• 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.

• Journal of the Korean GEO-environmental Society
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• v.8 no.2
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• pp.41-48
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• 2007

Zevo-valent iron (ZVI) has been widely used in permeable reactive barriers for reducing organic contaminants, such as trichloroethylene (TCE). The rapid reaction time, however, leads to decrease in reactivity and availability of ZVI. Shewanella algae BrY, a strain of dissimilatory iron reducing bacteria, can reduce the oxidized Fe (III) to Fe (II) and reduced Fe (II) can be reused to reduce the contaminant. The effect of Shewanella algae BrY on the reduction of the oxidized ZVI column and further TCE removal in the contaminated groundwater were studied at different flow rates and TCE input concentrations in this study. High input concentration of TCE and flow rate increase the amount of input contaminant and make to lower the effect of reduction by Shewanella algae BrY. Specially, the fast flow rate inhibits the direct contact and implantation on the surface of iron. The reduction of oxidized iron reactive barrier by Shewanella algae BrY can decrease the decreation of duration of PRBs by the precipitation of oxidized iron produced by dechlorination of TCE.

• 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.

• Korean Journal of Microbiology
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• v.41 no.3
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• pp.195-200
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• 2005

Comamonas sp. strain DJ-12 is a bacterial isolate capable of degrading of 4-chlorobiphenyl (4CB) as a carbon and energy source. The degradation pathway was characterized as being conducted by consecutive reactions of the meta-degradation of 4CB, hydrolytic dechlorination of 4-chlorobenzoate (4CBA), hydroxylation of 4-hydroxybenzoate, and meta-degradation of protocatechuate to product TCA metabolites. The 6.8 kb fragment from the chromosomal DNA of Comamonas sp. strain DJ-12 included the genes encoding for the meta-degradation of PCA; the genes of protocatechuate 4,5-dioxygenase alpha and beta subunits (pmcA and pmcB), 4-carboxy-2-hydroxymuconate-6-semialdehyde dehydrogenase (pmcC), 2-pyrone-4,6-dicarboxylate hydrolase (pmcD), 4-oxalomesaconate (OMA) hydratase(pmcE), 4-oxalocitramalate (OCM) aldolase (pmcF), and transporter gene (pmcT). They were organized in the order of pmcT-pmcE-pmcF-pmcD-pmcA-pmcB-pmcC. The amino acid sequences deduced from the nucleotide sequences of pmcABCDEFT genes from Comamonas sp. strain DJ-12 exhibited 94 to $98\%$ homologies with those of Comamonas testosteroni BR6020 and Pseudomonas ochraceae NGJ1, but only 52 to $74\%$ with homologies Sphingomonas paucimobilis SYK-6, Sphingomonas sp. LB126, and Arthrobacter keyseri 12B.

• Korean Journal of Environmental Agriculture
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• v.26 no.1
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• pp.55-61
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• 2007

Metolachlor may pose a threat to surface and ground water qualities due to its high solubility in water, Zerovalent iron (ZVI) releases $e^-$ which can degrade the organochlorinated compounds. The objective of this research was to evaluate the kinetics of metolachlor degradation as affected by ZVI sources [Peerless unannealed (PU) and Peerless annealed (PA)] and ZVI levels (1 and 5%) under batch conditions at different metolachlor concentrations (200 and 1000 mg/l) and temperatures (15, 25, and $35^{\circ}C$). The effectiveness of ZVI on metolachlor degradation was assessed by characterizing the dechlorinated metolachlor byproduct molecules. Metolachlor degradation by ZVI followed the first-ordered kinetics with a higher rate constant at higher level of ZVI treatment. At 5% (w/v) of PU and PA treatment, the half-lives of metolachlor degradation were 9.93 and 6.51 h and all of the initial metolachlor were degraded in 72 and 48 h, respectively. Rate constants (k) of metolachlor degradation were higher at the lower initial metolachlor concentration. The metolachlor degradation by ZVI was temperature dependent showing that the rate constant (k) at 15, 25, and $35^{\circ}C$ were 0.0805, 0.1017, and 0.3116 /h, respectively. The ZVI-mediated metolachlor degradation yielded two byproduct molecules identified as dechlorinated metolachlor $(C_{13}H_{18}NO)$ and dechlorinated-dealkylated metolachlor $(C_{12}H_{17}NO)$. The PA ZVI was more effective than PU ZVI in metolachlor degradation.

• Applied Biological Chemistry
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• v.20 no.1
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• pp.109-116
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• 1977

Much attention has been paid to the fact that quite a few herbicides such as phenylcarbamates, phenylureas, and acylanilides form azo compounds known as carcinogens by virtue of the microoranisms in soil. In consequence, many investigators synthesized. TCAB, an azo compound, starting from 3,4-dichloronitrobenzene for the related studies. However, the authors were under the necessity of synthesizing $^{14}C-ring-labeled$ TCAB from $^{14}C-ring-labeled$ 3,4-DCA available, in addition to making up for the disadvantage of dechlorination in the reduction of 3,4-dichloronitrobenzene. The new method is as follows:TCAB, $^{14}C-ring-labeled$ and non-labeled, was produced by aerial oxidation of 3,4-DCA catalyzed by CuCl with pyridine as solvent at $60^{\circ}C$ for 5-12 hrs, giving 80.2% yield. The procedure forpurification was described in detail. The identities of TCAB isomers were confirmed by means of autoradiography, TLC, GLC, IR, and MS.

• Microbiology and Biotechnology Letters
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• v.38 no.4
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• pp.448-454
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• 2010

This study investigated the effect of PCE and TCE as electron acceptors on the bacterial composition of dechlorinating communities. The enrichment cultures reductively dechlorinating PCE and TCE were developed from three environment samples using acetate as electron donor. The cultures were prepared by sequential enrichment, which was seeded with sediment and dredged soil. Denatured gradient gel electrophresis (DGGE) of 16S rRNA gene fragment was used to compare the microbial communities of these three enrichment cultures. After incubation for 4 weeks, the removal efficiencies of PCE and TCE were highest from Yeocheon site (87.37% and 84.46%, respectively). PCE and TCE as electron acceptors affected the bacterial diversity and community profiles in the enrichment cultures. DGGE analysis showed that the dominant bacteria in PCE and TCE enrichment were belonged to Clostridium sp., Desulfotomaculum sp., and uncultured bacteria.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.2
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• pp.123-129
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• 2005

In situ permeable reactive barrier (PRB) technologies have been proposed to reductively remove organic contaminants from the subsurface environment. The major reactive material, zero valent iron ($Fe^0$), is oxidized to ferrous iron or ferric iron in the barriers, resulting in the decreased reactivity. Iron-reducing bacteria can reduce ferric iron to ferrous iron and iron reduced by these bacteria can be applied to dechlorinate chlorinated organic contaminants. Iron reduction by iron reducing bacteria, Shewanella algae BrY, was observed both in aqueous and solid phase and the enhancement of TCE removal by reduced iron was examined in this study. S. algae BrY preferentially reduced Fe(III) in ferric citrate medium and secondly used Fe(III) on the surface of iron oxides as an electron acceptor. Reduced iron formed reactive materials such as green rust ferrihydrite, and biochemical precipitation. These reactive materials formed by the bacteria can enhance TCE removal rate and removal capacity of the reactive barrier in the field.

• 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.

• 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.