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Korean Journal of Environmental Agriculture Korean J Environ Agric. 2015;34(3):161-167. Korean Online ISSN: 2233-4173 Published online 2015 August 20. http://dx.doi.org/10.5338/kjea.2015.34.3.30 Print ISSN: 1225-3537 Research Article Open Access 폐금속광산하류논토양의중금속에대한인체흡수도평가 김민경, 홍성창, 김명현, 최순군, 이종식, 소규호, 정구복 * 국립농업과학원농업환경부기후변화생태과 Assessment of Human Bioavailability Quotient for the Heavy Metal in Paddy Soils Below Part of the Closed Metalliferous Mine Min-Kyeong Kim, Sung-Chang Hong, Myung-Hyun Kim, Soon-Kun Choi, Jong-Sik Lee, Kyu-Ho So and Goo-Bok Jung * (Climate Change & Agroecology Division, Department of Agricultural Environment, National Academy of Agricultural Science, Wanju 55365, Korea) Received: 20 January 2015 / Revised: 24 June 2015 / Accepted: 12 August 2015 Copyright c 2015 The Korean Society of Environmental Agriculture This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited. Abstract BACKGROUND: For the heavy metal cotamination sites, it is very important to estimate the human bioavailability quotients for heavy metals in paddy soils released from mine tailings, which is a major source of contamination in Korea, and to assess the human health risks of heavy metals. METHODS AND RESULTS: This experiment was carried out to investigate the human bioavailability quotient of the heavy metals in paddy soils below part of the closed metalliferous mine. For estimating the human bioavailability quotients for heavy metals, 30 paddy soils below part of the closed mine were collected, and analyzed for Cd, Cu, Pb, Zn, and As using simple bioavailability extraction test(sbet). The quantities of Cd, Cu, Pb, Zn and As extracted from paddy soils below part of the mine by using the SBET analysis were 28.1, 17.3, 34.1, 14.6 and 2.3% respectively. Specially, the maximum values of Cd, Pb and Zn were 73.3, 81.5 and 58.1% of human bioavailability quotient, respectively, and varied considerably among the sampling sites. The human bioavailability quotient of Cd, Cu, Pb and Zn in soils near the closed mine showed significant positive correlation among soil ph value, O.M. *Corresponding author: Goo-Bok Jung Phone: +82-63-238-2500; Fax: +82 63-238-3823; E-mail: gbjung@korea.kr and Ex. Ca. contents, while it correlated negatively between soil Ex. K and Ex. Mg contents in paddy soils. Also, its of Cd, Cu, Pb and Zn in paddy soils showed significant positive correlation with 0.1M HCl extractable and total contents, while in soils, it correlated negatively with As content in soil near the closed mine. CONCLUSION: The results of the simple bioavailability extraction test (SBET) indicate that regular ingestion of soils by the local population could be closed a potential health threat due to long-term heavy metals exposure in these mine areas. Key words: Bioavailability, Closed metalliferous mine, Heavy metal, Paddy soil, SBET 서론 우리나라의금속광산은 1980년대이후품위저하와채산성악화로인하여대부분폐광된상태로 1,000여개이상이전국에산재되어있는것으로알려져있다 (Jung et al., 2004; Jung et al., 2008). 금속광산은지하에있는광석을채굴하여선광 제련과정후남은광산폐기물및품질이낮은광석을광산주변에야적함으로써 2차환경오염의원인이된다. 환경부의토양환경보전법이 1995년에제정되면서폐금속광산주변에대한토양, 수질환경조사와더불어실질적인복원 161

162 Kim et al. Fig. 1. Study area and sampling locations of the closed metalliferous mine. 대책이실시되었다고볼수있다. 그럼에도불구하고, 폐광후적절한광해방지시설이없는지역에서는광산폐기물침출수및갱내수가발생하여하류수계와토양오염의원인이된다 (Lee and Chon, 2004; Jung et al., 2004; Lee et al., 2005). 또한폐광산주변토양의중금속오염정도와환경위해성은광산유형, 선광방법에의해좌우되는광미의오염특성, 주변의지형 지질 수리학적특성, 그리고토양의이화학적특성과관련성이높은것으로알려져있다 (Jung et al., 2004; Jung et al., 2008; Jung et al., 2012). 최근에는토양중금속의오염지수, 부화계수및지화학적농축계수를활용한상대적인오염상태해석과더불어토양내독성중금속들의인체위해성연구도활발하게진행되고있다.(Ruby et al., 1996; Lee et al., 2006; Ettler et al., 2012; Jung et al., 2012). 이러한상대적인지수값들은중금속오염의동 식물의영향, 독성및오염등급을간접적으로설명하는데유용한자료가될수있다. 본연구에서는중금속오염토양의인체위해성을살펴보기위해서충남서산에위치한 Pb Zn 폐광산하류의논토양 30 지점을대상으로 SBET(Simple Bioavailability Extraction Test) 분석을실시하여지역주민들의위에서흡수되는중금속의인체흡수도 (Bioavailability) 를평가하였다. 또한토양중금속의인체흡수도에영향을주는요인을밝히기위하여토양의화학성및중금속함량과의관련성을분석 검토하였다. 재료및방법 연구지역연구대상은일제시대부터개발된광산지역으로충남서산시지곡면에위치하며, 폐광된시기는알려지지않고있다. 주요광종은납, 아연, 금, 은으로광산일대의지질은선캄브리아기의백운모편암과이에협재하는결정질석회암으로구 성된다 (Hwang et al., 2000). 광상은석회암내의판상으로저온내지중온성열수교대와맥상광상으로채광량은납 4,199톤, 아연 2,209톤으로알려져있다. 과거에는주변의광산폐기물이 10,000m3정도있었으나현재는복원사업이완료된상태이다. 토양의대표적인광물조성은철백운석, 능철석, 석영, 운모, 카오린군의점토광물및미량의녹니석과각섬석등이나타났다. 폐석의연마편을관찰한결과, 함연 아연광물인방연석과섬아연석이주로괴상으로산출되는것으로알려져있다 (Hwang et al., 2000) 시료채취및분석방법연구대상지역주변의광산폐기물은 2개소 [WRD(Waste rock dumps)-1, WRD-2] 에적치되어있으며, 토양시료채취는 2006년 3월에 Fig. 1과같이 3개지역으로구분하여채취하였다. 채취지역은광산으로부터직접영향을받고광산폐기물이위치한 A지역, 그리고침출수에의한영향으로볼수있는중간 B지역과광미장반대편에위치한 C지역으로구분하였다. 시료채취점수는총 30지점으로 A지역에서 15지점 ( 시료 1~15), B지역에서 8지점 ( 시료 16~23), C지점에서 6 지점 ( 시료 24~28) 을채취하고, 대조토양으로 2개지점 ( 시료 29~30) 을채취하였다. 토양시료채취는분석에대한신뢰성을높이기위하여유기물을거른후표토 (0~20 cm) 5개지점을핸드오거드릴을이용하여채취한후혼합하여분석용시료로사용하였다. 토양시료는자연건조후전기오븐 (105 o C) 에서하루이상건조시킨다음 2 mm 입도로체질하여 1차로통과시켜화학성분분석용시료로사용하였다, 또한중금속분석용시료는다시마노유발을이용하여 150 mesh 이하로분쇄하여사용하였다 (Ministry of Environment, 2010). 토양의화학성분함량은농촌진흥청토양화학분석법 (Rural Development Adminstration-National Academy of Agricultural Science, 2010) 에준하여토양 ph는토양

Assessment of Human Bioavailability Quotient for the Heavy Metal in Paddy Soils 163 Table 1. Chemical properties in paddy soils below part of the closed metalliferous mine. Parameters ph Organic Matter Av.P 2O 5 Ex.Cations (Cmol + /kg) (1:5) (g/kg) (mg/kg) K Ca Mg Mean 6.40 18.3 43.3 1.23 6.55 3.95 Min. 5.20 2.2 8.5 0.50 3.50 1.64 Max. 7.69 35.8 481.6 2.04 10.42 6.67 Optimum 1) 6.0~6.5 25~30 80~120 0.25~0.30 5.0~6.0 1.5~2.0 Soils 2) 5.90 26.0 131.0 0.30 5.10 1.30 1) The optimum level of soil chemical properties in paddy soils(rural Development Adminstration-National Academy of Agricultural Science, 2011). 2) The chemical properties of paddy soils in korea(rural Development Adminstration-National Academy of Agricultural Science, 2011). Table 2. Average contents of 0.1M HCl extractable and total heavy metal in soils below part of the closed metalliferous mine. Analytical methods 0.1M HCl extractable Total content 1) 1M HCl extractable Contents of heavy metal in soil(mg/kg) Cd Cu Pb Zn As 1) 3.65 (0.08~19.07) 8.88 (2.97~32.48) 12.7 (2.4~49.5) 56.7 (14.3~123.2) 330 (7~2,848) 809 (33~4,453) 157 (5~160) 754 (67~3,208) 2.08 (0.50~13.58) 37.9 (6.6~123.1) 과증류수의비를 1:5로하여 30분간진탕한후 ph-meter (ORION R, EA-940, USA) 로측정하였다. 또한유기물은 Tyurin 법, 유효인산은 Lancaster 법, 치환성양이온은 1N-NH 4OAc (ph 7.0) 침출법으로분석하였다. 토양의중금속가용성함량은환경부의구토양오염공정시험법에준하여토양시료 10g을취하여 0.1M-HCl 용액 50 ml (As의경우 1M-HCl) 를가한다음 30 o C에서 1시간진탕한후여과하여분석용시료로사용하였다. 또한토양내중금속전함량분석은마이크로웨이브전처리장비 (Mars-X, CEM Corporation, USA) 를이용하여시료 0.5 g을마이크로웨이브 vessel에취하여분해액인왕수 (HNO 3:HCl=1:3) 12 ml를각각가한다음분해하여분석용시료로사용하였다 (Ministry of Environment, 2010; US-EPA, 1997). 본연구에서전처리된토양의화학성분및중금속분석은 ICP-OES (Inductively coupled plasma optical emission spectrometry, GBC Integra-XMP, Australia) 및 ICP-MS(Inductively coupled plasma mass spectrometry, Hewlett Packard, Agilent 7500cs, USA) 를이용하여정량하였다. Table 1과 Table 2는토양중금속별인체흡수도에영향을주는요인을평가하기위하여분석한화학성분및중금속함량을나타낸것이다. 토양의화학성분 (Table 1) 은우리나라논토양의평균치인 ph 5.9, OM 26.0 g/kg, Av.P 2O 5 131 mg/kg, Ex.K 0.3, Ex.Ca 5.1, Ex.Mg 1.3 Cmol + /kg (RDA-NAAS, 2011) 과비교하여 ph 값및양이온함량이높았으며, 유기물과유효인산함량은낮은경향을보였다. 또 한, 화학성분중 ph 값및치환성칼슘함량최고치가각각 7.69, 10.42 Cmol + /kg로매우높게나타났다. 토양중의 0.1M HCl 침출성 Cd, Cu, Pb, Zn 및 As 함량 (Table 2) 은각각 3.65, 12.7, 330, 157, 2.08 mg/kg이였으며, 시료채취지점간농도편차가큰것을알수있었다. 또한, 토양내 Cd, Pb, Zn 및 As 전함량평균치는토양환경보전법 (Ministry of Environment, 2013) 의토양오염우려기준 (Cd 4, Cu 150, Pb 200, Zn 300, As 25 mg/kg) 을초과하였다. 토양중금속의인체흡수도평가폐금속광산지역에거주하는주민들의위 (stomach) 에서흡수되는독성중금속들의인체흡수도를정량적으로평가하기위하여 SBET (Simple Bioavailability Extraction Test) 분석을실시하였다. 이분석방법은 Ruby et al. (1993, 1996, 1999) 에의해제시되고발달된 PBET (Physiologically Based Extraction Test) 분석방법을영국지질조사소에서단순화하여개발한것으로본연구에서이용한구체적인분석절차는다음과같다. 1 인공위산 (synthetic stomach solution) 을제작하기위하여글리신 (glycine) 60.06 g에증류수를넣어 2 L의추출용액을만든다. 2 제작된인공위산은인체의위의 ph와맞추기위해 37 o C로유지되고있는수조안에서염산 (HCl) 를사용하여 ph를 1.5에맞춘다. 3 HDPE (High density polyethylene) 시료용기에 80 mesh로체질한토양시료 1.0 g과 ph 1.5로맞춘인공위산, 즉추출용액 100 ml 을넣는다. 4 HDPE 시료용기의뚜껑은새지않게꼭닫은

164 Kim et al. Table 3. Human bioavailability quotient of heavy metals by SBET(simple bioavailability extraction test) analysis in paddy soils below part of the closed metalliferous mine. Basic statistics Cd Cu Pb Zn As -------------------------------- Extracted concentration by the SBET 2) analysis (mg/kg) -------------------------------- Mean 3.87 11.6 385 233 0.58 Min. 0.06 1.6 5 3 0.02 Max. 19.68 36.8 2,328 1,857 2.23 S.D. 1) 5.74 11.1 608 483 0.50 ---------------------------------------- Bioavailability 3) of heavy metals in soils (%) ---------------------------------------- Mean 28.1 17.3 34.1 14.6 2.3 Min. 2.0 6.9 10.2 2.7 0.1 Max. 73.3 38.3 81.5 58.1 9.0 S.D. 24.6 8.1 19.9 15.4 1.7 1) Standard diviation, 2) SBET; simple bioavailability extraction test. 3) Percentage ratio of SBET extractable against total content of heavy metals 후 ( 폐쇄계상태유지 ), 수조내회전반응기에고정시켜서인체의온도와같은 37 o C가유지되는수조안에완전히잠기도록한다. 5 수조내회전반응기는 1시간동안 30 rpm으로회전시켜반응이일어나도록한다. 6 1시간후에시료용기를수조에서꺼내어다시 ph를측정하고, 반응이완료된시료용기로부터분석하기위한용액을주사기로채취하고필터를사용하여분석용시험관으로옮긴다. 7 ICP-OES (Inductively coupled plasma optical emission spectrometry) 기기를이용하여추출된용액으로부터 Cd, Cu, Pb, Zn 및 As 성분을정량하였다. 결과및고찰 토양중금속의인체흡수도평가토양내중금속의인체위해성을평가하기위한방법으로중금속이다량함유된토양을무의식적으로섭취하였을때인체의위 (stomach) 와같은조건하에서토양으로부터용출되는농도를측정, 평가하는실험이개발되어연구되고있다. 본실험에서는 Ruby et al. (1996) 에의해제시된 PBET 방법을단순화한 SBET 분석법을적용하여광산지역에거주하는주민들이무의식적으로토양을섭취하였을때독성중금속들이인체에미칠수있는위해성을간접적으로평가하고자하였다. 강산성환경조건인인체의위 (stomach) 에서는토양내독성중금속들은빠르게용출되면서인체로흡수 축적되어건강상의문제점을야기시킬수있다. 토양중금속의인체흡수도 (Human bioavailability quotient) 는토양내중금속총함량에대한인공위산용액 (SBET) 으로추출된중금속함량의비를백분율 (%) 로환산하여산출하였다. 서성폐금속광산하류논토양에대한중금속의 SBET 분석결과및인체흡수도는 Table 3과같다. SBET 인공위산에서 1시간반응하여추출된중금속평균함량은 Table 2의 0.1M HCl 가용성함량과비교하면 Pb, Zn 성분이높았으나 Cd 및 Cu 성분은유사한경향이였다. 토양중금속의인체흡수도평균값은 Pb>Cd>Cu>Zn>As 순으로각각 34.1, 28.1, 17.3, 14.6 및 2.3% 로나타났다. 또한인체흡수도최고치도 Pb 81.5%, Cd 73.3%, Zn 58.1% 로매우높아인체에흡수가능성이매우크다고할수있다. 이와관련하여토양내중금속인체흡수도는폐광산주변논토양이 Cu>As> Pb>Zn>Cd, 밭토양 Cu>Pb>Zn>Cd>As(Lee and Chon, 2004), 도시공원토양이 Cd>Cu>Pb>Zn>Ni(Luo et al., 2012a), 도시도로변토양이 Pb>Ni>Cu>As(Wang et al., 2002) 순위로보고하여오염원및중금속종류에따라큰편차를보이는것을알수있었다 (Ettler et al., 2012; Kim et al., 2002). 또한 Lee et al. (2000) 은폐금속광산주변 Cd, Cu, Pb, Zn 및 As의인체흡수도가논토양 15.9~65.4% 로나타나밭토양 12.4~31.2% 와비교하여상대적으로높았다고하였다. Fig. 2은서성광산하류에위치한논토양의채취지점별중금속인체흡수도변화를나타낸것이다. 채취지역별중금속의인체흡수도평균값은대체적으로 A>C>B> 대조지역순으로나타나오염지역에따라큰차이를보였다. 또한동일한지역에서도오염정도가심한 Cd, Pb, Zn 성분은채취지점별로편차가큰것을알수있었다. 특히 Cd의인체흡수도값이 A지역 41.8%, C지역 26.7% 와비교하여 B지역이 9.6% 로상대적으로매우낮았는데, 이는 B지역에서 Cd 오염도가낮은데기인한다고볼수있다. 이와관련하여여러보고 (Lee and Chon, 2004; Kim et al., 2006; Lee et al., 2006) 에서폐광산종류와광미, 논, 밭등오염대상에따라토양중금속의인체흡수도는큰차이를보였다고하였다. 또한 Wang et al. (2007) 은토양중금속별인체흡수도는폐광산, 제련소, 도로변등오염원별, 그리고채취지역과지점에따라편차가크다고하였다 (Ettler et al., 2011). 이러한중금속오염의편차

Assessment of Human Bioavailability Quotient for the Heavy Metal in Paddy Soils 165 Fig. 2. Variations of human bioavailability quotient for heavy metals determined by the SBET(simple bioavailability extraction test) method at sampling site in paddy soils near the closed mine. Table 4. The relationship between the chemical properties and human bioavailability quotient of heavy metal in paddy soils below part of the closed mine (n=30). Chemical Bioavailability of heavy metal in soil characteristics Cd Cu Pb Zn As ph (1:5) 0.526 ** 0.488 ** 0.375 * 0.677 *** NS Organic Matter (g/kg) 0.584 *** 0.542 ** 0.535 ** 0.510 ** -0.435 * Av.P 2O 5 (mg/kg) NS NS NS NS NS Ex.K (Cmol + /kg) -0.515 ** -0.591 *** -0.453 ** -0.359 * 0.501 ** Ex.Ca (Cmol + /kg) 0.663 *** 0.578 *** 0.531 ** 0.703 *** NS Ex.Mg (Cmol + /kg) -0.529 ** -0.598 *** -0.460 ** -0.370 * 0.514 ** *, **, *** Significant at P=0.05, 0.01, 0.001 respectively, NS : Not significant. 는광산및제련소별광물종류등이다르고, 오염원에서거리별로오염정도가크게차이를보인데기인한다 (Jung et al., 2004). 중금속인체흡수도와관련영향인자분석 Table 4는서성폐금속광산하류논토양의화학성분과 SBET 분석에의한중금속별인체흡수도와의관계를나타낸것이다. 토양중 Cd, Cu, Pb 및 Zn의인체흡수도는 ph 값, 유기물, 치환성칼슘함량과정의상관을, 치환성칼륨및마그네슘과는부의상관을보였다. 또한토양 As의인체흡수도는유기물과부의상관, 치환성칼륨및마그네슘과는정의상관을보였다. 이와관련하여 Poggio et al. (2009) 은토양중 Cu, Pb 및 Zn의인체흡수도는유기물함량과고도의정의상관을 (r=0.69~0.99), 점토함량과는고도의부의상관 (r=-0.73~-0.96) 을보였다고하였다. 또한기존의연구 (Lee et al., 2005; Luo et al., 2012a,b) 에서토양중금속별인체흡수도는토성 ( 입경분포 ) 뿐만아니라토양 ph, EC 및유기물함량과의관련성이크다고하였다. 이러한경향치는일반적으로토양내이화학성이중금속의유효태함량비율과더불어 식물흡수도에크게영향을주는것과같은결과로볼수있다. Table 5는토양의중금속함량 (0.1M HCl 침출성, 전함량 ) 과중금속별인체흡수도와의관계를나타낸것이다. 토양내 Cd, Cu, Pb 및 Zn의인체흡수도는 0.1M HCl 침출성, 그리고총함량과정의상관을, As성분은부의상관을보였다. 특히 Zn의인체흡수도는상관계수가 0.1M HCl 침출성함량 (r=0.967) 및전함량 (r=0.917) 에서다른성분보다높게나타났다. 이와관련하여 Ettler et al. (2012) 은광산및제련소지역의토양내 Cu, Pb, Zn, As 인체흡수도는중금속별총함량과고도의정의상관을보였고, 오염원이상이한여러보고 (Wang et al., 2007; Poggio et al., 2009; Prathumratana et al., 2010; Luo et al., 2012b) 에서도토양내중금속별인체흡수도는총함량, 즉각중금속의오염정도에영향을받는다고하였다. 본연구결과에서토양중 Cd, Pb, Cu, Zn 및 As의인체흡수도는각각 28.1, 34.1, 17.3, 14.6, 2.3% 였고, 특히 Cd, Pb 및 Zn의인체흡수도최고값은각각 73.3, 81.5, 58.1% 로매우높게나타났다. 따라서폐광산하류논토양의 SBET 분석에의한중금속인체흡수도를볼때광산지역에거주하는

166 Kim et al. Table 5. The relationship between the heavy metal contents and human bioavailability quotient of heavy metal in paddy soils below part at closed mine (n=30). Heavy metal contents 0.1M HCl extractable Total content Bioavailability of heavy metal in soil Cd bio Cu bio Pb bio Zn bio As bio Cd 0.817 *** 0.776 *** 0.703 *** 0.905 *** -0.437 * Cu 0.678 *** 0.613 *** 0.613 *** 0.552 ** -0.499 ** Pb 0.469 ** NS 0.415 * NS -0.392 * Zn 0.753 *** 0.742 *** 0.698 *** 0.967 *** -0.393 * As 0.701 *** 0.581 *** 0.559 *** 0.789 *** -0.328 Cd 0.758 *** 0.770 *** 0.708 *** 0.937 *** -0.430 * Cu 0.784 *** 0.696 *** 0.697 *** 0.698 *** -0.539 ** Pb 0.661 *** 0.508 ** 0.535 ** 0.526 ** -0.488 ** Zn 0.819 *** 0.774 *** 0.705 *** 0.917 *** -0.455 ** As 0.797 *** 0.757 *** 0.679 *** 0.874 *** -0.477 ** *, **, *** Significant at P = 0.05, 0.01, 0.001 respectively, NS : Not significant. 주민들이장기간노출된다면잠재적으로건강상의위해성이있을것으로판단된다. National Academy of Agricultural Science, Rural Development Administration, Republic of Korea. 요약 폐금속광산하류토양의중금속인체위해성을평가하기위하여 Pb Zn 폐광산하류논토양 30점을대상으로 SBET (Simple Bioavailability Extraction Test) 분석하여중금속의인체흡수도 (Human bioavailability quotient) 를평가한결과는다음과같다. 토양중 Cd, Cu, Pb, Zn 및 As의인체흡수도는각각 28.1, 17.3, 34.1, 14.6 및 2.3% 로나타났다. 특히토양중 Cd, Pb 및 Zn의인체흡수도최고치는 73.3, 81.5 및 58.1% 로매우높았고, 채취지역및지점간의편차가크게나타났다. 토양중 Cd, Cu, Pb 및 Zn의인체흡수도는 ph 값, 유기물, 치환성칼슘함량과정의상관을, 치환성칼륨및마그네슘과는부의상관을보였다. 또한토양내 As의인체흡수도는유기물과부의상관, 치환성칼륨및마그네슘과는정의상관을보였다. 토양내 Cd, Cu, Pb 및 Zn의인체흡수도는 0.1M HCl 침출성, 그리고총함량과정의상관을, As성분과는부의상관을보였다. 특히 Zn의인체흡수도는상관계수가 0.1M HCl 침출성함량 (r=0.967) 및전함량 (r=0.917) 에서다른성분보다높게나타났다. 이상의결과에서폐광산하류토양의중금속인체흡수도를볼때광산지역에서거주하는주민들에게장기간노출된다면건강상의잠재적인위해성이있을것으로판단되었다. Acknowledgement This study was carried out with the support of Research Program for Agricultural Science & Technology Development (Project No. PJ010063), References Ettler, V., Kříbek, B., Majer, V., Knésl, I., & Mihaljevič, M. (2012). Differences in the bioaccessibility of metals/ metalloids in soils from mining and smelting areas (Copperbelt, Zambia). Journal of Geochemical Exploration, 113, 68-75. Hwang, E. H., Wee, S. M., Lee, P. K., & Choi, S. H. (2000). A study on the heavy metal contamination of paddy soil in the vicinity of the Seosung Pb-Zn mine. Korean Society of Soil and Groundwater Environment, 5(2), 67-85. Kim, J. Y., Kim, K. W., Lee, J. U., Lee, J. S., & Cook, J. (2002). Assessment of As and heavy metal contamination in the vicinity of Duckum Au-Ag mine, Korea. Environmental Geochemistry and Health, 24(3), 213-225. Jung, G. B., Kwon, S. I., Hong, S. C., Kim, M. K., Chae, M. J., Kim, W. I., Lee, J. S., & Kang, K. K. (2012). Contamination assessment of water quality and stream sediments affected by mine drainage in the Sambo mine creek. Korean Journal of Environmental Agriculture, 31(2), 122-128. Jung, G. B., Lee, J. S., Kim, W. I., Ryu, J. S., & Yun, S. G. (2008). Monitoring of seasonal water quality variations and environmental contamination in the sambo mine creek, Korea. Korean Journal of Environmental Agriculture, 27(4), 328-336. Jung, M. C., Jung, M. Y., & Choi, Y. W. (2004).

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