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.     

From sprawl to compactness and back: population dynamics (1848–2011) and the economic structure of a Mediterranean city

In the recent decades southern European cities experienced morphological changes and a demographic transition towards zero (or negative) growth and aging. Population dynamics shifted from the impressive growth of the post-industrial period into recent de-concentration processes determining the spillover of commercial and residential settlements across the surrounding rural areas. Based on long-term demographic data, the present study hypothesizes that urban expansion did not follow a one-way linear path from compactness to dispersion while reflecting differentiated growth patterns based on the specific socioeconomic context at the local scale. Along a sufficiently long time period non-linear expansion waves alternating settlement densification and scattering are expected to be found especially in complex urban contexts such as those developed in the Mediterranean region. This hypothesis was tested for a paradigmatic case study in southern Europe (Athens, Greece) using demographic data covering 160 years (1848–2011). Urban growth in Athens was assessed through the analysis of long-term census data made available on a district level. These data provide information on the spatial distribution of resident population and characterize distinct expansion waves according to the dominant socioeconomic context. Results of the study were discussed in the light of the debate on future development of the Mediterranean cities and the (changing) economic relations with the surrounding region.     

Deep tunnel fronts in cohesive soils under undrained conditions: a displacement-based approach for the design of fibreglass reinforcements

The fronts of tunnels excavated under particularly difficult ground conditions by employing conventional tunnelling methods are commonly supported: the stabilization is usually achieved either by improving the mechanical properties of the soil (injections, jet grouting, soil freezing, etc.) or by introducing linear inclusions. This last technique, consisting in the introduction of pipes (usually made of fibreglass reinforced polymers) in the front, is particularly popular since it is very simple to adapt the reinforcement geometry, length and number to the different conditions encountered during the excavation. The design of this reinforcement technique is nowadays based on very simplified approaches: on either empirical formula or the limit equilibrium method. In a previous paper, the authors numerically studied the mechanical response of unreinforced fronts in cohesive soils and defined a non-dimensional front characteristic curve. In this paper, the authors intend to take into consideration the role of reinforcements by following the same approach. A procedure allowing the definition of the reinforced non-dimensional front characteristic curve, once the reinforcement pattern is assigned, is introduced. The practical use of this curve is described.

     

A topical evaluation and discussion of data movement technologies for data-intensive scientific applications

Transferring large volumes of information from one location to potentially many others that are geographically distributed and across varying networks is still prevalent in modern scientific data systems. This is despite the movement to push computation to the data and to reduce data movement needed to compute answers to challenging scientific problems, to disseminate information to the scientific community, and to acquire data for curation and enrichment. Because of this, it is imperative that decisions made regarding data movement systems and architectures be backed by both analytical rigor, and also by empirical evidence and measurement. The purpose of this study is to expand on the work performed by our research team over the last decade and to take a fresh look at the evaluation of multiple topical data transfer technologies in use cases derived from data-intensive scientific systems and applications in the areas of Earth science. We report on the evaluation of a set of data movement technologies against a set of empirically derived comparison dimensions. Based on this evaluation, we make recommendations towards the selection of appropriate data movement technologies in scientific applications and scenarios.     

A Fe K-edge XAS study of amethyst

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.     

Chromium solubility in MgSiO3 ilmenite at high pressure

The crystal structure and chemical composition of crystals of (Mg_1?x Cr _x )(Si_1?x Cr _x )O₃ ilmenite (with x = 0.015, 0.023 and 0.038) synthesized in the model system Mg₃Cr₂Si₃O₁₂–Mg₄Si₄O₁₂ at 18–19 GPa and 1,600 °C have been investigated. Chromium was found as substitute for both Mg at the octahedral X site and Si at the octahedral Y site, according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a shortening of the <X–O> and a lengthening of the <Y–O> distances with respect to the values typically observed for pure MgSiO₃ ilmenite and eskolaite Cr₂O₃. Although no high Cr contents are considered in the pyrolite model, Cr-bearing ilmenite may be the host for chromium in the Earth’s transition zone. The successful synthesis of ilmenite with high Cr contents and its structural characterization are of key importance because the study of its thermodynamic constants combined with the data on phase relations in the lower-mantle systems can help in the understanding of the seismic velocity and density profiles of the transition zone and the constraining composition and mineralogy of pyrolite in this area of the Earth.