Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy: Organosulfates as photochemical smog constituents

Philippe Schmitt-Kopplin, A. Gelencsér, Ewa Dabek-Zlotorzynska, G. Kiss, Norbert Hertkorn, Mourad Harir, Yang Hong, Istvan Gebefügi

Research output: Contribution to journalArticle

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Abstract

Complementary molecular and atomic signatures obtained from Fourier transform ion cyclotron resonance (FTICR) mass spectra and NMR spectra provided unequivocal attribution of CHO, CHNO, CHOS, and CHNOS molecular series in secondary organic aerosols (SOA) and high-resolution definition of carbon chemical environments. Sulfate esters were confirmed as major players in SOA formation and as major constituents of its water-soluble fraction (WSOC). Elevated concentrations of SO2, sulfate, and photochemical activity were shown to increase the proportion of SOA sulfur-containing compounds. Sulfonation of CHO precursors by means of heterogeneous reactions between carbonyl derivatives and sulfuric acid in gas-phase photoreactions was proposed as a likely formation mechanism of CHOS molecules. In addition, photochemistry induced oligomerization processes of CHOS molecules. Methylesters found in methanolic extracts of a SOA subjected to strong photochemical exposure were considered secondary products derived from sulfate esters by methanolysis. The relative abundance of nitrogen-containing compounds (CHNO and CHNOS series) appeared rather dependent on local effects such as biomass burning. Extensive aliphatic branching and disruption of extended NMR spin-systems by carbonyl derivatives and other heteroatoms were the most significant structural motifs in SOA. The presence of heteroatoms in elevated oxidation states suggests a clearly different SOA formation trajectory in comparison with established terrestrial and aqueous natural organic matter.

Original languageEnglish
Pages (from-to)8017-8026
Number of pages10
JournalAnalytical Chemistry
Volume82
Issue number19
DOIs
Publication statusPublished - Oct 1 2010

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Atmospheric aerosols
Aerosols
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Sulfates
Esters
Nuclear magnetic resonance
Derivatives
Cyclotron resonance
Sulfonation
Oligomerization
Molecules
Photochemical reactions
Sulfur
Biological materials
Fourier transforms
Biomass
Nitrogen
Carbon
Gases

ASJC Scopus subject areas

  • Analytical Chemistry

Cite this

Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy : Organosulfates as photochemical smog constituents. / Schmitt-Kopplin, Philippe; Gelencsér, A.; Dabek-Zlotorzynska, Ewa; Kiss, G.; Hertkorn, Norbert; Harir, Mourad; Hong, Yang; Gebefügi, Istvan.

In: Analytical Chemistry, Vol. 82, No. 19, 01.10.2010, p. 8017-8026.

Research output: Contribution to journalArticle

Schmitt-Kopplin, Philippe ; Gelencsér, A. ; Dabek-Zlotorzynska, Ewa ; Kiss, G. ; Hertkorn, Norbert ; Harir, Mourad ; Hong, Yang ; Gebefügi, Istvan. / Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy : Organosulfates as photochemical smog constituents. In: Analytical Chemistry. 2010 ; Vol. 82, No. 19. pp. 8017-8026.
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