Simultaneous multi-residue pesticide analysis in soil samples with ultra-high-performance liquid chromatography–tandem mass spectrometry using QuEChERS and pressurised liquid extraction methods

Abstract

To assess soil contamination, it is important to be able to measure different classes of pesticides simultaneously. For this reason we developed a sensitive ultra-high-performance liquid chromatography–tandem mass spectrometry method for the simultaneous analysis of 25 pesticides in soil samples. Multi-class pesticides (triazines, phenylureas, phenoxy acid pesticides etc.) were analysed using a single mass spectrometry method with a fast polarity switching option, allowing the analysis of 19 compounds in the positive ionisation mode and six compounds in the negative ionisation mode. Extraction of pesticides from soil samples was performed employing a pressurised liquid extraction (PLE) and a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure, recently developed for the extraction of multi-residue pesticides from food matrices. The extraction efficiency, performance and recoveries of these two procedures were evaluated and compared. In addition, we studied the effect of matrix on signal suppression or enhancement. Isotope-labelled internal standards (ILIS) were used to compensate the suppression or enhancement of signal intensities in the extracted samples. The method was validated using reference soil material (EUROSOIL 7) spiked with 50 μg/kg of each pesticide. The average recovery by PLE varied between 65.1% and 122.2% with RSDs of 1.7–23.4%. QuEChERS provided better recoveries for most of the pesticides, the extraction recovery ranging from 79.4% to 113.3% with RSDs of 1.0–12.2%. Limits of quantification for all target compounds were within a range of 0.1–2.9 µg/kg.

Keywords:

• pesticides
• soil analysis
• ultra-high-performance liquid chromatography
• mass spectrometry
• QuEChERS
• pressurised liquid extraction

Acknowledgements

The authors would like to thank Dr. Martin Krauss (Helmholtz-Zentrum für Umweltforschung UFZ, Leipzig, Germany) and Dr. Thomas Poiger (Agroscope, Wädenswil, Switzerland) for their inputs during the method development and for the selection of pesticides, and Tobias Doppler (Eawag, Dübendorf, Switzerland) for providing the agricultural soil samples. Dominique Grandjean (École Polytechnique Fédérale de Lausanne EPFL, Lausanne, Switzerland) assisted with the UHPLC–MS/MS instrumentation and Alexandre Paccou (Waters, Paris, France) in the method development.