Enhanced breakage of the aggregates of nanoscale zero-valent iron via ball milling.

Aggregates of nanoscale zero-valent iron (nZVI) are commonly encountered for nZVI in aqueous solution, particularly during large-scale nZVI applications where nZVI is often in a highly concentrated slurry, and such aggregates lower nZVI mobility during its in-situ remediation applications. Herein, we report that the ball milling is an effective tool to break the nZVI aggregates and thereby improve the nZVI mobility. Results show that the milling (in just five minutes) can break the aggregates of a few tens of microns to less than one micron, which is one-tenth of the size that is acquired via the breakage using the mechanical mixing and ultrasonication. The milling breakage can also improve the efficacy of the chemical conditioning method that is commonly used for the nanoparticle stabilization and dispersion. The milling breakage is further optimized via a study of the milling operational factors including milling time, bead velocity, bead diameter, and chamber porosity, and an empirical equation is proposed combining the bead collision number during the milling. Mechanistic study shows that the high efficacy of the milling to break the aggregates can be explained by the small eddy created by the high shear rate produced by the close contact of the milling beads and may also relate to the direct mechanical pulverization effect. This study provides a high efficacy physical method to break the nanoparticle aggregates. The method can be used to improve the nZVI mobility performance by milling the nZVI slurry before its injection for in-situ remediation, and the milling may also replace the mechanical mixing during the nZVI stabilization via surface modification.

Biomass-derived cellulose nanocrystals modified nZVI for enhanced tetrabromobisphenol A (TBBPA) removal.

Nano zero-valent iron (nZVI) is an advanced environmental functional material for the degradation of tetrabromobisphenol A (TBBPA). However, high surface energy, self-agglomeration and low electron selectivity limit degradation rate and complete debromination of bare nZVI. Herein, we presented biomass-derived cellulose nanocrystals (CNC) modified nZVI (CNC/nZVI) for enhanced TBBPA removal. The effects of raw material (straw, filter paper and cotton), process (time, type and concentration of acid hydrolysis) and synthesis methods (in-situ and ex-situ) on fabrication of CNC/nZVI were systematically evaluated based on TBBPA removal performance. The optimized CNC-S/nZVI(in) was prepared via in-situ liquid-phase reduction using straw as raw material of CNC and processing through 44 % H2SO4 for 165 min. Characterizations illustrated nZVI was anchored to the active sites at CNC interface through electrostatic interactions, hydrogen bonds and FeO coordinations. The batch experiments showed 0.5 g/L CNC-S/nZVI(in) achieved 96.5 % removal efficiency at pH = 7 for 10 mg/L initial TBBPA. The enhanced TBBPA dehalogenation by CNC-S/nZVI(in), involving in initial adsorption, reduction process and partial detachment of debrominated products, were possibly attributed to elevated pre-adsorption capacity and high-efficiency delivery of electrons synergistically. This study indicated that fine-tuned fabrication of CNC/nZVI could potentially be a promising alternative for remediation of TBBPA-contaminated aquatic environments.

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.

TEMPO oxidized cellulose nanocrystal (TOCNC) scaffolded nanoscale zero-valent iron (nZVI) for enhanced chromium removal.

The conventional carboxymethyl cellulose (CMC) stabilization hampered available active sites of adsorption and reduction, due to irregular shape of nanoscale zero-valent iron (nZVI) particles with augmented average size and passivated surface, leading to insufficient removal and poor resistance against complex environmental conditions. Herein, we presented (2,2,6,6-Tetramethylpiperidine-1-oxyl)-mediated (TEMPO-mediated) oxidation of cellulose nanocrystal (TOCNC) scaffolded nZVI (nZVI@TOCNC) with enhanced efficiency for chromium removal in comparison with CMC stabilized nZVI (nZVI@CMC). The anchoring of nZVI at the functional sites of TOCNC was initiated by liquid-phase chemical reduction method. The nZVI@TOCNC showed improved nZVI distribution with uniform particle size and thinner shell (∼1 nm). Characterizations using FT-IR, XPS and XRD demonstrated that bindings between TOCNC and nZVI were through hydrogen bonds, electrostatic attractions, coordination-covalent bonds and bidentate chelation. TOCNC with shorter branch-chain (-COC-) surrounding the nZVI could potentially form a porous and compact "mesh" to rigidly encapsulate nZVI, while CMC wrapped around nZVI in the way of traditional polymeric stabilizers. Thus, 0.5 g/L nZVI@TOCNC achieved 99.96% Cr (Ⅵ) removal efficiency (20 mg/L) at pH = 7 and the removal capacity were up to 55.86 mg/g. The nZVI@TOCNC consistently presented higher removal efficiency than nZVI@CMC under wide pH range (3-7). Cr (Ⅵ) was reduced to Cr (Ⅲ) by nZVI@TOCNC with deposition of CrxFe1-x (OH)3 and Cr2O3. The predominant mechanisms of removal probably consisted of electrostatic attractions, reduction, co-precipitation and surface complexation. The pseudo-second-order kinetic model well-fitted the sorption kinetic, indicating TOCNC scaffold stabilized nZVI for efficient reduction of Cr (Ⅵ) through multi-layer adsorption. As a template and delivery carrier, TOCNC shows promising potential to further improve the capability and practice of nZVI for in situ treatment of industrial waste water with heavy metal pollution.

Electrochemical reduction of wastewater by non-noble metal cathodes: From terminal purification to upcycling recovery.

A shift beyond conventional environmental remediation to a sustainable pollutant upgrading conversion is extremely desirable due to the rising demand for resources and widespread chemical contamination. Electrochemical reduction processes (ERPs) have drawn considerable attention in recent years in the fields of oxyanion reduction, metal recovery, detoxification and high-value conversion of halogenated organics and benzenes. ERPs also have the potential to address the inherent limitations of conventional chemical reduction technologies in terms of hydrogen and noble metal requirements. Fundamentally, mechanisms of ERPs can be categorized into three main pathways: direct electron transfer, atomic hydrogen mediation, and electrode redox pairs. Furthermore, this review consolidates state-of-the-art non-noble metal cathodes and their performance comparable to noble metals (e.g., Pd, Pt) in electrochemical reduction of inorganic/organic pollutants. To overview the research trends of ERPs, we innovatively sort out the relationship between the electrochemical reduction rate, the charge of the pollutant, and the number of electron transfers based on the statistical analysis. And we propose potential countermeasures of pulsed electrocatalysis and flow mode enhancement for the bottlenecks in electron injection and mass transfer for electronegative pollutant reduction. We conclude by discussing the gaps in the scientific and engineering level of ERPs, and envisage that ERPs can be a low-carbon pathway for industrial wastewater detoxification and valorization.

Generation mechanism of singlet oxygen from the interaction of peroxymonosulfate and chloride in aqueous systems.

Peroxymonosulfate (PMS, HSO5-) is a widely-used disinfectant and oxidant in environmental remediation. It was deemed that PMS reacted with chloride (Cl-) to form free chlorine during water purification. Here, we demonstrated that singlet oxygen (1O2) was efficiently generated from PMS and Cl- interaction. Mechanism of 1O2 formation was uniquely verified by the reaction of HSO5- and chlorine molecule (Cl2) and the oxygen atoms in 1O2 deriving from the peroxide group of HSO5- were revealed. Density functional theory calculations determined that the reaction of HSO5- and Cl2 was thermodynamically favorable and exergonic at 37.8 kcal/mol. Quite intriguingly, 1O2 was generated at a higher yield (1.5 × 105 M - 1 s - 1) than in the well-known reaction of H2O2 with Cl2 (35 M - 1 s - 1). Besides chlorine, 1O2 formed in PMS-Cl- interaction dominated the degradation of micropollutants, also it substantially enhanced the damage of deoxynucleoside in DNA, which were beneficial to micropollutant oxidation and pathogen disinfection. The contribution of 1O2 for carbamazepine degradation was enhanced at higher Cl- level and lower pH, and reached 96.3% at pH 4.1 and 5 min. Natural organic matter (NOM) was a sink for chlorine, thereby impeding 1O2 formation to retard carbamazepine degradation. 1O2 also played important roles (48.3 - 63.5%) on the abatement of deoxyguanosine and deoxythymidine at pH 4.1 and 10 min in PMS/Cl-. On the other hand, this discovery also alerted the harm of 1O2 for human health as it can be formed during the interaction of residual PMS in drinking water/swimming pools and the high-level Cl- in human bodies.

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.

Iron-Based Nanocatalysts for Electrochemical Nitrate Reduction.

Nitrate has a high level of stability and persistence in water, endangering human health and aquatic ecosystems. Due to its high reliability and efficiency, the electrochemical nitrate reduction reaction (NO3 RR) is regarded as the best available option for mitigating excess nitrate in water and wastewater, especially for the removal of trace levels of nitrate. One of the most critical factors in the electrochemical reduction are the catalysts, which directly affect the reaction efficiency of nitrate removal. Iron-based nanocatalysts, which have the advantages of nontoxicity, wide availability, and low cost, have emerged as a promising electrochemical NO3 RR material in recent years. This review covers major aspects of iron-based nanocatalysts for electrochemical NO3 RR, including synthetic methods, structural design, performance enhancement, electrocatalytic nitrate reduction test, and reduction mechanism. The recent progress of iron-based nanocatalysts for electrochemical NO3 RR and the mechanism of functional advantages for modified structures are reviewed from the perspectives of loading, doping, and assembly strategies, in order to realize the conversion from pollutant nitrate to harmless nitrogen or ammonia and other sustainable products. Finally, challenges and future directions for the development of low-cost and highly-efficient iron-based nanocatalysts are explored.

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.

Nanocellulose fine-tuned poly(acrylic acid) hydrogel for enhanced diclofenac removal.

Hydrogel was recognized as one of the most promising materials for adsorption of pharmaceuticals and personal care products (PPCPs). The highly efficient bio-based nanocelluloses fine-tuned poly(acrylic acid) hydrogel (PAA/NC) adsorbent was constructed by adjusting aspect ratio, surface charge and crystallinity of NC. The cross-linked networks were fabricated through a single-step free-radical polymerization via steric effect and hydrogen bonds. The uniform three-dimensional structures with abundant macropores and mesopores were in-situ visualized by the cryogenic-scanning electron microscopy (Cryo-SEM). The diclofenac adsorption capacity of TEMPO oxidized cellulose nanofibers (TCNF) incorporated PAA hydrogel (PAA/TCNF, 559.8 mg·g-1) was circa 2.1 times higher than pristine PAA (293.5 mg·g-1) due to the elevated specific surface area, favorable spatial structure with unimpeded channels and abundant surface-charged carboxylic groups. Moreover, PAA/NC hydrogel exhibited a wide-pH applicability and high salinity tolerance. The adsorption was predominantly determined by hydrogen bonds, validated by XPS and FT-IR analysis. It was demonstrated developed PAA/NC hydrogel with unique porous structure significantly enhanced adsorption capacity for potential application in the purification of refractory organic pollutants-containing wastewater.

Visualizing hazardous solids with cryogenic electron microscopy (Cryo-EM).

Recent developments point to exciting potential of cryogenic electron microscopy (cryo-EM) for fundamental environmental research, especially for characterizing environmental samples with a high-water content. As a matter of fact, most environmental materials including soils, sediments, biomass, solid wastes and sludge are hydrated. This perspective provides a brief synopsis of cryo-EM and highlights emerging applications in environmental research. With cryogenic techniques, specimens are preserved by rapid freezing and observed with electron microscopes operating at high-vacuum and low temperature to keep the ice in amorphous state and reduce the effect of radiation damage. So far, cryo-EM has been successfully applied to advance fundamental understanding of physical, chemical and biological mechanisms due to its desirable properties to maintain the native state of hydrated samples and visualize structures at high resolution in three dimensions. The cryo-EM technique also has significant applications to the technology development of pathogen detection, sludge dewatering, waste treatment, and green chemical production from cellular biomass as cellular water content can be clearly observed and manipulated at the single cell level.

Engineering PD-L1 Cellular Nanovesicles Encapsulating Epidermal Growth Factor for Deep Second-Degree Scald Treatment.

Scars are common and intractable consequences after scalded wound healing, while monotherapy of epidermal growth factors does not solve this problem. Maintaining the stability of epidermal growth factors and promoting scarless healing of wounds is paramount. In this study, engineering cellular nanovesicles overexpressing PD-L1 proteins, biomimetic nanocarriers with immunosuppressive efficacy, were successfully prepared to encapsulate epidermal growth factors for maintaining its bioactivity. Remarkably, PD-L1 cellular nanovesicles encapsulating epidermal growth factors (EGF@PDL1 NVs) exerted desired therapeutic effect by attenuating the overactivation of T cell immune response and promoting skin cells migration and proliferation. Hence, EGF@PD-L1 NVs promoted wound healing and prevented scarring in deep second-degree scald treatment, demonstrating a better effect than using individual PD-L1 NVs or EGF. This research proved that EGF@PD-L1 NVs is considered an innovative and thorough therapy of deep second-degree scald.

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.

A win-win solution to chromate removal by sulfidated nanoscale zero-valent iron in sludge.

This study investigates the reaction between sulfidated nanoscale zero valent iron (S-nZVI) and Cr(VI) in the sludge system and explores the effect of S-nZVI on microbes. Results of the batch experiments indicated that the optimal Cr(VI) removal capacity (35.3 mg/g) was reached when the S/Fe ratio was at 0.05. It was about 20-time higher than that of nanoscale zero valent iron (nZVI) (<2.0 mg/g). However, the removal efficiency decreased as the S/Fe molar ratio further increased. Solid characterizations revealed that the S-nZVI consisted of a Fe0 core encapsulated by a flake FeS shell and had a similar "core-shell" structure to that of the nZVI. X-ray photoelectron spectroscopy (XPS) indicated that Cr(VI) was reduced to less toxic Cr(III). In addition, the 16 S rRNA gene and cryo-scanning electron microscopy (cryo-SEM) results showed S-nZVI mildly influenced the initial microbial diversity. Some microflora including Caldiserica, Planctomycetes were promoted, while others groups such as Actinobacteria, Bacteroidetes and Chloroflexi were inhibited: specifically, bacteria such as Proteobacteria (possibly related to sulfide oxidization) began to develop after the S-nZVI feeding. The high Cr(VI) removal efficiency and the mildly influenced microbial diversity make the usage of S-nZVI a win-win solution for Cr(VI) removal in sludge.

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.

How to Build a Microplastics-Free Environment: Strategies for Microplastics Degradation and Plastics Recycling.

Microplastics are an emergent yet critical issue for the environment because of high degradation resistance and bioaccumulation. Unfortunately, the current technologies to remove, recycle, or degrade microplastics are insufficient for complete elimination. In addition, the fragmentation and degradation of mismanaged plastic wastes in environment have recently been identified as a significant source of microplastics. Thus, the developments of effective microplastics removal methods, as well as, plastics recycling strategies are crucial to build a microplastics-free environment. Herein, this review comprehensively summarizes the current technologies for eliminating microplastics from the environment and highlights two key aspects to achieve this goal: 1) Catalytic degradation of microplastics into environmentally friendly organics (carbon dioxide and water); 2) catalytic recycling and upcycling plastic wastes into monomers, fuels, and valorized chemicals. The mechanisms, catalysts, feasibility, and challenges of these methods are also discussed. Novel catalytic methods such as, photocatalysis, advanced oxidation process, and biotechnology are promising and eco-friendly candidates to transform microplastics and plastic wastes into environmentally benign and valuable products. In the future, more effort is encouraged to develop eco-friendly methods for the catalytic conversion of plastics into valuable products with high efficiency, high product selectivity, and low cost under mild conditions.

Enhanced degradation of micropollutants over iron-based electro-Fenton catalyst: Cobalt as an electron modulator in mesochannels and mechanism insight.

Heterogeneous electro-Fenton (hetero-EF) process is an emerging alternative for effective oxidation of recalcitrant micropollutants, but it is hampered by limited hydroxyl radical (•OH) generation and low stability on the iron-based cathodes. Herein, we demonstrate an enhanced hetero-EF performance via modulation of iron electronic structure in an ordered mesoporous carbon (OMC). By tuning the cobalt incorporation, the highly-dispersed iron-cobalt (FeCo) nanoalloys in mesochannels (Fe0.5Co0.5@OMC) show a 3-fold increase in •OH yield compared with Fe@OMC, achieving degradation efficiency with 92% of sulfamethazine (SMT) and 99% of rhodamine B (RhB), and the corresponding total organic carbon (TOC) removal with 66% of SMT and 85% of RhB within 2 h in neutral pH, respectively. Experimental results and density functional theory (DFT) calculations demonstrate that iron incorporated with cobalt reduces energy barrier for facile generation of H2O2 and •OH from O2 through direct electron transfer, along with decreased overpotential. Meanwhile, cobalt doping promotes H2O2 decomposition by accelerated Fe(II)/Fe(III) cycle and Co(II)/Co(III) redox. Furthermore, spatially confined and half-embedded structure endows the nanocatalyst (8 nm) excellent durability within a wide pH value range and good stability in cycle tests. A plausible reaction mechanism and degradation pathway for SMT are proposed. Moreover, the superiority of Fe0.5Co0.5@OMC cathode is maintained in simulated wastewater, suggesting an enormous potential in practical wastewater treatment.

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.

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.

Enhanced aggregation and sedimentation of nanoscale zero-valent iron (nZVI) with polyacrylamide modification.

Nanoscale zero-valent iron (nZVI) settled slowly and incompletely in a nano-iron reactor (NIR) in wastewater treatment, and the effluent quality and processing capacity of nZVI were degenerated. Herein, three types of polyacrylamide (PAM), anionic-APAM (nZVIAPAM), cationic-CPAM (nZVICPAM), and nonionic-NPAM (nZVINPAM)) were applied to modify the nZVI (nZVIPAM), which were proved to enhance aggregation and sedimentation in the gravity settling clarifier of NIR. PAM modification lead to aggregate by forming large agglomerates. The median sizes of aggregates were 32, 194, 168 and 133 µm respectively for nZVI, nZVICPAM, nZVINPAM, and nZVIAPAM. Under quiescent conditions, bare nZVI needed 5 min to reach sedimentation equilibrium, while nZVIPAM just within 1 min nZVICPAM settled more quickly and completely than nZVINPAM and nZVIAPAM. The Fe concentration in the dynamic flow NIR effluent could keep a low level for 8 h for nZVIPAM, while bare nZVI for 6 h. Iron concentration was 3.11, 0.037, 0.93, and 1.20 mg·L-1 for nZVI, nZVICPAM, nZVINPAM, and nZVIAPAM after 8-h-reaction. Meanwhile, the reactivity of nZVIPAM was kept much longer for lead removal in the NIR. Results demonstrated PAM modifications (especially CPAM) provided a reliable solution for nZVI aggregation and sedimentation in wastewater treatment.