Inference of emission history of neonicotinoid pesticides from marine sediment cores impacted by riverine runoff of a developed agricultural region: The Pearl River Basin, China.

Neonicotinoids (NEOs), as the most-consumed pesticides on a global scale, have posed a serious threat to human health and ecological environment. Information regarding the emission history of NEOs is of great importance to improve the prediction of their environmental loading and biological risk potential. In the present study, contamination levels and compositions of 12 NEOs were identified in 8 sediment cores from the Lingdingyang Estuary, which was impacted by agricultural emissions in riverine runoff of the Pearl River Basin for centuries. The total concentration of 12 target NEOs (∑NEOs) ranged from 0.02 to 69.5 ng/g dw along the sediment core profile, with a mean of 12.9 ± 15.9 ng/g dw. Net deposition fluxes and concentrations of 5 parent NEOs experienced a remarkable exponential increase in the vertical profile of sediment cores, except for imidacloprid (IMI). Despite the similar exponential growth before 2012, subsequent decreased levels of IMI in historical sediment indicated its gradual replacement by other NEOs. IMI was the NEO with the highest frequency of 80.3% and the highest mean concentration of 7.66 ± 8.76 ng/g dw. The ecological risk assessment of NEOs suggests that 65.1% of sediment samples exceeded the chronic threshold for aqueous organisms using equilibrium partitioning approach. Since downward diffusion of NEOs in the Lingdingyang Estuary was rectified by their rapid desorption, the sedimentary record probably provided an accurate illustration of agricultural NEO emissions in the Pearl River Basin, China. The recent NEO inventory in the adjacent waters of core sites was estimated with a mean of 76.8 tons/yr. This study provides insights into the role of agricultural emission in riverine runoff in the environmental loads of NEOs in the historical sediment.