Comparison of salting-out assisted liquid-liquid extraction to polymeric solid phase extraction for liquid chromatography tandem mass spectrometry of neonicotinoids insecticides and metabolites in wastewater: Occurrence and aquatic risk assessment.

Neonicotinoids are among the most widely used insecticides worldwide. Many studies have revealed that this class of pesticides, used both in agricultural crops and for insect control in cities, can be metabolized to a variety of different compounds with varying effects in the environment and to human health. Considering the widespread use of neonicotinoids and likely occurrence of metabolites, new methodologies that evaluate the presence of these compounds in water and wastewater are crucial to better understand occurrence, exposure and to develop exposure control strategies. This study compares trace-level analysis of 7 neonicotinoids and 11 neonicotinoid metabolites in municipal wastewater samples, using polymeric solid phase extraction (SPE) and salting-out assisted liquid-liquid extraction (SALLE) sample preparation methodologies for liquid chromatography tandem mass spectrometry, with a new enhanced efficiency Uni-Spray™ ion source. Extraction comparison showed advantages of both methods and demonstrated good recovery to quantify the analytes at very low levels. Method detection limits of the SALLE method ranged from 0.0031 to 0.086 μg L. Nine effluent and nine influent samples, collected from wastewater treatment plants from 7 cities across Nebraska, were extracted by the SALLE method and analyzed by LC-MS/MS. Results showed that six compounds were not detected in these samples (clothianidin-desmethyl, thiacloprid, thiacloprid-amide, imidacloprid-olefin, thiamethoxam-urea and 5-hydroxy-imidacloprid), and the highest average measured concentrations were observed for clothianidin-urea, clothianidin, and dinotefuran (0.29, 0.11, and 0.088 μg L, respectively). In silico predictions of preliminary aquatic-life risk assessment demonstrated that no compound occurred above environmental risk concentrations. There are no wastewater discharge limits established for the contaminants evaluated, however, the measured wastewater concentrations for imidacloprid and clothianidin exceed limits established by U.S. EPA and RIVM for freshwater. The method demonstrates great potential as an occurrence and exposure monitoring method for neonicotinoids and their metabolites in wastewater.