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Mineral replacement reactions: from macroscopic observations to microscopic mechanisms

Published online by Cambridge University Press:  05 July 2018

A. Putnis
A. Putnis*
Affiliation:
Institut für Mineralogie, University of Münster, Corrensstrasse 24, 48149, Münster, Germany
*
*E-mail: putnis@nwz.uni-muenster.de
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Abstract

Mineral replacement reactions take place primarily by dissolution-reprecipitation processes. Processes such as cation exchange, chemical weathering, deuteric alteration, leaching, pseudomorphism, metasomatism, diagenesis and metamorphism are all linked by common features in which one mineral or mineral assemblage is replaced by a more stable assemblage. The aim of this paper is to review some of these aspects of mineral replacement and to demonstrate the textural features they have in common, in order to emphasize the similarities in the underlying microscopic mechanisms. The role of volume change and evolution of porosity is explored both from natural microtextures and new experiments on model replacement reactions in simple salts. It is shown that the development of porosity is often a consequence of mineral replacement processes, irrespective of the relative molar volumes of parent and product solid phases. The key issue is the relative solubility of the phases in the fluid phase. Concepts such as coupled dissolution-precipitation, and autocatalysis are important in understanding these processes. Some consequences of porosity generation for metamorphic fluid flow as well as subsequent crystal growth are also discussed.

Keywords

mineral replacementfluid-mineral reactionscation exchangedissolution-precipitationporositymetamorphic fluid flow
Type
Research Article
Information
Mineralogical Magazine , Volume 66 , Issue 5 , October 2002 , pp. 689 - 708
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2002

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References

Aharonov, E., Spiegelman, M. and Kelemen, P. (1997) Three-dimensional flow and reaction in porous media: Implications for the Earth's mantle and sedimentary basins. Journal of Geophysical Research, 102, 14821–14833.CrossRefGoogle Scholar
Anderson, J.G., Doraiswamy, L.K. and Larson, M.A. (1998 a) Microphase-assisted ‘autocatalysis’ in a solid-liquid reaction with a precipitating product – I. Theory. Chemical Engineering Science, 53, 2451–2458.CrossRefGoogle Scholar
Anderson, J.G., Larson, M.A. and Doraiswamy, L.K. (1998 b) Microphase-assisted ‘autocatalysis’ in a solid-liquid reaction with a precipitating product – II. Experimental. Chemical Engineering Science, 53, 2459–2468.CrossRefGoogle Scholar
Astilleros, J.M., Pina, C.M., Férnandez-Diaz, L. and Putnis, A. (2000) The effect of barium on calcite {1014} surfaces during growth. Geochimica et Cosmochimica Acta, 64, 2965–2972.CrossRefGoogle Scholar
Astilleros, J.M., Pina, C.M., Férnandez-Diaz, L. and Putnis, A. (2002) Molecular scale surface processes during the growth of calcite in the presence of manganese. Geochimica et Cosmochimica Acta (in press).CrossRefGoogle Scholar
Austrheim, H. (1987) Eclogitization of the lower crustal granulites by fluid migration through shear zones. Earth and Planetary Science Letters, 81, 221–232.CrossRefGoogle Scholar
Austrheim, H. and Engvik, A.K. (1997) Fluid transport, deformation and metamorphism at depth in a collison zone. Pp. 123–137 in: Fluid Flow and Transport in Rocks: Mechanisms and Effects (Jamtveit, B. and Yardley, B.W.D., editors). Chapman & Hall, London.CrossRefGoogle Scholar
Austrheim, H., Erambert, M. and Engvik, A.K. (1997) Processing of crust in the root of the Caledonian continental collision zone: the role of eclogitization. Tectonophysics, 273, 129–153.CrossRefGoogle Scholar
Banfield, J.F., Welch, S.A., Zhang, H., Ebert, T.T. and Penn, R.L. (2000) The role of aggregation in crystal growth and transformations in nanophase FeOOH biomineralization products. Science, 289, 751–754.CrossRefGoogle Scholar
Benavente, D., García del Cura, M.A., Fort, R. and Ordónez, S. (1999) Thermodynamic modelling of changes induced by salt pressure crystallisation in porous media of stone. Journal of Crystal Growth, 204, 168–178.CrossRefGoogle Scholar
Bickle, M.J. and McKenzie, D. (1987) The transport of heat and matter by fluids during metamorphism. Contributions to Mineralogy and Petrology, 95, 384–392.CrossRefGoogle Scholar
Brown, W.L. and Parsons, I. (1993) Storage and release of elastic strain energy: the driving force for low temperature reactivity and alteration of alkali feldspar. Pp. 267–290 in: Defects and Processes in the Solid State: Geoscience Applications. The McLaren volume. (Boland, J. and FitzGerald, J.D., editors ). Elsevier Science Publishers BV, Amsterdam.Google Scholar
Cardew, P.T. and Davey, R.J. (1985) The kinetics of solvent-mediated phase transformations. Proceedings of the Royal Society of London A, 398, 415–428.Google Scholar
Cartwright, I. (1997) Permeability generation and resetting of tracers during metamorphic fluid flow: impications for advection-dispersion models. Contributions to Mineralogy and Petrology, 129, 198–208.CrossRefGoogle Scholar
Cole, D.R. (2000) Isotopic exchange in mineral-fluid systems IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H2O and layer silicate-H2O systems. Geochimica et Cosmoschimica Acta, 64, 921–933.CrossRefGoogle Scholar
Connolly, J.A.D. (1997) Devolatilization-generated fluid pressure and deformation-propogated fluid flow during prograde regional metamorphism. Journal of Geophysical Research, 102, 18149–18173.CrossRefGoogle Scholar
Correns, D.W. (1949) Growth and dissolution of crystals under linear pressure. Discussions of the Faraday Society, 5, 267–271.CrossRefGoogle Scholar
Dewers, T. and Ortoleva, P. (1990) Force of crystallization during the growth of siliceous concretions. Geology, 18, 204–207.2.3.CO;2>CrossRefGoogle Scholar
Durham, G.S., Rock, E.J. and Frayn, S.F. (1953) Solid solutions of the alkali halides I. The systems KBr-KCl-H2O, RbBr-RbCl-H2O, RbBr-KBr-H2O at 25°C. Journal of the American Chemical Society, 75, 5793–5794.CrossRefGoogle Scholar
Edwards, R., Gillard, R.D., Williams, P.A. and Pollard, A.M. (1992) Studies of secondary mineral formation in the PbO-H2O-HCl system. Mineralogical Magazine, 56, 53–65.CrossRefGoogle Scholar
Erambert, M. and Austrheim, H. (1993) The effect of fluid and deformation on zoning and inclusion patterns in poly-metamorphic garnets. Contributions to Mineralogy and Petrology, 115, 204–214.CrossRefGoogle Scholar
Evans, R. (1999) Fluids in model pores or cavities: the influence of confinement on structure and phase behaviour. Pp. 153–172 in: New Approaches to Problems in Liquid State Theory (Caccamo, C. et al., editors). Kluwer Academic Publishers, Dordrecht, The Netherlands.CrossRefGoogle Scholar
Ferry, J.M. (1985) Hydrothermal alteration of Tertiary igneous rocks from the Isle of Skye, northwest Scotland. I: granites. Contributions to Mineralogy and Petrology, 91, 283–304.CrossRefGoogle Scholar
Ferry, J.M. (2000) Patterns of mineral occurrence in metamorphic rocks. American Mineralogist, 85, 1573–1588.CrossRefGoogle Scholar
Fiebig, J. and Hoefs, J. (2002) Hydrothermal alteration of biotite and plagioclase as inferred from intragranular oxygen isotope- and cation-distribution patterns. European Journal of Mineralogy, 14, 49–60.CrossRefGoogle Scholar
Fletcher, R.C. and Merino, E. (2001) Mineral growth in rocks: Kinetic-rheological models of replacement, vein formation and syntectonic crystallization. Geochimica et Cosmochimica Acta, 65, 3733–3748.CrossRefGoogle Scholar
Freij, S., Reyhani, M.M. and Parkinson, G.M. (1998) An AFM investigation of the mechanism of secondary nucleation induced by contact. Applied Physics A, 66, S507–S511.CrossRefGoogle Scholar
Geisler, T., Ulonska, M., Schleicher, H., Pidgeon, R.T. and von Bronswijk, W. (2001) Leaching and differential crystallization of metamict zircon under experimental hydrothermal conditions. Contributions to Mineralogy and Petrology, 141, 53–65.CrossRefGoogle Scholar
Glikin, A.E. (1995) To a theory of isomorphic mixedcrystal formation. Zapiski Vserossiiskogo Mineralogicheskogo Obshchestva. 5, 125–134 (in Russian).Google Scholar
Glikin, A.E. (1996) On equilibrium supercooled solutions in connection with isomorphic mixedcrystal formation. Zapiski Vserossiiskogo Mineralogicheskogo Obshchestva. 5, 103–111 (in Russian).Google Scholar
Glikin, A.E. and Sinai, M.Yu. (1991) Morphological-genetic classification of products of crystal replacement. Zapiski Vserossiiskogo Mineralogicheskogo Obshchestva. 1, 3–17 (in Russian).Google Scholar
Glikin, A.E. and Sinai, M.Yu. (1993) Experimental investigation of monocrystal pseudomorph formation. Zapiski Vserossiiskogo Mineralogicheskogo Obshchestva, 6, 742–748 (in Russian).Google Scholar
Glynn, P.D. and Reardon, E.J. (1990) Solid-solution aqueous-solution equilibria: thermodynamic theory and representation. American Journal of Science, 290, 164–201.CrossRefGoogle Scholar
Glynn, P.D., Reardon, E.J., Plummer, L.N. and Busenberg, E. (1990). Reaction paths and equilibrium end-points in solid-solutions aqueous solution systems. Geochimica et Cosmochimica Acta, 54, 267–282.CrossRefGoogle Scholar
Henisch, H.K. (1989) Crystals in Gels and Liesegang Rings. Cambridge University Press, Cambridge, UK.Google Scholar
Jamtveit, B. and Yardley, B.W.D. (1997) Fluid flow and transport in rocks: an overview. Pp. 1–14 in: Fluid Flow and Transport in Rocks: Mechanisms and Effects (Jamtveit, B. and Yardley, B.W.D., editors). Chapman & Hall, London.Google Scholar
Jamtveit, B., Bucher-Nurminen, K. and Austrheim, H. (1990) Fluid controlled eclogitization of granulites in deep crystal shear zones, Bergen Arcs, Western Norway. Contributions to Mineralogy and Petrology, 104, 184–193.CrossRefGoogle Scholar
Johannes, W., Koepke, J. and Behrens, H. (1994) Partial melting reactions of plagioclases and plagioclasebearing systems. Pp. 161–194 in: Feldspars and their Reactions (Parsons, I., editor). NATO ASI series, Kluwer Academic Publishers, Dordrecht, The Netherlands.CrossRefGoogle Scholar
Korzhinskii, D.S. (1970) Theory of Metasomatic Zoning. Clarendon Press, Oxford, UK.Google Scholar
Lee, M.R. and Parsons, I. (1997) Dislocation, formation and albitization in alkali feldspars from the Shap granite. American Mineralogist, 82, 557–570.CrossRefGoogle Scholar
Lee, M.R. and Parsons, I. (1998) Microtextural controls of diagenetic alteration of detrital alkali feldspars: a case study of the Shap Conglomerate (Lower Carboniferous), north-west England. Journal of Sedimentary Research, 68, 198–211.CrossRefGoogle Scholar
Lippmann, F. (1980) Phase diagrams depicting the aqueous solubility of mineral systems. Neues Jahrbuch für Mineralogie Abhandlungen, 139, 1–25.Google Scholar
Maliva, R.G. and Siever, R. (1988) Diagenetic replacement controlled by force of crystallization. Geology, 16, 688–691.2.3.CO;2>CrossRefGoogle Scholar
Melia, T.P. and Moffitt, W.P. (1964) Crystallisation from aqueous solution. Journal of Colloid Science, 19, 433–447.CrossRefGoogle Scholar
Merino, E. and Dewers, T. (1998) Implications of replacement for reaction-transport modeling. Journal of Hydrogeology, 209, 137–146.CrossRefGoogle Scholar
Merino, E., Nahon, D. and Wang. Y. (1993) Kinetics and mass transfer of pseudomorphic replacement: Application to replacement of parent minerals amd kaolinite by Al, Fe and Mn oxides during weathering. American Journal of Science, 293, 135–155.CrossRefGoogle Scholar
Merino, E., Wang, Y., Wang, Y. and Nahon, D. (1994) Implications of pseudomorphic replacement for reaction-transport modeling in rocks. Mineralogical Magazine, 58A, 599–601.CrossRefGoogle Scholar
Nahon, D. and Merino, E. (1996) Pseudomorphic replacement versus dilation in laterites: petrographic evidence, mechanisms, and consequences for modelling. Journal of Geochemical Exploration. 57, 217–225.CrossRefGoogle Scholar
Nahon, D. and Merino, E. (1997) Pseudomorphic replacement in tropical weathering: evidence, geochemical consequences, and kinetic-rheological origin. American Journal of Science, 297, 393–417.CrossRefGoogle Scholar
Nakamura, M. and Shimakita, S. (1998) Dissolution origin and syn-entrapment compositional change of melt inclusion in plagioclase. Earth and Planetary Science Letters, 161, 119–133.CrossRefGoogle Scholar
Nakamura, M. and Watson, E.B. (2001) Experimental study of aqueous fluid infiltration into quartzite: implications for the kinetics of fluid redistribution and grain growth driven by interfacial energy reduction. Geofluids, 1, 73–89.CrossRefGoogle Scholar
Oliver, N.H.S. (1996) Review and classification of structural controls on fluid flow during regional metamorphism. Journal of Metamorphic Geology, 14, 477–492.CrossRefGoogle Scholar
Oliver, N.H.S. and Bons, P.D. (2001) Mechanisms of fluid flow and fluid-rock interaction in fossil metamorphic hydrothermal systems inferred from vein-rock patterns, geometry and microstructure. Geofluids, 1, 137–162.CrossRefGoogle Scholar
O'Neil, J.R. (1977) Stable isotopes in Mineralogy. Physics and Chemistry of Minerals, 2, 105–123.CrossRefGoogle Scholar
O'Neil, J.R. and Taylor, H.P. Jr. (1967) The oxygen isotope and cation exchange chemistry of feldspars. American Mineralogist, 52, 1414–1437.Google Scholar
Ortoleva, P., Merino, E., Moore, C. and Chadam, J. (1987 a) Geochemical self-organization I: reaction-transport feedbacks and modeling approach. American Journal of Science, 287, 979–1007.CrossRefGoogle Scholar
Ortoleva, P., Chadam, J., Merino, E. and Sen, A. (1987 b) Geochemical self-organization II: the reactive-infiltration instability. American Journal of Science, 287, 1008–1040.CrossRefGoogle Scholar
Ozawa, H. (1997) Thermodynamics of frost heaving: a thermodynamic proposition for dynamic phenomena. Physical Review E, 56, 2811–2816.CrossRefGoogle Scholar
Penn, R.L. and Banfield, J.F. (1998) Oriented attachment and growth, twinning, polytypism and formation of metastable phases; insights from nanocrystalline TiO2 . American Mineralogist, 83, 1077–1082.CrossRefGoogle Scholar
Penn, R.L. and Banfield, J.F. (1999) Formation of rutile nuclei at anatase {112} twin interfaces and the phase transformation mechanism in nanocrystalline titania. American Mineralogist, 84, 871–876.CrossRefGoogle Scholar
Pina, C.M., Fernández-Díaz, L., Prieto, M. and Putnis, A. (2000) In situ atomic force microscope observations of a dissolution-crystallisation reaction: The phengite-cerussite transformation. Geochimica et Cosmoschimica Acta, 64, 215–221.CrossRefGoogle Scholar
Pollok, K., Austrheim, H. and Putnis, A. (2000) Analytical TEM on the mechanism of eclogitization: a study on complex garnet zoning patterns. Berichte der Deutsche n Mineralo gischen Gesellschaft. European Journal Mineralogy, 12, 156.Google Scholar
Pollok, K., Pina, C.M., Putnis, C., Glikin, A. and Putnis, A. (2001) Mineral replacement textures: from simple salts to complex textures. Berichte der Deutschen Mineralogischen Gesellschaft. European Journal Mineralogy, 13, 142.Google Scholar
Pollok, K., Pina, C., Putnis, C., Glikin, A. and Putnis, A. (2002) Replacement reactions in the KBr-KCl-H2O system I – Theory (in prep.).Google Scholar
Putnis, A. and Mauthe, G. (2001) The effect of pore size on cementation in porous rocks. Geofluids, 1, 37–41.CrossRefGoogle Scholar
Putnis, A., Putnis, C. and Giampaolo, C. (1994) The microstructure of analcime phenocrysts in igneous rocks. European Journal of Mineralogy, 6, 627–632.CrossRefGoogle Scholar
Putnis, A., Prieto, M. and Fernandez-Diaz, L. (1995) Supersaturation and crystallisation in porous media. Geological Magazine, 132, 1–13.CrossRefGoogle Scholar
Putnis, C., Pina, C.M. and Glikin, A. (2001) Mineral replacement reactions in solid solution – aqueous solution systems. The 11th Annual Goldschmidt Conference, 20–14 May 2001 Hot Springs, Virginia, p. 3555.Google Scholar
Putnis, C., Pina, C., Pollok, K., Glikin, A. and Putnis, A. (2002) Replacement reactions in the KBr-KCl-H2O system II – experimental (in prep.).Google Scholar
Ramdohr, P. (1980) The Ore Minerals and their Intergrowths. Pergamon Press, Oxford.Google Scholar
Rendon-Angeles, J.C., Yanagisawa, K., Ishizawa, N. and Oishi, S. (2000 a) Effect of metal ions of chlorapatite on the topotaxial replacement by hydroxylapatite under hydrothermal conditions. Journal of Solid State Chemistry, 154, 569–578.CrossRefGoogle Scholar
Rendon-Angeles, J.C., Yanagisawa, K., Ishizawa, N. and Oishi, S. (2000 b) Topotaxial conversion of chlorapatite and hydroxylapatite to fluorapatite by hydrothermal ion exchange. Chemical Materials, 12, 2143–2150.CrossRefGoogle Scholar
Rendon-Angeles, J.C., Yanagisawa, K., Ishizawa, N. and Oishi, S. (2000 c) Conversion of calcium fluorapatite into calcium hydroxylapatite under alkaline hydrothermal conditions. Journal of Solid State Chemistry, 151, 65–72.CrossRefGoogle Scholar
Reyhani, M.M. and Parkinson, G.M. (1996) A comparison of secondary nuclei produced by contact of different growth faces of potash alum crystals under supersaturated solutions. Journal of Crystal Growth, 166, 1068–1073.CrossRefGoogle Scholar
Reyhani, M.M., Freij, S. and Parkinson, G.M. (1999) In situ atomic force microscopy investigation of the growth of secondary nuclei produced by contact of different growth faces of potash alum crystals under supersaturated solutions. Journal of Crystal Growth, 198/99, 258–263.CrossRefGoogle Scholar
Roberts, D.E. and Travis, G.A. (1986) Microstructural evaluation of nickel sulphide gossans in Western Australia. Transactions of the Royal Society of Edinburgh: Earth Sciences, 77, 81–98.CrossRefGoogle Scholar
Rodriguez-Navarro, C. and Doehne, E. (1999) Salt weathering: Influence of evaporation rate, supersaturation and crystallization pattern. Earth Surface Processes and Landforms 24, 191–209.3.0.CO;2-G>CrossRefGoogle Scholar
Roedder, E. (1979) Origin and significance of magmatic inclusions. Bulletin de Mineralogie, 102, 487–510.CrossRefGoogle Scholar
Rubie, D.C. (1986) The catalysis of mineral reactions by water and restrictions on the presence of aqueous fluids during metamorphism. Mineralogical Magazine, 50, 399–415.CrossRefGoogle Scholar
Rumble, D. III and Spear, F.S. (1983) Oxygen isotope equilibration and permeability enhancement during regional metamorphism. Journal of the Geological Society, London, 140, 619–628.CrossRefGoogle Scholar
Scherer, G.W. (1999) Crystallization in pores. Cement and Concrete Research, 29, 1347–1358.CrossRefGoogle Scholar
Silcock, H.L. (1979) Solubilities of Inorganic and Organic Compounds, Vol. 3 Pergamon Press, Oxford, UK.Google Scholar
Solberg, C. and Hansen, S. (2001) Dissolution of hemihydrate and precipitation of gypsum – a kinetic study by synchrotron X-ray powder diffraction. Cement and Concrete Research, 31, 641–646.CrossRefGoogle Scholar
Steefel, C.I. and Lichtner, P.C. (1998) Multicomponent reactive transport in discrete fractures II: In. ltration of hyperalkaline groundwater at Maqarin, Jordan, a natural analogy site. Journal of Hydrology 209, 200–224.CrossRefGoogle Scholar
Straume, A.K. and Austrheim, H. (1999) Importance of fracturing during retro-metamorphism of eclogites. Journal of Metamorphic Geology, 17, 637–652.CrossRefGoogle Scholar
Tomaschek, F., Kennedy, A., Villa, I.M. and Ballhaus, C. (2001) Case study of metamorphic zircons from Alpine HP/LT metamorphic rocks of Syros, Cyclades, Greece. Journal of Conference Abstracts, 6, 678.Google Scholar
Tsuchiyama, A. (1985) Dissolution kinetics of plagioclase in the melt of the system diopside-albiteanorthite, and origin of dusty plagioclase in andesites. Contributions to Mineralogy and Petrology, 89, 1–16.CrossRefGoogle Scholar
Waldron, K.A., Parsons, I. and Brown, W.L. (1993) Solution-redeposition and the orthoclase-microcline transformation: evidence from granulites and relevance to 18O exchange. Mineralogical Magazine, 57, 687–695.CrossRefGoogle Scholar
Walker, F.D.L., Lee, M.R. and Parsons, I. (1995) Micropores and micropermeable texture in alkali feldspars: geochemical and geophysical implications. Mineralogical Magazine, 59, 505–534.CrossRefGoogle Scholar
Wang, Y., Wang, Y. and Merino, E. (1995) Dynamic weathering model: Constraints required by coupled dissolution and pseudomorphic replacement. Geochimica et Cosmoschimica Acta, 59, 1559–1570.CrossRefGoogle Scholar
Weyl, P.K. (1959) Pressure solution and the force of crystallization – a phenomenological theory. Journal of Geophysical Research, 64, 2001–2025.CrossRefGoogle Scholar
Winkler, E.M. and Singer, P.C. (1972) Crystallization pressure of salt in stone and concrete. Geological Society of America Bulletin, 83, 3509–3514.CrossRefGoogle Scholar
Worden, R.H., Walker, F.D.L., Parsons, I. and Brown, W.L. (1990) Development of microporosity, diffusion channels and deuteric coarsening in perthitic alkali feldspars. Contributions to Mineralogy and Petrology, 104, 507–515.CrossRefGoogle Scholar
Yanagisawa, K., Rendon-Angeles, J.C., Ishizawa, N. and Oishi, S. (1999) Topotaxial replacement of chlorapatite by hydroxyapatite during hydrothermal ion exchange. American Mineralogist, 84, 1861–1869.CrossRefGoogle Scholar
Yeadon, M., Ghaly, M., Yang, J.C., Averback, R.S. and Gibson, J.M. (1998) ‘Contact epitaxy’ observed in supported nanoparticles. Applied Physics Letters, 73, 3208–3210.CrossRefGoogle Scholar