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.     

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.     

Seismic performance of masonry walls retrofitted with steel reinforced grout

An innovative solution for the seismic protection of existing masonry structures is proposed and investigated through shake table tests on a natural scale wall assemblage. After a former test series carried out without reinforcement, the specimen was retrofitted using Steel Reinforced Grout. The strengthening system comprises horizontal strips of ultra‐high strength steel cords, externally bonded to the masonry with hydraulic lime mortar, and connectors to transversal walls, applied within the thickness of the plaster layer. In order to assess the seismic performance of the retrofitted wall, natural accelerograms were applied with increasing intensity up to failure. Test results provide a deep understanding of the effectiveness of mortar‐based composites for improving the out‐of‐plane seismic capacity of masonry walls, in comparison with traditional reinforcements with steel tie‐bars. The structural implications of the proposed solution in terms of dynamic properties and damage development under earthquake loads are also discussed.Copyright © 2015 John Wiley & Sons, Ltd.     

Impact of climate indicators on continental‐scale potential groundwater recharge in Africa

In the last decades, human activity has been contributing to climate change that is closely associated with an increase in temperatures, increase in evaporation, intensification of extreme dry and wet rainfall events, and widespread melting of snow and ice. Understanding the intricate linkage between climate warming and the hydrological cycle is crucial for sustainable management of groundwater resources, especially in a vulnerable continent like Africa. This study investigates the relationship between climate‐change drivers and potential groundwater recharge (PGR) patterns across Africa for a long‐term record (1960–2010). Water‐balance components were simulated by using the PCR‐GLOBWB model and were reproduced in both gridded maps and latitudinal trends that vary in space with minima on the Tropics and maxima around the Equator. Statistical correlations between temperature, storm occurrences, drought, and PGR were examined in six climatic regions of Africa. Surprisingly, different effects of climate‐change controls on PGR were detected as a function of latitude in the last three decades (1980–2010). Temporal trends observed in the Northern Hemisphere of Africa reveal that the increase in temperature is significantly correlated to the decline of PGR, especially in the Northern Equatorial Africa. The climate indicators considered in this study were unable to explain the alarming negative trend of PGR observed in the Sahelian region, even though the Standardized Precipitation‐Evapotranspiration Index (SPEI) values report a 15% drought stress. On the other hand, increases in temperature have not been detected in the Southern Hemisphere of Africa, where increasing frequency of storm occurrences determine a rise of PGR, particularly in southern Africa. Time analysis highlights a strong seasonality effect, while PGR is in‐phase with rainfall patterns in the summer (Northern Hemisphere) and winter (Southern Hemisphere) and out‐of‐phase during the fall season. This study helps to elucidate the mechanism of the processes influencing groundwater resources in six climatic zones of Africa, even though modelling results need to be validated more extensively with direct measurements in future studies. Copyright © 2016 John Wiley & Sons, Ltd.     

A conceptual hydrogeological model of ophiolitic aquifers (serpentinised peridotite): The test example of Mt. Prinzera (Northern Italy)

The main aim of this study is the experimental analysis of the hydrogeological behaviour of the Mt. Prinzera ultramafic massif in the northern Apennines, Italy. The analysed multidisciplinary database has been acquired through (a) geologic and structural survey; (b) geomorphologic survey; (c) hydrogeological monitoring; (d) physico‐chemical analyses; and (e) isotopic analyses. The ultramafic medium is made of several lithological units, tectonically overlapped. Between them, a low‐permeability, discontinuous unit has been identified. This unit behaves as an aquitard and causes a perched groundwater to temporary flow within the upper medium, close to the surface. This perched groundwater flows out along several structurally controlled depressions, and then several high‐altitude temporary springs can be observed during recharge, together with several perennial basal (i.e., low altitude) springs, caused by the compartmentalisation of the system because of high‐angle tectonic discontinuities.     

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.     

Room-temperature equation of state of Li<Subscript>2</Subscript>VOSiO<Subscript>4</Subscript> up to 8.5 GPa

High-pressure single-crystal X-ray diffraction measurements of lattice parameters of the compound Li₂VOSiO₄, which crystallises with a natisite-type structure, has been carried out to a pressure of 8.54(5) GPa at room temperature. Unit-cell volume data were fitted with a second-order Birch-Murnaghan EoS (BM-EoS), simultaneously refining V ₀ and K ₀ using the data weighted by the uncertainties in V. The bulk modulus is K ₀ = 99(1) GPa, with K′ fixed to 4. Refinements of third order equations-of-state yielded values of K′ that did not differ significantly from 4. The compressibility of the unit-cell is strongly anisotropic with the c axis (K ₀(c) = 49.7 ± 0.5 GPa) approximately four times more compressible than the a axis (K ₀(a) = 195 ± 3 GPa).     

Garnet and spinel in fertile and depleted mantle: insights from thermodynamic modelling

We performed thermodynamic calculations based on model and natural peridotitic compositions at pressure and temperature conditions relevant to the Earth’s upper mantle, using well-established free energy minimization techniques. The model is consistent with the available experimental data in Cr-bearing peridotitic systems and can therefore be used to predict phase relations and mineral compositions in a wide range of realistic mantle compositions. The generated phase diagrams for six different bulk compositions, representative of fertile, depleted and ultra-depleted peridotitic mantle, shown that the garnet + spinel stability field is always broad at low temperatures and progressively narrows with increasing temperatures. In lithospheric sections with hot geotherms (ca. 60 mW/m²), garnet coexists with spinel across an interval of 10–15 km, at ca. 50–70 km depths. In colder, cratonic, lithospheric sections (e.g. along a 40 mW/m² geotherm), the width of the garnet–spinel transition strongly depends on bulk composition: In fertile mantle, spinel can coexist with garnet to about 120 km depth, while in an ultra-depleted harzburgitic mantle, it can be stable to over 180 km depth. The formation of chromian spinel inclusions in diamonds is restricted to pressures between 4.0 and 6.0 GPa. The modes of spinel decrease rapidly to less than 1 vol % when it coexists with garnet; hence, spinel grains can be easily overlooked during the petrographical characterization of small mantle xenoliths. The very Cr-rich nature of many spinels from xenoliths and diamonds from cratonic settings may be simply a consequence of their low modes in high-pressure assemblages; thus, their composition does not necessarily imply an extremely refractory composition of the source rock. The model also shows that large Ca and Cr variations in lherzolitic garnets in equilibrium with spinel can be explained by variations of pressure and temperature along a continental geotherm and do not necessarily imply variations of bulk composition. The slope of the Cr# [i.e. Cr/(Cr + Al)mol] isopleths in garnet in equilibrium with spinel changes significantly at high temperatures, posing serious limitations to the applicability of empirical geobarometric methods calibrated on cratonic mantle xenoliths in hotter, off-craton, lithospheric mantle sections.