Nanoscale zerovalent iron (NZVI) is one of the most extensively studied nanomaterials in the fields of wastewater treatment and remediation of soil and groundwater. However, rapid oxidative ...transformations of NZVI can result in reduced NZVI reactivity. Indeed, the surface passivation of NZVI is considered one of the most challenging aspects in successfully applying NZVI to contaminant degradation. The oxidation of NZVI can lead to the formation of FeII-bearing phases (e.g., FeIIO, FeII(OH)2, FeIIFeIII 2O4) on the NZVI surface or complete oxidation to ferric (oxyhydr)oxides (e.g., FeIIIOOH). This corrosion phenomenon is dependent upon various factors including the composition of NZVI itself, the type and concentration of aqueous species, reaction time and oxic/anoxic environments. As such, the coexistence of different Fe oxidation states on NZVI surfaces may also, in some instances, provide a unique reactive microenvironment to promote the adsorption of contaminants and their subsequent transformation via redox reactions. Thus, an understanding of passivation chemistry, and its related mechanisms, is essential not only for effective NZVI application but also for accurately assessing the positive and negative effects of NZVI surface passivation. The aim of this review is to discuss the nature of the passivation processes that occur and the passivation byproducts that form in various environments. In particular, the review presents: (i) the strengths and limitations of state-of-the-art techniques (e.g., electron microscopies and X-ray-based spectroscopies) to identify passivation byproducts; (ii) the passivation mechanisms proposed to occur in anoxic and oxic environments; and (iii) the effects arising from synthesis procedures and the presence of inorganics/organics on the nature of the passivation byproducts that form. In addition, several depassivation strategies that may assist in increasing and/or maintaining the reactivity of NZVI are considered, thereby enhancing the effectiveness of NZVI in contaminant degradation.
While it has been recognized for some time that addition of nanoparticlate zerovalent iron (nZVI) to oxygen-containing water results in both corrosion of Fe0 and oxidation of contaminants, there is ...limited understanding of either the relationship between transformation of nZVI and oxidant formation or the factors controlling the lifetime and extent of oxidant production. Using Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, we show that while nZVI particles are transformed to ferrihydrite then lepidocrocite in less than 2 h, oxidant generation continues for up to 10 h. The major products (Fe(II) and H2O2) of the reaction of nZVI with oxygenated water are associated, for the most part, with the surface of particles present with these surface-associated Fenton reagents inducing oxidation of a target compound (in this study, 14C-labeled formate). Effective oxidation of formate only occurred after formation of iron oxides on the nZVI surface with the initial formation of high surface area ferrihydrite facilitating rapid and extensive adsorption of formate with colocation of this target compound and surface-associated Fe(II) and H2O2 apparently critical to formate oxidation. Ongoing formate oxidation long after nZVI is consumed combined with the relatively slow consumption of Fe(II) and H2O2 suggest that these reactants are regenerated during the nZVI-initiated heterogeneous Fenton process.
•As(III) can be effectively removed by ball milled, sulfidated ZVI (S-mZVIbm).•As(III) was removed primarily through As4S4 formation under anoxic conditions.•As(III) was removed through adsorption ...onto corrosion product under oxic conditions.•S-mZVIbm/sand column rapidly reduces As(III) in a groundwater from 300 to 10 µg/L.•S-mZVIbm in sand column treats >750 BV groundwater with a capacity of 12.2 mg/g.
The interaction of As(III) with micron-sized, mechanochemically sulfidated zero-valent iron (S-mZVIbm) has been studied under both anoxic and oxic conditions. The As(III) removal capacity varied with the increase of S/Fe molar ratio under anoxic conditions, while it continuously decreased under oxic conditions. A series of sequential extractions, X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) spectroscopy analyses were used to investigate As(III) removal mechanisms. In the absence of oxygen, As(III) was removed from solution primarily through the formation of As4S4 with less than half of the removal resulting from the adsorption of As(III)/As(V) and FeAsS precipitation. Under oxic conditions, adsorption onto iron (oxyhydr)oxides was the dominant mechanism of As(III) removal. Increasing sulfidation decreased particle Fe(0) content, which resulted in less production of iron (oxyhydr)oxides and therefore lower As(III) removal capacities. Column experiments showed that less than 2 wt% of S-mZVIbm in sand was able to rapidly reduce the As(III) concentration in a real groundwater from 300 to 10 µg/L, the Chinese drinking water standard, for up to 750 BV with an EBCT of 2.54 min. This study demonstrates that S-mZVIbm is an efficient and cost-effective material in treating As-contaminated water to ensure water safety.
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Iron oxychloride (FeOCl) has been reported to be a highly efficient heterogeneous Fenton catalyst over a wide pH range. In order to determine the true catalytic performance of FeOCl, we ...simultaneously quantified the adsorptive and oxidative removal of formate, oxalate, and rhodamine-B (RhB) and the formation of RhB oxidation products at both pH 4.0 and 7.0. FeOCl was found to be a poor Fenton catalyst at either pH, as gauged by the oxidation of formate, oxalate, and rhodamine B and the decomposition of H2O2, in comparison with ferrihydrite (Fhy), one of the most common Fe-containing Fenton catalysts. The adsorption of target contaminants to FeOCl and homogeneous Fenton processes, induced by dissolved iron, resulted in overevaluation of the catalytic performance of FeOCl, especially for (i) the use of strongly adsorbing target compounds, without consideration of the role of adsorption in their removal and (ii) exceedingly high concentrations of H2O2 to remove trace quantities of target contaminants. Overall, this study highlights that the systematic quantification of H2O2 decomposition, target compound adsorption, and oxidation as well as the concentrations of oxidized products formed are prerequisites for unequivocal elucidation of the catalytic nature and reaction mechanism of solid Fenton catalysts.
While flow-electrode CDI is a promising desalination technology that has major advantages when the electrodes are operated in the short-circuited closed-cycle (SCC) mode, little attention has been ...paid to the water recovery rate, which, in the SCC mode, is determined by the need for partial replacement of the saline electrolyte of the flow electrodes. Results of this study show that an extremely high water recovery rate of ∼95% can be achieved when desalting a 1000 mg NaCl L–1 brackish influent to a potable level of 150 mg L–1. The improved performance with regard to the electrical cost is related, at least in part, to the alleviated concentration polarization at the membrane/electrolyte interface during electrosorption. In effect, the current efficiency decreases with an increase in the water recovery rate. This finding is ascribed to inevitable co-ion leakage since the flow electrodes reject ions with the same charge. In addition, water transport across the ion exchange membranes also influences the water recovery rate. The effect of partial replacement of the saline electrolyte during (semi-)continuous operation requires particular consideration because the associated dilution of the carbon content in the flow electrodes results in a decrease in process performance.
We demonstrate that by altering the length of Cas9-associated guide RNA (gRNA) we were able to control Cas9 nuclease activity and simultaneously perform genome editing and transcriptional regulation ...with a single Cas9 protein. We exploited these principles to engineer mammalian synthetic circuits with combined transcriptional regulation and kill functions governed by a single multifunctional Cas9 protein.
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•Strengths and weaknesses of XAS as a speciation technique are reviewed.•We explain the novel XFM approach referred to as XANES image stacking.•The X-ray absorption process is ...explained tangibly.•Linear combination fitting and abstract factor analysis of mixtures is explained.•Examples of XAS on nanoparticles, redox species, ores and process tailings.
Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.
The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace ...metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, −13.5 and −122.3mV vs. SHE at pH 6.5, and −22.9, −84.1 and −189.7mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4mV to –126.4mV over a week, and from −20.1mV to −188.4mV (all vs. SHE) after 24h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II) species with which it is in equilibrium. As an Fe(III) (oxyhydr)oxide suspension in equilibrium with aqueous and adsorbed Fe(II) species possesses a single, unique reduction potential, this suggests that adsorbed Fe(II) is a more facile reductant than aqueous Fe(II).
Uranium(VI) interactions with three smectites (one montmorillonite and two nontronites – NAu1 and NAu2) were examined with 0, 1, and 2 mM aqueous concentrations of Fe(II) over the pH range of 3–9.5 ...in a background electrolyte of 100 mM NaCl and 1 mM CaCl2 in equilibration with 400 ppmv CO2(g) (U(VI) = 4 μM and 0.5 g smectite/L). In the absence of Fe(II), no differences were observed in the U(VI) sorption curves for the three clay minerals. In the presence of 1 or 2 mM Fe(II), under anoxic conditions, U(VI) uptake by the smectites changed slightly between ∼pH 3 and 6; however, uranium uptake increased significantly above ∼pH 6 and was proportional to the concentration of Fe(II) added to the system, particularly at pH values >8. The uptake of Fe(II) showed a sharp edge starting from ∼pH 6.5 with 95%–100% uptake occurring at pH values >7.5, with no difference observed between the iron-rich nontronites and montmorillonite. After 3 days of reaction at pH 7.6 (i.e., above the Fe(II) “sorption” edge), U(VI) was transformed to a mixture of U(IV) and U(VI) sorption complexes, and after 14 days of reaction, 100% of the U was found to be reduced to U(IV) in the form of nanocrystalline uraninite. In contrast, U remained as sorbed species until 14 days of reaction at pH 6.5. Ferrihydrite (NAu1), lepidocrocite, and magnetite (NAu2) were detected as secondary mineralization products upon reaction of the nontronites with Fe(II) but appeared to have no effect on the partitioning or speciation of uranium.
Aqueous ferrous iron (Fe(II)) accelerates the transformation of ferrihydrite into secondary, more crystalline minerals however the factors controlling the rate and, indeed, the underlying mechanism ...of this transformation process remain unclear. Here, we present the first detailed study of the kinetics of the Fe(II)-accelerated transformation of ferrihydrite to goethite, via lepidocrocite, for a range of pH and Fe(II) concentrations and, from the results obtained, provide insight into the factors controlling the transformation rate and the processes responsible for transformation. A reaction scheme for the Fe(II)-accelerated secondary mineralization of ferrihydrite is developed in which an Fe(II) atom attaches to the ferrihydrite surface where it is immediately oxidized to Fe(III) with the resultant electron transferred, sequentially, to other iron oxyhydroxide Fe(III) atoms before release to solution as Fe(II). This freshly precipitated Fe(III) forms the nuclei for the formation of secondary minerals and also facilitates the ongoing uptake of Fe(II) from solution by creation of fresh surface sites. The concentration of solid-associated Fe(II) and the rate of transport of Fe(II) to the oxyhydroxide surface appear to determine which particular secondary minerals form and their rates of formation. Lepidocrocite growth is enhanced at lower solid-associated Fe(II) concentrations while conditions leading to more rapid uptake of Fe(II) from solution lead to higher goethite growth rates.
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