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1 Printed in the Republic of Korea "/"-:5*$"- 4$*&/$& 5&$)/0-0(: Vol. 25, No. 6, , Distribution of heavy metals and mercury in sediment from the lake An-dong Jin-Ju Park, Ki-Joon Kim, Suk-Min Yoo, Eun-Hee Kim, Kwang-Seol Seok, In-Ah Huh 1 and Young-Hee Kim Chemical Research Division, National Institute of Environmental Research of Environmental Research,G Incheon , Korea 1 Water Environment & Engineering Research Division, National Institute of Environmental Research of Environmental Research, Incheon , Korea (Received September 26, 2012; Revised November 14, 2012; Accepted November 22, 2012) yn sp Á½» Á Á½ Á Ÿ Áx Á½ y w yw, 1 y œw Abstract: In this study, mercury, methylmercury and heavy metals in sediment from the lake Andong were analyzed, along with the estimation of mercury flux between sediments and water in the lake Andong. Average mercury concentrations in sediments sampled in 2009~2011 were 155.0±71.9 ng/g, 211±62 ng/g and 198±6.88 ng/g, respectively. The average methylmercury concentration were 1.85±1.09 ng/g (2009) and 3.49±1.79 ng/g (2011), and %methylmercury, the fraction of methylmercury in total mercury were 1.17±0.39% and 1.77±0.94%, respectively. Heavy metal (Zn, Cd, Pb, Cu) concentrations of the sediments exceeded ERL (Effect Range Low) level of US NOAA (National Oceanic and Atmospheric Administration)'s sediment quality criteria. Estimated mercury sedimentation flux was found to be 83.7 ng/cm 2 yr and mercury diffusion flux was estimated as 1.24 ng/cm 2 yr. : y n, p, wš n w. y n 2009~2011 ƒƒ 155.0±71.9 ng/g, 211±62 ng/g 198±6.88 ng/g, p ƒƒ 1.85±1.09 ng/g, 3.49±1.79 ng/g š, w p % p 1.17±0.39% 1.77±0.94% ùkû. n, e, û, 644 mg/kg, 7.3 mg/kg, 67 mg/kg, 42 mg/kg w» (NOAA, National Oceanic and Atmospheric Administration) w n» (SQGs, Sediment Quality Guidelines) w (ERL, Effect Range Low) w. y n 83.7 ng/cm 2 Á, n l y 1.24 ng/cm Á 2. Key words: mercury, methylmercury, heavy metal, sediment, sedimentation rate, diffusion flux Corresponding author Phone : +82-(0) Fax : +82-(0) heek89@korea.kr 441

2 442 Jin-Ju Park, Ki-Joon Kim, Suk-Min Yoo, Eun-Hee Kim, Kwang-Seol Seok, In-Ah Huh1 and Young-Hee Kim 1900 z, y w y y ƒ, w ƒ, 2008» 7438 m, 2320 m. 1 p y y, Ám Áw l 5118 m, l» ƒ ƒw š. z 2000 l w y w» w, UNEP w z 2010 l 5 e x x z w 2013 ¾ w» w UNEP š ù 9 ü p q w ƒ v w. y» xk, ù, wì t z, n l w p y š, n p mw. p y n š(sink) w w, mw z yw p Áe, n ü w w. w n ¾» l e š, n ü» w y y w w œw. 3 n k j w(digestion), (purification)/ (separation) (detection). w y w w, ƒ wù, š rw š. 4 w z, p py mw { g, p k z,» j m v z xÿÿ, w w. x y 1630 x k y ƒ š. 5 y ù ewš œy, y ü û, Ÿ yÿ ewš, yÿ 2009 y s Ÿ m k, s Ÿ ƒ 2 m 3, s 4 m 3 ƒ, m û, m» w ùkù, v w I Ÿ. 6 w y ¼ ƒ ü k y w w. 7 y p q w» w y n, p s w. x y n y d y 1, 2, l 2010 ¾ ƒ 6 9 g, 2011 td w. 50 cm ¼ g v w,, s p s þ w x w, 2 cm z, ¾ þ w. t ACS w, Fig. 1U Map of the Lake An-dong basin and sampling sites for sediments. Analytical Science & Technology

3 Distribution of heavy metals and mercury in sediment from the lake An-dong 443 Barnsted UC/A (Iowa, USA) w 3 w. p t (1 µg ml 1 ) 12.5 mg CH 3 HgCl (Aldrich, MO, USA) 0.5%V/ V p 0.2%V/V yw 100 ml ƒ w. Sodium acetate buffer (2 M) 54.4 g CH 3 COONa (Aldrich, MO, USA) 23.6 ml p z 200 mlƒ w. 2% sodium tetraethylborate 0.2 g sodium tetraethylborate[nab(c 2 H 5 ) 4 ] 10 ml 1%W/ V KOH w k z, ¾ þ w. y 7473 x w ƒ»y» (DMA-80, Milestone Srl, Italy) w w. n C o 1 ƒ, wì 650 C o 3 ƒ w ww.»(amalgamator) k w Hg(0) xk 750 C o 12 ƒ w k k z nm q ŸŸ d w. š t MESS-3 (NRC, Ottawa, Canada) l ƒ 2, 5, 10, 20 ng t 0.025, 0.054, 0.105, g w z, w ŸŸ w w. w t 20 w, s³ ƒ 93.8±1.7 ng/g y y ü ùkû. p n p y 1630 x w þ» xÿÿ (Cold vapor atomic fluorescence spectrometer) p» (BROOKS RAND, USA) w w ml» n 1.0 g y š 5 ml z ƒ w. 8 M y 1.5 ml 20% KCl 0.8 ml z 25 mlƒ z. š lv» 5 ml z» z 138~145 o C z ƒ e» ewš, 4 o C w þƒ e lv s» w. 7 ml š ƒ 50 ml» w w. 25 mlƒ wš y z x w, ¾ þ w. p py j» w (VOC vial) š 1 ml š» w,» 2 M acetate buffer 0.3 ml ph 4.9ƒ w 2% sodium tetraethylborate 0.05 ml ƒwš ó¾ œ»ƒ ƒ. p»(brooks RAND, USA) w w. p»»» Table 1. Instrumental operating conditions for methylmercury analysis Parameter Operating Condition Off set range 55,000~65,000 Gas flow Purge 45 ml/min Dry 35 ml/min GC 40 ml/min Run duration : 5 min Analyze step Purge duration : 5 min Drying duration : 3 min Heating time : 8.8 ~ 9.9 min Table 2. Instrumental operating conditions of ICP-OES Plasma Condition Plasma gas flow 15 L/min Auxiliary gas flow 0.2 L/min Nebulizer gas flow 0.80 L/min Purging gas flow Normal (1 L/min, N 2 ) Coolant gas flow Air R/F generator power 1400 W Sample Sample flow rate 1.50 ml/min Sample flush time 20 sec Equilibration delay 15 sec Read delay time 40 sec Analyzing condition Resolution High Int. Time (sec) 1-4 (auto) Replicates 3 times Plasma view Axial type Vol. 25, No. 6, 2012

4 444 Jin-Ju Park, Ki-Joon Kim, Suk-Min Yoo, Eun-Hee Kim, Kwang-Seol Seok, In-Ah Huh1 and Young-Hee Kim Table 1 w. w t IAEA-405 (CRM of Hg and MeHg determination in sediment samples) w wš w, s³ 5.3± 0.54 ng/g ƒ y y ü ew. 1P EPA method 3051 j (ETHOS1, Milestone Srl, Italy) wš ICP-OES (Optimer 5000DV, Perkin elmer) w,»» Table 2 w. n w w» w 210 Pb grand-daughter 210 Po q d»(canberra 7401 with PIPS PD AM detector) w d w. 9 š y n p s p y n s³ 2009~2011 ƒƒ 155.0±71.9 ng/g, 211±62 ng/g 198±6.88 ng/g ùkû. ù w n s³ 27 ng/g w, 10 w» (NOAA, National Oceanic and Atmospheric Administration) w n» (SQGs, Sediment Quality Guidelines) w (ERL, Effect Range Low) 150 ng/g ùkû (Fig. 2). 11 p ƒƒ 1.85± 1.09 ng/g, 3.49±1.79 ng/g, p % p 1.17±0.39% 1.77±0.94% ùkû. p p 2009 w 2 ƒ¾ ƒw, % p w 1.5 ƒ. y % p y ù n w ùkû s l n j ú d y 1 y 3 w n ƒ ùkû. tdn ƒ, p p p yáy d 0~2 cm tdn Fig. 2. Concentrations of total mercury and methylmercury, and %MeHg in sediments from the Lake An-dong in ƒ ùkû. p, R 0.82 (p<0.05) j (Fig. 3). n p R=0.4 w p š. ù y ü n p w, w q. n p» w R=0.51(p<0.05), p R=0.57 (p<0.05) w ùkû.» Analytical Science & Technology

5 Distribution of heavy metals and mercury in sediment from the lake An-dong 445 Fig. 3. Correlation between total mercury and methylmercury in sediments from the Lake An-dong. Mason et al. (R Hg-%C =0.49) w. 12 %S %N, p w ùkü. y n s y n 644 mg/kg, e 7.3 mg/kg, û 67 mg/kg, 42 mg/kg, w» SQGs ERL (Effect Range Low, w )» ( 150 mg/kg, e 1.2 mg/kg û 46.7 mg/ kg 34 mg/kg) ùkû. n p,» w Table 3 w ùkü, p m l» p, w. y n y n w» w 210 Po mw n n w. 200 ü x š, w n w Fig. 4. The concentrations of heavy metals in sediment from Lake An-dong. n ü 210 Po w. 13 y 1, 2, 3 w n d w y 3 ¾ 210 Po ƒ w š, l n 1.5~1.8 cm/yr, n 0.54 g/cm 2 Á n 83.7 ng/cm 2 Á. n f y (diffusion) (resuspension), œ (porewater) mw y w. w 15 cm j» g Table 3. Correlation table for the sediment dataset Parameter T-Hg MeHg LOI Pb Zn Mn T-Hg * * MeHg NC NC LOI 0.408* NC NC Pb NC * Zn 0.372* NC NC Mn NC * *p<0.05, others p<0.01 Vol. 25, No. 6, 2012

6 446 Jin-Ju Park, Ki-Joon Kim, Suk-Min Yoo, Eun-Hee Kim, Kwang-Seol Seok, In-Ah Huh1 and Young-Hee Kim w, 2 cm w z, n œ d w. œ s³ 30 ng/l, p 2.12 ng/l, % p 7.31%. n l y Choe, K (2004) 11 w w, l y n y 1.24 ng/cm 2 Á Lavaca d w ng/cm 2 Á 10 ùkû. 14 ù g ù y e s³ y w», n l y ü p w w ƒ d ƒ v w q. y n, p, wš n w. y n ù w n s³, NOAA» ùkû. p % p» w. û,, e w NOAA» ùkû. n p,» w w ùkü, p m l» p, w.» y y e n» w, y n» w ƒ ƒ v w q. w» w 210 Po. š x R. Friedli, J. Leaner, R. Mason, A. B. Mukherjee, G. B. Stracher, D. G. Streets and K. Telmer, Atmos. Chem. Phys., 10, (2010). 2. UNEP. Global Mercury Assessment. UNEP-Chemicals, Geneva, F. Sprovieri, N. Pirrone, M. S. Landis and R. K. Stevens, Atmos. Environ., 39, (2005). 4. M. Horvat, L. Liang and N. S. Bloom, Anal. Chim. Acta, 282, (1993). 5. US EPA method 1630, Methylmercury in water by distillation, aqueous ethylation, purge and trap, and CVAFS, Kyungpook Regional Environmental Technology Center, The environmental assessment and proper management of downriver district caused by closed and temporarily-closed mines in upriver district of Nakdong River-The research of environmental assessment of mineral-mixed deposits in the riverbed of upriver district, M. Byeon, J. Lee, J. Park, S. Shin, J. Han and Y. Kim. Anal. Sci. Technol., 23(5), (2010). 8. USEPA, SW-846 Method 7473: Mercury in Solids and Solutions by Thermal Decomposition Amalgamation and Atomic Absorption Spectrophotometry, D. N. Edington, J. A. Robbines, Determination of the activity of lead-210 in sediments and soils. In : Lake Michigan Mass Balance Study, Vol 3, Available online at Ministry of Environment, National Survey on mercury bioaccumulation in freshwater fish, Ministry of Environment, Republic of Korea, US NOAA, Sediment Quality Guidelines developed for the National Status and Trends Program, P. R. Mason and A. L. Lawrence, Environ. Toxicol. Chem., 18(11), (1999). 13. P. K. Lee, S. J. Youm, Y. S. Shin, S. J. Chi, J. W. Kim, C. W. Oh and S. O. Kim J. Soil & Groundwater Env., 10(1), (2005). 14. K. Y. Choe, G. A. Gill, R. D. Lehman, S. Han, W. A. Heim and K. H. Coale, Limnol. Oceanogr., 49, (2004). 1. N. Pirrone, S. Cinnirella, X. Feng, R. B. Finklman, H. Analytical Science & Technology