2014, Henning, S., Dieckmann, K., Ignatius, K., Schäfer, M., Zedler, P., Harris, E., Sinha, B., van Pinxteren, D., Mertes, S., Birmili, W., Merkel, M., Wu, Z., Wiedensohler, A., Wex, H., Herrmann, H., Stratmann, F.

Within the framework of the "Hill Cap Cloud Thuringia 2010" (HCCT-2010) international cloud experiment, the influence of cloud processing on the activation properties of ambient aerosol particles was investigated. Particles were probed upwind and downwind of an orographic cap cloud on Mt Schmücke, which is part of a large mountain ridge in Thuringia, Germany. The activation properties of the particles were investigated by means of size-segregated cloud condensation nuclei (CCN) measurements at 3 to 4 different supersaturations. The observed CCN spectra together with the total particle spectra were used to calculate the hygroscopicity parameter κ for the upwind and downwind stations. The upwind and downwind critical diameters and κ values were then compared for defined cloud events (FCE) and non-cloud events (NCE). Cloud processing was found to increase the hygroscopicity of the aerosol particles significantly, with an average increase in κ of 50%. Mass spectrometry analysis and isotopic analysis of the particles suggest that the observed increase in the hygroscopicity of the cloud-processed particles is due to an enrichment of sulfate and possibly also nitrate in the particle phase.

2016, Roth, A., Schneider, J., Klimach, T., Mertes, S., van Pinxteren, D., Herrmann, H., Borrmann, S.

Cloud residues and out-of-cloud aerosol particles with diameters between 150 and 900 nm were analysed by online single particle aerosol mass spectrometry during the 6-week study Hill Cap Cloud Thuringia (HCCT)-2010 in September–October 2010. The measurement location was the mountain Schmücke (937 m a.s.l.) in central Germany. More than 160 000 bipolar mass spectra from out-of-cloud aerosol particles and more than 13 000 bipolar mass spectra from cloud residual particles were obtained and were classified using a fuzzy c-means clustering algorithm. Analysis of the uncertainty of the sorting algorithm was conducted on a subset of the data by comparing the clustering output with particle-by-particle inspection and classification by the operator. This analysis yielded a false classification probability between 13 and 48 %. Additionally, particle types were identified by specific marker ions. The results from the ambient aerosol analysis show that 63 % of the analysed particles belong to clusters having a diurnal variation, suggesting that local or regional sources dominate the aerosol, especially for particles containing soot and biomass burning particles. In the cloud residues, the relative percentage of large soot-containing particles and particles containing amines was found to be increased compared to the out-of-cloud aerosol, while, in general, organic particles were less abundant in the cloud residues. In the case of amines, this can be explained by the high solubility of the amines, while the large soot-containing particles were found to be internally mixed with inorganics, which explains their activation as cloud condensation nuclei. Furthermore, the results show that during cloud processing, both sulfate and nitrate are added to the residual particles, thereby changing the mixing state and increasing the fraction of particles with nitrate and/or sulfate. This is expected to lead to higher hygroscopicity after cloud evaporation, and therefore to an increase of the particles' ability to act as cloud condensation nuclei after their cloud passage.

2012, Spiegel, J.K., Aemisegger, F., Scholl, M., Wienhold, F.G., Collett Jr., J.L., Lee, T., van Pinxteren, D., Mertes, S., Tilgner, A., Herrmann, H., Werner, R.A., Buchmann, N., Eugster, W.

In this work, we present the first study resolving the temporal evolution of δ2H and δ18O values in cloud droplets during 13 different cloud events. The cloud events were probed on a 937 m high mountain chain in Germany in the framework of the Hill Cap Cloud Thuringia 2010 campaign (HCCT-2010) in September and October 2010. The δ values of cloud droplets ranged from −77‰ to −15‰ (δ2H) and from −12.1‰ to −3.9‰ (δ18O) over the whole campaign. The cloud water line of the measured δ values was δ2H=7.8×δ18O+13×10−3, which is of similar slope, but with higher deuterium excess than other Central European Meteoric Water Lines. Decreasing δ values in the course of the campaign agree with seasonal trends observed in rain in central Europe. The deuterium excess was higher in clouds developing after recent precipitation revealing episodes of regional moisture recycling. The variations in δ values during one cloud event could either result from changes in meteorological conditions during condensation or from variations in the δ values of the water vapor feeding the cloud. To test which of both aspects dominated during the investigated cloud events, we modeled the variation in δ values in cloud water using a closed box model. We could show that the variation in δ values of two cloud events was mainly due to changes in local temperature conditions. For the other eleven cloud events, the variation was most likely caused by changes in the isotopic composition of the advected and entrained vapor. Frontal passages during two of the latter cloud events led to the strongest temporal changes in both δ2H (≈ 6‰ per hour) and δ18O (≈ 0.6‰ per hour). Moreover, a detailed trajectory analysis for the two longest cloud events revealed that variations in the entrained vapor were most likely related to rain out or changes in relative humidity and temperature at the moisture source region or both. This study illustrates the sensitivity of stable isotope composition of cloud water to changes in large scale air mass properties and regional recycling of moisture.

2015, Whalley, L.K., Stone, D., George, I.J., Mertes, S., van Pinxteren, D., Tilgner, A., Herrmann, H., Evans, M.J., Heard, D.E.

The potential for chemistry occurring in cloud droplets to impact atmospheric composition has been known for some time. However, the lack of direct observations and uncertainty in the magnitude of these reactions led to this area being overlooked in most chemistry transport models. Here we present observations from Mt Schmücke, Germany, of the HO2 radical made alongside a suite of cloud measurements. HO2 concentrations were depleted in-cloud by up to 90% with the rate of heterogeneous loss of HO2 to clouds necessary to bring model and measurements into agreement, demonstrating a dependence on droplet surface area and pH. This provides the first observationally derived assessment for the uptake coefficient of HO2 to cloud droplets and was found to be in good agreement with theoretically derived parameterisations. Global model simulations, including this cloud uptake, showed impacts on the oxidising capacity of the troposphere that depended critically on whether the HO2 uptake leads to production of H2O2 or H2O.