Document Type

Article

Publication Date

12-18-2013

Abstract

Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ∼0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOxoxidation. Multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite were observed, indicating the significance of nitrate radical reactions on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur-containing compounds) were also observed; however further investigation is needed to determine the origin of the reduced sulfur-containing compounds. Overall, the molecular composition determined using ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic anion composition in the Rocky Mountain area that could help to improve the understanding of aqueous-phase processes.

Publisher's Statement

© Author(s) 2013. Publisher's version of record: https://doi.org/10.5194/acp-13-12343-2013

Publication Title

Atmospheric Chemistry and Physics

Creative Commons License

Creative Commons Attribution 3.0 License
This work is licensed under a Creative Commons Attribution 3.0 License.

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