Mode coupling for precise measurements of the electronic g-factor of hydrogen-like ions in Penning traps

The g-factor is a constant which connects the magnetic moment $vec{mu}$ of a charged particle, of charge q and mass m, with its angular momentum $vec{J}$. Thus, the magnetic moment can be writen $ vec{mu}_J=g_Jfrac{q}{2m}vec{J}$. The g-factor for a free particle of spin s=1/2 should take the value g=2. But due to quantum electro-dynamical effects it deviates from this value by a small amount, the so called g-factor anomaly $a_e$, which is of the order of $10^{-3}$ for the free electron. This deviation is even bigger if the electron is exposed to high electric fields. Therefore highly charged ions, where electric field strength gets values on the order of $10^{13}-10^{16}$V/cm at the position of the bound electron, are an interesting field of investigations to test QED-calculations. In previous experiments [H"aff00,Ver04] using a single hydrogen-like ion confined in a Penning trap an accuracy of few parts in $10^{-9}$ was obtained. In the present work a new method for precise measurement of magnetic the electronic g-factor of hydrogen-like ions is discussed. Due to the unavoidable magnetic field inhomogeneity in a Penning trap, a very important contribution to the systematic uncertainty in the previous measurements arose from the elevated energy of the ion required for the measurement of its motional frequencies. Then it was necessary to extrapolate the result to vanishing energies. In the new method the energy in the cyclotron degree of freedom is reduced to the minimum attainable energy. This method consist in measuring the reduced cyclotron frequency $nu_{+}$ indirectly by coupling the axial to the reduced cyclotron motion by irradiation of the radio frequency $nu_{coup}=nu_{+}-nu_{ax}+delta$ where $delta$ is, in principle, an unknown detuning that can be obtained from the knowledge of the coupling process. Then the only unknown parameter is the desired value of $nu_+$. As a test, a measurement with, for simplicity, artificially increased axial energy was performed yielding the result $g_{exp}=2.000~047~020~8(24)(44)$. This is in perfect agreement with both the theoretical result $g_{theo}=2.000~047~020~2(6)$ and the previous experimental result $g_{exp1}=2.000~047~025~4(15)(44).$ In the experimental results the second error-bar is due to the uncertainty in the accepted value for the electron's mass. Thus, with the new method a higher accuracy in the g-factor could lead by comparison to the theoretical value to an improved value of the electron's mass. [H"af00] H. H"affner et al., Phys. Rev. Lett. 85 (2000) 5308 [Ver04] J. Verd'u et al., Phys. Rev. Lett. 92 (2004) 093002-1

Nuclear structure studies in the xenon and radon region and the discovery of a new radon isotope by Penning trap mass spectrometry

Heutzutage gewähren hochpräzise Massenmessungen mit Penning-Fallen tiefe Einblicke in die fundamentalen Eigenschaften der Kernmaterie. Zu diesem Zweck wird die freie Zyklotronfrequenz eines Ions bestimmt, das in einem starken, homogenen Magnetfeld gespeichert ist. Am ISOLTRAP-Massenspektrometer an ISOLDE / CERN können die Massen von kurzlebigen, radioaktiven Nukliden mit Halbwertszeiten bis zu einigen zehn ms mit einer Unsicherheit in der Größenordnung von 10^-8 bestimmt werden. ISOLTRAP besteht aus einem Radiofrequenz-Quadrupol zum akkumulieren der von ISOLDE gelieferten Ionen, sowie zwei Penning-Fallen zum säubern und zur Massenbestimmung der Ionen. Innerhalb dieser Arbeit wurden die Massen von neutronenreichen Xenon- und Radonisotopen (138-146Xe und 223-229Rn) gemessen. Für elf davon wurde zum ersten Mal die Masse direkt bestimmt; 229Rn wurde im Zuge dieses Experimentes sogar erstmalig beobachtet und seine Halbwertszeit konnte zu ungefähr 12 s bestimmt werden. Da die Masse eines Nuklids alle Wechselwirkungen innerhalb des Kerns widerspiegelt, ist sie einzigartig für jedes Nuklid. Eine dieser Wechselwirkungen, die Wechselwirkung zwischen Protonen und Neutronen, führt zum Beispiel zu Deformationen. Das Ziel dieser Arbeit ist eine Verbindung zwischen kollektiven Effekten, wie Deformationen und Doppeldifferenzen von Bindungsenergien, sogenannten deltaVpn-Werten zu finden. Insbesondere in den hier untersuchten Regionen zeigen deltaVpn-Werte ein sehr ungewöhnliches Verhalten, das sich nicht mit einfachen Argumenten deuten lässt. Eine Erklärung könnte das Auftreten von Oktupoldeformationen in diesen Gebieten sein. Nichtsdestotrotz ist eine quantitative Beschreibung von deltaVpn-Werten, die den Effekt von solchen Deformationen berücksichtigt mit modernen Theorien noch nicht möglich.

Complementary mass spectrometric techniques for the characterization of the organic fraction in atmospheric aerosols

Aerosol particles are strongly related to climate, air quality, visibility and human health issues. They contribute the largest uncertainty in the assessment of the Earth´s radiative budget, directly by scattering or absorbing solar radiation or indirectly by nucleating cloud droplets. The influence of aerosol particles on cloud related climatic effects essentially depends upon their number concentration, size and chemical composition. A major part of submicron aerosol consists of secondary organic aerosol (SOA) that is formed in the atmosphere by the oxidation of volatile organic compounds. SOA can comprise a highly diverse spectrum of compounds that undergo continuous chemical transformations in the atmosphere.rnThe aim of this work was to obtain insights into the complexity of ambient SOA by the application of advanced mass spectrometric techniques. Therefore, an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) was applied in the field, facilitating the measurement of ions of the intact molecular organic species. Furthermore, the high measurement frequency provided insights into SOA composition and chemical transformation processes on a high temporal resolution. Within different comprehensive field campaigns, online measurements of particular biogenic organic acids were achieved by combining an online aerosol concentrator with the APCI-IT-MS. A holistic picture of the ambient organic aerosol was obtained through the co-located application of other complementary MS techniques, such as aerosol mass spectrometry (AMS) or filter sampling for the analysis by liquid chromatography / ultrahigh resolution mass spectrometry (LC/UHRMS).rnIn particular, during a summertime field study at the pristine boreal forest station in Hyytiälä, Finland, the partitioning of organic acids between gas and particle phase was quantified, based on the online APCI-IT-MS and AMS measurements. It was found that low volatile compounds reside to a large extent in the gas phase. This observation can be interpreted as a consequence of large aerosol equilibration timescales, which build up due to the continuous production of low volatile compounds in the gas phase and/or a semi-solid phase state of the ambient aerosol. Furthermore, in-situ structural informations of particular compounds were achieved by using the MS/MS mode of the ion trap. The comparison to MS/MS spectra from laboratory generated SOA of specific monoterpene precursors indicated that laboratory SOA barely depicts the complexity of ambient SOA. Moreover, it was shown that the mass spectra of the laboratory SOA more closely resemble the ambient gas phase composition, indicating that the oxidation state of the ambient organic compounds in the particle phase is underestimated by the comparison to laboratory ozonolysis. These observations suggest that the micro-scale processes, such as the chemistry of aerosol aging or the gas-to-particle partitioning, need to be better understood in order to predict SOA concentrations more reliably.rnDuring a field study at the Mt. Kleiner Feldberg, Germany, a slightly different aerosol concentrator / APCI-IT-MS setup made the online analysis of new particle formation possible. During a particular nucleation event, the online mass spectra indicated that organic compounds of approximately 300 Da are main constituents of the bulk aerosol during ambient new particle formation. Co-located filter analysis by LC/UHRMS analysis supported these findings and furthermore allowed to determine the molecular formulas of the involved organic compounds. The unambiguous identification of several oxidized C 15 compounds indicated that oxidation products of sesquiterpenes can be important compounds for the initial formation and subsequent growth of atmospheric nanoparticles.rnThe LC/UHRMS analysis furthermore revealed that considerable amounts of organosulfates and nitrooxy organosulfates were detected on the filter samples. Indeed, it was found that several nitrooxy organosulfate related APCI-IT-MS mass traces were simultaneously enhanced. Concurrent particle phase ion chromatography and AMS measurements indicated a strong bias between inorganic sulfate and total sulfate concentrations, supporting the assumption that substantial amounts of sulfate was bonded to organic molecules.rnFinally, the comprehensive chemical analysis of the aerosol composition was compared to the hygroscopicity parameter kappa, which was derived from cloud condensation nuclei (CCN) measurements. Simultaneously, organic aerosol aging was observed by the evolution of a ratio between a second and a first generation biogenic oxidation product. It was found that this aging proxy positively correlates with increasing hygroscopicity. Moreover, it was observed that the bonding of sulfate to organic molecules leads to a significant reduction of kappa, compared to an internal mixture of the same mass fractions of purely inorganic sulfate and organic molecules. Concluding, it has been shown within this thesis that the application of modern mass spectrometric techniques allows for detailed insights into chemical and physico-chemical processes of atmospheric aerosols.rn

Tropospheric photochemistry of ozone, its precursors and the hydroxyl radical

Zusammenfassung Ein 3-dimensionales globales Modell der unterenAtmosphäre wurde für die Untersuchung derOzonchemie, sowie der Chemie des Hydroxylradikals (OH) undwichtiger Vorläufersubstanzen, wie reaktiverStickstoffverbindungen und Kohlenwasserstoffe, verwendet.Hierfür wurde die Behandlung vonNicht-Methan-Kohlenwasserstoffen (NMKW) hinzugefügt,was auch die Entwicklung einer vereinfachten Beschreibungihrer Chemie, sowie die Erfassung von Depositionsprozessenund Emissionen erforderte. Zur Lösung der steifengewöhnlichen Differentialgleichungen der Chemie wurdeeine schnelles Rosenbrock-Verfahren eingesetzt, das soimplementiert wurde, dass die Modell-Chemie fürzukünftige Studien leicht abgeändert werden kann. Zur Evaluierung des Modells wurde ein umfangreicherVergleich der Modellergebnisse mit Bodenmessungen, sowieFlugzeug-, Sonden- und Satelliten-Daten durchgeführt.Das Modell kann viele Aspekte der Beobachtungen derverschieden Substanzen realistisch wiedergeben. Es wurdenjedoch auch einige Diskrepanzen festgestellt, die Hinweiseauf fehlerhafte Emissionsfelder oder auf die Modell-Dynamikund auch auf fehlende Modell-Chemie liefern. Zur weiteren Untersuchung des Einflusses verschiedenerStoffgruppen wurden drei Läufe mit unterschiedlichkomplexer Chemie analysiert. Durch das Berücksichtigender NMKW wird die Verteilung mehrerer wichtiger Substanzensignifikant beeinflusst, darunter z.B. ein Anstieg desglobalen Ozons. Es wurde gezeigt, dass die biogene SubstanzIsopren etwa die Hälfte des Gesamteffekts der NMKWausmachte (mehr in den Tropen, weniger anderswo). In einer Sensitivitätsstudie wurden die Unsicherheitenbei der Modellierung von Isopren weitergehend untersucht.Dabei konnte gezeigt werden, dass die Unsicherheit beiphysikalischen Aspekten (Deposition und heterogene Prozesse)ebenso groß sein kann, wie die aus dem chemischenGasphasen-Mechanismus stammende, welche zu globalbedeutsamen Abweichungen führte. Lokal können sichnoch größere Abweichungen ergeben. Zusammenfassend kann gesagt werden, dass die numerischenStudien dieser Arbeit neue Einblicke in wichtige Aspekte derPhotochemieder Troposphäre ergaben und in Vorschläge fürweiter Studien mündeten, die die wichtigsten gefundenenUnsicherheiten weiter verringern könnten.

Soil biogenic emissions of nitric oxide from arid and semi-arid ecosystems

The biogenic production of NO in the soil accounts for between 10% and 40% of the global total. A large degree of the uncertainty in the estimation of the biogenic emissions stems from a shortage of measurements in arid regions, which comprise 40% of the earth’s land surface area. This study examined the emission of NO from three ecosystems in southern Africa which cover an aridity gradient from semi-arid savannas in South Africa to the hyper-arid Namib Desert in Namibia. A laboratory method was used to determine the release of NO as a function of the soil moisture and the soil temperature. Various methods were used to up-scale the net potential NO emissions determined in the laboratory to the vegetation patch, landscape or regional level. The importance of landscape, vegetation and climatic characteristics is emphasized. The first study occurred in a semi-arid savanna region in South Africa, where soils were sampled from 4 landscape positions in the Kruger National Park. The maximum NO emission occurred at soil moisture contents of 10%-20% water filled pore space (WFPS). The highest net potential NO emissions came from the low lying landscape positions, which have the largest nitrogen (N) stocks and the largest input of N. Net potential NO fluxes obtained in the laboratory were converted in field fluxes for the period 2003-2005, for the four landscape positions, using soil moisture and temperature data obtained in situ at the Kruger National Park Flux Tower Site. The NO emissions ranged from 1.5-8.5 kg ha-1 a-1. The field fluxes were up-scaled to a regional basis using geographic information system (GIS) based techniques, this indicated that the highest NO emissions occurred from the Midslope positions due to their large geographical extent in the research area. Total emissions ranged from 20x103 kg in 2004 to 34x103 kg in 2003 for the 56000 ha Skukuza land type. The second study occurred in an arid savanna ecosystem in the Kalahari, Botswana. In this study I collected soils from four differing vegetation patch types including: Pan, Annual Grassland, Perennial Grassland and Bush Encroached patches. The maximum net potential NO fluxes ranged from 0.27 ng m-2 s-1 in the Pan patches to 2.95 ng m-2 s-1 in the Perennial Grassland patches. The net potential NO emissions were up-scaled for the year December 2005-November 2006. This was done using 1) the net potential NO emissions determined in the laboratory, 2) the vegetation patch distribution obtained from LANDSAT NDVI measurements 3) estimated soil moisture contents obtained from ENVISAT ASAR measurements and 4) soil surface temperature measurements using MODIS 8 day land surface temperature measurements. This up-scaling procedure gave NO fluxes which ranged from 1.8 g ha-1 month-1 in the winter months (June and July) to 323 g ha-1 month-1 in the summer months (January-March). Differences occurred between the vegetation patches where the highest NO fluxes occurred in the Perennial Grassland patches and the lowest in the Pan patches. Over the course of the year the mean up-scaled NO emission for the studied region was 0.54 kg ha-1 a-1 and accounts for a loss of approximately 7.4% of the estimated N input to the region. The third study occurred in the hyper-arid Namib Desert in Namibia. Soils were sampled from three ecosystems; Dunes, Gravel Plains and the Riparian zone of the Kuiseb River. The net potential NO flux measured in the laboratory was used to estimate the NO flux for the Namib Desert for 2006 using modelled soil moisture and temperature data from the European Centre for Medium Range Weather Forecasts (ECMWF) operational model on a 36km x 35km spatial resolution. The maximum net potential NO production occurred at low soil moisture contents (<10%WFPS) and the optimal temperature was 25°C in the Dune and Riparian ecosystems and 35°C in the Gravel Plain Ecosystems. The maximum net potential NO fluxes ranged from 3.0 ng m-2 s-1 in the Riparian ecosystem to 6.2 ng m-2 s-1 in the Gravel Plains ecosystem. Up-scaling the net potential NO flux gave NO fluxes of up to 0.062 kg ha-1 a-1 in the Dune ecosystem and 0.544 kg h-1 a-1 in the Gravel Plain ecosystem. From these studies it is shown that NO is emitted ubiquitously from terrestrial ecosystems, as such the NO emission potential from deserts and scrublands should be taken into account in the global NO models. The emission of NO is influenced by various factors such as landscape, vegetation and climate. This study looks at the potential emissions from certain arid and semi-arid environments in southern Africa and other parts of the world and discusses some of the important factors controlling the emission of NO from the soil.