Binding mechanisms of trivalent chromium on colloidal phases from ultramafic systems: Insights from batch experiments and XAS analysis

Abstract

Understanding the availability and mobility of chromium is a key factor in gaining insight into the fate of chromium and thus essential for assessing the risk of contamination and developing effective remediation strategies. In the natural environment, such as ultramafic systems, which are natural pools of chromium, chromium occurs mostly in the trivalent state (Cr(III)), which is known to have a high affinity for the solid phases such as particles and colloids. However, since Cr(VI) is more toxic, the vast majority of experimental studies focus on its reduction to Cr(III), which is often considered to form (hydr)oxide precipitates due to its poor solubility. Furthermore, while the oxidation state of Cr dictates its geochemical behavior, its interaction with particles and colloids is rarely controlled or monitored. Therefore, the interaction mechanisms between Cr(III) and particles or colloids require further attention. In this study, ten mineral phases (goethite, hematite, pyrolusite, kaolinite, montmorillonite, chlorite, serpentine, fuchsite, amphibole, and chromite) and one organic phase (humic acid), relevant to chromium bearing and carrier phases in ultramafic soils, were investigated to explore their interaction with Cr(III) species. These phases were first characterized by various techniques (including XRD, XRF, SEM, and BET). Adsorption and desorption experiments of Cr(III) on these phases were then carried out, and the distribution of Cr oxidation states in both the aqueous and solid phases was carefully monitored using UV–vis spectroscopy, geochemical speciation modeling, and Cr K-edge XAS spectroscopy. With the exception of pyrolusite, where partial oxidation of Cr(III) to Cr(VI) occurred, Cr(III) was shown to persist as a single oxidation state in all experiments. Desorption analyses showed significantly low desorbed rates, which further confirmed the prevalence of Cr(III). Experimental sorption isotherm data were interpreted using the Langmuir model and its linearized form, which provides important thermodynamic characteristics of adsorbents related to their structural and surface features. This study will provide better constraints for the understanding and prediction of Cr behavior and fate in the environment, especially in ultramafic systems.