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The Cerro del Almirez massif (Spain) represents a unique fragment of serpentinized oceanic lithosphere that has been first equilibrated in the antigorite stability field (Atg-serpentinites) and then dehydrated into chlorite–olivine–orthopyroxene (Chl-harzburgites) at eclogite facies conditions during subduction. The massif preserves a dehydration front between Atg-serpentinites and Chl-harzburgites. It constitutes a suitable place to study redox changes in serpentinites and the nature of the released fluids during their dehydration. Relative to abyssal serpentinites, Atg-serpentinites display a low Fe 3+ /Fe Total(BR) (=0.55) and magnetite modal content (=2.8–4.3 wt%). Micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy measurements of serpentines at the Fe–K edge show that antigorite has a lower Fe 3+ /Fe Total ratio (=0.48) than oceanic lizardite/chrysotile assemblages. The onset of Atg-serpentinites dehydration is marked by the crystallization of a Fe 3+ -rich antigorite (Fe 3+ /Fe Total  = 0.6–0.75) in equilibrium with secondary olivine and by a decrease in magnetite amount (=1.6–2.2 wt%). This suggests a preferential partitioning of Fe 3+ into serpentine rather than into olivine. The Atg-breakdown is marked by a decrease in Fe 3+ /Fe Total(BR) (=0.34–0.41), the crystallization of Fe 2+ -rich phases and the quasi-disappearance of magnetite (=0.6–1.4 wt.%). The observation of Fe 3+ -rich hematite and ilmenite intergrowths suggests that the O 2 released by the crystallization of Fe 2+ -rich phases could promote hematite crystallization and a subsequent increase in f o 2 inside the portion of the subducted mantle. Serpentinite dehydration could thus produce highly oxidized fluids in subduction zones and contribute to the oxidization of the sub-arc mantle wedge.

Using large volume press, samples of bridgmanites (Bg) in equilibrium with both silicate melt and liquid Fe-alloy were synthesized to replicate the early period of core-mantle segregation and magma ocean crystallization. We observe that the Fe partition coefficient between Bg and silicate melt (DFeBg/melt) varies strongly with the degree of partial melting (F). It is close to 1 at very low F and adopts a constant value of ∼0.3 for F values above 10 wt%. In the context of a partially molten mantle, a larger F (closer to liquidus) should yield Fe-depleted Bg grains floating in the liquid mantle. In contrast, a low F (closer to solidus) should yield buoyant pockets of silicate melt in the dominantly solid mantle. We also determined the valence state of Fe in these Bg phases using X-ray absorption near-edge spectroscopy (XANES). Combining our results with all available data sets, we show a redox state of Fe in Bg more complex than generally accepted. Under the reducing oxygen fugacities (f02) of this study ranging from IW-1.5 and IW-2, the measured Fe3+ content of Bg is found moderate (Fe3+/ΣFe = 21 ± 4%) and weakly correlated with Al content. When fO2 is comprised between IW-1 and IW, this ratio is correlated with both Al content and oxygen fugacity. When fO2 remains between IW and Re/ReO2 buffers, Fe3+/ΣFe ratio becomes independent of fO2 and exclusively correlated with Al content. Due to the incompatibility of Fe in Bg and the variability of its partition coefficient with the degree of melting, fractional crystallization of the magma ocean can lead to important chemical heterogeneities that will be attenuated ultimately with mantle stirring. In addition, the relatively low-Fe3+ contents found in Bg (21%) at the reducing conditions (IW-2) prevailing during core segregation seem contradictory with the 50% previously suggested for the actual Earth's lower mantle. This suggests the presence of 1.7 wt% Fe3+ in the lower mantle, which reduces the difference with the value observed in the upper mantle (0.3 wt%). Reaching higher concentrations of trivalent Fe requires additional oxidation processes such as the late arrival of relatively oxidized material during the Earth accretion or interaction with oxidized subducting slabs.

This study aims at the characterisation of red and orange glass tesserae from the 4th-century Roman villa of Noheda (Spain). Due to the limited number of analyses available for such ancient materials, many questions remain unanswered about the production processes in the Roman period. Six samples were chosen for their hue variations, including two samples showing banded patterns of red and orange. Differences in copper speciation were investigated by X-ray absorption spectroscopy and compared with colour and compositional variations obtained by EPMA. The shapes and sizes of colouring crystals could be investigated using scanning and transmission electron microscope imaging. The brown-red colour is due to metallic copper nano-particles and corresponds to a low-copper and low-lead group usually described in the literature. The orange samples and bands are coloured by copper oxide Cu2O nanoparticles with remaining Cu+ in the glass and have greater contents of Cu. Compositional analyses reveal that the same base glass is used in the red and orange bands with additions of Cu, Sn, Pb and probable Fe. Furthermore, based on our results and on the literature review, a high-copper low-lead group of glasses highlights the variability of compositions observed in cuprite colours.

X-ray absorption spectroscopy at the Mg K -edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order.

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing \"naturally\" over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (â¼ 0-150 µm compared to â¼ 300-600 µm for \"natural\" patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO6 groups). This new coordination was achieved in AlPO4 doped SiO2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

Silicene, a new two-dimensional (2D) material has attracted intense research because of the ubiquitous use of silicon in modern technology. However, producing free-standing silicene has proved to be a huge challenge. Until now, silicene could be synthesized only on metal surfaces where it naturally forms strong interactions with the metal substrate that modify its electronic properties. Here, we report the first experimental evidence of silicene sheet on an insulating NaCl thin film. This work represents a major breakthrough; for the study of the intrinsic properties of silicene, and by extension to other 2D materials that have so far only been grown on metal surfaces.