Identification of water-soluble organic carbon in non-urban aerosols using ultrahigh-resolution FT-ICR mass spectrometry: Organic anions

Water-soluble organic carbon (WSOC) is a complex mixture of thousands of organic compounds which may have significant influence on the climate-relevant properties of atmospheric aerosols. An improved understanding of the molecular composition of WSOC is needed to evaluate the effect of aerosol composition upon aerosol physical properties. In this work, ultrahigh-resolution Fourier transformion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterise aerosol WSOC collected during the summer of 2010 at the Storm Peak Laboratory (3210m ASL) near Steamboat Springs, CO. Approximately 4000 molecular formulas were assigned in the mass range of 100800Da after negative-ion electrospray ionisation and more than 50% of them contained nitrogen or sulfur. The double bond equivalents (DBEs) of the molecular formulas were inversely proportional to the O:C ratio, despite a relatively constant H:C ratio of ∼1.5. Despite the range of DBE values, the elemental ratios and the high number of oxygen atoms per formula indicate that a majority of the compounds are aliphatic to olefinic in nature. These trends indicate significant non-oxidative accretion reaction pathways for the formation of high molecular weight WSOC components. In addition, a significant number of molecular formulas assigned in this work matched those previously identified as secondary organic aerosol components of monoterpene and sesquiterpene ozonolysis. © 2012 CSIRO.