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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.

Muon radiography (muography) is an imaging technique based on atmospheric muon absorption in matter that allows to obtain two and three-dimensional images of internal details of hidden objects or structures. The technique relies on atmospheric muon flux measurements performed around and underneath the object under examination. It is a non-invasive and passive technique and thus can be thought of as a valid alternative to common prospecting techniques used in archaeological, geological and civil security fields. This paper describes muon radiography measurements, in the context of archaeological and geological studies carried out at the Temperino mine (LI, Tuscany, Italy), for the search and three-dimensional visualisation of cavities. This mine has been exploited since Etruscan times until recently (1973), and is now an active tourist attraction with public access to the tunnels. Apart from the archaeological interest, the importance of mapping the cavities within this mine lies in identifying the areas where the extraction ores were found and also in the safety issues arising from the tourist presence inside the mine. The three-dimensional imaging is achieved with two different algorithms: one involving a triangulation of two or more measurements at different locations; the other, an innovative technique used here for the first time, is based on the back-projections of reconstructed muon tracks. The latter requires only a single muographic data tacking and is to be preferred in applications where more than one site location can be difficult to access. Finally the quality of the three-dimensional muographic imaging was evaluated by comparing the results with the laser scan profiles obtained for some known cavities within the Temperino mine.

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.

Campiglia Marittima (hereafter Campiglia) has a long record of attracting interest on its ore deposits that have been intermittently exploited from the Copper Age to the late XX century. Since the XIX century, Campiglia has been a key locality for the debate on skarn-forming processes due to the presence of mining activities ensuring access to ever new rock exposures. The pioneering study of vom Rath and the comparison with attractive chemical model (e.g., Korzhinskii’s theory) in the XX century made Campiglia a “classic” example of skarn ore deposit, from the causative intrusion to the marble host rock. In recent years, detailed field investigations integrated by petrographic, geochemical, and isotopic analyses revealed a more complex and stimulating geological history. The Campiglia skarn was later intruded by mafic magma causing textural reworking and chemical redistribution as well as the reverse telescoping process with Fe-Cu sulfides overprinting previously formed Pb-Zn ore. This work aims to trace the evolution of the scientific thinking on the Campiglia ore deposit by comparison with existing skarn-forming models and, ultimately, shows that the current skarn-forming model(s) cannot fully explain the textural and geochemical features of the Campiglia skarn.

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.

Petrology and timing of magmatic-hydrothermal systems and the linkage between plutonic and volcanic domains are central topics in geosciences, because of broad implications for natural hazards and exploitation of natural resources. We investigated by the

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.

Italy has no record of Li production, even though it is well known for its outstanding Li mineral specimens from the Elba Island pegmatites. Because of the current geopolitical situation, the opportunity for a systematic appraisal of resources is evident. Most European Li production comes from deposits associated with Late Paleozoic magmatic rocks. In Italy, such rocks occur extensively in Sardinia and Calabria, but their potential for Li is unknown, and deserves a more systematic exploration. Also of potential interest are the Permo–Triassic spodumene pegmatites in the Austroalpine units of the Central Alps. The Tertiary pegmatites (Elba Island and Central Alps) contain Li minerals, but do not appear large enough to warrant bulk mining. However, we notice that Tertiary–Quaternary magmatic rocks of the Tuscan and Roman magmatic provinces have systematically higher Li contents than those recorded in normal arc igneous rocks worldwide. Specifically, Tuscan granites contain up to 350 μg/g Li, mostly hosted by biotite (up to 4000 μg/g Li); the Capo Bianco aplite (Elba Island) contains up to 1000 μg/g. There are other small Li occurrences associated with Mn deposits and metabauxites, and there is a hypothetical potential for sediment-hosted deposits in the post-orogenic Lower Permian Alpine basins. However, the most promising potential seems to be associated with subsurface fluids. High-enthalpy fluids in geothermal fields may contain up to 480 mg/L Li. Lower-temperature thermal waters may also contain significant Li (>10 mg/L). Moreover, a visionary, but not impossible, perspective may consider a deep injection of water to interact with, and extract Li from, magmatic rocks.

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.

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.

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.

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."

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 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.

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.

The Naples Yellow pigment was apparently used for the first time by the Egyptians, as a glass-colouring agent. Also known in the Mesopotamian and Roman cultures, the recipe was lost in Western Europe between the fourth and the 16th centuries ad. The recipe for the production of lead antimonate recently discovered in the ‘Codice Calabranci’ (second half of the 15th century) at Montelupo, a small town near Florence (Italy) known for its large-scale ceramic production, possibly represents the very first evidence of the reintroduction of Naples Yellow in Western Europe after a long period of absence. The major-element composition of the lead antimonate pigment in the Montelupo ceramics of the 15th and 16th centuries is in accordance with the ‘Codice Calabranci’ recipes. Lead isotope analyses indicate that the lead used to produce the yellow pigments and the underlying glaze of the Montelupo majolica did not come from the Tuscan mining districts, but was possibly imported via Venice from more distant lead sources in Turkey.

Dykes feed laccoliths and sills; however, the link between feeder and intrusion is rarely observed. The felsic San Martino laccolith displays a clear feeder–intrusion link, allowing reconstruction of the influence of the size and location of feeder dykes on magma flow during formation of subhorizontal intrusions. This work uses anisotropy of magnetic susceptibility (AMS) combined with mineral shape-preferred orientations of sanidine megacrysts to examine magma flow pathways through feeders into a laccolith. Strong correlation between AMS and K-feldspar datasets indicates that alteration affecting the paramagnetic mineralogy did not influence AMS results. The well-established field relationships between feeder and laccolith provided a robust ‘geo-logical’ model for flow pathways that we have used as a framework to aid interpretation of AMS data. The position and size of the main feeder dyke helped to predict the flow paths in the overlying laccolith. Our results show that magma spread laterally from the feeding system and built the laccolith layers with propagating and inflating divergent flow where tabular particles became aligned perpendicular to the magma displacement direction. The lack of internal discontinuities indicates that the magma was injected as a single pulse or a series of quickly coalescing pulses. Supplementary material: AMS methods, AMS data and detailed fabric maps are available at www.geolsoc.org.uk/SUP18717.

The mineralogy, petrography and major- and trace-element composition of iron ores from Elba Island (Tuscany, Italy), one of the most important iron sources in the Mediterranean area since the first millennium bc, revealed that hematite-rich ores display prominent enrichments in W and Sn (up to 4950 μg g−1 and 8400 μg g−1, respectively). These two elements are hosted by tiny grains of W–Sn mineral phases (ferberite, scheelite and cassiterite) that are disseminated throughout the hematite matrix. A comparison with iron ores from many Italian and European localities (most of which were exploited in ancient times) suggests the uniqueness of the geochemical pattern of Elba Island hematite-rich ores (i.e., high W and Sn, low Mo and low Cu, Pb and Zn). We suggest that this geochemical signature may represent a new provenance marker not only for discarded ore at smelting/smithing sites, but, possibly, also for metallurgical slag and smelted metal produced in the chaine operatoire of the iron process.

A metabasite lens with eclogite-facies relics discovered within high-grade gneisses, at Punta Orvili (Posada) in NE Sardinia, has proven to be the first example of within-plate basalt among the eclogite-derived, tholeiitic metabasites from the Variscan belt in Sardinia. The composition of the Punta Orvili metabasite is unusual: SiO(2) < 47.6 wt%, Al(2)O(3) < 9.6 wt%, MgO >= 13 wt%, Fe(2)O(3tot) > 13 wt%, Cr > 550 ppm, Ni > 270 ppm, Mg # 68-70. Detailed investigation of the major and trace element content rules out any significant geochemical modification of the protolith by alteration and/or metamorphic processes. Normative contents of mafic minerals up to 55-79 wt%, very small amounts of Al(2)O(3) and Na(2)O and very high concentrations of MgO, Cr and Ni suggest a protolith of picritic nature. The steeply sloping REE patterns, with La(N)/Yb(N) = 13.0-17.3, suggest low-degree partial melting and the presence of garnet, as retention phase of HREE in the mantle source. Enrichment factors are 60-180 times higher for LREE, 30-60 times for MREE, 10-20 times for HREE. The primitive manntle-normalized trace element abundance patterns of the Punta Orvili metabasite show enrichment in Ba, Th, Nb, La, Ce, compared to eclogite-derived metabasites. Values of La/Nb, La//Ta, Ce/Nb, Th/Nb, Sm/Yb, Ce/Sm, Th/Y, Nb/Y, Th/Yb and Ta/Yb differ significantly from those of average crust, upper, lower and mid-crust, indicating an OIB-like source. Two values of (87)Sr/(86)Sr((i)) were obtained around 0.709 with epsilon(Sri) =+69-71. The corresponding values of the (143)Nd/(144)Nd((i)) are about 0.51197 with epsilon(Ndi) similar to -1.50 assuming an age of 460 Ma, i.e. the mean age of Sardinian eclogite. Isotope and geochemical data suggest that the Punta Orvili protolith was generated by interaction of OIB-like melts with an enriched sub-continental lithospheric mantle, similar in composition to Group II kimberlites and/or to their garnet peridotite xenoliths.

The magnesite deposits of Malentrata (Tuscany, Italy) were derived from serpentinite silicification–carbonation of the Ligurian ophiolite, and represent a natural analogue of in situ CO 2 mineral sequestration. Carbonation of magnesium silicate minerals (e.g. serpentine, olivine) at temperatures below 200 °C is an exothermal process, involving incorporation of carbon dioxide into stable carbonates (e.g. magnesite, dolomite). Serpentinites at Malentrata were transformed to a brownish friable rock characterized by the occurrence of opal, chromian montmorillonite, Fe-rich magnesite and minor iron sulfides and oxides. Widespread lenses of cohesive rocks occur within the altered serpentines, resulting from the complete silicification of the protolith. The pervasive alteration of serpentinite was accompanied by the formation of a network of magnesite and dolomite veinlets, and large magnesite–dolomite veins along major structures. Field observations, petrography and mineral chemistry define the following crystallization sequence in the major veins: i) early microgranular Fe-poor magnesite, ii) comb-textured Fe-rich magnesite and dolomite cementing the early brecciated magnesite vein infill, and iii) late quartz, chalcedony, and rare opal in the cavities. The mineral assemblage observed both in veins and in host rock is indicative of low-temperature hydrothermal alteration driven by Si- and CO 2 -rich fluids under relatively low pH conditions. Pervasive and cyclic hydraulic fracturing maintained a high structural permeability during the whole hydrothermal event, creating conduits for the input and output fluids. The concomitant presence of CO 2 and silica in the fluid enhanced the congruent dissolution of serpentine and hampered immediate carbonate deposition. The Mg-bearing solutions were focused out of the reactor zone, and promoted massive carbonate veining along the main structural discontinuities. This two-steps reaction (dissolution of serpentinite followed by carbonate precipitation outside the reacting volume) seems to be very efficient and provide new insights on in situ and ex situ induced mineral carbonation and its industrial applications.

An integrated study based on fluid inclusion, δ18O composition and structural analyses was carried out on a Pliocene fossil hydrothermal system, located to the South of the present active Larderello geothermal field, in the Boccheggiano-Montieri area. The study area is typified by mineralized cataclastic levels related to Late Oligocene–Early Miocene thrust surfaces, and to the following two generations of normal faults of Miocene and Pliocene ages, respectively. Within the damage zone of the Pliocene Boccheggiano fault, the mineralization is mainly made up of quartz and pyrite. Quartz + Pb–Zn sulfides, or quartz + Pb–Zn sulfides + fluorite + carbonates assemblages occur instead in the older cataclastic levels. Two generations of liquid-rich fluid inclusions were recognized in quartz and fluorite: the first one, with homogenization temperatures ranging between 172 and 331°C and salinity between 0.0 and 8.8 wt.% NaClequiv., records the early stage of hydrothermal activity. The second generation of fluid inclusions documents a later stage, with homogenization temperature from 124 to 288°C and salinity from 0.2 to 1.9 wt.% NaClequiv.. Fluid inclusions analyses also indicate that mixing of fluid with distinct salinities and/or temperatures was a widespread process during the early stage, and that fluid temperatures decreased moving from the Boccheggiano fault toward the more distal and older cataclastic levels. The δ18O values of water in equilibrium with hydrothermal quartz, which range from −5.7 to −0.1‰, are related to the circulation of meteoric water mixed with saline water that leached the evaporite level and enriched in δ18O through water–rock interaction, and/or with magmatically derived fluids. Results indicate that the damage zone of the Pliocene Boccheggiano fault represented the main channel for the flow of meteoric water, which was heated at depth, then mixed with high salinity fluids, and finally ascend to infiltrate along the older cataclastic levels. Our results, based on fluid inclusions, oxygen isotopic compositions and structural analyses indicate that a single fluid flow path run through the damage zone of the Boccheggiano fault and the older cataclasites, which were thus hydraulically connected.

Fluid inclusions are small portions, usually smaller than 100 μm, of fluid trapped within minerals during or after growth. Their characteristics provide therefore fundamental information on nature and evolution of fluids present in the past in different geological environments. At the LABEC laboratory in Firenze, high-salinity fluid inclusions in quartz crystals, coming from the Apuan Alps metamorphic complex, were analysed at the external scanning microbeam. Results, although still preliminary, have already provided us with hints on fluid-rock interaction processes during the metamorphism of the Apuan Alps.

The Lost City hydrothermal system at the southern Atlantis Massif (Mid-Atlantic Ridge, 30°N) provides a natural laboratory for studying serpentinization processes, the temporal evolution of ultramafic-hosted hydrothermal systems, and alteration conditions during formation and emplacement of an oceanic core complex. Here we present B, O, and Sr isotope data to investigate fluid/rock interaction and mass transfer during detachment faulting and exhumation of lithospheric sequences within the Atlantis Massif. Our data indicate that extensive serpentinization was a seawater-dominated process that occurred predominately at temperatures of 150–250 °C and at high integrated W/R ratios that led to a marked boron enrichment (34–91 ppm). Boron removal from seawater during serpentinization is positively correlated with changes in δ 11 B (11–16‰) but shows no correlation with O-isotope composition. Modeling indicates that B concentrations and isotope values of the serpentinites are controlled by transient temperature–pH conditions. In contrast to prior studies, we conclude that low-temperature marine weathering processes are insignificant for boron geochemistry of the Atlantis Massif serpentinites. Talc- and amphibole-rich fault rocks formed within a zone of detachment faulting at temperatures of approximately 270–350 °C and at low W/R ratios. Talc formation in ultramafic domains in the massif was subsequent to an early stage of serpentinization and was controlled by the access of Si-rich fluids derived through seawater–gabbro interactions. Replacement of serpentine by talc resulted in boron loss and significant lowering of δ 11 B values (9–10‰), which we model as the product of progressive extraction of boron. Our study provides new constraints on the boron geochemical cycle at oceanic spreading ridges and suggests that serpentinization associated with ultramafic-hosted hydrothermal systems may have important implications for the behavior of boron in subduction zone settings.

In various ancient authors (e.g. the ‘Argonautika’ of Apollonios Rhodios) curious news about the Island Elba can be found, concerning the existence, somewhere on the shore near Portoferraio, of pebbles that are ‘dirty’ from the Argonauts’ sweat. The Argonauts are said to have stopped on the island during their journey back from the looting of the ‘Golden Fleece’. These pebbles are found to be typical of the gravelly beaches below the Capo Bianco cliffs. Such walls are made up of a bony-white aplitic rock dotted with blue-black tourmaline spots. Capo Bianco aplite is the uncommon result of the solidification of a boron-rich magma in a subvolcanic setting. Here, the separation of a boron-rich fluid phase gave way to the crystallization of peculiar spherical dark tourmaline spots in a very fine-grained white groundmass. This rock was noted by Argonauts (i.e. the ancient travellers they represent) and used as a lighthouse to the harbour of Argoos limen (now Portoferraio). Also in the myth, the unique mottled pebbles were recorded as stained by the Argonauts’ sweat. The occurrence, within the same, complex myth, of ‘data’ concerning navigation (the white cliffs) and geology (description of the spotted aplite) identify the Argonauts as a blending of mineral prospectors, explorers and early eighteenth century-like naturalists, legitimatizing the commercial/political presence of Greeks in the region. Fanciful tales or myths have arisen during the course of each culture’s history, most often from either religious or social motivations. In some cases, a pre-scientific view of the natural world generated observations that became a relevant element of the structure of the myth. Only with progress in the scientific analysis of nature, perhaps first truly introduced by Herodotus, have we gradually developed a distinction between natural and mythical explanations. One aspect of myths is that they often recall specific places in which special or peculiar natural features are present, and for this reason, the Island of Elba could not be absent in the ancient mythology. In fact, this island has a privileged position for navigation in the central Mediterranean Sea, being located between Corsica and the Tuscan shoreline, and it was also famous in the classical world for its iron deposits, noted by Ps. Aristoteles (De Mirabilibus Auscultationibus, 93), Vergilius (Aeneis, X, 143–144) and Strabo (Geography, V); see also Corretti (2004a) and references therein. In particular, Elba occurs in the myth of Jason and the Argonauts that was codified by Apollonios Rhodios who describes the exceptional character of some unique rocks (perhaps the Capo Bianco aplite) as having both a special petrographical and mineralogical nature, as well as an extraordinarily bright, white colour of outcrop. In this paper we describe the geology and petrology of the tourmaline-rich Capo Bianco Aplite cropping out as a dismembered laccolith along the northern coast of central Elba, and we highlight the strict similarity between the petrographic features of the Capo Bianco rocks and the descriptions contained in the Argonauts’ myth reported by Apollonios Rhodios. Finally, we discuss how accurate observations on this oddity of nature were ‘metamorphosed’ in the structure of a mythic narration. The Tuscan Magmatic Province and the Island of Elba granitic rocks

Mobility of Au and related metals during metamorphism has been suggested to be the source of metals enriched in orogenic Au deposits. This study investigates the mobility of Au, As, and Sb during metamorphism of the Dalradian metasedimentary rocks of Scotland. The metamorphic processes in the Dalradian of Scotland are extremely well studied, and the terrane is an ideal area to investigate mobility of these metals. Our results show that of the 25 major and trace elements analysed, only Au, As, Sb, S and volatile contents as shown by loss on ignition (LOI) values show systematic variation with the metamorphic grade of the samples. Average Au concentrations decrease from 1.1 ± 0.55 ppb and 0.72 ± 0.34 ppb in chlorite and biotite zone rocks down to 0.4 ± 0.22 ppb and 0.34 ± 0.13 ppb in kyanite and sillimanite zone rocks. Average As concentrations decrease from 4.8 ppm (range 0.5 to 17.8 ppm) and 1.96 ± 1.9 ppm in chlorite and biotite zone rocks down to 0.24 ± 0.15 ppm and 0.2 ± 0.12 ppm in kyanite and sillimanite zone rocks. Average Sb concentrations decrease from 0.18 ± 0.15 ppm and 0.11 ± 0.10 ppm in chlorite and biotite zone rocks down to 0.04 ± 0.02 ppm in both kyanite and sillimanite zone rocks. Sulphur and LOI concentrations also show significant decreases. Mass balance calculations indicate that compared to chlorite and biotite zone samples, sillimanite zone samples have an average mass loss of 62 ± 14%, 94 ± 4% and 74 ± 14% for Au, As, and Sb respectively. Every 1 km3 of chlorite–biotite zone mixed psammitic–pelitic protolith rock that is metamorphosed to sillimanite zone conditions would release 1.5 t Au, 8613 t As, 270 t Sb, and 1.02 Mt S. The mobility of these elements is strongly controlled by the paragenesis of sulphide minerals. Pyrite, sphalerite, galena and cobaltite (as well as gersdorffite) decrease in abundance with increasing metamorphic grade in the Dalradian metasedimentary rocks. A critical aspect of the sulphide paragenesis is the transition of pyrite to pyrrhotite. This transition is complete by mid greenschist facies in the Loch Lomond samples but is more gradual at Glen Esk occurring between biotite and sillimanite zones. The Au, As, and Sb content of the sulphide assemblage also decreases with increasing metamorphic grade, and we suggest that this is a controlling factor on the mobility of these metals from the Dalradian metasedimentary rocks during metamorphism. Chlorite may be an important host mineral for As in the greenschist facies rocks. Breakdown of chlorite indirectly drives the mobility of Au, As, and Sb, as this produces the bulk of metamorphic fluid that drives transition between pyrite and pyrrhotite. We suggest that there is potential for significant undiscovered mineralisation in the Central and SW Highlands of Scotland. However, as the total mass of gold mobilised is lower than observed in other metasedimentary terranes such as the Otago and Alpine Schist's, New Zealand, very efficient fluid focussing and trapping mechanisms would be required to form large deposits in the Dalradian of Scotland.

Extensive, mainly acidic peraluminous magmatism affected the Tuscan Archipelago and the Tuscan mainland since late Miocene, building up the Tuscan Magmatic Province (TMP) as the Northern Apennine fold belt was progressively thinned, heated and intruded by mafic magmas. Between 3.8 and 1.3 Ma an intrusive complex was built on Larderello area (Tuscan mainland) by emplacement of multiple intrusions of isotopically and geochemically distinct granite magmas. Geochemical and isotopic investigations were carried out on granites cored during drilling exploration activity on the Larderello geothermal field. With respect to the other TMP granites the Larderello intrusives can be classified as two-mica granites due to the ubiquitous presence of small to moderate amounts of F-rich magmatic muscovite. They closely resemble the almost pure crustal TMP acidic rocks and do not show any of the typical petrographic features commonly observed in the TMP hybrid granites (enclaves, patchy zoning of plagioclase, amphibole clots). On the basis of major and trace elements, as well as REE patterns, two groups of granites were proposed: LAR-1 granites (3.8-2.3 Ma) originated by biotite-muscovite breakdown, and LAR-2 granites (2.3-1.3 Ma) generated by muscovite breakdown. At least three main crustal sources (at 14-23 km depth), characterized by distinct eNd(t) and 87Sr/86Sr values, were involved at different times, and the magmas produced were randomly emplaced at shallow levels (3-6 km depth) throughout the entire field. The partial melting of a biotite-muscovite-rich source with low qNd(t) value (about -10.5) produced the oldest intrusions (about 3.8-2.5 Ma). Afterwards (2.5-2.3 Ma), new magmas were generated by another biotite-rich source having a distinctly higher eNd(t) value (-7.9). Finally, a muscovite-rich source with high eNd(t) (about -8.9) gave origin to the younger group of granites (2.3-1.0 Ma). The significant Sr isotope disequilibrium recorded by granites belonging to the same intrusion is interpreted, as due to the short residence time of magmas in the source region followed by their rapid transfer to the emplacement level. Partial melting was probably triggered by multiple, small-sized mafic intrusions, distributed over the last 3.8 Ma that allowed temporary overstepping of biotite- and muscovite-dehydration melting reactions into an already pre-heated crust. Dilution in time of the magmatic activity probably prevented melt mingling and homogenization at depth, as well as the formation of a single, homogeneous, hybrid pluton at the emplacement level. Moreover the high concentrations of fluxing elements (B, F, Li) estimated for the LAR granites modified melt properties by reducing solidus temperatures, decreasing viscosity and increasing H2O solubility in granite melts. The consequences were a more efficient, fast, magma extraction and transfer from the source, and a prolonged time of crystallization at the emplacement level. These key factors explain the long-lived hydrothermal activity recorded in this area by both fossil (Plio-Quaternary ore deposits) and active (Larderello geothermal field) systems.

A banded amphibolite sequence of alternating ultramafic, mafic (amphibolite) and silicic layers, tectonically enclosed within Variscan migmatites, outcrops at Monte Plebi (NE Sardinia) and shows similarities with leptyno-amphibolite complexes. The ultramafic layers consist of amphibole (75–98%), garnet (0–20%), opaque minerals (1–5%) and biotite (0–3%). The mafic rocks are made up of amphibole (65–80%), plagioclase (15–30%), quartz (0–15%), opaque minerals (2–3%) and biotite (0–2%). The silicic layers consist of plagioclase (60–75%), amphibole (15–30%) and quartz (10–15%). Alteration, metasomatic, metamorphic and hydrothermal processes did not significantly modify the original protolith chemistry, as proved by a lack of K2O-enrichment, Rb-enrichment, CaO-depletion, MgO-depletion and by no shift in the rare earth element (REE) patterns. Field, geochemical and isotopic data suggest that ultramafic, mafic and silicic layers represent repeated sequences of cumulates, basic and acidic rocks similar to macrorhythmic units of mafic silicic layered intrusions. The ultramafic layers recall the evolved cumulates of Skaergaard and Pleasant Bay mafic silicic layered intrusions. Mafic layers resemble Thingmuli tholeiites and chilled Pleasant Bay mafic rocks. Silicic layers with Na2O: 4–6 wt%, SiO2: 67–71 wt% were likely oligoclase-rich adcumulates common in many mafic silicic layered intrusions. Some amphibolite showing a strong Ti-, P-depletion and REE-depletion are interpreted as early cumulates nearly devoid of ilmenite and phosphates. All Monte Plebi rocks have extremely low Nb, Ta, Zr, Hf content and high LILE/HFSE ratios, a feature inherited from the original mantle sources. The mafic and ultramafic layers show slight and strong LREE enrichment respectively. Most mafic layer samples plot in the field of continental tholeiites in the TiO2–K2O–P2O5 diagram and are completely different from N-MORB, E-MORB and T-MORB as regards REE patterns and Nd, Sr isotope ratios but show analogies with Siberian, Deccan and proto-Atlantic rift tholeiites. Comparisons with Thingmuli, Skaergaard and Kiglapait rocks and with experimental data suggest that the Monte Plebi intrusion was an open-to-oxygen system with fO2 ≥ FMQ. Mafic and ultramafic samples yielded eNd(460)=+0.79 /+3.06 and 87Sr/86Sr=0.702934–0.703426, and four silicic samples eNd(460)=−0.53/−1.13; 87Sr/86Sr=0.703239–0.703653. Significant differences in Nd isotope ratios between mafic and silicic rocks prove that both groups evolved separately in deeper magma chambers, from different mantle sources, with negligible interaction with crustal material, and were later repeatedly injected within a shallower magma chamber. The spectrum of Sr and Nd isotope data is consistent with a slightly enriched mantle metasomatized during an event earlier than 460 Ma. The metasomatising component was represented by alkali-Th-rich fluids of crustal origin rather than by sedimentary materials, able to modify alkali and Sr–Nd isotope systematics. Monte Plebi layered amphibolites might represent the first example of a strongly metamorphosed fragment of an early Paleozoic mafic silicic layered intrusion emplaced in a thinning continental crust and then tectonically dismembered by Variscan orogeny.

Structural studies on syn-tectonic veins cropping out in the northeastern sector of the Apuan Alps metamorphic complex (Northern Apennines, Italy) revealed two sets of veins: (1) type A fibrous veins within the “Scisti sericitici Formation”, related to a late-D1 tectonic phase; (2) B-veins, within the “Diaspri Formation” that developed between late-D1 and D2 tectonic phases. The mineralogy of the A (quartz, chlorite, hematite with minor amounts of apatite, allanite-(Ce), thorite and synchysite) and B-veins (quartz only) reflects the mineralogical composition of the host-rocks: quartz, chlorite, white mica and accessory minerals (apatite, zircon, titanite) occur in the “Scisti sericitici Formation”, while quartz is the main phase in the “Diaspri Formation”. The study of fluid inclusions trapped in quartz crystals of the syn-tectonic veins shows that the inclusions are always oversaturated in NaCl at room temperature and their salinities range from 29.5 to 37 wt.% NaCl equiv. The isochore of the earliest trapped fluid inclusions (type IA; primary inclusions in fiber quartz of A veins), coupled with mineralogical geothermometric data, constrains the pressure–temperature conditions to around 325–300 MPa and 370–380 °C during the late-D1 phase. Subsequent trapping of inclusion types IIA, IIB, IIIA, IIIB and VB in the two vein sets probably occurred during a pressure–temperature decrease (down to 220–245 MPa and 260–270 °C) at a lithostatic thermal gradient of 30 °C/km. Type IVB inclusions, on the other hand, were probably trapped at lower pressure (between lithostatic and hydrostatic conditions) during a transient pressure drop resulting from fault-valve action. SEM/EDS analyses on salts precipitated within opened inclusions confirmed the NaCl-rich compositions of the trapped fluids and also revealed the presence of minor amounts of Ca, K and Mn in the salts. A fluid circulation model, based on mineralogical and fluid inclusion data, was proposed for the high-salinity fluids found in the syn-tectonic veins: the high-salinity and NaCl-rich nature of the trapped fluids suggest that the original metamorphic fluids interacted with evaporite levels present at the base of the Tuscan Nappe, overlying Apuan Alps metamorphic Units. These fluids then infiltrated downward, possibly through shear zones crosscutting the stratigraphic sequence, into the syn-tectonic veins and interacted with the host-rocks to produce a local element mobilization and their precipitation in the vein minerals; as a result the latter reflect the mineralogy of the host-rocks.

The Istituto di Geoscienze e Georisorse (IGG), on behalf and with the support of the International Atomic Energy Agency (IAEA), prepared eight geological materials (three natural waters and five rocks and minerals), intended for a blind interlaboratory comparison of measurements of boron isotopic composition and concentration. The materials were distributed to twenty seven laboratories - virtually all those performing geochemical boron isotope analyses in the world -which agreed to participate in the intercomparison exercise. Only fifteen laboratories, however, ultimately submitted the isotopic and/or concentration results they obtained on the intercomparison materials. The results demonstrate that interlaboratory reproducibility is not well reflected by the precision values reported by the individual laboratories and this observation holds true for both boron concentration and isotopic composition. The reasons for the discrepancies include fractionations due to the chemical matrix of materials, relative shift of the zero position on the δ11B scale and a lack of well characterized materials for calibrating absolute boron content measurements. The intercomparison materials are now available at the IAEA (solid materials) and IGG (waters) for future distribution. L'Istituto di Geoscienze e Georisorse (IGG), pour le compte et avec le soutien de l'Agence Internationale de l'Energie Atomique (AIEA), a prepare huit materiaux geologiques (trois eaux naturelles et cinq roches et mineraux) destines a la conduite d'une comparaison en aveugle des mesures de composition isotopique et de concentration du bore entre differents laboratoires. Vingt-sept laboratoires -pratiquement tous ceux qui travaillent sur les isotopes du bore en geochimie - ont accepte de participer a cette intercomparaison, mais quinze seulement ont finalement envoye leurs donnees de composition isotopique et/ou de concentration du bore. Les resultats demontrent que la precision des valeurs indiquee par les laboratoires reflete mal la reproductibilite entre laboratoires des mesures de composition isotopique comme de concentration du bore. Les raisons de ces discordances peuvent comprendre l'existence de fractionnements isotopiques dus aux matrices chimiques des materiaux, un deplacement relatif du zero de l'echelle de δ11B, ainsi que le manque de materiaux bien caracterises pour calibrer les mesures de concentration du bore. Les materiaux utilises pour l'intercomparaison des mesures sont maintenant a disposition a l'AIEA (materiaux solides) et l'IGG (eaux) pour etre distribues.

Since late Miocene time, post-collisional extension of the internal parts of the Apennine orogenic belt has led to the opening of the Tyrrhenian basin. Extensive, mainly acidic peraluminous magmatism affected the Tuscan Archipelago and the Italian mainland during this time, building up the Tuscan Magmatic Province as the fold belt was progressively thinned, heated and intruded by mafic magmas. An intrusive complex was progressively built on western Elba Island by emplacement, within a stack of nappes, of multiple, shallow-level porphyritic laccoliths, a major pluton, and a final dyke swarm, all within the span from about 8 to 6.8 Ma. New geochemical and Sr–Nd isotopic investigations constrain the compositions of materials involved in the genesis of the magmas of Elba Island compared to the whole Tuscan Magmatic Province. Several distinct magma sources, in both the crust and mantle, have been identified as contributing to the Elba magmatism as it evolved from crust-, to hybrid-, to mantle-dominated. However, a restricted number of components, geochemically similar to mafic K-andesites of the Island of Capraia and crustal melts like the Cotoncello dyke at Elba, are sufficient to account for the generation by melt hybridization of the most voluminous magmas (c. εNd(t) −8.5, 87Sr/86Sr 0.715). Unusual magmas were emplaced at the beginning and end of the igneous activity, without contributing to the generation of these hybrid magmas. These are represented by early peraluminous melts of a different crustal origin (εNd(t) between −9.5 and −10.0, 87Sr/86Sr variable between 0.7115 and 0.7146), and late mantle-derived magma strongly enriched in incompatible elements (εNd(t) = −7.0, 87Sr/86Sr = 0.7114) with geochemical–isotopic characteristics intermediate between contemporaneous Capraia K-andesites and later lamproites from the Tuscan Magmatic Province. Magmas not involved in the generation of the main hybrid products are not volumetrically significant, but their occurrence emphasizes the highly variable nature of crust and mantle sources that can be activated in a short time span during post-collisional magmatism.

Elba Island intrusive complex: multisheet laccoliths, sheeted pluton, mafic dyke swarm. Laccolith magma fed from dykes and emplaced in crustal discontinuities (traps). Pluton growth by downward stacking of three magma pulses. Laccoliths and plutons: different outcomes of similar processes in different conditions. Emplacement of excess magma in a short time led to massive gravity slide.