Cd isotope fractionation in a soil-rice system: Roles of pH and mineral transformation during Cd immobilization and migration processes.

Cd speciation in soil and its transport to rice roots are influenced by the soil pH, oxidation-reduction potential, and mineral transformation; however, the immobilization and migration of Cd in soil-rice systems with different pH values under distinct water regimes remain unclear. This study used Cd isotope fractionation, soil physical analysis, and root gene quantification to elucidate the immobilization and transport of Cd in different soil-rice systems. In drainage soils, the high soil pH enhanced the transformation and magnitude of negative fractionation of Cd from MgCl₂ extract to FeMn oxide-bound pool; however, it favored Cd uptake and root-to-grain transport. Compared with drainage regimes, the flooding regimes shifted fractionation toward heavy isotopes from MgCl₂-extracted Cd to FeMn oxide-bound Cd in acidic soils (∆^114/110Cd_{MgCl2 extract - FeMn oxide-bound Cd} = -0.09 ± 0.03 ‰) and to light isotopes from MgCl₂-extracted Cd to carbonate-bound Cd in neutral and alkaline soils (∆^114/110Cd_{MgCl2 extract - carbonate-bound Cd} = 0.29-0.40 ‰). The submerged soils facilitated the forming of carbonate and poorly crystalline minerals (such as ferrihydrite), which were transformed into highly crystalline forms (such as goethite). These results demonstrated that the dissolution-precipitation process of iron oxides was essential for controlling soil Cd availability under flooding regimes, and the relative contribution of carbonate minerals to Cd immobilization was promoted by a high soil pH. Flooding regimes induced lower expressions of OsNRAMP1 and OsNRAMP5 to limit the uptake of light Cd isotopes from MgCl₂-extract pool, whereas a teeter-totter effect on gene expression patterns in roots (including those of OsHMA3 and OsHMA2) limited the transport of heavy Cd isotopes from root to grain. These findings demonstrate that flooding regimes could exert multiple effects on soil Cd immobilization and Cd transport to grain. Moreover, alkaline soil was conducive to forming carbonate minerals to sequester Cd.