U-Pb zircon ages of orthogneisses and supracrustal rocks of the Cariris Velhos belt: Onset of Neoproterozoic rifting in the Borborema Province, NE Brazil

New geochronological and geochemical constraints on Precambrian sedimentary and volcanic successions exposed in the western part of the Central Domain of the Borborema Province, NE Brazil, indicate the presence of two distinct tectono-stratigraphic complexes: Riacho Gravata and Sao Caetano. Both complexes and associated orthogneisses are referred in the literature as the Cariris Velhos belt, having depositional, extrusive, or intrusive ages within the interval 985-913 Ma. The Riacho Gravata complex consists of bimodal (but mostly felsic) volcanic and volcanoclastic rocks, muscovite+/-graphite schists, quartzites, and marble with local occurrences of banded-iron-formation. The Sao Caetano complex mainly consists of metagreywackes, marbles, calc-silicate rocks, and rare meta-mafic rocks. Meta-mafic rocks from both complexes have geochemical signatures similar to those of continental flood basalts, with epsilon Nd (1.0 Ga) values ranging from -1.0 to -2.8. Felsic volcanic rocks from the Riacho Gravata complex show epsilon Nd (1.0 Ga) values ranging from -1.0 to -7.4 and geochemical signatures similar to A(2)-type granitoids. New SHRIMP U-Pb zircon data from felsic volcanic rocks within the Riacho Gravata complex yielded ages of 1091 +/- 13 Ma and 996 +/- 13 Ma. In contrast, meta-graywackes from the Sao Caetano complex show a maximum deposition age of ca. 806 Ma in the northern part and ca. 862 Ma in the southern part of the outcrop area. The orthogneisses show epsilon Nd (1.0 Ga) values ranging from 1.0 to -4.2 with U/Pb TIMS and SHRIMP ages ranging from 960 to 926 Ma and geochemical signatures of A(2)-type granitoids. The data reported in this paper suggest at least two periods of extension within the Central Domain of the Borborema Province, the first starts ca. 1091 Ma with magmatism and deposition, creating the Riacho Gravata basin and continued intrusion of A-type granites to 920 Ma. A second rift event, which reactivated old faults, generated a basin with a maximum deposition age of ca. 806 Ma. Furthermore, the oldest granitoids cutting these metasedimentary rocks have crystallization ages of ca. 600 Ma. This suggests that the second rift event could be early Brasiliano in age. The resulting Sao Caetano basin received detritus from a variety of sources, although detritus from the Riacho Gravata complex dominated. Deposition ages of the Riacho Gravata and the Sao Caetano complexes are coeval with deposits in other basins of the Borborema Province (Riacho do Tigre in the Central Domain; Macurure and Maranco in the Sergipano Belt of the Southern domain). The Macaubas Group from SE Brazil and its counterparts in Africa, the Zadanian and Mayumbian Groups, in the western edge of the Congo Craton are also coeval. Closure of the Riacho Gravata and Sao Caetano basins occurred during the Brasiliano convergence (705-600 Ma). During the last stage of convergence, ca. 612 Ma, pull-apart basins were created and filled; final basin closure took place 605-592 Ma, after deposition ceased. (C) 2011 Elsevier B.V. All rights reserved.

Using AMS combined with mineral shape preferred orientation analysis to understand the emplacement fabrics of the Apiai gabbro-norite (Ribeira Belt, SE Brazil)

The Apiai gabbro-norite is a massive fine-grained Neoproterozoic intrusion emplaced in a core of synformal structure that deforms low-grade marine metasedimentary rocks of the Ribeira Belt of south-eastern Brazil. The lack of visible magmatic layering or any internal fabric has been a major limitation in deciding whether the emplacement occurred before or after the regional folding. To assist in the tectonic interpretations, we combine low-field anisotropy of magnetic susceptibility (AMS) and silicate shape preferred orientation (SPO) to reveal the internal structure of the mafic intrusion. Magnetic data indicate a mean susceptibility of about 10(-2) SI and a mean anisotropy degree (P) of about 1.08, essentially yielded by titanomagnetite. The magnetic and silicate foliations for P >= 1.10 are parallel to each other, while the lineations tend to scatter on the foliation plane, in agreement with the dominant oblate symmetry of the AMS and SPO ellipsoids. For lower P values, the magnetic and silicate fabrics vary from coaxial to oblique, and for P <= 1.05, their shapes and orientations can be quite distinct. The crystal size distribution (CSD) of plagioclase for P > 1.05 is log linear, in agreement with a bulk simple crystallisation history. These results combined show that for a strong SPO, corresponding to a magnetic anisotropy above 1.10, AMS is a reliable indicator of the magmatic fabric. They indicate that the Apiai gabbro-norite consists of sill-like body that was inclined gently to the north by the regional folding.

Effects of Hepatocyte Growth Factor Injection and Reinjection on Healing in the Rabbit Vocal Fold

Objectives/Hypothesis. Hepatocyte growth factor (HGF) is a multifunctional polypeptide that plays various roles in embryogenesis and tissue regeneration and exhibits marked antifibrotic activity. The present study sought to assess the effects of HGF injection and reinjection coinciding with its peak of activity on collagen density, vessel density, inflammatory reaction in the lamina propria, and mean epithelial thickness in the injured rabbit vocal fold. Study Design. Prospective, controlled, experimental animal study. Methods. Fourteen rabbits were subdivided into two groups and underwent injury of the vocal folds. Immediately after injury, animals in group 1 received HGF injections into the right vocal fold (RVF), whereas those in group 2 received bilateral HGF injections and a single reinjection into the RVF 10 days after the first, to coincide with the peak of HGF activity. The left vocal folds (LVFs) served as controls in both groups. Histological assessment of laryngeal specimens was performed at 30 and 40 days, respectively. Results. In both groups, collagen density was lower in the right (treated) vocal folds than in the left (control) folds (P = 0.018). Vessel density was higher in the RVFs in group 2 (P = 0.018). Differences were found in mean epithelial thickness and inflammatory reaction in the lamina propria but did not reach statistical significance. Conclusions. In the scarred rabbit vocal fold, HGF injection is associated with decreased collagen density in the lamina propria, whereas reinjection after 10 days produces decreased collagen density and higher vessel density.

On the three-finger protein domain fold and CD59-like proteins in Schistosoma mansoni

Background: It is believed that schistosomes evade complement-mediated killing by expressing regulatory proteins on their surface. Recently, six homologues of human CD59, an important inhibitor of the complement system membrane attack complex, were identified in the schistosome genome. Therefore, it is important to investigate whether these molecules could act as CD59-like complement inhibitors in schistosomes as part of an immune evasion strategy. Methodology/Principal Findings: Herein, we describe the molecular characterization of seven putative SmCD59-like genes and attempt to address the putative biological function of two isoforms. Superimposition analysis of the 3D structure of hCD59 and schistosome sequences revealed that they contain the three-fingered protein domain (TFPD). However, the conserved amino acid residues involved in complement recognition in mammals could not be identified. Real-time RT-PCR and Western blot analysis determined that most of these genes are up-regulated in the transition from free-living cercaria to adult worm stage. Immunolocalization experiments and tegument preparations confirm that at least some of the SmCD59-like proteins are surface-localized; however, significant expression was also detected in internal tissues of adult worms. Finally, the involvement of two SmCD59 proteins in complement inhibition was evaluated by three different approaches: (i) a hemolytic assay using recombinant soluble forms expressed in Pichia pastoris and E. coli; (ii) complement-resistance of CHO cells expressing the respective membrane-anchored proteins; and (iii) the complement killing of schistosomula after gene suppression by RNAi. Our data indicated that these proteins are not involved in the regulation of complement activation. Conclusions: Our results suggest that this group of proteins belongs to the TFPD superfamily. Their expression is associated to intra-host stages, present in the tegument surface, and also in intra-parasite tissues. Three distinct approaches using SmCD59 proteins to inhibit complement strongly suggested that these proteins are not complement inhibitors and their function in schistosomes remains to be determined.

Tectonics and kinematics of curved mountain belts: examples from the Andes and the Alps

Curved mountain belts have always fascinated geologists and geophysicists because of their peculiar structural setting and geodynamic mechanisms of formation. The need of studying orogenic bends arises from the numerous questions to which geologists and geophysicists have tried to answer to during the last two decades, such as: what are the mechanisms governing orogenic bends formation? Why do they form? Do they develop in particular geological conditions? And if so, what are the most favorable conditions? What are their relationships with the deformational history of the belt? Why is the shape of arcuate orogens in many parts of the Earth so different? What are the factors controlling the shape of orogenic bends? Paleomagnetism demonstrated to be one of the most effective techniques in order to document the deformation of a curved belt through the determination of vertical axis rotations. In fact, the pattern of rotations within a curved belt can reveal the occurrence of a bending, and its timing. Nevertheless, paleomagnetic data alone are not sufficient to constrain the tectonic evolution of a curved belt. Usually, structural analysis integrates paleomagnetic data, in defining the kinematics of a belt through kinematic indicators on brittle fault planes (i.e., slickensides, mineral fibers growth, SC-structures). My research program has been focused on the study of curved mountain belts through paleomagnetism, in order to define their kinematics, timing, and mechanisms of formation. Structural analysis, performed only in some regions, supported and integrated paleomagnetic data. In particular, three arcuate orogenic systems have been investigated: the Western Alpine Arc (NW Italy), the Bolivian Orocline (Central Andes, NW Argentina), and the Patagonian Orocline (Tierra del Fuego, southern Argentina). The bending of the Western Alpine Arc has been investigated so far using different approaches, though few based on reliable paleomagnetic data. Results from our paleomagnetic study carried out in the Tertiary Piedmont Basin, located on top of Alpine nappes, indicate that the Western Alpine Arc is a primary bend that has been subsequently tightened by further ~50° during Aquitanian-Serravallian times (23-12 Ma). This mid-Miocene oroclinal bending, superimposing onto a pre-existing Eocene nonrotational arc, is the result of a composite geodynamic mechanism, where slab rollback, mantle flows, and rotating thrust emplacement are intimately linked. Relying on our paleomagnetic and structural evidence, the Bolivian Orocline can be considered as a progressive bend, whose formation has been driven by the along-strike gradient of crustal shortening. The documented clockwise rotations up to 45° are compatible with a secondary-bending type mechanism occurring after Eocene-Oligocene times (30-40 Ma), and their nature is probably related to the widespread shearing taking place between zones of differential shortening. Since ~15 Ma ago, the activity of N-S left-lateral strike-slip faults in the Eastern Cordillera at the border with the Altiplano-Puna plateau induced up to ~40° counterclockwise rotations along the fault zone, locally annulling the regional clockwise rotation. We proposed that mid-Miocene strike-slip activity developed in response of a compressive stress (related to body forces) at the plateau margins, caused by the progressive lateral (southward) growth of the Altiplano-Puna plateau, laterally spreading from the overthickened crustal region of the salient apex. The growth of plateaux by lateral spreading seems to be a mechanism common to other major plateaux in the Earth (i.e., Tibetan plateau). Results from the Patagonian Orocline represent the first reliable constraint to the timing of bending in the southern tip of South America. They indicate that the Patagonian Orocline did not undergo any significant rotation since early Eocene times (~50 Ma), implying that it may be considered either a primary bend, or an orocline formed during the late Cretaceous-early Eocene deformation phase. This result has important implications on the opening of the Drake Passage at ~32 Ma, since it is definitely not related to the formation of the Patagonian orocline, but the sole consequence of the Scotia plate spreading. Finally, relying on the results and implications from the study of the Western Alpine Arc, the Bolivian Orocline, and the Patagonian Orocline, general conclusions on curved mountain belt formation have been inferred.

Tectonic geomorphology and active strain of the Northern Apennines mountain front

The Northern Apennines (NA) chain is the expression of the active plate margin between Europe and Adria. Given the low convergence rates and the moderate seismic activity, ambiguities still occur in defining a seismotectonic framework and many different scenarios have been proposed for the mountain front evolution. Differently from older models that indicate the mountain front as an active thrust at the surface, a recently proposed scenario describes the latter as the frontal limb of a long-wavelength fold (> 150 km) formed by a thrust fault tipped around 17 km at depth, and considered as the active subduction boundary. East of Bologna, this frontal limb is remarkably very straight and its surface is riddled with small, but pervasive high- angle normal faults. However, west of Bologna, some recesses are visible along strike of the mountain front: these perturbations seem due to the presence of shorter wavelength (15 to 25 km along strike) structures showing both NE and NW-vergence. The Pleistocene activity of these structures was already suggested, but not quantitative reconstructions are available in literature. This research investigates the tectonic geomorphology of the NA mountain front with the specific aim to quantify active deformations and infer possible deep causes of both short- and long-wavelength structures. This study documents the presence of a network of active extensional faults, in the foothills south and east of Bologna. For these structures, the strain rate has been measured to find a constant throw-to-length relationship and the slip rates have been compared with measured rates of erosion. Fluvial geomorphology and quantitative analysis of the topography document in detail the active tectonics of two growing domal structures (Castelvetro - Vignola foothills and the Ghiardo plateau) embedded in the mountain front west of Bologna. Here, tilting and river incision rates (interpreted as that long-term uplift rates) have been measured respectively at the mountain front and in the Enza and Panaro valleys, using a well defined stratigraphy of Pleistocene to Holocene river terraces and alluvial fan deposits as growth strata, and seismic reflection profiles relationships. The geometry and uplift rates of the anticlines constrain a simple trishear fault propagation folding model that inverts for blind thrust ramp depth, dip, and slip. Topographic swath profiles and the steepness index of river longitudinal profiles that traverse the anti- clines are consistent with stratigraphy, structures, aquifer geometry, and seismic reflection profiles. Available focal mechanisms of earthquakes with magnitude between Mw 4.1 to 5.4, obtained from a dataset of the instrumental seismicity for the last 30 years, evidence a clear vertical separation at around 15 km between shallow extensional and deeper compressional hypocenters along the mountain front and adjacent foothills. In summary, the studied anticlines appear to grow at rates slower than the growing rate of the longer- wavelength structure that defines the mountain front of the NA. The domal structures show evidences of NW-verging deformation and reactivations of older (late Neogene) thrusts. The reconstructed river incision rates together with rates coming from several other rivers along a 250 km wide stretch of the NA mountain front and recently available in the literature, all indicate a general increase from Middle to Late Pleistocene. This suggests focusing of deformation along a deep structure, as confirmed by the deep compressional seismicity. The maximum rate is however not constant along the mountain front, but varies from 0.2 mm/yr in the west to more than 2.2 mm/yr in the eastern sector, suggesting a similar (eastward-increasing) trend of the apenninic subduction.

Deep geometry of subduction below the Andean belt of Colombia as revealed by seismic tomography

In this study new tomographic models of Colombia were calculated. I used the seismicity recorded by the Colombian seismic network during the period 2006-2009. In this time period, the improvement of the seismic network yields more stable hypocentral results with respect to older data set and allows to compute new 3D Vp and Vp/Vs models. The final dataset consists of 10813 P- and 8614 S-arrival times associated to 1405 earthquakes. Tests with synthetic data and resolution analysis indicate that velocity models are well constrained in central, western and southwestern Colombia to a depth of 160 km; the resolution is poor in the northern Colombia and close to Venezuela due to a lack of seismic stations and seismicity. The tomographic models and the relocated seismicity indicate the existence of E-SE subducting Nazca lithosphere beneath central and southern Colombia. The North-South changes in Wadati-Benioff zone, Vp & Vp/Vs pattern and volcanism, show that the downgoing plate is segmented by slab tears E-W directed, suggesting the presence of three sectors. Earthquakes in the northernmost sector represent most of the Colombian seimicity and concentrated on 100-170 km depth interval, beneath the Eastern Cordillera. Here a massive dehydration is inferred, resulting from a delay in the eclogitization of a thickened oceanic crust in a flat-subduction geometry. In this sector a cluster of intermediate-depth seismicity (Bucaramanga Nest) is present beneath the elbow of the Eastern Cordillera, interpreted as the result of massive and highly localized dehydration phenomenon caused by a hyper-hydrous oceanic crust. The central and southern sectors, although different in Vp pattern show, conversely, a continuous, steep and more homogeneous Wadati-Benioff zone with overlying volcanic areas. Here a "normalthickened" oceanic crust is inferred, allowing for a gradual and continuous metamorphic reactions to take place with depth, enabling the fluid migration towards the mantle wedge.

Geochemistry, petrogenesis and tectonic setting of ophiolites and mafic-ultramafic complexes in the Northeastern Aegean Region

In this study two ophiolites and a mafic-ultramafic complexes of the northeastern Aegean Sea, Greece, have been investigated to re-evaluate their petrogenetic evolution and tectonic setting. These complexes are: the mafic-ultramafic complex of Lesvos Island and the ophiolites of Samothraki Island and the Evros area. In order to examine these complexes in detail whole-rock major- and trace-elements as well as Sr and Nd isotopes, and minerals were analysed and U-Pb SHRIMP ages on zircons were determined. The mafic-ultramafic complex of Lesvos Island consists of mantle peridotite thrusted over a tectonic mélange containing metasediments, metabasalts and a few metagabbros. This succession had previously been interpreted as an ophiolite of Late Jurassic age. The new field and geochemical data allow a reinterpretation of this complex as representing an incipient continental rift setting that led to the subsequent formation of the Meliata-Maliac-Vardar branches of Neotethys in Upper Permian times (253 ± 6 Ma) and the term “Lesvos ophiolite” should be abandoned. With proceeding subduction and closure of the Maliac Ocean in Late Jurassic times (155 Ma) the Lesvos mafic-ultramafic complex was obducted. Zircon ages of 777, 539 and 338 Ma from a gabbro strongly suggest inheritance from the intruded basement and correspond to ages of distinct terranes recently recognized in the Hellenides (e.g. Florina terrane). Geochemical similar complexes which contain rift associations with Permo-Triassic ages can be found elsewhere in Greece and Turkey, namely the Teke Dere Thrust Sheet below the Lycian Nappes (SW Turkey), the Pindos subophiolitic mélange (W Greece), the Volcanosedimentary Complex on Central Evia Island (Greece) and the Karakaya Complex (NW Turkey). This infers that the rift-related rocks from Lesvos belong to an important Permo-Triassic rifting episode in the eastern Mediterranean. The ‘in-situ’ ophiolite of Samothraki Island comprises gabbros, sparse dykes and basalt flows as well as pillows cut by late dolerite dykes and had conventionally been interpreted as having formed in an ensialic back-arc basin. The results of this study revealed that none of the basalts and dolerites resemble mid-ocean ridge or back-arc basin basalts thus suggesting that the Samothraki ophiolite cannot represent mature back-arc basin crust. The age of the complex is regarded to be 160 ± 5 Ma (i.e. Oxfordian; early Upper Jurassic), which precludes any correlation with the Lesvos mafic-ultramafic complex further south (253 ± 6 Ma; Upper Permian). Restoration of the block configuration in NE Greece, before extensional collapse of the Hellenic hinterland and exhumation of the Rhodope Metamorphic Core Complex (mid-Eocene to mid-Miocene), results in a continuous ophiolite belt from Guevgueli in the NW to Samothraki in the SE, thus assigning the latter to the Innermost Hellenic Ophiolite Belt. In view of the data of this study, the Samothraki ophiolite represents a rift propagation of the Sithonia ophiolite spreading ridge into the Chortiatis calc-alkaline arc. The ophiolite of the Evros area consists of a plutonic sequence comprising cumulate and non-cumulate gabbros with plagiogranite veins, and an extrusive sequence of basalt dykes, massive and pillow lavas as well as pyroclastic rocks. Furthermore, in the Rhodope Massif tectonic lenses of harzburgites and dunites can be found. All rocks are spatially separated. The analytical results of this study revealed an intra-oceanic island arc setting for the Evros ophiolitic rocks. During late Middle Jurassic times (169 ± 2 Ma) an intra-oceanic arc has developed above a northwards directed intra-oceanic subduction zone of the Vardar Ocean in front of the Rhodope Massif. The boninitic, island arc tholeiitic and calc-alkaline rocks reflect the evolution of the Evros island arc. The obduction of the ophiolitic rocks onto the Rhodope basement margin took place during closure of the Vardar ocean basins. The harzburgites and dunites of the Rhodope Massif are strongly depleted and resemble harzburgites from recent oceanic island arcs. After melt extraction they underwent enrichment processes by percolating melts and fluids from the subducted slab. The relationship of the peridotites and the Evros ophiolite is still ambiguous, but the stratigraphic positions of the peridotites and the ophiolitic rocks indicate separated origin. The harzburgites and dunites most probably represent remnants of the mantle wedge of the island arc of the Rhodope terrane formed above subducted slab of the Nestos Ocean in late Middle Jurassic times. During collision of the Thracia terrane with the Rhodope terrane thrusting of the Rhodope terrane onto the Thracia terrane took place, whereas the harzburgites and dunites were pushed between the two terranes now cropping out on top of the Thracia terrane of the Rhodope Massif.

Petrogenetic evolution of Uralian-Alaskan-type mafic-ultramafic complexes in the southern and middle Urals, Russia

The PhD thesis at hand consists of three parts and describes the petrogenetic evolution of Uralian-Alaskan-type mafic ultramafic complexes in the Ural Mountains, Russia. Uralian-Alaskan-type mafic-ultramafic complexes are recognized as a distinct class of intrusions. Characteristic petrologic features are the concentric zonation of a central dunite body grading outward into wehrlite, clinopyroxenite and gabbro, the absence of orthopyroxene and frequently occurring platinum group element (PGE) mineralization. In addition, the presence of ferric iron-rich spinel discriminates Uralian-Alaskan-type complexes from most other mafic ultramafic rock assemblages. The studied Uralian-Alaskan-type complexes (Nizhnii Tagil, Kytlym and Svetley Bor) belong to the southern part of a 900 km long, N–S-trending chain of similar intrusions between the Main Uralian Fault to the west and the Serov-Mauk Fault to the east. The first chapter of this thesis studies the evolution of the ultramafic rocks tracing the compositional variations of rock forming and accessory minerals. The comparison of the chemical composition of olivine, clinopyroxene and chromian spinel from the Urals with data from other localities indicates that they are unique intrusions having a characteristic spinel and clinopyroxene chemistry. Laser ablation-ICPMS (LA-ICPMS ) analyses of trace element concentrations in clinopyroxene are used to calculate the composition of their parental melt which is characterized by enriched LREE (0.5-5.2 prim. mantle) and other highly incompatible elements (U, Th, Ba, Rb) relative to the HREE (0.25-2.0 prim. mantle). A subduction-related geotectonic setting is indicated by a positive anomaly for Sr and negative anomalies for Ti, Zr and Hf. The mineral compositions monitor the evolution of the parental magmas and decipher differences between the studied complexes. In addition, the observed variation in LREE/HREE (for example La/Lu = 2-24) can be best explained with the model of an episodically replenished and erupted open magma chamber system with the extensive fractionation of olivine, spinel and clinopyroxene. The data also show that ankaramites in a subduction-related geotectonic setting could represent parental magmas of Uralian-Alaskan-type complexes. The second chapter of the thesis discusses the chemical variation of major and trace elements in rock-forming minerals of the mafic rocks. Electron microprobe and LA-ICPMS analyses are used to quantitatively describe the petrogenetic relationship between the different gabbroic lithologies and their genetic link to the ultramafic rocks. The composition of clinopyroxene identifies the presence of melts with different trace element abundances on the scale of a thin section and suggests the presence of open system crustal magma chambers. Even on a regional scale the large variation of trace element concentrations and ratios in clinopyroxene (e.g. La/Lu = 3-55) is best explained by the interaction of at least two fundamentally different magma types at various stages of fractionation. This requires the existence of a complex magma chamber system fed with multiple pulses of magmas from at least two different coeval sources in a subduction-related environment. One source produces silica saturated Island arc tholeiitic melts. The second source produces silica undersaturated, ultra-calcic, alkaline melts. Taken these data collectively, the mixing of the two different parental magmas is the dominant petrogenetic process explaining the observed chemical variations. The results further imply that this is an intrinsic feature of Uralian-Alaskan-type complexes and probably of many similar mafic-ultramafic complexes world-wide. In the third chapter of this thesis the major element composition of homogeneous and exsolved spinel is used as a petrogenetic indicator. Homogeneous chromian spinel in dunites and wehrlites monitors the fractionation during the early stages of the magma chamber and the onset of clinopyroxene fractionation as well as the reaction of spinel with interstitial liquid. Exsolved spinel is present in mafic and ultramafic rocks from all three studied complexes. Its composition lies along a solvus curve which defines an equilibrium temperature of 600°C, given that spinel coexists with olivine. This temperature is considered to be close to the temperature of the host rocks into which the studied Uralian-Alaskan-type complexes intruded. The similarity of the exsolution temperatures in the different complexes over a distance of several hundred kilometres implies a regional tectonic event that terminated the exsolution process. This event is potentially associated with the final exhumation of the Uralian-Alaskan-type complexes along the Main Uralian Fault and the Serov-Mauk Fault in the Uralian fold belt.

The effect of osmolytes on protein fold stability at the single-molecule level

By pulling and releasing the tension on protein homomers with the Atomic Force Miscroscope (AFM) at different pulling speeds, dwell times and dwell distances, the observed force-response of the protein can be fitted with suitable theoretical models. In this respect we developed mathematical procedures and open-source computer codes for driving such experiments and fitting Bell’s model to experimental protein unfolding forces and protein folding frequencies. We applied the above techniques to the study of proteins GB1 (the B1 IgG-binding domain of protein G from Streptococcus) and I27 (a module of human cardiac titin) in aqueous solutions of protecting osmolytes such as dimethyl sulfoxide (DMSO), glycerol and trimethylamine N-oxide (TMAO). In order to get a molecular understanding of the experimental results we developed an Ising-like model for proteins that incorporates the osmophobic nature of their backbone. The model benefits from analytical thermodynamics and kinetics amenable to Monte-Carlo simulation. The prevailing view used to be that small protecting osmolytes bridge the separating beta-strands of proteins with mechanical resistance, presumably shifting the transition state to significantly higher distances that correlate with the molecular size of the osmolyte molecules. Our experiments showed instead that protecting osmolytes slow down protein unfolding and speed-up protein folding at physiological pH without shifting the protein transition state on the mechanical reaction coordinate. Together with the theoretical results of the Ising-model, our results lend support to the osmophobic theory according to which osmolyte stabilisation is a result of the preferential exclusion of the osmolyte molecules from the protein backbone. The results obtained during this thesis work have markedly improved our understanding of the strategy selected by Nature to strengthen protein stability in hostile environments, shifting the focus from hypothetical protein-osmolyte interactions to the more general mechanism based on the osmophobicity of the protein backbone.

UHP metamorphic rocks of the Eastern Rhodope Massif, NE Greece: new constraints from petrology, geochemistry and zircon ages

In this PhD thesis, a multidisciplinary study has been carried out on metagranitoids and paragneisses from the Eastern Rhodope Massif, northern Greece, to decipher the pre-Alpine magmatic and geodynamic evolution of the Rhodope Massif and to correlate the eastern part with the western/central parts of the orogen. The Rhodope Massif, which occupies the major part of NE Greece and S Bulgaria, represents the easternmost part of the Internal Hellenides. It is regarded as a nappe stack of high-grade units, which is classically subdivided into an upper unit and a lower unit, separated by a SSE-NNW trending thrust plane, the Nestos thrust. Recent research in the central Greek Rhodope Massif revealed that the two units correspond to two distinct terranes of different age, the Permo-Carboniferous Thracia Terrane, which was overthrusted by the Late Jurassic/Early Cretaceous Rhodope Terrane. These terranes are separated by the Nestos suture, a composite zone comprising metapelites, metabasites, metagranitoids and marbles, which record high-pressure and even ultrahigh-pressure metamorphism in places. Similar characteristic rock associations were investigated during this study along several well-constrained cross sections in vincity to the Ada, Sidiro and Kimi villages in the Greek Eastern Rhodope Massif. Field evidence revealed that the contact zone of the two terranes in the Eastern Rhodope Massif is characterized by a mélange of metapelites, migmatitic amphibolites/eclogites, strongly sheared orthogneisses and marbles. The systematical occurrence of this characteristic rock association between the terranes implies that the Nestos suture is a continuous belt throughout the Greek Rhodope Massif. In this study, a new UHP locality could be established and for the first time in the Greek Rhodope, metamorphic microdiamonds were identified in situ in their host zircons using Laser-Raman spectroscopy. The presence of the diamonds as well as element distribution patterns of the zircons, obtained by TOF-SIMS, indicate metamorphic conditions of T > 1000 °C and P > 4 GPa. The high-pressure and ultrahigh-pressure rocks of the mélange zone are considered to have formed during the subduction of the Nestos Ocean in Jurassic times at ~150 Ma. Melting of metapelitic rocks at UHP conditions facilitated the exhumation to lower crustal levels. To identify major crust forming events, basement granitoids were dated by LA-SF-ICPMS and SHRIMP-II U-Pb analyses of zircons. The geochronological results revealed that the Eastern Rhodope Massif consists of two crustal units, a structurally lower Permo-Carboniferous unit corresponding to the Thracia Terrane and a structurally upper Late Jurassic/Early Cretaceous unit corresponding to the Rhodope Terrane, like it was documented for the Central Rhodope Massif. Inherited zircons in the orthogneisses from the Thracia Terrane of the Eastern Rhodope Massif indicate the presence of a pre-existing Neoproterozoic and Ordovician-Silurian basement in this region. Triassic magmatism is witnessed by the zircons of few orthogneisses from the easternmost Rhodope Massif and is interpreted to be related to rifting processes. Whole-rock major and trace element analyses indicate that the metagranitoids from both terranes originated in a subduction-related magmatic-arc environment. The Sr-Nd isotope data for both terranes of the Eastern and Central Rhodope Massif suggest a mixed crust-mantle source with variable contributions of older crustal material as already indicated by the presence of inherited zircons. Geochemical and isotopic similarity of the basement of the Thracia Terrane and the Pelagonian Zone implies that the Thracia Terrane is a fragment of a formerly unique Permo-Carboniferous basement, separated by rifting and opening of the Meliata-Maliac ocean system in Triassic times. A branch of the Meliata-Maliac ocean system, the Nestos Ocean, subducted northwards in Late Jurassic times leading to the formation of the Late Jurassic/Early Cretaceous Rhodope magmatic arc on remnants of the Thracia Terrane as suggested by inherited Permo-Carboniferous zircons. The ~150 Ma zircon ages of the orthogneisses from the Rhodope Terrane indicate that subduction-related magmatism and HP/UHP metamorphism occurred during the same subduction phase. Subduction ceased due to the closure of the Nestos Ocean in the Late Jurassic/Early Cretaceous. The post-Jurassic evolution of the Rhodope Massif is characterized by the exhumation of the Rhodope core complex in the course of extensional tectonics associated with late granite intrusions in Eocene to Miocene times.

Neoproterozoic to middle Palaeozoic evolution of the Central Asian Orogenic Belt in south-central Mongolia: chronological and geochemical perspectives

Mongolia occupies a central position within the eastern branch of the large accretionary Central Asian Orogenic Belt (CAOB) or Altaids. The present work aims to outline the geodynamic environment and possible evolution of this part of the eastern CAOB, predominantly from the Cambrian to the middle Palaeozoic. The investigation primarily focussed on zircon geochronology as well as whole-rock geochemical and Sm–Nd isotopic analyses for a variety of metaigneous rocks from the southern Hangay and Gobi-Altai regions in south-central Mongolia. The southern slope of the Hangay Mountains in central Mongolia exposes a large NWSE-trending middle Neoproterozoic ophiolitic complex (c. 650 Ma), which is tectonically integrated within an accretionary complex developed between the Precambrian Baydrag and Hangay crustal blocks. Formation of the entire accretionary system along the north-eastern margin of the Baydrag block mainly occurred during the early Cambrian, but convergence within this orogenic zone continued until the early Ordovician, because of on-going southward subduction-accretion of the Baydrag block. An important discovery is the identification of a late Mesoproterozoic to early Neoproterozoic belt within the northern Gobi-Altai that was reworked during the late Cambrian and throughout the late Ordovician/Devonian. Early Silurian low-grade mafic and felsic metavolcanic rocks from the northern Gobi-Altai display subduction-related geochemical features and highly heterogeneous Nd isotopic compositions, which suggest an origin at a mature active continental margin. Early Devonian protoliths of granodioritic and mafic gneisses from the southern Gobi-Altai display geochemical and Nd isotopic compositions compatible with derivation and evolution from predominantly juvenile crustal and mantel sources and these rocks may have been emplaced within the outboard portion of the late Ordovician/early Silurian active continental margin. Moreover, middle Devonian low-grade metavolcanic rocks from the southwestern Gobi-Altai yielded geochemical and Nd isotopic data consistent with emplacement in a transitional arc-backarc setting. The combined U–Pb zircon ages and geochemical data obtained from the Gobi-Altai region suggest that magmatism across an active continental margin migrated oceanwards through time by way of subduction zone retreat throughout the Devonian. Progressive extension of the continental margin was associated with the opening of a backarc basin and culminated in the late Devonian with the formation of a Japan-type arc front facing a southward open oceanic realm (present-day coordinates).