• 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 Korean Society of Environmental Engineers
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• v.38 no.9
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• pp.521-527
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• 2016

Nanoscale zero valent iron (nZVI) has been intensively studied for the treatment of a plethora of pollutants through reductive reaction, however, the nano size should be of concern when nZVI is considered for water treatment, due to difficulties in recovery. The loss of nZVI causes not only economical loss, but also potential risk to human health and environment. Thus, the immobilization onto coarse or structured support is essential. In this study, two representative processes for nZVI immobilization on granular activated carbon (GAC) were evaluated, and optimized conditions for synthesizing Fe/GAC composite were suggested. Both total iron content and $Fe_0$ content can be significantly affected by preparation processes, therefore, it was important to avoid oxidation during preparation to achieve higher reduction capacity. Synthesis conditions such as reduction time and existence of intermediate drying step were investigated to improve $Fe_0$ content of Fe/GAC composites. The optimal condition was two hours of $NaBH_4$ reduction without intermediate drying process. The prepared Fe/GAC composite showed synergistic effect of the adsorption capability of the GAC and the degradation capability of the nZVI, which make this composite a very effective material for environmental remediation.

• Advances in environmental research
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• v.3 no.2
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• pp.107-116
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• 2014

This study aimed to synthesize dispersed and reactive nanoscale zero-valent iron (nZVI) with poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA), nontoxic and biodegradable stabilizer. The nZVI used for the experiments was prepared by reduction of ferric solution in the presence of PVP/VA with specific weight ratios to iron contents. Colloidal stability was investigated based on the rate of sedimentation, hydrodynamic radius and zeta potential measurement. The characteristic time, which demonstrated dispersivity of particles resisting aggregation, increased from 21.2 min (bare nZVI) to 97.8 min with increasing amount of PVP/VA (the ratios of 2). For the most stable nZVI coated by PVP/VA, its reactivity was examined by nitrate reduction in a closed batch system. The pseudo-first-order kinetic rate constants for the nitrate reduction by the nanoparticles with PVP/VA ratios of 0 and 2 were 0.1633 and $0.1395min^{-1}$ respectively. A nitrogen mass balance, established by quantitative analysis of aqueous nitrogen species, showed that the addition of PVP/VA to nZVI can change the reduction capacity of the nanoparticles.

• Environmental Engineering Research
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• v.17 no.2
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• pp.111-116
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• 2012

This study investigates the complete removal of nitrate and the recovery of valuable ammonium salt by the combination of nanoscale zero-valent iron (NZVI) and a membrane contactor system. The NZVI used for the experiments was prepared by chemical reduction without a stabilizing agent. The main end-product of nitrate reduction by NZVI was ammonia, and the solution pH was stably maintained around 10.5. Effective removal of ammonia was possible with the polytetrafluoroethylene membrane contactor system in all tested conditions. Among the various operation parameters including influent pH, concentration, temperature, and contact time, contact time and solution pH showed significant effects on the ammonia removal mechanism. Also, the osmotic distillation phenomena that deteriorate the mass transfer efficiency could be minimized by pre-heating the influent wastewater. The ammonia removal rate could be maximized by optimizing operation conditions and changing the membrane configuration. The combination of NZVI and the membrane contactor system could be a solution for nitrate removal and the recovery of valuable products.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.6
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• pp.413-419
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• 2011

Nanoscale zero-valent iron (NZVI) particles were tested as remediation media for groundwater contaminated by organic pollutants (e.g., TCE, trichloroethylene). The contaminated groundwater contained anions ($NO_3^-$, $Cl^-$, $SO_4^{2-}$, and $HCO_3^-$) and natural organic matter (NOM). Treatability of commercial NZVI particles (NANOFER 25, Nanoiron, Czech) was tested by using a synthetic groundwater and the field groundwater samples. More than 95% of 1.8 mM TCE was removed within 20 hours with a NZVI dosage of 25 g/L ($k=0.15hr^{-1}$). Repetitive degradation experiments revealed that the removal capacity of NANOFER 25 was 0.19 mmole TCE/g NZVI. TCE degradation reactions were not substantially affected by the presence of each anion with concentrations as high as 100 times the average field concentrations. However, when the four anions ($NO_3^-$, $Cl^-$, $SO_4^{2-}$, $HCO_3^-$) were present simultaneously. the degradation reactivity and removal capacity were decreased by 60% ($k=0.069hr^{-1}$) and 10%, respectively. The k value of TCE degradation in the presence of NZVI (25 g/L) with dissovled organic carbon of 2.5 mg/L was also decreased by 84% ($k=0.025hr^{-1}$). In the experiments with the field groundwater, more than 90% of $1.8{\mu}M$ TCE, which is the concentration of TCE at the source zone, was removed within 10 hours with a NANOFER 25 dosage of 25 g/L. The results imply that the contaminated groundwater can effectively be treated by NANOFER 25 with more information on the hydrogeology of the site.

• Journal of Soil and Groundwater Environment
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• v.21 no.6
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• pp.192-203
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• 2016

A field investigation was conducted on an aquifer contaminated with trichloroethylene (TCE) for application of in situ reactive zone treatment using nanosized zero-valent iron (NZVI). The aquifer was an unconfined aquifer with a mean hydraulic conductivity of $5.14{\times}10^{-4}cm/sec$, which would be favorable for NZVI injection. Seasonal monitoring of TCE concentration revealed a presence of non-aqueous phase liquid form of TCE near IW (injection well). The hydrochemical data characterized the site groundwater to be a $Ca-HCO_3$ type. The average value of Langelier Saturation Index of the groundwater was -1.33, which implied that the site was favorable for corrosion of NZVI. Dissolved oxygen (DO) concentration varied between 2.5~11.5 mg/L, which indicated that DO would greatly compete with TCE as an electron acceptor. The hydrogeological and hydrochemical characterization reveals that the time around November would be appropriate for NZVI injection when water level and temperature are relatively high and DO concentration is low.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.1008-1012
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• 2008

Nanoscale zero-valent iron(nZVI) is famous for its high reactivity originated from its high surface area and it has received considerable attentions as one of the latest innovative technologies for treating contaminated groundwater. Due to its fine powdery form, nZVI has limited filed applications. The efforts to overcome this shortcoming by immobilizing nZVI on a supporting material have been made. This study investigated the differences of resin-supported nZVI's characteristics by changing the preparation methods and evaluated its reactivity. The borohydride reduction of an iron salt was proceeded in ethanol/water solvent containing a dispersant and the synthesis was conducted in the presence of ion-exchange resin. The resulting material was compared to that prepared in a conventional way of using de-ionized water by measuring the phyrical and chemical characteristics. BET surface area and Fe content of nZVI-attached resin was increased from $31.63m^2/g$ and 18.19 mg Fe/g to $38.10m^2/g$ and 22.44 mg Fe/g, respectively, by switching the solution medium from water to ethanol/water with a dispersant. The reactivity of each material was tested using nitrate solution without pH control. The pseudo first-order constant of $0.462h^{-1}$ suggested the reactivity of resin-supported nZVI prepared in ethanol/water was increased 61 % compared to that of the conventional type of supported nZVI. The specific reaction rate constant based on surface area was also increased. The results suggest that this new supported nZVI can be used successfully in on-site remediation for contaminated groundwater.

• Analytical Science and Technology
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• v.23 no.6
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• pp.560-565
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• 2010

Perchlorate ion ($ClO_4^-$) has been widely used as oxidizing agent in military weapon system such as rocket and missile fuel propellant. So it has been challenging to remove the pollutant of perchlorate ion. nanoscale zero valence iron (nZVI) particles are widely employing reduction catalyst for decomposition of perchlorate ion. nZVI particles has increasingly been utilized in groundwater purification and waste water treatment. But it have strong tendency of aggregation, rapid sedimentation and limited mobility. In this study, we focused on reduction of perchlorate ion using nZVI particles immobilized in alginate polymer bead for stabilization. The stabilized nZVI particles displayed much greater surface area, and much faster reaction rates of reduction of perchlorate ion. In this study, an efficient way to immobilize nZVI particles in a support material, alginate bead, was developed by using $Ca^{2+}$ as the cross-linking cations. The efficiency and reusability of the immobilized Fe-alginate beads on the reduction of perchlorate was tested at various temperature conditions.

• 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.

• 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.