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The new tourmaline supergroup mineral dutrowite, Na(Fe2.52+Ti0.5)Al6(Si6O18)(BO3)3(OH)3O, has been discovered in an outcrop of a Permian metarhyolite near the hamlet of Fornovolasco, Apuan Alps, Tuscany, Italy. It occurs as chemically homogeneous domains, up to 0.5 mm, brown in colour, with a light-brown streak and a vitreous lustre, within anhedral to subhedral prismatic crystals, up to 1 mm in size, closely associated with Fe-rich oxy-dravite. Dutrowite is trigonal, space group R3m, with a=15.9864(8), c=7.2187(4) Å, V=1597.68(18) Å3, and Z=3. The crystal structure was refined to R1=0.0257 for 1095 unique reflections with Fo>4σ (Fo) and 94 refined parameters. Electron microprobe analysis, coupled with Mössbauer spectroscopy, resulted in the empirical structural formula X(Na0.81Ca0.20K0.01)Σ1.02 Y(Fe1.252+Mg0.76Ti0.56Al0.42)Σ3.00 Z(Al4.71Fe0.273+V0.023+Mg0.82Fe0.182+)Σ6.00 T[(Si5.82Al0.18)Σ6.00O18] (BO3)3O(3)(OH)3O(1)[O0.59(OH)0.41]Σ1.00, which was recast in the empirical ordered formula, required for classification purposes: X(Na0.81Ca0.20K0.01)Σ1.02 Y(Fe1.432+Mg1.00Ti0.56)Σ3.00 Z(Al5.13Fe0.273+V0.023+Mg0.58)Σ6.00 T[(Si5.82Al0.18)Σ6.00O18] (BO3)3V(OH)3 W[O0.59(OH)0.41]Σ1.00. Dutrowite is an oxy-species belonging to the alkali group of the tourmaline supergroup. Titanium is hosted in octahedral coordination, and its incorporation is probably due to the substitution 2Al3+ = Ti4+ + (Fe,Mg)2+. Its occurrence seems to be related to late-stage high-T/low-P replacement of “biotite” during the late-magmatic/hydrothermal evolution of the Permian metarhyolite.

To face the growing demand for raw materials, the discovery of new mineral deposits is essential for the future. Geophysical methods, and in particular electrical and electromagnetic tools, have an important role in mineral exploration. Recently, new technological developments made possible targetting deeper ore bodies and large areas with logistical challenges. We use the Deep Electrical Resistivity Tomography (DERT) method to investigate its application in mineral exploration. In particular, we use the Fullwaver technology developed by IRIS Instruments to study the full 3D resistive structure of the Calamita distal Fe-skarn deposit, Elba Island, Italy. This innovative hardware allows a full 3D deployment of autonomous and cable-less receivers and contrasts with traditional resistivity methods by its easy set-up and applicability in difficult contexts.In November 2022, a 3D DERT survey has been carried out to investigate the Calamita deposit, consisting of massive magnetite-hematite ore bodies hosted in marbles overlaying micaschists of Tuscan Units. Skarn mineralogy/geochemistry and fluid inclusion characteristics suggest a magmatic source for the mineralizing fluids. 148 current injections have been performed on 48 receivers over an area of 2km² with the aim to reach exploration depths ranging from 600 m to 700 m. Geophysical data were combined with a high-resolution 3D Digital Elevation Model acquired by standard and thermal drone imagery.The 3D inverted resistivity and induced polarization models match with the surface geology and shallow exploration drill hole data and highlight the architecture of Calamita deposit. Strong resistivity contrasts reveal the presence of sub-vertical conductive and chargeable pipes connecting the different skarn bodies at depth, interpreted to represent the paleo-hydrothermal upflow zones. The pipes point towards the inferred cupola of a magmatic intrusion that potentially triggered the formation of the ore deposit. High chargeability anomalies suggest the presence of hidden massive ore bodies and disseminated mineralisation on the flanks of the system.DERT has the potential to investigate and explore mineral deposits in full 3D, with high sensitivity, and in logistically complex settings.

Muon radiography, or muography, is a non-invasive technique allowing imaging of the interior of large structures (target) thanks to the study of the absorption of atmospheric muons in materials. The muons absorption effect depends not only on the thickness, but also on the density of the target. Careful comparisons of the muographic results with simulations taking into account a precise description of the target's geometry, allow estimating the two dimensional distribution of the average density of the structure under study as seen from the measurement point of view. In this presentation an application in the geological field for the research and localization of low density anomalies attributable to cavities inside an abandoned mine will be shown. The aim of the study is to identify and locate areas that might be responsible for the production of anomalous concentrations of radon gas inside underground mining sites used for touristic itineraries. Radon is a natural radioactive gas that exposes tourists to ionizing radiation. Radon decay products are the second cause of lung cancer after smoking. It is important therefore to understand where the radon gas comes from before moving through the different galleries. The case study is the Temperino mine near Campiglia Marittima (LI-Italy). Here, the mining activity ended in 1980 and it was primarily focused on the extraction of copper, silver lead and zinc minerals. The area to be explored with muon radiography is part of an area dating back to the Etruscan period that has not yet been completely mapped and that is located above the tourist path of the Temperino mine at a depth of about 40 m from the surface of the hill above. Any nearby cavity could represent a prime conduit that brings radon gas into the tourist trail. The identification and localization in space of these ancient excavations is also interesting from a geological and archaeological point of view. The detector employed for the muographic measurements reported in this presentation, designed in Florence by the National Institute of Nuclear Physics (INFN) and the Department of Physics and Astronomy, is called MIMA (Muon Imaging for Mining and Archaeology) and has cubic shape and approximate dimensions of (50x50x50) cm3. MIMA is equipped with a special protective aluminum mechanism that allows its altazimuth orientation.

Transmission-based muography (TM) is an innovative imaging technique based on the measurement and analysis of the cosmic ray muons flux attenuation within the target under investigation. This technique allows imaging inner-body density differences and has successfully been applied in a wide range of research fields: geology, archaeology, engineering geology and civil engineering. The aim of this study is to show the reliability of TM as an innovative, noninvasive geophysical method for ore body prospecting and other mining related studies. The measurements were carried out at the Temperino mine in the San Silvestro Archaeological and Mining Park (Campiglia Marittima, Italy), where several magmatic and metasomatic geological units are embodied. Among them, a Cu–Fe–Zn–Pb(–Ag) sulfide skarn complex primarily composed by hedenbergite and ilvaite minerals. Using the acquired muon imaging data obtained with the MIMA (Muon Imaging for Mining and Archaeology) detector prototype (cubic detector of 0.5 × 0.5 × 0.5 m3), the presence of a high-density vein inside the skarn body within the rock volume above the muon detector was identified, localized and interpreted. Applying a back-projection algorithm to the obtained 2D transmission map made it possible to estimate and visualize as point cloud data, in a 2D or 3D environment, the identified high-density body and its relative distance from the detector. The results of this study highlight the potential of muography as a support tool to other geophysical methods in the field of mining exploration.

Geothermal systems in terrains affected by polyphase deformation have reservoirs with a 3D geometry that is always difficult to predict. In this paper we describe a fossil exhumed geothermal system exposed in eastern Elba Island that developed in a polyphase folded and faulted setting, which can help us to understand how geothermal fluids circulate in geological bodies with inherited structures. Geothermal circulation at Elba allowed the deposition of Fe-ore deposits (haematite/magnetite and pyrite) and altered rock volumes, which represent tracers of the palaeo-fluid flow. Normal and oblique-slip faults dissected a polyphase folded metasiliciclastic succession and produced a secondary permeability in the range of 5 × 10−13 to 5 × 10−16 m2. From the permeable fault zones acting as feeder conduits, geothermal fluids permeated the hydraulically connected metasiliciclastic rock bodies previously deformed by two generations of folds. Geothermal fluids followed the already defined geometry, thus giving rise to apparent folded mineralized levels. Fluid migration into the metasiliciclastic rocks was possible due to their chemical aggression, which favoured the dissolution and reprecipitation of quartz, and Fe-oxide and sulphide deposition. Renewed fluids maintained their chemical properties (pH value and temperature, mostly). This conclusion provides inputs for reconstructing geothermal conceptual models and evaluating the geothermal potentiality of exploitable areas developing in similar geological settings.

Magnesio-lucchesiite, ideally CaMg3Al6(Si6O18)(BO3)3(OH)3O, is a new mineral species of the tourmaline supergroup. The holotype material was discovered within a lamprophyre dike that cross-cuts tourmaline-rich metapelites within the exocontact of the O’Grady Batholith, Northwest Territories (Canada). Two additional samples were found at San Piero in Campo, Elba Island, Tuscany (Italy) in hydrothermal veins embedded in meta-serpentinites within the contact aureole of the Monte Capanne intrusion. The studied crystals of magnesio-lucchesiite are black in a hand sample with vitreous luster, conchoidal fracture, an estimated hardness of 7–8, and a calculated density of 3.168 (Canada) and 3.175 g/cm3 (Italy). In plane-polarized light, magnesio-lucchesiite is pleochroic (O = dark brown, E = colorless) and uniaxial (–); its refractive index values are nω = 1.668(3) and nε = 1.644(3) (Canada), and nω = 1.665(5) and nε = 1.645(5) (Italy). Magnesio-lucchesiite is trigonal, space group R3m, Z = 3, with a = 15.9910(3) Å, c = 7.2224(2) Å, V = 1599.42(7) Å3 (Canada) and with a = 15.9270(10) Å, c = 7.1270(5) Å, V = 1565.7(2) Å3 (Italy, sample 1). The crystal structure of magnesio-lucchesiite was refined to R1 = 3.06% using 2953 reflections with Fo > 4σ(Fo) (Canadian sample; 1.96% / 1225 for the Italian sample) The Canadian (holotype) sample has the ordered empirical formula X(Ca0.60Na0.39K0.01)Σ1.00Y(Mg2.02Fe0.622+Fe0.093+Ti0.25V0.01Cr0.01)Σ3.00Z(Al5.31Fe0.693+)Σ6.00[T(Si5.98Al0.02)Σ6.00O18](BO3)3V[(OH)2.59O0.41]Σ3.00W(O0.78F0.22)Σ1.00. The Italian (co-type) material shows a wider chemical variability, with two different samples from the same locality having ordered chemical formulas: X(Ca0.88Na0.12)Σ1.00Y(Mg1.45Fe0.402+Al0.79Fe0.363+)Σ3.00ZAl6[T(Si5.05Al0.95)Σ6.00O18](BO3)3V[(OH)2.90O0.10]Σ3.00W(O0.98F0.02)Σ1.00 (sample 1) and X(Ca0.71Na0.21☐0.08)Σ1.00Y(Mg2.49Fe0.412+Ti0.10)Σ3.00Z(Al5.44Fe0.463+Mg0.09V0.01)Σ6.00[T(Si5.87Al0.13)Σ6.00O18](BO3)3V(OH)3W[O0.61(OH)0.39]Σ1.00 (sample 2). Magnesio-lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. It is related to lucchesiite by the homovalent substitution YFe ↔ YMg, and to feruvite by the homovalent and heterovalent substitutions YFe ↔ YMg and ZAl3+ + WO2– ↔ ZMg2+ + W(OH)1–. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2019-025). Occurrences of magnesio-lucchesiite show that its presence is not restricted to replacement of mafic minerals only; it may also form in metacarbonate rocks by fluctuations of F and Al during crystallization of common uvitic tourmaline. High miscibility with other tourmaline end-members indicates the large petrogenetic potential of magnesio-lucchesiite in Mg, Al-rich calc-silicate rocks, as well as contact-metamorphic and metasomatic rocks.

In the last twenty years several applications of muography (or muon radiography) technique have been carried out for geological purposes. Among them, particular attention was given to underground ore bodies prospections. For thousands of years humans have been searching new methods to understand where to find underground ore bodies and how to localize it in the three-dimensional space. Often, economically useful minerals are bounded to other minerals, forming rocks of high density values that are hosted, usually, in rocks with lower density values. In literature gravimetry and magnetometry represent the most employed geophysical methods for imaging and detection of mineral-rich ore bodies. To verify the feasibility of muography as a non-invasive geophysical prospecting technique, our research group, composed by subnuclear physicists and geologists, carried out some underground measurement campaigns at the Temperino Mine (Campiglia Marittima, Italy). Here it is located a pliocenic metasomatic ore deposit, a Cu-Pb-Zn-Fe skarn complex composed by johannsenite, quartz, hedenbergite, ilvaite and accessory primary sulphides (chalcopyrite, galena, sphalerite, pyrite). These metalliferous bodies of skarn have tabular geometries with sub-vertical orientations. Currently, the first level of Temperino Mine has been equipped as a touristic path and belong to the Archeological Mining Park of San Silvestro. Along this gallery, carved both into the metamorphic and non-metamorphic rocks, it’s been installed the MIMA muon tracker (Muon Imaging for Mining and Archaeology), a small and rugged prototype (0.5 x 0.5. x 0.5 m3) developed by the physicists of the National Institute of Nuclear Physics (INFN), unit of Florence, and the Department of Physics and Astronomy of Florence. MIMA detector is able to measure the underground muon flux inside the mine gallery. Matching the simulated muon transmission rate with the experimentally measured one it’s possible to obtain a two dimensional average density angular map of the observed target. Also, using algorithms based on triangulation and back-projection techniques is possible to obtain a reconstruction of the 3D volume of high-density areas (and also low-density areas) inside the studied volume. The latter is the volume that falls within the detector’s acceptance. The aim of this research is to obtain a georeferenced 3D model of the Cu-Pb-Zn ore bodies hosted in the rocks between the top of the mine gallery and the surface of the Temperino Mine area. We want to confirm that muography technique could become a suitable and reliable tool for the mining prospections field.

Muon radiography is a non-invasive imaging technique that allows, through cosmic muon absorption measurements, to obtain two-dimensional and three-dimensional images of the internal structure and average density of very large material volumes. Its applications currently range from many fields: geological, archaeological, industrial, civil and nuclear safety. The technique of muon radiography being non-invasive represents a valid alternative to the common survey techniques in these fields of applications. In this presentation I will show some results obtained with this technique in the geological field for the three-dimensional imaging of cavities and tunnels within the Temperino mine located in the San Silvestro Archaeological Mining Park near Campiglia Marittima in the province of Livorno in Tuscany (Italy). The Temperino mine has ancient etruscan origins and still has areas which are not mapped in the available documentation. The mining activities of the area have always been focused on the search for a hard and dense rock called skarn in which there are metallic sulphides of Cu, Ag, Pb, Zn, Fe. Currently only one of the most superficial levels of the mine is accessible to the public through a tourist route. The muographic measurements on this site therefore have a dual objective, on the one hand to test the imaging technique on known cavities, on the other hand to discover new cavities whose knowledge could be useful, for example, for important assessments concerning historical and safety aspect of the site. All measurements were carried out with the muon detector MIMA (Muon Imaging for Mining and Archaeology) designed and built at the National Institute of Nuclear Physics (INFN) in Florence. MIMA is a cubic tracker of approximate dimensions (50x50x50) cm3and is equipped with a special protective aluminum mechanism that allows its altazimuth orientation. Various measurements were made within the tourist gallery located about 50 m below ground level for the observation of areas above. By comparing muon transmission measurements with simulations, it was possible to generate two-dimensional angular maps of average density of material observed in every direction within the detector's acceptance. The presence of some low-density anomalies associated with the presence of cavities was thus identified. Through algorithms based on the triangulation technique and on a track backprojection technique, the cavities were located in three-dimensions. For the known cavities it was also possible to compare the reconstructed development with their real profile that was acquired with the laser scanner technique, finding a good compatibility (average deviation below 1 m for a 7 m high cavity located 20 m above the detector’s installation location). These measurements therefore validate the muon radiography technique in the geological field for the search for cavities inside mines. The technique can be applied to identify not only low-density anomalies or voids, but also high-density areas: the application of the muon imaging technique for the identification of dense ore bodies is being studied at Temperino mine.

The world-class San Rafael tin (-copper) deposit (central Andean tin belt, southeast Peru) is an exceptionally large and rich (>1 million metric tons Sn; grades typically >2% Sn) cassiterite-bearing hydrothermal vein system hosted by a late Oligocene (ca. 24 Ma) peraluminous K-feldspar-megacrystic granitic complex and surrounding Ordovician shales affected by deformation and low-grade metamorphism. The mineralization consists of NW-trending, quartz-cassiterite-sulfide veins and fault-controlled breccia bodies (>1.4 km in vertical and horizontal extension). They show volumetrically important tourmaline alteration that principally formed prior to the main ore stage, similar to other granite-related Sn deposits worldwide. We present here a detailed textural and geochemical study of tourmaline, aiming to trace fluid evolution of the San Rafael magmatic-hydrothermal system that led to the deposition of tin mineralization. Based on previous works and new petrographic observations, three main generations of tourmaline of both magmatic and hydrothermal origin were distinguished and were analyzed in situ for their major, minor, and trace element composition by electron microprobe analyzer and laser ablation-inductively coupled plasma-mass spectrometry, as well as for their bulk Sr, Nd, and Pb isotope compositions by multicollector-inductively coupled plasma-mass spectrometry. A first late-magmatic tourmaline generation (Tur 1) occurs in peraluminous granitic rocks as nodules and disseminations, which do not show evidence of alteration. This early Tur 1 is texturally and compositionally homogeneous; it has a dravitic composition, with Fe/(Fe + Mg) = 0.36 to 0.52, close to the schorl-dravite limit, and relatively high contents (10s to 100s ppm) of Li, K, Mn, light rare earth elements, and Zn. The second generation (Tur 2)—the most important volumetrically—is pre-ore, high-temperature (>500°C), hydrothermal tourmaline occurring as phenocryst replacement (Tur 2a) and open-space fillings in veins and breccias (Tur 2b) and microbreccias (Tur 2c) emplaced in the host granites and shales. Pre-ore Tur 2 typically shows oscillatory zoning, possibly reflecting rapid changes in the hydrothermal system, and has a large compositional range that spans the schorl to dravite fields, with Fe/(Fe + Mg) = 0.02 to 0.83. Trace element contents of Tur 2 are similar to those of Tur 1. Compositional variations within Tur 2 may be explained by the different degree of interaction of the magmatic-hydrothermal fluid with the host rocks (granites and shales), in part because of the effect of replacement versus open-space filling. The third generation is syn-ore hydrothermal tourmaline (Tur 3). It forms microscopic veinlets and overgrowths, partly cutting previous tourmaline generations, and is locally intergrown with cassiterite, chlorite, quartz, and minor pyrrhotite and arsenopyrite from the main ore assemblage. Syn-ore Tur 3 has schorl-foititic compositions, with Fe/(Fe + Mg) = 0.48 to 0.94, that partly differ from those of late-magmatic Tur 1 and pre-ore hydrothermal Tur 2. Relative to Tur 1 and Tur 2, syn-ore Tur 3 has higher contents of Sr and heavy rare earth elements (10s to 100s ppm) and unusually high contents of Sn (up to >1,000 ppm). Existence of these three main tourmaline generations, each having specific textural and compositional characteristics, reflects a boron-rich protracted magmatic-hydrothermal system with repeated episodes of hydrofracturing and fluid-assisted reopening, generating veins and breccias. Most trace elements in the San Rafael tourmaline do not correlate with Fe/(Fe + Mg) ratios, suggesting that their incorporation was likely controlled by the melt/fluid composition and local fluid-rock interactions. The initial radiogenic Sr and Nd isotope compositions of the three aforementioned tourmaline generations (0.7160–0.7276 for 87Sr/86Sr(i) and 0.5119–0.5124 for 143Nd/144Nd(i)) mostly overlap those of the San Rafael granites (87Sr/86Sr(i) = 0.7131–0.7202 and 143Nd/144Nd(i) = 0.5121–0.5122) and support a dominantly magmatic origin of the hydrothermal fluids. These compositions also overlap the initial Nd isotope values of Bolivian tin porphyries. The initial Pb isotope compositions of tourmaline show larger variations, with 206Pb/204Pb(i), 207Pb/204Pb(i), and 208Pb/204Pb(i) ratios mostly falling in the range of 18.6 to 19.3, 15.6 to 16.0, and 38.6 to 39.7, respectively. These compositions partly overlap the initial Pb isotope values of the San Rafael granites (206Pb/204Pb(i) = 18.6–18.8, 207Pb/204Pb(i) = 15.6–15.7, and 208Pb/204Pb(i) = 38.9–39.0) and are also similar to those of other Oligocene to Miocene Sn-W ± Cu-Zn-Pb-Ag deposits in southeast Peru. Rare earth element patterns of tourmaline are characterized, from Tur 1 to Tur 3, by decreasing (Eu/Eu*)N ratios (from 20 to 2) that correlate with increasing Sn contents (from 10s to >1,000 ppm). These variations are interpreted to reflect evolution of the hydrothermal system from reducing toward relatively more oxidizing conditions, still in a low-sulfidation environment, as indicated by the pyrrhotite-arsenopyrite assemblage. The changing textural and compositional features of Tur 1 to Tur 3 reflect the evolution of the San Rafael magmatic-hydrothermal system and support the model of fluid mixing between reduced, Sn-rich magmatic fluids and cooler, oxidizing meteoric waters as the main process that caused cassiterite precipitation.

Distal skarns form by the metasomatic reactions of a host rock induced by far-traveled hydrothermal fluids. Physical and structural characteristics and geochemical patterns of distal Pb Zn skarn bodies were studied at the Petrovitsa deposit in southern Bulgaria. Skarn bodies formed from the interaction of hydrothermal fluids with reactive host lithologies (marble and gneiss). These fluids were transported along sub-vertical feeder structures and lithological contacts. Epidote skarn developed in gneiss protolith, and pyroxene (johannsenite) skarn developed in marble. Detailed geological mapping, complimented by measurements of the internal structure of the skarn body using pyroxene growth versors, quantifies the propagation direction of the skarn body: 1) away from the major local fluid conduit (feeder structure), and 2) away from lithological contacts between aluminosilicate rock and marble. Such growth suggests that fluid flow was generally orthogonal to the skarn front propagation direction in the pyroxene skarn. Textural, mineralogical and geochemical data from skarn samples reveal multiple growth generations of major skarn calc-silicates epidote and pyroxene. The epidote skarn is characterized by limited spatial distribution and fine-grained epidote/clinozoisite growth associated with massive replacement and sulfide mineralization. The pyroxene skarn consists of acicular clinopyroxene crystals which form spheroidal aggregates with discrete growth banding. These bands are the physical representation of the cyclic fluid pulses which resulted in rhythmic skarn growth marked by geochemical banding. In situ geochemical analyses in the epidote skarn reveal early Al-rich epidote overprinted by Fe-rich epidote associated with higher Mn and Sr contents and irregular compositional banding. Clinopyroxene (Jo60–95) shows general increase in Na, Al, Mn, and REE + Y with distance from the feeder structure and lithologic contacts. These elements correlate with the distance traveled by the hydrothermal fluid from the feeder to the site of skarnification, which we define using a proxy based on the Al content of pyroxene crystals. This reflects an increasing degree of fluid “contamination” by interaction with the aluminosilicate host rocks and functions as a proxy for fluid transport distance. The spatial distribution of trace-elements in pyroxene on an outcrop scale is indicative of discrete pulses of hydrothermal fluid resulting in precipitation of skarn calc-silicates along the increasingly tortuous fluid pathway between the feeder structure and the skarn front, resulting in both the macro- and micro-scale chemical and textural variability of the skarn body.

A series of tourmaline reference materials are developed for in situ oxygen isotope analysis by secondary ion mass spectrometry (SIMS), which allow study of the tourmaline compositions found in most igneous and metamorphic rocks. The new reference material was applied to measure oxygen isotope composition of tourmaline from metagranite, meta-leucogranite, and whiteschist from the Monte Rosa nappe (Western Alps). The protolith and genesis of whiteschist are highly debated in the literature. Whiteschists occur as 10 to 50 m tube-like bodies within the Permian Monte Rosa granite. They consist of chloritoid, talc, phengite, and quartz, with local kyanite, garnet, tourmaline, and carbonates. Whiteschist tourmaline is characterized by an igneous core and a dravitic overgrowth (XMg > 0.9). The core reveals similar chemical composition and zonation as meta-leucogranitic tourmaline (XMg = 0.25, δ18O = 11.3–11.5‰), proving their common origin. Dravitic overgrowths in whiteschists have lower oxygen isotope compositions (8.9–9.5‰). Tourmaline in metagranite is an intermediate schorl-dravite with XMg of 0.50. Oxygen isotope data reveal homogeneous composition for metagranite and meta-leucogranite tourmalines of 10.4–11.3‰ and 11.0–11.9‰, respectively. Quartz inclusions in both meta-igneous rocks show the same oxygen isotopic composition as the quartz in the matrix (13.6–13.9‰). In whiteschist the oxygen isotope composition of quartz included in tourmaline cores lost their igneous signature, having the same values as quartz in the matrix (11.4–11.7‰). A network of small fractures filled with dravitic tourmaline can be observed in the igneous core and suggested to serve as a connection between included quartz and matrix, and lead to recrystallization of the inclusion. In contrast, the igneous core of the whiteschist tourmaline fully retained its magmatic oxygen isotope signature, indicating oxygen diffusion is extremely slow in tourmaline. Tourmaline included in high-pressure chloritoid shows the characteristic dravitic overgrowth, demonstrating that chloritoid grew after the metasomatism responsible for the whiteschist formation, but continued to grow during the Alpine metamorphism. Our data on tourmaline and quartz show that tourmaline-bearing white-schists originated from the related meta-leucogranites, which were locally altered by late magmatic hydrothermal fluids prior to Alpine high-pressure metamorphism.

The genetic link between plutonic and volcanic realms is a key for understanding timescales of igneous plumbing systems, and precise geochronological records are pivotal in estimating the duration of processes at different levels in such plumbing systems. The Campiglia igneous complex, Tuscany, offers exposures of the full range of emplacement levels (plutonic, subvolcanic, volcanic) of mantle- and crust-derived magmas. Magma emplacement occurred astride the Miocene-Pliocene boundary. New high-precision U-Pb CA-ID-TIMS, zircon geochronological data, coupled with LA-HR-ICP-MS zircon dates for the whole Campiglia system define a short crystallization time span for zircon from the peraluminous granite pluton (~100 ka), intermediate for the shallow-level mafic porphyry (~450 ka), and longer for the rhyolite (~700 ka), at odd with what commonly expected. The oldest ages for the three units are the same, leading to hypothesize the occurrence of a bimodal deep reservoir remaining in melt-present conditions for some 700 ka. In this framework, early-crystallized zircons were cannibalized by younger melt batches that were sequentially extracted from the reservoir.

Italy has never been a lithium (Li) producer, and the potential for “hard rock” deposits is moderate at best. On the other hand, the increasing demand for Li-based rechargeable batteries fostered new interest in this metal, and prompted the quest for alternative resources. The extraction of Li from geothermal brines (“geothermal lithium”) is currently considered in several countries, including, in Europe, France, Germany, and UK (EGEC, 2020).Italy has vast geothermal resources, and there is a potential for “geothermal lithium” as well. A preliminary survey of literature data pointed out several occurrences of fluids with Li contents up to hundreds of mg/L. Among high-enthalpy fluids, we point out those of Cesano, Mofete, and Latera. At Cesano, geothermal fluids contain about 350 mg/L lithium (Calamai et al., 1976). Early studies conducted in the past century (Pauwels et al., 1990) suggested the feasibility of lithium recovery from these fluids. Even higher contents (480 mg/L) occur in the deep reservoir at Mofete (Guglielminetti, 1986), whereas fluids in the shallow and intermediate reservoir in the same field contain 28 to 56 mg/L. Geothermal fluids at Latera have somewhat lower contents (max 13.5 mg/L; Gianelli and Scandiffio, 1989). Several low-enthalpy thermal waters in Emilia-Romagna, Sardinia, Sicily and Tuscany also show significant (> 1 mg/L) Li contents (max 96 mg/L at Salsomaggiore; Boschetti et al., 2011). There are no published Li data for high-enthalpy fluids at Larderello; however, evidence of Li-rich fluids was found in fluid inclusions in hydrothermal minerals (Cathelineau et al., 1994). Moreover, the shallow (ca. 3.5 km) granitoid body underlying the field contains a Li-rich (about 1,000 ppm) biotite (A. Dini, unpublished data); it has been estimated that such rock may contain as much as 500 g Li per cubic meter. ReferencesBoschetti T., et al. - Aquat Geochem (2011) 17:71–108Calamai A., et al. - Proc. U.N. Symp. Development Use Geotherm. Energy, S. Francisco, USA (1976), 305-313Cathelineau M., et al. – Geochim. Cosmochim. Acta (1994) 58: 1083-1099EGEC (European Geothermal Council). https://www.egec.org/time-to-invest-in-clean-geothermal-lithium-made-in-europe/. Accessed December 2, 2020.Gianelli G., Scandiffio G. - Geothermics (1989) 18: 447-463Guglielminetti M. - Geothermics (1986) 15: 781-790Pauwels H., et al. - Proc. 12th New Zealand Geothermal Workshop (1990), 117-123

The 3D reconstruction of magmatic, metasomatic and/or ore bodies plays a major role in understanding the emplacement mechanisms for magmas and hydrothermal fluids in the upper crust.The Gavorrano Intrusive-Hydrothermal Complex (GIHC, Tuscany, Italy) is an excellent case study in which intrusive and hydrothermal rocks, as well as sulphides ore bodies are spatially associated.The evolution of the GIHC starts in the early Pliocene with the sequential emplacement, at the contact between the Paleozoic basement (metapelites) and the overlying Mesozoic limestone-dolostone formations, of a cordierite-biotite monzogranite and a tourmaline microgranite. The monzogranite is highly porphyritic with megacrysts of K-feldspar and phenocrysts of quartz, plagioclase, biotite, and cordierite. The microgranite is characterised by a huge number of euhedral microliths (10-500 µm) of black tourmaline set in a quartz-feldspars groundmass. The small size of the Gavorrano intrusion (ca. 3 x 1 km) and its shallow emplacement level (ca. 5 km) resulted in a thin contact aureole (< 100 m thick) made of phlogopite-olivine marble and biotite-andalusite pelitic hornfels. Isoclinal folds in marble are indicative of dynamic crystallization during contact metamorphism and point out an outward sense of movement of the aureole rocks with respect to the granite intrusion. At the contact with the intrusion, marbles were overprinted by a discontinuous (0.1-10 m thick) layer of vesuvianite-garnet exoskarn. Exoskarn, contact aureole and undisturbed host rocks, were subsequently affected by hydraulic brecciation. The closing stage of the evolution of the complex is characterized by mineralizing fluid circulation, producing widespread chloritization-silicification and decametric pyrite bodies (with adularia, fluorite, and base metal sulfides). Surface and underground mapping integrated by mining reports and drill logs allow us gave way to the reconstruction of the attitude and shape of magmatic and hydrothermal bodies. The NW-SE elongated intrusion is characterised by a pronounced asymmetry: the eastern part is made of sub-horizontal multiple bodies, locally with both roof and bottom contacts exposed; the western part has an overall sub-vertical, west-dipping attitude. Such an asymmetry is shown by each of the two intrusive units and highlighted by second order features: the monzogranite unit reaches its maximum thickness (0.8 km) in the central-western subvertical zone while in the subhorizontal eastern branches is few hundred meters thick, and the subhorizontal microgranite bodies display steep west-dipping offshoots. The GIHC asymmetry is also exhibited by the hydrothermal system: the pyrite orebodies mantle the top and the western flank of the intrusion, with the two main masses displaying, in vertical section, a sigmoidal shape with a steep west-dipping thick portion connecting upper and lower tails gently dipping to the west.The collected data indicate the west side of the GIHC as the focus zone for both magmas and hydrothermal fluids. The overall geometries of the intrusive units and pyrite bodies suggest a sense of movement top-down-to-the-west. This close spatial and shape relationship between intrusive rocks and hydrothermal bodies suggests a common extensional tectono-magmatic regime capable to produce asymmetric crustal traps (dilational structures) for magmas and fluids.

We present a high-resolution in situ study of oxygen and boron isotopes measured in tourmaline from the world-class San Rafael Sn (–Cu) deposit (Central Andean tin belt, Peru) aiming to trace major fluid processes at the magmatic-hydrothermal transition leading to the precipitation of cassiterite. Our results show that late-magmatic and pre-ore hydrothermal tourmaline has similar values of δ 18 O (from 10.6‰ to 14.1‰) and δ 11 B (from −11.5‰ to −6.9‰). The observed δ 18 O and δ 11 B variations are dominantly driven by Rayleigh fractionation, reflecting tourmaline crystallization in a continuously evolving magmatic-hydrothermal system. In contrast, syn-ore hydrothermal tourmaline intergrown with cassiterite has lower δ 18 O values (from 4.9‰ to 10.2‰) and in part higher δ 11 B values (from −9.9‰ to −5.4‰) than late-magmatic and pre-ore hydrothermal tourmaline, indicating important contribution of meteoric groundwater to the hydrothermal system during ore deposition. Quantitative geochemical modeling demonstrates that the δ 18 O- δ 11 B composition of syn-ore tourmaline records variable degrees of mixing of a hot Sn-rich magmatic brine with meteoric waters that partially exchanged with the host rocks. These results provide thus direct in situ isotopic evidence of fluid mixing as a major mechanism triggering cassiterite deposition. Further, this work shows that combined in situ δ 18 O and δ 11 B analyses of tourmaline is a powerful approach for understanding fluid processes in dynamic magmatic-hydrothermal environments.

The origin and evolution of an orebody hosted in metamorphic terrane is a prime topic in economic geology because they have implications on exploration as well as on related potential geo-environmental health hazards. The Alpi Apuane orebodies has long been known; however, their ore genesis and the relationships with the Apenninic age deformation and metamorphism is still a matter of debate. Indeed, they are still an interesting field of research, as proved by the recent discovery of a remarkable Tl anomaly associated to the baryte ± pyrite ± Fe-oxides ores of southern Alpi Apuane, northern Tuscany, Italy [1]. The present work reports a new detailed field and underground geological-structural investigation, performed from cartographic- to microscopic-scale, integrated by available drill-logs data, of one of these Tl-rich orebodies - the Buca della Vena ore.The present study gives new insights on some aspect of the ore-forming events and discusses previous interpretations. According to our investigations, the ore settings were acquired during successive geological events related to an early hydrothermal-magmatic phase, likely of Permian age, and to the more recent Apenninic deformations. We suggest that the proto-ore was produced by hydrothermal activity related to the post-Variscan magmatic cycle (documented by the Permian age “Fornovolasco metarhyolite” Fm [2]), causing ore-formation, tourmalinization and hydrothermal alteration halo in the Cambrian-Lower Ordovician phyllites host-rocks. In our model, the ores were then partially exhumed suffering supergene alteration with development of minor Fe-oxides sedimentary mineralizations during the upper Norian-Hettangian. Finally, the previous hydrothermal and sedimentary ores, along with the host-rocks, were involved in the Apenninic orogenesis, and were recrystallized, and partially remobilized acquiring the current mineralogical, textural, and structural settings.References:[1] Biagioni, C., D’Orazio, M., Vezzoni, S., Dini, A., Orlandi, P., 2013. Mobilization of Tl-Hg-As-Sb-(Ag,Cu)-Pb sulfosalt melts during low-grade metamorphism in the Alpi Apuane (Tuscany, Italy). Geology, 41, 747-750.[2] Vezzoni, S., Biagioni, C., D’Orazio, M., Pieruccioni, D., Galanti, Y., Petrelli, M., Molli, G., 2018. Evidence of Permian magmatism in the Alpi Apuane metamorphic complex (Northern Apennines, Italy): New hints for the geological evolution of the basement of the Adria plate. Lithos, 318-319, 104-123.

The reconstruction of the polymetamorphic history of basement rocks in orogens is crucial for deciphering past geodynamic evolution. However, the current petrographic features are usually interpreted as the results of the metamorphic recrystallization of primary sedimentary and/or magmatic features. In contrast, metamorphic rocks derived by protoliths affected by premetamorphic hydrothermal alterations are rarely recognized. This work reports textural, mineralogical and geochemical data of metasedimentary and metaigneous rocks from the Paleozoic succession of the Sant&rsquo, Anna tectonic window (Alpi Apuane, Tuscany, Italy). These rocks were recrystallized and reworked during the Alpine tectono-metamorphic event, but the bulk composition and some refractory minerals (e.g., tourmaline) are largely preserved. Our data show that the Paleozoic rocks from the Alpi Apuane were locally altered by hydrothermal fluids prior to Alpine metamorphism, and that the Permian magmatic cycle was likely responsible for this hydrothermal alteration. Finally, the Ishikawa Alteration Index, initially developed for magmatic rocks, was applied to metasedimentary rocks, providing a useful geochemical tool for unravelling the hydrothermal history of Paleozoic rocks, as well as a potential guide to the localization of hidden ore deposits in metamorphic terranes.

Understanding low temperature carbon sequestration through serpentinite&ndash, H2O&ndash, CO2 interaction is becoming increasingly important as it is considered a potential approach for carbon storage required to offset anthropogenic CO2 emissions. In this study, we present new insights into spontaneous CO2 mineral sequestration through the formation of hydromagnesite + kerolite with minor aragonite incrustations on serpentinite walls of the Montecastelli copper mine located in Southern Tuscany, Italy. On the basis of field, petrological, and geochemical observations coupled with geochemical modeling, we show that precipitation of the wall coating paragenesis is driven by a sequential evaporation and condensation process starting from meteoric waters which emerge from fractures into the mine walls and ceiling. A direct precipitation of the coating paragenesis is not compatible with the chemical composition of the mine water. Instead, geochemical modeling shows that its formation can be explained through evaporation of mine water and its progressive condensation onto the mine walls, where a layer of serpentinite powder was accumulated during the excavation of the mine adits. Condensed water produces a homogeneous film on the mine walls where it can interact with the serpentinite powder and become enriched in Mg, Si, and minor Ca, which are necessary for the precipitation of the observed coating paragenesis. The evaporation and condensation processes are driven by changes in the air flow inside the mine, which in turns are driven by seasonal changes of the outside temperature. The presence of &ldquo, kerolite&rdquo, a Mg-silicate, is indicative of the dissolution of Si-rich minerals, such as serpentine, through the water&ndash, powder interaction on the mine walls at low temperature (~17.0 to 18.1 &deg, C). The spontaneous carbonation of serpentine at low temperature is a peculiar feature of this occurrence, which has only rarely been observed in ultramafic outcrops exposed on the Earth&rsquo, s surface, where instead hydromagnesite predominantly forms through the dissolution of brucite. The high reactivity of serpentine observed, in this study, is most likely due to the presence of fine-grained serpentine fines in the mine walls. Further study of the peculiar conditions of underground environments hosted in Mg-rich lithologies, such as that of the Montecastelli Copper mine, can lead to a better understanding of the physical and chemical conditions necessary to enhance serpentine carbonation at ambient temperature.

The metamorphic core of the Betic-Rif orogenic chain (Alboran Domain) is made up of lower crustal rocks forming the envelope of the Ronda (Spain) and Beni Bousera (Morocco) peridotites. The deepest sections of the crustal envelopes are made of migmatitic granulites associated with diffuse acidic magmatic products, making these exposure and ideal site to investigate the textural and petrological connection between crustal anatexis and granite magmatism in the contintental crust. However, still debated is the timing of intracrustal emplacement of the peridotite bodies, with models proposing either Alpine (early Miocene) or Hercynian ages, and still uncertain is the linkage between peridotite emplacement and crustal anatexis. In this study, by combining rock textures with whole-rock geochemistry, metamorphic thermobarometry, the U-Pb zircon geochronology and the analysis of the garnet and zircon REE chemistry, we document the P-T-t evolution of the granulite fades migmatites that form the immediate envelope of the Beni Bousera peridotites of the Rif belt. A main episode of Permo-Carboniferous (ca. 300-290 Ma) deep crustal anatexis, melt extraction and migration is documented that we link to the crustal emplacement of the Beni Bousera peridotites during collapse of the Hercynian orogen. Correlation at a regional scale suggests that the Beni-Bousera section can be tentatively correlated with the pre-Alpine (Permo-Carboniferous) basement units tectonically interleaved within the orogenic structure of the Alpine chain. The results of this study provide ultimate constraints to reconstruct the tectono-metamorphic evolution of the Alboran Domain in the Western Mediterranean and impose re-assessment of the modes and rates through which Alpine orogenic construction and collapse occurred and operated in the region. (C) 2020 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

One of the most important authors of the Middle Ages, Petrarch occupies a complex position: historically, he is a medieval author, but, philosophically, he heralds humanism and the Renaissance. Teachers of Petrarch s "Canzoniere" and his formative influence on the canon of Western European poetry face particular challenges. Petrarch s poetic style brings together the classical tradition, Christianity, an exalted sense of poetic vocation, and an obsessive love for Laura during her life and after her death in ways that can seem at once very strange and because of his style s immense influence very familiar to students. This volume aims to meet the varied needs of instructors, whether they teach Petrarch in Italian or in translation, in surveys or in specialized courses, by providing a wealth of pedagogical approaches to Petrarch and his legacy.Part 1, Materials, reviews the extensive bibliography on Petrarch and Petrarchism, covering editions and translations of the "Canzoniere," secondary works, and music and other audiovisual and electronic resources. Part 2, Approaches, opens with essays on teaching the "Canzoniere" and continues with essays on teaching the Petrarchan tradition. Some contributors use the design and structure of the "Canzoniere" as entryways into the work; others approach it through discussion of Petrarch s literary influences and subject matter or through the context of medieval Christianity and culture. The essays on Petrarchism map the poet s influence on the Italian lyric tradition as well as on other national literatures, including Spanish, French, English, and Russian."

Loki's Castle at 73 degrees 30' N along the Arctic Mid-Ocean Ridge (AMOR) provides a natural laboratory to study the evolution of hydrothermal circulation in an ultraslow-spreading environment. In addition, a sedimentary input into the Loki's Castle hydrothermal circulation cell is indicated by vent fluid and gas chemistry. Here we present B and Sr isotope data to investigate interaction between fluid, MORB and sediment and to constrain mass transfer during hydrothermal circulation of a sediment-influenced, black smoker hydrothermal system. The high boron concentrations (1770-2170 mu mol/l) and the relatively low boron isotope composition of the vent fluids (delta B-11 values ranging from + 11.6 to + 15.2%) reflect not only fluid/rock interaction with mafic crust but indicates a significant contribution from sediments, in agreement with other chemical and isotopic (Sr-87/Sr-86) analyses. We present a model of B extraction from sediments at a temperature of 300 degrees C, which suggests a water/sediment ratio of approximately 2 to 3 at Loki's Castle. At these ratios, relative B extraction from sediment ranges from 35 to 55%. (C) 2016 Elsevier B.V. All rights reserved.

The Campiglia Marittima magmatic-hydrothermal system includes a peraluminous granite, its carbonatic host, and skarn. The system evolved generating a time-transgressive exchange of major and trace elements between granite, metasomatic fluids, and host rock. The process resulted in partial metasomatic replacement of the granite and severe replacement of the carbonate host rocks. The fluid activity started during a late-magmatic stage, followed by a potassic–calcic metasomatism, ending with a lower temperature acidic metasomatism. During the late-magmatic stage, B-rich residual fluids led to the formation of disseminated tourmaline–quartz orbicules. High-temperature metasomatic fluids generated a pervasive potassic–calcic metasomatism of the granite, with replacement of plagioclase, biotite, ilmenite, and apatite by K-feldspar, phlogopite–chlorite–titanite, titanite–rutile, and significant mobilization of Fe, Na, P, Ti, and minor HFSE/REE. The metasomatized granite is enriched in Mg, K, Rb, Ba, and Sr, and depleted in Fe and Na. Ca metasomatism is characterized by crystallization of a variety of calc-silicates, focusing along joints into the granite (endoskarn) and at the marble/pluton contact (exoskarn), and exchange of HFSE and LREE with hydrothermal fluids. Upon cooling, fluids became more acidic and fluorine activity increased, with widespread crystallization of fluorite from disequilibrium of former calc-silicates. At the pluton-host boundary, fluids were accumulated, and pH buffered to low values as temperature decreased, leading to the formation of a metasomatic front triggering the increasing mobilization of REE and HFSE and the late crystallization of REE–HFSE minerals.

The Campiglia Marittima Fe-Cu-Zn-Pb(-Ag) skarn deposit has long been regarded as a reference example of an exoskarn showing a symmetric outward mineralogical zoning of both skarn and ore minerals with respect to an axial mafic porphyry dike. Detailed field and underground mapping, along with three-dimensional reconstruction of the geometries of skarn and magmatic bodies, integrated with new petrographic, mineralogical and geochemical data, argue against this model. The shapes of the skarn bodies and the growth versors of skarn minerals in particular, are ascribed to the focusing of metasomatic fluids in sigmoid-shaped volumes of fractured host marble. After skarn formation, a mafic magma was emplaced, forming dikelets and filling residual pockets in the skarn. Field evidence and geochemical data show that the “hot” mafic magma interacted with the previously formed Zn-Pb(-Ag) skarn, triggering textural reworking and chemical redistribution of Zn-Pb sulfides as well as contributing to a late Fe-Cu mineralization. Campiglia Marittima skarn-ore system behaved at odd: a telescoping process is recorded, yet in a reverse way.

The Baccu Locci mine area is located in a sector of the Variscan Nappe zone of Sardinia (the Baccu Locci shear zone) that hosts several type of ore deposits mined until the first half of the last century. The orebodies consist of lenses of Zn&ndash, Cu sulphides, once interpreted as stratabound, and Qtz&ndash, As&ndash, Pb sulphide &plusmn, gold veins, the implication of structural controls in their origin were previously misinterpreted or not considered. Detailed field mapping, structural analyses, and ore mineralogy allowed for unraveling how different ore parageneses are superimposed each other and to recognize different relationships with the Variscan structures. The sulphide lenses are parallel to the mylonitic foliation, hosted in the hinges of minor order upright antiforms that acted as traps for hydrothermal fluids. The Qtz&ndash, Pb sulphide veins crosscut the sulphide lenses and are hosted in large dilatational jogs developed in the hanging wall of dextral-reverse faults, whose geometry is influenced by the attitude of reverse limbs of late Variscan folds. The ores in the Baccu Locci shear zone are best interpreted as Variscan orogenic gold-type, veins display mutual crosscutting relationships with mafic dikes dated in the same district at 302 &plusmn, 0.2 Ma, a reliable age for the mineralizing events in the area.

The different generations of calc‐silicate assemblages formed during sequential metasomatic events make the Campiglia Marittima magmatic&ndash, hydrothermal system a prominent case study to investigate the mobility of rare earth element (REE) and other trace elements. These mineralogical assemblages also provide information about the nature and source of metasomatizing fluids. Petrographic and geochemical investigations of granite, endoskarn, and exoskarn bodies provide evidence for the contribution of metasomatizing fluids from an external source. The granitic pluton underwent intense metasomatism during post‐magmatic fluid&ndash, rock interaction processes. The system was initially affected by a metasomatic event characterized by circulation of K‐rich and Ca(‐Mg)‐rich fluids. A potassic metasomatic event led to the complete replacement of magmatic biotite, plagioclase, and ilmenite, promoting major element mobilization and crystallization of K‐feldspar, phlogopite, chlorite, titanite, and rutile. The process resulted in significant gain of K, Rb, Ba, and Sr, accompanied by loss of Fe and Na, with metals such as Cu, Zn, Sn, W, and Tl showing significant mobility. Concurrently, the increasing fluid acidity, due to interaction with Ca‐rich fluids, resulted in a diffuse Ca‐metasomatism. During this stage, a wide variety of calc‐silicates formed (diopside, titanite, vesuvianite, garnet, and allanite), throughout the granite body, along granite joints, and at the carbonate&ndash, granite contact. In the following stage, Ca‐F‐rich fluids triggered the acidic metasomatism of accessory minerals and the mobilization of high-field-strength elements (HFSE) and REE. This stage is characterized by the exchange of major elements (Ti, Ca, Fe, Al) with HFSE and REE in the forming metasomatic minerals (i.e., titanite, vesuvianite) and the crystallization of HFSE‐REE minerals. Moreover, the observed textural disequilibrium of newly formed minerals (pseudomorphs, patchy zoning, dissolution/reprecipitation textures) suggests the evolution of metasomatizing fluids towards more acidic conditions at lower temperatures. In summary, the selective mobilization of chemical components was related to a shift in fluid composition, pH, and temperature. This study emphasizes the importance of relating field studies and petrographic observations to detailed mineral compositions, leading to the construction of litho‐geochemical models for element mobilization in crustal magmatic‐hydrothermal settings.

The Etruscan site of Populonia-Baratti (Southern Tuscany, Italy) became in the first millennium BCE one of the most important iron metalworking sites in the Mediterranean region thanks to the exploitation of nearby Elba Island iron ores. Recent studies, however, have demonstrated that, before iron, copper was smelted therein (9th–8th century BCE). The ancient Hellenistic text De mirabilibus auscultationibus by Pseudo-Aristotle states that the ancient inhabitants of Elba Island firstly exploited copper and that, later in, iron was won from the same mines by the inhabitants of Populonia. However, copper occurrences are extremely scanty on the island, while mainland southern Tuscany hosts a number of copper-rich deposits which could have been profitably exploited since Eneolithic. In order to investigate if, and to what extent, copper mining and smelting/working was practiced in this area in Final Bronze Age (FBA) to Early Iron Age (EIA), we have thus compared the lead isotope composition of copper slags found in the Populonia-Baratti area and dated to the 9th–8th century BCE with those of copper-rich ore deposits of southern Tuscany and Elba Island. In addition, few copper-based items from to FBA-EIA hoards of Elba Island have been investigated as well. All copper slag from Baratti-Populonia have lead isotope composition fully comprised within the nearby Campiglia Marittima district, but the ophiolitic copper (either form Tuscan mainland or the neighboring island of Elba) was never worked in this site. Differently, all items from the island of Elba do not show clear genetic relationship neither with Elban nor with the Tuscan mainland copper ores but display a “foreign” Pb signature, suggesting that, even before iron exploitation started, the island of Elba - one of the main crossroads of the Mediterranean Sea - was probably involved in metal trading (rather than metal working) with other regions.

In this paper we deal with the kinematic and chronological relationships among low angle normal faults and high angle strike- to oblique-slip faults in an exhumed mineralized area, where shear veins and minor associated structures filled with the same mineral assemblage has been interpreted as indicators of coeval fault activities. The study area is located in the eastern Elba Island, where a mineralized late Miocene-early Pliocene low-angle normal fault (Zuccale fault) and high-angle strike- to oblique-slip faults extensively crop out, the latter giving rise to the Capoliveri-Porto Azzurro shear zone. The field study highlighted that: (a) the damage zones of both fault sets are mineralized by syn-kinematic tourmaline, graphite, Fe-oxides and/or Fe-oxyhydroxides shear veins, thus indicating their coeval activity during the hydrothermal event (5.9–5.4 Ma); (b) the Capoliveri-Porto Azzurro shear zone is constituted by a network of fractures, whose geometry and kinematics display the evolution of a NE-trending left-lateral oblique-slip transtensional shear zone; (c) its internal architecture is defined by tourmaline and Fe-oxides and/or Fe-oxyhydroxides mineralized veins, framed in the same kinematic field characterizing the Zuccale fault evolution; for this reason, the Capoliveri–Porto Azzurro shear zone is interpreted as a transfer zone active during the low-angle fault activity; (d) the Capoliveri–Porto Azzurro shear zone played the role of a significant normal fault during the Late Pliocene–Pleistocene, therefore favouring the deepening of the Tyrrhenian Basin with respect to the uplift and exhumation of the mid-crustal rocks of the Elba Island. It is finally argued that the interaction between the low-angle normal fault and the almost vertical shear zone determined an increase of permeability, favouring the mineralizing fluid flow during the hydrothermal stage and, reasonably, the previous emplacement of the Porto Azzurro magmatic body.