Search

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.

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.

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.

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 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.

Geometric analysis of vein systems hosted in upper crustal rocks and developed in high and low temperature hydrothermal systems is presented. The high temperature hydrothermal system consists of tourmaline-rich veins hosted within the contact aureole of the upper Miocene Porto Azzurro pluton in the eastern Elba Island. The low temperature hydrothermal system consists of calcite-rich veins hosted within the Oligocene sandstones of the Tuscan Nappe, exposed along the coast in southern Tuscany. Vein thickness distribution is here used as proxy for inferring some hydraulic properties (transmissivity) of the fluid circulation at the time of veins’ formation. We derive estimations of average thickness of veins by using the observed distributions. In the case of power law thickness distributions, the lower the scaling exponent of the distribution the higher the overall transmissivity. Indeed, power law distributions characterised by high scaling exponents have transmissivity three order of magnitude lower than negative exponential thickness distribution. Simple observations of vein thickness may thus provides some clues on the transmissivity in hydrothermal systems.

We report the discovery of an exceptional assemblage of Tl-Hg-As-Sb-(Ag,Cu)-Pb sulfosalts showing textural evidence for their mobilization as melts in the barite-pyrite-iron oxide ore- bodies of the Monte Arsiccio mine (Alpi Apuane, Tuscany, Italy). The relative abundance of rare thallium sulfosalts (including three new mineral species), their peculiar textural features within the orebodies (e.g., migration along matrix grain boundaries, drop-like internal tex- tures, low interfacial angles between sulfosalts and matrix minerals), and the overall high thal- lium content in pyrite from the entire mining district (to ~900 ppm) make the barite-pyrite- iron oxide deposits of the Alpi Apuane a reference locality for studying low-temperature sulfosalt melts in low-grade metamorphic complexes (greenschist facies). Our study reveals how sulfosalt melting during low-grade regional metamorphism controls the redistribution of economically valuable and environmentally critical elements such as thallium in sulfide orebodies containing significant amounts of low-melting-point chalcophile elements.

The Monte Capanne pluton was emplaced during the Late Miocene in a post-collision extensional regime that generated the Tuscan Magmatic Province as the Adriatic (lower) plate underwent progressive crustal delamination. This dominantly monzogranitic pluton, generated by hybridization between mantle and crustal magmas, consists of mappable facies; end members range from less hybridized with high concentrations of very coarse K-feldspar megacrysts and abundant mafic microgranular enclaves, to more hybridized with low megacryst and enclave abundances. K-feldspar megacrysts from Monte Capanne and other related units of the province, along with their inclusions and associated late mineral phases, preserve evidence of chemical and 87Sr/86Sr disequilibrium (first rising and then falling) during evolution of the system. The concomitant occurrence of contrasting reaction microtextures in accessory phases in this anatectic-hybrid pluton, particularly involving monazite-(Ce), also suggests transient chemical conditions. The ubiquitous mafic microgranular enclaves, typically with high concentrations of xenocrysts from Monte Capanne magma, provide evidence of a highly dynamic system involving vigorous interaction between mafic and felsic magmas. The data suggest that rapid dehydration melting, driven by intrusions of fractionating mantle-derived magma near the base of the crust, was followed by magma mixing and K-feldspar megacryst growth. Segregation and ascent produced the hybridized products now observed at the emplacement level. RÉSUMÉ L'intrusion du pluton du mont Capanne est survenue au cours du Miocène tardif dans un régime d'extension de post-collision ayant produit la province magmatique de Toscane au fur et à mesure que la plaque (inférieure) de l'Adriatique a subi une delamination crustale progressive. Ces plutons principalement monzogranitiques, produits par hybridation entre les magmas mantéliques et crustaux, sont constitués de faciès cartographiables; les membres d'extrémité varient des membres peu hybridés renfermant de fortes concentrations de mégacristaux de feldspath potassique très grossiers et d'enclaves microgranulaires mafiques abondantes à des membres plus hybridés comportant de faibles abondances d'enclaves et de mégacristaux. Les mégacristaux de feldspath potassique du mont Capanne et des autres unités apparentés de la province, de même que leurs inclusions et leurs phases minérales tardives associées, préservent les indices d'un déséquilibre chimique et de 87Sr/86Sr (d'abord hausse, puis baisse) pendant l'évolution du système. La présence concomitante de microtextures à réactions opposées au cours de phases accessoires dans ce pluton anatectique-hybride, mettant en scène en particulier de la monazite-(Ce), permet par ailleurs de supposer des conditions chimiques transitoires. Les enclaves microgranulaires mafiques ubiquistes, présentant généralement des concentrations élevées de xénocristaux du magma du mont Capanne, témoignent d'un système extrêmement dynamique présentant une interaction prononcée entre les magmas mafiques et felsiques. Les données laissent supposer qu'une fusion à déshydratation rapide, animée par les intrusions de magma mantélique s'étant fractionné près de la base de la croûte, a été suivie d'un mixage de magma et de la croissance de mégacristaux de feldspath potassique. La ségrégation et l'ascension magmatiques ont fourni les produits hybridés maintenant observés au niveau de l'intrusion. [Traduit par la rédaction]

In 1999 the Istituto di Geoscienze e Georisorse (IGG), with the support of the International Atomic Energy Agency (IAEA), undertook the collection, preparation and distribution of eight geological materials intended for a blind interlaboratory comparison of measurements of boron isotopic composition and concentration. The materials came from Italian sources and consist of three natural waters (Mediterranean seawater and two groundwaters) and five rocks and minerals (tourmaline, basalt, obsidian, limestone and clay). The solid materials were crushed, milled and mixed, in preparation for distribution. Extensive assays performed at the IGG on these materials demonstrated that their boron isotopic and chemical compositions are homogeneous. Additional homogeneity tests were carried out on solid material fragments at the GeoForschungsZentrum Potsdam, with the specific objective of investigating the suitability of some of them for the calibration in situ of micro-analytical techniques. Two materials, B4 (tourmaline) and B6 (obsidian), proved to be isotopically homogeneous and may become excellent references for in situ microanalyses of boron isotopes. The materials described here were used as the basis of a major laboratory intercomparison study and are now available for further distribution from either the IAEA (solid materials) or the IGG (waters). L'Istituto di Geoscienze e Georisorse (IGG), avec le soutien de l'Agence Internationale de l'Energie Atomique (AIEA), a entrepris en 1999 la recolte, la preparation et la distribution de huit materiaux geologiques dans le but de conduire une comparaison en aveugle des mesures de composition isotopique et de concentration du bore entre differents laboratoires. Les materiaux, qui derivent tous de sites italiens, comprennent trois eaux naturelles (une eau de la Mer Mediterranee et deux eaux souterraines) et cinq roches et mineraux (tourmaline, basalte, obsidienne, calcaire et argile). Pour la distribution, les materiaux solides ont ete reduits en fragments, broyes et melanges et leur homogeneite de composition isotopique et chimique du bore a ete verifiee par des essais exhaustifs. D'autres essais d'homogeneite ont ete effectues au GeoForschungsZentrum Potsdam sur des fragments des materiaux solides avec le but particulier d'etudier la possibilite d'utilisation de ces materiaux pour la calibration in situ des techniques microanalytiques. Deux materiaux, le B4 (tourmaline) et le B6 (obsidienne), se sont reveles isotopiquement homogenes et donc peuvent devenir d'excellents materiaux de reference pour les microanalyses isotopiques in situ du bore. Les materiaux, qui sont decrits dans cette note, ont ete utilises pour une etude d'intercomparaison des mesures isotopiques et chimiques du bore entre differents laboratoire. Ils sont maintenant a disposition a l'AIEA (materiaux solides) et a l'IGG (eaux) pour leur distribution ulterieure.