ORI GI NAL ARTI CLE

Evaluation of elemental enrichments in surface sediments

off southwestern Taiwan
Chen-Tung Chen Selvaraj Kandasamy
Received: 5 May 2007 / Accepted: 25 June 2007
Springer-Verlag 2007
Abstract Surface slices of 20 sediment cores, off south-
western Taiwan, and bed sediment of River Kaoping were
measured for major and trace elements (Al, As, Ca, Cd, Cl,
Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn)
to evaluate the geochemical processes responsible for their
distribution, including elemental contamination. Major
element/Al ratio and mean grain size indicate quartz-
dominated, coarse grained sediments that likely derived
from sedimentary rocks of Taiwan and upper crust of
Yangtze Craton. Bi-plot of SiO
2
versus Fe
2
O
3
T
suggests the
possible iron enrichment in sediments of slag dumping
sites. Highest concentrations of Cr, Mn, P, S, and Zn found
in sediments of dumping sites support this. Correlation
analysis shows dual associations, detrital and organic car-
bon, for Cr, P, S, and V with the latter association typical
for sediments in dumping sites. Normalization of trace
elements to Al indicates high enrichment factors (>2) for
As, Cd, Pb, and Zn, revealing contamination. Factor
analysis extracted four geochemical associations with the
principal factor accounted for 25.1% of the total variance
and identies the combined effects of dumped iron and
steel slag-induced CSFe relationship owing to authigenic
precipitation of FeMn oxyhydroxides and/or metal sul-
des, and organic matter complexation of Fe, Mn, Ca, Cr,
P, and V. Factors 2, 3, and 4 reveal detrital association (Ti,
Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and
K) and anthropogenic component (As and Zn)-carbonate
link, respectively, in the investigated sediments.
Keywords Geochemistry Elemental contamination
Dumping Surface sediments Southwestern Taiwan
Introduction
Previous research on marine pollution is considered as
abundant; however, there is still a lack of global under-
standing on the impact of anthropogenic activities on the
marine environment owing to the lack of critical evalua-
tion of elemental contamination in many studies. Metals,
including metalloid, though they are natural components
of the Earths crust, have widely increased their distri-
bution in the environment as a consequence of modern
industrial and human activities (Grimalt et al. 2001). For
example, on the average, the anthropogenic emissions of
As, Cd, Cu, Ni, and Zn exceed the inputs of these ele-
ments from natural sources by about twofold or more; in
the case of lead, the same ratio is about 17 (Nriagu and
Pacyna 1988). Marine sediments, especially in coastal and
estuarine regions in the vicinity of urban and harbor areas,
are becoming increasingly polluted with heavy metals
(Loring and Rantala 1992; Szefer et al. 1995). Since the
sediments integrate the external environmental effects,
caused essentially by modernization, by the way of
accumulating elemental contaminants at the rate of
accurately detectable way, they become an ultimate res-
ervoir for metals and provide input records of metals to
the ecosystem (Zwolsman et al. 1996). In addition, a
knowledge of the concentration and distribution of trace
elements in sediments plays a key role in detecting
sources of pollution in aquatic systems (Forstner and
Wittmann 1981) and, for this reason, sediments can be
investigated as an important environmental parameter in
major marine monitoring programs.
C.-T. Chen S. Kandasamy (&)
Institute of Marine Geology and Chemistry,
National Sun Yat-Sen University,
Kaohsiung 804, Taiwan
e-mail: kselva8@yahoo.com
1 3
Environ Geol
DOI 10.1007/s00254-007-0916-2
The island of Taiwan has a length of 385 km with a
maximum width of 143 km and has an area of 36,000 km
2
(Fig. 1). Though the island is situated near a thermal
boundary, the southern tip of the island and many offshore
islands have well-developed fringing reefs (Fujiwara et al.
2000) with high biodiversity. For instance, Taiwans reefs
hold 300 species of Scleractinian corals and 1,200 species
of reef sh (Dai 1997). However, tremendous economic
development at the expense of environment has brought
prosperity to Taiwan thereby increasing the GNP from 12.3
million in 1951 to 9 trillion in 2004. As a result, severe
pollution has occurred in the coastal area adjacent to Tai-
wan due to industrialization and modernization of human
community (Lin and Wang 2004). Recent study of histor-
ical changes of trace metal pollution in sediments of
southwestern Taiwan has also indicated increased metal
pollution since 1970 (Hung and Hsu 2004). Previous
researchers have concentrated their efforts on river pollu-
tion rather than coastal sediments and very few investiga-
tions have previously been published on coastal sediments
and biota of Taiwan, especially on heavy metals (Chen
1977; Hung 1994, 1995; Chen and Wu 1995; Lee et al.
1998; Chen and Chen 2001; Chen 2002) but with a general
lack of majortrace element relationship. Thus, complete
evaluation of elemental contamination and majortrace
elements relationship of coastal sediments of this oceanic
island is still rudimentary. Therefore, we present here the
concentrations of 20 major, minor, and trace elements in
surface slices (02.5 cm) of 20 core sediments collected
during 1995 under the environmental monitoring program
of ocean dumping sites, off southwestern Taiwan. A
representative bed sediment of River Kaoping, a major
river discharging (water: 8.5 10
9
m
3
year
1
; sediment:
3.6 10
8
tonne year
1
) into the study area, collected dur-
ing the program was also included in order to compare the
results. The main objectives of this study are (1) to delin-
eate natural and anthropogenic levels of trace elements and
their association with major elements to deduce the pos-
sible carrier phases as well as geochemical factors that
control the levels of trace metals in the study area and (2)
to provide rst environmental assessment report from the
dumping sites as it is essential for Islands future envi-
ronmental monitoring issues related to offshore dumping.
To execute our aims, we have used normalization and
statistical techniques.
Study area
The factors adversely impacting the coastal part of south-
western Taiwan include dense population, many electro-
chemical plants, large industrial complexes, harbors, waste
dumping grounds, ocean outfalls, coal and nuclear power
plants (Lee et al. 1998). Moreover, southwestern coast of
Taiwan is famous for harbor activity as Kaohsiung Harbor
(KH), one of the worlds busiest maritime activity places,
advantageously situated in the vital sea lanes connecting
North Pacic and the Indian Ocean. This harbor is, there-
fore, home to the worlds fth largest container port. Off-
shore part of the study area has served as iron and steel slag
disposal sites. The two squared areas in Fig. 1 served as old
and new dumping sites between 1984 and 1988 and be-
tween 1988 and 1995, respectively. To study the impact of
disposed wastes on the chemistry of sediments, 12 gravity
cores were collected in and around old and new dumping
sites. Similarly, 8 core sediments were collected from the
Fig. 1 Study area and offshore
(open circles), coastal (open
triangles), and river (lled
triangle) sampling locations.
The two squared areas represent
new and old dumping (iron and
steel slag) sites
Environ Geol
1 3
coastal area adjoining KH to compare and delineate the
effect of dumped iron and steel slag on the sediment
chemistry.
Materials and methods
Sampling
A suite of 20 gravity cores was collected from water depths
varying up to 537 m in and around old and new dumping
sites, off southwestern Taiwan, and near coastal region
adjoining KH (Fig. 1) during 1995 using 2 m long gravity
corer onboard the R/V Ocean Researcher III (Cruise No.
274). Samples from the top 2.5 cm, representing age ranges
from ~18 to 22 years at the prevailing sedimentation rate
(0.13 cm year
1
; Hung and Hsu 2004) were carefully taken
from the each core to evaluate the levels of natural and
enhanced concentrations of different major and trace ele-
ments. One representative sample collected from River
Kaoping (Fig. 1) using a Shipek grab during the program
was included in the evaluation.
Analyses
Upon collection, pH and Eh of offshore core top samples
were measured using pH meter (Model: PHM 85 Precision)
with appropriate electrodes. The collected cores were then
capped, sealed airtight and frozen before they were brought
to shore laboratory for further investigation. Prior to de-
tailed chemical analysis, the surface slices of all the col-
lected cores were freeze dried, homogenized (removal of
particles >1 mm), and mean sediment grain size (Mz) ob-
tained using a Coulter LS-100 particle size analyzer after
proper removal of carbonate with 1 N HCl and organic
matter by 30% H
2
O
2
. Other portion of the each homoge-
nized sample of bulk sediment was nely ground (<200
mesh) in an agate mortar and organic carbon (OC) was
determined with the help of elemental analyzer (LECO
CHN-932) at 950C in the combustion chamber with a
precision of 1.2% (Lou and Chen 1997). Calcium car-
bonate (CaCO
3
) was calculated from the wt.% of sediment
inorganic carbon determined with the same elemental
analyzer after OC removal with 30% H
2
O
2
. Totally, 20
major, minor, and trace elements (Al, As, Ca, Cd, Cl, Cr,
Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn)
were determined using X-ray uorescence (XRF) spec-
trometer (Model: Rigaku RIX 2000) equipped with an Rh
tube. Briey, 23 g of each sample powder was compacted
into a round disc (30 mm diameter) under 20 ton pressures
for 20 min with cellulose as backing. These pellets were
X-rayed and the measurement was carried out at an
acceleration voltage of 50 kV and a current of 50 mA. The
accuracy of the analytical method was established with
standard reference materials (SRMs), BCSS-1, MESS-1,
PACS-1, SRM 2704, and NIES-2. Based on the analyses of
reference materials, accuracy of the measurements was
within 5% for major and trace elements such as Al (range
0.443.74), Ca (0.110.57), Cl (0.214.84), Cr (0.262.82),
Fe (0.444.65), K (0.101.43), Mg (0.563.08), Ni (0.26
3.60), Si (0.112.24), Ti (0.704.06), and Zn (0.402.72).
The same was 10 for Cd (2.558.92), Cu (0.388.90), Mn
(0.708.70), Na (0.608.54), P (0.135.48), Pb (0.294.02),
S (0.378.96), and V (1.498.91). Arsenic however shows
higher error of 25% (1.4624.43) likely because of its
metalloid nature. Three replicates of one sample were run
and the following coefcient of variation obtained: Al,
0.44%; As, 2.04%; Ca, 0.76%; Cd, 7.02%; Cl, 0.38%; Cr,
5.97%; Cu, 0.95%; Fe, 0.43%; K, 0.58%; Mg, 0.84%; Mn,
0.60%; Na, 4.97%; Ni, 1.86%; P, 0.29%; Pb, 3.04%; S,
0.34%; Si, 0.58%; Ti, 0.39%; V, 6.13%, and Zn, 2.22%.
Moreover, mean grain size and OC were not carried out in
bed sediment of River Kaoping due to its coarse, sandy
nature.
Results and discussion
Major element geochemistry
Coastal and offshore sediments are, in general, mixtures of
aluminosilicates and carbonate debris. Therefore, evalua-
tion in terms of element/Al ratios would normally yield
better understanding of elemental behaviors because such
ratios can be interpreted in terms of the texture and min-
eralogy (Calvert et al. 1993). For the purpose of initial
appraisal of sediment composition and provenance, we
have used different reference materials such as the upper
continental crust (UCC; Taylor and McLennan 1985), up-
per crust of Yangtze Craton (UC-YC; Gao et al. 1998) and
different shale compositions. The mean Si/Al ratios of
offshore and coastal sediments (3.42 and 3.89; Table 1)
were close to this ratio in average shale (3.13; Turekian and
Wedepohl 1961) and the UCC (3.85). The entire Si/Al
range (2.894.48) of coastal and offshore sediments further
well corresponds to Si/Al ratios of different shale compo-
sitions such as average shale, Post-Archean Australian
Shale-PAAS (2.94; Taylor and McLennan 1985) and North
American Shale Composite-NASC (4.66; Gromet et al.
1984). This suggests that the sediments are chemically
similar to shales, especially offshore sediments which are
all composed of ne to very ne silts (Mz range 6.47
15.08 lm). However, the bed sediment of River Kaoping
shows very high Si/Al ratio (5.16), even higher than the
UCC and UC-YC (4.17), which was attributed most likely
to sandstone mineralogy, a dominant rock type in the
Environ Geol
1 3
drainage basin of this river. The obtained Si/Al variations
appear to be produced by variations in the quartz and K-
feldspar (Si/Al = 3.1) contents rather than illite (1.7) and
kaolinite (1.2). According to Turekian and Wedepohl
(1961), the Si/Al ratio of 3 in sediments is taken as an
index of the presence of detrital clay minerals. The higher
Si/Al ratios (>3) obtained in all our samples (except one
sample, CS6; Table 1) further indicate the dominance of
sand and silt grains with higher amount of quartz and
feldspars rather than clays due to Islands highest erosion
but moderate chemical weathering rates (Selvaraj and Chen
2006). Our size analysis also showed quite similar infer-
ences: mean sediment grain sizes (6.4715.08 lm; Ta-
ble 2) of offshore sediments show their ne and very ne
silty nature in contrast to coarser (65452 lm) coastal
sediments which all fall under medium, ne and very ne
sand classes of siliclastic sediments of Shipboard Scientic
Party (2003) modied after Wentworth (1922). Calvert
et al. (1993) have also found highly variable ratios of Si/Al
in the coarse-grained, shallower surface sediments of South
China and Sulu Seas due essentially to variable proportions
of quartz and feldspars relative to clays.
Aluminum is believed to be an index element for the
terrigenous source (e.g., Nath et al. 1989) and both Ti and
Al are refractory elements which are extremely immobile
in the marine environment (Bischoff et al. 1979). The mean
ratios of Ti/Al in offshore and coastal sediments are 0.054
and 0.049 (Table 1), respectively, and these ratios are more
close to this ratio in UC-YC (0.053) and average compo-
sition of sedimentary rocks of Taiwan (ACST; 0.049;
Selvaraj and Chen 2006), suggesting that offshore and
coastal sediments were likely derived from upper crust of
Yangtze Craton and sedimentary rocks (metapelite, phyl-
lite, sandstone, and shale) of Taiwan, respectively. This
inference is further supported by the Ti/Al ratio (0.049) of
bed sediment of River Kaoping which was very similar to
the mean Ti/Al of coastal sediments. The mean Fe/Al ratios
of offshore and coastal sediments (0.49 and 0.47) closely
resemble the Fe/Al of UC-YC (0.50) and ACST (0.44;
Table 1), suggesting the absence of authigenic iron min-
erals in sediments. In other words, the iron presents in the
sediment was mostly in structural position of aluminosili-
cates. The mean, higher Ca/Al ratios of 0.22 and 0.21 for
offshore and coastal sediments were probably attributed to
shell materials and lower ratio of 0.18 found in the bed
sediment of River Kaoping supports this. The ratios are,
however, slightly lower than UC-YC (0.26), revealing the
initial loss of Ca from Ca-silicates during chemical
weathering process. Similarly, the mean ratios of Mg/Al,
K/Al, and P/Al of offshore and coastal sediments show
close association with these ratios in UC-YC and ACST.
Exceptionally, the Na/Al ratios in most of the sediments
were low when compared to crustal materials and ACST
indicating signicant loss of Na, similar to Ca, because
both elements are, in general, dissolved easily during initial
stages of weathering processes.
Table 1 Mean major element/Al ratios in surface sediments, off southwestern Taiwan, and bed sediment of River Kaoping, compared with
major element/Al ratios of UCC, UC-YC, ACST, and average shale
Si/Al Ti/Al Fe/Al Ca/Al Mg/Al Na/Al K/Al P/Al
Offshore sediments (water depths: 105537 m)
Minimum 2.89 0.052 0.42 0.064 0.13 0.077 0.25 0.005
Maximum 3.85 0.057 0.77 0.40 0.21 0.13 0.29 0.012
Mean 3.42 0.054 0.49 0.22 0.15 0.10 0.28 0.007
SD (N = 12) 0.28 0.001 0.09 0.11 0.03 0.01 0.01 0.002
Coastal sediments (water depths: <100 m)
Minimum 3.23 0.041 0.39 0.14 0.11 0.076 0.24 0.003
Maximum 4.48 0.056 0.57 0.34 0.28 0.25 0.39 0.007
Mean 3.89 0.049 0.47 0.21 0.16 0.14 0.30 0.005
SD (N = 8) 0.48 0.004 0.07 0.07 0.07 0.07 0.06 0.002
Bed sediment, River Kaoping 5.16 0.049 0.51 0.18 0.12 0.15 0.26 0.006
UCC
a
3.85 0.038 0.44 0.38 0.16 0.36 0.35 0.008
UC-YC
b
4.17 0.053 0.50 0.26 0.19 0.29 0.29 0.018
ACST
c
4.66 0.049 0.44 0.13 0.14 0.18 0.32 0.005
Average Shale
d
3.13 0.052 0.54 0.18 0.17 0.07 0.30 0.008
a
Taylor and McLennan (1985)
b
Gao et al. (1998)
c
Selvaraj and Chen (2006)
d
Turekian and Wedepohl (1961)
Environ Geol
1 3
Major elements such as Mg (0.86), K (0.84) Fe
(0.75), Ca (0.53), and Na (0.53) show signicant neg-
ative correlations with Si (Table 3) indicating the presence
of quartz-rich sand and silt. The negative correlations of Si
with almost all the major and trace elements as well as Cl,
OC, and S (Table 3) indicate dilution of particulate trace
elements by sandy, detrital sediments. The contrast in
composition between quartz-rich sand and heavy mineral-
rich sand has been clearly depicted by the negative corre-
lation between SiO
2
and Al
2
O
3
, Fe
2
O
3
, and MgO in shelf
sediments of the Gulf of the Farallones (Dean and Gardner
1995). A plot between SiO
2
and Fe
2
O
3
T
(Fig. 2a) shows a
deviation (marked with a dashed line) from its original
negative trend due to iron enrichment which is attributable
to dumped slag materials. It is also evident that because of
iron enrichment, SiO
2
value was reduced around 5%
(detrital dilution) in the sample CS12 collected from the
new dumping site when compared to the surrounding
samples. This inference is further substantiated by the Fe/
Al ratio of sample CS12 which shows 0.77 (Table 1). This
ratio is higher than 0.69, the value indicating the presence
of Fe held in structural position of aluminosilicates (Cal-
vert 1976), and suggestive of incorporation of iron into
sediment from slag materials. All other samples showing
Fe/Al ratio lower than 0.69 reveals that Fe in all the sed-
iments was associated with aluminosilicate. The linear
relationship between Al and K (r = 0.45; Table 3) suggests
the presence of illite, a product of moderate chemical
weathering, which is well in accordance with the X-ray
diffraction (XRD) patterns of these samples (Chen 1997).
Overall, the major element/Al ratios suggest that the
sediments are coarse-grained (sand and silt sizes), quartz-
dominated, authigenic Fe-free and moderately weathered
products of sedimentary rocks of Taiwan and UC-YC,
especially the latter source for offshore sediments. The
above interpretations are well consistent with their mean
values of weathering indices such as Chemical Index of
Alteration (CIA; 74, 73, and 63 for offshore, coastal, and
river sediments) and Plagioclase Index of Alteration (PIA;
84, 83, and 66); both show moderate chemical weathering
condition in Taiwan (Selvaraj and Chen 2006). Further-
more, the above inferences are well corroborated with
Table 2 Data of major elements, mean grain size (Mz), calcium carbonate (CaCO
3
) and organic carbon (OC) in surface sediments off
southwestern Taiwan
Sample Major elements (%)
Si Ti Al Fe
T
Mg Ca Na K P Cl S Mz (lm) CaCO
3
(%) OC (%)
Offshore sediments (water depth: 105537 m)
CS4 30.1 0.43 7.81 3.30 1.08 1.50 0.73 2.10 0.05 0.03 0.04 9.36 2.41 0.57
CS5 29.3 0.46 8.16 3.60 1.13 1.60 0.74 2.30 0.05 0.04 0.03 9.71 4.74 1.05
CS6 26.9 0.53 9.32 5.00 1.28 0.60 0.72 2.70 0.05 0.14 0.11 6.47 4.74 1.01
CS8 29.9 0.42 7.92 3.60 1.05 1.40 0.82 2.00 0.07 0.18 0.05 10.7 5.97 0.76
CS10 27.5 0.44 8.01 3.90 1.14 1.80 1.06 2.20 0.06 0.63 0.11 13.9 4.74 1.42
CS12 25.4 0.43 7.83 6.00 1.55 3.10 0.82 2.30 0.09 0.33 0.13 7.67 6.34 1.60
CS13 28.0 0.48 9.00 4.20 1.16 1.10 1.04 2.60 0.05 0.39 0.04 8.28 4.74 0.82
CS14 29.1 0.47 8.49 3.90 1.09 1.30 0.86 2.30 0.06 0.07 0.04 15.1 4.74 0.90
CS15 27.5 0.43 8.23 3.90 1.41 3.30 0.87 2.20 0.06 0.21 0.06 8.26 4.74 1.24
CS17 28.2 0.48 8.64 4.00 1.21 1.40 0.88 2.50 0.05 0.20 0.06 8.09 4.66 0.90
CS19 28.3 0.41 7.73 3.60 1.66 2.80 0.89 2.00 0.07 0.24 0.09 13.4 2.26 1.36
CS21 28.8 0.43 8.25 3.60 1.07 1.30 0.91 2.30 0.06 0.21 0.05 9.25 6.71 0.92
Coastal sediments (water depth <100 m)
HB005 24.1 0.38 7.47 4.26 2.09 2.56 1.76 2.92 0.04 0.85 0.06 102.6 6.68 0.30
HBT01 29.0 0.49 8.77 4.00 1.13 1.40 0.67 2.34 0.06 0.03 0.06 64.7 5.44 0.44
K1 25.3 0.32 7.25 4.08 2.01 2.28 1.82 2.84 0.03 0.81 0.01 451.7 4.10 0.12
KN2 31.2 0.35 7.58 3.32 0.96 1.38 0.78 2.07 0.05 0.02 0.02 380.0 4.54 0.08
KN12 31.4 0.38 7.50 3.43 1.01 1.35 0.77 2.00 0.05 0.02 0.04 197.0 3.74 0.29
KS2 31.5 0.39 7.47 3.28 1.00 1.27 0.75 2.01 0.05 0.02 0.03 145.7 4.56 0.16
KS11 31.7 0.36 7.70 3.20 0.95 1.09 0.77 2.13 0.04 0.01 0.02 330.0 4.32 0.13
S1 34.0 0.31 7.59 2.98 0.82 1.51 0.94 1.80 0.03 0.02 0.03 239.0 4.77 0.22
Bed sediment, River Kaoping
RK 33.8 0.32 6.56 3.32 0.78 1.19 0.97 1.72 0.04 0.04 0.03 ND ND ND
ND not determined, Fe
T
total Fe, OC organic carbon
Environ Geol
1 3
XRD patterns of these samples which all, except for bed
sediment of River Kaoping that was not analyzed for
minerals, show quartzfeldsparscalciteillitechlorite
kaolinite assemblage (Chen 1997).
Trace element geochemistry
Table 4 compares the range and mean concentrations of
total trace metals, including Fe, for the sediments studied
with those obtained for other areas of Taiwan, East China
Sea, the UCC, UC-YC, ACST and average shale as well as
fresh and recovered iron and steel slag. Cadmium values of
coastal and offshore surface sediments are within the range
of reported concentrations of Cd in sediments of other
areas of Taiwan coast. However, our Cd values (maximum
1.2 lg g
1
), including bed sediment of River Kaoping
(RK), are lower than those in sediments from Kaohsiung
River (KR; maximum 1.91 lg g
1
; Chen and Wu 1995)
and KH (maximum 6.6 lg g
1
; EPA 1992; Chen and Wu
1995). Table 4 demonstrates, in general, the high concen-
trations of Cr in offshore than coastal sediments (Table 5),
possibly attributed by dumped iron and steel slag which
contains considerable amount of Cr, the metal used to
harden steel to manufacture stainless steel alloys. Bed
sediment of RK shows low concentrations of Cr than
coastal and offshore sediments and the value is low against
the reported Cr in sediments of KH (EPA 1992; Hung
1994) and ACST, but higher with respect to coastal sedi-
ments of other parts of Taiwan and East China Sea. Sim-
ilarly, our Cu values are comparable to other coastal
sediments of Taiwan and the values are low with respect to
harbor sediments. We also obtained very low concentration
of Cu (14 lg g
1
; Table 4) from bed sediment of River
Kaoping, which is suggestive of uncontaminated condition
especially with this metal; the situation is contrary to
abnormal Cu concentrations (2005,000 lg g
1
) observed
in sediment and oyster samples of the northwestern Taiwan
(Lin and Hsieh 1999).
Iron shows higher values in offshore sediments and the
values are higher than previously reported values except
shelf sediments of East China Sea, where this element
shows comparatively higher values (Table 4); however, all
our values are lower than the UCC, except two samples,
CS6 and CS12, which show very high values of 5 and 6%,
respectively; both fall in the new dumping site (Fig. 1).
Strikingly, the highest values of Cr (158 lg g
1
), Mn
(2,773 lg g
1
), P (907 lg g
1
), S (1,267 lg g
1
), and Zn
(219 lg g
1
) are associated with CS12 (Table 5), revealing
the inuence of dumped iron and steel slag materials on the
chemistry of sediments. It is well known that steel contains
signicant amount of impurities like phosphorous and
sulfur. The other alloying elements such as Cr, Co, Cu, Mo,
Ni, Ti, and V are added to improve corrosive strength,
high temperature, and mechanical properties of steel. In
Table 3 Correlation coefcients (r) between different pairs of variable (N = 21)
Si Ti Al Fe Mg Ca Na K P S As Cd Cr Cu Mn Ni Pb V Zn Mz
Al 0.90
Fe 0.75 0.47
Mg 0.86 0.52
Ca 0.53 0.68
Na 0.53 0.74
K 0.84 0.45 0.58 0.72 0.59
P 0.56 0.54
Cl 0.77 0.81 0.48 0.89 0.69
S 0.51 0.50 0.71 0.69
Cr 0.59 0.52 0.79 0.53 0.83 0.78
Cu 0.66 0.63 0.53 0.44 0.56 0.46 0.45
Mn 0.55 0.68 0.70 0.68 0.81
Ni 0.78 0.60 0.57
Pb 0.54 0.49 0.69 0.59 0.55 0.70
V 0.47 0.81 0.78 0.66 0.63 0.67 0.71 0.44 0.46
Zn 0.48 0.62
Mz 0.81 0.62 0.71 0.60 0.45 0.61 0.59 0.55 0.74
CaCO
3
0.46 0.45
OC 0.49 0.62 0.48 0.57 0.76 0.78 0.50 0.50 0.79 0.70 0.79 0.78
Bold values are signicance at the 0.01 level and others are at the 0.05 level
Mz mean grain size, CaCO
3
calcium carbonate, OC organic carbon
Environ Geol
1 3
addition, the signicant amount of Mn acts as an important
components of steel (Fe: 8098%; Mn: 0.216%; C: 0.03
1.25%; P: maximum 0.05%; S: maximum 0.05%). Steel
slag or scrap also consist signicant amount of metals such
as Cr, Ni, V, and Mo. Coastal and river sediments show
lower concentrations of Mn with respect to UC-YC and
this element has not been reported previously from our
coast except one report (Lee et al. 2000) which shows a
consistent range (Table 4). It is interesting to note, how-
ever, that many offshore samples have higher concentra-
tions of Mn. Abnormal Mn values (2,773 and 2,475 lg g
1
)
associated with new and old dumping sites clearly indicate
the inuence of dumped materials and further supported by
very high concentrations of Mn obtained from fresh
(11,000 lg g
1
) and recovered slag (14,347 lg g
1
) (Chen
and Hungspreugs 1996; Table 4). Relatively low value of
Mn in old dumping site suggests dilution of contaminants
probably by recent sediments through natural attenuation
processes as observed in historical dumping site in Baltic
Sea (Leipe et al. 2005). Table 4 also shows, when com-
pared to the previously reported values, lower concentra-
tions of Ni and the values are lower than the average shale.
In contrast, the highest concentrations of offshore and
coastal sediments (46 and 40 lg g
1
) appear to be higher
than Ni values in source materials, ACST and UC-YC as
well as UCC, suggesting Ni enrichment in few locations.
Lead and zinc are mostly higher than reference and source
compositions, UCC, UC-YC, and ACST, as well as other
coastal sediments of Taiwan, which likely reveal contam-
ination, although the values of these elements in our study
are vefold lower than the reported values in sediments of
KH (EPA 1992; Hung 1994).
The entire geochemical data set including mean grain
size and OC of current study was subjected to correlation
analysis in order to explore the possible associations
existing between different variables. Table 3 shows a
correlation matrix for the parameters studied where tita-
nium, a detrital indicator, is positively correlated with Al
(0.90), V (0.81), Ni (0.78), Cu (0.63), and P (0.56). It re-
veals the association of V, Ni, and Cu in lattices of alu-
minosilicate minerals of continental origin and thereby
suggests the natural variability of these metals in the sed-
iments. This is further supported by the positive relation of
Al with V (0.78) and Ni (0.60). Iron exhibits positive
covariance with Cr, S, and V and this association probably
was induced by dumped materials because all these ele-
ments are important ingredients in the process of manu-
facturing different grades of steel. It is clear from Table 3
that the positive correlations among P, Cr, OC, Mn, Pb, S,
and V are mainly related to anthropogenic inputs and re-
ect the complexing nature of OC/matter. Note (Table 3)
that Cr, V, S, and P show dual associations, detrital (Ti and
Al) and OC, and these associations are conveniently
interpreted as normal and dumped material induced con-
ditions, respectively, in the study area. Recent study on
coastal sediments of southwestern Taiwan has also sug-
gested the relative enrichment of metals in areas of high
mud and OC contents (Hung and Hsu 2004). Mean grain
size, however, invariably exhibits negative or insignicant
Fig. 2 Plots of a SiO
2
versus Fe
2
O
3
T
, b OC versus S, and c OC versus
S/Fe total. Dashed line in top panel represents the iron enrichment in
sediments (CS12 and CS6) of new dumping site. Also note the
enrichment of sulfur (middle panel) and S/Fe ratio (lower panel) in
sediments (CS6, CS10, CS12, and CS19) of dumping sites
Environ Geol
1 3
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Environ Geol
1 3
correlations with almost all the elements studied here, ex-
cept Cd (r = 0.45; Table 3), suggesting weak granular
afnity of elements.
Normalization and enrichment factors
Normalization is a technique used to separate the metals of
natural variability from the metal fraction that is associated
with sediments due to modern activities. Normalization of
estuarine and coastal sediment trace elements data has been
achieved, in specic, by using Al (Windom et al. 1989), Fe
(Morse et al. 1993), Li (Loring 1991), Yb (Szefer et al.
1999; Szefer 2002), OC (Daskalakis and OConnor 1995),
and grain size (Palanques and Diaz 1994). Among these
proxies, Al is a conservative element and has been widely
used objectively to compensate for variations in both grain
size and composition. Besides, anthropogenic input of Al is
a very rare phenomenon. The characteristic advantages of
Al normalization over other proxies have been mentioned
elsewhere (Loring and Rantala 1992; Rubio et al. 2000;
Selvaraj et al. 2004). Normalization can also be applied to
determine enrichment factors (EFs) which provide a tool to
evaluate sediment quality. EFs close to unity point to
crustal origin and >10 are considered as non-crustal sour-
ces (Nolting et al. 1999). Since our major element/Al ratio
(see major element geochemistry section) indicates the
upper crust of Yangtze Craton (Gao et al. 1998) and
average composition of sedimentary rocks of Taiwan
(Selvaraj and Chen 2006) as the sources for offshore and
coastal sediments, respectively, we have chosen these two
reference materials to calculate EFs employing the equa-
tion: EF = (Metal/Al)
Sediment
/(Metal/Al)
UC-YC/ACST
.
The calculated EFs for the elements As, Cd, Cr, Cu, Mn,
Ni, Pb, V, and Zn in the studied sediments are presented in
Table 6. Enrichment factors calculated with respect to UC-
YC show higher mean values for Pb (2.65) and Cd (2.46),
well-established metals of anthropogenic origin, in off-
shore sediments. Metals such as Zn, Cr, As, and Mn are
also have EFs >1 thereby suggest their enrichments in
offshore sediments likely due to dumped iron and steel
slag. Similarly, mean EFs calculated with respect to ACST
were higher unity for Pb, Ni, Cu, Mn, V, and Zn, indicating
Table 5 Data of trace elements and physicochemcial parameters (E
h
and pH) in surface sediments off southwestern Taiwan
Sample Trace elements (lg/g)
As Cd Cr Cu Mn Ni Pb V Zn pH E
h
(mV)
Offshore sediments (water depth: 105537 m)
CS4 5.0 0.20 78 31 393 38 41 100 92 7.88 113
CS5 1.0 0.25 81 33 356 40 47 114 99 7.31 155
CS6 6.2 0.20 105 40 573 46 53 141 118 7.36 146
CS8 3.2 0.22 85 44 655 42 57 92 109 7.06 149
CS10 5.7 0.18 83 41 647 40 47 109 113 7.97 200
CS12 10.5 0.15 158 31 2,773 36 61 134 219 8.61 88
CS13 3.0 0.24 82 37 439 42 50 109 106 7.43 110
CS14 5.9 0.27 81 37 711 40 51 118 105 7.52 112
CS15 7.9 0.22 111 42 1,162 36 41 106 95 7.95 102
CS17 2.9 0.19 87 36 482 40 45 102 102 7.73 120
CS19 3.5 0.21 108 36 2,475 37 44 100 91 8.12 96
CS21 7.4 0.24 105 45 660 42 67 102 119 7.52 240
Coastal sediments (water depth <100 m)
HB005 14.5 0.60 84 57 371 37 45 81 198 ND ND
HBT01 19.9 0.29 96 49 379 40 53 101 244 ND ND
K1 7.2 0.22 64 26 357 36 42 68 163 ND ND
KN2 BDL 0.88 69 26 369 35 47 84 132 ND ND
KN12 17.8 1.20 76 30 368 37 53 74 143 ND ND
KS2 23.9 0.28 72 31 365 36 46 87 162 ND ND
KS11 BDL 0.43 67 27 356 36 42 70 140 ND ND
S1 BDL 0.33 56 14 390 26 21 87 85 ND ND
Bed sediment, River Kaoping
RK 15.2 0.23 58 14 320 38 40 54 94 ND ND
ND not determined, BDL below detectable limit (<0.1 ppm)
Environ Geol
1 3
sediment contamination, despite the EFs of studied metals
vary signicantly based on the reference materials used.
Coastal sediments also exhibit higher mean EFs for Cd
(6.98), As (2.77), Pb (2.48), and Zn (2.17) with respect to
UC-YC, which further supports the above inference. It has
been previously shown (Selvaraj and Chen 2006) that
coastal sediments of Taiwan were mainly derived from the
sedimentary rocks in Taiwan, and our EF calculation over
ACST further reveals contaminated condition of coastal
sediments by metals such as Pb, Zn, Ni, and Cu (Table 6).
Bed sediment of River Kaoping reveals more or less sim-
ilar results that also shows higher enrichment factors for As
(4.76), Cd (3.34), and Pb (2.65) against UC-YC but Pb
(2.16), Ni (1.86), and Zn (1.28) against ACST, indicating
considerable input of contaminated sediment through river
into the coastal zone.
It is worth mentioning here that our calculation of EFs
with respect to the UCC (not shown in Table 6) shows
polluted nature of coastal sediments in terms of As (EFs
range 5.3317.06; mean 8.21) but contaminated condition
for offshore sediments (EFs range 1.787.15; mean 3.18).
Although very high EF values obtained especially for As
and Cd in offshore and coastal sediments with respect to
the UC-YC indicate contaminated nature of sediments
(Table 6), lower EF values of these elements with respect
to real sources, UC-YC and ACST as revealed by element/
Al ratios, when compared to UCC, suggestive of two
points: (1) the UCC cannot be used as a reference material
to calculate EFs and, in turn, to study anthropogenic impact
on sediments derived from this small island (0.024%) of
the earths surface as we normally do for sediments that
integrate weathered materials from the larger continental
Table 6 Summary statistics of enrichment factors (EFs) with respect to upper crust of Yangtze Craton (UC-YC) and average composition of
sedimentary rocks of Taiwan (ACST) in sediments, off southwestern Taiwan, compared with EFs from other areas of Taiwan
As Cd Cr Cu Mn Ni Pb V Zn
Offshore sedimentsEFs with respect to UC-YC
a
Minimum 0.25 1.82 1.02 0.83 0.42 0.87 2.17 0.90 1.22
Maximum 2.76 3.03 2.26 1.17 3.39 1.06 3.54 1.33 2.96
Mean 1.29 2.46 1.32 0.97 1.12 0.96 2.65 1.04 1.46
SD 0.68 0.37 0.35 0.13 1.02 0.05 0.45 0.12 0.48
EFs with respect to ACST
b
Minimum 0.69 1.22 0.47 1.41 1.76 1.10 1.03
Maximum 1.54 1.71 3.81 1.71 2.87 1.62 2.51
Mean 0.90 1.41 1.26 1.55 2.16 1.26 1.24
SD 0.23 0.18 1.14 0.08 0.37 0.15 0.41
Coastal sedimentsEFs with respect to UC-YC
Minimum 2.05 2.89 0.82 0.39 0.41 0.69 1.20 0.71 1.18
Maximum 6.58 15.24 1.27 1.62 0.49 0.99 3.09 0.91 2.94
Mean 2.77 6.98 1.06 0.89 0.46 0.92 2.48 0.83 2.17
SD 2.61 4.33 0.15 0.37 0.02 0.10 0.56 0.08 0.56
EFs with respect to ACST
Minimum 0.56 0.57 0.46 1.10 0.98 0.86 1.00
Maximum 0.86 2.36 0.55 1.60 2.52 1.10 2.49
Mean 0.72 1.30 0.52 1.48 2.02 1.00 1.84
SD 0.10 0.54 0.03 0.16 0.45 0.09 0.48
Bed sediment, River Kaoping
EFs with respect to UC-YC 4.76 3.34 0.99 0.45 0.47 1.16 2.65 0.64 1.51
EFs with respect to ACST 0.97 0.66 0.52 1.86 2.16 0.78 1.28
Kaoping coastal sediments 0.16 0.85 0.53 1.20 1.18
Southwestern Taiwan
c
1.65 2.92 2.38 4.94 3.50
Kaohsiung coast, Southwestern Taiwan
d
1.20 0.60 0.90 1.50 4.50 3.40
a
Gao et al. (1998)
b
Selvaraj and Chen (2006)
c
Hung and Hsu (2004)
d
Lee et al. (1998)
Environ Geol
1 3
landmass and (2) very high EF values of As and Cd might
also be related to the method of analysis applied in this
study which showed wider error limits for these elements
(see Materials and Methods Section) rather than real situ-
ation of sediments. Nonetheless, the decreasing order of
mean EFs in sediments of offshore with respect to UC-YC
(Pb > Cd > Zn > Cr > As > Mn > V > Cu > Ni) and the
coastal (Pb > Zn > Ni > Cu > V > Cr > Mn) and river
(Pb > Ni > Zn > Cr > V > Cu > Mn) environments with
respect to ACST clearly suggest that the offshore and
costal sediments are burdened with metals such as Cd, As,
Pb, and Zn with EFs >2.
Factor analysis
Geochemical factor analyses are highly suitable for deter-
mining the factors that control the trace metal distribution
than measurement of absolute metal concentrations in
specic size grains or the use of metal/normalizing element
ratios (Loring 1991; Winters and Buckley 1992). This is
because such studies can provide information about the
association of metal-inorganic or metal-organic phases.
Therefore, to decipher signicant grouping of factors and
related possible geochemical controlling processes, the
whole sediment geochemical data including mean grain
size, CaCO
3
and OC were subjected to factor analysis
using SPSS software (Version 7.5). The factors were ex-
tracted using Varimax rotation scheme with Kaiser Nor-
malization.
The results show that four factors account for 80.9% of
total variance (Table 7). Factor 1 account for 25.1% of
variance and Mn, Cr, P, S, OC, Ca, Fe, and V are loaded in
this factor. Association of OC, S, and P with redox sensi-
tive elements (Mn, Fe, and V) suggests the oxygen
depletion condition; it might be a temporary, local phe-
nomenon, and active oxidation-reduction processes near
the sediment-water interface. Further, the above associa-
tion is very characteristic feature of only two samples,
CS12 and CS19, which fall in the new and old dumping
sites (Fig. 1). The oxygen depletion is also supported by
high concentrations of S (1,267 and 940 lg g
1
) in these
samples. Metals associated with sediments behave differ-
ently in anoxic/suboxic and oxic conditions which essen-
tially depend on physicochemical characteristics (pH, E
h
,
and O
2
) of the depositional environment. For instance, oxic
depositional environment always have high E
h
when
compared to suboxic environment where the E
h
is often
low. Very high values of pH (8.61 and 8.12) and low values
of E
h
(96 and 88) measured in the sediments of new and old
dumping sites were possibly as a result of production of
hydroxide ions during the dissolution of slag according to
equation: H
2
O + FeS M Fe
2+
+ HS

+ OH

. Such disso-
lution was possible due to the relative solubility of
iron suldes like pyrrhotite (Fe
1x
S) and/or mackinawite
(FeS
1x
) present in the slag when it sinks few cm below the
sediment-water interface due to its higher density to the
zone of low concentration of oxygen as also experimentally
demonstrated by Vdovic et al. (2006). Librated Fe
2+
along
with Mn
2+
which migrated upward in the sediment column
pore-water as dissolved species and oxidized as Fe
3+
and
Mn
4+
and get precipitated either as FeMn oxyhydroxides
in the presence of free hydroxyl ions (OH

) or metal sul-
des because of HS

. Increase of phosphate values around

100400 lg g
1
in samples of dumping sites (Table 2)
suggests an adsorption of phosphate on iron hydroxides as
indicated by their statistically signicant correlation
(r = 0.54; Table 3). Among the 12 samples collected in
and around the old and new dumping areas, CS12 exhibits
highest OC (1.60%) and pH (8.61) as well as lowest Eh
(88 mV), authenticating the presence of low oxygen con-
centration compared to the oxygen levels in coastal sedi-
ments studied. Sample CS12 therefore invariably shows
highest enrichment factors calculated with respect to UC-
YC for the elements such as As (2.76), Cd (3.03), Cr (2.26),
Mn (3.39), Pb (3.54), and Zn (2.96). This condition can
most likely be attributed to dumping of slag materials
Table 7 Varimax rotated factor matrix (N = 21)
Variable Factor 1 Factor 2 Factor 3 Factor 4
Si 0.39 0.36 0.83 0.00
Ti 0.29 0.92 0.00 0.00
Al 0.12 0.87 0.00 0.16
Fe 0.61 0.37 0.44 0.22
Mg 0.28 0.00 0.91 0.00
Ca 0.67 0.41 0.49 0.00
Na 0.23 0.28 0.90 0.00
K 0.00 0.47 0.82 0.00
P 0.83 0.37 0.16 0.26
Cl 0.00 0.00 0.93 0.00
S 0.79 0.31 0.13 0.00
As 0.11 0.29 0.16 0.79
Cd 0.31 0.27 0.14 0.48
Cr 0.89 0.32 0.13 0.17
Cu 0.20 0.64 0.40 0.27
Mn 0.94 0.15 0.00 0.00
Ni 0.00 0.87 0.00 0.00
Pb 0.33 0.61 0.00 0.49
V 0.58 0.67 0.00 0.19
Zn 0.17 0.00 0.31 0.84
Mz 0.54 0.66 0.00 0.23
CaCO
3
0.00 0.29 0.24 0.53
OC 0.80 0.41 0.00 0.34
Eigen values 8.91 4.49 2.84 2.34
Percent explained 25.1 24.1 20.7 11.0
Environ Geol
1 3
where the top 10 cm of our sediment core shows slag-
dominated sediments. Dumping-induced precipitation of
authigenic FeMn oxyhydroxide and complexation of or-
ganic matter with Fe, Mn, and Cr observed here are in good
agreement with earlier observations of the association of
organic matter with Fe, Mn (Krom and Sholkovitz 1978)
and Cr (Selvaraj et al. 2004).
Furthermore, Table 3 demonstrates that the variables
associated with factor 1 are controlled essentially by four
components, i.e. OCFePS. Among these, CSFe
relationships in marine sediments have been used to
determine palaeoredox conditions in the environment of
deposition (e.g., Berner 1970, 1984; Raiswell and Berner
1985; Passier et al. 1996). Since the above association is
typical for sediments of dumping sites, we speculate that
the dumped iron and steel slag likely facilitate the above
association. A cross-plot of OC versus sulfur (Fig. 2b)
shows that the dumping site sediments (CS6, CS10, CS12,
and CS19) are relatively enriched in sulfur (940
1,267 lg g
1
) with low OC/S ratios of 914 when com-
pared to the surrounding sediments (OC/S: 1640). Al-
though our OC/S range of sediments in dumping sites is
well consistent with established TOC/S ratios (range 313;
average 2.8) of normal modern marine sediments (Berner
and Raiswell 1984), their sulfur and iron enrichments
support strong C-S-Fe relationship, a characteristic feature
of redox condition which facilitates normally the formation
of pyrite. Our speculation is further supported by the sig-
nicant positive relationship between OC and S/Fe
T
(Fig. 2c), a measure of the degree of pyritization of the iron
(Gibson 1985), in sediments of dumping sites.
Factor 2 explains about 24.1% of variance and is char-
acterized by high loading for Ti, Al, Ni, Pb, Cu as well as V.
Correlation between Al and Ti is very high (0.90; Table 3)
and both Ti and Al are refractory elements which are ex-
tremely immobile in the marine environment (Bischoff et al.
1979). Therefore, Ti and Al in these sediments are consid-
ered to be of detrital origin. The association of Ni, Pb, Cu,
and V with detrital elements indicates the considerable ter-
rigenous input of these elements in the study area. This
inference, however, contrasts with the EFs of these elements
which all show the mean EF > 1, which further suggests
dual, including anthropogenic, sources for these metals.
Variables such as Cl, Na, Mg, and K are loaded in factor
3 which accounts for 20.7% of variance. This factor can
explain the effect of sea salt; the samples were not washed
free of salts. The presence of Mg
2+
in this factor could be
due to the fact that it replaces Na
2+
(Nath et al. 1989).
Association of K in this factor further suggests the presence
of sea salt mostly on illite, the dominant clay mineral in the
analyzed sediments (Chen 1997). Factor 4 accounting for
11.0% of total variance is characterized by high loading
of trace metals As and Zn, less likely Pb and Cd, along
with carbonate. This factor, without signicant positive
emphasis on metal variables such as grain size, OC, Al, Fe
or Mn, strongly suggests anthropogenic source for these
metals and association with carbonate. Very high EF values
for these elements, especially As and Cd with respect to
UC-YC (Table 6), further authenticate the industrially
inuenced As and Cd in the analyzed sediments and also
consistent with the high bioconcentration factors of these
elements in terrestrial biota of Taiwan (Hsu et al. 2006).
Conclusion
Concentrations of major elements and their ratios with Al
as well as mean grain size demonstrate that silty offshore
and sandy coastal sediments off southwestern Taiwan are
weathered products of upper crust of Yangtze Craton and
sedimentary rocks of Taiwan, respectively. Comparative
study of trace elements with published results indicates
higher Mn and Fe levels in sediments of dumping sites.
Correlation analysis differentiates the metals (V, Ni, and
Cu) of natural variability from elements (P, Cr, Mn, Pb,
and S) that are inuenced by dumped iron and steel slag-
induced redox processes. Normalization of total trace
metals to Al and their ratios with reference materials
(UCC, UC-YC, and ACST) demonstrated the higher mean
enrichment factors (>2) for As, Cd, Pb, and Zn, reveal
contamination of sediments by these metals from anthro-
pogenic sources. Factor analysis reveals four dominant
geochemical associations: (1) dumped iron and steel slag-
induced association of Mn, Cr, P, S, OC, Ca, Fe, and V due
to authigenic FeMn oxyhydroxides and/or metal suldes
precipitation; (2) terrigenous association of Ni, Pb, Cu, and
V; (3) sea salt association of Cl, Mg, Na, and K; and (4)
anthropogenic association of As, Zn, and Cd. The data
presented here suggest that metal contamination, especially
by As, Cd, Pb, and Zn, is a signicant factor in sediments
of southwestern Taiwan and justify the need for further
studies to ascertain long-term effects of contaminants as
well as dumped iron and steel slag on the sediment
chemistry.
Acknowledgments Financial supports from the China Steel
Corporation (84-Y93-003), the ROC National Science Council (NSC
86-2611-M110-007W, 93-2621Z-110-004, 95-2621-Z110-005, and
95-2611-M-110-001) and Aim for the Top University Plan (95C0312)
are greatly appreciated. Anonymous reviewer(s) are thanked for their
comments on an earlier draft of this manuscript.
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