Simultaneous determination of eight neonicotinoid insecticides, fipronil and its three transformation products in sediments by continuous solvent extraction coupled with liquid chromatography-tandem mass spectrometry.

Neonicotinoids (NEOs) and fipronil (FIP) are insecticides that are widely used in modern agriculture and have received considerable attention in recent years due to their adverse effects on non-target organisms in the environment. In the present study, a new method to simultaneously detect eight common NEO insecticides and FIP and its three transformation products (FIPs) in sediments was developed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) based on a combined pretreatment of continuous solvent extraction (CSE) and solid phase extraction (SPE). Under optimized conditions, 5.0 g of freeze-dried sediment samples were initially extracted with methanol (20 mL)-methanol (15 mL)-water (20 mL) in sequence, and then the extract was cleaned with hydrophilic-lypophilic balance SPE cartridges, and HPLC-MS/MS analysis was conducted. The established method was validated to be sensitive, linear, accurate, and precise. The limits of detection (LOD) and limits of quantification (LOQ) of target compounds were 0.012-0.055 μg/kg d.w and 0.031-0.091 μg/kg d.w, respectively. Good linearity (R2 > 0.990) was observed between 4.0 × 10-2 and 20.0 μg/kg d.w. The recovery rates of all target insecticides were between 75.5% and 98.5%, and the relative standard deviations (RSD) were all less than 15.0% at the low, medium, and high spiked levels. Finally, the optimized method was applied to analyze 12 target insecticides in the sediments obtained from Jiaozhou Bay of China and its main inflow rivers. Acetamiprid, thiamethoxam, fipronil sulfide, and fipronil sulfone were detected in the river sediment samples at the concentration from <LOQ to 0.197 μg/kg d.w. Thus, the two types of studied insecticides can enter the sedimentary environment. Overall, the proposed method can be used to investigate the contamination status of typical NEOs and FIP insecticides in sediments and provide base data to comprehensively understand their environmental behavior, safety, and fate.