Improved determination of femtogram-level organic explosives in multiple matrices using dual-sorbent solid phase extraction and liquid chromatography-high resolution accurate mass spectrometry

Abstract

Identification and trace quantification of multiple explosives residues, their precursors and transformation products in complex samples remains very challenging. For solid phase extraction (SPE) and liquid chromatography-high resolution accurate mass spectrometry-based methods (LC-HRMS), interferences from co-extracted matrix components can significantly affect recovery during extraction and/or detector signal. The aim of this work was to develop a new, improved and more generalisable extraction approach to trace explosives analysis in a range of matrices using dual-sorbent SPE with LC-HRMS. Recoveries of 44 organic explosives from model solutions were optimised and compared for seven different sorbents (Oasis HLB, HyperSep Retain PEP and Isolute ENV+, HyperSep SAX, HyperSep NH2, Strata Alumina-N and Bond Elut CN). On average, Oasis HLB and Isolute ENV+ yielded the best recoveries (>80%). For three sorbents, mean recoveries remained ≤1%, which made them potentially suitable for matrix removal when used in series with more analyte-selective sorbents. To evaluate matrix effects, a range of aqueous (river- and wastewater), solid (soil), dirty (road sign swabs), oily (oven hood swabs) and biological (dried blood) samples were selected based on complexity and forensic relevance. With the exception of river water, matrix effects were lowest using dual-sorbent SPE, with little/no compromise in recovery. Quantitative method performance assessment is presented for 14 selected explosives, representative of different classes, molecular weights and volatilities, and across three different matrices (i.e. untreated wastewater, cooking oil residues and dried blood). Limits of detection improved by ∼10-fold over a single sorbent approach, enabling low fg sensitivity in many cases. Finally, application of the method to untreated wastewater enabled detection of new explosives traces for the first time, which could be used to help identify clandestine manufacture or sources of environmental toxicity. This approach offered a versatile solution to sample preparation for robust and highly sensitive detection/quantification of large numbers of explosives residues in a range of complex sample types.