1. Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols
- Author
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Renato Zenobi, Markus Kalberer, Urs Baltensperger, Christian Panse, Christian Emmenegger, Bertran Gerrits, Alain Reinhardt, Josef Dommen, University of Zurich, and Kalberer, M
- Subjects
Aerosols ,1602 Analytical Chemistry ,Molecular mass ,Kendrick mass ,Chemistry ,Analytical chemistry ,610 Medicine & health ,10071 Functional Genomics Center Zurich ,Mass spectrometry ,Ion cyclotron resonance spectrometry ,Sensitivity and Specificity ,Fourier transform ion cyclotron resonance ,Mass Spectrometry ,Analytical Chemistry ,Mass ,Molecular Weight ,Spectroscopy, Fourier Transform Infrared ,Mass spectrum ,570 Life sciences ,biology ,U7 Systems Biology / Functional Genomics ,Organic Chemicals ,Low Mass - Abstract
Organic aerosols are a major fraction, often more than 50%, of the total atmospheric aerosol mass. The chemical composition of the total organic aerosol mass is poorly understood, although hundreds of compounds have been identified in the literature. High molecular weight compounds have recently gained much attention because this class of compounds potentially represents a major fraction of the unexplained organic aerosol mass. Here we analyze secondary organic aerosols, generated in a smog chamber from alpha-pinene ozonolysis with ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). About 450 compounds are detected in the mass range of m/z 200-700. The mass spectrum is clearly divided into a low molecular weight range (monomer) and a high molecular weight range, where dimers and trimers are distinguishable. Using the Kendrick mass analysis, the elemental composition of about 60% of all peaks could be determined throughout the whole mass range. Most compounds have high O:C ratios between 0.4 and 0.6. Small compounds (i.e., monomers) have a higher maximum O:C ratio than dimers and trimers, suggesting that condensation reactions with, for example, the loss of water are important in the oligomer formation process. A program developed in-house was used to determine exact mass differences between peaks in the monomer, dimer, and trimer mass range to identify potential monomer building blocks, which form the co-oligomers observed in the mass spectrum. A majority of the peaks measured in the low mass region of the spectrum (m/z < 300) is also found in the calculated results. For the first time the elemental composition of the majority of peaks over a wide mass range was determined using advanced data analysis methods for the analysis of ultra-high-resolution MS data. Possible oligomer formation mechanisms in secondary organic aerosols were investigated.
- Published
- 2007