• 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 the Mineralogical Society of Korea
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• v.28 no.2
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• pp.95-108
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• 2015

Nano-sized iron colloids are formed as acid mine drainage is exposed to surface environments and is introduced into surrounding water bodies. These iron nanomaterials invoke aesthetic contamination as well as adverse effects on aqueous ecosystems. In order to control them, the characteristics of their behaviour should be understood first, but the cumulative research outputs up to now are much less than the expected. Using zero-valent iron (ZVI) and magnetite, this study aims to investigate the behaviour of iron nanomaterials according to the change in the composition and pH of background electrolyte and the concentration of natural organic matter (NOM). The size and surface zeta potential of iron nanomaterials were measured using dynamic light scattering. Characteristic behaviour, such as aggregation and dispersion was compared each other based on the DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory. Whereas iron nanomaterials showed a strong tendency of aggregation at the pH near point of zero charge (PZC) due to electrostatic attraction between particles, their dispersions became dominant at the pH which was higher or lower than PZC. In addition, the behaviour of iron nanomaterials was likely to be more significantly influenced by cations than anions in the electrolyte solutions. Particularly, it was observed that divalent cation influenced more effectively than monovalent cation in electrostatic attraction and repulsion between particles. It was also confirmed that the NOM enhanced the dispersion nanomaterials with increasing the negative charge of nanomaterials by coating on their surface. Under identical conditions, ZVI aggregated more easily than magnetite, and which would be attributed to the lower stability and larger reactivity of ZVI.

• Clean Technology
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• v.15 no.3
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• pp.194-201
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• 2009

Reductive reactivity of zero-valent iron nanoparticles was investigated for removal of nitrate-nitrogen which is considered one of the major water pollutants. To elucidate the difference in reactivity between preparation methods, iron nanoparticles were synthesized respectively from microemulsion and aqueous solution of ferric ions. Iron nanoparticles prepared from microemulsion were deposited on aluminum by electrophoretic method, and their reaction kinetics was compared to that of the same nanoparticles suspended in aqueous batch reaction. With an approximation of pseudo-first-order reaction, rate constants for suspended nanoparticles prepared from microemulsion and dilute aqueous solution were $3.49{\times}10^{-2}min^{-1}$ and $1.40{\times}10^{-2}min^{-1}$, respectively. Iron nanoparticles supported on aluminum showed ca. 30% less reaction rate in comparison with the identical nanoparticles in suspended state. However, supported nanoparticles showed the superior effectiveness in terms of nitrate-nitrogen removal per zero-valent iron input especially when excess amounts of nitrates were present. Iron nanoparticles deposited on aluminum maintained reductive reactivity for more than 3 hours, and produced nitrogen gas as a final reduction product of nitrate-nitrogen.

• Journal of Soil and Groundwater Environment
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• v.11 no.6
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• pp.83-91
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• 2006

Reduction kinetics and the behaviour of intermediate of three high explosives (HMX, RDX, and TNT) were studies in batch reactors using nano- or micro- size zero valent iron(nZVI or mZVI) as reducing agent. The kinetic constants normalized by the mass of iron ($k_M$) or by the surface area ($k_{SA}$) were measured and compared along with the changes in the concentrations of intermediates. Results showed that $k_M$ and $k_{SA}$ values were not suitable to fully explain the behaviour of mother compounds and reduced intermediates in the batch reactor. The concentrations of initial explosives degradation products, such as nitroso-RDXs, nitroso-HMXs, and hydroxylamino-TNTs, were higher in mZVI treated reactor than in nZVI treated reactor, whereas more reduced polar intermediates such as TAT were accumulated in the nZVI reactor. Therefore, a new parameter, which accounted for the intermediates reduction, needs to be developed.

• Journal of Korean Society of Water and Wastewater
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• v.23 no.4
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• pp.471-479
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• 2009

A Nanoscale Zero-Valent Iron(NZVI) was modified to build a reactor system to treat nitrate. Shell layer of the NZVI was modified by slow exposure of the iron surface to air flow, which produced NZVI particles that are resistant to aerial oxidation. A XANES (X-ray Absorption Near-Edge Structure) analysis revealed that the shell consists of magnetite ($Fe_3O_4$) dominantly. The shell-modified NZVI(0.5 g NZVI/ 120 mL) was able to degrade more than 95% of 30 mg/L of nitrate within $30 hr^{-1}$ ( pseudo first-order rate constant($k_{SA}$) normalzed to NZVI surface area ($17.96m^2/g$) : $0.0050L{\cdot}m^{-2}{\cdot}hr^{-1}$). Ammonia occupied about 90% of degradation products of nitrate. Nitrate degradation efficiencies increased with the increase of NZVI dose generally. Initial pH values of the reactor systems at 4, 7, and 10 did not affect nitrate removal rate and final pH values of all experiments were near 12. Nitrate removal experiments by using the shell-modified NZVI immobilized on a cellulose acetate (CA) membrane were also conducted. The nitrate removal efficiency of the CA membrane supported NZVI ($k_{SA}=0.0036L{\cdot}m^{-2}{\cdot}hr^{-1}$) was less than that of the NZVI slurries($k_{SA}=0.0050L{\cdot}m^{-2}{\cdot}hr^{-1}$), which is probably due to less surface area available for reduction and to kinetic retardation by nitrate transport through the CA membrane. The detachment of the NZVI from the CA membrane was minimal and impregnation of up to 1 g of NZVI onto 1 g of the CA membrane was found feasible.

• Clean Technology
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• v.29 no.2
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• pp.118-125
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• 2023

Once a site is contaminated with polychlorinated biphenyls (PCBs), serious environmental and human health risks are inevitable. Therefore, innovative but economical in situ remediation technologies must be immediately applied to the contaminated site. Recently, nanoscale zero-valent iron (nano-ZVI) particles have successfully been applied for the dechlorination of various chlorinated organic compounds like TCE, PCE and DDT, and they are considered to be environmentally safe due to the high abundance of iron in the earth's crust. Nano-ZVIs are much more reactive than granular ones, but tend to agglomerate due to their high surface energy and magnetic properties. In order to prevent them from being agglomerated toward larger particles, TiO₂ was used as a support to immobilize the nano-ZVI particles as much as possible. 10wt% ZVI/TiO₂ was prepared by adding NaBH₄ slowly into an FeSO₄/TiO₂ aqueous slurry. In spite of their non-uniformity in size, the nano-ZVI particles were quite successfully dispersed onto the exterior surface of a non-porous TiO₂ powder. The ZVI/TiO₂ was then employed to degrade Aroclor 1242, a kind of PCBs standard, in spiked soil, and its reactivity towards the degradation of Aroclor 1242 was investigated. The fabricated ZVI/TiO₂ degraded Aroclor 1242 in soil quite effectively, but the creation of remaining dechlorinated compounds, possibly high molecular weight hydrocarbons, in the soil was unavoidable.