Impact of (nano)formulations on the distribution and wash-off of copper pesticides and fertilisers applied on citrus leaves

This study compares the rainfastness of nine forms of Cu, including nano and conventional Cu-based fungicide formulations, as well as their salt or bulk equivalents. Rainfastness is the ability to resist wash-off; it is a key property for improving pesticide formulations and for assessing the potential transfer of pesticides to the soil. A new protocol was developed to characterise losses of Cu from treated leaves. It consisted of dipping the leaves in rainwater and then in an acid/ethanol mixture followed by size fractionation. The proportion of Cu lost by wash-off from citrus leaves ranged from <2% (Tribasic, nCuO or Cu(OH)(2)) up to 93% (CuSO4) of the initial amount of Cu applied. Intermediate Cu losses were observed for formulations with silica (nano)particles (9-14% of applied Cu), Kocide (22 %), ChampDP (31 %), and a formulation with graphene oxide (47 %). Smaller particles generally resulted in less wash-off, possibly due to stronger attachment to the leaf surface, but other factors such as the particle shape and solubility also played an essential role. The retention of nCuO to the leaves was particularly high, and the exact mechanisms involved (e.g. foliar uptake) deserve further work. Most of the Cu was washed off in its ionic form (>74 %). Two Cu formulations (one commercial formulation and the formulation with graphene oxide) also showed wash off in significant proportions of Cu (similar to 17 %) in the nano-sized fraction. This study provides essential information on the amounts and forms of Cu that may reach the soil after the application of Cu-based agrochemicals. The great diversity in behaviour across the range of formulations considered highlights the need for more systematic research to fully exploit the potential improvements of current agrochemicals through (nano)formulation technologies.