1Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO, USA
2Department of Atmospheric and Oceanic Sciences, University of Colorado, Boulder, CO, USA
3Department of Environmental Sciences, Wageningen University and Research Centre, Wageningen, the Netherlands
4Department of Geography, University of Colorado, Boulder, CO, USA
5University of Michigan Biological Station, University of Michigan, Pellston, MI, USA
Abstract. The dynamic behavior of nitrogen oxides (NOx = NO + NO2) and ozone (O3) above and within the canopy at the University of Michigan Biological Station AmeriFlux (UMBS Flux) site was investigated by continuous multi-height vertical gradient measurements during the summer and the fall of 2008. A daily maximum in nitric oxide (NO) mixing ratios was consistently observed during the morning hours between 06:00 and 09:00 EST above the canopy. Daily NO maxima ranged between 0.1 and 2 ppbv (with a median of 0.3 ppbv), which were 2 to 20 times above the atmospheric background. The sources and causes of the morning NO maximum were evaluated using NOx and O3 measurements and synoptic and micrometeorological data. Numerical simulations with a multi-layer canopy-exchange model were done to further support this analysis. The observations indicated that the morning NO maximum was caused by the photolysis of NO2 from non-local air masses, which were transported into the canopy from aloft during the morning breakup of the nocturnal boundary layer. The analysis of simulated process tendencies indicated that the downward turbulent transport of NOx into the canopy compensates for the removal of NOx through chemistry and dry deposition. The sensitivity of NOx and O3 concentrations to soil and foliage NOx emissions was also assessed with the model. Uncertainties associated with the emissions of NOx from the soil or from leaf-surface nitrate photolysis did not explain the observed diurnal behavior in NOx (and O3) and, in particular, the morning peak in NOx mixing ratios. However, a ~30% increase in early morning NOx and NO peak mixing ratios was simulated when a foliage exchange NO2 compensation point was considered. This increase suggests the potential importance of leaf-level, bidirectional exchange of NO2 in understanding the observed temporal variability in NOx at UMBS.