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
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. \u
New U–Pb zircon ages from the Santa Olalla Igneous Complex have been obtained, which improve the knowledge of the precise timing of Variscan magmatism in the Ossa–Morena Zone, SW Iberia. This complex has a special relevance as it hosts the most important Ni–Cu–platinum group element (PGE) mineralization in Europe: the Aguablanca deposit. U–Pb zircon ages have been obtained for seven samples belonging to the Santa Olalla Igneous Complex and spatially related granites. With the exception of the Cala granite (352 ± 4 Ma), which represents an older intrusion, the bulk of samples yield ages that cluster around 340 ± 3 Ma: the Santa Olalla tonalite (341.5 ± 3 Ma), the Sultana hornblende tonalite (341 ± 3 Ma), a mingling area at the contact between the Aguablanca and Santa Olalla stocks (341 ± 1.5 Ma), the Garrote granite (339 ± 3 Ma), the Teuler granite (338 ± 2 Ma), and dioritic dykes from the Aguablanca stock (338.6 ± 0.8 Ma). The Bodonal–Cala porphyry, which has also been dated (530 ± 3 Ma), comprises a group of sub-volcanic rhyolitic intrusions belonging to the Bodonal–Cala volcano-sedimentary complex, which hosts the igneous rocks. The knowledge that emplacement of the Aguablanca deposit was related to episodic transtensional tectonic stages during the Variscan orogeny will be fundamental in future mineral exploration in the Ossa–Morena Zone.