title: Suspect screening and quantification of trace organic explosives in wastewater using solid phase extraction and liquid chromatography-high resolution accurate mass spectrometry.
abstract: The first comprehensive assessment of 34 solid phase extraction sorbents is presented for organic explosive residues in wastewater prior to analysis with liquid chromatography-high resolution accurate mass spectrometry (LC-HRMS). A total of 18 explosives were selected including nitramines, nitrate esters, nitroaromatics and organic peroxides. Three polymeric divinylbenzene-based sorbents were found to be most suitable and one co-polymerised with n-vinyl pyrrolidone offered satisfactory recoveries for 14 compounds in fortified wastewater (77-124%). Limits of detection in matrix ranged from 0.026-23μgL-1with R2≥0.98 for most compounds. The method was applied to eight 24-h composite wastewater samples from a London wastewater works and one compound, 2,4-dinitrotoluene, was determined over five days between 332 and 468g day-1(225-303ngL-1). To further exploit the suspect screening capability, 17 additional explosives, precursors and transformation products were screened in spiked wastewater samples. Of these, 14 were detected with recoveries from 62 to 92%, highlighting the broad applicability of the method. To our knowledge, this represents the first screen of explosives-related compounds in wastewater from a major European city. This method also allows post-analysis detection of new or emerging compounds using full-scan HRMS datasets to potentially identify and locate illegal manufacture of explosives via wastewater analysis.
authors.affiliation: Analytical & Environmental Sciences Division, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London SE1 9NH, UK.
authors.forename: Helena
authors.initials: H
authors.lastname: Rapp-Wright
authors.affiliation: Analytical & Environmental Sciences Division, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London SE1 9NH, UK.
authors.forename: Gillian
authors.initials: G
authors.lastname: McEneff
authors.affiliation: Analytical & Environmental Sciences Division, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London SE1 9NH, UK.
authors.forename: Bronagh
authors.initials: B
authors.lastname: Murphy
authors.affiliation: UCL Department of Security and Crime Science, 35 Tavistock Square, London WC1H 9EZ, UK.
authors.forename: Sally
authors.initials: S
authors.lastname: Gamble
authors.affiliation: UCL Department of Security and Crime Science, 35 Tavistock Square, London WC1H 9EZ, UK.
authors.forename: Ruth
authors.initials: R
authors.lastname: Morgan
authors.affiliation: Forensic Explosives Laboratory, Dstl Fort Halstead, TN14 7BP, UK.
authors.forename: Matthew
authors.initials: M
authors.lastname: Beardah
authors.affiliation: Analytical & Environmental Sciences Division, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London SE1 9NH, UK. Electronic address: leon.barron@kcl.ac.uk.
authors.forename: Leon
authors.initials: L
authors.lastname: Barron
keywords: 2,4-dinitrotoluene; Energetic materials; Micro-pollutants; Sample preparation; Sewage epidemiology