Effect of wetting-drying cycles on the Cu bioavailability in the paddy soil amended with CuO nanoparticles

The extensive application of metal-based nanoparticles can pose environmental risks, but how the alternation of wet and dry caused by natural precipitation and artificial irrigation affects the environmental fate of nanoparticles is still unclear. Here, we investigated the underlying mechanisms of wetting-drying cycles (WDCs) on the Cu bioavailability in paddy soil treated with CuO nanoparticles (100 and 500 mg/kg) during 140 days by comparing with drought and flooding conditions. The results show that soil moisture content greatly affected the soil pH and redox potential. The bioavailable Cu contents in the WDCs exposed to CuO nanoparticles were positively correlated to moisture content and WDCs number. The fit result of the pseudo-second-order equation indicates that WDCs greatly prevented the aging process of Cu in soil. Furthermore, WDCs transformed oxidizable Cu to water-soluble, acid extractable and reducible Cu. WDCs markedly promoted the degradation of dissolved organic matter and the transformation of acid-soluble sulfate to water-soluble inorganic sulfate, meanwhile, significantly enhanced the contents of crystalline iron oxides by 22-57% and 82-326% with respect to drought and flooding, but reduced the level of ferrous iron by 37-67% compared to the flooding. µ-XRF analysis shows that the fate of CuO nanoparticles might be mainly determined by Fe under WDCs condition but by S in flooded soil. This study can provide a comprehensive assessment on the impact of natural precipitation and artificial irrigation on the environmental risks of MNPs.