Shoshonite and sub-alkaline magmas from an ultrapotassic volcano: Sr–Nd–Pb isotope data on the Roccamonfina volcanic rocks,Roman Magmatic Province,Southern Italy

The Roccamonfina volcano is characterised by two stages of volcanic activity that are separated by volcano-tectonic caldera collapses. Ultrapotassic leucite-bearing rocks are confined to the pre-caldera stage and display geochemical characteristics similar to those of other volcanoes in the Roman Province. After the major sector collapse of the volcano, occurred at ca. 400 ka, shoshonitic rocks erupted from cinder cones and domes both within the caldera and on the external flanks of the pre-caldera Roccamonfina volcano. On the basis of new trace element and Sr–Nd–Pb isotope data, we show that the Roccamonfina shoshonitic rocks are distinct from shoshonites of the Northern Roman Province, but are very similar to those of the Neapolitan volcanoes. The last phases of volcanic activity erupted sub-alkaline magmas as enclaves in trachytic domes, and as lavas within the Monte Santa Croce dome. Ultrapotassic rocks of the pre-caldera composite volcano are plagioclase-bearing leucitites characterised by high levels of incompatible trace elements with an orogenic signature having troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of ⁸⁷Sr/⁸⁶Sr range from 0.70926 to 0.70999, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.51213 to 0.51217, while the lead isotope rations vary between 18.788–18.851 for ²⁰⁶Pb/²⁰⁴Pb, 15.685–15.701 for ²⁰⁷Pb/²⁰⁴Pb, and 39.048–39.076 for ²⁰⁸Pb/²⁰⁴Pb. Shoshonites show a similar pattern of trace element depletions and enrichments to the earlier ultrapotassic leucite-bearing rocks but have a larger degree of differentiation and lower concentrations of incompatible trace elements. On the other hand, shoshonitic rocks have Sr, Nd, and Pb isotopes consistently different than pre-caldera ultrapotassic leucite-bearing rocks. ⁸⁷Sr/⁸⁶Sr ranges from 0.70665 to 0.70745, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.51234 to 0.51238, ²⁰⁶Pb/²⁰⁴Pb ranges from 18.924 to 19.153, ²⁰⁷Pb/²⁰⁴Pb ranges from 15.661 to 15.694, and ²⁰⁸Pb/²⁰⁴Pb ranges from 39.084 to 39.212. High-K calc-alkaline samples have intermediate isotopic values between ultrapotassic plagioclase leucitites and shoshonites, but the lowest levels of incompatible trace element contents. It is argued that ultrapotassic magmas were generated in a modified lithospheric mantle after crustal-derived metasomatism. Interaction between the metasomatic agent and lithospheric upper mantle produced a low-melting point metasomatised veined network. The partial melting of the veins alone produced pre-caldera leucite-bearing ultrapotassic magmas. It was possibly triggered by either post-collisional isotherms relaxation or increasing T°C due increasing heat flow through slab tears. Shoshonitic magmas were generated by further melting, at higher temperature, of the same metasomatic assemblage with addition 10–20% of OIB-like astenospheric mantle material. We suggest that addition of astenospheric upper mantle material from foreland mantle, flowing through slab tearing after collision was achieved. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Nonlinear seismic behaviour of wall-frame dual systems accounting for soil–structure interaction

The aim of this paper is to study the effects of soil–structure interaction on the seismic response of coupled wall-frame structures on pile foundations designed according to modern seismic provisions. The analysis methodology based on the substructure method is recalled focusing on the modelling of pile group foundations. The nonlinear inertial interaction analysis is performed in the time domain by using a finite element model of the superstructure. Suitable lumped parameter models are implemented to reproduce the frequency-dependent compliance of the soil-foundation systems. The effects of soil–structure interaction are evaluated by considering a realistic case study consisting of a 6-storey 4-bay wall-frame structure founded on piles. Different two-layered soil deposits are investigated by varying the layer thicknesses and properties. Artificial earthquakes are employed to simulate the earthquake input. Comparisons of the results obtained considering compliant base and fixed base models are presented by addressing the effects of soil–structure interaction on displacements, base shears, and ductility demand. The evolution of dissipative mechanisms and the relevant redistribution of shear between the wall and the frame are investigated by considering earthquakes with increasing intensity. Effects on the foundations are also shown by pointing out the importance of both kinematic and inertial interaction. Finally, the response of the structure to some real near-fault records is studied. Copyright © 2012 John Wiley & Sons, Ltd.     

Chemical and isotopic assessment of surface water–shallow groundwater interaction in the arid Grande river basin,North-Central Chile

ABSTRACT

This paper analyses the composition of surface water and shallow groundwater in the Grande River basin, North-Central Chile, using this information to characterize water interactions. Chemical and isotopic data for surface water and groundwater (7 and 6 sampling locations, respectively) were obtained from three sampling campaigns performed in March–April (autumn), August–September (late winter) and December (early summer) 2012. Precipitation samples were also collected. Data was processed using spatial distribution charts, Piper and Stiff diagrams, and multivariate analysis. In general, the results for each method converge on a high degree of connectivity between surface water and shallow groundwater in the study area. Furthermore, approximately a 10% of groundwater contribution to the surface flow discharge was estimated for a particular reach. This multi-method approach was useful for the characterization of surface water–groundwater interactions in the Grande River basin, and may become a suitable and replicable scheme for studies in arid and semi-arid basins facing similar water management challenges.

Editor D. Koutsoyiannis; Associate editor B. Dewals     

Atomic structures and energies of grain boundaries in Mg2SiO4 forsterite from atomistic modeling

Grain boundaries influence many physical and chemical properties of crystalline materials. Here, we perform molecular dynamics simulations to study the structure of a series of [100] symmetric tilt grain boundaries in Mg₂SiO₄ forsterite. The present results show that grain boundary energies depend significantly on misorientation angle. For small misorientation angles (up to 22°), grain boundary structures consist of an array of partial edge dislocations with Burgers vector $\frac{1}{2}[001]$ associated with stacking faults and their energies can be readily fit with a model which adds the Peach-Koehler equation to the Read-Shockley dislocation model for grain boundaries. The core radius of partial dislocations and the spacing between the partials derived from grain boundary energies show that the transition from low- to high-angle grain boundaries occurs for a misorientation angle between 22° and 32°. For high misorientation angles (32.1° and 60.8°), the cores of dislocations overlap and form repeated structural units. Finally, we use a low energy atomic configuration obtained by molecular dynamics for the misorientation of 12.18° as input to simulate a high-resolution transmission electron microscopy (HRTEM) image. The simulated image is in good agreement with an observed HRTEM image, which indicates the power of the present approach to predict realistic atomic structures of grain boundaries in complex silicates.     

Seismic response of L��Aquila downtown from comparison between 2D synthetics spectral ratios of SH, P-SV and Rayleigh waves and observations of the 2009 earthquake sequence

This is the first part of a study on the seismic response of the L’Aquila city using 2D simulation and experimental data. We have studied two velocity-depth models with the aim of outlining the behavior of a velocity reversal in the top layer, which is associated with the stiff Brecce de L’Aquila unit (BrA). In this setting, the SMTH model is topped by a layer with about 2:1 impedance contrast with the underlying layer while the NORV model has no velocity reversal. We have simulated the propagation of SH and P-SV wavefields in the range 0–10 Hz for incidence 0°–90°. Earthquake spectral ratios of the horizontal and vertical components at six sites in L’Aquila downtown are compared to corresponding synthetics spectral ratios. The vertical component of P-SV synthetics enables us to investigate a remarkable amplification effect seen in the vertical component of the recorded strong motion. Sites AQ04 and AQ05 are best matched by synthetics from the NORV model while FAQ5 and AQ06 have a better match with synthetics spectral ratios from the SMTH model. All simulations show this behavior systematically, with horizontal and near-horizontal incident waves predicting the overall pattern of matches more clearly than vertical and near-vertical incidence. The model inferences are in agreement with new geological data reporting lateral passages in the top layer from the stiff BrA to softer sediments. Matches are good in terms of frequency of the first amplification peak and of spectral amplitude: the horizontal components have spectral ratio peaks predominantly at 0.5 Hz in the simulations and at 0.7 Hz in the data, both with amplitudes of 4, while the vertical component spectral ratios reach values of 6 at frequencies of about 1 Hz in both data and simulations. The vertical component spectral ratios are very well matched using Rayleigh waves with incidence at 90°. The NORV model without the velocity reversal predicts spectral ratio peaks for the horizontal components at frequencies up to 6 Hz. The reversal of velocity acts as a low-pass frequency filter on the horizontal components reducing the amplification effect of the sediment filled valley.     

Comparison of fluid geochemistry and microbiology of multiple organic-rich reservoirs in the Illinois Basin, USA: Evidence for controls on methanogenesis and microbial transport

Microbial methane in sedimentary basins comprises approximately 20% of global natural gas resources, yet little is known about the environmental requirements and metabolic rates of these subsurface microbial communities. The Illinois Basin, located in the midcontinent of the United States, is an ideal location to investigate hydrogeochemical factors controlling methanogenesis as microbial methane accumulations occur: (1) in three organic-rich reservoirs of different geologic ages and organic matter types - Upper Devonian New Albany Shale (up to 900 m depth), Pennsylvanian coals (up to 600 m depth), and Quaternary glacial sediments (shallow aquifers); (2) across steep salinity gradients; and (3) with variable concentrations of . For all three organic-rich reservoirs aqueous geochemical conditions are favorable for microbial methanogenesis, with near neutral pH, concentrations <2 mM, and Cl⁻ concentrations <3 M. Also, carbon isotopic fractionation of CH₄, CO₂, and DIC is consistent with microbial methanogenesis, and increased carbon isotopic fractionation with average reservoir depth corresponds to a decrease of groundwater flushing rates with average depth of reservoir. Plots of stable isotopes of water and Cl⁻ show mixing between a brine endmember and freshwater, suggesting that meteoric groundwater recharge has affected all microbial methanogenic systems. Additionally, similar methanogenic communities are present in all three reservoirs with comparable cell counts (8.69E3-2.58E6 cells/mL). TRFLP results show low numbers of archaea species with only two dominant groups of base pairs in coals, shale, and limestone aquifers. These results compare favorably with other methanogen-containing deep subsurface environments. Individual hydrogeochemical parameters that have a Spearman correlation coefficient greater than 0.3 to variations in methanogenic species include stable isotopes of water (δ¹⁸O and δD), type of substrate (i.e. coals versus shale), pH, and Cl⁻ concentration. The matching of variations between methanogenic TRFLP data and conservative tracers suggests that deep circulation of meteoric waters influenced archaeal communities in the Illinois Basin. In addition, coalification and burial estimates suggest that in the study area, coals and shale reservoirs were previously sterilized (>80 °C in nutrient poor environments), necessitating the re-introduction of microbes into the subsurface via groundwater transport.     

Sr-Nd-Pb isotopes from the Radicofani Volcano, Central Italy: constraints on heterogeneities in a veined mantle responsible for the shift from ultrapotassic shoshonite to basaltic andesite magmas in a post-collisional setting

The Radicofani Volcano is characterised by few lava flows, a cinder cone and a denudated neck, and is part of the Tuscan Magmatic Province, the northernmost volcanic region of the Italian peninsula. In spite of the short time span of activity, a large time-dependant chemical and isotopic variability is observed. Most of the rocks of the Radicofani volcano are ultrapotassic shoshonites associated to younger basaltic andesites, found at the bottom of the neck. K₂O contents are positively correlated with trace element and isotopic variations. Shoshonitic and high-K calc-alkaline rocks of the Radicofani volcano are significantly different from shoshonites occurring in association with leucite-bearing ultrapotassic rocks in the southernmost portion of the Roman Magmatic Province. The studied rocks are characterised by high, but variable, levels of incompatible trace elements with a subduction-related signature, with troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of ⁸⁷Sr/⁸⁶Sr range from 0.71333 to 0.71588, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.512050 to 0.512183, while the lead isotope ratios vary between 18.672 and 18.716 for ²⁰⁶Pb/²⁰⁴Pb, 15.665 to 15.696 for ²⁰⁷Pb/²⁰⁴Pb, and 39.981 to 39.081 for ²⁰⁸Pb/²⁰⁴Pb. Ultrapotassic shoshonites show the highest incompatible trace element contents coupled with the highest ⁸⁷Sr/⁸⁶Sr and the lowest ¹⁴³Nd/¹⁴⁴Nd. On the basis of geochemical and isotopic signatures it is argued that magmas were generated in a modified lithospheric peridotitic source containing metasomatic veins generated by K-rich melts from recycled sediments within the mantle via subduction. A further metasomatic event generated by slab-derived fluids pervasively enriched the peridotitic source. Partial melting of the veins produced leucite-free ultrapotassic magmas (i.e. lamproite), and was triggered by rising of the isotherms after the orogenic front migrated eastward in the Italian Peninsula. Further rise of the isotherms induced larger degrees of partial melting inducing melting of the surrounding wall peridotite. The variation of the degree of partial melting of such a heterogeneous peridotitic source produced a wide spectrum of magma compositions, which mimic a mixing line between two components: ultrapotassic magma from partial melting of the metasomatic vein and a basaltic andesitic magma from partial melting of the surrounding peridotite.     

A note on modeling double diffusive mixing in the global ocean

Though ubiquitous in the global oceans, double diffusive mixing has been largely ignored or poorly represented in the models of turbulent mixing in the ocean and in 3-D ocean models, until recently. Salt fingers occur in the interior of many marginal seas and ocean basins, the Tyrrhenian Sea and the subtropical Atlantic being two examples. Diffusive convection type of double diffusion occurs in the upper layers of many sub-polar seas and polar oceans due to cold melt water from sea ice. Consequently, it is important to be able to properly parameterize double diffusive mixing in basin scale and global ocean models, so that the water mass structure in the interior of the ocean can be properly simulated. This note describes a model for double diffusive mixing in the presence of background shear, based on Mellor–Yamada type second moment closure, more specifically Kantha, 2003, Kantha and Clayson, 2004 second moment closure models of resulting turbulence, following Canuto et al. (2008a) but employing a different strategy for modeling the pertinent terms in the second moment equations. The resulting model is suitable for inclusion in ocean general circulation models.     

Two GUIs-based analysis tool for spectroradiometer data pre-processing

A new graphical user interface (GUI) for pre-processing reflectance spectra, built using MATLAB and expressly designed for the ASD FieldSpec® spectroradiometer, was developed to solve problems that generally affect experimental ASD data. The GUI is characterised by an easily readable, graphic visualisation of spectra, from which the absorption band depth (ABD) can be obtained for a selected wavelength. The output format of the ASD data is a binary file with an .asd extension. The binary file, that provides a single spectrum, can be processed using a software functionality, by means of a GUI, that allows to select one or more binary files to produce a spectral library in a unique .txt file. The spectral reflectance is re-calibrated with the “convex-hull” methodology to eliminate the convex shape, which is typical of reflectance spectra. Different examples of the use of the new GUI are provided.