Partial Oxidation of FeS Nanoparticles Enhances Cr(VI) Sequestration

Iron sulfide nanoparticles (nano-FeS) have shown great potential for in situ remediation of Cr(VI) pollution by reducing Cr(VI) to the less soluble and toxic Cr(III). However, material oxidation that inevitably occurs during storage and application alters its reactivity. Herein, we show that partial oxidation of nanoparticulate mackinawite (FeS) significantly enhances its capability in sequestering Cr(VI). Oxidation of nano-FeS increases its binding affinity to Cr(VI), likely due to preferential inner-sphere complexation of Cr(VI) oxyanions to ferric over ferrous iron in mackinawite/lepidocrocite (FeS/γ-FeOOH) nanocomposites. A trade-off is that oxidation mitigates Cr(VI) reduction by lowering the electron-donating potential of the material and the electron transfer at a solution-material interface and consequently hinders the transformation of adsorbed Cr(VI) to Cr(III). Notably, the rate-limiting step of Cr(VI) sequestration transitions from adsorption to reduction during oxidation, as demonstrated with batch experiments coupled with kinetic modeling. Thus, an optimum oxidation degree exists, wherein the gain in the overall performance from enhanced adsorption overcompensates the loss from inhibited reduction, resulting in maximum sequestration of aqueous Cr(VI) as solid-phase Cr(III). Our findings inform better assessment and design of nanomaterials for Cr(VI) remediation and may be extended to interactions of other oxyanions with natural and engineered nanoparticles during oxidative aging.