Counterion condensation for rigid linear polyelectrolytes

Diese Doktorarbeit studiert steife, lineare Polyelektrolyteim Rahmen eines Zellenmodells. Im Mittelpunkt steht dabeidas Phänomen der Gegenionenkondensation an der Oberflächeeines geladenen Makroions. Seine Abhängigkeit vonParametern wie Dichte, Bjerrum-Länge, Valenz undIonenstärke wird untersucht, und seine Auswirkungen aufwichtige Observablen wie Ionenverteilungen und osmotischerDruck werden diskutiert. Von theoretischer Seite werdendiese Probleme mit Hilfe der nichtlinearen undlinearisierten Poisson-Boltzmann Gleichung sowieallgemeineren Dichtefunktionaltheorien behandelt.Molekulardynamik-Simulationen ergänzen die theoretischenErgebnisse und grenzen den Bereich ihrer Gültigkeit ab. Ausgehend von der Poisson-Boltzmann Theorie wird einneuartiges Kriterium fuer Gegenionenkondensationvorgeschlagen, welches mit der Manning-Theorie verträglichist. Ein neuer Korrekturterm fuer die freie Energie inPoisson-Boltzmann Näherung wird hergeleitet, ausgehend vomModell eines einkomponentigen Plasmas. Die entsprechendenFunktionale der freien Energie werden mittels einerneuartigen Monte-Carlo Methode minimiert. Diedurchgeführten Computersimulationen untersucheninsbesondere die qualitativ neuen Phänomene, welche beihoher Ionenstärke auftreten, wie etwa Ladungsumkehr, einnegativer osmotischer Druck oder ein nicht-monotoneszeta-Potential. In all diesen Fällen wird die Bedeutungmultivalenter Ionen offensichtlich. In den Simulationen werden elektrostatische Wechselwirkungenmittels Particle-Mesh-Ewald Algorithmen berechnet. DerenAufbau wird in einem einheitlichen mathematischen Rahmenanalysiert. Speziell fuer die P3M Methode wird erstmalseine analytische Fehlerabschätzung hergeleitet.

Measurement and modeling of cloud condensation nuclei in continental air

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. Knowledge of the spatial and temporal distribution of CCN in the atmosphere is essential to understand and describe the effects of aerosols in meteorological models. In this study, CCN properties were measured in polluted and pristine air of different continental regions, and the results were parameterized for efficient prediction of CCN concentrations.The continuous-flow CCN counter used for size-resolved measurements of CCN efficiency spectra (activation curves) was calibrated with ammonium sulfate and sodium chloride aerosols for a wide range of water vapor supersaturations (S=0.068% to 1.27%). A comprehensive uncertainty analysis showed that the instrument calibration depends strongly on the applied particle generation techniques, Köhler model calculations, and water activity parameterizations (relative deviations in S up to 25%). Laboratory experiments and a comparison with other CCN instruments confirmed the high accuracy and precision of the calibration and measurement procedures developed and applied in this study.The mean CCN number concentrations (NCCN,S) observed in polluted mega-city air and biomass burning smoke (Beijing and Pearl River Delta, China) ranged from 1000 cm−3 at S=0.068% to 16 000 cm−3 at S=1.27%, which is about two orders of magnitude higher than in pristine air at remote continental sites (Swiss Alps, Amazonian rainforest). Effective average hygroscopicity parameters, κ, describing the influence of chemical composition on the CCN activity of aerosol particles were derived from the measurement data. They varied in the range of 0.3±0.2, were size-dependent, and could be parameterized as a function of organic and inorganic aerosol mass fraction. At low S (≤0.27%), substantial portions of externally mixed CCN-inactive particles with much lower hygroscopicity were observed in polluted air (fresh soot particles with κ≈0.01). Thus, the aerosol particle mixing state needs to be known for highly accurate predictions of NCCN,S. Nevertheless, the observed CCN number concentrations could be efficiently approximated using measured aerosol particle number size distributions and a simple κ-Köhler model with a single proxy for the effective average particle hygroscopicity. The relative deviations between observations and model predictions were on average less than 20% when a constant average value of κ=0.3 was used in conjunction with variable size distribution data. With a constant average size distribution, however, the deviations increased up to 100% and more. The measurement and model results demonstrate that the aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the measurement results and parameterizations presented in this study can be directly implemented in detailed process models as well as in large-scale atmospheric and climate models for efficient description of the CCN activity of atmospheric aerosols.

Chemical composition measurements of cloud condensation nuclei and ice nuclei by aerosol mass spectrometry

In this study the Aerodyne Aerosol Mass Spectrometer (AMS) was used during three laboratory measurement campaigns, FROST1, FROST2 and ACI-03. The FROST campaigns took place at the Leipzig Aerosol Cloud Interaction Simulator (LACIS) at the IfT in Leipzig and the ACI-03 campaign was conducted at the AIDA facility at the Karlsruhe Institute of Technology (KIT). In all three campaigns, the effect of coatings on mineral dust ice nuclei (IN) was investigated. During the FROST campaigns, Arizona Test Dust (ATD) particles of 200, 300 and 400 nm diameter were coated with thin coatings (< 7 nm) of sulphuric acid. At these very thin coatings, the AMS was operated close to its detection limits. Up to now it was not possible to accurately determine AMS detection limits during regular measurements. Therefore, the mathematical tools to analyse the detection limits of the AMS have been improved in this work. It is now possible to calculate detection limits of the AMS under operating conditions, without losing precious time by sampling through a particle filter. The instrument was characterised in more detail to enable correct quantification of the sulphate loadings on the ATD particle surfaces. Correction factors for the instrument inlet transmission, the collection efficiency, and the relative ionisation efficiency have been determined. With these corrections it was possible to quantify the sulphate mass per particle on the ATD after the condensation of sulphuric acid on its surface. The AMS results have been combined with the ice nucleus counter results. This revealed that the IN-efficiency of ATD is reduced when it is coated with sulphuric acid. The reason for this reduction is a chemical reaction of sulphuric acid with the particle's surface. These reactions are increasingly taking place when the aerosol is humidified or heated after the coating with sulphuric acid. A detailed analysis of the solubility and the evaporation temperature of the surface reaction products revealed that most likely aluminium sulphate is produced in these reactions.