In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Dissolution mechanisms of silicate minerals yielded by intercomparison with glasses and radiation damage studies

The behaviour of two silicates (albite and olivine) toward aqueous dissolution has been investigated with emphasis to two aspects: (1) similarities and differences with silicate glasses; and (2) influence of ion bombardment which transforms the initially crystalline structure to a glass-like one. The occurrence on leached materials of hydrated layers enriched with metallic elements is checked by using high-energy ion beam analytical techniques.

It is shown that for both amorphous and crystalline silicates, dissolution involves competing processes responsible for either hydrated-layer generation (hydration by ion exchange and/or water permeation), or its destruction (hydrolysis of siloxane bonds and detachment of silica units). At moderate temperature ( 100°C), the latter processes dominate for crystalline silicates and the resulting dissolution is congruent. However, these silicates tend to behave like glasses upon ion bombardment above a critical dose. At higher temperature (> 200°C), hydration is markedly enhanced and thick altered layers are generated even on undamaged minerals such as albite and orthoclase, where alkali cations are easily exchangeable.     

Temperature,composition, and f O2 effects on intersite distribution of Mg and Fe2+ in olivines

Single-crystal X-ray structure refinement of natural olivines equilibrated at high temperature under controlled oxygen fugacity (f _O2) conditions, coupled with a structure-energy model were used to establish the influence of T, f _O2 and bulk chemistry on intracrystalline disorder.The results are: 1) The k _D (k _D = [(Fe M1·Mg M2)/(Fe M2·Mg M1)]) factor describing site population on M1, M2 polyhedra increases from values lower than 1 at T below 400–600° C (depending on composition) to values higher than 1 at higher temperature. 2) The increase of k _D with T is quite regular. 3) At constant temperature and pressure, k _D increases with increasing fayalite content in the mixture; 4) Contrary to previous observations (Will and Nover 1979; Nover and Will 1981) varying f _O2, within the stability range of the substance, has a negligible influence on intracrystalline disorder. 5) As ancillary results, the model confirms the defect scheme of Nakamura and Schmalzried (1983) for the investigated solids. Moreover, it shows that cationic vacancies are always created on M 1 site at the expense of Mg ions, while trivalent iron is always stabilized on M2 site. This explains the marked anisotropies observed in Fe-Mg interdiffusion (Buening and Busek 1973; Misener 1974; Schock et al. 1989).     

Geophysical evidence of mud diapirism on the Mediterranean Ridge accretionary complex

Mud volcanoes, mud cones, and mud ridges have been identified on the inner portion of the crestal area, and possibly on the inner escarpment, of the Mediterranean Ridge accretionary complex. Four areas containing one or more mud diapirs have been investigated through bathymetric profiling, single channel seismic reflection profiling, heat flow measurements, and coring. A sequence of events is identified in the evolution of the mud diapirs: initially the expulsion on the seafloor of gasrich mud produces a seafloor depression outlined in the seismic record by downward dip of the host sediment reflectors towards the mud conduit; subsequent eruptions of fluid mud may create a flat topped mud volcano with step-like profile; finally, the intrusion of viscous mud produces a mud cone.The origin of the diapirs is deep within the Mediterranean Ridge. Although a minimum depth of about 400 m below the seafloor has been computed from the hydrostatic balance between the diapiric sediments and the host sediments, a maximum depth, suggested by geometric considerations, ranges between 5.3 and 7 km. The presence of thermogenic gas in the diapiric sediments suggests a better constrained origin depth of at least 2.2 km.The heat flow measured within the Olimpi mud diapir field and along a transect orthogonal to the diapiric field is low, ranging between 16 ± 5 and 41 ± 6 mW m^–2. Due to the presence of gas, the thermal conductivity of the diapiric sediments is lower than that of the host hemipelagic oozes (0.6–0.9 and 1.0–1.15 W m^–1 K^–1 respectively).We consider the distribution of mud diapirs to be controlled by the presence of tectonic features such as reverse faults or thrusts (inner escarpment) that develop where the thickness of the Late Miocene evaporites appears to be minimum. An upward migration through time of the position of the décollement within the stratigraphic column from the Upper Oligocene (diapiric sediments) to the Upper Miocene (present position) is identified.     

Modeling Forest Emissivity at L-Band and a Comparison With Multitemporal Measurements

This letter describes recent advances in modeling forest emissivity at L-band. The formulation is based on a previously developed discrete model and includes a new representation of forest litter. Comparisons with multitemporal radiometric data collected in the framework of the ldquoBray 2004rdquo experiment, which was carried out within Les Landes forest, are shown and discussed. Input variables are given by using detailed ground measurements. In general, the model reproduces both absolute values and temporal variations of measured brightness temperature. The contribution of the litter to overall emission was found to be important.     

The XMM-Newton Bright Serendipitous Survey: First Extragalactic Results

We present here some initial results from the ongoing XMM-Newton bright serendipitous survey. The survey is aimed at selecting and spectroscopically identifying a large and statistically representative sample of bright (f _x ≳ 7× 10⁻¹⁴ c.g.s) serendipitous X-ray sources in the 0.5–4.5 keV energy band (BSS) and a complementary (smaller) sample in the 4.5–7.5 keV energy band (HBSS). The work is partly based on observations obtained with XMM-Newton, an ESA science mission with instruments and contributors directly founded by ESA member states and the USA(NASA) and on observations collected at TNG. The TNG telescope is operated on the island of La Palma by the Centro Galileo Galilei of the INAF in the Spanish Observatorio del Roque de Los Muchachos of the Instituto de Astrofísica de Canarias. On behalf of the XMM-Newton Survey Science Center.     

Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li 2Mg 3Fe 3+ 2Si 8O 22(OH) 2

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.