Implementing magnetically-active Sn-based nanocomposites in hexavalent chromium removal from drinking water.

A novel nanocomposite consisting of Fe3O4-loaded tin oxyhydroxy-chloride is demonstrated as an efficient adsorbent for the removal of hexavalent chromium in compliance to the new drinking water regulation. This study introduces a continuous-flow production of the nanocomposite through the separate synthesis of (i) 40 nm Fe3O4 nanoparticles and (ii) multilayered spherical arrangements of a tin hydroxy-chloride identified as abhurite, before the application of a wet-blending process. The homogeneous distribution of Fe3O4 nanoparticles on the abhurite's morphology, features nanocomposite with magnetic response whereas the 10 % loaded nanocomposite preserves a Cr(VI) uptake capacity of 7.2 mg/g for residual concentrations below 25 µg/L. Kinetic and thermodynamic examination of the uptake evolution indicates a relative rapid Cr(VI) capture dominated by interparticle diffusion and a spontaneous endothermic process mediated by reduction to Cr(III). The efficiency of the optimized nanocomposite was validated in a pilot unit operating in a sequence of a stirring reactor and a rotary magnetic separator showing an alternative and competitive application path than typical fixed-bed filtration, which is supported by the absence of any acute cellular toxicity according to human kidney cell viability tests.

Tin Oxide Nanoparticles via Solar Vapor Deposition for Hexavalent Chromium Remediation.

Tin oxide nanoparticles optimized to capture low concentrations of hexavalent chromium from water were developed through a facile, scalable, and low-cost one-step solar vapor deposition methodology. Considering the preservation of high electron donation capacity as the key to support the reduction of mobile Cr(VI) into insoluble forms, the growth of SnO nanoparticles was favored by the co-evaporation of SnO2 with Fe powders at various mass ratios. Characterization techniques indicated that the percentage and the stability of SnO is proportional to the Fe content in the target with a requirement of at least 50% wt to inhibit the formation of a passive SnO2 surface layer. The produced particles were evaluated regarding their efficiency to capture Cr(VI) under conditions similar to water treatment for drinking purposes (pH 7). It was revealed that passivation-free SnO nanoparticles deliver significant improvement in the adsorption capacity corresponding to the residual concentration of 25 µg/L, reaching a value of 1.74 mg/g for the sample prepared with 50% wt Fe in the target. The increase of water acidity was found responsible for the activation of more reduction sites on the particle surface, as reflected through the elevation of efficiency by more than 20% at pH 6.

Enhanced detoxification of Cr6+ by Shewanella oneidensis via adsorption on spherical and flower-like manganese ferrite nanostructures.

Maximizing the safe removal of hexavalent chromium (Cr6+) from waste streams is an increasing demand due to the environmental, economic and health benefits. The integrated adsorption and bio-reduction method can be applied for the elimination of the highly toxic Cr6+ and its detoxification. This work describes a synthetic method for achieving the best chemical composition of spherical and flower-like manganese ferrite (MnxFe3-xO4) nanostructures (NS) for Cr6+ adsorption. We selected NS with the highest adsorption performance to study its efficiency in the extracellular reduction of Cr6+ into a trivalent state (Cr3+) by Shewanella oneidensis (S. oneidensis) MR-1. MnxFe3-xO4 NS were prepared by a polyol solvothermal synthesis process. They were characterised by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometry (XPS), dynamic light scattering (DLS) and Fourier transform-infrared (FTIR) spectroscopy. The elemental composition of MnxFe3-xO4 was evaluated by inductively coupled plasma atomic emission spectroscopy. Our results reveal that the oxidation state of the manganese precursor significantly affects the Cr6+ adsorption efficiency of MnxFe3-xO4 NS. The best adsorption capacity for Cr6+ is 16.8 ± 1.6 mg Cr6+/g by the spherical Mn0.22+Fe2.83+O4 nanoparticles at pH 7, which is 1.4 times higher than that of Mn0.8Fe2.2O4 nanoflowers. This was attributed to the relative excess of divalent manganese in Mn0.22+Fe2.83+O4 based on our XPS analysis. The lethal concentration of Cr6+ for S. oneidensis MR-1 was 60 mg L-1 (determined by flow cytometry). The addition of Mn0.22+Fe2.83+O4 nanoparticles to S. oneidensis MR-1 enhanced the bio-reduction of Cr6+ 2.66 times compared to the presence of the bacteria alone. This work provides a cost-effective method for the removal of Cr6+ with a minimum amount of sludge production.

Correction: Enhanced detoxification of Cr6+ by Shewanella oneidensis via adsorption on spherical and flower-like manganese ferrite nanostructures.

[This corrects the article DOI: 10.1039/D2NA00691J.].

Hydrotalcite-Embedded Magnetite Nanoparticles for Hyperthermia-Triggered Chemotherapy.

A magnetic nanocomposite, consisting of Fe3O4 nanoparticles embedded into a Mg/Al layered double hydroxide (LDH) matrix, was developed for cancer multimodal therapy, based on the combination of local magnetic hyperthermia and thermally induced drug delivery. The synthesis procedure involves the sequential hydrolysis of iron salts (Fe2+, Fe3+) and Mg2+/Al3+ nitrates in a carbonate-rich mild alkaline environment followed by the loading of 5-fluorouracil, an anionic anticancer drug, in the interlayer LDH space. Magnetite nanoparticles with a diameter around 30 nm, dispersed in water, constitute the hyperthermia-active phase able to generate a specific loss of power of around 500 W/g-Fe in an alternating current (AC) magnetic field of 24 kA/m and 300 kHz as determined by AC magnetometry and calorimetric measurements. Heat transfer was found to trigger a very rapid release of drug which reached 80% of the loaded mass within 10 min exposure to the applied field. The potential of the Fe3O4/LDH nanocomposites as cancer treatment agents with minimum side-effects, owing to the exclusive presence of inorganic phases, was validated by cell internalization and toxicity assays.

Toxic and Microbiological Effects of Iron Oxide and Silver Nanoparticles as Additives on Extended Ram Semen.

The aim of the study was to investigate the effect of iron oxide (Fe) and silver (Ag) nanoparticles (NPs) on ram semen. A skim milk extender without antibiotics was used as a diluent of 21 ejaculates (8 rams; 2-3 ejaculates/ram). The groups of control (C; semen without NPs), Fe NPs (3.072 mg Fe3O4/mL semen), and Ag NPs (2.048 mg Ag-Fe/mL semen) were incubated (15 °C; 30 min), and then a magnetic field was used for NPs' removal. Standard microbiological procedures were performed for all groups. Post-treated samples were stored (15 °C) for 24 h, and sperm variables (kinetics by computer assisted sperm analysis (CASA); viability; morphology; HOST; DNA integrity) were evaluated at 6 and 24 h. Semen data were analyzed by a mixed model for repeated measures and microbiological data with Student's t-test for paired samples. At 6 h of storage, VCL and rapid movement-spermatozoa, and at 24 h, total/progressive motility and amplitude of lateral head displacement (ALH) were significantly decreased in group Ag compared to control. In group Fe, progressive/rapid movement-spermatozoa were significantly lower compared to control after 24 h of storage. Only in group Ag was a significant reduction of total bacterial count revealed. In conclusion, the examined Fe NPs demonstrated slight antibacterial effect, while the examined Ag NPs provided higher antibacterial properties accompanied by cytotoxicity.

Dimpled SiO2@γ-Fe2O3 nanocomposites - fabrication and use for arsenic adsorption in aqueous medium.

We report the synthesis of nanocomposites made of silica nanoparticles whose six surface dimples are decorated with magnetic maghemite nanoparticles and their use for detection and recovery of arsenic in aqueous media. Precursor silica nanoparticles have aminated polystyrene chains at the bottom of their dimples and the maghemite nanoparticles are surface functionalized with carboxylic acid groups in two steps: amination with 3-aminopropyltrimethoxysilane, then derivatization with succinic anhydride in the presence of triethylamine. In the end, the colloidal assembly consists of the regioselective grafting of the carboxylic acid-modified iron oxide nanoparticles onto the 6-dimple silica nanoparticles. Several characterization techniques such as transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) are employed to assess the grafting process and study the influence of the maghemite functional groups on the quality of the composites formed. The resulting magnetic nanocomposites are used for the environmentally benign detection and removal of arsenic from aqueous medium, being readily extracted through means of magnetic separation.

Iron Oxide Nanoparticles as an Alternative to Antibiotics Additive on Extended Boar Semen.

This study examined the effect of Fe3O4 nanoparticles on boar semen. Beltsville thawing solution without antibiotics was used to extend ejaculates from 5 boars (4 ejaculates/boar). Semen samples of control group (C) and group with Fe3O4 (Fe; 0.192 mg/mL semen) were incubated under routine boar semen storage temperature (17 °C) for 0.5 h and nanoparticles were removed by a magnetic field. Before and after treatment, aliquots of all groups were cultured using standard microbiological methods. The samples after treatment were stored (17 °C) for 48 h and sperm parameters (computer-assisted sperm analyzer (CASA) variables; morphology; viability; hypo-osmotic swelling test (HOST); DNA integrity) were evaluated at storage times 0, 24, 48 h. Semen data were analyzed by a repeated measures mixed model and microbial data with Student's t-test for paired samples. Regarding CASA parameters, Fe group did not differ from C at any time point. In group C, total motility after 24 h and progressive motility after 48 h of storage decreased significantly compared to 0 h. In group Fe, linearity (LIN) after 48 h and head abnormalities after 24 h of storage increased significantly compared to 0 h. The microbiological results revealed a significant reduction of the bacterial load in group Fe compared to control at both 24 and 48 h. In conclusion, the use of Fe3O4 nanoparticles during semen processing provided a slight anti-microbiological effect with no adverse effects on sperm characteristics.

Improvement of Manganese Feroxyhyte's Surface Charge with Exchangeable Ca Ions to Maximize Cd and Pb Uptake from Water.

The surface configuration of tetravalent manganese feroxyhyte (TMFx) was appropriately modified to achieve higher negative surface charge density and, hence, to improve its efficiency for the removal of dissolved Cd and Pb mostly cationic species from water at pH values commonly found in surface or ground waters. This was succeeded by the favorable engagement of Ca2+ cations onto the surface of a mixed Mn-Fe oxy-hydroxide adsorbent during the preparation step, imitating an ion-exchange mechanism between H+ and Ca2+; therefore, the number of available negatively-charged adsorption sites was increased. Particularly, the calcium coverage can increase the deprotonated surface oxygen atoms, which can act as adsorption centers, as well as maintain them during the subsequent drying procedure. The developed Ca-modified adsorbent (denoted as TMFx-Ca) showed around 10% increase of negative surface charge density, reaching 2.0 mmol [H+]/g and enabling higher adsorption capacities for both Cd and Pb aquatic species, as was proved also by carrying out specific rapid small-scale column tests, and it complied with the corresponding strict drinking water regulation limits. The adsorption capacity values were found 6.8 µg·Cd/mg and 35.0 µg·Pb/mg, when the restructured TMFx-Ca adsorbent was used, i.e., higher than those recorded for the unmodified material.

Reductive precipitation and removal of Cr(VI) from groundwaters by pipe flocculation-microfiltration.

Chromium (Cr(VI)) is a very toxic and carcinogenic element, which is widely present in groundwaters, mainly due to geogenic conditions. The limit of Cr(VI) in drinking water is expected to be reduced to 10 µg/L in both the USA and the European Union. Recent literature findings indicated that the most efficient process in reducing Cr(VI) levels to below 10 µg/L proved to be Cr(VI) reduction by Fe(II), by applying a molar ratio Fe(II)/Cr(VI) of around 9. In the present work, we investigated the reduction of Cr(VI) by Fe(II) in pipe flocculation reactors followed by filtration of insoluble products by microfiltration. The proposed technology involves re-circulation of a part of the sludge in the pipe reactors, in order to improve kinetics and efficiency of the process. The obtained results showed that with a Fe(II) dose of around 1 mg/L, Cr(VI) was reduced to below 10 µg/L, by even an initial concentration as high as 300 µg/L of Cr(VI), corresponding to a molar ratio Fe(II)/Cr(VI) of around 3, thus reducing the overall quantity of reductive reagents and of the produced sludge. This ratio was also confirmed by the XPS analysis, which also showed that Cr(VI) was reduced to Cr(III) and then precipitated either as Cr(OH)3 or associated with the produced iron oxides.

The use of Sn(II) oxy-hydroxides for the effective removal of Cr(VI) from water: Optimization of synthesis parameters.

The development of a novel adsorbent based on Sn(II) oxy-hydroxide nanoparticles and the optimization of main synthesis parameters was examined for the efficient removal of hexavalent chromium at low residual concentration levels. The aqueous hydrolysis of Sn(II) salts in a continuous-flow process was evaluated as an effective method to synthesize an appropriate material able to operate both as an electron donor for Cr(VI) reduction, and provide a suitable crystal structure that favors strong complexation with the formed Cr(III) species. Experimental results revealed that the main hydrolysis parameters, such as pH value and tin origin/source, can be used to determine the chemical formula of the produced materials and thereby, eventually improve their uptake capacity for Cr(VI). Among the tested sorbent materials, the synthetic nanostructured hydroromarchite, Sn6O4(OH)4, prepared by the hydrolysis of SnCl2 in a highly acidic environment (pH2), was deemed the best sorbent material and it was further investigated for its Cr(VI) uptake performance under reliable conditions (column experiments) for drinking water treatment. Specifically, Rapid Small-Scale (laboratory) Column Tests indicated that aggregates of the Sn6O4(OH)4 nanomaterial can achieve a maximum uptake capacity of around 19mg/g, keeping the levels of outflow Cr(VI) below 10µg/L during the treatment of natural-like water at pH7. The high efficiency is mainly attributed to the stabilization of Sn(II) content in nanoparticles, as well as the improved surface charge density, reaching 1.0mmol[OH-]/g, whereas the obtained thermodynamic data indicate a combined reduction-sorption process. The latter aspect was further verified by XPS, showing that even in the highly-loaded sorbent materials with adsorbed chromium, its trivalent form is the predominant one. These specific characteristics suggest that the product is a more favorable candidate for wider applications in water treatment units, regarding Cr(VI) removal, compared to other examined sorbent materials.

Enrichment and oral bioaccessibility of selected trace elements in fly ash-derived magnetic components.

The mineralogy, morphology, and chemical composition of magnetic fractions separated from fly ashes (FAs) originating from Greek lignite-burning power plants was investigated. The oral bioaccessibility of potentially harmful elements (PHEs) from the fly ash magnetic fractions (FAMFs) was also assessed using in vitro gastrointestinal extraction (BARGE Unified Bioaccessibility Method, UBM). The FAMFs isolated were in the range 4.6-18.4%, and their mass specific magnetic susceptibility ranged from 1138 × 10-8 to 1682 × 10-8 m3/kg. XRD analysis and Mossbauer spectroscopy indicated that the dominant iron species were Fe-rich aluminosilicate glass along with magnetite, hematite, and maghemite (in decreasing order). The raw FAs exhibited differences in their chemical composition, indicating the particularity of every lignite basin. The elemental contents of FAMFs presented trends with fly ash type; thus, the FAMFs of high-Ca FAs were enriched in siderophile (Cr, Co, Ni) and lithophile (Cs, Li, Rb) elements and those separated from low-Ca FAs were presented depleted in chalcophile elements. Based on UBM extraction tests, the PHEs were more bioaccessible from the non-magnetic components of the FAs compared to the magnetic ones; however, the bioaccessible fractions estimated for the FAMFs were exceeding 40 % in many cases. Arsenic was found to be significantly bioaccessible (median ~ 80 %) from FAMFs despite the lower As contents in the magnetic fraction.

In-situ particles reorientation during magnetic hyperthermia application: Shape matters twice.

Promising advances in nanomedicine such as magnetic hyperthermia rely on a precise control of the nanoparticle performance in the cellular environment. This constitutes a huge research challenge due to difficulties for achieving a remote control within the human body. Here we report on the significant double role of the shape of ellipsoidal magnetic nanoparticles (nanorods) subjected to an external AC magnetic field: first, the heat release is increased due to the additional shape anisotropy; second, the rods dynamically reorientate in the orthogonal direction to the AC field direction. Importantly, the heating performance and the directional orientation occur in synergy and can be easily controlled by changing the AC field treatment duration, thus opening the pathway to combined hyperthermic/mechanical nanoactuators for biomedicine. Preliminary studies demonstrate the high accumulation of nanorods into HeLa cells whereas viability analysis supports their low toxicity and the absence of apoptotic or necrotic cell death after 24 or 48 h of incubation.

One-Step Route to Iron Oxide Hollow Nanocuboids by Cluster Condensation: Implementation in Water Remediation Technology.

The fabrication procedure of hollow iron oxide nanoparticles with a large surface to volume ratio by a single-step gas condensation process at ambient temperature is presented. Fe clusters formed during the sputtering process are progressively transformed into hollow cuboids with oxide shells by the Kirkendall mechanism at the expense of oxygen captured inside the deposition chamber. TEM and Raman spectroscopy techniques point to magnetite as the main component of the nanocuboids; however, the magnetic behavior exhibited by the samples suggests the presence of FeO as well. In addition, these particles showed strong stability after several months of exposure to ambient conditions, making them of potential interest in diverse technological applications. In particular, these hierarchical hollow particles turned out to be very efficient for both As(III) and As(V) absorption (326 and 190 mg/g, respectively), thus making them of strong interest for drinking water remediation.

Fe3O4@NiFexOy Nanoparticles with Enhanced Electrocatalytic Properties for Oxygen Evolution in Carbonate Electrolyte.

The design and engineering of earth-abundant catalysts that are both cost-effective and highly active for water splitting are crucial challenges in a number of energy conversion and storage technologies. In this direction, herein we report the synthesis of Fe3O4@NiFexOy core-shell nanoheterostructures and the characterization of their electrocatalytic performance toward the oxygen evolution reaction (OER). Such nanoparticles (NPs) were produced by a two-step synthesis procedure involving the colloidal synthesis of Fe3O4 nanocubes with a defective shell and the posterior diffusion of nickel cations within this defective shell. Fe3O4@NiFexOy NPs were subsequently spin-coated over ITO-covered glass and their electrocatalytic activity toward water oxidation in carbonate electrolyte was characterized. Fe3O4@NiFexOy catalysts reached current densities above 1 mA/cm2 with a 410 mV overpotential and Tafel slopes of 48 mV/dec, which is among the best electrocatalytic performances reported in carbonate electrolyte.

Sn(II) oxy-hydroxides as potential adsorbents for Cr(VI)-uptake from drinking water: An X-ray absorption study.

The feasibility of implementing a Sn(II) oxy-hydroxide (Sn6O4(OH)4) for the reduction and adsorption of Cr(VI) in drinking water treatment was investigated using XAFS spectroscopies at the Cr-K-edge. The analysis of the Cr-K-edge XANES and EXAFS spectra verified the effective use of Sn6O4(OH)4 for successful Cr(VI) removal. Adsorption isotherms, as well as dynamic Rapid Small Scale Test (RSSCT) in NSF water matrix showed that Sn6O4(OH)4 can decrease Cr(VI) concentration below the upcoming regulation limit of 10µg/L for drinking water. Moreover, an uptake capacity of 7.2µg/mg at breakthrough concentration of 10µg/L was estimated from the RSSCT, while the residual Cr(VI) concentration ranged at sub-ppb level for a significant period of the experiment. Furthermore, no evidence for the formation of Cr(OH)3 precipitates was found. On the contrary, Cr(III)-oxyanions were chemisorbed onto SnO2, which was formed after Sn(II)-oxidation during Cr(VI)-reduction. Nevertheless, changes in the type of Cr(III)-inner sphere complexes were observed after increasing surface coverage: Cr(III)-oxyanions preferentially sorb in a geometry which combines both bidentate binuclear ((2)C) and monodentate ((1)V) geometries, at the expense of the present bidentate mononuclear ((2)E) contributions. On the other hand, the pH during sorption does not affect the adsorption mechanism of Cr(III)-species. The implementation of Sn6O4(OH)4 in water treatment technology combines the advantage of rapidly reducing a large amount of Cr(VI) due to donation of two electrons by Sn(II) and also the strong chemisorption of Cr(III) in a combination of the (2)C and (1)V configurations, which enhances the safe disposal of spent adsorbents.

In vitro application of Mn-ferrite nanoparticles as novel magnetic hyperthermia agents.

Manganese ferrite nanoparticles were synthesized by a facile, low-cost, environmentally friendly and high yield methodology based on the aqueous co-precipitation of proper salts. Firstly, structural, morphological and magnetic characterization schemes were performed to determine crucial factors for optimizing their heating potential, such as size, polydispersity, saturation magnetization and coercivity. In an effort to simulate the in vivo environment of animal tissue phantoms and study the thermal heating effects resulting from Brownian motion and hysteresis losses, nanoparticles at various concentrations were embedded in aqueous media of varying agar concentration. During the in vitro application healthy cells (primary bone marrow-derived osteoblasts and 3T3-L1 fibroblast-like preadipocytes) and human osteosarcoma Saos-2 cells were incubated with manganese ferrite nanoparticles. The heating profile of the particles was studied at different concentrations and in correlation with their potential cytotoxic effect. Our results revealed concentration dependent cytotoxicity profile and uptake efficiency together with variable specific loss power values yet with fast thermal response, opening novel pathways in material selection as hyperthermia agents.

A novel approach for arsenic adsorbents regeneration using MgO.

An integrated procedure for the regeneration of iron oxy-hydroxide arsenic adsorbents by granulated MgO is proposed in this study. A continuous recirculation configuration, with a NaOH solution flowing sequentially through the saturated adsorbent (leaching step) and the MgO (adsorption step) column beds, was optimized by utilizing the high arsenic adsorption efficiency of MgO at strong alkaline environments. Experimental results indicated that the total amount of leached arsenic was captured by MgO whereas the regenerated iron oxy-hydroxide recovered around 80% of its removal capacity upon reuse. The improved adsorption capacity of MgO for As(V), which is maximized at pH 10, is explained by the intermediate hydration to Mg(OH)2 and the following As(V) oxy-anions adsorption on its surface through the formation of monodentate inner sphere complexes, as it is deduced from the AsK-edge X-ray absorption fine structure (EXAFS) analysis. In addition to the economical-benefits, corresponding tests proved that the solid wastes of this process, namely spent MgO/Mg(OH)2, can be environmentally safely disposed as stable additives in cement products, while the alkaline solution is completely detoxified and can be recycled to the regeneration task.

Tetravalent manganese feroxyhyte: a novel nanoadsorbent equally selective for As(III) and As(V) removal from drinking water.

The development of a single-phase Fe/Mn oxy-hydroxide (δ-Fe0.76Mn0.24OOH), highly efficient at adsorbing both As(III) and As(V), is reported. Its synthesis involves the coprecipitation of FeSO4 and KMnO4 in a kilogram-scale continuous process, in acidic and strongly oxidizing environments. The produced material was identified as a manganese feroxyhyte in which tetravalent manganese is homogeneously distributed into the crystal unit, whereas a second-order hollow spherical morphology is favored. According to this structuration, the oxy-hydroxide maintains the high adsorption capacity for As(V) of a single Fe oxy-hydroxide combined with enhanced As(III) removal based on the oxidizing mediation of Mn(IV). Ion-exchange between arsenic species and sulfates as well as the strongly positive surface charge further facilitate arsenic adsorption. Batch adsorption tests performed in natural-like water indicate that Mn(IV)-feroxyhyte can remove 11.7 µg As(V)/mg and 6.7 µg As(III)/mg at equilibrium pH 7, before residual concentration overcomes the regulation limit of 10 µg As/L for drinking water. The improved efficiency of this material, its low cost, and the possibility for scaling-up its production to industry indicate the high practical impact and environmental importance of this novel adsorbent.