Remediation of Contaminated Groundwater: Change of Paradigm for Sustainable Use

Lee, Jin-Yong,Lee, Kang-Kun Korean Society of Soil and Groundwater Environment 2013 지하수토양환경 Vol.18 No.6

Groundwater development and use have been increasing in Korea causing frequent occurrences of related hazards such as groundwater level decline, land subsidence, and groundwater contamination. To tackle these groundwater problems, central and local governments have set-up and maintained many groundwater monitoring programs such as the National Groundwater Monitoring Network and the Groundwater Quality Monitoring Network, which collect very valuable data on the overall status of domestic groundwater to aid proper groundwater management. However, several problems mainly related to the remediation of contaminated groundwater remain unresolved. Recently, there have been some incidents related to the contamination of groundwater, and these have drawn the concern of the Korean people. Although groundwater contamination has been investigated in detail, actual groundwater remediation work has not yet been implemented. The remediation of the contaminated groundwater must begin immediately in order to sustain the eco-system service of clean groundwater and enhance the welfare of the Korean people.

Retardation Effect and Mobility of a Heavy Metal in a Sandy Soil

Kim, Dong-Ju,Baek, Doo-Sung Korean Society of Soil and Groundwater Environment 1998 지하수환경 Vol.5 No.3

토립자 표면에서의 흡착에 의한 토양에서의 중금속의 지연효과는 잘 알려진 현상이다. 본 연구에서는 배치시험과 주상시험을 수행함으로써 사질 토양에서 Zn의 이동성에 대한 지연효과를 조사하였다. 주상시험은 파과곡선(BTC)으로 알려진 시간에 따른 용액의 농도를 측정함으로써 수행되었다. 추적자로는 10 g/L 농도의 NaCl과 ZnCl$_2$를 사용하였고, 각각의 용액을 토양시료의 상부경계에 순간주입한 후 정상류 상태에서 배출구로 빠져나온 용탈수의 농도를 EC-meter와 ICP-AES를 이용하여 측정하였다. 배치시험은 표준절차에 근거하여 이루어졌으며, 토양시료로부터 선별된 미세입자들을 다양한 초기농도의 ZnCl$_2$용액과 반응시켜 평형상태의 Zn 이온의 농도를 ICP를 이용하여 분석하였다. 주상시험의 결과는 i) ICP-AES에 의해 분석된 ZnCl$_2$의 첨두농도는 NaCl이나 총전기전도도로부터 구한 값보다 상당히 낮았고, ii) 두 종류의 추적자 모두 첨두농도의 도달시간은 상당히 일치하였다. 상대적으로 낮은 Zn의 농도는 Zn과 다른 양이온들간의 이온교환반응이 일어났고, 용탈수의 pH가 높은 값의 범위(7.0~7.9)에 있는 것으로 보아 Zn(OH)$_2$의 형태로 침전되었을 가능성이 있다는 것으로 설명될 수 있다. 첨두농도의 도달시간이 일치한다는 결과는 토양시료에서 지연효과가 일어나지 않았다는 것을 지시한다. Zn 이온의 뚜렷한 감소를 설명할 수 있는 유일한 방법은 CDE 모델에 용액상태에서 Zn 이온의 절대적 감소를 고려하는 감쇄계수(decay or sink coefficient)를 적용하는 것이었다. Retardation effect of heavy metals in soils caused by adsorption onto the surfaces of solids particles is well known phenomenon. In this study, we investigated the retardation effect on the mobility of a Zn in a sandy soil by conducting batch and column tests. The column test consisted of monitoring the concentrations of effluent versus time known as a breakthrough curve (BTC). We used NaCl and ZnCl$_2$ solutions with the concentration of 10 g/L as a tracer, and injected them respectively into the inlet boundary of the soil sample as a square pulse type, and monitored the effluent concentrations at the exit boundary under a steady state condition using an EC-meter and ICP-AES. The batch test was conducted based on the standard procedure of equilibrating fine fractions collected from the soil with various initial ZnCl$_2$ concentrations, and analysis of Zn ions in the equilibrated solutions using ICP-AES. The results of column test showed that i) the peak concentration of ZnCl$_2$analyzed by ICP was far less than that of either NaCl or bulk electrical conductivity and ⅱ) travel times of peak concentrations for two tracers were more less identical. The relatively low concentration of Zn can be explained by ion exchange between Zn and other cations, and possible precipitation of Zn in the form of Zn(OH)$_2$due to high pH range (7.0∼7.9) of the effluent. The identical result of travel times of peak concentrations indicates that the retardation effect is not present in the soil. The only way to describe the prominent decrease of Zn ion was to introduce decay or sink coefficient in the CDE model to account for irreversible decrease of Zn ions in the aqueous phase.

A Study on Chemical Speciations and Leaching Potential of Heavy Metals in Polluted Wastes Soils

Kim Hee-Joung,Yang Jae-E,Park Byung-Kil,Kong Sung-Ho,Lee Jai-Young,Jun Sang-Ho Korean Society of Soil and Groundwater Environment 2005 지하수토양환경 Vol.10 No.3

Fractional compositions and leaching potentials of Cd, Cu and Zn were investigated in the soils which had been disposed with the metal processing wastes, tungsten mine tailings and low quality coal mine area. Total concentrations of metals in these soils were higher than in non-polluted paddy and upland soils. Fractions of Cd, Cu and Zn were mostly reducible, organic and residual forms, but varied with origins of wastes. Residual fraction was a predominant form in the nonpolluted soils. Leaching potentials of metals were higher in polluted soils than in non-polluted soils. Metals leached were higher at pH 4.0 than 7.0 and increased with the duration time. After 25 to 35 hrs, metals released from soils reached a pseudoequilibrium. Leaching potential of metals in non-polluted soils was low due to high percentage of residual fractions. 석탄저장소, 텅스텐 광산의 광미, 고철 제련장내의 오염된 토양을 대상으로 중금속의 존재형태와 용출 가능성에 대하여 조사하였다. 석탄저장소와 광미, 제련장 지역 내 토양의 중금속 농도는 논과 비 오염지역의 산 토양보다는 높게 나타났으며, 대부분의 중금속의 존재형태는 reducible, organic과 residual fraction이 높게 나타났다. 오염되지 않은 토양의 중금속의 존재형태는 residual 형태가 주를 이루었다. 용출 가능성에 대한 평가는 오염되지 않은 토양보다는 오염된 토양에서 높게 나타났으며, pH 7.0 보다는 pH 4.0에서 시간이 증가함에 따라 용출량이 증가하였다. 오염 된 토양으로부터 중금속의 용출은 Cu, Zn, Pb 등이 용출시간이 25시간 또는 35시간에 유사 평형에 도달했다. 오염되지 않은 토양의 낮은 용출은 중금속의 존재형태 중 높은 residual fraction의 비율에 의해 기인된 것으로 사료된다.

Groundwater quality in the Shallow Aquifer nearby the Gubong gold-mine Tailings

우남칠,최미정,Woo, N.-C.,Choi, M.-J. Korean Society of Soil and Groundwater Environment 1998 지하수환경 Vol.5 No.3

구봉광산은 과거 남한의 최대 금광중의 하나였다. 광산 주변 지역에서는 천부 지하수를 생활용과 농업용 수원으로 사용하여 왔다. 이 지역에서 Cd, Cu, Pb 및 Zn에 의한 토양오염이 보고되었으며, 이로부터 이 지역의 천부지하수의 수질과 광미로 인한 영향을 규명하고자 본 연구가 시작되었다. 인근의 하천수, 지하수 및 광미지역의 침출수 시료를 채취하여 Na, K Ca, Mg 등의 주양이온과 F, Cl, NO$_3$, SO$_4$, HCO$_3$, 등의 음이온 및 Al, Cr, Mn, Fe, Ni, Cu, Zn, Cd, Pb, Se, As, Hg 등의 미량 오염원소등을 분석하였다. 분석결과로부터 4가지 유형의 수질특성을 구분하였으며, 이 지역의 지하수는 알칼리니티와 염도에 의한 농업용수로서의 위해성은 없는 것으로 판명되었다. 지하수 중의 주요염물질은 비소였으며, 유비철석(arsenopyrite)의 산화로부터 기인되는 것으로 사료된다. 따라서 기매립된 광미와 퇴적물을 파내는 것은 비소성분의 지하수로의 이동을 유발할 수 있다. Gubong gold-mine, previously one of the largest gold mines in Korea, is located at the mid-west of the South Korea. In the areas nearby the mine, the shallow groundwater was the major source for domestic and farming water-supply. Soil contamination by Cd, Cu, Pb and Zn was previously known in this area. This study is objected to identify quality of the shallow groundwater, possibly affected by the mine tailings. Samples were collected from a nearby stream, shallow groundwater and seepage from the tailings. Chemical analysis for the water quality includes major cations such as Na, K, Ca, and Mg, anions as F, Cl, NO$_3$, SO$_4$, HCO$_3$, and trace elements as Al, Cr, Mn, Fe, Ni, Cu, Zn, Cd, Pb, Se, As, Hg. Water types could be drawn into four groups from the plots of Piper, Stiff diagrams and cluster analysis. SAR-Conductivity plot indicates the water does not pose either alkalinity or salinity hazards for irrigation. Major contaminant in groundwater appeared to be arsenic, released from arsenopyrites in tailings by oxidation. Dredging of buried railing materials could stimulate the release of arsenic from the sediments to the groundwater.

Recovery of Petroleum Hydrocarbons from Oily Sludge Landfilled Soil

Shin, Su-Yeon,Park, Sang-Min,Ko, Sung-Hwan,Jung, Hong-Bae,Baek, Kitae Korean Society of Soil and Groundwater Environment 2015 지하수토양환경 Vol.20 No.5

Three types of experiments, based on the physical properties of oily sludge landfilled soil, were conducted to recover total petroleum hydrocarbons (TPH) from the soil. These experiments included gravity separation, solvent extraction using water, and air floatation. The oil portion was not easily separated from the wet (raw) soil because water molecules aggregate the soil particles, despite the fact that the soil was sandy. However, the drying and grinding processes destroyed the aggregates, causing the TPH recovery to increase to approximately 60% when air floatation was used. The drying process decreased the specific gravity of the soil sample, thereby enhancing the overall recovery of TPH from the soil. Although thermal desorption and/or incineration are common choices for heavily dumped sites, physical separation can recover the oil portion instead of simply removing it.

Aging Effects On Partitioning Coefficients of Cd, Cu, and Zn in Metal-spiked Soils

김보정,Kim, Bo-Jeong,McBride, Murray B. Korean Society of Soil and Groundwater Environment 2008 지하수토양환경 Vol.13 No.5

금속이 염 용액 형태로 토양에 유입될 때, 그 금속의 용해도는 시간이 지남에 따라 감소하는 경향(aging)을 보이는데, 이러한 시간 의존성 외에 토양 내 금속 용해도의 변화에 영향을 미치는 또 다른 요인들에 대한 고찰은 아직 미비한 상태이다. 본 연구에서는 물리화학적 성질이 다른 5 종류의 토양 (히스토졸, 앤디졸, 옥시졸, 미세입자 알피졸, 조대입자 알피졸)에 여러 비율의 카드뮴(2.5-20 mg ${kg}^{-1}$)/ 구리(50-400 mg${kg}^{-1}$)/ 아연(50-400 mg ${kg}^{-1}$) 염 용액을 혼합하여, 상온에서 1년 동안 토양의 성질, 금속의 종류, 금속의 농도에 따른 용해도 변화관찰을 시도하였다. 그 결과, 히스토졸에서는 카드뮴이, 앤디졸에서는 구리가, 미세입자 알피졸에서는 아연이 가장 높은 분배 계수를 보였고, 옥시졸과 조대입자 알피졸에서는 모든 금속들이 가장 낮은 분배 계수를 나타내었다. 또한, 카드뮴과 아연의 경우 토양의 종류와는 무관하게 시간에 따른 분배 계수의 증가를 보였지만, 구리의 경우 토양 내 유입된 후 일주일 부터는 이러한 경향성를 찾아보기 어려웠다. 구리는 토양의 유기물이 많을 경우에는 빠른 흡착성을 보이지만, 토양수에 녹아있는 유기물이 많을 경우에는 그 흡착 특성이 제한됨을 관찰하였다. 더욱이, 흡수력이 높은 토양의 경우 금속의 분배 계수는 유입된 금속의 양과는 무관할 뿐만 아니라, 높은 농도로 처리된 토양의 금속 분배 계수가 낮은 농도로 처리된 토양의 분배계수와 유사해지기 까지는 더 오랜 시간이 요구되는 반면, 낮은 흡수력을 가진 토양의 경우에는 시간보다는 금속의 초기 유입양이 분배 계수 결정에 더욱 큰 영향을 미치는 것으로 밝혀졌다. 본 연구를 통해, 토양에 유입된 금속의 용해도 변화는 시간 뿐만 아니라, 토양의 성질, 금속의 종류와 농도에도 상당히 의존함을 입증하였다. Temporal changes of metal solubility have been repeatedly observed in soils equilibrated with metal salt solutions. This phenomenon is known as aging, yet factors that affect the degree of metal aging remain largely unexamined. In this study, we compared the extent of aging on metal partitioning depending on soil, metal, and metal loading. Five soils spiked with four levels of Cd (2.5-20 mg ${kg}^{-1}$), Cu, and Zn (50-400 mg ${kg}^{-1}$) salt solutions were aged in the laboratory up to 1 year. The partitioning coefficient ($K_d$) of each metal was calculated from the ratio of total to dissolved metal concentration in samples collected at times ranging from 1 day to 1 year. The highest $K_d$ values for Cd, Cu and Zn were recorded in a Histosol, Andisol, and fine-textured Alfisol, respectively, whereas the lowest $K_d$ was recorded for an Oxisol and coarsetextured Alfisol. For all soils, a pattern of increasing Kd with aging was evident for Cd and Zn, but not Cu. Rapid Cu sorption was limited when dissolved organic matter was high in soils. In highly-retentive soils, $K_d$ values seemed to be insensitive to metal loading, although a longer period was required for the higher metal loadings to reach the same degree of metal aging as the lower loadings. In soils with low sorption capacity, the $K_d$ values were determined more by metal loading than by aging. Therefore, marked differences can be expected in the degree of metal aging in spiked soils by the soil type, metal and amount of metal added.

Stabilization of Metals-contaminated Farmland Soil using Limestone and Steel Refining Slag

Lim, Jeong-Muk,You, Youngnam,Kamala-Kannan, Seralathan,Oh, Sae-Gang,Oh, Byung-Taek Korean Society of Soil and Groundwater Environment 2014 지하수토양환경 Vol.19 No.5

The metals contamination of farmland soil nearby abandoned metal mine was serious problem in Korea. Stabilization of contaminated soil was reported using various stabilizers. Application of limestone and steel refining slag was reported as effective stabilizers in the stabilization of metals. The batch studies confirmed that the mixture of limestone and steel refining slag was suitable for stabilization of metals in contaminated soil. The limestone and steel refining slag mixture (2 : 1 and 3 : 2) were used in column studies and it was confirmed that the stabilizers effectively stabilized heavy metals in contaminated soil. The pH of the soil was increased with the addition of stabilizers. Total leached concentration of metals from the column study was reduced 44, 17, and 93% in comparison to the control at arsenic, cadmium and copper, respectively. The sequential extraction studies showed that the exchangeable fraction was changed into carbonate bound fraction (Cd and Cu) and Fe-Mn oxide bound fraction (As). Based on the results we confirmed that 2:1 ratio of limestone and steel refining slag effectively stabilizes the heavy metals. The mixed treatment of lime stone with steel refining slag would be an effective and feasible method for controlling metals leaching in contaminated soil.

Surfactant-enhanced Soil Washing using Tween and Tergitol Series Surfactants for Kuwait Soil Heavily Contaminated with Crude Oil

Heo, Hyojin,Lee, Minhee Korean Society of Soil and Groundwater Environment 2015 지하수토양환경 Vol.20 No.5

Batch experiments were performed to investigate the feasibility of a surfactant-enhanced soil washing process for soils heavily contaminated with crude oil in Kuwait. TPH concentration of the contaminated soil was 223,754 mg/kg, sampled from the bottom of a vaporized oil extraction pond in the Burgan reservoir field. Commercialized eight nonionic surfactants (Tween and Tergitol series) were used to measure the aqueous solubility for the crude oil. Among them, two Tergitol surfactants were used to evaluate the TPH removal efficiency of the surfactant-enhanced soil washing for heavily contaminated Kuwait soil. The solubility of the crude oil in surfactant solution was in the order Tergitol 15-S-7 > Tergitol 15-S-9 > Tergitol 15-S-12 > Tween-80 > Tween-20 > Tween-60, which showed that the crude oil solubilities of the Tergitol series were higher than those of the Tween series. The TPH removal efficiencies of 2% and 5% Tergitol 15-S-9 solution were 59% and 65%, respectively. Because the residual TPH concentration in the washed soil was still higher than the clean-up level (10,000 mg/kg), the soil washing process was repeated five times. After the fifth washing, the residual TPH concentration in the soil went down to 7,680 mg/kg and its removal efficiency was 97%.

Geochemical Modeling of Groundwater in Granitic Terrain: the Yeongcheon Area

Koh, Yong-Kwon,Kim, Chun-Soo,Bae, Dae-Seok,Yun, Seong-Taek Korean Society of Soil and Groundwater Environment 1998 지하수환경 Vol.5 No.4

영천 도수터널 내 화강암 지역의 단열대를 따라 유출되는 지하수에 대하여 지화학 및 환경동위원소 연구를 수행하였다. Ca-HCO$_3$유형에 속하는 유출수의 화학 조성은 화강암을 구성하는 규산염 광물 및 열극 충진 방해석의 지화학적 용해 반응에 의해 설명되며, 그 수문지화학적 진화는 부분적 개방계에서 진행되었음을 보여준다. 환경동위원소 연구 결과, 유출수는 모두 강수 기원으로서 적어도 1953년 이전에 함양된(즉 체류 시간이 최소 45년 이상인) 지하수임을 지시해주며, 나아가 지표로부터의 거리와 단열대의 발달 상태에 따라 부분적으로 지표수의 혼입이 진행되고 있음을 지시한다. 지화학 반응 경로 모델인 CHILLER를 이용하여 본 지역 화강암 지하수의 수문지화학적 진화를 모델링 하였다. 그 결과, $Ca^{2+}$, $Na^{+}$, HCO$_3$$^{-}$ 및 pH는 규산염 광물 및 방해석의 용해 작용과 더불어 점차 증가되는 반면, $Mg^{2+}$ 및 $K^{+}$는 각각 몬트모릴로나이트와 백운모의 2차 생성과 더불어 감소됨을 보여준다. 2차 광물의 생성 순서는 적철석, 깁사이트, 카올리나이트, 몬트모릴로나이트, 백운모, 장석의 순이다. 모델링 결과는 유출수의 물리화학적 분석값과 2차 광물의 동정 결과와도 잘 일치한다. 따라서, 이러한 물-암석 상호 반응 모델링을 비교적 복잡한 암반 지하수의 수문지화학적 진화 해석에 타당성 있게 적용할 수 있음을 보여준다. We investigated the geochemistry and environmental isotopes of granite-bedrock groundwater in the Yeongcheon diversion tunnel which is located about 300 m below the land surface. The hydrochemistry of groundwaters belongs to the Ca-HCO$_3$type, and is controlled by flow systems and water-rock interaction in the flow conduits (fractures). The deuterium and oxygen-18 data are clustered along the meteoric water line, indicating that the groundwater are commonly of meteoric water origin and are not affected by secondary isotope effects such as evaporation and isotope exchange. Tritium data show that the groundwaters were mostly recharged before pre-thermonuclear period and have been mixed with younger surface water flowing down rapidly into the tunnel along fractured zones. Based on the mass balance and reaction simulation approaches, using both the hydrochemistry of groundwater and the secondary mineralogy of fracture-filling materials, we have modeled the low-temperature hydrogeochemical evolution of groundwater in the area. The results of geochemical simulation show that the concentrations of Ca$\^$2+/, Na$\^$+/ and HCO$_3$and pH of waters increase progressively owing to the dissolution of reactive minerals in flow paths. The concentrations of Mg$\^$2+/ and K$\^$+/ frist increase with the dissolution, but later decrease when montmorillonite and illitic material are precipitated respectively. The continuous adding of reactive minerals, namely the progressively larger degrees of water/rock interaction, causes the formation of secondary minerals with the following sequence: first hematite, then gibbsite, then kaolinite, then montmorillonite, then illtic material, and finally microcline. During the simulation all the gibbsite is consumed, kaolinite precipitates and then the continuous reaction converts the kaolinite to montmorillonite and illitic material. The reaction simulation results agree well with the observed, water chemistry and secondary mineralogy, indicating the successful applicability of this simulation technique to delineate the complex hydrogeochemistry of bedrock groundwaters.

The Removal Efficacy of Heavy Metals and Total Petroleum Hydrocarbons from Contaminated Soils by Integrated Bio-phytoremediation

Lai, Wen-Liang,Lee, Fang-Yin,Chen, Colin S.,Hseu, Zeng-Yei,Kuo, Yau-Lun Korean Society of Soil and Groundwater Environment 2014 지하수토양환경 Vol.19 No.5

In this study, the bio-phytoremediation and phytoremediation technologies were applied to the soils contaminated with total petroleum hydrocarbons (TPH) and heavy metals to evaluate the remediation efficacy from May 2012 to December 2013. Poplar (Populus bonatii Levl.) and Sun Hemp (Crotalaria juncea L.) were selected and planted in phytoremediation practice. These plants were also utilized in the bio-phytoremediation practice, with the addition of earthworm (Eisenia fetida) and petroleum-degrading bacteria (Pseudomonos sp. NKNU01). Furthermore, physiological characteristics, such as photosynthesis rate and maximal photochemical yield, of all testing plants were also measured in order to assess their health conditions and tolerance levels in adverse environment. After 20 months of remedial practice, the results showed that bio-phytoremediation practice had a higher rate of TPH removal efficacy at 30-60 cm depth soil than that of phytoremediation. However, inconsistent results were discovered while analyzing the soil at 100 cm depth. The study also showed that the removal efficiency of heavy metals was lower than that of TPH after remediation treatment. The results from test field tissue sample analysis revealed that more Zinc than Chromium was absorbed and accumulated by the tested plants. Plant height measurements of Poplar and Sun Hemp showed that there were insignificant differences of growth between the plants in remediation plots and those in the control plot. Physiological data of Poplar also suggested it has higher tolerance level toward the contaminated soils. These results indicated that the two testing plants were healthy and suitable for this remediation study.