Long-distance mobilization of chromium(III) in soil associated with submicron Cr2O3

Abstract

Trivalent chromium is generally assumed to form insoluble species, resulting in low mobility of Cr(III) in soils. Here, we report continuous distributions (0-19 m) of a high concentration of Cr(III) in the alkaline soils of a historically industrial site for producing Na₂Cr₂O₇, CrO₃, and Cr₂O₃, which challenges this abovementioned conventional wisdom. The thermodynamic equilibrium model showed the low possibility of Cr(III) originating from Cr(VI) reduction under the redox conditions of this study. The AF4-MALLS-ICP-MS and μ-XRF-XANES were used to identify the particle size distribution of Cr(III)-containing colloids and Cr(III) species in mobile colloids. In any soil layer, Cr(III) accounts for 71.1-94.3% of the total Cr in submicron soil colloids and is composed of submicron intrinsic Cr₂O₃ (55.2%-63.8%), Cr(OH)₃ (0-33.0%), and Cr(III) adsorbed by ferrihydrite (0-19.0%) and clay montmorillonite (11.1%-21.1%) colloid. On the contrary, Cr(VI) was mainly distributed in bulk soil (> 2 µm) except for the topsoil, accounting for 62.6-90.0% of total Cr(VI). Organic matter content and soil texture are the most critical factors driving the mobilization of submicron colloids in soils by principal component analysis. Humic acid (HA) formed HA-corona on Cr₂O₃ surface and enhanced colloidal dispersion, thereby accelerating the long-distance mobilization of submicron Cr₂O₃ colloids in alkaline soil layers, whereas the heteroaggregation of clay colloid with Cr₂O₃ was only favorable for short-distance mobilization. Our findings help to re-recognize the potential migration risks of insoluble heavy metals in soils.

Keywords: Cr(III); Intrinsic colloids; Mobility; Submicron Cr(2)O(3).