Environ Monit Assess (2008) 138:255–272
DOI 10.1007/s10661-007-9795-y
Distribution of heavy metals in the dissolved and suspended
phase of the sea-surface microlayer, seawater column
and in sediments of Singapore’s coastal environment
Dang The Cuong & Subramanian Karuppiah &
Jeffrey Philip Obbard
Received: 26 July 2006 / Accepted: 20 April 2007 / Published online: 12 June 2007
# Springer Science + Business Media B.V. 2007
Abstract Concentrations of heavy metals were de-
termined in the water column (including the sea-
surface microlayer, subsurface, mid-depth and bottom
water) and sediments from Singapore’s coastal envi-
ronment. The concentration ranges for As, Cd, Cr,
Cu, Ni, Pb and Zn in the seawater dissolved phase
(DP) were 0.34–2.04, 0.013–0.109, 0.07–0.35, 0.23–
1.16, 0.28–0.78, 0.009–0.062 and 0.97–3.66 μg L−1
respectively. The ranges for Cd, Cr, Cu, Ni, Pb and
Zn in the suspended particulate matter (SPM) were
0.16–0.73, 6.72–53.93, 12.87–118.29, 4.34–60.71,
1.10–6.08 and 43.09–370.49 μg g−1, respectively.
Heavy metal concentrations in sediments ranged
between 0.054–0.217, 37.48–50.52, 6.30–21.01,
13.27–26.59, 24.14–37.28 and 48.20–62.36 μg g−1
for Cd, Cr, Cu, Ni, Pb and Zn, respectively. The
lowest concentrations of metals in the DP and SPM
were most frequently found in the subsurface water
while the highest concentrations were mostly observed
in the SML and bottom water. Overall, heavy metals in
both the dissolved and particulate fractions have depth
D. T. Cuong : J. P. Obbard
Division of Environmental Science & Engineering,
National University of Singapore,
4 Engineering Drive 4,
Singapore 117576, Singapore
D. T. Cuong (*) : S. Karuppiah : J. P. Obbard
Tropical Marine Science Institute,
National University of Singapore,
14 Kent Ridge Road,
Singapore 119223, Singapore
e-mail: tmsdtc@nus.edu.sg
profiles that show a decreasing trend of concentrations
from the subsurface to the bottom water, indicating that
the prevalence of metals is linked to the marine
biological cycle. In comparison to data from Greece,
Malaysia and USA, the levels of metals in the DP are
considered to be low in Singapore. Higher concentra-
tions of particulate metals were reported for the
Northern Adriatic Sea and the Rhine/Meuse estuary in
the Netherlands compared to values reported in this
study. The marine sediments in Singapore are not
heavily contaminated when compared to metal levels
in marine sediments from other countries such as
Thailand, Japan, Korea, Spain and China.
Keywords Sea-surface microlayer . Seawater .
Suspended particulate matter . Sediments .
Southeast Asia
Introduction
Many heavy metals are essential to the metabolism of
many marine organisms and are bio-accumulated from
the marine environment. However, all metals become
toxic above threshold bio-available levels (Blackmore
1998). Their global distribution and impact upon
marine organisms and human health are of great
concern due to their persistent, non-biodegradable and
toxic properties (Florence 1982; Tokalioğlu et al. 2002;
Yuan et al. 2004). Sources of heavy metals in the
marine environment include atmospheric fallout (con-
sisting of both wet and dry deposition) riverine inputs,
256
wastewater discharges and re-suspension of contami-
nated bottom sediments (Mart et al. 1982; Poikāne
et al. 2005). Suspended particulate matter (SPM) and
sediments are the main sources of heavy metals in the
marine ecosystem and play an important role in the
transport and storage of potentially hazardous metals.
There are various processes affecting the distribu-
tion and behavior of heavy metals in the seawater
column and underlying sediments, including hydro-
dynamic mixing, adsorption onto both inorganic and
organic phases, complexation, precipitation, biologi-
cal uptake and diffusion from bottom sediments
(Blackmore 1998; Zeri and Voutsinou-Taliadouri
2003). The fate and transfer of many heavy metals
is mediated by biogeochemical cycling processes,
where metals are often depleted in the surface water
and enriched with depth due to gravitational settling
of dead biota and faecal pellets, and subsequent
decomposition and release of metals into the water
column (Mart et al. 1982; Westerlund and Öhman
1991). Meanwhile, the sea-surface microlayer (SML),
which represents the uppermost layer of the ocean
(thickness 50–100 μm), can serve as a reservoir for
heavy metals with enrichment relative to the under-
lying water column. The enrichment of heavy metals,
especially particulate metals, in the SML may be
derived from both atmospheric deposition and bubble
floatation from the water column (Hardy 1982; Migon
and Nicolas 1998).
Although a number of studies have been completed
on the distribution and fate of heavy metals in the water
column and sediments around the world (Kuwabara
et al. 1989; Westerlund and Öhman 1991; Poikāne
et al. 2005), available data for the Asian region are
sparse. In Singapore, there have been a few studies
providing some data on dissolved and particulate
metal concentrations in sea water and marine sedi-
ments. Goh and Chou (1997) carried out an investi-
gation over a period of two years to monitor the levels
of copper, zinc, lead, cadmium at twenty locations
comprising mainland coastal and offshore areas
around Singapore from December, 1990 to July,
1992. In 1993, a study of the metal concentrations
in sediment cores collected along the east–west axis
of the Strait of Johor between Singapore and Malaysia
was undertaken (Wood et al. 1997). More recently, a
study on the environmental impact of heavy metals
from dredged and re-suspended sediments on phyto-
plankton and bacteria was conducted at Ponggol
Environ Monit Assess (2008) 138:255–272
Estuary, located on the north-eastern coast of Singa-
pore (Nayar et al. 2004). To date, however, vertical
distribution data of heavy metals in seawater columns
of Singapore’s marine environment are lacking. In
this study, heavy metal concentrations were deter-
mined in both seawater and suspended particulate
matter in the water column, as well as in sediments
from two coastal regions of Singapore. The objectives
of this study were to: (1) determine prevailing heavy
metal levels and their distribution in the water column
and sediments at two sampling sites with contrasting
hydrodynamic characteristics in the coastal marine
environment of Singapore; (2) determine the enrich-
ment of heavy metals in the sea-surface microlayer
and the sediment-bottom water layer, which represent
the uppermost and the lowest boundary layer of the
water column; and (3) evaluate levels relative to
similar data reported from other countries.
Materials and methods
Study area
Samples including seawater, suspended particulate
matters and sediments were collected from two coastal
regions of Singapore (Kranji and Pulau Tekong) in
June and July, 2004 (see Fig. 1). Kranji (Station 1) is
situated in the West Johor Strait, adjacent to man-
grove habitat and nearby fish farming activities. This
station is also close to a causeway built across the
Johor Straits in 1924, linking Singapore and Malay-
sia. As a result, the water flow in this coastal region is
negligible and fine-grained sediments are readily
deposited. Water currents are not strong enough to
disperse pollutants to oceanic waters at the ends of the
Johor Straits (Wood et al. 1997). Meanwhile, Pulau
Tekong, the largest of Singapore’s outlying islands, is
situated at the confluence of the Johor Straits and the
Sungai Johor estuaries, with Singapore to the east and
Malaysia to the south, where water currents are strong
and the water column is well-mixed. This station is
adjacent to heavy shipping traffic and river dis-
charges.
Cleaning procedure
All containers, syringes, pipette tips, centrifuge tubes,
beakers, volumetric flask, sample vials used for sample
Environ Monit Assess (2008) 138:255–272
Fig. 1 Location of Kranji
and Tekong in Singapore
collection and storage were made of high density
polyethylene (HDPE) or polytetrafluoroethylene
(PTFE). The lab-ware was soaked for 24 h in a hot
2% detergent solution, and then thoroughly rinsed with
hot tap water followed by DI water. Materials were
then allowed to stand for 24 h at room temperature in a
5% HNO3 solution and then thoroughly rinsed with
DI water. Volumetric flasks and sample containers
were filled with 5% HNO3 until use. Beakers,
syringes and pipette tips were dried in the oven at
50°C and kept wrapped in pre-cleaned plastic. Filters
were rinsed with 5% HNO3 solution three times prior
to use.
Sample collection
Seawater samples (2 L each) were collected in duplicate
from the SML, subsurface, mid and bottom layer of the
water column at the two sampling sites. As the
maximum depths of the two sampling sites differed
(6.8 and 11 m at Station 1 and Station 2, respectively),
samples from subsurface, mid and bottom water were
collected at depths of 1, 4.8, and 6.5 m at Station 1 and at
1, 7, and 10.5 m at Station 2, respectively. The SML
samples (2 L each) were collected using a rotating drum
257
sampler (Harvey 1966; Carlson et al. 1988). The
detailed sampling procedure for collecting the SML
has been described in a previous manuscript (Wurl and
Obbard 2006). Briefly, the SML sampler consisting of
a rotating glass drum, Teflon tubing, pump and a
sample container was attached to a research vessel by a
5 m long aluminum bar fixed on the starboard. Before
sample collection, the sampler was operated in the sea
for 10 min to rinse the tubing, pumps and the glass
drum with seawater. The SML sample on the surface
of the rotating glass drum (diameter 300 mm, length
500 mm, RPM 7-8) was collected into the container
using a rubber blade, then pumped into the plastic
sampling bottles. The subsurface, mid and bottom
water from the water column samples was collected
using a 12 V DC Teflon pump. Sediment samples were
collected in triplicate from the surface layer (10–
15 cm) of the sea bed using a Van Veen grab sampler.
This 1,000 cm2-sample-area grab sampler is made of
AISI 316 stainless steel and the surface is electro
polished with the dimensions of 33×33×115 cm.
Sediment sub-samples were taken with a disposable
plastic spoon. Samples were stored in polypropylene
centrifuge tubes and kept in the ice box prior to
laboratory analysis.
258
Sample preparation
All seawater samples (the SML, subsurface, mid and
bottom waters) were immediately filtered onboard
through acid pre-cleaned cellulose nitrate membrane
filters (Whatman, 0.45 μm, 47 mm ∅) under vacuum.
In the laboratory, the filtered seawater samples were
then acidified by addition of nitric acid to a pH<2 and
stored at 4°C. The 0.45 μm filters containing SPM
were kept in acid pre-cleaned plastic petri dishes and
stored at −20°C prior to further processing and
analysis. Sediment samples were stored in polypro-
pylene centrifuge tubes and kept in the freezer at
−20°C prior to processing and analysis.
In the laboratory, the 0.45 μm filters containing
SPM from the SML, subsurface, mid and bottom
layer were dried at room temperature (30±2°C) and
heated in the oven at 60°C for 24 h. Sediment
samples were defrosted and air-dried at 30±2°C and
then ground with a pestle and mortar and sieved
(<63 μm). Metal analyses was conducted on the
<63 μm fraction due to the strong association of
metals with fine-grained sediments (Horowitz and
Elrick 1987; Moore et al. 1989; Goh and Chou 1997;
Tam and Wong 2000; Che et al. 2003). The moisture
content of the dried sediment samples was calculated
by heating a portion of sediment in an oven at 105±2°C
to constant weight. Sediment data in this study are
reported on a dry weight basis.
Sub-samples for SPM, DOC and TOC analysis
were filtered onboard through a pre-cleaned GF/A
filter (Whatman, 1.6 μm, 47 mm) under vacuum.
Sub-samples for DOC analysis were kept in glass test
tubes with teflon-lined caps and stored at −20°C. The
GF/A filters for SPM and TOC analysis were stored
in glass petri dishes at −20°C.
Sample analysis
The filtered seawater samples were directly analyzed
by inductively coupled plasma-mass spectroscopy
(ICP-MS) using an ELAN 6100 instrument. The
precision and accuracy of the analytical procedure was
validated using a seawater reference material (CASS-4,
National Research Council, Ottawa, Ontario, Canada)
for four replicates.
The dried 0.45 μm filters and sediment samples
were digested using a microwave-assisted acid diges-
tion procedure. A detailed description of this procedure
Environ Monit Assess (2008) 138:255–272
is described in U.S. EPA method 3052. Briefly, three
replicates of 0.5 g dried sediment sample were
analyzed by digestion with a mixture (3:1) of acid
(9 ml concentrated nitric acid and 3 ml concentrated
hydrofluoric acid). The sediment samples were
heated in the microwave unit to a temperature of
180+5°C for 9.5 min with a ramp of 10 min.
Digests were centrifuged at 3,000 rpm for 10 min to
clear the supernatant which was then analyzed by
graphite furnace atomic absorption spectrophotome-
try (GFAAS) using a Perkin-Elmer AAnalyst 600.
Similarly, two replicates of the dried 0.45 μm filters
were digested with a mixture of 3 ml of concentrated
nitric acid and 1 ml of hydrofluoric acid following the
microwave-assisted acid digestion procedure as de-
scribed above for sediments. Concentrations of heavy
metals in the SPM are given in terms of both water
volume (μg L−1) and SPM mass (μg g−1).
TOC was quantified using a Shimadzu TOC5000A
and a solid combustion unit SSM5000. A continuous
flow analyzer (AutoAnalyzer 3, Bran-Luebbe, Ger-
many) was used for measurement of DOC.
Results and discussion
Quality assurance
In order to verify the accuracy of the analytical methods,
a seawater standard reference material CASS-4 and a
sediment standard reference material PACS-2 (National
Research Council, Ottawa, Ontario, Canada) were
analyzed using four replicates. Heavy metal concen-
trations and recoveries of the standard reference
materials used are presented in Table 1. The recoveries
were good, averaging 114±10% for seawaters and 94±
11% for sediments. The analysis of all metals from the
seawater standard reference material CASS-4 showed
satisfactory accuracy, ranging from 103 to 117%
except for Cd (132%) with a relative standard deviation
of less than 26%. The recoveries for metals in the
sediment standard reference material PACS-2 were
between 84 and 110% with a relative standard
deviation of less than 15%.
In-situ analysis
Salinity at the two sampling sites during the sampling
events was 6.5 ppt (Station 1) and 22 ppt (Station 2),
Environ Monit Assess (2008) 138:255–272 259

Table 1 Measured and cer-

tified values for standard Standard reference Analyzed SRM Certified SRM Average recovery
reference materials (seawa- material value value (%)
ter and marine sediment)
CASS-4 – seawater (n=4)
As 1.14±0.04 1.11±0.16 103±4
Cd 0.030±0.007 0.026±0.003 116±26
Cr 0.189±0.012 0.144±0.029 132±8
Cu 0.609±0.037 0.592±0.055 103±6
Ni 0.355±0.020 0.314±0.030 113±6
Pb 0.0115±0.0011 0.0098±0.0036 117±11
Zn 0.438±0.020 0.381±0.057 115±5
PACS-2 – marine sediment (n=4)
Cd 2.20±0.31 2.11±0.15 104±15
Cr 77.1±1.2 90.7±4.6 85±1
Cu 340±29 310±12 110±9
Ni 37.2±2.8 39.5±2.3 94±7
Pb 160±3 183±8 87±1
Zn 305±6 364±23 84±2

resulting from abundant rainfall and a restricted
hydrodynamic exchange of coastal waters at Station
1 (Wood et al. 1997). The vertical profiles of DOC,
TOC and SPM in the water column from the two
sampling stations are illustrated in Fig. 2 (Fig. 2a,c,e
for Station 1 and Fig. 2b,d,f for Station 2). In
addition, enrichment factors (EF) of these parameters
at two sampling sites were calculated.
EF is defined as the ratio of the concentration found
in the sea-surface microlayer (SML) to that of the sub-
surface water layer (1 m below the sea surface).

EF ¼ ½XSML ½XSUB
Where [X]SML is the sea-surface microlayer concentra-
tion of parameter X, and [X]SUB is the concentration of
X in bulk (sub-surface water). EF values greater than
unity indicate enrichment in the SML, while EF values
less than 1 indicate depletion.
In general, DOC and TOC were present at higher
levels while SPM was lower at Station 1 relative to
Station 2. The vertical distribution of DOC, TOC and
SPM in the water column differed between sampling
sites. At Station 1, the profiles were similar between
sample events. DOC was enriched by a factor of
approximately two in the SML compared to the
subsurface water and this ratio decreased with depth.
SPM profiles also showed an enrichment by a factor
of approximately two in the SML, but concentrations
increased with depth relative to the subsurface waters.
The depth profiles of TOC showed a depletion in the
SML and a decrease with depth compared to the
subsurface waters. The enrichment of DOC and TOC
in the surface water (the SML and subsurface water)
compared to the underlying water at Station 1, a
mangrove area of Singapore, suggests higher levels of
biological activity in surface compared to the deeper
waters. At Station 2, the profiles of DOC, TOC and
SPM were quite different between sampling events.
Overall, DOC and TOC at this station varied little
with depth whilst SPM was enriched in the SML
relative to the subsurface water by factors of
approximately two-fold.
Concentrations of heavy metals in the water column
and sediments
Dissolved heavy metals in the water column
The dissolved phases of As, Cd, Cr, Cu, Ni, Pb and
Zn at Station 1 were lower, ranging from 0.34 to 0.87,
0.013 to 0.109, 0.07 to 0.16, 0.23 to 0.70, 0.28 to
0.70, 0.009 to 0.062 and 0.97 to 3.66 μg L−1
respectively, relative to those measured at Station 2,
ranging from 0.82 to 2.04, 0.014 to 0.044, 0.16 to
0.35, 0.52 to 1.16, 0.35 to 0.78, 0.022 to 0.059 and
1.19 to 3.42 μg L−1 respectively. The highest
concentrations of heavy metals were found in the
SML and the bottom waters, whilst the lowest
concentrations were present in the subsurface waters
at both sampling sites. There was a little enrichment
of heavy metals in the SML relative to subsurface
water. The enrichment factors (EF), reflecting the
260 Environ Monit Assess (2008) 138:255–272

a b
Station 1 - DOC (mg/L) Station 2 - DOC (mg/L)

0.00 5.00 10.00 15.00 20.00 25.00 30.00 0.00 2.00 4.00 6.00 8.00 10.00
0 0
1 2
2
4

Depth (m)
Depth (m)

Round 1
3 Round 1
6 Round 2
4 Round 3
8 Round 3
5
6 10

7 12

c d
Station 1 - TOC (mg/g) Station 2 - TOC (mg/g)

0.00 5.00 10.00 15.00 20.00 25.00 0.00 1.00 2.00 3.00 4.00 5.00 6.00
0 0
1 2
2
4
Depth (m)

Round 1 Depth (m) Round 1

3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

e f
Station 1 - SPM (mg/L) Station 2 - SPM (mg/L)

0 50 100 150 0 20 40 60 80 100 120

0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12
Fig. 2 DOC (mg/L), TOC (mg/g) and SPM (mg/L) profiles in the water column from two coastal regions of Singapore (a, c, e for
Station 1 – Kranji and b, d, f for Station 2 – Pulau Tekong)

relative level of contamination between the SML and
subsurface seawaters, for all metals with the exception
of Pb at Station 1 and Cd at Station 2, were slightly
greater than 1 and reached up to 1.1 for As, 1.9 for
Cd, 1.1 for Cr, 1.2 for Cu, 1.2 for Ni, 2.2 for Pb and
1.8 for Zn (Table 2). These results suggest that the
prevailing SML at both sampling stations was not
highly contaminated relative to subsurface waters,
except for Cd, Pb and Zn. The mechanism of
dissolved metal enrichment in the SML is complicat-
ed, but Hunter and Liss (1981) suggested that
dissolved metals could be enriched in the SML due
to complexation reactions between metal-ions and
organic ligands normally enriched in the SML.
Similarly, the formation of temporary surface com-
plexes or ‘metal–organic ligand–solid particles’ in the
SML may account for the accumulation of dissolved
metals in this layer (Zhang et al. 1996, 1997, 2003).
The ranges of heavy metal concentrations in the
dissolved phase of seawater samples from Singapore
and comparative available data from other countries
are presented in Table 3. There is little previous data
Environ Monit Assess (2008) 138:255–272 261

Table 2 Concentration (μg L−1) and enrichment factors (EF) of heavy metals in the sea-surface microlayer water from Singapore and
other locations

Region Heavy metal Concentration (μg L−1) Enrichment factor (EF) Reference
Total Particulate Dissolved Total Particulate Dissolved

Southern North Sea off Pb N.A.a N.A. 0.29–1.00 N.A. N.A. 140–410 Pattenden et al.
Lowestoft Zn N.A. N.A. 0.17–0.55 N.A. N.A. <5–<50 1981
Cheaspeake Bay Cd 0.11– 0.05–0.16 0.04–0.09 0.4 9 0.2 Hardy et al. 1990
0.20
Cu 4.20– 1.76– 1.10–3.00 8 >62 1.6
16.20 13.20
Pb 4.90– 4.73–23.7 0.21–1.00 43 105 4.7
24.20
Zn 18.90– 9.70– 9.20– 2.6 >45 1.5
58.90 26.90 32.00
Xiamen Bay, China Cd 0.02– 0.007– 0.02–0.03 1.1– 0.89–1.9 1.1–1.6 Hong and Lin 1990
0.08 0.013 1.6
Cu 0.60– 0.40–1.00 0.90–1.30 1– 1.2–6.5 1.2–1.5
2.30 2.61
Baltic Sea Cd N.A. <0.0001– 0.001– N.A. 5.7 1.5 Brügmann et al.
0.03 0.10 1992
Cu N.A. 0.001– <0.001– N.A. 4.2 1.5
0.90 2.20
Pb N.A. 0.004– <0.001– N.A. 3.6 2.2
0.30 0.40
Zn N.A. 0.015– 0.20– N.A. 4.1 2
0.80 5.80
German Bright Cd 0.02– N.A. N.A. 1.6– N.A. N.A. Hardy and Cleary
18.40 2.7 1992
Cu 1.40– N.A. N.A. 1.9– N.A. N.A.
4.70 8.7
Pb 0.77– N.A. N.A. 1.9– N.A. N.A.
2.07 6.1
Zn 10.20– N.A. N.A. 1.1– N.A. N.A.
20.50 4.7
North-western Cd 4.8 N.A. N.A. 55 N.A. N.A. Migon and Nicolas
Mediterranean Sea Pb 1.2–6.5 N.A. N.A. 19 N.A. N.A. 1998
Western Ross Sea, Antarctica Cu N.A. 0.06 N.A. 1.6 N.A. N.A. Grotti et al. 2001
Kranji and Pulau Tekong, As N.A. N.A. 0.34– N.A. N.A. 0.9–1.1 This study
Singapore 1.19
Cd 0.02– 0.005– 0.02– 0.7– 0.8–4.7 0.6–1.9 This study
0.08 0.036 0.05 2.6
Cr 0.65– 0.53–2.50 0.07– 1.4– 1.4–3.4 1.0–1.1 This study
2.72 0.22 2.8
Cu 1.25– 0.91–5.11 0.27– 1.7– 2.2–8.4 0.9–1.2 This study
5.72 0.72 5.0
Ni 0.46– 0.15–1.69 0.31– 0.9– 1.1–3.4 0.9–1.2 This study
2.10 0.50 2.2
Pb 0.11– 0.08–0.45 0.02– 1.9– 1.9–4.8 1.1–2.2 This study
0.51 0.12 3.4
Zn 5.42– 5.99– 1.79– 1.6– 1.6–5.0 0.8–1.8 This study
15.37 12.98 3.31 3.0
a
N.A. Not available
262
available on arsenic and chromium levels in seawater
from other parts of the world. The concentration
levels of arsenic in the dissolved phase in this study
are comparable to levels reported for Houston Ship
Channel, USA (Saleh and Wilson 1999) and the north
Australian coast and estuaries (Munksgaard and Parry
2001), whilst levels of chromium are low in Singapore
compared to those found in Houston Ship Channel,
USA (Saleh and Wilson 1999). Cadmium concentra-
tions in the dissolved phase are in a similar range of
values reported for the Arabian Sea, and coastal waters
of Malaysia, England, Wales and France (Fowler et al.
1984; Seng et al. 1987; Harper 1991; Law et al. 1994;
Kraepiel et al. 1997), but elevated relative to those
reported for Australia, Korea and USA (Mackey et al.
1996; Munksgaard and Parry 2001; Lee et al. 1998;
Beck et al. 2002). Levels of copper and nickel found in
Singapore are also similar to results reported elsewhere
(Harper 1991; Kraepiel et al. 1997; Apte and Day
1998; Lee et al. 1998), but low compared to available
data reported for the Northern Aegean Sea (Fytianos
and Vasilikiotis 1983), Arabian Sea (Fowler et al.
1984), Red Sea (El-Moselhy and Gabal 2004) and
coastal waters of the USA (Saleh and Wilson 1999;
Beck et al. 2002), England and Wales (Law et al.
1994). As shown in Table 3, lead concentrations in the
dissolved phase are within range or lower than data
reported from most previous studies conducted else-
where. Meanwhile, zinc concentrations are elevated
relative to those reported in Australia and USA
(Munksgaard and Parry 2001; Beck et al. 2002), but
much lower than data reported for the Northern
Aegean Sea and Red Sea (Fytianos and Vasilikiotis
1983; El-Moselhy and Gabal 2004). In general, the
concentrations of heavy metals in the sea-water column
of Singapore are very low in comparison to the
Criterion Continuous Concentration (CCC) given in
the National Recommended Water Quality Criteria (US
EPA 2006; see Table 3).
Particulate heavy metals in the water column
Concentrations of heavy metals in suspended partic-
ulate matter (SPM) at the two stations are expressed
in terms of both water volume (μg L−1) and SPM
mass (μg g−1). As measured in SPM mass (μg g−1),
the concentrations of Cd, Cr, Cu, Ni, Pb and Zn
ranged from 0.16 to 0.73, 6.73 to 53.93, 12.87 to
118.29, 4.34 to 60.71, 1.10 to 6.08, and 43.09 to
Environ Monit Assess (2008) 138:255–272
370.49 (μg g−1), respectively. The concentration
ranges of heavy metals in the SPM in terms of water
volume (μg L−1) were between 0.005 to 0.045 for Cd,
0.20 to 2.88 for Cr, 0.42 to 8.73 for Cu, 0.14 to 1.89
for Ni, 0.019 to 0.566 for Pb and 2.15 to 15.38 for Zn.
From the analytical results, it can be noted that all
heavy metals in the water column of both sampling
sites, except for Cd, are dominant in the particulate
fraction relative to the dissolved fraction, which is
consistent with the higher particulate fraction of Cu,
Ni, Pb and Zn in the water column compared to the
dissolved fraction reported by Nguyen et al. (2005).
The weak binding of Cd to organic compounds in
seawater may account for the predomination of Cd in
the dissolved fraction of the water column (Sadiq
1992; Wurl and Obbard 2004). As shown in Table 2,
the EFs in the SML of heavy metals in the SPM were
higher than those in the DP, ranging from 0.8 to 4.7
for Cd, 1.4 to 3.4 for Cr, 2.2 to 5.8 for Cu, 1.1 to 3.4
for Ni, 1.9 to 4.8 for Pb and 1.6 to 5.0 for Zn. These
results are consistent with findings from Cheaspeake
Bay, USA (Hardy et al. 1990), Xiamen Bay, China
(Hong and Lin 1990) and the Baltic Sea (Brügmann et
al. 1992), where the EFs for the particulate form of
Cd, Cu, Pb and Zn were greater than those for the
dissolved form. This suggests that the SPM in the
SML plays an important role in the enrichment of
heavy metals. The enrichment of particulate metals in
the SML is mainly derived from atmospheric deposi-
tion and bubble floatation from the water column
(Hardy 1982).
Table 4 shows the concentration ranges of partic-
ulate metals in terms of SPM mass (μg g−1) in
seawater samples from Singapore and other locations.
Cadmium is comparable to available data reported for
the Gulf and Western Arabian Sea (Fowler et al.
1984), the Gironde estuary in Southwestern France
(Kraepiel et al. 1997) and Lake Balaton, the largest
lake in Central Europe (Nguyen et al. 2005) and
substantially lower compared to levels elsewhere
(Paalman and Van der Weijden 1992; Price et al.
1996; Tankéré et al. 2001). Copper and nickel are also
lower than values reported for the Rhine/Meuse
estuary in the Netherlands (Paalman and Van der
Weijden 1992) and the Northern Adriatic Sea (Price
et al. 1996), but higher than results for the English
Channel (Statham et al. 1993) and Northern Adriatic
Sea (Price et al. 1996). As shown in Table 4,
compared with data from other locations in the world,
Environ Monit Assess (2008) 138:255–272 263

Table 3 Dissolved metal concentrations (μg L−1) in the coastal waters from Singapore and other locations
Region As Cd Cr Cu Ni Pb Zn Reference

Northern Aegean Sea, Greece N.A. 0.160– N.A. 0.700– 0.500– 3.500– 13.400– Fytianos and Vasilikiotis 1983
0.520 2.080 1.500 20.500 23.000
Coastal water of the Gulf and N.A. 0.002– N.A. 0.020– N.A. 0.020– 0.002– Fowler et al. 1984
Western Arabian Sea 0.100 5.600 0.120 0.910
Juru Estuary, Penang, Malaysia N.A. 0.600– N.A. 0.600– 1.600– 2.000– 4 .000– Seng et al. 1987
0.800 0.800 1.800 2.800 10.600
San Francisco Bay, USA N.A. 0.035– N.A. 1.520– N.A. N.A. 2.020– Kuwabara et al. 1989
0.528 4.190 6.990
Central North Sea N.A. 0.015– N.A. 0.230– N.A. 0.017– 0.160– Fileman et al. 1991
0.025 0.390 0.032 0.610
Bristol Channel, England N.A. 0.012– N.A. 0.200– N.A. 0.020– N.A. Harper 1991
0.050 1.000 0.040
England and Wales (1992) Law et al. 1994
Estuarine, coastal sites N.A. 0.012– N.A. 0.350– 0.230– 0.024– 0.430–
0.220 4.000 4.900 0.880 15.000
Offshore locations N.A. 0.004– N.A. 0.140– 0.220– 0.020– 0.220–
0.069 0.900 0.640 0.071 2.100
Southwestern Tasmania, Mackey et al. 1996
Australia
Macquarie Harbour N.A. 0.005– N.A. 2.351– 0.282– N.A. 0.392–
0.028 6.989 0.552 2.027
Bathurst Harbour N.A. 0.002– N.A. 0.140– 0.141– N.A. 0.392–
0.007 0.235 0.288 2.942
Gironde estuary in N.A. 0.024– N.A. 0.388– 0.267– 0.021– 0.471– Kraepiel et al. 1997
southwestern France 0.131 1.347 0.536 0.062 2.000
Torres Strait and Gulf of N.A. <0.001– N.A. 0.032– 0.094– N.A. N.A. Apte and Day 1998
Papua, Australia 0.029 0.986 0.460
Korean coastal environment Lee et al. 1998
East coast N.A. 0.024– N.A. 0.170– N.A. 0.068– 1.010–
0.102 0.980 0.075 4.910
South coast N.A. 0.022– N.A. 0.450– N.A. 0.029– 0.380–
0.028 0.540 0.064 2.150
West coast N.A. 0.014– N.A. 0.420– N.A. 0.033– 0.250–
0.030 1.230 0.091 0.760
Houston ship channel, Texas, 0– 0.314– 5.398– 29.970– 6.176– 0.215– 16.430– Saleh and Wilson 1999
USA 1.983 3.273 7.752 280.200 26.480 1.257 77.220
Australian coast and Munksgaard and Parry 2001
stuaries
Karumba Offshore 0.714– 0.001– N.A. 0.148– 0.116– 0.004– <0.010–
1.210 0.006 0.254 0.215 0.018 0.120
North Australian coast 0.394– 0.002– N.A. 0.151– 0.116– <0.002– 0.018–
and estuaries 1.350 0.034 1.040 0.552 0.057 0.498
Northwestern Black N.A. 0.004– N.A. 0.184– 0.500– 0.006– 0.070– Tankéré et al. 2001
Sea 0.018 1.830 1.030 0.126 2.940
San Francisco Bay, N.A. 0.027– N.A. 0.790– 1.070– N.A. 0.468– Beck et al. 2002
USA 0.033 1.670 2.030 0.785
The northern part of N.A. 0.150– N.A. 1.16– N.A. 1.840– 8.130– El-Moselhy and Gabal 2004
the Gulf of Suez, Red 0.180 5.33 2.570 23.240
Sea, Egypt
The Criterion 36 8.7 49.7 2.6 7.7 8.1 76.6 National Recommended Water Quality Criteria
Continuous (US EPA 2006)
Concentration
(CCCa)
Coastal sites, Singapore 0.335– 0.013– 0.072– 0.228– 0.282– 0.009– 0.974– This study
2.035 0.109 0.350 1.163 0.784 0.062 3.662
a
The Criterion Continuous Concentration (CCC) is an estimate of the highest concentration of a material in surface water to which an
aquatic community can be exposed indefinitely without resulting in an unacceptable effect.
264 Environ Monit Assess (2008) 138:255–272

Table 4 Concentration of particulate metals (μg g−1) in the coastal waters from Singapore and other locations

Region Cd Cu Ni Pb Zn Reference

The Gulf and Western Arabian Sea 0.13– 0.70–14.50 N.A. 10.00– N.A. Fowler et al. 1984
0.97 180.00
The Rhine/Meuse Estuary, The 9.60 138.00 69.00 131.00 908.00 Paalman and Van der
Netherlands Weijden 1992
English Channel 0.70– 0.10–49.60 <0.10– 5.00– 2.00–141.00 Statham et al. 1993
6.90 23.20 137.00
Northern Adriatic Sea 0.66– 21.00– 12.00–92.00 9.70– 166.00– Price et al. 1996
20.00 1,560.00 496.00 2,020.00
Gironde estuary, southwestern 0.38–1.05 32.41–47.02 45.79–57.53 30.25–63.20 215.75–281.13 Kraepiel et al. 1997
France
Southern North Sea ND–8.30 25.00–45.00 ND–5.60 13.00–341.00 31.00–115.00 Millward et al. 1998
North Western Black Sea 0.34–6.30 5.00–225.00 2.00–36.00 2.40–121.00 12.00–359.00 Tankéré et al. 2001
Lake Balaton 0.12–1.25 5.00–50.00 1.00–67.00 10.00–77.00 18.00–140.00 Nguyen et al. 2005
Coastal sites, Singapore 0.16–0.73 12.87–118.27 7.16–60.71 1.10–6.08 43.09–370.49 This study

the levels of Pb in Singapore are relatively low. Zinc
levels in this study are similar to values reported from
the English Channel (Statham et al. 1993), Southern
North Sea (Millward et al. 1998) and North Western
Black Sea (Tankéré et al. 2001), but still lower than
those reported elsewhere (Paalman and Van der
Weijden 1992; Price et al. 1996). Overall, concen-
trations of heavy metals in the SPM are not elevated
in Singapore compared to those recorded from the
Rhine/Meuse estuary in the Netherlands (Paalman and
Van der Weijden 1992) and the Northern Adriatic Sea
(Price et al. 1996), where the levels of Cd, Cu, Ni, Pb
and Zn are significantly higher than the reported
levels in this study.
Heavy metals in sediments
Levels of metals in sediments (μg g−1) at two
sampling sites ranged from 0.05 to 0.22 for Cd,
37.48 to 50.52 for Cr, 6.30 to 21.01 for Cu, 13.27 to
26.59 for Ni, 24.14 to 37.28 for Pb and 48.20 to 62.36
for Zn. There were relative differences in the levels of
heavy metals in sediment samples between two
sampling stations, where the concentrations of all
metals, except for Pb, in the sediments from Station 1
were between one and three times greater than those
from Station 2. Anthropogenic discharges from the
city of Johor as well as the restricted hydrodynamics
at Station 1 likely account for the elevated levels of
heavy metals in sediments from Station 1 relative to
Station 2. Of the heavy metals studied, Zn was
present at the highest concentration in sediments from
both sampling sites, most likely due to the release of
anti-fouling paints from boats (Goh and Chou 1997).
A comparison of metal levels in SPM and bottom
sediments from both sampling stations indicates that
concentrations of Cd, Cu, Ni and Zn in the bottom
sediments are generally similar to or higher than
levels in the SPM. These results are in agreement with
the findings from the Ob-Irtysh river, in Russia
(Moran and Woods 1997) and Lake Balaton in central
Europe (Nguyen et al. 2005) which suggested that the
sources of particulate metals included re-suspended
sediments, anthropogenic discharges and inputs from
continental weathering.
As presented in Table 5, the metal levels from this
study are compared to levels for marine sediments
from other local investigations conducted earlier
(Wood et al. 1997; Nayar et al. 2004). Concentrations
of Cd, Ni and Pb in this study are relatively higher,
while Cu is lower compared to recent sediment results
obtained for Ponggol, Singapore (Nayar et al. 2004).
Levels of Cd, Cr and Ni in sediments from Station 1
are similar to sediment results obtained from the
Straits of Johor, Singapore in July, 1993 (Wood et al.
1997), while Cu, Pb and Zn are around two times
lower than values from the Straits of Johor. The levels
of metals in sediments from Station 2 are also lower than
those measured in the sediments from the Straits of
Johor (Wood et al. 1997), indicating that the burden of
heavy metals in marine sediments from the Straits of
Johor, Singapore has decreased over the last decade.
Environ Monit Assess (2008) 138:255–272 265

Table 5 Concentration of heavy metals in sediments (μg g−1) from Singapore and other locations
Region Cd Cr Cu Ni Pb Zn Reference

Chao Phrya Estuary, Thailand 1.20± N.A. 26.00± N.A. 140.00± 28.00 71.00± Menasveta and Cheevaparanapiwat
0.50 10.00 6.9.00 1981
Northern Aegean Sea, Greece 0.62– N.A. 0.60– 4.10– 6.40– 10.40– Fytianos and Vasilikiotis 1983
1.14 2.30 9.10 27.80 28.2
Juru Estuary, Penang ND– N.A. 9.30– 24.80– 20.80– 73.50– Seng et al. 1987
Malaysia 6.80 13.80 46.70 33.00 109.80
Tokyo bay, Japan 0.53– N.A. 16.60– 16.40– 25.20– 106.00– Fukushima et al. 1992
1.40 79.80 44.10 58.30 405.00
Korean coasts 0.14– N.A. 9.80– N.A. 23.50– 45.60– Lee et al. 1998
2.40 59.90 62.60 102.00
Queensland, Australia Esslemont 2000
Pioneer Bay 0.01– 0.14– 0.51– 0.98– 1.49–3.42 1.55–
0.67 11.18 1.30 3.77 3.08
Nelly Bay 0.04– 0.73– 0.41– 0.32– 2.84–7.42 1.40–
0.68 11.60 1.39 4.10 5.52
Townsville 0.06– 7.28– 35.01– 21.13– 29.42– 122.98–
0.69 16.90 48.23 32.40 39.78 148.02
The northern part of the Gulf 2.26– N.A. 1.84– N.A. 13.90– 4.26– El-Moselhy and Gabal 2004
of Suez, Egypt 4.40 10.25 28.34 23.68
The southwest coast of Spain 0.19– 32–92 41–336 10–50 20–197 141–649 Morillo et al. 2004
2.50
The Harbor of Barcelona, 0.43– 38.80– 70.6– 18.3– 86.3–589 213– Guevara-Riba et al. 2004
Spain 2.76 110 531 34.3 1133
The East China Sea, China 0.03– 33–86 4–40 19–47 22–44 33–131 Yuan et al. 2004
0.16
Canadian marine The National Guidelines and Standards Office
sediment (NGSO) Environment Canada (2002)
quality guidelines
ISQGsa 0.7 52.3 18.7 N.A. 30.2 124
PELsb 4.2 160 108 N.A. 112 271
Singapore
Straits of Johor 0.18± 45.2± 30.7± 30.2± 42.3±11 132.5± Wood et al. 1997
0.06 11.2 22.5 6.6 52.6
Ponggol estuary 0.24 NA 34.65 6.07 17.30 N.A. Nayar et al. 2004
Kranji 0.15– 44.36– 14.65– 25.76– 24.14– 61.69– This study
0.22 50.52 21.01 26.59 27.74 62.36
Pulau Tekong 0.05– 37.48– 6.30– 13.27– 24.47– 48.20– This study
0.07 43.74 8.70 20.00 37.27 52.05
a
ISQGs Interim freshwater sediment quality guidelines (dry weight)
b
PELs Probable effect levels (dry weight)

In general, levels of all metals, except for Cd, in
sediments for the Northern Aegean Sea, Greece
(Fytianos and Vasilikiotis 1983), Pioneer Bay and
Nelly Bay, Australia (Esslemont 2000) and the
northern part of the Gulf of Suez, Egypt (El-Moselhy
and Gabal 2004) are lower than the reported levels in
this study. However, Singapore’s marine sediments are
still relatively uncontaminated with heavy metals when
compared to available data for other countries including
Thailand, Japan, Korea, Spain and China (Menasveta
and Cheevaparanapiwat 1981; Fukushima et al. 1992;
Lee et al. 1998; Morillo et al. 2004; Guevara-Riba
et al. 2004; Yuan et al. 2004). In comparison with the
ISQG and PEL values given in the Canadian Sediment
266 Environ Monit Assess (2008) 138:255–272

Quality Guidelines for the Protection of Aquatic Life
(The National Guidelines and Standards Office
(NGSO) Environment Canada 2002), the concentra-
tions of all metals in sediments obtained from this
study are lower than the ISQG and PEL values, except
for the concentration of Cu at Kranji and the
concentration of Pb at Pulau Tekong that are slightly
greater than the ISQG values, but still much lower than
the PEL values.
Vertical distribution of heavy metals
in the water column
The depth profiles of all metals in the DP from the two
stations are presented in Fig. 3 (Fig. 3a,c,e,g,i,k,m for
Station 1 and Fig. 3b,d,f,h,j,l,n for Station 2). Concen-
trations of arsenic, cadmium, chromium and copper
show little difference in vertical profiles between the
two locations. The profiles of these metals at Station 2

a b
Station 1 - Arsenic (µg/L) Station 2 - Arsenic (µg/L)

0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.50 1.00 1.50 2.00 2.50
0 0
1 2
2
4

Depth (m)
Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

c d
Station 1 - Cadmium (µg/L) Station 2 - Cadmium (µg/L)

0.00 0.05 0.10 0.15 0.00 0.01 0.02 0.03 0.04 0.05
0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

e f
Station 1 - Chromium (µg/L) Station 2 - Chromium (µg/L)

0.00 0.05 0.10 0.15 0.20 0.00 0.10 0.20 0.30 0.40
0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 Round 3
8
5
6 10

7 12

Fig. 3 Dissolved metal profiles in the water column from two coastal regions of Singapore (a, c, e, g, i, k, m Station 1 Kranji
and b, d, f, h, j, l, n Station 2 Pulau Tekong)
Environ Monit Assess (2008) 138:255–272 267

g h
Station 1 - Copper (µg/L) Station 2 - Copper (µg/L)

0.00 0.20 0.40 0.60 0.80 0.00 0.50 1.00 1.50

0 0
1 2
2
4
Depth (m)

Depth (m)
Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

i j
Station 1 - Nickel (µg/L) Station 2 - Nickel (µg/L)

0.00 0.20 0.40 0.60 0.80 0.00 0.20 0.40 0.60 0.80 1.00
0 0
1 2
2
4
Depth (m)

Depth (m)
Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

k l
Station 1 - Lead (µg/L) Station 2 - Lead (µg/L)

0.00 0.05 0.10 0.15 0.00 0.02 0.04 0.06 0.08

0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

m n
Station 1 - Zinc (µg/L) Station 2 - Zinc (µg/L)

0.00 1.00 2.00 3.00 4.00 0.00 1.00 2.00 3.00 4.00
0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

Fig. 3 (continued)

show a slight enrichment in the SML by factors of up of these metals between the SML and subsurface water
to 1.10 for As, 1.90 for Cd, 1.07 for Cr and 1.15 for Cu, at Station 1. However, higher concentrations of As, Cd,
while there is no clear difference in the concentrations Cr and Cu in the DP were found in the mid-depth and
268 Environ Monit Assess (2008) 138:255–272

bottom water at both sampling sites compared to the
SML and subsurface layer. The profiles for these
metals show a depletion in the subsurface water and an
increase with depth, with the highest metal concen-
trations generally observed in near-bottom water and
the lowest concentrations in the subsurface water,
indicating a trend of declining concentration from the
subsurface to bottom water. The vertical distribution of
Ni and Zn in the water column at both stations is
relatively similar (Fig. 3i,m for station 1 and Fig. 3j,n
for station 2) with no apparent enrichment of the
dissolved metals in the SML and a depletion in the
surface layer (the SML and subsurface) compared to
underlying water. For Pb, the profiles show an
enrichment in the SML by a factors up to 2.24, with
little variation with depth at Station 1 (Fig. 3k). A
similar finding has been reported for the water column
of the Weddell Sea, Antarctica (Westerlund and Öhman
1991). Similarly, Pb was enriched in the SML by
factors of up to 1.54 at Station 2, but there is no clear
concentration trend for this metal throughout the water
column at this station (Fig. 3l).
The depth profiles for Cd, Cr, Cu, Ni, Pb and Zn in
the SPM in the water column for all sampling events
at the both sampling sites are summarized in Fig. 4.
The vertical distribution for all metals studied was
similar at both sampling stations. Cd, Cr, Cu, Ni, Pb
and Zn in the SPM were significantly enriched in the

a Station 1 - Cadmium (µg/L)

b Station 2 - Cadmium (µg/L)

0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04
0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

c d
Station 1 - Chromium (µ g/L) Station 2 - Chromium (µ g/L)

0.00 1.00 2.00 3.00 4.00 0.00 0.50 1.00 1.50 2.00 2.50 3.00
0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

e f
Station 1 - Copper (µ g/L) Station 2 - Copper (µ g/L)

0 2 4 6 8 10 0.00 1.00 2.00 3.00 4.00 5.00 6.00

0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12
Fig. 4 Particulate metal profiles in the water column from two coastal regions of Singapore (a, c, e, g, i, k for Station 1
Kranji and b, d, f, h, j, l for Station 2 Pulau Tekong)
Environ Monit Assess (2008) 138:255–272 269

g h
Station 1 - Nickel (mg/L) Station 2 - Nickel (µg/L)

0.00 0.50 1.00 1.50 2.00 0.00 0.50 1.00 1.50 2.00
0 0
1 2
2
4
Depth (m)

Depth (m)
Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

i j
Station 1 - Lead (µg/L) Station 2 - Lead (µg/L)

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.00 0.10 0.20 0.30 0.40 0.50
0 0
1 2
2
4
Depth (m)

Depth (m)
Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

k Station 1 - Zinc (µg/L)

l Station 2 - Zinc (µg/L)

0.00 5.00 10.00 15.00 20.00 0 5 10 15

0 0
1 2
2
4
Depth (m)

Depth (m)

Round 1 Round 1
3
Round 2 6 Round 2
4
Round 3 8 Round 3
5
6 10

7 12

Fig. 4 (continued)

SML, depleted in the subsurface layer and progres-
sively enriched in the underlying water column. The
lowest concentrations of all metals in the SPM were
found in subsurface water at both stations, while the
highest concentrations were generally observed in the
bottom water at Station 1 and in the SML water at
Station 2. EFs of heavy metals associated with the
SPM in the SML, relative to the subsurface water,
were notably higher than EFs of dissolved metals and
ranged from 1 to 5. Also, heavy metals in the SPM in
the bottom water at both stations were enriched by
factors of 1 to 18 compared to the overlying water.
As mentioned above, the formation of metals and
organic ligand complexes, as well as the presence of
solid particles enriched in the SML are likely to
account for the accumulation of dissolved metals in
this layer, while the accumulation of particulate
metals is most likely due to the deposition of particles
from the atmosphere and bubble floatation from the
water column. Overall, the profiles for the heavy
metals in the DP and SPM measured in this study
show a decreasing trend of metal concentrations from
the subsurface water to the bottom water. This
phenomenon suggests that the vertical distribution of
these metals is controlled by biogeochemical cycling
processes. Most marine organisms, especially phyto-
plankton, are confined to the surface layers and these
organisms uptake nutrients, dissolved carbon and
metals such as As, Cd, Cr, Cu, Ni and Zn resulting
in the depletion of metals in the surface water. Dead
270
organisms and fecal pellets sink into the deeper water
and are mineralized thereby returning metals to the
water column. As a result, metals are depleted in the
surface water and enriched with depth.
Conclusions
In order to investigate the levels and the vertical
distribution of heavy metals in the near shore water
column of Singapore’s coastal environment, sea-
surface microlayer, subsurface, mid-depth and bottom
water, and sediment samples were collected from two
locations with contrasting hydrodynamic character-
istics. This represents the first such study of its kind in
Singapore and contributes to the database for Asia.
Overall, the levels of metals in the dissolved phase of
seawater in Singapore are comparable to values
reported in the literature for the coastal waters of
England, France, Australia and Korea, but still lower
than levels reported for Greece, Malaysia and the
USA. Similarly, elevated concentrations of metals in
the SPM have been reported for the Northern Adriatic
Sea and the Rhine/Meuse estuary in the Netherlands
compared to the reported values in this study. For
sediments, although the metals are present at higher
levels in Singapore relative to reported vales for
coastal marine sediments for Greece, Australia and
Egypt, Singapore’s marine sediments are relatively
uncontaminated compared to values reported for many
other countries including Thailand, Japan, Korea, Spain
and China. The vertical profiles of heavy metals in the
water column show a depletion in the subsurface water
and a progressive enrichment with depth, most likely
due to biogeochemical cycling processes associated
with gravitational settlement and decomposition of dead
organic matter. The profiles also show a slight enrich-
ment of dissolved metals in the SML and a notable
enrichment of particulate metals in this layer, meaning
that SPM plays an important role in the accumulation of
metals in the SML.
Acknowledgement The authors would like to thank the
Tropical Marine Science Institute and the National University
of Singapore for facilities in the sampling of the samples and
for facilities in measurement techniques. We gratefully thank
the crew of Hammerhead, especially Dr Subramanian
Karuppiah and Oliver Wurl for their skilled assistance in both
field and laboratory work.
Environ Monit Assess (2008) 138:255–272
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