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Chemosphere 56 (2004) 1–6
www.elsevier.com/locate/chemosphere
Seasonal flux of nonylphenol in Han River, Korea
Donghao Li a,*, Minseon Kim a, Won Joon Shim a, Un Hyuk Yim a,Jae-Ryoung Oh a, Young-Jin Kwon b
a South Sea Institute, Korea Ocean Research and Development Institute, Jangmok-myon 391, Geoje-shi,
Gyungsangnamdo 656-834, South Koreab Department of Environmental Science, Kangwon National University, 192-1 Hyoja-dong, Chunchon 200-701, South Korea
Received 14 October 2003; received in revised form 7 January 2004; accepted 27 January 2004
Abstract
In order to understand the behavior of nonylphenol (NP) in Han River, water, suspended particle and sediment
samples were analyzed during summer, autumn and winter. Concentrations of nonylphenol in water ranged from 23.2
to 187.6 ng/l, in suspended particle from 6.8 to 190.8 ng/l and in sediment from 25.4 to 932.0 ng/g drywt. An increasing
trend in the concentration is noticed in all matrices along down the river. In case of water and suspended particle,
concentrations were higher in warmer season than in colder season. Percentage of nonylphenol in the suspended particle
phase decreased from 67% to 28% with decreasing temperature in water. A reasonable correlation (R2 ¼ 0:63) wasobtained for water and suspended particle. The partition coefficient LogKp is 4.8. No seasonal variation of the con-
centration in sediment is noticed in this study.
� 2004 Elsevier Ltd. All rights reserved.
Keywords: Alkylphenols (APs); Nonylphenol (NP); Endocrine disruptor chemical; River
1. Introduction
Nonylphenol is an endocrine disruptor. It is a deg-
radation product of alkylphenol polyethoxylates (APn-
EOs) that is used in the world as nonionic surfactant and
detergent in industrial and domestic applications over
the last five decades (Giger et al., 1984). Due to persis-
tence in the environment, it is bioconcentrated in or-
ganisms. In fact, high levels of nonylphenol were found
from seafood and fish caught in Italian coast and Japa-
nese rivers, respectively (Ferrara et al., 2001; Tsuda et al.,
2001). Although the APnEOs are less toxic to human and
organisms, the degradation products such as nonylphe-
nol is toxic with hormone like properties. Yadetie and
Male (2002) and Hemmer et al. (2002) reported that
*Corresponding author. Tel.: +82-55-639-8671; fax: +82-55-
639-8689.
E-mail address: [email protected] (D. Li).
0045-6535/$ - see front matter � 2004 Elsevier Ltd. All rights reserv
doi:10.1016/j.chemosphere.2004.01.034
nonylphenol has adverse effect on fish hormone system
even at low concentrations. In order to avoid any adverse
toxic effect on humans and biota, many countries have
banned or regulated recently the production and appli-
cation of APnEOs (Renner, 1997; Isobe et al., 2001).
Though APnEOs have been in use for several decades,
research on nonylphenol that helps to regulate these
chemicals is hardly found in Korea. As a result, high
levels of nonylphenol were found in several river estu-
aries and lakes in Korea. For examples, we reported in a
recent paper (Li et al., 2004) that the average concen-
tration of nonylphenol in creek water was 3.6 lg/l. Khim
et al. (1999) reported nonylphenol concentrations rang-
ing from 20.2 to 1820 ng/g drywt in Shihwa Lake sedi-
ments. However, there is no reported data in riverine
system though most of APnEOs is disposed as surfactant
and detergent, directly into aquatic systems such as riv-
ers, lakes and seas via drainage. In fact, the rivers are
the major transport media of alkylphenol pollutants in
Korea.
ed.
2 D. Li et al. / Chemosphere 56 (2004) 1–6
Han River is the longest and biggest in Korea. It
flows over a distance of 482 km, with an area of 26 000
km2. The average depth of the river in the center is about
6 m. It supplies drinking water to over twenty millions
people living around the river. Among them, twelve
millions live in Seoul City. Several sub-streams of Han
River pass through the city. As a result, this river
accumulates large amount of wastewater and sewage
from Seoul. It is doubtful that the Seoul wastewater
facility removes these compounds before allowing the
drainage to the river (on the contrary, the warm water
condition in the facility promotes degradation of APn-
EOs to nonylphenol). The chemical burden of nonyl-
phenol increases tremendously during monsoon season
with heavy floods when wastewater is discharged di-
rectly into the river. The capacity of the plant is insuf-
ficient to treat the large volume of waste water produced
during the rainy seasons. According to Korean Envi-
ronmental Ministry report in 2001, the COD and BOD
ranged from 3.8 to 59.4 and from 0.8 to 19.7 mg/kg,
respectively, and the suspended particle in the river
ranged from 4.4 to 20.0 mg/l (Ministry of Environment
Republic of Korea, 2002).
In order to understand quantitatively the distribution
and behavioral characteristics of phenolic compounds
in the Han River environment, nonylphenol was deter-
mined from water, suspended particle and sediment
samples in this study. Modeling of nonylphenol in the
Han River environment is essential for regulation of
these compounds in the Korean environment. One such
modeling study was carried out in our laboratory and in
Seoul University recently.
2. Materials and methods
2.1. Solvents and standards
All organic solvents including acetone, dichlorome-
thane and hexane were of pesticide grade and were
purchased from Caledon (Canada). Nonylphenol, sily-
lation reagent BSTFA (N,O-bis(trimethylsilyl) trifluo-
roacetamide), surrogate standard (bisphenol A-d14), gas
chromatography internal standards (GCIS) including
naphthalene-d8, phenanthrene-d10 and pyrene-d10 were
obtained form Chem Service (USA). The purity of all
standards was up to 98%. HCl was purchased from
Merck. Florisil was obtained from Supelco. In order to
remove contaminants, the Florisil, Glass Fiber Filter
and aluminum foil were burned at 450 �C for 12 h, then
Florisil was activated at 120 �C until used and Glass
Fiber Filter and aluminum foil were stored in vacuum
desiccator. The copper was obtained from Merck, it was
used to remove sulfur from the environmental sample
extract after activating with concentrated HCl. All
standards were prepared at 100 mg/l as a stock solution
with hexane acetone mixture (1:1). It was diluted
approximately to calibration standards, surrogate stan-
dard (2 mg/l) and gas chromatography internal standard
(GCIS) (2 mg/l) with acetone.
2.2. Sampling sites and sample collection
In order to understand spatial distribution of no-
nylphenol in overall Han River, sediment samples were
collected from ten sites in Aug. 2001 as shown in Fig. 1.
Among them, site CC, CP, YZ, YP and PD were located
in upstream, site KP, TY and KH were located in
downstream, site KN and MW were located in the Seoul
City vicinity. In order to study seasonal flux of nonyl-
phenol in Han River, the study focused on KN and
MW, and the sites were divided into five stations,
respectively. Water, suspended particle and sediment
samples were collected seasonally at these sites. The
average water temperature in Aug., Oct. and Dec. were
27, 19 and 5 �C, respectively. One liter of filtered water
sample (0.45 lm) was collected in 1 l glass bottle with
Teflon lined cap. It was acidified to 0.01 M with 6 M
HCl in order to protect it from biodegradation and to
increase the stability of target phenolic analytes. The
water samples were analyzed within 3 days. The filtered
suspended particle matrix were wrapped with aluminum
foil and stored in a glass bottle at )20 �C until analyzed.
The surface sediment samples were sampled with van
Veen Grap, then collected in glass bottle with Teflon
lined cap and stored at about )20 �C until analysis.
2.3. Extraction and analysis
Water, suspended particle and sediment samples were
treated according to methods reported by Li et al. (2001,
2003). The brief analytical procedures were as follows.
Acidified water samples were extracted using liquid li-
quid extraction (LLE) with dichloromethane after
addition of appropriate amount of surrogate internal
standard. The extracts were concentrated to 2 ml with
rotary evaporator at 35 �C and reduced pressure. It was
concentrated again with a gentle flow of dry nitrogen
following addition of acetone in order to carry out fast
silyl derivatization. It was submitted to on column
derivatization and Florisil cleanup. Six milliliters of
hexane was used as eluent. The concentrated eluents
were analyzed by gas chromatography (Shimadzu GC-
17A)–mass spectrometry (Shimadzu MS QP-5000) with
selected ion monitoring mode after addition of 200 ng of
GCIS. Conditions of GC/MS analysis were described in
a previous report (Li et al., 2001). Wet suspended par-
ticle and 3 g of wet sediment samples were treated into a
solid suspension by adding appropriate amount of 0.1 M
HCl solution. It was digested for 10 min, and then ex-
tracted three times using shaking technique with three
portions of 5 ml dichloromethane. The combined extract
Fig. 1. Location of sampling sites.
D. Li et al. / Chemosphere 56 (2004) 1–6 3
was concentrated to about 1 ml under a gentle dry
nitrogen flow. In order to remove water and sulfur from
the extract, anhydride sodium sulfate and copper were
added sequentially into the extract. The extract was
transferred into another glass vial that was cleaned
previously with two rinsing of dichloromethane. It was
concentrated again to 0.2 ml under a gentle flow of dry
nitrogen, and then 1 ml of acetone was added to the
concentrated extract. It was concentrated further to
0.5 ml. Following processes including derivatization,
clean-up and concentration steps were same with in
water sample treatment.
3. Results and discussion
In Aug. 2001, sediment samples were collected in
Han River, from upstream to downstream as indicated
in Fig. 1. The results are shown in Fig. 2. Nonylphenol
concentrations ranged from 46 to 256 ng/g drywt. Levels
0
50
100
150
200
250
CC CP YZ YP PD KN MW KP TY KH
Sampling site along the river flow down
Con
cent
ratio
n (n
g/g
dry
wt.)
of
nony
lphe
nol i
n se
dim
ent
upstream Seoul city Downstream
Fig. 2. Nonylphenol distribution in the sediment of the Han
River.
of nonylphenol recorded in downstream river were
generally higher than in the upstream. Though an in-
creasing trend was noticed just downstream the city of
Seoul, a dramatic increase in concentration was noticed
in locations near Seoul City. This is up to five times, the
concentration noticed elsewhere. This might be due to
discharge of effluents containing large amount of sewage
and wastewater from Seoul City.
In order to understand seasonal distribution levels of
nonylphenol in Han River, water, suspended particle
and sediment samples were analyzed in Aug. (warmer),
Oct. (medium), Dec. (colder) in 2001. As listed in Table
1, concentration levels of nonylphenol in water de-
creased with decreasing water temperature and in sum-
mer is generally two times higher. Usage of APnEOs in
general and the activity of microorganism in the riverine
system may play a role on the levels of nonylphenol.
Among them, the amounts of APnEOs used are not
likely to change during seasons and hence the seasonal
variation of nonylphenol levels noticed in our study is
principally due to microbial activity. Several papers re-
ported that APnEOs have rapidly degraded into no-
nylphenol and shortened alkylphenol ethoxylates at high
temperature, while the degradation rate becomes very
slow at low temperature (Tanghe et al., 1998; Staples
et al., 1999; Manzano et al., 1999).
The concentration of nonylphenol showed not only
seasonal flux but showed a spatial trend as well. Levels
of nonylphenol increased in the downstream water in all
seasons as shown in Table 1. For example, over 100 ng/l
(except St 7) of nonylphenol were determined at the
downstream site in Aug., while less than 85 ng/l (except
St 5) of it was found at the upstream site in the same
season. Ding et al. (1999) and Sabik et al. (2003) in the
Lao-Jie and St. Lawrence River reported similar trends,
respectively. The river after passing through the city gets
R2
= 0.63
0
50
100
150
200
250
0 50 100 150 200
NP in water
NP
in s
uspe
nded
par
ticle
Fig. 3. Correlation of nonylphenol in water (ng/l) and sus-
pended particle (ng/l).
Table 1
Concentrations of nonylphenol in water, suspended particle and sediment from Han River in 2001
Site Water (ng/l) Suspended particle (ng/l) Sediment (ng/g drywt)
Aug. Oct. Dec. Aug. Oct. Dec. Aug. Oct. Dec.
St1 83.0 42.0 23.2 123.5(5.9)b 18.0(1.4) 20.9(6.9) 114.3 79.6 67.3
St2 NAa 46.2 17.3 190.8(9.5) 26.0(1.1) 6.8(1.6) 87.4 81.3 40.3
St3 71.4 44.6 72.0 115.9(3.8) 18.0(6.2) 7.8(2.3) 95.4 35.1 116.8
St4 83.1 56.3 36.7 NA 22.0(9.3) 17.1(4.3) 69.8 194.1 25.4
St5 109.7 60.2 20.3 130.8(9.2) 34.0(5.9) 13.4(2.8) 56.3 85.0 44.9
St6 104.5 50.3 50.8 151.0(8.9) 28.0(1.9) 20.4(4.2) 231.2 305.2 249.3
St7 79.0 70.9 27.9 133.1(7.1) 44.0(1.9) 26.0(2.8) 249.7 550.2 374.7
St8 105.2 68.5 55.7 109.6(9.5) 48.0(3.1) 14.4(1.0) 356.5 144.5 411.8
St9 187.6 76.5 71.3 156.1(16.6) 60.0(2.2) 20.4(2.3) 235.0 228.0 259.3
St10 100.7 84.1 56.9 160.1(7.9) 56.0(3.3) 23.0(2.6) 207.6 732.4 932.0
aNA means not analyzed.bConcentration (lg/g drywt) was normalized by dry weight of suspended particle.
4 D. Li et al. / Chemosphere 56 (2004) 1–6
contaminated thus showing high levels along the
downstream.
Nonylphenol, the degradation product of APnEOs,
is relatively hydrophobic compared with its parental
compound that is readily water-soluble as detergents
and surfactants. So nonylphenol is readily adsorbed on
surfaces of suspended particle and sediment in aquatic
systems, for a long period. Table 1 shows concentrations
of nonylphenol in suspended particles that ranged from
1.0 to 6.9 in Dec., from 1.1 to 9.3 in Oct. and from 3.8 to
16.6 lg/g drywt in Aug. The levels of nonylphenol in
suspended particle varied by season and increased along
the downstream water in all seasons except a few sites.
High concentrations of nonylphenol were found in
warmer season, and the concentrations reduced with
decreasing water temperature resulting in low concen-
tration in winter. Takada et al. has reported similar re-
sults in the investigation of nonylphenol from the
Shiwada River, the average concentration of nonylphe-
nol in suspended particle are 3.54 lg/g dry wt and the
concentrations varied by season. As described above, the
behavior of nonylphenol in water showed similar trend.
It indicates that equilibrium of nonylphenol in water
and suspended particle is reached rapidly and that pri-
marily affect the concentration levels of nonylphenol in
suspended particle. In such a case, reasonable correla-
tion of nonylphenol in water and suspended particle is
expected. Our results are presented in Fig. 3. In which,
the partition coefficient was obtained as following:
LogKp ¼ LogCss dry wt=Cw:
The Css and Cw are representing concentration of no-
nylphenol in suspended particle and in water, respec-
tively. Calculated average of LogKp is 4.8 with 13.5 of
relative standard deviation. Since there is reasonable
seasonal and spatial trend correlation of nonylphenol
distribution profile in water and suspended particle, a
reasonable correlation (R2 ¼ 0:63) was obtained. It
clearly indicates that nonylphenol was readily absorbed
to suspended particle in the Han River water system.
In the Han River, over 60% of nonylphenol were
found in suspended particle phase in Aug. as shown in
Fig. 4. This decreased with decreasing temperatures in
the winter. This could also be due to the fact that high
particle concentrations are usually seen in the rainy
season (Aug.) and low concentrations in the dry season
(Dec.). The nonylphenol level in suspended particle in
our study is two times higher than those reported by
others. In the Tamagawa river and the Sumidagawa
river in Japan, only about 20% of nonylphenol were
found in the suspended particle due to effective removal
of suspended particles during sewage treatment pro-
cesses (Isobe et al., 2001).
These contaminated suspended particles settle finally
into the bottom of the river. It is reasonable to expect
that large amount of nonylphenol is present in the sed-
iment of the Han River as well. In fact high concentra-
tions of nonylphenol were detected from the sediment.
The nonylphenol ranged from 25.4 to 932.0 ng/g drywt
Aug. Oct. Dec.Sampling date
Perc
enta
ge (
%)
of n
onyl
phen
ol
water
0
20
40
60
80
100
suspended particle
Fig. 4. Percentage of nonylphenol in water and suspended
particle.
D. Li et al. / Chemosphere 56 (2004) 1–6 5
as shown in Table 1. Seasonal variation of nonylphenol
as seen in water and particles are not seen with sedi-
ments (Figure not shown). The spatial distribution
indicates an increasing trend in river sediment, down-
stream. This is at least three times higher downstream
than those found in the upstream sampling sites. It
indicates that most of the nonylphenol adsorbed by
suspended particle during the river flow thorough the
Seoul City settled finally to the bottom. The average
partition coefficient (LogKp) calculated from the every
site and season ranged from 2.7 to 4.2. There is no
reasonable correlation between nonylphenol in sediment
and water (R2 ¼ 0:02) (Figure not shown). This might be
due to (1), flow rate of Han River is relatively fast, not
allowing time for equilibrium partitioning (2), degrada-
tion rates of nonylphenol and its mother compound
APnEOs in the water are significantly faster than those
in sediment. (3), concentration of nonylphenol in water
varied through seasons. Various factors such as tem-
perature, flow rate, sedimentation rate, and particle size
etc., may affect concentration of nonylphenol in sedi-
ment and water and a detailed study is needed to
understand this fully.
Although measured average concentrations of no-
nylphenol in water, suspended particle and sediment are
much lower than reported acute toxicity levels, some
individual values in suspended particle are nearly the
same as that of reported toxic levels. Regulatory levels of
nonylphenol in USA and Europe are 1 lg/l in water
(Renner, 1997). Naylor (1995) reported that the lowest
effective concentration of nonylphenol in shrimp for
subacute toxicity is 26 ng/g drywt in sediment. The
threshold level of nonylphenol for fish vitellogenin
stimulation is 1 lg/l (Schwaiger et al., 2002). Nice et al.
(2000) also reported that the exposure of Pacific oyster
larvae, Crassostrea gigas, to nonylphenol is as low as 0.1
lg/l causing delay in development and a significant de-
crease in survival rate. Based on those reports, levels of
nonylphenol in suspended particle might be potentially
hazardous to organisms in the river. In addition, the ef-
fect on humans and other aquatic organisms through
accumulation and persistence in the long term is not
negligible. In order to protect humans and biota from the
environmental effect of nonylphenol, selective removal of
suspended particle from the Han River and restrictions
on the usage and discharge of APnEOs are necessary.
Acknowledgements
The authors are grateful to Dr. Narayanan Kannan
for his valuable comments on our manuscripts. This
study is a part of a project supported by National
Institute of Environmental Research, Korea (Project
No. PG333-00). We thank the captain and crews of
boats in the Han River Management Office for helping
the sample collection.
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