Suspect screening and quantification of trace organic explosives in wastewater using solid phase extraction and liquid chromatography-high resolution accurate mass spectrometry

Helena Rapp-Wright; Gillian McEneff; Bronagh Murphy; Sally Gamble; Ruth Morgan; Matthew Beardah; Leon Barron

doi:10.1016/j.jhazmat.2017.01.008

Suspect screening and quantification of trace organic explosives in wastewater using solid phase extraction and liquid chromatography-high resolution accurate mass spectrometry

J Hazard Mater. 2017 May 5:329:11-21. doi: 10.1016/j.jhazmat.2017.01.008. Epub 2017 Jan 6.

Authors

Helena Rapp-Wright¹, Gillian McEneff¹, Bronagh Murphy¹, Sally Gamble², Ruth Morgan², Matthew Beardah³, Leon Barron⁴

Affiliations

¹ Analytical & Environmental Sciences Division, King's College London, Franklin-Wilkins Building, 150 Stamford Street, London SE1 9NH, UK.
² UCL Department of Security and Crime Science, 35 Tavistock Square, London WC1H 9EZ, UK.
³ Forensic Explosives Laboratory, Dstl Fort Halstead, TN14 7BP, UK.
⁴ 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.

PMID: 28119193
DOI: 10.1016/j.jhazmat.2017.01.008

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^-1 with 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.

Keywords: 2,4-dinitrotoluene; Energetic materials; Micro-pollutants; Sample preparation; Sewage epidemiology.