Search

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.

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.

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 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.

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.

The Larderello geothermal field, located in southern Tuscany (Italy), is one of the most important long-living hydrothermal system in the world. The inner zone of the Northern Apennines is characterized by high heat flow, well constrained by several hundred measurements deriving from both shallow boreholes and deep exploration wells. It is widely accepted that the interplay among extensional tectonics, thinning of the previously overthickened crust and lithosphere, and magmatism related to crustal melting and hybridism, controlled the NW-SE trending geothermal anomaly occurring in southern Tuscany. At Larderello, the geothermal exploitation started at the beginning of the last century from the shallow evaporitecarbonate reservoir (about 700 - 1000 m b.g.l. on average) hosting a super-heated steam with temperature ranging from 150C to 260C. A deep exploration program was carried out in the early 1980s. Deep boreholes found a super-heated steam-dominated system hosted in the metamorphic basement (about 2500 - 4000 m b.g.l), characterized by temperatures ranging from 300C to 350C. In the SW part of the Larderello area (Lago locality), a temperature exceeding 400C was measured down to 3000 m b.s.l. The 2D and 3D seismic exploration activities provided evidences of a seismic marker, locally showing bright spot features, defining the top of a deeper reflective crustal interval, named as "K-horizon". The K-horizon has not yet been drilled, but some boreholes approached it. This seismic reflector exhibits interesting positive correlation with the maximum peak of the hypocentre distribution of low-magnitude earthquakes and, at the same time, its shape coincides with the thermal anomaly distribution, in plain view. The review and updating of the velocity and resistivity models suggest the existence of over-pressurized fluids, likely of magmatic and/or thermo-metamorphic origin, which originate the seismic velocity anomalies. The upward migration and storage of the fluids can be controlled by: i) structural conduits crossing a multi-layered crust affected by magmatic intrusions; ii) mechanisms controlling the fluid migration in different rheological settings; and iii) self-sealing processes of magmatic hypersaline fluids arising from the brittle/ductile transition. Our study is addressed to the better understanding of the structure of the deepest part of the Larderello geothermal field, by integrating structural, geological, geochemical and geophysical data. Based on downward temperature extrapolation, fluid inclusions and geothermometers analyses, the possible occurrence of super-hot fluids, in supercritical conditions, nearby the K-horizon is envisaged. The final goal is to achieve a comprehensive understanding of the geological structure and the physical conditions (pressure and temperature) of the deep reservoir including also the zone corresponding to the K-horizon, to characterize the supercritical geothermal system as well as the deep crustal processes that work in synergy leading to the regional anomaly.

he southern sector of the Apuan Alps (AA) mas- sif, Tuscany, Italy, is characterized by the occurrence of a series of baryte-pyrite-iron oxide orebodies whose Tl-rich nature was recognized only recently. The geochemistry of the pyrite ore was investigated through inductively coupled plasma mass spectrometry. In addition, lead isotope data for selected pyrite ores from AA were collected. Pyrite ores are characterized by a complex geochemistry, with high concen- trations of Tl (up to 1100 ?g/g) coupled with high As and Sb contents; the Co/Ni ratio is always

A crystal-chemical study of historical specimens as well as new ones belonging to the jordanite–geocronite series from the Pollone baryte + pyrite ± (Pb-Zn-Ag) ore deposit (Valdicastello Carducci, Apuan Alps, Tuscany, Italy) has been performed. These crystals were collected in quartz extension veins embedded in three different occurrences: (i) baryte + pyrite orebodies; (ii) schist layers interbedded between baryte + pyrite orebodies; and (iii) schists at the contact with pyrite-poor baryte orebodies. Electron-microprobe data indicated the occurrence of three distinct groups of compositions within the sample suite. These correspond to As-bearing geocronite, Sb-rich jordanite, and Sb-bearing jordanite, with mean compositions Pb14Sb3.8As2.2S23, Pb14Sb2.9As3.1S23, and Pb14Sb2.6As3.4S23, respectively. Crystals representative of these different compositions have been investigated through single-crystal X-Ray diffraction studies and their crystal structures have been solved to R1 = 0.078, 0.069, and 0.033, respectively. The unit-cell volume decreases passing through As-bearing geocronite (V = 2149.5(3) Å3) to Sb-bearing jordanite (V = 2132.3(3) Å3). The As-to-Sb substitution takes place preferentially at the Sb4 site; through the increasing of the Sb content, Sb can substitute As also at the As6 site. According to the structural study of the ore deposit, formation of jordanite–geocronite is subordinated to a late Alpine deformative D2 stage, which permitted in situ remobilization of preexisting sulfide ore in small quartz extension veins. Such a local recrystallization would explain the variability of the As/(As + Sb) ratio of the members of the jordanite series, reflecting the heterogeneity of the orebody.

This paper reports the first example of fault mirrors developed in an unusual protolith, consisting of tourmaline crystals with interstitial goethite. The deformation mechanisms active in the fault zone have been investigated from the outcrop to the nanoscale, aiming to identify possible traces of frictional heating at seismic slip rate, as observed for other fault mirrors in different protoliths. The investigation revealed the superposition of two main deformational stages. The first was dominated by brittle processes and produced a cataclastic/ultracataclastic principal slip zone, a few mm thick; the second was associated with seismic slip and produced a sharp discontinuity (the principal slip surface) within the cataclastic/ultracataclastic zone. The mirror-like coating, a few microns thick, occurs on the principal slip surface, and is characterized by 1) absence of interstitial goethite; 2) occurrence of truncated tourmaline crystals; 3) highly variable grain size, from 200 μm to 200 nm; 4) tourmaline close packing with interlobate grain boundaries, and 5) tourmaline random crystallographic orientation. Micro and nanostructural investigations indicate the occurrence of thermally-activated processes, involving both interstitial goethite and tourmaline. In particular, close to the principal slip surface, goethite is completely decomposed, and produced an amorphous porous material, with local topotactic recrystallization of hematite. Tourmaline clasts are typically characterized by strongly lobate boundaries, indicative of reaction and partial decomposition at grain boundaries. TEM observations revealed the occurrence of tourmaline nanograins, a few tens of nm in size, characterized by rounded shape and fading amorphous boundaries, that cannot be obtained by brittle processes. Lastly, the peculiar interlobate microstructure of the mirror surface is interpreted as the result of grain boundary recrystallization processes taking place by deformation at high-T conditions. Our results show that tourmaline fault mirrors recorded localized high-T processes triggered by frictional heating and can be therefore considered as reliable traces of ancient earthquakes.