Simultaneous determination of neonicotinoid insecticides in sunflower-treated seeds (hull and kernel) by LC-MS/MS

A validated analytical method to determine seven neonicotinoids (dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid, acetamiprid and thiacloprid) in sunflower seeds (hull and kernel) using HPLC coupled to electrospray ionisation mass spectrometry (ESI-MS) is presented. Sample clean-up based on a solid–liquid extraction, and the removal of lipid fraction, in the case of kernels, is proposed and optimised. Low limits of detection and quantification were obtained, ranging from 0.3 × 10^–3 to 1.2 × 10^–3 µg g^–1 and from 1.0 × 10^–3 to 4.0 × 10^–3 µg g^–1, with good precision, and recovery values ranged from 90% to 104% for hulls and kernels. The method was applied for the analysis of five thiamethoxam-dressed sunflower seeds and four non-treated seeds, where, besides thiamethoxam, residues of the other neonicotinoid, clothianidin, were also detected and confirmed via tandem mass spectrometry (LC-ESI-MS/MS). Finally, the presence of residues of thiamethoxam and clothianidin in collected sunflower seeds (hulls) coming from coated seeds confirmed the translocation of these neonicotinoids through the plant up to these seeds.