Properties of gas and dark matter in X-ray galaxy clusters with Sunyaev Zel'dovich measurements

I have studied entropy profiles obtained in a sample of 24 X-ray objects at high redshift retrieved from the Chandra archive. I have discussed the scaling properties of the entropy S, the correlation between metallicity Z and S, the profiles of the temperature of the gas, Tgas, and performed a comparison between the dark matter 'temperature' and Tgas in order to constrain the non-gravitational processes which affect the thermal history of the gas. Furthermore I have studied the scaling relations between the X-ray quantities and Sunyaev Zel'dovich measurements. I have observed that X-ray laws are steeper than the relations predicted from the adiabatic model. These deviations from expectations based on self-similarity are usually interpreted in terms of feedback processes leading to non-gravitational gas heating, and suggesting a scenario in which the ICM at higher redshift has lower both X-ray luminosity and pressure in the central regions than the expectations from self-similar model. I have also investigated a Bayesian X-ray and Sunyaev Zel'dovich analysis, which allows to study the external regions of the clusters well beyond the volumes resolved with X-ray observations (1/3-1/2 of the virial radius), to measure the deprojected physical cluster properties, like temperature, density, entropy, gas mass and total mass up to the virial radius.

Erosione e sollevamento nell'arco calabro-peloritano

The Calabrian-Peloritani arc represents key site to unravel evolution of surface processes on top of subducting lithosphere. During the Pleistocene, in fact the arc uplifted at rate of the order of about 1mm/yr, forming high-standing low-relief upland (figure 2). Our study is focused on the relationship between tectonic and land evolution in the Sila Massif, Messina strait and Peloritani Mts. Landforms reflect a competition between tectonic, climatic, and surficial processes. Many landscape evolution models that explore feedbacks between these competing processes, given steady forcing, predict a state of erosional equilibrium, where the rates of river incision and hillslope erosion balance rock uplift. It has been suggested that this may be the final constructive stage of orogenic systems. Assumptions of steady erosion and incision are used in the interpretation of exhumation and uplift rates from different geologic data, and in the formulation of fluvial incision and hillslope evolution models. In the Sila massif we carried out cosmogenic isotopes analysis on 24 samples of modern fluvial sediments to constrain long-term (~103 yr) erosion rate averaged on the catchment area. 35 longitudinal rivers profiles have been analyzed to study the tectonic signal on the landscape evolution. The rivers analyzed exhibit a wide variety of profile forms, diverging from equilibrium state form. Generally the river profiles show at least 2 and often 3 distinct concave-up knickpoint-bounded segments, characterized by different value of concavity and steepness indices. River profiles suggest three main stages of incision. The values of ks and θ in the lower segments evidence a decrease in river incision, due probably to increasing uplift rate. The cosmogenic erosion rates pointed out that old landscape upland is eroding slowly at ~0.1 mm/yr. In the contrary, the flanks of the massif is eroding faster with value from 0.4 to 0.5 mm/yr due to river incision and hillslope processes. Cosmogenic erosion rates mach linearly with steepness indices and with average hillslope gradient. In the Messina area the long term erosion rate from low-T thermochronometry are of the same order than millennium scale cosmogenic erosion rate (1-2 mm/yr). In this part of the chain the fast erosion is active since several million years, probably controlled by extensional tectonic regime. In the Peloritani Mts apatite fission-track and (U-Th)/He thermochronometry are applied to constraint the thermal history of the basement rock. Apatite fission-track ages range between 29.0±5.5 and 5.5±0.9 Ma while apatite (U-Th)/He ages vary from 19.4 to 1.0 Ma. Most of the AFT ages are younger than the overlying terrigenous sequence that in turn postdates the main orogenic phase. Through the coupling of the thermal modelling with the stratigraphic record, a Middle Miocene thermal event due to tectonic burial is unravel. This event affected a inner-intermediate portion of the Peloritani belt confined by young AFT data (<15 Ma) distribution. We interpret this thermal event as due to an out-of–sequence thrusting occurring in the inner portion of the belt. Young (U-Th)/He ages (c. 5 Ma) record a final exhumation stage with increasing rates of denudation since the Pliocene times due to postorogenic extensional tectonics and regional uplift. In the final chapter we change the spatial scale to insert digital topography analysis and field data within a geodynamic model that can explain surface evidence produced by subduction process.

Liquid crystal polymers: macromolecular design for enhanced performances

During this work, done mainly in the laboratories of the department of Industrial Chemistry and Materials of the University of Bologna but also in the laboratories of the Carnegie Mellon University in collaboration with prof. K. Matyjaszewski and at the university of Zaragoza in collaboration with prof. J. Barberá, was focused mainly on the synthesis and characterization of new functional polymeric materials. In the past years our group gained a deep knowledge about the photomodulation of azobenzene containing polymers. The aim of this thesis is to push forward the performances of these materials by the synthesis of well defined materials, in which, by a precise control over the macromolecular structures, better or even new functionality can be delivered to the synthesized material. For this purpose, besides the rich photochemistry of azoaromatic polymers that brings to the application, the control offered from the recent techniques of controlled radical polymerization, ATRP over all, gives an enormous range of opportunity for the developing of a new generation of functional materials whose properties are determinate not only by the chemical nature of the functional center (e.g. azoaromatic chromophore) but are tuned and even amplified by a synergy with the whole macromolecular structure. Old materials in new structures. In this contest the work of this thesis was focused mainly on the synthesis and characterization of well defined azoaromatic polymers in order to establish, for the first time, precise structure-properties correlation. In fact a series of well defined different azopolymers, chiral and achiral, with different molecular weight and highly monodisperse were synthesized and their properties were studied, in terms of photoexpansion and photomodulation of chirality. We were then able to study the influence of the macromolecular structure in terms of molecular weight and ramification on the studied properties. The huge amount of possibility offered by the tailoring of the macromolecular structure were exploited for the synthesis of new cholesteric photochromic polymers that can be used as a smart label for the certification of the thermal history of any thermosensitive product. Finally the ATRP synthesis allowed us to synthesize a total new class of material, named molecular brushes: a flat surface covered with an ultra thin layer of polymeric chain covalently bond onto the surface from one end. This new class of materials is of extreme interest as they offer the possibility to tune and manage the interaction of the surface with the environment. In this contest we synthesized both azoaromatic surfaces, growing directly the polymer from the surface, and mixed brushes: surfaces covered with incompatible macromolecules. Both type of surfaces acts as “smart” surfaces: the first it is able to move the orientation of a LC cell by simply photomodulation and, thanks to the robustness of the covalent bond, can be used as a command surface overcoming all the limitation due to the dewetting of the active layer. The second type of surface, functionalized by a grafting-to method, can self assemble the topmost layer responding to changed environmental conditions, exposing different functionality according to different environment.

Thermochronologic and geodynamic evolution of the Pontides: Sakarya terrane (Karakaya Complex) and Istanbul terrane, Turkey.

An integrated array of analytical methods -including clay mineralogy, vitrinite reflectance, Raman spectroscopy on carbonaceous material, and apatite fission-track analysis- was employed to constrain the thermal and thermochronological evolution of selected portions of the Pontides of northern Turkey. (1) A multimethod investigation was applied for the first time to characterise the thermal history of the Karakaya Complex, a Permo-Triassic subduction-accretion complex cropping out throughout the Sakarya Zone. The results indicate two different thermal regimes: the Lower Karakaya Complex (Nilüfer Unit) -mostly made of metabasite and marble- suffered peak temperatures of 300-500°C (greenschist facies); the Upper Karakaya Complex (Hodul and the Orhanlar Units) –mostly made of greywacke and arkose- yielded heterogeneous peak temperatures (125-376°C), possibly the result of different degree of involvement of the units in the complex dynamic processes of the accretionary wedge. Contrary to common belief, the results of this study indicate that the entire Karakaya Complex suffered metamorphic conditions. Moreover, a good degree of correlation among the results of these methods demonstrate that Raman spectroscopy on carbonaceous material can be applied successfully to temperature ranges of 200-330°C, thus extending the application of this method from higher grade metamorphic contexts to lower grade metamorphic conditions. (2) Apatite fission-track analysis was applied to the Sakarya and the İstanbul Zones in order to constrain the exhumation history and timing of amalgamation of these two exotic terranes. AFT ages from the İstanbul and Sakarya terranes recorded three distinct episodes of exhumation related to the complex tectonic evolution of the Pontides. (i) Paleocene - early Eocene ages (62.3-50.3 Ma) reflect the closure of the İzmir-Ankara ocean and the ensuing collision between the Sakarya terrane and the Anatolide-Tauride Block. (ii) Late Eocene - earliest Oligocene (43.5-32.3 Ma) ages reflect renewed tectonic activity along the İzmir-Ankara. (iii) Late Oligocene- Early Miocene ages reflect the onset and development of the northern Aegean extension. The consistency of AFT ages, both north and south of the tectonic contact between the İstanbul and Sakarya terranes, suggest that such terranes were amalgamated in pre-Cenozoic times. (3) Fission-track analysis was also applied to rock samples from the Marmara region, in an attempt to constrain the inception and development of the North Anatolian Fault system in the region. The results agree with those from the central Pontides. The youngest AFT ages (Late Oligocene - early Miocene) were recorded in the western portion of the Marmara Sea region and reflect the onset and development of northern Aegean extension. Fission-track data from the eastern Marmara Sea region indicate rapid Early Eocene exhumation induced by the development of the İzmir-Ankara orogenic wedge. Thermochronological data along the trace of the Ganos Fault –a segment of the North Anatolian Fault system- indicate the presence of a tectonic discontinuity active by Late Oligocene time, i.e. well before the arrival of the North Anatolian Fault system in the area. The integration of thermochronologic data with preexisting structural data point to the existence of a system of major E-W-trending structural discontinuities active at least from the Late Oligocene. In the Early Pliocene, inception of the present-day North Anatolian Fault system in the Marmara region occurred by reactivation of these older tectonic structures. 


Polymeric membranes for CO2 separation: effect of aging, humidity and facilitated transport

Polymeric membranes represent a promising technology for gas separation processes, thanks to low costs, reduced energy consumption and limited waste production. The present thesis aims at studying the transport properties of two membrane materials, suitable for CO2 purification applications. In the first part, a polyimide, Matrimid 5218, has been throughout investigated, with particular reference to the effect of thermal treatment, aging and the presence of water vapor in the gas transport process. Permeability measurements showed that thermal history affects relevantly the diffusion of gas molecules across the membrane, influencing also the stability of the separation performances. Subsequently, the effect of water on Matrimid transport properties has been characterized for a wide set of incondensable penetrants. A monotonous reduction of permeability took place at increasing the water concentration within the polymer matrix, affecting the investigated gaseous species to the same extent, despite the different thermodynamic and kinetic features. In this view, a novel empirical model, based on the Free Volume Theory, has been proposed to qualitatively describe the phenomenon. Moreover, according to the accurate representation of the experimental data, the suggested approach has been combined with a more rigorous thermodynamic tool (NELF Model), allowing an exhaustive description of water influence on the single parameters contributing to the gas permeation across the membrane. In the second part, the study has focused on the synthesis and characterization of facilitated transport membranes, able to achieving outstanding separation performances thanks to the chemical enhancement of CO2 permeability. In particular, the transport properties have been investigated for high pressure CO2 separation applications and specific solutions have been proposed to solve stability issues, frequently arising under such severe conditions. Finally, the effect of different process parameters have been investigated, aiming at the identification of the optimal conditions capable to maximize the separation performance.

Ion fractionation in young sea ice from Kongsfjorden, Svalbard

The fractionation of major sea-water ions, or deviation in their relative concentrations from Standard Mean Ocean Water ratios, has been frequently observed in sea ice. It is generally thought to be associated with precipitation of solid salts at certain eutectic temperatures. The variability found in bulk sea-ice samples indicates that the fractionation of ions depends on the often unknown thermal history of sea ice, which affects the structure of pore networks and fate of solid salts within them. Here we investigate the distribution of ions in Arctic sea ice that is a few weeks old with a reconstructible thermal history. We separate the centrifugable (interconnected) and entrapped (likely disconnected) contributions to the ice salinity and determine their ion fractionation signatures. The results indicate that differential diffusion of ions, rather than eutectic precipitation of cryohydrates, has led to significant ion fractionation. The finding emphasizes the role of coupled diffusive–convective salt transport through complex pore networks in shaping the biogeochemistry of sea ice.

Comparison of magnetic properties and petrography between dykes and lava flows from La Cienega, New Mexico and Thunder Bay area, Canada

Data on the evolution of geomagnetic paleointensity are crucial for understanding the geodynamo and Earth’s thermal history. Although basaltic flows are preferred for paleointensity experiments, quickly cooled mafic dykes have also been used. However, the paleointensity values obtained from the dykes are systematically lower than those from lava flows. This bias may originate from the difference in cooling histories and resultant magnetic mineralogies of extrusive and intrusive rocks. To explore this hypothesis, the magnetic mineralogy of two feeder dyke-lave flow systems, from Thunder Bay (Canada) and La Cienega (New-Mexico), has been studied using magnetic and microscopy methods. Within each system, the flow and dyke show different stages of deuteric oxidation of titanomagnetite, but the oxidation stages also differ between the two systems. It is concluded that the tested hypothesis is viable, but the relationships between the magnetic and mineralogical properties of flows and dykes are complex and need a further investigation.

(Table 1) Oxygen isotopes in minerals at DSDP Hole 83-504B basalts

The D/H, 18O/16O and 87Sr/86Sr ratios of the basaltic basement from the Leg 83 section of DSDP Hole 504B show that in that area the oceanic crust has experienced intensive but not pervasive alteration. Isotope ratios of the basalts are very heterogeneous because of an input of oxygen, hydrogen, and strontium from seawater. The hydrogen isotopic composition of many samples displays the complete thermal history of the water-rock interactions. High-temperature mineral formations (actinolites, epidotes, and chlorites) were overgrown by a mineralization at lower temperatures (mixedlayer smectites, iddingsites, and smectites) during successive stages of cooling of the oceanic crust by cold seawater. From 87Sr/86Sr data bulk water/rock ratios up to 5:1 have been calculated. There is evidence that some primary minerals like high-An plagioclases contain oxygen from altered basalts. We have discussed the probability that there existed a seawater/crust interface, now at a depth of 620 m sub-basement, during the high-temperature water/rock interactions. This interface was covered during later magmatism by thick flows, pillow lavas, and intrusives.

Geothermal measurements at ODP Leg 127 and 128 sites

Downhole temperature and thermal conductivity measurements in core samples recovered during Legs 127 and 128 in the Japan Sea resulted in five accurate determinations of heat flow through the seafloor and accurate estimates of temperature vs. depth over the drilled sections. The heat flows measured at these sites are in excellent agreement with nearby seafloor measurements. Drilling sampled basaltic rocks that form the acoustic basement in the Yamato and Japan basins and provided biostratigraphic and isotopic estimates of the age of these basins. The preliminary age estimates are compared with predicted heat flow values for two different thermal models of the lithosphere. A heat flow determination from the crest of the Okushiri Ridge yielded an anomalously high heat flow of 156 mW/m**2. This excessive heat flow value may have resulted from frictional heating on an active reverse fault that bounds the eastern side of the Ridge. Accurate estimates of sedimentation rates and temperatures in the sedimentary section combined with models of basin formation provide an opportunity to test thermochemical models of silica diagenesis. The current location of the opal-A/opal CT transition in the sedimentary section is determined primarily by the thermal history of the layer in which the transition is now found. Comparison of the ages and temperatures of the layer where the opal-A/opal-CT is found today is compatible with an activation energy of 14 to 17 kcal/mole.

Apatite fission track analytical data for samples from ODP Leg 152

We test a new approach to understanding the tectonic evolution of passive margins by using fission-track analysis on detrital apatites from sediments deposited offshore East Greenland. These apatites have not undergone postdepositional track annealing and therefore reflect provenance. The apatites preserve a component of the source rocks' thermal history that otherwise may not be retained within the present-day outcrop. Fission-track derived denudational histories from samples at Ocean Drilling Program drill sites offshore East Greenland at lat 63°N are compared with data from the onshore Singertat Complex. Previous apatite fission-track studies and geomorphic mapping of the East Greenland coast have shown that locally up to 6 km of denudation may have occurred, implying significant tectonic or magmatic activity starting as much as 30 m.y. after breakup at 56 Ma. In contrast, apatite fission-track data presented here record <2 km of Cenozoic denudation in southeast Greenland, probably driven by magmatic underplating at the time of breakup. Large-magnitude, postrift denudation of East Greenland is restricted to the area around Kangerdlugssuaq (68°N). The timing (<40-50 Ma) and magnitude are in accord with revised plume track models suggesting that the Iceland plume crossed the margin here during the late Eocene.

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

Fission track age determinations of rocks from north Greenland

Apatite fission track (FT) ages and length characteristics of samples obtained from Cambrian to Paleocene-aged sandstones collected along the margin of Nares Strait in Ellesmere Island in the Canadian Arctic Archipelago are dominated by a thermal history related to Paleogene relative plate movements between Greenland and Ellesmere Island. A preliminary inverse FT thermal model for a Cambrian (Archer Fiord Formation) sandstone in the hanging wall of the Rawlings Bay thrust at Cape Lawrence is consistent with Paleocene exhumational cooling, likely as a result of erosion of the thrust. This suggests that thrusting at Cape Lawrence occurred prior to the onset of Eocene compression, likely due to transpression during earlier strikeslip along the strait. Models for samples from volcaniclastic sandstones of the Late Paleocene Pavy Formation (from Cape Back and near Pavy River), and a sandstone from the Late Paleocene Mount Lawson Formation (at Split Lake, near Makinson Inlet) are also consistent with minor burial heating following known periods of basaltic volcanism in Baffin Bay and Davis Strait (c. 61-59 Ma), or related tholeiitic volcanism and intrusive activity (c. 55-54 Ma). Thermal models for samples from sea level dykes from around Smith Sound suggest a period of Late Cretaceous - Paleocene heating prior to final cooling during Paleocene time. These model results imply that Paleocene tectonic movements along Nares Strait were significant, and provide limited support for the former existence of the Wegener Fault. Apatite FT data from central Ellesmere Island suggest however, that cooling there occurred during Early Eocene time (c. 50 Ma), which was likely a result of erosion of thrusts during Eurekan compression. This diachronous cooling suggests that Eurekan deformation was partitioned at discrete intervals across Ellesmere Island, and thus it is likely that displacements along the strait were much less than the 150 km that has been previously suggested for the Wegener Fault.