Chemical and structural characterization of As immobilization by nanoparticles of mackinawite (FeS_m)

The mobility and availability of arsenite, As(III), in anoxic environments is largely controlled by adsorption onto iron sulfides and/or precipitation of arsenic in solid phases. The interaction of As(III) with synthetic mackinawite (FeS_m) in pH 5 and 9 suspensions was investigated using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM), STEM elemental mapping, high resolution TEM, and X-ray photoelectron spectroscopy (XPS). At pH 5, arsenic sulfide phases precipitate among the FeS_m particles as discrete particles that are an amorphous hydrous phase of arsenic sulfide. The oxidation state of As in the surface layers of the arsenic sulfide precipitates is 'realgar-like' based on XPS results showing that > 75% of the As 3d peak area is due to As with oxidation states between 0 and 2+. Discrete, arsenic sulfide precipitates are absent at pH 9, but elemental mapping in STEM-EDX mode shows that arsenic is uniformly distributed on the FeS_m, suggesting that uptake is caused by the sorption of As(III) oxyanions and/or the precipitation of highly dispersed arsenic sulfides on FeS_m. XPS also revealed that the FeS_m that equilibrated without As(III) has a more oxidized surface composition than the sample at pH 9, as indicated by the higher concentration of O (∼ three times greater than that at pH 9) and the larger fraction of Fe(III) species making up the total Fe (2p_3/2) peak. These findings provide a better understanding of redox processes and phase transitions upon As(III) adsorption on iron sulfide substrates.