Abstract

Abstract. The photooxidation of pinonaldehyde, one product of the α-pinene degradation, was investigated in the atmospheric simulation chamber SAPHIR under natural sunlight at low NO concentrations (<0.2 ppbv) with and without an added hydroxyl radical (OH) scavenger. With a scavenger, pinonaldehyde was exclusively removed by photolysis, whereas without a scavenger, the degradation was dominated by reaction with OH. In both cases, the observed rate of pinonaldehyde consumption was faster than predicted by an explicit chemical model, the Master Chemical Mechanism (MCM, version 3.3.1). In the case with an OH scavenger, the observed photolytic decay can be reproduced by the model if an experimentally determined photolysis frequency is used instead of the parameterization in the MCM. A good fit is obtained when the photolysis frequency is calculated from the measured solar actinic flux spectrum, absorption cross sections published by Hallquist et al. (1997), and an effective quantum yield of 0.9. The resulting photolysis frequency is 3.5 times faster than the parameterization in the MCM. When pinonaldehyde is mainly removed by reaction with OH, the observed OH and hydroperoxy radical (HO2) concentrations are underestimated in the model by a factor of 2. Using measured HO2 as a model constraint brings modeled and measured OH concentrations into agreement. This suggests that the chemical mechanism includes all relevant OH-producing reactions but is missing a source for HO2. The missing HO2 source strength of (0.8 to 1.5) ppbv h−1 is similar to the rate of the pinonaldehyde consumption of up to 2.5 ppbv h−1. When the model is constrained by HO2 concentrations and the experimentally derived photolysis frequency, the pinonaldehyde decay is well represented. The photolysis of pinonaldehyde yields 0.18 ± 0.20 formaldehyde molecules at NO concentrations of less than 200 pptv, but no significant acetone formation is observed. When pinonaldehyde is also oxidized by OH under low NO conditions (maximum 80 pptv), yields of acetone and formaldehyde increase over the course of the experiment from 0.2 to 0.3 and from 0.15 to 0.45, respectively. Fantechi et al. (2002) proposed a degradation mechanism based on quantum-chemical calculations, which is considerably more complex than the MCM scheme and contains additional reaction pathways and products. Implementing these modifications results in a closure of the model–measurement discrepancy for the products acetone and formaldehyde, when pinonaldehyde is degraded only by photolysis. In contrast, the underprediction of formed acetone and formaldehyde is worsened compared to model results by the MCM, when pinonaldehyde is mainly degraded in the reaction with OH. This shows that the current mechanisms lack acetone and formaldehyde sources for low NO conditions like in these experiments. Implementing the modifications suggested by Fantechi et al. (2002) does not improve the model–measurement agreement of OH and HO2.

Highlights

  • Emissions of biogenic non-methane volatile organic compounds (NMVOCs) in the atmosphere are ten times higher than emissions of anthropogenic NMVOCs (Guenther et al, 2012)

  • Potential wall loss of pinonaldehyde in the chamber was tested in separate experiments, in which pinonaldehyde was injected into the dark chamber

  • The photooxidation of pinonaldehyde was investigated under natural sunlight at low nitric oxide (NO) concentrations (< 0.2 ppbv) in the presence and absence of an OH scavenger

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Summary

Introduction

Emissions of biogenic non-methane volatile organic compounds (NMVOCs) in the atmosphere are ten times higher than emissions of anthropogenic NMVOCs (Guenther et al, 2012). Of these emissions, monoterpenes (C10-compounds) represent approximately 15 % (Guenther et al, 2012) of the total emissions. Monoterpenes are mainly oxidized in the atmosphere 5 by ozonolysis or their reaction with the hydroxyl radical (OH) during daytime. Oxidation by the nitrate radical (NO3) during nighttime can be of importance enhanced by nocturnal monoterpene emissions (Calogirou et al, 1999; Atkinson and Arey, 2003). The oxidation of monoterpenes and their oxidation products is of importance for 10 the tropospheric ozone production (Schwantes et al, 2020)

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