Primeros datos del magmatismo pérmico medio-superior del SE de la Cordillera Ibérica: caracterización y comparación con magmatismos contemporáneos del Tethys occidental

A multiple basic to intermediate sill is reported for the first time in the south-eastern Iberian Ranges. It is composed of several tabular to irregular levels intercalated within the fluvial sediments of the Alcotas Formation (Middle-Upper Permian). The sill could represent the youngest Paleozoic subvolcanic intrusion in the Iberian Ranges. The igneous rocks are classified as basaltic andesites. They show a subophitic microstructure constituted by plagioclase (An62 – An6), augite (En48Wo44Fs7 –En46Wo39Fs15), pseudomorphosed olivine, minor amounts of oxides (magnetite and ilmenite) and accessory F-apatite. According to the mineralogy and whole-rock composition, their geochemical affinity is transitional from subalkaline to alkaline. Radiometric dating of the sill is not feasible due to its significant alteration. Field criteria, however, suggest an emplacement coeval to the deposition of the Alcotas Formation (Middle-Upper Permian). This hypothesis is supported by the transitional affinity of these rocks, similar to other Middle-Upper Permian magmatisms in the western Tethys, e.g., from the Pyrenees. Taking into account their isotopic signature (εSr: -6.8 to -9.2; εNd: +1.7 to +8.3), an enriched mantle source with the involvement of a HIMU component has been identified. This interpretation is supported by the trace element contents. Some of these HIMU characteristics have been recognised in the Middle-Upper Permian magmatisms of the Central Pyrenees (Anayet Basin) and the High Atlas (Argana Basin). However, none of these source features are shared with other Middle-Upper Permian magmatisms of the western Tethys (Catalonian Coastal Ranges, Corsica-Sardinia and southern France), nor with the Lower Permian magmatism of the Iberian Ranges. These differences support the presence of a heterogeneous mantle in the western Tethys during the Permian.Se describe por primera vez en el sudeste de la Cordillera Ibérica un sill múltiple de carácter básico a intermedio. Está compuesto por varios cuerpos tabulares a irregulares intercalados entre los sedimentos de origen fluvial de la Formación Alcotas (Pérmico Medio-Superior). El sill podría representar la intrusión subvolcánica paleozoica más reciente en la Cordillera Ibérica. Estas rocas subvolcánicas se clasifican como andesitas basálticas. Muestran una textura subofítica constituida por plagioclasa (An62 – An6), augita (En48Wo44Fs7 –En46Wo39Fs15), pseudomorfos de olivino, minerales opacos (magnetita e ilmenita) y F-apatito accesorio. De acuerdo con su composición mineral y de roca total, su afinidad geoquímica es transicional entre subalcalina y alcalina. La datación radiométrica del sill no es posible debido a su elevado grado de alteración. No obstante, los criterios de campo sugieren un emplazamiento contemporáneo con el depósito de la Formación Alcotas (Pérmico Medio-Superior). Esta hipótesis está apoyada por la afinidad transicional de estas rocas, similar a otros episodios magmáticos del Pérmico Medio-Superior en el Tethys occidental, como los que afloran en los Pirineos. Teniendo en cuenta su signatura isotópica (εSr: -6.8 a -9.2; εNd: +1.7 a +8.3), se propone un origen a partir de un manto enriquecido, con la participación de un componente de tipo HIMU. Esta interpretación está apoyada por sus contenidos en elementos traza. Algunas de estas características del protolito han sido reconocidas en los magmatismos del Pérmico Medio-Superior del Pirineo (cuenca del Anayet) y del Alto Atlas (cuenca de Argana), pero no son habituales en otros magmatismos de edad Pérmico Medio-Superior del Tethys occidental (Cadenas Costero Catalanas, Córcega-Cerdeña y Sur de Francia), ni en el magmatismo Pérmico Inferior de la Cordillera Ibérica. Estas diferencias apoyan la presencia de un manto heterogéneo en el Tethys occidental durante el Pérmico

Transition between Variscan and Alpine cycles in the Pyrenean-Cantabrian Mountains (N Spain): Geodynamic evolution of near-equator European Permian basins

In the northern Iberian Peninsula, the Pyrenean-Cantabrian orogenic belt extends E-W for ca. 1000 km between the Atlantic Ocean and Mediterranean Sea. This orogen developed from the collision between Iberia and Eurasia, mainly in Cenozoic times. Lower-middle Permian sediments crop out in small, elongated basins traditionally considered independent from each other due to misinterpretations on incomplete lithostratigraphic data and scarce radiometric ages. Here, we integrate detailed stratigraphic, sedimentary, tectonic, paleosol and magmatic data from well-dated lithostratigraphic units. Our data reveal a similar geodynamic evolution across the Pyrenean-Cantabrian Ranges at the end of the Variscan cycle. Lower-middle Permian basins started their development under an extensional regime related to the end of the Variscan Belt collapse, which stars in late Carboniferous times in the Variscan hinterland. This orogenic collapse transitioned to Pangea breakup at the middle Permian times in the study region. Sedimentation occurred as three main tectono-sedimentary extensional phases. A first phase (Asselian-Sakmarian), which may have even started at the end of the Carboniferous (Gzhelian) in some sections, is mainly represented by alluvial sedimentation associated with calc-alkaline magmatism. A second stage (late Artinskian-early Kungurian), represented by al-luvial, lacustrine and palustrine sediments with intercalations of calc-alkaline volcanic beds, shows a clear up-ward aridification trend probably related to the late Paleozoic icehouse-greenhouse transition. The third and final stage (Wordian-Capitanian) comprised of alluvial deposits with intercalations of alkaline and mafic beds, rarely deposited in the Cantabrian Mountains, and underwent significant pre-and Early Mesozoic erosion in some segments of the Pyrenees. This third stage can be related to a transition towards the Pangea Supercontinent breakup, not generalized until the Early/Middle Triassic at this latitude because the extensional process stopped about 10 Myr (Pyrenees) to 30 Myr (Cantabrian Mountains). When compared to other well-dated basins near the paleoequator, the tectono-sedimentary and climate evolution of lower-middle Permian basins in Western and Central Europe shows common features. Specifically, we identify coeval periods with magmatic activity, extensional tectonics, high subsidence rates and thick sedi-mentary record, as well as prolonged periods without sedimentation. This comparison also identifies some evolutionary differences between Permian basins that could be related to distinct locations in the hinterland or foreland of the Variscan orogen. Our data provide a better understanding of the major crustal re-equilibration and reorganization that took place near the equator in Western-Central Europe during the post-Variscan period

New lithostratigraphy for the Cantabrian Mountains: A common tectono-stratigraphic evolution for the onset of the Alpine cycle in the W Pyrenean realm, N Spain

The Pyrenean-Cantabrian Orogen arose through the collision of the Iberian and Eurasian plates, mostly in Cenozoic times. This orogen comprises two main mountain ranges, the Pyrenees to the east, and the Cantabrian Mountains to the west. To date, the early Alpine tectono-sedimentary phases preserved in the Cantabrian Mountains, of Permian and Triassic age, have been considered independently from the same phases in neighbouring basins of SW Europe, and even from the eastern part of the same orogeny (the Pyrenean orogeny). In consequence, the beginning of the Alpine cycle in the Cantabrian Mountains has been interpreted within a specific geodynamic context, far from the general evolutionary phases of the western Peri-Tethys basins. Through detailed field work, including geological mapping, sedimentology, lithostratigraphy and petrology of volcanic rocks, and new palaeontological data, here we define several new lithostratigraphical formations and five new tectono-sedimentary cycles (TS I-V) for the initial phases of evolution of the Mesozoic Basque-Cantabrian Basin, interrupted by periods of tectonic stability. To complete this information, we include data from an onshore borehole (Villabona Mine) and two offshore boreholes constrained by 2D reflection seismic profiles acquired in the North Iberian continental platform. The main tectono-sedimentary cycles, related to the deposition of five major identified lithostratigraphic units, can be described as follows: TS I (late Gzelian-early Asselian), relating to the late Variscan deformation and preserved in a single outcrop in all the Cantabrian Mountains (San Tirso Formation). This formation is constituted by medium-distal alluvial fan deposits in which humid intervals predominate, forming some thin coal beds. TS II (Asselian-Sakmarian), a post-Variscan extensional phase with associated calc-alkaline magmatism, represented by profuse volcanic and volcanosedimentary intercalations in the early Permian sedimentary basins (Acebal Formation) and small plutons in surrounding areas. TS III (Kungurian), or reactivation of the post-Variscan extension leading to alluvial and lacustrine carbonate sedimentation in arid climate conditions, which do not change during the rest of the Permian and Triassic periods (Sotres Formation). A generalized karstification in the basin represents the end of Permian deposition, followed by an interruption in sedimentation longer than 30 Myr. The Permian tectono-sedimentary cycles (TS II and TS III) are contemporary with Variscan belt collapse and the basins are controlled by extensional reactivation of NE-SW and E-W Variscan structures, and NW-SE late Variscan structures. TS IV (late Anisian–middle Carnian), renewed sedimentation in more extensive basins, precursors of the great Mesozoic Basque-Cantabrian Basin. This cycle is represented by fluvial deposits (Cicera Formation, or Buntsandstein facies), which are interrupted by the first Mesozoic marine ingression (Rueda Formation, or Muschelkalk facies). TS V (Norian-Rhaetian), or shallow marine carbonate deposits (Transición Formation) related to increasingly compartmentalized sub-basins, controlled by normal faults. This final TS is broadly connected with different basins of the western Peri-Tethys domain. The identification of units TS I-V in the Cantabrian Mountains along with the volcanic character of TS II, all indicate the development of a common post-Variscan to early Alpine tectono-sedimentary evolution for the whole Pyrenean-Cantabrian realm

Key factors controlling massive graphite deposition in volcanic settings : an example of a self-organized critical system

Massive graphite deposition resulting in volumetrically large occurrences in volcanic environments is usually hindered by the low carbon contents of magmas and by the degassing processes occurring during and after magma emplacement. In spite of this, two graphite deposits are known worldwide associated with volcanic settings, at Borrowdale, UK, and Huelma, Spain. As inferred from the Borrowdale deposit, graphite mineralization resulted from the complex interaction of several factors, so it can be considered as an example of self-organized critical systems. These factors, in turn, could be used as potential guides for exploration. The key factors influencing graphite mineralization in volcanic settings are as follows: (1) an unusually high carbon content of the magmas, as a result of the assimilation of carbonaceous metasedimentary rocks; (2) the absence of significant degassing, related to the presence of sub-volcanic rocks or hypabyssal intrusions, acting as barriers to flow; (3) the exsolution of a carbon-bearing aqueous fluid phase; (4) the local structural heterogeneity (represented at Borrowdale by the deep-seated Burtness Comb Fault); (5) the structural control on the deposits, implying an overpressured, fluid-rich regime favouring a focused fluid flow; (6) the temperature changes associated with fluid flow and hydration reactions, resulting in carbon supersaturation in the fluid, and leading to disequilibrium in the system. This disequilibrium is regarded as the driving force for massive graphite precipitation through irreversible mass-transfer reactions. Therefore, the formation of volcanic-hosted graphite deposits can be explained in terms of a self-organized critical system

Graphite morphologies from the Borrowdale deposit (NW England, UK) : Raman and SIMS data

Graphite in the Borrowdale (Cumbria, UK) deposit occurs as large masses within mineralized pipe-like bodies, in late graphite–chlorite veins, and disseminated through the volcanic host rocks. This occurrence shows the greatest variety of crystalline graphite morphologies recognized to date from a single deposit. These morphologies described herein include flakes, cryptocrystalline and spherulitic aggregates, and dish-like forms. Colloform textures, displayed by many of the cryptocrystalline aggregates, are reported here for the first time from any graphite deposit worldwide. Textural relationships indicate that spherulitic aggregates and colloform graphite formed earlier than flaky crystals. This sequence of crystallization is in agreement with the precipitation of graphite from fluids with progressively decreasing supersaturation. The structural characterization carried out by means of Raman spectroscopy shows that, with the exception of colloform graphite around silicate grains and pyrite within the host rocks, all graphite morphologies display very high crystallinity. The microscale SIMS study reveals light stable carbon isotope ratios for graphite (δ 13C = −34.5 to −30.2‰), which are compatible with the assimilation of carbon-bearing metapelites in the Borrowdale Volcanic Group magmas. Within the main mineralized breccia pipe-like bodies, the isotopic signatures (with cryptocrystalline graphite being lighter than flaky graphite) are consistent with the composition and evolution of the mineralizing fluids inferred from fluid inclusion data which indicate a progressive loss of CO2. Late graphite–chlorite veins contain isotopically heavier spherulitic graphite than flaky graphite. This agrees with CH4-enriched fluids at this stage of the mineralizing event, resulting in the successive precipitation of isotopically heavier graphite morphologies. The isotopic variations of the different graphite morphologies can be attributed therefore, to changes in the speciation of carbon in the fluids coupled with concomitant changes in the XH2O during precipitation of graphite and associated hydrous minerals (mainly epidote and chlorite)

Graphite deposition related to degassing a silicate melt: the Huelma mineralization (South Spain)

Graphite deposition related to degassing a silicate melt: the Huelma mineralization (South Spain). Abstract of IMA-2002, Edinburgh, Scotlan

Carbon isotopes of graphite: Implications on fluid history

Stable carbon isotope geochemistry provides important information for the recognition of fundamental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elaboration of models for the global carbon cycle. Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon (organic matter, mantle, or carbonates) and help to constrain the fluid history and the mechanisms involved in graphite deposition. Graphite precipitation in fluid-deposited occurrences results from CO2- and/or CH4-bearing aqueous fluids. Fluid flow can be considered as both a closed (without replenishment of the fluid) or an open system (with renewal of the fluid by successive fluid batches). In closed systems, carbon isotope systematics in graphite is mainly governed by Rayleigh precipitation and/or by changes in temperature affecting the fractionation factor between fluid and graphite. Such processes result in zoned graphite crystals or in successive graphite generations showing, in both cases, isotopic variation towards progressive 13C or 12C enrichment (depending upon the dominant carbon phase in the fluid, CO2 or CH4, respectively). In open systems, in which carbon is episodically introduced along the fracture systems, the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of δ13C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation

Vein graphite deposits: geological settings, origin, and economic significance

Graphite deposits result from the metamorphism of sedimentary rocks rich in carbonaceous matter or from precipitation from carbon-bearing fluids (or melts). The latter process forms vein deposits which are structurally controlled and usually occur in granulites or igneous rocks. The origin of carbon, the mechanisms of transport, and the factors controlling graphite deposition are discussed in relation to their geological settings. Carbon in granulite-hosted graphite veins derives from sublithospheric sources or from decarbonation reactions of carbonate-bearing lithologies, and it is transported mainly in CO2-rich fluids from which it can precipitate. Graphite precipitation can occur by cooling, water removal by retrograde hydration reactions, or reduction when the CO2-rich fluid passes through relatively low-fO2 rocks. In igneous settings, carbon is derived from assimilation of crustal materials rich in organic matter, which causes immiscibility and the formation of carbon-rich fluids or melts. Carbon in these igneous-hosted deposits is transported as CO2 and/or CH4 and eventually precipitates as graphite by cooling and/or by hydration reactions affecting the host rock. Independently of the geological setting, vein graphite is characterized by its high purity and crystallinity, which are required for applications in advanced technologies. In addition, recent discovery of highly crystalline graphite precipitation from carbon-bearing fluids at moderate temperatures in vein deposits might provide an alternative method for the manufacture of synthetic graphite suitable for these new applications

Microstructure and mineralogy of lightweight aggregates manufactured from mining and industrial wastes

The microstructure and mineralogy of lightweight aggregates manufactured with washing aggregate sludge, sewage sludge and a clay-rich sediment have been studied. The mineralogical analysis revealed the neo-formation of plagioclase and pyroxene group minerals and a minor presence of gehlenite. Some relationships may be established: (i) heating temperature and dwell time affect the formation of new porosity; (ii) the disappearance of pyroxenes could produce changes in the density of the solid material in the lightweight aggregates; (iii) when an external glassy film is not present, water absorption values depend on the size and number of each type of pore

Deposition of highly crystalline graphite from moderate-temperature fluids

Recognized large occurrences of fluid-deposited graphite displaying high crystallinity were previously restricted to high-temperature environments (mainly granulite facies terranes). However, in the extensively mined Borrowdale deposit (UK), the mineralogical assemblage, notably the graphite-epidote intergrowths, shows that fully ordered graphite precipitated during the propylitic hydrothermal alteration of the volcanic host rocks. Fluids responsible for graphite deposition had an average X CO2/(XCO2 + X CH4) ratio of 0.69, thus indicating temperatures of ~500 °C at the fayalite-magnetite-quartz buffered conditions. Therefore, this is the first reported evidence indicating that huge concentrations of highly crystalline graphite can precipitate from moderate-temperature fluids