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The Malaysian Journal of Analytical Sciences Vol 11 No 2 (2007): 336-339

THE GEOCHEMICAL PROFILE OF Mn, Co, Cu AND Fe IN KERTEH MANGROVE FOREST, TERENGGANU

*1Kamaruzzaman, B.Y., 2Antotina, A., 1Airiza, Z., 1Syalindran, S. and 1Ong M.C.

Institute of Oceanography and Maritime Studies, International Islamic University Malaysia, Jalan Istana, 25200 Kuantan, Pahang.

2 Institute of Oceanography, University Malaysia Terengganu, 21030, Kuala Terengganu, Terengganu, Malaysia. *Corresponding author: [email protected] 1

Keywords - Manganese, Cobalt, Copper, Iron, ICP-MS, mangrove forest Abstract The geochemical profile of Kerteh mangrove sediments was analyzed for the vertical and horizontal distribution. The 100 cm core sediment sample and 15 surface sediments samples were taken from the field. The geochemical elements of Mn, Co, Cu and Fe of the sediments were analyzed. Geochemical proxy of Mn, Co, Cu and Fe were analyzed by using Inductively Coupled Plasma ­ Mass Spectrometry (ICP­MS). The mean concentrations of Mn, Co, Cu and Fe for the vertical distribution were 210.18µg/g, 15.55µg/g, 43.65µg/g and 1.88µg/g respectively. On the other hand, the mean concentrations of the geochemical elements for horizontal distributions were 230.50µg/g for Mn, 17.57µg/g for Co, 43.381µg/g for Cu and 2.93µg/g for Fe. Enrichment factor and normalization was used to point out the level of pollution. The EF and the normalization indicated that all the geochemical elements were from the natural sources.

Introduction The mangrove systems in tropical and subtropical countries have led to a strong risk of heavy metal contamination in the coastal environment with the high degree of industrialization and urbanization. Mangrove sediment is being anaerobic, reduced and favors the retention and accumulation of heavy metals [1]. A high heavy metal concentration in sediment from the geological material is rather than contamination [2]. Clay minerals and organic matter build aggregates and flocks, which effectively concentrate trace metal and sink down to form a `fluffy layer' [3]. The cycling of heavy metals, because of their toxicity, bio-accumulation capacity and persistence, is a serious question recently addressed by many studies on mangrove environments [4, 5, 6, 7, 8, 9 and 10]. Materials and Methods Sampling site Sampling was done on May 2005 at Kerteh mangrove forest. The research area located at 04o 31' 25" N; 103o 27' 03" E for the horizontal distribution and 04o 31' 23" N; 103o 26' 48" E for vertical distribution. The vertical distribution samples were taken by using D-section corer while the horizontal distribution samples were taken by using the scoop. A core (1 to 2 m deep) was collected at low tide and in shore faces sediments . Analytical method for heavy metal Sediments were dried and ground with an agate pestle and mortar. The sediment sample were digested and the analyses for heavy metal concentration following the published methodologies with some modifications [11,12].

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Kamaruzzaman et al.: THE GEOCHEMICAL PROFILE OF Mn, Co, Cu AND Fe The samples sediments were digested with concentrated of HF, HNO3, HCl, boric aids and EDTA. The digested samples were meshed up to 10mL with Mili-Q water and analyzed by ICP-OES PESCIEX ELLAN 6000 model. The accuracy was examined by analyzing duplicate a Canadian Certified Reference Materials Project standard. Result and Discussion The vertical distribution of heavy metals (Mn, Co, Cu and Fe) concentration for Kerteh mangrove forest is shown in Figure 1. The heavy metals concentrations are variable from the surface layer to the 100cm depth. Mn concentration varies from 160.12 µg/g dry weights to 317.08 µg/g dry weights with average concentration 210.18 µg/g dry weights. The concentrations are still below the mean crustal materials (950 µg.g­1 dry weights). The core sediment samples in the depth 5-10cm indicate the highest concentration whereas the 85-90cm depth indicates the lowest Mn concentration. From the graph, the Mn concentration was decreasing from the surface sediment to the bottom sediments. The concentrations of vertical distribution of Co range from 4.75 µg/g dry weights to 36.18 µg/g dry weights with average 15.55µg/g dry weights. Co concentration is the highest at 15-20 cm depth and the lowest at 9095 cm depth. From the graph, Co concentration considered as decreased with the depth. The distribution of Cu concentration is constantly from surface to the bottom sediments but increased rapidly at 65 cm depth. The maximum concentration was observed at 65 cm depth with 88.22 µg/g dry weight and minimum concentration at 25 cm depth, 35.71µg/g dry weight. The mean value of Cu was 43.65 µg/g dry weights. From the graph, the distribution of Fe concentration was invariable. The highest concentration was at 30cm depth and the lowest concentration at 20 cm depth with 2.81µg/g dry weights and 1.24 µg/g dry weights respectively. The mean concentration of Fe for vertical distribution was 1.88µg/g dry weights.

400.0 300.0 200.0 100.0 0.0

05 10 -1 5 Y 20 -2 5 Y 30 -3 5 Y 40 -4 5 Y 65 -7 0 Y 80 -8 5 Y 90 -9 5 Y

40.0 30.0 20.0 10.0 0.0

Mn (ug/g)

Co (ug/g)

Y

depth (cm )

100.0 80.0 60.0 40.0 20.0 0.0

10 -1 5 Y 20 -2 5 Y 30 -3 5 Y 40 -4 5 Y 65 -7 0 Y 80 -8 5 Y 90 -9 5 05 Y

3.0 2.5 2.0 1.5 1.0 0.5 0.0

05 10 -1 5 Y 20 -2 5 Y 30 -3 5 Y 40 -4 5 Y 65 -7 0 Y 80 -8 5 Y 90 -9 5 Y Y

Cu (ug/g)

Y

depth (cm )

Fe (ug/g)

Figure 1: The concentration of Mn, Co, Cu and Fe in the bottom sediment of Kerteh mangrove forest.

Figure 2 shows the horizontal distribution of Mn, Co, Cu and Fe concentration in Kerteh mangrove forest sediment. From the graph, G3 shows the highest Mn concentration and G9 shows the lowest, 367.77 µg/g dry weights and 115.18 µg/g dry weights respectively. The mean concentration of Mn was 230.50 µg/g dry weights. For Co concentration, the maximum concentration was at Station G5, 29.46 µg/g dry weights and Station G3 was the minimum, 5.70 µg/g dry weights. The mean concentration of Co was 17.57 µg/g dry weights. As for Cu, the highest concentration was obtained at Station G7 and the lowest was obtained at Station G3, 87.21 µg/g dry weights and 27.68 µg/g dry weights respectively. The mean concentration for Cu was 43.38 µg/g dry weights. The concentration

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10 -1 5 20 -2 5 Y 30 -3 5 Y 40 -4 5 Y 65 -7 0 Y 80 -8 5 Y 90 -9 5 Y

depth (cm )

depth (cm )

Y

Y

05

The Malaysian Journal of Analytical Sciences Vol 11 No 2 (2007): 336-339 of Fe was the highest at Station G3 with 3.5% and was the lowest at Station G9 with 2.3%. The mean Fe concentration for horizontal distribution was 2.93%.

400.0 Mn (ug/g)

35.0 30.0

Co (ug/g)

G1 G2 G3 G4 G5 G6 G7 G8 G9 G 10 Station

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25.0 20.0 15.0 10.0 5.0 0.0 G1 G2 G3 G4 G5 G6 G7 G8 G9 G 10

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100.0 80.0 60.0 40.0 20.0 0.0 G1 G2 G3 G4 G5 G6 G7 G8 G9 G 10 Station

4.0 Fe (%) 3.0 2.0 1.0 0.0 G1 G2 G3 G4 G5 G6 G7 G8 G9 Station G 10

Cu (ug/g)

Figure 2: The concentration of Mn, Co, Cu and Fe in the surface sediment of Kerteh Mangrove Forest.

Heavy metals concentration showed variation with depth. There was a high variability in metal concentrations at different stations of surface sediments and core sediments within a station. If the anthropogenic input dominates the metal distribution in sediments, the lower concentrations observed in surface sediments in comparison to core sediments suggest a recent decrease of anthropogenic metal emissions for the study area [13]. Cd, Pb, Zn and Cu are anthropogenically enriched in top layers of core sediment from the Kerteh mangrove forest, but the decrease of these elements with depth in the core is not systematic. Metal concentrations are generally higher and more variable downstream from metal-producing locations and in the vicinity of industrial facilities [14]. Five contamination categories are recognized on the basis of the enrichment factor (EF). EF used to identify the chemical elements entering the area anthropogenic. From Table 1, Mn and Fe were categorized as natural-minimum enrichment. Mn and Fe exist in the area naturally. Co and Cu were categorized as moderate enrichment. Small amount of Co and Cu were entering the area anthropogenic. As for horizontal distribution, only Mn was categorized as natural-minimum enrichment and Co, Cu and Fe significantly enrichment. Large amount of Co, Cu and Fe existed in the area anthropogenic. Cu compounds from anthropogenic source are more available to plants than the ones from natural sources.

Table 1: Contamination Categories based on EF for Mn, Co, Cu and Fe in the study area.

Heavy Metal Mn Co Cu Fe

Enrichment Factor 0.93+0.24 3.16+2.78 3.83+1.77 1.43+0.25

Source of Element natural-minimum enrichment moderate enrichment moderate enrichment natural-minimum enrichment

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Kamaruzzaman et al.: THE GEOCHEMICAL PROFILE OF Mn, Co, Cu AND Fe Conclusion From the EF calculation, Mn and Fe in the study area of vertical distribution occurs naturally and not greatly caused by anthropogenic and human activities. Co and Cu has occurs moderately caused by anthropogenic. On the other hand, for horizontal distribution, Co, Cu and Fe occur significantly caused by anthropogenic and human activities. Anthropogenic sources from the fishing activities and industrial area at the upstream may be the main reasons contributing insignificant heavy metal to the river system, but can be conclude that there were no serious heavy metal contaminations in Kerteh mangrove forest. Acknowledgement This research was organized with joint funding from the Malaysia Ministry of Science Technology and Innovation under the Intensified Research for Priority Areas (IRPA). The authors wish to express their appreciation to Oceanography Laboratory and INOS and INOCEM, UIAM team for their priceless assistance and hospitality throughout the sampling period.

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