Fe Crystalline Phases in Fe/C Composites Modulated the Selective Adsorption of Pb(II) from Industrial Wastewater with Cd(II): An Electronic-Scale Perspective.

Fe oxide or Fe0-based materials display weak removal capacity for Pb(II), especially in the presence of Cd(II), and the electronic-scale mechanisms are not reported. In this study, Fe3C(220) modified black carbon (BC) [Fe3C(220)@BC] with high adsorption and selectivity for Pb(II) from industrial wastewater with Cd(II) was developed. The quantitative experiment suggested that Fe species accounted for 80.5-100 and 18.4-33.8% of Pb(II) and Cd(II) removal, respectively. Based on X-ray absorption near-edge structure analysis, 57.3% of adsorbed Pb2+ was reduced to Pb0; however, 61.6% of Cd2+ existed on Fe3C@BC. Density functional theory simulation unraveled that Cd(II) adsorption was attributed to the cation-π interaction with BC, whereas that of Pb(II) was ascribed to the stronger interactions with different Fe phases following the order: Fe3C(220) > Fe0(110) > Fe3O4(311). Crystal orbital bond index and Hamilton population analyses were innovatively applied in the adsorption system and displayed a unique discovery: the stronger Pb(II) adsorption on Fe phases was mediated by a combination of covalent and ionic bonding, whereas ionic bonding was mainly accounted for Cd(II) adsorption. These findings open a new chapter in understanding the functions of different Fe phases in mediating the fate and transport of heavy metals in both natural and engineered systems.

Hydrogen Nanobubbles Generated In Situ from Nanoscale Zerovalent Iron with Water to Further Enhance Selenite Sequestration.

Gas nanobubbles used for water treatment and recovery give rise to great concern for their unique advantages of less byproducts, higher efficiency, and environmental friendliness. Nanoscale zerovalent iron (nZVI), which has also been widely explored in the field of environmental remediation, can generate gas hydrogen by direct reaction with water. Whether nanoscale hydrogen bubbles can be produced to enhance the pollution removal of the nZVI system is one significant concern involved. Herein, we report direct observations of in situ generation of hydrogen nanobubbles (HNBs) from nZVI in water. More importantly, the formed HNBs can enhance indeed the reduction of Se(IV) beyond the chemical reduction ascribed to Fe(0), especially in the anaerobic environment. The possible mechanism is that HNBs enhance the reducibility of the system and promote electron transport in the solution. This study demonstrates a unique function of HNBs combined with nZVI for the pollutant removal and a new approach for in situ HNB generation for potential applications in the fields of in situ remediation agriculture, biotechnology, medical treatment, health, etc.

Research updates and progress on nutritional significance of the amides I and II, alpha-helix and beta-sheet ratios, microbial protein synthesis, and steam pressure toasting condition with globar and synchrotron molecular microspectroscopic techniques with chemometrics.

This article aims to review research updates and progress on the nutritional significance of the amides I and II, the alpha-helix and beta-sheet ratios, the microbial protein synthesis, and the steam pressure toasting condition in food and feed with globar and synchrotron molecular microspectroscopic techniques plus chemometrics (both univariate and multivariate techniques). The review focused on (I) impact of the amides I and II, and the alpha-helix and beta-sheet-structure ratios in food and feeds; (II) Current research progress and update in synchrotron technique and application in feed and food molecular structure studies that are associated with nutrition delivery; (III) Impact of thermal processing- steam pressure toasting condition on feed and food; (IV). Impact of the microbial protein synthesis and methodology on feed and food; and (V). Impact on performance and production of ruminants with Faba beans.

Insights into the Selective Transformation of Ceria Sulfation and Iron/Manganese Mineralization for Enhancing the Selective Recovery of Rare Earth Elements.

To cope with the urgent and unprecedented demands for rare earth elements (REEs) in sophisticated industries, increased attention has been paid to REE recovery from recycled streams. However, the similar geochemical behaviors of REEs and transition metals often result in poor separation performance due to nonselectivity. Here, a unique approach based on the selective transformation between ceria sulfation and iron/manganese mineralization was proposed, leading to the enhancement of the selective separation of REEs. The mechanism of the selective transformation of minerals could be ascribed to the distinct geochemical and metallurgical properties of ions, resulting in different combinations of cations and anions. According to hard-soft acid-base (HSAB) theory, the strong Lewis acid of Ce(III) was inclined to combine with the hard base of sulfates (SO42-), while the borderline acid of Fe(II)/Mn(II) prefers to interact with oxygen ions (O2-). Both in situ characterization and density functional theory (DFT) calculation further revealed that such selective transformation might trigger by the generation of an oxygen vacancy on the surface of CeO2, leading to the formation of Ce2(SO4)3 and Fe/Mn spinel. Although the electron density difference of the configurations (CeO2-x-SO4, Fe2O3-x-SO4, and MnO2-x-SO4) shared a similar direction of the electron transfer from the metals to the sulfate-based oxygen, the higher electron depletion of Ce (QCe = -1.91 e) than Fe (QFe = -1.66 e) and Mn (QMn = -1.64 e) indicated the higher stability in the Ce-O-S complex, resulting in the larger adsorption energy of CeO2-x-SO4 (-6.88 eV) compared with Fe2O3-x-SO4 (-3.10 eV) and MnO2-x-SO4 (-2.49 eV). This research provided new insights into the selective transformation of REEs and transition metals in pyrometallurgy and thus offered a new approach for the selective recovery of REEs from secondary resources.

Prognostic impact of muscle invasion in buccal mucosa squamous cell carcinoma.

OBJECTIVE: The objective of the study was to assess the prognostic value of muscle invasion (MI), a key histopathological feature of tumor aggressiveness, and construct a superior prognostic prediction model combining the current TNM staging system. MATERIALS AND METHODS: MI was analyzed in the whole-slide images from a total of 301 patients with primary buccal mucosa squamous cell carcinoma (BMSCC). Survival times of patients with/without MI were evaluated by Kaplan-Meier analysis. MI was further combined with the TNM staging system to explore its predictive value for prognosis. Moreover, 204 cases of head and neck carcinoma from the TCGA database were included. RESULTS: MI positive rate reached to 76% (229/301) in patients with BMSCC. MI was associated with poor overall survival (p = 0.012) and disease-free survival (p = 0.022). The novel system (TNM staging combined with MI) revealed strong predictive performance, with the largest area under the curve (OS: p < 0.001, DFS: p < 0.004). MI and the established classification system were also had good predictive ability in the TCGA cohort. CONCLUSIONS: MI is an independent predictor of poor prognosis of BMSCC. The inclusion of MI in prediction system can augment the risk stratification of patients with oral squamous cell carcinoma and may assist in the clinical decision-making process.

Electrocatalytic reduction of nitrate - a step towards a sustainable nitrogen cycle.

Nitrate enrichment, which is mainly caused by the over-utilization of fertilisers and industrial sewage discharge, is a major global engineering challenge because of its negative influence on the environment and human health. To solve this serious problem, many technologies, such as the activated sludge method, reverse osmosis, ion exchange, adsorption, and electrodialysis, have been developed to reduce the nitrate levels in water bodies. However, the applications of these traditional techniques are limited by several drawbacks, such as a long sludge retention time, slow kinetics, and undesirable by-products. From an environmental perspective, the most promising nitrate reduction technology is enabled to convert nitrate into benign N2, and features low cost, high efficiency, and environmental friendliness. Recently, electrocatalytic nitrate reduction has been proven by satisfactory research achievements to be one of the most promising methods among these technologies. This review provides a comprehensive account of nitrate reduction using electrocatalysis methods. The fundamentals of electrocatalytic nitrate reduction, including the reaction mechanisms, reactor design principles, product detection methods, and performance evaluation methods, have been systematically summarised. A detailed introduction to electrocatalytic nitrate reduction on transition metals, especially noble metals and alloys, Cu-based electrocatalysts, and Fe-based electrocatalysts is provided, as they are essential for the accurate reporting of experimental results. The current challenges and potential opportunities in this field, including the innovation of material design systems, value-added product yields, and challenges for products beyond N2 and large-scale sewage treatment, are highlighted.

Dry heating, moist heating, and microwave irradiation of cold-climate-adapted barley grain-Effects on ruminant-relevant carbohydrate and molecular structural spectral profiles.

Different feed processing techniques affect barley digestibility and nutrient utilization in ruminants. To our knowledge, there are few studies on the interactive relationship between carbohydrate molecular structure profiles of cool-season-adapted barley grain and nutritional characteristics for ruminants. The objectives of this study were: (1) to investigate the effect of different technological processing methods on carbohydrate chemical profiles, Cornell Net Carbohydrate and Protein System-carbohydrate subfractions, ruminal and intestinal carbohydrate digestion of barley grain in dairy cows; (2) to study the effect of heat processing on carbohydrate molecular structure of barley grain using advanced molecular spectroscopy; and (3) to associate processing-induced changes in carbohydrate molecular structure with changes in carbohydrate metabolic profiles in dairy cows. Barley grain samples collected from Crop Research Field in Western Canada underwent four different processing treatments: control, dry heating (120°C for 60 min in an air-ventilated oven), moist heating (120°C for 60 min in an autoclave), and microwave irradiation (900 W and 2450 MHz for 5 min in a microwave). The heating conditions used in the current study induced some changes in rumen-degradable and -undegradable digestible fibre (CB3) fraction. Intestinally digestible CB3 was decreased after moist heating. Moist heating decreased starch digestibility compared to the other three treatments. The processing-induced carbohydrate molecular structure changes, which was revealed by advanced vibrational molecular spectroscopic technique (attenuated total reflectance-Fourier transform infrared), could be used to predict carbohydrate nutritional value.

Electrocatalytic Hydrogenation Boosts Reduction of Nitrate to Ammonia over Single-Atom Cu with Cu(I)-N3C1 Sites.

The conversion of nitrate to ammonia can serve two important functions: mitigating nitrate pollution and offering a low energy intensity pathway for ammonia synthesis. Conventional ammonia synthesis from electrocatalytic nitrate reduction reactions (NO3RR) is often impeded by incomplete nitrate conversion, sluggish kinetics, and the competition of hydrogen evolution reactions. Herein, atomic Cu sites anchored on micro-/mesoporous nitrogen-doped carbon (Cu MNC) with fine-tuned hydrophilicity, micro-/mesoporous channels, and abundant Cu(I) sites were synthesized for selective nitrate reduction to ammonia, achieving ambient temperature and pressure hydrogenation of nitrate. Laboratory experiments demonstrated that the catalyst has an ammonia yield rate per active site of 5466 mmol gCu-1 h-1 and transformed 94.8% nitrate in wastewater containing 100 mg-N L-1 to near drinking water standard (MCL of 5 mg-N L-1) at -0.64 V vs RHE. Extended X-ray absorption fine structure (EXAFS) and theoretical calculations showed that the coordination environment of Cu(I) sites (Cu(I)-N3C1) localizes the charge around the central Cu atoms and adsorbs *NO3 and *H onto neighboring Cu and C sites with balanced adsorption energy. The Cu(I)-N3C1 moieties reduce the activation energy of rate-limiting steps (*HNO3 → *NO2, *NH2 → *NH3) compared with conventional Cu(II)-N4 and lead to a thermodynamically favorable process to NH3. The as-prepared electrocatalytic cell can run continuously for 84 h (14 cycles) and produce 21.7 mgNH3 with only 5.64 × 10-3 kWh energy consumption, suitable for decentralized nitrate removal and ammonia synthesis from nitrate-containing wastewater.

Microbes team with nanoscale zero-valent iron: A robust route for degradation of recalcitrant pollutants.

Integrating nanoscale zero-valent iron (nZVI) with biological treatment processes holds the promise of inheriting significant advantages from both environmental nano- and bio-technologies. nZVI and microbes can perform in coalition in direct contact and act simultaneously, or be maintained in separate reactors and operated sequentially. Both modes can generate enhanced performance for wastewater treatment and environmental remediation. nZVI scavenges and eliminates toxic metals, and enhances biodegradability of some recalcitrant contaminants while bioprocesses serve to mineralize organic compounds and further remove impurities from wastewater. This has been demonstrated in a number of recent works that nZVI can substantially augment the performance of conventional biological treatment for wastewaters from textile and nonferrous metal industries. Our recent laboratory and field tests show that COD of the industrial effluents can be reduced to a record-low of 50 ppm. Recent literature on the theory and applications of the nZVI-bio system is highlighted in this mini review.

Processing induced changes in physicochemical structure properties and nutrient metabolism and their association in cool-season faba (CSF: Vicia L.), revealed by vibrational FTIR spectroscopy with chemometrics and nutrition modeling techniques.

This review aims to update recent progress in processing induced molecular structure changes in the association of physicochemical structure properties with nutritional metabolism in cool-season faba bean (Vicia L.), which was revealed using advanced vibrational molecular spectroscopy in combination with chemometrics and advanced nutrient modeling techniques. The review focused on strategies to improve the utilization of the cool-season faba bean through heat-related technological treatments and the relationship of the processing induced molecular structural changes to nutrient delivery and metabolism in ruminant systems. The updated methods with truly absorption nutrient modeling techniques and advanced vibrational molecular spectroscopy techniques sourced by globar and synchrotron radiation (e.g. NIR, near Infrared, FTIR, Fourier transform infrared, DRIFT, diffuse reflectance infrared Fourier transform, ATR-FTIR, attenuated total reflectance-FTIR, FTIRM, FTIR micro-spectroscopy, SR-FTIRM, synchrotron radiation- FTIRM) to study cool-season faba bean were reviewed. This article provides an insight and a new approach on how to combine advanced nutrient modeling techniques with cutting-edge vibrational molecular spectroscopic techniques to study the processing induced molecular structure change in relation to molecular nutrition of cool-season Vicia faba as well as the interaction between molecular structure and molecular nutrition.

Application of advanced molecular spectroscopy and modern evaluation techniques in canola molecular structure and nutrition property research.

This review aims to provide research update and progress on applications of advanced molecular spectroscopy to current research on canola related bio-processing technology, molecular structure, and nutrient utilization and availability. The studies focused on how inherent molecular structure changes affect nutritional quality of canola and its co-products from bio-processing. The molecular spectroscopic techniques (SR-IMS, DRIFT, ATR-FTIR) used for molecular structure and nutrition association were reviewed, including the synchrotron radiation with infrared microspectroscopy, the synchrotron radiation with soft x-ray microspectroscopy, the diffuse reflectance infrared Fourier transform spectroscopy, the grading near infrared reflectance spectroscopy, and the Fourier transform infrared vibrational spectroscopy. Nutritional evaluation with other techniques in association with molecular structure was also reviewed. This study provides updated research progress on application of molecular spectroscopy in combination with various nutrition evaluation techniques to current research in the canola-related bio-oil/bio-energy processing and nutrition sciences.

Visualizing Trace Pollutants in Solids at Nanoscale via Electron Tomography.

Visualizing trace pollutants such as toxic metals and viruses in environmental solids such as soils, sediments, aerosols, and suspended particles in water has long been the holy grail for scientists and engineers. In this Perspective, progress on the state-of-the-art electron tomography is highlighted as an increasingly indispensable tool for visualizing contaminant distribution and transformation in three-dimension (3D), including environmental pollutants at the water-minerals interfaces, toxicology assessment, environmental behavior of viruses in heterogeneous environmental media, etc. Adding a third dimension to the pollutant characterization will surely enrich our understanding on the complex and emerging environmental issues facing the global society, and provide vital support to the ongoing research and development of life-saving mitigation technologies from air filtration, to drinking water purification, to virus disinfection.

Architectural Genesis of Metal(loid)s with Iron Nanoparticle in Water.

Reactions of core-shell iron nanoparticles with metal(loid)s in water can form an array of nanostructures such as Ag-seed/dendrite, As-subshell, U-yolk, Co-hollowshell, and Cs-spot. Nonetheless, there is a lack of profound understanding in the genesis of these amazing geometries. Herein, we propose a concept to unravel the interdiffusion between the core-shell iron nanoparticle and metal(loid)s, where several key interactions including the Kirkendall effect, metal(loid) character effect, and reaction condition effect are involved in determining the structure of the final solid reaction products. Particularly, the architectural growths of metal(loid)s with iron nanoparticles in water can be manipulated mutually or singly by the following factors: standard redox potential difference, magnetic property, electrical charge and conductivity, as well as the iron (hydr)oxide shell structure under different solution chemistry and operation conditions. This contribution provides a theoretical basis to rationalize the architectural genesis of various metal(loid)s with iron nanoparticles, which will benefit the real practice for synthesizing functional iron-based nanoparticles and recovering the rare/precious metal(loid)s by iron nanoparticles from water.

Dendritic Cell-Inspired Designed Architectures toward Highly Efficient Electrocatalysts for Nitrate Reduction Reaction.

Electrocatalysis for nitrate reduction reaction (NRR) has recently been recognized as a promising technology to convert nitrate to nitrogen. Catalyst support plays an important role in electrocatalytic process. Although porous carbon and metal oxides are considered as common supports for metal-based catalysts, fabrication of such architecture with high electric conductivity, uniform dispersion of nanoparticles, and long-term catalytic stability through a simple and feasible approach still remains a significant challenge. Herein, inspired by the signal transfer mode of dendritic cell, an all-carbon dendritic cell-like (DCL) architecture comprising mesoporous carbon spheres (MCS) connected by tethered carbon nanotubes (CNTs) with CuPd nanoparticles dispersed throughout (CuPd@DCL-MCS/CNTs) is reported. An impressive removal capacity as high as 22 500 mg N g-1 CuPd (≈12 times superior to Fe-based catalysts), high nitrate conversion (>95%) and nitrogen selectivity (>95%) are achieved under a low initial concentration of nitrate (100 mg L-1 ) when using an optimized-NRR electrocatalyst (4CuPd@DCL-MCS/CNTs). Remarkably, nitrate conversion and nitrogen selectivity are both close to 100% in an ultralow concentration of 10 mg L-1 , meeting drinking water standard. The present work not only provides high electrocatalytic performance for NRR but also introduces new inspiration for the preparation of other DCL-based architectures.

Removal Efficacy of Opportunistic Pathogens and Bacterial Community Dynamics in Two Drinking Water Treatment Trains.

Drinking water treatment processes (DWTPs) impact pathogen colonization and microbial communities in finished water; however, their efficacies against opportunistic pathogens are not fully understood. In this study, the effects of treatment steps on the removal of Legionella spp., Legionella pneumophila, nontuberculous mycobacteria, Mycobacterium avium, and two amoeba hosts (Vermamoeba vermiformis, Acanthamoeba) are evaluated in two parallel trains of DWTPs equipped with different pretreatment units. Quantitative polymerase chain reaction analysis demonstrates significantly reduced numbers of total bacteria, Legionella, and mycobacteria during ozonation, followed by a rebound in granular activated carbon (GAC) filtration, whereas sand filtration exerts an overarching effect in removing microorganisms in both treatment trains. V. vermiformis is more prevalent in biofilm (34%) than water samples (7.7%), while Acanthamoeba is not found in the two trains of DWTPs. Illumina sequencing of bacterial 16S rRNA genes reveals significant community shifts at different treatment steps, as well as distinct bacterial community structures in water and biofilm samples in parallel units (e.g., ozonation, GAC, sand filtration) between the two trains (analysis of similarities (ANOSIM), p < 0.05), implying the potential influence of different pretreatment steps in shaping the downstream microbiome. Overall, the results provide insights to mitigation of opportunistic pathogens and engineer approaches for managing bacterial communities in DWTPs.

Stabilization of nanoscale zero-valent iron in water with mesoporous carbon (nZVI@MC).

Two challenges persist in the applications of nanoscale zero-valent iron (nZVI) for environmental remediation and waste treatment: limited mobility due to rapid aggregation and short lifespan in water due to quick oxidation. Herein, we report the nZVI incorporated into mesoporous carbon (MC) to enhance stability in aqueous solution and mobility in porous media. Meanwhile, the reactivity of nZVI is preserved thanks to high temperature treatment and confinement of carbon framework. Small-sized (~16 nm) nZVI nanoparticles are uniformly dispersed in the whole carbon frameworks. Importantly, the nanoparticles are partially trapped across the carbon walls with a portion exposed to the mesopore channels. This unique structure not only is conductive to hold the nZVI tightly to avoid aggregation during mobility but also provides accessible active sites for reactivity. This new type of nanomaterial contains ~10 wt% of iron. The nZVI@MC possesses a high surface area (~500 m2/g) and uniform mesopores (~4.2 nm) for efficient pollutant diffusion and reactions. Also, high porosity of nZVI@MC contributes to the stability and mobility of nZVI. Laboratory column experiments further demonstrate that nZVI@MC suspension (~4 g Fe/L) can pass through sand columns much more efficiently than bare nZVI while the high reactivity of nZVI@MC is confirmed from reactions with Ni(II). It exhibits remarkably better performance in nickel (20 mg/L) extraction than mesoporous carbon, with 88.0% and 33.0% uptake in 5 min, respectively.

Porous-Carbon-Confined Formation of Monodisperse Iron Nanoparticle Yolks toward Versatile Nanoreactors for Metal Extraction.

All-in-one architectures in which uniform nanoscale zero-valent iron nanoparticles are wrapped in hollow porous carbon shells are highly desirable for environmental applications such as wastewater treatment and for use as catalysts, but their preparation remains a significant challenge. Herein, a spatially confined strategy for the in situ preparation of uniform Fe0 @mC (mC=micro/mesoporous carbon) yolk-shell nanospheres, in which the iron nanoparticles are encapsulated in thin, porous carbon shells, is reported. The elaborately designed Fe0 @mC yolk-shell nanospheres were obtained by utilizing silica- and phenolic-resin-coated magnetite nanoparticle core-shell structures as templates by means of selective etching and in situ thermal reduction. The highly dispersed iron nanoparticles with superior reduction capability can effectively remove metal pollutants (e.g., AuIII , AgI , and CuII ), the carbon shell acts as protective cover and prevents aggregation of iron nanoparticles, and the void space in the capsules serves as a reactor for reduction and catalytic reactions.

Selective Nitrate Reduction to Dinitrogen by Electrocatalysis on Nanoscale Iron Encapsulated in Mesoporous Carbon.

Excessive nutrients (N and P) are among the most concerned pollutants in surface and ground waters. Herein, we report nanoscale zero-valent iron supported on ordered mesoporous carbon (nZVI@OMC) for electrocatalytic reduction of nitrate (NO3-) to nitrogen gas (N2). This material has a maximum removal capacity of 315 mg N/g Fe and nitrogen selectivity up to 74%. The Fe-C nanocomposite is prepared via a postsynthetic modification including carbon surface oxidation, in-situammonia prehydrolysis of iron precursor and hydrogen reduction. The synthesized materials have large surface areas (660-830 m2/g) and small iron nanoparticles (3-9 nm) uniformly dispersed in the carbon mesochannels. The iron loading can be adjusted in the range of 0-45%. Results demonstrate that the reaction reactivity of electrocatalysis can be fine-tuned by manipulating iron nanoparticle size, degree of crystallization, as well as porous structure. Meanwhile, the small, uniform, and stable iron nanoparticle promotes fast hydrogen generation for rapid cleavage of the N-O bond. Furthermore, this material can maintain its high performance over repetitive experimental cycles. Results suggest a new approach for fast and eco-friendly nitrate reduction and a novel nZVI application.

Nanoencapsulation of hexavalent chromium with nanoscale zero-valent iron: High resolution chemical mapping of the passivation layer.

Solid phase reactions of Cr(VI) with Fe(0) were investigated with spherical-aberration-corrected scanning transmission electron microscopy (Cs-STEM) integrated with X-ray energy-dispersive spectroscopy (XEDS). Near-atomic resolution elemental mappings of Cr(VI)-Fe(0) reactions were acquired. Experimental results show that rate and extent of Cr(VI) encapsulation are strongly dependent on the initial concentration of Cr(VI) in solution. Low Cr loading in nZVI (<1.0wt%) promotes the electrochemical oxidation and continuous corrosion of nZVI while high Cr loading (>1.0wt%) can quickly shut down the Cr uptake. With the progress of iron oxidation and dissolution, elements of Cr and O counter-diffuse into the nanoparticles and accumulate in the core region at low levels of Cr(VI) (e.g., <10mg/L). Whereas the reacted nZVI is quickly coated with a newly-formed layer of 2-4nm in the presence of concentrated Cr(VI) (e.g., >100mg/L). The passivation structure is stable over a wide range of pH unless pH is low enough to dissolve the passivation layer. X-ray photoelectron spectroscopy (XPS) depth profiling reconfirms that the composition of the newly-formed surface layer consists of Fe(III)-Cr(III) (oxy)hydroxides with Cr(VI) adsorbed on the outside surface. The insoluble and insulating Fe(III)-Cr(III) (oxy)hydroxide layer can completely cover the nZVI surface above the critical Cr loading and shield the electron transfer. Thus, the fast passivation of nZVI in high Cr(VI) solution is detrimental to the performance of nZVI for Cr(VI) treatment and remediation.

Visualizing Arsenate Reactions and Encapsulation in a Single Zero-Valent Iron Nanoparticle.

A nanostructure-based mechanism is presented on the enrichment, separation, and immobilization of arsenic with nanoscale zero-valent iron (nZVI). The As-Fe reactions are studied with spherical aberration corrected scanning transmission electron microscopy (Cs-STEM). Near-atomic resolution (<1 nm3) electron tomography discovers a thin continuous layer (23 ± 3 Å) of elemental arsenic sandwiched between the iron oxide shell and the zerovalent iron core. This points to a unique mechanism of nanoencapsulation and proves that the outer layer, especially the Fe(0)-oxide interface, is the edge of the As-Fe reactions. Atomic-resolution imaging on the grain boundary provides strong evidence that arsenic atoms diffuse preferably along the nonequilibrium, high-energy, and defective polycrystalline grain boundary of iron oxides. Results also offer direct evidence on the surface sorption or surface complex formation of arsenate on ferric hydroxide (FeOOH). The core-shell structure and unique properties of nZVI clearly underline rapid separation, large capacity, and stability for the treatment of toxic heavy metals such as cadmium, chromium, arsenic, and uranium.