Chemosphere 67 (2007) 456–463

www.elsevier.com/locate/chemosphere

Vertical distributions of persistent organic pollutants (POPs)

caused from organochlorine pesticides in a sediment
core taken from Ariake bay, Japan
Yun-Seok Kim a, Heesoo Eun a,*
, Takao Katase b, Hideshi Fujiwara a

a
National Institute for Agro-Environmental Sciences, 3-1-3 Kannondai, Tsukuba, Ibaraki 305-8604, Japan
b
College of Bioresource Sciences, Nihon University, 1866 Kameino, Fujisawa, Kanagawa 252-8510, Japan

Received 11 April 2006; received in revised form 10 August 2006; accepted 24 September 2006
Available online 15 November 2006

Abstract

Persistent organic pollutants (POPs) of organochlorine pesticides such as dichlorodiphenyl trichloroethane (DDTs) and its metabo-
lites, hexachlorobenzene (HCB), heptachlor, chlordane compounds (CHLs), aldrin, dieldrin, endrin, mirex and isomers of hexachloro-
cyclohexane (HCHs), were analyzed in sediment cores collected from Ariake Bay, Japan. Although Chikugo River has the largest flow in
Ariake Bay, the total concentration of POPs in surface sediment was found in St.3, mouth of the Yabe River, where that level was two
times higher than St.1, mouth of the Chikugo River. It could be assumed that the potential source of POPs contamination is relatively
close to this study area. Relatively high residue levels of HCB, HCHs and DDTs in sediment core were found during the period from
1967 to 1970. In this layer, the HCB concentration investigated in sediment cores of Ariake Bay was maximum, 2.6 ng g1 dry weight and
higher than that of Tokyo Bay and subsequently detected in deeper sediment cores. The ratio of (DDD + DDE)/RDDTs was high in top
sediments (0–2 cm). Although there was a concentration of DDTs in the top sediment, it was noticed that DDT emission did not cause
direct input of DDT recently. The HCHs determined in upper sediment cores might be originated from long-range accumulation in envi-
ronment after dispersing of technical-grade HCH. Moreover, the CHLs, dieldrin and heptachlor concentrations were detected and
recently increased in sediment core. POPs in sediment cores of Ariake Bay based on the possibility of PCP contamination during the
early 1960s were reflected.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Sediment cores; Persistent organic pollutants; Organochlorine pesticides; Ariake Bay; HRGC–HRMS

1. Introduction
Ariake Bay is located in Kyushu Island, western Japan,
and has large tidal ranges to 5 m and Japan’s largest tidal
flat, approximately 230 km2(Nakata et al., 2002). This tidal
flat ecosystem is inhabited by several unique benthic organ-
isms, such as mudskipper fish, crabs, clams, and lugworms
(Nakata et al., 2003). Ariake Bay is one of the major inland
seas with many fishery resources in Japan. In these four
prefectures, Fukuoka, Kumamoto, Nagasaki and Saga,
*
Corresponding author. Tel.: +81 29 8387351; fax: +81 29 38 7352.
E-mail address: eun@affrc.go.jp (H. Eun).
which face the Ariake Bay, the edible laver (Japanese is
‘‘nori’’) that is well known for its high quality accounts
for approximately 40% of the total domestic production
(Shimatsu, 2003). The seaweed plants were damaged in
the autumn of 2000 in this Bay. The other marine produc-
tivity, such as fish, shellfish and others was also decreased
in the period of the 1960s and from the 1980s to the recent
years. Societal concern about this problem has become
high in Japan. Choi et al. (2003) reported the historical
distribution of PCDDs/DFs and dioxin-like polychlorin-
eated biphenyls (PCBs) in sediment cores of Tokyo
Bay, Japan. This study would provide the valuable infor-
mation to understand the behavior of persistent organic

0045-6535/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2006.09.063
 Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463
pollutants (POPs) caused from organochlorine pesticides,
such as dichlorodiphenyl trichloroethane and its metabo-
lites (DDTs), hexachlorobenzene (HCB), heptachlor, chlor-
dane compounds (CHLs), aldrin, dieldrin, endrin, mirex
and isomers of hexachlorocyclohexane (HCHs) in the envi-
ronment from the point of view of environmental pollution
in Ariake Bay, Japan.
POPs are endocrine disrupters and persistent in the envi-
ronment, having long half-lives in air, soil, sediments or
biota (Jones and Voogt, 1999). Because of their lipophilic
nature, they tend to accumulate in higher trophic animals
through food chains (Nakata et al., 2004). In early July
of 1961, a large number of fish and shellfish were killed
suddenly on the coast of the Ariake Bay. The main cause
of this phenomenon was assumed to be the toxic effect of
an herbicide PCP, pentachlorophenol (Ikematsu et al.,
1963). The use of PCP in this area was expanded enor-
mously since 1961. Soon after PCP was employed that
year, a great deal of water overflowed from the paddy fields
and ran into the Bay as a result of heavy rainfall over
150 mm d1 (Ikematsu et al., 1963; Okubo and Okubo,
1965). In Japan, PCBs, DDTs and HCHs were widely used
in industries and in agriculture during the 1950s and 1960s,
a period of rapid development. The CHLs were used as ter-
micide from 1962 (Loganathan et al., 1989). The POPs
determined in sediment and water samples from Onsan
Bay, Korea, has a significant dioxinlike activity in approxi-
mately 80% of analyzed samples (Koh et al., 2002). How-
ever, very little information is available to understand the
historical trend of environmental contamination by these
persistent organochlorines.
The concentration and composition of PCBs and PAHs
in sediment and some biota taken from Ariake Bay, Japan
has been reported previously (Nakata et al., 2002, 2003). In
this study, 23 compounds of POPs including their isomers,
degradations or metabolites in sediment cores were deter-
mined to understand their historical status of contamina-
tions. In terms of assessing the levels of contamination,
recovery of POPs from environmental samples is important
(Scott and Dean, 2003). We analyzed the POPs in order to
increase precision and sensitivity for chemical analysis using
high-resolution gas chromatography coupled with a high-
resolution mass spectrometric detector (HRGC–HRMS).
This study also investigated the vertical concentrations of
POPs and the specific compositional characteristics in the
sediment cores.
2. Materials and methods
2.1. Materials
2.1.1. Reagents and chemicals
Commercially available POPs, DDTs, HCB, heptachlor,
CHLs, aldrin, dieldrin, endrin and mirex and persistent
organochlorines such as isomers of HCHs were used. Their
surrogate substances of stable isotopically labeled internal
standards were purchased from Wellingtone Isotope Labo-
457
ratories, Inc., USA. In solvents, persistent pesticides and
the PCB analytical grade of hexane, acetone and diethyl
ether were purchased from Kanto Chemical Co., Japan.
Laboratory water was used with a Milli-Q system water
purification (Millipore, USA) and hexane-washed water
for analysis.
2.1.2. Environmental sample collection
The sampling locations are shown in Fig. 1. A sediment
core, which was a cylindrical sample with a diameter of
11 cm and a length of 350 cm was obtained from the north-
ern part of Ariake Bay, the Yanagawa coast (St.2;
N33°05 0 47700 and E130°23 0 43100 ) by the scuba divers on
01 November 2005. In the nearby area where this study
was presented, PCP containing some toxic dioxins as their
impurity has been produced since the late 1960s by chemi-
cal factories. Surface sediment samples were collected at
two stations, St.1 (N33°09 0 12300 and E130°21 0 48200 ) and
St.3 (N33°05 0 37000 and E130°24 0 73500 ) in the Ariake Bay
using an Ekman–Berge dredge. Then, seawater was also
collected from same locations. The samples of sediment
core were sliced into 2 cm thick disks up to 50 cm of depth
and a 4 cm thick disk from 50 cm to 350 cm of depth. Ana-
lysis samples were selected from 20 disks, which had 5 cm
intervals from top core to 50 cm, 10 cm intervals from
50 cm to 100 cm and 50 cm intervals from 100 cm to
350 cm. All the sediment samples were stored at 20 °C
until analysis.
2.2. Methods
2.2.1. Analytical procedure
Isomer-specific analysis of individual POPs based on
relative response factor (RRF) quantification by HRGC–
HRMS in environmental samples, seawater, surface sedi-
ments and sediment cores was carried out. Twelve liters
Fig. 1. Sampling locations (water and surface sediments: St.1 and St.3,
3 m sediment core: St.2).
458 Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463

of seawater were filtered using an Empore (3M) of extrac-
tion disk. The disk filtered was extracted by Soxhlet appa-
ratus with acetone for 16 h. The sediment samples were
extracted, fractionated and analyzed following the methods
reported by Eun et al. (2005). Briefly, approximately 30 g
of core samples were homogenized after air-dried at room
temperature and extracted with 300 ml acetone for 16 h by
Soxhlet apparatus. The extract was concentrated by 10 ml
and an aliquot was transferred to hexane in a separating
funnel. Seventeen 13C-labeled compounds were spiked into
a separating funnel as clean-up spikes. After shaking in a
separating funnel, the hexane layer was concentrated.
The POPs were eluted and subsequently treated with a flor-
isil cartridge (5 g, glass tube 20 ml, Varian) and passed
through a cartridge of active carbon (0.25 g, ENVI-Carb
SPE Tubes 3 ml, Supelco) to remove color. The cartridges
had been washed with 10 ml of hexane before using.
After spike surrogate standards as syringe spikes into elu-
ate, the final eluate was concentrated to 0.1 ml under a
gentle stream of nitrogen gas. A procedural blank was
run for a set of three samples to check for cross-contamina-
tion. All data presented here were corrected for each blank
value.
2.2.2. Method of Identification
(a) HRGC–HRMS
GC–MS analysis was performed using a high-resolution
mass selective detector (HRMS) (Micromass Autospec-
Ultima) interfaced to a HP6890 series high-resolution gas
chromatograph (HRGC). All samples were identified and
quantified by injecting an aliquot into a HRGC–HRMS
using a selective ion monitoring (SIM) mode. The SIM
mode was constituted by tracing M+ and (M+2)+ ions of
each compound. Two mass methods for determination of
POPs were accomplished with its most intensive ions.
The range from m/z 210 to 300 for low mass compounds,
HCHs, aldrin, dieldrin, endrin, DDTs, heptachlor, HCB,
mirex and m/z 350–420 for high mass compounds, hepta-
chlor-epoxide, chlordane, nonachlor and oxy-CHL was
used for the identification and quantification. Quantifica-
tion of the individual compound of POPs in the samples
was conducted by the internal standard method using a
RRF. The list of POPs investigated for the clean-up spikes
and syringe spikes is shown in Table 1. Two surrogate stan-
dards of 13C-labeled PCB, #81 and #153 were spiked into
the final eluate to calculate recovery as internal standard.
Recovery of POPs in spiked samples ranged from 50% to
120% except aldrin (less than 30%). In addition, reproduc-
ibility of each individual POP compounds showed less than
10% except the mirex (23%) only. The detection limit (ND)
was calculated to 3-fold value of the blank value for each
POP. HRGC–HRMS system conditions are as follows: A
sample injection separated an autosampler onto a 30 m
ENV-8MS column (i.d. 250 lm, film thickness 0.25 lm,
Kanto Chemical Co., Japan). The HRMS was operated
in an electron impact and SIM mode at resolution more
than 10 000 (10% valley). Helium was used as the carrier
gas at a constant flow of 1.0 kg cm2. The temperature pro-
gram for the column began with a 0.5 min held at 120 °C,
followed by a 10 °C min1 ramp-up to 180 °C, then a rate
of 4 °C min1 to 210 °C held for 12 min and a rate of
10 °C min1 to the final temperature of 300 °C. After elut-
ing from the HRGC column, the samples were carried
through a 260 °C transfer line into the ion source of the
mass spectrometer held at 260 °C. The electron energy
was 70 eV.

Table 1
List of investigated pesticides of POPs and clean-up spikes and syringe spike for analysis
Compounds Clean-up spike Syringe spike
13 13
Hexachlorobenzene (HCB) HCB C–HCB C–PCB #81
13
Hexachlorocyclohexane (HCHs) a-HCH C–a-HCH
13
b-HCH C–b-HCH
13
c-HCH C–c-HCH
13
d-HCH C–d-HCH
13
Heptachlors Heptachlor C–Heptachlor
13 13
Heptachlor epoxide C–Heptachlor Epoxide C–PCB #153
13
Chlordanes (CHLs) trans-Chlordane C–trans-Chlordane
cis-Chlordane
13
trans-Nonachlor C–trans-Nonachlor
cis-Nonachlor
13
Oxychlordane C–Oxychlordane
13 13
Dichlorodiphenyl trichloroethane (DDTs) o,p 0 -DDE C–p,p 0 -DDE C–PCB #81
p,p 0 -DDE
o,p 0 -DDD D8  p,p 0  DDD
p,p 0 -DDD
13
o,p 0 -DDT C–p,p 0 -DDT
p,p 0 -DDT
13
Drins Aldrin C-Aldrin
13
Dieldrin C-Dieldrin
13
Endrin C-Endrin
13
Mirex Mirex C-Mirex
 Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463 459

(b) Sedimentation rate
The sediment cores were analyzed for 210Pb, 226Ra and
137
Cs by direct gamma assay using a high purity germa-
nium detector (Canberra; BE5025). The 210Pb was deter-
mined via its gamma emissions at 46.5 keV, and 226Ra by
the 352 keV c-rays emitted by its daughter isotope 214Pb
following three weeks storage in sealed containers to allow
radioactive equilibration. The 137Cs was measured by their
emissions at 661.6 keV. Supported 210Pb in each sample
was assumed to be in equilibrium with the in situ 226Ra,
and unsupported 210Pb 210Pbex was calculated by subtract-
ing 226Ra activity from total 210Pb (Baskaran and Naidu,
1995; Kanai, 2000). The sedimentation rate and radiomet-
ric dates were calculated from the 210Pb records based on
the constant initial concentration model.
3. Results and discussion
3.1. POPs in sediment core
The 210Pb and 137Cs concentrations in sediment cores
taken from Ariake Bay, Japan are given in Table 2. The
vertical variation of 210Pb concentration was obviously
observed decreasing downward the core. This trend implies
that the top 50 cm of the core spans a little more than a
century. However, vertical 137Cs activity in our sediment
cores did not find that the 137Cs depositional flux reached
a maximum in 1963, which serves as a geochronological
marker (Baskaran and Naidu, 1995). The age determina-
tion with 210Pb isotope revealed that the sedimentary rate
in Ariake Bay (St.2) is 0.35 cm per year.
Residual concentrations of the POPs caused from pesti-
cides such as HCB, DDTs, HCHs, CHLs, Drins, heptach-
lors and mirex in sediment cores are presented in Table 3.
The maximum concentration of HCB, HCHs and DDTs
was presented during the late 1960s. The results showed
that the relatively high concentrations of HCB, HCHs
and DDTs in the core ranged from 0.03 to 2.65, 0.01 to
2.01 and 0.01 to 1.16 ng g1 dry weight, respectively. The
vertical distribution of POPs was relatively considered with
historical term. The concentration profiles of HCB, HCHs
and DDTs were similar to those of Tokyo Bay, Japan and
as described by Shimizu et al. (2005). These substances’
concentration began suddenly increasing in the early
1950s, showing the peak near 1970 and rising again toward
upper sediment core. However, the reason for relatively
high concentration kept until today is unknown.
Unlike the above mentioned compounds, CHLs, Drins
and heptachlors concentrations were observed in very low
levels until the 1990s and then detected rather an increasing
trend toward the current. The concentration of mirex,
which has never been used in Japan and never imported
from foreign sites was detectable in all samples but below
detected limits.
In this study, although the river flow on St.1 is the high-
est amount of inputting to Ariake Bay, the concentration
of total POPs in surface sediments collected from St.3
was approximately two times higher than the St.1 (Table
4). Peng et al. (2005) reported that river inflow and surface
runoff might be assumed significant contributors for rela-
tively high concentrations of HCH compounds and DDT
compounds and other organochlorine pesticides species in
sediment of Lake Taihu, China. This implied that the pol-
lution source might be emitted nearby St.3.
3.2. Hexachlorobenzene (HCB)
The total concentration of HCB in sediment cores of Ari-
ake Bay was the predominant residue among the POPs
as shown in Table 3. The concentration of HCB began
abruptly rising at 20 cm depth, the corresponding years
from 1950 to 1953. Then the maximum concentration of
HCB was found from 1967 to 1970 (2.6 ng g1 dry wt.), indi-
cating that the large amounts of HCB discharge occurred in
this period. The data observed showed that maximum con-
centration investigated in the cores of Ariake Bay was
higher than those of Tokyo Bay, Japan, where industrial
pollution is heavily progressing (Shimizu et al., 2005).
According to Hirai et al. (2001), emission sources of HCB
in sediment cores were considered as follows; impurities

Table 2
Sedimentation rate and corresponding year in sediment core taken from Ariake Bay
Depth Mass depth Pb-210ex Error Cs-137 Error Apparent year
(cm) (g cm2) dry (Bq kg1) (Bq kg1) (Bq kg1) (Bq kg1)
0–2 1.88 NM NM 2002–2005
4–6 6.14 37.2 3.4 1.35 0.4 1993–1997
10–12 14.3 10.9 3.0 1.39 0.2 1977–1981
14–16 20.2 11.2 2.7 1.38 0.1 1966–1970
20–22 28.7 2.56 2.8 0.45 0.3 1950–1953
26–28 37.5 2.11 3.2 0.16 0.3 1932–1936
30–32 43.6 0.37 3.4 ND 1921–1924
36–38 52.2 0.26 3.6 ND 1904–1908
42–44 60.5 ND 0.30 0.3 1888–1892
46–48 66.0 3.81 5.2 ND 1877–1881
NM: not measured.
ND: not detected.
 460
Table 3
Concentrations (ng g1 dry wt.) of POPs in sediment core from Ariake Bay, Japan
Depth (cm) 0–2 4–6 10–12 14–16 20–22 26–28 30–32 36–38 40–42 46–48 50– 62– 70– 82– 90– 102– 154– 202– 254– 306–
54 66 74 86 94 106 158 206 258 310
Apparent year 2005– 1997– 1981– 1970– 1953– 1936– 1924– 1908– 1892– 1881– NM NM NM NM NM NM NM NM NM NM
2002 1993 1977 1966 1950 1932 1921 1904 1888 1877
HCB 1.5 0.65 1.7 2.6 0.24 0.16 0.092 0.094 0.050 0.031 <ND 0.003 0.000 0.002 0.002 0.001 0.002 0.013 0.001 0.0
a-HCH 0.29 0.20 0.47 0.74 0.20 0.093 0.053 0.046 0.021 0.002 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
b-HCH 0.40 0.20 0.43 0.60 0.16 0.079 0.040 0.035 0.017 0.002 <ND <ND <ND <ND 0.000 <ND <ND <ND <ND <ND
c-HCH 0.098 0.047 0.11 0.18 0.044 0.025 0.014 0.014 0.006 0.001 <ND 0.001 <ND <ND <ND <ND 0.001 <ND 0.001 0.002
d-HCH 0.16 0.092 0.29 0.48 0.094 0.049 0.027 0.024 0.010 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
RHCHs 0.95 0.54 1.3 2.0 0.50 0.25 0.13 0.12 0.053 0.006 <ND 0.001 <ND <ND 0.000 <ND 0.001 <ND 0.001 0.002
Heptachlor 0.008 <ND <ND <ND <ND 0.000 0.000 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND

Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463

Heptachlor <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
Epoxide
RHeptachlor 0.008 <ND <ND <ND <ND 0.000 0.000 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
trans-Chlordane 0.15 0.038 0.023 0.016 0.007 0.008 0.009 0.009 0.013 0.011 0.004 0.018 0.013 0.010 0.010 0.009 0.009 0.014 0.005 0.006
cis-Chlordane 0.077 0.018 0.010 0.007 0.002 0.003 0.003 0.003 0.004 0.005 0.001 0.007 0.005 0.004 0.004 0.002 0.003 0.006 0.001 0.003
trans-Nonachlor 0.075 0.016 0.006 0.004 0.000 0.001 0.001 0.002 0.003 0.002 0.000 0.004 0.002 0.002 0.001 0.001 0.002 0.004 0.000 0.002
cis-Nonachlor 0.040 0.014 0.003 0.002 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
Oxychlordane 0.001 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
RCHLs 0.35 0.086 0.043 0.029 0.009 0.012 0.013 0.014 0.020 0.018 0.005 0.029 0.020 0.015 0.015 0.012 0.014 0.023 0.007 0.011
o,p 0 -DDE 0.029 0.017 0.005 0.001 0.002 0.000 0.001 0.004 0.003 0.001 <ND 0.001 0.001 0.001 0.001 0.000 0.000 0.000 <ND <ND
p,p 0 -DDE 0.61 0.38 0.46 0.49 0.19 0.094 0.056 0.056 0.019 0.005 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
RDDE 0.64 0.40 0.47 0.49 0.19 0.094 0.057 0.060 0.022 0.005 <ND 0.001 0.001 0.001 0.001 0.000 0.000 0.000 <ND <ND
o,p 0 -DDD 0.10 0.062 0.056 0.085 0.039 0.025 0.006 0.016 0.004 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
p,p 0 -DDD 0.32 0.21 0.23 0.34 0.14 0.086 0.044 0.057 0.016 0.002 <ND 0.001 0.001 <ND 0.001 <ND 0.000 0.000 <ND <ND
RDDD 0.41 0.27 0.29 0.42 0.18 0.11 0.051 0.074 0.019 0.002 <ND 0.001 0.001 <ND 0.001 <ND 0.000 0.000 <ND <ND
o,p 0 -DDT 0.048 <ND 0.013 0.005 <ND 0.034 0.005 0.022 0.006 <ND <ND <ND 0.003 <ND <ND <ND <ND <ND <ND <ND
p,p 0 -DDT 0.052 <ND 0.024 0.034 <ND 0.009 <ND 0.004 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND
RDDT 0.10 <ND 0.036 0.039 <ND 0.043 0.005 0.026 0.006 <ND <ND <ND 0.003 <ND <ND <ND <ND <ND <ND <ND
RDDTs 1.2 0.67 0.79 0.95 0.37 0.25 0.11 0.16 0.047 0.007 <ND 0.002 0.005 0.001 0.001 0.000 0.001 0.000 <ND <ND
(DDD + DDE)/ 0.90 1.00 0.93 0.94 1.00 0.78 0.85 0.77 0.73 0.65 0.62 0.58 0.41 0.53 0.51 0.42 0.76 0.42 1.00 1.00
RDDTs
Aldrin 0.011 <ND <ND <ND <ND 0.013 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND ND
Dieldrin 0.15 0.006 0.010 <ND <ND <ND <ND <ND <ND <ND <ND 0.000 <ND <ND <ND <ND <ND <ND <ND ND
Endrin 0.009 0.009 0.026 0.017 0.004 <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND ND
Mirex <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND <ND ND
RPOPs 4.1 2.0 3.8 5.6 1.1 0.66 0.35 0.39 0.17 0.063 0.005 0.035 0.025 0.018 0.018 0.013 0.018 0.037 0.010 0.028
NM: not measured.
ND: not detected.
 Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463 461

Table 4 3 12
Concentrations (ng g1 dry wt.) of POPs in surface sediments from
HCB
northen part in Ariake Bay
OCDD
St.1 St.3

OCDD Conc. (ng g-1 dry wt)

HCB Conc. (ng g-1 dry wt.)
2 8
HCB 0.83 2.3
a-HCH 0.26 0.52
b-HCH 0.31 0.55
c-HCH 0.059 0.13 4
1
d-HCH 0.15 0.26
RHCHs 0.78 1.5
Heptachlor <ND <ND
Heptachlor Epoxide 0.000 0.001 0 0
RHeptachlor 0.000 0.001 0 50 100 150 200 250 300 350

trans-Chlordane 0.16 0.16 Depth (cm)

cis-Chlordane 0.090 0.091
Fig. 2. Vertical distributions in sediment core of concentrations of HCB
trans-Nonachlor 0.072 0.094
and OCDD.
cis-Nonachlor 0.056 0.058
Oxychlordane 0.001 0.000
RCHLs 0.38 0.40
3.3. Hexachlorocyclohexanes (HCHs)
o,p 0 -DDE 0.035 0.050
p,p 0 -DDE 0.64 0.96 The HCH residues are among the most widely distrib-
RDDE 0.68 1.0
uted and frequently detected organochlorine contaminants
o,p 0 -DDD 0.062 0.097 in the environment. The concentrations of HCHs in sedi-
p,p 0 -DDD 0.21 0.32 ment cores of Ariake Bay also showed and increasing trend
RDDD 0.27 0.41
from the early 1950s (Table 2) and a peak in the late 1960s.
o,p 0 -DDT <ND 0.048 Interestingly, production of HCH in Japan was highest in
p,p 0 -DDT <ND 0.052
this period and the trend of the residues level investigated
RDDT <ND 0.10
in biota was dependent on its usage (Loganathan et al.,
RDDTs 1.0 1.5 1989).
Aldrin <ND 0.011 The compositions of HCH isomers exhibited similar dis-
Dieldrin 0.006 0.15 tribution patterns as shown in Fig. 3. Concentrations and
Endrin 0.009 0.009
compositions of HCH isomers were found to be in order
Mirex <ND <ND
a-HCH > b-HCH > d-HCH > c-HCH in almost all cores
RPOPs 3.0 5.8
ND: not detected.
60

in pesticides such as PCP, pentachloronitrobenzene, 40

Composition (%)

dimethyl-tetrachloroterephthalate, incineration of HCB

containing waste from tetrachloroethylene production and
incineration of municipal solid waste. Homologue profiles 20
of PCP samples revealed that the most abundant impurity
of dioxin was O8CDD (Masunaga et al., 2001). Vertical
distributions of HCB and O8CDD concentration were 0
0.9
presented as shown in Fig. 2. The vertical profile of the 1966-1970
HCB is shown corresponding to that of O8CDD. Thus,
the maximum concentration of HCB observed from 1967
(ng g -1 dry wt.)
Concentration

0.6
to 1970 could be assumed that it was attributed to the 1977-1981

herbicide, PCP. In fact, a large number of fish and shellfish 1950-1953

were killed suddenly in Ariake Bay during 1961 and 1962. 0.3
Ikematsu et al. (1963) reported that this phenomenon
might be caused from the use of PCP in paddy fields. The
similar vertical trend of HCB and O8CDD concentration 0
0 10 20 30 40 50
in this study supports this assumption. Nevertheless, the Depth (cm)
sediment core corresponding to the early 1960s was not
Fig. 3. Vertical distributions of compositions and concentrations of HCH
determined, HCB concentration might be found higher isomers in sediment core. Lozenge (r) denotes a-HCH, squares (j)
concentrations than 2.6 ng g1 dry weight in Ariake Bay, denote b-HCH, black circles (d) correspond c-HCH, triangle (m) denote
Japan. d-HCH.
462 Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463
except surface sediment core. Decreasing concentration
after early 1970s might be reflected to that prohibited the
production and use of HCHs in the early 1970s in Japan.
Regarding the composition of HCH isomers in the envi-
ronment, a-HCH was overall predominant in sediment
cores except the top sediment core. Ramesh et al. (1989)
reported that a high percentage of a isomer was reflecting
the composition of technical-grade HCHs (a; 70%, b; 9%,
c; 14%, d; 7%). According to Loganathan et al. (1989),
the nationwide HCHs usage in Japan was approximately
400 metric tons. This is an extremely large amount when
compared with DDTs and PCBs in Japan. Therefore, it
can be assumed that HCHs contamination might have
occurred through the use of technical-grade HCHs until
the early 1970s. The composition of b-HCH has been
reported predominant in environment because it is most
stable among HCH isomers and resistant to microbial
degradation (Tanabe et al., 1991; Walker et al., 1999; Lee
et al., 2001). On the other hand, the decreasing trend for
composition of a isomer and the increasing trend for the
b-isomer after they were officially banned in the early
1970s were observed in upper sediment cores. This implies
that HCHs contamination in upper cores might have orig-
inated from a relatively remote source or long-time accu-
mulation after dispersing.
3.4. DDTs
The vertical concentrations of DDTs are shown in Table
3. Concentrations and compositions of DDT isomers were
found to be in order DDE > DDD > DDT (including o,p 0 -
and p,p 0 -) in almost all cores. Particularly, the concentra-
tion of p,p 0 -DDE dominated in most of all cores. This
metabolite was indicated higher persistency. Although, in
Japan, about 30 000 tons of DDT was used up until 1972
(Loganathan et al., 1989), the highest residual concentra-
tion of 1.2 ng g1 dry weight in topper sediment core was
observed. The concentrations of DDTs in Ariake Bay
was similar to San Pedro Lake (0.64–1.4 ng g1 dry wt.),
Chile (Barra et al., 2001) and lower than those of Tokyo
Bay (0.22–26 ng g1 dry wt.), Japan (Shimizu et al.,
2005), Lake Taihu (0.65–38 ng g1 dry wt.), China (Peng
et al., 2005) and San Francisco Bay (4–21 ng g1 dry
wt.), CA (Venkatesan et al., 1999). It is assumed that the
Ariake Bay seemed to be relatively less contaminated with
DDT compounds than other areas.
The composition of organochlorines and their metaboli-
ties can provide some information for a better understanding
of the origin and transport of these contaminants in the envi-
ronment. Peng et al. (2005) reported a possibility of the con-
tinuous illegal use of DDT in China using the ratio of
(DDD + DDE)/RDDTs. Microbial degradation of DDT,
DDD and DDE is generally slow, resulting in environmental
persistence of these compounds and DDT may degrade to
DDD with a half-life of a few days under certain conditions
(Garrison et al., 2000). The ratios of (DDE+DDD)/RDDTs
in the sediment cores ranged from 0.65 to 1.00 in Ariake Bay,
Japan (Table 3). The ratios were declining toward down
cores, which it could be explained that DDT emission
occurred in the past input. According to record of the Min-
istry of Agriculture, Forestry and Fisheries, Japan, the
banned pesticides were buried in one location in Fukuoka
Prefecture. Therefore, it can be assumed as a possibility that
it might be reflected by buried pesticides somewhere after
banned them in 1970s. However, it should need more
evidences and information about their transportation and
sedimentation into sediment to confirm the possibility.
Acknowledgements
This study is supported by Japanese Society of the Pro-
motion of Science (JSPS), Tokyo, Japan. The authors
thank to Drs. D.-S. Choi and T. Fukuyama, National
Institute of Agricultural Science and Technology, South
Korea and University of Tsukuba, Japan, respectively,
for his help in chemical experiment and some advices to as-
sess the calculation of age in sediment cores. The authors
are thankful to James J. Berger for his kindly discussion.
References
Barra, R., Cisternas, M., Urruita, R., Pozo, K., Pacheco, P., Parra, O.,
Focardi, S., 2001. First report on chlorinate pesticide deposition in a
sediment core from a small lake in central Chile. Chemosphere 45,
749–757.
Baskaran, M., Naidu, S., 1995. 210Pb-derived chronology and the fluxes of
210
Pb and 137Cs isotopes into continental shelf sediments, East
Chukchi Sea, Alaskan Arctic. Geochim. Cosmochim. Acta 59, 4435–
4448.
Choi, J.-W., Fujimaki, S., Kitamura, K., Hashimoto, S., Ito, H., Sakurai,
T., Suzuki, N., Nagasaka, H., Tanabe, K., Sakai, S.-I., 2003. Historical
trends of PBDD/Fs, PBDEs, PCDD/Fs and dioxin-like PCBs in
sediment cores from Tokyo Bay. Organiohalogen Compds. 61, 119–122.
Eun, H., Arao, T., Watanabe, E., Bsba, K., Endo, S., 2005. Fate and
behavior of POPs in general and agricultural environment by using
HRGC/HRMS. Symp. Environ. Chem., Jpn., 518–519.
Garrison, A., Nzengung, V., Avants, J., Ellington, J.J., Hones, W.J.,
Rennels, D., Wolfe, N.L., 2000. Phytodegradation of p.p 0 -DDT and
the enantiomers of o,p 0 -DDT. Environ. Sci. Technol. 34, 1663–1670.
Hirai, Y., Kato, T., Takatsuki, H., Sakai, S., 2001. Simulation of historical
trend of hexachlorobenzene in sediment cores using the emission
estimate and dynamic multimedia environmental fate model. J.
Environ. Chem. 11, 793–804.
Ikematsu, W., Tanaka, Y., Azeta, Y., Ehira, S., Morokuma, H.,
Yamaguchi, S., 1963. The toxic effect of pentachlorophenate, a
herbicide, on aquatic organisms. Bull. Seikai Nat. Fish. Res. Instit.
Nagasaki 28, 1–23.
Jones, K.C., Voogt, P.de., 1999. Persitent organic pollutants (POPs): state
of the science. Environ. Pollut. 100, 209–221.
Kanai, Y., 2000. A study on lead-210 dating. Chikyukagaku 34, 23–39.
Koh, C.-H., Khim, J.S., Villeneuve, D.L., Kannan, K., Giesy, J.P., 2002.
Analysis of trace organic contaminants in sediment, pour water, and
water samples from Onsan Bay, Korea: instrumental anlaysis and
in vitro gene expression assay. Environ. Toxicol. Chem. 21, 1796–1803.
Lee, K.T., Tanabe, S., Koh, C.H., 2001. Distribution of organochlorine
pesticides in sediments from Kyeonggi Bay and nearby areas, Korea.
Environ. Pollut. 114, 207–213.
Loganathan, B.G., Tanabe, S., Goto, M., Tatsukawa, R., 1989. Temporal
trends of organochlorine residues in lizard goby Rhinogobious flumin-
eus from the river Nagaragawa, Japan. Environ. Pollut. 62, 237–251.
 Y.-S. Kim et al. / Chemosphere 67 (2007) 456–463
Masunaga, S., Takasuga, T., Nakanishi, J., 2001. Dioxin and dioxin-like
PCB impurities in some Japanese agrochemical formulations. Chemo-
sphere 44, 873–885.
Nakata, H., Miyawaki, T., Sakai, Y., 2002. Concentrations and isomer
compositions of polychlorinated biphenyls (PCBs) in tidal flat
sediments from the Ariake Sea and their implications for sources
and distribution. J. Environ. Chem. 12, 127–134.
Nakata, H., Sakai, Y., Miyawaki, T., Takemura, A., 2003. Bioaccumu-
lation and toxic potencies of polychlorinated biphenyls and polycyclic
aromatic hydrocarbons in tidal flat and coastal ecosystems of the
Ariake Sea, Japan. Environ. Sci. Technol. 37, 3513–3521.
Nakata, H., Hirayama, Y., Sakai, Y., Takemura, A., 2004. Variations in
organochlorine concentrations and patterns with growth and trophic
status of tidal flat and species from the Ariake Sea. Symp. Environ.
Chem., Jpn., 724–725.
Okubo, K., Okubo, T., 1965. Influence of diluted seawater on the
physiological activity of babyneck clam, Venerupis Japonica, and the
toxic effect of a herbicide PCP, pentachlorophenate. Bulletin of the
Tokai Regional Fisheries Research Laboratory 44, 31–40.
Peng, X., Zhang, G., Zheng, L., Mai, B., Zeng, S., 2005. The vertical
variations of hydrocarbon pollutants and organochlorine pesticide
residues in a sediment core in Lake Taihu, East China. Geochem.:
Explor. Environ. Anal. 5, 99–104.
463
Ramesh, A., Tanabe, S., Tatsukawa, R., Subramanian, A.N., 1989.
Seasnol variation of organochlorine insecticide residues in air from
Porto Novo, South India. Environ. Pollut. 62, 289–304.
Scott, W.C., Dean, J.R., 2003. Selective extraction of persistent organic
pollutants from environmental matrics. J. Environ. Monit. 5, 724–
731.
Shimatsu, Y., 2003. Research on the environmental change and degrada-
tion and its influence to fisheries production in the Ariake-Bay.
Nippon Suisan Gakkaishi 69, 439–443.
Shimizu, J., Yamao, S., Nosaka, T., Noguchi, K., Mine, M., Matsumoto,
K., Oichi, K., Tsutsumi, K., Miyamoto, T., Ikeda, Y., 2005.
Distributions of sedimentary POPs (persistent organic pollutants) in
Tokyo Bay-results from the survey of POPs in Tokyo Bay in 2002.
Rep. Hydrogr. Oceanogr. Res. 41, 35–50.
Tanabe, S., Ramesh, A., Sakashita, D., Iwata, H., Tatsukawa, R., 1991.
Fate of HCH (BHC) in tropical paddy field: application test in south
India. Int. J. Environ. Anal. Chem. 45, 45–53.
Venkatesan, M.I., Leon, R.P., Geen, A.V., Luoma, S.N., 1999. Chlori-
nated hydrocarbon pesticides and polychlorinated biphenyls in sedi-
ment cores from San Francisco Bay. Mar. Chem. 64, 85–97.
Walker, K., Vallero, D.A., Lewis, R.G., 1999. Factors influencing the
distribution of lindane and other hexachlorocyclohexanes in the
environment. Environ. Sci. Technol. 33, 4373–4378.