서울시 도로변의 빗물받이에서 채취한 하수슬러지의 중금속 오염 평가

이평구,윤성택,최상훈,최병영 대한자원환경지질학회 1999 자원환경지질 Vol.32 No.6

Gully pot is a part of urban darainage system to butter the runoff water fluxes from road to rivers and to minimize environmental pollution by prevending over the surrounding area. A series of studies have been carried out concerning the physicochemical characteristics of the sewage sludge sediments sttling down in such a gully pot in order to over to evaluate the contamination for heavy metals such as pb, Zn, Cu and Cd. The roadside soil and sewage sludge samples from gully pots were characterized by XRD analyses and sequential extraction : Zn 2595.7μg/g; Cd9.8μ/g; Cu602.5μg/g; Pb260.0μg/g),because of a long-term accumulation of vehicle- and industrial-related pollutants. Mean Zn concentration in Yeouido (3873μg/g) and Junggu(3262μg/g)areas are 4-5 times higher than those in Dobonggu area, suggesting that Zn may be derived from automobile traffic (including the rubber of automobile tires). The mean concentrations of Cu and Cr are very significantly high in Junggu and Gurogu areas, possibly due to the industrial activities in these areas. The low Pb levels throughtotut the whole study areas in Seoul can be accounted for the use of unleaded gasoline since 1987. Sequential extraction experiments illustrate that a major part of Zn is bound to FII and FIII, representing about 88% of the total Zn concentration. Fraction IV, related to orgnic matter, is mostly significant for Cu accounting for 60% of the total Cu, and FII is next in importance. The main carriers of Pb are the fractions III, II and FIV, and in that order. The behavior of Cd is quite different from other elements (Zn, Cu, Pb), and most of the Cd is associated with FV. Changes in the physicochemical environments (such as acidification) may result in severe environmental pollution of surface water and rivers with respect to heavy metals (especially Zn and Cu).

주암호 집수유역 내 용존 및 입자상 미량원소의 거동 특성

이평구,지세정,염승준,Lee, Pyeong-Koo,Chi, Se-Jung,Youm, Seung-Jun 대한자원환경지질학회 2008 자원환경지질 Vol.41 No.4

하천수와 하천퇴적물에 의한 주암호 내 미량원소의 유입량 및 하천퇴적물 입도에 따른 미량원소의 지구화학적 거동을 규명하기 위하여 주암호 주변의 3 4차 수계 32 지점에서 채취한 하천퇴적물과 하천수의 미량원소(비소, 카드뮴, 크롬, 구리, 니켈, 납, 아연)를 분석하였고, 하천수의 경우에는 주요 양이온 및 음이온을 함께 분석하였다. 또한 집수 유역 내 모암 및 오염원 분포를 고려하여, 대표적인 8개 지점의 하천퇴적물을 선택하고, 입도($2\;mm{\sim}200\;{\mu}m$, $200{\sim}100\;{\mu}m$, $100{\sim}50\;{\mu}m$, $50{\sim}20\;{\mu}m$, < $20\;{\mu}m$) 별로 미량원소 함량을 구하였다. 주암호 집수유역 하천수는 오염원(탄광, 금속광, 농경지, 주거) 별로 4개 유형의 수질유형(Ca-Mg-$HCO_3$, Ca-Na-$HCO_3$-Cl, Ca-Na-$HCO_3-SO_4$, Ca-Na-$HCO_3$)의 특성을 반영하고 있다. 하천퇴적물의 입도와 미량원소 농도와의 상관성은 주암호으로 유입되는 미량원소의 지화학적 거동을 규명하는데 중요하다. 하상퇴적물의 입도가 작아질수록 미량원소 함량이 증가되는 뚜렷한 경향을 나타내고 있다. 폐금속광산 하류 하천퇴적물의 구리, 아연 및 납은 실트 입도(< $20\;{\mu}m$)에서 급격하게 증가되는 경향을 보이는 반면, 비소의 경우는 모래 입도($2\;mm{\sim}100\;{\mu}m$)에서 높은 함량을 나타내고 있다. 이는 퇴적물내의 구리, 아연, 납, 등 미량원소들은 실트 크기의 입자에 흡착된 상태고 주암호로 쉽게 이동됨을 지시해주고 있는 반면, 비소는 함 비소 광물상으로 이동되어 주암호로 유입될 가능성이 미약한 것으로 판단된다. In order to investigate the amounts of trace elements flowing into reservoir, and to elucidate the relationship between trace element mobility and fraction size, the stream water and sediment samples were collected from thirty-two sites of the 3rd or 4th order stream within watershed surrounding the Juam reservoir. Chemical analyses of trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) for all samples were completed, and additionally cationi and anion for stream water samples. Considering the distribution of rocks and contamination sources in watershed, the eight stream sediments were selected from typical sites representing study areas, and we determined the concentrations of trace elements according to size fractions ($2\;mm{\sim}200\;{\mu}m$, $200{\sim}100\;{\mu}m$, $100{\sim}50\;{\mu}m$, $50{\sim}20\;{\mu}m$ and < $20\;{\mu}m$). The correlation relationships between concentrations and size fractions of stream sediments were important to identify the hydro-geochemical behavior of trace elements that flow into Juam reservoir. Stream waters showed four water types (Ca-Mg-$HCO_3$, Ca-Na-$HCO_3$-Cl, Ca-Na-$HCO_3-SO_4$, Ca-Na-$HCO_3$) depending on pollution sources such as coal mine, metal mine, farm-land and dwellings. Concentrations of trace elements increased clearly with the decrease in size fractions of stream sediments. Concentrations of Cu, Pb and Zn increased dramatically in silt size (< $20\;{\mu}m$) fraction, while As had high concentrations in sand size ($2\;mm{\sim}100\;{\mu}m$) fraction in downstream sediments of metal mines. These indicate that Cu, Zn, and Pb moved into Juam reservoir easily in the adsorbed form on silt size grain in sediments, and As was transported as As-bearing mineral facies, resulting in its less chance to reach into Juam reservoir.

우수관퇴적물에 함유된 탄산염광물이 산성환경에서 중금속 용출거동에 미치는 영향 평가

이평구,유연희 대한자원환경지질학회 2002 자원환경지질 Vol.35 No.3

만장광산에서 산출되는 황동석의 산화과정과 중금속 거동 특성

이평구,이인경,최상훈,김지수 대한자원환경지질학회 2004 자원환경지질 Vol.37 No.3

만장광산 폐광석 내의 황동석 풍화과정과 용해된 금속이온의 거동을 밝히고자 광물학적 연구를 수행하였다. 광물학적 연구는 반사현미경 관찰, XRD 분석, SEM/EDS 분석을 실시하였다. 현미경 관찰 결과 황동석의 풍화는 주로 입자내의 균열부와 입자 가장자리를 따라 진행되고 있으며, 풍화정도에 따라 4단계로 구분할 수 있었다. 2차 광물에 대한 광물학적 연구결과 침철석, 코벨라이트, 구리탄산염광물(남동석, 공작석), 브로칸타이트 등이 인지되었다. 철수산화광물은 구리와 비소를 흡착하고 있으며, 흡착된 비소의 함량은 결정도가 낮은 경우 상대적으로 높았다. 산화환경에서 황동석의 풍화작용은 입자 내부의 균열부에서 우세하였으나, 코벨라이트와 브로칸타이트로의 치환반응은 입자내부에서 우세하였다. 황화광물의 풍화로 용해된 금속이온(구리, 철, 비소)은 철수산화광물에 흡착, 혹은 구리탄산염광물로 침전 등을 통해 자연적으로 고정화되어지고 있음이 확인된다. In order to charaterize weathering of chalcopyrite and behavior of dissolved metal ions in waste rocks from Manjang Cu mine, mineralogical studies such as refractive microscope, XRD and SEM/EDS analyses carried out. The weathering was mainly occurred in fractures and edge of the chalcopyrite within the mine waste rocks. The weathering process can be seen to reflect four stages based on the weathering degree of chalcopyrite. The main secondary minerals are goethite, covellite, azurite, malachite and brochantite. Dissolved Cu and As were mainly adsorbed Fe-hydroxide. Poorly crystalline Fe-oxide contains relatively high As contents. In oxdizing condition, the weathering of chalcopyrite mainly occurs along the fracture, while the replacement of chalcopyrite observed mainly in the grain and produced covellite and brochantite. The dissolved metals (Cu, Fe, As) in waste rocks from the abandoned Manjang mine area could attenuate naturally by precipitation, adsorption and replacement reaction.

공주 금흥매립지의 중간복토재 및 차수재(논토양)의 중금속 오염과 존재형태 연구

이평구,박성원,염승준 대한자원환경지질학회 2001 자원환경지질 Vol.34 No.3

공주시 금흥 생활쓰레기 매립지의 중간 복토재와 차수재에서 채취한 시료에 대해 0.1N HCI 용축, 전함량 분석 및 연속추출분석을 실시하여 As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Ti와 Zn 함량을 ICP-AES로 분석하였다. 또한, 비교를 위해 오염되지 않은 토양과 퇴적물 시료를 분석하였다. 연속추출 결과, Cu는 유기물이 용해되는 단계에서 우세하였으며, As, Ni, Sr, Ba와 Mn은 이온교환단계에서 우세하였다. 대부분의 Zn와 Mn은 산화광물, 탄산염광물 및 규산염광물과 수반되었다. Cd와 Pb는 주로 산화광물과 유기물과 수반되었다. Co, Cr, Fe와 Ti의 주요 운반자는 규산염광물이었으며, 다음으로 중요한 운반자는 산화광물이었다. 중간복토재와 차수재 시료에서 유기물과 수반된 금속의 백분율은 Cu(48%)〉Ti(42%)〉Pb(27%)〉As(25%)〉Cd(20%)의 순이었다. 연속추출결과를 근거로 추정하면, 중간복토재와 차수재에 함유된 금속의 이동도는 다음과 같이 제시되었다. : Cd〉Sr〉Ni〉Mn〉Ba〉Cu〉Pb〉Zn〉〉Co〉Ti〉Fe〉Cr. 'Geoaccmulation index'와 'enrichment factor'에 근거하면, 금흥 매립지와 농경지에서 채취한 시료들은 Cu, Ni과 Cr의 오염수준이 의미가 있었다. 이들 원소의 농집은 오염에 기인하였다. The middle cover soils and clay liners collected from the Kumheung landfill in Gongiu City were analysed for As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Ti and Zn concentrations using 0.] N HCl digestion and total/sequential extraction experiments followed by ICP-AES determination. The uncontaminated soil and sediment samples were also analyzed for the comparison. The results of sequential extraction showed that Cu was dominant in the oxidizable fraction, and As, Ni, Sr, Ba, and Mn were in the exchangeable fraction. Zinc and Mn occurred mostly in association with reducible, residual and carbonate fractions. Most of Cd and Pb were bound to the reducible and oxidizable fractions. The main carrier of Co, Cr, Fe and 11 was the residual fraction and another important carrier was the reducible fraction. The percentage of the metals of organically-bound form in the middle cover soils and clay liner was in the order of Cu(48%) > Ti(42%) > Pb(27%) > As(25%) > Cd(20%). As deduced from sequential extraction analysis, potential order of metal mobility in the middle cover soils and clay liner from the landfill was proposed: Cd > Sr > As > Ni > Mn > Ba > Cu > Pb > Zn » Co > 11 > Fe > Cr. Based on the 'geoaccumulation index' and the 'enrichment factor' normalized to A], the level of contamination of Cu, Ni and C1' was significant in the samples from Kumheung landfill and surrounding farmland. Their enrichments were attributed partly to anthropogenic pollutions.

광미 및 오염된 토양에서 중금속의 존재형태 및 잠재적인 이동도

이평구,강민주,최상훈,신성천 대한자원환경지질학회 2004 자원환경지질 Vol.37 No.1

Tailings and contaminated soils from Cheongyang mine and Seobo mine have been analysed by ICP-AES from 5-step sequential extraction method of multielement determination on extraction solutions at each step. As and Co within tailings and contaminated soils from Cheongyang mine and Seobo mine are mainly in the residual phase. In case of Cd, Cu and Zn, the most dominant fraction for tailings of Cheongyang mine is the oxidizable phase, while tailings of Seobo mine is dominated by the residual phase. In contaminated soils from Seobo mine, the predominant fraction for Cd, Cu and Zn is the Fe-Mn oxide phase. The exchangeable fraction of Pb in tailings from Cheongyang mine and Seobo mine is relatively high compared with those of other metals; whereas Pb fraction in contaminated soils from Seobo mine is largely associated with the residual fraction. 청양광산과 서보광산의 광미와 오염된 토양은 5단계 연속추출법을 실시한 후 추출된 중금속 함량을 ICP-AES로 각 단계별로 분석하였다. 청양광산과 서보광산의 광미와 오염된 토양 내 비소와 코발트는 대부분 잔류형태 단계에서 우세하였다. 카드뮴, 구리 및 아연의 경우, 청양광산의 광미는 산화성 형태가 우세한 반면에, 서보광산의 광미는 잔류형태로 안정하였다. 서보광산의 오염된 토양에 함유된 이들 원소는 산화철망간과 수반되었다. 청양광산과 서보광산의 광미 내 함유된 납은 다른 금속에 비해 이온교환형태로 존재하는 함량이 높아 오염 확산의 우려가 있다. 그러나 서보광산의 오염된 토양은 잔류형태로 존재하여 안정하였다.

도로변 토양의 오염 특성과 Pb, Zn, Cd 및 Mn의 침출거동에 미치는 pH와 반응시간의 영향

이평구 대한자원환경지질학회 1999 자원환경지질 Vol.32 No.1

The possibility of heavy metal pollution by contaminated roadside soils was studied under controlled conditions. The soil samples from roadside and those from a retention pond consisting of settling particles were characterized by the XRD analyses and the sequential extraction experiments. Characterization by sequential extraction, for roadside soil indicates elevate total concentrations of heavy metals. The leaching behavior of the samples under different pH and time conditions were also studied. Differences between both types of samples result mainly from the buffering effect of carbonates, present in roadside soils and lacking from settling particles. Acid leaching of the settling particles is equivalent to the sum of FI+FII+FIII, while the amounts leached from roadside soil are lower probably from kinetic reasons. The buffering effects of carbonates were found to greatly delay the onset of the leaching reactions and the extent of dissolution in most metals except for Ca and Mn. The study of leaching kinetics at pH of 6.5 and 5 showed that Cd and Zn reached the maximum possible concentration within 3 days, while Pb did not show any sign of dissolution at both ph values. The absolute amounts of dissolved Cd and Zn increased by 7 to 9 times by decreasing the pH from 6.5 to 5, indicating slightly acidified rain may result in significant metal dissolution. As deduced from both sequential extraction and leaching experiments, the relative mobility of heavy metals is found to be : Mn=Cd>Zn>>Pb>Fe, in spite of large differences in heavy metal contents and localizations.

제2연화광산 직내골 광미장 침출수에 오염된 하천수계의 시.공간적 수질변화 및 중금속 제거효율

이평구,강민주,최상훈,Lee, Pyeong-Koo,Kang, Min-Ju,Choi, Sang-Hoon 한국지하수토양환경학회 2011 지하수토양환경 Vol.16 No.1

This study had been carried out to investigate spatial and temporal variations of the concentrations of trace metals for contaminated surface water in creek affected by leachate from the tailings impoundment of the Yeonhwa II mine for about 2 years. It was also to ascertain the metal removal efficiency for potentially deleterious metals by the artificial and natural attenuation processes such as retention ponds and hydrologic mixing of uncontaminated tributaries. The concentrations of As, Pb, Cd, and Cu for leachate in the rainy season were not detected. On the other hand, the concentrations of Zn, Fe, Mn, Al, and $SO_4^{2-}$ in the rainy season for leachate were 2-66 times higher than those in the dry season, due to the oxidation of the sulfide minerals and the dissolution of the secondary minerals. The concentrations of Zn and Cd for leachate and surface water of the upper creek in the rainy season exceeded the criteria of River Water Quality and Drinking Water Quality but in the dry season, those of analyzed all the metals (As, Pb, Cd, Cu, Zn, Cd, Fe, Mn, and Al) for surface water sampled at the study area were below the criteria of River Water Quality and Drinking Water Quality. In regard of the attenuation efficiency for the concentrations of metals, Fe, Mn, Al, Zn, Cd, As, and Cu were removed highly at retention ponds, while the removal efficiency for major cations and sulfate ($SO_4^{2-}$) were related to mixing of the uncontaminated tributaries. Therefore, the major attenuation processes of the metal and sulfate contents in creek affected by leachate from a tailing dump were precipitation (accompanied by metal co-precipitation and sorption), water dilution, and neutralization.

부산시 회동저수지 집수분지 내 국도도로변 퇴적물의 미량원소 오염 및 존재형태

이평구,강민주,염승준,이인경,박성원,이욱종,Lee Pyeong-Koo,Kang Min-Joo,Youm Seung-Jun,Lee In-Gyeong,Park Sung-Won,Lee Wook-Jong 한국지하수토양환경학회 2006 지하수토양환경 Vol.11 No.5

이 연구는 부산시 회동저수지의 집수분지 내 7번국도 도로변 퇴적물(70개 시료 미량원소(아연, 구리, 납, 크롬, 니켈 및 카드뮴) 함량에 미치는 인위적인 오염 및 연속추출방법을 이용하여 미량원소의 잠재적인 이동도를 평가하기 위하여 수행되었다. 이번 연구에서는 특히 아연, 구리 및 납의 함량이 높은 것으로 밝혀졌으며, 이들 원소가 인위적인 오염에 의해 영향을 받고 있음을 보여주고 있다. 오염되지 않은 회동저수지 집수유역 내 하천퇴적물의 미량원소 평균함량과 비교하면, 집수유역 내 국도 도로변 퇴적물은 구리가 7배, 아연이 4배, 납과 크롬이 3배, 비소와 니켈이 2배 높은 것으로 나타났다. 연속추출방법에 의한 존재형태 연구결과는 각각 전체 함량의 29.3%와 25.8%가 이온교환형으로 존재하는 카드뮴과 니켈을 제외하면 대부분의 미량원소는 이온교환형태로 존재하는 양이 크게 않음을 지시 하였다. 아연(51%)과 납(45.2%)과 같은 금속은 주로 비정질산화광물과 수반된 형태이었으며, 따라서 pH가 감소하거나 산화환원전위의 변화에 의해 잠재적으로 용해될 수 있다. 구리는 주로 유기물형태로 존재하는 것으로 나타났으며, 카드뮴은 양이온교환형태가 가장 우세하였고 크롬과 니켈은 잔류형태가 우세하였다. 양이온교환형태와 탄산염광물과 수반된 형태의 금속함량 비율을 고려하면, 금속의 상대적인 이동도는 Cd>Ni>Pb>Zn>Cr>Cu의 순서로 감소한다. 총 함량자료로 볼 때 아연 함량이 높아 가장 해로운 원소일 것으로 보일지라도, 금속의 존재형태에 관한 자료는 도로 유출수에 가장 유해한 미량원소는 카드뮴, 니켈 및 납일 것으로 예측되었다. 산화환원전위 및 pH가 변화한다면 탄산염광물, 비정질산화광물 혹은 유기물 등의 형태로 수반된 금속은 재이동할 수 있을 것이며, 용해된 금속이온은 회동저수지 집수분지 내 수계로 유입될 수 있으므로 환경적인 현황에 대한 정밀한 모니터링이 매우 중요한 것으로 보인다. This study was undertaken to assess the anthropogenic impact on trace metal concentrations (Zn, Cu, Pb, Cr, Ni, and Cd) of roadside sediments (N = 70) from No.7 national road within the watershed of Hoidong Reservoir in Pusan City and to estimate the potential mobility of selected metals using sequential extraction. We generally found high concentrations of metals, especially Zn, Cu and Pb, affected by anthropogenic inputs. Compared to the trace metal concentrations of uncontaminated stream sediments, arithmetic mean concentrations of roadside sediments were about 7 times higher for Cu, 4 times higher for Zn, 3 times higher for Pb and Cr and, 2 times higher for Ni and As. Speciation data on the basis of sequential extraction indicate that most of the trace metals considered do not occur in significant quantities in the exchangeable fraction, except for Cd and Ni whose exchangeable fractions are appreciable (average 29.3 and 25.8%, respectively). Other metals such as Zn (51.4%) and Pb (45.2%) are preferentially bound to the reducible fraction, and therefore they can be potentially released by a pH decrease and/or redox change. Copper is mainly found in the organic fraction, while Cd is highest in the exchangeable fraction, and Cr and Ni in the residual fraction. Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Cd>Ni>Pb>Zn>Cr>Cu. Although the total concentration data showed that Zn was typically present in potentially harmful concentration levels, the data on metal partitioning indicated that Cd, Ni and Pb pose the highest potential hazard for runoff water. As potential changes of redox state and pH may remobilize the metals bound to carbonates, amorphous oxides, and/or organic matter, and may release and flush them through drain networks into the watershed of Hoidong Reservoir, careful monitoring of environmental conditions appears to be very important.

석산개발에 따른 주변 환경오염 및 석분토 처리를 위한 연구

이평구,염승준,강민주,Lee, Pyeong-Koo,Youm, Seung-Jun,Kang, Min-Ju 대한자원환경지질학회 2010 자원환경지질 Vol.43 No.4

이번 연구에서는 석산 내부(광산) 및 외부(주변 환경)에서 채취한 모든 물 시료와 응집제를 함유한 석분토에 대해서 중금속, 시안, 독성 유기화합물 및 유기인의 총함량을 분석하였다. 그리고 EDTA 용출실험법 및 산농도 변화에 따른 용출실험법 등을 이용하여 석분토를 장기간 석산 내부에 보관할 경우 발생할 수 있는 중금속 원소의 용출특성을 평가하였다. 모든 물 시료와 석분토에서 검출된 $Cr^{6+}$, Hg, CN, TCE/PCE 및 총 인의 농도는 모두 검출한계 이하로, 오염되지 않았음을 확인하였다. 석산 내부 및 외부에서 채취한 물 시료에서는 Pb과 CD이 검출되지 않았고 구리와 아연은 일부 시료에서만, 비소는 일반적으로 검출되었으나 검출된 비소 함량은 모두 먹는 물 수질기준보다 훨씬 낮은 값을 보여주고 있다. EDTA 및 산도변화를 이용한 용출실험 등의 결과에서 Pb, Cr, Cd, Cu 및 Zn의 용출함량은 검출한계 이하 혹은 매우 낮은 함량만이 검출되었으며, 비소는 pH 3의 용출실험에서 검출되었다. 따라서 석산 개발에 따른 수계 오염은 없는 것으로 판단된다. All of the water and stone-dust samples with or without flocculant, in and around quarry mines, were analyzed for total concentrations of heavy metals, cyanide(CN), toxic organic compounds and organic phosphorus. Extraction experiments on stone-dust by EDTA and various pH solutions were also carried out, in order to evaluate the contaminant leaching from the long-term heaped stone-dust within quarry mines. The concentrations of $Cr^{6+}$, Hg, CN, TCE/PCE and total phosphorus in all samples (water and stone-dust) were under detection limits, confirming no environmental contamination from stone-dust in quarry mine areas. Lead and cadmium were not detected in all water samples. Copper and zinc were found in some water samples, and arsenic was detected in a few water samples. But they also showed levels much lower than the drinking water standard. Results of the extraction experiments by EDTA and pH solutions showed that Pb, Cr, Cd, Cu and Zn were leached out in less amounts or under detection limits. Arsenic was detected only at pH 3. From above results, we suggested that environmental contamination by quarry mine development is likely to be minor or negligible.