Iron isotope fractionation between pyrite (FeS2), hematite (Fe2O3) and siderite (FeCO3): A first-principles density functional theory study

In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α⁵⁷Fe/⁵⁴Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III)_aq-hematite and Fe(II)_aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions (β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived β-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined.     

Ecological Differences in the Distribution of two Tethya (Porifera, Demospongiae) Species Coexisting in a Mediterranean Coastal Lagoon

Abstract. In the Sicilian lagoon Stagnone di Marsala, Tethya aurantium and T. citrina show different ecological distributions, although some overlapping occurs. The first species reaches its highest density where linear currents are maximal, and in this habitat it is particularly frequent on Posidonia oceanica rhizomes. The second species is more abundant in still water locations and is equally common on Posidonia rhizomes and on calcareous concretions. Such distributions can be related to water movement, Posidonia shoot density, and associated factors such as sedimentation and food availability. These observations are consistent with an adaptive interpretation of the morphofunctional features distinguishing the two species.     

Statistical assessment of trends and oscillations in rainfall dynamics: Analysis of long daily Italian series

Since the 18th century systematic measurements of rainfall have been collected in Italy. The daily rainfall series observed in Milan (1835–2001), Genoa (1833–2000), Bologna (1813–2001) and Palermo (1797–1999) are examples of available long rainfall records. These data series can help analyzing the evolution of precipitation. The present paper deals with long term evolution of: (i) annual rainfall amount; (ii) annual number of rainy events; (iii) intensity of rainfall, (iv) inter-annual rainfall partitioning, i.e. the duration of wet and dry periods, and (v) maximum annual values of daily rainfall amount, duration of wet and dry periods. The evolution is studied analyzing the first two order statistics and the 30-year return period quantiles via moving window analysis. Confidence intervals are introduced to check the statistical significance of the estimated statistics and quantiles. The results are compared with those provided by the traditional Mann-Kendall test. The analysis shows how the annual precipitation exhibits a negative trend in the first half of 20th century, with a subsequent positive trend in northern Italy (Genoa, Milan and Bologna). Conversely, the dataset for Palermo (southern Italy) displays only a negative trend. Because the number of precipitation episodes is found to decrease in the investigated period, the average rain rate is significantly increasing especially in northern Italy. This is also associated with shorter duration of rain episodes with an evident effect on rainfall extremes. Dry periods tend to be longer with increasing variability. The Mann-Kendall test and its progressive form have shown to be well suited for monotonic trend, but the confidence interval analysis, introduced here, is more appropriate if oscillations are significant.     

The lattice energy of forsterite. Charge distribution and formation enthalpy of the SiO 4 4− ion

In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z _o, the hardness parameter ρ and the repulsive radii r _Mg and r _Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO ₄ ^4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z _o=?1.34, ρ=0.27 Å, r _Mg=0.72 Å, r _Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol^?1 were obtained, respectively, for the lattice energy E _Land for its ionic component E _L ⁰ ,which accounts for interactions between Mg²⁺ and SiO ₄ ^4? ions only. The charge distribution calculated on the SiO ₄ ^4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO ₄ ^4? were estimated to be: ΔH _f(SiO ₄ ^4? )=2117.6 and E(SiO ₄ ^4? )=708.6 kJ mol^?1, respectively.     

Analysis with C- and X-band satellite SAR data of the Portalet landslide area

This paper describes the use of the Stable Point Network technique, a Persistent Scatterer Interferometry SAR technique, for the analysis of the Portalet landslide area (Central Pyrenees, Spain). For this purpose, different SAR datasets acquired by ERS-1, ERS-2, ENVISAT and TerraSAR-X satellites have been analysed. The use of different SAR images acquired by satellite radar sensors operating at different microwave lengths has allowed for a comparative assessment and illustration of the advantages and disadvantages of these satellites for landslide detection and monitoring. In the introduction, differential interferometry and the study area are briefly described. Then the specifics of the SPN processing and the results of the different datasets are described and compared. In Analysis of the results: the Portalet landslide area, the Portalet landslide area is introduced and the radar displacement measurements are analysed with available geo-information data. Additionally, X-band measurements are compared with those gathered by a ground-based SAR for a previous project. Finally, the most relevant conclusions of this work are discussed.     

The transition between ‘orogenic’ and ‘anorogenic’ magmatism in the western Mediterranean area: the Middle Miocene volcanic rocks of Isola del Toro (SW Sardinia,Italy)

The Isola del Toro is a small island (∼1 km²) about 5 nautical miles SW of Sardinia entirely made up of mildly alkaline sodic evolved rocks (benmoreites and trachytes) related to each other by fractionation processes. ⁴⁰Ar/³⁹Ar dating of an anorthoclase mineral separate from a trachyte gave an age of 11.83 ± 0.10 Ma. This age estimate falls within an interval previously considered a‐magmatic in Sardinia. The results of this study shift the beginning of the Middle Miocene–Quaternary anorogenic volcanism of Sardinia back to the Late Serravalian. The transition between orogenic and anorogenic activity in Sardinia is markedly different from that recorded in the rest of the circum‐Mediterranean area, where this transition is much more gradual, both in time and in terms of magma composition. On the other hand, the transition between orogenic and anorogenic magmatism in Sardinia is rather sharp and lacks hybrid compositions. The Isola del Toro volcanic rocks represent the first anorogenic products produced during the opening of the western Mediterranean Sea.     

Detection of Miocene saucer‐shaped sills (offshore Senegal) via integrated interpretation of seismic,magnetic and gravity data

The Atlantic margin offshore Senegal has been explored by seismic reflection and GRAV‐MAG surveys. High‐amplitude, laterally transgressive seismic reflectors are found to coincide with gravimetric and magnetic highs. Once seismic data are integrated with potential fields modelling, these reflectors can be safely interpreted as saucer‐shaped igneous sills, up to some hundreds of metres thick, some km wide. The occurrence of hydrothermal vent complexes and forced folds in the stratigraphic sequence above the sills constrain the intrusion age to the Miocene. Field observations and in‐situ magnetic susceptibility measurements of Oligocene–Miocene and Quaternary igneous rocks emplaced in coastal Senegal support this interpretation.