Catena 165 (2018) 454–464

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Catena
journal homepage: www.elsevier.com/locate/catena

Distribution of heavy metals and metalloid in surface sediments of heavily- T

mined area for bauxite ore in Pengerang, Malaysia and associated risk
assessment
⁎
Faradiella Mohd Kusina,b, , Nur Najihah Mohd Azania, Sharifah Nur Munirah Syed Hasana,
Nur Aqilah Sulonga
a
Department of Environmental Sciences, Faculty of Environmental Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
Environmental Forensics Research Unit (ENFORCE), Faculty of Environmental Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: A detailed investigation has been conducted to evaluate the distribution of heavy metals and metalloid in the
Bauxite surface sediments of a bauxite mining area in association with the potential ecological and human health risk.
Mining sediment Field sampling was carried out within the Pengerang bauxite mining areas, including mine tailings, ex-mining
Heavy metals pond and streams. Distribution of heavy metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Pb, Sr, Zn) and metalloid such as As
Geochemical indices
in sediments indicated that Fe and Al constituted the greatest portion of metal elements in the sediment while Pb
Potential ecological risk
Human health risk
and Cu were found exceeding the recommended guideline values at some locations. Assessment of potential
ecological risk (PERI) demonstrated low to medium ecological risk in the metal-contaminated sediments with
Cd, As and Pb have generally greater risk compared to other metals, contributing the most to the total risk index
(RI). The sediment enrichment factor (EF) indicated no enrichment of most metals while Pb and As at some
locations were classified as having minor and moderately to severe enrichment. The geo-accumulation index
(Igeo) and contamination factor (CF) indicated that the sediments were classified uncontaminated with respect
to most metals. Assessment of potential human health risk revealed that the hazard index (HI) values of the
carcinogenic and non-carcinogenic risks were an order of magnitude higher among children compared to adults.
There were no significant non-carcinogenic risk due to metals and metalloid in the study area as HIs < 1.
However, the lifetime cancer risk (LCR) for As is relatively higher than other metals and falls within tolerable
LCR for regulatory purposes. Therefore, this study has highlighted the implication on potential ecological and
human health risks of heavy metal occurrence in sediments of bauxite mining areas thus indicating the im-
portance of geomorphological changes due to land exploitation for mining sector.

1. Introduction
Mineral resources are very crucial for country's mining sector de-
velopment and Malaysia's national economy during the 20th century. In
Malaysia, mineral resources such as iron, tin, gold, coal, silica sand,
bauxite, antimony, barite, clays, copper, lead and limestone have
played important roles in country's mineral production, although ex-
ploitation of some minerals had decreased significantly (Majid et al.,
2013; Tse, 2015). Throughout Malaysia, minerals such as bauxite, coal,
copper, gold, kaolin, silica, sand, and silver have been found in abun-
dance in the states of Kelantan, Pahang, Sabah, and Sarawak. Specifi-
cally for bauxite, occurrence of this mineral in Peninsular Malaysia has
been mostly found in Pengerang, Johor (southern Malaysia) and
Kuantan, Pahang (new hot spot for bauxite mines in east-coast
Malaysia) (Kusin et al., 2017). These two areas are found to be suitable
for bauxite formation due to high soil temperature and annual rainfall
throughout the year (Jusop, 2016). The areas are also under stable
geological conditions for maximal degree of weathering of basalt and
volcanic rocks, which are the major rock types in Peninsular Malaysia.
Bauxite is an ore that is mined for aluminum (Al) extraction used for
production of many industrial goods, whereby the Al content could be
about 12 to 25% in bauxite ore (Paramananthan, 1977). The main
composition in bauxite are mineral gibbsite [Al(OH)3], goethite
(FeOOH), hematite (Fe2O3) and kaolin (Tessens and Shamshuddin,
1983; Shamshuddin and Fauziah, 2010). Bauxite is reddish brown in
color which is due to the presence of mineral hematite. After the pro-
cess of Al extraction, bauxite residues that consist mainly of insoluble
fraction of the bauxite ore would remain. Besides aluminum, bauxite is

⁎
Corresponding author at: Department of Environmental Sciences, Faculty of Environmental Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
E-mail address: faradiella@upm.edu.my (F.M. Kusin).

https://doi.org/10.1016/j.catena.2018.02.029
Received 10 April 2017; Received in revised form 21 February 2018; Accepted 22 February 2018
0341-8162/ © 2018 Elsevier B.V. All rights reserved.
F.M. Kusin et al.
also mined for Fe, Ti, Ca, Si and Na and kaolin (Jusop, 2016).
Bauxite is usually strip-mined because it is found one or two meters
below the surface of the soil layer (Rajah, 1986; Paramananthan, 1977).
This is typically found in open pit mining, i.e. a type of strip mining,
where the material is excavated from an open pit. During every step of
the process, there is always a hazard to the environment. Crushing of
rock will generate large quantity of dust. During the separation process,
rock slurries will produce free metals and if not properly handled, the
liquids can leak into bedrocks (Saxena and Singh, 2000).
Habitat destruction, soil erosion, increase in turbidity, disturbance
of hydrology are among the main impacts of mining activities (Tajam
and Kamal, 2013; Demirak et al., 2013). Bauxite mining can cause
caustic effluents and red-mud (Renforth et al., 2012). Harmful sub-
stances may then be released into the soil, air, and water, due to un-
regulated mining processes. Malaysian Ministry of Health has recently
reported that increased bauxite mining activities have caused re-
spiratory and allergy problems, and potential long-term effect of cancer
(Abdullah et al., 2016). This is because the presence of metals may
introduce toxicity on living organisms and also ability to be entering
into the food chain (Ololade et al., 2008; Mmolawa et al., 2011; Shaari
et al., 2015).
Acid mine drainage (AMD) can occur if the mined materials are
exposed to the air (oxygen) and water. AMD contains high concentra-
tion of heavy metals (e.g. arsenic, cadmium, copper, lead, zinc, etc.)
and sulfate. Even though the condition at the site is not acidic, toxic
metals such as arsenic, cadmium and lead can leach and contaminate
the ground waters and environment. The precipitates generated smo-
thers the river bed with fine silt and hence would affect benthic or-
ganisms and the entire food chain (Penreath, 1994). This will appar-
ently lead to huge impact on rivers and aquatic ecosystems over the
long term.
It has been noted that metal contamination and land degradation
from mining can give harmful effects to communities living in nearby
areas (Yelpaala, 2004; Pan and Li, 2016). Therefore, it is important to
understand properly the characteristics of trace metals contamination
in mine-impacted areas particularly in water and sediments and their
potential impact. Viers et al. (2009) stated that people are confronting
with the increments of threat with regard to water security because of
the sediments in many rivers and lakes that have been polluted by trace
metals. Therefore, this study was conducted to determine the compo-
sition of metals and the extent of contamination in the surface sedi-
ments from bauxite mining activities, and to determine the impact in
terms of the potential ecological risk and also impact on human health.
2. Materials and methods
2.1. Site description
The study was undertaken in the vicinity of bauxite mining areas
located in the Pengerang, Johor (southern Malaysia) (Fig. 1). The
Pengerang was once known as the only bauxite mining area in Ma-
laysia. A new area was recently found in the Kuantan, Pahang (east-
coast Malaysia). The Pengerang bauxite mining area is located on the
south-eastern of Johor state and approximately 50 km from east of
Singapore, specifically within the area of the Teluk Ramunia, Johor.
Historically, since the early 50's, Teluk Ramunia has been well known
as progressive bauxite mining town.
The Pengerang bauxite mines have been said to have the best grade
of bauxite but are mostly exported. In the Pengerang, the valuable
bauxite occurs in alluvial and residual deposits. In these deposits,
bauxite occurs in concretions, pisolites, nodules and in shaly structure
(Patterson et al., 1986). Geologically, the bauxites in the vicinity of
Pengerang are formed from the acid volcanic rock coupled with stable
geological conditions that has favored sufficient weathering of the rocks
(Raj, 2009; Jusop, 2016). The area mined for bauxite in Pengerang is
about 1800 ha which is on formerly agricultural land prior to bauxite
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Catena 165 (2018) 454–464
discovery in the 50–60's (Paramananthan, 2000; Jusop, 2016).
2.2. Field sediment sampling and analysis
Sampling was carried out at several locations of the bauxite mines
(Fig. 1). Triplicate sampling was done by stainless steel trowel, whereby
(0−20) cm surface sediments were collected into a zip locked bag. The
sampling was performed in May 2016 at seven sampling points. There
were four samples that were collected from the mine tailings (S3, S4, S5
and S6), and the rest were collected at the nearby streams (S1 and S2)
and an ex-mining pond (S7). The samples were kept in an icebox
(< 4 °C) and transported to laboratory for further analysis. Sediments
were maintained at room temperature, air-dried and homogenized by
using mortars and pestles. Then, they were sieved through 2 mm sieve
for physicochemical analyses. The sample preparation for analyses was
carried out according to the EPA method 3050B (US Environmental
Protection Agency (USEPA), 1996).
The sediments had to be completely decomposed before analyzing it
using ICP-MS. Acid digestion method was applied for the extraction of
heavy metals using hydrochloric and nitric acids (3:1 ratio).
Approximately, 1 g of sediment sample was weighed and placed in di-
gestion tubes, then, were allowed to pre-digestion overnight. The
samples were digested at 40 °C in first hour, 80 °C in second hour,
120 °C in third hour and 140 °C in the fourth hour. The obtained sus-
pensions were then filtered using 0.45 μm membrane filter. Afterwards
the suspensions were placed into centrifuge tube and ready for heavy
metals analyses using an ICP-MS (Perkin Elmer ELAN DRC-e). For
quality assurance/quality check (QA/QC) procedure, the analytical
instrument was checked with standard reference material NIST, SRM
1646a (estuarine sediment). The percentage of recoveries for the metals
studied ranged between 82 and 117% (Table 1).
2.3. Potential ecological risk index (PERI)
Potential ecological risk index (PERI) can be used to determine the
potential risk due to exposure to ecological sensitivity, concentration
and toxicity of heavy metals (Nabholz, 1991; Douay et al., 2013). It is
also regarded as a comprehensive potential ecological risk assessment,
Eir, which is the sum of the potential risk of individual metal element. It
represents the sensitivity of the biological community to the toxic
substance and illustrates the potential ecological risk caused by the
overall contamination. The estimation of total risk index (RI) of PERI
was calculated using Eq. (1) as proposed by Guo et al. (2010) and was
first introduced by Hakanson (1980):
RI = ∑ Eri = ∑ Tir (Csi /C1n) (1)
where, RI is the sum of all the potential risk factors for all heavy metal,
Eri is the potential ecological risk index for single heavy metal pollution
that can be calculated as:
Eri = Cri × Tri (2)
Tri is the toxic-response factor for a single heavy metal contamina-
tion. Cri is the pollution index for a given heavy metal and can be de-
fined as:
Cri = Csi/ Cni (3)
where Csi is the present concentration of heavy metal in the sediment
and Cni is the reference value of heavy metal in the sediment. The toxic-
response factors were taken as 5 for Cu, Pb and Co, 1 for Zn, 10 for As
and 30 for Cd (Guo et al., 2012; Islam et al., 2015). The classification of
the potential ecological hazard and the risk criteria of heavy metals in
surface sediments are given in Table 2.
F.M. Kusin et al. Catena 165 (2018) 454–464

Peninsular
Malaysia

Pengerang

Johor

Fig. 1. Locations of bauxite mining in Pengerang, Johor and the sampling locations.

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F.M. Kusin et al. Catena 165 (2018) 454–464

Table 1 element (Fe) in the average shale or undisturbed sediment. Fe was

Measured and certified values of the standard reference material and percentage re- chosen as the element of normalizer, because it is a natural resource
coveries of metals.
vastly dominated in most soils or sediments (Baptista-Neto et al., 2000;
Element Certified value (mg/kg) Measured value (mg/kg) Recovery (%) Zhang et al., 2009; Cevik et al., 2009). The classification of the en-
richment factor is as given in Table 3.
Al 22,970 ± 180 22,140 ± 160 96.3
Cd 0.148 ± 0.007 0.128 ± 0.006 86.4
Co 5a 4.256 ± 0.032 85.1
2.4.3. Contamination factor (CF)
Cr 40.9 ± 1.9 34.253 ± 1.235 83.7 Contamination factor was used to determine the contamination
Cu 10.01 ± 0.34 10.728 ± 0.341 107.2 status in the sediments by evaluating the level of pollution by single
Fe 20,080 ± 390 20,018 ± 395 99.7 substances. The equation for estimating contamination factor as in-
Mn 234.5 ± 2.8 192.42 ± 3.345 82.1
troduced by Hakanson (1980):
Pb 11.7 ± 1.2 13.701 ± 0.251 117.1
Sr 68a 60.242 ± 1.257 88.6 CF = CM / CB (6)
Zn 48.9 ± 1.6 44.012 ± 1.654 90.0
where, CF is the contamination factor, CM is the mean concentration of
a
Non-certified value, for information only. each metal in the sediment and CB is the background concentration of
the metal in the local region. Classification of the contamination level is
Table 2 given in Table 3.
Classification of potential ecological risk coefficient (Eri) and risk index (RI).

EiR Risk classification RI Risk classification 2.5. Potential human health risk assessment

EiR < 40 Low risk RI < 50 Low risk Health risk assessment (HRA) is typically used for risk estimation of
40 ≤ EiR < 80 Moderate risk 50 ≤ RI < 200 Moderate risk
the exposure of human to certain contaminants of known amount (Lee
80 ≤ EiR < 160 Considerable risk 200 ≤ RI < 300 Considerable risk
160 ≤ EiR < 320 High risk RI ≥ 300 High risk et al., 2005; Lim et al., 2007; Khan et al., 2008; Li et al., 2014). Human
EiR ≥ 320 Very high risk exposure to impacts of heavy metals may occur through three major
pathways such as i) direct oral ingestion of heavy metal particles ii)
Adapted from Mamat et al. (2016) based on ecological risk classification introduced by inhalation of heavy metal particles through mouth and nose and iii)
Hakanson (1980).
dermal absorption of heavy metal particles on exposed skin (Luo et al.,
2012). Therefore, in typical HRA, the key elements assessed include
2.4. Geochemical indices hazard identification, exposure assessment, dose-response assessment,
and risk characterization (Lee et al., 2006; Luo et al., 2012).
2.4.1. Geo-acccumulation index (Igeo) Specifically, the estimation of the health risks via ingestion, in-
Geo-accumulation index (Igeo) determines the enrichment of metal halation and dermal contact pathways on both adults and children can
concentration above background or baseline concentration. The Igeo be predicted through the estimation of the chronic daily intake (CDI)
was calculated to estimate metal accumulation in sediment when the (mg/kg/day). The equations below were used to estimate the CDI va-
concentration of toxic heavy metal is 1.5 or greater than their lithogenic lues as a result of exposure to heavy metals of different pathways:
background values as follows (Gaur et al., 2005):
Csed. × IngR × EF × ED
Igeo = log2 [Cn/1.5Bn ] (4) CDIingest = × CF
BW × AT (7)
where, Cn is the measured concentration of metal in sediment n, Bn is Csed. × InhR × EF × ED
the geochemical background value of element n and factor 1.5 is the CDIinhale =
PEF × BW × AT (8)
coefficient variation of the background data due to lithogenic impacts.
The Igeo index distinguishes 6 classes of quality for sediments as given Csed. ×SA × AFsoil ABS × EF × ED
CDIdermal = × CF
in Table 3. BW × AT (9)

where Csed. is the concentration of heavy metal in sediment sample

2.4.2. Enrichment factor (EF)
Enrichment factor has been widely used to assess the degree of
pollutant enrichment and sources of pollution as follows:
(Ci/ Cref )sample
EF =
(Bn / Bref ) background
where, Ci is the concentration of heavy metal in sediment; Cref is the
concentration of the reference element (Fe) in the sediment; Bn is the
background concentration of metal in the average shale or undisturbed
sediment and Bref is the background concentration of the reference
(mg/kg), IngR indicates the ingestion rate of the soil (mg/day), EF is the
exposure frequency (days/year), ED is the exposure duration (years),
BW is the average body weight (kg), AT is the averaging time (days), CF
is the conversion factor (kg/mg), the InhR is the inhalation rate (mg/
cm2), PEF is the particle emission factor (m3/kg), SA is the surface area
(5)
of the skin that is in contact with the soil (cm2), AFsoil is the skin ad-
herence factor for soil (mg/cm2), and ABS is the dermal absorption
factor. The exposure factors used in the estimation of CDI are given in
Table 4.
In the HRA, the estimated bioavailable concentration of heavy

Table 3
Geochemical index classification; Igeo, EF and CF.

Igeo Classification EF Classification CF Classification

Igeo < 0 Uncontaminated EF < 2 Deficiency to minimal enrichment CF < 1 Low contamination
0 ≤ Igeo < 1 Uncontaminated to moderately contaminated 2 ≤ EF < 5 Moderate enrichment 1 ≤ CF < 3 Moderate contamination
1 ≤ Igeo < 2 Moderately contaminated 5 ≤ EF < 20 Significant enrichment 3 ≤ CF < 6 Considerable contamination
2 ≤ Igeo < 3 Moderately to strongly contaminated 20 ≤ EF < 40 Very high enrichment CF≥6 Very high contamination
3 ≤ Igeo < 4 Strongly contaminated EF≥40 Extremely high enrichment
4 ≤ Igeo < 5 Strongly to extremely contaminated
Igeo ≥6 Extremely contaminated

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F.M. Kusin et al. Catena 165 (2018) 454–464

Table 4 cancer risks for each exposure pathways by using Eq. (7). The cancer
Exposure factors used in CDI estimation for non-carcinogenic risk. slope factor (CSF) values for Cd, Cr, Pb and As are 6.3, 0.5, 0.0085 and
1.5 mg/kg/day (US Environmental Protection Agency (USEPA), 2012).
Parameter Value
The acceptable threshold value of the cancer risk is 1.0E-04 whilst the
IngR 100 mg/day (adult), 200 mg/day (children) tolerable LCR for regulatory purposes is in the range of 1.0E-06–1.0E-
EF 350 days 04 (US Environmental Protection Agency (USEPA), 2012).
ED 24 years (adult), 6 years (children)
BW 70 kg (adult), 15 kg (children) Cancer risk = CDI × CSF
AT 365 × ED adult/children
CF 1 × 10−6 kg/mg
∑ Cancer Risk = LCR = Cancer risking + Cancer riskinh
InhR 20 mg/cm2 + Cancer riskdermal (12)
PEF 1.36 × 109 m3/kg
SA 5700 cm2 event−1
AFsoil 0.07 mg/cm2
ABS 0.001
3. Results and discussion

Adapted from US Environmental Protection Agency (USEPA) (2002). 3.1. Distribution of heavy metals and metalloid

metals was applied to estimate the carcinogenic and non-carcinogenic 3.1.1. Iron and aluminum
risk exposures for both children and adults. The elements associated Interpretation of heavy metal content is very crucial for determining
with the estimation of carcinogenic health risks are heavy metal Cd, Cr, potential impact on surrounding ecosystems and also on public health
Pb and metalloid As that can induce carcinogenesis as classified by the so as for sustainable environmental protection. Table 6 summarizes the
International Agency for Research on Cancer (IARC, 2012), whilst, Pb, concentration of heavy metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Pb, Sr, Zn and
Cu, Zn, Fe, As, Cd, Cr, Al and Co were also estimated of their non- metalloid As in sediments of Pengerang bauxite mining area. The mean
carcinogenic risk. heavy metals (and metalloid) concentrations in the surface sediments
Hazard Index (HI) which represents the cumulative non-carcino- for all stations were found to be in the order of Fe > Al > Mn >
genic risk is estimated by summing up all the hazard quotients (HQ) as Pb > Zn > Cu > Cr > As > Sr > Co > Cd. Generally, Al and Fe
expressed in Eqs. 5 and 6: are the major elements in most sediments and soils and is usually
present in high concentrations compared to other heavy metals
CDI (Hutchison, 2009; Iqbal and Shah, 2014). This is usually followed by
HQ =
RfD (10) relatively high amount of Mn particularly in mining-related soils and
sediments (Diami et al., 2016; Kutty and Al-Mahaqeri, 2016; Kusin
Where,
et al., 2016). This has been anticipated because Al and Fe are known to
HI = ∑ HQ = HQing + HQinh + HQdermal be the most abundant elements in most upper and lower earth's crust
(11)
(Wedepohl, 1995).
The RfD in the equation refers to reference dose based on US As in the case of bauxite mining, formation of bauxite requires long
Environmental Protection Agency (USEPA) (2012) for the HRA calcu- term weathering under intense leaching condition, i.e. of Si, with sub-
lation. The values of RfD are different for each element of heavy metal. sequent formation of gibbsite (Al(OH)3) (Jusop, 2016). Apparently, this
Table 5 shows the values of the reference dose for different heavy has resulted in relatively high amount of Al in the mined-impacted
metals. Based on the HI values, no significant risk of non-carcinogenic sediments, i.e. mean value of 22,824 mg/kg (Table 6). The variation of
effects is anticipated if the value is less than one (HI < 1). However, in Fe and Al concentration was quite similar because these elements are
the case of HI value exceeds one (HI > 1), there is a probability that important in the stabilization and formation of most soil aggregates
non-carcinogenic risk effects may occur which tends to increase with (Bartoli et al., 1992; Tarchitzky et al., 1993). Fig. 3 shows that the S5
the increment of HI value (US Environmental Protection Agency and S6 have great amount of Fe between 31,345 and 31,762 mg/kg.
(USEPA), 2002). As noted earlier, using the total concentration of heavy The concentrations of Al in the bauxite mining area were ranging
metals of the surface sediments for the calculation of health risk index from 15,675 to 22,149 mg/kg, whereby S5 and S6 indicated the highest
may result in the overestimation of the chronic daily intake (CDI) and concentration. Alongside the sediment analysis, hydrochemistry of the
the resulting health hazard index (HI). Therefore, the fractions of mine-impacted water has also been evaluated, which demonstrates
bioavailable concentration of the heavy metals found in Yuswir et al. highly acidic pH at the S5 and S6 of between 4.53 and 4.76. When pH of
(2015) were adopted in the estimation of the HRA. the water was below 5, Al3+ tends to be hydrolyzed further lowering
The health risk for carcinogenic metals expressed by the total life- the water pH. Over time and due to exposure to oxygen and water, this
time cancer risk (LCR) was determined by estimating the total value of will result in the accumulation of precipitated Al deposited in the se-
diment. The impact of sediment contaminated with Al can be associated
Table 5 with the sensitiveness of many plant species towards the micro-molar
The reference dose (RfD) values of heavy metals. concentrations of Al affecting the plants growth (Delhaize and Ryan,
1995). The water that is very acidic in nature would certainly expose
Heavy metal RfD
plants and trees to low pH stress thus affecting their growth (Jusop,
(mg/kg/day)
2016).
Cu 0.0371
Co 0.02 3.1.2. Other metals and metalloid
Fe 0.7
Pb 0.0035
The mean values and distribution concentration of other trace ele-
Zn 0.3 ments (Mn, Pb, Zn, Cu, Cr, Sr, Co, Cd) and metalloid As in the surface
Cr 0.003 sediment of the Pengerang bauxite mining area are given in Fig. 2.
Cd 0.001 While Mn, Zn, Cr, Sr, Co, Cd and As in all stations were found within the
Al 0.0004
guidelines acceptable values (e.g. Canadian Council of Ministers of
As 0.0003
Environment, UK Environment Agency, Hong Kong Environmental
Source: US Environmental Protection Agency (USEPA) Protection), Pb and Cu have exceeded the recommended values at some
(2012). locations. Copper was found at 45.2 mg/kg (S1), exceeding the

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Table 6
Mean concentration of heavy metals (and metalloid) in surface sediments of bauxite mining area.

Station Cu Fe Mn Pb Zn As Cd Cr Al Co Sr

S1- stream 45.2 21,267.8 208.5 21.3 45.0 1.8 0.20 17.9 19,446.8 2.7 5.2
S2- stream 6.0 20,703.6 148.4 58.6 40.9 3.5 0.05 3.2 20,203.9 0.7 3.6
S3- mine tailings 1.9 19,441.8 31.3 13.3 12.1 0.2 0.08 1.1 15,675.7 0.1 0.6
S4- mine tailings 7.9 18,840.6 130.4 40.6 11.0 1.8 0.14 0.5 16,474.0 0.1 1.1
S5- mine tailings 9.1 31,345.0 221.2 62.3 13.8 3.4 0.19 1.8 22,149.1 0.1 1.2
S6- mine tailings 22.7 31,762.0 124.4 30.8 12.8 0.8 0.03 12.0 17,686.5 0.2 1.1
S7- ex-mining pond 17.3 16,408.9 6.6 12.1 8.2 5.9 0.08 8.9 13,735.1 0.3 1.5
Hong Kong Environmental Protection Department
b b b b b b
ISQG-low 65 75 200 8 80
b b b b b b
ISQG-high 270 218 270 70 370
b b b b b
Canadian Council of Ministers of Environment 35.7 35 123 5.9 0.6 37.3
UK Environment Agency:
TEL – Threshold effects level 36.7 b b
35 123 5.9 0.6 37.3 b b b

PEL – Predicted effects level 197 b b

91.3 315 17 3.53 b b b b

Crust averagea 70 50,000 950 13 132 1.8 0.2 100 79,000 38 350

a
Smith and Huyck (1999).
b
Not specified.

Canadian Council of Ministers of Environment and UK Environment
Agency guidelines of 36.7 mg/kg. Lead concentration was found >
recommended values of 35 mg/kg at 58.6 mg/kg (S2), 40.6 mg/kg (S4)
and 62.3 mg/kg (S5).
From the mining perspective, heavy metals such as Cu and Pb have
been reported to be present in the main ore body (Taylor, 1971; Zin
et al., 2015). The presence of metal sulfides such as galena (PbS) and
chalcopyrite (CuS) is typically associated with the presence of sulfide
minerals already exist in most soils and sediments. Copper were mainly
attributed to covellite (CuS), chalcocite (Cu2S) and native copper (Cu).
Copper also tends to accumulate in sediments because of its corre-
spondence for particulate organic matter (Campbell and Tessier, 1996).
The organic matter could be coming from various sources most im-
portantly from the topsoil of the mine land (Jusop, 2016). In most
acidic soils, Pb and Cu were strongly retained, due to greater compe-
titive adsorption of these metals onto the soil (Pérez-novo et al., 2008).
On the other hand, As was found just at the recommended guideline
value of 5.9 mg/kg at S7 (ex-mining pond). This suggests that previous
bauxite mining activities might have resulted in As-containing minerals
mobilized during mining exploration, being deposited onto the sedi-
ment. In addition, Arsenic might have been released due to natural
processes of abundant crust as it is already present in most ore body
(Taylor, 1971; Chen et al., 2007) and from within palm oil plantations
along the areas (Kusin et al., 2017). The presence of As is typically
associated with the weathering of arsenopyrite which is among the
main sulfide phase in the ore deposit.
For other metals such as Mn, Zn, Cr, Sr, Co and Cd, despite being
lower or within the recommended guideline values, the metals were
found at relatively higher concentration in the S1, which is the nearby
stream affected by the bauxite mining. Although it is likely that the
bauxite mining activities could have been the plausible cause of the
metal contamination, contribution from other sources cannot be ruled
out. Visual observation indicates that the S1 is relatively near to an
open dumping area; there is therefore potential of metal leaching from
the site contributing to more inputs of heavy metals. Despite this, the
discharge from uncovered mine waste dumps might have resulted in
continuous accumulation of these metal residues within the river eco-
systems (Olivares-Rieumonta et al., 2005; Varol, 2011).
Manganese was found in rather high concentration, because it is
among the major elements in most soils and sediments (Iqbal and Shah,
2014). Zinc on the other hand may be present as a molecular substitute
for iron in the chlorite, which appears to be derived from the weath-
ering of iron oxide-hydroxides (Taylor, 1971). The accumulation of soil
organic matter can also be the factor attributable to the presence of Cd.
Soluble organic matter content and formation of clay have been found
to be the major factors governing Cd speciation, distribution and ad-
sorption in sediments. In addition, Cd would present through the in-
teraction with Cu, Pb and Zn. This is also supported by the strong
correlation found between Cd-Cu and Cd-Pb (r = 0.915 and 0.959, re-
spectively, p < 0.01). Meanwhile, it has been reported that the source
of Cr in the surface sediments was due to the accumulation of sediments
mobilized from the drainage of the opencast bauxite mines (Gunkel-
Grillon et al., 2014).
The relationships between the metals and metalloid were in-
vestigated using Pearson's correlation coefficient to measure the
strength of the association among the variables (Table 7). There were
highly strong positive correlations found between Cu-Cd,Cr,Sr; Mn-Al;
Pb-Cd,Co,Sr; Cd-Co,Sr; and Co-Sr (r above 0.87; p < 0.01) and strong

35,000

30,000
Concentraon (mg/kg)

25,000

20,000
Al
15,000 Fe
10,000

5,000

0
S1 S2 S3 S4 S5 S6 S7
Fig. 2. Variation of heavy metals Al and Fe in the surface sediments.

459
F.M. Kusin et al. Catena 165 (2018) 454–464

250
Mn
200 Cd

Concentraon (mg/kg)
Zn
150
As
Cr
100
Pb
Co
50
Sr

0 Cu
S1 S2 S3 S4 S5 S6 S7
Fig. 3. Variation of heavy metals Co, Sr, Cu, Mn, Pb, Zn, Cr and metalloids As in the surface sediments.

100%

90%

80%
Percentage to total RI (%)

70% Co
Ni
60%
Cr
50%
Cd
40%
As
30% Zn
20% Cu
Pb
10%

0%
S1 S2 S3 S4 S5 S6 S7
Sampling locaon
Fig. 4. Percentage of potential ecological risk index (Eir) for single heavy metals to total RI.

correlations between Cu-Pb,Co; Pb-Zn, Zn-Co; Cd-Cr; Cr-Co, Sr (r above of the total RI in S5. Other locations were found to be in the range of
0.75; p < 0.05). During migration and transformation processes, ele- low risk. Individual EiR of each single element was lower than 40,
ments with high correlation values can share analogous behavior and suggesting low potential risk. Despite being low in risk, Cd, As and Pb
common sources (Wang et al., 2014). The correlations between the have generally greater risk compared to other metals, i.e. elements that
elements can be an indicative that they are aligned with their parent contribute the most to the total RI; mean value of 16.5, 13.8 ad 13.1 for
materials (Diami et al., 2016). Cd, As and Pb, respectively (Fig. 4). Furthermore, Cd and Pb were long
known of their high environmental risk.
Previous studies have suggested that from mining perspective, Cd is
3.2. Potential ecological risk index (PERI)
one of the elements that have high level of toxicity that possess a huge
distribution in the soil or sediment contamination from mining activ-
The degree to which the sediment has been contaminated in the
ities (Zheng-Qi et al., 2008; Pan and Li, 2016). A study on toxic metal
presence of metals other than major elements such Fe, Al and Mn can be
concentration and ecological risk assessment for sediments of major
more appropriately estimated using potential ecological risk index. This
freshwater lakes in China has shown that contaminated with Cd has
index takes into account the toxicity effect of the metals alongside the
resulted in moderate potential risk on a national scale. This is due to the
measured concentration of sediment in comparison with the reference
fact that Cd is one of the largest emissions from human activities (Cheng
value of the heavy metal in the earth's crust (Diami et al., 2016). The
et al., 2015). In S1, Cd recorded the highest EiR with the value of 30,
potential toxicity response indices (EiR) for individual elements and total
which is about 57% of contribution to total RI in the station and the
ecological risk index (RI) of heavy metals in the sediments of the
lowest at the S6 (19.7% contribution). Meanwhile, As and Pb have
bauxite mining areas are presented in Table 8 and are illustrated in
equally important contributions to the total RI. EiR for As was the
Fig. 4.
highest among all at the S7 with the value of 32 and which is about
The range of risk index (RI) in the study areas were found to be
64.3% contribution to total RI. Lead has the highest contribution with
between 18.49 and 72.15 indicating low to medium ecological risk in
EiR value of 23.9, which is about 52% contribution to total R1 at the S6.
the metal-contaminated sediments according to the risk classification
Generally, Cd, As and Pb have also been found to contribute to large
(Table 1). The highest RI found at the S5, which is classified as having
proportions of potential risk with respect to metal contamination in the
moderate ecological risk was apparently due to contribution from Cd
soil and sediment from mining activities (e.g. Zheng-Qi et al., 2008; Pan
and Pb, EiR of 28.5 and 23.9 respectively, contributing to about 72.7%

460
F.M. Kusin et al. Catena 165 (2018) 454–464

12 Pb be minor but the S2, S4 & S5 show moderately to severe enrichment

Cu
with Pb. Arsenic poses minor enrichment at the S1, moderate enrich-
10
Enrichment factor (EF)

ment at S2, S4 & S5, and moderately to severe enrichment at S7. Ac-
Zn
8 cording to the mean values of EFs, the descending order of heavy metals
Mn
enrichment in the sediments is: Pb > As > Cu > Al > Zn > Mn >
6 As Cr > Co > Sr (greater to lower).
Cd
4
Cr 3.3.2. Geo-accumulation index (Igeo)
2 Ni The analysis of Igeo indicates that the sediment was classified un-
contaminated with respect to most metals such as Fe, Al, Mn, Zn, Cr, Al,
Co
0 Co, Cd and Sr (Fig. 5b). However, Pb at the S2, S4 & S5 were classified
Sr
0 1 2 3 4 5 6 7 as having moderate contamination with Pb in the sediment, and were
categorized between uncontaminated to moderately contaminated at
4 the S1 and S6. Meanwhile, sediment was classified uncontaminated to
Pb
moderately contaminated with As at S2 & S5, and with moderate
Geo-accumulaon index (Igeo)

2 Cu
Zn
contamination at S7. None of the metals belong strong to extremely
0 Mn strong contamination with the metals.
0 1 2 3 4 5 6 7 Fe
-2
As 3.3.3. The contamination factor (CF)
-4 Cd The contamination factors (CF) in the surface sediments are de-
Cr
-6 picted in Fig. 5c. As with the distribution of Igeo, the sediment was
Ni
generally uncontaminated with Mn, Fe, Al, Zn, Cr, Al, Co, Cd and Sr.
-8 Co
Sr
Low contamination factors were found at the S1, S2, S4 & S5 with re-
-10 spect to As and at the S1, S4 & S6 with respect to Pb. Moderate con-
-12 tamination was found for Pb and As at the S2, S5 & S7.

3.3.4. Potential human health risk

4.0 Pb Pollution caused by heavy metal toxicity would impact human
Contaminaon Factor (CF)

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0 1 2 3 4 5
Staon
Fig. 5. Goechemical indices: a) Enrichment factor (EF) b) Geo-accumulation index (Igeo)
c) Contamination factor (CF) values for heavy metals in the surface sediments.
and Li, 2016; Pandey et al., 2016). Despite this, the RI values demon-
strated low ecological risk for the entire bauxite mining area.
3.3. Geochemical indices
3.3.1. Enrichment factor (EF)
Mining sediments are also subjected to high metal and metalloid
enrichment suggesting a strong influence of ore deposits on the mi-
neralogy of the sediments (Gomez et al., 2016). Enrichment factor (EF)
can be used to assess the degree to which the sediment has been con-
taminated with metals. However, EF unable to identify its biologic and
chemical activity but could recommend the source of metal and me-
talloids in a particular area (Guo et al., 2010). The EF for each heavy
metal element was calculated relative to the background values after
normalization with Fe element. Generally, there were no enrichment of
Mn, Zn, Cr, Al, Co, Cd and Sr in the sediments as the EF values were
lower than 1 (Fig. 5a). These metals were primarily natural in origin
and therefore the sediment was classified as being uncontaminated with
respect to these elements. There was no enrichment of Cu in sediment
also except for the S1 whereby EF indicates minor enrichment. Pb was
considered to poses moderate enrichment in the sediment, if based on
the mean the EF value of Pb, which was 4.36. However, when assessed
individually enrichment of Pb at the S2, S3, S6 & S7 was considered to
health and the environment. Metals such as As, Cr and Pb have high
Cu
toxicity level, and they have been grouped in the priority metals that
Zn
are important for public health. Even at bottommost levels of vulner-
Mn
ability, they are considered toxic that would influence damages of
Fe
multiple organs and these metallic elements were categorized as human
As
carcinogens (International Agency for Research on Cancer (IARC),
Cd 2012; Paul et al., 2014). Therefore, estimation of the human health risk
Cr of the heavy metals found in the surface sediments is presented here in
Al terms of their potential carcinogenic and non-carcinogenic health risks.
6 7
Co For estimation of potential human health risk, bioavailable metal
concentrations were incorporated into the calculation of chronic daily
intake (CDI) and the resulting health hazard index (HI) as noted earlier.
This is because the use of total metal concentration may result in
overestimation of the health risk (Diami et al., 2016; Halim et al.,
2017). The chronic daily intake, hazard quotient and the cumulative
hazard index for non-carcinogenic risk of heavy metals and metalloid
from the three exposure pathways (ingestion, inhalation and dermal
contact) on adults and children are presented in Table 7, while the
carcinogenic risk (lifetime cancer risk) of several metal elements (Pb,
Cd, Cr) and metalloid As from the different exposure pathways are
provided in Table 8.
For non-carcinogenic risk, it was found that the HI values were an
order of magnitude higher among children compared to the adults
(Table 9 and Fig. 6a). The HI values for children range between 1.751E-
05 - 5.725E-02, while HIs for adults were found in the range of 1.877E-
06 - 6.135E-03. Irrespective of the children or adults, the HI values of
the heavy metals were found in the order of Al > As > Cu > Fe >
Pb > Cd > Cr > Co > Zn. HI values of greater than one (HI > 1)
indicates the potential that the metal may possess non-carcinogenic
effects (US Environmental Protection Agency (USEPA), 2012). Notably,
the HI values were all below one (HI < 1) indicating that there is no
significant non-carcinogenic risk of the metals and metalloid in the area
studied.
On the other hand, the total carcinogenic risks (i.e. lifetime cancer
risk, LCR) of the heavy metals (Pb, Cd, Cr) and metalloid As are illu-
strated in Fig. 6b. As shown in Table 10, the LCR from different ex-
posure pathways indicate greater potential risk among children com-
pared to the adults, i.e. also by an order of magnitude higher. The LCR

461
F.M. Kusin et al. Catena 165 (2018) 454–464

6.00E-02 presence of the heavy metals and metalloid in the mining area. This
Adult indicates that children are more likely to experience adverse health
Non-carcinogenic Hazard Index

5.00E-02 effects from the exposure to heavy metals, because they are more likely
Children
to have hand-to-mouth oral ingestion (Luo et al., 2012). Generally, the
4.00E-02 HIs for both non-carcinogenic and carcinogenic risks demonstrate that
ingestion pathway contributes to most of the risk, followed by dermal
3.00E-02 and inhalation pathways. Similar findings have also been reported by
previous studies (e.g. Luo et al., 2012; Karim and Qureshi, 2014; Perez-
2.00E-02
Vazquez et al., 2016).

1.00E-02
4. Conclusions
0.00E+00
Pb Cu Fe Zn Cd Cr Co As Al The potential ecological and human health risks, due to heavy metal
composition and metalloid (Cr, Cu, Fe, Mn, Pb, Sr, Zn and As), in the
surface sediments associated with bauxite ore mining area have been
1.40E-06
assessed in the sediments of Pengerang bauxite mining area. The mean
Adult heavy metals (and metalloid) concentrations in the surface sediments
1.20E-06
Child for all locations were found to be in the order of
1.00E-06
Carcinogenic Risk

8.00E-07
6.00E-07
4.00E-07
2.00E-07
0.00E+00
Pb Cd
Fig. 6. Cumulative potential (a) non-carcinogenic and (b) carcinogenic risk for adults and
children of different metal elements.
ranged between 8.728E-08- 1.314E-06for children and between
1.870E-08- 2.817E-07 for adults. It is noticeable that the LCR for As is
relatively higher than other metals following the order of As > Pb >
Cr > Cd indicating that As has notably greater potential carcinogenic
risk. The LCR for As (children) was at 1.314E-06 which falls within the
tolerable LCR for regulatory purposes i.e., 1.0E-06– 1.0E-04 (USEPA,
2002), suggesting necessary monitoring of this element in the surface
sediment to meet regulatory requirement. The LCRs for other metals
such as Pb, Cr and Cd were found below the acceptable threshold value
of 1.0E-04, indicating no significant carcinogenic risk of these heavy
metals. Similarly, higher level of risk due to As have been found in other
mine-impacted soil studies (e.g. Liao et al., 2016; Carvalho et al., 2016)
that the risk has also been associated with the effect on plants the
human. It has been found that the risks were relatively higher in an
active iron ore mining site compared to abandoned mining area (Zin
et al., 2015; Diami et al., 2016).
Regardless of the carcinogenic or non-carcinogenic risk, children
were found to be more susceptible to the potential health risk due to the
Fe > Al > Mn > Pb > Zn > Cu > Cr > As > Sr > Co > Cd. Fe
and Al were found the greatest portion of metal elements in the sedi-
ment while Pb and Cu were found exceeding the recommended
guideline values at some locations.
Other metals such as Mn, Zn, Cr, Sr, Co, Cd and As in all stations
were found within the guidelines acceptable values. Assessment of PERI
has demonstrated low to medium ecological risk (RI of between 18.49
and 72.15) in the metal-contaminated sediments whereby Cd, As and
Cr As Pb have contributed the most to the total RI. The EF indicated no en-
richment of most metals while Pb and As at some locations were clas-
sified as having minor and moderately to severe enrichment.
The Igeo and CF have classified the sediments as being un-
contaminated with respect to most metals except for As and Pb at some
locations. HI values of the heavy metals were found in the order of
Al > As > Cu > Fe > Pb > Cd > Cr > Co > Zn but there were
no significant non-carcinogenic risk due to metals and metalloid as
HIs < 1. The LCR for carcinogenic risk was found in the order of
As > Pb > Cr > Cd, whereby As fell within tolerable LCR for reg-
ulatory purposes.
Regardless of the carcinogenic or non-carcinogenic risk, children
were found to be more susceptible to the potential health risk due to the
presence of the heavy metals and metalloid, whereby the hazard ex-
posure pathways were found to be in the order of ingestion >
dermal > inhalation. Findings have demonstrated that the impact of
previous and existing bauxite mining activities on the surrounding
ecosystems provide useful information for future management of the
mine-impacted sites.
Acknowledgements
Funding for this research was provided through the FRGS

Table 7
Correlation matrix among heavy metal (and metalloid) elements studied.

Cu Fe Mn Pb Zn As Cd Cr Al Co Sr

Cu 1
Fe 0.089 1
Mn 0.369 0.563 1
Pb 0.814⁎ 0.026 0.675 1
Zn 0.5 −0.109 0.541 0.789⁎ 1
As −0.041 −0.283 −0.15 −0.127 −0.033 1
Cd 0.915⁎⁎ 0.026 0.528 0.959⁎⁎ 0.653 −0.219 1
Cr 0.957⁎⁎ 0.102 0.188 0.661 0.445 −0.01 0.792⁎ 1
Al 0.113 0.626 0.913⁎⁎ 0.48 0.528 −0.081 0.285 −0.005 1
Co 0.852⁎ −0.162 0.452 0.955⁎⁎ 0.823⁎ −0.065 0.946⁎⁎ 0.760⁎ 0.274 1
Sr 0.875⁎⁎ −0.12 0.467 0.965⁎⁎ 0.73 −0.139 0.983⁎⁎ 0.757⁎ 0.253 0.984⁎⁎ 1

⁎
Significant coefficient at a level of p < 0.05 (2-tailed).
⁎⁎
Significant coefficient at a level of p < 0.01 (2-tailed).

462
F.M. Kusin et al. Catena 165 (2018) 454–464

Table 8
Potential ecological risk index for heavy metals in the surface sediments at Pengerang bauxite mining site.

Sampling Station Potential ecological risk indices for single heavy metal (Eir) Total ecological risk index (RI)

Pb Cu Zn As Cd Cr Co

S1 8.192 3.229 0.341 10.000 30.000 0.358 0.355 52.475

S2 22.538 0.429 0.310 19.444 7.500 0.064 0.092 50.377
S3 5.115 0.136 0.092 1.111 12.000 0.022 0.013 18.489
S4 15.615 0.564 0.083 10.000 21.000 0.010 0.013 47.286
S5 23.962 0.650 0.105 18.889 28.500 0.036 0.013 72.154
S6 11.846 1.621 0.097 4.444 4.500 0.240 0.026 22.775
S7 4.654 1.236 0.062 32.778 12.000 0.178 0.039 50.947

Table 9
Chronic daily intake (CDI), hazard quotient (HQ) and cumulative hazard index (HI) for non-carcinogenic risk.

Adults

Metal element CDIing CDIinh CDIderm HQing HQinh HQderm HI

Pb 9.354E-08 1.376E-11 3.732E-10 2.673E-05 3.930E-09 1.066E-07 2.684E-05

Cu 2.155E-06 3.169E-10 8.597E-09 2.870E-04 4.220E-08 1.145E-06 2.881E-04
Fe 2.189E-05 3.219E-09 8.733E-08 3.127E-05 4.598E-09 1.248E-07 3.140E-05
Zn 5.628E-07 8.277E-11 2.246E-09 1.876E-06 2.759E-10 7.485E-09 1.884E-06
Cd 2.712E-08 3.989E-12 1.082E-10 2.712E-05 3.989E-09 1.082E-08 2.714E-05
Cr 5.331E-08 7.839E-12 2.127E-10 1.777E-05 2.613E-09 7.090E-08 1.784E-05
Co 1.479E-07 2.176E-11 5.903E-10 7.397E-06 1.088E-09 2.952E-08 7.428E-06
As 4.086E-07 6.009E-11 1.630E-09 1.362E-03 2.003E-07 5.435E-06 1.368E-03
Al 2.453E-05 3.608E-09 9.789E-08 6.134E-03 9.020E-07 2.447E-05 6.159E-03

Children

Metal element CDIing CDIinh CDIderm HQing HQinh HQderm HI

Pb 8.731E-07 6.420E-11 1.742E-09 2.494E-04 1.834E-08 1.252E-07 1.834E-08

Cu 2.011E-05 1.479E-09 4.012E-08 2.678E-03 1.969E-07 5.343E-06 1.969E-07
Fe 2.043E-04 1.502E-08 4.075E-07 2.918E-04 2.146E-08 5.822E-07 2.146E-08
Zn 5.253E-06 3.862E-10 1.048E-08 1.751E-05 1.287E-09 6.843E-13 1.287E-09
Cd 2.532E-07 1.861E-11 5.050E-10 2.532E-04 1.861E-08 9.469E-12 1.861E-08
Cr 4.975E-07 3.658E-11 9.926E-10 1.658E-04 1.219E-08 1.705E-12 1.219E-08
Co 1.381E-06 1.015E-10 2.755E-09 6.904E-05 5.077E-09 3.079E-14 5.077E-09
As 3.814E-06 2.804E-10 7.608E-09 1.271E-02 9.347E-07 6.005E-11 9.347E-07
Al 2.290E-04 1.684E-08 4.568E-07 5.725E-02 4.209E-06 8.500E-11 4.209E-06

Table 10
Carcinogenic risk for different exposure pathways for adults and children.

Adults Children

Metal element CrIng Crinh Crderm LCR (HI) CrIng Crinh Crderm LCR (HI)

Pb 6.427E-08 2.398E-14 2.269E-10 6.450E-08 2.999E-07 1.119E-13 1.059E-09 3.010E-07

Cd 1.863E-08 6.351E-15 6.581E-11 1.870E-08 8.697E-08 3.244E-14 3.071E-10 8.728E-08
Cr 3.663E-08 1.366E-14 1.293E-10 3.676E-08 1.709E-07 6.377E-14 6.035E-10 1.715E-07
As 2.807E-07 1.047E-13 9.914E-10 2.817E-07 1.310E-06 4.888E-13 4.626E-09 1.314E-06

(5524757) funded by the Ministry of Higher Education, Malaysia
(MOHE) and Putra IPM/IPS (9433300 and 9453700) research grants
funded by the Universiti Putra Malaysia (UPM) and Ministry of Higher
Education, Malaysia (MOHE). The authors would also like to ac-
knowledge technical assistance of the laboratory staffs of Faculty of
Environmental Studies UPM.
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