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Environmental problems - Chemical approaches
RESEARCH ARTICLE

Online analysis of secondary organic aerosols from OH-initiated photooxidation and ozonolysis of α-pinene, β-pinene, Δ3-carene and d-limonene by thermal desorption–photoionisation aerosol mass spectrometry

Wenzheng Fang A B C , Lei Gong A and Liusi Sheng A C
+ Author Affiliations
- Author Affiliations

A National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China.

B Present address: Section for Earth and Environmental Sciences, Department of Environmental Science and Analytical Chemistry, Bolin Centre for Climate Research, Stockholm University, Svante Arrhenius Väg 8, Stockholm 10691, Sweden.

C Corresponding authors. Email: fangwz@ustc.edu.cn; lssheng@ustc.edu.cn

Environmental Chemistry 14(2) 75-90 https://doi.org/10.1071/EN16128
Submitted: 16 July 2016  Accepted: 27 October 2016   Published: 22 November 2016

Environmental context. Secondary organic aerosol, formed by oxidation of volatile precursors such as monoterpenes, is a major contributor to the total atmospheric organic aerosol. We focus on the online mass spectrometric analysis of the aerosol generated by oxidation products of four major monoterpenes in an environmental chamber. Numerous important monoterpene oxidation products were clearly observed and provided a direct comparison of the formation of biogenic secondary organic aerosols.

Abstract. We present here thermal desorption–tunable vacuum ultraviolet time-of-flight photoionisation aerosol mass spectrometry (TD-VUV-TOF-PIAMS) for online analysis of biogenic secondary organic aerosols (BSOAs) formed from OH-initiated photooxidation and dark ozonolysis of α-pinene, β-pinene, Δ3-carene and d-limonene in smog chamber experiments. The ‘soft’ ionisation at near-threshold photon energies (≤10.5 eV) used in this study permits direct measurement of the fairly clean mass spectra, facilitating molecular identification. The online BSOA mass spectra compared well with previous offline measurements and most of the important monoterpene oxidation products were clearly found in the online mass spectra. Oxidation products such as monoterpene-derived acids (e.g. pinic acid, pinonic acid, 3-caronic acid, limononic acid, limonalic acid), ketones (e.g. norpinone, limonaketone), aldehydes (e.g. caronaldehyde, norcaronaldehyde, limononaldehyde) and multifunctional organics (e.g. hydroxypinonaldehydes, hydroxy-3-caronic aldehydes, hydroxylimononic acid) were tentatively identified. The online TD-VUV-TOF-PIAMS mass spectra showed that the OH-initiated photooxidation and ozonolysis of the same monoterpenes produced some similar BSOA products; for example, 3-caric acid, 3-caronic acid, 3-norcaronic acid, 3-norcaralic acid, caronaldehyde and norcaronaldehyde were observed in both photooxidation and ozonolysis of Δ3-carene. However, they could be formed through different pathways. Some of the same products and isomers (e.g. 10-oxopinonic acid, pinonic acid, norpinic acid, hydroxyl pinonaldehyde, norpinonic acid, norpinone) were formed during the photooxidation and ozonolysis of α-pinene and β-pinene. However, several different BSOA products were generated in these photooxidation and ozonolysis reactions due to their different parent structures. The OH–monoterpene reaction generated higher-molecular-weight products than O3–monoterpene owing to multiple OH additions to the unsaturated carbon bond. The online observation of key BSOA products provided a direct comparison of BSOA formation among different monoterpenes and insights into the formation pathways in the OH-initiated photooxidation and ozonolysis of monoterpenes.


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