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The XAS analysis of a blue-and-white Ming porcelain's decorations has been used to elucidate the porcelain's production technology. The porcelain exhibits the typical blue decorations with dark spots that are constituted by dendritic aggregates enriched in Mn and Fe. The XAS revealed that during firing Mn2+ and Fe2+ ions diffused into the glaze and started to crystallize at 900 °C as rhodonite and hausmannite-jacobsite intermediate compounds. The study of the Fe XAS pre-edges provided to be a powerful tool to assess the redox record from the porcelain. The natural basalt calibration determined the Fe3+/ƩFe × 100 in the glaze and confirmed the oxidizing conditions during its production. Hence, the obtained XAS helped to elucidate the temperatures at which the wares were produced by identifying the porcelain's pigments and the redox conditions during their production. This novel approach can also be applied on a broad range of modern and archaeological ceramics to elucidate their production technology.

MAP2XANES is an intuitive Jupyter notebook that automatizes the analysis of synchrotron X-ray fluorescence imaging and X-ray absorption spectroscopy for the characterization of complex and heterogeneous samples. The notebook uses basic modules and functions from Numpy, Scipy, Pandas, iPywidgets and Matplotlib libraries for a powerful data reduction process that, in just a few clicks, guides the user through the visualization of elemental maps, space-resolved absorption spectra and their automatized analysis. In particular, by means of linear combination fit of the XANES spectra, the notebook determines the chemical species distribution in the sample under investigation. The direct output of the analysis process is the correlation between the different elemental distributions and the spatial localization of the chemical species detected. An application to mineralogy is thus presented, analyzing the Mn2+, Mn3+ and Mn4+ distribution in a mineral sample of hausmannite (Mn2+Mn2 3+O4), courtesy of the Museum of Natural Science of Barcelona.

The basement of eastern Mexico comprises Grenvillian-age granulite-facies metamorphic rocks. The Oaxacan Complex represents the largest outcrop belt of this basement in Mexico. In this work, southwestern Oaxacan Complex garnets are studied from a petrographical, geochemical, and geothermobarometrical perspective for the first time. The studied garnets display different grain sizes nucleated in a polyphase evolution. The almandine end member proportion is similar in all of the studied lithotypes. The highest pyrope concentrations are found in Qz Fsp paragenesis and ultramafic rocks and the lowest pyrope concentrations are found in amphibolite. The highest grossular and spessartine concentrations are found in the amphibolite lithotype. Southwestern Oaxacan Complex garnets from paraderivate samples are more enriched in Rb, Ba, Pb, Ni, and Zn than those from orthoderivate samples enriched in Ti and V. This fact is related to the nature of the protoliths and the mineral phases that fractionate the same minor and trace elements. Garnets from para-and orthoderivate samples display 0.02–1.1 Eu/Eu* anomalies. This fact indicates that almost all of the garnets formed while the plagioclase was stable, and it does not rule out the interpretation that some garnets were peritectic. The pressure obtained using a Grt-Opx-Pl-Qz geobarometer in the southwestern Oaxacan Complex is higher than the pressure obtained in the northern part of the Complex, and it is consistent with the pressure obtained in the Grenvillian-age granulites of the Novillo Gneiss from northeastern Mexico. Geothermobarometric studies reveal different P-T features at the study site, so different structural levels of the orogen are inferred. Published version This research was funded by CONACYT grant number 240226 and DGAPA-UNAM grant number IN111917.

One of the limiting factors for the analysis of minor elements in multiphase materials by electron probe microanalysis is the effect of secondary fluorescence (SF), which is not accounted for by matrix corrections. Although the apparent concentration due to SF can be calculated numerically or measured experimentally, detailed investigations of this effect for fine-grained materials are scarce. In this work, we use the Monte Carlo simulation program PENEPMA to examine and correct the effect of SF affecting micron-sized mineral inclusions hosted by other minerals. A concentration profile across an olivine [(Mg,Fe)2SiO4] inclusion in chromite (Fe2+Cr2O4) is measured and used to assess the reliability of calculations, where different boundary geometries are examined. Three application examples are presented, which include the determination of Cr in olivine and serpentine [Mg3Si2O5(OH)4] inclusions hosted by chromite and of Fe in quartz (SiO2) inclusions hosted by almandine garnet (Fe3Al2Si3O12). Our results show that neglecting SF leads to concentrations that are overestimated by ~0.1–0.8 wt%, depending on inclusion size. In addition, assuming a straight boundary yields to an underestimation of SF effects by a factor of ~2–4. Because its long-range nature, SF severely compromises trace element analyses even for phases as large as 1 mm in size.

The essential role of Critical Elements (CE) in 21st century economy has led to an increasing demand of these metals and promotes the exploration of non-conventional deposits such as weathering profiles. The present work is focused on the study of a weathering profile located at the Archaeological Park of the Gav&agrave, Neolithic Mines, Barcelona, Catalonia, Spain. In the Gav&agrave, deposit, acid and oxidising meteoric fluids generated intense weathering during the early Pleistocene, affecting series of Llandoverian black shales and associated syn-sedimentary phosphates. The circulation of these acid fluids at deeper levels of the profile generated supergene vein-like mineralisations comprised of secondary phosphates (e.g., variscite, perhamite, crandallite, phosphosiderite) and sulphates (e.g., jarosite, alunite). This supergene mineralisation is significantly enriched in certain CE (e.g., Ga, Sc, REE, In, Co and Sb) that were mobilised from host rock components and later hosted in the crystal lattice of supergene minerals. Weathering processes and corresponding supergene enrichment of CE at the Gav&agrave, deposit could be used as an example to determine exploration guidelines of CE in weathering profiles and associated supergene phosphates worldwide.

A volcanic dome complex of Miocene age hosts the In-bearing &Aacute, nimas&ndash, Chocaya&ndash, Siete Suyos district in SW Bolivia. Ore mineralization occurs as banded and massive infillings in sub-vertical, NE-SW striking veins. In this article, a detailed petrographic study is combined with in situ mineral geochemistry determinations in ore from the Arturo, Chorro and Diez veins in the Siete Suyos mine, the &Aacute, nimas, Burton, Colorada, and Rosario veins in the &Aacute, nimas mine and the Nueva vein in the Chocaya mine. A three-stage paragenetic sequence is roughly determined for all of them, and includes (1) an early low-sulfidation stage that is dominated by cassiterite, pyrrhotite, arsenopyrite, and high-Fe sphalerite (FeS &gt, 21 mol. %), (2) a second intermediate-sulfidation stage dominated by pyrite + marcasite &plusmn, intermediate product, sphalerite (FeS &lt, 21 mol. %), stannite, and local famatinite, and, (3) a late intermediate-sulfidation stage dominated by galena and Ag-Pb-Sn sulfosalts. Electron-probe microanalyses reveal high indium enrichment in stage-2 sphalerite (up to 9.66 wt.% In) and stannite (up to 4.11 wt.% In), and a moderate enrichment in rare wurtzite (up to 1.61 wt.% In), stage-1 sphalerite (0.35 wt.% In), cassiterite (up to 0.25 wt.% In2O3), and ramdohrite (up to 0.24 wt.% In). Therefore, the main indium mineralization in the district can be associated to the second, intermediate-sulfidation stage, chiefly in those veins in which sphalerite and stannite are more abundant. Atomic concentrations of In and Cu in sphalerite yield a positive correlation at Cu/In = 1 that agrees with a (Cu+ + In3+) 2Zn2+ coupled substitution. The availability of Cu in the mineralizing fluids during the crystallization of sphalerite is, in consequence, essential for the incorporation of indium in its crystal lattice and would control the distribution of indium enrichment at different scales. The highest concentrations of indium in sphalerite, which is found in the Diez vein in the Siete Suyos mine, occur in crustiform bands of sphalerite with local &ldquo, chalcopyrite disease&rdquo, texture, which has not been observed in the other studied veins. In stannite, the atomic concentrations of In are negatively correlated with those of Cu and Sn at Cu + In = 2 and Sn + In = 1. Thus, atomic proportions and correlations suggest the contextualization of the main indium mineralization in the sphalerite&ndash, stannite&ndash, roquesite pseudoternary system.

The tin-rich polymetallic epithermal deposit of Poop&oacute, of plausible Late Miocene age, is part of the Bolivian Tin Belt. As an epithermal low sulfidation mineralisation, it represents a typological end-member within the &ldquo, family&rdquo, of Bolivian tin deposits. The emplacement of the mineralisation was controlled by the regional fault zone that constitutes the geological border between the Bolivian Altiplano and the Eastern Andes Cordillera. In addition to Sn and Ag, its economic interest resides in its potential in critical elements as In, Ga and Ge. This paper provides the first systematic characterisation of the complex mineralogy and mineral chemistry of the Poop&oacute, deposit with the twofold aim of identifying the mineral carriers of critical elements and endeavouring to ascertain plausible metallogenic processes for the formation of this deposit, by means of a multi-methodological approach. The poor development of hydrothermal alteration assemblage, the abundance of sulphosalts and the replacement of l&ouml, llingite and pyrrhotite by arsenopyrite and pyrite, respectively, indicate that this deposit is ascribed to the low-sulphidation subtype of epithermal deposits, with excursions into higher states of sulphidation. Additionally, the occurrence of pyrophyllite and topaz has been interpreted as the result of discrete pulses of high-sulphidation magmatic fluids. The &delta, 34SVCDT range in sulphides (&minus, 5.9 to &minus, 2.8&permil, ) is compatible either with: i. hybrid sulphur sources (i.e., magmatic and sedimentary or metasedimentary), or ii. a sole magmatic source involving magmas that derived from partial melting of sedimentary rocks or underwent crustal assimilation. In their overall contents in critical elements (In, Ga and Ge), the key minerals in the Poop&oacute, deposit, based on their abundance in the deposit and compositions, are rhodostannite, franckeite, cassiterite, stannite and, less importantly, teallite, sphalerite and jamesonite.

The pyroclastic carbonatitic rocks from the Catanda volcanic area (Angola) contain annite and phlogopite grains which have been affected to a significant extent by vermiculitization. A mineralogical study of these micas has revealed that the annite was altered to K-vermiculite while vermiculitization of phlogopite generated Ca-vermiculite. Intermediate alteration products such as intergrowths of phlogopite/Ca-vermiculite were also found, but interstratified crystals of phlogopite/ vermiculite, a common intermediate product during vermiculitization processes, are not reported in the Catanda rocks. The two types of vermiculitized micas show ‘accordion’ textures, related to the expansion of vermiculite. To the authors’ knowledge, the present study is the first report of expanded vermiculites described in natural rocks and not generated as a consequence of industrial processing.

The Eureka deposit in Castell-esta&oacute, in the Catalan Pyrenees is a Cu&ndash, U&ndash, V deposit, hosted by Triassic red-bed sandstones, and classified here as a low-temperature, sandstone-hosted stratabound metamorphite U deposit. The main mineralisation is stratabound, related to coal-bearing units and produced during the Alpine deformation by migration of hydrothermal fluids. In this stage, the original sedimentary and diagenetic components (quartz and calcite, micas, hematite and locally apatite) were replaced by a complex sequence of roscoelite, fine-grained REE phosphates, sulphides and Ni&ndash, Co arsenides and sulpharsenides, Ag&ndash, Pb selenides, bismuth phases, sulphosalts and uraninite. The black shales of the Silurian sediments underlying the deposit and the nearby Carboniferous volcanoclastic rocks are interpreted as the source of the redox-sensitive elements concentrated in Eureka. The sulphur source is related to leaching of the evaporitic Keuper facies. The REE transport would be facilitated by SO4-rich solutions. The reduction of these solutions by interaction with organic matter resulted in the widespread precipitation of REE and redox-sensitive elements, including many critical metals (V, Bi, Sb, Co), whereas barite precipitated in the oxidized domains. The occurrence of similar enrichments in critical elements can be expected in other similar large uranium deposits, which could be a source of these elements as by-products.

The polymetallic Huanuni deposit, a world-class tin deposit, is part of the Bolivian tin belt. As a likely case for a &ldquo, mesothermal&rdquo, or transitional deposit between epithermal and porphyry Sn types (or shallow porphyry Sn), it represents a case that contributes significantly to the systematic study of the distribution of critical elements within the &ldquo, family&rdquo, of Bolivian tin deposits. In addition to Sn, Zn and Ag, further economic interest in the area resides in its potential in critical elements such as In, Ga and Ge. This paper provides the first systematic characterisation of the complex mineralogy and mineral chemistry of the Huanuni deposit with the twofold aim of identifying the mineral carriers of critical elements and endeavouring plausible metallogenic processes for the formation of this deposit, by means of a multi-methodological approach. With In concentrations consistently over 2000 ppm, the highest potential for relevant concentrations in this metal resides in widespread tin minerals (cassiterite and stannite) and sphalerite. Hypogene alteration assemblages are hardly developed due to the metasedimentary nature of host rocks, but the occurrence of potassium feldspar, schorl, pyrophyllite and dickite as vein material stand for potassic to phyllic or advanced argillic alteration assemblages and relatively high-temperature (and low pH) mineralising fluids. District-scale mineralogical zonation suggests a thermal zonation with decreasing temperatures from the central to the peripheral areas. A district-scale zonation has been also determined for &delta, 34SVCDT values, which range &minus, 7.2&permil, to 0.2&permil, (mostly &minus, 7&permil, to &minus, 5&permil, ) in the central area and &minus, 4.2&permil, to 1.0&permil, (mainly constrained between &minus, 2&permil, and 1&permil, ) in peripheral areas. Such values stand for magmatic and metasedimentary sources for sulfur, and their spatial zoning may be related to differential reactivity between mineralising fluids and host rocks, outwardly decreasing from the central to the peripheral areas.

The Kunene Intrusive Complex (KIC), in NW Namibia and SW Angola, is one of the largest Proterozoic anorthosite massif-type exposures in the world. A geochemical, mineralogical and petrological study of four Fe–Ti(–V) oxide bodies located in the understudied Angolan part of the KIC has been performed. The massive Fe–Ti(–V) oxide bodies, locally apatite-rich (nelsonites), are lenticular or dike-like. They consist mostly of titaniferous magnetite, ilmenite and minor aluminous spinel, apatite, olivine and graphite. Titaniferous magnetite displays a wide variety of subsolvus features, including aluminous spinel–magnetite–ulvöspinel exsolutions and ilmenite (Trellis) exsolutions. This work estimated the composition of the titaniferous magnetite prior to the exsolution, in order to calculate the temperature and oxygen fugacity of the different lithologies of each ore body. The thermo-oxybarometry results obtained range from 600 ºC to 820 º C and ƒO2 from 10-24.7 to 10-14.7. These values do not correspond to magmatic crystallization in equilibrium, but to a later re-equilibration. In addition, the mineralogical and geochemical results indicate that the studied ore bodies contain economic reserves of Ti, V, and possibly of P and REE.

The origin of intraplate carbonatitic to alkaline volcanism in Africa is controversial. A tectonic control, i.e., decompression melting associated with far-field stress, is suggested by correlation with lithospheric sutures, repeated magmatic cycles in the same areas over several million years, synchronicity across the plate, and lack of clear age progression patterns. Conversely, a dominant role for mantle convection is supported by the coincidence of Cenozoic volcanism with regions of lithospheric uplift, positive free-air gravity anomalies, and slow seismic velocities. To improve constraints on the genesis of African volcanism, here we report the first radiometric and isotopic results for the Catanda complex, which hosts the only extrusive carbonatites in Angola. Apatite (U-Th-Sm)/He and phlogopite 40Ar/39Ar ages of Catanda aillikite lavas indicate eruption at ca. 500-800 ka, more than 100 m.y. after emplacement of abundant kimberlites and carbonatites in this region. The lavas share similar high-μ (HIMU)-like Sr-Nd-Pb-Hf isotope compositions with other young mantle-derived volcanics from Africa (e.g., Northern Kenya Rift; Cameroon Line). The position of the Catanda complex in the Lucapa corridor, a long-lived extensional structure, suggests a possible tectonic control for the volcanism. The complex is also located on the Bié Dome, a broad region of fast Pleistocene uplift attributed to mantle upwelling. Seismic tomography models indicate convection of deep hot material beneath regions of active volcanism in Africa, including a large area encompassing Angola and northern Namibia. This is strong evidence that intraplate late Cenozoic volcanism, including the Catanda complex, resulted from the interplay between mantle convection and preexisting lithospheric heterogeneities.

The Virulundo carbonatite in Angola is one of the largest in the world and contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias and trachytoids). The primary magmatic pyrochlore is fluorine dominant and typically contains about equal molar quantities of Ca and Na at the A site. High-temperature hydrothermal processes have resulted in the pseudomorphic replacement of the primary pyrochlore by a second generation of pyrochlore with less F and Na. Low-temperature hydrothermal replacement of the first and second generation pyrochlore, associated with quartz-carbonate-fluorite vein formation in the carbonatite, has produced a third generation of pyrochlore, with a high Sr content. The Sr appears to have been released by low-temperature hydrothermal replacement of the primary magmatic carbonates. Finally, supergene alteration processes have produced late-stage carbonates, goethite, hollandite and rare earth element (REE) minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Cerium separated from the other REE s in oxidizing conditions and Ce4+ was incorporated into a late generation of supergene pyrochlore, which is strongly enriched in Ba and strongly depleted in Ca and Na.