세창 폐금속광산 수계에서 미량원소의 지구화학적 거동특성 규명 = Characteristics of Geochemical Behaviors of Trace Metals in Drainage from Abandoned Sechang Mine

국문 초록 (Abstract)

자연저감의 메커니즘을 설명하기 위하여 납과 비소 함량이 높은 세창광산 지역의 광산배수, 침출수 및 지표수의 지구화학적 변화를 연구하였다. 주요 오염원인 폐광석에서 미량원소의 분산 및 물리화학적인 조건의 변화에 따른 미량원소의 이동도를 평가하기 위하여 총함량 분석 및 연속추출을 수행하였다. 이러한 광산배수, 침출수 및 지표수의 화학성분은 시료채취의 위치 및 시기별로 변화가 컸으며, 특히 pH가 매우 낮고(pH 2.1-3.3), 황산염(최대 661mg/l) 및 미량원소의 함량(최대 169mg/l Zn, 27mg/l As, 3.97mg/l Pb, 2.99mg/l Cu and 1.88mg/l Cd)이 매우 높은 경우가 관찰되었다. 그러나 지표수에서의 비소와 미량원소의 함량은 특별한 처리를 하지 않아도 광산배수와 침출수가 배출되는 지점으로부터 가까운 거리인 지류와 합류되는 지점(8번, 16번)에서 자연배경값과 거의 유사한 함량으로 낮아졌다. 철-황화광물의 산화작용과 가수분해에 따른 비정질 철-2차광물의 침전작용은 하천으로 유입되는 미량원소의 이동을 크게 감소시켜주는 효과적인 자연저감 메커니즘이었다. 또한 오염되지 않은 지표수와의 합류에 의한 희석효과도 미량원소의 함량을 감소시키고 점진적으로 pH를 증가시켰다. 한편, 가장 용해성이 높은 원소인 아연은 pH가 거의 중성에 가까워질 때까지 상당량이 용해된 용질상태로 남아있었다. 환경독성학적인 관점으로 볼 때, 세창광산 지역에서는 아연에 의한 오염에 특별한 관심을 가져야 한다. 이러한 것은 수분을 함유한 폐광석에서 아연의 대부분이 양이 온교환형(전체 함량의 65-89%)으로 존재하고, 납은 전체함량의 65-89%가 산화광물 및 탄산염광물형태와 수반되었으며, 카드뮴, 구리 및 비소는 잔류형태가 우세한 것으로 나타난 연속추출실험 결과에 의해서도 확인되었다. 건조상태의 폐광석에서는 전체 납 함량의 34-48%가 쉽게 용출될 수 있는 양이온교환형태로 존재하였다. 양이온교환 및 탄산염광물 수반된 금속의 비율을 고려하면 각 미량원소의 상대적인 이동도는 Zn>Pb>Cd>As=Cu의 순서로 감소하는 것으로 판단된다.

다국어 초록 (Multilingual Abstract)

The geochemical evolution of mine drainage and leachate from waste rock dumps and stream water in Pb-As-rich abandoned Sechang mine area was investigated to elucidate mechanisms of trace metals. Total and sequential extractions were applied to estimate the distribution of trace metals in constituent phases of the waste rocks and to assess the mobility of trace metals according to physicochemical conditions. These discharged waters varied largely in chemical composition both spatially and temporally, and included cases with significant]y low pH (in the range 2.1-3.3), and extremely sulphate (up to 661 mg/l and metal contents (e.g. up to 169 mg/l for Zn, 27 mg/l for As, 3.97 mg/l for Pb, 2.99 mg/l for Cu, and 1.88 mg/l for Cd). Arsenic and heavy metal concentrations at the down-stream of Sechang mine have been decreased nearly to the background level in downstream sites (sites 8 and 16) without any artificial treatments. The oxidation of Fe-sulfides and the subsequent hydrolysis, of Fe(II), with precipitation of poorly crystallized minerals, constituted an efficient mechanism of natural attenuation which reduces considerably the transference of trace metals (i.e. Fe and As) to rivers. The dilution of drainage by mixing with pristine waters provoked an additional decrease of trace metal concentrations and a progressive pH increase. On the other hand, the most soluble cations (i.e. Zn) remained significantly as dissolved solutes until the pH was raised to approximately neutral values. With respect to ecotoxicity, it is likely that the Zn pollution is of particular concern in Sechang mine area. This was confirmed by the sequential extraction experiment, where Zn in wet waste-rock samples occurred predominantly in the exchangeable fraction (65-89% of total), while Pb was the highest in the reducible and carbonate fractions, and Cd, Cu and As in the residual fraction. Pb concentration in the readily available exchangeable fraction (34-48% of total) was dominated for dried waste rock samples. Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreased in the order of Zn>Pb>Cd>As=Cu.

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