Modellazione e simulazione di sistemi meccanici ad elevato numero di gradi di libertà mediante metodi non convenzionali e sistemi CAD

Recent developments in piston engine technology have increased performance in a very significant way. Diesel turbocharged/turbo compound engines, fuelled by jet fuels, have great performances. The focal point of this thesis is the transformation of the FIAT 1900 jtd diesel common rail engine for the installation on general aviation aircrafts like the CESSNA 172. All considerations about the diesel engine are supported by the studies that have taken place in the laboratories of the II Faculty of Engineering in Forlì. This work, mostly experimental, concerns the transformation of the automotive FIAT 1900 jtd – 4 cylinders – turbocharged – diesel common rail into an aircraft engine. The design philosophy of the aluminium alloy basement of the spark ignition engine have been transferred to the diesel version while the pistons and the head of the FIAT 1900 jtd are kept in the aircraft engine. Different solutions have been examined in this work. A first V 90° cylinders version that can develop up to 300 CV and whose weight is 30 kg, without auxiliaries and turbocharging group. The second version is a development of e original version of the diesel 1900 cc engine with an optimized crankshaft, that employ a special steel, 300M, and that is verified for the aircraft requirements. Another version with an augmented stroke and with a total displacement of 2500 cc has been examined; the result is a 30% engine heavier. The last version proposed is a 1600 cc diesel engine that work at 5000 rpm, with a reduced stroke and capable of more than 200 CV; it was inspired to the Yamaha R1 motorcycle engine. The diesel aircraft engine design keeps the bore of 82 mm, while the stroke is reduced to 64.6 mm, so the engine size is reduced along with weight. The basement weight, in GD AlSi 9 MgMn alloy, is 8,5 kg. Crankshaft, rods and accessories have been redesigned to comply to aircraft standards. The result is that the overall size is increased of only the 8% when referred to the Yamaha engine spark ignition version, while the basement weight increases of 53 %, even if the bore of the diesel version is 11% lager. The original FIAT 1900 jtd piston has been slightly modified with the combustion chamber reworked to the compression ratio of 15:1. The material adopted for the piston is the aluminium alloy A390.0-T5 commonly used in the automotive field. The piston weight is 0,5 kg for the diesel engine. The crankshaft is verified to torsional vibrations according to the Lloyd register of shipping requirements. The 300M special steel crankshaft total weight is of 14,5 kg. The result reached is a very small and light engine that may be certified for general aviation: the engine weight, without the supercharger, air inlet assembly, auxiliary generators and high pressure body, is 44,7 kg and the total engine weight, with enlightened HP pump body and the titanium alloy turbocharger is less than 100 kg, the total displacement is 1365 cm3 and the estimated output power is 220 CV. The direct conversion of automotive piston engine to aircrafts pays too huge weight penalties. In fact the main aircraft requirement is to optimize the power to weight ratio in order to obtain compact and fast engines for aeronautical use: this 1600 common rail diesel engine version demonstrates that these results can be reached.

Crustal heterogeneities and complexities of fault processes

In this work we study the relation between crustal heterogeneities and complexities in fault processes. The first kind of heterogeneity considered involves the concept of asperity. The presence of an asperity in the hypocentral region of the M = 6.5 earthquake of June 17-th, 2000 in the South Iceland Seismic Zone was invoked to explain the change of seismicity pattern before and after the mainshock: in particular, the spatial distribution of foreshock epicentres trends NW while the strike of the main fault is N 7◦ E and aftershocks trend accordingly; the foreshock depths were typically deeper than average aftershock depths. A model is devised which simulates the presence of an asperity in terms of a spherical inclusion, within a softer elastic medium in a transform domain with a deviatoric stress field imposed at remote distances (compressive NE − SW, tensile NW − SE). An isotropic compressive stress component is induced outside the asperity, in the direction of the compressive stress axis, and a tensile component in the direction of the tensile axis; as a consequence, fluid flow is inhibited in the compressive quadrants while it is favoured in tensile quadrants. Within the asperity the isotropic stress vanishes but the deviatoric stress increases substantially, without any significant change in the principal stress directions. Hydrofracture processes in the tensile quadrants and viscoelastic relaxation at depth may contribute to lower the effective rigidity of the medium surrounding the asperity. According to the present model, foreshocks may be interpreted as induced, close to the brittle-ductile transition, by high pressure fluids migrating upwards within the tensile quadrants; this process increases the deviatoric stress within the asperity which eventually fails, becoming the hypocenter of the mainshock, on the optimally oriented fault plane. In the second part of our work we study the complexities induced in fault processes by the layered structure of the crust. In the first model proposed we study the case in which fault bending takes place in a shallow layer. The problem can be addressed in terms of a deep vertical planar crack, interacting with a shallower inclined planar crack. An asymptotic study of the singular behaviour of the dislocation density at the interface reveals that the density distribution has an algebraic singularity at the interface of degree ω between -1 and 0, depending on the dip angle of the upper crack section and on the rigidity contrast between the two media. From the welded boundary condition at the interface between medium 1 and 2, a stress drop discontinuity condition is obtained which can be fulfilled if the stress drop in the upper medium is lower than required for a planar trough-going surface: as a corollary, a vertically dipping strike-slip fault at depth may cross the interface with a sedimentary layer, provided that the shallower section is suitably inclined (fault "refraction"); this results has important implications for our understanding of the complexity of the fault system in the SISZ; in particular, we may understand the observed offset of secondary surface fractures with respect to the strike direction of the seismic fault. The results of this model also suggest that further fractures can develop in the opposite quadrant and so a second model describing fault branching in the upper layer is proposed. As the previous model, this model can be applied only when the stress drop in the shallow layer is lower than the value prescribed for a vertical planar crack surface. Alternative solutions must be considered if the stress drop in the upper layer is higher than in the other layer, which may be the case when anelastic processes relax deviatoric stress in layer 2. In such a case one through-going crack cannot fulfil the welded boundary conditions and unwelding of the interface may take place. We have solved this problem within the theory of fracture mechanics, employing the boundary element method. The fault terminates against the interface in a T-shaped configuration, whose segments interact among each other: the lateral extent of the unwelded surface can be computed in terms of the main fault parameters and the stress field resulting in the shallower layer can be modelled. A wide stripe of high and nearly uniform shear stress develops above the unwelded surface, whose width is controlled by the lateral extension of unwelding. Secondary shear fractures may then open within this stripe, according to the Coulomb failure criterion, and the depth of open fractures opening in mixed mode may be computed and compared with the well studied fault complexities observed in the field. In absence of the T-shaped decollement structure, stress concentration above the seismic fault would be difficult to reconcile with observations, being much higher and narrower.

Studio Sperimentale e Modellazione della Separazione di Proteine con Membrane di Affinità

Chromatography represents one of the most important and widely used unit operation in the biotechnology industry. However this technique suffers from several limitations such as high pressure drop, slow mass transfer through the diffusive pores and strong dependence of the binding capacity on flow rate. In this work, affinity membranes with improved capacity have been considered as an alternative technology for the capturing step in antibody manufacturing. Several affinity membranes have been prepared starting from various membrane supports. Different affinity ligands have been utilized like Protein A, the natural ligand of choice for antibodies, as well as synthetic ligands that exhibit affinity for the Fc portion of antibodies. The membranes have been characterized in detail: binding and elution performance was evaluated in adsorption experiments using pure IgG solutions, while membrane selectivity was evaluated using complex solutions like a cell culture supernatant. The most promising affinity membranes were extensively tested in dynamic experiments. The effects of operating parameters like feed concentration and flow rate on separation performances like binding capacity, selectivity and process yield have been studied in detail in order to find the optimal conditions for binding and elution steps. The membranes have been used over several complete chromatographic cycles to evaluate the effects of ageing and of membrane regeneration on dynamic binding capacity. A novel mathematical model is proposed that can describe all the chromatographic steps involved in the membrane affinity chromatography process for protein purification. The mathematical description is based on the species continuity equation coupled with a proper binding kinetic equation, and suitable to describe adequately the dispersion phenomena occurring both in the micro-porous membranes as well as in the extra-column devices used in the system. The model considers specifically all the different chromatographic steps, namely adsorption, washing and elution. The few relevant fitting parameters of the model were derived from a calibration with the experimental affinity cycles performed with pure IgG solutions, then the model is used to describe experimental data obtained in chromatographic cycles carried out with complex feeds as the cell culture supernatant. Simulations reveal a good agreement with experimental data in all the chromatography steps, both in the case of pure IgG solutions and for the cell culture supernatant considered.

Überkritisches Kohlendioxid als Reaktionsmedium für die Dispersionspolymerisation

Überkritisches Kohlendioxid (CO2) ist für die Polymerisation von besonderem Interesse. Die Dispersionspolymerisation von N-Vinylpyrrolidon (VP) wurde mit Polystyrol-Polydimethylsiloxan Diblockcopolymeren (PS-b-PDMS) in diesem Medium durchgeführt. Hierfür wurde ein neues Hochdrucklabor eingerichtet, eine Sichtzelle und eine neuartige Lichtstreuzelle konstruiert. Für die Durchführung von Lichtstreuexperimenten wurde der Brechungs-index von CO2 bis zu hohen Dichten an einer Reflexionsapparatur bestimmt. Mittels dynamischen Lichtstreumessungen an Polydimethylsiloxan (PDMS) in überkritischem CO2 wurden unter den untersuchten Bedingungen ein Radius bestimmt, wie er für ungestörte Knäueldimensionen erwartet wurde. Das PS-b-PDMS wurde mittels anionischer Polymerisation mit verschiedenen Blocklängen und sehr engen Molekulargewichtsverteilungen synthetisiert. Das Phasenverhalten von PS-b-PDMS wurde in überkritischem CO2 visuell und in einer VP/CO2-Mischung mittels Turbidimetrie untersucht. Das Monomer wirkt als Co-Solvens für den PDMS-Block des Stabilisators. Bei einer Konzentration von ca. 1 Gew.-% PS-b-PDMS (pro Monomer) in CO2 bei 38 MPa und 80°C wurden sphärische ca. 1µm große PVP-Partikeln synthetisiert. PS-b-PDMS ist unter diesen Bedingungen ein geeigneter Stabilisator für die Polymerisation von VP in überkritischem CO2. Bei Konzentrationen von mehr als ca. 5 Gew.-% PS-b-PDMS wurden agglomerierte Partikeln beobachtet. Die Kinetik der Partikelentstehung wurde turbidimetrisch untersucht. Bereits in der frühen Phase der Polymerisation wurde eine anwachsende Partikelgröße gefunden.

Entwicklung eines Verfahrens zur Ultraspurenbestimmung der Platingruppenelemente in Umwelt- und geologischen Proben mit einem ICP-QMS unter Verwendung der Isotopenverdünnungsanalyse sowie geeigneter Separationstechniken

ZusammenfassungSchwerpunkt dieser Arbeit war die Verfahrensentwicklung zur Ultraspurenbestimmung der Platingruppenelemente (PGE) in Umwelt- und geologischen Proben unter Verwendung der massenspektrometrischen Isotopenverdünnungsanalyse mit anschließender Bestimmung an einem Quadrupol ICP-MS (ICP-QMSIVA). Geeignete Separationstechniken in der Probenaufbereitung, um die PGE von der Matrix der untersuchten Proben zu trennen, stellten eine richtige und präzise Bestimmung der Ultraspuren an einem Quadrupol ICP-MS sicher.Das Verfahren konnte anhand von geologischen Referenzmaterialien aus Kanada sichergestellt werden. Gerade die Wiederholungsbestimmungen der verschiedenen Referenzmaterialien unter Verwendung des ICP-QMSIVA Verfahrens sind beispiellos und in dieser Form noch nicht in der Literatur beschrieben. Durch systematische Messungen konnten Richtigkeit und Präzision des Verfahrens bestätigt werden und die Inhomogenität des Referenzmaterials UMT-1 bezüglich Pt bewiesen werden. Das in dieser Arbeit entwickelte Verfahren zur Ultraspurenbestimmung der PGE mit ICP-QMSIVA wurde im Rahmen des Projektes 'Production and certification of a road dust reference material for platinum, palladium and rhodium (PGEs) in automative catalytic converters (PACEPAC)' der Europäischen Union zur Zertifizierung von zwei Referenzmaterialien für Umweltproben eingesetzt. Hierbei wurde bei der Zertifizierung ('intercomparison round') eine sehr gute Übereinstimmung der Ergebnisse mit dem gewichteten Mittelwert der Ergebnisse für Pd und Pt mit den übrigen teilnehmenden Laboratorien festgestellt. Die mit der hier entwickelten Methode erhaltenen Ergebnisse wurden ohne Ausnahme für alle gemessenen Elemente zur Zertifizierung herangezogen. Damit leistete die vorliegende Arbeit einen erheblichen Beitrag zum erfolgreichen Abschluß dieses Projekts. Den Erwartungen hinsichtlich Richtigkeit und Reproduzierbarkeit des entwickelten Verfahrens wurde somit voll entsprochen. Erneut konnte die große Bedeutung der Isotopenverdünnungstechnik für die Zertifizierung von Referenzmaterialien aufgezeigt werden, da mit dieser Technik bei sachgerechtem Einsatz Ergebnisse hoher Richtigkeit erzielt werden. Durch vergleichende Messungen mit der NiS-Dokimasie und NAA, die in einer Kooperation mit dem Kernchemischen Institut der Universität Mainz durchgeführt wurden, und dem hier verwendeten Verfahren, konnten übereinstimmende Daten, hinsichtlich der Abnahme der Konzentrationen von Pd und Pt in Abhängigkeit von der Entfernung zu einer Autobahn, erzielt werden. Diese Arbeit und die Forschungsergebnisse, die mit der anerkannten NAA erzielt wurden, zeigen, daß die PGE durch Katalysatoren von Automobilen überwiegend metallisch emittiert werden. Der anthropogene Eintrag der PGE in die Umwelt kann mit dem ICP-QMSIVA Verfahren weiterhin sehr gut verfolgt werden.

Geological evolution of the Monte Rosa

Eine detaillierte geochemische und geochronologische Studie an Gesteinen der Monte Rosa Decke (MR; Westalpen) wurde durchgeführt. Die MR wurde während der alpinen Orogenese zunächst eklogitfaziell und nachfolgend grünschieferfaziell überprägt.Eine detaillierte U-Pb geochronologische Studie an Zirkonen und Monaziten des MR Granits ergab ein Permisches Intrusionsalter (270 ± 4 Ma). Der MR Granit gehört zu den post-variszischen magmatischen Einheiten, welche die Instabilität der variszischen kontinentalen Kruste andeuten. Für die MR kann eine paläogeographische Position als Teil der 'Briançonnais-Schwelle' angenommen werden.Innerhalb des MR Granits treten Talk-Kyanit-Chloritoid-Gesteine ('Weißschiefer') auf. Diese stellen wesentliche Indikatoren für eine alpine Hochdruckmetamorphose in der MR dar. Massenbilanzberechnungen wurden durchgeführt, um den Massentransfer zu quantifizieren, welcher für die Bildung eines Weißschiefers aus einem granitischen Protolith notwendig ist. Ein Modell für die Entwicklung der Weißschiefer wurde entwickelt.Es wurde eine in-situ 40Ar/39Ar UV-Laser-Ablationsstudie an Hellglimmern der alpinen Mineralparagenese durchgeführt. Sie ergab eine heterogene Altersverteilung. Diese Alter können durch Glimmerrekristallisation unter relativ 'trockenen' hochdruckmetamorphen Bedingungen begleitet von partiellem Verlust von radiogenem Argon während der alpinen Metamorphose erklärt werden. Eine ähnlich komplexe Entwicklung mit partieller Homogenisierung des Isotopensystems kann in der Strontium-Isotopie beobachtet werden. Diese Isotopenstudien liefern Hinweise auf das Schließverhalten von Isotopensystemen unter hochdruckmetamorphen Bedingungen.

The prediction of flash evaporation in superheated fuel injections for automotive applications

In gasoline Port Fuel Injection (PFI) and Direct Injection (GDI) internal combustion engines, the liquid fuel might be injected into a gaseous ambient in a superheated state, resulting in flash boiling of the fuel. The importance to investigate and predict such a process is due to the influence it has on the liquid fuel atomization and vaporization and thus on combustion, with direct implications on engine performances and exhaust gas emissions. The topic of the present PhD research involves the numerical analysis of the behaviour of the superheated fuel during the injection process, in high pressure injection systems like the ones equipping GDI engines. Particular emphasis is on the investigation of the effects of the fuel superheating degree on atomization dynamics and spray characteristics. The present work is a look at the flash evaporation and flash boiling modeling, from an engineering point of view, addressed to keep the complex physics involved as simple as possible, however capturing the main characteristics of a superheated fuel injection.

Contribution of tectonic processes to the exhumation of the Cycladic blueschist unit, Greece and Turkey

In dieser Studie werden strukturgeologische, metamorphe und geochronologische Daten benutzt, um eine Quantifizierung tektonischer Prozesse vorzunehmen, die für die Exhumierung der Kykladischen Blauschiefereinheit in der Ägäis und der Westtürkei verantwortlich waren. Bei den beiden tektonischen Prozessen handelt es sich um: (1) Abschiebungstektonik und (2) vertikale duktile Ausdünnung. Eine finite Verformungsanalyse an Proben der Kykladischen Blauschiefereinheit ermöglicht eine Abschätzung des Beitrags von vertikaler duktiler Ausdünnung an der gesamten Exhumierung. Kalkulationen mit einem eindimensionalen, numerischen Model zeigt, daß vertikale duktile Ausdünnung nur ca. 10% an der gesamten Exhumierung ausmacht. Kinematische, metamorphe und geochronologische Daten erklären die tektonische Natur und die Evolution eines extensionalen Störungssystems auf der Insel Ikaria in der östlichen Ägäis. Thermobarometrische Daten lassen erkennen, daß das Liegende des Störungssystems aus ca. 15 km Tiefe exhumiert wurde. Sowohl Apatit- und Zirkonspaltspurenalter als auch Apatit (U-Th)/He-Alter zeigen, daß sich das extensionale Störungssystem zwischen 11-3 Ma mit einer Geschwindigkeit von ca. 7-8 km/Ma bewegte. Spät-Miozäne Abschiebungen trugen zur Exhumierung der letzten ~5-15 km der Hochdruckgesteine bei. Ein Großteil der Exhumierung der Kykladischen Blauschiefereinheit muß vor dem Miozän stattgefunden haben. Dies wird durch einen Extrusionskeil erklärt, der ca. 30-35 km der Kykladischen Blauschiefereinheit in der Westtürkei exhumierte. 40Ar/39Ar und 87Rb/86Sr Datierungen an Myloniten des oberen Abschiebungskontakts zwischen der Selçuk Decke und der darunterliegenden Ampelos/Dilek Decke der Kykladischen Blauschiefereinheit als auch des unteren Überschiebungskontakts zwischen der Ampelos/Dilek Decke und den darunterliegenden Menderes Decken zeigt, daß sich beide mylonitische Zonen um ca. ~35 Ma formten, was die Existenz eines Spät-Eozänen/Früh-Oligozänen Extrusionskeils beweist.

Finite-strain analysis in orthogneiss of the Gran Paradiso massif, Western Alps, Italy

A finite-strain study in the Gran Paradiso massif of the Italian Western Alps has been carried out to elucidate whether ductile strain shows a relationship to nappe contacts and to shed light on the nature of the subhorizontal foliation typical of the gneiss nappes in the Alps. The Rf/_ and Fry methods used on feldspar porphyroclasts from 143 augengneiss and 11 conglomerate samples of the Gran Paradiso unit (upper tectonic unit of the Gran Paradiso massif), as well as, 9 augengneiss (Erfaulet granite) and 3 quartzite conglomerate samples from the underlying Erfaulet unit (lower unit of the Gran Paradiso massif), and 1 sample from mica schist. Microstructures and thermobarometric data show that feldspar ductility at temperatures >~450°C occurred only during high-pressure metamorphism, when the rocks were underplated beneath the overriding Adriatic plate. Therefore, the finite-strain data can be related to high-pressure metamorphism in the Alpine subduction zone. The augen gneiss was heterogeneously deformed and axial ratios of the strain ellipse in XZ sections range from 2.1 to 69.8. The long axes of the finite-strain ellipsoids trend W/WNW and the short axes are subvertical associated with a subhorizontal foliation. The strain magnitudes do not increase towards the nappe contacts. Geochemical work shows that the accumulation of finite strain was not associated with any significant volume strain. Hence, the data indicate flattening strain type in the Gran Paradiso unit and constrictional strain type in the Erfaulet unit and prove deviations from simple shear. In addition, electron microprobe work was undertaken to determine if the analysed fabrics formed during high-P metamorphism. The chemistry of phengites in the studied samples suggests that deformation and final structural juxtaposition of the Gran Paradiso unit against the Erfaulet took place during high-pressure metamorphism. On the other hand, nappe stacking occurred early during subduction probably by brittle imbrication and that ductile strain was superimposed on and modified the nappe structure during high-pressure underplating in the Alpine subduction zone. The accumulation of ductile strain during underplating was not by simple shear and involved a component of vertical shortening, which caused the subhorizontal foliation in the Gran Paradiso massif. It is concluded that this foliation formed during thrusting of the nappes onto each other suggesting that nappe stacking was associated with vertical shortening. The primary evidence for this interpretation is an attenuated metamorphic section with high-pressure metamorphic rocks of the Gran Paradiso unit juxtaposed against the Erfaulet unit. Therefore, the exhumation during high-pressure metamorphism in the Alpine subduction zone involved a component of vertical shortening, which is responsible for the subhorizontal foliation within the nappes.

Bioactive and toxic compounds in different foodstuffs: analytical techniques and sensory analysis

Foods that provide medical and health benefits or have a role in disease risk prevention are termed functional foods. The functionality of functional foods is derived from bioactive compounds that are extranutritional constituents present in small quantities in food. Bioactive components include a range of chemical compounds with varying structures such as carotenoids, flavonoids, plant sterols, omega-3 fatty acids (n-3), allyl and diallyl sulfides, indoles (benzopyrroles), and phenolic acids. The increasing consumer interest in natural bioactive compounds has brought about a rise in demand for these kinds of compounds and, in parallel, an increasing number of scientific studies have this type of substance as main topic. The principal aim of this PhD research project was the study of different bioactive and toxic compounds in several natural matrices. To achieve this goal, chromatographic, spectroscopic and sensorial analysis were performed. This manuscript reports the main results obtained in the six activities briefly summarized as follows: • SECTION I: the influence of conventional packaging on lipid oxidation of pasta was evaluated in egg spaghetti. • SECTION II: the effect of the storage at different temperatures of virgin olive oil was monitored by peroxide value, fatty acid activity, OSI test and sensory analysis. • SECTION III: the glucosinolate and phenolic content of 37 rocket salad accessions were evaluated, comparing Eruca sativa and Diplotaxis tenuifolia species. Sensory analysis and the influence of the phenolic and glucosinolate composition on sensory attributes of rocket salads has been also studied. • SECTION IV: ten buckwheat honeys were characterised on the basis of their pollen, physicochemical, phenolic and volatile composition. • SECTION V: the polyphenolic fraction, anthocyanins and other polar compounds, the antioxidant capacity and the anty-hyperlipemic action of the aqueous extract of Hibiscus sabdariffa were achieved. • SECTION VI: the optimization of a normal phase high pressure liquid chromatography–fluorescence detection method for the quantitation of flavanols and procyanidins in cocoa powder and chocolate samples was performed.

Investigations on maar-diatreme volcanoes by inversion of magnetic and gravity data from the Eifel area, Germany

A study of maar-diatreme volcanoes has been perfomed by inversion of gravity and magnetic data. The geophysical inverse problem has been solved by means of the damped nonlinear least-squares method. To ensure stability and convergence of the solution of the inverse problem, a mathematical tool, consisting in data weighting and model scaling, has been worked out. Theoretical gravity and magnetic modeling of maar-diatreme volcanoes has been conducted in order to get information, which is used for a simple rough qualitative and/or quantitative interpretation. The information also serves as a priori information to design models for the inversion and/or to assist the interpretation of inversion results. The results of theoretical modeling have been used to roughly estimate the heights and the dip angles of the walls of eight Eifel maar-diatremes — each taken as a whole. Inversemodeling has been conducted for the Schönfeld Maar (magnetics) and the Hausten-Morswiesen Maar (gravity and magnetics). The geometrical parameters of these maars, as well as the density and magnetic properties of the rocks filling them, have been estimated. For a reliable interpretation of the inversion results, beside the knowledge from theoretical modeling, it was resorted to other tools such like field transformations and spectral analysis for complementary information. Geologic models, based on thesynthesis of the respective interpretation results, are presented for the two maars mentioned above. The results gave more insight into the genesis, physics and posteruptive development of the maar-diatreme volcanoes. A classification of the maar-diatreme volcanoes into three main types has been elaborated. Relatively high magnetic anomalies are indicative of scoria cones embeded within maar-diatremes if they are not caused by a strong remanent component of the magnetization. Smaller (weaker) secondary gravity and magnetic anomalies on the background of the main anomaly of a maar-diatreme — especially in the boundary areas — are indicative for subsidence processes, which probably occurred in the late sedimentation phase of the posteruptive development. Contrary to postulates referring to kimberlite pipes, there exists no generalized systematics between diameter and height nor between geophysical anomaly and the dimensions of the maar-diatreme volcanoes. Although both maar-diatreme volcanoes and kimberlite pipes are products of phreatomagmatism, they probably formed in different thermodynamic and hydrogeological environments. In the case of kimberlite pipes, large amounts of magma and groundwater, certainly supplied by deep and large reservoirs, interacted under high pressure and temperature conditions. This led to a long period phreatomagmatic process and hence to the formation of large structures. Concerning the maar-diatreme and tuff-ring-diatreme volcanoes, the phreatomagmatic process takes place due to an interaction between magma from small and shallow magma chambers (probably segregated magmas) and small amounts of near-surface groundwater under low pressure and temperature conditions. This leads to shorter time eruptions and consequently to structures of smaller size in comparison with kimberlite pipes. Nevertheless, the results show that the diameter to height ratio for 50% of the studied maar-diatremes is around 1, whereby the dip angle of the diatreme walls is similar to that of the kimberlite pipes and lies between 70 and 85°. Note that these numerical characteristics, especially the dip angle, hold for the maars the diatremes of which — estimated by modeling — have the shape of a truncated cone. This indicates that the diatreme can not be completely resolved by inversion.

Measurement of nonmethane organic carbon

The present dissertation focuses on the measurement of nonmethane organic carbon compounds (NMOC) and their exchange by biosphere-atmosphere interactions. To access the accuracy, precision, and reproducibility of NMOC analysis, two intercomparison experiments were carried out during the present study. These experiments comprised the sampling of NMOCs on graphitised carbon blacks, followed by gas-chromatographic analysis. Furthermore, they comprised the sampling of short chain carbonyl compounds on solid phase extraction cartridges and their analysis by high pressure liquid chromatography. To investigate the exchange of NMOCs between vegetation and the atmosphere, plant enclosure studies were performed on two European deciduous tree species. These measurements were conducted during two consecutive summer seasons by utilisation of the above specified techniques on sunlit and shaded leaves of European beech (Fagus sylvatica L., monoterpene emitter) and sunlit leaves of English oak (Quercus robur L., isoprene emitter). According to its broad geographical distribution, the impact of European beech on the European monoterpene budget was characterized by a model simulation. Complementary an instrument was developed, that is capable of measuring the amount of total NMOC that is exchanged by biosphere-atmosphere interactions. The instrument was tested under laboratory conditions and was evaluated versus an independent method performing branch enclosure measurements.

Petrogenesis of dunite, wehrlite and websterite xenoliths from Kimberley, South Africa: Origin as mantle peridotites of cumulates

Dunite, wehrlite and websterite xenoliths occur amongst a large abundance of mantle xenoliths in kimberlites of the Kimberley cluster in South Africa. Up to know they have mostly been neglected. On the basis of texture, major and trace elements, oxygen isotopes as well as Re-Os isotope characteristics, they can be subdivided into two groups. A coarse-grained mantle peridotite group, comprising dunite, wehrlite and websterite xenoliths, that are similar to fertile peridotites and represent upper mantle assemblages that are differently influenced by mantle metasomatism. And a cumulate group, containing fine-grained Fe-rich dunite xenoliths that represent cumulates of flood basalt magmatism related to ~183 Ma Karoo and ~2.7 Ga Ventersdorp events in southern Africa. Dunite, wehrlite and websterite xenoliths have preserved a complex history of melt depletion and metasomatic re-enrichment events, which gives information about the different re-enrichment stages of the subcratonic lithospheric mantle and the spatial differences within the Kaapvaal craton upper mantle. Websterite xenoliths comprise orthopyroxene (40-85 Vol. %), clinopyroxene (5-42 Vol. %), garnet (4-10 Vol. %) and subordinately olivine, while dunite and wehrlite xenoliths contain predominantly olivine (65-100 Vol %) and subordinately orthopyroxene, clinopyroxene and garnet. High melt depletion and a dunitic to harzburgitic protolith composition are reflected by high forsterite (Fo90-92) and high olivine NiO contents (2800-5000 ppm) and high orthopyroxene Mg# (Mg/(Mg+Fe)) of 0.91-0.93. Re-depletion ages of predominantly 2.9 Ga reflect a minimum age of melt depletion. Melt depletion ceased in conjunction with collision of the Kimberley block with the Witwatersrand block ~2.9 Ga ago. Subduction related re-fertilisation of the previously depleted mantle xenoliths is documented by i) amoeboid textured orthopyroxene, clinopyroxene and garnet, which crystallized in schlieren along olivine grain boundaries, ii) high whole-rock SiO2, Al2O3, CaO, TiO2, FeO contents, iii) low oxygen isotope ratios in clinopyroxene and garnet of 4.8-5.4 ‰ and 4.7-5.3 ‰, respectively and iv) trace element compositions of wehrlitic clinopyroxene and garnet in equilibrium with high-pressure partial melts of eclogite. Trace element disequilibrium of orthopyroxene with clinopyroxene and garnet indicates a separate origin for orthopyroxene, on one side as primary mantle orthopyroxene in dunite and wehrlite xenoliths and on the other side as reaction product with Si-rich melts produced by partial melting of eclogite. This reaction triggered replacement of olivine by orthopyroxene in the surrounding mantle and produced the typical Si-rich composition of Kaapvaal mantle peridotites. Partial melting of eclogite at higher temperatures produced a second metasomatic melt with lower SiO2, but higher Al2O3, CaO, FeO, Ti, Zr, Hf and a low oxygen isotope ratio. This melt triggered clinopyroxene and locally garnet and rutile crystallization in percolation veins, replacing olivine and orthopyroxene in the Kaapvaal upper mantle. Additionally, websterite xenoliths have experienced late stage cryptic metasomatism by the host kimberlite melt, changing the trace element composition of clinopyroxene, orthopyroxene and garnet to different extent. Hence websterite and most fertile lherzolite xenoliths have experienced three metasomatic events: i) reaction with high-Si melt, ii) percolation of subduction related silica melt with lower SiO2 content and iii) cryptic metasomatism by kimberlite. In contrast, dunite and wehrlite xenoliths have only experienced the second metasomatic event. They represent mantle lithologies further away from metasomatising agents. The Fe-rich dunites comprise olivine neoblasts with subordinate olivine porphyroclasts and parallel-orientated needles of ilmenite, which may enclose spinel. The lower forsterite and NiO contents of olivine in Fe-rich dunites compared to mantle peridotite xenoliths (Fo87-89 vs. Fo93-95 and 1300-2800ppm vs. 2200-3900 ppm, respectively), rules out a restitic origin. Cr-rich spinels are remnants of the original cumulate mineralogy that survived a late stage metasomatic overprint related to the production of the host kimberlite, producing ilmenite and phlogopite in some samples. Olivine porphyroclasts and neoblasts have different trace element compositions, the latter having high Ti, V, Cr and Ni and low Zn, Zr and Nb contents, indicating contrasting origins for neoblasts and porphyroclasts. The dunites have high 187Os/188Os ratios (0.11-0.15) indicating young (Phanerozoic) model ages for most samples, whereas three samples show isotopic mixtures between Phanerozoic neoblasts and ancient porphyroclastic material. Most Fe-rich dunite xenoliths can be interpreted as cumulates of fractional crystallization of Karoo magmatism, whereas the porphyroclasts are interpreted to be remnants from the much earlier Archaean Ventersdorp magmatism.

Structural and strain analysis in the Late Paleozoic coastal accretionary wedge of central Chile

Abstract In this study structural and finite strain data are used to explore the tectonic evolution and the exhumation history of the Chilean accretionary wedge. The Chilean accretionary wedge is part of a Late Paleozoic subduction complex that developed during subduction of the Pacific plate underneath South America. The wedge is commonly subdivided into a structurally lower Western Series and an upper Eastern Series. This study shows the progressive development of structures and finite strain from the least deformed rocks in the eastern part of the Eastern Series of the accretionary wedge to higher grade schist of the Western Series at the Pacific coast. Furthermore, this study reports finite-strain data to quantify the contribution of vertical ductile shortening to exhumation. Vertical ductile shortening is, together with erosion and normal faulting, a process that can aid the exhumation of high-pressure rocks. In the east, structures are characterized by upright chevron folds of sedimentary layering which are associated with a penetrative axial-plane foliation, S1. As the F1 folds became slightly overturned to the west, S1 was folded about recumbent open F2 folds and an S2 axial-plane foliation developed. Near the contact between the Western and Eastern Series S2 represents a prominent subhorizontal transposition foliation. Towards the structural deepest units in the west the transposition foliation became progressively flat lying. Finite-strain data as obtained by Rf/Phi and PDS analysis in metagreywacke and X-ray texture goniometry in phyllosilicate-rich rocks show a smooth and gradual increase in strain magnitude from east to west. There are no evidences for normal faulting or significant structural breaks across the contact of Eastern and Western Series. The progressive structural and strain evolution between both series can be interpreted to reflect a continuous change in the mode of accretion in the subduction wedge. Before ~320-290 Ma the rocks of the Eastern Series were frontally accreted to the Andean margin. Frontal accretion caused horizontal shortening and upright folds and axial-plane foliations developed. At ~320-290 Ma the mode of accretion changed and the rocks of the Western Series were underplated below the Andean margin. This basal accretion caused a major change in the flow field within the wedge and gave rise to vertical shortening and the development of the penetrative subhorizontal transposition foliation. To estimate the amount that vertical ductile shortening contributed to the exhumation of both units finite strain is measured. The tensor average of absolute finite strain yield Sx=1.24, Sy=0.82 and Sz=0.57 implying an average vertical shortening of ca. 43%, which was compensated by volume loss. The finite strain data of the PDS measurements allow to calculate an average volume loss of 41%. A mass balance approximates that most of the solved material stays in the wedge and is precipitated in quartz veins. The average of relative finite strain is Sx=1.65, Sy=0.89 and Sz=0.59 indicating greater vertical shortening in the structurally deeper units. A simple model which integrates velocity gradients along a vertical flow path with a steady-state wedge is used to estimate the contribution of deformation to ductile thinning of the overburden during exhumation. The results show that vertical ductile shortening contributed 15-20% to exhumation. As no large-scale normal faults have been mapped the remaining 80-85% of exhumation must be due to erosion.

Lattice preferred orientation in omphacite: Examples from the Tauern Window, Austria and the Western Gneiss Region, Norway

It is lively debated how eclogites find their way from deep to mid-crustal levels during exhumation. Different exhumation models for high-pressure and ultrahigh-pressure rocks were suggested in previous studies, based mainly on field observations and less on microstructural studies on the exhumed rocks. The development and improvement of electron microscopy techniques allows it, to focus interest on direct investigations of microstructures and crystallographic properties in eclogites. In this case, it is of importance to study the applicability of crystallographic measurements on eclogites for exhumation processes and to unravel which processes affect eclogite textures. Previous studies suggested a strong relationship between deformation and lattice preferred orientation (LPO) in omphacite but it is still unclear if the deformation is related to the exhumation of eclogites. This study is focused on the questions which processes affect omphacite LPO and if textural investigations of omphacite are applicable for studying eclogite exhumation. Therefore, eclogites from two examples in the Alps and in the Caledonides were collected systematically and investigated with respect to omphacite LPO by using the electron backscattered diffraction (EBSD) technique. Omphacite textures of the Tauern Window (Austria) and the Western Gneiss Region (Norway) were studied to compare lattice preferred orientation with field observations and suggested exhumation models from previous studies. The interpretation of omphacite textures, regarding the deformation regime is mainly based on numerical simulations in previous studies. Omphacite LPO patterns of the Eclogite Zone are clearly independent from any kind of exhumation process. The textures were generated during omphacite growth on the prograde path of eclogite development until metamorphic peak conditions. Field observations in the Eclogite Zone show that kinematics in garnet mica schist, surrounding the eclogites, strongly indicate an extrusion wedge geometry. Stretching lineations show top-N thrusting at the base and a top-S normal faulting with a sinistral shear component at the top of the Eclogite Zone. The different shear sense on both sides of the unit does not affect the omphacite textures in any way. The omphacite lattice preferred orientation patterns of the Western Gneiss Region can not be connected with any exhumation model. The textures were probably generated during the metamorphic peak and reflect the change from subduction to exhumation. Eclogite Zone and Western Gneiss Region differ significantly in size and especially in metamorphic conditions. While the Eclogite Zone is characterized by constant P-T conditions (600-650°C, 20-25 kbar), the Western Gneiss Region contains a wide P-T range from high- to ultrahigh pressure conditions (400-800°C, 20-35 kbar). In contrast to this, the omphacite textures of both units are very similar. This means that omphacite LPO is independent from P-T conditions and therefore from burial depth. Further, in both units, omphacite LPO is independent from grain and subgrain size as well as from any shape preferred orientation (SPO) on grain and subgrain scale. Overall, omphacite lattice preferred orientation are generated on the prograde part of omphacite development. Therefore, textural investigations on omphacite LPO are not applicable to study eclogite exhumation.