title: Characterizing an extractive electrospray ionization (EESI) source for the online mass spectrometry analysis of organic aerosols.
abstract: Organic compounds comprise a major fraction of tropospheric aerosol and understanding their chemical complexity is a key factor for determining their climate and health effects. We present and characterize here a new online technique for measuring the detailed chemical composition of organic aerosols, namely extractive electrospray ionization mass spectrometry (EESI-MS). Aerosol particles composed of soluble organic compounds were extracted into and ionized by a solvent electrospray, producing molecular ions from the aerosol with minimal fragmentation. We demonstrate here that the technique has a time resolution of seconds and is capable of making stable measurements over several hours. The ion signal in the MS was linearly correlated with the mass of aerosol delivered to the EESI source over the range tested (3-600 μg/m(3)) and was independent of particle size and liquid water content, suggesting that the entire particle bulk is extracted for analysis. Tandem MS measurements enabled detection of known analytes in the sub-μg/m(3) range. Proof-of-principle measurements of the ozonolysis of oleic acid aerosol (20 μg/m(3)) revealed the formation of a variety of oxidation products in good agreement with previous offline studies. This demonstrates the technique's potential for studying the product-resolved kinetics of aerosol-phase chemistry at a molecular level with high sensitivity and time resolution.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom.
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Gallimore
authors.forename: Markus
authors.initials: M
authors.lastname: Kalberer
mesh_terms: D000336:Aerosols / Q000032:analysis* / Q000737:chemistry; D000393:Air Pollutants / Q000032:analysis* / Q000737:chemistry; D004784:Environmental Monitoring / Q000295:instrumentation* / Q000379:methods; D019301:Oleic Acid / Q000032:analysis / Q000737:chemistry; D009862:Online Systems; D010126:Ozone / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000295:instrumentation*; D053719:Tandem Mass Spectrometry; D013644:Tartrates / Q000032:analysis
chemical_list: D000336:Aerosols; D000393:Air Pollutants; D013644:Tartrates; D019301:Oleic Acid; D010126:Ozone; C029768:tartaric acid