Environmental Pollution 265 (2020) 115035

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Nationwide levels and distribution of endosulfan in air, soil, water, and

sediment in South Korea
Leesun Kim a, 1, Jin-Woo Jeon a, 1, Ji-Young Son a, Chul-Su Kim b, Jin Ye b, Ho-Joong Kim c, d,
Chang-Ho Lee c, Seung-Man Hwang c, Sung-Deuk Choi a, b, *
a
School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea
b
UNIST Environmental Analysis Center, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea
c
POPs Monitoring Division, Korea Environment Corporation, Incheon, 22689, Republic of Korea
d
Department of Environmental Engineering, Inha University, Incheon, 22212, Republic of Korea

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

Article history: We investigated the levels and distribution patterns of a- and b-endosulfan and endosulfan sulfate in air,
Received 23 February 2020 soil, water, and sediment samples collected from the South Korean persistent organic pollutants (POPs)
Received in revised form monitoring networks. In the air samples, the highest concentrations of the total (S3) endosulfan (50.3
12 June 2020
e611 pg/m3, mean: 274 pg/m3) were observed during summer. Spearman analysis revealed a good
Accepted 12 June 2020
correlation between agricultural land area and atmospheric concentrations of S3 endosulfan except
Available online 23 June 2020
during winter. Regardless of the season, the ratio of the two isomers (a/b) was 3.6e4.9 in the air samples,
higher than that observed in technical mixtures (2.0e2.3), possibly due to the higher volatility of a-
Keywords:
Endosulfan
endosulfan, compared to b-endosulfan. Concentrations of S3 endosulfan in the soil samples
OCPs (n.d.
13.4 ng/g, mean: 0.8 ng/g) were not significantly different except at some stations adjacent to large
POPs areas of farmland. The average levels of S3 endosulfan in the water and sediment samples were 2.1 ng/L
Multimedia and 0.1 ng/g dw, respectively. In analyzing the four largest rivers, it was observed that a few water
South Korea stations during spring and fall and sediment stations in fall had high concentrations of the two isomers
and endosulfan sulfate, particularly around the Yeoungsan and Nakdong Rivers near large areas of
agricultural land. Endosulfan sulfate was dominant at most water and sediment sampling stations. This
study demonstrates that the endosulfan found in most environmental compartments most probably
derives from agricultural areas despite its ban as a pesticide. On the other hand, given that it was also
detected in industrial and urban areas, in which pesticide application does not occur, it can be conjec-
tured that endosulfan is aerially transported at higher temperatures and continuously circulates within
the environment.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction Macdonald, 2005). However, due to threats to human health and

After its introduction in the USA by Farbwerke Hoechst in 1954
as an organochlorine insecticide and acaricide (Watts, 2008),
endosulfan became widely used in many countries over the
following five decades due to its effectiveness against various pests
and mites. The cumulative global use of endosulfan in agriculture
was estimated to be 308 kt between 1950 and 2000 (Li and
* Corresponding author. School of Urban and Environmental Engineering, Ulsan
National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of
Korea.
E-mail address: sdchoi@unist.ac.kr (S.-D. Choi).
1
These two authors contributed equally to this work as co-first authors.
the environment (ATSDR, 2015; Hwang et al., 2015; Watts, 2008), it
is now classified as one of persistent organic pollutants (POPs)
under the Stockholm Convention (UNEP, 2011), and its manufacture
and use have been banned worldwide since mid-2012. More than
80 countries, including Australia, Brazil, Canada, members of the
European Union, New Zealand, the USA, and several West African
nations, had already banned endosulfan or announced its phasing
out by the time this global ban was put in place. However, several
manufacturers in China and India still produce organochlorine
pesticides (OCPs), and China (Fang et al., 2016), India, and some
other countries (Nasir et al., 2014; Yadav et al., 2016) still exten-
sively use endosulfan.
Both before and after its ban, many countries regularly

https://doi.org/10.1016/j.envpol.2020.115035
0269-7491/© 2020 Elsevier Ltd. All rights reserved.
2 L. Kim et al. / Environmental Pollution 265 (2020) 115035
monitored endosulfan in various environmental compartments,
including air, biota, sediment, soil, and water. Previous research has
shown that it generally enters the environment at locations where
it is directly applied. The OCP levels were higher in semi-enclosed
environments such as bays and estuaries in South America
(Girones et al., 2020). In addition, in Huai’an City, China, its levels in
the soil indicated a potential ecological risk (Wang et al., 2012),
while it accounted for the highest concentration of any OCP in the
atmosphere in Pakistan, which is the biggest importer of endo-
sulfan (Nasir et al., 2014). Insecticide manufacturing sites in China
were also major contamination sources, and ecosystems adjacent
to these production sites have been found to be seriously polluted
with endosulfan (Fang et al., 2016). It also remained one of the
major OCPs in urban soils in Nepal (Yadav et al., 2016).
Various studies have also reported that endosulfan can often be
detected far away from where it was originally applied because of
medium- and long-range atmospheric transport on a global scale
via global distillation due to its high volatility (Weber et al., 2010).
Subsequently, endosulfan has been found to accumulate in nearly
all environmental media, thousands of kilometers away from areas
where it was used (Miranda-Filho et al., 2007). For example,
endosulfan is one of the generally detected organochlorines in the
Arctic (Cabrerizo et al., 2019; Weber et al., 2010). Among various
environmental compartments, soil generally acts as both a sec-
ondary source and a sink for POPs including endosulfan in the
environment, with increasing volumes of evidence demonstrating
that POPs that have accumulated in the soil can be re-emitted back
into the atmosphere under the influence of global climate change
(Ma et al., 2011). It has also been reported that soils from arid and
semiarid areas of northwest China (Huang et al., 2014) and from
India (Chakraborty et al., 2015) act as a secondary source. Under the
brand name Thiolix, endosulfan was used in pest control in South
Korea for various crops, including tobacco, Chinese cabbage, and
mulberries, for several decades (Kang et al., 2008; Yeo et al., 2003).
In 2011, its use, manufacture, and import were banned in accor-
dance with the Agrochemical Control Act. However, it is still found
in various environmental media in South Korea, such as the soil
(Choi et al., 2017; Lee et al., 2013), which may lead to human
exposure and/or damage to ecosystems via the food chain. Since
2013, endosulfan and other OCPs in air, soil, water, and sediment
have been monitored on a regular basis in national POPs moni-
toring networks run by the Korean Ministry of Environment
(KMOE). In particular, there remains concerns that endosulfan,
obtained through illegal imports or pre-ban purchases, is still being
applied to crops in agricultural areas. Therefore, continuous
monitoring is required to prevent serious contamination. It is also
important to understand the behavior and fate of endosulfan in
various environmental compartments.
This study aimed to (1) investigate the levels and spatial dis-
tribution of a- and b-endosulfan and endosulfan sulfate in air,
surface soil, water, and surface sediment samples collected from
across South Korea, and (2) construct profiles of each isomer and
their metabolite to understand their behavior and fate within the
environment.
2. Materials and methods
2.1. Chemicals and solvents
Standards for a- and b-endosulfan and endosulfan sulfate were
obtained from Cambridge Isotope Laboratories, USA (native stan-
dards: ES-5464-A; surrogate standards: ES-5465-A-5X; internal
standards: EC-5350). Florisil cartridges (Bond Elut Mega BE-Fl, 5 g/
20 mL) for cleanup procedures were obtained from Agilent Tech-
nologies, USA. Acetone, n-hexane, toluene (HPLC grade), and
dichloromethane (DCM, HPLC grade) were purchased from Hon-
eywell Burdick & Jackson, USA. A Barnstead GenPure  CAD Plus
water cleanup system (Thermo Scientific, USA) was used to produce
deionized water (18.2 MU,cm at 25  C).
2.2. Sampling
In 2015, multimedia environmental samples were collected
from the national POPs monitoring networks (air: 38 stations; soil:
61 stations; water and sediment: 36 stations). The sampling was
conducted based on the “POPs Monitoring Network Installation and
Operation Plan”, established by the KMOE. The air, soil, and water
and sediment sampling stations are shown in Fig. 1, and the
longitude and latitude of each are listed in Tables S1eS3 in the
Supplementary Information. The sampling stations for air and soil
samples can be classified into four land-use types: agricultural,
urban, suburban, and industrial areas. Some urban and industrial
stations near extensive agricultural land (i.e., within 5 km) were
also considered as agricultural stations.
For the air samples, quartz fiber filters (QFFs, 203  254 mm,
Whatman, UK) were baked at 600  C for 5 h to remove any inter-
ference. The baked QFFs were wrapped with aluminum foil and
stored in a desiccator until sampling. Activated carbon felts (ACFs,
84 mm, Sibata, Japan) and polyurethane foam plugs (PUFs, 84 mm
diameter  50 mm height, Sibata, Japan) were cleaned with toluene
using Soxhlet extractors for 16 h. The ACF was also rinsed with
acetone. Using high-volume air samplers (HVe1000 F, Sibata,
Japan), a total of 114 samples was collected at 38 sampling stations
at 750 L/min for 72 h during three seasons: winter (January and
February), spring (April and May), and summer (July and August).
The samples were collected for three consecutive days in each
season, and the sampling media were replaced every day to avoid
breakthrough. The total volume of the three-day sample was about
3,018 m3, and 130 m3 was used for endosulfan analysis. After
sampling, the QFF, PUF, and ACF samples were wrapped with
aluminum foil, placed in polyethylene zipper bags, and kept in a
freezer at
4  C. Prior to the sample extraction step, the three-day
samples were composited to one sample.
The water sampling stations are located along four major rivers
(the Han, Geum, Yeoungsan, and Nakdong Rivers) and several mi-
nor rivers in South Korea. Sampling was conducted during spring
(April and May) and fall (October and November). Each water
sample (35 L at each station) was collected at 36 sampling stations
using stainless-steel samplers (1.5 L, DAIHAN-brand®, Korea). The
total number of water samples was 72. Details of the water sam-
pling process are provided in Jeon et al. (2019). The water samples
were transferred into amber glass bottles (W216950, USA) for
storage at 4  C.
Surface soil samples (depths of 0e10 cm) were collected from
five points within a 10  10 m area using pre-cleaned stainless-
steel scoops in spring (April and May) at 61 sampling stations,
thoroughly mixed as a composite sample, and transferred into
amber glass bottles. Using a Petite Ponar grab sampler (1728-G40,
Wildlife Supply Co., USA), each sediment sample was obtained in
fall (October and November) at 36 sampling stations. Surface
sediment (top 2 cm) was sub-sampled and transferred into amber
glass bottles. After both soil and sediment samples were freeze-
dried using a vacuum freeze dryer (Biocryos, Korea), they were
passed through a sieve (<2 mm). The amber bottles were then
washed with, in order, acetone, toluene, n-hexane, and DCM before
storing them at
20  C until sample analysis.
2.3. Sample pretreatment
The samples for each medium were prepared based on US EPA
 L. Kim et al. / Environmental Pollution 265 (2020) 115035
Fig. 1. Sampling stations for (a) air (38 stations), (b) soil (61 stations), and (c) water and sediment (36 stations) in the national POPs monitoring networks of South Korea.
Method 1699 (US EPA, 2007) and official Korean methods. The two
endosulfan isomers and their metabolite were extracted from the
air (130 m3), soil (10 g), and sediment (5 g) samples using Soxhlet
extractors for 24 h with 350 mL of DCM. For the water samples (2 L),
the suspended solids were filtrated using glass microfiber filters
(GF/C, 150 mm, Whatman, UK), and the target analytes from GF/C
were Soxhlet extracted with DCM. Separatory funnels were used to
extract the target compounds in the dissolved phase of two sub-
samples (1 L) with 200 mL of DCM. The funnels were shaken us-
ing a funnel shaker for 20 min and left until the solvent and water
phase were separated. The organic layer was collected for the
cleanup process. This liquideliquid extraction process was repeated
three times. Extracts from the air, soil, sediment, and water samples
were concentrated using rotary evaporators (Hei-VAP Precision,
Heidolph, Germany).
Surrogate standards (ES-5465-A-5X) containing 13C9-a- and b-
endosulfan, and endosulfan sulfate were added to the extracts
before the cleanup procedure. Then, they were cleaned up using
florisil solid phase extraction (SPE) cartridges. The SPE cartridge
was conditioned with n-hexane, and then the target compounds
were eluted with 150 mL of n-hexane. The extracts were concen-
trated to 1 mL using a Turbo Vap II (Biotage, Sweden). Finally, the
samples were concentrated using a nitrogen evaporator (MG-2200,
Eyela, Japan) then vaporized to 50 mL at room temperature for
instrumental analysis.
2.4. Instrumental analysis and QA/QC
A gas chromatograph (GC; Agilent Technologies 7890 A, USA)
coupled with a high-resolution mass spectrometer (HRMS, Waters
Autospec Premier™, USA) was used for the analysis of endosulfan.
Using electron-impact ionization mode, mass spectra were ob-
tained at 35 eV. Each sample (1 mL) was injected into the GC system
in splitless mode at an injection temperature of 280  C. A constant
flow rate was 1.0 mL/min with helium as the carrier gas. Target
compounds were separated using a DB-CLP1 column
(30 m  0.32 mm i. d.  0.25 mm film thickness, Agilent Technol-
ogies, USA). The initial oven temperature was set at 80  C, raised to
 
150  C at 20 C/min, then to 235  C at 5 C/min, and finally to 300  C

at 15 C/min, where it was held for 5 min. All data were obtained in
3
selective ion monitoring (SIM) mode. Quantification was performed
with labeled internal standards using the isotope dilution method.
The information on the monitored fragment ions and the QC limit
of measured ion abundance ratios are summarized in Table S4.
The recovery rate of each surrogate standard was 51%e112% for
air (n ¼ 38), 57e102% for soil (n ¼ 61), 57e105% for water (n ¼ 36),
and 53e107% for sediment (n ¼ 36). Method detection limits
(MDLs) were derived from a Student’s t-value of 3.14 (99% confi-
dence level, n ¼ 7) multiplied by the standard deviation of seven
replicates of the spiked blank samples. The MDLs for a- and b-
endosulfan and endosulfan sulfate were 0.48, 0.58, and 0.25 pg/m3
for the air samples, 2.95, 5.59, and 4.08 pg/g for the soil and sedi-
ment samples, and 31.6, 30.2, and 43.4 pg/L for the water samples,
respectively. Laboratory blank samples for each compartment were
analyzed in the same way as the real samples. No target analyte was
detected in these blank samples.
2.5. Data analysis and collection
A spatial distribution map for the levels of endosulfan found at
the sampling stations for each compartment was created using
ArcGIS 10.1 (Esri, USA). Mann-Whitney rank sum tests were per-
formed using SigmaPlot 12.0 (Systat Software, USA), and Spearman
correlation analysis was carried out using SPSS Statistics 20.0 (IBM,
USA). The area of agricultural land (km2) within the individual sub-
provinces and cities of South Korea was taken from Statistics Korea
(http://kostat.go.kr).
3. Results and discussion
3.1. Endosulfan levels and seasonal variation
The total (S3) concentrations of endosulfan (i.e., the sum of the
two isomers and their metabolite) in the four environmental
compartments are presented in Fig. 2 and summarized in Table S5.
The mean concentrations of the endosulfan isomers and endo-
sulfan sulfate in this study were also compared with those reported
in previous studies from other countries (Tables 1 and 2).
4 L. Kim et al. / Environmental Pollution 265 (2020) 115035

Fig. 2. Spatial distributions of the concentrations of S3 endosulfan in (a) air, (b) soil, (c) water, and (d) sediment samples collected from the national POPs monitoring networks in
2015. The agricultural land area (km2) in individual sub-provinces and cities is presented as the shaded background.

3.1.1. Air and soil (Pokhrel et al., 2018).

The atmospheric concentrations of S3 endosulfan in winter
(8.2e43.9 pg/m3; mean: 19.6 pg/m3) were significantly lower than
in spring (59.8e359 pg/m3; mean: 154 pg/m3) and summer
(50.3e611 pg/m3; mean: 274 pg/m3) (rank sum test, p < 0.05)
(Fig. 2a). During summer, several stations including A32 (537 pg/
m3), A31 (524 pg/m3), A16 (480 pg/m3), A29 (445 pg/m3), A34
(434 pg/m3), and A35 (404 pg/m3) showed higher concentrations of
S3 endosulfan than other stations. The elevated concentrations of
S3 endosulfan in the warmer seasons may be the result of greater
volatilization due to higher temperatures and of more extensive use
The mean concentration of S3 endosulfan obtained in the pre-
sent study from the air samples over the three sampling seasons
(129 pg/m3) was lower than that reported for Anseong (808 pg/m3)
in South Korea (Chung et al., 2001), suggesting that endosulfan
levels have decreased since its national ban. This level was also
lower than that reported in Konya, Turkey (980 pg/m3) (Ozcan and
Aydin, 2009), New Brunswick, New Jersey, USA (182 pg/m3) (Gioia
et al., 2005), Southern Anhui Province, China (298 pg/m3) (Wang
et al., 2017), and seven cities in India (120e390 pg/m3)
(Chakraborty et al. (2010). However, it was similar to that reported
 L. Kim et al. / Environmental Pollution 265 (2020) 115035 5

Table 1
Endosulfan concentrations in air and soil samples from selected studies from other countries.

Country Area a-Endosulfan b-Endosulfan Endosulfan sulfate S3 Endosulfan Reference

Air (pg/m3)

India Imphal 29.3 24.5 6.0 59.8 Devi et al. (2011)

Thoubal 84.8 45.5 9.0 139
Waithou 81.8 37.8 15.3 135
Bangalore 130 e e 130 Chakraborty et al. (2010)
Chennai 120 e e 120
Agra 340 e e 340
Goa 390 e e 390
New Delhi 230 e e 230
Munbai 200 e e 200
Kolkata 130 e e 130
Turkey Konya 380 90 510 980 Ozcan and Aydin (2009)
Horozgedigi 92.7 16.2 3.2 112 Odabasi and Cetin (2012)
China Southern Anhui Province 298 e e 298 Wang et al. (2017)
USA Camden 104 6.0 1.7 112 Gioia et al. (2005)
Jersey City 14.0 3.5 0.8 18.3
Delaware Bay 32.8 2.3 1.0 36.1
Sandy Hook 15 2 e 17.0
Pinelands 59.9 12.2 1.4 73.5
New Brunswick 168 12.1 1.0 182
Korea Anseong 618 153 36.6 808 Chung et al. (2001)
Nationwide 104 20.3 3.9 129 This study
Soil (ng/g dw)
Brazil Northeastern part of Sao Paulo 0.2 0.6 0.6 11.5 Rissato et al. (2006)
Canada Rocky Mountains 0.2 0.4 3.7 4.3 Becker et al. (2011)
China Xiaodian 0.1 0.3 1.4 1.7 Zhang et al. (2013)
Ethiopia Arsi 2,073 1,891 155 44,118 Westbom et al. (2008)
Pakistan Kalasha Kaku n.d. 0.24 e 0.24 Syed and Malik (2011)
Uganda Kihiihi 7.2 9.2 2.6 19.0 Ssebugere et al. (2009)
India Bangalore 0.6 0.1 16 17 Chakraborty et al. (2015)
Chennai 6.1 0.4 3.8 10
Agra 1.1 0.3 20 21
Goa 17 6.0 88 111
New Delhi 1.0 0.3 7.9 9.2
Munbai 1.5 0.1 3.0 4.3
Kolkata 1.6 0.3 13 15
Korea North Jeolla Province 0.06 0.09 0.15 0.31 Kim and Smith (2001)
Nationwide 0.06 0.09 0.63 0.77 This Study

for most cities in India (111 pg/m3) (Devi et al., 2011), and Hor-
ozgedigi in Izmir, Turkey (112 pg/m3) (Odabasi and Cetin, 2012) and
higher than that in Camden, Jersey, Delaware Bay, Sandy Hook, and
Pinelands in New Jersey, USA (51.4 pg/m3) (Gioia et al., 2005).
For the soil samples, the concentrations of S3 endosulfan in
spring (Fig. 2b) ranged from undetected (16 of the 61 stations) to
13.4 ng/g (mean: 0.8 ng/g). Several stations, including S20 (5.4 ng/
g), S31 (6.2 ng/g), S37 (2.1 ng/g), S47 (13.9 ng/g), and S55 (1.9 ng/g),
showed higher concentrations of S3 endosulfan than other stations.
S47 is located at the foot of mountains in a broad expanse of
developed farmlands. The mean concentration of S3 endosulfan in
the soil was not greatly different from that recorded in most cities
in other countries (0.3e19 ng/g), except Arsi, Ethiopia (44,118 ng/g)
(Westbom et al., 2008) and Goa, India (111 ng/g) (Chakraborty et al.,
2015). The rather homogeneous spatial distribution of endosulfan
in the soil and the relatively high non-detection rate indicate that
endosulfan does not remain in large quantities in the soil after it has
been applied to agricultural land. In support of this, a previous
study reported that over 70% of endosulfan sprayed on cotton fields
in Australia was volatilized as mostly a-endosulfan, polluting the
surrounding environment (Kennedy et al., 2001). One month after
the insecticide was applied (95% to soil and 5% to plants), 25e30% of
the total volume had been degraded by soil microorganisms or
absorbed by plants, 2% was lost in runoff, and 1% remained in the
soil.
3.1.2. Water and sediment
Endosulfan may move beyond the area in which it is used via
volatilization and atmospheric transport (Rice et al., 1997). It can
reach the water column through dry/wet deposition, spray drift,
and soil runoff (Shivaramaiah et al., 2005), after which it can sorb to
benthic sediment, which may eventually become a source of
redistributed endosulfan in overlying waters. The spatial distribu-
tion of endosulfan in the four major rivers of South Korea will be
discussed further in Section 3.3. The mean concentration of S3
endosulfan in the water samples was 2.75 ng/L during spring and
1.78 ng/L during fall (Fig. 2c). The mean concentration in spring was
significantly higher than that in fall (rank sum test, p < 0.05). The
much higher concentrations at some stations (W26: 14.0 ng/L;
W17: 11.0 ng/L; W25: 6.67 ng/L; W24: 4.84 ng/L) during spring may
result from the frequent use of the insecticide in agricultural areas.
For the sediment samples collected in fall, the concentrations of S3
endosulfan ranged from undetected (19 out of 36) to 0.70 ng/g dw
(Fig. 2d). Some stations (SD2: 1.0 ng/g dw, SD9: 0.71 ng/g dw, SD17:
0.55 ng/g dw, and SD20: 0.38 ng/g dw) showed much higher con-
centrations than the mean, indicating the significant use of endo-
sulfan in nearby areas or long-term pollution.
The mean concentration of S3 endosulfan in the water samples
(2.16 ng/L) was higher than that in Baiertang water column in the
Pearl River Delta region, China (0.26 ng/L) (Luo et al., 2004).
However, it was slightly lower than that in surface water (Xiaohe
and Fenhe Rivers) of Taiyuan city, China (3.89 ng/L) (Zhang et al.,
6 L. Kim et al. / Environmental Pollution 265 (2020) 115035

Table 2
Endosulfan concentrations in water and sediment samples from selected studies in other countries.

Country Area a-Endosulfan b-Endosulfan Endosulfan sulfate S3 Endosulfan Reference

Water (ng/L)

China Beijing (Tonghui River) 13.7 67.0 N.D. 80.8 Zhang et al. (2004)
Taiyuan (Xiaohe and Fenhe Rivers) 0.19 0.63 3.07 3.89 Zhang et al. (2013)
Pearl River Delta (Biaertang) 0.75 0.11 0.01 0.86 Luo et al. (2004)
Pearl River Delta (Macao) 3.19 1.46 0.37 5.02
Brazil Northeastern part of Sao Paulo 34.5 19.0 6.0 59.5 Rissato et al. (2006)
Greece Northern (Rivers) 2.0 1.4 14.8 18.1 Golfinopoulos et al. (2003)
Northern (Lakes) 6.3 n.d. 18.5 24.8
Turkey Aegean (Küçük Menderes River) 5 12 70 87 Turgut (2003)
USA Homestead, Everglades, and Biscayne 8.3 13.9 3.3 25.4 Potter et al. (2014)
Pakistan Punjab (Chenab River) 1.8 4.8 3.3 9.9 Eqani et al. (2012)
India Kasargod (stream) 81 123 N.D. 204 Yadav (2004)
Kasargod (pond) 138 416 118 667
Korea Nationwide 0.12 0.06 1.98 2.16 This Study
Sediment (ng/g dw)
China Beijing (Tonghui River) 0.02 0.09 n.d. 0.11 Zhang et al. (2004)
Daya Bay 0.04 0.20 0.64 0.88 Wang et al. (2008)
Taihu Lake 0.15 0.02 0.73 0.90 Zhao et al. (2010)
Taiwan Wu-Shi River Estuary 1.21 0.56 1.50 3.27 Doong et al. (2002)
Singapore Southwestern coast 0.4 0.2 0.6 1.3 Wurl and Obbard (2005)
Northeastern coast 0.1 0.2 0.2 0.5
Uganda Lake Victoria 3.7 0.1 2.2 6.0 Wasswa et al. (2011)
Korea Nationwide 0.01 0.01 0.09 0.12 This study

2013), Macao water column in the Pearl River Delta region, China
(5.02 ng/L) (Luo et al., 2004), and Chenab River across some cities of
Punjab province, Pakistan (9.9 ng/L) (Eqani et al., 2012). It was
much lower than those in rivers flowing through cities: Beijing,
China (80.8 ng/L) (Zhang et al., 2004), Sao Paulo, Brazil (59.5 ng/L)
(Rissato et al., 2006), Homestead, Everglades, and Biscayne in
Florida, USA (25.4 ng/L) (Potter et al., 2014), and Kasargod, India
(204 ng/L for stream and 667 ng/L for pond) (Yadav, 2004) in
Table 2. The mean concentration of S3 endosulfan in the sediment
(0.12 ng/g dw) was not greatly different from that in Tonghui River,
China (0.11 ng/g dw) (Zhang et al., 2004) and lower than those in
most of the places listed in Table 2 (0.5e6.0 ng/g dw).

3.2. Endosulfan profiles

The endosulfan profiles obtained based on the concentrations of

a- and b-endosulfan and endosulfan sulfate in the four environ-
mental compartments are presented in Fig. 3. Technical endosulfan
is commercially available as mixtures typically containing the two
isomers in a ratio (a/b) of 2:1 to 7:3 depending on the product
(Nasir et al., 2014). However, both endosulfan isomers can be
metabolized into endosulfan sulfate within the environment (US
EPA, 2002; Mir et al., 2017), which has a similar structure to the
parent compounds and is also of toxicological concern. The ratio of
the two isomers in the environment reflects the history and envi-
ronmental behavior of the technical endosulfan present in the
environment (Dores et al., 2016).
3.2.1. Air and soil
In most air samples, regardless of the season, a-endosulfan was
dominant (54e100%) (Fig. 3), which is consistent with the previous
studies (Table 1). On the other hand, b-endosulfan accounted for
less than 40% of the total concentration. Endosulfan sulfate in
spring and summer accounted for less than 5.2%, and in winter, at
four sampling stations, it accounted for around 10%. The ratio of the
two isomers (a/b) in the air samples was 1.5e6.2 (mean: 3.6) in
winter, 5.4e11.1 (mean: 7.8) in spring, and 2.5e9.3 (mean: 4.9) in
summer. In most cases, the ratio was greater than in the technical
mixtures (2.0e2.3). The ratio in the most previous studies from
cities of India, Turkey, the USA, China, and Korea ranged from 1.2 to
Fig. 3. Ternary plots of a- and b-endosulfan and endosulfan sulfate in air, soil, water,
and sediment samples.
17.3. It may be due to an increase in the a-endosulfan released from
the soil into the air because the volatility of a-endosulfan is higher
than that of b-endosulfan (US EPA, 2002; Rice et al., 2002).
Considering that this pesticide is applied to crops from spring to
summer, the ratio of the two isomers in the soil was also expected
to be similar to those of the technical mixtures. However, in this
study, the mean a/b ratio of the soil was 0.7 with a range of 0.0e2.0,
which differed dramatically from that of the technical products. It
has been reported that the levels of b-endosulfan in the soil are
consistently higher than those of a-endosulfan (Wang et al., 2012),
and most of the previous studies listed in Table 2 have higher levels
of b-endosulfan in the soil, which is consistent with the present
study.
In this study, the concentration of b-endosulfan was higher than
that of a-endosulfan in the air samples collected during winter and
the soil samples collected during spring despite accounting for a
 L. Kim et al. / Environmental Pollution 265 (2020) 115035 7

lower proportion of the technical mixture and the possible con- deposited in the sediment. In sediment, both endosulfan isomers
version of symmetric b-endosulfan to asymmetric a-endosulfan at are also quickly degraded due to microbial activity. A previous
high temperatures in the environment (Schmidt et al., 1997). There study has shown that the two isomers degrade twice as quickly in
are three possible reasons for this. First, a-endosulfan volatilizes to non-sterilized than in sterilized sediment (Jesitha et al., 2015).
a much greater extent from a solid form compared to b-endosulfan,
which has a lower volatility. The vapor pressure of a- and b-
3.3. Variation in endosulfan concentration by land use and between
endosulfan and endosulfan sulfate is 3.0  10
6, 7.2  10
7, and
rivers
1.0  10
11 mmHg at 25  C, respectively (US EPA, 2013; Rossi, 2002).
Second, b-endosulfan has greater soil enrichment than a-endo-
3.3.1. Air and soil
sulfan due to its higher organic carbon normalized partition coef-
The concentrations of S3 endosulfan in air samples from the four
ficient (KOC; log KOC-a ¼ 3.6, log KOC-b ¼ 4.3 at 25  C) (Jia et al., 2009;
land-use types were not significantly different during winter and
Weber et al., 2010). As in the soil, the greater enrichment of b-
spring (rank sum test, p > 0.05), but the concentrations of S3
endosulfan in sediment and sediment pore water was also
endosulfan in agricultural areas were significantly higher than
observed (Walse et al., 2002). Finally, b-endosulfan (half-life of
those in other areas during summer (rank sum test, p < 0.05)
33e376 days) is known to degrade more slowly than a-endosulfan
(Fig. 4a). High Spearman correlations were also found between
(half-life of 7e75 days) in the soil environment (US EPA, 2002;
agricultural land area and the atmospheric concentration of S3
Weber et al., 2010).
endosulfan in spring (r ¼ 0.478, p < 0.01) and summer (r ¼ 0.487,
p < 0.01) (Table S5), but not in winter, which may be due to the very
low concentrations of endosulfan during this season. On the other
3.2.2. Water and sediment
hand, the mean concentration of S3 endosulfan in the soil samples
During spring, endosulfan sulfate was dominant at many water
from the four land-use types were not significantly different (rank
sampling stations (57e100%, except for W27 and W28), but the two
sum test, p > 0.05) except for some stations in agricultural areas
isomers were also detected (a-endosulfan: 0.0e27.1%; b-endo-
(Fig. 4b) that appear to be directly contaminated by its illegal use.
sulfan: 0.0e15.9%). The mean ratio of a/b-endosulfan (0.6) differed
It should be noted that two endosulfan isomers and endosulfan
from the technical mixtures (2.0e2.3), indicating that a-endosulfan
sulfate were detected in both air and soil samples not only from
is converted more readily to endosulfan sulfate than is b-endo-
agricultural areas, but also from urban, suburban, and industrial
sulfan (Walse et al., 2003). More rapid biological degradation of the
areas, where pesticides are not generally used. In the urban and
endosulfan isomers to endosulfan sulfate may occur in rivers as a
suburban areas, the insecticide can be used to kill insects in gardens
result of microbial activities (Shivaramaiah et al., 2005).
or at graves. However, previous air and soil monitoring results
In the water samples collected during fall, a- and b-endosulfan
demonstrated that endosulfan can be aerially transported from
were rarely detected, and endosulfan sulfate (100%) was dominant
other areas through atmospheric dispersion and subsequent
at most sampling stations except for W17, W23, W25, and W26. All
temperature-induced volatilization (Weber et al., 2010). This
samples are located in the lower-left corner of the ternary plot
interpretation is supported by various studies that have investi-
(Fig. 3). This result is consistent with previous research reporting
gated the theoretical and experimental quantification of interphase
that endosulfan sulfate is the most frequently detected form of
transfer, including airesoil (Fang et al., 2016; Odabasi and Cetin,
endosulfan in river water (Shivaramaiah et al., 2005). Most endo-
2012; Pokhrel et al., 2018), airewater (Weber et al., 2006),
sulfan sulfate, which is metabolized from both isomers in the soil, is
wateresediment (El Nemr et al., 2012), and various biological in-
likely to have entered the river system via runoff, either in solution
terphases (Weber et al., 2010).
with water or carried on other particles. In addition, the two iso-
mers can enter water systems via air deposition and subsequently
be converted into endosulfan sulfate. 3.3.2. Water and sediment
In sediment samples collected during fall, a- (7.6e19.6%) and b- Of the four major rivers in South Korea, Yeongsan River, which
endosulfan (15.6e31.8%) and endosulfan sulfate (48.5e76.7%) were runs through several regions in South Jeolla Province (Fig. 1c), had
all detected at only five sampling stations (SD2, SD9, SD17, SD20, the highest mean concentrations of S3 endosulfan in the water
and SD31) located within 10 km of extensive agricultural land. samples collected during both spring (6.62 ng/L) and fall (3.86 ng/L)
Endosulfan sulfate alone was detected at 12 sampling stations, (Fig. 5a). However, these were not significantly different from the
which is consistent with the results from the water samples other rivers (rank sum test, p > 0.05). The high levels of endosulfan
collected during fall. It is likely that endosulfan sulfate converted in these rivers are possibly due to the illegal application of endo-
from the two isomers in river water or in the soil was directly sulfan to agricultural land in surrounding areas. Historically, many

Fig. 4. Box plots for the concentrations of S3 endosulfan in (a) air and (b) soil samples by land-use type and season.
8 L. Kim et al. / Environmental Pollution 265 (2020) 115035
Fig. 5. Box plots for the concentration of S3 endosulfan in (a) water and (b) sediment samples from major river systems in South Korea.
types of crop, including rice, barley, wheat, cotton, pulses, vegeta-
bles, and fruits, have been established alongside rivers (e.g,
Seomjin, Yeongsan, and Tamjin). The Nakdong River, which flows
from Gangwon Province through Gyeongsang Province to Busan
Metropolitan City, making it the longest river in Korea, had the
second-highest concentrations of S3 endosulfan in spring (3.45 ng/
L) and fall (2.15 ng/L) (Fig. 5a). The highest concentration of S3
endosulfan (a-endosulfan: 2.29 ng/L; b-endosulfan: 1.65 ng/L;
endosulfan sulfate: 10.1 ng/L) was measured at a station in the
Yeongsan River in spring, while a station in the Nakdong River had
the second-highest concentration of S3 endosulfan (a-endosulfan:
0.56 ng/L; b-endosulfan: n. d.; endosulfan sulfate: 10.2 ng/L) in
spring. At both stations, the concentration of S3 endosulfan was
dominated by endosulfan sulfate, which was also detected at every
other station in the study, unlike the two isomers. This is possibly
due to its long-term accumulation after being metabolized from a-
and b-endosulfan following the past application of endosulfan in
agricultural areas. A recent study reported that endosulfan sulfate
(22.0e87.8 ng/g) was detected in greenhouse soil, while a- and b-
endosulfan were not detected (Lim et al., 2016).
The concentrations of S3 endosulfan in the sediment samples
from the four major rivers in fall were not significantly different
(rank sum test, p > 0.05) (Fig. 5b). This may be because pollutants
can accumulate in the sediment without significant movement
over time, unlike the constant movement of pollutants in the water,
meaning that their concentration may differ significantly by region.
In addition, the concentration of pollutants in water is influenced
by the activity of benthic organisms, and they are adsorbed by
sediment or the tissue of fish (Quinete et al., 2013). Endosulfan
sulfate was consistently found in the sediment, while the two
isomers were only occasionally detected. In addition, Spearman
analysis revealed a weak correlation between agricultural land area
in the sub-provinces and cities and the concentration of S3 endo-
sulfan (r ¼ 0.311, p < 0.05) in the sediment (Table S6). These results
indicate that the pesticides sprayed onto agricultural land possibly
contaminated the water through runoff and subsequently trans-
ferred into the sediment.
4. Conclusions
The results of this study suggest that the endosulfan present in
the environmental media primarily originates from agricultural
areas despite the ban on its production and use in South Korea. The
concentration of S3 endosulfan in the environment was similar to
or lower than that reported for other countries. Endosulfan sulfate,
a metabolite of a- and b-endosulfans, was the dominant form of
endosulfan in soil, water, and sediment monitored in this study.
However, a- and b-endosulfans were dominant in air samples,
indicating the recent application of this banned pesticide. There-
fore, it is important to continuously monitor endosulfan in all
environmental compartments to control its illegal use. It should
also be noted that the two isomers and their metabolite were
detected at many sampling stations that were distant from possible
sources of direct application, possibly due to transport and redis-
tribution among the compartments. The endosulfan profiles in the
environmental media reflected their physicochemical properties
and the characteristics of the individual environmental compart-
ment. Based on the results of this study, the Korea Environment
Corporation has started to monitored endosulfan and other OCPs
every year. Data from this long-term monitoring project will be
presented in future research.
CRediT authorship contribution statement
Leesun Kim: Writing - original draft. Jin-Woo Jeon: Writing -
original draft, Formal analysis. Ji-Young Son: Formal analysis. Chul-
Su Kim: Resources. Jin Ye: Resources. Ho-Joong Kim: Project
administration. Chang-Ho Lee: Project administration. Seung-Man
Hwang: Project administration. Sung-Deuk Choi: Supervision,
Project administration.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was mainly supported by the Korea Environment
Corporation through the Korean Ministry of Environment as a na-
tional POPs monitoring project. This work was also supported by
the National Research Foundation of Korea (2017R1A2B4003229)
and the Rural Development Administration of the Republic of Korea
(PJ014297012019).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.115035.
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