BackgroundImidacloprid is among the most widely used insecticides and today is found in surface and ground water worldwide. It has been registered in the EU watchlist for monitoring. To prevent imidacloprid from entering water bodies, advanced oxidation processes (AOP) have been intensely researched. Photo-irradiation proved one of the most efficient methods to degrade and eliminate anthropogenic micropollutants from waters. The ecotoxicity assessment of photoinduced degradation and transformation products especially in the absence of reference standards is still heavily explored.ResultsIn this study, UVA and UVC irradiation in combination with titanium dioxide P25 as photocatalyst were investigated for their degrading and eliminating effects and effectiveness on imidacloprid. Humic acid was used as natural organic matter additive. High-performance liquid chromatography coupled with high-resolution mass spectrometry allowed to identify and monitor imidacloprid and its degradation intermediates yielding seven new structures and concentration–time (c–t) profiles. The correlation of structures and the application of radical scavengers and photocatalyst helped distinguish between direct photoinduced and indirect hydroxyl radical-induced degradation mechanisms. The identification of hydroxylated products and intermediates indicated the indirect degradation pathway, which could be suppressed by addition of a radical scavenger. The absence of hydroxylated intermediates and fragments pointed towards the direct absorption-induced degradation. Two degradations products were traced back to the direct mechanism, whereas all other products followed the indirect mechanism. The ecotoxicity of the identified compounds was assessed by quantitative structure–activity relationship (QSAR) analysis. Most products were predicted as less ecotoxic. Ecotoxicity equivalents (ETEs) were introduced allowing a classified ranking of the products and an assessment of the overall hazardous potential of the irradiated solution at a given moment. Generally, the number of hydroxyl substituents was inversely correlated to ecotoxicity. From the c-t curves, time-dependent ETE profiles were established.ConclusionsStructure elucidation and c-t profiles from liquid chromatography–high-resolution mass spectrometry allowed to distinguish between direct and indirect degradation mechanisms. Structure specific ecotoxicity assessment could be achieved through QSAR analysis. Ecotoxicity hazard was ranked based on ETEs. The time-dependent ETE profile proved suitable to reflect the effect of irradiation duration and allow to estimate the irradiation time required to eliminate ecotoxicity, which may be relevant for potential applications in wastewater treatment plants.