Citric acid-induced photochemical behavior of Cr(III)-substituted ferrihydrite: Fe and Cr release, mineral transformation and reactive oxygen species generation

Cr(III)-substituted ferrihydrite (Fh-Cr(III)) is widespread in the surrounding environment of mining areas. Fh-Cr(III) is unstable and susceptible to the influence of environmental factors, such as dissolved organic matter (DOM) and light, so Cr species embedded in mineral crystal layers are likely to have more profound negative effects on the environment with the photochemical behaviors of minerals. However, the photochemical behaviors of Fh-Cr(III) in the presence of DOM remains poorly understood. For this reason, citric acid (CA) was chosen as the representative DOM to study its combined effects with visible light irradiation on Fh-Cr(III) dissolution and phase transition. The results showed that CA hindered the agglomeration of Fh-Cr(III) particles, thereby slowing the phase transition of Fh-Cr(III). However, CA exacerbated the release of Fe and Cr by maintaining Fh-Cr(III) under unstable crystal structure. Moreover, due to the occurrence of ligand-metal charge transfer (LMCT) in (CA)n-Fh-Cr(III) formed on the Fh-Cr(III) surface, the synergistic effect between CA and light irradiation greatly promoted the dissolution of Fh-Cr(III). In the mixed system of Fh-Cr(III) (3 g/L) and CA (5 mM) at initial pH 3.0, the maximum concentrations of TFe and TCr were 18.17 and 5.68 mg/L after 6 h of light reaction, which were 1.82 and 3.62 times of those in the corresponding system in the darkness. Meanwhile, the Fe(III)/Fe(II) cycling in solution and solid surfaces was affected by various reactive oxygen species (ROS) generated from the LMCT process, in which the photoproduced Fe(II) further accelerated Cr(III) dissolution under acidic solution. The fast release of Cr(III) may pose greater danger to the environment as the more toxic Cr(VI) can be easily formed through the oxidation of dissolved Cr(III). This work offers fresh insights into the migration and transformation of Cr elements in the natural environment.