• Title/Summary/Keyword: Reductive dechlorination

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Effects of Calcium on TCE Degradation Reaction in Cement/Fe(II) and Hematite/Fe(II) Systems (시멘트/Fe(II) 및 hematite/Fe(II) 시스템의 TCE 분해반응 시 Ca 성분의 영향)

  • Kim, Hong-Seok;Hwang, Kyung-Yup;Ahn, Jun-Young;Yi, Jou-Young;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.16 no.1
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    • pp.82-90
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    • 2011
  • Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons have not been identified. The previous studies showed that a hematite/CaO/Fe(II) system had TCE degradation characteristics similar to those of cement/Fe(II) systems with regard to degradation kinetics and that lime (CaO) plays an important role in enhancing the reactivity for TCE dechlorination. The current study shows identified the formation of gypsum ($CaSO_4$) in the hematite/CaO/$FeSO_4$ system through the XRD analysis. The amounts of the gypsum increased with increment of the initial CaO dose. However, when CaO in the hematite/CaO/$FeSO_4$ system was replaced with gypsum, TCE degradation was not observed. Ca-removed Portland cement extracts (CPCX) in combination with $FeSO_4(CPCX/FeSO_4)$ showed no TCE degradation. On the other hands, the Portland cement extracts (PCX) in the presence of $FeSO_4(PCX/FeSO_4)$ and CPCX/CaO/$FeSO_4$ systems degraded 0.2 mM TCE within 5 days, indicating that CaO also played an important role dechlorination reactions in the systems. The pseudo-first-order rate constants (k) of the CPCX/CaO/$FeSO_4$ systems were 0.20, 0.24, and 0.72 $day^{-1}$, when the CaO dosages were 25, 50 and 75 g/L, respectively. The XRD analyses showed identified the common peaks having the d-values of 3.02, 2.27, and 1.87 in the reaction systems that showed TCE degradation. However, it was not possible to clearly identify the crystalline minerals having the three peaks from the references in JCPDS cards. This study reveals that the reactive agents in the cement/Fe(II) and the hematite/Fe(II) systems are likely to be those containing CaO and Fe(II).

Assessment of Natural Attenuation Processes in the Groundwater Contaminated with Trichloroethylene (TCE) Using Multi-Species Reactive Transport Modeling (다성분 반응 이동 모델링을 이용한 트리클로로에틸렌(TCE)으로 오염된 지하수에서의 자연저감 평가)

  • Jeen, Sung-Wook;Jun, Seong-Chun;Kim, Rak-Hyeon;Hwang, Hyoun-Tae
    • Journal of Soil and Groundwater Environment
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    • v.21 no.6
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    • pp.101-113
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    • 2016
  • To properly manage and remediate groundwater contaminated with chlorinated hydrocarbons such as trichloroethylene (TCE), it is necessary to assess natural attenuation processes of contaminants in the aquifer along with investigation of contamination history and aquifer characterization. This study evaluated natural attenuation processes of TCE at an industrial site in Korea by delineating hydrogeochemical characteristics along the flow path of contaminated groundwater, by calculating reaction rate constants for TCE and its degradation products, and by using geochemical and reactive transport modeling. The monitoring data showed that TCE tended to be transformed to cis-1,2-dichloroethene (cis-1,2-DCE) and further to vinyl chloride (VC) via microbial reductive dechlorination, although the degree was not too significant. According to our modeling results, the temporal and spatial distribution of the TCE plume suggested the dominant role of biodegradation in attenuation processes. This study can provide a useful method for assessing natural attenuation processes in the aquifer contaminated with chlorinated hydrocarbons and can be applied to other sites with similar hydrological, microbiological, and geochemical settings.

SYNTHESIS OF NANO-SIZED IRON FOR REDUCTIVE DECHLORINATION. 1. Comparison of Aerobic vs. Anaeriobic Synthesis and Characterization of Nanoparticles

  • Song, Ho-Cheol;Carraway, Elizabeth R.;Kim, Young-Hun
    • Environmental Engineering Research
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    • v.10 no.4
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    • pp.165-173
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    • 2005
  • Nano-sized iron particles were synthesized by reduction of $Fe^{3+}$ in aqueous solution under two reaction conditions, aerobic and anaerobic, and the reactivity of iron was tested by reaction with trichloroethene (TCE) using a batch system. Results showed that iron produced under anoxic condition for both synthesis and drying steps gave rise to iron with higher reduction reactivity, indicating the presence of oxygen is not favorable for production of nano-sized iron deemed to accomplish reactivity enhancement from particle sized reduction. Nano-sized iron sample obtained from the anoxic synthesis condition was further characterized using various instrumental measurements to identity particle morphology, composition, surface area, and particle size distribution. The scanning electron microscopic (SEM) image showed that synthesized particles were uniform, spherical particles (< 100 nm), and aggregated into various chain structures. The effects of other synthesis conditions such as solution pH, initial $Fe^{3+}$ concentration, and reductant injection rate on the reactivity of nano-sized iron, along with standardization of the synthesis protocol, are presented in the companion paper.

Effects of Electron Donor and Electron Acceptor on Biodegradation of $CCl_4$ (Electron Donor와 Electron Acceptor의 농도가 사염화탄소의 생물분해에 미치는 영향)

  • 배우근
    • Proceedings of the Korea Society of Environmental Toocicology Conference
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    • 1991.05a
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    • pp.8-12
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    • 1991
  • Biodegradation of carbon tetrachloride (CTC) in denitrifying and aerobic columns was investigated under various conditions of electron-acceptor and electron-donor availability. CTC removal increased when the electron-acceptor (nitrate) injection was stopped in the denitrifying column ; however, CTC removal decreased when electron donor (acetate) was deleted in the denitrifying and the aerobic column. Small fractions of the CTC removed appeared as chloroform, indicating that reductive dechlorination of CTC was occurring. The results from the denitrifying column support the hypothesis that CTC behave as an electron acceptor that competes for the pool of available electrons inside the bacterial cells.

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Reductive degradation of Chlorinated compounds by using Iron Minerals (철 광물에 의한 염소계 유기화합물의 환원적분해)

  • Kim, Sung-Kuk;Park, Sang-Won
    • Journal of Soil and Groundwater Environment
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    • v.9 no.2
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    • pp.11-19
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    • 2004
  • Chlorinated and nitroaromatic compounds are non-degradable substances that are extremely toxic and are known to be carcinogens and mutation causing agents. Moreover, the half-lives of substances such as carbon tetrachloride, hexachloroethane and nitroaromatic compounds are several decades. In this study, the optimal conditions to detoxify chlorinated compounds by the reductive degradation were investigated. The following results were obtained in the reductive degradation of CCl$_4$, C$_2$Cl$\_$6/, C$_2$HCl$\_$5/, C$_2$Cl$_4$, and C$_2$HCl$\_$5/ by using Fe, FeS and FeS$_2$ as mediators. CCl$_4$ was reduced to CH$_2$Cl$_3$ and CH$_2$Cl$_2$in anaerobic conditions when FeS was used as a mediator. While the reduction of CCl$_4$ to CHCl$_3$ was rapidly proceeded, the reduction of CHCl$_3$ to CH$_2$Cl$_2$ was occurred slowly. Further reduction to CH$_3$Cl was not observed. Unlike CCl$_4$, C$_2$Cl$\_$6/ was degraded to C$_2$HCl$\_$5/, C$_2$Cl$_4$. C$_2$HCl$_3$ and cis-1,2-C$_2$H$_2$Cl$_2$ by complicated pathways such as hydrogenolysis, dehalo-elimination and dehydrohalogenation. A small amount of C$_2$HCl$\_$5/ was detected only in the early stages of the reduction. However, majority of the C$_2$Cl$\_$6/ was reduced to C$_2$Cl$_4$. cis-1,2-C$_2$H$_2$C1$_2$ was the only product among other possible isomers.

Analysis of Microbial Community During the Anaerobic Dechlorination of Perchloroethylene and Trichloroethylene (Perchloroethylene과 Trichloroethylene의 혐기적 탈염소화 및 미생물 군집 분석)

  • Lee Jae-Won;Kim Byung-Hyuk;Ahn Chi-Yong;Kim Hee-Sik;Yoon Byung-Dae;Oh Hee-Mock
    • Korean Journal of Microbiology
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    • v.41 no.4
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    • pp.281-286
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    • 2005
  • In this study, the anaerobic enrichment cultivation was performed with the sediments and the dredged soils from the cities of Ulsan, Masan, Yeosu, Gwangyang, Ansan and Seongnam. Acetate as an electron donor and PCE (perchloroethylene) or TCE (trichloroethylene) as an electron acceptor were injected into the serum bottle with an anaerobic medium. After the incubation of 12 weeks, the removal efficiency of PCE was highest at $70\%$ in the treatment with the sediment of Ulsan. Also, the bacterial community structure was analyzed by D-DGGE (double denatured gradient gel electrophoresis) through PCR-based 16S rDNA approaches. The dominant species id the anaerobic enrichment were found to belong to the genus of Desulfovibrio.

Hydrochemical Investigation for Site Characterization: Focusing on the Application of Principal Component Analysis (부지특성화을 위한 지하수의 수리화학 특성 연구: 주성분 분석을 중심으로)

  • Yu, Soonyoung;Kim, Han-Suk;Jun, Seong-Chun;Yi, Jong Hwa;Yun, Seong-Taek;Kwon, Man Jae;Jo, Ho Young
    • Journal of Soil and Groundwater Environment
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    • v.27 no.spc
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    • pp.34-50
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    • 2022
  • Principal component analysis (PCA) was conducted using hydrochemical data in four testbeds (A to D) built for the development of site characterization technologies to assess the hydrochemical processes controlling the hydrochemistry in each site. The PCA results indicated the nitrogen loading to deep bedrock aquifers through permeable fractures in Testbed A, the chemical weathering enhanced with the biodegradation of petroleum hydrocarbons in Testbed B, the reductive dechlorination in Testbed C, and the different hydrochemistry depending on the depth to bedrock in Testbed D, consistent with the characteristics of each site. In Testbeds B and D, outliers seemed to affect the PCA result probably due to the small number of samples, whereas the PCA result was still consistent with site characteristics. This study result indicates that the PCA is widely applicable to hydrochemical data for the assessment of major hydrochemical processes in contamination sites, which is useful for site characterization when combined with other site characterization technologies, e.g., geological survey, geophysical investigation, borehole logging. It is suggested that PCA is applied in contaminated sites to interpret hydrochemical data not only for the distribution of contamination levels but also for the assessment of major hydrochemical processes and contamination sources.

Synthesis of Oxidation Resistant Core-shell Nanoscale Zero-valent Iron by Controlled Air Contact (공기접촉 제어를 통한 산화방지 Core-Shell 나노영가철의 제조)

  • Ahn, Jun-Young;Kim, Hong-Seok;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.13 no.6
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    • pp.93-102
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    • 2008
  • Experimental studies were conducted to characterize the synthesized nanoscale zero-valent iron (NZVI) which is resistant to oxidation in the atmospheric environment. XRD, XPS, and TEM analyses revealed that the oxidation-resistant NZVI particles formed under various controlled air contact conditions (4, 8 and 12 mL/min) have shells with ${\sim}$5 nm thickness. The shells consist of magnetite (${Fe_3}{O_4}$) and maghemite (${\gamma}-{Fe_2}{O_3}$), predominantly. No substantial differences were found in the shell components and thickness among NZVI particles formed under the various air flow rates. On the other hand, shell was not detected in the TEM image of rapidly oxidized NZVI particles. NZVI particles synthesized under the various air flow rates showed similar TCE degradation performances ($k_{obs}$= 0.111, 0.102, and 0.086 $hr^{-1}$), which are equivalent to approximately 80% of those obtained by the fresh NZVI particles. TCE degradation efficiencies of the NZVI particles(fresh, controlled air contact and rapidly oxidized) were improved after equilibrating with water for one day, indicating that depassivation of the shells occurred. The performances of NZVI particles decreased to 90% and 50% of those of the fresh NZVI particles, when they were equilibrated with the atmosphere for a week and two months, respectively. The NZVI particles synthesized under the controlled air contact would have advantages over traditional NZVI particles in terms of practical application into the site, because of their inertness toward atmospheric oxygen.

Diversity of Uncultured Microorganisms Associated with the Anaerobic Pentachlorophenol Degradation Estimated by Comparative RELP Analysis of PCR-Amplified 16S rDNA Clones (16S rDNA 클론들의 RFLP 비교분석에서 얻어진 Pentachlorophenol의 혐기성 분해에 따른 미생물군집의 변화)

  • 성창수;권오섭;박영식
    • Korean Journal of Microbiology
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    • v.33 no.2
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    • pp.149-156
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    • 1997
  • We have employed comparative RFL,P(Restriction Fragment Ixngth Pol~iniorphism) analysis and molecular phylogenetic techniques to investigate the diversity of uncultured microorganisms associated with the anaerobic PCP degradation in PCP-adapted enrichment cultures inoculated by samples from anaerobic cewage sludgc(Jangrim, Pusan) and leachate of landfill site(Kimhae). 16s rDNA cloncs were obtairted by PCR amplification of mixed population DNAs extracted directly from the nonactive and active stage ol each PCP-adapted culture. After three rounds of comparative RFLP analyses. two RFLP types. designated as Ala and Hld, were found prevalent and common in both active stage samples. Thc analysis of phylogenctic diversity bawd on the 5'-terminal 180 nt of sequences from whole clones of the Ala and Bld RFLP types showed close similarity among themselves. In case of Bld clones, 7XQ of them shared identical sequences. Thcse resuliq suggest that the clones of both RFLP types wcre originated from highly affiliated microorganisms which are e~iriched as a result of metabolic activity to PCP. The full-length 16s rRNA sequence of each representative clone from both RFLP types was determined. and an Ala clone w i n found to he related to Clo.strrdiurn ulfutzac~(Genk~ank No. Z69203) and a Bld clone to Thermobacteroides proteolyticus(Genbank No. X09335), with sequence similarities of 89%' and 97%. respectively.

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Oxidative Degradation of the Herbicide Dicamba Induced by Zerovalent Iron (Zerovalent Iron에 의해 유도되는 제초제 Dicamba의 산화적 분해)

  • Lee, Kyung-Hwan;Kim, Tae-Hwa;Kim, Jang-Eok
    • Korean Journal of Environmental Agriculture
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    • v.27 no.1
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    • pp.86-91
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    • 2008
  • Dicamba(3,6-dichloro-2-methoxybenzoic acid) is used to control for pre and post-emergence of annual and perennial broad-leaf weeds. It is very soluble in water and highly mobile, acidic herbicide. So it is easily moved and detected in groundwater. Zerovalent iron(ZVI) has been used for the reductive degradation of certain compounds through amination of nitro-substituted compounds and dechlorination of chloro-substituted compounds. In this study, we investigated the potential of ZVI for the oxidative degradation of dicamba in water. The degradation rate of dicamba by ZVI was more rapidly increased in pH 3.0 than pH 5.0 solution. The degradation percentage of dicamba was increased with increasing amount of ZVI from 0.05% to 1.0%(w/v) and reached above 90% within 3 hours of reaction. As a result of identification by GC-MS after derivatization with diazomethane, we obtained three degradation products of dicamba by ZVI. They were identified 4-hydroxy dicamba or 5-hydroxy dicamba, 4,5-dihydroxy dicamba and 3,6-dichloro-2-methoxyphenol. 4-Hydroxy dicamba or 5-hydroxy dicamba and 4,5-dihydroxy dicamba are hydroxylation products of dicamba. 3,6-dichloro-2-methoxyphenol is hydroxyl group substituted compound instead of carboxyl group in dicamba. We also confirmed the same degradation products of dicamba in the Fenton reaction which is one of oxidation processes using ferric sulfate and hydrogen peroxide. But we could not find out the dechlorinated degradation products of dicamba by ZVI.