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Water Air Soil Pollut (2010) 207:391–401 DOI 10.

1007/s11270-009-0144-3

Mercury and Methylmercury in Freshwater Fish and Sediments in South Korea Using Newly Adopted Purge and Trap GC-MS Detection Method
Jae-Sung Park & Jung-Sub Lee & Gun-Bae Kim & Jun-Seok Cha & Sun Kyoung Shin & Hak-Gu Kang & Eun-Jin Hong & Gi-Taeg Chung & Young-Hee Kim

Received: 22 September 2008 / Accepted: 7 July 2009 / Published online: 26 July 2009 # Springer Science + Business Media B.V. 2009

Abstract The use of purge and trap gas chromatography– mass spectrometry (GC-MS) technique for the determination of methylmercury in biological and sediment samples was described. The GC-MS detection system was combined with the dithizone extraction method for biological samples and the distillation method for sediment samples to alleviate matrix interference problems. The method was validated by analysis of CRMs such as SRM 966 (human blood), BCR 463 (tuna fish), IAEA 407 (fish), ERM CC580 (estuarine sediment), and IAEA 405 (sediment). The performance of the purge and trap GC-MS method was also tested on field samples of freshwater fish and sediment. The results were compared with those of the GC-ECD and the GCCVAFS, which were used widely for methylmercury analysis. Additionally, total mercury and methylmercury levels in freshwater fish and sediments from various reservoirs and streams in Korea were measured to understand mercury contamination status in Korean peninsula. Methylmercury concentrations in freshwater fish were found to correlate with body weight, diet habit,

and food availability. In sediment, total mercury concentrations correlated with methylmercury concentrations and organic matter such as %C and %S. However, no significant relationships between methylmercury and sediment organic matter have been found. Keywords Methylmercury . Mercury . Dithizone extraction . Distillation technique . Purge and Trap GC-MS . Sediment . Freshwater fish

1 Introduction Among many pollutants, methylmercury has been concerned as the most harmful mercury species due to its high toxicity, high solubility in lipids, which increases the potential for biological uptake and bioconcentration, and common occurrences in the environment (Horvat 1996). Some inorganic mercury released into the aquatic system is known to be converted to methylmercury via biotic production by sulfate-reducing bacteria in sediment (Mason et al. 1999; Mason and Lawrence 1999). These methylmercury are uptaken by benthic organisms and accumulated in fish through the food chain, which is the major pathway for human exposure to methylmercury (Boening 2000; Henny et al. 2002; and Mergler et al. 2007). Generally, the concentration of total mercury is used as a biomarker for evaluation of the exposure level of methylmercury in blood because more than

J.-S. Park : J.-S. Lee : G.-B. Kim : J.-S. Cha : S. K. Shin : H.-G. Kang : E.-J. Hong : G.-T. Chung : Y.-H. Kim (*) Chemicals Behavior Research Division, National Institute of Environmental Research, Environmental Research Complex, Kyungseo-dong, Seo-gu, Incheon, Republic of Korea 404-708 e-mail: heek89@korea.kr

it was considered appropriate to develop the accurate and simplified methylmercury analytical method using popularized analytical instrument such as purge and trap GC-MS. Lindberg et al. a succession of analytical stages is required. Purified .1 Sample Collection and Preparation From June to September 2006. Thus. The samples were kept frozen until further analysis. urban stream.392 Water Air Soil Pollut (2010) 207:391–401 80% of mercury in human blood exists as methylmercury forms and determination of total mercury is simple compared to that of methylmercury (Akagi and Naganuma 2000. atomic fluorescence spectroscopy (AFS). river 1 (with biochemical oxygen demand (BOD) lower than 3). The solvent extraction method using toluene or dichloromethane generally gave low extraction efficiencies in certain matrix (Akagi and Nishimura 1991). 2000. 2 Experimental Section 2. Hammerschmidt and Fitzgerald 2001). separation. The performance of the purge and trap GC-MS method was validated by analyzing CRMs. Thus. for the analysis of sediment. Additionally.2 mg/L. MO. a solvent extraction technique and a distillation technique are commonly used (Westöö 1966.8∼7. especially at low exposure levels. For methylmercury clean-up process. the distillation technique with H2SO4/KCl was preferred due to easy preparation and no use of harmful organic solvents. in this study. the extraction of methylmercury from biological samples. Logar et al. 2000. The filet of fish samples were cut into small pieces with dissection scissors and homogenized to a pastry state. The GC-MS detection system was combined with the dithizone extraction method and clean-up process by Na2S for biological samples since the dithizone extraction process showed improved extraction efficiencies by the complexation between dithizone and methylmercury (Akagi and Nishimura 1991. total mercury and methylmercury levels in freshwater fish and sediments from various reservoirs and streams in Korea were measured to understand mercury contamination status in Korean peninsula and the analytical results were compared with those of the GC-ECD and the GC-cold vapor atomic fluorescence spectrometry (CVAFS). Ignacio et al. 1). 2007). and plant effluents. 2000). respectively. Horvat et al. Blanco et al. The main steps to speciate mercury are digestion. The sediment were categorized into groups by sampling sites as lake. Additionally.1∼15. Bloom 1989. 1997. 2. Methylmercury standard stock solution (1 mg∙mL−1) was prepared by dissolving the appropriate amount of CH3HgCl (Aldrich.6 mg/m3 and 1. USA). the distillation technique has a drawback such as codistillation of large amounts of volatile compounds in blood and these volatile compounds transferred to the distillate can interfere with the ethylation reaction and/or deposit on the GC column leading to inaccurate determinations (Liang et al.2 Experimental Materials and Apparatus All reagents used were of ACS grade and all water was used as doubly distilled and de-ionized water obtained from Barnsted UC/A56220-8 (IA. and mercury-specific detection. However. reservoirs. Quevauviller et al. clean-up. However. Rice 2004). 57 freshwater fish samples were collected from reservoirs. and inductively coupled plasma–mass spectroscopy (ICPMS) have been widely used (Westöö 1966. Ullrich et al. especially in blood has been a difficult task because of severe matrix interferences. 1). 1993). 2002). the distillation conditions were controlled with great cautions to prevent the production of methylmercury artifacts by over-distillation (Horvat et al 1993. USA) in toluene. recent studies showed that the mercury speciation in human blood is needed to evaluate the sources of exposure. Eighty-one sediment samples were also sampled from June to September 2007 by using a Ponar grab sampler (Fig. and streams in Korea (Fig. there is a growing need for a more simplified and popularized analytical method for the determination of methylmercury in environmental species (Vidler et al. Coupled techniques including separation by gas chromatography (GC) or liquid chromatography (LC) and detection by electron capture dissociation (ECD). lakes. In this study. 2001. Baxter et al 2007). respectively. river 2 (with BOD higher than 3). All the samples were kept frozen until further analysis. The water characteristics of the sites are various with chlorophyll a concentrations and chemical oxygen demand ranging 1. However. atomic absorption spectroscopy (AAS). (2004) revealed that the proportions of methylmercury to total mercury in blood of non-fish-eating people are relatively lower than those of fish-eating people and inorganic mercury in blood has a significant association with the number of dental amalgam fillings. For methylmercury analysis.

The injection port and detector were operated at 220°C and 230°C. .Water Air Soil Pollut (2010) 207:391–401 Fig. The sample was purged with helium at 40 mL∙min−1 for 15 min at 40°C and followed by desorption at 200°C for 3 min. Sodium acetate buffer (0.2 g of sodium tetraethylborate [NaB(C2H5)4] powder in 10 mL of 1% w/v KOH solution and was kept in ice and darkness after preparation and throughout the analysis. 30 m×0. 1 Sampling sites of sediments and freshwater fish in Korean peninsula 393 S-River S-Lake & Reservoir S-Urban stream S-Plant effluent S Freshwater Fish 0. 10 mL of 1 N HCl was added followed by washing with 5 mL of n-hexane.15 g of Na2S9H2O in 10 mL of distilled water. Walpole’s buffer was prepared by mixing 200 mL of 1 M CH3COONa and about 200 mL of 1 N HCl to adjust to pH 3.9. USA) equipped with Agilent 5973N MS operating in selected ion monitoring (SIM) mode. The column temperature was programmed as follows: 40°C for 4 min. At each use. increasing to 280°C at 15°C∙min−1 then holding for 5 min. 0.1 mL of stock solution was diluted with 50 mL of 0. 2. Alkaline sodium sulfide stock solution was prepared by dissolving 0.64 g of CH3COONa in distilled water and added with acetic acid to adjust pH at 4. MO. Approximately 0.1 N NaOH and 50 mL of ethanol. After cooling to room temperature. USA) as adsorbent trap. was prepared by dissolving with 0. respectively. Ethylating reagent.25 μm) was used with helium as carrier gas at a flow rate of 1 mL∙min−1.0.D.2 M) was prepared by dissolving 1. 2% sodium tetraethylborate.02% dithizone solution was prepared by dissolving 0.011 g of diphenylthiocarbazone in 100 mL toluene..3 Determination of Methylmercury in Biological Samples Using Dithizone Extraction Followed by the Purge and Trap GC-MS Method Details of dithizone extraction procedures for methylmercury analysis are given elsewhere (Akagi and Ikingura 1999). The DB-5MS capillary column (5% phenyl–95% dimethylpolysiloxane. USA) with a Tenax A trap (Suppleco. Chromatographic analysis was performed with Agilent 6890N GC (CA. OH. 0. the volatile derivatized ethylmethylmercury were concentrated and injected using Tekmar–Dohrmann purge-andtrap (Mason.5 mm I. For purge and trap GC-MS method.5∼1 g of biological sample and 10 mL of 1 N KOH–ethanol solution were placed in a 40-mL screw-capped conical centrifuge tube and heated at 100°C for 1 h.

The remaining excess dithizone in toluene phase was removed by washing with 5 mL of 1 N NaOH. 217. The commercially available blood samples were obtained from Centre de Toxicologie du Québec (Québec.5) 26.6 RSD (%) 4. The calibration curve was evaluated in the range from 0. followed by adding 0. Belgium) for fish and standard reference material (SRM) 966 (NIST. Vienna.9 3. 0.8±0.1a (4.4 Recovery (%) 93∼105 86∼93 79∼91 Data from the total mercury analysis and the materials were spiked with methylmercury . 2.6 5. MD. Blanks and standard solutions for a calibration curve were treated in a similar manner.394 Fig. the distilled water was analyzed in order to clean the system and eliminate carryover effects. Lastly. the following ions were monitored using SIM mode: m/z 202. Austria) and BCR 463 (ERM.5 mL of 50% sulfuric acid and 0.1 to 5 ng (as Hg) and obtained with a determination coefficient. USA) for blood were analyzed.3) a Determined value (ng∙g−1) 16. For quality control purpose. Five milliliters of purified 0. and 260 for Hg (C2H5)2.4 7. CRMs of IAEA 407 (IAEA.6 mL of 20% KCl solution in 22. 231.6±1. 2 GC chromatogram obtained from CRM IAEA 407 sample by the purge and trap GC-MS method Water Air Soil Pollut (2010) 207:391–401 and then. A fixed volume of the toluene phase (7 mL) was transferred into 10-mL centrifuged tube with glass stopper and 2 mL of Na2S solution was added to back-extract the methylmercury into aqueous phase.2±1.0∼32. During MS detection. Between two consecutive analyses. One milliliter of Table 1 Determination of methylmercury in blood CRM and commercially available blood materials Materials SRM 966 (n =5) M 0605 (n =3) M 0618 (n =3) a Certified value (ng∙g−1) 16. and 246 for CH3HgC2H5.1 ng∙g−1 for biological samples.5∼1 g of solid samples was distilled with a 1.8 23. m/z 202. Briefly. r2 >0.9 mL of distilled water to isolate methylmercury from constituents. The combined solution in the syringe was injected into the sparser connected on the purge and trap sampler.4 Determination of Methylmercury in Sediment Using Distillation Technique Followed by the Purge and Trap GC-MS Method Details of distillation protocols for methylmercury analysis are given elsewhere (Mason et al. The solution was acidified with 3∼5 drop of 1 N HCl and aerated with N2 at 50 mL∙min−1 for 3 min to expel the excess sulfide ions. Canada).01% dithizone-toluene was added and the aqueous phase was discarded.995 and less than 7% of RSD of calibration factors. Brussels.6∼9.2 mL of sodium tetraethylborate solution.3 6.05∼1 mL) of the aerated solution was added into 10 mL of distilled water and 5 mL of sodium acetate buffer in a 20-mL syringe.1 mL (0.3 (20.4±1. 2 mL of 20% EDTA–4Na solution was added into the extracted aqueous phase to mask other metal ions contained in the samples. 1999). The method detection limit was defined as the concentration equivalent to three times standard deviation of concentrations of spiked methylmercury solutions and was found to be 0. 0.

USA) was used for all statistical analysis.5 5. and Pb). The combined solution in the syringe was injected into the sparser connected on the purge and trap sampler. The significant level was set to p ≤ 0. After determining the water content of the sediment.27±0. For quality control purpose.2 mL of sodium tetraethylborate solution. Canada) were analyzed for quality control.05 ng∙g−1 for sediment samples. the samples were heated at 550°C overnight. causing peak broadening and ghost peaks (Caricchia Determined values (ng∙g−1) GC-MS GC-CVAFS GC-MS GC-CVAFS 74.28 5.49±0. 2.1 5. adsorption processes of methylmercury occur on the stationary phase during the chromatographic analysis.0 for Windows (SPSS Inc. Cu. Milestone Srl) and CRM of MESS-3 (NRC. Chicago.5 5.16 Determined values (ng∙g−1) GC-MS GC-ECD GC-MS GC-ECD 0.016 0.83±0.53 other metal analysis in sediment.26 2.0 73.1 Optimization and Validation of Purge and Trap GC-MS Method Due to polarity of methylmercury compound.7 4.Water Air Soil Pollut (2010) 207:391–401 Table 2 Determination of methylmercury in fish CRMs CRMs IAEA 407 (n =7) BCR 463 (n =7) Certified values (ng∙g−1) 0.022 2.05. Pearson’s correlation analysis to determine statistical significance between total mercury and methylmercury concentrations was also undertaken. Perkin Elmer). The t test and ANOVA were used to compare blood mercury and methylmercury concentrations between groups. Ni. USA) was used for quality control materials. followed by adding 0.5 Ancillary Chemical Measurements for Sediment Analysis Weighed sediment samples were heated at 105°C for 4 h and reweighed in order to calculate the water content.19±0. A multiple regression statistical analysis of the sediment dataset was used to access the primary correlations between total mercury.5±1. the samples were digested using EPA method 3051 with HNO3/HCl and analyzed by ICP-OES (Optimer 5000DV. Total mercury for sediment samples were analyzed by EPA method 7473 (DMA-80.2 13. and other metals (Fe. Austria). The total sulfur contents were determined using PE 2400 series II analyzer (Perkin Elmer.76±0. Belgium) were analyzed.20±0. For Table 3 Determination of methylmercury in sediment CRMs CRMs ERM CC 580 (n =7) IAEA 405 (n =7) Certified values (ng∙g−1) 75.32 RSD (%) 3.6 Statistical Analyses SPSS version 10.20±0. Cr. IL. CRMs of IAEA 405 (IAEA. 2.9 5. The conditions of separation and detection system were identical with those for biological samples.9 395 Recovery (%) 85∼95 92∼101 98∼108 91∼107 distillate was added into 10 mL of distilled water and 5 mL of sodium acetate buffer in a 20-mL syringe.76 Recovery (%) 85∼108 83∼111 89∼102 90∼109 .8 5. The commonly used distillation/GC-CVAFS method (USEPA 2001) was used as a control method to compare the results obtained by the GC-MS method. and BCR CC580 (ERM. The samples were then reweighed and the percent organic matter in the sediment was determined by the difference as loss on ignition. %C.41±0. ERA Soil CRM (ERA. Zn. USA).89±0.0±4. 3 Results and Discussion 3.1±1.31 RSD (%) 14. Brussels. methylmercury. Mn.3 5. %S. The method detection limit was found to be 0. Vienna.012 2..

8±117.8 357.2 141.3±41.6±1.2±10. was used for the derivatization of polar methylmercury compounds to nonpolar ethylated methylmercury compounds.0±45. The most consistent sensitivity was obtained from 15 min of purging by monitoring the changes of analytical signals. The accuracy of the purge and trap GC-MS method was evaluated by analysis of CRMs such as SRM 966 (human blood). NaBEt4.8±82.7 254.5±62.2±68. As shown in Table 1.7 89. and IAEA 405 (sediment).2 191. and 246 were monitored for CH3HgC2H5 and m/z 202.2 206.3 175.0 102.1±106.9±75.16 MeHg 219.0 49. The concentrated methylmercury in Tenax trap was introduced to GC-MS and was analyzed by using selected ion monitoring mode. BCR 463 (tuna fish).1±159.7 50.9 140. and 260 for Hg(C2H5)2. IAEA 407 (fish).8 59.6±58. 231.4 35. which were within the certified range and the average RSD was 4.4 136. Snake head Skygager Korean piscivorius chub Common carp 0 500 1000 weight (g) 1500 2000 . Although not certified for their methylmercury concentrations. Polar methylmercury compounds are needed to convert into nonpolar methylmercury compounds before chromatographic separation (Young and Josep 1995).2±34.1±16.9±3. which were in good agreement with the certified values.9±0.4 116.396 Table 4 Comparison of total mercury and methylmercury concentrations (ng∙g−1) in freshwater fish Species Mandarin fish Korean piscivorous chub Skin carp Catfish Skygager Sharpbelly Northern snake head Largemouth bass Carssius cuvieri Crusian carp Common carp Leather carp Japanese dace No of samples 2 5 4 7 6 1 6 9 1 2 11 2 1 Water Air Soil Pollut (2010) 207:391–401 T-Hg 413. 217. High and low concentrations of commercially available blood samples were also analyzed.1 24. The spectrum in Fig.1±57.1 42.3 216. the analytes are purged with helium at 40 mL∙min−1 to adsorb methylmercury on the trap.6 ng∙g−1 (95% confidence interval with n =5). obtained results of SRM 966 were 16. In this study. In the SIM mode the ions of m/z 202.8 151. After the derivatization reaction.4±90.8±53. 1997). these material was expected to be available for methylmercury analysis because they were spiked with methylmercury. The analytical results of fish CRM and sediment CRM were shown in Tables 2 and 3.6 153.7±118.3 125. 3 Correlations between methylmercury concentrations and fish weight of specific species [MeHg] (ng/g) 500 400 300 200 100 0 CH3HgC2H5 and Hg(C2H5)2 peaks which are contributed from CH3Hg+ and Hg2+ in the sample.7 77. showing Fig.3±71.4 %MeHg 53 86 88 68 90 50 69 84 82 74 69 72 77 et al. sodium tetraethylborate.9%.7 183.7 220. 2 is the GC chromatogram of CRM IAEA 407 sample. ERM CC580 (estuarine sediment).

2 8.6±0.6 1. methylmercury concentrations of freshwater fish and sediment were investigated by the purge and trap GC-MS method and the analytical results were compared with those of the GC-ECD for freshwater fish and the GC-CVAFS for sediment. p < 0. Thus. Paired t test results showed no statistically significant differences (p =0. 3.8 Dam-Yang 13±2 . while their body weight was much less than that of other species.7±8.05).9 ng∙g−1) were found in polyphagia species such as common carp.71 0.0 0.05). As shown in Table 5. it is likely that Korean piscivorous chub can accumulate methylmercury over their life span with minimal growth dilution.0±0. For freshwater fish analysis.05) except Largemouth bass (Fig. minnows. Subsequently. 1997.6 7. Generally.01 6.9∼424 ng∙g−1 (mean 143. Wagemann et al. i. compared to Bass 1. 4.e.6±0.5±4. Despite the small number of samples. It is interesting to note that Korean piscivorous chub showed statistically high methylmercury concentrations.88.04±0.05) and no statistically significant differences were found by the paired t test (p =0. the relationship between methylmercury concentration and body weight were divided into two groups.2±0.1 ng∙g−1) and methylmercury concentrations were in the range of 12.0 Ju-Nam 17±1 7.0 2. while methylmercury concentrations increased as fish weight increased. the average ratio of methylmercury concentrations between the methods ([MeHg]CVAFS/[MeHg]GC-MS) was 0.28±0. different species showed different patterns and methylmercury concentration was significantly correlated with fish body weight (R =0. the result clearly showed a distinct pattern that methylmercury body burden was much higher in Bass 2. Sveinsdottir and Mason 2005).07±0.88 (p <0.9 and its correlation coefficient was 0.02 21. Overall. growth dilution) (Bloom 1992.37> 0. Largemouth bass are carnivores and their food preference is crayfish.5±0. Bass 1 from Ju-Nam reservoir and Bass 2 from Dam-Yang artificial reservoir.5±0. two groups were collected from different locations.2 ng∙g−1) (Table 4). Ju-Nam reservoir showed more eutrophic characters with high Table 5 Water quality of Ju-Nam and Dam-Yang reservoirs during 2002~2006 Reservoirs Temp (°C) pH DO (mg/L) Conditions COD (mg/L) SS (mg/L) TN (mg/L) TP (mg/L) Chlorophyll A (μmho/cm) (mg/m3) 210±25 64±15 7.5 2.65±0. while lower concentrations (12. Thus.58∼0. Korean piscivorous chub are actually the top predator and long-lived fish with small body size.5±0. and frogs.9 to 59.22>0. the GC-MS method was used as an alternative for a commonly used the GCECD and GC-CVAFS method. for the sediment analysis.2 Analysis of Total Mercury and Methylmercury in Freshwater Fish For 57 freshwater fish analysis. The relatively high methylmercury concen- trations (216 to 424 ng∙g−1) were found in predatory species such as Korean piscivorous chub.0±4.05). 3).4 11.24 1. total mercury concentrations were in the range of 20.3 9.Water Air Soil Pollut (2010) 207:391–401 250 200 [MeHg] (ng/g) 150 100 50 0 100 Bass 1 Bass 2 397 300 weight (g) 500 700 Fig. As seen in Fig.79 (p <0. methylmercury concentrations in fish are expected to be proportional to trophic level and its size while methylmercury bioaccumulation is a function of several factors such as uptake (diet) and elimination pathways (excretion. The average concentrations of water quality-related parameters from 2002 to 2006 were obtained from the data of water quality monitoring networks in Korea. Additionally. 4 Correlations between methylmercury concentrations and fish weight of Largemouth bass: Bass 1 from Ju-Nam reservoir and Bass 2 from Dam-Yang reservoir Additionally.4∼454 ng∙g−1 (mean 175. even though their body weights were comparable. resulting in high methylmercury body burden. methylmercury concentrations between two methods were significantly related with Person’s coefficient of 0.

Hutchson et al. methylmercury. chlorophyll a. %MeHg is generally known to be less than 5% and the range in %MeHg observed in this study (0. and %MeHg in sediments [T-Hg] (ng/g) 500 Water Air Soil Pollut (2010) 207:391–401 5 [T-Hg] [MeHg] %MeHg 10 400 4 8 200 2 4 100 1 2 0 Plant effluent (n=8) Urban Stream (n=5) River 2 Lake & River 1 (BOD<3) (BOD>3) Reservoir (n=23) (n=13) (n=23) 0 0 concentrations of total phosphorous.∼5. The proportion of methylmercury to total mercury in sediment samples (n =68) were 2.3 Analysis of Total Mercury and Methylmercury in Sediment Eighty-one sediment samples were collected from various sites in Korea to understand the impact of Fig. 6 Plots of the correlation between total mercury and methylmercury concentrations in sediments 100 contaminated sediments on regional scale. 10 [MeHg] (ng/g) 1 0.D.01 1 10 100 1000 10000 [T-Hg] (ng/g) %MeHg 300 3 [MeHg] (ng/g) 6 .398 Fig. (2008) and Krabbenhoft et al.39%. Methylmercury were found below the detection limit of 0.95 ng∙g−1. Methylmercury concentrations and %MeHg in sediment are useful indicators reflecting the changes of mercury loading. Total mercury concentrations in sediment were in the range of 2. 2008). Lower mercury level in fish from Ju-Nam reservoir might be related to dilution effects with faster fish growth and longer food chain due to easy food availability than Dam-Yang reservoir.52±2.564.43∼1. 3.17 ng∙g−1 and methylmercury concentrations were in the range of N. 5 Comparison of total mercury. even though it is difficult to conclude without comparison of mercury levels in water and sediment (Sveinsdottir and Mason 2005.86∼3. (2006). bioaccessibility of inorganic mercury. and changes in bacterial activities. and chemical oxygen demand than Dam-Yang reservoir and these indicators are generally related with fish growth rates.1 Plant effulent Urban stream River 1(BOD<3) River 2(BOD>3) Lake & Reservoir 0.27%) is similar to values reported by Stephenson et al.05 ng∙g−1 in 13 sediment samples.

To access the interrelationships between methylmercury and other chemical parameters in sediment. urban stream.40) of previous study (Benoit et al.41. While there was an indication of a correlation between total mercury and sediment organic content. values listed are correlation coefficients obtained from a multivariate analysis Parameter T-Hg MeHg Organic content. These results are expressed as the high %MeHg of lake and reservoir sites (3. and other metals (Cu.285 NC Organic content.667 1 0.648 NC NC 399 %S 0. Thus.05). Choi et al. However.Water Air Soil Pollut (2010) 207:391–401 Table 6 Correlation table for the sediment dataset.773 0.587 0. Sulfate ions. Ni. As shown in Fig.73 ng∙g−1).86%). 5. % 0.667 0. 2009).408 0. Recent studies showed that atmospheric total gaseous mercury levels were around 2.509 NC NC MeHg 0. were found to be the major contributors of the wet deposition in Korea. river and lake. Pb. 2007. p <0.408 0.410 1 0. % %S Cr Ni Zn Pb Fe NC no correlation Mn T-Hg 1 0.283 NC NC NC NC NC 0.622 0.893 0.283 1 0.78 ng∙g−1). 2003).388 0. 7 Heavy metal concentrations in catergorized sediment (mean±1SD) 1800 1600 1400 1200 1000 800 600 400 200 0 Cr al. methylation in sediment was possibly enhanced by newly uploaded mercury and high sulfate concentrations from atmospheric deposition.94 ng∙g−1) and low total mercury concentrations (27. the relationship between ecosystem (categorized as plant effluent. there was also clear differences in %MeHg observed in different sampling sites.27%) compared to plant effluent sites (0. and reservoir) was not included in this study (Fig. The concentrations of total mercury and methylmercury showed statistically significant correlation (RT-Hg-MeHg =0.410 0.720 0. sulfur contents. one of the limiting factors for methylation.455 0. 6). it appeared to Plant effluent Urban stream River 1 River 2 Lake & Reservoir [Metal] (mg/kg) Ni Cu Zn Pb Fe(x100) Mn . Fe. organic contents.504 0.4 ng∙g−1) but only moderate in methylmercury (1. Zn.481 NC 0.667 0.37 ng/m3 in Korean Peninsula and were enhanced by longrange transport from East Asia (Hong et al.481 0. the lake and reservoir sites had comparatively high methylmercury concentration (0. which was a similar value (RT-Hg-MeHg =0.911 NC NC However. whereas sediments from the effluent sites were relatively high in total mercury (433.63∼4. which was mainly contributed by acidic precipitation (Han et Fig. and Mn) were examined and the correlations matrix was summarized in Table 6. 2008).

R. F. (2000). A. A. W. I..) found by Mason et al.. it is worthy to evaluate the degree of methylmercury contaminations in sediment and freshwater fish since recent study showed the total mercury level of blood in Korean was much higher than those in other countries (investigated by Korea Ministry of Environment in 2005). preconcentration and determination of mercury species in river waters.. Benoit. G. P. Heyes. (1997). Gilmour. N. 5930–5936. In Y.28) showed similar values with those (RT-Hg-%C =0.400 Water Air Soil Pollut (2010) 207:391–401 be nonlinear. 323–328. R. Analytical Chemistry. J. Hong. N.. Human exposure to mercury and the accumulation of methylmercury that is associated with gold mining in the Amazon basin.. Mason and Lawrence 1999). 111–116. Microchemical Journal. (2003). 213–231. Pb. A..). Environmental Pollution. except at elevated mercury concentration. C. (2000). Canadian Journal of Fisheries and Aquatic Sciences.. T. Ahn.48. the effect by input sources is likely more important than sediment characteristics (Benoit et al. At high mercury concentration sites. Generally. (2002). (2007). 137–144. New York: Plenum Press. D. Kim. Cr. 1998. Hill.C. Ecotoxicology. J. Ubaldi..... Ni. Bloom. G. the current study is preliminary and cannot represent the mercury contamination status in Korea. Methylmercury production and distribution in aquatic systems. T. R. H. Canadian Journal of Fisheries and Aquatic Sciences. National Institute of Environmental Research Report. R. M. Clinical Chemistry.. 157(3). H. S. Braids (Eds. & Ikingura. Even though. Han. Villanueva. Methylmercury measurement in whole blood by isotope-dilution GC-ICPMS with 2 sample preparation methods. Nineteenth Century mercury: Hazard to wading birds and cormorants of the Carson River. Henny. E. D. J. & Yi.. 7. K. J. Y.. S. M. J. H.. 2008-78-1028.. G. Sources and cycling of mercury in the Patuxent estuary. M. & Naganuma. Zn. Nevada. C. E. J. 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