International Journal of Sediment Research 25 (2010) 340-354

Geochemical baselines of major, minor and trace elements

in the tropical sediments of the Terengganu River basin, Malaysia
Khawar SULTAN1 and Noor Azhar SHAZILI2
Abstract
The geochemical baselines and distribution of 31 elements (Al, Fe, K, Na, Mg, Ca, Mn, Ba, Cr, Zr,
Ni, Sr, Zn, Y, Li, Cu, Mo, Nb, Th, Co, Ga, W, Ta, Be, Ti, Ge, Se, Bi, Te, Sc and Re) and
physico-chemical parameters of the tropical surface sediments of the Terengganu River basin,
Malaysia, are reported. Sediments are sandy loam to sand in texture consisting of mostly quartz, low
organic matter content (average2.68%), low CEC (average2.02 cmol(+)/kg) and mildly acidic pH1:5
(average5.91). Concentrations of Mn, Fe, Ba, Cr, Ni, Cu, Mo and Se were measured to be above the
environmental sediment quality criteria at various locations. Lake sediments registered significantly
higher Al, Fe, Ti, Mg, Ca, Mn, Te and Sc concentrations as compared to the river sediments. Most of
the elements investigated showed an association with silt size fraction (263 m). Among the
investigated metals, Mo and Fe concentrations showed an increasing (>5-fold) and decreasing
(>3-fold) trend, respectively, along the river path from the upstream to the downstream depending on
the stream pH-redox conditions. The enrichment factor values (EF >5) of Cr, Ni, Mo and Se indicated
enrichment from anthropogenic activities. Alkali and alkali earth metals registered a significant
depletion (EF values <0.7) as compared to the Earths crust. Principal component analysis of the two
main components (PC1, 87.4% and PC2, 8.7%) revealed a well-defined group of estuary sediments.
Lake and river sediment sampling locations did not form defined groups revealing heterogeneity in
the origin of geologic material and the in-stream geochemical processes. However, Cr, Ni, Mo and Se
formed a separate group with elevated concentrations (e.g. Cr>1,000 mg/kg) indicating contamination
of sediments. This work presents the geochemical baselines of the tropical sediments as industrial
development and urbanization along the north east coast of Peninsular Malaysia are advancing
rapidly.
Key Words: Tropical, Sediment, Environment, Elements, Geochemistry, Malaysia

1 Introduction
The significance of the lake, river and estuary sediment contamination by inorganic metals has been
emphasized in studies around the world due to the adverse biological effects on the health of the aquatic
environment (NRC, 1989; EC, 2006; Yi et al., 2008; Duan et al., 2009; Ezemonye et al., 2009).
Contaminants originating from urban, industrial and agricultural activities, atmospheric deposition and
from natural geological sources may accumulate in sediments up to several times the background
concentrations and may serve as the potential storage (> 90% of the heavy metal loads; Calmano et al.,
1993) for both the inorganic and organic contaminants (McGrath, 1995; Miller, 1997; Zheng et al., 2008;
Sumith et al., 2009; Reczynski et al., 2010). This build up of potentially toxic metals carries a huge risk to
the beneficial uses and sustainability of the natural resources such as water, plants and aquatic animals.
Particle-reactive heavy metals upon entering into the water bodies may be quickly adsorbed onto
1

Dr., Department of Hydrology, University of Bayreuth, 95440 Bayreuth, Germany, Corresponding author. Fax:
+49(0)921 55-2366. E-mail: sultan.khawar@uni-bayreuth.de; sultankha@gmail.com (K. Sultan)
2
Dr., Prof., Institute of Oceanography, University Malaysia Terengganu, Mengabang Telipot, 21030 Kuala
Terengganu, Malaysia
Note: The original manuscript of this paper was received in Sept. 2009. The revised version was received in May
2010. Discussion open until Sept. 2011.
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suspended matter and ultimately move to bottom sediments. For the identification of hot spots of elevated
metal concentrations, monitoring and control of pollution sources and the development of sediment
quality guidelines, an understanding of ambient background and baseline concentrations of metals in
sediments is extremely important. The sediment geochemical baseline values can be used to assess the
quality of dredged materials, remedial rehabilitation of contaminated sites and ecological risk assessment
(Smith et al., 1996; Atgin et al., 2000). The geochemical signature of sediments is, therefore, a useful
indicator of the environmental state of the watershed by reflecting on the geochemistry of the drainage
basin from the heavily urbanized and industrialized land to pristine regions.
The tropical region of the east coast of Peninsular Malaysia is undergoing rapid development in the
industry sector and urbanization, especially along the coastal areas of the South China Sea. Industrial
effluent, municipal discharge, agricultural runoff and past mining waste materials may result in
contamination of the food chain when entering the river system. It is, therefore, important to document
the prevailing concentrations, distribution and geochemistry of the elements to monitor any changes
caused by anthropogenic activities in the future. In Malaysia, there are currently no comprehensive
sediment reference values available to establish levels of potentially toxic elements. Hence, this work is
significant in understanding the geochemical baselines of the major and trace elements by presenting
detailed documentation of the current state of tropical river, estuary and lake sediments of the northeast
coastal region of Peninsular Malaysia. The average concentrations for the measured elements were also
compared with the environmental guideline and geochemical baseline values established for sediments
around the world.
2 Methods
2.1 Study area
The Terengganu River basin lies in the wet tropics (4o41- 5o20N, 102o31-103o09E) covering
approximately 5,000 km2 with the Kenyir Lake in the west, the main channel and five major tributaries of
the Terengganu River, and the estuary (cross section area987 km2; discharge16.5109 m3/year) to the
east as shown in Fig. 1. The study area consists of freshwater Kenyir Lake forming a forested upper
watershed which drains into the main channel of the Terengganu River that meanders across the lowland
coastal region before flowing into the South China Sea. The study area is rural with a relatively pristine
environment in the upstream catchment area becoming urbanized and industrialized downstream with the
major settlement of Kuala Terengganu city at the river mouth. Prevailing and important land uses include
forest, commercial plantation (e.g., oil palm, coconut, rubber, cocoa), agriculture, rural/urban settlements,
past mining activities and industry.
The drainage pattern of the Terengganu River basin is set by the interior highland and is mainly
rectangular or angulate controlled by rock type and structure. Streams cut into various geological units
with forested inaccessible terrains marked by a rapid flow until reaching the relatively plain areas
downstream to the east. The water level rises and falls significantly depending on the seasonal rainfall. A
dry and wet season cycle causes alluvium to be deposited and removed in the riverbed as controlled by
the outflow of the river. The construction of a hydro electric power dam upstream has altered the
hydrogeochemical compartments consisting of the Kenyir Lake and the main tributary of the Terengganu
River (Fig. 1).
The study area lies in the tropical zone with annual temperatures varying between 23 and 31 with an
average of 26. The climate is governed by the northeast (October to March) and southwest (May to
September) monsoon rains. The mean annual rainfall is 3,200 mm.
2.2 Sampling
Surface sediments (depth < 10 cm) from 42 sampling locations along the Terengganu River and Kenyir
Lake were collected by gently scraping the surface using a plastic scoop in October 2007. Out of 42
sediment sampling locations 13 were from the Kenyir Lake, 26 from the main river channel and
tributaries, and 3 from the estuary with an aim to cover the Terengganu River basin (Fig. 1). Sediment
sampling locations were chosen randomly keeping in view the geological units, agriculture land, human
settlement and accessibility.
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Fig. 1 Map showing sampling locations of surface sediments (n = 42)

from the lake, river and estuary in the Terengganu River basin

The sediment samples were stored in sealed plastic bags and transported to the laboratory in cold boxes.
A GPS was used to record the coordinates of all the sampling locations for map development and spatial
distribution analysis. This study is a part of a project on the hydrogeochemistry of heavy metals surface
waters and topsoils of the Terengganu River basin.
2.3 Analysis
Sediment samples were oven dried ( 40) and passed through a 2 mm mesh sieve to remove coarser
particles. Sediment size analysis of clay (< 2m), silt (2-20 m) and sand (20-2,000m) size fractions
was performed using a Malvern Instrument by laser scattering at 5-10% sample obscuration. The
percentage of organic matter was determined by the weight loss on ignition (LOI%, 5 g, 4 h at 500) of
the oven dried sediment samples (Allen et al., 1974).
Sediment pH (pH1:5) and electrical conductivity (EC1:5) were determined in 1:5 sediment: distilled water
(w/v) suspensions after shaking for 1 hour on an end-over-end shaker followed by 1 h equilibration
(Rayment and Higginson, 1992). Cation exchange capacity (CEC) was determined by extraction of
exchangeable Ca, Mg, Na and K with an unbuffered ammonium acetate (1M NH4OH, 12 h) solution
(Sumner and Miller, 1996) and measured by inductively coupled plasma optical emission spectrometry
(ICP-OES). Exchangeable Al and H were extracted with IM KCl and measured by titration.
About 0.1 g of each sediment sample was digested in HNO3:HCl:HF (9:3:2, v/v) in a Teflon vessel and
heated in a microwave oven at 150 for 10 minutes. After cooling, 9 ml of 5% boric acid (B(OH)3) was
added to remove the fluoride residue. A clear solution with no residue was obtained at this stage. The
cooled acid digest was then filtered into 50 mL volumetric flasks and brought to volume with ultrapure
deionized water. Major and minor elements were analyzed by ICP-OES and trace elements were analyzed
by inductively coupled plasma mass spectrometry (ICP-MS Perkin Elmer ELAN 6100) at the Department
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of Chemistry and Institute of Oceanography, respectively. Elements with values below detection limits
were arbitrarily assigned half of the detection limits for the statistical analysis. All element concentrations
are reported as dry weight of sediments.
From certified standards (Merck), working standards of various concentrations were prepared.
Standard reference materials (PACS-2 and GBW-07401) and appropriate batch blanks were included with
each set of samples for the QA/QC program. All reagents used were of high quality and ultrapure
deionized water (18M) was employed throughout the analytical procedures. The accuracy error and
precision as relative percentage difference (%RPD) were determined following the methods described by
Cicchella et al. (2008). The detection limit, laboratory accuracy error and precision for the elements
measured are given in Table 1.
Table 1
Elements
Al
Fe
K
Na
Mg
Ti
Ca
Ba
Mn
Cr
Sr
Zr
Zn
Ni
Y
Li
Cu
Nb
Ga
Co
Th
Sc
Mo
W
Be
Ta
Bi
Se
Te
Re

Detection limits, accuracies and precisions for major and trace elements
Unit
Detection limit
Accuracy (%)
Precision (%PRD)
%
0.01
2.4
1.3
%
0.003
0.1
3.8
%
0.01
0.3
0.7
%
0.001
0.4
9.9
%
0.001
0.5
3.2
%
0.003
0.2
12.8
%
0.005
0.5
1.2
mg/kg
0.02
0.4
0.3
mg/kg
0.01
0.7
2.8
mg/kg
0.01
2.9
4.3
mg/kg
0.02
2.8
3
mg/kg
0.08
7.3
4.4
mg/kg
0.02
0.9
1.7
mg/kg
0.04
8.4
2.9
mg/kg
0.002
1.1
3.6
mg/kg
0.01
3.2
11.7
mg/kg
0.001
2.1
1.3
mg/kg
0.002
5.2
4.7
mg/kg
0.004
1.6
7.1
mg/kg
0.001
0.7
3.2
mg/kg
0.002
1.7
3.1
mg/kg
0.01
3.9
4.6
mg/kg
0.002
11.4
2
mg/kg
0.005
4.7
2.6
mg/kg
0.001
3.2
5.1
mg/kg
0.001
0.2
3.5
mg/kg
0.001
2.5
4.7
mg/kg
0.004
5
1.2
mg/kg
0.01
2.1
0.6
mg/kg
0.002
6.7
5.3

Sediment samples were mounted on aluminum SEM stub with an adhesive carbon tape and coated with
gold for the scanning electron microscope (SEM, JEOL-JSM 5310) analysis of the grain morphology. The
concentration distribution and sampling location maps were developed by using GIS (ArcView)
software. SPSS software was used for statistical analysis. Principal component analysis was performed
on 38 variable and 42 sampling locations using statistical software.
2.4 Geology
Large alluvial deposits of both continental and marine origin of Quaternary age are found along the east
coast and the floors of inland valleys and include gravel, sand, mud, clay and peat. Alluvium also contains
a valuable concentration of ores of various elements (Gobbett and Hutchison, 1973). The second most
dominant rock type is granite (Permian to lower Triassic) appearing as outcroppings in the form of high
International Journal of Sediment Research, Vol. 25, No. 4, 2010, pp. 340354

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peaks. Primary minerals associated with the Main Range Granite contain deposits of significant economic
value. Massive hill-forming limestone rock of the Permian period is present in the southeastern part of the
study area, however, limestone outcrops are restricted.
Volcanic rocks of the Carboniferous age occur interbedded with sedimentary rocks with localized
exposures. The majority of volcanic rocks are andesitic and rhyolitic. Argillaceious and arenacious rocks
of the Carboniferous to Permian age are the most dominant rock types (>43% area). Pelitic schist forms
north-northwest trending elongated body with major minerals including quartz, muscovite, biotite and
garnet. Other metamorphic rocks include phyllite and slate (Chand, 1978; Hadi and Fadzali, 2006).
3 Results
Summary statistics of 38 variables, including physico-chemical parameters and concentrations of major,
minor and trace elements of surface sediments of the Terengganu River basin, are listed in Table 2. The
correlation matrix depicting correlations between all elements is presented in Table 3.
Table 2

Physico-chemical parameters and element concentration data

of sediments in the Terengganu River basin

Parameter

Unit

Min

Average

Max

Median

Clay (<2 m)
Silt (263 m )
Sand (632,000 m)
CEC
LOI
pH1:5 H2O
EC1:5 H2O
Al
Fe
Ti
K
Na
Mg
Ca
Mn
Ba
Cr
Zr
Ni
Sr
Zn
Y
Li
Cu
Mo
Nb
Th
Co
Ga
W
Ta
Be
Ge
Se
Bi
Te
Sc
Re

%
%
%
cmol(+)/kg
%
s/cm
wt.%
wt.%
wt.%
wt.%
wt.%
wt.%
wt.%
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
g/kg
g/kg
g/kg

0.03
1.23
4.91
0.50
0.42
5.01
5.64
0.633
0.170
0.056
0.242
0.075
0.015
0.008
27.24
40.01
3.29
9.09
2.22
10.85
6.47
0.15
1.99
0.20
0.12
1.34
0.05
0.60
0.86
0.08
0.01
0.19
0.07
0.04
0.02
19.30
4.10
0.05

7.45
20.43
72.11
2.02
2.68
5.91
31.80
6.409
2.437
1.189
1.484
0.387
0.179
0.103
363.73
271.05
225.41
111.35
106.61
86.84
71.27
19.74
17.34
15.01
12.32
8.75
8.55
8.25
7.22
2.74
1.45
1.44
0.57
0.45
0.20
71.70
37.01
0.51

34.52
64.37
98.75
5.80
9.08
6.39
118.10
14.758
5.306
6.288
3.226
1.099
0.419
0.228
2047.93
636.35
1970.19
467.74
888.42
269.84
178.66
48.17
37.69
60.52
114.11
22.16
36.04
31.81
13.91
10.83
6.15
5.89
1.00
3.25
0.63
168.80
68.20
1.50

3.46
15.32
79.47
1.58
1.88
5.99
17.14
6.430
2.455
1.030
1.384
0.323
0.162
0.094
308.91
269.50
56.81
99.55
36.83
76.13
65.82
19.55
17.04
10.16
3.38
8.44
6.09
6.92
7.28
1.98
0.56
1.25
0.56
0.35
0.16
65.87
38.98
0.46

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Standard
deviation
9.10
18.41
26.30
1.32
2.25
0.29
29.10
3.159
1.154
1.103
0.771
0.248
0.106
0.06
325.91
129.05
420.65
79.71
193.13
48.57
35.74
10.23
6.26
15.20
24.55
5.05
7.26
5.63
2.84
2.40
1.79
0.96
0.20
0.52
0.15
31.35
17.33
0.22

N
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42
42

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3.1 Physico-chemical parameters

Sand size fraction (average72.11%) dominated over the silt size fraction (average20.43%) and clay
size fraction (average7.45%). Lake sediments measured a higher clay size fraction (average10.1%) than
the river sediments (average6.28%). In appearance the grains were generally angular and light colored
consisting of mostly quartz and feldspar with a lesser proportion of mafic minerals.
Organic matter content (LOI) varied from 0.42 to 9.08% with an average value of 2.68%. Lake sediment
average organic matter content was measured to be slightly higher (LOI2.95%) than the river sediments
(LOI2.56%).
Lake sediments registered higher CEC values (average2.55 cmol(+)/kg) than the river sediments
(average1.79 cmol(+)/kg). About 60% of soil samples measured CEC values below 2.0 cmol(+)/kg .
Overall, among the measured cations, Ca concentration dominated (57%) as an exchangeable cation
followed by Mg. Hydrogen and Al contributed only 4.4% of the total exchangeable cations.
The average river sediment pH1:5 value (5.93) was measured to be slightly higher than the average lake
sediment pH1:5 value (5.86). Lower pH values (< 5.5) were measured at locations in the vicinity of
metasedimentary rocks (TR2, TR23 and TR48) and higher values (pH>6.20) at locations closer to the
estuary (TR26, TR27 and TR28) and in the vicinity of granite rock units.
The average river sediments EC1:5 value (39.61 S/cm) was measured to be more than two times higher
than the lake sediments (14.38 S/cm). Sediment EC1:5 values were measured to be higher (>65 S/cm)
at the sampling locations closer to the estuary and coastal area. Sediment EC1:5 generally measures the
water-soluble concentrations of elements including exchangeable and/or specifically adsorbed forms
(Beckett, 1989).
3.2 Major and trace elements
Lake sediments registered higher Al, Fe, Ti, Mg, Ca, Mn, Te and Sc concentrations (average6.71; 2.75;
1.70; 0.19; 0.11 wt.%, and 397.87; 76.24 and 41.6 mg/kg, respectively) as compared to the river
sediments. Most of the elements including K, Na, Ba, Cr, Zr, Ni, Sr, Y, Mo, Th, Co, Ga, Be, Ge, Se, Bi
and Re, however, registered higher concentrations in river sediments (average1.63; 0. 41 wt.%, and
289.34; 282.31; 117.79; 122.27; 90.2; 20.27; 16.46; 10.29; 8.56; 6.19; 1.6; 0.62; 0.54; 0.21 and 0.53
mg/kg, respectively) than the lake sediments. Localized mineralization related transition metals such as
Nb, Ta and W, also measured higher concentrations in river sediments (average9.47- Nb; 1.68 Ta; and
3.01- W, mg/kg, respectively) than the lake sediments. Thorium is a radioactive element and is generally
higher in concentration in sediments derived from granitic rock material. Thorium concentration showed
a positive correlation Nb (r = 0.70) concentration.
Concentrations of Li, Zn and Cu did not show significant spatial variations and were measured to be
similar in both the lake (average17.24, 71.4 and 14.9 mg/kg, respectively) and river sediments
(average17.38, 71.1 and 15.05 mg/kg, respectively).
While most of the elements registered concentrations well below the environmental benchmark values
of USEPA (2008), MHSPE (1994) and ANZECC (1992), the total concentrations of Fe (65% of samples
above 2.0 wt.%), Mn (25% samples above 460 mg/kg), Ba (70% above 200 mg/kg), Cr (60% above 43.4
mg/kg), Ni (20% above 75 mg/kg), Cu (15% above 31.6 mg/kg) and Mo (16% above 10mg/kg) exceeded
permissible levels. High Cr concentrations (>1,000 mg/kg) were measured at locations (TR3, TR15 and
TR30) in the vicinity of commercial plantation and human settlement areas. A higher Cr concentration is
likely to have originated from the use of pesticides (e.g. CCA) as a wood preservative in the study area as
indicated by a positive correlation between Cr and Cu (r = 0.79) concentrations. Four sampling locations
registered elevated Zn concentrations (>121 mg/kg) and three of these sampling locations (TR24, TR29
and TR40) are closer to the human settlement areas. Guideline values for Al concentration in sediments
for the protection of aquatic animals and plants have not been established yet, however, Al dissolution
occurs under low pH conditions (Sultan, 2003) and consequently may pose a threat to the aquatic life.
The concentrations of major elements including Ca, Mg, Na, Fe and Mn were measured to be 56.3, 9.9,
3, 1.7 and 3.1 times higher, respectively, in the European geochemical baseline values as reported by De
Vos et al. (2006) than the sediments of the study area. The higher Ca concentration in the European
stream sediments (5.81 wt.% of Ca; De Vos et al., 2006) is due to the dominance of limestone and
dolomite rocks. The concentrations of Li, Sr, Zn, Cu, Ba, Ga and Zr also recorded to be more than 1.5
times higher in the European stream sediments as compared to the sediments of the study area reflecting
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higher total elemental budget in the source rocks and/or low weathering rates. The total concentrations of
Ta and W, however, recorded to be 1.1 and 1.3 times higher in the tropical sediments as compared to the
European geochemical baseline values (De Vos et al., 2006) of 1.3 and 2.12 mg/kg, respectively, which
pointed to the mineralized zones in the study area. Gobbett and Hutchison (1973) reported the presence of
W-Ta-Nb deposits (e.g. columbite ((Fe,Mn)(Nb,Ta)2O6), scheelite (CaWO4), wolframite ((Fe, Mn)WO4))
associated with both primary mineralization and placers in Peninsular Malaysia which is probably the
reason for higher W and Ta concentrations. Niobium is a rare transition metal and is found in the mineral
pyrochlore (Na,Ca)2Nb2O6(OH,F)) which generally occurs in granite pegmatites and has been mined for
its commercial value in the region. A positive correlation between Ta and Nb (r= 0.57) concentrations was
observed.
A 4.7 times lower Zr concentrations in sediments as compared to the European geochemical baseline
value of 519 mg/kg (De Vos et al., 2006) is possibly due to the chhemical weathering processes under
tropical conditions which seem to enhance dissolution of even the most resistant Zr-minerals as compared
to the temperate environmental conditions. Balan et al. (2001) reported the dissolution and transport
features on the surface of zircon grains which prevent Zr reaching the saturation level with respect to
ZrO2 or Zr(OH)4. There are only a few minerals in which Sc is a major constituent, among them are
wolframite and cassiterite that contain higher Sc concentrations. Das et al. (1971) reported higher Sc
concentrations in ultramafic basic rocks than the acidic rocks. Geology of the study area is dominated by
acidic rocks over ultramafic rocks, hence, lower Sc concentration was measured. Relatively higher Ti
concentrations (average1.19 wt.%) measured in the study area is due to the slow weathering rate of Ti
minerals (e.g. residual rutile (TiO2) which are generally resistant to weathering and this is in agreement
with the finding of enrichment of Ti in the tropical Hawaiian soils (Sherman, 1952).
Asami and Fukazawa (1985) reported an average Be concentration of 1.29 mg /kg in Tokyo and Sagami
bay sediments in Japan which is slightly lower as compared to the average Be concentration measured in
the study area. Beryllium concentrations showed a positive correlation with Ga and Nb (r 0.60)
concentrations.
4 Discussion
Surface sediments are sandy loam to sand in texture with the clay size fraction of 10 and 6% in the lake
and river sediments, respectively (Fig. 2). The higher water flushing conditions caused by the monsoon
rainfall (highest recorded155 mm/day) and the resultant flooding remove fine size particles leaving
sediments rich in coarse size fractions dominated by quartz. The SEM analysis of the edges morphology
of sediment grains revealed a sub-rounded shape in the downstream location and relatively sharp edges in
the upstream location (Fig. 2, a and b). The highly flushed water conditions under which removal and
transport of particles occur seem to allow relatively insufficient residence time to transform angular edges
to a well-rounded shape. The color of the studied sediments revealed the dominance of light minerals (e.g.
quartz, feldspar, carbonates) over opaque minerals (e.g. magnetite, hematite). However, a brown to red
color coating on the sediments was also observed which is likely due to the Fe oxidation.
Sediment pH1:5 values were measured to be mildly acidic (average pH1:55.9). The lower pH1:5 values
(<5.5) were measured at locations in the vicinity of metasedimentary rocks which are possibly due to the
lack of acid neutralizing minerals that significantly reduce the buffering capacity against acidic input. The
pH1:5 values (>6.2) at locations closer to the estuary are likely due to the higher pH sea water mixing with
low pH fresh river water.
Overall, sediments measured low CEC values (average2.25 cmol(+)/kg) with a decreasing order of
abundance of exchange cations Ca>Mg>K>Na>>H>Al. Exchangeable Ca was measured to be higher in
the lake sediments (average62.7%) as compared to the river sediments (average52.8%) which is due to
the localized limestone bedrock in the lake area. A negative correlation between CEC and sand size
fraction (r = -0.46) indicated the low exchange bases on the sand size particles.
Sediment EC1:5 values and Mo concentrations showed an increasing trend and Fe concentrations showed
a decreasing trend along the river path from the upstream to the downstream locations (Fig. 3). Sediment
EC1:5 values increased more than four times along the flow path with higher values at locations closer to
the estuary which is possibly due to the higher salt content resulting from the mixing of fresh river water
with saline water from the South China Sea. Sediment Mo concentrations showed an increasing trend
(> 5-fold) with the flow path from the upstream to the downstream. However, sediments from the
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locations at the estuary registered lower concentrations. Sediment Fe concentrations decreased (> 3-fold)
along the flow path with higher concentrations in the lake sediments and lower concentrations in the river
and estuary sediments. The change in Fe and Mo concentrations is probably due to the pH-redox
conditions which favor dissolution or adsorption depending upon the environmental drivers. The lack of
systematic change in concentration of most of the elements along the flow path indicated the
heterogeneity of material sources such as local geology and in-stream geochemical processes.

Fig. 2

Textural classification chart showing dominance of sand size fraction. SEM images of
sediments showing a sub-rounded grain (a) from the downstream location (TR29) and a
sharp edged grain (b) from the upstream location (TR36) in the Terengganu River basin

Among the elements investigated Mn, Fe, Cr, Ba, Ni, Zn, Cu, Mo, Co and Se concentrations exceeded
the environmental guideline values for sediments at a few locations (Fig. 4) closer to the human
settlement areas. Elevated levels of these metals also reflected enrichment in the source rocks of the study
area. Gobbett and Hutchison (1973) reported the presence of metalliferous deposits that are associated
with both primary mineralization and placers in Peninsular Malaysia which also carried significant
economic importance. Sultan and Shazili (2009) reported enrichment of elements such as Fe, Cr, Zn, Ni,
Mo, W, Bi and Se in surface soils as compared to the upper continental crust element concentrations.
However, the distribution of Cr concentrations (> 1,000 mg/kg) at locations closer to the human
settlement areas and agricultural land revealed anthropogenic input into the rivers (Fig. 5). The higher
concentrations of Cr in the river sediments are probably due to the use of chromated copper arsenate
(CCA) as a wood preservative which is washed out by the runoff in to the nearby steams. The prevailing
pH-redox conditions seem to favor the retentions of Cr onto the sediments. Sediment pH1:5 values at these
locations were measured to be 5.8 pH units. The higher Cr concentration in a lake sediment sample
(location TR48611.4 mg/kg) is highly reflective of the geological origin as the environment at this
remote location is relatively pristine.
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Fig. 3 Changes in sediment EC1:5 values, and Fe and Mo concentrations with distance from
the estuary to the upstream Kenyir Lake in the Terengganu River basin

Fig. 4 Box- plot showing the 10th, 25th, 75th and 90th percentiles, and mean and median of selected
element concentrations in the river and lake sediments. Environmental guideline values of
MHSPE (1994), ANZECC (1992) and USEPA (2008) are represented as circles ()
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Fig. 5 Distribution of Cr in the river and lake sediments of the Terengganu River basin

4.1 Enrichment factor

Enrichment factor (EF) is a geochemical approach based on the assumption that there is a linear
relationship between a reference element and the measured elements. EF is a useful tool to determine the
degree of modification in sediment composition. Normalization to a reference element (Al80,400 mg/kg;
Taylor and McLennen, 1985) was evaluated by EF, which is calculated as:
EF = [(CElement / CAluminum) Sediment Sample] / [(CElement / CAluminum) Earths crust]
where (CElement / CAluminum) Sediment Sample is the ratio of concentration of the measured element to that of Al
as a reference element in the sediment sample, and (CElement / CAluminum) Earths crust is the same reference ratio
as in the Earths crust. The EF values are shown in Fig. 6. Among all the elements, Cr, Ni, Zn, Y, Li, Mo,
Co, W, Se, Bi, Te, Sc and Re registered the EF values >1 indicating abundance in the sediment sample as
compared to the Earths crust. However, EF values <5 are not significant and point to the accumulation
but not contamination of the sediments (Atgin et al., 2000). The EF values of elements including Cr, Ni,
Mo, Se and Te were measured to be >5 and hence indicated significant enrichment by the anthropogenic
activities. Past mining operations in the study area, the scale and extent of which is unknown, possibly
contributed to the elevated levels metals. Alkali and alkali earth metals registered a significant depletion
(EF values < 0.7) as compared to the Earths crust. This is possibly due to the preferential dissolution and
mobilization of minerals containing alkali and alkaline earth metals (e.g., carbonate fraction) under acidic
water conditions.
4.2 Principal component analysis
Principal component analysis of all data revealed two main components (PC1, 87.4% and PC2, 8.7%)
accounting for 96.1% of the total variance. The projection of 42 sampling locations on the bi-dimensional
space is shown in Fig. 7 (a). The sampling locations from the estuary formed a well-defined group on the
negative part of the PC1 axis and on the lower left side of the chart in a convincing way revealing similar
characteristics affected by sources of similar origin. Sampling locations of lake sediments were randomly
distributed and did not form a common group with most locations on the positive side of the PC2 axis.
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This is likely due to the heterogeneity among sources of sediments from the various rock units and
hydrochemical processes in the lake. River sediment sampling locations also showed a random
distribution on the chart. This can be explained by the variation in land uses such as forest, agriculture,
commercial tree plantation, human settlements and industry. Furthermore, there are five main tributaries
of the Terengganu River which differ in characteristics, especially the geological material. Most of the
streams and tributaries cut into various geological units with the exception of S.Tersat (Fig. 1), which
dominantly drains the granitic rocks and therefore groups together in the positive PC1 axis on the lower
right of the chart around zero as shown by the shaded area in Fig. 7 (a).

Fig. 6 Element concentrations of the sediments normalized to

the Upper Continental Crust (Taylor and McLennan, 1985)

Fig. 7

Projections of 42 sediment sampling locations (a), and 39 physico-chemical variables

(b) in the bi-dimensional space of two principle components
(PC1 and PC2, 87.4% and 8.7%, respectively)

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The projection of 39 variables on the bi-dimensional space is shown in Fig. 7 (b). Most of the elements
gathered on the positive PC1 axis on the upper right side of the PC2 axis. The length and position of the
line on the bi-dimensional space indicated the degree of association among the variables. Elements such
as Ca, Mg, Fe and Mn showed an association with clay and silt size fraction, and CEC and organic matter
content (LOI). Sediment Zn concentrations showed an association with Fe concentrations which can be
explained due to the adsorption of Zn onto the secondary Fe-(hydr) oxides. Most of the elements seemed
to be associated with the silt size fraction (2-20 m). Metal concentrations generally increased as grain
size decreased. Elements such as Li, Zn, Cu, Te and Mg grouped together and did not register significant
spatial change in concentrations between the river and lake sediments (shaded area in Fig. 7 (b)).
Variables like Cr, Ni, Mo, Se and Co grouped on the negative PC1 axis on the upper side of the PC2 axis.
All of these elements showed enrichment in sediments and generally exceeded the environmental
guideline values at many locations and therefore represent contamination. Alkali metals (Na and K) and
alkali earth metals (Sr and Ba) grouped on the negative PC1 axis on the lower side of PC2 axis. These
metals showed similarity in characteristics and seemed to originate from similar sources. Other trace
elements such as Th, Ta, Sc and Y showed an association with Al in sediments. Aluminum oxides have
the potential to retain elements by providing adsorption sites which depends upon pH-redox conditions as
shown by Sparks (2003). Sand size fraction projected the opposite to most of the variables on the negative
side of the PC1 axis and on the left lower side of the PC2 axis revealing a negative correlation with most
of the measured elements.
5 Conclusions
Sediments are sandy loam to sand in texture with coarse size fraction consisting of mostly quartz
reflecting local geology and high flushing conditions. Sediments are mildly acidic and exhibited low CEC
and low organic matter content.
Among the 31 investigated elements, the concentrations of Mn, Fe, Ba, Cr, Ni, Cu, Mo and Se exceeded
the environmental sediment guideline values at a few locations. Elevated levels of Cr (>1,000 mg/kg) in
the river sediments indicated anthropogenic input.
Concentrations of K, Na, Ba, Cr, Zr, Ni, Sr, Y, Mo, Th, Co, Ga, Be, Ge, Se, Bi and Re were measured to
be significantly higher in the river sediments as compared to the lake sediments. Among all the measured
metals, only Mo and Fe concentrations showed a multifold increasing and decreasing trend, respectively,
along the river path from the upstream to the downstream locations. Lack of systematic change in
concentrations of most of the elements along the flow path revealed heterogeneity of the source material
and in-stream geochemical processes. The enrichment factor values (EF >5) of Cr, Ni, Mo and Se
indicated significant enrichment by the anthropogenic activities. Alkali and alkali earth metals registered
a significant depletion (EF values < 0.7) as compared to the Earths crust.
Principal component analysis of the two main components revealed a well-defined group of estuary
sediments as compared to the lake and river sediment group. Most of the elements showed an association
with the silt size fraction, and Fe and Al concentrations. It seemed that secondary (hydr) oxides of Fe and
Al play a significant role in the metal adsorption in the study area.
This work is important in presenting geochemical baselines of surface sediments at a time when
industrial development and urbanization along the north east coast of Peninsular Malaysia are advancing
at a rapid rate.
Acknowledgements
The authors would like to thank INOS, University Malaysian Terengganu for the funding given to
support the research. Thanks also to the Alexander von Humboldt Foundation (AvH), Germany, for the
financial support in carrying out the research work.
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