Title: Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

Abstract

We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO–HR-ToF-CIMS are highly correlated with, and explain at least 25–50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonlymore » measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. In conclusion, the volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Authors:

Lopez-Hilfiker, F. D.; Mohr, C. ;

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Ehn, M.; Rubach, F.; Kleist, E.; Wildt, J.; Mentel, Th. F.; Carrasquillo, A. J.; Daumit, K. E.; Hunter, J. F.; Kroll, J. H.; Worsnop, D. R.; Thornton, J. A.

Publication Date:

Thu Jul 16 00:00:00 EDT 2015

Research Org.:

Univ. of Washington, Seattle, WA (United States)

Sponsoring Org.:

USDOE Office of Science (SC)

OSTI Identifier:

1213806

Alternate Identifier(s):

OSTI ID: 1441182

Grant/Contract Number:  

SC0006867; SC0004577

Resource Type:

Published Article

Journal Name:

Atmospheric Chemistry and Physics (Online)

Additional Journal Information:

Journal Name: Atmospheric Chemistry and Physics (Online) Journal Volume: 15 Journal Issue: 14; Journal ID: ISSN 1680-7324

Publisher:

Copernicus Publications, EGU

Country of Publication:

Germany

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY