• Journal of Environmental Science International
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• v.32 no.1
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• pp.57-65
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• 2023

The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

• Journal of Environmental Science International
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• v.25 no.4
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• pp.517-524
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• 2016

In order to treat groundwater containing high levels of nitrate, nitrate reduction by nano sized zero-valent iron (nZVI) was studied using batch experiments. Compared to nitrate removal efficiencies at different mass ratios of $nitrate/Fe^0$, the removal efficiency at the mass ratio of 0.02% was the highest(54.59%). To enhance nitrate removal efficiency, surface modification of nZVI was performed using metallic catalysis such as Pd, Ni and Cu. Nitrate removal efficiency by Cu-nZVI (at $catalyst/Fe^0$ mass ratio of 0.1%) was 66.34%. It showed that the removal efficiency of Cu-nZVI was greater than that of the other catalysts. The observed rate constant ($k_{obs}$) of nitrate reduction by Cu-nZVI was estimated to $0.7501min^{-1}$ at the Cu/Fe mass ratio of 0.1%. On the other hand, TEM images showed that the average particle sizes of synthetic nZVI and Cu-nZVI were 40~60 and 80~100 nm, respectively. The results imply that catalyst effects may be more important than particle size effects in the enhancement of nitrate reduction by nZVI.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.12
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• pp.667-675
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• 2016

Nanoscale zero-valent iron (nZVI) has been effectively applied for environmental remediation due to its ability to reduce various toxic compounds. However, quantification of nZVI reactivity has not yet been standardized. Here, we adapted colorimetric assays for determining reductive activity of nZVIs. A modified indophenol method was suggested to determine reducing activity of nZVI. The method was originally developed to determine aqueous ammonia concentration, but it was further modified to quantify phenol and aniline. The assay focused on analysis of reduction products rather than its mother compounds, which gave more accurate quantification of reductive activity. The suggested color assay showed superior selectivity toward reduction products, phenol or aniline, in the presence of mother compounds, 4-chlorophenol or nitrobenzene. Reaction conditions, such as reagent concentration and reaction time, were optimized to maximize sensitivity. Additionally, pretreatment step using $Na_2CO_3$ was suggested to eliminate the interference of residual iron ions. Monometallic nZVI and bimetallic Ni/Fe were investigated with the reaction. The substrates showed graduated reactivity, and thus, reduction potency and kinetics of different materials and reaction mechanism was distinguished. The colorimetric assay based on modified indophenol reaction can be promises to be a useful and simple tool in various nZVI related research topics.

• Journal of Environmental Science International
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• v.26 no.7
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• pp.859-868
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• 2017

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, $Fe^0$) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when $Fe^0$ and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the $Fe^0$ and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the $Fe^0$ and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > $Fe^0$, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

• Journal of Soil and Groundwater Environment
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• v.17 no.2
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• pp.15-21
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• 2012

MTBE (Methyl tertiary-butyl ether) has been commonly used as an octane enhancer to replace tetraethyl lead in gasoline, because MTBE increases the efficiency of combustion and decreases the emission of carbon monoxide. However, MTBE has been found in groundwater from the fuel spills and leaks in the UST (Underground Storage Tank). Fenton's oxidation, an advanced oxidation catalyzed with ferrous iron, is successful in removing MTBE in groundwater. However, Fenton's oxidation requires the continuous addition of dissolved $Fe^{2+}$. Zero-valent iron is available as a source of catalytic ferrous iron of MFO (Modified Fenton's Oxidation) and has been studied for use in PRBs (Permeable Reactive Barriers) as a reactive material. Therefore, this study investigated the condition of optimization in MFO-PRBs using waste zero-valent iron (ZVI) with the waste steel scrap to treat MTBE contaminated groundwater. Batch tests were examined to find optimal molar ratio of MTBE : $H_2O_2$ on extent to degradation of MTBE in groundwater at pH 7 with 10% waste ZVI. As the results, the ratio of optimization of MTBE to hydrogen peroxide for MFO was determined to be 1:300[mM]. The column experiment was conducted to know applicability of MFO-PRBs for MTBE remediation in groundwater. As the results of column test, MTBE was removed 87% of the initial concentration during 120days of operational period. Interestingly, MTBE was degraded not only within waste ZVI column but also within sand column. It means the aquifer may affect continuously the MTBE contaminated groundwater after throughout the waste ZVI barrier. The residual products showed acetone, TBF (Tert-butyl formate) and TBA (Tert-butyl acetate) during this test. The results of the present study showed that the recycled materials can be effectively used for not only a source of catalytic ferrous iron but also a reactive material of the MFO-PRBs to remove MTBE in groundwater.

• Journal of Soil and Groundwater Environment
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• v.14 no.6
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• pp.101-107
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• 2009

Carboxymethyl cellulose (CMC) as stabilizer is expected to facilitate in-situ delivery of zero-valent iron (ZVI) nanoparticles in a contaminated aquifer because it increases dispersity of ZVI nanoparticles. This work investigated the transport of CMC-stabilized ZVI nanoparticles (CMC-Fe) using column breakthrough experiments. The ZVI nanoparticles (100 mg/L Fe) were transportable through sand porous media. In contrast, non-stabilized ZVI nanoparticles rapidly agglomerate in solution and are stopped in sand porous media. At pH 7 of solution approximately 80% CMC-Fe were eluted. When the pH of solution is below 5, 100% CMC-Fe were eluted. These results suggest that the mobility of CMCFe was increased as pH decreases. In the mobility test under different ionic strengths using $Na^+$ and $Ca^{2+}$ ions, there was no signigficant difference in the mobility of CMC-Fe. Also, in the experiments of effect of clay and natural organic mater (NOM) on the mobility of ZVI, there was no significant difference in the mobility of CMC-Fe not only between 1 and 5% clay, but 100 and 1000 mg/L NOM. The results from this work suggests that the CMC-Fe nanoparticles could be easily delivered into the subsurface over a broad range of ionic strength, clay and NOM.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2002.09a
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• pp.67-70
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• 2002

Remediation of groundwater contaminated with chlorinated organics, nitro aromatics, and heavy metals using zero valent iron (ZVI) filings has paid considerable attention in recent years. When the contaminants of high concentration leaked abundantly in subsurface environment, permeable reactive barrier technology using iron filing is taken a long time for the remediation of contaminated groundwater, The problem of contaminant shock is able to be solved using surfactant (hexadecyltrimethylammonium, HDTMA) modified bentonite (SMB) as immobilizing material. Therefore, the purpose of this research was to develop the combined remediation technology using conventional permeable reactive and immobilizing barrier for the enhanced decontamination of chlorinated compounds. Four column experiments were conducted to assess the performance of the mixed reactive materials with Ottawa sand, iron filing, and HDTMA-bentonite for trichloroethylene (TCE) removal under controlled groundwater flow conditions. TCE reduction rates with sand/iron filing/HDTMA-bentonite were highest among four column due to dechlorination of TCE by iron filing and sorption of TCE by SMB.

• Journal of Environmental Science International
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• v.25 no.12
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• pp.1717-1726
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• 2016

In this study, the reductive decolorization of three acid and basic dyes using modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium coated iron (Pd/Fe)) at various pH conditions (pH 3~5) was experimentally investigated and the decolorization characteristics were evaluated by analyzing the absorbance spectra and reaction kinetics. In the case of acid dyes such as methyl orange and eriochrome black T, color removal efficiencies increased as initial pH of the dye solution decreased. However, the color removal of methylene blue, a basic dye, was not affected much by the initial pH and more than 70% of color was removed within 10 min. During the decolorization reaction, the absorbance of methyl orange (${\lambda}_{max}=464nm$) and eriochrome black T (${\lambda}_{max}=528nm$) decreased in the visible range but increased in the UV range. The absorbance of methylene blue (${\lambda}_{max}=664nm$) also decreased gradually in the visible range. Pseudo-zero order, pseudo-first order, and pseudo-second order kinetic models were used to analyze the reaction kinetics. The pseudo-second order kinetic model was found to be the best with good correlation. The decolorization reaction rate constants ($k_2$) of methylene blue were relatively higher than those of methyl orange and eriochrome black T. The reaction rate constants of methyl orange and eriochrome black T increased with a decrease in the initial pH.