NO₃ reactivity during a summer period in a temperate forest below and above the canopy

Abstract. We present direct measurements of BVOC-induced nitrate radical (NO3) reactivity (kVOC) through the diel cycle in the suburban, temperate forest of Rambouillet near Paris (France). The data were obtained in a six-week summer period in 2022 as part of the ACROSS campaign (Atmospheric ChemistRy Of the Suburban foreSt). kVOC was measured in a small (700 m2) clearing mainly at a height of 5.5 m above ground level, but also at 40 m (for 5 days/nights). At nighttime, mean values of knightVOC(5.5 m) = (0.24 ± 0.27) s-1 and knightVOC(40 m) = (0.016 ± 0.007) s-1 indicate a significant vertical gradient and low NO3 reactivity above the canopy, whereas knightVOC(5.5 m) showed peak values of up to 2 s-1 close to the ground. The strong vertical gradient in NO3 reactivity could be confirmed by measurements between 0 and 24 m on one particular night characterised by a strong temperature inversion, and is a result of the decoupling of air masses aloft from the ground- and canopy-level sources of BVOCs (and NO). No strong vertical gradient was observed in the mean daytime NO3 reactivity with kdayVOC(5.5 m) = (0.12 ± 0.04) s-1 for the entire campaign and kdayVOC(40 m) = (0.07 ± 0.02) s-1 during the 5-day period. Within the clearing, the fractional contribution of VOCs to the total NO3 loss rate (LNO3, determined by photolysis, reaction with NO and VOCs) was 80–90 % during the night and ~50 % during the day. In terms of chemical losses of α-pinene below canopy height in the clearing, we find that at nighttime OH and O3 dominate with NO3 contributing “only” 17 %, which decreases further to 8.5 % during the day. Based on OH, O3 and NO3 concentrations, the chemical lifetime of BVOCs at noon is about one hour and is likely to be longer than timescales of transport out of the canopy (typically in the order of minutes), thus significantly reducing the importance of daytime, in-canopy processing. Clearly, in forested regions where sufficient NOX is available, the role of NO3 and OH as initiators of BVOC oxidation are not strictly limited to the night and to the day, respectively, as often implied in e.g. atmospheric chemistry text-books.