Volatile organic compound fluxes over a winter wheat field by PTR-Qi-TOF-MS and eddy covariance

Benjamin Loubet,Valérie Gros,Michael Staudt,Olivier Zurfluh,François Truong,Nora Zannoni,Julien Kammer,Sandy Bsaibes,Olivier Fanucci,Jean-Christophe Gueudet,Florence Lafouge,Letizia Abis,Christophe Boissard,Pauline Buysse,Dominique Baisnée,Lais Gonzaga-Gomez,Brigitte Durand,Raluca Ciuraru,Roland Sarda‐Estève ,Céline Decuq

doi:10.5194/acp-22-2817-2022

Abstract

Abstract. Volatile organic compounds (VOCs) contribute to air pollution through the formation of secondary aerosols and ozone and extend the lifetime of methane in the atmosphere. Tropospheric VOCs originate to 90 % from biogenic sources on a global scale, mainly from forests. Crops are also a potentially large yet poorly characterized source of VOCs (30 % of the VOC emissions in Europe, mostly oxygenated). In this study, we investigated VOC fluxes over a winter wheat field by eddy covariance using a PTR-Qi-TOF-MS with high sensitivity and mass resolution. The study took place near Paris over a 5-week period and included flowering, crop maturity and senescence. We found a total of 123 VOCs with fluxes 3 times above the detection limit. Methanol was the most emitted compound with an average flux of 63 µg m−2 h−1, representing about 52 % of summed VOC emissions on a molar basis (36 % on a mass basis). We also identified ethanol, acetone, acetaldehyde and dimethyl sulfide among the six most emitted compounds. The third most emitted VOC corresponded to the ion m/z 93.033. It was tentatively identified as furan (C6H4O), a compound not previously reported to be strongly emitted by crops. The average summed VOC emissions were about 173 ± 6 µg m2 h−1, while the average VOC depositions were about 109 ± 2 µg m−2 h−1 and hence 63 % of the VOC emissions on a mass basis. The net ecosystem flux of VOCs was an emission of 64 ± 6 µg m−2 h−1 (0.5 ± 0.05 nmol m−2 s−1). The most deposited VOCs were identified as hydroxyacetone, acetic acid and fragments of oxidized VOCs. Overall, our results reveal that wheat fields represent a non-negligible source and sink of VOCs to be considered in regional VOC budgets and underline the usefulness and limitations of eddy covariance measurements with a PTR-Qi-TOF-MS.

Highlights

Volatile organic compounds (VOCs) are key compounds for atmospheric chemistry that contribute to the production of harmful pollutants to human health, among which are ozone (O3) and secondary organic aerosols (SOAs) (Monks et al, 2015; Lang-Yona et al, 2010)
Because of the air density fluctuations, the Webb–Pearman– Leuning (WPL) correction needs to be applied to the eddy covariance flux (Webb et al, 1980)
We showed that the bias is a function of the w cpsH3O + covariance, which is not null since H3O+ is consumed by VOCs and water vapour that are themselves correlated to vertical wind speed

Summary

Introduction

Volatile organic compounds (VOCs) are key compounds for atmospheric chemistry that contribute to the production of harmful pollutants to human health, among which are ozone (O3) and secondary organic aerosols (SOAs) (Monks et al, 2015; Lang-Yona et al, 2010). Ozone, which is a powerful greenhouse gas (IPCC, 2018), affects vegetation growth with an estimated annual cost of EUR 11–18 billion on agricultural production worldwide in the last decade (Ashmore, 2005; Avnery et al, 2011). The main regulations in Europe, resulting from the Gothenburg Protocol of 1999, concern the limitation of their emissions from industrial plants and the limitation of their concentrations in consumer products. Since VOCs are precursors of harmful air pollutants, their sources need to be better quantified to identify potential remedies to mitigate PM2.5 and ozone threats

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