Day and night-time formation of organic nitrates at a forested mountain site in south-west Germany

We report in situ measurements of total peroxy nitrates (ΣPNs) and total alkyl nitrates (ΣANs) in a forested–urban location at the top of the Kleiner Feldberg mountain in south-west Germany. The data, obtained using thermal dissociation cavity ring-down spectroscopy (TD-CRDS) in August–September 2011 (PARADE campaign) and July 2015 (NOTOMO campaign), represent the first detailed study of ΣPNs and ΣANs over continental Europe. We find that a significant fraction of NOx (up to 75 %) is sequestered as organics nitrates at this site. Furthermore, we also show that the night-time production of alkyl nitrates by reaction of NO3 with biogenic hydrocarbons is comparable to that from daytime OH-initiated oxidation pathways. The ΣANs ∕ ozone ratio obtained during PARADE was used to derive an approximate average yield of organic nitrates at noon from the OH initiated oxidation of volatile organic compounds (VOCs) of ∼ 7 % at this site in 2011, which is comparable with that obtained from an analysis of VOCs measured during the campaign. A much lower AN yield, < 2 %, was observed in 2015, which may result from sampling air with different average air mass ages and thus different degrees of breakdown of assumptions used to derive the branching ratio, but it may also reflect a seasonal change in the VOC mixture at the site.

Day- and Night-time Formation of Organic Nitrates at a Forested Mountain-site in South West Germany

We report in-situ measurement of total peroxy-nitrates (ƩPNs) and total alkyl nitrates (ƩANs) in a forested/urban location at the top of the Kleiner Feldberg mountain in South-West Germany. The data, obtained using Thermal Dissociation Cavity Ring Down Spectroscopy (TD-CRDS) in August-September 2011 (PARADE campaign) and July–August 2015 (NOTOMO campaign), represent the first detailed study of ƩPNs and ƩANs over continental Europe. We find that a significant fraction of NOx (up to 75 %) is sequestered as organics nitrates at this site. Futher, we also show that the night-time production of alkyl nitrates by reaction of NO3 with biogenic hydrocarbons is comparable to that from day-time, OH-initiated oxidation pathways. The ƩANs-to-ozone ratio obtained during PARADE was used to derive an approximate, average yield of organic nitrates at noon time from the OH initiated oxidation of VOCs of 7 % at this site in 2011, which is comparable with that obtained from an analysis of VOCs at the site. A much lower yield,

In Situ Measurements of Atmospheric CO And Its Correlation With Nox And O3 at a Rural Mountain Site

Ambient concentrations of CO, as well as NOx and O3, were measured as a part of the PARADE campaign conducted at the Taunus Observatory on the summit of the Kleiner Feldberg between the 8th of August and 9th of September 2011. These measurements were made in an effort to provide insight into the characteristics of the effects of both biogenic and anthropogenic emissions on atmospheric chemistry in the rural south-western German environment. The overall average CO concentration was found to be 100.3±18.1 ppbv (within the range of 71 to 180 ppbv), determined from 10-min averages during the summer season. The background CO concentration was estimated to be ~90 ppbv. CO and NOx showed bimodal diurnal variations with peaks in the late morning (10:00-12:00 UTC) and in the late afternoon (17:00-20:00 UTC). Strong correlations between CO and NOx indicated that vehicular emission was the major contributor to the notable CO plumes observed at the sampling site. Both local meteorology and backward trajectory analyses suggest that CO plumes were associated with anthropogenically polluted air masses transferred by an advection to the site from densely populated city sites. Furthermore, a good linear correlation of R2 = 0.54 between CO and O3 (∆O3/∆CO=0.560±0.016 ppbv/ppbv) was observed, in good agreement with previous observations

A Particle-Surface-Area-Based Parameterization of Immersion Freezing on Desert Dust Particles

In climate and weather models, the quantitative description of aerosol and cloud processes relies on simplified assumptions. This contributes major uncertainties to the prediction of global and regional climate change. Therefore, models need good parameterizations for heterogeneous ice nucleation by atmospheric aerosols. Here the authors present a new parameterization of immersion freezing on desert dust particles derived from a large number of experiments carried out at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber facility. The parameterization is valid in the temperature range between −12° and −36°C at or above water saturation and can be used in atmospheric models that include information about the dust surface area. The new parameterization was applied to calculate distribution maps of ice nuclei during a Saharan dust event based on model results from the regional-scale model Consortium for Small-Scale Modelling–Aerosols and Reactive Trace Gases (COSMO-ART). The results were then compared to measurements at the Taunus Observatory on Mount Kleiner Feldberg, Germany, and to three other parameterizations applied to the dust outbreak. The aerosol number concentration and surface area from the COSMO-ART model simulation were taken as input to different parameterizations. Although the surface area from the model agreed well with aerosol measurements during the dust event at Kleiner Feldberg, the ice nuclei (IN) number concentration calculated from the new surface-area-based parameterization was about a factor of 13 less than IN measurements during the same event. Systematic differences of more than a factor of 10 in the IN number concentration were also found among the different parameterizations. Uncertainties in the modeled and measured parameters probably both contribute to this discrepancy and should be addressed in future studies.