Measuring urinary concentrations of neonicotinoid insecticides by modified solid-phase extraction-ultrahigh performance liquid chromatography-tandem mass spectrometry: Application to human exposure and risk assessment.

Neonicotinoid insecticides are the most widely used insecticides in the world. However, some experiments in vivo and vitro have shown association between neonicotinoids exposure and adverse effects in non-target mammals. The aims of this study were to 1) develop a robust method for simultaneous quantification of urinary neonicotinoids with a wide water solubility range by modified solid-phase extraction-ultrahigh performance liquid chromatography- tandem mass spectrometry and 2) quantify the concentrations of ten neonicotinoids in 386 adolescents in Chongqing of Southwest China by using the developed method and assess health risks of exposure to neonicotinoids. The introduction of extractive crystallization effectively removed interfering inorganic salts and improved the sensitivity of the method. The mean recoveries of all the analytes were satisfactory in the range of 89.1-104.8% and the limits of detection ranged from 0.001 to 0.02 ng/mL. The developed method was sensitive, accurate and suitable for trace detection and batch analysis in biomonitoring-based studies. Of the ten examined neonicotinoids, acetamiprid had the highest geometric mean concentration (49.43 μg/g creatinine), followed by clothianidin (5.01), imidacloprid (3.80), thiamethoxam (3.24), thiacloprid (2.25), nitenpyram (1.79), dinotefuran (1.76), sulfoxaflor (1.65), imidaclothiz (1.28) and flonicamid (1.01). High detection rates of neonicotinoids (79.3-100.0%) indicated a ubiquitous adolescents' exposure to neonicotinoids in urban areas of Chongqing. Nevertheless, hazard quotient and hazard index data exhibited a low health risk caused by the individual and cumulative exposure to neonicotinoids on the basis of the reference limit values recommended by the U.S. Environmental Protection Agency and the National Food Safety Standard of China.