Tracing Wastewater Contamination in Sediments from Ulsan Bay of Korea Using Nonylphenolic Compounds

Abstract

Nonylphenolic compounds (NPs) were determined in 38 surface sediment samples from Ulsan Bay and vicinity. Concentrations of NPs were compared with the levels of other anthropogenic contaminants, to have a better understanding of the contamination origin. Concentrations of nonylphenol (NP), and nonylphenol mono-and di-ethoxylates (NP 12 EO) were 12.8-5772 ng/g dry wt (average: 351 ng/g dry wt), and 29.8-1204 ng/g dry wt (average: 194 ng/g dry wt), respectively. The range of NPs in the present study was higher than or comparable to those reported in other locations of Korean coastal waters. High concentrations of NPs were found in river and/or stream sediments receiving wastewater discharges from industrial complexes, and often exceeded the screening and ecotoxicological benchmarks. The concentrations of NPs in sediments correlated well with coprostanol (a fecal sterol) and polybrominated diphenyl ethers, suggesting that contamination from NPs in the bay are closely associated with industrial and domestic effluents containing wastewater con-taminants and toxic chemicals.

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한국환경분석학회지 제14권 (제1호) 5~11, 2011
J. of the Korea Society for Environmental Analysis
Tracing Wastewater Contamination in Sediments from Ulsan Bay
of Korea Using Nonylphenolic Compounds
Minkyu Choi†, Hyo-Bang Moon1, and Hee-Gu Choi
Marine Environment Research Division, National Fisheries Research and Development Institute (NFRDI),
Busan 619-705, Korea
1Department of Environmental Marine Sciences, College of Science and Technology, Hanyang University,
Ansan 426-791, Korea
Received February 9, 2011/Accepted March 11, 2011
Nonylphenolic compounds (NPs) were determined in 38 surface sediment samples from Ulsan Bay and
vicinity. Concentrations of NPs were compared with the levels of other anthropogenic contaminants, to have
a better understanding of the contamination origin. Concentrations of nonylphenol (NP), and nonylphenol
mono- and di-ethoxylates (NP12EO) were 12.8-5772 ng/g dry wt (average: 351 ng/g dry wt), and 29.8-1204
ng/g dry wt (average: 194 ng/g dry wt), respectively. The range of NPs in the present study was higher than
or comparable to those reported in other locations of Korean coastal waters. High concentrations of NPs were
found in river and/or stream sediments receiving wastewater discharges from industrial complexes, and often
exceeded the screening and ecotoxicological benchmarks. The concentrations of NPs in sediments correlated
well with coprostanol (a fecal sterol) and polybrominated diphenyl ethers, suggesting that contamination from
NPs in the bay are closely associated with industrial and domestic effluents containing wastewater con-
taminants and toxic chemicals.
Key words: nonylphenol, industrial wastewater, sewage, coprostanol, PBDEs
1. Introduction
Nonylphenolic compounds (NPs) are a group of non-
ionic surfactants widely used in a variety of industrial
processes as detergents, wetting agents, dispersing
agents and emulsifiers, and residential and commercial
cleaning products since the 1940s. Among the NPs,
nonylphenol (NP) and nonylphenol mono- and di-
ethoxylates (NP12EO) are the most persistent and
therefore most prominent in the aquatic environment1,2).
These contaminants are frequently found in municipal
effluents, particularly in effluents from industrial
areas3-6) and have been used as a marker for industrial
contamination6-8).
Low concentration of NPs can disrupt the endocrine
systems of aquatic organisms9,10). At present, guidelines
have been proposed in various countries for NPs in sed-
iments to protect aquatic life1,11,12). In Korea, all NPs
(11,200 tons in 2004) are imported, and used primarily
as surfactants (60%), followed by additives for paints
and epoxy resins (12%), copper laminates (9%), ink
binder (5%), agricultural pesticides (2%), and other
uses13). The Korean government has managed NPs as
priority chemicals since 2001. A ban on their use was
started for kitchen cleaners in 2002, for all domestic
applications in 2007, and for inks and paints in 2010.
Industrial complexes and urban areas located in
industrialized bays have been reported to be major
sources of organic contamination in Korean coastal
waters6,14-19). Trace organic contaminants including
xenoestrogens are introduced into the industrialized
bays from point and/or nonpoint sources such as rivers
through discharge of industrial waste, municipal sew-
age, and urban runoff6,14,15,17,18), and wastewater treat-
†To whom correspondence should be addressed.
Tel: 82-51-720-2531, Fax: 82-51-720-2515, E-mail: mkchoi@nfrdi.go.kr

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6Minkyu Choi, Hyo-Bang Moon, and Hee-Gu Choi
ment plant effluents20). Ulsan Bay is one of the most
industrialized bays in Korea and the special manage-
ment coastal zone, which contains the most active
industrial ports which contribute to about 20% of the
total import and export activities in Korea, and has also
large industrial area with more than 500 factories
(chemical and oil-refining plants, shipyards, motors,
etc), contributing to 12.2% of industrial production in
Korea21). Ulsan City of 1,055 km2 area surrounding the
bay is highly populated (over 1 million people). The
industrialization and urbanization in Ulsan Bay is asso-
ciated with increased organic contaminant levels6,14,17,18).
Although intensive surveys of NPs contamination at
locations adjacent to industrial areas have been reported
in Lake Shihwa and Masan Bay5,14,15,22-24), little atten-
tion has been focused in Ulsan Bay14). The present
study investigated current contamination levels, and
sources of NPs in marine sediments from Ulsan bay,
Korea. We also investigated correlation between NPs
and other anthropogenic contaminants such as copros-
tanol (a fecal sterol), polybrominated diphenyl ethers
(PBDEs), and butyltins (BTs), to provide implications
for coastal management.
2. Materials and Methods
2.1. Sample collection
A total of 38 sediment samples from Ulsan Bay and
its vicinity were collected in February 2003 (Fig. 1).
The sampling area includes Ulsan Bay (U1-U15), Onsan
Bay (O1-O8), Jangsaengpo Harbor (G1-G5), Taehwa
River (T1-T7), and Woihang River (W1-W3). Sediment
samples (0-4 cm depth) were collected using a box core
sampler, on the basis of the National Marine Environ-
mental Monitoring Program in Korea. The collected
samples were individually wrapped in aluminum foil and
immediately frozen. Sediment samples were trans-
ported to the laboratory, stored at -20oC, and subse-
quently freeze dried.
2.2. Analytical procedures
The sediment samples were analyzed for NPs (NP
and NP12EO) according to the method of Choi et al6).
For NPs (NP and NP12EO; Cambridge Isotope Labora-
tories, Andover, MA, USA), the freeze-dried sediment
samples were extracted by a mechanical shaker using
dichloromethane (ultra residue analysis; J.T. Baker, Phil-
lipsburg, NJ, USA). A surrogate standard, nonylphenol-
13C6 (Cambridge Isotope Laboratories, Andover, MA,
USA) was added to the matrix before extraction. The
extracts were concentrated to about 1 ml under a gentle
stream of dry nitrogen. Water and sulfur were removed
from the extract using anhydrous sodium sulfate (Kanto,
Tokyo, Japan) and copper (Sigma-Aldrich, St. Louis,
MO, USA), respectively. The extract was concentrated
to 0.5 ml, derivatized using N,O-bis [trimethylsilyl] tri-
fluoroacetaminide (BSTFA, Sigma-Aldrich), and then
cleaned by passage through a Florisil (60-100 mesh,
reagent grade, Sigma-Aldrich) chromatography column.
After the addition of internal standards, the concen-
trated eluents were transferred to vials for instrumental
analysis.
NPs were quantified using a gas chromatograph (GC-
6890 series; Agilent, Wilmington, DE, USA) equipped
with an MS (5973N; Agilent). The capillary column
used was a DB-5MS (30 m length, 0.25 mm inner diam-
Fig. 1. Sampling locations of surface sediments from
Ulsan Bay and its vicinity, Korea.