• 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 the Korean Electrochemical Society
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• v.18 no.2
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• pp.81-85
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• 2015

A method for degradation of the perchlorate anion ($ClO{_4}^-$) has been studied using electrochemically generated zero-valent iron (ZVI) deposited on a porous carbon electrode. The first strategy of this study is to produce the ZVI via the electrochemical reduction of iron (II) on a porous carbon electrode coated with a conducting polymer, instead of employing expensive $NaBH_4$. The present method produced well distributed ZVI on conducting polymer (polypyrrole thin film) and increased surface area. ZVI surface can be regenerated easily for successive reduction. The second strategy is to apply a mild reducing condition (-0.3 V) to enhance the efficiency of the degradation of perchlorate with ZVI without the evolution of hydrogen. The electrochemically generated ZVI nanoparticles may offer an alternative means for the complete destruction perchlorate without evolution of hydrogen in water with high efficiency and at low cost.

• 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.

• 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 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 Soil and Groundwater Environment
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• v.19 no.6
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• pp.80-90
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• 2014

The laboratory and field studies were conducted to identify an optimal injection concentration of nanoscale zero-valent iron particles (NZVI) and to evaluate the applicability of NZVI-based reactive zone technology to the site contaminated with trichloroethylene (TCE) DNAPL (Dense Non-Aqueous Phase Liquid). The laboratory test found an optimal injection concentration of NZVI of 5 g/L that could remove more than 95% of 0.15 mM TCE within 20 days. Eleven test wells were installed at the aquifer that was mainly composed of alluvial and weathered soils at a strong oxic condition with dissolved oxygen concentration of 3.50 mg/L and oxidation-reduction potential of 301 mV. NZVI of total 30 kg were successfully injected using a centrifugal pump. After 60 days from the NZVI injection, 86.2% of the TCE initially present in the groundwater was removed and the mass of TCE removed was 405 g. Nonchlorinated products such as ethane and ethene were detected in the groundwater samples. Based on the increased chloride ion concentration at the site, the mass of TCE removed was estimated to be 1.52 kg. This implied the presence of DNAPL TCE which contributed to a higher estimate of TCE removal than that based on the TCE concentration change.

• Journal of Soil and Groundwater Environment
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• v.18 no.3
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• pp.109-118
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• 2013

Characteristics of the transport of zero-valent iron nanoparticles (nZVI) in an aquifer were investigated to evaluate an application of nZVI-based reactive zone technology. Main flow direction of groundwater was north. Preferential flow paths of the groundwater identified by natural gradient tracer test were shown northeast and northwest. The highest groundwater velocity was $4.86{\times}10^{-5}$ m/s toward northwest. When the breakthrough curves obtained from the gravity injection of nZVI were compared with the tracer curves, the transport of nZVI was retarded and retardation factors were 1.17 and 1.34 at monitoring wells located on the northeast and northwest, respectively. The ratios of the amount of nZVI delivered to the amount of tracer delivered at the two wells mentioned above were 24 and 28 times greater than that of the well on the main flow direction, respectively. Attachment efficiency based on a filtration theory was $4.08{\times}10^{-2}$ along the northwest direction that was the main migration route of nZVI. Our results, compared to attachment efficiencies obtained in other studies, demonstrate that the mobility of nZVI was higher than that of results reported in previous studies, regardless of large iron particle sizes of the current study. Based on distribution of nZVI estimated by the attachment efficiency, it was found that nZVI present within 1.05 m from injection well could remove 99% of TCE within 6 months.

• Environmental Engineering Research
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• v.10 no.4
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• pp.165-173
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• 2005

Nano-sized iron particles were synthesized by reduction of $Fe^{3+}$ in aqueous solution under two reaction conditions, aerobic and anaerobic, and the reactivity of iron was tested by reaction with trichloroethene (TCE) using a batch system. Results showed that iron produced under anoxic condition for both synthesis and drying steps gave rise to iron with higher reduction reactivity, indicating the presence of oxygen is not favorable for production of nano-sized iron deemed to accomplish reactivity enhancement from particle sized reduction. Nano-sized iron sample obtained from the anoxic synthesis condition was further characterized using various instrumental measurements to identity particle morphology, composition, surface area, and particle size distribution. The scanning electron microscopic (SEM) image showed that synthesized particles were uniform, spherical particles (< 100 nm), and aggregated into various chain structures. The effects of other synthesis conditions such as solution pH, initial $Fe^{3+}$ concentration, and reductant injection rate on the reactivity of nano-sized iron, along with standardization of the synthesis protocol, are presented in the companion paper.