Geochemical Fractionation of Copper (Cu), Lead (Pb), and Zinc (Zn) in Sediment and their Correlations with Concentrations in Bivalve Mollusc Anadara indica from Coastal Area of Banten Province, Indonesia  

Noverita Dian Takarina1 , Dietriech G Bengen2 , Harpasis S Sanusi2 , Etty Riani2
1. Student of Doctoral Degree Program on Marine Science, Post Graduate School, Bogor Agricultural University, Indonesia
2. Faculty of Fisheries and Marine Science, Bogor Agricultural University, Bogor, Indonesia
Author    Correspondence author
International Journal of Marine Science, 2013, Vol. 3, No. 30   doi: 10.5376/ijms.2013.03.0030
Received: 07 May, 2013    Accepted: 03 Jun., 2013    Published: 07 Jun., 2013
© 2013 BioPublisher Publishing Platform
This is an open access article published under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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Takarina et al., 2013, Geochemical Fractionation of Copper (Cu), Lead (Pb), and Zinc (Zn) in Sediment and Their Correlations with Concentrations in Bivalve Mollusc Anadara indica from Coastal Area of Banten Province, Indonesia, International Journal of Marine Science, Vol.3, No.30 238-243 (doi: 10.5376/ijms.2013.03.0030)

Abstract

Surface sediments collected from four sampling stations, each from the coastal area of Tanjung Pasir, Tangerang, and coastal areas of Panimbang, Pandeglang, Banten Province have been geochemically [easily, freely, leachable or exchangeable (EFLE), acid-reducible/Fe-Mn Oxides, oxidisable-organic and resistant] analyzed using AAS Shimadzu 6300 series. Cu, Pb, and Zn content in sediment fraction were correlated with the respective metal concentrations in tissues of Anadara indica collected from the same stations as for those sediment samples. The objective of this study was to determine the concentrations of heavy metals Cu, Pb and Zn in sediments and A. indica as well as to relate the possible differences in the accumulation patterns of Cu, Pb and Zn in A. indica to those in the geochemical fractions in the surface sediment. The results revealed that heavy metal concentrations were recorded to be higher in stations closed to the industries and anthropogenic activities (Garapan rivermouth, Tanjung Pasir) compared to agricultural activities (Cibungur rivermouth, Panimbang). Significant (p < 0.01) correlations were observed between Cu in the soft tissue of A. indica with exchangeable, Fe-Mn oxides, oxidisable organic, residual fractions of Cu in the sediment, and Fe-Mn oxides, oxidisable organic, residual fraction for Pb, while significant correlations were observed between Zn in soft tissue of A. indica with Fe-Mn oxides and oxidisable organic fractions. It is suggested that the soft tissue of A. indica could be used as a useful biomonitoring agent for Cu, Pb, and Zn pollution.

Keywords
Geochemical fractionation; Heavy metals; Anadara indica; Sediment

Nowadays, detectable trace metal contamination occurs in many aquatic environments as a result of human activities. The biological impacts of that contamination are poorly understood (Cairns, 1984), especially the processes that control accessibility of metals to aquatic biota (i.e. the biological availability) (Luoma, 1983). Sediments constitute a concentrated pool of metals in aquatic environments. Thus, understanding metal bioavailability from sediments is especially important.

Lead is a naturally occuring metal found in small amounts in the earth’s crust. It can be found in all parts of our environment. Lead (Pb) may be present in hazardous concentrations in food, water, and air. Sources include paint, urban dust, folk remedies, mining, smelting and non-ferrous metal industries. Lead poisoning is the leading environmentally induced illness in children. At greatest risk are children under the age of six because they are undergoing rapid neurological and physical development.
Copper (Cu) is used in manufacturing of steel foundries, etc. Copper (Cu) exists in the final effluent as dissolved species representing as much as 80 % of the total concentration, and they are most bioavailable form. It tends to have a high affinity for the clay/silt fraction (Bubb et al.,1991) and invariably highly complex in polluted and unpolluted freshwater (Moriber, 1974).
Zinc (Zn) is among the most prevalent of metal contaminants in the environment, especially in aerobic water. A significant fraction is likely to exist as simple ionic forms such as carbonate and hydroxyl complexes, hydrated ion, and stable organic or inorganic colloids particularly hurnics (Bubb et al.,1991). Levels of Zn in coastal areas and estuaries are often much higher than oceanic concentrations (Bruland et al., 1979) in Bryan and Langston, 1992. The most available and abundant form of Zn is the free ion Zn2+. Due to its comparatively high solubility, Zn tends to exist in the dissolved forms (Bryan and Langston, 1992; Bubb et al., 1991).
Though Cu and Zn are essential nutrients, it can cause toxicity when not present in sufficient concentrations. Excess amounts of those toxic when they interact with certain biomolecules in an organism. These features, along with the fact that metals persist as inorganic forms in environmental sinks (e.g., soil & sediments) are cycled through the biotic components of an ecosystem.
In sediments, metals also partition among different types of ligands associated with the various components of the particulate material. Metals are distributed predominantly among sites on iron oxides, manganese oxides and various types of organic materials in oxidized sediments (Jenne, 1968; Jenne, 1977; Luoma and Davis, 1983; Davies-Colley et al., 1984). Table 1 shows how availability and mobility of trace metals in the environment.


Table 1 Availability and mobility of trace metals

Deposit/detritus feeding animals are exposed to metals both in solution and through ingestion of metal-enriched particulate material (Luoma, 1983). Thus knowledge of the geochemical reactions of metals in both water and sediments is critical to understanding what controls metal bioavailability. Interactions between water and sediment also are important. For example, total concentrations of most metals in sediments are orders of magnitude higher than concentrations in solution. Thus, proportionally small changes in metal exchange between water and sediments may profoundly influence total concentrations in solution, and affect that route of exposure.
Metals may bind to a wide variety of molecules in the organism. Metals can bind to biomolecules that are essential to cellular function (e.g. enzymes, structural proteins), alter their function, and cause toxicity. In some cases, metals bind to metallothioneins or phytochelatins, cysteine-rich compounds, or to other ligands that can help the organism regulate the metal within cells and detoxify the metal by preventing the binding to receptors that may result in toxicity. Metals may also be precipitated in phosphate or sulfide bodies within cells, thereby sequestering them and preventing mobility and subsequent toxicity.
Over the past decade, significant scientific advances have been made in addressing metals bioavailability in sediments in relation to their toxicity to benthic organisms e.g. molluscs. Metals such as Ag, Cd, Zn, Cu and Hg are generally bioaccumulated to much higher concentrations and vary very markedly among different species of marine bivalves. Bivalves species (mussels, oysters, scallops), especially, have been used as biological indicatororganisms to monitor marine environmental pollution by heavy metals and chemicals due to their own properties of inhabitation. Heavy metal concentrations in soft bodies have been discussed in all of the investigations concerned (Moloukhia and Sleem, 2011). Among the many bivalve species mentioned, scallops can accumulate metals to very high concentrations. Belcheva et al (2006) found that Cd concentrations in the digestive glands of the Japanese scallop Patinopecten yessoensis from the Sea of Japan were as high as 150 μg/g dry weights, and increased significantly with age. According to Gundacker (1999), zebra mussels also can accumulate high amounts of potentially toxic heavy metals. The objective of this study was to investigate the relationship between heavy metal concentrations in the different geochemical speciation of sediment and metal concentrations in soft tissues of bivalve mollusc A. indica.
2 Result and Discussion
Bioavailability of contaminant in the environment is a function of processes working on them, either increase or decrease their mobility, therefore it will be readily available (more available), less available for organism accumulate in the body.
The total concentrations of Cd, Cu, Pb and Zn and its percent contribution in all the geochemical fractions (EFLE/F1, acid-reducible/F2, oxidisable-organic/F3, resistant/F4) of sediment are presented in Figure 1 and Figure 2, respectively.


Figure 1 Heavy metals content(µg/g) Cu (a), Pb (b), dan Zn (c) in sediment of Tanjung Pasir (TJP) and Panimbang (PNB) estuary


Figure 2 Percentage fractionation (F1, F2, F3 and F4) of heavy metals(%) Cu (a),Pb (b), Zn (c), in sediment of Tanjung Pasir (TJP) and Panimbang (PNB) estuary

From Figure 1, it can bee seen that total concentration of heavy metals Cu, Pb, and Zn in Tanjung Pasir (TJP) are higher than in Panimbang (PNB) estuary. This is because there are many industries, housings, and commercial activities in Tanjung Pasir. Beside that, coastal area of Tanjung pasir is located close to Jakarta Bay which has level pollution medium-heavy category. According to Bappedalda (2005), seawater carried by surface current from Jakarta Bay flushed into Tanjung Pasir. On the contrary, Panimbang coastal area has lower concentration of heavy metals due to low input of industrial activities and housings.
 
Figure 2 showed that percent of non resistant/non residual fraction (F1 + F2 + F3) of heavy metals Cu, Pb, and Zn in Tanjung Pasir coastal area is higher than in Panimbang. This suggests that in Tanjung Pasir surroundings, anthropogenic activities is more dominant compared to Panimbang. Moreover, Figure 3 showed that heavy metals content/bioaccumulation of Cu, Pb, and Zn in soft tissues of A. indica collected from Tanjung Pasir are higher in small individual compared to large or medium individual. This is because Cu and Zn are essential elements that are needed for metabolism/ growth. According to Prartono (1985), there was no correlation between size of individual and content of heavy metals. In Panimbang coastal areas, heavy metals content in A. indica showed no big difference among sizes of individual.


Figure 3 Heavy metals content/bioaccumulation of Cu (a), Pb (b), Zn (c) in A. indica size large, medium, and small collected from Tanjung Pasir (TJP) and Panimbang (PNB) estuary

From Table 2, it can be seen that Cu was significantly correlated (p<0.01; r: 0.538-0.624) with all fraction, while Pb correlated (p<0.01; r: 0.554-0.662) with Fe-Mn oxides, organic, residual fraction, and Zn correlated (p<0.01; r: 0.494-0.508) only with Fe-Mn oxides and organic fraction.


Table 2 Correlation between geochemical fractionation (F1, F2, F3 and F4) and bioaccumulation in A. indica collected from Tanjung Pasir and Panimbang Estuaries
 
Giordano et al (1991) found that Pb concentration in bivalve M. galloprovincialis was significantly correlated with Pb level in sediments (p < 0.01). Yap et al (2002b) also reported that Pb concentration in the soft tissues of P. viridis was significantly correlated with the resistant and total fractions of Pb in sediments. Soto-Jimenev et al (2001) and Shulkin et al (2003) also found that Pb in oyster Crassostrea iridescens and C. gigas, respectively, were related to the metal concentrations in the associated sediments. Based on his study in Hong Kong waters, Phillips (1985) had also confirmed the capacity of the soft tissue of mollusc to monitor Pb in coastal environment.
3 Conclusions
1. There werestrong correlation between all fraction with heavy metal Cu in A. indica.
2. Pb in A. indica was significantly correlated with Fe-Mn oxides, organic, residual fraction.
3. Zn in A. indica was significantly correlated only with Fe-Mn oxides and organic fraction.
4. A. indica could be used as a useful biomonitoring agent for Cu, Pb, and Zn pollution.
4 Data and Methods
4.1 Sampling time and location
Coastal areas of Tanjung Pasir Tangerang Subdistrict, Banten Province located at 5°57′77″~6°02′42″ Latitude and 106°37′33″~107°42′54″ Longitude (Figure 4). Tanjung Pasir is anarea where there are many industries, housings, and commercial activities found. Coastal areas ofPanimbang, Pandeglang, Banten Province, geographically located at 6°21′~7°10′ Latitude and 104°48′~106°11′ Longitude, administratively bordered bySerang District in the North and Hindia Ocean in the South, and Sunda Strait in the West. Here many agricultural activities, husbandry, and housings are found. Surounding this place, there are many rivermouths where many rivers flowtheirwater to Jakarta Bay carrying industrial,agricultural, domestic wastes/sewagecontaining pesticides, PAH, heavy metals, etc. (Arifin, 2005).


Figure 4 Sampling stations of sediments and bivalve mollusc (Anadara indica) at Tanjung Pasir (above-right) and Panimbang (below-right)
4.2 Field sampling
Sediment samples were collected using a 3.5 L Ekman grab sampler. The top 2–3 cm of the sediment layer was collected using a plastic spatula, and subsequently placed in the acid-washed plastic-bags and stored at -4℃ during transportation to the laboratory.
4.3 Heavy metals analysis in sediment
Sequential extraction procedures are available for characterizing sediments (Tessier et al., 1979), but it is well established that such approaches do not remove metals selectively from specific components of the sediments (Kheboian and Bauer, 1987; Rendell et al., 1980; Guy et al., 1980; Luoma and Jenne, 1976). Geochemical fractions of Cd, Cu, Pb, and Zn in sediments were obtained by using the modified Sequential Extraction Technique. The four fractions considered, the extraction solutions, and the conditions employed were:
1) Easily, freely, leachable or exchangeable (EFLE) (Fraction 1): About 10 g of sample was continuously shaken for 3 h with 50 ml 1.0 M ammonium acetate (NH4CH3COO), pH 7.0 at room temperature.
2) Acid-reducible (Fraction 2): The residue from (1) was continuously shaken for 3 h with 50 ml 0.25 M hydroxyl-ammoniumchloride (NH2OH.HCl) acidified to pH 2 with HCl, at room temperature.

3) Oxidisable-organic (Fraction 3): The residue from (2) was first oxidized with 15 mL hydrogen peroxide (30%) in a water bath at 80℃. After cooling, the metal released from the organic complexes was continuously shaken for 3 h with 50 mL of 1.0 M ammonium acetate (NH4CH3COO) acidified to pH 2.0 with HCl, at room temperature.
4). Resistant (Fraction 4): The residue from (3) was digested in a 10 mL combination (ratio of 3:1 of concentrated nitric acid and perchloric acid).
4.4 Heavy metals analysis in Anadara indica
About 1 g of the soft tissues of A. indica were thoroughly washed with Milli-Q water, and extracted for further processing. Soft tissue was macerated into 1-2 cm clumps, dried at 70℃~80℃, grinded and stored until chemical analysis. Copper (Cu), Lead (Pb), and Zinc (Zn) were analyzed by digesting the homogenized samples in a mixture of nitric and perchloric acids. After being centrifuged the supernatant was filtered through syringe filter paper (45 µm). After filtration, heavy metals were determined for Cu, Pb and Zn using an air-acetylene flame atomic absorption spectrophotometer (AAS) Shimadzu Model 6300 series.
4.5 Statistical Analyze
Statistical analyses were performed using Statistical Package for Social Science (SPSS) version 20. The Spearman’s rank correlation coefficient was applied in order to determine the strength and significance of the relationships between the concentrations of Cu, Pb, and Zn in A. indica with the geochemical fractions of respective metals in the sediment.
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