The supergene origin of ruthenian hexaferrum in Ni‐laterites

For two decades, the nature of Fe‐rich, oxygen‐bearing, Ru–Os compounds found in the supergene environment has been debated. Ru–Os–Fe‐oxides and nano‐intergrowths of ruthenium with magnetite have been proposed. We applied FE‐SEM, EMPA, μ‐Raman spectroscopy and synchrotron tts‐μXRD to Ru–Os–Fe compounds recovered from Ni‐laterites from the Dominican Republic. The results demonstrate that a significant portion of Fe exists in a common structure with the Ru–Os alloy, that is, ruthenian hexaferrum. This mineral occurs both as nanoparticles and as micrometric patches within a matrix of Fe‐oxide(s). Our data suggest that supergene ruthenian hexaferrum with a (Ru_0.4(Os,Ir)_0.1Fe_0.5)_?1.0 stoichiometry represents the most advanced weathering product of primary laurite within Ni‐laterites from the Dominican Republic.     

The accuracy of standard enthalpies and entropies for phases of petrological interest derived from density-functional calculations

The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO₃–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al₂SiO₅ polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.     

New observations on high‐pressure phases in a shock melt vein in the Villalbeto de la Peña meteorite: Insights into the shock behavior of diopside

The petrology and mineralogy of shock melt veins in the L6 ordinary chondrite host of Villalbeto de la Peña, a highly shocked, L chondrite polymict breccia, have been investigated in detail using scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and electron probe microanalysis. Entrained olivine, enstatite, diopside, and plagioclase are transformed into ringwoodite, low‐Ca majorite, high‐Ca majorite, and an assemblage of jadeite‐lingunite, respectively, in several shock melt veins and pockets. We have focused on the shock behavior of diopside in a particularly large shock melt vein (10 mm long and up to 4 mm wide) in order to provide additional insights into its high‐pressure polymorphic phase transformation mechanisms. We report the first evidence of diopside undergoing shock‐induced melting, and the occurrence of natural Ca‐majorite formed by solid‐state transformation from diopside. Magnesiowüstite has also been found as veins injected into diopside in the form of nanocrystalline grains that crystallized from a melt and also occurs interstitially between majorite‐pyrope grains in the melt‐vein matrix. In addition, we have observed compositional zoning in majorite‐pyrope grains in the matrix of the shock‐melt vein, which has not been described previously in any shocked meteorite. Collectively, all these different lines of evidence are suggestive of a major shock event with high cooling rates. The minimum peak shock conditions are difficult to constrain, because of the uncertainties in applying experimentally determined high‐pressure phase equilibria to complex natural systems. However, our results suggest that conditions between 16 and 28 GPa and 2000–2200 °C were reached.     

Petroleum accumulation and leakage in a deeply buried carbonate reservoir,Níspero field (Mexico)

The filling history of the Níspero deeply buried Lower Cretaceous carbonate reservoir (below 4000 m) from the south part of Gulf of Mexico was studied using a combination of data from petrography, stable isotopes and fluid inclusions and compared with a one-dimensional burial model to derive timing.     

Heat capacity of γ-Fe2SiO4 between 5 and 303 K and derived thermodynamic properties

A multi-anvil device was used to synthesize 24 mg of pure γ-Fe₂SiO₄ crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (C _p) of γ-Fe₂SiO₄ was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured heat capacity data show a broad λ-transition at 11.8 K. The difference in the C _p between fayalite and γ-Fe₂SiO₄ is reduced as the temperature increases in the range of 50–300 K. The gap in C _p data between 300 and 350 K of γ-Fe₂SiO₄ is an impediment to calculation of a precise C _p equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The C _p and entropy of γ-Fe₂SiO₄ at standard temperature and pressure (S°₂₉₈) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol⁻¹ K⁻¹, respectively. The Gibbs free energy at standard pressure and temperature (ΔG° _f,298) is calculated to be −1,369.3 ± 2.7 J mol⁻¹ based on the new entropy data. The phase boundary for the fayalite–γ-Fe₂SiO₄ transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent with extrapolated results of previous experimental studies.     

The heat capacity of two natural chlorite group minerals derived from differential scanning calorimetry

The heat capacity of natural chamosite (X_Fe=0.889) and clinochlore (X_Fe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol^?1?K^?1 give: C _p,CA = 1224.3–10.685?×?10³?×?T ^??0.5???6.4389?× 10⁶?×T ^??2?+?8.0279?×?10⁸?×?T ^??3 and for the natural clinochlore (CE): C _p,CE = 1200.5–10.908?×?10³?×T ^??0.5?? 5.6941?×?10⁶?×?T ^??2?+?7.1166?×?10⁸?×?T ^??3. The corrected C _p-polynomial for pure end-member chamosite (Fe₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CAcor = 1248.3–11.116?× 10³?×?T ^??0.5???5.1623?×?10⁶?×?T ^??2?+?7.1867?×?10⁸×T ^??3 and the corrected C _p-polynomial for pure end-member clinochlore (Mg₅Al)[Si₃AlO₁₀](OH)₈ is C _p,CEcor = 1191.3–10.665?×?10³?×?T ^??0.5???6.5136?×?10⁶?×?T ^??2?+ 7.7206?×?10⁸?×?T ^??3. The corrected C _p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C _p-polynomial for chamosite (C _p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C _p-polynomial (C _p,CAcor) is, however, in excellent agreement with the computed C _p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.     

Comparing palaeolimnological and instrumental evidence of climate change for remote mountain lakes over the last 200 years

This paper compares the palaeolimnological evidence for climate change over the last 200 years with instrumental climate data for the same period at seven European remote mountain lakes. The sites are Øvre Neådalsvatn (Norway), Saanajärvi (Finland), Gossenköllesee (Austria), Hagelseewli (Switzerland), Jezero v Ledvici (Slovenia), Estany Redó (Spain, Pyrenees), and Niné Terianske Pleso (Slovakia). We used multiple regression analysis to transfer homogenised lowland air temperature records to each of the sites, and these reconstructions were validated using data from on-site automatic weather stations. These data showed that mean annual temperature has varied over the last 200 years at each site by between 1 and 2 °C, typical of the high frequency variability found throughout the Holocene, and appropriate, therefore, to test the sensitivity of the various proxy methods used. Sediment cores from each site were radiometrically dated using ²¹⁰Pb, ¹³⁷Cs and ²⁴¹Am and analysed for loss-on-ignition, C, N, S, pigments, diatoms, chrysophytes, Cladocera and chironomids. Comparisons between the proxy data and the instrumental data were based on linear regression analysis with the proxy data treated as response variables and the instrumental data (after smoothing using LOESS regressions) as predictor variables. The results showed few clear or consistent patterns with generally low or very low r² values. Highest values were found when the data were compared after smoothing using a broad span, indicating that some of the proxy data were capturing climate variability but only at a relatively coarse time resolution. Probable reasons for the weak performance of the methods used include inaccurate dating, especially for earlier time periods, the influence of confounding forcing factors at some sites e.g., air pollution, earthquakes, and the insensitivity of some methods to low amplitude climate forcing. Nevertheless, there were trends in some proxy records at a number of sites that had a relatively unambiguous correspondence with the instrumental climate records. These included organic matter and associated variables (C and N) and planktonic diatom assemblages at the majority of sites and chrysophytes and chironomids at a few sites. Overall for longer term studies of the Holocene, these results indicate the need to be cautious in the interpretation of proxy records, the importance of proxy method validation, the continuing need to use reinforcing multi-proxy approaches, and the need for careful site and method selection.     

Alpine geodynamic evolution of passive and active continental margin sequences in the Tauern Window (eastern Alps, Austria, Italy): a review

The Penninic oceanic sequence of the Glockner nappe and the foot-wall Penninic continental margin sequences exposed within the Tauern Window (eastern Alps) have been investigated in detail. Field data as well as structural and petrological data have been combined with data from the literature in order to constrain the geodynamic evolution of these units. Volcanic and sedimentary sequences document the evolution from a stable continent that was formed subsequent to the Variscan orogeny, to its disintegration associated with subsidence and rifting in the Triassic and Jurassic, the formation of the Glockner oceanic basin and its consumption during the Upper Cretaceous and the Paleogene. These units are incorporated into a nappe stack that was formed during the collision between a Penninic Zentralgneis block in the north and a southern Austroalpine block. The Venediger nappe and the Storz nappe are characterized by metamorphic Jurassic shelf deposits (Hochstegen group) and Cretaceous flysch sediments (Kaserer and Murtörl groups), the Eclogite Zone and the Rote Wand–Modereck nappe comprise Permian to Triassic clastic sequences (Wustkogel quartzite) and remnants of platform carbonates (Seidlwinkl group) as well as Jurassic volcanoclastic material and rift sediments (Brennkogel facies), covered by Cretaceous flyschoid sequences. Nappe stacking was contemporaneous to and postdated subduction-related (high-pressure) eclogite and blueschist facies metamorphism. Emplacement of the eclogite-bearing units of the Eclogite zone and the Glockner nappe onto Penninic continental units (Zentralgneis block) occurred subsequent to eclogite facies metamorphism. The Eclogite zone, a former extended continental margin, was subsequently overridden by a pile of basement-cover nappes (Rote Wand–Modereck nappe) along a ductile out-of-sequence thrust. Low-angle normal faults that have developed during the Jurassic extensional phase might have been inverted during nappe emplacement.