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.

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.

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