Precursor ion scanning-mass spectrometry for the determination of nitro functional groups in atmospheric particulate organic matter

An analytical method for the quantitative determination of the total nitro functional group (R-NO2) content in atmospheric particulate organic matter is developed, The method is based on the selectivity of NO2- (m/z 46) precursor ion scanning (PAR 46) by atmospheric pressure chemical ionization-tandem mass spectrometry (APCI-MS/MS). PAR 46 was experimented on 16 nitro compounds of different molecular structures and was compared with a neutral loss of NO (30 amu) technique in terms of sensitivity and efficiency to characterize the nitro functional groups. Covering a wider range of compounds, PAR 46 was preferred and applied to reference mixtures containing all the 16 compounds under study. Repeatability carried out using an original statistical approach, and calibration experiments were performed on the reference mixtures proven the suitability of the technique for quantitative measurements of nitro functional groups in samples of environmental interest with good accuracy. A linear range was obtained for concentrations ranging between 0.005 and 0.25 mM with a detection limit of 0.001 mM of nitro functional groups. Finally, the analytical error based on an original statistical approach applied to numerous reference mixtures was below 20%. Despite of potential artifacts related to nitro-alkanes and organonitrates, this new methodology offers a promising alternative to FT-IR measurements. The relevance of the method and its potentialities are demonstrated through its application to aerosols collected in the EUPHORE simulation chamber during o-xylene photooxidation experiments and in a suburban area of a French alpine valley during summer. (c) 2008 Elsevier B.V. All rights reserved.