Enhanced water decontamination from methylated arsenic by utilizing ultra-small hydrated zirconium oxides encapsulated inside gel-type anion exchanger

Abstract

Methylated arsenic species, including monomethyl arsenate (MMA) and dimethyl arsenate (DMA), are frequently detected in natural waters due to the biochemical methylation of arsenic and various human activities. The presence of MMA/DMA may cause excess total arsenic (>10 μg/L) in drinking water, yet the efficient removal of methylated arsenic still remains challenging. Herein, we reported the utilization of a recently developed nanocomposite HZO@N201 for selective removal of MMA and DMA from water. HZO@N201 contains the gel-type anion exchanger N201, i.e., quaternary ammoniated poly(styrene-co-divinylbenzene) beads, as the host, and the embedded sub-5 nm hydrated zirconium oxide (HZO) for specific adsorption. In comparison with the commercially available nanocomposite HZO@D201, which was prepared through in-situ growth of HZO inside the macroporous anion exchanger D201, the adsorption capacities of HZO@N201 toward MMA and DMA ascended by ∼ 1.9 and ∼ 2.2 times, respectively, mainly benefitting from the sub-5 nm nature of HZO@N201. The competing anions including sulfate, chloride and bicarbonate exerted negligible impact on the removal efficiency toward MMA/DMA, due to inner-sphere complex formation between HZO NPs and MMA/DMA, as verified by SEM-EDS and XPS Zr 3d analysis. The exhausted HZO@N201 was fully regenerated by alkaline treatment for cyclic utilization without obvious efficiency loss. In fixed-bed experiments, HZO@N201 column was able to successively produce ∼ 4000 and ∼ 160 bed volume (BV) clean water from the feeding solutions containing MMA and DMA, while the values for HZO@D201 column were merely ∼ 1600 BV and ∼ 70 BV, respectively.