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- ItemStable water isotopologue ratios in fog and cloud droplets of liquid clouds are not size-dependent(München : European Geopyhsical Union, 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 observations of stable water isotopologue ratios in cloud droplets of different sizes collected simultaneously. We address the question whether the isotope ratio of droplets in a liquid cloud varies as a function of droplet size. Samples were collected from a ground intercepted cloud (= fog) during the Hill Cap Cloud Thuringia 2010 campaign (HCCT-2010) using a three-stage Caltech Active Strand Cloud water Collector (CASCC). An instrument test revealed that no artificial isotopic fractionation occurs during sample collection with the CASCC. Furthermore, we could experimentally confirm the hypothesis that the δ values of cloud droplets of the relevant droplet sizes (μm-range) were not significantly different and thus can be assumed to be in isotopic equilibrium immediately with the surrounding water vapor. However, during the dissolution period of the cloud, when the supersaturation inside the cloud decreased and the cloud began to clear, differences in isotope ratios of the different droplet sizes tended to be larger. This is likely to result from the cloud's heterogeneity, implying that larger and smaller cloud droplets have been collected at different moments in time, delivering isotope ratios from different collection times.
- ItemHygroscopic behavior of atmospherically relevant water-soluble carboxylic salts and their influence on the water uptake of ammonium sulfate(München : European Geopyhsical Union, 2011) Wu, Z.J.; Nowak, A.; Poulain, L.; Herrmann, H.; Wiedensohler, A.The hygroscopic behavior of atmospherically relevant water-soluble carboxylic salts and their effects on ammonium sulfate were investigated using a hygroscopicity tandem differential mobility analyzer (H-TDMA). No hygroscopic growth is observed for disodium oxalate, while ammonium oxalate shows slight growth (growth factor = 1.05 at 90%). The growth factors at 90% RH for sodium acetate, disodium malonate, disodium succinate, disodium tartrate, diammonium tartrate, sodium pyruvate, disodium maleate, and humic acid sodium salt are 1.79, 1.78, 1.69, 1.54, 1.29, 1.70, 1.78, and 1.19, respectively. The hygroscopic growth of mixtures of organic salts with ammonium sulfate, which are prepared as surrogates of atmospheric aerosols, was determined. A clear shift in deliquescence relative humidity to lower RH with increasing organic mass fraction was observed for these mixtures. Above 80% RH, the contribution to water uptake by the organic salts was close to that of ammonium sulfate for the majority of investigated compounds. The observed hygroscopic growth of the mixed particles at RH above the deliquescence relative humidity of ammonium sulfate agreed well with that predicted using the Zdanovskii-Stokes-Robinson (ZSR) mixing rule. Mixtures of ammonium sulfate with organic salts are more hygroscopic than mixtures with organic acids, indicating that neutralization by gas-phase ammonia and/or association with cations of dicarbonxylic acids may enhance the hygroscopicity of the atmospheric particles.
- ItemQuasi 18 h wave activity in ground-based observed mesospheric H2O over Bern, Switzerland(Katlenburg-Lindau : EGU, 2017-12-18) Lainer, Martin; Hocke, Klemens; Rüfenacht, Rolf; Kämpfer, NiklausObservations of oscillations in the abundance of middle-atmospheric trace gases can provide insight into the dynamics of the middle atmosphere. Long-term, high-temporal-resolution and continuous measurements of dynamical tracers within the strato- and mesosphere are rare but would facilitate better understanding of the impact of atmospheric waves on the middle atmosphere. Here we report on water vapor measurements from the ground-based microwave radiometer MIAWARA (MIddle Atmospheric WAter vapor RAdiometer) located close to Bern during two winter periods of 6 months from October to March. Oscillations with periods between 6 and 30 h are analyzed in the pressure range 0.02–2 hPa. Seven out of 12 months have the highest wave amplitudes between 15 and 21 h periods in the mesosphere above 0.1 hPa. The quasi 18 h wave signature in the water vapor tracer is studied in more detail by analyzing its temporal evolution in the mesosphere up to an altitude of 75 km. Eighteen-hour oscillations in midlatitude zonal wind observations from the microwave Doppler wind radiometer WIRA (WInd RAdiometer) could be identified within the pressure range 0.1–1 hPa during an ARISE (Atmospheric dynamics Research InfraStructure in Europe)-affiliated measurement campaign at the Observatoire de Haute-Provence (355 km from Bern) in France in 2013. The origin of the observed upper-mesospheric quasi 18 h oscillations is uncertain and could not be determined with our available data sets. Possible drivers could be low-frequency inertia-gravity waves or a nonlinear wave–wave interaction between the quasi 2-day wave and the diurnal tide.
- ItemTowards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol(Cambridge : Soc., 2015) Alberico, E.; Nielsen, M.The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous catalytic systems have been reported which are able to promote either one or the other of the two reactions under mild conditions. Here, we review and discuss these developments.
- ItemExcited-state relaxation of hydrated thymine and thymidine measured by liquid-jet photoelectron spectroscopy: experiment and simulation(Washington, DC : ACS Publications, 2015) Buchner, Franziska; Nakayama, Akira; Yamazaki, Shohei; Ritze, Hans-Hermann; Lübcke, AndreaTime-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys.2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.
- ItemCompetition between excited state proton and OH- transport via a short water wire: Solvent effects open the gate(London [u.a.] : Royal Society of Chemistry, 2014) Bekçioǧlu, G.; Allolio, C.; Ekimova, M.; Nibbering, E.T.J.; Sebastiani, D.We investigate the acid-base proton exchange reaction in a microsolvated bifunctional chromophore by means of quantum chemical calculations. The UV/vis spectroscopy shows that equilibrium of the keto-and enol-forms in the electronic ground state is shifted to the keto conformation in the excited state. A previously unknown mechanism involving a hydroxide ion transport along a short water wire is characterized energetically, which turns out to be competitive with the commonly assumed proton transport. Both mechanisms are shown to have a concerted character, as opposed to a step-wise mechanism. The alternative mechanism of a hydrogen atom transport is critically examined, and evidence for strong solvent dependence is presented. Specifically, we observe electrostatic destabilization of the corresponding πσ* state by the aqueous solvent. As a consequence, no conical intersections are found along the reaction pathway.
- ItemTime-resolved photoelectron spectroscopy of adenine and adenosine in aqueous solution(London [u.a.] : Royal Society of Chemistry, 2013) Buchner, F.; Ritze, H.-H.; Lahl, J.; Lübcke, A.Time-resolved photoelectron spectroscopy is applied to study the excited state dynamics of the DNA base adenine and its ribonucleoside adenosine in aqueous solution for pump and probe photon energies in the range between 4.66 eV and 5.21 eV. We follow the evolution of the prepared excited state on the potential energy surface and retrieve lifetimes of the S1 state under different excitation conditions.
- ItemFew-cycle laser driven reaction nanoscopy on aerosolized silica nanoparticles([London] : Nature Publishing Group UK, 2019) Rupp, Philipp; Burger, Christian; Kling, Nora G; Kübel, Matthias; Mitra, Sambit; Rosenberger, Philipp; Weatherby, Thomas; Saito, Nariyuki; Itatani, Jiro; Alnaser, Ali S.; Raschke, Markus B.; Rühl, Eckart; Schlander, Annika; Gallei, Markus; Seiffert, Lennart; Fennel, Thomas; Bergues, Boris; Kling, Matthias F.Nanoparticles offer unique properties as photocatalysts with large surface areas. Under irradiation with light, the associated near-fields can induce, enhance, and control molecular adsorbate reactions on the nanoscale. So far, however, there is no simple method available to spatially resolve the near-field induced reaction yield on the surface of nanoparticles. Here we close this gap by introducing reaction nanoscopy based on three-dimensional momentum-resolved photoionization. The technique is demonstrated for the spatially selective proton generation in few-cycle laser-induced dissociative ionization of ethanol and water on SiO2 nanoparticles, resolving a pronounced variation across the particle surface. The results are modeled and reproduced qualitatively by electrostatic and quasi-classical mean-field Mie Monte-Carlo (M3C) calculations. Reaction nanoscopy is suited for a wide range of isolated nanosystems and can provide spatially resolved ultrafast reaction dynamics on nanoparticles, clusters, and droplets.
- ItemWater scarcity hotspots travel downstream due to human interventions in the 20th and 21st century(London : Nature Publishing Group, 2017) Veldkamp, T.I.E.; Wada, Y.; Aerts, J.C.J.H.; Döll, P.; Gosling, S.N.; Liu, J.; Masaki, Y.; Oki, T.; Ostberg, S.; Pokhrel, Y.; Satoh, Y.; Kim, H.; Ward, P.J.Water scarcity is rapidly increasing in many regions. In a novel, multi-model assessment, we examine how human interventions (HI: land use and land cover change, man-made reservoirs and human water use) affected monthly river water availability and water scarcity over the period 1971-2010. Here we show that HI drastically change the critical dimensions of water scarcity, aggravating water scarcity for 8.8% (7.4-16.5%) of the global population but alleviating it for another 8.3% (6.4-15.8%). Positive impacts of HI mostly occur upstream, whereas HI aggravate water scarcity downstream; HI cause water scarcity to travel downstream. Attribution of water scarcity changes to HI components is complex and varies among the hydrological models. Seasonal variation in impacts and dominant HI components is also substantial. A thorough consideration of the spatially and temporally varying interactions among HI components and of uncertainties is therefore crucial for the success of water scarcity adaptation by HI.
- ItemCharlemagne's summit canal: An early medieval hydro-engineering project for passing the Central European Watershed(San Francisco, CA : Public Library of Science, 2014) Zielhofer, C.; Leitholdt, E.; Werther, L.; Stele, A.; Bussmann, J.; Linzen, S.; Schneider, M.; Meyer, C.; Berg-Hobohm, S.; Ettel, P.The Central European Watershed divides the Rhine-Main catchment and the Danube catchment. In the Early Medieval period, when ships were important means of transportation, Charlemagne decided to link both catchments by the construction of a canal connecting the Schwabian Rezat and the Altmü hl rivers. The artificial waterway would provide a continuous inland navigation route from the North Sea to the Black Sea. The shortcut is known as Fossa Carolina and represents one of the most important Early Medieval engineering achievements in Europe. Despite the important geostrategic relevance of the construction it is not clarified whether the canal was actually used as a navigation waterway. We present new geophysical data and in situ findings from the trench fills that prove for the first time a total length of the constructed Carolingian canal of at least 2300 metres. We have evidence for a conceptual width of the artificial water course between 5 and 6 metres and a water depth of at least 60 to 80 cm. This allows a crossing way passage of Carolingian cargo scows with a payload of several tons. There is strong evidence for clayey to silty layers in the trench fills which reveal suspension load limited stillwater deposition and, therefore, the evidence of former Carolingian and post-Carolingian ponds. These findings are strongly supported by numerous sapropel layers within the trench fills. Our results presented in this study indicate an extraordinarily advanced construction level of the known course of the canal. Here, the excavated levels of Carolingian trench bottoms were generally sufficient for the efficient construction of stepped ponds and prove a final concept for a summit canal. We have evidence for the artificial Carolingian dislocation of the watershed and assume a sophisticated Early Medieval hydrological engineering concept for supplying the summit of the canal with adequate water.