• Journal of Soil and Groundwater Environment
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• v.10 no.5
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• pp.11-17
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• 2005

Characteristics of phenanthrene removal in the Electrokinetic (EK)-Fenton process were investigated in a 2-dimensional test cell in a viewpoint of the effect of gravity and electrosmotic flow (EOF). When the constant voltage of 100 V was applied to this system, the current decreased from 1,000 to 290 mA after 28 days, because soil resistance increased due to the exhaustion of ions in soil by electroosmosis and electromigration. Accumulated EOF in two cathode reservoirs was 10.3 L and the EOF rate was kept constant for 28 days. At the end of operation, the concentration of phenanthrene was observed to be very low near the anode and increased in the cathode region because hydrogen peroxide was supplied from anode to cathode region following the direction of EOP. Additionally, the concentration of phenanthrene decreased at the bottom of the test cell because the electrolyte solution containing hydrogen peroxide was largely transported toward the bottom due to a low capillary action in the soil with high porosity. Average removal efficiency of phenanthrene by EK-Fenton process was 81.4% for 28 days. In-situ EK-Fenton process would overcome the limitations of conventional remediation technologies and effectively remediate the contaminated sites.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1785-1790
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• 2006

A novel kinetic method for determination of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition in water is described. In this study, potential interferences of $O_3$ and the hydroxyl radicals, $^{\cdot}OH_{(O3)}$, are suppressed by $HSO_3{^-}/SO_3{^{2-}}$. $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ formed in ozone decomposition reduces $Fe^{3+}$-EDTA into $Fe^{2+}$-EDTA and subsequently the well-known Fenton-like (FL) reaction of $H_2O_2$ and $Fe^{2+}$-EDTA produces the hydroxyl radicals, $^{\cdot}OH_{(FL)}$. Benzoic acid (BA) scavenges $^{\cdot}OH_{(FL)}$ to produce OHBA, which are analyzed by fluorescence detection (${\lambda}_{ex}=320nm$ and ${\lambda}_{ex}=400nm$). The concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition has been determined by the novel kinetic method using the experimentally determined half-life ($t_{1/2}$). The steady-state concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ is proportional to the $O_3$ concentration at a given pH. However, the steady-state concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition is inversely proportional to pH values. This pH dependence is due to significant loss of $O_2{^{{\cdot}-}}$ by $O_3$ at higher pH conditions. The steady-state concentrations of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ are in the range of $2.49({\pm}0.10){\times}10^{-9}M(pH=4.17){\sim}3.01({\pm}0.07){\times}10^{-10}M(pH=7.59)$ at $[O_3]_o=60{\mu}M$.

• Korean Journal of Microbiology
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• v.47 no.4
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• pp.356-363
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• 2011

The accidental releases of total petroleum hydrocarbons (TPH) due to oil spills frequently ended up with soil and ground water pollution. TPH may be degraded through physicochemical and biological processes in the environment but with relatively slow rates. In this study an attempt has been made to develop an integrated chemical and biological treatment technology in order to establish an efficient and environment-friendly restoration technology for the TPH contaminated soils. A Fenton-like reaction was employed as a preceding chemical treatment process and a bioaugmentation process utilizing a diesel fuel degrader consortium was subsequently applied as a biological treatment process. An efficient chemical removal of TPH from soils occurred when the surfactant OP-10S (0.05%) and oxidants ($FeSO_4$ 4%, and $H_2O_2$ 5%) were used. Bioaugmentation of the degrader consortium into the soil slurry led to an increase in their population density at least two orders of magnitude, indicating a good survival of the degradative populations in the contaminated soils ($10^8-10^9$ CFU/g slurry). TPH removal efficiencies for the Fenton-treated soils increased by at least 57% when the soils were subjected to bioaugmentation of the degradative consortium. However, relatively lower TPH treatment efficiencies (79-83%) have been observed in the soils treated with Fenton and the degraders as opposed to the control (95%) that was left with no treatment. This appeared to be due to the presence of free radicals and other oxidative products generated during the Fenton treatment which might inhibit their degradation activity. The findings in this study will contribute to development of efficient bioremediation treatment technologies for TPH-contaminated soils and sediments in the environment.

• BMB Reports
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• v.31 no.2
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• pp.161-169
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• 1998

TThe reactive oxygen species oxidatively modify the biological macromolecules, including proteins, lipids, and nucleic acids. Iron- and heme-mediated Fenton-like reactions produce different pro-oxidants. However, these reactive products have not been clearly characterized. We examined the nature of the oxidizing species from the different iron sources by measuring oxidative protein modification and spectroscopic study. Hemoglobin (Hb) and methemoglobin (metHb) were oxidatively modified in $O{\array-\\\dot{2}}$ and $H_{2}O_{2}$ generating systems. Globin and bovine serum albumin (BSA) were also modified by iron, iron-EDTA, hematin, and Hb in an $O{\array-\\\dot{2}}$ generating system. In a $H_{2}O_{2}$ generating system, the iron- and iron-EDTA-mediated protein modifications were markedly reduced while the Hb-and hematin-mediated modifications were slightly increased. In the $O{\array-\\\dot{2}}$ generating system, the iron- and iron-EDTA-mediated protein modifications were strongly inhibited by superoxide dismutase (SOD) or catalase, but heme- and Hb-mediated protein modifications were inhibited only by catalase and slightly increased by SOD. Mannitol, 5,5-dimethyl-l-pyrroline-N-oxide (DMPO), deoxyribose, and thiourea inhibited the iron-EDTA-mediated protein modification. Mannitol and DMPO, however, did not exhibit significant inhibition in the hematin-mediated modification. Desferrioxamine (DFO) inhibited protein modification mediated by iron, but cyanide and azide did not, while the hematin-mediated protein modification was inhibited by cyanide and azide, but not significantly by DFO. The protein-modified products by iron and heme were different. ESR and UV-visible spectroscopy detected the DMPO spin adduct of the hydroxyl radical and ferryl ion generated from iron-EDTA and metHb, respectively. These results led us to conclude that the main oxidizing species are hydroxyl radical in the iron-EDTA type and the ferry I ion in the hematin type, the latter being more effective for protein modification.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.24-29
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• 1999

Naturally-occurring iron minerals, goethite, magnetite, and hydrogen peroxide were used to catalyze and initiate Fenton-like oxidation of silica sand contaminated with mixture of diesel and kerosene in batch system. Optimal reaction conditions were investigated by varying pH(3, 7), $H_2O_2$ concentration(0%, 1%, 7%, 15%, 35%), initial contaminant concentration(0.2, 0.5, 1.0 g-mixture of diesel and kerosene/ kg-soil), and iron mineral contents(1, 5, and 10 wt % magnetite or goethite). Contaminant degradations in silica sand-iron mineral-$H_2O_2$ systems were identified by determining total petroleum hydrocarbon(TPH) concentration. The optimal pH of the system was 3. The system which iron minerals were the only iron source was more efficient than the system with $FeSO_4$ solution due to lower $H_2O_2$ consumption. In case of initial contaminant concentration of 1g-contaminant/kg-soil with 5 wt % magnetite, addition of 0%, 1%, 7%, 15%, and 35% of $H_2O_2$ showed 0%, 24.5%, 44%, 52%, and 70% of TPH reduction in 8 days, respectively. When the mineral contents were varied 0, 1, 5, and 10wt%, removal of contaminants were 0%, 33.5%, 50%, and 60% for magnetite and 0%, 29%, 41%, and 53% for goethite, respectively. Reaction of magnetite system showed higher degradation than that of goethite system due to dissolution of iron and mixed presence of iron(II) and iron(III); however, dissolved iron precipitated on the surface of iron mineral and seemed to cause reducing electron transfer activity on the surface and quenching $H_2O_2$. The system using goethite has better treatment efficiency due to less $H_2O_2$ consumption. When cach system was mixed by shaker, removal of contaminants increased by 41% for magnetite and 30% for goethite. Results of this study showed catalyzed $H_2O_2$ system made in-situ treatment of soil contaminated with petroleum possible without addition of iron source since natural soils generally contain iron minerals such as magnetite and goethite.

• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2873-2876
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• 2010

Excess free iron generates oxidative stress that may contribute to the pathogenesis of various causes of neurodegenerative diseases. Previous studies have shown that one of the primary causes of increased brain iron may be the release of excess iron from intracellular iron storage molecules. In this study, we attempted to characterize the oxidative damage of DNA induced by the reaction of ferritin with $H_2O_2$. When DNA was incubated with ferritin and $H_2O_2$, DNA strand breakage increased in a time-dependent manner. Hydroxyl radical scavengers strongly inhibited the ferritin/$H_2O_2$ system-induced DNA cleavage. We investigated the generation of hydroxyl radical in the reaction of ferritin with $H_2O_2$ using a chromogen, 2,2'-azinobis-(2-ethylbenzthiazoline-6-sulfonate) (ABTS), which reacted with ${\cdot}OH$ to form $ABTS^{+\cdot}$. The initial rate of $ABTS^{+\cdot}$ formation increased as a function of incubation time. These results suggest that DNA strand breakage is mediated in the reaction of ferritin with $H_2O_2$ via the generation of hydroxyl radicals. The iron-specific chelator, deferoxamine, also inhibited DNA cleavage. Spectrophotometric study using a color reagent showed that the release of iron from $H_2O_2$-treated ferritin increased in a time-dependent manner. Ferritin enhanced mutation of the lacZ' gene in the presence of $H_2O_2$ when measured as a loss of $\alpha$-complementation. These results indicate that ferritin/$H_2O_2$ system-mediated DNA cleavage and mutation may be attributable to hydroxyl radical generation via a Fenton-like reaction of free iron ions released from oxidatively damaged ferritin.

• Journal of the Korean Ceramic Society
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• v.47 no.2
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• pp.169-176
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• 2010

The Fe-treated CNT/$TiO_2$ photocatalysts mixed with anatase and rutile phase have been developed for the decomposition of non-biodegradable different organic dyes like methylene blue (MB), rhodamine B (Rh.B), and methyl orange (MO) in two conditions as ultraviolet and visible light respectively. The results indicate that all the Fe-CNT/$TiO_2$ composites proved to be more efficient photocatalysts since degradation of MB at higher reaction rates, tthe decomposition rate of different dyes increases with an increase of $Fe^{3+}$ concentration in composites the highest rate of decomposition of different dyes was noted under UV irradiation. These results can indicate that the large CNT network is facilitate the electron transfer and strongly adsorb dye molecules on the texted photocatalysts, iron is reactive in the photo-Fenton process resulting in high production of OH radicals and also high activity of the photocatalyst. And Fe particles can generate more photoinduced electrons to conduction band of $TiO_2$ under visible light irradiation. The composites of Fe-CNT/$TiO_2$ photocatalysts synthesized by a sol-gel method were characterized by BET, TEM, SEM, XRD and EDX.

• Molecules and Cells
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• v.38 no.8
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• pp.715-722
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• 2015

In Gram-negative bacteria in the periplasmic space, the dimeric thioredoxin-fold protein DsbC isomerizes and reduces incorrect disulfide bonds of unfolded proteins, while the monomeric thioredoxin-fold protein DsbA introduces disulfide bonds in folding proteins. In the Gram-negative bacteria Salmonella enterica serovar Typhimurium, the reduced form of CueP scavenges the production of hydroxyl radicals in the copper-mediated Fenton reaction, and DsbC is responsible for keeping CueP in the reduced, active form. Some DsbA proteins fulfill the functions of DsbCs, which are not present in Gram-positive bacteria. In this study, we identified a DsbA homologous protein (CdDsbA) in the Corynebacterium diphtheriae genome and determined its crystal structure in the reduced condition at $1.5{\AA}$ resolution. CdDsbA consists of a monomeric thioredoxin-like fold with an inserted helical domain and unique N-terminal extended region. We confirmed that CdDsbA has disulfide bond somerase/reductase activity, and we present evidence that the N-terminal extended region is not required for this activity and folding of the core DsbA-like domain. Furthermore, we found that CdDsbA could reduce CueP from C. diphtheriae.

• Journal of Environmental Science International
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• v.23 no.5
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• pp.903-910
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• 2014

This study examined the treatment characteristics of hard-to-degrade pollutants such as TCE which are found in organic solvent and cleaning wastewater by nZVI that have excellent oxidation and reduction characteristics. In addition, this study tried to find out the degradation characteristics of TCE by Fenton-like process, in which $H_2O_2$ is dosed additionally. In this study, different ratios of nZVI and $H_2O_2$, such as 1.0 mM : 0.5 mM, 1.0 mM : 1.0 mM, and 1.0 mM : 2.0 mM were used. When 1.0 mM of nZVI was dosed with 1.0 mM of $H_2O_2$, the removal efficiency of TOC was the highest and the first order rate constant was also the highest. When 1mM of nZVI was dosed with 0.5 mM of $H_2O_2$, the first order rate constant and removal efficiency were the lowest. The size of first order rate constant and removal efficiency was in the order of nZVI 1.0 mM : $H_2O_2$ 1.0 mM > nZVI 1.0 mM : $H_2O_2$ 2.0 mM > nZVI 1.0 mM : $H_2O_2$ 0.5 mM > $H_2O_2$ 1.0 mM > nZVI 1.0 mM. It is estimated that when 1.0 mM of nZVI is dosed with 1.0 mM of $H_2O_2$, $Fe^{2+}$ ion generated by nZVI and $H_2O_2$ react in the stoichiometric molar ratio of 1:1, thus the first order rate constant and removal efficiency are the highest. And when 1.0 mM of nZVI is dosed with 2.0 mM of $H_2O_2$, excessive $H_2O_2$ work as a scavenger of OH radicals and excessive $H_2O_2$ reduce $Fe^{3+}$ into $Fe^{2+}$. As for the removal efficiency of TOC in TCE by simultaneous dose and sequential dose of nZVI and $H_2O_2$, sequential dose showed higher first order reaction rate and removal efficiency than simultaneous dose. It is estimated that when nZVI is dosed 30 minutes in advance, pre-treatment occurs and nanoscale $Fe^0$ is oxidized to $Fe^{2+}$ and TCE is pre-reduced and becomes easier to degrade. When $H_2O_2$ is dosed at this time, OH radicals are generated and degrade TCE actively.

• Journal of the Korean GEO-environmental Society
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• v.11 no.7
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• pp.45-49
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• 2010

We have developed and demonstrated the use of a new kinetic method as an analytical tool for the measurement of $HO_2{\cdot}/O_2{\cdot}^-$. This new method is based on the reduction of $Fe^{3+}$-Ethylene Diamine Tetra Acetate, EDTA) into $Fe^{2+}$-EDTA by $HO_2{\cdot}/O_2{\cdot}^-$ and the well-known Fenton-like reaction of $H_2O_2$ and $Fe^{2+}$-EDTA to yield the hydroxyl radicals ($OH{\cdot}$). Since this method for $HO_2{\cdot}/O_2{\cdot}^-$ shows high sensitivity and allows a simple calibration system, it can contribute significantly to understanding the basic functions of $HO_2{\cdot}/O_2{\cdot}^-$ in advanced oxidation processes for water treatment. Moreover, the present technique has the advantage of using inexpensive and easily available nonenzymatic reagents and of being insensitive to the moderate concentration of possible interferences often found in aqueous phase.