Investigation on YSZ- and SiO2-Doped Mn-Fe Oxide Granules Based on Drop Technique for Thermochemical Energy Storage.

The Mn-Fe oxide material possesses the advantages of abundant availability, low cost, and non-toxicity as an energy storage material, particularly addressing the limitation of sluggish reoxidation kinetics observed in pure manganese oxide. However, scaling up the thermal energy storage (TCES) system poses challenges to the stability of the reactivities and mechanical strength of materials over long-term cycles, necessitating their resolution. In this study, Mn-Fe granules were fabricated with a diameter of approximately 2 mm using the feasible and scalable drop technique, and the effects of Y2O3-stabilized ZrO2 (YSZ) and SiO2 doping, at various doping ratios ranging from 1-20 wt%, were investigated on both the anti-sintering behavior and mechanical strength. In a thermal gravimetric analyzer, the redox reaction tests showed that both the dopants led to an enhancement in the reoxidation rates when the doping ratios were in an appropriate range, while they also brought about a decrease in the reduction rate and energy storage density. In a packed-bed reactor, the results of five consecutive redox tests showed a similar pattern to that in a thermal gravimetric analyzer. Additionally, the doping led to the stable reduction/oxidation reaction rates during the cyclic tests. In the subsequent 120 cyclic tests, the Si-doped granules exhibited volume expansion with a decreased crushing strength, whereas the YSZ-doped granules experienced drastic shrinkage with an increase in the crushing strength. The 1 wt% Si and 2 wt% Si presented the best synthetic performance, which resulted from the milder sintering effects during the long-term cyclic tests.

Enhancing soil redox dynamics: Comparative effects of Fe-modified biochar (N-Fe and S-Fe) on Fe oxide transformation and Cd immobilization.

Biochar and modified biochar have gained wide attention for Cd-contaminated soil remediation. This study investigates the effects of rape straw biochar (RSB), sulfur-iron modified biochar (S-FeBC), and nitrogen-iron modified biochar (N-FeBC) on soil Fe oxide transformation and Cd immobilization. The mediated electrochemical analysis results showed that Fe modification effectively enhanced the electron exchange capacity (EEC) of biochar. After 40 days of anaerobic incubation, compared to the treatment without biochar (CK), the concentrations of CaCl2-extractable Cd in N-FeBC, S-FeBC, and RSB treatments decreased by 79%, 53%, and 23%, respectively. Compared with S-FeBC, N-FeBC significantly decreased the soil Eh and increased soil pH within the first 15 days, which could be attributed to its higher EEC and alkalinity. There is a negative correlation between the concentration of CaCl2-extractable Cd and soil pH (p < 0.01). The sequential extraction results showed that both N-FeBC and S-FeBC promoted Cd transfer from acid-soluble to Fe/Mn oxides bound fraction (Fe/Mn-Cd). N-FeBC significantly increased the concentration of amorphous Fe oxides (amFeox) from 4.0 g kg-1 in day 1 to 4.6 g kg-1 in day 15 by promoting the NO3--reducing Fe(II) oxidation process, while S-FeBC significantly increased amFeox from 4.0 g kg-1 in day 15 to 4.8 g kg-1 in day 40 by promoting the Fe(II) recrystallization. There is a positive correlation between the concentration of amFeox and Fe/Mn-Cd (p < 0.01). The scanning electron microscopy analysis showed that Cd was bound to the amFeox coating on the surface of Fe-modified biochar. By acting as an electron shuttle, the active surface of Fe-modified biochar may serve as a hotspot for Fe transformation, which promotes amFeox formation and Cd immobilization. This study highlights the potential of Fe-modified biochar for the remediation of Cd-contaminated soils and provides valuable insights into the development of effective remediation approaches for Cd-contaminated soils.

Characterization of Root and Foliar-Applied Iron Oxide Nanoparticles (α-Fe2O3, γ-Fe2O3, Fe3O4, and Bulk Fe3O4) in Improving Maize (Zea mays L.) Performance.

Iron (Fe) oxide nanoparticles (NPs) improve crop growth. However, the comparative effect of root and foliar-applied different sources of Fe oxide NPs on plant performance at morphological and physiological levels still needs to be discovered. In this study, we characterized the growth and physiological responses of hydroponic-cultured maize seedlings to four sources of Fe (i.e., α-Fe2O3, γ-Fe2O3, Fe3O4 NPs, and bulk Fe3O4) and two application methods (root vs. foliar). Results showed that Fe concentration in root and shoot increased by elevating the level of NPs from 100 mg L-1 to 500 mg L-1. Overall, the responses of maize seedlings to different sources of Fe oxide NPs were as follows: Fe3O4 > γ-Fe2O3 > α-Fe2O3 > bulk Fe3O4. The application of Fe at concentrations ranging from 100 mg L-1 to 500 mg L-1 had no significant effects on various growth parameters of maize, including biomass, chlorophyll content, and root length. Iron oxide NPs increased the plant biomass by 23-37% by root application, whereas it was 5-9% by foliar application. Chlorophyll contents were increased by 29-34% and 18-22% by foliar and root applications, respectively. The non-significant response of reactive oxygen species (i.e., superoxide dismutase, catalase, and peroxidase) suggested optimum maize performance for supplementing Fe oxide NPs. A confocal laser scanning microscope suggested that Fe oxide NPs entered through the epidermis and from the cortex to the endodermis. Our results provide a scientific basis that the root application of Fe3O4 at the rate of 100 mg L-1 is a promising approach to obtain higher maize performance and reduce the quantity of fertilizer used in agriculture to minimize environmental effects while improving crop productivity and quality. These findings demonstrated the tremendous potential of Fe NPs as an environmentally friendly and sustainable crop approach.

Importance of inner-sphere P-O-Fe bonds in natural and synthetic mineral-organic associations.

Sorption of organic molecules on mineral surfaces can occur through several binding mechanisms of varying strength. Here, we investigated the importance of inner-sphere P-O-Fe bonds in synthetic and natural mineral-organic associations. Natural organic matter such as water extracted soil organic matter (WESOM) and extracellular polymeric substances (EPS) from liquid bacterial cultures were adsorbed to goethite and examined by FTIR spectroscopy and P K-edge NEXAFS spectroscopy. Natural particles from a Bg soil horizon (Gleysol) were subjected to X-ray fluorescence (XRF) mapping, NanoSIMS imaging, and NEXAFS spectro-microscopy at the P K-edge. Inner-sphere P-O-Fe bonds were identified for both, adsorbed EPS extracts and adsorbed WESOMs. Characteristic infrared peaks for P-O-Fe stretching vibrations are present but cannot unambiguously be interpreted due to possible interferences with mono- and polysaccharides. For the Bg horizon, P was only found on Fe oxides, covering the entire surface at different concentrations, but not on clay minerals. Linear combination fitting of NEXAFS spectra indicates that this adsorbed P is mainly a mixture of orthophosphate and organic P compounds. By combining atomic force microscopy (AFM) images with STXM-generated C and Fe distribution maps, we show that the Fe oxide surfaces were fully coated with organic matter. In contrast, clay minerals revealed a much lower C signal. The C NEXAFS spectra taken on the Fe oxides had a substantial contribution of carboxylic C, aliphatic C, and O-alkyl C, which is a composition clearly different from pure adsorbed EPS or aromatic-rich lignin-derived compounds. Our data show that inner-sphere P-O-Fe bonds are important for the association of Fe oxides with soil organic matter. In the Bg horizon, carboxyl groups and orthophosphate compete with the organic P compounds for adsorption sites.

A Novel Experimental Approach to Understand the Transport of Nanodrugs.

Nanoparticle-based drugs offer attractive advantages like targeted delivery to the diseased site and size and shape-controlled properties. Therefore, understanding the particulate flow of the nanodrugs is important for effective delivery, accurate prediction of required dosage, and developing efficient drug delivery platforms for nanodrugs. In this study, the transport of nanodrugs including flow velocity and deposition is investigated using three model metal oxide nanodrugs of different sizes including iron oxide, zinc oxide, and combined Cu-Zn-Fe oxide synthesized via a modified polyol approach. The hydrodynamic size, size, morphology, chemical composition, crystal phase, and surface functional groups of the water-soluble nanodrugs were characterized via dynamic light scattering, transmission electron microscopy, scanning electron microscopy-energy dispersive X-ray, X-ray diffraction, and fourier transform infrared spectroscopy, respectively. Two different biomimetic flow channels with customized surfaces are developed via 3D printing to experimentally monitor the velocity and deposition of the different nanodrugs. A diffusion dominated mechanism of flow is seen in size ranges 92 nm to 110 nm of the nanodrugs, from the experimental velocity and mass loss profiles. The flow velocity analysis also shows that the transport of nanodrugs is controlled by sedimentation processes in the larger size ranges of 110-302 nm. However, the combined overview from experimental mass loss and velocity trends indicates presence of both diffusive and sedimentation forces in the 110-302 nm size ranges. It is also discovered that the nanodrugs with higher positive surface charges are transported faster through the two test channels, which also leads to lower deposition of these nanodrugs on the walls of the flow channels. The results from this study will be valuable in realizing reliable and cost-effective in vitro experimental approaches that can support in vivo methods to predict the flow of new nanodrugs.

Ni-Fe Oxides/TiO2 Heterojunction Anodes for Reactive Chlorine Generation and Mediated Water Treatment.

Reactive chlorine-mediated electrochemical water treatment necessitates selective chlorine evolution reaction (ClER) versus parallel oxygen evolution reaction (OER) in mild pH (7-10), with minimal deployments of precious electrocatalysts. This study reports Ni0.33Fe0.67Oy/TiO2 heterojunction anode prepared by a straightforward sol-gel coating with thermal decomposition at 425 °C. The ClER current efficiency (CE, 70%) and energy efficiency (2.3 mmol W h-1) were comparable to benchmarking Ir7Ta3Oy/TiO2 at 30 mA cm-2 in 50 mM NaCl solutions with near-neutral pH. Correlations of ClER CE of variable NixFe1-xOy/TiO2 (x: 0.33, 0.8-1) with the flat-band potential and p-band center, as experimental descriptors for surface charge density, nominated the outer TiO2 to be the active ClER center. The underlying Ni0.33Fe0.67Oy, characterized as biphasic NiFe2O4 and NiO, effectively lowered the O binding energy of TiO2 by electronic interaction across the junction. The OER activity of Ni0.33Fe0.67Oy superior to the other Fe-doped Ni oxides suggested that the conductive OER intermediates generated on Ni0.33Fe0.67Oy could also facilitate the ClER as an ohmic contact. Stability tests and NH4+ degradation in synthetic and real wastewater confirmed the feasibility of Ni0.33Fe0.67Oy/TiO2 heterojunction anode for mediated water treatments in mild pH.

Enhanced oxidation and stabilization of arsenic in a soil-rice system by phytosynthesized iron oxide nanomaterials: Mechanistic differences under flooding and draining conditions.

Despite arsenic (As) bioavailability being highly correlated with water status and the presence of iron (Fe) minerals, limited information is currently available on how externally applied Fe nanomaterials in soil-rice systems affect As oxidation and stabilization during flooding and draining events. Herein, the stabilization of As in a paddy soil by a phytosynthesized iron oxide nanomaterials (PION) and the related mechanism was investigated using a combination of chemical extraction and functional microbe analysis in soil at both flooding (60 d) and draining (120 d) stages. The application of PION decreased both specifically bound and non-specifically bound As. The As content in rice root, stem, husk and grain was reduced by 78.5, 17.3, 8.4 and 34.4%, respectively, whereas As(III) and As(V) in root declined by 96.9 and 33.3% for the 1% PION treatment after 120 d. Furthermore, the 1% PION treatment decreased the ratio of As(III)/As(V) in the rhizosphere soil, root and stem. Although PION had no significant effect on the overall Shannon index, the distribution of some specific functional microbes changed dramatically. While no As(III) oxidation bacteria were found at 60 d in any treatments, PION treatment increased As(III) oxidation bacteria by 3-9 fold after 120 d cultivation. Structural equation model analysis revealed that the ratio of Fe(III)/Fe(II) affected As stabilization directly at the flooding stage, whereas nitrate reduction and As(III) oxidation microbial groups played a significant role in the stabilization of As at the draining stage. These results highlight that PION exhibits a robust ability to reduce As availability to rice, with chemical oxidation, reduction inhibition and adsorption dominating at the flooding stage, while microbial oxidation, adsorption and coprecipitation dominant during draining.

Ca2Fe2O5 powder antifungal activity to the Candida utilis culture upon its growth.

This study reports the impact of Ca2Fe2O5 porous powder on the yeast Candida utilis-as a fungal model-at different phases of growth, i.e., early exponential (6 h), mid-log (11 h), and stationary (17 h) phases. Ca2Fe2O5 inhibited the cell growth in a time-dependent manner. After 120 min incubation, the fungicidal activity of porous powder was observed, i.e., log reduction of 2.81 and 2.58 for 11 and 17 h cultures, respectively, reaching the maximum of 4 log reduction after 7 days. Nevertheless, the 6 h culture of C. utilis showed enhanced resistance to Ca2Fe2O5 with a ≤ 0.4 log reduction during the 7 days exposure. Our results not only showed that Ca2Fe2O5 has the potential to effectively eliminate the C. utilis cell growth but also indicated the importance of the yeast culture physiological state for resistance to Ca2Fe2O5. To the best of our knowledge, this is the first study that evaluated the fungicidal activity of Ca2Fe2O5 porous powder on C. utilis and the impact of the C. utilis phase of growth on the cell susceptibility.

Water dissociation on mixed Co-Fe oxide bilayer nanoislands on Au(111).

We investigate the hydroxylation behaviour of mixed Co-Fe oxide nanoislands synthesized on a Au(111) surface under exposure to water vapour at vacuum conditions. The pure Co and Fe bilayer oxides both become hydroxylated by water exposure in vacuum conditions, albeit to a very different extent. It is however an open question how mixed oxides, exposing sites with a mixed coordination to Fe and Co, behave. By forming surface O species with a mixed Fe/Co coordination, we can investigate the nature of such sites. By means of scanning tunnelling microscopy and x-ray photoelectron spectroscopy, we characterize a series of Co-Fe oxides samples with different Fe contents at the atomic scale and observe a scaling of the hydroxylation degree with the amount of Fe inside the Co-Fe oxides. Our results indicate that the Fe dopants within the Co-Fe oxides have opposing effects on edge and basal plane sites modifying the maximum hydroxylation degree of pure cobalt oxide, perturbing the original binding sites of H, releasing the absorbed H or blocking the diffusion pathway of H.

Enrichment and speciation of chromium during basalt weathering: Insights from variably weathered profiles in the Leizhou Peninsula, South China.

Basalt-derived soils are widespread worldwide. Such soils contain high levels of heavy metals like chromium (Cr), which is a serious environmental concern. However, little is known regarding the enrichment and speciation of Cr during the basalt weathering process. Therefore, two basalt-derived soil profiles (Nitisol and Ferralsol) in the Leizhou Peninsula, south tropical China, were investigated to explore the redistribution and transformation of Cr during basalt weathering. All profiles could be divided into three layers: rocks, saprolites, and soils. The Nitisol and Ferralsol profiles exhibited strong (kaolinization) and extreme (laterization) degrees of weathering, respectively. Results showed that Cr concentrations in the saprolites (234 to 315 mg·kg-1) were higher than those in basalt rocks (139 to 159 mg·kg-1), indicating that Cr was enriched with the continuous loss of Si and other mobile macro-elements. While high levels of Cr were also enriched in the soils (178 to 430 mg·kg-1) accompanied with Fe. However, in the upper soils of the Ferralsol profile, the acidity and organic matter could promote the leaching of Cr. Geochemical fractions and EPMA mapping showed that chromite and olivine were the main Cr-bearing minerals in basalt, but Fe-oxides (e.g., goethite and hematite) contained the highest portion of Cr in weathered saprolites and soils. The availability of Cr in the soil was extremely low due to the high stability of Cr bound to Fe-oxides. However, the decreasing contents of Cr bound to Fe-oxides in the upper soils of the Ferralsol profile indicated that Cr could also be released during Fe leaching. In conclusion, the weathering of basalt can lead to the enrichment of Cr in Fe-(hydro)oxides, which are the main controlling minerals for Cr mobility in basalt-derived soils. Further research is needed to evaluate the effect of Fe-(hydro)oxide formation and dissolution on the release of soil Cr.

Accessible Silver-Iron Oxide Nanoparticles as a Nanomaterial for Supported Liquid Membranes.

The present study introduces the process performances of nitrophenols pertraction using new liquid supported membranes under the action of a magnetic field. The membrane system is based on the dispersion of silver-iron oxide nanoparticles in n-alcohols supported on hollow microporous polypropylene fibers. The iron oxide-silver nanoparticles are obtained directly through cyclic voltammetry electrolysis run in the presence of soluble silver complexes ([AgCl2]-; [Ag(S2O3)2]3-; [Ag(NH3)2]+) and using pure iron electrodes. The nanostructured particles are characterized morphologically and structurally by scanning electron microscopy (SEM and HFSEM), EDAX, XRD, and thermal analysis (TG, DSC). The performances of the nitrophenols permeation process are investigated in a variable magnetic field. These studies show that the flux and extraction efficiency have the highest values for the membrane system embedding iron oxide-silver nanoparticles obtained electrochemically in the presence of [Ag(NH3)2]+ electrolyte. It is demonstrated that the total flow of nitrophenols through the new membrane system depends on diffusion, convection, and silver-assisted transport.

Impact of Antimony(V) on Iron(II)-Catalyzed Ferrihydrite Transformation Pathways: A Novel Mineral Switch for Feroxyhyte Formation.

The environmental mobility of antimony (Sb) is controlled by interactions with iron (Fe) oxides, such as ferrihydrite. Under near-neutral pH conditions, Fe(II) catalyzes the transformation of ferrihydrite to more stable phases, thereby potentially altering the partitioning and speciation of associated Sb. Although largely unexplored, Sb itself may also influence ferrihydrite transformation pathways. Here, we investigated the impact of Sb on the Fe(II)-induced transformation of ferrihydrite at pH 7 across a range of Sb(V) loadings (Sb:Fe(III) molar ratios of 0, 0.003, 0.016, and 0.08). At low and medium Sb loadings, Fe(II) induced rapid transformation of ferrihydrite to goethite, with some lepidocrocite forming as an intermediate phase. In contrast, the highest Sb:Fe(III) ratio inhibited lepidocrocite formation, decreased the extent of goethite formation, and instead resulted in substantial formation of feroxyhyte, a rarely reported FeOOH polymorph. At all Sb loadings, the transformation of ferrihydrite was paralleled by a decrease in aqueous and phosphate-extractable Sb concentrations. Extended X-ray absorption fine structure spectroscopy showed that this Sb immobilization was attributable to incorporation of Sb into Fe(III) octahedral sites of the neo-formed minerals. Our results suggest that Fe oxide transformation pathways in Sb-contaminated systems may strongly differ from the well-known pathways under Sb-free conditions.

Removal of heavy metals from contaminated paddy soils using chemical reductants coupled with dissolved organic carbon solutions.

General acid washing is commonly used to treat heavy metal-contaminated soils, but it is sometimes difficult to achieve remediation aims in severely polluted soils. If we expose the surfaces of Fe oxide minerals to reductive dissolution during washing treatment, more of the metals initially adsorbed to these surfaces will be liberated, which may encourage the removal of heavy metals. Initially, the metal extraction capabilities of nine chemical reductants were compared in ten soil samples polluted by Cr, Cu, Zn, and Ni. Sodium dithionite (Na2S2O4) and ferrous sulfate (FeSO4) were screened for subsequent intensive research. In summary, the Na2S2O4 solutions had higher Cr, Cu, and Zn removal rates than either the FeSO4 or acid solution. Application of dissolved organic carbon (DOC) further increased the removal of heavy metals by complexation. About 15%, 86%, 32%, and 52% of the Cr, Cu, Zn, and Ni, respectively, were removed from the representative soil (M-2) by two-stage washing using 0.2 M Na2S2O4 coupled with 1,500 mg L-1 DOC solution at pH 2.0. Meanwhile, most soil fertility was preserved: ammonium nitrogen was increased 3.9 times; the increase in exchangeable potassium was 33%; and the reduction in available P was only 10%.

Vehicle-derived ultrafine particulate contaminating bees and bee products.

Despite adverse health effects, ultrafine particulate matter (UFP), i.e., PM less than 0.1 µm in diameter, is an emerging pollutant not subject to regulation. UFP may cause both lung inflammation and cardiopulmonary disease and may enter the brain directly via the olfactory bulb, affecting the nervous system. In highly urbanized environments, diesel and gasoline vehicles are among the major sources of UFP including combustion-generated solid particle pollutant and metal-based particles. Metal-based UFP are of much concern, as they may promote inflammation and DNA damage via oxidative stress with generation of free radicals and reactive oxygen species (ROS). We used the honeybee as an alternative sampling system of UFP in an area of the Po Valley (Northern Italy), which is subject to intense traffic. Worker bees are widely recognised as efficient samplers of air pollutants, including airborne PM. During flight and foraging activity, pubescence of the bees promotes the accumulation of electrical charge on the body's surface, enhancing attraction to air pollutants. Bees living near the main Italian highway, the Autostrada A1, displayed a contamination of nanosized Fe-oxides/hydroxides and baryte. Sources of Fe-bearing and baryte ultrafine particles are primarily the vehicles speeding on the motorway. Pollen collected by forager bees and honey produced by the bee colony displayed contamination by nanosized Fe-oxides/hydroxides and baryte. Such a contamination exposes pollinators and humans to UFP ingestion, endangering the safety of food produced at traffic-influenced sites. Given the global spread of traffic, our findings suggest that exposure and environmental impact of ultrafine Fe-oxides/hydroxides and baryte are potentially ubiquitous, although usually overlooked in environmental policy discussions.

Reduction of bioaccessibility of As in soil through in situ formation of amorphous Fe oxides and its long-term stability.

The bioaccessibility of As in soil, rather than its total concentration, is closely related to its potential risk. In this study, the in situ formation of amorphous Fe oxides was applied to As-contaminated soil to induce As-Fe coprecipitates that can withstand the gastric digestion condition of human beings. To promote the formation of Fe oxides, 2% ferric nitrate (w/w) and 30% water (v/w) were introduced, and the pH was adjusted to ~7. The chemical extractability of As in soil was determined using the solubility/bioavailability research consortium method and five-step sequential extraction. In situ formation of Fe oxides resulted in a remarkable increase in the As associated with amorphous Fe oxides, decreasing most of the exchangeable As (i.e., the sum of SO42- and PO43- extractable As), and thereby reducing the bioaccessibility of As. The types of association between As and Fe oxides were investigated using X-ray absorption spectroscopy analysis. Linear combination fit (LCF) analysis demonstrated that As bound to amorphous Fe oxides could exist as coprecipitates with ferrihydrite and schwertmannite after stabilization. The bioaccessibility of the coprecipitated As in soil further decreased as amorphous Fe oxides transformed to crystalline form with time, which was supported by the LCF results showing an increase of goethite in aged soil.

Role of phosphate concentration in control for phosphate removal and recovery by layered double hydroxides.

Phosphorus removal from wastewater has become urgent because of eutrophication control. Phosphate concentration in control for phosphate removal and recovery by Mg-Fe oxide has been investigated. The results show that the adsorption capacity of phosphate by Mg-Fe oxide calcined at 450 °C was 28.3 mg/g, and it was kept at wide optimal adsorption pH ranges (4-10). The coexisting ions had influenced phosphate adsorption process and the order is CO32- > SO42- > NO3- > Cl-, with the inhibition rate of CO32- being 43%. Interestingly, phosphate concentration plays an important role in phosphate removal by Mg-Fe oxide. Under higher initial phosphate concentrations (200-800 mg/L), Sips model was well fitted. In addition, the adsorption kinetics was well described by the pseudo-second-order kinetic model before 25 min and the pseudo-first-order kinetic model after 25 min. In contrast, Langmuir model and pseudo-second-order kinetic model were fitted under lower initial phosphate concentrations (20-200 mg/L). The results of XRD, XPS, SEM, and TEM characterization show that Mg3(PO4)2 was formed by surface precipitation under 800 mg/L phosphate solution, and Mg-Fe layered structure was present via the unique memory effect under 20 mg/L phosphate solution. Mg-Fe oxide can be recovered through CO32- ion exchange, and the removal efficiency of phosphate was 56% after seven cycles.

Glassy Magnetic Behavior and Correlation Length in Nanogranular Fe-Oxide and Au/Fe-Oxide Samples.

In nanoscale magnetic systems, the possible coexistence of structural disorder and competing magnetic interactions may determine the appearance of a glassy magnetic behavior, implying the onset of a low-temperature disordered collective state of frozen magnetic moments. This phenomenology is the object of an intense research activity, stimulated by a fundamental scientific interest and by the need to clarify how disordered magnetism effects may affect the performance of magnetic devices (e.g., sensors and data storage media). We report the results of a magnetic study that aims to broaden the basic knowledge of glassy magnetic systems and concerns the comparison between two samples, prepared by a polyol method. The first can be described as a nanogranular spinel Fe-oxide phase composed of ultrafine nanocrystallites (size of the order of 1 nm); in the second, the Fe-oxide phase incorporated non-magnetic Au nanoparticles (10-20 nm in size). In both samples, the Fe-oxide phase exhibits a glassy magnetic behavior and the nanocrystallite moments undergo a very similar freezing process. However, in the frozen regime, the Au/Fe-oxide composite sample is magnetically softer. This effect is explained by considering that the Au nanoparticles constitute physical constraints that limit the length of magnetic correlation between the frozen Fe-oxide moments.

Organic matter facilitates the binding of Pb to iron oxides in a subtropical contaminated soil.

The bioavailability and potential uptake of heavy metals by crops is fundamentally influenced by the forms of metals in soils. Organic matter plays an important role in controlling the transformation of heavy metal fractionations in soils. However, long-term effects of organic matter on heavy metal speciation remains highly uncertain. In this study, rice straw was introduced to a subtropical Pb-contaminated soil for 2-year period so as to clarify the redistribution of Pb fractions and their correlations with soil properties. By combining sequential extraction and X-ray absorption fine structure spectroscopy, we find that lead is predominantly presented in Fe oxide-bound, surface adsorbed, and residual fractions in the soil. The incorporation of rice straw can effectively reduce the labile species of Pb by promoting the binding of Pb to iron oxides. Furthermore, aging leads to the transfer of considerable amounts of Pb to the association with Fe oxides and this transformation is enhanced by the presence of organic matter. Organic matter input and soil aging tend to shift Pb to amorphous Fe oxides than crystalline Fe oxides. The correlation analysis shows that Fe oxide fractions play vital roles in controlling the forms of Pb in soil. This study presents the first result regarding the long-term effect of organic matter on the redistribution of Pb in naturally polluted soil, which is useful for understanding the fate of Pb and developing remediation strategies for Pb-polluted soils.

Self-Supported Stainless Steel Nanocone Array Coated with a Layer of Ni-Fe Oxides/(Oxy)hydroxides as a Highly Active and Robust Electrode for Water Oxidation.

Highly efficient, robust, and cheap water oxidation electrodes are of great significance for large-scale production of hydrogen by electrolysis of water. Here, a self-supported stainless steel (SS) nanocone array coated with a layer of nanoparticulate Ni-Fe oxides/(oxy)hydroxides was fabricated by a facile, low-cost, and easily scalable two-step process. The construction of a nanocone array on the surface of an AISI 304 SS plate by acid corrosion greatly enlarged the specific surface area of the substrate, and the subsequent formation of a layer of Ni-Fe oxides/(oxy)hydroxides featuring the NiFe2O4 spinel phase on the nanocone surface by electrodeposition of [Ni(bpy)3]2+ significantly enhanced the intrinsic activity and the stability of the SS-based electrode. The as-prepared electrode demonstrated superior activity for the oxygen evolution reaction (OER) in 1 M KOH, with 232 and 280 mV overpotentials to achieve 10 and 100 mA cmgeo-2 current densities, respectively. The high activity of the electrode was maintained over 340 h of chronopotentiometric test at 20 mA cmgeo-2, and the electrode also showed good stability over 100 h of electrolysis at high current density (200 mA cm-2). More important for practical application, the used SS-based electrode can be easily regenerated with the original OER activity. The superior activity of this SS-based electrode stems from synergistic combination of high conductivity of the SS substrate, a large electrochemically active surface area of the nanocone array, and a uniformly coated nanoparticulate Ni-Fe oxide/(oxy)hydroxide layer with an optimal Ni/Fe ratio.

Speciation, mobilization, and bioaccessibility of arsenic in geogenic soil profile from Hong Kong.

The behaviour of arsenic (As) from geogenic soil exposed to aerobic conditions is critical to predict the impact of As on the environment, which processes remain unresolved. The current study examined the depth profile of As in geologically derived subsoil cores from Hong Kong and investigated the mobilization, plant availability, and bioaccessibility of As in As-contaminated soil at different depths (0-45.8 m). Results indicated significant heterogeneity, with high levels of As in three layers of soil reaching up to 505 mg/kg at a depth of 5 m, 404 mg/kg at a depth of 15 m, and 1510 mg/kg at a depth of 27-32 m. Arsenic in porewater samples was <11.5 µg/L in the study site. X-ray absorption spectroscopy (XAS) indicated that main As species in soil was arsenate (As(V)), as adsorbed fraction to Fe oxides (41-69% on goethite and 0-8% on ferrihydrite) or the mineral form scorodite (30-57%). Sequential extraction procedure demonstrated that 0.5 ± 0.4% of As was exchangeable. Aerobic incubation experiments exhibited that a very small amount (0.14-0.48 mg/kg) of As was desorbed from the soil because of the stable As(V) complex structure on abundant Fe oxides (mainly goethite), where indigenous microbes partly (59 ± 18%) contributed to the release of As comparing with the sterilized control. Furthermore, no As toxicity in the soil was observed with the growth of ryegrass. The bioaccessibility of As was <27% in the surface soil using simplified bioaccessibility extraction test. Our systematic evaluation indicated that As in the geogenic soil profile from Hong Kong is relatively stable exposing to aerobic environment. Nevertheless, children and workers should avoid incidental contact with excavated soil, because high concentration of As was present in the digestive solution (<0.1-268 µg/L).