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Dry deposition of peroxyacetyl nitrate (PAN) is known to have a phytotoxicimpact on plants under photochemical smog conditions, but it may also leadto higher productivity and threaten species richness of vulnerableecosystems in remote regions. However, underlying mechanisms or controllingfactors for PAN deposition are not well understood and studies on drydeposition of PAN are limited. In this study, we investigate the impact ofPAN deposition on a nutrient-poor natural grassland ecosystem situated atthe edge of an urban and industrialized region in Germany. PAN mixing ratioswere measured within a 3.5 months summer to early autumn period. Inaddition, PAN fluxes were determined with the modified Bowen ratio techniquefor a selected period. The evaluation of both stomatal and non-stomataldeposition pathways was used to model PAN deposition over the entiresummer–autumn period. We found that air masses at the site were influencedby two contrasting pollution regimes, which led to median diurnal PANmixing ratios ranging between 50 and 300 ppt during unpolluted and between200 and 600 ppt during polluted episodes. The measured PAN fluxes showed aclear diurnal cycle with maximal deposition fluxes of ~−0.1 nmol m−2 s−1 (corresponding to a deposition velocity of0.3 cm s−1) during daytime and a significant non-stomatal contributionwas found. The ratio of PAN to ozone deposition velocities was found to be~0.1, which is much larger than assumed by current depositionmodels. The modelled PAN flux over the entire period revealed that PANdeposition over an entire day was 333 μg m−2 d−1 underunpolluted and 518 μg m−2 d−1 under polluted episodes.Additionally, thermochemical decomposition PAN deposition accounted for 32%under unpolluted episodes and 22% under polluted episodes of the totalatmospheric PAN loss. However, the impact of PAN deposition as a nitrogensource to the nutrient-poor grassland was estimated to be only minor, underboth unpolluted and polluted episodes

Influence of local air pollution on the deposition of peroxyacetyl nitrate to a nutrient-poor natural grassland ecosystem