Influence of the structure and composition of Fe-Mn binary oxides on rGO on As(III) removal from aquifers.

Fe-Mn binary oxide (FMBO) possesses high efficiency for As(III) abatement based on the good adsorption affinity of iron oxide and the oxidizing capacity of Mn(IV), and the composition and structure of FMBO play important roles in this process. To compare the removal performance and determine the optimum formula for FMBO, magnetic graphene oxide (MRGO)-FMBO and MRGO-MnO2 were synthesized with MRGO as a carrier to improve the dispersity of the adsorbents in aquifers and achieve magnetic recycling. Results indicated that MRGO-FMBO had higher As(III) removal than that of MRGO-MnO2, although the ratios of Fe and Mn were similar, because the binary oxide of Fe and Mn facilitated electron transfer from Mn(IV) to As(III), while the separation of Mn and Fe on MRGO-MnO2 restricted the process. The optimal stoichiometry x for MRGO-FMBO (MnxFe3-xO4) was 0.46, and an extraordinary adsorption capacity of 24.38 mg/g for As(III) was achieved. MRGO-FMBO showed stable dispersive properties in aquifers, and exhibited excellent practicability and reusability, with a saturation magnetization of 7.6 emu/g and high conservation of magnetic properties after 5 cycles of regeneration and reuse. In addition, the presence of coexisting ions would not restrict the practical application of MRGO-FMBO in groundwater remediation. The redox reactions of As(III) and Mn(IV) on MRGO-FMBO were also described. The deprotonated aqueous As(III) on the surface of MRGO-FMBO transferred electrons to Mn(IV), and the formed As(V) oxyanions were bound to ferric oxide as inner-sphere complexes by coordinating their "-OH" groups with Mn(IV) oxides at the surface of MRGO-FMBO. This work could provide new insights into high-performance removal of As(III) in aquifers.

Reduced graphene oxide-nano zero value iron (rGO-nZVI) micro-electrolysis accelerating Cr(VI) removal in aquifer.

Nanoscale zero-valent iron (nZVI) assembled on graphene oxide (GO) (rGO-nZVI) composites were synthesized by reduction of GO and ferrous ions with potassium borohydride, for use in Cr(VI) removal from aqueous solution. The results showed that the two-dimensional structure of GO could provide a skeleton support for Fe0, thus overcoming the bottleneck of aggregation for nZVI. Also, rGO-nZVI would form a ferric-carbon micro-electrolysis system in Cr(VI)-contaminated aquifers, enhancing and accelerating electron transfer, exhibiting high rate and capacity for Cr(VI) removal. The optimum dosage of the applied rGO-nZVI was linearly correlated with the initial Cr(VI) concentration. Characterization of rGO-nZVI before and after reaction with Cr(VI) revealed the process of Cr(VI) removal: rGO-nZVI firstly transferred electrons from Fe0 cores via their Fe(II)/Fe(III) shells to the GO sheet; there, negatively charged Cr(VI) received electrons and changed into positively charged Cr(III), which was adsorbed by the negatively charged GO sheet, avoiding the capping and passivating of nZVI. rGO-nZVI formed a good electrically conductive network, and thus had long-term electron releasing properties, which was important for groundwater remediation.