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 d13C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation

Contrasting Mineralizing Processes in Volcanic-Hosted Graphite Deposits

The only two known graphite vein-deposits hosted by volcanic rocks (Borrowdale, United Kingdom, and Huelma, Southern Spain) show remarkable similarities and differences. The lithology, age of the magmatism and geodynamic contexts are distinct, but the mineralized bodies are controlled by fractures. Evidence of assimilation of metasedimentary rocks by the magmas and hydrothermal alteration are also common features to both occurrences. Graphite morphologies at the Borrowdale deposit vary from flakes (predominant) to spherulites and cryptocrystalline aggregates, whereas at Huelma, flaky graphite is the only morphology observed. The structural characterization of graphite indicates a high degree of ordering along both the c axis and the basal plane. Stable carbon isotope ratios of graphite point to a biogenic origin of carbon, most probably related to the assimilation of metasedimentary rocks. Bulk į13C values are quite homogeneous in both occurrences, probably related to precipitation in short time periods. Fluid inclusion data reveal that graphite precipitated from C-O-H fluids at moderate temperature (500 ºC) in Borrowdale and crystallized at high temperature from magma in Huelma, In addition, graphite mineralization occurred under contrasting fO2 conditions. All these features can be used as potential exploration tools for volcanic-hosted graphite deposits

Assimilation, Hydrothermal Alteration and Graphite Mineralization in the Borrowdale Deposit (UK)

The volcanic-hosted graphite deposit at Borrowdale was formed through precipitation from C-O-H fluids. The G13C data indicate that carbon was incorporated into the mineralizing fluids by assimilation of carbonaceous metapelites of the Skiddaw Group by andesite magmas of the Borrowdale Volcanic Group. The graphite mineralization occurred as the fluids migrated upwards through normal conjugate fractures forming the main subvertical pipe-like bodies. The mineralizing fluids evolved from CO2-CH4-H2O mixtures (XCO2=0.6-0.8) to CH4-H2O mixtures. Coevally with graphite deposition, the andesite and dioritic wall rocks adjacent to the veins were intensely hydrothermally altered to a propylitic assemblage. The initial graphite precipitation was probably triggered by the earliest hydration reactions in the volcanic host rocks. During the main mineralization stage, graphite precipitated along the pipe-like bodies due to CO2 -> C+O2. This agrees with the isotopic data which indicate that the first graphite morphologies crystallizing from the fluid (cryptocrystalline aggregates) are isotopically lighter than those crystallizing later (flakes). Late chlorite-graphite veins were formed from CH4-enriched fluids following the reaction CH4 + O2 -> C+ 2H2O, producing the successive precipitation of isotopically lighter graphite morphologies. Thus, as mineralization proceeded, water-generating reactions were involved in graphite precipitation, further favouring the propylitic alteration

Assimilation, Hydrothermal Alteration and Graphite Mineralization in the Borrowdale Deposit (UK)

The volcanic-hosted graphite deposit at Borrowdale was formed through precipitation from C-O-H fluids. The G13C data indicate that carbon was incorporated into the mineralizing fluids by assimilation of carbonaceous metapelites of the Skiddaw Group by andesite magmas of the Borrowdale Volcanic Group. The graphite mineralization occurred as the fluids migrated upwards through normal conjugate fractures forming the main subvertical pipe-like bodies. The mineralizing fluids evolved from CO2-CH4-H2O mixtures (XCO2=0.6-0.8) to CH4-H2O mixtures. Coevally with graphite deposition, the andesite and dioritic wall rocks adjacent to the veins were intensely hydrothermally altered to a propylitic assemblage. The initial graphite precipitation was probably triggered by the earliest hydration reactions in the volcanic host rocks. During the main mineralization stage, graphite precipitated along the pipe-like bodies due to CO2 -> C+O2. This agrees with the isotopic data which indicate that the first graphite morphologies crystallizing from the fluid (cryptocrystalline aggregates) are isotopically lighter than those crystallizing later (flakes). Late chlorite-graphite veins were formed from CH4-enriched fluids following the reaction CH4 + O2 -> C+ 2H2O, producing the successive precipitation of isotopically lighter graphite morphologies. Thus, as mineralization proceeded, water-generating reactions were involved in graphite precipitation, further favouring the propylitic alteration

DFT investigation of Ca mobility in reduced-perovskite and oxidized-marokite oxides

Progress in the development of rechargeable Ca-ion batteries demands the discovery of potential cathode materials. Transition metal oxides are interesting candidates due to their theoretical high energy densities, but with the drawback of a low Ca mobility. Previous computational/experimental investigations associate the electrochemical inactivity of various oxides (CaMO3-perovskite, CaMn2O4-post-spinel and CaV2O5) to high energy barriers for Ca migration. The introduction of oxygen and/or Ca vacancies in ternary transition metal oxides is a likely way to reshape the local topology and hence improve the Ca diffusivity. In this work, the energy barriers for Ca migration are calculated and discussed for (i) oxygen-deficient perovskites within the related Ca2Fe2O5-brownmillerite and Ca2Mn2O5 structures, and (ii) tunnel CaMn4O8, a derivative of the CaMn2O4-marokite with Ca vacancies

Analysis of Minerals as Electrode Materials for Ca-based Rechargeable Batteries

Rechargeable lithium-ion batteries dominate the consumer electronics and electric vehicle markets. However, concerns on Li availability have prompted the development of alternative high energy density electrochemical energy storage systems. Rechargeable batteries based on a Ca metal anode can exhibit advantages in terms of energy density, safety and cost. The development of rechargeable Ca metal batteries requires the identification of suitable high specific energy cathode materials. This work focuses on Ca-bearing minerals because they represent stable and abundant compounds. Suitable minerals should contain a transition metal able of being reversibly reduced and oxidized, which points to several major classes of silicates and carbonates: olivine (CaFeSiO4; kirschsteinite), pyroxene (CaFe/MnSi2O6; hedenbergite and johannsenite, respectively), garnet (Ca3Fe/Cr2Si3O12; andradite and uvarovite, respectively), amphibole (Ca2Fe5Si8O22(OH)2; ferroactinolite) and double carbonates (CaMn(CO3)2; kutnahorite and CaFe(CO3)2; ankerite). This work discusses their electrode characteristics based on crystal chemistry analysis and density functional theory (DFT) calculations. The results indicate that upon Ca deintercalation, compounds such as pyroxene, garnet and double carbonate minerals could display high theoretical energy densities (ranging from 780 to 1500 Wh/kg) with moderate structural modifications. As a downside, DFT calculations indicate a hampered Ca mobility in their crystal structures. The overall analysis then disregards olivine, garnet, pyroxene, amphibole and double carbonates as structural types for future Ca-cathode materials design

Los ladrillos del recinto amurallado de Talamanca de Jarama, Madrid: criterios para su diferenciación

El recinto amurallado de Talamanca de Jarama tiene una larga historia llena de conflictos bélicos que lo han destruido en numerosas ocasiones. Por este motivo, la muralla ha sufrido numerosas etapas de reconstrucción y ampliación (s.IX, s.XIII, s.XIV y s.XVII), a las que hay que añadirle numerosas intervenciones de restauración en el último siglo (s.XX). Los ladrillos junto con los tapiales y las piedras son los principales materiales de construcción identificados. Los ladrillos estudiados por microscopía de luz polarizada (MO), difracción de rayos X (DRX), espectroscolorometría, ultrasonidos y porosimetria de intrusión de mercurio, han permitido diferenciar cinco tipos, pertenecientes a distintas épocas de fabricación. Son los ladrillos más antiguos (tipo I) y los más modernos (tipo V), los que más diferencias muestran entre sí. En general, los cinco tipos de ladrillos presentan eterogeneidades debidas a una fabricación deficiente y que son las responsables del proceso de deterioro que les afecta, aunque estos ladrillos hayan sido colocados recientemente, en la última intervención

Graphite–sulfide deposits in Ronda and Beni Bousera peridotites (Spain and Morocco) and the origin of carbon in mantle-derived rocks

This paper describes unusual graphite–sulfide deposits in ultramafic rocks from the Serranı´a de Ronda (Spain) and Beni Bousera (Morocco). These deposits occur as veins, stockworks and irregular masses, ranging in size from some centimeters to a few meters in thickness. The primary mineral assemblage mainly consists of Fe–Ni–Cu sulfides (pyrrhotite, pentlandite, chalcopyrite and cubanite), graphite and chromite. Weathering occurs in some sulfide-poor deposits that consist of graphite (up to 90%), chromite and goethite. Texturally, graphite may occur as flakes or clusters of flakes and as rounded, nodule-like aggregates. Graphite is highly crystalline and shows light carbon isotopic signatures (δ13C ≈ - 15‰ to -21‰). Occasionally, some nodule-like graphite aggregates display large isotopic zoning with heavier cubic forms (probably graphite pseudomorphs after diamond with δ13C up to -3.3‰) coated by progressively lighter flakes outwards (δ13C up to -15.2‰). Asthenospheric-derived melts originated the partial melting (and melt–rock reactions) of peridotites and pyroxenites generating residual melts from which the graphite–sulfide deposits were formed. These residual melts concentrated volatile components (mainly CO2 and H2O), as well as S, As, and chalcophile elements. Carbon was incorporated into the melts from the melt–rock reactions of graphite-bearing (formerly diamonds) garnet pyroxenites with infiltrated asthenospheric melts. Graphite-rich garnet pyroxenites formed through the UHP transformation of subducted kerogen-rich crustal material into the mantle. Thus, graphite in most of the studied occurrences has light (biogenic) carbon signatures. Locally, reaction of the light carbon in the melts with relicts of 13C-enriched graphitized diamonds (probably generated from hydrothermal calcite veins in the subducting oceanic crust) reacted with the partial melts to form isotopically zoned nodule-like graphite aggregates. D 2005 International Association for Gondwana Research

Conditions of graphite precipitation in the volcanic-hosted deposits at Borrowdale (Cumbria, UK)

Depto. de Mineralogía y PetrologíaFac. de Ciencias GeológicasTRUEpu

Palaeogeographical significance of clay mineral assemblages in the Permian and Triassic sediments of the SE Iberian Ranges, eastern Spain

The evolution of the palaeogeography of the SE Iberian Basin during the Permian and Triassic represents a general evolution from continental to marine environments. It has been recently studied from the sedimentological, stratigraphical, tectonic and palaeontological points of view. In spite of these results, many aspects of this palaeogeography are still a matter of discussion. In this study, clay mineralogy analysis complements previous studies representing a new aspect for understanding the evolution of the sedimentary environment and the palaeogeography of the Iberian Basin during the periods in question and thus of the palaeogeography and the location of the major high areas in the westernmost border of the Tethys sea. In spite of late diagenetic transformations the original clay mineral associations of the Permian-Triassic sediments of the SE Iberian Ranges can be reconstructed. Seventy-seven samples of siliciclastic and carbonate sediments of these ages have been studied (SEM and XRD), revealing six new aspects that help to precise the palaeogeographical interpretation of the area: (1) Two major mineral assemblages have been found: illite+ kaolinite +pyrophyllite in the continental facies and illite + chlorite + vermiculite + mixed-layer clays in the marine facies. (2) The Mg-rich clay minerals are here considered to be of marine origin. (3) Active phases of basin boundary faults are marked in the sediments by the presence of pyrophyllite, derived directly from the Palaeozoic metamorphic basement. (4) Unconformities separating major depositional sequences also separate formations with different clay mineralogy. (5) Different groups of clay minerals can be separated clearly coinciding with the different palaeogeographical stages also distinguished in the westernmost border of the Tethys sea. (6) The clay mineral associations back up the data of a previous hypothesis of a humid climate for the end of the Permian in the study area just prior to the first incursion of the Tethys sea