Fungicide application can intensify clay aggregation and exacerbate copper accumulation in citrus soils

Highlights: • Fungicide application introduces more copper into citrus soils. • Copper reduces negative surface charge of clay and favours clay aggregation. • Increasing doses of fungicides inadvertently inhibit clay transport. • Co-aggregation of clay and fungicides exacerbate the contamination in citrus soils. Fungicide application for controlling fungal diseases can increase copper (Cu) accumulation in soil. More urgently, Cu released from fungicides can associate with soil clay and favour the mutual aggregation of Cu and soil clay, thereby potentially intensifying the accumulation of Cu. We investigated the effects of Cu salt and six common Cu-based fungicides on colloidal dynamics of a clay fraction from citrus cultivated soil. Batch experiments were carried out to provide the loading capacity of the clay fraction for Cu. The colloidal dynamic experiments were performed over a pH range from 3 to 8 following a test tube method, while surface charge, the key electrochemical factor of the solid-liquid interface, was quantified by a particle charge detector. It was found that all the studied fungicides, via releasing Cu²⁺, acted to effectively favour clay aggregation. The dissolved organic matter obtained from the dissolution of polymers in fungicides can theoretically stimulate clay dispersion. However, their effects were obscured due to the overwhelming effect of Cu²⁺. Therefore, Cu²⁺ appears as the most active agent in the fungicides that intensifies clay aggregation. These findings imply that the intensive application of fungicides for plant protection purposes can inadvertently reduce clay mobility, favour the co-aggregation of clay and fungicides, and hence potentially exacerbate the contamination of the citrus soil.