Atmospheric Environment 64 (2013) 40e46

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Spatial distribution of polychlorinated biphenyls, organochlorine pesticides,

and dechlorane plus in Northeast Asia
Song-Yee Baek a,1, Jongsoo Jurng b, Yoon-Seok Chang a, b, *
a
School of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong, Nam-gu, Pohang 790-784, Republic of Korea
b
Division of Environmental Welfare Research, Korea Institute of Science and Technology, Seoul, Republic of Korea

h i g h l i g h t s

< XAD-2 resin-based PAS were deployed for one year in three Asian countries.
< The spatial distributions of PCBs, OCPs, and DP were investigated.
< Different distributions were observed among Mongolia, China, and South Korea.

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

Article history: XAD-2 resin-based passive air samplers (PAS) were deployed for one year at eight cities in Mongolia,
Received 6 April 2012 China, and South Korea to investigate the spatial distribution of polychlorinated biphenyls (PCBs),
Received in revised form organochlorine pesticides (OCPs), and dechlorane plus (DP). PCB levels were highly correlated with
5 September 2012
population size and density in China and South Korea. In Mongolia, PCB levels were relatively high
Accepted 10 September 2012
considering the low population. In the cases of OCPs and DP, a country-specific distribution was
observed. The highest levels of HCHs (hexachlorocyclohexane isomers) and DDTs (dichlorodiphenyl
Keywords:
trichloroethane isomers) were detected at sites in China, whereas the highest endosulfan and DP levels
Persistent organic pollutants
Polychlorinated biphenyls
were measured at South Korean sites. These results strongly reflected the patterns of use of these
Organochlorine pesticides chemicals. Mirex, an insecticide never registered in Mongolia and South Korea, was detected at all
Dechlorane plus sampling sites; this is likely to have resulted from long-range transport. Nevertheless, OCPs were
Passive air sampling generally low in Mongolia. This study confirms that PAS results reflect well the past and current usage of
Northeast Asia POPs in Northeast Asia.
Long-range transport Ó 2012 Elsevier Ltd. All rights reserved.
PCB-11

1. Introduction polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers

Persistent organic pollutants (POPs) have been released into the
environment over the past several decades, and are now widely
distributed due to their physico-chemical properties, such as
persistence and capacity for long-range transport. The Stockholm
Convention on Persistent Organic Pollutants specifies the need to
identify the source of POPs (e.g. organochlorine pesticides (OCPs),
* Corresponding author. School of Environmental Science and Engineering,
Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong,
Nam-gu, Pohang 790-784, Republic of Korea. Tel.: þ82 54 279 2281; fax: þ82 54
279 8299.
E-mail address: yschang@postech.ac.kr (Y.-S. Chang).
1
Current address: Center for Analytical Chemistry, Division of Metrology for
Quality of Life, Korea Research Institute of Standards and Science (KRISS), 267
Gajeong-Ro, Yuseoang-gu, Daejeon 305-340, Republic of Korea.
(PBDEs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs))
and to monitor these chemicals. Under this treaty, signed in 2001,
parties to the convention should develop a national inventory of
POPs. However, it is very difficult to determine the past use of these
chemicals. Whilst there is some information available on past usage
and current inventories of chemicals in many countries, environ-
mental measurements aid in better understanding of the sources
and transport of POPs (Du et al., 2009; Liu et al., 2009; Zheng et al.,
2010).
PCBs have been commercially produced for use in dielectric
fluids and insulators, and high levels have been detected in
industrialised and urban areas (Jamshidi et al., 2007; Du et al.,
2009). Stockholm Convention OCPs include dichlorodiphenyl tri-
chloroethane (DDT), hexachlorocyclohexane (HCH) isomers, aldrin,
dieldrin, endrin, heptachlor, chlordane, toxaphen, and mirex.
Developed countries have banned many OCPs because of their

1352-2310/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.atmosenv.2012.09.015
 S.-Y. Baek et al. / Atmospheric Environment 64 (2013) 40e46
toxicity to humans as well as ecosystems. In some developing
countries, however, several OCPs are still in use. An emerging
pollutant, dechlorane plus (DP), is a polychlorinated flame retar-
dant produced in the last four decades (Hoh et al., 2006; Wang
et al., 2010). Ever since the presence of DP was first reported in
air, sediment, and fish around the manufacturing plant (Hoh et al.,
2006), research activities on this chemical have increased
dramatically.
The atmosphere plays an important role in the movement of
POPs. POPs originating from the middle latitudes in the northern
hemisphere are believed to be transported by westerly winds.
China is a great user of OCPs such as HCHs and DDTs (Wei et al.,
2007), and several recent studies in China have shown a high
concentration of POPs in the air (Jaward et al., 2005; Liu et al.,
2009). Korea is downwind of China and thus air masses passing
over China flow into Korea (see Fig. S1 in supplementary data).
Among the countries of Northeast Asia, the investigation of
Mongolia in particular is a novel one, as there has been no POP
monitoring in this area before the present study. Global monitoring
networks have never included this area (Pozo et al., 2006; Lee et al.,
2007; Shunthirasingham et al., 2010).
The purpose of this study was to compare the contamination
levels of PCBs, OCPs, and DP and to better characterise the spatial
distributions of those chemicals in Northeast Asia. XAD-2 resin-
based passive air samplers (PAS) were deployed at eight cities in
three Asian countriesdMongolia, China, and South Koreadfor one
year. This is the first, preliminary study of POPs in Mongolia, done
for the purposes of expanding the atmospheric monitoring
network.
2. Materials and methods
2.1. Passive air sampling
Passive air sampling was conducted for a year at eight cities in
northeast Asia: Khovd and Ulan Bator in Mongolia; Beijing and
Yanji in China; and Seoul, Busan, Pohang, and Jeju in South Korea
(Fig. 1). Sampling sites included not only the capital and largest city
of each country (Beijing, Seoul, and Ulan Bator) but also regions
which have never been included in POP monitoring studies (e.g.
Khovd, Ulan Bator, and Yanji). Detailed sampling information is
given in Table S1 (in supplementary data). An XAD-2 resin-based
PAS exclusively collects the gas-phase contaminants in the air.
Thus, the results obtained in our study are the gas-phase concen-
trations rather than the total air concentrations of the target
compounds (Baek et al., 2011). The details of the XAD-2 resin PAS
Fig. 1. Location of passive air sampling sites.
41
have been presented in previous papers (Wania et al., 2003;
Shunthirasingham et al., 2010; Baek et al., 2011). Duplicate
samplers were deployed for both China and Korea. In the case of
Mongolia, three samplers were deployed at different buildings;
each of them is within several-hundred metres of one another.
Field blanks were deployed at all cities except for Seoul and Jeju.
2.2. Extraction and pre-treatment
The target compounds for analysis were all PCBs (209 conge-
ners) and OCPs (a-, b-, g-, and d-HCH, aldrin, dieldrin, endrin,
heptachlor (HEPT), heptachlor epoxide (HEPX), endosulfan (I and
II), oxychlordane, cis- and trans-chlordane (CC and TC), cis- and
trans-nonachlor (CN and TN), o,p0 - and p,p0 -DDE, o,p0 - and p,p0 -DDD,
o,p0 - and p,p0 -DDT, mirex, and DP).
The retrieved XAD-2 resin was divided into two fractions of
equal weight: one for PCBs, and the other for OCPs and DP. The
divided resins were Soxhlet-extracted for 20 h with 300 mL of
toluene for PCBs and 300 mL of acetone:hexane (1:1, v:v) for OCPs.
For PCBs, cleanup was performed with multi-layer silica columns
(from top to bottom: sodium sulphate, silicaesulphuric acid (8 g,
44% of H2SO4), silica (2 g), silicaesodium hydroxide (4 g, 30% of
NaOH), silica, and sodium sulphate). The columns were conditioned
with hexane and then samples were eluted with 130 mL of hexane.
For OCPs and DP, extracts were separated on silica/florisil (5 g ea.)
columns. The columns were conditioned with hexane and then
samples were eluted with 100 mL of hexane, followed by 100 mL of
hexane:dichloromethane (1:1, v:v). The column-treated samples
were concentrated with a rotary evaporator (R124-A, Buchi) to
0.5 mL and transferred to GC vials. Finally, the solvent was totally
evaporated through N2 purging. Then the target compounds were
reconstituted in 20 mL of nonane and 1 mL of sample was injected
into the GC injection port.
2.3. Instrumental analysis
All compounds were analysed by gas-chromatography (Agilent-
6890)/high-resolution mass spectrometry (Jeol JMS-800D). Details
of the measurement method are described in a previous article
(Baek et al., 2011) and Supplementary data.
2.4. Quality control
Prior to extraction, 13C-PCBs (1, 3, 4, 15, 19, 28, 37, 54, 77, 81, 104,
105, 111, 114, 118, 123, 126, 155, 156, 157, 167, 169, 178, 188, 189, 202,
205, 206, 208, and 209) and 13C-OCPs (a-HCH, g-HCH, heptachlor,
heptachlor epoxide, aldrin, dieldrin, o,p0 -DDT, p,p0 -DDT, o,p0 -DDE,
p,p0 -DDE, o,p0 -DDD, p,p0 -DDD, mirex, trans-chlordane, trans-non-
achlor, and cis-nonachlor) were added as internal standards for
PCBs and OCPs, respectively. Prior to instrumental analysis, 13C-
PCBs (9, 52, 101, 138, and 194) and 13C-PCB (15, 70) were added as
injection internal standards. For calculating the recovery of DP, 13C-
mirex was used as an internal standard. The average recoveries of
PCBs (61e124%) and OCPs (53e113%) were acceptable. Data were
recovery- and field blank-corrected. The limit of detection (LOD)
was determined as a signal-to-noise ratio of 2.5:1. Details of quality
control method are described in Supplementary data.
3. Results and discussion
3.1. Introductory remarks
The amount sequestered in a PAS can be converted to an estimate
of air concentration (pg m3), using sampling rate (R: m3 day1) and
sampling period (day). R is dependent on ambient temperature and
42 S.-Y. Baek et al. / Atmospheric Environment 64 (2013) 40e46

ambient pressure, which is correlated with T1.75/P (Wang et al.,
2010). In previous studies, the average R was 0.52 and
2.1 m3 day1 for Arctic regions and tropical environments, respec-
tively (Wania et al., 2003; Gouin et al., 2008). In addition, R varies
with the physico-chemical properties of chemicals, such as KOA
(Melymuk et al., 2011). Therefore, in the present paper, we focused
on spatial comparisons, so the data are presented in pg day1 PAS1
to allow for slight differences in deployment time between locations
and sampling occasions.
3.2. Source and distribution of PCBs
The PCB levels of all sampling sites are presented in Tables 1 and
S2. Owing to the low recovery of mono-PCBs, only levels of di- to
deca-PCBs are reported in this study. The capital and most popu-
lated city of each countrydUlan Bator, Beijing, and Seouldshowed
the highest level of PCBs. The levels of marker PCBs (the sum of Tr-
31/28, TeCB-52, PeCB-101, PeCB-118, HxCB-153/168, HxCB-138, and
HpCB-180/193) were highly correlated with the level of total PCBs
(di- to deca-PCBs) (r2 ¼ 0.958, p < 0.01).
There was a strong correlation between the marker PCB level
and the population of each city, excluding Mongolia sites
(r2 ¼ 0.838, p < 0.05). Whilst, when including Mongolia sites, there
was no correlation between the marker PCB level and the pop-
ulation (r2 ¼ 0.417, p > 0.05). Interestingly, we found that Mongo-
lian cities had relatively high levels of PCBs considering their low
population. One possible reason for the high levels of PCBs in
Mongolian cities is the inadequate management of PCB-containing
equipments. Almost 96% of the transformers currently in use were
manufactured in the former Soviet Union during 1968e1980, and
most are now in fairly poor conditions. It is believed that 96e98% of
all transformers used in Mongolia could have PCB-containing oils
(GEF/UNIDO, 2006). Another possible reason is a high sampling rate
(R) due to low atmospheric pressure in Mongolia (Average altitude:
1580 m above sea level). The high sampling rate might lead to high
PCB amounts sequestered in PAS in this area. However, considering
the second reason, the PCB level of Mongolia was rather high.
In South Korea in particular, the levels of total PCBs and marker
PCBs were highly correlated with the population (total PCBs:
r2 ¼ 0.982, p < 0.05, marker PCBs: r2 ¼ 0.956, p < 0.05) and pop-
ulation density (total PCBs: r2 ¼ 0.983, p < 0.05, marker PCBs:
r2 ¼ 0.956, p < 0.05) of each city. The PCB sources include trans-
formers and capacitors as well as PCB-containing building mate-
rials (Jin et al., 2011, Herrick et al., 2004). Some previous studies
have reported an “urban pulse”, whereby the highest PCB
concentration was found in the city centre (Jamshidi et al., 2007; Du
et al., 2009).
A non-commercial PCB, PCB-11, was detected at all sites
(Table 1). The levels of PCB-11 were correlated with the population
of each city (r2 ¼ 0.816, p < 0.05). However, low fractions of PCB-11
were observed at Mongolian sites, even though these sites had high
levels of commercial-PCBs. Previous studies have revealed a yellow

Table 1
Amount (pg day1 PAS1) of PCBs and OCPs.

pg day1 PAS1 Khovd Ulan Bator Beijing Yanji Seoul Busan Pohang Jeju
PCBs
Marker PCBs 41.0  17.7 251  17.7 197  9.84 101  17.1 67.1  2.99 35.8  2.80 27.3  7.46 10.8
Total PCBs 172  67.0 1003  97.4 1019  231 701  22.9 450  20.2 215  10.0 151  19.5 78.2
DiCB-11 18.0  2.34 84.1  25.8 276  161 319  82.8 128  14.6 67.3  13.1 41.6  1.68 31.1
OCPs
a-HCH 136  26.2 98.5  23.4 406  91.0 201  51.6 84.0  15.4 43.6  2.32 42.0  11.2 61.5
b-HCH 17.4  7.14 7.03  2.13 49.3  4.28 20.0  1.07 5.57  1.11 2.73  1.24 1.47  0.074 2.26
g-HCH 30.2  3.19 33.9  9.73 200  40.6 44.5  3.50 35.1  2.58 20.6  0.98 10.3  0.35 12.8
d-HCH 2.38  0.99 1.46  0.69 20.7  1.52 4.08  1.46 1.25  0.22 0.44  0.012 0.39  0.032 0.55
a/g-HCH 4.52 2.91 2.03 4.52 2.39 2.11 4.08 4.82
HEPT 0.18  0.12 0.77  0.32 1.22  0.005 0.32  0.043 0.53  0.042 0.38  0.025 0.13  0.022 0.10
t-HEPX 0.68  0.16 0.66  0.14 1.15  0.13 0.52  0.079 1.85  0.10 1.74  0.16 0.89  0.14 1.17
c-HEPX ND ND ND ND ND ND ND ND
HEPT/HEPX 0.27 1.17 1.06 0.61 0.28 0.22 0.14 0.08
Aldrin ND 0.28  0.066 2.15  0.17 0.083  0.12 ND ND ND ND
Dieldrin 0.48  0.23 0.55  0.22 1.15  0.12 0.37  0.015 1.21  0.055 0.49  0.70 0.53  0.007 0.49
Endrin ND ND ND ND ND ND ND ND
Endos-I 19.0  5.11 7.50  1.96 81.2  5.90 6.10  2.19 199  12.6 209  18.0 185  16.5 222
Endos-II 2.80  0.43 0.66  0.24 27.7  5.03 0.77  1.09 92.9  24.1 124  4.45 77.3  14.2 109
Endos-I/II 6.8 11.3 2.9 7.9 2.1 1.7 2.4 2
Oxychlordane 0.36  0.076 0.37  0.077 0.65  0.016 0.28  0.073 0.69  0.039 0.61  0.14 0.45  0.044 0.76
TC 0.18  0.11 0.46  0.093 1.82  0.20 0.86  0.093 1.59  0.095 2.81  0.23 1.26  0.060 1.88
CC 0.56  0.12 0.61  0.11 1.52  0.20 0.93  0.087 1.84  0.13 2.92  0.30 1.71  0.031 2.41
TC/CC 0.33 0.75 1.2 0.92 0.86 0.96 0.74 0.78
TN 0.46  0.12 0.50  0.081 1.36  0.18 0.64  0.067 1.29  0.14 2.26  0.10 1.31  0.082 1.98
CN 0.019  0.017 0.04  0.004 0.066  0.011 0.020  0.029 0.12  0.034 0.26  0.009 0.13  0.032 0.19
o,p0 -DDE 0.36  0.088 1.64  0.41 16.6  1.67 2.07  0.43 1.43  0.006 0.79  0.012 0.59  0.036 2.09
p,p0 -DDE 1.46  0.57 6.97  1.56 64.7  9.46 8.18  0.43 5.75  0.46 3.85  0.24 3.31  0.38 6.67
o,p0 -DDD 0.17  0.033 0.59  0.21 2.28  0.061 1.59  1.06 0.40  0.12 0.29  0.024 0.17  0.030 0.46
p,p0 -DDD 0.21  0.042 0.61  0.26 1.54  0.046 0.91  0.46 0.36  0.10 0.30  0.10 0.15  0.006 0.30
o,p0 -DDT 1.20  0.21 4.04  2.43 27.3  1.24 2.83  0.10 3.77  0.068 2.23  0.029 1.42  0.003 3.36
p,p0 -DDT 1.32  0.16 5.13  2.14 17.8  2.74 2.68  0.33 2.89  0.33 2.17  0.17 1.13  0.065 2.03
Mirex 0.064  0.025 0.069  0.025 1.67  0.19 2.61  0.24 0.14  0.006 0.13  0.001 0.08  0.016 0.17
Syn-DP 0.31  0.15 0.19  0.05 0.28 0.16  0.03 5.30  1.51 1.79  0.87 1.30  0.21 2.45
Anti-DP 0.70  0.44 0.36  0.11 0.69 0.39  0.30 39.5  13 8.08  0.42 8.68  0.42 11.0

Value: average þ standard deviation: average values of duplicate samples for Chinese and Korean samples; average values of samples from three different sites in Khovd and
Ulan Bator.
ND: below detection limit. a/Y-HCH: the ratio of a-HCH to Y-HCH, HEPT/HEPX: the ratio of HEPT to HEPX, Endos-I/II: the ratio of endosulfan-I to endosulfan-II, TC/CC: the ratio
of TC to CC.
The amount of each marker PCBs and each PCB homologues is presented in Supplementary data.
 S.-Y. Baek et al. / Atmospheric Environment 64 (2013) 40e46
commercial pigment to be a source of PCB-11 (Hu and Hornbuckle,
2009; Baek et al., 2010). Thus, painted surfaces of buildings can be
significant sources of PCB-11. One possible reason for the lower
levels of PCB-11 in Khovd is the prevalence of traditional housing. In
the Mongolian grasslands, much of the population live in a tradi-
tional style of house (known as Ger) consisting of a circular wooden
frame with a felt cover. This type of housing occupies most of the
Khovd area. This means there could be fewer sources of PCB-11 in
Mongolia compared with other countries.
3.3. Country-specific source of OCPs
3.3.1. HCHs
Technical HCH consists of approximately 60e70% a-HCH, 5e12%
b-HCH, 10e15% g-HCH, P
and 6e10% d-HCH (Buser and Mueller,
1995). The highest HCHs (i.e., the sum of a-, b-, g-, and d-HCH)
were observed at Chinese cities; Beijing had the highest level
(675 pg day1 PAS1), followed by Yanji (270 pg day1 PAS1)
(Table 1, Fig. 2). Four South Korean sites showed relatively low
levels of HCHs, ranging from 54.2 to 126 pg day1 PAS1 with an
average of 81.1 pg day1 PAS1. Slightly higher average amounts of
HCHs (164 pg day1 PAS1) were detected in Mongolian sites than
in South Korean sites. These levels appear to reflect HCH usage:
before it was banned, 4.46 million tons (t) of HCHs were used in
China between 1951 and 1983, much higher amounts than was
used in Mongolia (1985 t) or South Korea (1908 t) (Yeo et al., 2004;
GEF/UNIDO, 2006; Wei et al., 2007).
Re-evaporation from earlier agricultural chemical application is
the main source of banned OCPs (Park et al., 2011). There is little
Fig. 2. Spatial distribution of (a) total PCBs, (b) HCHs, (c) DDTs, and (d) endosulfans across Northeast Asia.
43
doubt that China is still a significant source of HCHs (Li, 1999). The
Khovd region had the lowest level of almost all measured POPs,
whilst a relatively high level of HCHs (186 pg day1 PAS1) was
measured in this region. In fact, large amounts of HCHs had been
used in Khovd for controlling grasshoppers in pastureland (100 t
between 1959 and 1992) (GEF/UNIDO, 2006). The fractions of HCH
isomers in samples are shown in Fig. 3. The average fraction of all
air samples was 71% a-HCH, 5% b-HCH, 23% g-HCH, and 1% d-HCH,
which is similar to the composition of technical HCH. However, the
proportion of g-HCH in air samples is higher than that in technical
HCH. Urban and densely populated sites (Beijing, Seoul, and Busan)
showed the high proportion of g-HCH (Fig. 3). Products that contain
>99% g-HCH are referred to as lindane. Unlike technical HCH,
lindane is still used for the pharmaceutical treatment of scabies and
head lice, and is therefore a significant contaminant in urban sewer
systems (Humphreys et al., 2008). The high contribution of g-HCH
in urban sites could be attributed to the relatively high usage of
lindane products in urban areas.
3.3.2. DDTs and DDT metabolites
China is a significant user of DDTs; 4.6 million t of DDTs were
used for agricultural purposes from 1951 to 1983 (Wei et al., 2007)
and it is still used today to control disease vectors. In contrast,
South Korea banned the use of DDTs in 1971, and just 2000 t were
used between the 1940s and the early 1970s (KMOE, 2004). Thus,
P
an extremely high level of DDTs (i.e., the sum of p,p0 - and o,p0 -
DDE, p,p - and o,p -DDD, p,p0 - and o,p0 -DDT), 130 pg day1 PAS1,
0 0
was detected at the Beijing site, 7e30 times higher than at the other
sites (Table 1, Fig. 2). Only 4.73e19.0 and 6.76e14.9 pg day1 PAS1
44 S.-Y. Baek et al. / Atmospheric Environment 64 (2013) 40e46

1.0 April 2011. China began to produce endosulfan in 1994 and has
since used approximately 3,000 t annually (Jia et al., 2009). South
Korea has used this chemical since 1971 and the annual use is
0.8 estimated to be 900e1000 t y1 (Choi and Chun, 2007). Since
endosulfan was widely used until recent times, and is still in use in
some countries, the levels of endosulfan (endosulfan-I and -II) were
0.6
Fraction

0.4
0.2
0.0
Khovd UB BE YJ SE BS
Fig. 3. Fraction of HCH isomers in air samples from Khovd, Ulan Bator (UB), Beijing
(BE), Yanji (YJ), Seoul (SE), Busan (BS), Pohang (PH), and Jeju (JJ).
P endosulfan-I/II were found to be 1.7e2.4 at the South Korean sites
of DDTs were observed at the Mongolian and South Korean sites,
respectively. A small value of p,p0 -DDT/p,p0 -DDE is indicative of
aged DDTs (Qiu et al., 2005; Li et al., 2009; Zheng et al., 2010).
All sites showed low values of p,p0 -DDT/p,p0 -DDE (<1.0), which
implies no recent DDT input in those sites (Fig. 4).
Dicofol, an organochlorine pesticide, can also be a source of
DDTs, because the dicofol products contain DDTs as impurities.
Dicofol is still in use, largely in the production of cotton, fruits, and
vegetables. Technical DDT and dicofol have different ratios of o,p0 -
DDT/p,p0 -DDT: the o,p0 -DDT/p,p0 -DDT ratio of dicofol type DDT
(w28) is much higher than that of technical DDT (0.74e0.96) (Liu
et al., 2009). Thus, the o,p0 -DDT/p,p0 -DDT ratio can be used to
trace the sources of DDTs. The Jeju site showed a relatively high
value of o,p0 -DDT/p,p0 -DDT compared with the other Korean sites
(Fig. 4). This corresponds with dicofol usage in the Jeju region.
About 1515 t of dicofol have been used as a pesticide by citrus and
gerbera growers in South Korea (KMOE, 2004). Citriculture is con-
ducted particularly and intensively in the Jeju region. Consequently,
all sampling sites were mainly influenced by past-use technical
DDT, but the Jeju site might be more contributed by dicofol type
DDT than the other sites.
3.3.3. Endosulfan
Endosulfan is listed as a POP and the global ban on its manu-
facture and use was negotiated under the Stockholm Convention in
1.8
JJ old
1.6
BE
o,p'-DDT/p,p'-DDT
higher than other OCPs in this study, ranging between 8.16 and
333 pg day1 PAS1 (Table 1). In particular, all sites in South Korea
showed extremely high levels of endosulfan (mean: 305, range:
262e333 pg day1 PAS1), revealing that South Korea is signifi-
α-HCH
cantly contaminated by endosulfan. In contrast, levels of endo-
β-HCH
γ-HCH sulfan in Beijing (109 pg day1) were a third of Korean levels, whilst
δ-HCH the other sites (Khovd, Yanji, and Ulan Bator) showed a tenth of
Korean levels.
Among isomers, endosulfan-I was dominant at all sites,
PH JJ
which is consistent with the results of previous global study
(Shunthirasingham et al., 2010). Technical endosulfan mixture
contains differing ratios of endosulfan-I:endosulfan-II, ranging
from 2:1 to 7:3 (UNECE, 2010; Weber et al., 2010). The ratios of
and 2.9 at the Beijing site, which is a similar ratio to that of technical
endosulfan, whilst the ratios were 7.9 at the Yanji site and 6.8e11.3
at the Mongolian sites. The higher endosulfan-I/II ratio indicates
the influence of long-range transport, because endosulfan-II is
likely to be lost during atmospheric transport (Shunthirasingham
et al., 2010). Consequently, the low level of endosulfan and the
high value for endosulfan-I/II ratio at the Yanji, Ulan Bator, and
Khovd sites may largely be the results of long-range transport (LRT)
from surrounding regions.
3.3.4. Mirex
Mirex has been used in China since 1958, and is still in use for
termite control. Mirex for pesticide use is not registered in Mongolia
and South Korea (KMOE, 2004; GEF/UNIDO, 2006; Wei et al., 2007).
Thus, the highest level of mirex was observed at the sites of Beijing
(1.67 pg day1 PAS1) and Yanji (2.61 pg day1 PAS1) (Table 1).
However, mirex was also detected at low concentrations at the
other sites, suggesting the LRT of mirex.
3.3.5. Heptachlor, chlordane, and their metabolites
Between 1963 and 1979, 16,617 t of heptachlor (HEPT) was
produced in South Korea (Park et al., 2011). Mongolia has used
564.5 t of HEPT between 1972 and 2003 (GEF/UNIDO, 2006).
Despite the much lesser amount of HEPT used in Mongolia, the Ulan
Bator site showed similar HEPT levels (0.77 pg day1 PAS1) with
the South Korean sites (0.1e0.53 pg day1 PAS1). This is likely to be
a result of Mongolia’s more recent use of this chemical. Despite the
fresh extensive usage in South Korea, HEPT was one of the lowest
occurring OCPs, measuring about 1 pg day1 PAS1. This may be
due to the shorter half-life of HEPT in the environment, air, soil, and

1.4 sediment compared to other OCPs (Mackay et al., 2000). A very

SE small quantity (approximately 17 t) of HEPT was used from 1948 to
PH
1.2 1982 in China (Wei et al., 2007), yet the Beijing site also showed
similar levels (1.22 pg day1 PAS1) with South Korea. The similar
YJ
1.0 BS Technical DDT ratio in air HEPT level in China may be partially the result of the application of
Khovd technical chlordane. Technical chlordane is composed of 24% TC,
0.8
22% CC, 10% HEPT, and 7% TN (Hinckley et al., 1990; Park et al., 2011).
UB
Whilst the application of chlordane for agricultural purposes has
been banned in all sampling regions, a large amount of chlordane is
0.6
still in use in China for termite control in urban construction (Wei
0.2 0.4 0.6 0.8 1.0 1.2 1.4
et al., 2007).
p,p'-DDT/p,p'-DDE HEPX (heptachlor epoxide) is a breakdown product of HEPT,
Fig. 4. Plot for the ratios p,p0 -DDT/p,p0 -DDE and o,p0 -DDT/p,p0 -DDT in air samples from
which can stay in soil and water for many years. Thus, a high ratio of
Khovd, Ulan Bator (UB), Beijing (BE), Yanji (YJ), Seoul (SE), Busan (BS), Pohang (PH), and HEPT/HEPX (about one) is indicative of the presence of fresh
Jeju (JJ). heptachlor. In the case of chlordane, the different degradation and
 S.-Y. Baek et al. / Atmospheric Environment 64 (2013) 40e46
reaction rate of chlordane isomers lead to change the ratio of TC/CC
in the air (Bidleman et al., 2002; Pozo et al., 2004; Shen et al., 2004).
TC/CC ratio (1.56) of the technical chlordane is likely to decrease
with increasing distance from sources (Bidleman et al., 2002). The
higher ratios of HEPT/HEPX and TC/CC in Beijing (1.06 and 1.20)
may indicate the recent application of technical chlordane
(Table 1). Whilst less chlordane was used in South Korea, the
P
atmospheric level of chlordanes (i.e., the sum of TC, CC, TN, and
CN) was relatively high in this area. This may have been influenced
by the LRT of chlordane from China. This could be supported by the
lower ratios of TC/CC (0.74e0.96) in the Korean sites (Table 1).
3.3.6. Dechlorane plus (DP)
In the present study, the Korean sites showed high concentra-
tions of DPs (anti-DP þ syn-DP) ranging from 9.87 to
44.8 pg day1 PAS1, much higher than those of the Mongolian and
Chinese sites (w1 pg day1 PAS1) (Table 1). Although no DP
manufacturing occurred in South Korea, DP has been sold there for
more than 40 years. A DP manufacturer is located in Jiangsu
Province in China (Wang et al., 2010), however, the China sampling
sites are located far from this manufacturer. This spatial distribu-
tion of DP is also in agreement with the results of previous studies.
The highest DP concentrations have been observed in tree bark
samples from South Korea (Qiu and Hites, 2008). Moreover, DP
concentrations in fish samples from South Korea have been found
to be several orders of magnitude greater than those of the Great
Lakes (Kang et al., 2010). The average fanti value (the anti-DP
proportion of total DP) was 0.77  0.09 for all sampling sites,
close to that of commercial DP (0.75e0.8) (Hoh et al., 2006). This
suggests that the commercial DP products had a substantial impact
on the air quality of sampling sites.
4. Conclusions
Since the early 2000s, worldwide regulations (e.g. the
Stockholm Convention) have been implemented in an attempt to
protect against significant adverse human health and environ-
mental effects of POPs. Accordingly, individual countries have
begun to regulate and ban the use and manufacturing of these
chemicals. However, the scope and timing of the regulations differ
among nations. Thus, the differing contamination levels among
countries are to be expected. Furthermore, in many cases air
pollution is not limited to one country, so it is necessary to take into
account the impact of transport from surrounding countries. In
Northeast Asia, westerly winds prevail throughout the year, and the
transport of pollutants over this region has been studied exten-
sively. However, developing countries like Mongolia have always
been excluded from POP monitoring studies. Developing countries
are in the early stages of the POP monitoring system and there is
less data available on local usage. In the present study, the sites in
Mongolia had lower levels of most POPs than those in other
countries, as expected. Nevertheless, we found that the Mongolian
sites were highly contaminated by PCBs. This finding is contrary to
previous studies that found PCB contamination to be closely related
to population. We are currently planning to investigate further the
extent of PCB contamination in Mongolia, through the installation
of PAS in other cities and by examining annual or seasonal varia-
tions. At the same time, the calibration study for calculating uptake
rates of PAS should also be examined in this area.
Acknowledgements
This study was financially supported by the Korean Food and
Drug Administration (12162KFDA015) and by the National Research
Foundation of Korea (NRF) grant funded by the Korea government
45
(MEST) (No. 2011-0028723). We would like to thank Dr. Sungmin
Hong at Inha University for his efforts in deploying samplers. We
are very grateful to Dr. Sung-Deuk Choi at Ulsan National Institute
of Science and Technology (UNIST) for his support and advice.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.atmosenv.2012.09.015.
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