• 한국지하수토양환경학회지:지하수토양환경
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• 제6권3호
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• pp.31-41
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• 2001

본 논문에서는 순수균주인 ENV425와 오염된 토양으로부터 분리한 혼합균주를 이용하여 가솔린 산화제인 MTBE에 대한 분해 가능성을 조사했다. MTBE는 n-butane에서 성장한 ENV425와 혼합균주에 의해 공대사적으로 분해가 이루어졌다. 또한 아세틸렌의 첨가에 의해 n-butane과 MTBE의 분해가 완전히 방해되어짐에 따라 두 기질 모두 부탄 분해 효소에 의해 분해되어짐을 알 수 있었다. n-butane에서 성장한 ENV42S와 혼합균주는 MTBE를 분해하고, MTBE의 분해산물로 TBA가 생성되었다. TBA의 생성은 분해된 MTBE에 대하여 ENV425와 혼합균주 각각 54.7%, 58.6%가 관찰되었다. 그러나, Resting cell 실험에서는 ENV425와 혼합균주에 의한 산화 생성물로 TBA와 TBF가 생성되었다. ENV425와 혼합균주에 의한 최대 MTBE 분해속도는 각각 52.3 그리고 62.3 (nmol MTBE degraded/hr/mg TSS), 최대 $T_y$ (Transformation yield)는 각각 44.7, 34.0 (nmol MTBE degraded/$\mu$mol n-butane utilized)으로 나타났고, 최대 $T_c$ (Transformation capacity)는 각각 199, 226 (nmol MTBE degraded/mg TSS used)으로 나타났다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제11권6호
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• pp.69-75
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• 2006

지하 저장 탱크로부터의 유류 유출로 인하여 전세계적으로 넓은 지역의 토양 및 지하수가 오염되고 있다. Methyl tert-butyl ether(MTBE)는 대기 오염 감소를 위하여 널리 사용되고 있는 유류 첨가제이지만 토양 및 지하수로 유입되어 섭취 되었을 때 발암 가능성이 있는 유독 물질이다. 본 연구는 고도 산화 처리 기법 중 유기 오염물의 분해에 높은 효율을 나타내는 고전적 Fenton reaction의 최대 단점인 강한 산성(pH 2.5-3) 의존성을 극복한 새로운 산화 처리 기법을 개발하여 고농도의 MTBE를 효과적으로 분해 하는 것을 그 목적으로 하여 자연 친화적인 chelating agents를 사용하여 중성 영역에서 Fenton reaction을 가능하게 하는 기법인 Modified Fenton reaction과 Ultra Violet light(UV)를 이용하여 분해효율을 극대화 하는 Photo-assisted Fenton reaction을 응용한 Modified Photo-Fenton reaction system을 개발하여 최적 반응 조건 및 반응 차수, 반응 메커니즘을 밝혀내었다. 낮은 독성과 높은 생분해성을 나타낸 Citrate ion을 chelating agents로 선정하였으며 최적 반응 조건은 [$Fe^{3+}$] : [Citrate] = 1 mM : 4 mM, 3% $H_2O_2$, 17.4 kWh/L UV dose, 초기 pH 6.0이며 이 조건에서 1000 ppm MTBE를 분해한 결과 6시간 후 86.75%, 16시간 후 99.99%의 높은 분해율을 나타냈으며 최종 pH는 6.02로 안정적이었다. 또한 Modified Photo-Fenton reaction을 이용한 MTBE 분해 반응은 유사 1차 반응을 나타내었으며 methoxy group이 ${\cdot}OH$ radical과 주로 반응하여 tert-butyl formate(TBF)가 주요 분해 산물이 되는 분해 경로를 따른 다는 것이 밝혀졌다. 본 연구로 개발된 Modified Photo-Fenton reaction에서 발생되는 산화제인 ${\cdot}OH$ radical의 비선택적 반응성을 고려할 때 본 system은 다른 종류의 유기 오염물 분해에도 효과적일 것으로 판단된다.

• 한국물환경학회지
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• 제21권4호
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• pp.403-409
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• 2005

Methyl tert-butyl ether (MTBE) contamination in groundwater often coexists with benzene, toluene, ethylbenzene, and xylene (BTEX) near the source of the plume. Then, groundwater contamination problems have been developed in areas where the chemical is used. Common sources of water contamination by BTEX and MTBE include leaking underground gasoline storage tanks and leaks and spills from above ground fuel storage tanks, etc. In oil-contaminated environments, anaerobic biodegradation of BTEX and MTBE depended on the concentration and distribution of terminal electron acceptor. In this study, effect of electron acceptor on the anaerobic biodegradation for BTEX and MTBE-contaminated soil was investigated. This study showed the anaerobic biodegradation of BTEX and MTBE in two different soils by using nitrate reduction, ferric iron reduction and sulfate reduction. The soil samples from the two fields were enriched for 65 days by providing BTEX and MTBE as a sole carbon source and nitrate, sulfate or iron as a terminal electron acceptor. This study clearly shows that degradation rate of BTEX and MTBE with electron acceptors is higher than that without electron acceptors. Degradation rate of Ethylbenzene and Xylene is higher than that of Benxene, Toluene, and MTBE. In case of Benzene, Ethylbenzene, and MTBE, nitrate has more activation. In case of Toluene and Xylene, sulfate has more activation.

• 한국지반환경공학회 논문집
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• 제15권5호
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• pp.39-46
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• 2014

본 연구에서는 다양한 호기/혐기조건에서 유류오염물질인 및 MTBE의 생분해 특성을 비교하고, 특히 탈질 조건에서 질산염 영향을 조사하여 유류오염지역의 혐기적 자연정화방법의 적용 가능성을 평가하고자 한다. 단일기질 및 혼합기질 분해실험 결과, BTEX는 3가지 실험조건에서 차이는 있었으나 모두 분해가 일어났다. 그러나 benzene과 p-xylene은 호기성 조건에서 초기 공급된 용존 산소의 부족으로 인하여 분해가 지연되는 것으로 나타났다. 또한 혼합기질에서는 단일기질에 비해 BTEX 분해가 기질 경쟁관계로 인해 다소 지연되는 경향이 관찰되었다. MTBE는 탈질 조건에서만 생분해가 관찰되었으나, TBA 축적 없이 $CO_2$로 무기화되는 것으로 추정된다. 또한 BTEX 및 MTBE 분해에 대한 질산염 농도의 영향 실험 결과, 저농도(>50 mg/L)에서 BTEX 분해는 제한되었으며, 고농도 질산염(<200 mg/L) 조건하에서는 BTEX 분해가 억제되는 현상이 관찰되었다. 본 연구에서 도출된 결과는 유류오염지역의 경우 호기/혐기성 조건에서 자연 생분해를 유도할 수 있을 것으로 예상된다.

• Advances in environmental research
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• 제3권1호
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• pp.11-28
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• 2014

Advanced oxidation processes using UV and catalysts like $TiO_2$ and ZnO have been recently applied for the photocatalytic degradation of MTBE in water. Attempts have been made to replace the UV radiation by the solar spectrum. This review intends to shed more light on the work that has been done so far in this area of research. The information provided will help in crystallizing the ideas required to shift the trend from UV photocatalysis to sunlight photocatalysis. The careful optimization of the reaction parameters and the type of the dopant employed are greatly responsible for any enhancement in the degradation process. The advantage of shifting from UV photocatalysts to visible light photocatalysts can be observed when catalysts like $TiO_2$ and ZnO are doped with suitable metals. Therefore, it is expected that in the near future, the visible light photocatalysis will be the main technique applied for the remediation of water contaminated with MTBE.

• 한국지하수토양환경학회지:지하수토양환경
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• 제21권3호
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• pp.88-94
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• 2016

The simultaneous biodegradation between MTBE (Gasoline additives) and BTEX (Benzene, Toluene, Ethyl-benzene, o-Xylene, m-Xylene, p-Xylene) was achieved within a competitive inter-relationship, with not only electron accepters such as nitrate, sulfate, and iron(III) without oxygen, but also with electron donors such as MTBE and BTEX. Preexisting indigenous microorganisms from a domestic sample of gasoline contaminated soil was used for a lab-scale batch test. The result of the test showed that the biodegradation rate of MTBE decreased when there was co-existing MTBE and BTEX, compared to having just MTBE present. The growth of indigenous microorganisms was not affected in the case of the MTBE treatment, whereas the growth of the microorganisms was decreased in combined MTBE and BTEX sample. This may indicate that an inhibitor related to biodegradation when BTEX and MTBE are mixed will be found. This inhibitor may be found to retard the anaerobic conditions needed for efficient breakdown of these complex carbon chain molecules in-situ. Moreover, it is also possible that an unknown competitive reaction is being imposed on the interactions between MTBE and BTEX dependent on conditions, ratios of mixture, etc.

• 한국환경과학회지
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• 제13권3호
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• pp.289-295
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• 2004

The objective of this study is to delineate removal efficiency of the MTBE in solution by $TiO_2$ photocatalytic degradation as a function of the following different experimental conditions: Initial concentration of MTBE, air flow rate in solution, $H_2O_2$ dosage and pH of the solution. Photodegradation rate was increased with decreasing initial concentration of MTBE. The removal efficiency was 82% after 180 min in the case of MTBE concentration of 100 mg/L but 100% after 180 min in the case of 20 mg/L. Removal efficiency was increased with increasing pH, $H_2O_2$ dosage and air flow rate in solution.

• 한국지하수토양환경학회지:지하수토양환경
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• 제19권5호
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• pp.9-17
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• 2014

This paper reported the use of real-time polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE), and the culture-based method in the intrinsic bioremediation study at a petroleum contaminated site. The study showed that phenol hydroxylase gene was detected in groundwater contaminated with benzene, toluene, ethylbenzene, xylene isomers (BTEX) and methyl tert-butyl ether (MTBE). This indicated that intrinsic bioremediation occurred at the site. DGGE analyses revealed that the petroleum-hydrocarbon plume caused the variation in microbial communities. MTBE degraders including Pseudomonas sp. NKNU01, Bacillus sp. NKNU01, Klebsiella sp. NKNU01, Enterobacter sp. NKNU01, and Enterobacter sp. NKNU02 were isolated from the contaminated groundwater using the cultured-based method. Among these five strains, Enterobacter sp. NKNU02 is the most effective stain at degrading MTBE without the addition of pentane. The MTBE biodegradation experiment indicated that the isolated bacteria were affected by propane. Biodegradation of MTBE was decreased but not totally inhibited in the mixtures of BTEX. Enterobacter sp. NKNU02 degraded about 60% of MTBE in the bioreactor study. Tert-butyl alcohol (TBA), acetic acid, 2-propanol, and propenoic acid were detected using gas chromatography/mass spectrometry during MTBE degraded by the rest cells of Enterobacter sp. NKNU02. The effectiveness of bioremediation of MTBE was assessed for potential field-scale application.

• 한국환경보건학회지
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• 제24권3호
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• pp.63-69
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• 1998

The treatment of soils and water contaminated with MTBE using the Fenton oxidation was investigated. The effects of dosage of $H_{2}O_{2}$, and Fe$^{2+}$ concentrations, and solution pH on transformation and mineralization in soil were evaluated. Generation of TBA and acetone following Fenton-oxidation of MTBE in water and generation of acetone following Fenton-oxidation of TBA were observed. Therefore TBA and acetone are degradation intermediates of MTBE. There was a large difference of treatment efficiency in Fenton oxidation of MTBE between soil and water system. This may be caused by the complex nature of soil, soil organic matter which can consumed OH $\cdot$ radicals, and interacting with inorganic-soil constituents. The pH of soil was observed to have a significant effect on the chemical oxidation efficient of MTBE in soil The data demonstrated that optimal pH range were pH 3~4 and around 6. The soil batch studies demonstrated that treatment efficiency of MTBE was enhanced by adding additional ferrous salts but Fenton-oxidation occurred in no additional iron which indicated that iron in soil can catalyze the Fenton-oxidation. The most effective parameter of Fentonoxidation was $H_{2}O_{2}$/Fe$^{2+}$ ratio which theocratical ratio is 0.5. The optimal range of this ratio was found to be 0.6~2.3. In evaluating effect of $H_{2}O_{2}$ dosage on treatment efficiency, the increase of $H_{2}O_{2}$ did not always lead to increase of decompositions of MTBE in soil. Fenton oxidation was effective in destroying MTBE in aqueous extracts of contaminated soil and water. Experimental data provided evidence that the Fenton oxidation can effectively remediate MTBE-contaminated water and soil.

• 한국지반환경공학회 논문집
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• 제12권9호
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• pp.55-61
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• 2011

본 연구는 UV와 $H_2O_2$를 통한 광분해 반응기에서의 Methyl Tert Butyl Ether(MTBE) 제거에 대해 조사하였다. 이 공정은 일반적으로 UV의 존재 하에 수용액 상에 생성되는 OH 라디칼을 요구하며, 이 라디칼들은 MTBE 분자를 공격하여 최종적으로 파괴하거나 무해한 단순 화합물로 전환시킨다. 반응들은 조사강도, MTBE 초기농도와 $H_2O_2$/MTBE비의 독립변수를 수학적으로 표현하였고, 반응표면법(Response Surface Methodology; RSM)을 사용하여 모델화하였다. 이 실험들은 Box-Behnken Design(BBD)를 통한 15개의 실험을 포함하여 실시하였다. ANOVA의 회귀분석 항은 유의한 p-value(p<0.05)와 높은 결정계수($R^2$=94.60%)를 나타내어 2차 회귀모델의 예측이 적절한 것으로 나타났다. 그리고 반응에 대한 정준분석을 통해 예측된 Y에 대한 최적 반응과 최대반응의 예측된 능선을 통해 최적조건은 각각 조사강도인 $x_1$=25.75W, MTBE 초기농도의 $x_2$=7.69mg/L 와 $H_2O_2$/MTBE비인 $x_3$=11.04로 관찰되었다. 본 연구는 RSM이 MTBE 제거의 최대화와 운전조건의 최적화에 적용하기에 알맞은 것으로 나타났다.