본 연구에서는 폐금속 광산 주변 비소와 중금속으로 오염된 논토양을 효과적으로 복원하기 위한 안정화 제로써 석회석과 제강슬래그의 처리효과와 그 적용성을 검토하기 위해 담수답의 환원 환경을 적용한 컬럼 실험을 실시하였다. 실험결과 담수된 논토양의 환원 환경에서는 철과 망간 성분이 환원되어 급격하게 용출되는 시점에 중금속 성분도 급격하게 용출되는 경향이 나타났으며, 대조구(무처리)의 경우 침출수에서 오염기준을 초과한 시료가 나타났다. 그러나 석회석 5%와 제강슬래그 5%로 각각 처리한 토양은 모두 오염기준 이하로 대조구보다 중금속 농도가 매우 낮게 검출되었다. 석회석과 제강슬래그 모두 담수답의 환원 환경에서 좋은 처리효과를 나타내어 효과적인 안정화제로 판단되었으며, 특히 제강슬래그는 담수답 환 경에서 지속적으로 증가하는 비소 성분에 대해서 좋은 처리효과를 나타내었다.

The purpose of this study was to suggest feasible disposal methods for heavy-metal-contaminated soil or mine tailings through solidification/stabilization. To improve the compressive strength and enhance the heavy-metal stabilization after solidification/stabilization, we used the industrial wastes (oyster shell powder and waste gypsum) and indigenous bacteria as immobilization agents. Three indigenous bacteria were isolated from each heavy-metal-contaminated soil or mine tailing site, and the bacteria were identified by cellular fatty acid composition analysis. The results of cellular fatty acid composition analysis showed that the closest strains of these bacteria are Brevibacillus centrosporus, Lysinibacillus sphaericus, and Bacillus megaterium. To the best of our knowledge, this research was the first report of biomineralization by Brevibacillus centrosporus. As a result of mixing additives with the optimum mixing ratio suggested in this study, the compressive strengths of specimens were satisfied in accordance with the US Environmental Protection Agency (EPA) waste treatment standard after 28 days of aging. Additionally, the results of the Toxicity Characteristics Leaching Procedure (TCLP) and Synthetic Precipitation Leaching Procedure (SPLP) analysis showed the successful immobilization of heavy metals after 28 days of specimen formation for solidification/stabilization.

According to a report ‘2012 Present Condition of National Household Refuse Resource Recovery Facility’, about 582,178 tons/year of household refuse were processed in the incineration plant, and 465,087 tons/year of bottom ash and 117,091 tons/year of fly ash were produced respectively. As incineration ash contains many kind of heavy metals such as soluble salt, copper and lead, it may lead to the leaching potential of heavy metals according to the environmental change, so it requires special care in landfill and recycling. In this study CO2 was injected into the bottom ash, so that environmental stability such as leaching of heavy metals was reduced and increased the possibility of CO2 fixation ability of the bottom ash was analyzed. Bottom ash of the household refuse incineration plant of I City was used as the sample of the fixation ability particle size was divided into 3 sections to analyze its components before and after carbonation using XRF. Stability of the sample was identified by the leaching test through KSLT and TCLP, and CO2 fixation ability by the DT-TGA analysis. Test results of the fixation ability shows that stabilization of the bottom ash produced in the household refuse incineration plant by carbonation is evaluated as there is little environmental problem caused by heavy metals when it is utilized into the recycled aggregate, and economic profits can be expected due to securing new agents of the supply and demand for the recycled aggregates, the greenhouse gas emission reduction by CO2 fixation.

2012년도 ‘전국 생활폐기물 자원회수시설 현황’ 에 따르면 소각장에 약 582,178톤/년의 생활폐기물이 반입되어, 바닥재 465,087톤/년, 비산재 117,091톤/년이 발생된 것으로 나타났다. 소각시설에서 배출되는 소각재는 그레이트 상에 남아있는 재(grate ash)와 그레이트 하단으로 떨어지는 재(grate siftings)가 포함된 바닥재(bottom ash) 그리고 폐열 보일러 재와 배출가스 비산재 및 부산물을 포함하는 비산재로 분류된다. 소각재에는 많은 양의 용해성 염과 구리, 납 등의 중금속을 함유하고 있어 환경의 변화에 따라 2차적으로 높은 중금속의 용출가능성을 초래할 수 있으므로 매립 및 재활용 시 주의가 요구되고 있다. 한편 생활폐기물 소각장에서 발생되는 바닥재는 주로 철, 유리, 도자기 등 재활용 가능한 성분으로 구성되어 있지만 일반폐기물로 분류되어 매립되고 있는 실정이다. 반면에 유럽의 독일, 덴마크, 네덜란드 등은 고형화, 세척, 숙성 등의 처리를 통해 바닥재를 도로 건설의 경량 골재로서 이용하거나 아스팔트 또는 콘크리트에 사용하는 등 발생된 바닥재의 60 ~ 90%를 재이용하고 있다. 본 연구에서는 ‘한국 지질자원 연구원 프론티어 무기성 폐기물의 복합처리를 통한 토건 재료화 연구’ 의 내용을 바탕으로 바닥재로부터의 중금속 용출 저감 등 환경적 안정성을 증진시키기 위한 방법으로서 CO2가스 주입을 통한 바닥재의 안정화 처리를 사용하였다. 이에 따른 중금속의 용출 결과 변화를 우리나라 폐기물 공정법상의 용출 시험법 KSLT(Korea Standard Leaching Test)와 미국 EPA의 TCLP(Toxicity Characteristic Leaching Procedure)에 의해 비교 하였으며, 바닥재 재활용에 의한 토양으로의 중금속 용출 영향을 기존 연구에 추가하여 실시하였다. 또한 온실가스인 CO2가스가 바닥재에 고용되는 효과를 실험에 의해 측정하였으며, 이에 따른 부가가치 가능성을 평가하였다.

본 연구에서는 표면개질 활성탄을 이용하여 수용액상에서 혼합 중금속(Cr6+, As3+)의 흡착능을 평가하였고 또한 표면개질 활성탄을 안정화제로 활용하여 해양오염퇴적물 내 As 및 Cr에 대하여 중금속 안정화 실험을 수행하였다. 실험결과, 흡착평형은 약 120분 후에 도달하였다. 또한, 중금속 등온 흡착 특성은 Freundlich 및 Langmuir 방정식을 이용하여 해석하였으며, 평형흡착 실험결과는 Langmuir 모델에 잘 부합되었고 As3+ (28.47 mg/g)가 Cr6+ (13.28 mg/g)보다 평형 흡착량이 많았다. Cr6+인 경우, 용액의 pH가 6에서 10으로 증가함에 따라서 흡 착량은 감소하는 것으로 나타났다. 하지만 pH 증가 변화에서 As3+의 흡착량은 미미한 증가를 보였다. 안정화 방법은 오염퇴적물에 표면 개질한 활성탄 첨가 후 120일간 습윤 양생하였다. 연속추출 실험결과로부터, 미처리 오염퇴적물과 비교해서 Cr 및 As의 이온교환, 탄산염, 산화물 및 유기물 존재 형태 합의 비는 각각 5.8% 및 7.6% 감소하였다.

본 연구에서는 해양오염퇴적물 내 Ni, Cu, Pb 및 Zn 등 중금속에 대하여 벤토나이트를 이용한 안정화 처리를 수행하였다. 안정화 실 험은 해양오염퇴적물에 벤토나이트 첨가 후 150일간 습윤 양생 하여 실시하였다. 중금속 연속추출 결과로부터, 미처리 오염퇴적물과 비교해서 Ni, Cu, Pb 및 Zn은 용이하게 용출가능한 존재형태(이온교환, 탄산염, 산화물 형태)가 벤토나이트에 의해 각각 8.5%, 5.6%, 19.2% 및 28.2% 감 소하였다. 또한, 안정화제 의한 오염퇴적물의 용출저감 평가를 위해 TCLP(Toxicity Characteristic Leaching Procedure)를 수행한 결과, 미처리 오염퇴적물과 비교하여 안정화 처리 퇴적물인 경우 중금속의 용출량이 각각 Ni 95.7%, Cu 96.8%, Pb 99.2%, Zn 85.9%씩 크게 감소하는 것을 확인하였다. 이러한 결과로부터, 벤토나이트를 해양오염퇴적물의 피복소재로 사용할 경우 시험 대상 중금속의 안정화 효과가 확인되었다.

본 연구에서는 제강슬래그를 이용하여 수용액상에서 혼합 중금속의 흡착능을 평가하였다. 게다가, 제강슬래그를 안정화제로 활용하 여 해양오염퇴적물 내 Ni, Zn, Cu, Pb 및 Cd에 대하여 중금속 안정화 실험을 수행하였다. 중금속 흡착 특성은 Freundlich 및 Langmuir 방정식 을 이용하여 해석하였으며, 평형흡착 실험결과는 Langmuir 모델에 잘 부합되었고 Pb2+ > Cd2+ > Cu2+ > Zn2+ > Ni2+순으로 평형흡착량이 많았 다. 안정화 방법은 오염퇴적물에 제강슬래그 첨가 후 150일간 습윤 양생 하였다. 연속추출 실험결과로부터, 미처리 오염퇴적물과 비교해서 Ni, Zn, Cu, Pb 및 Cd의 이온교환, 탄산염, 산화물 형태는 제강슬래그에 의해 각각 13%, 6.0%, 1.3%, 17% 및 50% 감소하였다.

In this study, an accelerated carbonation process was applied to stabilize hazardous heavy metals of industrial solid waste incineration (ISWI) bottom ash and fly ash, and to reduce CO2 emissions. The most commonly used method to stabilize heavy metals is accelerated carbonation using a high water-to-solid ratio including oxidation and carbonation reactions as well as neutralization of the pH, dissolution, and precipitation and sorption. This process has been recognized as having a significant effect on the leaching of heavy metals in alkaline materials such as ISWI ash. The accelerated carbonation process with CO2 absorption was investigated to confirm the leaching behavior of heavy metals contained in ISWI ash including fly and bottom ash. Only the temperature of the chamber at atmospheric pressure was varied and the CO2 concentration was kept constant at 99% while the water-to-solid ratio (L/S) was set at 0.3 and 3.0 dm3/kg. In the result, the concentration of leached heavy metals and pH value decreased with increasing carbonation reaction time whereas the bottom ash showed no effect. The mechanism of heavy metal stabilization is supported by two findings during the carbonation reaction. First, the carbonation reaction is sufficient to decrease the pH and to form an insoluble heavy metal-material that contributes to a reduction of the leaching. Second, the adsorbent compound in the bottom ash controls the leaching of heavy metals; the calcite formed by the carbonation reaction has high affinity of heavy metals. In addition, approximately 5 kg/ton and 27 kg/ton CO2 were sequestrated in ISWI bottom ash and fly ash after the carbonation reaction, respectively.

소각처리에서 나오는 잔사는 전체 투입 폐기물 부피의 약 10% 정도로 매립지의 사용연한을 연장시키는 장점을 가지고 있다. 하지만 소각 시 발생되는 비산재와 바닥재에서는 유해중금속(Pb, Cu, Cd 등)이 고농도로 함유되어 있어 매립 시 용출에 의한 2차 토양오염을 유발할 가능성이 높다. 이에 따라 환경부에서는 유해중금속에 대한 배출기준을 마련하였으며 사업장에서는 배출기준 준수를 위해 추가적인 수세 및 약품처리 등을 하고 있는 실정이다. 본 연구는 I시 C광역쓰레기 소각시설에서 발생하는 소각재를 대상으로 유해중금속의 안정적 처리방안과 킬레이트제의 적정사용량 산출을 통해 처리비용을 절감하고 소각재의 재활용 가능성을 파악하기 위하여 수행하였다. 킬레이트제 희석에 따른 바닥재의 Cu 처리효율은 10배 희석 시 91.1%, 11배 희석 시 76.6%, 12배 희석시 60.5%, 13배 희석 시 56.7%로 조사되었으며 소각재(바닥재+비산재)의 Pb 처리효율은 10배 희석 시 72.8%, 11배 희석 시 65.9%, 12배 희석 시 64.9%, 13배 희석 시 61.2%로 조사되었다.

The objective of this study was to evaluate the leaching characteristics of heavy metals (Cu, Pb, Zn and Cd) in an abandoned mine soil stabilized by applying both soluble phosphates and steel slag. Leaching characteristics of heavy metals in the contaminated soils was evaluated by toxicity characteristics leaching procedure (TCLP) and Column test. After leaching batch (TCLP) and column, Pb was found that the most greatly reduced by immobilized. Among the tested three phosphates (Na2HPO4·12H2O, Ca(H2PO4)2·H2O, (NH4)2HPO4), the leaching concentration of Ca(H2PO4)2·H2O and (NH4)2HPO4 decreased more than those of Na2HPO4·12H2O. The rate constant (k1) value was found to be about 1.5 ~ 2.0 times higher than ever before, it could be fast immobilized. The rate constant (k1) of Zn was the highest as 0.1629 ~ 0.1991/ day, it was followed by Zn > Pb > Cd > Cu. Especially, Cu increased more than 2.0 times with the steel slag added, so it was very effective. Total leaching amount of heavy metal was the most TCLP test due to differences in the leaching conditions. Added with the slag, TCLP, Column and Exchangeable form (F1) more decreased. Phosphorus (P) leaching, stabilized by phosphate only, increased than the contaminated soil. But Leaching of P decreased considerably when it was processed in combination with slag. In particular Ca(H2PO4)2·H2O of phosphates showed to be the least leaching, it was expected made of metal-phosphate immobilized.

Difference in immobilization effect of heavy metal-contaminated soil between two different amendment methods was evaluated; 1) both of steel slag (i.e., consisted in solid phase) and soluble phosphate (i.e., consisted in liquid phase) were simultaneously applied to contaminated soil (i.e., simultaneous amendment methods) and 2) soluble phosphate and steel slag was applied sequentially to the contaminated soil (i.e., sequentially amendment methods). The application rate of stabilizers to soils was determinated based on weight/weight ratio of 5% for steel slag and PO4/Pb molar ratio of 2.0 for phosphates, respectively. To identify difference of immobilization effect to test soil, three different soluble phosphates, such as Na2HPO4·12H2O, Ca(H2PO4)2·H2O and (NH4)2HPO4 were used. The sequential amendment was 6 ~ 27% more effective than the simultaneous amendment in terms of the immobilization efficiency for Pb, Cu, and Cd in the contaminated soil. There was little difference in case of Zn. Among the three phosphates tested, (NH4)2HPO4 was clearly the most effective. Residual form of heavy metals concentration in sequentially methods is higher than those in simultaneously methods. At the same time, more exchangeable and carbonate-bound forms of heavy metals in simultaneously methods were observed than in sequentially case. These result implies that the sequential amendment method was more effective than the simultaneous amendment method in terms of heavy metal immobilization in the contaminated soil.

In this study, to stabilize the heavy metal in the contaminated soils, the column leaching test based on rainfall and pH value was performed by using coal mine drainage sludge(CMDS): which was generated during electrical purification of abandoned coal mine wastewater. Four types of testing column were used in this study. That were the CMDS and the heavy metal contaminated soils well mixed in 0 wt%, 1 wt%, 3 wt% and 3 wt% layered column. According to the investigation, when the influent pH was 5.5∼6.2, there were no heavy metal elution at all conditions, and when the influent pH was 3∼3.3, the order of Cu, Zn, Pb, Cr elution concentration was 3 wt% M(mixed)＜3 wt% S(separation)＜1 wt% M＜0 wt% and the average elution concentration was quite low, the value was 0.005 mg/L. Therefore, CMDS can used as new stabilizer of the heavy metal in the contaminated soils.