Abstract
Volatile organic compounds (VOC) contribute to air pollution through the formation of secondary aerosols and ozone and contribute to increasing the lifetime of methane in the atmosphere. Tropospheric VOC are 90 % originating from biogenic sources at the global scale. Forests are the main contributors to these emissions with isoprene and monoterpenes being the most emitted compounds. Crops are also a potentially large, yet poorly characterised, source of VOC. In particular, measurements of VOC fluxes for wheat at the ecosystem scale are scarce, although this is the most cultivated crop in Europe. Available evidence indicates that crops may contribute to 30% of the VOC emissions in Europe, especially oxygenated, low-molecular-weight VOC such as methanol, acetone and acetaldehyde. In this study, which is part of the COV3ER French national project, we investigated VOC fluxes over a wheat field in-situ by eddy covariance using a PTR-Qi-TOF-MS with an outmost sensitivity and mass resolution. We found 264 compounds to have a flux three times above the flux detection limit. Methanol was the most emitted compound, with an averaged flux of 63 µg m−2 h−1, representing around 60 % of summed VOC emissions on a molar basis (40 % on a mass basis). This finding is in line with previous measurements at canopy and plant scales. We also measured acetone, acetaldehyde and dimethyl sulphide among the five most emitted compounds. The second most emitted VOC corresponded to the ion m/z 93.037, tentatively identified as C6H4O. This compound was not reported previously as one of the most emitted compound by terrestrial ecosystems. Summed VOC emissions amounted around 150 µg m−2 h−1. Summed VOC deposition amounted to around −125 µg m−2 h−1, which represented about 70 % of the VOC emissions on a mass basis. The most depositing VOC were tentatively identified as hydroxyacetone and fragments of oxidised VOC with a flux of −16 µg m−2 h−1. Overall, our results reveal that wheat fields represent a non-negligible source and sink of VOC to be considered in regional VOC budgets, and underline the usefulness and limitations of eddy covariance measurements with PTR-Qi-TOF-MS.
Highlights
Volatile organic compounds (VOC) are key compounds for atmospheric chemistry that contribute to the 45 production of harmful pollutants to human health, among which ozone (O3) and secondary organic aerosols (SOA)(Lang-Yona et al, 2010; Monks et al, 2015)
790 We found that the PTR-Qi-TOF-MS was sensitive enough to measure fluxes of 264 VOC by eddy covariance (77 emitting and 187 depositing, fluxes > 3 LODf) above a wheat canopy during a mature and a senescing period
795 The eddy-covariance flux computation was analysed in detail showing that the Webb Penman Leuning (WPL) correction was negligible
Summary
Volatile organic compounds (VOC) are key compounds for atmospheric chemistry that contribute to the 45 production of harmful pollutants to human health, among which ozone (O3) and secondary organic aerosols (SOA)(Lang-Yona et al, 2010; Monks et al, 2015). According to Karl et al (2009a), in Europe forests account for 55 % 60 of the total emission, agricultural lands for 27 %, and grasslands, wetlands and shrubs for 18 % These values are based on few datasets of BVOC fluxes (Keenan et al, 2009) and this is especially the case for crops. The emergence of highly sensitive PTR-TOF-MS (Sulzer et al, 2014) enables the 80 detection of a lot more VOC than with previous quadrupoles PTRMS, and allows ecosystem scale measurement of their fluxes by direct eddy covariance instead of virtual disjunct eddy covariance This opens the possibility to get a much more complete spectrum of VOC emitted by crops than in previous studies. The methodology to compute the fluxes and their uncertainties is presented in detail, and the emission and deposition fluxes are discussed in terms of their magnitude and temporality
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