Investigations into the degassing and eruption mechanisms of Nyamuragira volcano, Democratic Republic of the Congo (Africa)

One of two active volcanoes in the western branch of the East African Rift, Nyamuragira (1.408ºS, 29.20ºE; 3058 m) is located in the D.R. Congo. Nyamuragira emits large amounts of SO2 (up to ~1 Mt/day) and erupts low-silica, alkalic lavas, which achieve flow rates of up to ~20 km/hr. The source of the large SO2 emissions and pre-eruptive magma conditions were unknown prior to this study, and 1994-2010 lava volumes were only recently mapped via satellite imagery, mainly due to the region’s political instability. In this study, new olivine-hosted melt inclusion volatile (H2O, CO2, S, Cl, F) and major element data from five historic Nyamuragira eruptions (1912, 1938, 1948, 1986, 2006) are presented. Melt compositions derived from the 1986 and 2006 tephra samples best represent pre-eruptive volatile compositions because these samples contain naturally glassy inclusions that underwent less post-entrapment modification than crystallized inclusions. The total amount of SO2 released from the 1986 (0.04 Mt) and 2006 (0.06 Mt) eruptions are derived using the petrologic method, whereby S contents in melt inclusions are scaled to erupted lava volumes. These amounts are significantly less than satellite-based SO2 emissions for the same eruptions (1986 = ~1 Mt; 2006 = ~2 Mt). Potential explanations for this observation are: 1) accumulation of a vapor phase within the magmatic system that is only released during eruptions, and/or 2) syn-eruptive gas release from unerupted magma. Post-1994 Nyamuragira lava volumes were not available at the beginning of this study. These flows (along with others since 1967) are mapped with Landsat MSS, TM, and ETM+, Hyperion, and ALI satellite data and combined with published flow thicknesses to derive volumes. Satellite remote sensing data was also used to evaluate Nyamuragira SO2 emissions. These results show that the most recent Nyamuragira eruptions injected SO2 into the atmosphere between 15 km (2006 eruption) and 5 km (2010 eruption). This suggests that past effusive basaltic eruptions (e.g., Laki 1783) are capable of similar plume heights that reached the upper troposphere or tropopause, allowing SO2 and resultant aerosols to remain longer in the atmosphere, travel farther around the globe, and affect global climates.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Processing and characterization of PbSnTe-based thermoelectric materials made by mechanical alloying

The research reported in this dissertation investigates the processes required to mechanically alloy Pb1-xSnxTe and AgSbTe2 and a method of combining these two end compounds to result in (y)(AgSbTe2)–(1 - y)(Pb1-xSnxTe) thermoelectric materials for power generation applications. In general, traditional melt processing of these alloys has employed high purity materials that are subjected to time and energy intensive processes that result in highly functional material that is not easily reproducible. This research reports the development of mechanical alloying processes using commercially available 99.9% pure elemental powders in order to provide a basis for the economical production of highly functional thermoelectric materials. Though there have been reports of high and low ZT materials fabricated by both melt alloying and mechanical alloying, the processing-structure-properties-performance relationship connecting how the material is made to its resulting functionality is poorly understood. This is particularly true for mechanically alloyed material, motivating an effort to investigate bulk material within the (y)(AgSbTe2)–(1 - y)(Pb1-xSnx- Te) system using the mechanical alloying method. This research adds to the body of knowledge concerning the way in which mechanical alloying can be used to efficiently produce high ZT thermoelectric materials. The processes required to mechanically alloy elemental powders to form Pb1-xSnxTe and AgSbTe2 and to subsequently consolidate the alloyed powder is described. The composition, phases present in the alloy, volume percent, size and spacing of the phases are reported. The room temperature electronic transport properties of electrical conductivity, carrier concentration and carrier mobility are reported for each alloy and the effect of the presence of any secondary phase on the electronic transport properties is described. An mechanical mixing approach for incorporating the end compounds to result in (y)(AgSbTe2)–(1-y)(Pb1-xSnxTe) is described and when 5 vol.% AgSbTe2 was incorporated was found to form a solid solution with the Pb1-xSnxTe phase. An initial attempt to change the carrier concentration of the Pb1-xSnxTe phase was made by adding excess Te and found that the carrier density of the alloys in this work are not sensitive to excess Te. It has been demonstrated using the processing techniques reported in this research that this material system, when appropriately doped, has the potential to perform as highly functional thermoelectric material.

A Study of Metallic Eutectics

All of the metals have definite melting points. When a metal is heated above the melting point, it exists as a liquid. Now if the melt is allowed to cool, it will solidify when a temperature corresponding to the melting point is reached. However, if one metal is added to another metal, both of which are mutually soluble in the liquid state, a certain effect can be noted. The melt will not solid­ify when the melting point of the pure metal is reached, but will freeze at a lower temperature.

Electrolysis of Molten Mixtures of Galena and Lead Chloride.

Electrolysis of molten mixtures of lead chloride and galena was carried out under various conditions of temperature, time, composition, and current densities; without a diaphram, and with various diaphrams. Continuous runs, with necessary additions of lead sulfide and lead chloride to maintain a melt of the proper composition, were attempted on a small scale.

The Electroformation of Lithium-Lead Alloys from Molten Electrolytes

An attempt was made to make lead-lithium alloys by electrodeposition of lithium using a molten bath and a molten lead cathode.The variables taken into consideration were: composition of the melt, temperature of the melt, and current density. The purpose of changing these factors was to determine what effect each had on the current efficiency.

Electrospun Quaternized Chitosan Fibers for Virus Removal from Drinking Water

Membrane filtration has become an accepted technology for the removal of pathogens from drinking water. Viruses, known to contaminate water supplies, are too small to be removed by a size-exclusion mechanism without a large energy penalty. Thus, functionalized electrospun membranes that can adsorb viruses have drawn our interest. We chose a quaternized chitosan derivative (HTCC) which carries a positively-charged quaternary amine, known to bind negatively-charged virus particles, as a functionalized membrane material. The technique of electrospinning was utilized to produce nanofiber mats with large pore diameters to increase water flux and decrease membrane fouling. In this study, stable, functionalized, electrospun HTCC-PVA nanofibers that can remove 3.6 logs (99.97%) of a model virus, porcine parvovirus (PPV), from water by adsorption and filtration have been successfully produced. This technology has the potential to purify drinking water in undeveloped countries and reduce the number of deaths due to lack of sanitation.

Thermographie zur Temperaturmessung beim Laser-Sintern – ein Beitrag zur Qualitätssicherung?

Beim Laser-Sintern wird das Pulverbett durch Heizstrahler vorgeheizt, um an der Pulveroberfläche eine Temperatur knapp unterhalb des Materialschmelzpunktes zu erzielen. Dabei soll die Temperaturverteilung auf der Oberfläche möglichst homogen sein, um gleiche Bauteileigenschaften im gesamten Bauraum zu erzielen und den Bauteilverzug gering zu halten. Erfahrungen zeigen jedoch sehr inhomogene Temperaturverteilungen, weshalb oftmals die Integration von neuen oder optimierten Prozessüberwachungssystemen in die Anlagen gefordert wird. Ein potentiell einsetzbares System sind Thermographiekameras, welche die flächige Aufnahme von Oberflächentemperaturen und somit Aussagen über die Temperaturen an der Pulverbettoberfläche erlauben. Dadurch lassen sich kalte Bereiche auf der Oberfläche identifizieren und bei der Prozessvorbereitung berücksichtigen. Gleichzeitig ermöglicht die Thermografie eine Beobachtung der Temperaturen beim Lasereingriff und somit das Ableiten von Zusammenhängen zwischen Prozessparametern und Schmelzetemperaturen. Im Rahmen der durchgeführten Untersuchungen wurde ein IR-Kamerasystem erfolgreich als Festeinbau in eine Laser-Sinteranlage integriert und Lösungen für die hierbei auftretenden Probleme erarbeitet. Anschließend wurden Untersuchungen zur Temperaturverteilung auf der Pulverbettoberfläche sowie zu den Einflussfaktoren auf deren Homogenität durchgeführt. In weiteren Untersuchungen wurden die Schmelzetemperaturen in Abhängigkeit verschiedener Prozessparameter ermittelt. Auf Basis dieser Messergebnisse wurden Aussagen über erforderliche Optimierungen getroffen und die Nutzbarkeit der Thermografie beim Laser-Sintern zur Prozessüberwachung, -regelung sowie zur Anlagenwartung als erster Zwischenstand der Untersuchungen bewertet.

Prozessoptimierung des SLM-Prozesses mit hoch-reflektiven und thermisch sehr gut leitenden Materialien durch systematische Parameterfindung und begleitende Simulationen am Beispiel von Silber

Additive Manufacturing durch Aufschmelzen von Metallpulvern hat sich auf breiter Front als Herstellverfahren, auch für Endprodukte, etabliert. Besonders für die Variante des Selective Laser Melting (SLM) sind Anwendungen in der Zahntechnik bereits weit verbreitet und der Einsatz in sensitiven Branchen wie der Luftfahrt ist in greifbare Nähe gerückt. Deshalb werden auch vermehrt Anstrengungen unternommen, um bisher nicht verarbeitete Materialien zu qualifizieren. Dies sind vorzugsweise Nicht-Eisen- und Edelmetalle, die sowohl eine sehr hohe Reflektivität als auch eine sehr gute Wärmeleitfähigkeit aufweisen – beides Eigenschaften, die die Beherrschung des Laser-Schmelzprozesses erschweren und nur kleine Prozessfenster zulassen. Die Arbeitsgruppe SLM des Lehr- und Forschungsgebietes Hochleistungsverfahren der Fertigungstechnik hat sich unter der Randbedingung einer kleinen und mit geringer Laserleistung ausgestatteten SLM Maschine der Aufgabe gewidmet und am Beispiel von Silber die Parameterfelder für Einzelspuren und wenig komplexe Geometrien systematisch untersucht. Die Arbeiten wurden von FEM Simulationen begleitet und durch metallographische Untersuchungen verifiziert. Die Ergebnisse bilden die Grundlage zur schnellen Parameterfindung bei komplexen Geometrien und bei Veränderungen der Zusammensetzung, wie sie bei zukünftigen Legierungen zu erwarten sind. Die Ergebnisse werden exemplarisch auf unterschiedliche Geometrien angewandt und entsprechende Bauteile gezeigt.

Identification of glacial meltwater runoff in a karstic environment and its implication for present and future water availability

Glaciers all over the world are expected to continue to retreat due to the global warming throughout the 21st century. Consequently, future seasonal water availability might become scarce once glacier areas have declined below a certain threshold affecting future water management strategies. Particular attention should be paid to glaciers located in a karstic environment, as parts of the meltwater can be drained by underlying karst systems, making it difficult to assess water availability. In this study tracer experiments, karst modeling and glacier melt modeling are combined in order to identify flow paths in a high alpine, glacierized, karstic environment (Glacier de la Plaine Morte, Switzerland) and to investigate current and predict future downstream water availability. Flow paths through the karst underground were determined with natural and fluorescent tracers. Subsequently, geologic information and the findings from tracer experiments were assembled in a karst model. Finally, glacier melt projections driven with a climate scenario were performed to discuss future water availability in the area surrounding the glacier. The results suggest that during late summer glacier meltwater is rapidly drained through well-developed channels at the glacier bottom to the north of the glacier, while during low flow season meltwater enters into the karst and is drained to the south. Climate change projections with the glacier melt model reveal that by the end of the century glacier melt will be significantly reduced in the summer, jeopardizing water availability in glacier-fed karst springs.

Importance of vegetation, topography and flow paths for water transit times of base flow in alpine headwater catchments

The mean transit time (MTT) of water in a catchment gives information about storage, flow paths, sources of water and thus also about retention and release of solutes in a catchment. To our knowledge there are only a few catchment studies on the influence of vegetation cover changes on base flow MTTs. The main changes in vegetation cover in the Swiss Alps are massive shrub encroachment and forest expansion into formerly open habitats. Four small and relatively steep headwater catchments in the Swiss Alps (Ursern Valley) were investigated to relate different vegetation cover to water transit times. Time series of water stable isotopes were used to calculate MTTs. The high temporal variation of the stable isotope signals in precipitation was strongly dampened in stream base flow samples. MTTs of the four catchments were 70 to 102 weeks. The strong dampening of the stable isotope input signal as well as stream water geochemistry points to deeper flow paths and mixing of waters of different ages at the catchments' outlets. MTTs were neither related to topographic indices nor vegetation cover. The major part of the quickly infiltrating precipitation likely percolates through fractured and partially karstified deeper rock zones, which increases the control of bedrock flow paths on MTT. Snow accumulation and the timing of its melt play an important role for stable isotope dynamics during spring and early summer. We conclude that, in mountainous headwater catchments with relatively shallow soil layers, the hydrogeological and geochemical patterns (i.e. geochemistry, porosity and hydraulic conductivity of rocks) and snow dynamics influence storage, mixing and release of water in a stronger way than vegetation cover or topography do.

A satellite-based snow cover climatology (1985–2011) for the European Alps derived from AVHRR data

Seasonal snow cover is of great environmental and socio-economic importance for the European Alps. Therefore a high priority has been assigned to quantifying its temporal and spatial variability. Complementary to land-based monitoring networks, optical satellite observations can be used to derive spatially comprehensive information on snow cover extent. For understanding long-term changes in alpine snow cover extent, the data acquired by the Advanced Very High Resolution Radiometer (AVHRR) sensors mounted onboard the National Oceanic and Atmospheric Association (NOAA) and Meteorological Operational satellite (MetOp) platforms offer a unique source of information. In this paper, we present the first space-borne 1 km snow extent climatology for the Alpine region derived from AVHRR data over the period 1985–2011. The objective of this study is twofold: first, to generate a new set of cloud-free satellite snow products using a specific cloud gap-filling technique and second, to examine the spatiotemporal distribution of snow cover in the European Alps over the last 27 yr from the satellite perspective. For this purpose, snow parameters such as snow onset day, snow cover duration (SCD), melt-out date and the snow cover area percentage (SCA) were employed to analyze spatiotemporal variability of snow cover over the course of three decades. On the regional scale, significant trends were found toward a shorter SCD at lower elevations in the south-east and south-west. However, our results do not show any significant trends in the monthly mean SCA over the last 27 yr. This is in agreement with other research findings and may indicate a deceleration of the decreasing snow trend in the Alpine region. Furthermore, such data may provide spatially and temporally homogeneous snow information for comprehensive use in related research fields (i.e., hydrologic and economic applications) or can serve as a reference for climate models.

Seasonality and magnitude of floods in Switzerland under future climate change

The flood seasonality of catchments in Switzerland is likely to change under climate change because of anticipated alterations of precipitation as well as snow accumulation and melt. Information on this change is crucial for flood protection policies, for example, or regional flood frequency analysis. We analysed projected changes in mean annual and maximum floods of a 22-year period for 189 catchments in Switzerland and two scenario periods in the 21st century based on an ensemble of climate scenarios. The flood seasonality was analysed with directional statistics that allow assessing both changes in the mean date a flood occurs as well as changes in the strength of the seasonality. We found that the simulated change in flood seasonality is a function of the change in flow regime type. If snow accumulation and melt is important in a catchment during the control period, then the anticipated change in flood seasonality is most pronounced. Decreasing summer precipitation in the scenarios additionally affects the flood seasonality (mean date of flood occurrence) and leads to a decreasing strength of seasonality, that is a higher temporal variability in most cases. The magnitudes of mean annual floods and more clearly of maximum floods (in a 22-year period) are expected to increase in the future because of changes in flood-generating processes and scaled extreme precipitation. Southern alpine catchments show a different signal, though: the simulated mean annual floods decrease in the far future, that is at the end of the 21st century. Copyright © 2013 John Wiley & Sons, Ltd.

Magmatic–hydrothermal molybdenum isotope fractionation and its relevance to the igneous crustal signature

We analysed the Mo isotope composition of a comprehensive series of molybdenite samples from the porphyry- type Questa deposit (NM, USA), as well as one rhyolite and one granite sample, directly associated with the Mo mineralization. The δ98Mo of the molybdenites ranges between −0.48‰ and +0.40‰, with a median at −0.05‰. The median Mo isotope composition increases from early magmatic (−0.29‰) to hydrothermal (−0.05‰) breccia mineralization (median bulk breccia = −0.17‰) to late stockwork veining (+0.22‰). Moreover, variations of up to 0.34‰ are found between different molybdenite crystals within an individual hand specimen. The rhyolite sample with 0.12 μg g−1 Mo has δ98Mo = −0.57‰ and is lighter than all molybde- nites from the Questa deposit, interpreted to represent the igneous leftover after aqueous ore fluid exsolution. We recognize three Mo isotope fractionation processes that occur between about 700 and 350 °C, affecting the Mo iso- tope composition of magmatic–hydrothermal molybdenites. Δ1Mo: Minerals preferentially incorporate light Mo isotopes during progressive fractional crystallization in subvolcanic magma reservoirs, leaving behind a melt enriched in heavy Mo isotopes. Δ2Mo: Magmatic–hydrothermal fluids preferentially incorporate heavy Mo iso- topes upon fluid exsolution. Δ3Mo: Light Mo isotopes get preferentially incorporated in molybdenite during crys- tallization from an aqueous fluid, leaving behind a hydrothermal fluid that gets heavier with progressive molybdenite crystallization. The sum of all three fractionation processes produces molybdenites that record heavier δ98Mo compositions than their source magmas. This implies that the mean δ98Mo of molybdenites published so far (~0.4‰) likely represents a maximum value for the Mo isotope composition of Phanerozoic igneous upper crust.

Magma differentiation fractionates Mo isotope ratios: Evidence from the Kos Plateau Tuff (Aegean Arc)

We investigated high temperature Mo isotope fractionation in a hydrous supra-subduction volcano-plutonic system (Kos, Aegean Arc, Greece) in order to address the debate on the δ98/95Mo variability of the continental crust. In this igneous system, where differentiation is interpreted to be dominated by fractional crystallization, bulk rock data from olivine basalt to dacite show δ98/95Mo ratios increasing from +0.3 to +0.6‰ along with Mo concentrations increasing from 0.8 to 4.1 μg g−1. Data for hornblende and biotite mineral separates reveal the extraction of light Mo into crystallizing silicates, with minimum partition coefficients between hornblende- silicate melt and biotite-silicate melt of 0.6 and 0.4 δ98/95Mo, respectively. Our data document significant Mo isotope fractionation at magmatic temperatures, hence, the igneous contribution to continental runoff is variable, besides probable source-related variability. Based on these results and published data an average continental δ98/95Mo of +0.3 to +0.4‰ can be derived. This signature corresponds more closely to the average of published data of dissolved Mo loads of large rivers than previous estimates and is consistent with an upper limit of δ98/95Mo = 0.4‰ of the Earth's upper crust as derived from the analysis of molybdenites.