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Abstract. Methyl ethyl ketone (MEK) enters the atmosphere following direct emission from vegetation and anthropogenic activities, as well as being produced by the gas-phase oxidation of volatile organic compounds (VOCs) such as nbutane. This study presents the first overview of ambient MEK measurements at six different locations, characteristic of forested, urban and marine environments. In order to understand better the occurrence and behaviour of MEK in the atmosphere, we analyse diel cycles of MEK mixing ratios, vertical profiles, ecosystem flux data, and HYSPLIT back trajectories, and compare with co-measured VOCs. MEK measurements were primarily conducted with protontransfer-reaction mass spectrometer (PTR-MS) instruments. Results from the sites under biogenic influence demonstrate that vegetation is an important source of MEK. The diel cycle of MEK follows that of ambient temperature and the forest structure plays an important role in air mixing. At such sites, a high correlation of MEK with acetone was observed (e.g. r 2 = 0.96 for the SMEAR Estonia site in a remote hemiboreal forest in Tartumaa, Estonia, and r 2 = 0.89 at the ATTO pristine tropical rainforest site in central Amazonia). Under polluted conditions, we observed strongly enhanced MEK mixing ratios. Overall, the MEK mixing ratios and flux data presented here indicate that both biogenic and anthropogenic sources contribute to its occurrence in the global atmosphere.

Abstract. Total OH reactivity, defined as the total loss frequency of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify the total loading of reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites.Our study presents atmospheric mixing ratios of biogenic compounds and total OH reactivity measured during late spring 2014 at the forest of downy oak trees of the Observatoire de Haute Provence (OHP), France. Air masses were sampled at two heights: 2 m, i.e., inside the canopy, and 10 m, i.e., above the canopy, where the mean canopy height is 5 m.We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long-lived atmospheric compounds (up to 26 % during daytime). During daytime, no significant missing OH reactivity was reported at the site, either inside or above the canopy. However, during two nights we determined a missing fraction of OH reactivity up to 50 %, possibly due to unmeasured oxidation products. We confirmed that no significant oxidation of the primary species occurred within the canopy; primary compounds emitted by the forest were fast transported to the atmosphere. Finally, the OH reactivity at this site was maximum 69 s−1, which is a high value for a forest characterized by a temperate climate. Observations in various and diverse forests in the Mediterranean region are therefore needed to better constrain the impact of reactive gases over this area.

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