• Journal of Korean Society of Environmental Engineers
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• v.31 no.2
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• pp.125-131
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• 2009

Reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) and its toxicity change were predicted by the linear free energy relationship (LFER) model to assess the zero-valent iron (ZVI) and anaerobic dechlorinating bacteria (ADB) as electron donors in PCDDs dechlorination. Reductive dechlorination of PCDDs involves 256 reactions linking 76 congeners with highly variable toxicities, so is challenging to assess the overall effect of this process on the environmental impact of PCDD contamination. The Gibbs free energies of PCDDs in aqueous solution were updated to density functional theory (DFT) calculation level from thermodynamic results of literatures. All of dechlorination kinetics of PCDDs was evaluated from the linear correlation between the experimental dechlorination kinetics of PCDDs and the calculated thermodynamics of PCDDs. As a result, it was predicted that over 100 years would be taken for the complete dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) to non-chlorinated compound (dibenzo-p-dioxin, DD), and the toxic equivalent quantity (TEQ) of PCDDs could increase to 10 times larger from initial TEQ with the dechlorination process. The results imply that the single reductive dechlorination using ZVI or ADB is not suitable for the treatment strategy of PCDDs contaminated soil, sediment and fly ash. This LFER approach is applicable for the prediction of dechlorination process for organohalogen compounds and for the assessment of electron donating system for treatment strategies.

• Journal of Korean Society of Environmental Engineers
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• v.34 no.5
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• pp.304-311
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• 2012

Chlorinated ethylenes such as perchloroethylene (PCE) and trichloroethylene (TCE) are widely used as industrial solvents and degreasing agents. Because of improper handling, these highly toxic chlorinated ethylenes have been often detected from contaminated soils and groundwater. Biological PCE dechlorination activities were tested in bacterial cultures inoculated with 10 different environmental samples from sediments, sludges, soils, and groundwater. Of these, the sediment using culture (SE 2) was selected and used for establishing an efficient PCE dechlorinating enrichment culture since it showed the highest activity of dechlorination. The cathode chamber of bioelectrochemical system (BES) was inoculated with the enrichment culture and the system with a cathode polarized at -500 mV (Vs Ag/AgCl) was operated under fed-batch mode. PCE was dechlorinated to ethylene via TCE, cis-dichloroethylene, and vinyl chloride. Microbial community analysis with polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) showed that the microbial community in the enrichment culture was significantly changed during the bio-electrochemical PCE dechlorination in the BES. The communities of suspended-growth bacteria and attached-growth bacteria on the cathode surface are also quite different from each other, indicating that there were some differences in their mechanisms receiving electrons from electrode for PCE dechlorination. Further detailed research to investigate electron transfer mechanism would make the bioelctrochemical dechlorination technique greatly useful for bioremediation of soil and groundwater contaminated with chlorinated ethylenes.

• 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.

• Journal of Soil and Groundwater Environment
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• v.11 no.5
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• pp.35-42
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• 2006

The following results were obtained in the reductive degradation of hexachloroethane (HCA), and surface characteristics by using iron sulfide ($FeS,\;FeS_{2}$) mediators. HCA was degraded to pentachloroethane (PCA), tetrachloroethylene(PCE), trichloroethylene(TCE) and cis-l,2-dichloroethylene (cis-1,2-DCE) by complicated pathways such as hydrogenolysis, dehaloelimination and dehydrohalogenation. FeS had more rapid degradation rates of organic solvent than $FeS_{2}$. In liquidsolid reaction, the reaction rates of organic solvents were investigated to explain surface characteristics of FeS and $FeS_{2}$.. To determine surface characteristics of FeS and $FeS_{2}$, the specific surface area and surface potential of each mineral was determined and the hydrophilic site ($N_{s}$) was calculated. The specific surface area ($107.0470m^{2}/g\;and\;92.6374m^{2}/g$) and the $pH_{ZPC}$ of minerals ($FeS\;PH_{ZPC}=7.42,\;FeS_{2},\;PH_{ZPC}=7.80$) were measured. The results showed that the Ns of FeS and $FeS_{2}$ were $0.053\;site/mm^{2}\;and\;0.205\;site/mm^{2}$, respectively. $FeS_{2}$ had more hydrophilic surface than FeS. In other words, FeS have more hydrophobic surface site than $FeS_{2}$.

• Proceedings of the Korean Society of Postharvest Science and Technology of Agricultural Products Conference
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• 2003.04a
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• pp.117.2-118
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• 2003

절임식품은 우리 고유의 먹거리이지만 체계적인 연구가 부족하여 품질표준화가 이루어지지 않고 있어 우리의 전통식품을 세계적인 식품으로 개발하기 위해서는 전통식품을 과학화하고 현대화할 수 있는 연구가 필요하다. 새로운 된장절임 가공법을 개발하고자 blanching, salting, drying 등의 전 처리를 행한 후 된장 절임기간에 따른 새송이 버섯의 수분함량, 염도, 색상, 조직특성, 관능특성 등의 변화를 조사하였다. 된장절임기간에 따른 새송이 버섯의 수분함량 변화는 숙성시간이 경과함에 따라 감소하였으며 염도는 시간이 지남에 따라 증가하는 경향을 보였으나 무처구를 제외하고는 숙성 30일 이후부터는 변화가 거의 없었다. 숙성기간에 따른 색상의 변화를 보면 블랜칭이 매우 효과적으로 변색을 방지하였다. 숙성 30일부터는 모든 처리구에서 강도가 저하하는 경향을 보였으며 관능평가 결과 숙성 40일째에 맛과 조직감 그리고 기호도 등 모든 항목에서 B(B)와 E(BSD) 처리구가 높은 점수를 받아 관능적 품질 특성이 가장 우수하였다. 이상의 결과로 볼 때 전처리공정에 있어서는 7$0^{\circ}C$에서 10분간 블랜칭처리한 B(B)처리구가 가장 우수하였으나 된장 절임후 숙성기간이 경과함에 따라서는 7$0^{\circ}C$에서 10분간 블랜칭처리후 5% 염용액에서 72시간 절임한 후 4$0^{\circ}C$에서 30분간 탈염하고, 다시 5$0^{\circ}C$의 온도에서 3시간 건조시킨 E(BSD)처리구도 우수한 품질을 유지할 수 있어 새송이 버섯을 이용한 장류절임가공법으로 활용이 가능함을 확인하였다.d, citric acid 그리고 shikimic acid가 검출되었고 수확시기에 3품종에서 모두 malic acid 함량이 가장 높았고 malic acid와 citric acid의 함량이 풍수와 신고에서는 약 0.3%, 추황은 0.4% 이상으로 나타났다. 또한 3품종 모두에서 총산과 같은 추세로 성숙기의 유기산의 함량이 생장초기의 함량보다 많이 감소되었음을 알 수 있었다. 배의 가용성 고형물은 전체적으로 과실의 성장이 진행됨에 따라 증가하는 추세를 나타내었다. 풍수와 신고 과피의 총당과 환원당은 거의 같은 추세로 증가하였고 성숙이 가까워지면서 환원당이 감소하였다. 배 과육의 총당과 환원당 또한 거의 같은 추세로 증가를 하다가 수확 전 20일 혹은 30일부터 총당의 함량은 계속 증가하지만 환원당의 함량은 큰 변화가 없는 것으로 나타났다. 배 과실의 전반 성장과정에 있어서 전분함량은 감소하였고 총탄수화물의 함량은 과육에서는 증가하나 과피에서는 반대로 감소하는 경향을 보였다. 풍수의 전분함량은 최고 2.19%에서 0.23%로 감소하였고 신고에서는 0.43%로 추황에서는 0.48%로 감소하였다. 배 유리당은 fructose, glucose, sorbitol, sucrose 둥 4종류의 당이 검출되었고 3품종 모두에서 생장과정 중 비환원당인 sucrose 함량은 계속 증가하였고 fructose, glucose, sorbitol의 함량(추황의 sorbitol을 제외)은 생장이 촉진됨에 따라 증가하다가 다시 점차적으로 감소하였다. 이러한 결과는 총당과 환원당의 측정결과와 일치한 것으로 나타났다. 결론적으로 배의 성장에 따라 산 함량은 감소하였고 당 함량은 증가하였다.luco-pyranosi

• Applied Biological Chemistry
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• v.17 no.3
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• pp.149-176
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• 1974

Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

• Applied Biological Chemistry
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• v.23 no.2
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• pp.131-139
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• 1980

TOK (2,4-Dichlolo-4'-nitrodiphenyl ether) was applied to two Korean soils possessing different physico-chemical properties at a certain concentration and incubated for a certain time under flooded conditions. The metabolites and the soil microorganisms involved in the degradation of TOK are studied. Chong Ju and Chung Ju soils treated with TOK at a concentration of 500 ppm and incubated for two, four, and six months at $30^{\circ}C$ yielded 4-chloro-4'-amino diphenyl ether, 2, 4-dichloro-4'-amino diphenyl ether(amino-TOK), N-[4'-(4-chloro-phenoxy)] phenyl acetamide, and N-[4'-(4-chloro-phenoxy)] phenyl formamide as the major metabolites. TOK underwent the reduction of nitrogroup to amino group, dechlorination, acetylation, and formylation. No cleavage at the ether linkage was recognized. TOK was more readily degraded in Chung Ju soil which is characterized by the higher pH (PH 6.43), clay loam in textural class, and the higher cation exchange capacity. The toxicity of TOK as a possible environmental contaminant is expected to be considerably reduced as a result of the above degradation Twelve strains of soil bacteria were isolated from the TOK-treated Chong Ju and Chung Ju soils. As a result of the incubation of TOK in pure cultures of the isolates, T-1-1 strain isolated from Chong Ju soil had almost no degradability, whereas T-2-3 strain turned out to be the most potent. The degradation of TOK by the isolates constituted mostly the reduction of the nitro group to amino group. The citrate buffer extract of Chung Ju soil reduced TOK more readily to amino-TOK than that of Chong Ju soil.