F.J. Luque

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.

Graphite geothermometry in low and high temperature regimes: two case studies

This paper examines the potential use of the variation of the c o parameter of graphite with temperature for geothermometric estimations. Two examples are presented in which graphite geothermometry, at low-and high-temperature conditions, is tested against other widely used geothermometers. The results obtained indicate that, at low-grade metamorphic conditions, the c o parameter of graphite is affected by other factors besides the temperature, so graphite geothermometry (based on c o ) can only be used in such rocks for qualitative estimations. For temperatures above 500 °C, when the fully ordered graphite appears, there is a close correlation between the temperature estimations based on the structural ordering of graphite and from mineral-exchange geothermometry. The temperature calculations based on the c o parameter of graphite are not influenced by factors (such as pressure or retrometamorphism) that clearly affect the exchange equilibria. Thus, graphite thermometry is a useful tool, for temperatures above 500 °C.

Influence of grinding on graphite crystallinity from experimental and natural data: implications for graphite thermometry and sample preparation

Abstract This paper examines the effects of shear stress on the structural parameters that define the ‘crystallinity’ of graphite. The results show that highly crystalline graphite samples ground for up to 120 min do not undergo detectable changes in the three-dimensional arrangement of carbon layers but crystallite sizes (Lc and La) decrease consistently with increasing grinding time. Grinding also involves particle-size diminution that results in lower temperatures for the beginning of combustion and exothermic maxima in the differential thermal analysis curves. These changes in the structural and thermal characteristics of graphite upon grinding must be taken into account when such data are used for geothermometric estimations. Tectonic shear stress also induces reduction of the particle size and the Lc and La values of highly crystalline graphite. Thus, the temperature of formation of graphite according to structural as well as thermal data is underestimated by up to 100°C in samples that underwent the most intense shear stress. Therefore, application of graphite geothermometry to fluid-deposited veins where graphite is the only mineral found should take into consideration the effect of tectonic shearing, or the estimated temperatures must be considered as minimum temperatures of formation only.

Formation of nontronite from oxidative dissolution of pyrite disseminated in Precambrian felsic metavolcanics of the southern Iberian Massif (Spain)

This paper describes a rare occurrence of nontronite associated with sulfide-bearing felsic metavolcanics, providing evidence of colloidal deposition in open spaces as result of a low-temperature water-rock interaction. Microbotryoidal masses of green nontronite with impurities of kaolinite, illite, barite, amorphous silica and iron oxyhydroxides are found as vein and cavity fillings in deeply kaolinized rhyolites and rhyolitic tuffs of Precambrian age, at Oliva de Merida in SW Spain. Clay mineral characterization has been carried out by X-ray diffraction, infrared spectroscopy, thermal analysis, analytical electron microscopy and stable isotope (oxygen and hydrogen) analysis. Nontronite was formed under low-temperature alteration conditions, from a continuous sequence of reactions and aqueous solution compositions, involving two basic processes that acted in concert: oxidative dissolution of pyrite and hydrolysis of K-feldspar. After acidity neutralization, dissolved silica released by incongruent dissolution of K-feldspar reacted with ferric sulfate derived from pyrite oxidation to form nontronite under oxidizing conditions, in the presence of relatively warm meteoric water.

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.