Gas-particle interactions above a Dutch heathland: III. Modelling the influence of the NH3-HNO3-NH4NO3 equilibrium on size-segregated particle fluxes
Abstract. Micrometeorological measurements of size-segregated particle number fluxes above Dutch heathlands and forests have repeatedly shown simultaneous apparent emission of particles with a diameter (Dp)<0.18 µm and deposition of larger particles when measured with optical particle counters. In order to assess whether this observation may be explained by the equilibrium reaction of ammonia (NH3), nitric acid (HNO3) and ammonium (NH4+), a new numerical model is developed to predict the vertical concentration and flux profiles of the different species as modified by the interaction of equilibration and surface/atmosphere exchange processes. In addition to former studies, the new approach explicitly models the height-dependence of the NH4+ and total aerosol size-distribution. Using this model, it is demonstrated that both gas-to-particle conversion (gtpc) and aerosol evaporation can significantly alter the apparent surface exchange fluxes, and evoke the observed bi-directional particle fluxes under certain conditions. Thus, in general, the NH3-HNO3-NH4NO3 equilibrium needs to be considered when interpreting eddy-covariance particle fluxes. Applied to an extensive dataset of simultaneous flux measurements of particles and gases at Elspeet, NL, the model reproduces the diurnal pattern of the bi-directional exchange well. In agreement with the observation of fast NH4+ deposition, slow nitric acid deposition (both as measured by the aerodynamic gradient method) and small concentration products of NH3×HNO3 at this site, this study suggests that NH4+ evaporation at this site significantly alters surface exchange fluxes.