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- 340 - International Journal of Sediment Research, Vol. 25, No. 4, 2010, pp. 340354

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) andphysico-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, loworganic 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 theenvironmental 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 ofthe elements investigated showed an association with silt size fraction (263 m). Among theinvestigated 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 indicatedenrichment from anthropogenic activities. Alkali and alkali earth metals registered a significantdepletion (EF values 1,000 mg/kg) indicating contaminationof sediments. This work presents the geochemical baselines of the tropical sediments as industrialdevelopment and urbanization along the north east coast of Peninsular Malaysia are advancingrapidly.

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 backgroundconcentrations 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 tothe 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: [email protected]; [email protected] (K. Sultan)

2 Dr., Prof., Institute of Oceanography, University Malaysia Terengganu, Mengabang Telipot, 21030 Kuala

Terengganu, MalaysiaNote: 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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International Journal of Sediment Research, Vol. 25, No. 4, 2010, pp. 340354 - 341 -

suspended matter and ultimately move to bottom sediments. For the identification of hot spots of elevatedmetal concentrations, monitoring and control of pollution sources and the development of sediment

quality guidelines, an understanding of ambient background and baseline concentrations of metals insediments 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 usefulindicator 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 documentthe 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 issignificant 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 alsocompared with the environmental guideline and geochemical baseline values established for sediments

around the world.

2 Methods

2.1 Study areaThe Terengganu River basin lies in the wet tropics (4o41- 5o20N, 102o31-103o09E) covering

approximately 5,000 km2with the Kenyir Lake in the west, the main channel and five major tributaries of

the Terengganu River, and the estuary (cross section area987 km2; discharge16.510

9m3/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 pristineenvironment in the upstream catchment area becoming urbanized and industrialized downstream with themajor 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. Adry 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 anaverage 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 KenyirLake 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). Sedimentsampling 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 spatialdistribution 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 fractionswas 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 NH 4OH, 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 analyzedby 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 limitswere 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 ultrapuredeionized 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 elementsmeasured are given in Table 1.

Table 1 Detection limits, accuracies and precisions for major and trace elements

Elements Unit Detection limit Accuracy (%) Precision (%PRD)

Al % 0.01 2.4 1.3

Fe % 0.003 0.1 3.8

K % 0.01 0.3 0.7

Na % 0.001 0.4 9.9

Mg % 0.001 0.5 3.2

Ti % 0.003 0.2 12.8

Ca % 0.005 0.5 1.2

Ba mg/kg 0.02 0.4 0.3

Mn mg/kg 0.01 0.7 2.8

Cr mg/kg 0.01 2.9 4.3

Sr mg/kg 0.02 2.8 3

Zr mg/kg 0.08 7.3 4.4

Zn mg/kg 0.02 0.9 1.7

Ni mg/kg 0.04 8.4 2.9

Y mg/kg 0.002 1.1 3.6

Li mg/kg 0.01 3.2 11.7

Cu mg/kg 0.001 2.1 1.3

Nb mg/kg 0.002 5.2 4.7Ga mg/kg 0.004 1.6 7.1

Co mg/kg 0.001 0.7 3.2

Th mg/kg 0.002 1.7 3.1

Sc mg/kg 0.01 3.9 4.6

Mo mg/kg 0.002 11.4 2

W mg/kg 0.005 4.7 2.6

Be mg/kg 0.001 3.2 5.1

Ta mg/kg 0.001 0.2 3.5

Bi mg/kg 0.001 2.5 4.7

Se mg/kg 0.004 5 1.2

Te mg/kg 0.01 2.1 0.6

Re mg/kg 0.002 6.7 5.3

Sediment samples were mounted on aluminum SEM stub with an adhesive carbon tape and coated withgold 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 performedon 38 variable and 42 sampling locations using statistical software.

2.4 GeologyLarge 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 mostdominant rock type is granite (Permian to lower Triassic) appearing as outcroppings in the form of high

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peaks. Primary minerals associated with the Main Range Granite contain deposits of significant economicvalue. 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 formsnorth-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. Thecorrelation matrix depicting correlations between all elements is presented in Table 3.

Table 2 Physico-chemical parameters and element concentration dataof sediments in the Terengganu River basin

Parameter Unit Min Average Max MedianStandarddeviation

N

Clay (

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3.1 Physico-chemical parametersSand 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%) thanthe 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 pH1:5value (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 theestuary (TR26, TR27 and TR28) and in the vicinity of granite rock units.

The average river sediments EC1:5value (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 elementsLake 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, Biand 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; and3.01- W, mg/kg, respectively) than the lake sediments. Thorium is a radioactive element and is generallyhigher 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 samplesabove 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 andTR30) 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 asindicated by a positive correlation between Cr and Cu (r = 0.79) concentrations. Four sampling locationsregistered 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 anddolomite 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 ofTa 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, whichpointed 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 wasobserved.

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 undertropical 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 toZrO

2 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 Timinerals (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 Sagamibay 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 monsoonrainfall (highest recorded155 mm/day) and the resultant flooding remove fine size particles leavingsediments 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 edgesto 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 pH1:5values were measured to be mildly acidic (average pH1:55.9). The lower pH1:5values

(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 tothe 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 showeda 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-redoxconditions 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 ofsediments 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 exceededthe 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 associatedwith 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 prevailingpH-redox conditions seem to favor the retentions of Cr onto the sediments. Sediment pH1:5values 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 fromthe 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 ofMHSPE (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 linearrelationship 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 Sampleis the ratio of concentration of the measured element to that of Al

as a reference element in the sediment sample, and (CElement / CAluminum) Earths crustis the same reference ratioas 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 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 acidicwater 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-dimensionalspace 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 randomlydistributed 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 andhydrochemical 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), whichdominantly 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 tothe 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 theline 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 beexplained 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 environmentalguideline 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 traceelements 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 negativeside 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 CECand 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 measuredmetals, 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 registereda 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 andAl 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 tosupport 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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