Surface protection method for the magnetic core using covalent organic framework shells and its application in As(III) depth removal from acid wastewater.

Fe3O4-based materials are widely used for magnetic separation from wastewater. However, they often suffer from Fe-leaching behavior under acidic conditions, decreasing their activity and limiting sustainable practical applications. In this study, covalent organic frameworks (COFs) were used as the shell to protect the Fe3O4 core, and the Fe3O4@COF core-shell composites were synthesized for As(III) removal from acid wastewater. The imine-linked COFs can in situ grow on the surface of the Fe3O4 core layer by layer with [COFs/Fe3O4]mol ratio of up to 2:1. The Fe-leaching behavior was weakened over a wide pH range of 1-13. Moreover, such composites keep their magnetic characteristic, making them favorable for nanomaterial separation. As(III) batch adsorption experiments results indicated that, when COFs are used as the shell for the Fe3O4 core, a balance between As(III) removal efficiencies and the thickness of the COF shell exists. Higher As(III) removal efficiencies are obtained when the [COFs/Fe3O4]mol ratios were < 1.5:1, but thicker COF shells were not beneficial for As(III) removal. Such composites also exhibited better As(III) removal performances in the pH range of 1-7. Over a wide pH range, the zeta potential of Fe3O4@COF core-shell composites becomes more positive, which benefits the capture of negative arsenic ions. In addition, thinner surface COFs were favorable for mass transfer and facilitating the reaction of Fe and As elements. Our study highlights the promise of using COFs in nanomaterial surface protection and achieving As(III) depth removal under acidic conditions.

The differential inhibitive effects and fates of As(III) and As(V) mediated by Sulfobacillus thermosulfidooxidans grown on S0, Fe2+ and FeS2.

Arsenic often coexists with metal sulfide minerals and occurs in different speciation and different toxicity in responding to Fe/S biooxidation. The differential inhibitive effects and fates of As(III) and As(V) during biooxidations of elemental sulfur (S0), ferrous ions (Fe2+) and pyrite (FeS2) by Sulfobacillus thermosulfidooxidans were studied. The results revealed that the arsenic species hardly changed for the biooxidation of S0, but dramatically changed for the biooxidation of Fe2+ and FeS2. Different transformation degree between As(III) and As(V) occurred for biooxidation of FeS2 in the presence of arsenic, where about 72% of As(III) was transformed to As(V) for the group with As(III) added, and 16% of As(V) was transformed to As(III) for that with As(V) added. Both formation and dissolution of amorphous ferric arsenate occurred during biooxidation of FeS2 with the addition of As(III) or As(V) and for the group grown on Fe2+ with added As(V), which were controlled by the changes of Fe/As molar ratio and pH value in the solution. Jarosite was detected for the group grown on Fe2+ and could adsorb As(III) and As(V). The inhibitive effects of As(V) were higher than As(III) when the strain grew on FeS2, which was contrary to those when the strain grew on S0 and Fe2+. The above results signify that the fates and inhibitive effects of arsenic are much related to each other, and such a relationship is significantly affected by the utilization of Fe/S energy substrates by the sulfur- and ferrous-oxidizing microorganisms.

A Colorimetric Probe Based on Functionalized Gold Nanorods for Sensitive and Selective Detection of As(III) Ions.

A colorimetric probe for determination of As(III) ions in aqueous solutions on basis of localized surface plasmon resonance (LSPR) was synthesized. The dithiothreitol molecules with two end thiols covalently combined with Au Nanorods (AuNRs) with an aspect ratio of 2.9 by Au-S bond to form dithiothreitol coated Au Nanorods (DTT-AuNRs), acting as colorimetric probe for the determination of As(III) ions. With the adding of As(III) ions, the AuNRs will be aggregated and leading the longitudinal SPR absorption band of DTT-AuNRs decrease due to the As(III) ions can bind with three DTT molecules through an As-S linkage. The potential factors affect the response of DTT-AuNRs to As(III) ions including the concentration of DTT, pH values of DTT-AuNRs, reaction time and NaCl concentration were optimized. Under optimum assay conditions, the DTT-AuNRs colorimetric probe has high sensitivity towards As(III) ions with low detection limit of 38 nM by rules of 3σ/k and excellent linear range of 0.13⁻10.01 µM. The developed colorimetric probe shows high selectivity for As(III) ions sensing and has applied to determine of As(III) in environmental water samples with quantitative spike-recoveries range from 95.2% to 100.4% with low relative standard deviation of less than 4.4% (n = 3).

Alendronate-Functionalized Graphene Quantum Dots as an Effective Fluorescent Sensing Platform for Arsenic Ion Detection.

Alendronate-functionalized graphene quantum dots (ALEN-GQDs) with a quantum yield of 57% were synthesized via a two-step route: preparation of graphene quantum dots (GQDs) by pyrolysis method using citric acid as the carbon source and post functionalization of GQDs via a hydrothermal method with alendronate sodium. After careful characterization of the obtained ALEN-GQDs, they were successfully employed as sensing materials with superior selectivity and sensitivity for the detection of nanomolar levels of arsenic ions (As(III)). According to the mechanistic investigation, arsenic ions can quench the fluorescence intensity of ALEN-GQDs through metal-ligand interaction between the As(III) ions and the surface functional groups of the fluorescent probe. This probe provided a rapid method to monitor As(III) with a wide detection range (44 nM-1.30 µM) and a low detection limit of 13 nM. Finally, to validate the applicability, this novel fluorescent probe was successfully applied for the quantitative determination of As(III) in rice and water samples.

Adsorption of arsenic in aqueous solution onto iron impregnated bagasse fly ash.

The present study examined the adsorption of As(III) and As(V) (arsenics) from aqueous solutions using FeCl3 impregnated bagasse fly ash (BFA-Fe). Batch adsorption studies were carried out to evaluate the effect of various parameters like initial pH (pH 0 ), adsorbent dose (m), contact time (t), initial concentration (C 0 ) and temperature (T) on the removal of As(III) and As(V) from aqueous solutions. The maximum removal of As(III) and As(V) was found ~ 95% and ~ 97% at lower concentration (< 20 µg/dm3) and ~ 86% and ~ 87% at higher concentration (500 µg/dm3), respectively, using 3 g/dm3 of BFA dosage at 303 K. The adsorption of arsenics on BFA-Fe was very rapid. Pseudo-second-order kinetic model well represented the adsorption kinetics of both As(III) and As(V). Error analyses functions for adsorption of As(III) and As(V) onto BFA-Fe. Based on these error analyses, R-P isotherm was found to be fitted. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 25.0 to 45.0 °C, the values of ΔG° lie in the range of -43.85, -45.34, -48.82, -51.31, -53.8, and -44.75, -48.3, -51.84, -55.39, -58.93, -55.57 for As (III), and As (V) respectively, indicating that adsorption is spontaneous and exothermic in nature. Regeneration study was carried out by different solvent and thermal methods. Our results revealed that BFA-Fe can be reused directly for making fire-briquettes to explore its energy value. From this study, As containment is most effective removal from aqueous solution and mimic to any contaminated water resources.

Metallothionein Attenuated Arsenic-Induced Cytotoxicity: The Underlying Mechanism Reflected by Metabolomics and Lipidomics.

Arsenic ions (As3+) have been recognized as a hazard that threatens the health of humans. Metallothionein (MT) rich in cysteine may provide favorable binding sites for chelation of As3+. However, the influence of MT on As3+-induced toxicity and the underlying mechanism are poorly understood, especially at the metabolic level. Herein, the effects of MT on As3+-induced toxicity were evaluated. Cell viability analysis suggested that MT alleviated As3+-induced cytotoxicity. The metabolic response of PC12 cells to As3+ investigated by lipidomics and metabolomics indicated that the presence of As3+ disrupted phospholipids metabolism and induced cell membrane damage. Moreover, energy and amino acid metabolism were perturbed by As3+. The perturbation of As3+ on metabolism was further illustrated by the decrease of the mitochondrial membrane potential and the rise of cellular reactive oxygen species (ROS). On the contrary, MT rescued As3+-induced metabolic disorder and suppressed ROS accumulation. In addition, the binding process between As3+ and MT was characterized. The results proved that the As3+-MT complex was formed and chelated As3+-scavenged ROS, thus alleviating the toxic effects of As3+. These results revealed that MT would be a potential agent to reduce As3+-induced cytotoxicity.

Magnetic mesoporous Fe/carbon aerogel structures with enhanced arsenic removal efficiency.

Wastewater treatment has drawn significant research attention due to its associated environmental issues. Adsorption is a promising method for treating wastewater. The development of an adsorbent with a high surface area is important. Therefore, we successfully developed mesoporous Fe/carbon aerogel (CA) structures with high specific surface areas of 48 7m(2)/g via the carbonization of composite Fe3O4/phenol-formaldehyde resin structures, which were prepared using a hydrothermal process with the addition of phenol. The mesoporous Fe/CA structures were further used for the adsorption of arsenic ions with a maximum arsenic-ion uptake of calculated 216.9 mg/g, which is higher than that observed for other arsenic adsorbents. Ferromagnetic behavior was observed for the as-prepared mesoporous Fe/CA structures with an excellent response to applied external magnetic fields. As a result, the adsorbent Fe/CA structures can be easily separated from the solution using an external magnetic field. This study develops the mesoporous Fe/CA structures with high specific surface areas and an excellent response to an applied external magnetic field to provide a feasible approach for wastewater treatment including the removal of arsenic ions.