Pharmaceuticals are identified in insects in River Fyris – A study with both tandem quadrupole and quadrupole-time-of-flight mass spectrometry

Abstract

The internal concentrations of active pharmaceutical compounds in insects/macroinvertebrates in River Fyris, Uppsala, Sweden, have for the first time been investigated. Specimen of backswimmer, caddisfly larva, damselfly larva, mayfly larva and water louse were caught in the river downstream a waste-water treatment plant. After homogenization and extraction, analysis was carried out with Ultra-High Performance Liquid Chromatography – Electrospray – Tandem Mass Spectrometry (UHPLC-ESI-MS/MS) using both a tandem quadrupole (QqQ) and a quadrupole-time-of-flight (qToF) mass spectrometer. A combined qualitative/quantitative screening method for 89 pharmaceutical compounds in the selective reaction monitoring mode was applied to the samples using the QqQ instrument. Thirty-three different drugs were detected and quantified in the macroinvertebrate samples, covering a wide range of pharmacological classes, the most common being antidepressants, psycholeptics and antihistamines. Drug concentrations up to 260 ng/g (for tetracycline) were determined. A subset of thirteen compounds were selected for a complementary qualitative UHPLC-qToF-MS/MS analysis. This way, the confidence in the substance identifications was significantly strengthened by the availability of full scan high-resolution spectra and accurate mass measurements. This is the first study demonstrating the uptake of pharmaceuticals in water-living macroinvertebrates in Sweden. Since these organisms are in the lower part of the food chain, pharmaceuticals might accumulate in predators leading to ecotoxicological effect at higher trophic levels. Macroinvertebrates might be promising indicator organisms for pharmaceutical pollution.

Keywords

• Pharmaceuticals
• Insects
• Macroinvertebrates
• Internal concentration
• Mass spectrometry
• Liquid chromatography