Fe (hydr)oxides and organic colloids mediate colloid-bound chromium mobilization in Cr(VI) contaminated paddy soil

The association of chromium (Cr) with colloidal particles transport in contaminated sites can affect hexavalent chromium (Cr(VI)) migration and transformation, which is an important mechanism for Cr pollutants in soil and groundwater systems. Here, we investigated colloid and particle-bound Cr migration and transformation effects on rice Cr accumulation during different rice growth stages and different redox conditions in Cr(VI) contaminated soil by pot experiment. Results showed that 13-29% of soil Cr was water dispersible colloid-bound (100-1000 nm) form during rice growth. Using transmission electron microscopy - energy dispersion spectroscopy and asymmetric flow field - flow separation, we identified colloid-bound organic matter (OM) and iron (Fe), most likely in the form of Fe (hydr)oxides - clay composites, as the primary Cr carrier. Specifically, colloid-bound Cr was mainly associated with 125-350 nm soil particle size. Under different redox conditions, colloid- and nanoparticle-bound Cr concentration decreased with increasing nanoparticles zero-valent iron (nZVI) dose. Soil reoxidation promoted the colloid- and nanoparticle-bound Cr release due to the weakly crystalline Fe-(hydr)oxides reprecipitation. Further quantitative analysis showed that colloid-bound Cr concentrations were positively correlated with colloid-bound Mn concentrations during the whole rice growth soils. Most important of all, Cr content in rice grain was positively correlated with colloid-bound Cr significantly. This study provides a quantitative and size-resolved understanding of particle-bound Cr in paddy soils, highlighting the importance of colloid-bound Cr and Fe interactions in Cr geochemical cycle of paddy soil.