Two optimized methods for the quantification of anthropogenic and biogenic markers in aerosol samples using liquid chromatography mass spectrometry and gas chromatography mass spectrometry

Abstract. In this study, we present two optimized analytical methods for the quantification of molecular markers to attribute the contribution of various Volatile Organic Compounds (VOC) oxidation products to Secondary Organic Aerosol (SOA). Those involve Ultrahigh Performance Liquid Chromatography Electrospray Ionization coupled to Ion Mobility Time of Flight Mass Spectrometry (UPLC/ESI-IMS-QTOFMS) and Gas Chromatography Mass Spectrometry (GC-MS). Liquid extraction was performed for both techniques, with an extra derivatisation step with N,O-Bis(trimethylsilyl)trifluoroacetamide (BSTFA) containing 1 % trimethylchlorosilane (TMCS) for GC-MS analysis, enhancing the compound detection capacity. Between the two techniques, 23 biogenic and anthropogenic markers were identified, with five common species detected. Recoveries > 80 % were observed for nitro-containing compounds and > 66 % for aromatic and non-aromatic acids except for 3-methyl-1,2,3-butanetricarboxylic acid. Limits of detection < 5 ng were observed by UPLC/ESI-IMS-QTOFMS analysis for 4-nitrophenol and 2-methyl-4-nitrophenol, while GC-MS (with BSTFA derivatisation) analysis allowed better detection of lower mass compounds (for example limit of detection for 2-methylerythritol was 0.10 ng). While UPLC/ESI-IMS-QTOFMS allow the analysis of high molecular weight compounds at high resolution and sensitivity, GC-MS analysis focus on compounds of lower mass and higher polarity, together, these complementary methods provide a comprehensive tool for the quantification of organic markers arising from the airborne transformation of compounds of both biogenic and anthropogenic origins.