Redistribution of iron oxides in aggregates induced by pe + pH variation alters Cd availability in paddy soils

In this study, the effect of unstable pe + pH levels on the transformation of Fe oxides in different-sized soil fractions and its impact on Cd speciation were explored. Paddy soil samples collected from two locations in China were cultivated for two months under one of four pe + pH conditions: flooding + N₂ (T1), flooding (T2), 70% water holding capacity (T3), and 70% water holding capacity + O₂ (T4). Chemical analysis and X-ray diffraction (XRD) were used to identify the mineralogical phases and species of Fe and Cd in paddy soils. The results show that the decrease of soil pe + pH level favored the transformation of well-crystallized Fe oxides (Fe_c), such as hematite and goethite, into poorly-crystallized (Fe_o) and organically-complexed (Fe_p) forms. The transformation promoted the binding of Cd to Fe oxides and was primarily responsible for up to a 41.8% decrease of soil DTPA (diethylenetriaminepentaacetic acid)-extractable-Cd content. In addition, the decline in pe + pH value reduced Fe concentrations in soil particle fractions of 0.2-2-mm (17.8%-30.6%) and <0.002-mm (20.7%-31.7%) of the two flooding treatments. The decreased Fe concentrations were closely associated with less Fe_c contents in these same fractions and more Fe_o and Fe_p in coarser aggregates (P < 0.01). Importantly, the increase in contents of Fe_o and Fe_p in the 0.002-2 mm fraction were significantly correlated with content of Fe-/Mn-oxide-bound Cd (OX-Cd) in larger particle-size fractions (P < 0.01). Furthermore, the increasing content of OX-Cd played a crucial role in reducing DTPA-Cd content. This study demonstrates that low pe + pH values favor the transformation of crystalline Fe oxides into a poorly-crystallized and organically-complexed phase, which facilitates Cd accumulation in coarser aggregates and enhances Cd stability in paddy soils.