Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities (\({f_{{{\text{O}}_{\text{2}}}}}\)), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V³⁺ and V⁴⁺ in magnetite, and a mixture of IV- and VI-fold V⁵⁺ and V⁴⁺ in the melt. The magnitude of the fractionation factor systematically increases with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\) relative to the Fayalite–Magnetite–Quartz buffer (FMQ), from ?⁵¹V_mag-gl = ? 0.63?±?0.09‰ at FMQ ? 1 to ? 0.92?±?0.11‰ (SD) at ≈?FMQ?+?5, reflecting constant V³⁺/V⁴⁺ in magnetite but increasing V⁵⁺/V⁴⁺ in the melt with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\). These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.     

Geochemistry of igneous rocks associated with ultramafic–mafic-hosted Cu (Co, Ni, Au) VMS deposits from the Main Uralian Fault (Southern Urals, Russia)

Ultramafic–mafic- and ultramafic-hosted Cu (Co, Ni, Au) volcanogenic massive sulfide (VMS) deposits from ophiolite complexes of the Main Uralian Fault, Southern Urals, are associated with island arc-type igneous rocks. Trace element analyses show that these rocks are geochemically analogous to Early Devonian boninitic and island arc tholeiitic rocks found at the base of the adjacent Magnitogorsk volcanic arc system, while they are distinguished both from earlier, pre-subduction volcanic rocks and from later volcanic products that were erupted in progressively more internal arc settings. The correlation between the sulfide host-rocks and the earliest volcanic units of the Magnitogorsk arc suggests a connection between VMS formation and infant subduction-driven intraoceanic magmatism.     

Phosphate defects and apatite inclusions in coral skeletal aragonite revealed by solid-state NMR spectroscopy

Recent development of paleo-nutrient proxies based on the phosphorus/calcium (P/Ca) ratio in tropical- and deep-water corals (also known as cold-water corals) require an understanding of the processes by which P is incorporated into the coral skeletal aragonite. Here, we apply single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy to determine the speciation of P in coral aragonite. The results show that the majority of P occurs as phosphate defects in the aragonite structure, but in many samples a significant fraction of the P occurs also in crystalline hydroxylapatite inclusions. Quantification of the amount of hydroxylapatite indicates that its presence is not related simply to external environmental factors and that it can occur at varying abundances in different parts of the same corallite. Since there is currently no model available to describe the relationship between dissolved inorganic phosphate and its incorporation as apatite inclusions into carbonates, careful screening of samples which contain only phosphate in the aragonite structure or selective microsampling could improve proxy development.     

Lateral variations in tectonic style across cross-strike discontinuities: an example from the Central Apennines belt (Italy)

In foreland thrust belts, abrupt lateral changes in tectonic style, structural–stratigraphic features, and topography usually occur across cross-strike faults. The Central Apennines of Italy offer an exceptional scenario of lateral variations in tectonic setting. Here, the Sangro Volturno oblique thrust ramp (SVOTR) represents the outer thrust front of the Pliocene–Quaternary foreland thrust system, confining southward the axial culmination of the orogen that occurs in the Central Apennines. We present an interpretation of the Pliocene–Quaternary evolution of this cross-strike fault through an integrated dataset including structural-geological mapping and subsurface onshore seismic reflection profiles. The interpretation of the structural framework is augmented by the analysis of low-temperature thermochronometers from 32 new sites extending across the subsurface transverse structure. As evidenced by seismic line interpretation, the localization and development of the SVOTR have been influenced by inherited extensional faults within a positive inversion tectonics context. The regional distribution of the maximum paleotemperature values across the SVOTR constrains the original extent of the allochthonous thrust sheet over all its hanging-wall and footwall blocks. The Pliocene–Quaternary thrusting and inversion of SVOTR caused the strong hanging-wall uplift, which brought to the complete erosion of the allochthonous units and the exhumation of the Adria units. The integrated analysis of low-temperature thermochronometers and structural evidence as applied in the study case can define the role of major cross-strike discontinuities in foreland thrust belts, by constraining and verifying their tectonics inversion significance and the amount of related exhumation.     

Natural Gas Hazard (CO2, 222 Rn) within a Quiescent Volcanic Region and Its Relations with Tectonics: The Case of the Ciampino-Marino Area, Alban Hills Volcano, Italy

Groundwater surveys were performed by detailed(around 300 sites) grid-analysis of water temperature, pH, redox potential, electrical conductivity, ²²²Rn, alkalinity and by calculating the pCO₂, throughout the Ciampino and Marino towns in the Alban Hills quiescent volcano (Central Italy). Following several episodes of dangerous CO₂ exhalation from soils during the last 20 years and earlier ashistorically recorded, the work aimed at assessing the Natural Gas Hazard (NGH) including the indoor-Rn hazard. The NGH was defined as the probability of an area to become a site of poisonous peri-volcanic gas exhalations from soils to the lower atmosphere (comprising buildings). CO₂ was found to be a ``carrier' for the other poisonous minor and in trace components (H<sub>s</sub>S, CH<sub>4</sub>, <sup>222</sup>Rn, etc.). This assessment was performed by extrapolating in the aquifer CO<sub>2</sub> and <sup>222</sup>Rn conditions, and discriminating sectors where future CO<sub>2</sub> flux in soils as well as indoor-Rn measurements have to be noted. A preliminary indoor-Rn survey was performed at about 200 sites. The highest values were found in the highest pCO<sub>2</sub> and high <sup>222</sup>Rn values in groundwater. This indicates convection and enhanced permeability in certain sectors of the main aquifer, i.e., along the bordering faults and inside the gas-trap of the Ciampino Horst., where ``continuous gas-phase micro-macro seepage mechanism' is invoked to explain the high peri-volcanic gases flux.     

Stability of an undercut sea-cliff along a Cilento coastal stretch (Campania,Southern Italy)

This paper deals with a finite element stability analysis performed on a sea-cliff affected by a deep notch. The cliff is about 200 m long with height ranging between 8 and 19 m. The notch at the cliff base is about 1 m above sea level, nearly stretching along the entire cliff toe. Detailed geo-structural and geo-mechanical surveys were performed in situ, and rock samples were tested in laboratory. The relevant physical and mechanical properties were used for determining rock mass strength parameters. A finite element approach was implemented using a two-dimensional elasto-plastic finite-element stress analysis program. The stability analysis shows that the notch causes increasing shear strains spreading from the notch end towards the top cliff. Decreasing strength reduction factors affect the cliff as the notch reaches increased depth into the rock mass, and when its depth is about 2 m the analysis results do not converge. At this stage, an uninterrupted shear plane develops along which a roughly prismatic rock block can slide and then topple.     

Debris-flow Indicator for an early warning system in the Aosta valley region

Natural Hazards - Aosta Valley, an Alpine region in north-western Italy, has an early warning system (EWS) that issues hydrogeological alerts based on hydrological modelling and rainfall thresholds...