An all-solid state laser system for the laser ion source RILIS and in-source laser spectroscopy of astatine at ISOLDE,CERN

This doctoral thesis describes the extension of the resonance ionization laser ion source RILIS at CERN/ISOLDE by the addition of an all-solid state tunable titanium:sapphire (Ti:Sa) laser system to complement the well-established system of dye lasers. Synchronous operation of the so called Dual RILIS system of Ti:Sa and dye lasers was investigated and the potential for increased ion beam intensity, reliability, and reduced setup time has been demonstrated. In-source resonance ionization spectroscopy was performed at ISOLDE/CERN and at ISAC/TRIUMF radioactive ion beam facilities to develop an efficient and selective three-colour ionization scheme for the purely radioactive element astatine. A LabVIEW based monitoring, control and measurement system was conceived which enabled, in conjunction with Dual RILIS operation, the spectroscopy of high lying Rydberg states, from which the ionization potential of the astatine atom was determined for the first time experimentally.

Spins, moments and radii of cd isotopes

The complex nature of the nucleon-nucleon interaction and the wide range of systems covered by the roughly 3000 known nuclides leads to a multitude of effects observed in nuclear structure. Among the most prominent ones is the occurence of shell closures at so-called ”magic numbers”, which are explained by the nuclear shell model. Although the shell model already is on duty for several decades, it is still constantly extended and improved. For this process of extension, fine adjustment and verification, it is important to have experimental data of nuclear properties, especially at crucial points like in the vicinity of shell closures. This is the motivation for the work performed in this thesis: the measurement and analysis of nuclear ground state properties of the isotopic chain of 100−130Cd by collinear laser spectroscopy.rnrnThe experiment was conducted at ISOLDE/CERN using the collinear laser spectroscopy apparatus COLLAPS. This experiment is the continuation of a run on neutral atomic cadmium from A = 106 to A = 126 and extends the measured isotopes to even more exotic species. The required gain in sensitivity is mainly achieved by using a radiofrequency cooler and buncher for background reduction and by using the strong 5s 2S1/2 → 5p 2P3/2 transition in singly ionized Cd. The latter requires a continuous wave laser system with a wavelength of 214.6 nm, which has been developed during this thesis. Fourth harmonic generation of an infrared titanium sapphire laser is achieved by two subsequent cavity-enhanced second harmonic generations, leading to the production of deep-UV laser light up to about 100 mW.rnrnThe acquired data of the Z = 48 Cd isotopes, having one proton pair less than the Z = 50 shell closure at tin, covers the isotopes from N = 52 up to N = 82 and therefore almost the complete region between the neutron shell closures N = 50 and N = 82. The isotope shifts and the hyperfine structures of these isotopes have been recorded and the magnetic dipole moments, the electric quadrupole moments, spins and changes in mean square charge radii are extracted. The obtained data reveal among other features an extremely linear behaviour of the quadrupole moments of the I = 11/2− isomeric states and a parabolic development in differences in mean square nuclear charge radii between ground and isomeric state. The development of charge radii between the shell closures is smooth, exposes a regular odd-even staggering and can be described and interpreted in the model of Zamick and Thalmi.

Wetting and spreading of a surfactant film on solid particles: influence of sharp edges and surface irregularities

In addition to particle size and surface chemistry, the shape of particles plays an important role in their wetting and displacement by the surfactant film in the lung. The role of particle shape was the subject of our investigations using a model system consisting of a modified Langmuir-Wilhelmy surface balance. We measured the influence of sharp edges (lines) and other highly curved surfaces, including sharp corners or spikes, of different particles on the spreading of a dipalmitoylphosphatidyl (DPPC) film. The edges of cylindrical sapphire plates (circular curved edges, 1.65 mm radius) were wetted at a surface tension of 10.7 mJ/m2 (standard error (SE) = 0.45, n = 20) compared with that of 13.8 mJ/m2 (SE = 0.20, n = 20) for cubic sapphire plates (straight linear edges, edge length 3 mm) (p < 0.05). The top surfaces of the sapphire plates (cubic and cylindrical) were wetted at 8.4 mJ/m2 (SE = 0.54, n = 20) and 9.1 mJ/m2 (SE = 0.50, n = 20), respectively, but the difference was not significant (p > 0.05). The surfaces of the plates showed significantly higher resistance to spreading compared to that of the edges, as substantially lower surface tensions were required to initiate wetting (p < 0.05). Similar results were found for talc particles, were the edges of macro- and microcrystalline particles were wetted at 7.2 mJ/m2 (SE = 0.52, n = 20) and 8.2 mJ/m2 (SE = 0.30, n = 20) (p > 0.05), respectively, whereas the surfaces were wetted at 3.8 mJ/m2 (SE = 0.89, n = 20) and 5.8 mJ/m2 (SE = 0.52, n = 20) (p < 0.05), respectively. Further experiments with pollen of malvaceae and maize (spiky and fine knobbly surfaces) were wetted at 10.0 mJ/m2 (SE = 0.52, n = 10) and 22.75 mJ/m2 (SE = 0.81, n = 10), respectively (p < 0.05). These results show that resistance to spreading of a DPPC film on various surfaces is dependent on the extent these surfaces are curved. This is seen with cubic sapphire plates which have at their corners a radius of curvature of about 0.75 microm, spiky malvaceae pollen with an even smaller radius on top of their spikes, or talc with various highly curved surfaces. These highly curved surfaces resisted wetting by the DPPC film to a higher degree than more moderately curved surfaces such as those of cylindrical sapphire plates, maize pollens, or polystyrene spheres, which have a surface free energy similar to that of talc but a smooth surface. The macroscopic plane surfaces of the particles demonstrated the greatest resistance to spreading. This was explained by the extremely fine grooves in the nanometer range, as revealed by electron microscopy. In summary, to understand the effects of airborne particles retained on the surfaces of the respiratory tract, and ultimately their pathological potential, not only the particle size and surface chemistry but also the particle shape should be taken in consideration.

Detection of approximal caries with a new laser fluorescence device

The laser device DIAGNOdent developed for the detection of occlusal caries has limited value on approximal surfaces. The aim of this study was to develop and to test a new laser fluorescence (LF) device for the detection of approximal caries. Light with a wavelength of 655 nm was transported to the approximal surface using two different sapphire fibre tips. Seventy-five teeth were selected from a pool of extracted permanent human molars, frozen at -20 degrees C until use. Before being measured, they were defrosted, cleaned and calculus was removed with a scaler. The molars were set in blocks simulating the contact area of adults. Bitewing radiographs were obtained using Kodak Insight films. After two independent assessments with the new LF device, the teeth were histologically prepared, and assessed for caries extension. Using the laser, specificity values for D1 threshold (outer half of enamel), D2 threshold (inner half of enamel), D3 threshold (dentine) ranged between 0.81 and 0.93, sensitivity between 0.84 and 0.92 with no difference between the two tips. Bitewing radiography showed an inferior performance compared to LF (p<0.05). Intraex aminer reproducibility was high (kappa>.74). The new LF system might be a useful additional tool in detecting approximal caries. Because of its good reproducibility, it could be used to monitor caries regression or progression on approximal surfaces.

Performance of a new laser fluorescence device for the detection of occlusal caries in vitro

The new device DIAGNOdent pen based on red laser light induced fluorescence was introduced for the detection of approximal and occlusal caries. The aim of this study was to test its performance on occlusal surfaces. The new device comes with two different sapphire fibre tips: a cylindrical tip and a conical tip. The two new sapphire fibre tips were used and compared with the tip currently available with DIAGNOdent (DD). METHODS: The teeth were selected from a pool of extracted permanent human molars, which were stored frozen at -20 degrees C, until use. Prior to being measured the teeth were defrosted and cleaned. One hundred and nineteen teeth were selected and measured with the old tip and with the two new tips of the new device by two independent assessments. The teeth were histologically prepared and assessed for caries extension. RESULTS: Specificity values for D(1), D(2) and D(3) ranged between 0.69 and 0.89, sensitivity between 0.78 and 0.96. There were no statistically significant differences obtained between the two tips of the new and the one tip of the old device (p>0.05). Intra-examiner reliability with kappa values of >0.83 was high. CONCLUSIONS: In this study, the new laser fluorescence device performed on occlusal surfaces as well as the available device.

Investigation into the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film gadolinium-doped ceria

The research reported in this dissertation investigates the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film Gd-doped CeO2 (GDC). Chapter 2 of this work addresses claims in the literature that submicron grain boundaries have the potential to dramatically increase the ionic conductivity of GDC films. Unambiguous testing of this claim requires directly comparing the ionic conductivity of single-crystal GDC films to films that are identical except for the presence of submicron grain boundaries. In this work techniques have been developed to grow GDC films by RF magnetron sputtering from a GDC target on single crystal r plane sapphire substrates. These techniques allow the growth of films that are single crystals or polycrystalline with 80 nm diameter grains. The ionic conductivities of these films have been measured and the data shows that the ionic conductivity of single crystal GDC is greater than that of the polycrystalline films by more than a factor of 4 over the 400-700°C temperature range. Chapter 3 of this work investigates the ionic conductivity of surface and interface regions of thin film Gd-doped CeO2. In this study, single crystal GDC films have been grown to thicknesses varying from 20 to 500 nm and their conductivities have been measured in the 500-700°C temperature range. Decreasing conductivity with decreasing film thickness was observed. Analysis of the conductivity data is consistent with the presence of an approximately 50 nm layer of less conductive material in every film. This study concludes that the surface and interface regions of thin film GDC are less conductive than the bulk single crystal regions, rather than being highly conductive paths. Chapter 4 of this work investigates the ionic conductivity of thin film Gd-doped CeO2 (GDC) as a function of crystallographic orientation. A theoretical expression has been developed for the ionic conductivity of the [100] and [110] directions in single crystal GDC. This relationship is compared to experimental data collected from a single crystal GDC film. The film was grown to a thickness of _300 nm and its conductivity measured along the [100] and [110] orientations in the 500-700°C temperature range. The experimental data shows no statistically significant difference in the conductivities of the [100] and [110] directions in single crystal GDC. This result agrees with the theoretical model which predicts no difference between the conductivities of the two directions.

AMS radiocarbon dates and pollen analysis of ODP Hole 175-1078C

ODP Site 1078 situated under the coast of Angola provides the first record of the vegetation history for Angola. The upper 11 m of the core covers the past 30 thousand years, which has been analysed palynologically in decadal to centennial resolution. Alkenone sea surface temperature estimates were analysed in centennial resolution. We studied sea surface temperatures and vegetation development during full glacial, deglacial, and interglacial conditions. During the glacial the vegetation in Angola was very open consisting of grass and heath lands, deserts and semi-deserts, which suggests a cool and dry climate. A change to warmer and more humid conditions is indicated by forest expansion starting in step with the earliest temperature rise in Antarctica, 22 thousand years ago. We infer that around the period of Heinrich Event 1, a northward excursion of the Angola Benguela Front and the Congo Air Boundary resulted in cool sea surface temperatures but rain forest remained present in the northern lowlands of Angola. Rain forest and dry forest area increase 15 thousand years ago. During the Holocene, dry forests and Miombo woodlands expanded. Also in Angola globally recognised climate changes at 8 thousand and 4 thousand years ago had an impact on the vegetation. During the past 2 thousand years, savannah vegetation became dominant.

XRF scanning, pollen and spores of ODP Site 108-659

Pliocene vegetation dynamics and climate variability in West Africa have been investigated through pollen and XRF-scanning records obtained from sediment cores of ODP Site 659 (18°N, 21°W). The comparison between total pollen accumulation rates and Ti/Ca ratios, which is strongly correlated with the dust input at the site, showed elevated aeolian transport of pollen during dusty periods. Comparison of the pollen records of ODP Site 659 and the nearby Site 658 resulted in a robust reconstruction of West African vegetation change since the Late Pliocene. Between 3.6 and 3.0 Ma the savannah in West Africa differed in composition from its modern counterpart and was richer in Asteraceae, in particular of the Tribus Cichorieae. Between 3.24 and 3.20 Ma a stable wet period is inferred from the Fe/K ratios, which could stand for a narrower and better specified mid-Pliocene (mid-Piacenzian) warm time slice. The northward extension of woodland and savannah, albeit fluctuating, was generally greater in the Pliocene. NE trade wind vigour increased intermittently around 2.7 and 2.6 Ma, and more or less permanently since 2.5 Ma, as inferred from increased pollen concentrations of trade wind indicators (Ephedra, Artemisia, Pinus). Our findings link the NE trade wind development with the intensification of the Northern Hemisphere glaciations (iNHG). Prior to the iNHG, little or no systematic relation could be found between sea surface temperatures of the North Atlantic with aridity and dust in West Africa.

Distribution of pollen and spores in sediments of ODP Hole 175-1078C

The distribution of pollen in marine sediments is used to record vegetation change on the continent. Generally, a good latitudinal correspondence exists between the distribution patterns of pollen in the marine surface sediments and the occurrence of the source plants on the adjacent continent. To investigate land-sea interactions during deglaciation, we compare proxies for continental (pollen assemblages) and marine conditions (alkenone-derived sea surface temperatures) of two high-resolution, radiocarbon-dated sedimentary records from the tropical southeast Atlantic. The southern site is located West of the Cunene River mouth; the northern site is located West of the Angolan Huambe Mountains. It is inferred that the vegetation in Angola developed from Afroalpine and open savannah during the last Glacial maximum (LGM) via Afromontane Podocarpus forest during Heinrich Event 1 (H1), to an early increase of lowland forest after 14.5 ka. The vegetation record indicates dry and cold conditions during the LGM, cool and wet conditions during H1 and a gradual rise in temperature starting well before the Younger Dryas (YD) period. Terrestrial and oceanic climate developments seem largely running parallel, in contrast to the situation ca. 5° further South, where marine and terrestrial developments diverge during the YD. The cool and wet conditions in tropical West Africa, South of the equator, during H1 suggest that low-latitude insolation variation is more important than the slowdown of the thermohaline circulation for the climate in tropical Africa.

Palynology of marine sediment cores from the West African coast

Seven sediment cores from the cruises of the "Meteor" and "Valdivia" were examined palynologically. The cores were retrieved from the lower continental slope in the area of between 33.5° N and 8° N, off the West African coast. Most of the cores contain sediments from the last Glacial and Interglacial period. In some cases, the Holocene sediments are missing. Some individual cores contain sediments also from earlier Glacial and Interglacial periods. The main reason for making this palynological study was to find out the differences between the vegetation of Glacial and Interglacial periods in those parts of West Africa which at present belong to the Mediterranean zone, the Sahara and the zones of the savannas and tropical forests. In today's Mediterranean vegetation zone at core 33.5° N, forests and deciduous forests in particular, are missing during Glacial conditions. Semi-deserts are found instead of these. In the early isotope stage 1, there is a very significant development of forests which contain evergreen oaks; this is the Mediterranean type of vegestation development. The Sahara type of vegetation development is shown in four cores from between 27° N and 19° N. The differences between Glacial and Interglacial periods are very small. It must be assumed therefore that in this latitudes, both Glacial and Interglacial conditions gave rise to desert generally. The results are in favour of a slightly more arid climate during Glacial and more humid one during Interglacial periods. The southern boundary of the Sahara and the adjacent savannas with grassland and tropical woods were situated more to the south during the Glacial periods than they were during the Interglacial ones. In front of today's savanna belt, it can be seen from the palynological results that there are considerable differences between the vegetation of Glacial and Interglacial periods. The woods are more important in Interglacial periods. During the Glacial periods these are replaced from north to south decreasingly by grassland (savanna and rainforest type of vegetation development). The southern limit of the Sahara during stage 2 was somewhat between 12° N and 8° N which is between 1.5 and 5 degrees in latitude further south than it i s today. Not only do these differences in climate and vegetation apply to the maximum of the last Glacial and for the Holocene, but they apparently apply also to the older Glacial and Interglacial periods, where they have been found in the profiles. The North African deset belt can be said to have expanded during Glacial times both towards the north and towards the south. All the available evidence of this study indicates that the grass land or the semi-desert of the Southern Europe cam einto connection with those of the N Africa; there could not have been any forest zone between them. The present study was also a good opportunity for investigating some of the basic marine palynological problems. The very well known overrepresentation of pollen grains of the genus Pinus in marine sediments can be traced as fa as 21° N. The present southern limit for the genus Pinus is on the Canaries and on the African continent as approximately 31° N. Highest values of Ephedra pollen grains even occur south of the main area of the present distribution of that genus. These does not seem to be any satisfactory explanation for this. In general, it would appear that the transport of pollen grains from the north is more important than transport from the south. The results so far, indicate strongly that further palynological studies are necessary. These should concentrate particularly on cores from between 33° N and 27° N as well as between 17° N and 10° N. It would also be useful to have a more detailed examination of sediments from the last Intergalcial period (substage 5 e). Absolute pollen counts and more general examination of surface samples would be desirable. Surface samples should be taken from the shelf down to the bottom of the continental slope in different latitudes.

Palynology of ODP Site 108-658

Ocean Drilling Program Site 658 at 21°N off northwest Africa has a high sedimentation rate and a high concentration of pollen grains and is thus very suitable for detailed pollen analysis. The time scale for the upper 100 m (the last 670 k.y.) of Site 658 is based on biostratigraphic data and isotope stratigraphy. The pollen record has been divided into 34 zones. These are classified into 7 zone types covering a range from very arid to rather humid conditions. The sequence shows a long-term climatic decline: strong glacial stages were found only after 480 k.y. and strong interglacial stages only before 280 k.y. The Site 658 record correlates well with a terrestrial sequence from northern Greece, although both records differ in their response to global climatic change. Spectral analysis shows a 100- and a 42-k.y. period in the curves of pollen brought in by the northwest trade winds and only a 42-k.y. period in the curves of pollen mostly transported by the African Easterly Jet. A 31-k.y. period is found in the curves for Ephedra and Chenopodiaceae-Amaranthaceae. In addition, Ephedra shows a 54-k.y. period.

Pollen distribution in marine sediment samples along the south-western African coast

The distribution of pollen in marine sediments is used to reconstruct pathways of terrigenous input to the oceans and provides a record of vegetation change on adjacent continents. The wind transport routes of aeolian pollen is comprehensively illustrated by clusters of trajectories. Isobaric, 4-day backward trajectories are calculated using the modelled wind-field of ECHAM3, and are clustered on a seasonal basis to estimate the main pathways of aeolian particles to sites of marine cores in the south-eastern Atlantic. Trajectories and clusters based on the modelled wind-field of the Last Glacial Maximum hardly differ from those of the present-day. Trajectory clusters show three regional, and two seasonal patterns, determining the pathways of aeolian pollen transport into the south-eastern Atlantic ocean. Mainly, transport out of the continent occurs during austral fall and winter, when easterly and south-easterly winds prevail. South of 25°S, winds blow mostly from the west and southwest, and aeolian terrestrial input is very low. Generally, a good latitudinal correspondence exists between the distribution patterns of pollen in marine surface sediments and the occurrence of the source plants on the adjacent continent. The northern Angola Basin receives pollen and spores from the Congolian and Zambezian forests mainly through river discharge. The Zambezian vegetation zone is the main source area for wind-blown pollen in sediments of the Angola Basin, while the semi-desert and desert areas are the main sources for pollen in sediments of the Walvis Basin and on the Walvis Ridge. A transect of six marine pollen records along the south-western African coast indicates considerable changes in the vegetation of southern Africa between glacial and interglacial periods. Important changes in the vegetation are the decline of forests in equatorial Africa and the north of southern Africa and a northward shift of winter rain vegetation along the western escarpment.

Pollen analysis of sediment cores from the mouth of the river Congo to Walvis Bay and Lüderitz

The distribution of pollen in marine sediments is used to record vegetation changes over the past 30,000 years on the adjacent continent. A transect of marine pollen sequences from the mouth of the river Congo (~5°S) to Walvis Bay and Lüderitz (~25°S) shows vegetation changes in Congo, Angola and Namibia from the last glacial period into the Holocene. The comparison of pollen records from different latitudes provides information about the latitudinal shift of open forest and savannahs (Poaceae pollen), the extension of lowland forest (rain forest pollen) and Afromontane forest (Podocarpus pollen), and the position of the desert fringe (pollen of Caryophyllaceae, Chenopodiaceae and Amaranthaceae). High Cyperaceae pollen percentages in sediments from the last glacial period off the mouth of the river Congo suggest the presence of open swamps rather than savannah vegetation in the Congo Basin. Pollen from Restionaceae in combination with Stoebe-type pollen (probably from Elytropappus) indicates a possible northwards extension of winter rain vegetation during the last glacial period. The record of Rhizophora (mangrove) pollen is linked to erosion of the continental shelf and sea-level rise. Pollen influx is highest off river mouths (10-2000 grains year**-1 cm**-2), close to the coast (300-6000 grains year**-1 cm**-2), but is an order of magnitude lower at sites situated far from the continent (<10 grains year**-1 cm**-2).

Pollen analysis and age model of sediment core GIK-15856-2

Pollen and spores from a deep-sea core located west of the Niger Delta record an uninterrupted area of lowland rain forest in West Africa from Guinea to Cameroon during the last Interglacial and the early Holocene. During other periods of the last 150 ka, a savanna corridor between the western - Guinean - and the eastern - Congolian - part of the African lowland rain forest existed. This so-called Dahomey Gap had its largest extension during Glacial Stages 6, 4, 3, and 2. Reduced surface salinity in the eastern Gulf of Guinea as recorded by dinoflagellate cysts indicates sufficient precipitation for extensive forest growth during Stages 5 and 1. The large modern extension of dry forest and savanna in West Africa cannot be solely explained by climatic factors. Mangrove expansion in and west of the Niger Delta was largest during the phases of sea-level rise of Stages 5 and 1. During Stages 6, 4, 3, and 2, shelf areas were exposed and the area of the mangrove swamps was minimal.

Pollen record and dating of sediment core GIK16776-1 off Liberia

Based on pollen analysis of a sediment core from the Atlantic Ocean off Liberia the West African vegetation history for the last 400 ka is reconstructed. During the cold oxygen isotope stages 12, 10, 8, 6, 4, 3 and 2 an arid climate is indicated, resulting in a southward shifting of the southern border of the savanna. Late Pleistocene glacial stages were more arid than during the Middle Pleistocene. A persistence of the rain forest in the area, even during the glacial stages, is recorded. This suggests a glacial refuge of rain forest situated in the Guinean mountains. Afromontane forests with Podocarpus occurred in the Guinean mountains from the stages 12 to 2 and disappeared after. The tree expanded from higher to lower elevations twice in the warm oxygen isotope stage 11 (pollen subzones 11d, 11b) and at least twice during the warm stage 5 (pollen subzones 5d, 5a), indicating a relative cool but humid climate for these periods.