Measurement-model comparison of stabilized Criegee intermediate and highly oxygenated molecule production in the CLOUD chamber

作者：Sarnela Nina; Jokinen Tuija; Duplissy Jonathan; Yan Chao; Nieminen Tuomo; Ehn Mikael; Schobe**erger Siegfried; Heinritzi Martin; Ehrhart Sebastian; Lehtipalo Katrianne; Trostl Jasmin; Simon Mario; Kurten Andreas; Leiminger Markus; Lawler Michael J; Rissanen Matti P; Bianchi Federico; Praplan Arnaud P; Hakala Jani; Amorim Antonio; Gonin Marc; Hansel Armin; Kirkby Jasper; Dommen Josef; Curtius Joachim; Smith James N^*; Petaja Tuukka; Worsnop Douglas R

来源：Atmospheric Chemistry and Physics, 2018, 18(4): 2363-2380.

DOI：10.5194/acp-18-2363-2018

Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5% for HOM formation and 22-32% for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

• 出版日期2018-2-19