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Diamonds and their inclusions are unique fragments of deep Earth, which provide rare samples from inaccessible portions of our planet. Inclusion-free diamonds cannot provide information on depth of formation, which could be crucial to understand how the carbon cycle operated in the past. Inclusions in diamonds, which remain uncorrupted over geological times, may instead provide direct records of deep Earth’s evolution. Here, we applied elastic geothermobarometry to a diamond-magnesiochromite (mchr) host-inclusion pair from the Udachnaya kimberlite (Siberia, Russia), one of the most important sources of natural diamonds. By combining X-ray diffraction and Fourier-transform infrared spectroscopy data with a new elastic model, we obtained entrapment conditions, P trap  = 6.5(2) GPa and T trap  = 1125(32)–1140(33) °C, for the mchr inclusion. These conditions fall on a ca. 35 mW/m 2 geotherm and are colder than the great majority of mantle xenoliths from similar depth in the same kimberlite. Our results indicate that cold cratonic conditions persisted for billions of years to at least 200 km in the local lithosphere. The composition of the mchr also indicates that at this depth the lithosphere was, at least locally, ultra-depleted at the time of diamond formation, as opposed to the melt-metasomatized, enriched composition of most xenoliths.

Detrital spinel is a widespread heavy mineral in sandstones from the Maastrichtian--Middle Eocene sedimentary basins in the SE Alps. Chemistry of detrital spinels from the Claut/Clauzetto and Julian Basins (N Italy and NW Slovenia) is used to constrain petrological and geochemical affinities and tectonic provenance of the source rocks.

The main objective of this work was to evaluate the potential of Montmorillonite nanoclay (Mt), readily and inexpensively available, for the simultaneous adsorption (and removal) of two classes of pollutants: metal ions and dyes. The attention was focused on two “model” pollutants: Ce(III) and crystal violet (CV). The choice is due to the fact that they are widespread in wastewaters of various origins. These characteristics, together with their effect on human health, make them ideal for studies on water remediation. Moreover, when separated from wastewater, they can be recycled individually in industrial production with no or simple treatment. Clay/pollutant hybrids were prepared under different pH conditions and characterized through the construction of the adsorption isotherms and powder X-ray diffraction. The adsorption behavior of the two contaminants was revealed to be significantly different: the Langmuir model reproduces the adsorption isotherm of Ce(III) better, thus indicating that the clay offers a unique adsorption site to the metal ions, while the Freundlich model proved to be the most reliable for the uptake of CV which implies heterogeneity of adsorption sites. Moreover, metal ions do not adsorb at all under acidic conditions, whereas the dye is able to adsorb under all the investigated conditions. The possibility to modulate the adsorption features by simply changing the pH conditions was successfully employed to develop an efficient protocol for the removal and separation of the different components from aqueous solutions mimicking wastewaters.

Thirteen Cr-bearing spinels from major horizons of magma replenishment in the open-system Rum Layered Suite have been analysed by X-ray single crystal diffraction and electron microprobe analyses. On the basis of the structural parameters and the chemistry of these spinels the so-called Rum trend, in which Al-content increases at the expense of Cr and Fe 3+ , has been easily recognised. In addition, natural spinels with Fe 3+ content similar to synthetic spinels on the MgCr 2 O 4 –MgFe 2 O 4 join have been analysed for the first time. Layers of chromitite, anorthosite and peridotite situated within several cm of one another have yielded different intracrystalline exchange temperatures using an intercrystalline spinel-olivine thermometer. The Rum anorthosite Cr-spinels are interpreted as having crystallised within the cumulus pile following rejuvenation of the crystal mush. Their low Al-content is a function of simultaneous plagioclase crystallisation, reducing the amount of Al 3+ present for the Cr-spinel. By contrast, Cr-spinels in well-known Archean anorthosites (e.g. Ujaragssuit nunât and Fiskenæsset, western Greenland) and Sittampundi (southern India) are very aluminous in composition, attributed to crystallisation of Cr-spinel from high-alumina basalts in lower crustal magma chambers and linked to the control exerted by plagioclase crystallisation on Al content of the melt, in the absence of clinopyroxene crystallisation. The compositional differences between the Rum anorthosite Cr-spinels and the Fiskenæsset and Sittampundi Cr-spinels suggest that postcumulus reaction of Cr-spinel and melt to low (800–900°C) temperatures, as invoked for the Rum crystals, may not have been as important a process in the Archean anorthosites.

We analysed the major, minor and trace elements chemistry of forty-two Cr-spinels from four Siberian kimberlites. They showed a wide range in Mg# (Mg/(Mg + Fe2+); 0.42–0.78) and Cr# (Cr/(Cr + Al); 0.32–0.92) and a common trend of increasing Cr# with decreasing Mg#. The major element classification schemes suggested that there were spinels deriving from a peridotitic source (Xen) and spinels crystallised from kimberlitic melts (Chr). Laser-Ablation Inductively Coupled Plasma Mass Spectrometry on both groups showed that the trace elements with the highest abundance were Mn (985–3390 ppm), Ni (531–3162 ppm), V (694–2510 ppm) and Zn (475–2230 ppm). Testing the effectiveness of trace elements in determining the source for Cr-spinels, we found out that Cr-spinels crystallised directly from a kimberlitic melt usually showed higher Mn, Ni, Sc and V concentrations with respect to those of peridotitic origin. In addition, using the available partitioning models, we found that the correlations between major elements and Ni, Co, Sc and Ga in the Xen group could be explained by subsolidus equilibration between spinel, olivine and clinopyroxene at 800–1000 °C, thus supporting a peridotitic source for this group. Finally, we calculated the composition of the possible melts in equilibrium with the Cr-spinels of the Chr group, using a selected set of partition coefficients. Calculated abundances of Cu, Ga and Zr were comparable to those of the kimberlite, while V was never close to the kimberlite composition. This simulation highlighted the need for new data on the trace elements partition coefficients between kimberlitic melts and Cr-spinel.

The crystal chemistry of six clinopyroxenes enclosed in protogranular spinel-peridotite mantle xenoliths from Lake Nji (Cameroon, W Africa) was studied by means of single-crystal X-ray diffraction and electron microprobe.

About 20 Late Copper Age bowls with cross-shaped foots from Deschmann’s pile dwellings (Ljubljansko barje, central Slovenia) and Trieste Karst (North-Eastern Italy) have been investigated using X-ray computed microtomography (microCT) in order to study the vessel-forming technique, to characterise their pastes and to test the hypothesis that some Karst bowls could have been imported from nowadays central Slovenia or even more distant regions. In three selected virtual slices per sample, clay, lithic inclusions and pores have been segmented and quantified. In addition, the area, maximum length and width of each lithic inclusion have been calculated. Then, the microCT-derived results have been statistically analysed by principal component analysis (PCA). The orientation of pores and disjunctions in microCT volumes show that the basins of the bowls were built using mainly the coiling technique, while the base was shaped starting from a central piece, to which a layer of clay was added and then reshaped in order to produce the foots. The Slovenian bowls include both medium/coarse-grained and very fine- or fine-grained vessels mainly tempered with carbonate inclusions. The pastes of the Karst bowls are considerably heterogeneous. One bowl was most likely imported to the Karst but not from central Slovenia as it shows peculiar components, shape and decoration. The other two imported vessels show a very fine-grained paste comparable to the one of several samples from Deschmann’s pile dwellings. Such technological similarity is confirmed by PCA of microCT data and petrographic observations. Our study confirms the existence of strong cultural connections between central Slovenia and the northernmost Adriatic coast during the Late Copper Age.

Oxygen fugacity ( f O 2 ) is a fundamental but little known intensive variable in mantle processes. It influences the P/T position of a mantle solidus and the composition of mantle-derived melts and fluids and constrains mantle-core equilibria and a number of geophysical properties of the mantle. An important source of information on oxidation states is the ferric–ferrous iron ratio in mantle spinels. Since the magnetite component is low in mantle spinels, normal analytical errors translate into considerable f O 2 uncertainties. In this study, we analyzed the Fe 3+ –Fe tot ratio of chromites present as inclusions in diamond and other mantle-related occurrences by point-source Mössbauer spectroscopy using single-crystal absorbers as well as conventional Mössbauer spectroscopy using powder absorbers. The studied spinels have been previously analyzed by single-crystal X-ray diffraction and electron microprobe. The ferric–ferrous ratios found are normally similar to the different techniques apart from some samples where a large number of grains have been used for the analyses (powder absorbers). The general agreement between the different techniques allows us to conclude that the studied chromites are stoichiometric. However, conventional Mössbauer spectroscopy on powder absorbers should be conducted with great care, since the method requires a relatively large amount of sample material. Spinel frequently occurs as small grains, and the large number of crystals required may possess different degrees of oxidation/alteration and, consequently, different ferric–ferrous ratio leading to possible errors in the interpretation of the results.

In order to characterize the pressure-induced decomposition of ringwoodite (γ-Mg 2 SiO 4 ), the topological analysis of the electron density ρ( r ), based upon the theory of atoms in molecules (AIM) developed by Bader in the framework of the catastrophe theory, has been performed. Calculations have been carried out by means of the ab initio CRYSTAL09 code at the HF/DFT level, using Hamiltonians based on the Becke- LYP scheme containing hybrid Hartree–Fock/density functional exchange–correlation terms. The equation of state at 0 K has been constructed for the three phases involved in the post-spinel phase transition (ringwoodite → Mg-perovskite + periclase) occurring at the transition zone–lower mantel boundary. The topological results show that the decomposition of the ringwoodite at high pressures is caused by a conflict catastrophe. Furthermore, topological evidences of the central role played by the oxygen atoms to facilitate the pressure-induced ringwoodite decomposition and the subsequent phase transition have been noticed.

The Šambron–Kamenica Zone is situated on the northern margin of the Levočské vrchy mountains and Šarišskà vrchovina Highland, where the Central Carpathian Paleogene joins the Pieniny Klippen Belt. Sandstone outcrops in this area. From Cretaceous to Late Oligocene in age, these sediments suggest transport directions from S and SE. The heavy mineral assemblages of this sandstone include Cr-spinel grains, mainly displaying types II and III alpine-peridotite affinities, and are representative of Ocean Island Basalt volcanism. A sample from Upper Eocene sediments at Vit’az shows a clear change in Cr-spinel composition, which turns out to have types I and II peridotite affinities, and to derive from arc and Middle Ocean Ridge Basalt volcanism, with sediment transport directions from SW and WSW. These data indicate major variations in the Upper Eocene tectonic setting, giving constraints to paleogeographic reconstruction of the Slovak Central Carpathians.