Reaction-induced fluid flow in synthetic quartz-bearing marbles

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Contributions to Mineralogy and Petrology
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The reaction kinetics and fluid expulsion during the decarbonation reaction of calcite+quartz=wollastonite+CO2 in water-absent conditions were experimentally investigated using a Paterson-type gas apparatus. Starting materials consisted of synthetic calcite/quartz rock powders with variable fractions of quartz (10, 20, and 30 wt%) and grain sizes of 10 mum (calcite) and 10 and 30 mum (quartz). Prior to reaction, samples were HIPed at 700degreesC and 300 MPa confining pressure and varying pore pressures. Initial porosity was low at 2.7-6.3%, depending on pore pressure during HIP and the amount and grain size of quartz particles. Samples were annealed at reaction temperatures of 900 and 950degreesC at 150 and 300 MPa confining pressures, well within the wollastonite stability field. Run durations were between 10 min and 20 h. SEM micrographs of quenched samples show growth of wollastonite rims on quartz grains and CO2-filled pores between rims and calcite grains and along calcite grain boundaries. Measured widths of wollastonite rims vs. time indicate a parabolic growth law. The reaction is diffusion-controlled and reaction progress and CO2 production are continuous. Porosity increases rapidly at initial stages of the reaction and attains about 10-12% after a few hours. Permeability at high reaction temperatures is below the detection limit of 10(-21) m(2) and not affected by increased porosity. This makes persistent pore connectivity improbable, in agreement with observed fluid inclusion trails in form of unconnected pores in SEM micrographs. Release of CO2 from the sample was measured in a downstream reservoir. The most striking observation is that fluid release is not continuous but occurs episodic and in pulses. Ongoing continuous reaction produces increase in pore pressure, which is, once having attained a critical value (P-crit), spontaneously released. Connectivity of the pore space is short-lived and transient. The resulting cycle includes pore pressure build-up, formation of a local crack network, pore pressure release and crack closure. Using existing models for plastic stretching and decrepitation of pores along with critical stress intensity factors for the calcite matrix and measured pore widths, it results that P-crit is about 20 MPa. Patterns of fluid flow based on mineralogical and stable isotope evidence are commonly predicted using the simplifying assumption of a continuous and constant porosity and permeability during decarbonation of the rock. However, simple flow models, which assume constant pore pressure, constant fluid filled porosity, and constant permeability may not commonly apply. Properties are often transient and it is most likely that fluid flow in a specific reacting rock volume is a short-lived episodic process.


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DOI 10.1007/s00410-003-0504-8