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This paper presents simulations of different concentration plants that use Inert Construction and Demolition Waste as feed to generate coarse aggregates from old concretes. Different feed materials were studied: CDW generated in Spain; low-strength concretes, C16/20, which are ordinary concrete used in civil construction; and high-strength concretes, C50/60, from specific demolitions, such as old viaducts and bridges. Granulometric and densimetric analyses were performed, and the composition of the granulometric fractions of the proposed concretes were analyzed based on previous studies carried out, to understand the materials that can be recovered and considered for reinvestment in the market. Investment analysis considering the CAPEX, OPEX, revenue, IRR, MIRR, NPV, and DPP of the different concentrating plants with varying streams of concentration to recover the materials of interest (coarse aggregates) are presented and discussed. The results of the analyses indicate greater viability in plants that use mobile plants and the use of water jigs. [ABSTRACT FROM AUTHOR]

Electromagnetic (EM) methods belong to the main geophysical techniques used in the mineral exploration of massive sulphides. For selecting EM anomalies as possible massive sulphide targets, it is important to combine the geophysical results with other geological and/or geochemical techniques. In 2015, Atalaya Mining started a new mineral exploration project in the Touro Cu deposit, combining geological, geochemical (ore over 0.2% Cu), and geophysical techniques. The geophysical survey consisted of helicopter-borne EM using the versatile time-domain electromagnetic (VTEM™) max system operated by Geotech Ltd. with full-waveform processing. In total, 509 line-km of geophysical data were acquired during the survey that was completed in 2018. The results showed the massive sulphide Touro ore to be typically of the order of 0.25 ohm·m (4S/m conductivity) and host rock in the range of 1000–30,000 ohm·m, measured directly on the drill core. This modelling agreed well with the sub-horizontal dips observed for the known Touro ore bodies. The conductance modelled by the plate estimation of the VTEM data were also in good agreement with those provided by Geotech Ltd. and the resistivity/conductivity measurements we made on the massive sulphide samples from several Touro ore bodies. The combination of flat dips, good conductance, shallow depth, and, lastly, lack of conductive overburden or noneconomic conductive stratigraphy, i.e., graphitic shales and sulphide iron formation make the Touro project an ideal target for airborne electromagnetic prospecting. This paper presents the excellent correlation observed between the EM airborne anomalies and the massive sulphide blocks of the Touro copper deposit. Favourable factors contributing to the success of the survey were the high contrast in resistivity/conductivity between the massive sulphide Touro ore and the amphibolite host rock and minimal interference from "nuisance" conductors, such as graphitic shales. [ABSTRACT FROM AUTHOR]

A multi-technique approach combining petrographic, cathodoluminescence, and stable isotope analyses is commonly used in provenance studies of archaeological marbles. In the present paper, this characterization approach transcends provenance, and it is applied to the reconstruction of fragmented sculptures. The potential of this novel application of archaeometric measurements is illustrated with a case study consisting in 16 scattered marble fragments retrieved from a Roman villa (Els Munts) near Tarraco (presently Northeastern Spain). The samples were grouped taking into account their similarity in quantified parameters such as the cathodoluminescence color clusters and the stable carbon and oxygen isotopic ratios. The results permitted classification of the fragments into three groups corresponding to three different statues depicting Antinous (7 fragments), Minerva goddess (4 fragments), and an undetermined character (3 fragments). Two other fragments could not be ascribed to any particular statue. The archaeometric grouping provides arguments that can be used to confirm or refute archaeological hypotheses of statue reconstructions. [ABSTRACT FROM AUTHOR]

The traditional pottery industry was an important activity in Catalonia (NE Spain) up to the 20th century. However, nowadays only few workshops persist in small villages were the activity is promoted as a touristic attraction. The preservation and promotion of traditional pottery in Catalonia is part of an ongoing strategy of tourism diversification that is revitalizing the sector. The production of authenticable local pottery handicrafts aims at attracting cultivated and high-purchasing power tourists. The present paper inspects several approaches to set up a scientific protocol based on the chemical composition of both raw materials and pottery. These could be used to develop a seal of quality and provenance to regulate the sector. Six Catalan villages with a renowned tradition of local pottery production have been selected. The chemical composition of their clays and the corresponding fired products has been obtained by Energy dispersive X-ray fluorescence (EDXRF). Using the obtained geochemical dataset, a number of unsupervised and supervised machine learning methods have been applied to test their applicability to define geochemical fingerprints that could allow inter-site discrimination. The unsupervised approach fails to distinguish samples from different provenances. These methods are only roughly able to divide the different provenances in two large groups defined by their different SiO2 and CaCO3 concentrations. In contrast, almost all the tested supervised methods allow inter-site discrimination with accuracy levels above 80%, and accuracies above 85% were obtained using a meta-model combining all the predictive supervised methods. The obtained results can be taken as encouraging and demonstrative of the potential of the supervised approach as a way to define geochemical fingerprints to track or attest the provenance of samples. [ABSTRACT FROM AUTHOR]

Phosphorus is a key element for identifying past human activity. Recently, phosphorus analyses have been extended to archaeological objects, aiming at distinguishing how depositional contexts contribute to its enrichment. In archaeological pottery, phosphorus might depend on several manufacturing and postdepositional processes (i.e., addition of organic temper, pigments, diagenetic incorporation). We analyzed by XRD, XRF, and mid-infrared (FTIR-ATR) spectroscopy 178 pots from eight NW Spain archaeological sites. These sites encompass different chronologies, contexts, and local geology. The phosphorus content was highly variable (224–27,722 mg kg−1) overall but also between archeological sites (1644 ± 487 to 13,635 ± 6623 mg kg−1) and within archaeological sites (4–36, max/min ratio). No phosphate minerals were identified by XRD nor FTIR-ATR, but correlations between phosphorus content and MIR absorbances showed maxima at 1515 and 980 cm−1, suggesting the presence of two sources: one organic (i.e., phosphorylated aromatic compounds) and another inorganic (i.e., albite and K-feldspar). Phosphorylated aromatics were most likely formed during pottery firing and were preserved due to their high resistance to temperature and oxidation. Meanwhile, albite and K-feldspar are among the P-bearing minerals with higher P concentrations. Our results suggest that P content is related to intentional and non-intentional actions taken in the pottery production process. [ABSTRACT FROM AUTHOR]

In the watersheds of abandoned mining districts, it is common to find remains of former facilities and waste dams on stream banks and slopes—a situation that results in the transport and accumulation of metal(loid)s in alluvial deposits. To analyze this problem, an area of the former mining district of Linares–La Carolina (southern Spain) was selected to evaluate the contents and distributions of Ag, As, Ba, Cu, and Pb as potentially toxic elements (PTEs) found in the mineral paragenesis. Specifically, this study focused on the Siles Stream, which runs through a sector where underground mining for the exploitation of galena veins generated abundant mining wastes, mainly waste rock and tailings. Thirty-four sediment samples from the stream bed of the Siles Stream and two sediment samples from the Guadiel River, of which it is a tributary, were analyzed. Floodplain sediments were sampled in the stream banks at the middle and lower reaches (11 samples), as well as the riverine soils developed at the mouth of the Siles Stream (22 samples). The analyzed samples presented high levels of PTEs, in most cases with values much higher than the generic reference levels established by European and regional legislation for PTEs in soils. In the case of Pb, the main metal mined in this district, contents of up to 27,074 mg·kg−1 were observed in the stream bed sediments. Very high concentrations of Pb also appeared in the floodplain sediments, with maximum values in the middle course of the stream, where the concentration reached 43,692 mg·kg−1. With respect to the sediments of the Guadiel river bed, the Pb content was 699 mg·kg−1 before the confluence with the stream and 2537 mg·kg−1 downstream, which clearly reflects the influence of the contributions from the Siles Stream. The enrichment factors (EFs) show that the sediments present a severe to very severe anthropogenic influence for Ag, As, Ba, Cu, and Pb. The geoaccumulation index (Igeo) indicates that the entire basin is extremely polluted by Pb, to which As and Ag are added in the middle course of the stream. The potential ecological risk index (RI) and pollution load index (PLI) based on the contamination factor (CF) suggested that metal loads far exceeded the reference values. Selective chemical extraction methods were used to assess the potential bioavailability of these elements in sediment and soil samples. The results showed high concentrations of Pb in the exchangeable fraction, which poses a significant ecological risk and potential human health risks. [ABSTRACT FROM AUTHOR]

This study addresses the in situ mobility of fluoride and aluminum in two different ashfall deposits accumulated during the 2021 eruption of the Tajogaite volcano (La Palma, Canary Islands, Spain), which were exposed to contrasting conditions of ambient humidity and precipitation. We selected one site to the east of the volcanic emission center, located near the top of Cumbre Vieja Ridge and exposed to continuous humidity and rain, and another site to the west of the volcano situated in a lowland and characterized by much drier conditions. The mobility of fluoride and aluminum is markedly different at both sites, with the first sequence suggesting a downwards migration of Al and F, and the second sequence showing no sign of mobility. The migration of aluminum and fluorine results from the dissolution of different fluoride salts (mostly AlF3 and CaF2, as suggested by scanning electron microscopy) followed by vertical transport as ionic complexes (AlF3, AlF2+, AlF4−) during the percolation of rainwater through the ashfall deposits. Geochemical calculations suggest that the mobility of fluorine at neutral to alkaline conditions (pH 7.0–9.0) is likely limited by the solubility of fluorite (CaF2), whereas at slightly acidic conditions (pH < 6.5), the aqueous concentration of aluminum seems to be controlled by the solubility of gibbsite (Al(OH)3). This study demonstrates that aluminum and fluoride can be transported from volcanic ash to the underlying soil or groundwater, which is an environmental concern that should be followed in the future. [ABSTRACT FROM AUTHOR]

Fluid inclusions in stalagmites are becoming increasingly important for paleoclimate research. Within this framework, noble gas thermometry, based on noble gases dissolved in water from fluid inclusions, provides quantitative estimations of cave air paleotemperature. Two major issues of Noble Gas Temperature (NGT) determination on speleothems are (1) the potential lack of enough water for the analysis and (2) the presence of trapped gas not dissolved in water that can be released during the analysis from biphasic or all-gas fluid inclusions, as its contribution to the bulk noble gas signal can hinder NGT results. Although the step-crushing method helps to reduce the second issue, it also decreases the amount of water available for the calculations. In order to obtain reliable NGT results with low uncertainties, a major challenge is still to reach a balance between sufficient water for analysis and a small amount of "atmospheric" gas. The difficulty is that the extraction process cannot be standardized since it strongly depends on the type of sample. The objective of this work is to investigate how the characteristics of the speleothem can determine the adequacy of the extraction process. For this purpose, we consider a stalagmite from a Mediterranean cave that consists of columnar elongated calcite and contains a significant quantity of fluid inclusions, which suggests good potential for NGT analysis. Results, however, were poorly satisfactory. Trying to understand the source of the problems, an integrated study of petrography and petrophysical features was performed. The samples were found to be different depending on the stage of coalescence of crystals and thus separated into "open" and "closed" fabrics. Classic petrographic analysis and non-destructive (nuclear magnetic resonance) techniques were used to characterize the type and amount of fluid inclusions present in both types of fabrics. The study indicates that the closed fabric (total coalescence of calcite crystals) has most water trapped in water-filled, small intracrystalline fluid inclusions that usually contain very little gas. This fabric is very suitable for NGT determination, but since the amount of water is quite small, the sample should be crushed in only one step with a large number of beats to break all the inclusions. In contrast, samples with open fabric (partial coalescence of calcite crystals) contain a higher amount of water and, also, gas-filled large intercrystalline fluid inclusions. For this fabric, step-crushing of the sample is necessary. However, the low amount of water left for the second and third crushings could lead to flawed NGT results. Thus, we suggest modifying the method to get rid of part of the gas in the first crushing while leaving enough water for the following steps. This work shows the importance of characterizing speleothems and fluid inclusions, including their petrography and petrophysical characteristics, before starting NGT analysis, allowing the selection of the most favorable samples and the customization of the step-crushing procedure. [ABSTRACT FROM AUTHOR]

The European Union (EU) is responsible for generating quantities ranging from 310 to almost 700 million tons of construction and demolition waste (CDW) per year. Consisting of over 70% inert material (concrete, ceramics, plaster, bricks, and rocks), CDW can be recycled for various uses, and studies on the concentration of the materials of interest are necessary to improve the management of this material and reduce waste. In CDW recycling plants in Spain, there is a significant presence of limestone from old houses (a common material used in civil construction before new construction materials and technologies emerged) that were demolished and mixed with CDW that can be recovered for use as aggregates in concretes with process density concentration processes such as water jigging. The jigging process is based on the difference in density between materials, allowing the concentration of the densest material at the bottom of the jig. Concrete, conventional construction bricks, and rocks from old houses were taken separately and then were crushed and mixed based on binary and ternary tests, and each test was performed in this study by applying the jigging separation method. The physical characterization tests of these materials was carried out to observe the jigging performance in the concentration of rocks as well as the aggregates present in concrete. Binary tests (with two different materials) and ternary tests (with three different materials) were carried out to analyze the concentration of particles with a density greater than 2.55 g/cm3. The efficiency of jigging in the concentration of these materials was proven, and products were generated with more than 70% recovery of this material, with a concentration comprised of more than 95% rocks and concrete. [ABSTRACT FROM AUTHOR]

In this paper, we addressed the chemical composition and main features of a glazed Almohad ceramic assemblage recovered from Puig de Sa Morisca, a rural Islamic site located in southwest Mallorca. The glazes were analyzed by means of scanning electron microscope equipped with energy-dispersive spectrometer (SEM-EDS). The archaeometrical analysis conducted allowed us to characterize the technological choices applied by potters from the end of the 12th century and the beginning of the 13th century. The exclusive use of lead-silica glazes was confirmed, which in some cases was opacified with tin. We also established that some tableware vessels, which were imported to the island, have shown glazes with a particular composition within the analyzed record. [ABSTRACT FROM AUTHOR]

This study provides a characterization of materials from wastes and outcrops of two inactive bauxite mines located close to Sant Joan de Mediona and Peramola, Spain. Mineralogy was determined via powder X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Thermal properties were measured via differential thermal analysis–thermogravimetry (DTA-TG) and gresification tests. The crystalline phases are medium-high crystalline kaolinite and variable amounts of illite, quartz, calcite, boehmite, hematite and rutile/anatase. DTA show two endothermic peaks produced by the dehydroxylation of minerals: the first peak, at 530–538 °C, belongs to boehmite; the second peak, at 535–568 °C, corresponds to kaolinite. An exothermic peak at 950–978 °C is associated with mullite crystallization. The optimal sintering temperatures obtained from the gresification curves (firing shrinkage and water absorption) were 970 °C for carbonate-poor, illite-rich clays; 1100 °C for illite- and carbonate-poor samples; and near 1190 °C for carbonate-rich materials. The carbonate-poor samples fired at 1300 °C contain sillimanite and mullite, and the carbonate-rich materials are rich in gehlenite, anorthite, and hedenbergite. The mineralogy of these materials is sufficient to obtain ceramic materials with suitable properties, but not their low plasticity. They could be used in the formulation of bricks or as part of mixtures to produce refractory ceramics. [ABSTRACT FROM AUTHOR]

Demand for niobium and tantalum is increasing exponentially as these are essential ingredients for the manufacture of, among others, capacitors in technological devices and ferroniobium. Mine tailings rich in such elements could constitute an important source of Nb and Ta in the future and alleviate potential supply risks. This paper evaluates the possibility of recovering niobium and tantalum from the slags generated during the tin beneficiation process of mine tailings from the old Penouta mine, located in Spain. To do so, a simulation of the processes required to beneficiate and refine both elements is carried out. After carbothermic tin reduction, the slags are sent to a hydrometallurgical process where niobium oxide and tantalum oxide are obtained at the end. Reagents, water, and energy consumption, in addition to emissions, effluents, and product yields, are assessed. Certain factors were identified as critical, and recirculation was encouraged in the model to maximise production and minimise reagents' use and wastes. With this simulation, considering 3000 production hours per year, the metal output from the tailings of the old mine could cover around 1% and 7.4% of the world annual Nb and Ta demand, respectively. [ABSTRACT FROM AUTHOR]

Archaeometric studies on mosaics often concentrate only on glass tesserae, while comprehensive studies including both stone and glass tesserae are scarce; however, both types of tesserae can sometimes bring relevant data to elaborate archaeological knowledge on a studied mosaic. In this paper, a representative set of tesserae from a large polychrome Roman mosaic retrieved in Barcelona (NE Spain) is investigated using various methods. Most of the techniques were directly applied on samples prepared as petrographic thin sections (including polarized-light, cathodoluminescence and electron microscopies, and synchrotron through-the-substrate μX-ray diffraction). The results indicate that, from the ten sampled stone tesserae, there are (i) seven limestones, one of them identified as Alveolina limestone (early Eocene) from the southern Pyrenees (ii) two sandstones from Barcelona's Montjuïc hill (Miocene) and, (iii) a Carrara white marble from the Apuan Alps (Italy). The profuse presence of tesserae of both local and imported materials with well-known uses in architecture, epigraphy, and sculpture could imply that tesserae were a by-product of their main use. Two different production technologies were identified for the three sampled glass tesserae. The concurrent use of antimony- and tin-based opacifiers is in agreement with the accepted archaeological chronology of the mosaic (4th century AD). [ABSTRACT FROM AUTHOR]

This paper draws on the study of the prehistoric art site of Penedo Gordo (NW Spain) resulting from a collaborative interdisciplinary research. One of its primary goals was to design and put into practice a multi-analytical protocol for characterising prehistoric rock paintings, combining in situ and laboratory analytical techniques. Thus, following the archaeological assessment of the site, the panels exhibiting red paintings were analysed by colour spectrophotometry and portable Raman spectroscopy. Analytical techniques were applied to a collection of samples exhumed from the excavation that simultaneously took place on site. These included three red accretions on different substrates (compact soil, white quartzite and grey quartzite) and stone fragments representative of the outcrop's petrographic variability, aiming to determine their mineralogical composition, texture and study the stone-paint boundaries. Moreover, colouring materials exhumed from the excavation and collected in the immediate surroundings of the rock outcrop were analysed in order to scrutinise the provenience rock art's raw materials. Laboratory analysis consisted of stereomicroscopy, X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. One of the major outcomes was the discovery of a drop of red pigment preserved in an archaeological layer associated with Late Neolithic/Copper Age material remains. [ABSTRACT FROM AUTHOR]

We evaluated the mobility of a wide suite of economic metals (Ni, Co, REE, Sc, PGE) in Ni-laterites with different maturities, developed in the unconventional humid/hyper-humid Mediterranean climate. An embryonic Ni-laterite was identified at Los Reales in southern Spain, where a saprolite profile of ~1.5 m thick was formed at the expense of peridotites of the subcontinental lithospheric mantle. In contrast, a more mature laterite was reported from Camán in south-central Chile, where the thicker (~7 m) weathering profile contains well-developed lower and upper oxide horizons. This comparative study reveals that both embryonic and mature laterites can form outside the typical (sub)-tropical climate conditions expected for lateritic soils, while demonstrating a similar chemical evolution in terms of major (MgO, Fe2O3, and Al2O3), minor (Ni, Mn, Co, Ti, Cr), and trace (REE, Y, Sc, PGE, Au) element concentrations. We show that, even in the earliest stages of laterization, the metal remobilization from primary minerals can already result in uneconomic concentration values. [ABSTRACT FROM AUTHOR]

The aim of this study was to analyze HTO, 36Cl, and 75Se(IV) diffusion behavior in a sedimentary rock, which was obtained from the site initially selected for the emplacement of centralized temporal disposal of radioactive waste in Spain. Different experimental methodologies were used to analyze radionuclide diffusion in this rock: the through-diffusion (TD) method and the instantaneous planar source (IPS) methods. For the conservative tracers HTO and 36Cl, the effective diffusion coefficients, De, were obtained by the TD method, which was applied to the consolidated material taken at different orientations with respect to the bedding plane (parallel and normal). This revealed a negligible anisotropy of the rock. To analyze the effect of the water saturation degree, the IPS method was used, which was shown to be very suitable for evaluating these effects. For these tests, the samples were crushed, adequately hydrated, and compacted. The apparent diffusion coefficient, Da, was determined for all the tracers at five different water saturation degrees. For each of the tracers investigated, the results indicated that, when the water saturation decreased from 100% to 60%, the Da also decreased by at least one order of magnitude: for HTO, this decrease was from 1.5 × 10−9 to 2.3 × 10−10 m2/s; that for 36Cl was from 4.6 × 10−10 to 2.8 × 10−11 m2/s; and that for 75Se was from 3.6 × 10−11 to 8.3 × 10−13 m2/s. The experimental diffusion profiles of HTO and 36Cl could be satisfactorily fitted considering a unique diffusion coefficient, whereas the profiles of 75Se could not. This behavior is related to the existence of different species of selenium in the system, or to different retention mechanisms. [ABSTRACT FROM AUTHOR]

The formation of thin mineral films or encrustations floating on the water surface of low-flow or stagnant zones of acid mine drainage (AMD)-affected streams is probably among the most exotic features that can be found in mining areas. However, most fundamental questions about their origin (biotic vs. abiotic), structure, mineralogy, physical stability and metal-retention capacity remain unanswered. This study aims to reveal the factors promoting their formation and to clarify their composition in detail. With this purpose, the major mineral phases were studied with XRD in surface film samples found in different mine sites of the Iberian Pyrite Belt mining district (SW Spain), and the major oxide and trace metal concentrations were measured with XRF and/or ICP-MS. Fe(III) minerals dominated these formations, with mineralogy controlled by the pH (jarosite at pH~2.0, schwertmannite at pH 2.5–3.5, ferrihydrite at pH > 6.0). Other minerals have also been identified in minor proportions, such as brushite or khademite. These mineral formations show an astounding capacity to concentrate, by orders of magnitude (×102 to ×105), many different trace metals present in the underlying aqueous solutions, either as anionic complexes (e.g., U, Th, As, Cr, V, Sb, P) or as divalent metal cations (e.g., Cu, Zn, Cd, Pb). These floating mineral films are usually formed in Fe(II)-rich acidic waters, so their formation necessarily implies the oxidation of Fe(II) to Fe(III) phases. The potential involvement of Fe(II)-oxidizing microorganisms was investigated through 16S rRNA gene amplicon sequencing of water underneath the Fe(III)-rich floating mineral films. The sequenced reads were dominated by Ferrovum (51.7 ± 0.3%), Acidithiobacillus (18.5 ± 0.9%) and Leptospirillum (3.3 ± 0.1%), three well-known Fe(II)-oxidizing genera. These microorganisms are major contributors to the formation of the ferric mineral films, although other genera most likely also play a role in aspects such as Fe(III) sequestration, nucleation or mineral growth. The floating mineral films found in stagnant acidic mine waters represent hotspots of biosphere/hydrosphere/atmosphere interactions of great value for the study of iron biogeochemistry in redox boundaries. [ABSTRACT FROM AUTHOR]

The El Robledal deposit is a Mg-Fe-B skarn hosted in a dismembered block from the footwall contact of the Ronda orogenic peridotites in the westernmost part of the Betic Cordillera. The skarn is subdivided into two different zones according to the dominant ore mineral assemblage: (1) the ludwigite–magnetite zone, hosted in a completely mineralized body along with metasomatic forsterite, and (2) the magnetite–szaibelyite zone hosted in dolomitic marbles. In the ludwigite–magnetite zone, the massive mineralization comprises ludwigite (Mg2Fe3+(BO3)O2), Mg-rich magnetite, and magnetite, with minor amounts of kotoite (Mg3(BO3)2), szaibelyite (MgBO2(OH)), accessory schoenfliesite (MgSn4+(OH)6), and pentlandite. The ratio of ludwigite–magnetite decreases downwards in the stratigraphy of this zone. In contrast, the mineralization in the magnetite–szaibelyite zone is mainly composed of irregular and folded magnetite pods and bands with pull-apart fractures, locally associated with a brucite-, szaibelyite-, and serpentine-rich groundmass. The set of inclusions identified within these ore minerals, using a combination of a focused ion beam (FIB) and high-resolution transmission electron microscope (HRTEM), supports the proposed evolution of the system and reactions of the mineral formation of the skarn. The analysis of the microstructures of the ores by means of electron backscatter diffraction (EBSD) allowed for the determination that the ores experienced ductile deformation followed by variable degrees of recrystallization and annealing. We propose a new classification of the deposit as well as a plausible genetic model in a deposit where the heat source and the ore-fluid source are decoupled. [ABSTRACT FROM AUTHOR]

This paper analyses the mineralogical composition, texture, and structure of a stalactite sampled from the city-wall storerooms of the Nueva Tabarca fortress (southeast Spain). This speleothem presents an uncommon mineral assemblage: aragonite, brucite, gypsum, silica, and halite. Internally, it shows complex structure: (1) a central soda-straw composed by aragonite; (2) an external puff-pastry cone-crust formed preferentially by aragonite and brucite; and (3) an internal branching of coralloids, showing a subtle layering between brucite and aragonite. Gypsum, halite, and silica locate in the outer coating of the cone-crust. The sequent mineral precipitation sequence has been established: aragonite > brucite > gypsum/silica > halite. Speleothem formation is directly related to the chemical weathering of the rocks and mortars used as building materials of the city-wall. Brucite precipitates has been always linked to the presence of MgO-based geomaterials. However, the lack of these compounds as building materials in Nueva Tabarca fortress makes this investigation a unique example of brucite precipitation. PHREEQC calculations showed that interaction between pore waters and the minerals of mortar aggregates (dolomite, pyroxene, and amphibole) leads to rich-magnesium solutions. Evaporation modelling of lixiviated waters describes the precipitation of the mineral assemblage of the brucite-aragonite speleothems. [ABSTRACT FROM AUTHOR]

Excavations at the Roman villa of Noheda (Spain) revealed the remains of an exceptionally elaborate fourth-century floor mosaic that contains a surprisingly large number of glass tesserae, representing a broad spectrum of colors. This paper presents the results of the chemical (LA-ICP-MS) and microstructural analyses (SEM-EDS, XRPD) of 420 glass tesserae from these mosaics. The high number of data allowed us to establish the compositional variability and to elucidate questions of supply in relation to a large-scale artistic campaign. The tesserae from Noheda were almost exclusively made from recycled mixed Roman Mn and Sb base glass, thus demonstrating that recycling of Roman base glasses was common practice in the fourth century, occurring on a near industrial scale. It also suggests that the workshops specializing in the production of mosaic tesserae might have been in the western Mediterranean. A limited number of coloring and opacifying additives (Mn, Co, Cu, Sb, Pb) were identified, which resulted in a wide range of hues. These were differentially associated with various trace elements, which implies the use of different raw materials. A sub-set of red, green, and orange tesserae reflect distinct base glass characteristics as well as coloring technologies that point to an Egyptian provenance. [ABSTRACT FROM AUTHOR]

The utility of the Mg/Ca elemental ratio of calcite ((Mg/Ca)calcite) as a temperature indicator in continental carbonate deposits is a matter of debate due to the different results obtained by diverse authors. In this study, we aimed to test the reliability of the (Mg/Ca)calcite in fluvial carbonates. We selected the recent tufa stromatolite records of four rivers on the Iberian Peninsula for the trace element analysis based on six-monthly sampling. Previous sedimentary and hydrological studies on these fluvial basins provided the information for this work. The water temperature estimates for the stromatolite (Mg/Ca)calcite substantially differed from the measured water temperatures in most of the studied cases. We thus assessed other factors that participate in the control of the Mg partitioning between water and calcite. The correction of the detrital Mg content yielded water temperatures that matched the measured ones in one of the rivers. The (Mg/Ca)water, water discharge and calcite precipitation rates may also occasionally influence the (Mg/Ca)calcite. The six-month behaviour of some of these parameters could interfere with the relationship between the (Mg/Ca)calcite and water temperature. According to these results, and their comparison with other non-marine carbonates, the wide variety of parameters that are involved in the (Mg/Ca)calcite limit it as a geochemical thermometer in continental sedimentary environments. [ABSTRACT FROM AUTHOR]

Lithofacies belonging to mud-flat and palustrine deposits (lake margin) in the Miocene of the Madrid Basin (Spain) have been studied. Four lithofacies corresponding to mud flat (1 and 3) and palustrine (2 and 4) deposits have been differentiated. Units 1 and 3 consist mainly of mudstones and carbonates (calcretes and diolocretes). The clay fraction is dominated by trioctahedral smectite (up to 79%) with illite and kaolinite as minor components. The d(060) spacing value shows reflections at 1.52 and 1.50 Å indicating also the presence of dioctahedral phyllosilicates. Unit 2 consists predominantly of lutites (claystones), locally with carbonate and chert nodules. The clay fraction is dominated by sepiolite (up to 96%) with variable contents of smectite and subordinate illite. The d(060) spacing value shows reflections at 1.51 and 1.52 Å indicating trioctahedral clay minerals. Unit 4 consists mostly of carbonates (limestones) with mudstone and lutite inserts. The clay fraction shows different contents of sepiolite, palygorskite and dioctahedral smectite. The analysis of a selection of trace elements (Cr, Co, Th, La, Sc) has allowed us to determine the characteristics of the source area as dioritic, somewhat different from those of the nearby materials from the Batallones sector. Sepiolite shows FWHM values ranging between 0.68 and 1.10 (2θ), indicating "low crystallinity sepiolite". Differences in the conditions of formation of magnesian smectite and palygorskite have been observed in the mud-flat and palustrine deposits. The formation of sepiolite mainly by neoformation in palustrine deposits with different hydrochemistry is remarkable, leading to differences in fibre size and crystallinity of the fibrous clay mineral. Authigenic transformation processes from previous Al-rich phases would be responsible for the formation of saponite and palygorskite in mud flat and palustrine environments, with different pH conditions. [ABSTRACT FROM AUTHOR]

Mortars from different stratigraphic units at Portilla Castle (Alava, North Spain) have been analyzed for mineralogical characterization before radiocarbon dating. The mortar binder at Portilla Castle is composed not only of neoformation calcite but also of double-layered hydroxide (LDH) minerals such as hydrotalcite and hydrocalumite. The mineralogy of several fractions of the binder has been analyzed to determine the granulometric distribution of minerals in the binder. The continuous monitoring of mineralogy during the extraction of different grain size fractions has been performed by using a scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analyses (TGA). Hydrotalcite and hydrocalumite-bearing mortar binders give older ages than expected since they introduce dead carbon into the system. [ABSTRACT FROM AUTHOR]

Ball clay deposits in the SE of the Iberian Range (NE Iberian Peninsula) consist of Albian clays and siltstones with greyish and blackish colors, interbedded with subbituminous coals. The ball clays are nowadays mined for the manufacture of white color ceramics. The mineralogy of these deposits consists mainly of kaolinite, illitic phases, and quartz. The euhedral to sub-euhedral morphology of the kaolinites suggests their in-situ origin. The anhedral morphology of the illites and the presence of frayed illites suggest a detrital origin. At the micro-scale, authigenic kaolinite booklets are observed filling pores and forming mica/kaolinite intergrowths, in which the kaolinite grows between the cleavage sheets of pre-existing detrital mica. At nanometer scale, illite/smectite (IS) phases are detected forming interlayers with mica and kaolinite, and evidence of the replacement of mica by kaolinite is observed. The matrix consists of defective illite and kaolinite, and random mixed layers of kaolinite-I/S (Kln-IS), illite-I/S (Ilt-IS), and I/S-smectite (IS-S). The textures of illite and the presence of different types of mixed layers suggest that the expandable phases and kaolinite are products of mica alteration. The effectivity of the alteration was probably a consequence of the low pH that occurred in the environment due to the presence of abundant organic- and acidic- rich fluids. [ABSTRACT FROM AUTHOR]

A set of 14 glass fragments and production remains dated to the 16th and 17th centuries was collected during rescue archaeological works conducted in Granada, Spain, and was characterised by µ-PIXE. This preliminary study constitutes the first analytical approach to glass manufacturing remains from a Spanish production dated to the early-modern period. µ-PIXE allowed for the quantification of major, minor and some trace elements of the glass fragments. It also allowed mapping the elemental distribution on the fragments that were identified as an interface of crucible/glass. This analysis constitutes an evaluation of the ionic exchange between glass and crucible. The glass colours vary from the natural green and blue hues to completely colourless samples. The results show that the majority of the glass samples are of soda-lime-silicate composition, and only one proved to be of a potassium-rich composition. From this, one can hypothesise that glass rich in sodium (following the Mediterranean tradition) and potassium-rich glass (following a central and north European tradition) were both locally produced. Since this location was known as la Calle Horno del Vidrio (Glass Furnace Street) and several production evidences were found, it is highly probable that an artisanal glass production existed in this area. [ABSTRACT FROM AUTHOR]

Chert samples from different coastal and inland outcrops in the Eastern Asturias (Spain) were mineralogically investigated for the first time for archaeological purposes. X-ray diffraction, X-ray fluorescence, transmission electron microscopy, infrared and Raman spectroscopy and total organic carbon techniques were used. The low content of moganite, since its detection by X-ray diffraction is practically imperceptible, and the crystallite size (over 1000 Å) of the quartz in these cherts would be indicative of its maturity and could potentially be used for dating chert-tools recovered from archaeological sites. Also, this information can constitute essential data to differentiate the cherts and compare them with those used in archaeological tools. However, neither composition nor crystallite size would allow distinguishing between coastal and inland chert outcrops belonging to the same geological formations. [ABSTRACT FROM AUTHOR]

This study was focused on the historical evolution of the waste management policy carried out by the Spanish industry devoted to titanium dioxide pigments manufacturing for minimising its environmental impact. This challenge was achieved by modifying the original chemical process and converting the originally dissolved sulphate and sulphuric acid present in the final streams of the factory into sulphate minerals (melanterite FeSO4·7H2O, szomolnokite FeSO4·H2O, and gypsum CaSO4·2H2O). These by-products were physicochemically, mineralogically and radiologically characterised in order to gain basic information for its subsequent commercial use. Some of the uses summarised in this study for both ferrous sulphates are as a supplier of iron to prevent chlorosis, animal food, manufacture of cement (to reduce Cr VI), primary flocculants for ferrous sulphates, magnetite nanoparticle and nano-Fe2O3 formation, production of magnetite concentrate, remediation of polluted soils with metals, and treatment of wastewaters. Red gypsum was analysed as a substitute for natural gypsum in the manufacture of cement, construction materials, inhibitor in soil erosion, and the immobilisation of heavy metals in agricultural soils and carbonation processes. [ABSTRACT FROM AUTHOR]

Glaucony is a significant green marine facies in the northwestern passive margin of the Guadalquivir Basin (Spain), where glauconite formed authigenically on a sediment-starved continental shelf, with fecal pellets and benthic foraminiferal tests being the main glauconitized substrates. Results from a study using XRD, TGA-DSC, SEM-EDS, and EPMA have revealed that glauconite is remarkably heterogeneous in mineral composition and chemical maturity, even in a single grain, reflecting a complex interaction of micro-environmental factors, substrate influences and post-depositional alterations. In its early stage, the glauconitization process is consistent with the slow precipitation of a Fe-rich smectite phase, most likely intergrade between nontronite and Fe-montmorillonite end-members, which evolved to a regularly interstratified glauconite-smectite (Gl/S). The Fe-smectite-to-Gl/S transformation is interpreted as a diffusion-controlled reaction, involving sufficient Fe availability in pore water and the constant diffusive transport of seawater K+ and Mg2+ ions towards the substrate. The pelletal glauconite is actually a highly evolved Gl/S consisting almost totally of mica layers, with 0.74 ± 0.05 apfu of K+ in the interlayer, while the Gl/S occurring as replacements of foraminiferal tests contains a mean of 7% of expandable layers in the walls and 16% in the chamber fillings, due to rate-limited ion diffusion. [ABSTRACT FROM AUTHOR]

In this work, an examination of mining wastes of an albite deposit in south Spain was carried out using X-ray Fluorescence (XRF), X-ray diffraction (XRD), particle size analysis, thermo-dilatometry and Differential Thermal Analysis (DTA) and Thermogravimetric (TG) analysis, followed by the determination of the main ceramic properties. The albite content in two selected samples was high (65–40 wt. %), accompanied by quartz (25–40 wt. %) and other minor minerals identified by XRD, mainly kaolinite, in agreement with the high content of silica and alumina determined by XRF. The content of Na2O was in the range 5.44–3.09 wt. %, being associated with albite. The iron content was very low (<0.75 wt. %). The kaolinite content in the waste was estimated from ~8 to 32 wt. %. The particle size analysis indicated values of 11–31 wt. % of particles <63 µm. The ceramic properties of fired samples (1000–1350 °C) showed progressive shrinkage by the thermal effect, with water absorption and open porosity almost at zero at 1200–1250 °C. At 1200 °C, the bulk density reached a maximum value of 2.38 g/cm3. An abrupt change in the phase evolution by XRD was found from 1150 to 1200 °C, with the disappearance of albite by melting in accordance with the predictions of the phase diagram SiO2-Al2O3-Na2O and the system albite-quartz. These fired materials contained as main crystalline phases quartz and mullite. Quartz was present in the raw samples and mullite was formed by decomposition of kaolinite. The observation of mullite forming needle-shape crystals was revealed by Scanning Electron Microscopy (SEM). The formation of fully densified and vitrified mullite materials by firing treatments was demonstrated. [ABSTRACT FROM AUTHOR]

The elemental content—mainly trace elements—of samples from two boreholes (PLN, CM) with evidence of tsunamiites, located in the Doñana National Park (SW Spain), were studied. The geochemical variations of the REE, LILE, HFSE, and other elements (Al, Ti, S, Na, Br, Sc, Co, Cr) were interpreted according to the mineralogy present in the samples. The results obtained show the geochemical complexity of the estuarine paleoenvironments, in this case with the existence of three Holocene-age tsunamigenic deposits (around 4.25, 3.56 and 2.2–2 kyr BP). The statistical analysis of the samples' geochemistry, by means of linear correlation and factor analysis, made it possible to differentiate two associations. The first is representative of an inherited mineralogy (REE-Y-Rb-Sr-Cs-Th-U-Hf-Al-Ti-Co-Cr-Sc); the second includes elements (Br-Na) linked to mineral formation under evaporite conditions (halite). The trace element geochemistry of sediments thus becomes an excellent tool to identify tsunamiites in the studied zone, especially those elements that are clear proxies for marine incursions (Na, Br, Sr) and high energy events (Hf, Ti). The parent area of the provenance of the materials is mainly of felsic composition. [ABSTRACT FROM AUTHOR]

We have studied damage zones of two active faults, Baza and Padul faults in Guadix-Baza and Granada basins, respectively, in South Spain. Mineral and microstructural characterization by X-ray diffraction and field emission electron microscopy studies have been combined with structural fieldwork and in situ measurements of rock properties (permeability and Young's modulus) to find out the relation between deformation behavior, mineral processes, and changes in the soft rock and sediment properties produced by fluid flow during seismic cycles. Our results show that microsealing produced by precipitation of dolomite and aragonite along fractures in the damage zone of Baza Fault reduces the permeability and increases the Young's modulus. In addition, deformation bands formed in sediments richer in detrital silicates involved cataclasis as deformation mechanism, which hamper permeability of the sediments. In the Granada Basin, the calcarenitic rocks rich in calcite and clays in the damage zone of faults associated to the Padul Fault are characterized by the presence of stylolites without any carbonate cement. On the other hand, marly lithofacies affected by faults are characterized by the presence of disaggregation bands that involve cracking and granular flow, as well as clay smear. The presence of stylolites and deformation bands in these rocks reduces permeability. [ABSTRACT FROM AUTHOR]

The Oiola archeological site, located in the mining complex of La Arboleda (Biscay, North Spain) was an important iron smelting center from the Roman Period to the Middle Ages and even in more current times (19th–20th centuries). Tap-slags and some plano-convex slags were identified as smelting slags. Samples were analyzed by optical microscopy, X-ray powder diffraction, scanning electron microscopy coupled with electron-dispersive spectroscopy and Raman microspectroscopy to perform a mineralogical and textural characterization. Additionally, thermogravimetric and thermodiffraction analyses were carried out to determine furnace operating temperatures. The mineral assemblage reflects furnace temperatures and cooling rates and the addition of quartz as the main flux to decrease the melting temperature of the iron ore. The comparison of slags from the Roman Period and the Middle Age reveals changes in the pyrometallurgical process through time. [ABSTRACT FROM AUTHOR]

The Messinian microbialites of the Terminal Carbonate Complex (TCC) from the Neogene basins of southeastern Spain show both diversified morphologies and an excellent preservation of primary microbial microstructures. Their stratigraphic architecture, fabric (micro-, meso-, and macro-fabric), and mineralogical composition were investigated in eight localities from three sedimentary basins of southeastern Spain: The Sorbas and Bajo Segura basins and the Agua Amarga depression. Two recurrent microbialite associations were distinguished. Laterally linked low relief stromatolites predominated in Microbialite Association 1 (MA1), which probably formed in low energy lagoons or lakes with fluctuating normal marine to hypersaline water. The microfabrics of MA1 reflected the predominance of microbially induced/influenced precipitation of carbonates and locally (Ca)-Mg-Al silicates. Microbialite Association 2 (MA2) developed in high energy wave and tidal influenced foreshore to shoreface, in normal marine to hypersaline water. High-relief buildups surrounded by mobile sediment (e.g., ooids or pellets) dominated in this environment. MA2 microbialites showed a significant proportion of thrombolitic mesofabric. Grain-rich microfabrics indicated that trapping and binding played a significant role in their accretion, together with microbially induced/influenced carbonate precipitation. The stratigraphic distribution of MA1 and MA2 was strongly influenced by water level changes, the morphology and nature of the substratum, and exposure to waves. MA1 favorably developed in protected areas during third to fourth order early transgression and regression phases. MA2 mostly formed during the late transgressions and early regressions in high energy coastal areas, often corresponding to fossil coral reefs. Platform scale syn-sedimentary gypsum deformation and dissolution enhanced microbial carbonate production, microbialites being thicker and more extended in zones of maximum deformation/dissolution. Microbial microstructures (e.g., microbial peloids) and microfossils were preserved in the microbialites. Dolomite microspheres and filaments showed many morphological similarities with some of the cyanobacteria observed in modern open marine and hypersaline microbialites. Dolomite potentially replaced a metastable carbonate phase during early diagenesis, possibly in close relationship with extracellular polymeric substances (EPS) degradation. Double-layered microspheres locally showed an inner coating made of (Ca)-Mg-Al silicates and carbonates. This mineral coating could have formed around coccoid cyanobacteria and indicated an elevated pH in the upper part of the microbial mats and a potential dissolution of diatoms as a source of silica. Massive primary dolomite production in TCC microbialites may have resulted from enhanced sulfate reduction possibly linked to the dissolving gypsum that would have provided large amounts of sulfate-rich brines to microbial mats. Our results open new perspectives for the interpretation of ancient microbialites associated with major evaporite deposits, from microbe to carbonate platform scales. [ABSTRACT FROM AUTHOR]

Coarse comminution test-work and modeling are powerful tools in the design and optimization of mineral processing plants and provide information on energy consumption. Additional information on mineral liberation characteristics can be used for assessing the potential of pre-concentration stages or screens in the plant design. In ores of high-value metals (e.g., Ta, W), standard techniques—such as the mineralogical quantification of grain mounts by quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) or chemical analysis by X-ray fluorescence (XRF) can be challenging, due to the low relative abundance of such valuable minerals. The cost of QEMSCAN is also a limiting factor, especially considering the large number of samples required for the optimization of coarse comminution. In this study, we present an extended analytical protocol to a well-established mechanical test of interparticle breakage to improve the assessment of coarse mineral liberation characteristics. The liberation of ore minerals is a function of the rock texture and the difference in size and mechanical properties of the valuable minerals relative to gangue minerals and they may fraction in certain grain sizes if they behave differently during comminution. By analyzing the bulk-chemistry of the different grain size fractions produced after compressional testing, and by generating element by size diagrams, it is possible to understand the liberation characteristics of an ore. We show, based on a case study performed on a tantalum ore deposit, that element distribution can be used to study the influence of mechanical parameters on mineral liberation. This information can direct further mineralogical investigation and test work. [ABSTRACT FROM AUTHOR]

The present study deals with a particular clastic rock from the Montjuïc hill exploited since Roman times in Barcino (present-day Barcelona (NE Spain)). Polarized and cathodoluminescence microscopies have been used to describe the main petrographic features of Montjuïc sandstones. Several characteristic provenance markers have been identified; among them the most specifically restricted to Montjuïc sandstone are the K-feldspar clasts with authigenic overgrowths. A petrographic survey oriented to the detection of such markers has been fruitfully applied to sculptures, architectural elements, mosaics, and pottery. The petrographic approach has demonstrated that some Roman heritage materials had been erroneously assigned to Montjuïc sandstone and the revision of all the pieces macroscopically assigned to this provenance is advised. The use of Montjuïc sandstone in Roman tesserae has been reported for the first time with interesting implications on previously unreported evidence of Roman extraction at the bottom part of the Montjuïc cliff. Finally, Montjuïc crushed sandstone used as pottery temper has been also reported in the productions of a medieval (12–13th century) workshop in Barcelona. This encourages the study of the distribution of pottery with this particular temper. [ABSTRACT FROM AUTHOR]

The present article evaluated the mineralogical composition of 85 mortar samples from some emblematic monuments of Ávila city (Spain), which were collected during the restoration of the monuments. The aim of this article is to try to extract the relationship between the composition and the origin of the raw materials, as well as to identify possible alterations in the samples. The study of the samples was carried out using visual and petrographic techniques such as stereoscopic microscope, XRD, and SEM/EDX analysis. The main components of the mortars were calcite, feldspar and quartz, although small amounts of phyllosilicates were also identified. The minerals of the mortars came from the surroundings of the city, and some of the samples presented evident alteration of the original materials due to humidity, salt concentration, and biological weathering, possibly inducted by unfortunate effects of the restoration. Finally, a study of the salts present in some mortars showed that most samples display contamination of soluble salts such as halite, thenardite, hexaedrite, and carnalite. This investigation offers fresh insight into historic building activity and related techniques, and should provide knowledge useful for restoration and conservation processes. [ABSTRACT FROM AUTHOR]

This work presents an integral methodological approach to assess the environmental potential hazards posed by metals and metalloids hosted by spolic technosols derived from old tailings from a mining operation for galena (PbS, with high Ag contents)-sphalerite (ZnS, with a varied cohort of trace elements contents) in central Spain. We studied the total and soluble concentrations and spatial distribution of Pb, Zn, Cd, As, and Fe and the mineralogy of these soils, as well as an ecotoxicological evaluation by means of bioassays. The indices assessing soil contamination such as pollution load index (PI) and natural mobility index (NMI) have been calculated. Furthermore, the phytotoxic effect of the soil samples has been determined and a chronic sediment toxicity test using the benthic ostracod Heterocypris incongruens was applied. The geochemical study of 33 spolic technosols samples indicates large to extremely large metal and metalloid total contents: up to 48,600 mg kg−1 Pb, 34,000 mg kg−1 Zn, 500 mg kg−1 Cd, and 1000 mg kg−1 As. Given that sphalerite is usually the most important host mineral for cadmium in hydrothermal mineral deposits, there is a high correlation (R = 0.75) between this element and Zn. On the other hand, despite being two metallogenically intertwined elements in ore deposits, Pb and Zn show a less significant relationship, which can be attributed both to heterogeneities in the mineralogical composition of the veins, and to the complex history of the mineral concentration process: In the older process, the interest was only for Pb, meanwhile in the late period, the interest was focused in Zn. The Phytotoxkit® bioassay showed that soils with high PTEs presented very high toxicity, particularly the inhibition germination is related to Pb, As, and Cd content and root inhibition with Pb content. Both indexes were correlated with pH and electrical conductivity; samples with lower pH and higher soluble salt content are those with higher seed germination inhibition and root growth inhibition. On the other hand, the Ostracodtoxkit® bioassay showed very high sensitivity, with 100% mortality. The applied bioassays confirmed the soil toxicity and it is highly recommended to complement the results from environmental chemistry with results from bioassays, in order to provide a more complete and relevant information on the bioavailability of contaminants and to characterize the risk of contaminated areas. [ABSTRACT FROM AUTHOR]

We report the first results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of zoned laurite (RuS2)-erlichmanite (OS2) in mantle-hosted chromitites. These platinum-group minerals form isolated inclusions (<50 µm across) within larger crystals of unaltered chromite form the Ojén ultramafic massif (southern Spain). High-magnification electron microscopy (HMEM), high angle-annular dark field (HAADF) and precession electron diffraction (PED) data revealed that microscale normal zoning in laurite consisting of Os-poor core and Os-rich rims observed by conventional micro-analytical techniques like field emission scanning electron microscope and electron microprobe analysis (FE-SEM and EPMA) exist at the nanoscale approach in single laurite crystals. At the nanoscale, Os poor cores consist of relatively homogenous pure laurite (RuS2) lacking defects in the crystal lattice, whereas the Os-richer rim consists of homogenous laurite matrix hosting fringes (10–20 nm thickness) of almost pure erlichmanite (OsS2). Core-to-rim microscale zoning in laurite reflects a nonequilibrium during laurite crystal growth, which hampered the intra-crystalline diffusion of Os. The origin of zoning in laurite is related to the formation of the chromitites in the Earth's upper mantle but fast cooling of the chromite-laurite magmatic system associated to fast exhumation of the rocks would prevent the effective dissolution of Os in the laurite even at high temperatures (~1200 °C), allowing the formation/preservation of nanoscale domains of erlichmanite in laurite. Our observation highlights for the first time the importance of nanoscale studies for a better understanding of the genesis of platinum-group minerals in magmatic ore-forming systems. [ABSTRACT FROM AUTHOR]

Manganese oxides are widespread in soils and natural waters, and their capacity to adsorb different trace metals such as Co, Ni, or Zn is well known. In this study, we aimed to compare the extent of trace metal coprecipitation in different Mn oxides formed during Mn(II) oxidation in highly concentrated, metal-rich mine waters. For this purpose, mine water samples collected from the deepest part of several acidic pit lakes in Spain (pH 2.7–4.2), with very high concentration of manganese (358–892 mg/L Mn) and trace metals (e.g., 795–10,394 µg/L Ni, 678–11,081 µg/L Co, 259–624 mg/L Zn), were neutralized to pH 8.0 in the laboratory and later used for Mn(II) oxidation experiments. These waters were subsequently allowed to oxidize at room temperature and pH = 8.5–9.0 over several weeks until Mn(II) was totally oxidized and a dense layer of manganese precipitates had been formed. These solids were characterized by different techniques for investigating the mineral phases formed and the amount of coprecipitated trace metals. All Mn oxides were fine-grained and poorly crystalline. Evidence from X-Ray Diffraction (XRD) and Scanning Electron Microscopy coupled to Energy Dispersive X-Ray Spectroscopy (SEM–EDX) suggests the formation of different manganese oxides with varying oxidation state ranging from Mn(III) (e.g., manganite) and Mn(III/IV) (e.g., birnessite, todorokite) to Mn(IV) (e.g., asbolane). Whole-precipitate analyses by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES), and/or Atomic Absorption Spectrometry (AAS), provided important concentrations of trace metals in birnessite (e.g., up to 1424 ppm Co, 814 ppm Ni, and 2713 ppm Zn), while Co and Ni concentrations at weight percent units were detected in asbolane by SEM-EDX. This trace metal retention capacity is lower than that observed in natural Mn oxides (e.g., birnessite) formed in the water column in a circum-neutral pit lake (pH 7.0–8.0), or in desautelsite obtained in previous neutralization experiments (pH 9.0–10.0). However, given the very high amount of Mn sorbent material formed in the solutions (2.8–4.6 g/L Mn oxide), the formation of these Mn(III/IV) oxides invariably led to the virtually total removal of Co, Ni, and Zn from the aqueous phase. We evaluate these data in the context of mine water pollution treatment and recovery of critical metals. [ABSTRACT FROM AUTHOR]