본 연구에서는 중금속 오염토양 및 광미의 고형화 처리를 위한 보통 포틀랜드 시멘트의 혼화재로서 제강슬래그의 처리효과를 검토하였다. 대상시료는 충청남도 청양군 남양면 구룡리의 구봉광산 주변 하천퇴적토와 강원도 영월군 상동읍 내덕리의 상동광산에 위치한 광미를 채취하여 사용하였다. 경화제는 시멘트 95%에 제강슬래그 분말 5%를 혼합하여 제조하였으며, 하천퇴적토 및 광미오염토양에 5%, 10% 및 15%(w/w)의 경화제를 첨가하였다. 이때 이 결과들은 시멘트만을 사용한 것과 Ca 함량이 제강슬래그 보다 상대적으로 높은 굴폐각 분말을 사용하여 배합한 결과와 함께 비교하였다. 공시체는 지름 5cm, 높이 10 cm의 몰드를 이용하여 혼합토를 채워 넣은 후, 습윤양생기에서 1일간 양생시킨 다음 탈형 후, 수조에 수중양생을 실시하였다. 7일, 14일 및 28일 경과된 시료를 대상으로 강도시험 및 중금속 용출시험을 실시하여 처리효과를 비교·검토하였다. 광미시료의 경우, 시멘트, 제강슬래그 그리고 굴폐각 순으로 강도 개선의 효과가 큰 것으로 나타나 제강슬래그의 효과를 확인할 수 없었고, 하천퇴적토의 경우는 혼합비 15%에서 제강슬래그를 혼합한 경우에서 우수한 효과를 나타내 혼화재로서 적용을 기대할 수 있을 것으로 판단되었다. 폐기물용출시험 및 0.1 N 염산추출법 결과 경화제의 혼합비가 증가할수록 중금속 및 비소의 농도가 감소하는 경향이 나타났고 특히 비소에 있어서는 제강슬래그의 효과가 가장 좋게 나타났다. 산도가 가장 높은 1N 염산추출법의 결과에서는 광미의 경우 대조구 보다 제강슬래그로 처리한 시료에서 중금속 및 비소의 농도가 아주 낮게 나타났다. 그러나 하천퇴적토는 대조구와 큰 차이가 없이 중금속 및 비소가 용출되었다. 이는 하천퇴적토가 95%이상의 모래로 토양의 입경이 크기 때문에 상대적으로 중금속의 고정화율이 상대적으로 낮은 것으로 판단되었다.

Trophic groups and functional guilds were studied of soil nematodes from the soils of two abandoned mines in Ilkwang and Gunbuk, South Korea to compare nematode communities between the heavy metal contaminated soil and the nonheavy metal contaminated soil. No obvious correlation was found between the level of heavy metal and the total number of nematodes statistically. However the overall densities of bacterial, hyphal, omnivorous and predatory nematodes from the non-heavy metal contaminated soil was higher than those from the heavy metal contaminated soil. Also the densities of c-p 2, c-p 3, c-p 4 and c-p 5 nematodes were higher from the non-heavy metal contaminated soil than those from the heavy metal contaminated soil. MI, MI 2-5 and ΣMI 2-5 were higher, but there were no significant differences.

This study aimed to remove organic matter and heavy metals that could affect the recycling of soils contaminated by heavy metals, by means of electrolysis, carried out simultaneously with the leaching of the soil. To ensure better experimental equipment, a soil electrolysis apparatus, equipped with spiral paddles, was used to agitate the heavy-metal-contaminated soil effectively. The heavy-metal-contaminated soil was electrolyzed by varying the voltage to 5 V(Condition 1), 15 V(Condition 2), and 20 V(Condition 3), under the optimal operating conditions of the electrolysis apparatus, as determined through previous studies. The results showed that the pH of the electrolyte solution and the heavy-metal-contaminated soil, after electrolysis, tended to decrease with an increase in voltage. The highest removal efficiencies of TOC and CODCr were 18.8% and 29.1%, 38.8% and 4.2%, and 33.3% and 50.0%, under conditions 1, 2 and 3, respectively. Heavy metals such as Cd and As were not detected in this experiment. The removal efficiencies of Cu, Pb and Cr were 4.7%, 8.3% and 2.1%, respectively, under Condition 1, while they were 42.9%, 15.2% and 22.1%, respectively, under Condition 2, and 4.7%, 23.0%, and 24.9%, respectively, under Condition 3. These results suggest that varying the voltage with the soil electrolysis apparatus for removing contaminants for the recycling of heavy-metal-contaminated soil allows the selective removal of contaminants. Therefore, the results of this study can be valuable as basic data for future studies on soil remediation.

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.

슬래그를 매립한 토양을 대상으로 자기분리연구를 수행하였다. 토양세척을 거친 토양과 토양세척 전 토양을 대상으로 습식자기분리와 건식자기분리를 수행하여 분리된 부분과 분리되지 않은 부분의 중금속 농도를 측정하여 중금속의 농축효과를 측정하였다. 습식자기분리의 경우 토양세척 전 시료의 자력분리율이 상대적으로 높으며 토양세척 후 시료의 경우 약 40% 정도가 자기분리 되었다. 토양 : 물의 비가 농축효과에는 큰 영향을 미치지 못하며, Fe, Pb, Cu, Zn, Cd의 세척 전 토양과 세척 후 토양의 자기분리에 의한 평균 농축비는 3.2, 2.1, 12.1, 2.5, 1.5와 17.4, 7.0, 15.7, 9.6, 7.0으로 토양 세척을 거친 경우 자기분리에 의해 토양 세척 전 토양에 비해 더 큰 토양 부피 감량효과를 기대할 수 있다. 건식자기분리의 경우에도 자기분리에 의해 중금속의 농축효과를 얻을 수 있으나 자기분리에 의한 회수율이 너무 높은 경우 오염토 저감을 기대하기 어렵다. 철과 같은 강자성체를 포함하는 토양의 경우 자기분리에 의해 토양세척의 효과와 유사하게 오염토양의 양을 줄일 수 있고, 오염이 한쪽에 농축되는 결과를 얻을 수 있다.

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.

국내 강원광산과 동해광산 주변 토양입자의 이화학적 광물학적 특성을 이용해 이들 광산주변내 토양 중금속 오염 원인을 규명하고자 하였다. 입도에 따른 중금속의 농도를 분석한 결과 강원광산의 경우 가장 큰 입경군인 10~18 mesh 구간에서 비소가 250.5 ppm, 가장 작은 325 mesh 이하 구간에서 445.7 ppm으로 나타났다. 동해광산의 경우에도 마찬가지로 10~18 mesh 구간에서 비소 70.4 ppm, 납 1,055 ppm, 아연 789.9 ppm으로 나타났으며 325 mesh 이하 구간에서 비소 117.7 ppm, 납 2,295 ppm, 아연 1,346 ppm으로 입도가 작아질수록 농집되는 경향을 보였다. 중금속과 토양 내 광물의 상호작용을 분석하기 위해 물리적 선별(자력, 부유선별) 후, 이들 시료에 대한 X-선 회절분석과 주사전자현미경 분석결과 강원광산 시료의 주 구성광물은 석영, 운모, 조장석, 녹니석, 자철석, 각섬석으로 확인되었으며 동해광산 시료에서는 석영, 운모, 고령석, 녹니석, 각섬석, 금홍석이 주 광물들로 나타났다. 강원광산의 자철석은 비소 농도와의 상관성이 매우 좋은 것으로 나타난 반면, 동해광산 시료에서는 티탄철석이 확인되었으며 미량의 비소를 포함하는 것으로 나타났다. 이 같은 결과들은 토양 내 광물의 이화학적 정보와 광물학적 특성 규명이 토양 오염원 형태와 이를 바탕으로 한 토양환경 오염처리에 매우 중요함을 시사하고 있다.

The objective of this study was to evaluate the immobilization of heavy metals (Cu, Pb, Zn and Cd) in an abandoned mine soil by applying both soluble phosphates and steel slag as stabilizers. The application rate of stabilizers to soils was determinated based on PO4/Pb molar ratio of 2.0 for phosphates and on weight/weight ratio of 2, 5, 10% for steel slag, respectively. Immobilization efficiency of heavy metals in the contaminated soils was evaluated by toxicity characteristics leaching procedure (TCLP). After adding both phosphate and slag, the immobilization efficiencies of Cu, Zn and Cd increased significantly (about 14% - 40%) compared to those of treatment with soluble phosphate alone. The increae in immobilization efficiencies of Cu was the greatest. Whereas, immobilization efficiency of Pb was not significantly different from those with soluble phosphate alone. Among the tested three phosphates (Na2HPO4 ·12H2O, Ca(H2PO4)2 ·H2O, (NH4)2HPO4), the immobilization efficiencies with Na2HPO4 ·12H2O increased more than those of other phosphates. Results of sequential extraction analysis indicated that fraction of reducible form (F3) and residual form (F5) increased, while mobile forms (F1, and F2) decreased after immobilization treatment with both stabilizers resulting in decrease in leachability of heavy meyals in the treated soils. Residual fraction of Cu after treatnment was the highest as 68.5%, it was followed by Cu > Pb > Zn > Cd.

The amount of contaminated dredged materials are increasing every year in Korea. Secondary contamination would be expected, if contaminated marine clayey slurry remains without treatment. Therefore, the appropriate remedial treatments are required in order to prevent secondary contamination. Electrokinetic method is especially suitable for low permeability dredged clayey soils because pore fluid can be easily transported by electric field. Hydrogen ions created by electrolysis enhance the remedial processes by desorbing heavy metal contaminants from slurry soil surfaces. This study investigated variation of electrical current and voltage gradient during the treatment, and ICP analysis as well as pH measurements were carried out to measure zinc concentration during and after the treatment.

The objective of this study was to evaluate the immobilization efficiency and sequential extraction of soluble phosphates (Na2HPO4 ·12H2O, Ca(H2PO4)2 ·H2O, (NH4)2HPO4) for the stabilization of heavy metals (Cu, Pb, Zn and Cd) in abandoned mine soil. The application rate of stabilizers to soils was determinated PO4/Pbtotal molar ratio of 0.5, 1.0, 2.0, 4.0. The immobilization efficiency was evaluate of TCLP (EPA method 1311) used in a landfill for heavy metals. After processing stabilization, the immobilization efficiency of Pb is more than 95% at molar ratio of 2.0 regardless kind of phosphate. For Cu Zn and Cd, on the other hand, the efficiency has the range of from 30% to 50%, even though molar ratio increase up to 4.0. It is relatively low in comparison with Pb. Leachability of heavy metals was reduced with increasing amounts of added phosphate. Phosphates, Na2HPO4 ·12H2O was more immobilization than Ca(H2PO4)2 ·H2O, (NH4)2HPO4. After sequential extraction, form of heavy metals in soil tends to increase strongly bond like forms of organic matter-bound(F4) and residual (F5). Especially the stable residual form increases in all metals. The growth rate of residual fraction was a little different heavy metals. The growth rate of Zn is greatest increased from 17% to 22% than other metals, it was followed by Zn > Cd > Pb > Cu. Phosphates, Ca(H2PO4)2 ·H2O was the greatest increased for residual fraction.

A stabilization/solidification (S/S) process for lead (Pb) contaminated soils was evaluated using waste cow bone containing apatite like compounds. Soil samples obtained form firing range were treated with waste cow bone. The effectiveness of stabilization was evaluated based on the Korean Standard Leaching Test (KSLT) and soil pH. The leached concentration reduced with increased in dose of waste cow bone. Overall, the KSLT results showed that Pb concentration in soils are significantly affected by amount of waste cow bone. When soil amended with 20 % of waste cow bone, less than 0.1 mg/kg was leached, and soil pH was increased from 6.5 to 8.4. Same results were obtained when finer waste cow bone was applied. The reachable concentration of Pb in soil showed in inversely proportional to solid/liquid ratio. Aging periods indicate improving mix design was applied. Relatively high lead concentrations was observed at the first 1 days, however leaching profile are reduced significantly over time for all mix designs.

For the remediation of the contaminated soil with heavy metals, Cd, Cr, Cu, and Pb, the reaction parameters were optimized. Tartaric acid (TA) and oxalic acid(OA) as a washing agent were evaluated as a function of concentration, reaction time, mixing ratio of washing agent and recovery of metals. The optimum washing conditions of TA and OA were in the ratio of 1 : 20 between soil and acid solution during 2 hr reaction under unbuffered pH solutions. At the optimized reaction conditions, the removal efficiencies were compared with that of 0.1 M HC1 and ethylenediamine tetraacetic acid(EDTA). TA showed higher efficiency on the removal of Pb than that of EDTA, which established for the remediation of contaminated soil with Pb and Cd metals. The recovery of metal ions from washing solution was achieved by adding calcium hydroxide and sodium sulfide by forming the precipitation of metal hydroxide and metal sulfide. Optimum amounts of sodium sulfide and calcium hydroxide were Cd = 25g/ℓ, Cu = 5∼10g/ℓ and Pb = 5∼10g/ℓ for the washing solution of OA and 2∼5g/ℓ for the washing solution of TA, respectively. The amounts of Na2S and Ca(OH)2 for the tartaric acid was less than that of oxalic acid.