Heavy Metal Concentrations in
Sediments and Fishes from Lake Chini, Pahang, Malaysia
ABSTRACT
A study was
conducted to determine water quality and cadmium, copper, lead and zinc
concentrations in sediments and 15 fish species from Lake Chini, Pahang.
Physical parameters measured were water temperature, dissolved oxygen concentration, pH
and conductivity. Sequential sediment extraction was conducted to extract
metals from sediment, which involves three different of non-residual fractions.
Fish tissues were extracted using wet digestion method. Metals concentration in
sediment and fish were measured using atomic absorption spectrophotometer AAS
4100 Perkin Elmer. According to Malaysian National Interim Water Quality
Standards (INWQS), Lake Chini was classified between moderate to good quality.
Lake Chini was found to have low metal concentrations in sediments and fish,
which indicates no significant anthropogenic metals input to the lake. One-way
ANOVA test indicated that all metal concentrations were significantly different
(p<0.05) between fish species, but not between feeding behavior. Heavy metal
concentrations in fish tissues were found lower than the maximum allowable
limit suggested by the Malaysian Food Act, which ascertain that the fish is
safe to be eaten.
INTRODUCTION
Malaysia as a developing country is
facing with various types of pollutions risk. Heavy metals are amongst main pollutants that cause
serious adverse effects to aquatic pollution. These elements are discharge
through numerous anthropogenic sources and collective into receiving systems
such as sediment, soil and water. Various studies have concerns on metal
dispersion into these receiving systems (Kim et
al., 2002;
Lee et
al., 2001).
Increase of industrialization and agriculture could contribute their elevation
level in aquatic system (Whalberg
et al., 2001).
Some metals are essential to biotic but could be very harmful when present at
excessive concentration. Heavy metals are non-degradable and very harmful to
plants, aquatic organisms and human health at certain levels of exposure (Mustafa
and Nilgun, 2006).
Pollutants in the aquatic ecosystems
will precipitate on the sediment surface and form as deposited pollutants.
Sediments naturally consist of a complex mixture of organic and inorganic
components like clays, silicates, carbonate, sulphide, minerals and bacteria.
Sediment is well known as an important sink and a source for metal contaminants
(Li and
Thornton, 2001).
Pollutants like heavy metals are spread in sediment components and react
through ion exchange, absorption and precipitation (Yuan et
al., 2004).
There are three major mechanisms in heavy metals intake by sediments, which are
physico-chemical absorption from water, biological
intakes and accumulation of metals that are enriched with particles (Hart, 1982).
Fish occupies the highest tropic level
in aquatic system (APHA, 1981). Besides that, it
has high economical values, thus fish is suitable for water quality symbol and
easy to be interpreted by public. Fish can response to environmental changes
that can be used for pollution indicator study. Fish is a good bio-indicator
because it is easy to be obtained in large quantity, potential to accumulate
metals, long lifespan, optimum size for analysis and easy to be sampled (Batvari et
al., 2007).
Heavy metal intakes by fish in polluted aquatic environment are different
depends on ecological requirements, metabolisms and other factors such as
salinity, water pollution level, food and sediment. Fish accumulates metals in
its tissues through absorption and human can be exposed to metals via food web.
This will cause acute and chronic effect to human (Dogan and
Yilmaz, 2007;
Fidan et
al., 2007).
The use of fish as bioindicator can determine the actual situation of pollution
level before and during monitoring.
In Malaysia, there are some studies on
heavy metals in lakes and rivers such as Bera Lake, Lake Chini, Kenyir Lake and
Rompin River were conducted (Shuhaimi-Othman
et al., 2007;
Mushrifah
and Ahmad, 2005;
Ebrahimpour
and Mushrifah, 2008,
2009). Lake Chini is one
of the tourism attraction destinations that have wide swamp areas and can be
considered as pristine. This wet land can react to control water quality and
quantity, maintain ecological system and also as a habitat for various species
of flora and fauna. Fish from Lake Chini are widely caught by local aborigine
for their daily diet or to be sold. Thus, study on metals concentration in
sediment and fishes is very crucial to assess the current threats to human
health from heavy metal pollution. This study was conducted to establish the
concentrations of copper, cadmium, lead and zinc in sediments and fishes from
Lake Chini.
MATERIALS AND METHODS
Study area: Lake Chini is the
second largest Malaysia’s natural lake after Bera Lake. The lake is located at
South East of Pahang Darul Makmur. Lake Chini has 12 open water areas that are
known as ‘sea’ by the aborigines. The areas are Laut Gumum, Laut Pulau Balai,
Laut Cenahan, Laut Tanjung Jerangking, Laut Genting Teratai, Laut Mempitih,
Laut Kenawar, Laut Serodong, Laut Melai, Laut Batu Busuk, Laut Labuh and Laut
Jemberau (Shuhaimi-Othman
et al., 2007).
Chini River is the only river that link Lake Chini with Pahang River (Fig. 1).
In general, the lake is considered as
pristine and free from metal pollutions even though it has encountered with
water overflow and sedimentation which caused by the construction of small
barrage at Chini River. Lake Chini is important in tourism industry and fishing
activities and generates good incomes to the state government. A number of
twelve random sampling sites were chosen within the lake to collect sediment
samples, whereas fish were caught at various sites within the lake. The in
situ measurement was undertaken for selected water quality parameters
namely dissolved oxygen, pH, water temperature and
conductivity using YSI meter model 85.
Fish and sediment sampling: The study was
undertaken in December 2007. Fish were randomly caught using gill net and cast
net. A total of fifteen fish species were randomly caught, whereas twelve
sediment samples were systematically collected using a soil grab. The fish’s
physical parameters such as weight and total length were measured prior to the
preservation. The fish samples were kept frozen prior to analysis. Water
quality measurements were carried out at five stations to determine existing
water quality of the study area. The Hydrolab YSI model 85 was used to measure
Dissolved Oxygen (DO), pH, temperature (°C) and Total Dissolved Solid (TDS) and
conductivity (μS cm-1).
Extraction and determination of metals
in fish and sediment:
Fish samples were washed with distilled water and scale was removed. Only
tissues without bone were selected for extraction. In order to get boneless
tissues,only ventro-lateral tissues were taken for further analysis.
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Fig. 1:
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(a)
Malaysian Peninsular and (b) Lake Chini and feeder rivers
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About 5 g of dry tissues samples were
used for extraction. The wet digestion method based on Agemian et
al. (1980)
was used to extract fish tissues. The dry tissue samples were extracted with
concentrates nitric acid (HNO3) followed by perchlorid acid (HCLO4)
and digestion was done on the hot sand bath. The sample mixtures (yellowish
colour mixture) were then filtered through 0.45 μm pore size and the filtrates
were then analyzed using the atomic absorption spectrophotometer AAS model
Perkin Elmer 4100B for metal detection.
Sediment samples were dried prior to
extraction. Sediment samples (<63 μm) were extracted according to Badri and
Aston (1983)
and Tessier et
al. (1979)
with some modifications. The sequential extraction was performed by means the three
steps in the non-resistant fraction. The three fractions that focus in this
study are exchangeable (EFLE), Acid-Reduction (AR) and Organic Oxidation (OO).
Ammonium acetate (pH 7) was used to extract metals from EFLE fraction, 0.25 M
hydroxylamine (pH 2) was used in AR fraction and ammonium acetate (pH 3.5) and hydrogen peroxide (30%) were used in OO fraction.
Determination of cadmium, copper, lead
and zinc in fish and sediment were performed using flame atomic absorption
spectrophotometer Perkin Elmer Analyst 800 model. For quality control,
procedural blanks and triplicates of the samples were analyzed. Validity of
extraction methodology for fish was checked using Standard Reference Material
(SRM). TORT-2 (Lobster Hepatopancreas marine) (National Research Council,
Canada). All data are measured in μg g-1 dry wt.
RESULTS
Water quality: Table 1 shows mean results
of the water quality parameters that been determined in situ at the
study sites. Data shown are an average of three measurements that taken at each
of twelve sampling sites. Average Lake Chini water temperature was 29.3±0.87°C
with the range of 27.6 to 30.9°C. The pH level of this lake was slightly acidic
(5.1 to 6.4). The dissolved oxygen concentration was varied and differed
significantly between stations (3.5 to 6.0 mg L-1). Mean water
electric conductivity was 31.6±9.44 μS cm-1. Data obtained indicates
that dissolved oxygen and pH value were varied between
sites. One-way ANOVA test (post-hoc test) demonstrates that both parameters
were significantly different between each sampling sites. However, an opposite
result was obtained for water temperature and conductivity (p>0.05). As
regards to Malaysian Interime Water Quality Standards (INWQS), the lake can be
classified between classes I to III which is still suitable for water contact
recreational activities.
Table 1:
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Mean
value of selected water quality parameters in Lake Chini
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Table 2:
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Validation
of extraction and analysis with standard reference materials (TORT-2)
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Table 3:
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Concentrations
of anthropogenic metals in sediment from twelve sampling stations (mg kg-1
dry wt.)
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Standard reference materials: Table 2 shows the measured
values for TORT-2 standards reference materials. The result from the analysis
shows a strong agreement with the certified reference values provided by the
NRC of Canada. Only lead exhibits low recovery which is below 80% of total metal
concentrations.
Anthropogenic metals in sediment: The total metal
concentrations in non-resistant fraction frequently used to indicates the level
of pollution in aquatic systems. Although, various name and chemical were used
to extract metals from non-resistant fraction, the aim is similar that is to
estimate metals load in aquatic systems. Concentration of anthropogenic metals
in sediment is the total concentration of heavy metals in three non-resistant
fractions, which includes easily and free leachable and exchangeable fraction,
acid reduction and organic oxidation fraction (Table 3). Zinc was detected
at highest concentrations in every sample as compared to other metals. Cadmium
was the most mobile metals which found highest in EFLE fraction followed by Zn
and Cu, respectively. Similar rank of metals concentrations was recorded in
acid reduction fraction (Fig. 2). The organic
oxidation fraction contains highest Pb (almost 100%) followed by Cu, Zn and Cd.
This fraction bound metals harder than other fractions and reduces metal
mobility in aquatic systems. Therefore, Pb was found to be the least mobile and
in contrast Cd was the most mobile metal.
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Fig. 2:
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Proportion
of heavy metals in sediments non-residual fraction (anthropogenic)
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Table 4:
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Mean
concentrations of heavy metals in sediment from 12 stations (μg g-1
dry wt.)
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Table 5:
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Sediment
criteria according to EPA region Va
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aConcentration in mg kg-1 dry wt.
|
Metal concentrations in sediment
exhibit significant variation between sampling stations. Station 9 contained
the highest levels of Zn and Cu (96.85±1.91 mg kg-1 and 9.65±0.52 mg
kg-1, respectively). Pb and Cd were detected highest in sediments
from station 11 (30.64±3.94 and 2.22±0.25 mg kg-1, respectively).
Although, metals on sediments vary
between sampling stations, the mean concentrations of anthropogenic metals
(combination of three fractions) obtained from 12 stations (Table 4) were found to be
low even lower than EPA guideline concentrations in unpolluted area (Table 5). None of studied
metals found exceed the maximum recommended concentration in sediment from
unpolluted sediments. This indicates that Lake Chini is considered as
unpolluted from those metals.
Metal concentrations in fish muscles: Study on metals
concentration in fish muscles of the means to estimate amount of metals
transported into human body through feeding. Table 6 shows the physical
characteristics of collected fish. The physical parameters were used to
estimate fish age. The fish age provides an ideas on how long the fish are
exposed to studied metals.
Table 6:
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Physical
data and age estimation for collected fishes
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*Source: Mohsin and Ambak (1991)
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Table 7:
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Mean metal concentrations in
various fish species (mg kg-1)
|
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As regards to (Mohsin and
Ambak, 1991)
classification, this study found that most of the fish samples were considered
as an adult. The mean metal concentrations (μg g-1 wet wt.) in 15
fish species are shown in Table 7. The average
concentrations of Cu, Zn, Pb and Cd are 0.46±0.023, 4.46±0.051 and 0.45±0.024
and 0.28±0.020 μg g-1, respectively. Zinc mean concentrations was
the highest as compared to other metals and ranged from 1.69-6.76 μg g-1.
Copper was detected highest in Channa micropeltes (snake head) followed
by Zn. Most of fishes have Zn concentrations above 2 μg g-1 except Helostoma
temmincki (gouramy). Cylocheiiichtys apogon and Hampala
macrolepidota accumulated the highest level of Zn concentrations
(6.76±0.055 and 6.75±0.163 μg g-1, respectively). Metals
accumulation in fish was found in the order of Zn>Cu>Pb>Cd. Not like
in sediments, metals concentration in fish tissues were detected at small
variations.
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Fig. 3:
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Heavy metals in fishes of different feeding behavior
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Data for metals in fish were tested for
normality using Kolmogorov-Smirnov test and result indicates that Cu and Zn
concentrations were following normal distribution. One-way ANOVA test indicated
significant variation of Cu and Zn across various fish species (p<0.05).
Post hoc Turkey (One-way ANOVA) test pointed that the concentration of Cu in Chana
micropeltes was significantly different compared to other fishes, whereas
Zn in Hampala macrolepidota, Cylocheinichtys apogon and
Helostoma temmincki were dissimilar from the others. Average concentrations
of Cd in fish tissues ranged from 0.15-0.47 μg g-1. Various fishes
such as Ompok bimaculatus, Puntius bulu, Osteochilus
melanopleura, Mystus nigriceps and Barbichthys laevis have Cd
less than 0.2 μg g-1. Concentrations of Pb in all species were also
low and not more than 0.70 μg g-1 even below the detection limit in Cylocheinichtys
apogon and Chana micropeltes. However, multiple comparison test
using Post hoc Turkey test indicates that Osteochilus hasseltii, Notopterus
notopterus, Puntius bulu and Helostoma temmincki accumulated
significantly higher.
Fishes collected were grouped according
to their feeding behavior and average metal concentration in the muscle are
presented in Fig. 3. Each metal found
approximately at similar concentration and not significantly differ between
feeding groups (p>0.05, α = 0.05).
DISCUSSION
Water quality: The average Lake
Chini’s water temperature recorded in this study was slightly higher compared
to other researches (Shuhaimi-Othman
et al., 2007).
This could due to long sampling duration that was conducted continuously from
10 am to 4 pm. Lake Chini is a shallow natural lake and receives high sunlight
exposure. However, water temperature recorded was still normal for lake water
body in tropical countries. Shuhaimi-othman et al. (2007) from their
study reported that the mean temperature of Lake Chini was ranged between 27.3
to 31.4°C.
This study found that Lake Chini water
body was slightly acidic with the mean value was 5.8±0.30 and ranges from 4 to
6. Shuhaimi-Othman
et al. (2007)
found that the average pH level was 6.49±0.15. The presence of water gate
(barrage) at Sungai Chini has increase Lake Chini water level and inundated
various riparian plants and other aquatic plants such as water lily and lotus.
Thus, dead plants were decayed and created eutrophic condition and drop water
alkalinity. However, the value is still suitable for freshwater ecosystem (Kutty et
al., 2005).
Fish will die if the pH value is lower than 4 or more than 10. According to
Malaysian Interims Water Quality Standards (INWQS), the measured pH value
classify Lake Chini in class III, which is moderate condition.
Lake Chini has low mean dissolved oxygen concentrations (4.7±0.77 mg L-1).
In recent years, various major developments such as oil palm plantation and
illegal logging activities are happening nearby the lake. Soil erosions and
forest clearance expected to cause sedimentation and reduce oxygen
concentration in water. High decomposition of organic matters in the lake could enhance dissolved oxygen depletion in water. The water gate at
Chini River reduces dissolved oxygen concentrations in the lake by reducing
water flow. As regards to Malaysian National Water Quality Standard (NWQS), the
dissolved oxygen concentrations classify Lake Chini in
class III. Water conductivity value recorded was within the natural range of
concentration. According to Chapman
(1996),
conductivity level for most of the freshwater areas are ranged between 10 to
1000 μS cm-1. The conductivity recorded classified Lake Chini in
class I. Result from few water quality analysis demonstrates that Lake Chini is
characterized by good to moderate quality. A temporal water quality monitoring
conducted by Shuhaimi-Othman
et al. (2007) demonstrates
that Lake Chini water quality was varied between seasons and locations.
Heavy metals in sediment: The anthropogenic
metal concentrations obtained in this study were compared with other previous
studies such as Juru River and Klang River which are declared by Malaysian
Department of Environment (DOE) as polluted rivers. Direct comparison is not
very suitable since some researches may differ in their methods. However, rough
comparison is appropriate in order to estimate metal concentrations in
sediments. Result of the study demonstrates that Lake Chini has lower Pb and Cu
concentrations compared to the Juru River and Klang River, however higher Zn
and Cd concentrations than Juru River. Although, Lake Chini has higher Zn and
Cd concentrations, but the values still within the range of other unpolluted
river such as Sg. Kelantan (Ahmad et
al., 2009).
Shuhaimi-Othman
et al. (2007)
reported that Lake Chini is potentially to receive some effluents from the
nearby mining project through the seepage process.
Although Lake Chini has higher
elevation for some metals, the concentrations still below the pollution
benchmark as published by EPA (Table 5). This study reveals
that although Lake Chini is located far from developed area and free from
anthropogenic sources, some metals namely Zn and Cd were found high and
potential to contaminate the lake in the future. Improper agriculture and
illegal mining activities and land clearance could lead to contamination in
future.
Factors that affect the concentrations
of heavy metals in fish tissues: The accumulation of metals by the fish
depends on the location, feeding behaviour, trophic level, age, size, duration
of exposure to metals and homeostatic regulation activities of fish (Sankar et
al., 2006).
Kargin
(1996)
has listed multiple factors that influence metals accumulation in fish such as
season, physical and chemical properties of water. Knowledge of metals
concentration in fish is important to management for various purposes such as
risk of taking fish as part of diet and metals pollution control strategies.
Most of fish are at top in aquatic food chain and have potential to accumulate
high metals content even in mild polluted conditions. Therefore, metals
concentration in fish could be used as an index to estimate level of pollution
especially in aquatic bodies (Karadede-Akin
and Unlu, 2007)
even in the lake system. Although, fish muscle was reported have lowest metal
concentrations compare to bone, gill and liver, this study focus metals in fish
muscle since, people eat fish muscle and not others.
Fishes collected from Lake Chini are
comprises of three different types of feeding behaviors; herbivor, omnivor and
carnivor. Chana micropeltes, Hampala macrolepidota, Notopterus
notopterus and Ompok bimaculatus are carnivores (consume small
fishes); Osteochilus melanopleura and Thynnichthys thynnoides are
herbivores (consume plants) while the Puntius schwanenfeldii,
Cylocheinichtys apogon, Osteochilus hasseltii, Puntius bulu,
Labiobarbus festiva, Chela oxygastroides, Mystus nigriceps,
Barbichthys laevis and Helostoma temmincki are omnivores (Mohsin and
Ambak, 1991).
Feeding behaviour is one of the decisive factors of heavy metals accumulation
in fish. Although, many studies showed carnivores accumulate higher metal
concentrations (Mohsin and
Ambak, 1991;
Amundsen et
al., 1997)
result of this study demonstrates that metal concentrations in three different
feeding behavior are not significantly differ (Fig. 3). Low metal
concentrations in lake ecosystem could limits the absorption these metals in
the organisms.
Age factor or maturity of fish may
influence the accumulation of heavy metals (Mohsin and
Ambak, 1991).
Growth rate is important to stabilize the accumulation of metals. Fish can accumulates
high level of pollutants if it has a constant growth and live in polluted
ecosystem. This study indicates that mature fish accumulated higher metals
compared to juvenile and premature fish. Labiobarbus festiva, Chela
oxygastroides and Osteochilus hasseltii (mature omnivour fish)
accumulated higher concentrations of Cd rather than Osteochilus melanopleura
and Ompok bimaculatus (premature). Although, comparison between same
species is more appropriate, however, the comparison made was based on similar
feeding behaviour. This study was unable to obtain sufficient number of fish to
make comparison between age for the same species.
Comparison of various studies on metal
concentrations in fish muscle is shown in Table 8. This study found Cu
and Zn concentrations were almost as low as from unpolluted lake likes Eber
(Findan et al., 2007). However, Cd and Pb concentrations were higher
than fishes from Eber Lake and Taihu Lake (Chi et
al., 2007).
Both metals were probably contributed to the lake through various sources, such
as agriculture activities likes oil palm and rubber plantations nearby lake. A
large scale of oil palm plantation was developed nearby the lake and the use of
chemical fertilization could introduce Cd to the lake.
Table 8:
|
Comparison of metals in fish from
other sampling locations
|
|
|
Excessive fertilizer may be transported
to the lake through surface run off. Lake Chini has several main feeder streams
that could transport these metals into the lake. The inflow water from Pahang
River to Lake Chini during rainy season or monsoon season also could bring
pollutants including metals into the lake. Nonetheless, the concentrations of
these metals were still below the permissible limit suggested by the Malaysian
Food Act (1983).
This study indicates that although
still below hazardous level, non-essential metals namely, Pb and Cd and
essential metal namely Zn were quite high and continues input could risk the
lake ecosystem. Continual accumulation in fish muscle could transports metals
to human through diet. Local aborigines surround the lake catch fish for their
daily diet.
CONCLUSION
According to Malaysian Interim Water
Quality Standards, Lake Chini can be classified between classes I to III which
is suitable for aquatic organisms growth. Heavy metals concentrations in
sediment’s non-residual fraction ascertain that Lake Chini is free from metal
contaminants, although Pb, Cd and Zn were exhibits slightly high concentration.
Fishes are safe to be taken for daily diet since all metals detected in fishes
were below the permissible limit suggested by the Malaysian
Food Act (1983).
ACKNOWLEDGMENT
The research was supported by a grant
(04-01-02-SF0428) Universiti Kebangsaan Malaysia.
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