L. Ortega

U-Pb age constraints on Variscan magmatism and Ni-Cu-PGE metallogeny in the Ossa-Morena Zone (SW Iberia)

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.

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.

Platinum-group elements-bearing pyrite from the Aguablanca Ni-Cu sulphide deposit (SW Spain): a LA-ICP-MS study

Despite the fact that pyrite is a relatively common phase in Ni-Cu-Platinum-Group Elements (PGE) magmatic sulphide deposits, the trace element content of the pyrite has been neglected in the studies of these deposits with most attention being paid to the PGE concentrations of pyrrhotite, pentlandite and chalcopyrite. Pyrite in these deposits exhibits a range of textures, from euhedral to xenomorphic. The origin of the different pyrites is not always clear; they could have formed by exsolution from monosulphide solid solution (mss), by replacement of the existing minerals during cooling or metamorphism or directly from hydrothermal fluids. In order to provide data on trace element contents of pyrite in a magmatic sulphide deposit and to investigate the origin of the pyrite, we have measured the content of PGE and other chalcophile elements (Au, Ag, Co, Ni, Cu, Se, Sb, As, Bi and Te) by laser ablation ICP-MS in pyrite exhibiting different textures from the Aguablanca Ni-Cu deposit (Spain). The results show that 1) large idiomorphic pyrite is compositionally-zoned with Os-Ir-Ru-Rh-As-rich layers and Se-Co-rich layers; 2) some idiomorphic pyrite grains contain unusually high PGE contents (up to 32 ppm Rh and 9 ppm Pt); 3) ribbon-like and small-grained pyrite hosts IPGE (i.e., Iridium-group PGE, Os, Ir, Ru and Rh) in similar contents (100–200 ppb each) than the host pyrrhotite; and 4) pyrite replacing plagioclase is depleted in most metals (i.e., PGE, Co, Ni and Ag). Overall, the different textural types of pyrite have similar abundances of Pd, Au, Se, Bi, Te, Sb and As. Mineralogical and compositional data suggest that the formation of pyrite is the result of the activity of late magmatic/hydrothermal fluids that triggered the partial replacement of pyrrhotite and plagioclase by pyrite, probably due to an increase in the sulphur fugacity on cooling. During this episode, pyrite inherited the IPGE content of the replaced mineral, whereas other elements such as Pd, Au and semi-metals were likely partially introduced into pyrite via altering fluids. These results highlight that pyrite can host appreciable amounts of PGE and therefore it should not be overlooked as a potential carrier of these metals in Ni-Cu-(PGE) sulphide deposits.

Origin and emplacement of the Aguablanca magmatic Ni-Cu-(PGE) sulfide deposit, SW Iberia: A multidisciplinary approach

A model is proposed for the origin and emplacement of the ca. 341 Ma Aguablanca magmatic Ni-Cu-(platinum group element [PGE]) sulfi de deposit (SW Iberia) integrating petrological, geochemical, structural, and geophysical data. The Aguablanca deposit occurs in an unusual geodynamic context for this ore type (an active plate margin) as an exotic , magmatic subvertical breccia located at the northern part of the coeval gabbronorite Aguablanca stock (341 ± 1.5 Ma). Structural and gravity data show that mineralized breccia occurs inside the inferred feeder zone for the stock adjacent to the Cherneca ductile shear zone, a Variscan sinistral transpressional structure. The orientation of the feeder zone corresponds to that expected for tensional fractures formed within the strain fi eld of the adjacent Cherneca ductile shear. Two distinctive stages are established for the origin and emplacement of the deposit: (1) initially, the ore-forming processes are attributed to magma emplacement in the crust, assimilation of crustal S, and segregation and gravitational settling of sulfi de melt (a scenario similar to most plutonic Ni-Cu sulfi de ores), and (2) fi nal emplacement of the Ni-Cu sulfi de-bearing rocks by multiple melt injections controlled by successive opening events of tensional fractures related to the Cherneca ductile shear zone.

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.

Liquid immiscibility between arsenide and sulfide melts: evidence from a LA-ICP-MS study in magmatic deposits at Serranía de Ronda (Spain)

The chromite-Ni arsenide (Cr-Ni-As) and sulfide-graphite (S-G) deposits from the Serranía de Ronda (Málaga, South Spain) contain an arsenide assemblage (nickeline, maucherite and nickeliferous löllingite) that has been interpreted to represent an arsenide melt and a sulfide-graphite assemblage (pyrrhotite, pentlandite, chalcopyrite and graphite) that has been interpreted to represent a sulfide melt, both of which have been interpreted to have segregated as immiscible liquids from an arsenic-rich sulfide melt. We have determined the platinum-group element (PGE), Au, Ag, Se, Sb, Bi and Te contents of the arsenide and sulfide assemblages using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to establish their partitioning behaviour during the immiscibility of an arsenide melt from a sulfide melt. Previous experimental work has shown that PGE partition more strongly into arsenide melts than into sulfide melts and our results fit with this observation. Arsenide minerals are enriched in all PGE, but especially in elements with the strongest affinity for the arsenide melt, including Ir, Rh and Pt. In contrast and also in agreement with previous studies, Se and Ag partition preferentially into the sulfide assemblage. The PGE-depleted nature of sulfides in the S-G deposits along with the discordant morphologies of the bodies suggest that these sulfides are not mantle sulfides, but that they represent the crystallization product of a PGE-depleted sulfide melt due to the sequestering of PGE by an arsenide melt.

The Mari Rosa late Hercynian Sb-Au deposit, western Spain

The central Iberian zone of the Hesperian Massif hosts a series of late Hercynian vein-type Sb deposits. One of them is the Mari Rosa mineralization, hosted by metagreywackes and slates of the Schist-Greywacke Complex (Upper Precambrian). The mineralization is characterized by a complex paragenesis comprising three hydrothermal stages: stage H1 → arsenopyrite-(pyrite); stage H2 → stibnite-gold; and stage H3 → pyrite-pyrrhotite-galena-sphalerite-chalcopyrite-tetrahedrite-boul-angerite-stibnite. Of these only the second episode was of importance and gave rise to the main mineralized bodies of the deposit. Hydrothermal alteration consists of a mild sericitization, chloritization and carbonatization of the metasedimentary rocks around the veins. Chemical changes in the hydrothermal halos include a remarkable increase in the ratio K2O/Na2O, and a decrease in the ratio SiO2/volatiles, together with a sharp increase in Sb, Mo, Au and N. Fluids associated with ore deposition lie in the H2O-NaCl-CO2-CH4-N2 compositional system. These fluids evolved, progressively cooling, from initial circulaion temperatures close to 400 °C in the early stage (H1) to temperatures of approximately 150 °C in the late one (H3). Fluid composition evolution was characterized by a progressive increase in the bulk water content of the fluids and with an increase in the relative proportion of N2 with respect to CH4 and CO2 in the volatile fraction. Massive stibnite deposition resulted from a boiling process developed at 300 °C and 0.9–1 Kb at a depth of 4–5 km. Geological, geochemical and fluid inclusion evidence suggest that the intrusion of the Alburquerque batholith (late Hercynian S-type granitoids) triggered hydrothermal activity leading to the transport and deposition of Sb and Au in Mari Rosa.

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.