Nanoscale zero-valent iron (NZVI) was synthesized and tested for the removal of As(III), which is a highly toxic, mobile, and predominant arsenic species in anoxic groundwater. We used SEM-EDX, AFM, and XRD to characterize particle size, surface morphology, and corrosion layers formed on pristine NZVI and As(III)-treated NZVI. AFM results showed that particle size ranged from 1 to 120 nm. XRD and SEM results revealed that NZVI gradually converted to magnetite/maghemite corrosion products mixed with lepidocrocite over 60 d. Arsenic(III) adsorption kinetics were rapid and occurred on a scale of minutes following a pseudo-first-order rate expression with observed reaction rate constants (K(obs)) of 0.07-1.3 min(-1) (at varied NZVI concentration). These values are about 1000x higher than K(obs) literature values for As(III) adsorption on micron size ZVI. Batch experiments were performed to determine the feasibility of NZVI as an adsorbent for As(III) treatment in groundwater as affected by initial As(III) concentration and pH (pH 3-12). The maximum As(III) adsorption capacity in batch experiments calculated by Freundlich adsorption isotherm was 3.5 mg of As(III)/g of NZVI. Laser light scattering (electrophoretic mobility measurement) confirmed NZVI-As(III) inner-sphere surface complexation. The effects of competing anions showed HCO3-, H4SiO4(0), and H2P04(2-) are potential interferences in the As(III) adsorption reaction. Our results suggest that NZVI is a suitable candidate for both in-situ and ex-situ groundwater treatment due to its high reactivity.

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

The usefulness of water quality indices, as the indicators of water pollution, for assessment of spatial-temporal changes and classification of river water qualities was verified. Four water quality indices were investigated: WQI (considering 18 water quality parameters), WQI(min) and WQI(m) (considering five water quality parameters: temperature, pH, DO, EC and TSS) and WQI(DO) (considering a single parameter, DO). The water quality indices WQI(min), WQI(m) and WQI(DO) could be of particular interest for the developing countries because of the minimum analytical cost involved. As a case study, water quality indices were used to evaluate spatial and temporal changes of the water quality in the Bagmati river basin (Nepal) for the study period 1999-2003. The results allowed us to determine the serious negative effects of the city urban activity on the river water quality. In the studied section of the river, the water quality index (WQI) was 71 units (classified as good) at the entry station and 47.6 units (classified as bad) at the outlet station. For the studied period, a significant decrease in water quality (mean WQI decrease = 11.6%, p = 0.042) was observed in the rural areas. A comparative analysis revealed that the urban water quality was significantly bad as compared with rural. The analysis enabled to classify the water quality stations into three groups: good water quality, medium water quality and bad water quality. WQI(min) resulted in overestimation of the water quality but with similar trend as with WQI and is useful for the periodic routine monitoring program. The correlation of WQI with WQI(min) and DO resulted two new indices WQI(m) and WQI(DO), respectively. The classification of waters based on WQI(m) and WQI(DO) coincided in 90 and 93% of the samples, respectively.

Batch experiments were performed to investigate the feasibility of humic acid (HA) removal by synthetic nanoscale zerovalent iron (NZVI) and its interaction with As(III) and As(V), the most poisonous and abundant of groundwater pollutants. High-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) were used to characterize the particle size, surface morphology of the pristine NZVI and HA-treated NZVI (NZVI-HA), and the zero valence state of the pristine NZVI. It was determined that HA was completely removed by NZVI (0.3 g/L) within a few minutes, at a wide range of initial pH values (approximately 3.0-12.0). Fourier transform infrared (FTIR) and laser light scattering (zeta potential measurement) studies confirmed that NZVI-HA forms inner-sphere surface complexation at different initial pH conditions. The effects of competing anions showed that there was complete removal of HA in the presence of 10 mM NO(-3) and SO4(2-) whereas HA removal was observed 0%, 18% and 22% in presence of 10 mM H2PO4(2-), HCO(3-) and H4SiO4(0), respectively. However, the presence of 2 mM CA2+ and Mg2+ enhanced HA removal from 17 mg g(-1) to 76 mg g(-1) and 55 mg g(-1), respectively. Long-term time-resolved studies of XRD and field emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray (EDX) revealed the formation of various types of new iron oxides (magnetite, maghemite, and lepidocrocites) during the continuous reaction of HA in the presence of water and NZVI at 1, 30, 60, and 90 days. In addition, the surface-area-normalized rate constant (ksa) of adsorption of As(III) and As(V) onto NZVI was reduced in the presence of HA (20 mg L(-1)), from 100% to 43% and 68%, respectively. Our results show the potential use of NZVI in removing HA and its possible effects on arsenic removal during the application of NZVI in groundwater remediation.

The reaction of hexavalent chromium (Cr(VI)) with zerovalent iron (Fe0) during soil and groundwater remediation is an important environmental process. This study used several techniques including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy to investigate nanometer scale Fe0 particles (nano Fe0) treated with Cr(III) and Cr(VI). X-ray diffraction and XPS analyses of oxidized nano Fe0 showed the crystalline Fe(III) phase is composed of lepidocrocite (gamma-FeOOH). Results of XPS Cr 2p data and Cr K-edge X-ray absorption near edge spectroscopy (XANES) provided evidence that Cr(VI) was entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after reaction. In addition, XPS and XANES results of Cr(III) precipitated as Cr(OH)3 in the presence of corroding nano Fe0 were nearly identical to the Cr(VI)-nano Fe0 reaction product. Detailed analysis of XPS O 1s line spectra revealed that both Cr(III)- and Cr(VI)-treated nano Fe0 yielded a predominantly hydroxylated Cr(OH)3 and/ or a mixed phase CrxFe(1 - x)(OH)3 product. The structure of the Cr(III)- and Cr(VI)-treated nano Fe0 determined using extended X-ray absorption fine structure spectroscopy (EXAFS) revealed octahedral Cr(III) with Cr-O interatomic distances between 1.97 and 1.98 A for both Cr(III) and Cr(VI) treatments and a pronounced Cr-Cr second interatomic shell at 3.01 A. Our results suggest that the reaction product of Cr(VI)-treated nano Fe0 is either a poorly ordered Cr(OH)3 precipitate or possibly a mixed phase CrxFe(1 - x)(OH)3 product, both of which are highly insoluble under environmental conditions.

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