• 한국환경보건학회지
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• 제40권2호
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• pp.147-156
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• 2014

Objectives: This study was carried out to examine whether the apparent photolysis with or without sensitizers [NaOH and humic acid (HA)] was prompted photodegradation of polychlorinated biphenyl (PCB) in aqueous solution. Methods: PCBs photodegradation occurred using fluorescence black lamps at ${\lambda}_{max}=300nm$. PCB congeners were exposed in 10 ppm HA or 0.05N NaOH solutions, to investigate the decreasing profile of PCB concentration with time. The PCBs were then analyzed by gas chromatography/mass spectrometry (GC-MS). Reductive degradation profile of PCB congeners in the presence of both sensitizers under oxygen-saturated protic conditions was described using the wind-rose diagrams. Results: Use of HA or NaOH decreased PCB concentration with time in the dark and on irradiation, indicating that photolysis underwent through reductive dechlorination through energy transfer and possibly with reactive oxygens. The dechlorination was marked by a chromatographic shift, observed in the GC-MS plots. Therefore it is logical to assume that increasing the dose of sensitizers would increase the photodegradation rates of PCBs. The half-lives of pentachloro-PCB (penta-3) in 0.05N NaOH and 10 ppm HA were estimated at about 47 hours and 39 hours, respectively, under the same experimental conditions of photolysis. It was found that the rate of photolysis of pentachloro-PCB in aqueous solution followed apparent first-order kinetics compared to other congeners. Conclusion: Photochemical degradation (using 328 nm UV light) of penta- and hexa-PCBs in HA or alkaline solution is a viable method for pretreatment method. The results are helpful for the further comprehension of the reaction mechanism for photolytic dechlorination of PCBs in aquatic system.

• Environmental Engineering Research
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• 제16권4호
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• pp.187-203
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• 2011

Chlorophenols (CPs) are widely used industrial chemicals that have been identified as being toxic to both humans and the environment. Zero valent iron (ZVI) and iron based bimetallic systems have the potential to efficiently dechlorinate CPs. This paper reviews the research conducted in this area over the past decade, with emphasis on the processes and mechanisms for the removal of CPs, as well as the characterization and role of the iron oxides formed on the ZVI surface. The removal of dissolved CPs in iron-water systems occurs via dechlorination, sorption and co-precipitation. Although ZVI has been commonly used for the dechlorination of CPs, its long term reactivity is limited due to surface passivation over time. However, iron based bimetallic systems are an effective alternative for overcoming this limitation. Bimetallic systems prepared by physically mixing ZVI and the catalyst or through reductive deposition of a catalyst onto ZVI have been shown to display superior performance over unmodified ZVI. Nonetheless, the efficiency and rate of hydrodechlorination of CPs by bimetals depend on the type of metal combinations used, properties of the metals and characteristics of the target CP. The presence and formation of various iron oxides can affect the reactivities of ZVI and bimetals. Oxides, such as green rust and magnetite, facilitate the dechlorination of CPs by ZVI and bimetals, while oxide films, such as hematite, maghemite, lepidocrocite and goethite, passivate the iron surface and hinder the dechlorination reaction. Key environmental parameters, such as solution pH, presence of dissolved oxygen and dissolved co-contaminants, exert significant impacts on the rate and extent of CP dechlorination by ZVI and bimetals.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 2000년도 창립총회 및 춘계학술발표회
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• pp.108-111
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• 2000

FeS/FeS$_2$ minerals have been known to be potentially useful reductant to the removal of common organic contaminants in groundwater and soil. This research is aimed at improving our understanding of factors affecting the pathways and rates of reductive transformation of Hexachloroethane by catalytical iron minerals in natural system. Hexachloroethane is reduced by FeS/FeS$_2$ minerals under anaerobic condition to tetrachloroethylene and trichloroethylene with pentachloroethyl radical as the intermediate products. The kinetics of reductive transformations of the Hexachloroethane have been investigated in aqueous solution containing FeS, FeS$_2$. The proposed reduction mechanism for the adsorbed nitrobenzene involves the electron donor-acceptor complex as a precursor to electron transfer. The adsorbed Hexachloroethane undergo a series of electron transfer, proton transfer and dehydration to achieve complete reduction. It can be concluded that the reductive transformation reaction takes place at surface of iron-bearing minerals and is dependent on surface area and pH. Nitrobenzene reduction kinetics is affected by reductant type, surface area, pH, the surface site density, and the surface charge. FeS/FeS$_2$-mediated reductive dechlorination may be an important transformation pathway in natural systems.

• 한국지하수토양환경학회지:지하수토양환경
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• 제17권5호
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• pp.49-55
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• 2012

A 1.28 L-batch reactor and continuous-flow stirred tank reactor (CFSTR) fed with formate and trichloroethene (TCE) were operated for 120 days and 56 days, respectively, to study the effect of formate as electron donor on anaerobic reductive dechlorination (ARD) of TCE to cis-1,2-dichloroethylene (c-DCE), vinyl chloride (VC), and ethylene (ETH). In batch reactor, injected 60 ${\mu}mol$ TCE was completely degraded in the presence of 20% hydrogen gas ($H_2$) in less than 8 days by anaerobic dechlorination mixed-culture (300 mg-soluble protein), Evanite Culture with ability to completely degrade tetrachloroethene (PCE) and -TCE to ETH under anaerobic conditions. Once the formate was used as electron donor instead of hydrogen gas in batch or chemostat system, the TCE-dechlorination rate decreased and acetate production rate increased. It indicates that the concentration of hydrogen produced in both systems is possibly more close to threshold for homoacetogenesis process. Soluble protein concentration of Evanite culture during the batch test increased from 300 mg to 688 mg for 120 days. Through the protein monitoring, we confirmed an increase of microbial population during the reactor operation. In CFSTR test, TCE was fed continuously at 9.9 ppm (75.38 ${\mu}mol/L$) and the influent formate feed concentration increased stepwise from 1.3 mmol/L to 14.3 mmol/L. Injected TCE was accumulated at 18 days of HRT, but TCE was completely degraded at 36 days of HRT without accumulation of the injected-TCE during the left of experiment period, getting $H_2$ from fermentative hydrogen production of injected formate. Although c-DCE was also accumulated for 23 days after beginning of CFSTR operation, it reached steady-state in the presence of excessive formate. We also evaluated microbial dynamic of the culture at different chemical state in the reactor by DGGE (denaturing gradient gel electrophoresis).

• Environmental Analysis Health and Toxicology
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• 제11권3_4호
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• pp.33-44
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• 1996

Photolysis of TCBs in aqueous solutions of sodium nitrite and triethylamine (TEA) at neutral pH has been investigated. TCBs yielded trichloronitrobenzenes(TCNBs) as primary photoproducts, and their corresponding trichlorophenols (TCPs) via two types of reaction, one, nitration, and the other, by direct hydroxylation with OH radical. Isomerized products and TCBs were also identified. Photosensitization with TEA resulted in the formation of small yields of dichlorobenzenes(DCBs) by reductive dechlorination of TCBs.

• 미생물학회지
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• 제45권2호
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• pp.140-147
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• 2009

경기도 김포 지역과 인천 서구 지역공단 주변에 위치한 소하천의 저니(sediment)에서 난분해성 염소화합물인 PCE (tetrachloroethylene)의 혐기성 탈염소화 능력이 있는 군집을 선별하고, 탈염소화에 관여하는 미생물을 탐색하였다. 혐기성 탈염소화 능력을 조사하기 위해 전자공여체로 lactate를 사용하여 혐기성 회분식 실험을 실시하였으며, 탈염소화 능력을 가진 군집을 선별하였다. 선발된 미생물군집은 분자생물학적 기법인 16S rRNA gene의 Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) 기법과 탈염소화 미생물을 선택적으로 탐색할 수 있는 species-specific primer를 이용하여 분석하였다. 총 16개의 시료 중에서 접종 8주 만에 3개의 시료에서 ethene까지 탈염소화시켰으며, 4개의 시료에서 cis-1,2-dichloroethene (cis-DCE)까지 탈염소화시켰다. 또한, 16S rRNA gene을 이용한 PCR-DGGE와 탈염소화 species-specific primer를 이용하여 분석한 결과, PCE 탈염소화 시료 내에는 Dehalococcoides sp.와 Geobacter sp.가 주로 존재하였으며, Dehalobacter sp.도 일부 시료에서 검출되었다.

• 환경생물
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• 제17권2호
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• pp.129-138
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• 1999

난분해성 유기화합물의 일종인 염화 방향족화합물은 냉각제, 소화제, 페인트, 용매, 플라스틱류, 유압제, 제초제, 농약, 그리고 화학합성에 필요한 전구물질 등에 널리 사용된다. 이들은 친지질 특성을 가지므로 생물체의 세포막에 쉽게 흡착되며 먹이사슬에 의한 생물학적 농축과정을 통해 인간을 포함하는 각종 생물체에 축적된다. 그 결과 생물체의 세포막 구조가 변화되고 기능이 저해될 뿐더러 암과 돌연변이를 유발하고 $\ulcorner$환경호르몬$\lrcorner$으로서 생물체의 내분비계 기능을 교란하는 등 심각한 보건학적 그리고 환경생물학적 문제를 일으키고 있다. 염화 방향족화합물들은 벤젠고리 구조와 벤젠고리에 염소가 치환된 탄소-염소 결합을 공통적으로 가지고 있으며 벤젠고리에 치환된 염소의 수와 같은 수의 염소라도 붙어있는 위치에 따라 난분해 특징이 결정된다. 염화 방향족화합물들의 분해를 위해서는 미생물에 의한 벤젠 구조의 개환과정과 함께 벤젠 고리구조로부터 염소 치환기를 제거하는 탈염소화 과정이 반드시 일어나야만 한다. 호기적 환경에서 미생물에 의한 탈염소화는 분해 초기단계에서 dehalogenase라는 효소에 의해 촉매되는 oxygenolytic, reductive, 그리고 hydrolytic catalysis에 의해 일어나거나, 분해 대사과정 중에 저절로 염소치환기가 떨어져 나가는 경우도 있다. 탈염소화 과정을 거쳐 분해하는 미생물들을 이용한 염화 방향족 오염물질의 생물학적 분해방법은 이미 사용되고 있는 물리ㆍ화학적 방법보다 경제적이며 2차 오염의 부작용 없이 그 오염물질들을 매우 효과적으로 처리할 수 있다. 따라서 탈염소화 기작을 포함한 분해과정의 이해는 생물학적 분해의 기본적인 정보를 제공할 뿐더러 난분해성 환경 오염물질의 분해처리를 위하여 보다 집중적으로 연구해야 할 과제라고 할 것이다.

• Membrane and Water Treatment
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• 제13권2호
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• pp.85-95
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• 2022

Tetrachloroethylene (PCE) and trichloroethylene (TCE), critical pollutants to human health and groundwater ecosystems, are managed by groundwater quality standards (GQS) in South Korea. However, there are no GQSs for their by-products, such as cis-dichloroethylene (DCE) and vinyl chloride (VC) produced through the dechlorination process of PCE and TCE. Therefore, in this study, we monitored PCE, TCE, cis-DCE, and VC in 111 national groundwater wells for three years (2016 to 2018) to evaluate their distributions, a biological dechlorination possibility, and human risk assessment. The detection frequency of them was 30.2% for PCE, 45.1% for TCE, 43.9% for cis-DCE and 13.4% for VC. The four chlorinated compounds were commonly detected in 21 out of 111 wells. In the results of statistical analysis with 21 wells data, DO and ORP also had a negative correlation with four organic chlorinated compounds, while EC and sulfate has a positive correlation with the compounds. This indicates that the 21 wells were relatively met with suitable environments for a biological dechlorination reaction compared to the other wells. Finally, cis-DCE had a non-carcinogenic risk of 10^-1 and the carcinogenic risk of VC was 10^-6 or higher. Through this study, the distribution status of the four chlorinated compounds in groundwater in South Korea and the necessity of preparing plans to manage cis-DCE and VC were confirmed.

• Advances in environmental research
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• 제3권2호
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• pp.151-162
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• 2014

Among the combination of 4 different second metals and 3 different noble metals, Ni 10%-Pd 1%/hematite (Ni(10)-Pd(1)/H) showed best tetrachloroethylene (PCE) removal (75.8%) and production of non-toxic products (39.8%) in closed batch reactors under an anaerobic condition. The effect of environmental factors (pH, contents of Ni and Pd in catalyst, and hydrogen gas concentration) on the reductive dechlorination of PCE by Pd-Ni/hematite catalysts was investigated. PCE was degraded less at the condition of Ni(5)/H (13.7%) than at the same condition with Ni(10)/H (20.6%). Removals of PCE were rarely influenced by the experimental condition of different Pd amounts (Pd(1)/H and Pd(3)/H). Acidic to neutral pH conditions were favorable to the degradation of PCE, compared to the alkaline condition (pH 10). Increasing Ni contents from 1 to 10% increased the PCE removal to 89.8% in 6 hr. However, the removal decreased to 74.2% at Ni content of 20%. Meanwhile, increasing Pd contents to 6% showed no difference in PCE removal at Pd content of more than 1%. Increasing H2 concentration increased the removal of PCE until 4% H2 which was maximumly applied in this study. Chlorinated products such as trichloroethylene, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, and vinyl chloride were not observed while PCE was transformed to acetylene (24%), ethylene (5%), and ethane (11%) by Ni(10)-Pd(1)/H catalyst in 6hr.

• 한국지하수토양환경학회지:지하수토양환경
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• 제11권6호
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• pp.35-42
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• 2006

본 연구는 시멘트/Fe(II) 시스템에서 TCE의 환원성 탈염소화에 관여하는 유효반응성분을 규명하기 위하여 수행되었다. 먼저 시멘트 자체에 존재하거나 혹은 그 수화물에 존재하는 성분을 다량 함유하고 있는 hematite(${\alpha}-Fe_2O_3$), lepidocrocite(${\gamma}$-FeOOH), akaganeite(${\beta}$-FeOOH), ettringite($Ca_6Al_2(SO_4)_3(OH)_{12}$)를 대상으로 TCE 분해실험을 수행하여 이러한 물질이 시멘트/Fe(II) 시스템에서 탈염소반응에 관여할 수 있는지 고찰한 결과, hematite가 잠재적 유효반응성분으로 선정되었다. 각 시스템의 반응속도상수를 비교해 본 결과 200 mM Fe(II)에 hematite와 CaO를 1 : 4(몰비)로 주입한 시스템($k\;=\;0.637\;day^{-1}$)이 기존의 cement와 Fe(II)을 이용한 경우($k\;=\;0.645\;day^{-1}$)와 가장 비슷한 동력학적 분해경향을 보인다는 것을 알 수 있었다. 처음에 pH 조절이 주목적으로 주입되었던 CaO 역시 분해반응에서 중요한 역할을 담당하는 것으로 나타났는데, CaO 첨가량이 증가할수록 hematite/CaO/Fe(II) 시스템의 분해능은 증가하다가 CaO 양이 일정 수준에 다다르면 증가세가 둔화되는 경향을 보여 주었다. SEM(Scanning Electron Microscopy) 분석을 통해서는 hematite/CaO/Fe(II) 시스템 내에서 분해능이 커질수록 육각형 판상의 결정이 새롭게 형성된다는 것을 확인 할 수 있었으며 이 결정은 portlandite, green rust($SO_4$), Friedel's salt 등일 가능성이 높은 것으로 판단되었다. 그리고 동일 시료의 XRD(X-Ray Diffraction) 분석을 통해서는 hematite, magnetite/maghemite, green rust($SO_4$)의 존재를 확인할 수 있었다. SEM 및 XRD 분석에서 공통적으로 나타나는 green rust($SO_4$)가 유효반응성분일 가능성이 높다고 판단되었다.