Dissolved organic matter (DOM) serves as a critical link in the migration and transformation of heavy metals at the soil–solid interface, influencing the migration behaviour and transformation processes of Cu²⁺ in soil. There have been studies on the combination mechanisms between DOM and Cu²⁺ in paddy soils. However, the adsorption/complexation and redox processes between DOM and Cu²⁺ in other agricultural soil types (such as dry farmland and vegetable fields) are unclear. In order to reveal the combination process of DOM with Cu in different agricultural soil types and the dynamic changes in chemical behaviour that occur, this study analysed the variability of DOM components and structure in three soils using three-dimensional fluorescence spectroscopy and X-ray photoelectron spectroscopy. In addition, the priority order of different DOM compounds in combination with Cu and the change process in relation to the Cu valence state in the soil of Lujiang County, Anhui Province, was revealed based on laboratory experiments. The results showed that the composition of soil DOM was mainly composed of humic-like and fulvic-like substances with a clear terrestrial origin and that the organic matter showed a high degree of decomposition characteristics. The results indicated that the composition of soil DOM is mainly composed of humic and fulvic acid-like substances, and they have obvious characteristics of terrestrial origin. In addition, the soil organic matter showed high decomposition characteristics. The complex stability constants (lgK_M) of humic acid-like substances with Cu²⁺ follow the order of forest land (lgK_M = 5.21), vegetable land (lgK_M = 4.90), and dry farmland (lgK_M = 4.88). The lgK_M of fulvic acid-like substances with Cu²⁺ is in the order of dry farmland (lgK_M = 4.51) and vegetable land (lgK_M = 4.39). Humic acid-like substances in soil DOM combine preferentially with Cu²⁺, showing a stronger chelating affinity than fulvic acid-like substances. Cu²⁺ complexes mainly include hydroxyl, phenolic hydroxyl and amino functional groups are included in soil DOM, accompanied by redox reactions. In comparison to dry farmland, the soil DOM in forest and vegetable fields undergoes more intense redox reactions simultaneously with the chelation of Cu²⁺. Therefore, the application of organic fertilisers to vegetable and forest soils may lead to uncertainties concerning the fate of heavy metals with variable chemical valence. These results contribute to a deeper understanding of the interaction mechanisms between DOM and Cu²⁺ in agricultural soils.

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