Assessment of sulfamethoxazole removal by nanoscale zerovalent iron.

Removal of pharmaceutical compounds, such as sulfamethoxazole (SMX) from the aquatic environments, is critical in order to mitigate their adverse environmental and human health effects. In this study, the effectiveness of nanoscale zerovalent iron (nZVI) particles for the removal of SMX was investigated under varying conditions of initial solution pH (3, 5, 7 and 11) and nZVI to SMX mass ratios (1:1, 5:1, 10:1, 13:1, 25:1). Batch kinetic studies, which were well represented using both pseudo-first-order and pseudo-second-order kinetic models (R2 > 0.98), showed that both solution pH and mass ratios strongly influenced SMX removal. At a fixed mass ratio of 10:1, removal efficiencies were higher in acidic conditions (83% to 91%) compared to neutral (29%) and alkaline (6%) conditions. A similar trend was observed for removal rates and removal amounts. For mass ratios between 1:1 and 10:1, an optimum pH existed (pH 5) wherein highest removal efficiencies were attained. Increasing the mass ratio above 10:1 resulted in virtually complete removal efficiencies at pH 3 and 5, and 70% at pH 7. Analysis of SMX speciation and zeta potential of nZVI particles provided insights into the role of pH on the efficiencies, rates and extents of SMX removal. Total organic carbon analysis and mass spectrometry measurements of SMX solution before and after exposure to nZVI particles suggested the transformation of SMX via redox reactions, which are likely the dominant process compared to adsorption. Five transformation products were observed at m/z 156 (TP1), 192 (TP2), 256 (TP3), 294 (TP4) and 296 (TP5). TP1, TP2 and TP3 were further identified using ion fragment analysis. Overall, results from this study indicate a strong potential for SMX removal by nZVI particles, and could be useful towards identifying reaction conditions for optimum SMX transformation.

Optimal Design of Sulfidated Nanoscale Zerovalent Iron for Enhanced Trichloroethene Degradation.

Sulfidated nanoscale zerovalent iron (S-nZVI) has the potential to be a cost-effective remediation agent for a wide range of environmental pollutants, including chlorinated solvents. Various synthesis approaches have yielded S-nZVI consisting of a Fe0 (or Fe0/S0) core and FeS shell, which are significantly more reactive to trichloroethene (TCE) than nZVI. However, their reactivity is not as high as palladium-doped nZVI (Pd-nZVI). We synthesized S-nZVI by the co-precipitation of FeS and Fe0 by using Na2S during the borohydride reduction of FeSO4 (S-nZVIco). This resulted in FeS structures bridging the nZVI core and the surface, as confirmed by electron microscopy and X-ray analyses. The TCE degradation capacity of up to 0.46 mol TCE/mol Fe0 was obtained for S-nZVIco at a high S loading and was comparable to Pd-nZVI but 60% higher than the currently most reactive S-nZVI, in which FeS only coats the nZVI (S-nZVIpost). The high TCE degradation was due to complete utilization of Fe0 (2 e-/mol Fe0) toward the formation of acetylene. Although Pd-nZVI yielded 3 e-/mol Fe0, TCE degradation was comparable because it reduced acetylene further to ethene and ethane. Under Fe0-limited conditions, the S-nZVIco TCE degradation rate was 16 times higher than that of Pd-nZVI (0.5 wt % Pd) and 90 times higher than that of S-nZVIpost.

Phase Transfer of Palladized Nanoscale Zerovalent Iron for Environmental Remediation of Trichloroethene.

Palladium-doped nanoscale zerovalent iron (Pd-NZVI) has been shown to degrade environmental contaminants such as trichloroethene (TCE) to benign end-products through aqueous phase reactions. In this study we show that rhamnolipid (biosurfactant)-coated Pd-NZVI (RL-Pd-NZVI) when reacted with TCE in a 1-butanol organic phase with limited amounts of water results in 50% more TCE mass degradation per unit mass of Pd-NZVI, with a 4-fold faster degradation rate (kobs of 0.413 day(-1) in butanol organic phase versus 0.099 day(-1) in aqueous phase). RL-Pd-NZVI is preferentially suspended in water in biphasic organic liquid-water systems because of its hydrophilic nature. We demonstrate herein for the first time that their rapid phase transfer to a butanol/TCE organic phase can be achieved by adding NaCl and creating water-in-oil emulsions in the organic phase. The significant enhancement in reactivity is caused by a higher electron release (3e(-) per mole of Fe(0)) from Pd-NZVI in the butanol organic phase compared to the same reaction with TCE in the aqueous phase (2e(-) per mole of Fe(0)). XPS characterization studies of Pd-NZVI show Fe(0) oxidation to Fe(III) oxides for Pd-NZVI reacted with TCE in the butanol organic phase compared to Fe(II) oxides in the aqueous phase, which accounted for differences in the TCE reactivity extents and rates observed in the two phases.

Effects of Rhamnolipid and Carboxymethylcellulose Coatings on Reactivity of Palladium-Doped Nanoscale Zerovalent Iron Particles.

Nanoscale zerovalent iron (NZVI) particles are often coated with polymeric surface modifiers for improved colloidal stability and transport during remediation of contaminated aquifers. Doping the NZVI surface with palladium (Pd-NZVI) increases its reactivity to pollutants such as trichloroethylene (TCE). In this study, we investigate the effects of coating Pd-NZVI with two surface modifiers of very different molecular size: rhamnolipid (RL, anionic biosurfactant, M.W. 600 g mol(-1)) and carboxymethylcellulose (CMC, anionic polyelectrolyte, M.W. 700 000 g mol(-1)) on TCE degradation. RL loadings of 13-133 mg TOC/g NZVI inhibited deposition of Pd in a concentration-dependent manner, thus limiting the number of available Pd sites and decreasing the TCE degradation reaction rate constant from 0.191 h(-1) to 0.027 h(-1). Furthermore, the presence of RL in solution had an additional inhibitory effect on the reactivity of Pd-NZVI by interacting with the exposed Pd deposits after they were formed. In contrast, CMC had no effect on reactivity at loadings up to 167 mg TOC/g NZVI. There was a lack of correlation between Pd-NZVI aggregate sizes and TCE reaction rates, and is explained by cryo-transmission electron microscopy images that show open, porous aggregate structures where TCE would be able to easily access Pd sites.