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.     

Chemical composition of precipitation at Mt. Vesuvius and Vulcano Island,Italy: volcanological and environmental implications

Natural precipitation and water samples from passive devices were collected at Mt. Vesuvius and Vulcano Island, Italy, during the period 2004–2006, in order to investigate its possible interactions with fumarolic gases. Evidence of chemical reactions between fumarolic fluids and rain samples before and after its deposition into the sampling devices was found at Vulcano Island. Very low pH values (down to 2.5) and significant amounts of chlorine and sulfate (up to 22 mEq/l) were measured at sampling points located close to the fumarolic field. In contrast, anthropogenic contributions and/or dissolution of aerosols (both maritime and continental) influence the chemistry of rainwaters at Mt. Vesuvius, which show inter-annual variations that are highly consistent with those recorded at the coastal site at Vulcano Island. Chemistry of waters directly exposed to fumarolic fluids may then give useful information about its temporal evolution, holding the signal of the “maximum” chemical event occurred in the meanwhile. In addition, the observation of the health status of vegetation colonizing the immediate surroundings of the fumarolic fields, due to its strong dependence on the interactions with these fluids, may work as a possible biomarker of volcanic activity.     

Seismic fragility of reinforced concrete girder bridges using Bayesian belief network

Infrastructure owners and operators, or governmental agencies, need rapid screening tools to prioritize detailed risk assessment and retrofit resources allocation. This paper provides one such tool, for use by highway administrations, based on Bayesian belief network (BBN) and aimed at replacing so‐called generic or typological seismic fragility functions for reinforced concrete girder bridges. Resources for detailed assessments should be allocated to bridges with highest consequence of damage, for which site hazard, bridge fragility, and traffic data are needed. The proposed BBN based model is used to quantify seismic fragility of bridges based on data that can be obtained by visual inspection and engineering drawings. Results show that the predicted fragilities are of sufficient accuracy for establishing relative ranking and prioritizing. While the actual data and seismic hazard employed to train the network (establishing conditional probability tables) refer to the Italian bridge stock, the network structure and engineering judgment can easily be adopted for bridges in different geographical locations. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Procedures for calibration of linear models for damage limitation in design of masonry‐infilled RC frames

Recent earthquakes have confirmed the role played by infills in the seismic response of reinforced concrete buildings. The control and limitation of damage to such nonstructural elements is a key issue in performance‐based earthquake engineering. The present work is focused on modeling and analysis of damage to infill panels, and, in particular, it is aimed towards linear analysis procedures for assessing the damage limitation limit state of infilled reinforced concrete frames. First, code provisions on infill modeling and acceptance criteria at the damage limitation limit state are reviewed. Literature contributions on damage to unreinforced masonry infill panels and corresponding displacement capacity are reported and discussed. Two procedures are then proposed aiming at a twofold goal: (i) the determination of ‘equivalent’ interstory drift ratio limits for a bare frame model and (ii) the estimation of the stiffness of equivalent struts representing infill walls in a linear model. These two quantities are determined such that a linear model ensures a reliable estimation of seismic capacity at the damage limitation limit state, providing the same intensity level as that obtained from nonlinear analyses carried out on structural models with infills. Finally, the proposed procedures are applied to four‐story and eight‐story case study‐infilled frames, designed for seismic loads according to current technical codes. The results of these application examples are presented and discussed. Copyright © 2016 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.