Ge and Si differ strongly in their biogeochemical behavior due to the differences in binding capacity to organic matter. The mechanisms of soil organic matter affecting the mobility and bioavailability of Ge in soil-plant system remain unclear. This work aimed to investigate the soil Ge fractions and Ge binding to humic substances in paddy soil. Paddy soil samples taken from Changxing County, Zhejiang Province, China, were investigated by the sequential extraction method. Humic acid (HA) and fulvic acid (FA) isolated from paddy soils were characterized by Fourier transform infrared spectrometry (FT-IR) and 3-dimensional excitation-emission matrix (3D-EEM). The effect of humic substances on the binding of Ge was studied by fluorescence-quenching titration. Results showed that residual Ge was the dominant fraction in soil (up to 85%). The mobile Ge, organic matter bound Ge and easily reduceable compounds bound Ge accounted for approximately 10% of soil TGe and may represented critical labile pools of soil Ge. Organic matter bound Ge significantly correlated (r = 0.56, p < 0.01) with rice Ge concentrations. The fluorescence of HA and FA was markedly quenched by the addition of Ge. The conditional stability constant of HA-Ge complexes was larger than that of FA-Ge complexes, and the complexation capacity of HA-Ge complexes was lower than that of FA-Ge complexes. Humic substances played a dual role in affecting the behavior of dissolved Ge in paddy soil. HA formed stable complexes with Ge and tended to sequester Ge, while FA formed soluble and unstable complexes with Ge and tended to act as a Ge carrier in soil-plant system.
Keywords: Complexation; Germanium; Humic substances; Organic matter-bound germanium; Soil germanium fractions; Stability constants.