A continuous process of persulfate oxidation and citric acid washing was investigated for ex-situ remediation of complex contaminated soil containing total recoverable petroleum hydrocarbons (TRPHs) and heavy metals (Cu, Pb, and Zn). The batch experiment results showed that TRPHs could be degraded by Fe2+ activated persulfate oxidation and that heavy metals could be removed by washing with citric acid. For efficient remediation of the complex contaminated soil, two-stage and three-stage processes were evaluated. Removal efficiency of the two-stage process (persulfate oxidation - citric acid washing) was 83% for TRPHs and 49%, 53%, 24% for Cu, Zn, and Pb, respectively. To improve the removal efficiency, a three-stage process was also tested; case A) water washing - persulfate oxidation - citirc acid washing and case B) persulfate oxidation - citric acid washing (1) - citric acid washing (2). In case A, 63% of TRPHs, 73% of Cu, 60% of Zn, and 55% of Pb were removed, while the removal efficiencies of TRPHs, Cu, Pb, and Zn were 24%, 68%, 62%, and 59% in case B, respectively. The results indicated that case A was better than case B. The three-stage process was more effective than the two-stage process for the remediation of complex-contaminated soil in therms of overall removal efficiency.

중금속으로 오염된 토양과 광미는 지하수 및 생태계에 추가적으로 피해를 발생시킨다. 이러한 독성 금속의 축적은 식물의 성장억제 및 인체의 발달이상, 발암과 같은 다양한 질병의 원인이 된다. 오염된 토양에서 중금속을 정화하는 방법으로는 고형화/안정화, 토양세척, 토양경작법 등과 같이 다양한 방법이 있다. 하지만 부지 및 오염특성에 따라 적절한 방법을 사용해야 한다. 적절한 방법 중 하나는 오염된 토양의 고형화/안정화이다. 본 연구의 목적은 오염된 토양 및 광미 내 존재하고 있는 중금속을 고형화/안정화 공법을 적용하여 정화하는 방법을 제안하는데 있다. 본 연구에서는 오염토양 내 중금속을 고형화/안정화 시키고 강도 증진을 위해 MICP 토착미생물과 산업폐기물인 굴패각, 폐석고를 배합하여 고화제로 사용하였다. 국내의 중금속 오염토양과 광미에서 MICP 토착미생물을 분리하였고 균체 지방산 분석을 통하여 동정을 진행하였다. 각각의 시료에서 분리한 균주를 동정한 결과 가장 많이 유사성을 보이는 균주는 Brevibacillus centrosporus 와 Bacillus megaterium 이었다. 또한 MICP 토착미생물의 최적 성장 조건을 도출하였으며, 산업폐기물과 MICP 토착미생물의 최적 배합비를 적용한 공시체의 일축압축강도 분석을 진행하였다. 그 결과 28일 경과 후 일축압축강도는 미국 EPA 폐기물처리 표준 기준을 만족하였으며, 위해성 평가를 위한 TCLP, SPLP 분석 결과 미국 EPA 기준을 만족하였다.

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.

물은 22.1 MPa의 압력하에 100℃ - 374℃의 온도범위에서 액체상태로 존재하며, 이를 아임계수라 한다. 아임계수 조건에서 물은 분자간 수소결합이 약해지면서 유전상수, 점성, 표면장력이 감소되어 유기용매와 유사한 특성을 지니게 된다. 원유오염토양은 전남 여수지역 공단 내에 있는 유류로 오염된 토양을 이용하였으며, 오염기간은 약 1년이며 저분자성 휘발유류성분 및 고분자성 유류로 오염되어 있었다. 초기 오염된 TPH농도는 16,895 mg/kg였다. 원유오염토양은 고분자성 물질이 다량 함유되어 있어 기존정화방법으로는 처리하기 어려운 점이 있다. 이를 해결하기 위하여 상기 아임계수 특성을 이용하여 원유로 오염된 토양으로부터 오염물질을 추출하는 연구를 수행하였다. 이와 함께 친유성 용매인 등유를 이용하여 토양으로부터 원유 일부를 탈착(전처리)시킨 후, 아임계수로 토양 내에 잔류되어 있는 유류성분을 제거하는 실험도 수행하였다. 이를 통해 아임계수 추출만을 적용하였을 경우와 등유 전처리가 추가된 경우의 제거율과 정화공정상 효율을 비교하였다. 아임계수 추출 시 275℃에서 2시간 추출을 5회 반복 진행하였을 때, 토양 내의 잔류 유류 농도가 498 mg/kg(제거율 97%)로 나타났다. 등유 전처리(토양 : 등유=1 : 0.5 wt%)후 아임계수 적용시 250℃에서 1시간동안 추출 시, 토양 내 잔류 유류 농도는 223 mg/kg로 나타났다. 적용된 두가지 공정 모두 토양1지역 우려기준(500mg/kg)이하로 정화되었으나, 상대적으로 등유전처리가 포함된 공정이 아임계수 기술만을 적용하여 추출을 진행한 것보다 상대적으로 높은 제거율을 보였다. 또한 등유 전처리가 추가된 아임계 공정이 추출시간, 공정수, 투입에너지(가열)에 있어 경제적으로 판단되며, 따라서 원유 오염토양의 아임계수 정화공정에서는 등유전처리 도입이 효과적인 것으로 판단된다.

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.

This study was performed to develop the efficient phytoremediation model in the paddy soil contaminated with heavy metals by cultivating Pteris multifida and Artemisia princeps with different mixing ratios (1:0, 8:1, 6:1, 4:1). As a result of investigating the heavy metal accumulation of each plant per dried material (1 ㎏), content of arsenic and cadmium was the highest in aerial part of P. multifida (169.82, 1.70 ㎎·㎏-1 DW, each) among the treated group. Lead content was the highest (12.58 ㎎·㎏-1 DW) in the aerial part of P. multifida cultivated with 8:1 mixed planting. But the content of copper and zinc was the highest (33.94, 61.78 ㎎·㎏-1 DW, each) in the aerial part of A. princeps with 8:1 treatment. Regardless of heavy metals, plant uptake from the 1 ㎡ soil was the highest in 4:1 mixed planting group, which showed the best yield of A. princeps.

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.

Asbestos contaminated soil remediation was performed depending on wind velocity and water content using a wind remediation treatment device. The soil samples were collected from upland and paddy soil near inactive asbestos mine and 8% wollastonite was applied instead of asbestos due to health hazard. The wollastonite in soil was analyzed by scanning electron microscopy (SEM) combined with energy dispersive spectrometer (EDS). With 8 m/s of wind velocity, 86% and 92.8% of wollastonite in upland soil and paddy soil were releasable, respectively. When distance from air blast module in the device was 1 ~ 1.5 m, the removal efficiency was highly significant. The removal efficiency decreased as increased as the distance. The releasable wollastonite was significantly affected by water content rather than wind velocity, and this tendency was pronounced with paddy soil. With 0% water content, the correlation between distance and residual amount of wollastonite was low, while the removal efficiency of wollastonite was the highest. Consequently, the removal efficiency of wollastonite was increased with high wind velocity and low water content. For the effective asbestos contaminated soil remediation based on this study, controlling equipment for wind velocity and water content requires in pilot-scale plant and additionally enough air injection and sufficient volume of dust collection module are necessary.

본 연구는 중금속 오염지역의 토양정화에 적합한 식물을 선발하기 위해 양치식물 12종을 중금속으로 오염된 토양에 8주 동안 재배한 다음 생육반응과 부위별 비소, 카드뮴, 구리, 납, 아연 등의 중금속의 축적능을 분석하였다. 봉작고사리(Adiantum capillus-veneris)를 제외한 양치식물 11종의 생육은 비교적 양호하였다. 봉의꼬리 (Pteris multifida, 66.9mg․kg-1 DW)와 사다리봉의꼬리(P. vitata, 62.2mg․kg-1 DW)의 지상부에서 비소 축적능이 가장 우수하였으며, 사다리봉의꼬리(13.6mg․kg-1 DW)는 지하부의 비소 축적능도 가장 높았다. 반면, 카드뮴 축적능은 양치식물 12종 모두가 저조하였다. 구리의 축적능은 창날봉의꼬리(P. ensiformis)의 지하부가 44.4mg․kg-1 DW로 가장 높았으며, 지상부는 봉작고사리(26.8mg․kg-1DW)가 가장 우수하였다. 양치식물 12종의 지상부는 1.2(뱀고사리, Athyrium yokoscens)∼8.8mg․kg-1 DW(봉의꼬리)의 납이 축적되었으며, 지하부는 1.2(창날봉의꼬리)～10.3mg․kg-1 DW(반쪽고사리, P. dispar)가 축적되어 있었다. 아연의 축적능은 푸른각시고사리(Thelypteris viridifrons)의 지상부(96.8mg․kg-1 DW)에서 가장 높았으며, 지하부는 봉의꼬리(63.6mg․kg-1 DW)에서 가장 우수하였다.

Various foreign materials such as contaminated soil, woody waste, drums containing waste oil, waste transformer, and waste pressure vessel are generated during the collecting and sorting processes of steel scrap. Recently, environmental problems have occurred because of the use of steel scrap that contained contaminants and was not separated properly. And this has also affected the quality of iron products made of steel scrap. Particularly, contaminated soil is highly likely to contain various hazardous substances including heavy metals, which is why proper management standards for contaminated soil are necessary. In this study, concentrations of heavy metals, BTEX, TPH, PAHs, and hazardous materials in contaminated soil were analyzed. It was found that the concentrations of lead and zinc were higher than other heavy metals and iron also showed high concentration. The very high TPH concentration in contaminated soil implies that contaminated soil was polluted by diesel, fuel oil or lubricant. So the comprehensive management regulatory plan and management standard for the hazardous materials are necessary for environmentally-friendly recycling of steel and iron scrap.

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.

The effects of sole, mixture heavy metals and soil samples was assessed based on the seed (Lactuca sativa L.) germination. In general, tested sole metals were showed considerable sensitivity on the germination, showing following EC50s: As(III) 1.02 mg/L, Cr(VI) 1.33 mg/L, Cu 2.26 mg/L, Cd 2.61 mg/L, As(V) 3.00 mg/L. Though obvious patterns were not observed on the effects by binary mixture metal, generally more synergistic mode was observed rather than antagonistic or additive. No significant correlation between toxicity and total metal contents was observed, but two groups classified according to contaminated arsenic concentration, showed considerable differences. Interactive effects of metals may vary depending on the bioassays used as well as on the mixture metals and their respective concentrations. Therefore, more detailed evaluation, such as with battery of assays, sample grouping and various mixtures, may comprise a useful tool for the assessment of the environmental samples with mixture contaminants.

The objectives of this study are to examine the processing of oils contamination soil by means of using a micronano-bubble soil washing system, to investigate the various factors such as washing periods, the amount of micro-nano bubbles generated depending on the quantity of acid injection and quantity of air injection, to examine the features involved in the elimination of total petroleum hydrocarbons (TPHs) contained in the soil, and thus to evaluate the possibility of practical application on the field for the economic feasibility. The oils contaminated soil used in this study was collected from the 0~15 cm surface layer of an automobile junkyard located in U City. The collected soil was air-dried for 24 hours, and then the large particles and other substances contained in the soil were eliminated and filtered through sieve No.10 (2 mm) to secure consistency in the samples. The TPH concentration of the contaminated soil was found to be 4,914～5,998 mg/kg. The micronano-bubble soil washing system consists of the reactor, the flow equalization tank, the micronano- bubble generator, the pump and the strainer, and was manufactured with stainless material for withstanding acidic phase. When the injected air flow rate was fixed at 2 L/min, for each hydrogen peroxide concentrations (5, 10, 15%) the removal percents for TPH within the contaminated soil with retention times of 30 minutes were respectively identified as 4,931 mg/kg (18.9%), 4,678 mg/kg (18.9%) and, 4,513 mg/kg (17.7%). And when the injected air flow rate was fixed at 2 L/min, for each hydrogen peroxide concentrations (5, 10, 15%) the removal percents for TPH within the contaminated soil with retention times of 120 minutes were respectively identified as4,256 mg/kg (22.3%), 4,621 mg/kg (19.7%) and 4,268 mg/kg (25.9%).

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.