The spectral characteristics and cadmium complexation of soil dissolved organic matter in a wide range of forest lands

The quality and quantity of dissolved organic matter (DOM) greatly controls the fate of heavy metals. The characteristics of DOM and its interaction with metals are essential for the metal ecological risk assessment of soils. In this study, the DOM spectral characteristics of representative forest soils and the complex capacities between fluorescent DOM components and cadmium (Cd) were analyzed. Functional groups, such as carboxylic acids, alcohols and phenols, were determined by FT-IR analysis. Chromophoric DOM, fluorescent DOM and dissolved organic carbon (DOC) concentrations exhibited strong correlations with each other, indicating that variations of DOC could be well explained by Chromophoric DOM or fluorescent DOM due to high correlation coefficients. The spectral slope ratio was in the range of 0.85–5.90, implying an abundance of heavy macromolecular humic acids, peptides, and polycondensates. The absorbance spectral at 254 nm (SUVA₂₅₄) strongly correlated with SUVA₂₆₀ (r = 0.992, P < 0.01), indicating that hydrophobicity closely related with aromatic structure, and aromatic groups could be broadly hydrophobic. Fluorescence indices were from 1.62 to 2.21 and biological index values ranged from 0.54 to 1.14, where the DOM was mainly sourced from mixed terrestrial and autogenous inputs in most sites. Four universal fluorescence components were identified and characterized by fluorescence EEM-PARAFAC, including two humic-like (components 1 and 2), one tyrosine-like (components 3) and one fulvic-like (components 4) component. Both components 3 and 4 showed fluorescence quenching with increasing Cd concentrations, while components 1 and 2 had no evident change in fluorescence intensity. The logK₃ and logK₄ values ranged from 4.41 to 5.29 and 4.71 to 5.54, respectively, with most logK values of component 3 for Cd binding being smaller than that of component 4, thus, indicating that the fulvic acid substances exhibited stronger and more stable interactions with Cd than protein-like components.