Calorimetric study of high-pressure polymorphs of MnSiO3

With increasing pressure, MnSiO₃ rhodonite stable at atmospheric pressure transforms to pyroxmangite, then to clinopyroxene and further to tetragonal garnet, which finally decomposes into MnO (rocksalt) plus SiO₂ (stishovite). High temperature solution calorimetry of synthetic rhodonite, clinopyroxene and garnet forms of MnSiO₃ was used to measure the enthalpies of these transitions. ΔH ₉₇₄ ⁰ for the rhodonite-clinopyroxene and ΔH ₂₉₈ ⁰ for the clinopyroxene-garnet transition are 520±490 and 8,270±590 cal/mol, respectively. The published data on the enthalpy of the rhodonite-pyroxmangite transition, phase equilibrium boundaries, compressibility and thermal expansion data are used to calculate entropy changes for the transitions. The enthalpy, entropy and volume changes are very small for all the transitions among rhodonite, pyroxmangite and clinopyroxene. The calculated boundary for the clinopyroxene-garnet transition is consistent with the published experimental results. The pyroxene-garnet transition in several materials, including MnSiO₃, is characterized by a relatively small negative entropy change and large volume decrease, resulting in a small positiveP – T slope. The disproportionation of MnSiO₃ garnet to MnO plus stishovite and of Mn₂SiO₄ olivine to garnet plus MnO are calculated to occur at about 17–18 and 14–15 GPa, respectively, at 1,000–1,500 K.     

Paleoproterozoic mafic dyke swarms of the Belomorian Province,eastern Fennoscandian Shield

Paleoproterozoic mafic igneous rocks (2450–1970 Ma) are exposed in the form of layered intrusions, dykes, and volcanic rocks in the Karelian, Kola and Murmansk provinces and in the form of dykes and small intrusions in the Belomorian Province, Eastern Fennoscandian Shield. The age and sequence of mafic dyke emplacement during the Paleoproterozoic are very similar in these regions. Further comparisons of geochemical characteristics of mafic dyke swarms in the Belomorian Province and neighboring cratons show considerable similarities.     

Energetics of nanoparticle oxides: interplay between surface energy and polymorphism†

Many oxides tend to form different structures (polymorphs) for small particles. High temperature oxide melt solution calorimetry has been used to measure the enthalpy as a function of polymorphism and surface area for oxides of Al, Ti, and Zr. The results confirm crossovers in polymorph stability at the nanoscale. The energies of internal and external surfaces of zeolitic silicas with open framework structures are an order of magnitude smaller than those of oxides of normal density.     

Thermodynamics of element partitioning: (1) Systematics of transition metals in crystalline and molten silicates and (2) Defect chemistry and “the Henry's law problem”

The distribution of Mg, Mn, Fe, Co and Ni among olivine, orthopyroxene, calcic clinopyroxene and liquid can be described by exchange reactions of the form: M (phase A) + Mg (phase B) = M (phase B) + Mg (phase A). The thermochemical data predict the observed partitioning within the limits of error of both sets of data when assumptions of ideal solid solution are used, except for Mn-Mg exchange. Because ΔS and ΔV for these exchange reactions are generally small, K_D varies relatively little with temperature and pressure, although individual ion distribution coefficients (D values) are more sensitive to these variables and to changing liquid composition.Trace elements present at the ppm level can enter crystals in normal lattice sites, can participate in point defect equilibria and can enter various defect sites present metastably in the crystal as a result of its P,T history. Metastable defect equilibria, in which the number of sites (grain boundaries, surfaces, intergrowths, etc.) is fixed, can lead to enhanced trace element solubility in the crystal at very low concentrations and thus to apparent deviations from Henry's law.     

Surface studies of water isotopes in Antarctica for quantitative interpretation of deep ice core data

Polar ice cores are unique climate archives. Indeed, most of them have a continuous stratigraphy and present high temporal resolution of many climate variables in a single archive. While water isotopic records (δD or δ¹⁸O) in ice cores are often taken as references for past atmospheric temperature variations, their relationship to temperature is associated with a large uncertainty. Several reasons are invoked to explain the limitation of such an approach; in particular, post-deposition effects are important in East Antarctica because of the low accumulation rates. The strong influence of post-deposition processes highlights the need for surface polar research programs in addition to deep drilling programs. We present here new results on water isotopes from several recent surface programs, mostly over East Antarctica. Together with previously published data, the new data presented in this study have several implications for the climatic reconstructions based on ice core isotopic data: (1) The spatial relationship between surface mean temperature and mean snow isotopic composition over the first meters in depth can be explained quite straightforwardly using simple isotopic models tuned to d-excess vs. δ¹⁸O evolution in transects on the East Antarctic sector. The observed spatial slopes are significantly higher (～ 0.7–0.8‰·°C^?1 for δ¹⁸O vs. temperature) than seasonal slopes inferred from precipitation data at Vostok and Dome C (0.35 to 0.46‰·°C^?1). We explain these differences by changes in condensation versus surface temperature between summer and winter in the central East Antarctic plateau, where the inversion layer vanishes in summer. (2) Post-deposition effects linked to exchanges between the snow surface and the atmospheric water vapor lead to an evolution of δ¹⁸O in the surface snow, even in the absence of any precipitation event. This evolution preserves the positive correlation between the δ¹⁸O of snow and surface temperature, but is associated with a much slower δ¹⁸O-vs-temperature slope than the slope observed in the seasonal precipitation. (3) Post-deposition effects clearly limit the archiving of high-resolution (seasonal) climatic variability in the polar snow, but we suggest that sites with an accumulation rate of the order of 40 kg.m^?2.yr^?1 may record a seasonal cycle at shallow depths.     

Monitoring and early warning of the 2012 Preonzo catastrophic rockslope failure

In this paper, we describe the investigations and actions taken to reduce risk and prevent casualties from a catastrophic 210,000 m³ rockslope failure, which occurred near the village of Preonzo in the Swiss Alps on May 15, 2012. We describe the geological predisposition and displacement history before and during the accelerated creep stage as well as the development and operation of an efficient early warning system. The failure of May 15, 2012, occurred from a large and retrogressive instability in gneisses and amphibolites with a total volume of about 350,000 m³, which formed an alpine meadow 1250 m above the valley floor. About 140,000 m³ of unstable rock mass remained in place and might collapse partially or completely in the future. The instability showed clearly visible signs of movements along a tension crack since 1989 and accelerated creep with significant hydromechanical forcing since about 2006. Because the active rockslide at Preonzo threatened a large industrial facility and important transport routes located directly at the toe of the slope, an early warning system was installed in 2010. The thresholds for prealarm, general public alarm, and evacuation were derived from crack meter and total station monitoring data covering a period of about 10 years, supplemented with information from past failure events with similar predisposition. These thresholds were successfully applied to evacuate the industrial facility and to close important roads a few days before the catastrophic slope failure of May 15, 2012. The rock slope failure occurred in two events, exposing a compound rupture plane dipping 42° and generating deposits in the midslope portion with a travel angle of 39°. Three hours after the second rockslide, the fresh deposits became reactivated in a devastating debris avalanche that reached the foot of the slope but did not destroy any infrastructure. The final run-out distance of this combined rock collapse–debris avalanche corresponded to the predictions made in the year 2004.     

Analysis of the incommensurately modulated OS phase of SiO2 tridymite

The structure, symmetry and origin of the incommensurately modulated OS phase of tridymite (SiO₂) and its lock-in to the OP three-fold superlattice structure are discussed in a computational study. The structure of the OS phase (which has not been determined experimentally) is deduced as the only geometrically possible structure derived from the parent OC phase by rotation and translation of the SiO₄ tetrahedra without significant distortion of these units. It can be visualised conveniently in terms of the McConnell formalism of two component difference structures C₁ and C₂ whose space group symmetries are derived. The results are in accordance with the known lock-in structure at wave vector Q= a ^*. In the latter, the ±C₁ regions expand and the structure can square up in a very general way to take advantage of the lost symmetries (lost compared with the OC phase). Received: 4 August 1997 / Revised, accepted 24 November 1997     

Transition zone structure under a stationary hot spot: Cape Verde

We report on a two-year seismic deployment in the Cape Verde Islands, one goal of which was to study the upper mantle to determine its structure under a hot spot that is stationary in the hot spot reference frame. We find from analysis of P-to-S receiver functions estimated from broadband seismic recordings that, within uncertainty, the time separation between the 410 and 660 km discontinuities is normal compared to radial earth models. Thus, to exist, even stationary hot spots do not require vertical thermal anomalies from deep melting sources anchored in the lower mantle or at the core–mantle boundary or their anomalies are narrower than ～ 250 km in the upper mantle.     

An upwelling filament off southwest Iberia: Effect on the chlorophyll a and nutrient export

The present paper describes the chemical and biological characteristics of an upwelling filament off southern Iberia in October 2004, based on a total of 42 CTD casts, along with ADCP velocity measurements distributed by an almost regular grid of 15 km mean spacing. Stations were sampled from the surface to a maximum depth of 400 dbar, for nutrients (nitrate, phosphate and silicate) and chlorophyll a determination. The effect of cross-shelf exchange of nutrients and chlorophyll a between the coastal and oceanic waters was also investigated. Data revealed that, during the cruise conducted under relaxed winds, a relatively small filament was formed down to 75 m. However, an amount of 180 t of chlorophyll a was estimated there accompanied by low nutrient concentrations. The observed water properties reveal that SW Iberia is similar to NW Iberia, showing the continuity of the Canary Upwelling System along the Iberian Peninsula, one of poorest upwelling systems of the oceanic eastern boundaries. Nevertheless, the amounts of chlorophyll and nutrients transported through the filament are significant, revealing that those play a key role in the seaward export of matter with an important impact on the regional oceanography of this region. Considering the periods of strong upwelling events and the extent of their duration along the year, the amounts of exported matter must be hugely increased and responsible for the high productivity of these waters.