Chemical Species of Metallic Elements in the
Aquatic Environment of an
Ex-Mining Catchment
Muhammad Aqeel Ashraf1*, Mushtaq Ahmad2, Shatirah Akib3, Khaled S. Balkhair4, Nor Kartini Abu Bakar5
ABSTRACT: This study was conducted to investigate the chemical
speciation of dissolved and particulate elements (lead, zinc, copper,
chromium, arsenic, and tin) in the mining wastewater of a former tin-
mining catchment. The speciation patterns of dissolved elements were
estimated by an adsorptive stripping voltammeter (ASV), while
particulate elements were analyzed by using a newly developed
sequential-extraction leaching procedure. The procedure has been
operationally defined among five host fractions, namely exchangeable,
carbonate, reducible, organic bound, and residual fractions. A total of six
elements (lead, zinc, copper, chromium, arsenic, and tin) were analyzed
in thirty samples at ten locations (P1-P10), with three samples taken
from each of the ten locations, to get the average value from the former
tin-mining catchment. The results showed that the heavy metal
pollutions in locations P4 and P8 were more severe than in other
sampling sites, especially tin and lead pollution. In the water samples
from locations P4 and P8, both the total contents and the most
dangerous non-residual fractions of tin and lead were extremely high.
More than 90% of the total concentrations of arsenic and chromium
existed in the residual fraction. Concentrations of copper and zinc
mainly occurred in the residual fraction (more than 60%), while lead and
tin presented mostly in the non-residual fractions in surface water. For
all of the six dissolved elements, the less-labile species formed the
predominant fraction in their speciation patterns. The speciation
patterns of particulate elements showed that most of the concentrations
of zinc, copper, chromium, and arsenic were found in the reducible
fraction; whereas lead and tin were mainly associated with the organic
fraction. Water Environ. Res., 86, 717 (2014).
KEYWORDS: particulate metals, dissolved metals, anodic stripping,
sequential leaching, fractions.
doi:10.2175/106143014X13975035525825
Introduction
Metals and metalloids are ubiquitous in the worlds environ-
ment. They exist naturally as ions, compounds, and complexes.
1
Department of Geology, University of Malaya, Kuala Lumpur 50603,
Malaysia
2 accepted that the distribution, mobility, bioavailability, and
Department of Plant Sciences, Quaid-i-Azam University 45320
Islamabad, Pakistan
3
Department of Civil Engineering, University of Malaya 50603 Kuala
Lumpur, Malaysia
4
Depertment of Hydrology and Water Resources Management, King
Abdulaziz University, Jeddah 22254, Saudi Arabia
5
Department of Chemistry, University of Malaya, 50603 Kuala
Lumpur, Malaysia
August 2014
The earths crust is the natural reservoir for all the chemical
elements of various species. Over 99% of the total mass of the
earths crust is made up of oxygen (46.4%), silicon (28.15%),
aluminium (8.23%), iron (5.63%), calcium (4.15%), sodium
(2.36%), magnesium (2.33%), and potassium (2.09%). Besides
these eight elements, the remaining 80 elements of the periodic
table that occur naturally make up less than 1% to the
composition of the earths crust (Markert et al., 2000). During
the long history of geologic processes, solid rocks are weathered,
and mountain ridges are eroded. The eroded materials are
suspended and dissolved in river water and rainwater, and
transported in ice and wind. These processes cause the
distribution of chemical elements (Kabata-Pendias and Pendias,
2001).
Natural waters acquire their chemical compositions from
various sources. They collect the suspended and dissolved
components through contact with the solids, liquids, and gases
that they encounter during their hydrologic cycles. The
composition of surface waters and ground waters changes on
time scales from minutes to years; however, the composition of
the oceans has been constant for millions of years (Puxbaum and
Limbeck, 2008). The main factors affecting the composition of
natural waters are interactions between water and the gases,
liquids, and solids that the waters contact when they pass
through the hydrologic cycle. These interactions determine the
chemical environments where trace elements exist and influence
the transport and fate of the elements in their environmental
behaviors (Philos and Philos, 1995).
Heavy metals exist in a wide range of chemical forms in
environmental systems. In the case of surface waters, they are
present in both dissolved and particulate phases. The former
phase includes hydrated ions, inorganic and organic complexes,
and the species associated with heterogeneous colloidal
dispersions and organometallic compounds. The latter phase
contains the chemical associations ranging from weak adsorp-
tion to binding in the mineral matrix. It has been generally
toxicity of chemical elements depend not only on their total
concentrations, but also on their chemical forms. Various
changes in the environmental conditions such as redox
potential, pH, complexing ligands, and adsorbing sites can
highly alter the elements chemical forms, and thus influence the
physical and chemical associations which they undergo in
environmental systems (Dodge and Theis, 1979).
717
Ashraf et al.
Toxicity occurs when an organism cannot deal with the
additional elemental concentrations (Angelika et al., 1998; Du et
al., 1996; Huang et al., 1995; Nicole et al., 2001; Petersen et al.,
1997). The interactions between elements and intracellular
components depend strongly on their chemical forms. Some
species may be able to react directly with proteins, enzymes, and
other biological molecules, while others may diffuse through cell
membranes and interfere with the enzyme reactions.
The distribution of an element among different inorganic
compounds and organic complexes profoundly impacts its
transport and bioavailability by determining its physical and
chemical properties such as charge, solubility, and diffusion
coefficient. To fully understand the environmental chemistry of
an element, it is necessary to completely ascertain the
concentrations and chemistry of its various species under the
different conditions possible in natural environments. Speciation
science aims to characterize an elements forms in order to
understand the transformations between different forms, and to
make inferences about the environmental processes controlling
these transformations (Gjerde et al., 1993). According to the
International Union of Pure and Applied Chemistry (IUPAC)s
standards, chemical species are the chemical compounds that
differ in isotopic composition, conformation, oxidation, or
electronic state, or in the nature of their complexes or covalently
bound substances (Templeton et al., 2000).
For the analysis of chemical speciation, different methods
have been employed by various researchers. Among these
methods are the voltammetric method (Bard and Faulkner, 1980;
Bond, 1980), the liquid-liquid extraction method (Francis et al.,
2001; Meera et al., 2001), the ion-exchange and adsorption
columns/resins method (Morel et al., 2008; Sweileh et al., 1987),
the gas chromatography method (Dietz et al., 2000; Rodil et al.,
2002), the liquid chromatography method (Ibrahim et al., 1984;
Weber et al., 2002), the capillary electrophoresis (CE) method
(Rocha et al., 2000; Yin et al., 2002), and the Inductively Coupled
Plasma Mass Spectrometry (ICP-MS) method (Butcher, 2007;
Medel et al., 2003). The ICP-MS method in particular can be a
good tool for sensitive speciation analyses of many environ-
mentally important elements. The analysis of heavy metal
species in soil, dust, or sediment can be undertaken by either
acid digestion or sequential extraction techniques. Sequential
extraction (SE) techniques (Tessier et al., 1979) use successive
chemical extractants of various types, in order of greater
destructive ability; these techniques therefore possess greater
sensitivity than a single extraction procedure. Speciation, or
using sequential extraction schemes, has been developed for
assessing geochemical forms in soil and sediment (Harrison et
al., 1981; Lagerwerff and Specht, 1970; Ma and Rao, 1997;
Zufiaurre et al., 1998).
Fractionation by selective chemical extraction removes or
dissociates a specific phase with the associated metal bonded to
it. The geochemical fractions most commonly analyzed are as
follows: exchangeable, bound to carbonates, reducible, oxidiz-
able, and residual. Among the sequential extraction schemes
which have been proposed to investigate the distribution of
heavy metals in soil and sediments, the five-step and six-step
extraction schemes developed by Tessier and by Kersten, and
Forstner (Tessier et al. 1979; Kersten and Forstner, 1986),
respectively, have been used most widely. Building on these two
basic schemes, some modified procedures with different
sequences of reagents or operational conditions have been
718
developed (Borovec et al., 1993; Campanella et al., 1995; Gomez
Ariza et al., 2000; Zdenek, 1996).
Bodies of water are essential parts of the ecological system. In
recent years, due to rapid industrialization and excessive mining
activities, many bodies of water have been contaminated by
different forms of heavy metals. These contaminations pose
severe ecotoxicological threats to aquatic wildlife and to
humans. The bio-geochemical behavior, nutritional bioavailabil-
ity, and toxicity of metals are largely dependent on their
chemical speciation. These studies have received extensive
attention in recent years. The objective of this study was to
investigate the speciation of heavy metals and arsenic by
developing a suitable sequential extraction procedure, followed
by ICP-MS detection, in the water from a former tin mining
catchment, in Bestari Jaya, Sengalor, Peninsular Malaysia.
Study Area. Morphological Characterization. The study
area of the Bestari Jaya catchment is located at 38 24 0 40.41 0 0 N
and 1018 24 0 56.23 0 0 E. The catchment is part of Daerah Kuala
Selangor, in Selangor state, that includes three towns: Mukim
Batang Berjuntai, Mukim Ulu Tinggi, and Mukim Tanjong
Karang (Figure 1). Bestari Jaya was formerly named Batang
Berjuntai. In 2007, however, Batang Berjuntai was renamed
Bestari Jaya due to censorship by the government, as Batang
Berjuntai has phallic meanings in the Malay language. Bestari
Jaya has a tropical, humid climate, with very little variation in
temperature throughout the year. The average temperature of
the area is 328 C during the day and 238 C at night. The annual
average rainfall is between 2 and 3 meters, with a potential
evaporation of 1.6 meters per year (Department of Irrigation and
Drainage, 2009). The Bestari Jaya area has been an old tin mining
area for over 10 years. The whole catchment covers an area of
2656.31 hectacres, located downstream at the embankment of
Kampung Bestari Jaya and the University Industry of Selangor
(UNISEL)s main campus. The catchment runoff flows down-
stream to the rivers of Sungai Ayer Hitam and Sungai Udang,
which ultimately merge with the river Sungai Selangor, five
kilometers upstream of Batang Berjunti Water Treatment Plants
SSP1 and SSP2. These water treatment plants are major water
distributors to federal territories (Kuala Lumpur and Putrajaya)
and the state of Selangor as well (Ashraf et al., 2011). The area
consists of myriad ecosystems which can be subdivided into
several categories, such as degraded land, large open lakes and
small ponds, earth drains and wetland areas, tin tailings (sand
and slime tailings), and logged peat-swamp forest land in the
east. The contributions of storm water, peat-swamp forest water,
and recent sand mining activity have caused severe environ-
mental pollution issues, due to drainage problems in the area.
The area has many large lakes and small ponds that are
interconnected by earth drains. Excess water from these lakes
and ponds is discharged to the existing earth drains downstream
of the lakes and ponds. The precipitation rate is high in some
stagnant ponds (Ashraf et al., 2011).
Geological Characterization. Tin mining at the Bestari Jaya
catchment was carried out mainly in the alluvium, because of the
rich concentration of cassiterite which was found in the
catchment soil and trapped within the troughs of the pinnacled
limestone bedrock. However, in a few areas of the catchment,
such as the northeast and west, mining was carried out in the
residual granitic soil (Widya and Tresna, 1984). Cassiterite was
also mined from lodes which dipped steeply into the limestone
bedrock, forming what are known as pipes. A byproduct of
Water Environment Research, Volume 86, Number 8

Figure 1Map of Bestari Jaya Catchment.
mining in almost all cases is the formation of lakes, except in the
case of stripping of cassiterite-disseminated residual soil from
the hill slopes. The bedrock underlying the alluvium, mine
tailings, and ex-mining lakes in the Bestari Jaya catchment
consists mainly of limestone, with interbeds of schists, shale, and
rarely quartzite (Sarif, 1990). The most common type of bedrock
found in the floor of the mine pits is limestone. Sarif (1990)
stated that the close association of rich alluvium tin deposits
with limestone is the result of a fortuitous combination of
several geological events and factors, such as the style of
mineralization, past paleoclimatic conditions, changes in sea
levels and base levels of erosion, weathering characteristics of
bedrock, and the sequence of occurrence of these events (Widya
and Tresna, 1984).
In the Bestari Jaya catchment, the most common method of
mining was to use traditional gravel pumps. This method, which
is labor-intensive, was very popular with the local miners.
Another widely used method was to use capital intensive
dredges. Most of these dredges were European-owned. Other
methods, which included mining cassiterite-disseminated resid-
ual soil from hill slopes, and lode mining along pipes, were used
only rarely. On most occasions, areas which were mined with
dredges were often later re-mined with gravel pumps, the reason
being that the buckets in the dredges could not recover
cassiterite-rich alluvium trapped within the troughs of the lime
stone pinnacles. There are now a total of 442 mined-out ponds
at the Bestari Jaya catchment; these include 273 dredged ponds,
27 dredged sedimentation ponds, 167 gravel pump mine pits,
and 108 open cast tailings (Chow and Yunus, 1992).
Material and Methods
Sampling and Sample Pre-Treatment. Due to the large size of
the study area, a Global Positioning System (GPS) was used to
determine the actual coordinates of the sampling sites and to
reconfirm the location of the sampling site during subsequent
sampling periods. The physio-chemical parameters of water
samples (pH, temperature, electric conductivity, dissolved
oxygen (DO), total dissolved solids (TDS), chlorides, ammoni-
um, and nitrates) were analyzed in situ by using a hydrolab (MS5
USA) on an engine boat. The hydrolab was recalibrated every
August 2014
Ashraf et al.
three hours or every third site, depending upon which came first.
The meter electrodes were rinsed with de-ionized water before
and after each measurement. A total of thirty water samples
were collected for speciation analysis from ten different
locations at the catchment in December, 2010 (Figure 2). Fifteen
days were spent collecting samples at each location, with 3
subsequent samples collected on the same days. Water samples
were collected using a Van Dorn horizontal (KC-Denmark)
water sampler. The sampler is made of sturdy transparent PVC
and has a double releaser, activated by a drop messenger. The
vessel of the sampler has a capacity of 5 liters. The total depth of
each sampling station was measured with a Garmin Fish Finder
160C. Three subsequent water samples were collected at the
same location from the midstream after calculating total depth
at the sampling point. The samples were then transferred to 1-
liter acid-washed polyethylene water sampling bottles and
refrigerated (at 48 C) immediately to avoid changes in heavy
metal distribution among different phases.
Analytical Methods. Development of New Sequential
Extraction Leaching Procedure for Particulate Phase of Water.
The sequential extraction procedures available in literature are
only subjected to the analysis of soil and sediment samples
(Borovec et al., 1993; Campanella et al., 1995; Gomez Ariza et al.,
2000; Zdenek, 1996). A new sequential leaching procedure was
developed, following the five-step and six-step extraction
schemes of Tessier et al., (1979) and Kersten and Forstner
(1986). The method identifies the metal among five operation-
ally-defined host fractions, namely exchangeable, carbonate,
reducible, organically bound, and residual fractions (Scheme 1).
Determination of Total, Dissolved and Particulate Metal
Concentrations. The amounts of total metals in the water
samples were measured by inductively coupled plasma optical
emission spectrometry, or ICP-OES (Perkin Elmer AA Analyst).
Working standards for chemical analyses were prepared from
Perkin-Elmer stock solutions. The methodology for measuring
total metal concentrations in soil was referenced using the
(SRM-1643e) Standard Reference Material (National Institute of
Standards & Technology (NIST), USA) and samples were
analyzed concurrently with the water samples. Recoveries of
metals were 99% for tin, 97% for arsenic, 92% for copper, 99% for
719
Ashraf et al.

Figure 2Land-use map of Bestari Jaya Catchment (boxed area representing water sampling for speciation studies)

zinc, and 94% for lead; the coefficient of variation was between
3% and 10% when analyzed in triplicate.
To determine the amounts of total dissolved and particulate
metals, samples were centrifuged at 8000 rpm for 20 minutes,
and the supernatants were then filtered through 0.45lm
membrane filters to be separated into particulate and dissolved
fractions. Exactly 40 milliliters of the filtrate was digested in a
Teflon bomb, with 5 milliliters concentrated HNO3, using a
microwave digester (Multiwave 3000, Perkin Elmer) (Che et al.,
2003; Horowitz and Elrick, 1987; Moore et al., 1989; Tam and
Wong, 2000). The digested sample was then analyzed for the
total dissolved metal concentration using inductively coupled

Scheme 1Sequential extraction leaching procedure for particulate phase of water samples.

720 Water Environment Research, Volume 86, Number 8

 Ashraf et al.

Table 1Geography of sampling locations. mercury drop electrode, a AgCl/Ag reference, and a platinum
counter electrode). The remaining sample was passed through a
Sampling site Geographic position Total depth (m) pH
column packed with the ammonia form of the Chelex-100 resin
P1 38 27 0 04.86 0 0 N 1018 26 0 08.69 0 0 E 6.8 4.3 of 50100 mesh size (Riley and Taylor, 1968). The difference
P2 38 26 0 59.53 0 0 N 1018 26 0 33.19 0 0 E 5.4 3.9 between the Chelex-labile and ASV-labile species indicates the
P3 38 26 0 52.72 0 0 N 1018 26 0 31.64 0 0 E 8.1 4.6 amount of the moderately labile species. Effluent from the resin
P4 38 26 0 41.82 0 0 N 1018 26 0 11.55 0 0 E 9.8 4.4 column was then shaken with the Chelex resins for 72 hours to
P5 38 26 0 38.16 0 0 N 1018 26 0 30.58 0 0 E 7.9 3.8 determine the slowly-labile and inert metal species using the
P6 38 26 0 26.70 0 0 N 1018 26 0 46.43 0 0 E 10.6 4.1 batch procedure (Figura and McDuffie, 1980). The concentra-
P7 38 26 0 17.65 0 0 N 1018 26 0 20.04 0 0 E 6.4 4.9
tions of Chelex-labile, moderately-labile, and slowly-labile
P8 38 25 0 46.98 0 0 N 1018 26 0 28.12 0 0 E 3.2 5.2
P9 38 25 0 20.74 0 0 N 1018 26 0 12.91 0 0 E 1.6 5.3
species, as well as the inert metal species, were determined
P10 38 24 0 27.34 0 0 N 1018 25 0 55.22 0 0 E 1.9 6.7 using inductively coupled plasma optical emission spectrometry
(ICP-OES) (Perkin Elmer AA Analyst).
Speciation Study of Particulate Metals. The sequential
plasma optical emission spectrometry (ICP-OES) (Perkin Elmer extraction leaching procedure for the particulate phase of water
AA Analyst). samples (Scheme 1) generally follows that of Tessier et al. (1979)
The membrane filter after filtration, together with the residue and Kersten and Forstner (1986). One difference was that 1.0 M
after centrifuging, was dried in an oven at 1038 C for 24 hours. A (molar solution) ammonium acetate at pH 7.0 was used as the
known weight of the particulate was digested in a Teflon bomb extraction reagent for the exchangeable fraction, instead of 1.0
with 5 milliliters of 30% H2O2, and 5 milliliters of 65% HNO3 M magnesium chloride, due to the lower matrix effect posed by
the former reagent in the ICP-OES determination. This
using a microwave digester (Guevara-Riba et al., 2004; Martin et
procedure was developed for the partitioning of particulate
al., 1998; Morillo et al., 2004; Usero et al., 1998; Yuan et al.,
metals into exchangeable, carbonate, reducible, organic/sul-
2004). The digested sample was then analyzed for the total
phide, and residual fractions. For this procedure, 0.2 grams of
particulate metal concentrations using ICP-OES.
particulate samples in triplicate were weighed accurately and put
Speciation Study of Dissolved Metals. Species of heavy metals through the sequential extraction leaching procedure in acid-
in the dissolved phase were differentiated utilizing an adsorptive washed 50-milliliter polyethylene centrifuge tubes with screw-on
stripping voltammeter (ASV). and their labilities were measured caps. Each successive extraction was then separated by
towards an ammonium form of Chelex resin in successive centrifugation at 3000 rpm for 30 minutes. All extracts were
column and batch procedures (Figura and McDuffie, 1980). An stored in acid pre-washed polyethylene bottles for trace metals
aliquot of the filtered sample was set aside for the determination determinations.
of ASV-labile metal species by differential pulsed ASV, using a Quality Assurance of Data. All reagents used were at least of
Metrohm 693 VA processor in combination with a Metrohm analytical grade. Ultrapure water, of 18 MW-cm resistivity, was
694 VA stand (a multimode electrode operation with a hanging used in this study for the blank and the preparation of standard

Table 2Mean dissolved metal concentrations at different sampling locations.

Metals Specification P1 P2 P3 P4 P5 P6 P7 P8 P9 P10

Arsenic ASV Labile 0.3060.1 0.160.06 0.3160.07 0.7260.20 0.2560.12 1.160.07 1.060.03 1.260.28 0.2160.08 0.2860.12
Labile 0.2260.2 0.1660.09 0.2560.12 0.8760.09 0.1460.1 1.360.09 1.460.04 1.660.21 0.1860.32 0.1960.08
Slowly Labile 0.1460.1 0.1960.08 0.2960.09 0.8060.12 0.1660.09 0.860.07 1.860.03 0.9260.11 0.1460.1 0.2160.09
Inert 0.4060.1 0.1760.03 0.3660.10 1.060.21 0.1460.1 1.360.03 0.1460.1 1.060.23 0.3060.10 0.1060.02
Chromium ASV Labile 0.9060.2 0.8360.07 0.7160.12 0.9860.17 0.3860.12 0.6760.13 0.8260.12 1.0260.24 0.7260.09 0.5060.04
Labile 0.8660.08 0.7860.10 0.9660.24 0.8760.14 0.5660.10 0.7360.11 0.6560.10 0.9860.30 0.5860.02 0.6960.05
Slowly Labile 0.9760.04 0.6760.41 0.6560.18 1.060.21 0.7160.16 0.4560.21 0.3960.09 1.1060.29 0.6960.01 0.8360.05
Inert 1.060.04 0.8760.34 0.4260.20 0.9360.18 0.5960.23 0.6360.11 0.8460.20 0.9160.32 0.8260.01 0.5660.07
Copper ASV Labile 1.6260.18 1.2060.15 1.5260.18 1.9260.20 1.3860.12 1.2960.10 1.2060.15 2.1260.23 1.3860.12 1.4360.12
Labile 1.9060.90 1.6460.12 1.6260.11 1.8560.18 1.7260.20 1.5260.18 1.6060.15 1.9560.18 1.4560.17 1.6060.15
Slowly Labile 1.7260.20 1.8560.10 1.4360.10 2.060.20 1.6460.12 1.8060.15 1.6860.12 1.8860.19 1.6860.12 1.8260.11
Inert 1.8060.80 1.9060.14 1.7960.14 1.9360.14 1.9060.90 1.8060.15 1.3860.12 2.0860.15 1.8060.15 1.2960.10
Zinc ASV Labile 2.3461 4.3463 2.8363 2.8663 2.1963 1.9462 2.1363 3.6464 1.9562 2.0363
Labile 3.9262 2.9462 3.9663 3.1863 2.9862 2.6663 2.9563 4.0763 2.0563 1.3362
Slowly Labile 4.6463 1.7763 2.1262 3.9464 2.0563 2.2662 1.9562 3.4963 1.6763 1.8762
Inert 1.9361 3.5462 1.5863 2.9763 2.9862 1.7363 2.0362 3.5662 2.1363 1.6662
Lead ASV Labile 10.3263 8.9063 5.6662 12.0464 7.4462 8.2862 9.4763 12.0663 9.6663 3.8861
Labile 12.5262 4.6065 8.4463 10.4363 8.6863 4.7461 8.8362 14.0663 10.3262 6.6362
Slowly Labile 4.2563 7.9663 9.6762 11.0762 10.5863 6.3963 11.4662 16.6064 8.1764 9.0062
Inert 6.3762 4.9262 9.2264 14.3963 9.3463 7.6062 6.4663 18.0063 7.4363 8.3163
Tin ASV Labile 11.1363 13.3663 14.0865 22.0363 16.3762 19.4464 15.5863 26.0764 14.5863 15.9363
Labile 5.4963 10.1161 6.3862 13.5762 9.2563 8.8262 10.0663 18.9064 7.5262 9.2762
Slowly Labile 20.0564 18.4465 17.0563 24.0663 16.6362 18.9063 19.0764 25.0062 13.3863 14.7264
Inert 31.068 17.5264 19.4864 38.6863 28.5065 18.0062 23.0563 40.0665 21.2263 28.4264

August 2014 721

Ashraf et al.

Table 3Recovery of the sequential extraction leaching procedure and the total digestion.
Concentration[lg/g1]

Element SumC Total Reference value Recovery (1)a Recovery (2)b

Pb 25.5460.41 28.9860.19 27.063.0 88.162.1 107.362.7

Zn 59.8262.74 52.0561.53 46.065.0 114.962.8 113.264.2
Cu 19.2460.89 20.1360.69 22.662.0 95.663.6 89.162.4
As 0.9960.05 1.0560.03 1.1260.12 97.461.9 93.461.5
Sn 734.65619.5 945.2368.96 1013.0644.0 77.761.9 93.362.4
a
Recovery (1): Sum/Total
b
Recovery (2): Total/Reference Value
c
Sum Fraction A Fraction B Fraction C Fraction D Fraction E
Where
Fraction A corresponds to Exchangeables
Fraction B corresponds to Carbonates
Fraction C corresponds to Reducibles
Fraction D corresponds to Organics
Fraction E corresponds to Residuals

solutions. All glassware and plastics that were used for the
experiments were previously soaked in 10% nitric acid (v/v) and
rinsed with de-ionized water. To evaluate the reproducibility and
accuracy of the method, a lake water reference material (SRM-
1643e) was subjected to the extraction protocol. Three
subsamples (Sets A, B and C) were taken through the sequential
extraction leaching procedure in parallel. The results and the
relative standard deviations (R.S.D) are listed in Table 4.
An internal check was performed on the results of the
sequential extraction by comparing the total amount of metals,

Table 4Reproducibility of sequential extraction procedure.

Set A (n3) Set B (n3) Set C (n3) Set D (n3)

Element Step Meana R.S.Db Meana R.S.Db Meana R.S.Db Meana R.S.Db Grand Meana R.S.Db

Pb A 1.82 3.12 2.02 1.65 1.95 2.46 1.88 0.91 1.93 5.2
B 1.01 5.8 0.02 3.67 0.02 1.24 1.78 0.65 0.02 34.4
C 9.7 2.28 10.78 6.01 10.2 2.16 2.1 0.56 10.23 5.3
D 7.08 2.2 6.26 1.62 6.69 1.89 0.98 0.34 6.68 6.1
E 8.73 0.16 8.28 0.52 8.85 0.48 1.93 1.53 8.62 3.5
Zn A 4.14 0.89 4.59 1.56 4.66 2.88 4.84 1.23 4.46 6.3
B 7.03 0.91 7.99 1.62 7.58 0.55 6.91 0.91 7.53 6.4
C 11.6 0.7 11.68 2.1 11.42 0.42 8.36 0.65 11.9 5.7
D 15.17 0.35 13.1 1.12 10.21 0.58 13.78 0.34 12.46 3.6
E 23.78 0.5 20.13 0.56 26.35 0.16 19.25 0.88 23.46 5.9
Cu A 0.26 1.08 0.33 2.13 0.29 1.56 1.46 1.02 0.29 12.2
B 1.66 1.46 1.78 2.18 1.59 0.95 2.34 0.48 1.68 5.7
C 2.52 0.76 2.72 0.65 2.81 3.33 1.98 0.76 2.68 5.6
D 4.56 0.72 8.42 0.96 10.58 0.21 2.71 0.91 14.59 6.2
E 10.62 0.66 5.13 1.56 4.82 0.55 1.14 1.42 4.46 6.3
AS A 0.2 2.93 0.25 1.65 0.24 1.75 1.72 0.21 0.23 12.2
B 0.26 3.97 0.28 1.85 0.33 1.48 1.98 0.3 0.32 6.1
C 0.13 2.19 0.12 2.79 0.11 0.99 1.46 0.18 0.12 10.2
D 0.2 1.1 0.15 1.71 0.15 1.89 0.91 0.25 0.27 7.4
E 0.18 1.23 0.17 0.68 0.19 2.16 2 0.27 0.18 4.5
Sn A 65.1 0.75 71.87 2.31 70.08 3.11 71.23 4.14 70.08 6.2
B 420.98 0.86 210.28 0.62 228.85 0.49 212.67 0.42 214.65 2.6
C 297.42 2.46 136.68 1.14 144.9 0.13 132.1 0.1 144.9 5.2
D 123.56 0.98 207.02 2.08 184.15 2.28 276.55 1.21 198.38 2.9
E 106.26 0.89 104.04 1.96 106.65 4.23 156.02 5.26 106.65 2.6
Cr A 0.49 2.42 0.68 2.81 0.6 2.24 2.1 1.34 0.6 12.8
B 2.64 1.68 2.68 0.95 2.71 0.86 1.88 0.93 2.71 3.2
C 19.91 0.95 18.84 0.31 19.32 0.64 5.88 0.45 19.32 2.8
D 12.1 0.62 13.55 0.29 12.22 0.22 12.76 1.1 21.1 2.8
E 81.16 0.33 74.8 0.21 78.16 0.38 19.45 0.45 69.28 3.4
a
Units lg/g1
b
Units %

722 Water Environment Research, Volume 86, Number 8

 Ashraf et al.

Figure 3Water quality characterization of the catchment.

August 2014 723

Ashraf et al.
Figure 4Speciation of dissolved metals in wastewaters from Bestari Jaya Catchment.
extracted by different reagents during the sequential extraction
procedure, with the results of the total digestion. The recovery of
the sequential extraction was calculated as follows:
Recovery C FractionA C FractionB C FractionC
C FractionD =C TotalDigestion  3 100
The results shown in Table 3 indicate that the sums of the four
fractions are in good agreement with the total digestion results,
with satisfactory recovery rates (77.7116.7%) and that the
method used is reliable and repeatable.
Results and Discussion
Samples were taken at ten different locations at the
catchment. The geography of the sampling locations is
represented in Table 1.
Water Quality Characterization. Water quality parameters for
the whole study area are shown in Figure 3. Results showed that
there is a variation in water quality at the catchment. Average
values for the studied water quality parameters at the catchment
were as follows: temperature 32.518 C, pH 5, conductivity 1756
lmhos/cm, dissolved oxygen 5.82 mg/L, and total dissolved
solids 2998 mg/L. At the downstream sampling site (the junction
of River Ayer Hitam and Sungai Selangor) water quality
parameters were as follows: temperature 32.198 C, pH 6.47,
conductivity 1640 lmhos/cm, dissolved oxygen 6.59 mg/L, and
total dissolved solids 2654 mg/L. Variation trends were evident
at all sampling stations from upstream to downstream. Possible
factors involved in these variations may include the formation of
wetlands, the activities of palm oil plantations, and the dilution
factor of water as it flows downstream to the river Selangor. A
comparison with Malaysian Interim Water Quality Standards
(INWQS) showed that at all sampling stations, the temperature
724
lay in the normal range, the pH was class III, the electric
conductivity fell into class III, dissolved oxygen was in class III,
and the total dissolved solids were in class III. An acidic pH and
low concentrations of dissolved oxygen are the characteristics of
peat swamp water (flowing into the catchment) and also of the
metal and sand mining waste water runoff into the catchment.
The high conductivity values represent a high concentration of
total dissolved solids (TDS). The main source of the high TDS
value is the recent sand mining activity going on in the study
area. The results of this study show that the water quality is
highly degraded in the area.
Speciation Study of Dissolved Metals. The speciation
patterns are controlled by the processes that occur in the water
column such as complexation, coprecipitation, and sorption.
Research shows that complexation is the most important
mechanism in controlling speciation in wastewater (Jardim
and Allen, 1984). Complexation of the metal with ligands, such
as humic-type substances, usually leads to the formation of high
molecular-weight compounds, resulting in an increase of the
percentages of less labile species (such as slowly labile and inert
species). Coprecipitation and sorption are basically scavenging
processes involving particulates which remove dissolved metal
species from the solution.
The mean concentrations of the ASV-labile, moderately labile,
slowly labile, and inert metal species along the treatment path
are shown in Table 2, whereas the dissolved metal speciation
patterns are depicted in Figure 4. Slowly labile species and inert
species formed the dominant fraction. It was also observed that
there was an increase in the less labile fractions at the expense of
the more labile fractions at P4 and P8. This can partly be
explained by complexation processes, as evidenced by the
decreasing complexing capacity from the mining source to the
Water Environment Research, Volume 86, Number 8

Figure 5ASpeciation of arsenic and chromium in wastewaters from Bestari Jaya Catchment.
river outlet. However, this study could not ascertain the
dominant process controlling the metal speciation patterns
among the processes involved, namely complexation, copreci-
pitation, and sorption.
Speciation Study of Particulate Metals. The concentrations of
metals in the water samples from each extraction step are shown
in Figures 5A5C. The discussion on the distribution patterns of
elements is divided into four groups, depending on the degree of
their association with the different phases. Arsenic and
chromium are assigned to a group which is present mainly in
the residual fraction (more than 90% of the total concentration),
copper and zinc in a group presenting dominantly in the residual
fraction (60% of the total concentration), and tin and lead in a
group with the large proportion of the total concentration
presenting in the non-residual fractions (FA FB FC FD).
Arsenic and Chromium. The distribution patterns of arsenic
and chromium are illustrated in Figure 5A. These elements were
found in all of the five operationally-defined aquatic phases. The
dominant phase was in the residual fraction, which accounted
for more than 50% of the total concentration of metals. The
phase distribution of chromium in this study is similar to the
results reported by Martin et al. (1998), which found that
chromium was mostly retained in the residual fraction. Metals
associated with the residual fraction are likely to be incorporated
in aluminosilicate minerals and therefore are unlikely to be
released to pore-water through dissociation. The non-residual
fractions (exchangeable carbonates reducibles organics)
for chromium and arsenic were high at sites P5 and P6,
respectively. Since there are only low concentrations of these
elements in the residual fractions, these elements are unlikely to
Figure 5BSpeciation of copper and zinc in wastewaters from Bestari Jaya Catchment.
August 2014
Ashraf et al.
pose a direct and significant threat to their surroundings. It
should be noted that because sediments always act as a reservoir
for metals, their potential risk of pollution to the environment
must be considered.
Copper and Zinc. The distribution patterns of copper and zinc
metals are illustrated in Figure 5B. These metals were found in all
of the five operationally-defined aquatic phases. The dominant
phase was in the residual fraction, which accounted for more than
50% of the total concentration of metals at most of the sampling
sites, notably for copper at site P8. More than 70% of the total
concentration of metals at that site was in the residual fraction,
while for zinc at site P6, more than 60% of the total concentration
of metals was in the residual fraction. There was lift variation in
the phase distribution for copper and zinc among sampling sites,
except for sites P8 and P3, in which 22% of the total zinc was in
the fraction B (carbonates). High copper content in the residual
fraction of river sediments was also found by Budimir and Marko
(1995). The high proportion of copper in this fraction is likely due
to the fact that copper is chemisorbed on or incorporated in clay
minerals (Pickering, 1986). About 60% of zinc, on average, was
found in the non-residual fraction in this study. This was higher
than the 40% reported by Usero et al. (1998).
Lead and Tin. The results of the sequential extraction
leaching method for lead and tin are illustrated in Figure 5C.
Much concern has been focused on the levels of lead in water
because of its high toxicity. In literature several sequential
extraction procedures, including the BCR protocol, have been
used to obtain information on the distribution of lead in
sediment (Ngiam and Lim, 2001; Serife et al., 2000; Zdenek,
1996). Furthermore, not only sediments but also other samples,
725
Ashraf et al.
Figure 5CSpeciation of lead and tin in wastewaters from Bestari Jaya Catchment.
such as soil (Stalikas et al., 1999) and fly ash samples (Ildiko et
al., 1996) have been studied by sequential extraction methods for
the concentrations of lead phase distribution. The lead in the
organic fraction is the most labile; hence, it may be available for
uptake by the total biota. A higher concentration of metals in
this fraction could be regarded as a pollution indicator (Forstner
and Whittmann, 1979). A considerable proportion of tin was
found in all of the five analyzed fractions. The adsorption of
metals is directly related to changes in water ionic strength that
probably affect sorptiondesorption processes (Tessier et al.,
1979), and it is known that the carbonates in water contain
significant metal concentrations, which are sensitive to changes
in pH (Thomas et al., 1994).
Moreover, the distributions of tin also differed significantly
between sampling sites. About 80% of tin was in the non-
residual fractions (exchangeable carbonates reducible
organic) at site P1, while almost 70% of the total tin was found in
the organic fraction at site P7. Evidently the pollution of tin was
mainly from the ex-tin mining catchment bound with organics,
since the sites (P4, P5, P6 and P7) with higher concentrations of
tin are close to the rivers and all of them are at the flow
directions of River Ayer Hitam which ultimately joins with River
Selangor. The distribution pattern of lead may be explained by
the fact that 70% of the lead was bound to organic matter and
sulphides at site P2, whereas approximately 80% of the lead was
bound to the non-residual fraction and 66% was found in the
oxidizable fraction at site P4. The acid-soluble proportion was
small but the sum concentration of the non-residual fractions
was significant. The metals in this fraction may be released into
the environment if conditions become more oxidizing. The
planar distribution of the metals indicated high pollution levels
(especially of tin and lead) at sites P2, P4, and P7. The non-
residual fractions of tin and lead in the water were found to be
high at P4 and P8 (Figure 5A5C). The results of this study
verified the assumption that the sampling sites of P4 and P8 are
at risk of being polluted heavily.
Conclusion
The newly developed sequential extraction leaching method
for the particulate phase of water has been successfully applied
to the analysis of the metal distributions in the mining waste
waters of a former tin-mining catchment in Bestari Jaya,
Peninsular Malaysia. The results obtained provide the following
information:
(1) Arsenic and chromium were found mostly in the residual
fraction in the studied region. The other elements were
726
found in all of the fractions, in different proportions. A
significant proportion of the total concentration was also in
the residual fraction. The dominant proportion was found in
the non-residual fractions for tin to lead, and the sum
concentration of the non-residual fractions was significant.
(2) Overall, the planar distribution of metals indicated that
study sites P4 and P8 were more severely polluted than
other sampling sites by heavy metals, especially by tin and
lead. Interventions should be made to reduce anthropogenic
discharges in this region.
Conflict of Interest
The authors certify that there is no conflict of interest
between any financial organization and the authors regarding
the material discussed in the paper.
Acknowledgments
The authors would like to express their thanks to the
Department of Irrigation and Drainage and the Department of
Environment, Malaysia for their co-operation in performing this
study. The authors also express gratitude to the University of
Malaya for supporting this study through research grants BK006-
2013, RG257-13AFR, and FP038-2013B. Finally, the authors are
grateful to the reviewers for their valuable suggestions, which led
to a substantial improvement of the article.
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