Oxidation product characterization from ozonolysis of the diterpene ent-kaurene

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http://urn.fi/URN:NBN:fi-fe2022050231954 http://hdl.handle.net/10138/343383
Title: Oxidation product characterization from ozonolysis of the diterpene ent-kaurene
Author: Luo, Yuanyuan; Garmash, Olga; Li, Haiyan; Graeffe, Frans; Praplan, Arnaud P.; Liikanen, Anssi; Zhang, Yanjun; Meder, Melissa; Peräkylä, Otso; Pẽnuelas, Josep; Yáñez-Serrano, Ana María; Ehn, Mikael
Contributor organization: Ilmatieteen laitos
Finnish Meteorological Institute
Publisher: Copernicus Publ.
Date: 2022
Language: en
Belongs to series: Atmospheric chemistry and physics
ISSN: 1680-7316
1680-7324
DOI: https://doi.org/10.5194/acp-22-5619-2022
URI: http://urn.fi/URN:NBN:fi-fe2022050231954
http://hdl.handle.net/10138/343383
Abstract: Diterpenes (C20H32) are biogenically emitted volatile compounds that only recently have been observed in ambient air. They are expected to be highly reactive, and their oxidation is likely to form condensable vapors. However, until now, no studies have investigated gas-phase diterpene oxidation. In this paper, we explored the ozonolysis of a diterpene, ent-kaurene, in a simulation chamber. Using state-of-the-art mass spectrometry, we characterized diterpene oxidation products for the first time, and we identified several products with varying oxidation levels, including highly oxygenated organic molecules (HOM), monomers, and dimers. The most abundant monomers measured using a nitrate chemical ionization mass spectrometer were C19H28O8 and C20H30O5, and the most abundant dimers were C38H60O6 and C39H62O6. The exact molar yield of HOM from kaurene ozonolysis was hard to quantify due to uncertainties in both the kaurene and HOM concentrations, but our best estimate was a few percent, which is similar to values reported earlier for many monoterpenes. We also monitored the decrease in the gas-phase oxidation products in response to an increased condensation sink in the chamber to deduce their affinity to condense. The oxygen content was a critical parameter affecting the volatility of products, with four to five O atoms needed for the main monomeric species to condense onto 80 nm particles. Finally, we report on the observed fragmentation and clustering patterns of kaurene in a Vocus proton-transferreaction time-of-flight mass spectrometer. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation, but more studies on different diterpenes are needed for a broader view of their role in atmospheric chemistry.
Subject: dieterpenes
ent-kaurene
atmospheric chemistry
Rights: CC BY 4.0


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