
Calculated by the percentage of each isomers.
f)
Calculated by mean of DDT metabolites.
g)
Sum of p, p -DDD, p, p -DDE and p, p -DDT.
h)
Sum of α-HCH and γ-HCH.
i)
Sum of p, p -DDT, p, p -DDE, p, p -DDD, o, p -DDT, o, p -DDE and o, p -DDD.
184 D. YANG et al.

level of HCHs (mean of 3.03–4.53 ng g−1 ) in the soil of ng g−1 ) in Leipzig–Halle region of Germany (Manz et
the current study was similar to the values of the agri- al., 2001), but significantly lower than cotton field soil
cultural land (2.41 ng g−1 ) from Shanghai (Jiang et (211 ± 343 ng g−1 ) from the southern US (Bidleman
al., 2009), the irrigated soil (3.70 ± 0.52 ng g−1 ) from and Leone, 2004) and agricultural land (18 500 ng g−1 )
Beijing (Sun et al., 2009), the agricultural soil (6.53 ± from Southern Ontario, Canada (Kurt-Karakus et al.,
0.17 ng g−1 ) from Hong Kong (Zhang et al., 2006) and 2006). Ratios of o, p -DDT/p, p -DDT (mean of 2.37–
the rice growing land and industrial land (5.22 ng g−1 ) 74.75 ng g−1 ) in this study were much higher than
from South Korea (Kim and Smith, 2001). However, those of other regions (Table II), and reflected the no-
it was much lower than the concentrations of HCHs in table input from dicofol in the Zhangzhou agricultural
the vegetable and paddy fields from Taihu Lake (Gao area.
et al., 2005; Wang et al., 2007) and the agricultural The mean values of HCHs and DDTs in the present
soil (23.7–173 ng g−1 ) from Leipzig-Halle region, Ger- study were significantly higher than background levels
many (Manz et al., 2001). Ratios of α-HCH/γ-HCH in reported in UK soils (Meijer et al., 2001), but not
agricultural area (mean of 1.11–1.25, Table II) of the over the first grade of Chinese Environmental Qua-
present study did not show much variation compared lity Standard for Soils (GB15618-1995) (HCHs, 50 ng
to other regions (all less than 4) except Hong Kong g−1 ; DDTs, 50 ng g−1 ). Overall, the OCPs levels in
(6.0) (Zhang et al., 2006), indicating that usage of lin- soils of agricultural soils from Zhangzhou can be cate-
dane would be the main source of HCH in agricultural gorized as ‘slight pollution’. Nevertheless, this level
soils. of contamination should not be considered insignif-
Compared with the research in Fujian in 1997, the icant. In light of possible bioaccumulation of OCPs
present study shows a similar mean of total HCHs in through food chain into higher trophic organisms, in-
tea plantations soils, but the mean of total DDTs was cluding human beings, even low levels of contamina-
about 2–3 times higher (Sun et al., 1997). Without tion could exert harmful effects on ecology and human
detailed information on the sample sites in the 1997 health (Zhang et al., 2006). It was reported that the
study, it is not clear whether the much higher DDTs concentrations of HCHs and DDTs in human milk in
concentrations in soils were from the follow-up appli- Hong Kong and Guangzhou, China were higher than
cation of DDTs or other reasons. In comparison with those of some developed countries including the Swe-
other regions of China, the level of DDTs in tea plan- den, Canada, the United States and Germany (New-
tation soil (22.08 ng g−1 ) was similar to that of agri- some et al., 1995; Noren, 1988; Noren and Meironyte,
cultural soil (21.41 ng g−1 ) from Shanghai (Jiang et 2000). Therefore it is important to pay more attention
al., 2009) and the irrigated soil (31.27 ± 6.65 ng g−1 ) to domestic pesticide usage in agricultural production.
from Beijing (Sun et al., 2009), while in paddy fields, As Zhangzhou City is an important agricultural region
DDTs concentrations (7.67 ng g−1 ) were about 7 times in Fujian Province, application of OCPs should receive
lower than the values (50.23 ± 28.70 ng g−1 ) of Taihu improved and unified management and control.
Lake (Wang et al., 2007). For vegetable land the con-
OCPs in different landform regions
centration of DDTs (6.6 ng g−1 ) in the present study
was 12 times higher than for Taihu Lake (82 ng g−1 ) Zhangzhou City, with many estuary sedimentary,
(Gao et al., 2005). For DDTs, however, in the four land coastal and valley plains, has the highest mountain in
use types, soil concentrations were much higher than the region with an altitude of 1 544 m. The range of al-
agricultural soil (1.85 ± 1.64 ng g−1 ) from Hong Kong titudes for sampling sites selected in this study was ap-
(Zhang et al., 2006), but less than, and significantly proximately 800 meters (0–791 m above sea level). As-
lower than the soil from cotton fields (183.07 ± 171.68 suming the study region was a slope from low lying
ng g−1 ) in Nantong (Yang et al., 2008), respectively. plains to uplands, the distribution of OCPs would be
Compared with soil from outside China, the concen- expected to vary with elevation owing to their physi-
tration of DDTs in soil of paddy field (7.67 ng g−1 ) cal and chemical properties. These properties result in
in Zhangzhou was approximately 2–3 times more than the OCPs settling out of the atmosphere and deposi-
that in rice growing and industrial areas (2.93 ng g−1 ) ting on terrestrial surfaces as temperature decreases.
of south Korea (Kim and Smith, 2001). The four land Positive relationships between the OCP concentrations
types had higher DDT concentrations than the agricul- and increasing altitude have been reported by many re-
tural land (9.63 ng g−1 ) in the United States corn belt searches (Simonich and Hites, 1995; Blais et al., 1998;
(Aigner et al., 1998), and agricultural land (4.60–10.00 Daly et al., 2007). In the present study, concentrations
ORGANOCHLORINE PESTICIDES IN AGRICULTURAL SOILS 185

of OCPs in agricultural soil did change significantly paddy fields but poor in orchards (r < 0.1), indicating
with elevation, but had no obvious regular patterns. HCHs and DDTs appeared to originate from the simi-
It should also be noted that in the present study the lar source in all the paddy fields. As HCHs correlated
different land use types were not evenly distributed with DDTs (r = 0.562, P < 0.05) in vegetable lands,
over the whole elevation range, thus variable inputs of they probably originated from similar sources, but the
OCPs at different altitudes may have influenced resi- correlation of altitude with HCHs was much lower than
dual OCPs in the soil. with DDTs. This could be due to the greater solubi-
In this study, soils from paddy fields, vegetable lity and volatility of HCHs (Loganathan and Kannan,
lands, orchards and tea plantations were sampled in 1994). This suggested that they could easily migrate
the altitude ranges of 0–791, 0–439, 2–336 and 490–539 to other regions by transportation via irrigation wa-
m, respectively. For the first three land use types, the ter or through volatilization to the atmosphere. Thus,
soils were sampled within a relative large variation in the contents of HCHs in surface soil are not as stable
altitude, thus the discussion of different distributions as DDTs. In vegetable lands, high concentrations of
of OCPs in plains and mountains, and relationship be- HCHs and DDTs both focused on the plain regions,
tween altitude and concentrations of OCPs will focus which were below an altitude of 100 m. This may be
on the samples taken from paddy fields, vegetable lands due to the fact that the plain is an intensive agricul-
and orchards only. tural region, where high application of OCPs is re-
The distributions of HCHs and DDTs at diffe- quired. Additionally, the concentration of HCHs and
rent altitudes are shown in Fig. 3. In paddy fields DDTs varied considerably below the altitude of 100
and orchards, concentrations of HCHs and DDTs va- m, indicating the use of OCPs was non-uniform.
ried only very slightly with increasing altitude, impl- Overall, concentrations of HCHs and DDTs in
ying poor correlations between altitude and OCPs con- plain and mountain regions did not show significantly
centrations. However, the correlation between HCHs different distributions, indicating a fragmentation of
and DDTs was significant (r = 0.883, P < 0.01) in the agricultural model in Zhangzhou. Furthermore,

Fig. 3 Correlation between altitude and organochlorine pesticides (OCPs) contents in soils of three land use types. HCHs
(hexachlorocyclohexanes) refer to the sum of α-HCH, β-HCH, γ-HCH and δ-HCH; DDTs (dichlorodiphenyltrichloroethanes)
refer to the sum of p, p -DDT, p, p -DDE, p, p -DDD and o, p -DDT.
186 D. YANG et al.

high OCP concentrations were observed in Longhai which has the highest stability of the HCH isomers
(Fig. 2). OCPs residuals could potentially be persistent (Manz et al., 2001).
in the soil around the site for a long time, and may have The concentration of total DDTs residues in sur-
acted as continuous point source of pollution via emis- face soils was significantly higher than the total HCHs.
sion to the atmosphere. The re-release of OCPs from HCHs are more water-soluble than DDTs (Loganathan
Longhai might be an important factor influencing the and Kannan, 1994), and so more downward migration
spatial distribution of OCPs in Zhangzhou. and accumulation were expected. Therefore, the con-
centration disparity between HCHs and DDTs dimi-
Vertical distribution of OCPs in agricultural soil nished along with depth. The burden of γ-HCH was
much lower than other HCH isomers above the 50 cm
The concentrations and distribution features of depth. This may be due to the shorter half-life of γ-
OCPs in the agricultural soil profile are shown in Fig. 4. HCH in HCH isomers (Willett et al., 1998), and there-
This figure shows similar distribution patterns of HCHs fore will degrade at a faster rate compared to other
and DDTs in relation to depth in paddy fields, de- HCH isomers. In the waterlogged soil of the paddy
creasing from topsoil to subsoil and showing a rapid fields, the rate of degradation was around 2–4 times
decline at a depth of 50 cm. Similar results were re- greater than other isomers (Zhang et al., 1983). Ano-
ported for soil profiles in cultivated land from Tianjin ther reason may be due to the limited number of sam-
(Wang et al., 2006) and paddy fields in the Yangtze pling profile. The ratios of α-HCH/γ-HCH were not
River Delta Region (Zhang et al., 2009), in which, the in the range of 4–7, which demonstrates lindane input
reason was attributed to that, plough pan of Stagnic here after technical HCHs were banned. The ratios
Anthrosols, formed by the compaction of tillage ma- of p, p -DDE/p, p -DDD were greater than 1 at depths
chine, probably played an important role in retarding above 30 cm and were less than 1 in deeper soil, possi-
the OCPs downward-transported from the upper layer bly due to the amount of oxygen decreasing with depth.
of soil. Thus, horizon of 50 cm in the present study The DDT residue data showed that the concentrations
probably performed as plough pan led to this result. of o, p -DDT were much lower and only observed above
In the depth range of 0–50 cm, the concentration of the depth of 30 cm, indicating lower historical use and
β-HCH was significantly higher than that of any other more current use of dicofol. As technical DDTs were
HCH isomers. It was approximately 2 times greater banned in China in 1983, dicofol began to be used in
than that of α-HCH, indicating high levels of degrada- agriculture as a replacement, and was produced for
tion of technical HCHs in the relatively shallow agri- malaria control for domestic use and export from China
cultural soils in Zhangzhou. This is because of the iso- (Qiu et al., 2005).
merization of α- to β-HCH and of γ- via α- to β-HCH, Total organic carbon (TOC) plays an important

Fig. 4 Vertical distributions of organochlorine pesticides (OCPs) in soil profile. HCH = hexachlorocyclohexane; DDE =
dichlorodiphenyldichloroethylene; DDD = dichlorodiphenyldichloroethane; DDT = dichlorodiphenyltrichloroethane.
ORGANOCHLORINE PESTICIDES IN AGRICULTURAL SOILS 187

role in the OCPs fate and behaviour in soils, because highest concentration of dicofol (73%) in total DDTs
OCPs tend to accumulate and persist in organic rich was found in tea plantations. The significantly differ-
soil as they have an affinity with organic matter. Some ent ratios of p, p -(DDE+DDD)/p, p -DDT in the four
researches have shown significant correlation between land use types demonstrated that land use type influ-
TOC and OCPs. However, the present analysis demon- enced the degradation of DDT in soils. Concentrations
strated there was no obvious relationship (Table I) be- of HCHs and DDTs in plain and mountain soils did
tween the accumulations of persistent organic pollu- not show significantly different features in distribution,
tants with the TOC in the soils. This outcome is sim- which may be due to the fragmentation of the agricul-
ilar to research conducted in the agricultural land in tural model in Zhangzhou and the re-release of OCPs
the suburbs of Beijing (Chen et al., 2005) and the soils source from Longhai where soil OCPs concentrations
on the eastern slope of the Tibetan Plateau (Xing et were high. As for the depth distributions of HCHs
al., 2010). Frequent ploughing, crop alternative and and DDTs in soil profile, concentrations of HCHs and
the quality and quantity of irrigation water all affect DDTs all decreased from topsoil to subsoil with a rapid
the fate of OCPs in agricultural soil. It may therefore decline under plough pan of Stagnic Anthrosols. There
be difficult to assign a single soil-geochemical factor was no obvious relationship between the OCPs and
to predict the distribution of OCP residues in soils at TOC in the soil profile. Based on the rough estimate
regional scale (Hao et al., 2008). of the amounts of the HCHs and DDTs burden in the
Estimations of soil burdens in Zhangzhou region surface soil (0–20 cm layer) and top 50 cm soil, we
were based on the mean concentrations of OCPs in found that the majority of the HCH and DDT resid-
the top 20 cm surface soils. Assuming a soil density of ual were buried in the layer of 20–50 cm in Zhangzhou
2 400 kg m−3 and area of Zhangzhou of 12 607 km2 , the region.
estimates of the amounts of the HCHs and DDTs bur-
den (Zhang et al., 2009) in the layer of 0–20 cm were ACKNOWLEDGEMENTS
0.44 and 1.55 t, respectively. Moreover, assuming that
The authors are grateful for the assistance of Miss
the sampled soil profile of the current study is repre-
Lan Lan, Miss Zhang Wan-Jia, Miss Qi Shu-Lei for soil
sentative for the whole agricultural areas of Zhangzhou
extraction in the State Key Laboratory of Biogeology
City, the amounts of DDTs and HCHs burden in the
and Environmental Geology, China University of Geo-
top 50 cm could be estimated, as the highest concen-
sciences, China, and sincerely appreciate the work of
trations of OCPs were observed between 0–50 cm of
Prof. Kevin C Jones and Dr. Andrew Sweetman, Lan-
the soil profile. The result showed that about 1.10 t
caster Environment Centre, Lancaster University, UK
HCHs and 3.87 t DDTs were stored in the 0–50 cm
in reviewing the manuscript and providing suggestions.
layer in the whole Zhangzhou region. It is interesting
to find that storage of HCHs and DDTs in soil surface
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