Reactive flow of mixed CO2–H2O fluid and progress of calc‐silicate reactions in contact metamorphic aureoles: insights from two‐dimensional numerical modelling

Previous models of hydrodynamics in contact metamorphic aureoles assumed flow of aqueous fluids, whereas CO2 and other species are also common fluid components in contact metamorphic aureoles. We investigated flow of mixed CO2-H2O fluid and kinetically controlled progress of calc-silicate reactions using a two-dimensional, finite-element model constrained by the geological relations in the Notch Peak aureole, Utah. Results show that CO2 strongly affects fluid-flow patterns in contact aureoles. Infiltration of magmatic water into a homogeneous aureole containing CO2-H2O sedimentary fluid facilitates upward, thermally driven flow in the inner aureole and causes downward flow of the relatively dense CO2-poor fluid in the outer aureole. Metamorphic CO2-rich fluid tends to promote upward flow in the inner aureole and the progress of devolatilization reactions causes local fluid expulsion at reacting fronts. We also tracked the temporal evolution of P-T-XCO2 conditions of calc-silicate reactions. The progress of low- to medium-grade (phlogopite- to diopside-forming) reactions is mainly driven by heat as the CO2 concentration and fluid pressure and temperature increase simultaneously. In contrast, the progress of the high-grade wollastonite-forming reaction is mainly driven by infiltration of chemically out-of-equilibrium, CO2-poor fluid during late-stage heating and early cooling of the inner aureole and thus it is significantly enhanced when magmatic water is involved. CO2-rich fluid dominates in the inner aureole during early heating, whereas CO2-poor fluid prevails at or after peak temperature is reached. Low-grade metamorphic rocks are predicted to record the presence of CO2-rich fluid, and high-grade rocks reflect the presence of CO2-poor fluid, consistent with geological observations in many calc-silicate aureoles. The distribution of mineral assemblages predicted by our model matches those observed in the Notch Peak aureole.

[1]  D. DePaolo,et al.  Field Measurement of Slow Metamorphic Reaction Rates at Temperatures of 500° to 600°C , 2000 .

[2]  G. Dipple,et al.  IRREGULAR ISOGRADS, REACTION INSTABILITIES, AND THE EVOLUTION OF PERMEABILITY DURING METAMORPHISM , 1998 .

[3]  J. Ague,et al.  Simple Models of CO2 Release from Metacarbonates with Implications for Interpretation of Directions and Magnitudes of Fluid Flow in the Deep Crust , 1999 .

[4]  B. Dutrow,et al.  Evolution of fluid pressure and fracture propagation during contact metamorphism , 1995 .

[5]  C. Forster,et al.  Contact metamorphism surrounding the Alta Stock; finite element model simulation of heat- and 18 O/ 16 O mass-transport during prograde metamorphism , 1997 .

[6]  X. Cui,et al.  Heat and fluid flow in contact metamorphic aureoles with layered and transient permeability, with application to the Notch Peak aureole, Utah , 2001 .

[7]  L. Baumgartner,et al.  Stable isotope evidence of heterogeneous fluid infiltration at the Ubehebe Peak contact aureole, Death Valley National Park, California , 1999, American Journal of Science.

[8]  P. Richet,et al.  High-pressure and temperature equation of state and calculation of the thermodynamic properties of gaseous carbon dioxide , 1981 .

[9]  R. Powell,et al.  A Compensated-Redlich-Kwong (CORK) equation for volumes and fugacities of CO2 and H2O in the range 1 bar to 50 kbar and 100–1600°C , 1991 .

[10]  B. Wood,et al.  Experimental measurements of the properties of H2OCO2 mixtures at high pressures and temperatures , 1997 .

[11]  R. Powell,et al.  An internally consistent dataset with uncertainties and correlations: 3. Applications to geobarometry, worked examples and a computer program , 1988 .

[12]  W. Wakeham,et al.  The Transport Properties of Carbon Dioxide , 1990 .

[13]  D. Mctigue Elastic stress and deformation near a finite spherical magma body: Resolution of the point source paradox , 1987 .

[14]  J. Ferry,et al.  Formation and destruction of periclase by fluid flow in two contact aureoles , 1997 .

[15]  J. Ferry Patterns of mineral occurrence in metamorphic rocks , 2000 .

[16]  Elaine S. Oran,et al.  Numerical Simulation of Reactive Flow , 1987 .

[17]  I. Cartwright,et al.  Two‐dimensional patterns of metamorphic fluid flow and isotopic resetting in layered and fractured rocks‘pa , 1997 .

[18]  P. Nabelek Calc‐silicate reactions and bedding‐controlled isotopic exchange in the Notch Peak aureole, Utah: implications for differential fluid fluxes with metamorphic grade , 2002 .

[19]  C. Steefel,et al.  Approaches to modeling of reactive transport in porous media , 1996 .

[20]  J. Ferry,et al.  Structurally controlled fluid flow during contact metamorphism in the Ritter Range pendant, California, USA , 1998 .

[21]  Thomas J. Ahrens,et al.  Equation of State , 1993 .

[22]  A. Lasaga,et al.  Kinetics of Heterogeneous Reactions , 1991 .

[23]  J. Papike,et al.  The Notch Peak Granitic Stock, Utah: Origin of Reverse Zoning and Petrogenesis , 1986 .

[24]  R. Bodnar,et al.  Synthetic fluid inclusions; X, Experimental determination of P-V-T-X properties in the CO 2 -H 2 O system to 6 kb and 700 degrees C , 1991 .

[25]  S. Takenouchi,et al.  The binary system H 2 O-CO 2 at high temperatures and pressures , 1964 .

[26]  U. Fehn Qualitative models of spreading-center processes, including hydrothermal penetration: discussion , 1978 .

[27]  J. B. Walsh,et al.  The effect of pressure on porosity and the transport properties of rock , 1984 .

[28]  J. Walther Fluid production and isograd reactions at contacts of carbonate‐rich and carbonate‐poor layers during progressive metamorphism , 1996 .

[29]  H. Taylor,et al.  Quantitative Simulation of the Hydrothermal Systems of Crystallizing Magmas on the Basis of Transport Theory and Oxygen Isotope Data: An analysis of the Skaergaard Intrusion , 1979 .

[30]  M. Person,et al.  Convective fluid flow through heterogeneous country rocks during contact metamorphism , 1998 .

[31]  S. Ingebritsen,et al.  Multiphase groundwater flow near cooling plutons , 1997 .

[32]  S. Ingebritsen,et al.  Permeability of the continental crust: Implications of geothermal data and metamorphic systems , 1999 .

[33]  R. Hanson The hydrodynamics of contact metamorphism , 1995 .

[34]  W. Heinrich,et al.  Fluid flow patterns and infiltration isograds in melilite marbles from the Bufa del Diente contact metamorphic aureole, north‐east Mexico , 1994 .

[35]  J. Ferry,et al.  Fluid flow, mineral reactions, and metasomatism , 1991 .

[36]  H. Taylor,et al.  Oxygen and hydrogen isotope studies of contact metamorphism in the Santa Rosa Range, Nevada and other areas , 1969 .

[37]  L. Shampine,et al.  Computer solution of ordinary differential equations : the initial value problem , 1975 .

[38]  W. Brace Permeability of crystalline rocks: New in situ measurements , 1984 .

[39]  J. Papike,et al.  The Notch Peak Contact Metamorphic Aureole, Utah: Petrology of the Big Horse Limestone Member of the Orr Formation , 1983 .

[40]  J. A. Schramke,et al.  The reaction muscovite + quartz andalusite + K-feldspar + water; Part 1, Growth kinetics and mechanism , 1987 .

[41]  S. Cook,et al.  Mineralogical Evidence for Fluid–Rock Interaction Accompanying Prograde Contact Metamorphism of Siliceous Dolomites: Alta Stock Aureole, Utah, USA , 2000 .

[42]  J. Ferry,et al.  Fluid infiltration during contact metamorphism of interbedded marble and calc‐silicate hornfels, Twin Lakes area, central Sierra Nevada, California , 1993 .

[43]  I. Buick,et al.  Fluid flow in metacarbonates associated with emplacement of the Bushveld Complex, South Africa , 2000 .

[44]  J. Ferry Prograde and retrograde fluid flow during contact metamorphism of siliceous carbonate rocks from the Ballachulish aureole, Scotland , 1996 .

[45]  N. Oliver,et al.  Fluid Flow During Contact Metamorphism at Mary Kathleen, Queensland, Australia , 1994 .

[46]  J. R. O'neil,et al.  Contrasting fluid/rock interaction between the Notch Peak granitic intrusion and argillites and limestones in western Utah: evidence from stable isotopes and phase assemblages , 1984 .

[47]  J. Ferry A historical review of metamorphic fluid flow , 1994 .

[48]  B. Jamtveit,et al.  Contact Metamorphism of Layered Shale-Carbonate Sequences in the Oslo Rift: I. Buffering, Infiltration, and the Mechanisms of Mass Transport , 1992 .

[49]  P. Nabelek,et al.  Implications of geochemical fronts in the Notch Peak contact-metamorphic aureole, Utah, USA , 1993 .

[50]  A. Lasaga,et al.  Fluid flow and chemical reaction kinetics in metamorphic systems , 1993 .

[51]  Roger Powell,et al.  An internally consistent thermodynamic data set for phases of petrological interest , 1998 .

[52]  G. Strang On the Construction and Comparison of Difference Schemes , 1968 .

[53]  J. Papike,et al.  Fluid infiltration through the Big Horse Limestone Member in the Notch Peak contact-metamorphic aureole, Utah , 1988 .

[54]  J. Gallagher,et al.  NBS/NRC Steam Tables: Thermodynamic and Transport Properties and Computer Programs for Vapor and Liquid States of Water in SI Units, , 1984 .

[55]  J. Ferry,et al.  The effect of thermal history on the development of mineral assemblages during infiltration-driven contact metamorphism , 1996 .

[56]  J. Szuber,et al.  oxygen and hydrogen , 2001 .

[57]  F. Stauffer,et al.  Modeling of chemically reactive groundwater transport , 1994 .

[58]  X. Cui,et al.  Numerical modeling of fluid flow and oxygen isotope exchange in the Notch Peak contact-metamorphic aureole, Utah , 2002 .

[59]  J. Ferry,et al.  Models for coupled fluid flow, mineral reaction, and isotopic alteration during contact metamorphism; the Notch Peak aureole, Utah , 1992 .

[60]  Hugh Hudson,et al.  The Binary System , 1988 .

[61]  V. S. Tripathi,et al.  A critical evaluation of recent developments in hydrogeochemical transport models of reactive multichemical components , 1989 .

[62]  S. Hoernes,et al.  Detrital Quartz and K-Feldspar in Quartzites as Indicators of Oxygen Isotope Exchange Kinetics , 1991 .

[63]  Edward W. Bolton,et al.  Long-term flow/chemistry feedback in a porous medium with heterogenous permeability: Kinetic control of dissolution and precipitation , 1999 .

[64]  M. Etheridge,et al.  The role of the fluid phase during regional metamorphism and deformation , 1983 .

[65]  J. Ferry Contact metamorphism of roof pendants at Hope Valley, Alpine County, California, USA , 1989 .

[66]  J. Ferry,et al.  The direction of fluid flow during contact metamorphism of siliceous carbonate rocks: new data for the Monzoni and Predazzo aureoles, northern Italy, and a global review , 2002 .

[67]  C. Welty,et al.  A Critical Review of Data on Field-Scale Dispersion in Aquifers , 1992 .

[68]  S. Cox,et al.  Reaction-enhanced permeability during decarbonation of calcite+quartz=wollastonite + carbon dioxide. , 2000 .

[69]  C. Steefel,et al.  A coupled model for transport of multiple chemical species and kinetic precipitation/dissolution rea , 1994 .

[70]  B. Yardley,et al.  Modeling metamorphic fluid flow with reaction-compaction permeability feedbacks , 1998 .

[71]  J. E. Knight,et al.  Differential thermal expansion of pore fluids: Fracture propagation and microearthquake production in hot pluton environments , 1977 .

[72]  J. Ferry,et al.  Formation of Wollastonite by Chemically Reactive Fluid Flow During Contact Metamorphism, Mt. Morrison Pendant, Sierra Nevada, California, USA , 2001 .

[73]  J. Ferry,et al.  CHEMICALLY REACTIVE FLUID FLOW DURING METAMORPHISM , 1998 .

[74]  B. Yardley,et al.  Why metasomatic fronts are really metasomatic sides , 1995 .

[75]  P. Nabelek,et al.  Stable Isotope Evidence for the Role of Diffusion, Infiltration, and Local Structure on Contact Metamorphism of Calc-Silicate Rocks at Noth Peak, Utah , 1992 .

[76]  Albert J. Valocchi,et al.  Accuracy of operator splitting for advection‐dispersion‐reaction problems , 1992 .

[77]  D. Norton,et al.  Transport phenomena in hydrothermal systems; cooling plutons , 1977 .

[78]  C. Voss,et al.  SUTRA (Saturated-Unsaturated Transport). A Finite-Element Simulation Model for Saturated-Unsaturated, Fluid-Density-Dependent Ground-Water Flow with Energy Transport or Chemically-Reactive Single-Species Solute Transport. , 1984 .

[79]  John H. Weare,et al.  An equation of state for the CH4-CO2-H2O system: II. Mixtures from 50 to 1000°C and 0 to 1000 bar , 1992 .

[80]  Andreas Luettge,et al.  The influence of CaCl 2 on the kinetics of the reaction 1 tremolite + 3 calcite + 2 quartz --> 5 diopside + 3 CO 2 + 1 H 2 O; an experimental investigation , 1999 .

[81]  A. Lasaga,et al.  Dynamic treatment of invariant and univariant reactions in metamorphic systems , 2000 .