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A kinetic model of metamorphism: an application to siliceous dolomites

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Abstract

We use a kinetic model of a metamorphic system to study the effect of competing rates of reaction, fluid injection, and heating on the evolution of the “reaction pathway” in temperature/composition space at constant pressure. We show that for rocks in contact with mixed volatile (e.g., CO2-H2O) fluids the reaction path may be quite different from what is expected from equilibrium-based petrologic models. Equilibrium-based models, used to understand the development of rock systems undergoing mineral reactions during a metamorphic event, rely on the Gibbs’ phase rule and only consider stable phases. For constant pressure, the temperature-composition paths follow univariant curves and significant reactions may occur at invariant points. By contrast, the more general kinetic treatment is not constrained by equilibrium, although with the proper competing rates equilibrium is a possible endmember of the kinetic approach. The deviation from equilibrium depends on the competing rates of reaction, heating, and fluid injection. A key element required by the kinetic approach is the inclusion of metastable reactions in the formulation, whereas such reactions are irrelevant for equilibrium-based models. Metastable reactions are often involved in a complex interplay with common prograde stable metamorphic reactions. We present model results for the well-studied CaO-MgO-SiO2-CO2-H2O (CMS) system to show how the system evolves under kinetic control. Our simulations and discussion focus on the behavior of the CMS system under a number of closed and open system conditions. Special attention is paid to closed system behavior in the vicinity of the (first) isobaric invariant point (with Dol, Qtz, Tlc, Cal, and Tr). Also, for open systems with massive fluid infiltration we consider heating rates varying from contact to regional metamorphic conditions. For some geologically reasonable rates of reactions, heating, and fluid injection, our results demonstrate that equilibrium conditions may be significantly overstepped in metamorphic systems. We used overall mineral reactions in this model with rates based on experimental results. Future models could rely on more fundamental dissolution and precipitation reactions. Such an extension would require additional kinetic rate data, as well as mineral solubilities in mixed volatile fluids.

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Acknowledgments

The authors want to thank J.J. Ague, M.J. Davis, P. Metz, N.M. Ribe, D. Rosner, R. Rye, J. Sisson, B.J. Skinner, and G. Veronis for helpful discussions. We also acknowledge R.F. Dymek, C.E. Manning, J.V. Walther, Tom Torgersen, and G.M. Dipple for critical, but helpful, comments and careful reviews of drafts of an earlier manuscript from which this version has evolved. We also thank J.M. Ferry and R. Milke for careful reviews and thoughtful comments, as well as editorial handling by J. Hoefs. Thanks also goes to A.C. Lasaga. EWB and AL would like to thank him for discussions regarding methods for calculation of enthalpies, Gibbs free energies, fugacities, composition evolution, and standard states of gases and minerals. Parts of the study were funded by the Department of Energy (DE-FG02-90ER14153, DE-FG02-01ER15216, DE-FG03-02ER63427, and DE-FG07-01R63295), the National Science Foundation (grants EAR-9628238, EAR-9526794, EAR-9727134, EAR-0125667), the Alexander von Humboldt-Foundation, EXXON MOBIL Upstream Research Productions, and the Schlumberger-Doll Research in Ridgefield, Connecticut.

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  1. Department of Geology and Geophysics, Yale University, New Haven, CT, 06520-8109, USA

    Andreas Lüttge, Edward W. Bolton & Danny M. Rye

  2. Department of Earth Science, Rice University, Houston, TX, 77251-1892, USA

    Andreas Lüttge

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  1. Andreas Lüttge
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Lüttge, A., Bolton, E.W. & Rye, D.M. A kinetic model of metamorphism: an application to siliceous dolomites. Contrib Mineral Petrol 146, 546–565 (2004). https://doi.org/10.1007/s00410-003-0520-8

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