Biological niches within human calcified aortic valves. Towards understanding of the pathological biomineralization process

Despite recent advances, mineralization site, its microarchitecture, and composition in calcific heart valve remain poorly understood. A multiscale investigation, using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectrometry (EDS), from micrometre up to nanometre, was conducted on human severely calcified aortic and mitral valves, to provide new insights into calcificationp rocess. Our aim was to evaluate the spatial relationship existing between bioapatite crystals, their local growing microenvironment, and the presence of a hierarchical architecture. Here we detected the presence of bioapatite crystals in two different mineralization sites that suggest the action of two different growth processes:a pathological crystallization process that occurs in biological niches and is ascribed to a purely physicochemical process and a matrix- mediated mineralized process in which the extracellular matrix acts as the template for a site-directed nanocrystals nucleation. Different shapes of bioapatite crystallization were observed at micrometer scale in each microenvironment but at the nanoscale level crystals appear to be made up by the same subunit

Micro-imaging VIS-IR spectroscopy of Martian meteorites in support of the future MaMIss spectrometer measurements

In the view of the future ExoMars 2020 mission, an activity of VIS-IR spectral investigations on terrestrial and extraterrestrial Mars Analogues is ongoing, in support of the Ma Miss in situ measurements. Ma_Miss is an imaging spectrometer that works in the range 0.4-2.2 μm with 20nm spectral sampling and that will observe the lateral wall of the borehole generated by ExoMars Rover's drill (Coradini et al., 2001). In this abstract, we describe some results about the spectral properties and characterization of mineral grains of the slabs of two Martian meteorites by means of the SPIM imaging spectrometer. SPIM works in the 0.22-5.05 μm spectral range, with a spatial resolution of 38x38 μm on the sample and represents the spare of the spectrometer on Dawn spacecraft (De Angelis et al., 2015). The meteorites investigated are North West Africa 8657 (NWA8657) and Dar Al Gani 489 (DAG489), basaltic shergottites. The average spectrum of the NWA8657 slab, in comparison with spectral measurements on other martian meteorites (Mcfadden & Cline, 2005) shows low reflectance values and 1 and 2 μm spectral absorptions indicating the strong presence of Ca-pyroxenes. The successive pixel by pixel analyses for the pyroxenes spectral speciation showed a great variability of clinopyroxenes in NWA8657. In fact, the 2 μm absorption at longer wavelength in some pixel does not always correspond to the 1 μm feature at longer wavelength. The average spectrum of DAG 489 is marked by a signature typical of low-Ca pyroxenes. Pixel by pixel analyses of DAG489 shows a more homogeneous composition of the pyroxenes characterized by the two major features centered at 0.98-0.99 and 1.98-2 μm. Further spectral absorptions related to sulfates, phosphates and carbonates were detected that are being validated by SEM-BSD to constrain the formation hystories of these two shergottites

A multi-scale investigation of biological niches within human calcified aortic valves helps to understand the pathological biomineralization process

Calcific aortic valve stenosis (CAVS) is the most common form of heart valve disease in the industrialized countries, being an important public health problem [1]. Ectopic calcifications within aortic valve leaflets are strictly associated with CAVS, interfering with cusps opening, they lead to ventricular outflow obstruction [2]. Up to date no proven medical therapy stops CAVS course progression, so valve replacement is the only possible treatment of severe CAVS. Unfortunately, the degenerative valve calcification process, affects also bioprosthetic implants [3]. Being the molecular mechanisms leading to valve calcification still not understood, our aim was to carry on a multi-scale investigation using Scanning Electron Microscopy, Transmission Electron Microscopy and Energy Dispersive X-ray Spectrometry, to provide new insights into calcification process. Severely calcified aortic (tricuspid type, n = 29; bicuspid type, n = 3) and mitral valves (n = 4) were obtained from patients of both sexes (males=25) and different ages (mean age 72±10, range 41-90 years old) undergoing valve replacement due to severe aortic and mitral valve stenosis. We detected bioapatite crystals in two different mineralization sites: niches and extracellular matrix. This suggests the action of two different growth processes: the first occurs in biological niches and it is ascribed to a purely physico-chemical process; the second has the extracellular matrix acting ass the template for a site-directed nanocrystals nucleation. Different shapes of bioapatite crystallization were observed at micrometer scale in each microenvironment but at the nanoscale level crystals appear made up by the same subunits. We suggest that bioapatite nanocrystals in heart valve may activate a strong inflammatory process leading to irreversible pathological condition that, once activated,may aggravate the inflammatory response against bioapatite nanocrystals leading to a severe calcification process

A geo-chemo-mechanical study of a highly polluted marine system (Taranto, Italy) for the enhancement of the conceptual site model

The paper presents the results of the analysis of the geo-chemo-mechanical data gathered through an innovative multidisciplinary investigation campaign in the Mar Piccolo basin, a heavily polluted marine bay aside the town of Taranto (Southern Italy). The basin is part of an area declared at high environmental risk by the Italian government. The cutting-edge approach to the environmental characterization of the site was promoted by the Special Commissioner for urgent measures of reclamation, environmental improvements and redevelopment of Taranto and involved experts from several research fields, who cooperated to gather a new insight into the origin, distribution, mobility and fate of the contaminants within the basin. The investigation campaign was designed to implement advanced research methodologies and testing strategies. Differently from traditional investigation campaigns, aimed solely at the assessment of the contamination state within sediments lying in the top layers, the new campaign provided an interpretation of the geo-chemo-mechanical properties and state of the sediments forming the deposit at the seafloor. The integrated, multidisciplinary and holistic approach, that considered geotechnical engineering, electrical and electronical engineering, geological, sedimentological, mineralogical, hydraulic engineering, hydrological, chemical, geochemical, biological fields, supported a comprehensive understanding of the influence of the contamination on the hydro-mechanical properties of the sediments, which need to be accounted for in the selection and design of the risk mitigation measures. The findings of the research represent the input ingredients of the conceptual model of the site, premise to model the evolutionary contamination scenarios within the basin, of guidance for the environmental risk management. The study testifies the importance of the cooperative approach among researchers of different fields to fulfil the interpretation of complex polluted eco-systems

Paradoxical co-existing base metal sulphides in the mantle: The multi-event record preserved in Loch Roag peridotite xenoliths, North Atlantic Craton

The role of the subcontinental lithospheric mantle as a source of precious metals for mafic magmas is contentious and, given the chalcophile (and siderophile) character of metals such as the platinum-group elements (PGE), Se, Te, Re, Cu and Au, the mobility of these metals is intimately linked with that of sulphur. Hence the nature of the host phase(s), and their age and stability in the subcontinental lithospheric mantle may be of critical importance. We investigate the sulphide mineralogy and sulphide in situ trace element compositions in base metal sulphides (BMS) in a suite of spinel lherzolite mantle xenoliths from northwest Scotland (Loch Roag, Isle of Lewis). This area is situated on the margin of the North Atlantic Craton which has been overprinted by a Palaeoproterozoic orogenic belt, and occurs in a region which has undergone magmatic events from the Palaeoproterozoic to the Eocene. We identify two populations of co-existing BMS within a single spinel lherzolite xenolith (LR80) and which can also be recognised in the peridotite xenolith suite as a whole. Both populations consist of a mixture of Fe-Ni-Cu sulphide minerals, and we distinguished between these according to BMS texture, petrographic setting (i.e., location within the xenolith in terms of ‘interstitial’ or within feldspar-spinel symplectites, as demonstrated by X-ray Computed Microtomography) and in situ trace element composition. Group A BMS are coarse, metasomatic, have low concentrations of total PGE (< 40 ppm) and high (Re/Os)N (ranging 1 to 400). Group B BMS strictly occur within symplectites of spinel and feldspar, are finer-grained rounded droplets, with micron-scale PtS (cooperite), high overall total PGE concentrations (15–800 ppm) and low (Re/Os)N ranging 0.04 to 2. Group B BMS sometimes coexist with apatite, and both the Group B BMS and apatite can preserve rounded micron-scale Ca-carbonate inclusions indicative of sulphide-carbonate-phosphate immiscibility. This carbonate-phosphate metasomatic association appears to be important in forming PGE-rich sulphide liquids, although the precise mechanism for this remains obscure. As a consequence of their position within the symplectites, Group B BMS are particularly vulnerable to being incorporated in ascending mantle-derived magmas (either by melting or physical entrainment). Based on the cross-cutting relationships of the symplectites, it is possible to infer the relative ages of each metasomatic BMS population. We tally these with major tectono-magmatic events for the North Atlantic region by making comparisons to carbonatite events recorded in crustal and mantle rocks, and we suggest that the Pt-enrichment was associated with a pre-Carboniferous carbonatite episode. This method of mantle xenolith base metal sulphide documentation may ultimately permit the temporal and spatial mapping of the chalcophile metallogenic budget of the lithospheric mantle, providing a blueprint for assessing regional metallogenic potential. Abbreviations: NAC, North Atlantic Craton; GGF, Great Glen Fault; NAIP, North Atlantic Igneous Province; BPIP, British Palaeogene Igneous Province; SCLM, subcontinental lithospheric mantle; PGE, platinum-group elements; HSE, highly siderophile elements; BMS, base metal sulphid

Homogenisation of sulphide inclusions within diamonds: A new approach to diamond inclusion geochemistry

Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100 °C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages. We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source

Non-Destructive In Situ Study of Plastic Deformations in Diamonds: X-ray Diffraction Topography and µFTIR Mapping of Two Super Deep Diamond Crystals from São Luiz (Juina, Brazil)

Diamonds from Juina, Brazil, are well-known examples of superdeep diamond crystals formed under sublithospheric conditions and evidence would indicate their origins lie as deep as the Earth’s mantle transition zone and the Lower Mantle. Detailed characterization of these minerals and of inclusions trapped within them may thus provide precious minero-petrogenetic information on their growth history in these inaccessible environments. With the aim of studying non-destructively the structural defects in the entire crystalline volume, two diamond samples from this locality, labelled JUc4 and BZ270, respectively, were studied in transmission mode by means of X-ray Diffraction Topography (XRDT) and micro Fourier Transform InfraRed Spectroscopy (µFTIR). The combined use of these methods shows a good fit between the mapping of spatial distribution of extended defects observed on the topographic images and the µFTIR maps corresponding to the concentration of N and H point defects. The results obtained show that both samples are affected by plastic deformation. In particular, BZ270 shows a lower content of nitrogen and higher deformation, and actually consists of different, slightly misoriented grains that contain sub-grains with a rounded-elongated shape. These features are commonly associated with deformation processes by solid-state diffusion creep under high pressure and high temperature

Crystal Chemical Characterisation of Red Beryl by "Standardless" Laser Induced Breakdown Spectroscopy and Single Crystal Refinement by X‐Ray Diffraction: An Example of Validation of an Innovative Method for the Chemical Analyses of Minerals

Laser induced breakdown spectroscopy (LIBS) is a valuable technique for performing qualitative and quantitative chemical analyses of all elements in one shot, including low atomic number elements such as Li and Be. This technique does not require any sample preparation to reveal the atomic species, even when present in trace amounts (< 0.01% m/m ). In this study, for the first time, we provide an accurate mineral formula for a Cs‐rich red beryl by combining crystallographic data obtained using the traditional single‐crystal X‐ray diffraction technique and quantitative chemical analysis data obtained with an innovative "standardless" method: Calibration Free‐LIBS (CF‐LIBS). In particular, a new LIBS prototype coupled with a petrographic microscope (CF‐μLIBS) was used to analyse chemically homogeneous areas of about 10 μm spot size, causing minimal damage to the mineral. The results showed that calibration‐free quantitative analysis is suitable for the quantification of major and minor low and high atomic number elements in beryl. The accuracy of quantification of low atomic number elements by CF‐μLIBS led to the empirical formula: [12](Cs0.006Na0.019K0.017Ca0.019)Σ0.061 [4](Be2.989Li0.011)Σ3.000 [6](Ti0.053Mn0.051Mg0.007Al1.890)Σ2.000 [4](Be0.116Fe0.024Si5.860)Σ6.000 O18. This formula is consistent with the crystal‐structure refinement data and demonstrates the validity of CF‐μLIBS for chemical analyses of minerals containing low atomic number elements

Application of Laser Induced Breakdown Spectroscopy on gem quality minerals: some cases of study

The application of the Laser Induced Breakdown Spectroscopy (LIBS) to gemmological materials is well known for the gemstone treatment detection but LIBS can also provide a useful contribution in mineralogical studies in which the chemical analyses is essential, playing a key role in the studies on the origin of minerals (Agrosì et al., 2014). The possibility to detect simultaneously all elements, including also light elements such as boron, lithium, and beryllium in a fast way and without sample preparation its clearly a great advantage of the LIBS. Moreover this technique is able to detect chromophorous elements even if they are in very low concentration. Nevertheless the main problems affecting LIBS are the difficulties to perform quantitative analyses and the partial destructivity of the method. Recently, with the development of the technique and in particular with the development of a new softwares there is also the possibilities to perform quantitative analyses with or without calibration. The last examples are the standard Calibration-Free LIBS and the One Point Calibration LIBS, CF-LIBS and OPC-LIBS respectively (Cavalcanti et al., 2013). The improvement of the instrumentation performance and the possibility to focalize the laser beam with an optical lens of a microscope allow to obtain an high resolution and a low destructivity of the sample. Moreover, the use of a double-pulse laser produce a signal enhancement useful for the quantitative chemical analyses guaranteeing a minimal sample damage. In this way we may obtain a considerable improvement on the detection limit of the trace elements, whose determination is essential to define the origin of gemstones. In the mineralogical studies the μ-LIBS appear very attractive because the possibility to select the smallest sampling areas ensures a better reconstruction of the chemical zoning and consequently allows to stimate the rock forming condition because the chemical zoning is sensitive to the changing of the physical and chemical parameters. Some cases of study have been performed on beryls and corundums with different objectives and the results will be discuss