NO3 Reactivity During a Summer Period in a Temperate Forest below and above the Canopy

We present direct measurements of biogenic volatile organic compound (BVOC)-induced nitrate radical (NO3) reactivity (k(VOC)) through the diel cycle in the suburban, temperate forest of Rambouillet near Paris (France). The data were obtained in a 6-week summer period in 2022 as part of the Atmospheric ChemistRy Of the Suburban foreSt (ACROSS) campaign. k(VOC) was measured in a small (700 m(2)) clearing mainly at a height of 5.5 m above ground level but also at 40 m (for 5 d and nights). At nighttime, mean values (and 25th-75th percentile ranges) of k(night)(VOC)(5.5m) = (0.24(-0.06)(+0.32)) s(-1) and k(night)(VOC)(40m) = (0.016(-0.007)(+0.018)) s(-1) indicate a significant vertical gradient and low NO3 reactivity above the canopy, whereas k(night)(VOC)(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 characterized 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 nitric oxide, NO). No strong vertical gradient was observed in the mean daytime NO3 reactivity, with k(day)(VOC)(5.5m) = (0.12 +/- 0.04) s(-1) for the entire campaign and k(day)(VOC)(40m) = (0.07 +/- 0.02) s(-1) during the 5 d period. Within the clearing, the fractional contribution of VOCs to the total NO3 loss rate coefficient (k(tot), determined by photolysis, reaction with NO and VOCs) was 80 %-90 % during the night and similar to 50 % during the day. In terms of chemical losses of alpha-pinene below canopy height in the clearing, we find that at nighttime hydroxyl radicals (OH) and ozone (O-3) dominate, with NO3 contributing "only" 17 %, which decreases further to 8.5 % during the day. Based on measured OH, measured O-3, and calculated NO3 concentrations, the chemical lifetime of BVOCs at noon is about 1 h and is likely to be longer than timescales of transport out of the canopy (typically of the order of minutes), thus significantly reducing the importance of daytime in-canopy processing. Clearly, in forested regions where sufficient nitric oxide and nitrogen dioxide (NOx) is available, the role of NO3 and OH as initiators of BVOC oxidation is not strictly limited to nighttime and daytime, respectively, as often implied in e.g. atmospheric chemistry textbooks.