• The Korean Journal of Pesticide Science
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• v.12 no.1
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• pp.43-49
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• 2008

This study is conducted to determine the potential of zerovalent iron (ZVI), pyrolusite and birnessite to remediate water contaminated with chlorothalonil. The degradation rate of chlorothalonil by treatment of ZVI, pyrolusite and birnessite was much higher in low condition of pH. Mixing an aqueous solution of chlorothalonil with 1.0% (w/v) ZVI, pyrolusite and birnessite resulted in 4.7, 13.46 and 21.38 hours degradation half-life of chlorothalonil, respectively. Dechlorination number of chlorothalonil by treaonent of ZVI, pyrolusite and birnessite exhibited 2.85, 1.12 and 1.09, respectively. Degradation products of chlorothalonil by teartment of pyrolusite and birnessite were confirmed as trichloro-1,3-dicyanobenzene and dichloro-1,3-dicyanobenzene which were dechlorinated one and two chlorine atoms from parent chlorothalonil by GC-mass. Degradation products of chlorothalonil by ZVI were identified not only as those by pyrolusite and birnessite but as further reduced chloro-1,3-dicyanobenzene and chlorocyanobenzene.

• Korean Journal of Environmental Agriculture
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• v.25 no.3
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• pp.257-261
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• 2006

Zerovalent iron (ZVI) has been recently used for environmental remediation of soils and groundwaters contaminated by chlorinated organic compounds. As a new approach to improve its reductive activity and stability, zerovalent iron-montmorillonites (ZVI-Mt) complex are synthesized by simple process. Therefore, this study was carried out to elucidate the characteristics of ZVI-Mt complex and to investigate degradation effects of fungicide chlorothalonil. The XRD patterns of ZVI-Mt complex showed distinctive peaks of ZVI and montmorillonite. In ZVI-Mt complex, the oval particles of ZVI were partly surrounded by montmorillonite layers that could prevent ZVI surface oxidation by air. The degradation ratio of chlorothalonil after 60 min exhibited 71% by ZVI and 100% by ZVI-Mt complex. ZVI-Mt21 complex exhibited much higher and faster degradation ratio of chlorothalonil compare to that of ZVI or ZVI-Mt11 complex. Also, degradation rate of chlorothalonil was increased with increasing ZVI or ZVI-Mt complex content and with decreasing initial solution pH.

• Korean Journal of Environmental Agriculture
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• v.29 no.4
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• pp.402-407
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• 2010

Zerovalent iron (ZVI) is one of the most commonly used metallic reducing agents for the treatment of toxic contaminants in wastewater. Traditional ZVIs are less effective than nanoscale ZVI (nZVI) due to prolonged reaction time. However, the reactivity can be significantly increased by reducing the size of ZVI particles to nanoscale. In this study, nZVI particles were synthesized under laboratory condition and their efficiency in removing hexavalent chromium (Cr(VI)) from aqueous solutions were compared with commercially available ZVI particles. The results showed that the synthesized nZVI particles (SnZVI) reduced >99% of Cr(VI) at the application rate of 0.2% (w/v), while commercial nZVI (CnZVI) particles resulted in 59.6% removal of Cr(VI) at the same application rate. Scanning electron micrographs (SEM) and energy dispersive spectra (EDS) of the nZVI particles revealed the formation of Fe-Cr hydroxide complex after reaction. Overall, the SnZVI particles can be used in treating chromium contaminated wastewater.

• Korean Journal of Environmental Agriculture
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• v.28 no.2
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• pp.202-208
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• 2009

The dechlorination of endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) and its metabolite, endosulfan sulfate via reaction with zerovalent iron under various pH conditions was studied using aqueous solution. The reaction products, which were probably produced from endosulfan and endosulfan sulfate by ZVI were identified by GC-MS. The lower the pH of reaction solution, the higher the transformation rate of endosulfan and endosulfan sulfate. The transformation rates of endosulfan and endosulfan sulfate in pH 3.0 by ZVI were 28% and 90% but those of endosulfan and endosulfan sulfate in mixture solution of water/acetone were 65% and 92%, respectively. The pH of reaction solution after ZVI treatment was increased to pH 10. Endosulfan was hydrolyzed at pH 10 but endosulfan sulfate was not hydrolyzed. Two unknown peaks were produced from endosulfan sulfate by treatment of ZVI. As a result of GC-MS analysis, unknown peaks were guessed to be structural isomer substituted hydrogen for chlorine.

• Journal of Applied Biological Chemistry
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• v.50 no.1
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• pp.6-12
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• 2007

Feasibility of laboratory-synthesized zerovalent iron was investigated to remove arsenic from leachates of tailings taken from an Au-Ag abandoned mine. The tailings were seriously contaminated with arsenic, and its potential adverse effect on the ecosystems around the mine seems to be significantly high. Long-term column experiments were conducted for about 3.5 months to evaluate the effectiveness of the synthesized zerovalent iron for removal of arsenic. Over than 95% removal efficiency of As was observed in the zerovalent iron mediated tests. In addition, the XRD data suggest that the corrosion products of ZVI were identified magnetite, maghemite, goethite, and lepidocrocite, all of which support Fe(II) oxidation as an intermediate step in the zerovalent iron corrosion process. The results indicate that arsenic can be removed from the tailing-leachate by the mechanism of coprecipitation and/or adsorption onto those iron oxides formed from ZVI corrosion.

• 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.

• 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.50 no.4
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• pp.321-326
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• 2007

An organophosphorus insecticide, chlorpyrifos, has been of a great concern due to persistence, toxicity and accumulation in soils and groundwaters. This study deals with degradation efficiency and dechlorination kinetics of chlorpyrifos by various types of zerovalent irons (ZVIs) for effective remediation of the soils contaminated with chlorinated pesticides. Chlorpyrifos degradation rate was increased with increasing ZVI treatment amount and reaction time. The degradation rate and dechlorination kinetics of chlorpyrifos increased in the order of mZVI > nZVI > cZVI in solutions and soils. Dechlorination number value of chlorpyrifos by cZVI, nZVI and mZVI treatment exhibited 1.08, 3.09 and 3.18, respectively. In soils, degradation efficiency and kinetics of chlorpyrifos significantly were affected by moisture content because of the limited contact between ZVIs and chlorpyrifos. These results suggest that nanosized and functionalized mZVI could be effectively applied to degradation of chlorinated pesticides in the soil and aqueous environments.

• Korean Journal of Environmental Agriculture
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• v.29 no.4
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• pp.396-401
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• 2010

Tolclofos-methyl is one of the most widely used organophosphorous pesticides in control of soil-borne diseases in ginseng field. In Korea, residues of tolclofosmethyl in ginseng and cultivation soil is quite often detecting. The objective of this study was to know the possibility for the accelerated degradation of tolclofos-methyl by various chemical treatment under soil slurry condition. The degradation of tolclofos-methyl was accelerated by zerovalent metals treatment in soil slurry. The degradation rate of tolclofos-methyl was found to be at higher zerovalent zinc than unannealed zerovalent and annealed zerovalent iron. The effect of different sizes of zerovalent iron on tolclofos-methyl degradation was showed that the smaller size of zerovalent iron, the greater the degradation rate. In aqueous solution of pH 4.0 below the degradation rate of tolclofos-methyl was very high. Under this experimental condition, tolclofos-methyl degradation was the greatest at 2% (w/v) of ZVI under 0.1 N of HCl in 24 hours, the degradation rate was 94.4%. By testing various chemicals, it was found that $Fe_2(SO_4)_3$ as iron source showed better for degrading tolclofos-methyl in $H_2O_2$ 500 mM treatment and sodium sulfite also showed the degradable possibility tolclofos-methyl in soil slurry.

• Environmental Engineering Research
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• v.19 no.1
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• pp.9-14
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• 2014

Fenton reaction with zerovalent iron (ZVI) and $Fe^{2+}$ ions was studied to treat pharmaceutical wastewaters (PhWW) including antibiotics and non-biodegradable organics. Incremental biodegradability was assessed by monitoring biochemical oxygen demand (BOD) changes during Fenton reaction. Original undiluted wastewater samples were used as collected from the pharmaceutical factory. Experiments were carried out to obtain optimal conditions for Fenton reaction under different $H_2O_2$ and ion salts (ZVI and $Fe^{2+}$) concentrations. The optimal ratio and dosage of $H_2O_2$/ZVI were 5 and 25/5 g/L (mass basis), respectively. Also, the optimal ratio and dosage of $H_2O_2/Fe^{2+}$ ions were 5 and 35/7 g/L (mass basis), respectively. Under optimized conditions, the chemical oxygen demand (COD) removal efficiency by ZVI was 23% better than the treatment with $Fe^{2+}$ ion. The reaction time was 45 min for ZVI and shorter than 60 min for $Fe^{2+}$ ion. The COD and total organic carbon (TOC) were decreased, but BOD was increased under the optimal conditions of $H_2O_2$/ZVI = 25/5 g/L, because organic compounds were converted into biodegradable intermediates in the early steps of the reaction. The BOD/TOC ratio was increased, but reverse-wise, the COD/TOC was decreased because of generated intermediates. The biodegradability was increased about 9.8 times (BOD/TOC basis), after treatment with ZVI. The combination of chemical and biological processes seems an interesting combination for treating PhWW.