ISSN: 1693-3044

Banda Aceh, 22-23 December 2010

Green Engineering: Challenge for Chemical Engineers in the Future

PROCEEDINGS

Chemical Engineering Department Engineering Faculty Syiah Kuala University

National Conference on Chemical Engineering Science and Applications (ChESA) 2010

Total Mercury Concentrations in Organisms from Kr. Meurebo River, Meulaboh, Indonesia
Suhendrayatna1*, Kosei Haraguchi2, Tsunenori Nakajima2, Akira Ohki2
1

Department of Chemical Engineering, Faculty of Engineering, Syiah Kuala University Jalan Tgk. Abdurrauf No. 7, Darussalam, Banda Aceh, Indonesia, 23111 *Corresponding author: suhendrayatna@unsyiah.ac.id

Department of Chemistry, Biotechnology, and Chemical Engineering, Graduate School of Science and Engineering, Kagoshima University, Kagoshima, 890-0065, Japan

ABSTRACT With the purpose of knowing distribution and relative concentrations of mercury in the main tissues of freshwater organisms, levels of Mercury in head, eye, gill, bone, and muscle of fish and shellfish from Kr. Meurebo River were investigated. Freshwater fish and shellfish were caught in the estuary from Kr. Meurebo River, Meulaboh, Indonesia on September 2010. All organisms were transported live to the laboratory and sampled dissected after death. Organs from each organism were removed and grained after freeze-dried. Total mercury analyzed using a HeatVaporization Atomic Absorption Spectrometry (HV-AAS), MA2000 automatic mercury analyzer. The results showed that total mercury was detected in all fish and shellfish and the accumulated mercury in organisms were significantly greater in shellfish than in fish which mean concentrations were 2.882+148 and 0.321+18.7 mg/kg-dry weight, respectively. High mercury levels in organism samples provided strong indication of a high bioaccumulation from the Kr. Meurebo River area. Bioaccumulation of mercury by fish found minimum in head (197.8+10.2 g/kg-dry weight), whereas maximum bioaccumulation founded in the eye (382+1.3 g/kg-dry weight). Mercury concentrations varied in the order: Eye > Muscle > Gill > Bone > Head. Based on these results, a regular monitoring program in Kr. Meurebo River is necessary conducted in order to better elucidate the rate of bioaccumulation and biomagnification by organisms. Keywords: mercury; bioaccumulation; Kr. Meurebo River; and Meulaboh.

1. Introduction Mercury (Hg) enters aquatic ecosystem from natural process (mineral deposits, volcanoes, forest fires, oceanic emission, and crust degassing) or be released by human activities such as smelters processing sulfide ores (i.e., in the production of metals such as gold, copper, iron, lead and zinc) and cement kilns, roasting of sulfide ores for production of sulfuric acid (Hylander and Meili, 2003). Andre et al., 1990 reported the contamination of the marine environment by mercury compounds is the
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result of natural phenomena in conjunction with anthropogenic discharge, especially near the coastline; anthropogenic discharges contribute to an increase of the mercury flux and to the alteration of the chemical forms and species of this trace element present in the water column and sediments. Lindqvist et al. (1991) estimated a mean of 4500 metric tons per year of anthropogenic mercury emissions, these measurements indicate that present-day mercury deposition is a factor of two to five times greater than preindustrial deposition measurements. When mercury is released to the atmosphere in the elemental form (Hg0), this is transformed into a soluble species (Hg2+), such transition from an inorganic compound into an organic form (mainly as methyl mercury) is the first step in the accumulation process in aquatic biota; the conversion of mercury forms is enhanced by bacteria that operate under aerobic and anaerobic conditions (Ruelas-Inzunza, et al., 2004). After bacterial activity, methyl mercury enters food chains and is eventually accumulated (Fitzgerald and Mason, 1996). Methyl mercury in aquatic biota is a major public health concern internationally (Wheatley and Wheatley, 2000). Large-size marine organisms, such as dolphin and tuna, contain high levels of mercury. For medium-size fish, the mercury level is relatively small in their muscles, however their internal organs, such as liver, may contain much more mercury (Kamps et al., 1972; Mishra et al., 2005; and Endo et al., 2003). Ruelas-Inzunza, et al. (2004) reported the distribution and relative concentrations of Mercury in the main tissues of penaeid shrimps mostly accumulated in hepatopancreas, followed by muscle and exoskeleton. Limbong et al., 2003 observed the emissions of mercury from artisanal gold mining in North Sulawesi and indicated that an increase took place along the three main rivers in the watershed. Solutions to this problem must be formulated as soon as possible in order to avoid a major health, economic, and ecological disaster arising from the continuing discharge of mercury in North Sulawesi. The contamination of mercury in the rivers in Indonesia mosly caused by the gold mining activities, such as Ciliunggunung River in Sukabumi Regency (Widodo, 2008), Tawalaan, Bailang, and Kima River in North Sulawesi (Limbong et al., 2003), and Barito, Kahayangan, and Rungan River in Central Kalimantan (Gumiri et al., 2009). The gold ore from the mining is processed with a direct amalgamation method and produces low gold concentrate, but the concentrate of mercury discarded to the river is high enough. Furthermore, low levels of technical knowledge and skills and no regulation are also applied in all related gold mining processes in Indoenesia (Limbong et al., 2003). Kr. Meurebo River is located in Meulaboh, the west part of Aceh, Indonesia and only 4 m deep on average. The major source of pollution is predicted by the waste effluents from the artisanal gold plant that all gold separated processes are undertaken with a low level of technical knowledge and skills, no regulation, and with disregard for the safety of human and environment health. The situation is generating serious potential health and environmental risks in that area. As part of an ongoing monitoring program, total mercury concentrations were examined in the organisms samples from the Kr. Meurebo River, which receives drainage from gold plant practices. This study assessed the levels of mercury concentration in biological samples from organisms such as fishes and shellfish in a watershed of Kr. Meurebo
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River, Meulaboh. With the purpose of knowing distribution and relative concentrations of mercury in the main tissues of organisms, levels of mercury in head, eye, gill, bone, and muscle of fish from Kr. Meurebo River were measured.

2. Methodology 2.1 Reagents All solutions were prepared in ultrapure water prepared by a Purelab Ultra Ionic (Organo Co., Ltd.). Hg2+ standard solution (1000 mg/L, HgCl2 in 0.02 M HCl), methylmercury(II) chloride, and hydrochloric acid were purchased from Wako Pure Chemical Industries, Ltd. All chemicals used were analytical grade quality. 2.2 Experimental Procedure Freshwater organisms (fish and shellfish) were caught in the estuary from Kr. Meurebo River, Meulaboh, on September 2010. Sampling sites were selected about 1 km near contaminant sources as illustrated in Fig. 1. All organisms were transported live to the laboratory and sampled dissected after death. Organs from each organism were removed and grained after dried. Freeze-dried conducted in Vacuum Oven Eyella VOS 450SD follow with liquid Nitrogen at 60oC.
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Sampling Location

Fig. 1 Map of sampling location

2.3 Analysis Procedure Total mercury analyzed using a Heat-Vaporization Atomic Absorption Spectrometry (HV-AAS), MA2000 automatic mercury analyzer (Nippon Instruments Co., NIC, Ltd.). Hg2+ standard solutions adequately diluted and added directly to the
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ceramic samples boats. Organisms sample (20-30 mg) added to ceramic boats with two types of additives, that one consists of activated alumina (additive B) and the other consists of a mixture of sodium carbonate and calcium hydroxide (additive M), which were purchased from NIC. All ceramics boats and additives heated in a muffle furnace at 700-800oC for 6 hours to remove any background mercury. The standard solutions and samples in the boats put into the sample loader part of analyzer to measure the total mercury concentration in samples. All glasses and ceramic boat wares were cleaned by soaking with a cleaning solution followed by a Millipore water rinse prepared by a Purelab Ultra Ionic (Organo Co., Ltd.) before use. Quality control was assured by DOLT3 Dogfish liver (National Research Council, Canada) and recoveries of mercury ranged 110.4%. 3. Results and Discussion Kr. Meurebo River is situated at the Aceh west coastal which has 188 km long and it drains an area of 1,632 km2. Average annual rainfall of the basin amounts to ca. 3,500 mm and annual maximum daily rainfall can be up to more 250 mm/d. River slopes in many places are depth while downstream the river bed is shallow due to sedimentation (Sea Defence Consultants, 2009). Thus, river flow conveyance capacity is limited. These factors cause, among others, river flooding in Kr. Meurebo River basin. Flooding information of 2003 to 2007 indicates that floods often occurred in river valleys and mostly in downstream flat coastal areas. Flooding occurs in those areas with a frequency higher than twice in a year. In the vicinity of the river, there are some people's activities, and the main contamination source of mercury predicted is the artisanal gold plant. This activity relies mainly on manual labor and makes use of simple methods. The processing plant is built at the side of the river, because water necessary for the processing of ore. Total mercury was detected in all organisms sample and the concentration of mercury in shellfish and fish are presented in Fig. 2, while the summary of concentrations in tissues of freshwater fish from different locations is given in Table 1. Mean concentrations were significantly greater in shellfish than in fish and the mean concentrations were 2.882+148 mg/kg-dry weight and 0.321+18.7 mg/kg-dry weight, respectively. A comparison with literature data (Table 1) showed that the specimens here analyzed had mercury level higher in freshwater fish and shellfish than those reported for freshwater fishes in other parts of the world (FDA, 2009a; FDA, 2009b), except for freshwater fish from mercury contaminated area in Sulawesi, Mexico, and North Mississippi (Ache et al., 2000, Hugget et al., 2001; Limbong et al., 2003), which showed comparable levels. Nearly all fish and shellfish contain traces of methyl mercury. However, larger fish that have lived longer have the highest levels of methyl mercury because they've had more time to accumulate it. These large fish (swordfish, shark, king mackerel, and tilefish) pose the greatest risk. Small fish absorb methyl mercury from water as they feed on aquatic organisms. The longer fish lives causes more methyl mercury accumulated in its body. Large, longlived, larger fish that feed on other fish (high in the food chain) accumulate the highest levels of methyl mercury. In the United States the limit for methyl mercury in
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commercial marine and freshwater fish is 1.0 parts per million (mg/kg). In Canada the limit for total mercury content is 0.5 mg/kg (FDA, 2009a; FDA, 2009b). Although the mercury levels in fishes from Kr. Meurebo River found are below these limits, the mercury levels found in shellfishes frequently exceed 1.0 mg/kg.

Fig. 2 Mercury levels in shellfish and fish muscles from the Kr. Meureubo River

Table 1 Mercury concentration in tissues of freshwater organisms from different locations

Species Location Fish, C. canos Kr. Meurebo River, Meulaboh Shellfish, P. exilis Kr. Meurebo River, Meulaboh Trout FDA 2002-04, USA T. mossambica FDA 1990-02, USA Catfish FDA 1990-04, USA Perch FDA Survey 1990-02, USA Shrimp FDA 1990-02, USA Small fish Talawaan River, Sulawesi Small fish Bailang River Sulawesi Small fish Kima River, Sulawesi M. Salmoides Gulf coast, Mexico Carp Enid Lake, North Mississippi Note: ND = not detected Hg Concentration (mg/kg-dry weight) 0.321 2.882 0.072 0.010 0.049 0.140 ND 3.140 0.510 0.453 0.430 0.352 References This study This study FDA, 2009b FDA, 2009b FDA, 2009b FDA, 2009b FDA, 2009b Limbong et al., 2003 Limbong et al., 2003 Limbong et al., 2003 Ache et al., 2000 Hugget et al., 2001

The differential accumulation of mercury in various tissues in fish was observed. The minimum content was in head (197.8+10.2 g/kg-dry weight), whereas the maximum content was in the eye (382+1.3 g/kg-dry weight) as shown in Fig. 3. Mercury concentrations varied in the order: Eye > Muscle > Gill > Bone > Head. Not all tissues will receive the same blood flow, and the distribution of mercury in the various tissues will be different (Suhendrayatna et al., 2001). Mercury accumulation in tissues will be a function of uptake and clearance rates of the individual organs. The significant correlations of mercury concentrations between
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tissues indicated that co-accumulation of mercury is occurring in tissues in a form suitable for accumulation.

Fig. 3 Distribution of mercury in fish tissues caught from Kr. Meurebo River

4. CONCLUSIONS This present study has shown that total mercury was detected in all fishes and shellfishes from the Kr. Meurebo River and the accumulated mercury in the organisms were significantly greater in shellfish than in fish which mean concentrations were 2.882+148 mg/kg-dry weight and 0.321+18.7 mg/kg-dry weight, respectively. High mercury levels in organism samples provided strong indication of a high bioaccumulation from the Kr. Meurebo River area. The bioaccumulation of mercury by fish found minimum in head (197.8+10.2 g/kg-dry weight), whereas the maximum bioaccumulation founded in the eye (382+1.3 g/kg-dry weight). Mercury concentrations varied in the order: Eye > Muscle > Gill > Bone > Head. A regular monitoring program in Kr. Meurebo River is necessary conducted in order to better elucidate the rate of bioaccumulation and biomagnification by organisms.

ACKNOWLEDGEMENTS This study is conducted on the collaboration research between Syiah Kuala University and Kagoshima University under the Professional Human Resources Development Project Phase III (PHRDP-III), Japan International Cooperation Agency (JICA) Loan Agreement IP-535. The authors acknowledge to Pusat Pembinaan Diklat Perencana, Bappenas, Indonesia, which have funded this program. We also thank Mr. Edi and Eko for their enthusiastic assistance with organisms collection.

REFERENCES Ache, B.W., Boyle, J.D., Moore, C.E., 2000, A survey of the occurrence of mercury in the fishery resources of the Gulf of Mexico, USEPA Gulf of Mexico Program, Stennis Space Center, MS.
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Andre, J.M., Ribeyre, F., Boudou, A., 1990. Mercury contamination levels and distribution in tissues and organs of delphinids (Stenella attenuata) from the Eastern Tropical Pacific, in relation to biological and ecological factors. Mar. Environ. Res., 30, 43-72. Endo, T., Hotta, Y., Haraguchi, K., Sakata, M., 2003, Environ. Sci. & Tech., 37(12), 2681. FDA, 2009a, What you need to know about mercury in fish and shellfish, FDA/Center for food safety & Applied Nutrition, http://www.fda.gov/Food/FoodSafety/ProductSpecificInformation/Seafood/FoodbornePathogensContaminants/Methylmercur y/ucm115662.htm, update November 17, 2009. FDA, 2009b, Mercury levels in commercial fish and shellfish, FDA/Center for food safety & Applied Nutrition, http://www.fda.gov/Food/FoodSafety/ProductSpecificInformation/Seafood/FoodbornePathogensContaminants/Methylmercur y/ucm115644.htm, update November 19, 2009. Fitzgerald, W.L., Mason, R.P., 1996. The global mercury cycle: oceanic and anthropogenic aspects. In: Baeyens, et al. (Eds.), Global and Regional Mercury Cycles: Sources, Fluxes and Mass Balances, Kluwer Academic Publishers, Netherlands, pp. 85-108. Gumiri, S., Dohong, S., Iqbal, R., Ardianor, Darung, U., Inoue, T., Elvince, R., Kawakami, T., Nagafuchi, O., Tsushima, K., 2009, The concentration and Distribution of mercury contamination in Central Kalimantan, Indonesia, Compilation of Research Results JSPA-DGHE Joint Research Project 20062009, DGHE, Indonesia-JSPS, Japan, 1-9. Huggett, D.B., Steevens, J.A., Allgood, J.C., Lutken, C.B., Grace, C.A., Benson, W.H., 2001, Mercury in sediment and fish from North Mississippi Lakes, Chemosphere, 42, 932-929. Hylander, L.D., Meili, M., 2003, 500 years of mercury production: global annual inventory by region until 2000 and associated emissions, Sci. Total Environ., 304, 13-27. Kamps, L. R., Carr, R., and Miller, H., 1972, Bull. of Environ. Cont. and Toxicol., 8(5), 273. Lewis, M., Chancy, C., 2008, A summary of total mercury concentrations in flora and fauna near common contaminant sources in the Gulf of Mexico, Chemosphere, 70, 2016-2024. Limbonga, D., Kumampunga, J., Rimpera, J., Arai, T, Miyazaki, N., 2003, Emissions and environmental implications of mercury from artisanal gold mining in north Sulawesi, Indonesia, The Sci. of the Tot. Environ., 302, 227-236. Lindqvist, O., Johansson, K., Astrup, M., Andersson, A., Bringmark, L., Hovsenius, G., Iverfeldt, A., Mieli, M., Timm, B., 1991. Mercury in the Swedish environment. Recent research on causes, consequences and corrective methods. Water Air Soil Pollut., 55, 251-261. Mishra, S., Tripathi, R.M., Bhalke, S., Shukla, V.K., Puranik, V.D., 2005, Anal. Chim. Acta, 551(1-2), 192.

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Ruelas-Inzunza, J., Garca-Rosales, S.B., Paez-Osuna, F., 2004, Distribution of mercury in adult penaeid shrimps from Altata-Ensenada del Pabellon lagoon (SE Gulf of California), Chemosphere, 57, pp. 1657-1661 Sea Defence Consultants, 2009, Kr. Meurebo basin floods and flood protection, SDC-R-90030. Suhendrayatna, Ohki, A., Nakajima, T., Maeda, S., 2001, Metabolism and Organ Distribution of Arsenic in the Freshwater Fish, Tilapia mossambica, Appl. Organometal. Chem., 15, 566-571. Wheatley, B., Wheatley, M.A., 2000. Methylmercury and the health of indigenous peoples: a risk management challenge for physical and social sciences and for public health policy., Sci. Total Environ., 259, 23-29. Widodo, 2008, Pencemaran air raksa (Hg) sebagai dampak pengolahan bijih emas di Sungai Ciliunggunung, Waluran, Kabupaten Sukabumi, Jurnal Geologi Indonesia, 3, 139-149.

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