• Journal of Soil and Groundwater Environment
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• v.17 no.2
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• pp.15-21
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• 2012

MTBE (Methyl tertiary-butyl ether) has been commonly used as an octane enhancer to replace tetraethyl lead in gasoline, because MTBE increases the efficiency of combustion and decreases the emission of carbon monoxide. However, MTBE has been found in groundwater from the fuel spills and leaks in the UST (Underground Storage Tank). Fenton's oxidation, an advanced oxidation catalyzed with ferrous iron, is successful in removing MTBE in groundwater. However, Fenton's oxidation requires the continuous addition of dissolved $Fe^{2+}$. Zero-valent iron is available as a source of catalytic ferrous iron of MFO (Modified Fenton's Oxidation) and has been studied for use in PRBs (Permeable Reactive Barriers) as a reactive material. Therefore, this study investigated the condition of optimization in MFO-PRBs using waste zero-valent iron (ZVI) with the waste steel scrap to treat MTBE contaminated groundwater. Batch tests were examined to find optimal molar ratio of MTBE : $H_2O_2$ on extent to degradation of MTBE in groundwater at pH 7 with 10% waste ZVI. As the results, the ratio of optimization of MTBE to hydrogen peroxide for MFO was determined to be 1:300[mM]. The column experiment was conducted to know applicability of MFO-PRBs for MTBE remediation in groundwater. As the results of column test, MTBE was removed 87% of the initial concentration during 120days of operational period. Interestingly, MTBE was degraded not only within waste ZVI column but also within sand column. It means the aquifer may affect continuously the MTBE contaminated groundwater after throughout the waste ZVI barrier. The residual products showed acetone, TBF (Tert-butyl formate) and TBA (Tert-butyl acetate) during this test. The results of the present study showed that the recycled materials can be effectively used for not only a source of catalytic ferrous iron but also a reactive material of the MFO-PRBs to remove MTBE in groundwater.

• Journal of Soil and Groundwater Environment
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• v.14 no.2
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• pp.26-32
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• 2009

In this study, the degradation of BTEX (benzene, toluene, ethylbenzene, xylene) was tested in both (Fe$^{3+}$+chelating agent)/H$_2$O$_2$system [Fe(III) 1 mM, oxalate 6 mM, H$_2$O$_2$ 3%, and pH 6] and UV/(Fe3++ chelating agent)lHzOz system [UV dose 17.4 kWhlL, Fe(III) 1mM, oxalate 6 mM,H$_2$O$_2$ 1%, and pH 6]. The types of chelating agents used in experiments were catechol, NTA, gallic, acetyl acetone, succinic, acetate, EDTA, citrate, malonate, and oxalate and the optimum chelating agent for BTEX degradation was determined. The results showed that acetate was the optimum chelating agent for BTEX degradation in both (Fe$^{3+}$+chelating agent)/H$_2$O$_2$ and UV/(Fe$^{3+}$+chelating agent)/H$_2$O$_2$ system, and UV radiation enhanced the degradation of BTEX with any types of chelating agents. Moreover, UV/(Fe$^{3+}$+chelating agent)/H$_2$O$_2$ system, which chelating agent was acetate, removed effectively mixtures of BTEX and MTBE (methyl tert-butyl ether) when the concentration of both BTEX and MTBE was 200 mg/L, respectively. In this system, BTEX was degraded completely and 85% of MTBE was degraded at the reaction time of 180 min. Therefore, UV/((Fe$^{3+}$+chelating agent)/H$_2$O$_2$ system with acetate as a chelating agent removed not only BTEX but also BTEX and MTBE, effectively.

• Journal of Soil and Groundwater Environment
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• v.12 no.2
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• pp.27-36
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• 2007

A recent study showed that MTBE can be degraded by Fenton's Reagent (FR). The treatment of MTBE with FR, however, has a definite limitation of extremely low pH requirement (optimum pH $3{\sim}4$) that makes the process impracticable under neutral pH condition on which the ferrous ion precipitate forming salt with hydroxyl anion, which result in the diminishment of the Fenton reaction and incompatible with biological treatment. Consequently, this process using only FR is not suitable for in-situ remediation of MTBE. In order to overcome this limitation, modified Fenton process using NTA, oxalate, and acetate as chelating reagents was introduced into this study. Modified Fenton reaction, available at near neutral pH, has been researched for the purpose of obtaining high performance of oxidation efficiency with stabilized ferrous or ferric ion by chelating agent. In the MTBE degradation experiment with modified Fenton reaction, it was observed that this reaction was influenced by some factors such as concentrations of ferric ion, hydrogen peroxide, and each chelating agent and pH. Six potential chelators including oxalate, succinate, acetate, citrate, NTA, and EDTA were tested to identify an appropriate chelator. Among them, oxalate, acetate, and NTA were selected based on their remediation efficiency and biodegradability of each chelator. Using NTA, the best result was obtained, showing more than 99.9% of MTBE degradation after 30 min at pH 7; the initial concentration of hydrogen peroxide, NTA, and ferric ion were 1470 mM, 6 mM, and 2 mM, respectively. Under the same experimental condition, the removal of MTBE using oxalate and acetate were 91.3% and 75.8%, respectively. Optimum concentration of iron ion were 3 mM using oxalate which showed the greatest removal efficiency. In case of acetate, $[MTBE]_0$ decreased gradually when concentration of iron ion increased above 5 mM. In this research, it was showed that modified Fenton reaction is proper for in-situ remediation of MTBE with great efficiency and the application of chelatimg agents, such as NTA, was able to make the ferric ion stable even at near neutral pH. In consequence, the outcomes of this study clearly showed that the modified Fenton process successfully coped with the limitation of the low pH requirement. Furthermore, the introduction of low molecular weight organic acids makes the process more available since these compounds have distinguishable biodegradability and it may be able to use natural iron mineral as catalyst for in situ remediation, so as to produce hydroxyl radical without the additional injection of ferric ion.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2005.10a
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• pp.34-37
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• 2005

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.3049-3052
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• 2009

Methyl tert-butyl ether (MTBE) is added to gasoline to enhance the octane number of gasoline, tert-butyl alcohol (TBA) is major degradation intermediate of MTBE in environment, and benzene, toluene, ethyl benzene and xylene (BTEX) are also major constituents of gasoline. In this study, a simplified headspace analysis method was adapted for simultaneous determination of MTBE, TBA and BTEX in ground water samples. The sample 5.0 mL and 2 g NaCl were placed in a 10 mL vial and the solution was spiked with fluorobenzene as an internal standard and sealed with a cap. The vial was placed in a heating block at 85 $^{\circ}C$ for 30 min. The detection limits of the assay were 0.01 ${\mu}$g/L for MTBE and BTEX, and 0.02 ${\mu}$g/L for TBA. The method was used to analyze 110 ground water samples from various regions in Korea, and to survey the their background concentration in ground water in Korea. The samples revealed MTBE concentrations in the range of 0.01 - 0.45 ${\mu}$g/L (detection frequency of 57.3%), TBA concentrations in the range of 0.02 - 0.08 ${\mu}$g/L (detection frequency of 5.5%), and total BTEX concentrations in the range of 0.01 - 2.09 ${\mu}$g/L (detection frequency of 87.3%). The developed method may be used when simultaneously determining the amount of MTBE, TBA and BTEX in water.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2008.11a
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• pp.110-113
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• 2008

최근 가시광선에서 응답하는 광촉매를 이용하여 저농도의 일반적인 실내 대기 오염물질 제어를 위한 적용가능성에 대해 많은 평가가 있어왔다. 가시광선에서 활성을 보이는 질소 원소가 도핑된 TiO$_2$광촉매를 이용하여 대표적인 휘발성유기화합물질들 중에 하나인 MTBE의 분해율에 대한 실험을 실시하였다. 본 연구에서 여러 가지 변수들 중에 농도와 상대습도에 따라 MTBE의 분해율에 대하여 실험하였으며, 본 연구의 실험조건하에서 질소가 도핑된 TiO$_2$ 광촉매를 통해서 효과적으로 MTBE가 제거됨을 확인 할 수 있었다.

• Journal of the Korean GEO-environmental Society
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• v.12 no.10
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• pp.57-62
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• 2011

This study investigated the effects of various inorganic anions($Cl^-$, $NO_3{^-}$, $HCO_3{^-}$) on the Methyl tert Butyl Ether(MTBE) degradation by photocatalysis using statistical method. Generally, this process in general demands the generation of hydroxyl radicals(OH radical) in solution in the presence of UV light. The generation of radicals were affected by inorganic anions in solution that inhibited the photodegradation by their trapping hydroxyl radicals. The effects of inorganic anions were mathematically described as the independent variables such as $Cl^-$, $NO_3{^-}$, and $HCO_3{^-}$, and these were designed by mixture analysis that was one of the response surface methodology(RSM). Regression analysis on ANOVA showed significant p-value(p<0.0001) and high coefficients for determination value($R^2$=99.28%, ${R^2}_{adj}$=98.91%). Contour and response surface plots showed that the effects of inorganic anions for MTBE photodegradation based on $UV/H_2O_2$ process. In the result, $Cl^-$ and $HCO_3{^-}$ inhibited the photodegradation of the MTBE by their trapping hydroxyl radicals, and the interaction by these two factors was observed.

• Journal of the Korean GEO-environmental Society
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• v.11 no.8
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• pp.65-71
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• 2010

In this study, we have evaluated biodegradability of diesel-oxygenates including DBM and gasoline-oxygenates having similar physio-chemical properties using indigenous aerobic microorganisms from a diesel-contaminated soil. Toluene and Ethanol have shown higher biological activity and the first-order degradation rate constants ranged around $0.11{\sim}0.3day^{-1}$. However, MTBE, gasoline-oxygenate has shown as a limited substrate. Moreover, As increased initial concentrations of DBM and TGME, degradation rates of those were decreased relatively. As a strategy to evaluate biodegradability of DBM and TGME, reduction of diesel-oxygenates, $CO_2$ production and toxicity by algae were monitored. This results indicated possible mineralization of diesel-oxygenates, But we could predict that residual byproduct produced even though complete consumption of diesel-oxygenates were observed if algal toxicity variation considered. In conclusion, it is the first report that diesel-oxygenates including DBM could be biodegraded effectively by indigenous soil microorganisms and this result increased the possibility of bioremediation technology to apply into oil-contaminated sites.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.4
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• pp.393-400
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• 2008

1,4-Dioxane($C_4H_8O_2$), which is used as a solvent stabilizer, could make harmful effects on ecosystem because of its higher solubility, toxicity and carcinogenic by US EPA. From 2011, its discharge limit to waterbody will be regulated at 5 mg/L by Ministry of Environment Republic of Korea. It was thus to investigate that the currently operating activated sludge in polyester manufacturing processes in Gumi can properly treat it to meet with the regulation standard. For that purpose, the removal rate of 1,4-dioxane and its microbial properties were assessed for a few companies(i.e. K, H and T). Its removal efficiency was the most highly recorded in H as 98% and then 77% for K, which met with the regulation standard. However, concentration of 1,4-dioxane of T was 23 mg/L in the effluent, which is more than the regulation standard. Aside from, microbial degradation test was done for 100 ppm of 1,4-dioxane in BSM (Basal salt medium) inoculated with each of activated sludge. After 7 days, 1,4-dioxane was completely removed in the test bottle inoculated with H sludge, 67% in T and 52% in K, which could confirm that the given activated sludge might have different biodegradability against the amount of 1,4-dioxane. Therefore, microbial diversity in each company was investigated by 16s rDNA cloning methods where a species, e.g. Methylibium petroleiphilum PM1, was the greatest observed from H and in lesser from K, but it was not detected from T. Methylibium petroleiphilum PM1 is known to efficiently degrade ether like methyl tertiary-butyl ether(MTBE). It is concluded that the activated sludge in H can be most effectively adopted for a biodegradation of 1,4-dioxane in the concern of industrial sector.