In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Decadal climate variability in the Mediterranean region: roles of large-scale forcings and regional processes

We analyze decadal climate variability in the Mediterranean region using observational datasets over the period 1850–2009 and a regional climate model simulation for the period 1960–2000, focusing in particular on the winter (DJF) and summer (JJA) seasons. Our results show that decadal variability associated with the winter and summer manifestations of the North Atlantic Oscillation (NAO and SNAO respectively) and the Atlantic Multidecadal Oscillation (AMO) significantly contribute to decadal climate anomalies over the Mediterranean region during these seasons. Over 30% of decadal variance in DJF and JJA precipitation in parts of the Mediterranean region can be explained by NAO and SNAO variability respectively. During JJA, the AMO explains over 30% of regional surface air temperature anomalies and Mediterranean Sea surface temperature anomalies, with significant influence also in the transition seasons. In DJF, only Mediterranean SST still significantly correlates with the AMO while regional surface air temperature does not. Also, there is no significant NAO influence on decadal Mediterranean surface air temperature anomalies during this season. A simulation with the PROTHEUS regional ocean–atmosphere coupled model is utilized to investigate processes determining regional decadal changes during the 1960–2000 period, specifically the wetter and cooler 1971–1985 conditions versus the drier and warmer 1986–2000 conditions. The simulation successfully captures the essence of observed decadal changes. Model set-up suggests that AMO variability is transmitted to the Mediterranean/European region and the Mediterranean Sea via atmospheric processes. Regional feedbacks involving cloud cover and soil moisture changes also appear to contribute to observed changes. If confirmed, the linkage between Mediterranean temperatures and the AMO may imply a certain degree of regional decadal climate predictability. The AMO and other decadal influences outlined here should be considered along with those from long-term increases in greenhouse gas forcings when making regional climate out-looks for the Mediterranean 10–20?years out.     

Gravity constraints on the dynamics of the crust–mantle system during Calabrian subduction

The thermomechanic evolution of the lithosphere–upper mantle system during Calabrian subduction is analysed using a 2-D finite element approach, in which the lithosphere is compositionally stratified into crust and mantle. Gravity and topography predictions are cross-checked with observed gravity and topography patterns of the Calabrian region. Modelling results indicate that the gravity pattern in the arc-trench region is shaped by the sinking of light material, belonging to both the overriding and subduction plates. The sinking of light crustal material, up to depths of the order of 100–150 km is the ultimate responsible for the peculiar gravity signature of subduction, characterized by a minimum of gravity anomaly located at the trench, bounded by two highs located on the overriding and subducting plates, with a variation in magnitude of the order of 200 mGal along a wavelength of 200 km, in agreement with the isostatically compensated component of gravity anomaly observed along a transect crossing the Calabrian Arc, from the Tyrrhenian to the Ionian Seas. The striking agreement between the geodetic retrieved profiles and the modelled ones in the trench region confirms the crucial role of compositional stratification of the lithosphere in the subduction process and the correctness of the kinematic hypotheses considered in our modelling, that the present-day configuration of crust–mantle system below the Calabrian arc results from trench's retreat at a rate of about 3 cm yr⁻¹, followed by gravitational sinking of the subducted slab in the last 5 Myr.     

Alpine tectonic evolution and thermal water circulations of the Argentera Massif (South-Western Alps)

Three groups of thermal springs with temperatures close to 70 °C discharge both in the core (at Bagni di Vinadio and Terme di Valdieri) and on the external margin (at Berthemont-Les-Bains) of the Argentera Massif. Detailed structural field analysis carried out on the hydrothermal sites allows us to delineate both a model of Alpine tectonic evolution of the Argentera Massif and the patterns of hydrothermal circulation that were active during its final exhumation. The observed fault rock assemblages provide information relative to deformation that occurred in viscous, frictional-to-viscous and frictional crustal regimes. During the Early Miocene, the Bersezio Fault Zone and the Fremamorta Shear Zone, two main mylonitic shear zones, mainly accommodated regional transpression and provided pathways for fluid flow promoting mineral reactions in greenschist facies. During the Late Miocene–Early Pliocene, frictional-to-viscous deformation affected the massif, which underwent predominant transpression in the internal sectors and extension on the external margin. During the Plio-Pleistocene, deformation in frictional condition accompanied the final exhumation of the massif in a transpressive regime and resulted in the development of the NW–SE striking cataclastic zones. The hydraulic properties of these structures mainly influence the patterns of the active thermal circulations and the localization of the recharge and discharge zones. At Berthemont these faults represent conduits, whereas at Vinadio and Valdieri they form complex systems of conduits and barriers. In these two latter sites, the cataclastic faults compose flower structures that constrain laterally the thermal fluid flows while intensely fractured granites sited at depth constitute a highly-transmissive geothermal reservoir. Less permeable migmatitic gneisses overlaying the granites prevent a massive infiltration of the cold fluids at depth. This context favours within the high-permeability fractures granites the development of buoyancy-driven flows which combined with topographically-driven flows, provided the conditions for the upflow of the high-temperature waters.     

The primordial excitation and clearing of the asteroid belt—Revisited

We have performed new simulations of two different scenarios for the excitation and depletion of the primordial asteroid belt, assuming Jupiter and Saturn on initially circular orbits as predicted by the Nice Model of the evolution of the outer Solar System [Gomes, R., Levison, H.F., Tsiganis, K., Morbidelli, A., 2005. Nature 435, 466-469; Tsiganis, K., Gomes, R., Morbidelli, A., Levison, H.F., 2005. Nature 435, 459-461; Morbidelli, A., Levison, H.F., Tsiganis, K., Gomes, R., 2005. Nature 435, 462-465]. First, we study the effects of sweeping secular resonances driven by the depletion of the solar nebula. We find that these sweeping secular resonances are incapable of giving sufficient dynamical excitation to the asteroids for nebula depletion timescales consistent with estimates for solar-type stars, and in addition cannot cause significant mass depletion in the asteroid belt or produce the observed radial mixing of different asteroid taxonomic types. Second, we study the effects of planetary embryos embedded in the primordial asteroid belt. These embedded planetary embryos, combined with the action of jovian and saturnian resonances, can lead to dynamical excitation and radial mixing comparable to the current asteroid belt. The mass depletion driven by embedded planetary embryos alone, even in the case of an eccentric Jupiter and Saturn, is roughly 10-20× less than necessary to explain the current mass of the main belt, and thus a secondary depletion event, such as that which occurs naturally in the Nice Model, is required. We discuss the implications of our new simulations for the dynamical and collisional evolution of the main belt.     

Elastic properties and stability of coexisting 3T and 2M 1 phengite polytypes

The elastic properties of coexisting natural 3T and 2M ₁ phengite samples (Cima Pal, Sesia Zone; Val Savenca; Western Alps, Italy) with similar chemical compositions have been studied by room temperature–high pressure powder diffraction, using synchrotron radiation on the ID9A beam-line at ESRF (Grenoble, France). The P–V curves have been modelled by the Birch–Murnaghan model; a third-order expansion fitted to the experimental data yields for 3T and 2M ₁ K ₀=60.4(±0.7) GPa, K′=5.79(±0.11) at V ₀=703.8851 ų, and K ₀=57.3(±1.0) GPa, K′=6.97(±0.24) at V ₀=938.8815 ų, respectively. The relative stability of 3T vs. 2M ₁ has been explored as a function of pressure and temperature in terms of configuration and deformation contributions to the Gibbs energy, using the elastic properties determined here and other thermodynamic parameters from earlier investigations. The results presented agree with the hypothesis of stability of the 3T polytype in the high pressure regime.     

Biosedimentary record of postglacial coastal dynamics: high‐resolution sequence stratigraphy from the northern Tuscan coast (Italy)

Integrating analysis of the benthic palaeoecological record with multivariate ordination techniques represents a powerful synergy able to provide an improved characterization of coastal depositional facies in a sequence stratigraphical perspective. Through quantitative analysis of benthic foraminifer, ostracod and mollusc associations from the postglacial succession of Core M3 (Arno coastal plain, Tuscany, Italy), and application of detrended correspondence analysis (DCA) to the mollusc sub‐data set, we offer a refined picture of stratigraphical variations in faunal content from a paralic depositional setting, and reconstruct the palaeoenvironmental gradients that account for such variations. Despite distinct ecological behaviours, and taphonomic and sedimentological constraints, a strong ecological control on meio‐ and macrofaunal biofacies and taxa turnover is documented across the study succession. Amongst all possible mechanisms that may play a role in ‘shaping’ fossil distribution, the ecological signal driven by salinity represents the most prominent factor controlling the composition of fossil associations in the cored succession. Molluscs can even provide outstanding quantitative estimates of palaeosalinity along the sampled core. When plotted stratigraphically, the three fossil sub‐data sets show consistent patterns of vertical evolution that enable prompt identification of the key surfaces for sequence stratigraphical interpretation in otherwise lithologically indistinguishable deposits. The concomitant maximum richness of species with strong marine affinity, paralleled by the highest DCA salinity estimates, allows recognition of the maximum flooding zone, dated to ～7.7 cal. ka BP, within a homogeneous succession of outer lagoon clays. These clays are sandwiched between early transgressive, swamp to inner lagoon deposits and overlying prograding coastal?alluvial plain facies.