Startseite The replacement of a carbonate rock by fluorite: Kinetics and microstructure
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The replacement of a carbonate rock by fluorite: Kinetics and microstructure

  • Elisabete Trindade Pedrosa EMAIL logo , Lena Boeck , Christine V. Putnis und Andrew Putnis
Veröffentlicht/Copyright: 3. Januar 2017
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 102 Heft 1

Abstract

Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has applications in Earth sciences and engineering. Samples of Carrara marble were reacted with an ammonium fluoride (NH4F) solution for different reaction times and temperatures. The microstructure of the product phase (fluorite) was analyzed using SEM. The kinetics of replacement was monitored using Rietveld refinements of X-ray powder diffraction patterns of the products. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement). The grain boundaries of the original marble were preserved although each calcite grain was replaced by multiple fine crystals of fluorite creating inter-crystal porosity. The empirical activation energy Ea (kJ/mol) of the replacement reaction was determined by both model-fitting and model-free methods. The isoconversional method yielded an empirical activation energy of 41 kJ/mol, and a statistical approach applied to the model-fitting method revealed that the replacement of Carrara marble by fluorite is better fitted to a diffusion-controlled process. These results suggest that the replacement reaction depends on the ion diffusion rate in the fluid phase through the newly formed porosity.

Keywords: Calcite; fluorite; replacement; dissolution-precipitation; kinetics; porosity

Acknowledgments

This project has received funding from the European Union’s Seventh Framework Program for research, technological development and demonstration, a Marie Curie initial training network (Flowtrans) under grant agreement number 316889. Andrew Putnis and Christine V. Putnis also acknowledge funding within the EU Initial Training Networks CO2-React and MINSC.

References cited

Aldaco, R., Garea, A., and Irabien, A. (2007) Calcium fluoride recovery from fluoride wastewater in a fluidized bed reactor. Water Research, 41, 810–818.10.1016/j.watres.2006.11.040Suche in Google Scholar PubMed

Altree-Williams, A., Pring, A., Ngothai, Y., and Brugger, J. (2015) Textural and compositional complexities resulting from coupled dissolution–reprecipitation reactions in geomaterials. Earth-Science Reviews, 150, 628–651.10.1016/j.earscirev.2015.08.013Suche in Google Scholar

Ames, L.L. Jr. (1960) Anion replacement reactions for the removal of strontium from aqueous solutions, 34 p. U.S. Atomic Energy Commission, Washington, D.C.Suche in Google Scholar

—(1961) The metasomatic replacement of limestones by alkaline, fluoride-bearing solutions. Economic Geology, 65, 730–739.Suche in Google Scholar

Avrami, M. (1939) Kinetics of phase change. I. General theory. The Journal of Chemical Physics, 7, 1103.10.1063/1.1750380Suche in Google Scholar

Baer, N.S., and Lewin, S.Z. (1970) The replacement of calcite by fluorite: A kinetic study. American Mineralogist, 55, 466–476.Suche in Google Scholar

Batchelder, D.N., and Simmons, R.O. (1964) Lattice constants and thermal expansivities of silicon and of calcium fluoride between 6° and 322 °K. The Journal of Chemical Physics, 41, 2324–2329.10.1063/1.1726266Suche in Google Scholar

Brindha, K., and Elango, L. (2011) Fluoride in groundwater: causes, implications and mitigation measures. In S.D. Monroy, Ed., Fluoride Properties, Applications and Environmental Management, p. 111–136. Nova Science Publishers, Huntington, New York.Suche in Google Scholar

Engvik, A.K., Mezger, K., Wortelkamp, S., Bast, R., Corfu, F., Korneliussen, A., Ihlen, P., Bingen, B., and Austrheim, H. (2011) Metasomatism of gabbro— mineral replacement and element mobilization during the Sveconorwegian metamorphic event. Journal of Metamorphic Geology, 29, 399–423.10.1111/j.1525-1314.2010.00922.xSuche in Google Scholar

Gagnon, J.E., Samson, I.M., Fryer, B.J., and Williams-Jones, A.E. (2003) Compositional heterogeneity in fluorite and the genesis of fluorite deposits: insights from LA-ICP-MS analysis. Canadian Mineralogist, 41, 365–382.10.2113/gscanmin.41.2.365Suche in Google Scholar

Ghosh, A., Mukherjee, K., Ghosh, S.K., and Saha, B. (2013) Sources and toxicity of fluoride in the environment. Research on Chemical Intermediates, 39, 2881–2915.10.1007/s11164-012-0841-1Suche in Google Scholar

Glover, E.D., and Sippel, R.F. (1962) Experimental pseudomorphs: Replacement of calcite by fluorite. American Mineralogist, 47, 1156–1165.Suche in Google Scholar

Godinho, J.R.A., Putnis, C.V., and Piazolo, S. (2014) Direct observations of the dissolution of fluorite surfaces with different orientations. Crystal Growth & Design, 29, 69–77.10.1021/cg401119pSuche in Google Scholar

Hancock, J., and Sharp, J. (1972) Method of comparing solid-state kinetic data and its application to the decomposition of kaolinite, brucite, and BaCO3. Journal of the American Ceramic Society, 55, 74–77.10.1111/j.1151-2916.1972.tb11213.xSuche in Google Scholar

Heness, G., and Ben-Nissan, B. (2004) Innovative bioceramics. Materials Forum, 27, 104–114.Suche in Google Scholar

Hövelmann, J., Putnis, A., Geisler, T., Schmidt, B.C., and Golla-Schindler, U. (2010) The replacement of plagioclase feldspars by albite: Observations from hydrothermal experiments. Contributions to Mineralogy and Petrology, 159, 43–59.10.1007/s00410-009-0415-4Suche in Google Scholar

Jonas, L., John, T., and Putnis, A. (2013) Influence of temperature and Cl on the hydrothermal replacement of calcite by apatite and the development of porous microstructures. American Mineralogist, 98, 1516–1525.10.2138/am.2013.4288Suche in Google Scholar

Jonas, L., John, T., King, H.E., Geisler, T., and Putnis, A. (2014) The role of grain boundaries and transient porosity in rocks as fluid pathways for reaction front propagation. Earth and Planetary Science Letters, 386, 64–74.10.1016/j.epsl.2013.10.050Suche in Google Scholar

Kar, A., McEldrew, M., Stout, R.F., Mays, B.E., Khair, A., Velegol, D., and Gorski, C.A. (2016) Self-gnerated electrokinetic flows during pseudomorphic mineral replacement reactions. Langmuir, 32, 5233–5240.10.1021/acs.langmuir.6b00462Suche in Google Scholar PubMed

Kasioptas, A., Geisler, T., Putnis, C.V., Perdikouri, C., and Putnis, A. (2010) Crystal growth of apatite by replacement of an aragonite precursor. Journal of Crystal Growth, 312, 2431–2440.10.1016/j.jcrysgro.2010.05.014Suche in Google Scholar

Kasioptas, A., Geisler, T., Perdikouri, C., Trepmann, C., Gussone, N., and Putnis, A. (2011) Polycrystalline apatite synthesized by hydrothermal replacement of calcium carbonates. Geochimica et Cosmochimica Acta, 75, 3486–3500.10.1016/j.gca.2011.03.027Suche in Google Scholar

Khawam, A. (2007) Application of solid-state kinetics to desolvation reactions, 321 p. Ph.D. thesis, University of Iowa.10.17077/etd.vtiuca3sSuche in Google Scholar

Khawam, A., and Flanagan, D.R. (2005a) Complementary use of model-free and modelistic methods in the analysis of solid-state kinetics. Journal of Physical Chemistry B, 109, 10073–10080.10.1021/jp050589uSuche in Google Scholar PubMed

—(2005b) Role of isoconversional methods in varying activation energies of solid-state kinetics: II. Nonisothermal kinetic studies. Thermochimica Acta, 436, 101–112.10.1016/j.tca.2005.05.015Suche in Google Scholar

Maslen, E.N., Streltsov, V.A., and Streltsova, N.R. (1993) X-ray study of the electron density in calcite, CaCO3. Acta Crystallographica, B49, 636–641.10.1107/S0108768193002575Suche in Google Scholar

Niedermeier, D.R.D., Putnis, A., Geisler, T., Golla-Schindler, U., and Putnis, C.V. (2009) The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions. Contributions to Mineralogy and Petrology, 157, 65–76.10.1007/s00410-008-0320-2Suche in Google Scholar

Parkhurst, D.L., and Appelo, C.A.J. (1999) User’s guide to PHREEQC (ver. 2)—a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. U.S. Geological Survey, Water Resources, Denver, Colorado.Suche in Google Scholar

Pasteris, J.D., and Ding, D.Y. (2009) Experimental fluoridation of nanocrystalline apatite. American Mineralogist, 94, 53–63.10.2138/am.2009.2926Suche in Google Scholar

Pearce, M.A., Timms, N.E., Hough, R.M., and Cleverley, J.S. (2013) Reaction mechanism for the replacement of calcite by dolomite and siderite: Implications for geochemistry, microstructure and porosity evolution during hydrothermal mineralisation. Contributions to Mineralogy and Petrology, 166, 995–1009.10.1007/s00410-013-0905-2Suche in Google Scholar

Pedrosa, E.T., Putnis, C.V., and Putnis, A. (2016) The pseudomorphic replacement of marble by apatite: The role of fluid composition. Chemical Geology, 425, 1–11.10.1016/j.chemgeo.2016.01.022Suche in Google Scholar

Pollok, K., Putnis, C.V., and Putnis, A. (2011) Mineral replacement reactions in solid solution-aqueous solution systems: Volume changes, reactions paths and end-points using the example of model salt systems. American Journal of Science, 311, 211–236.10.2475/03.2011.02Suche in Google Scholar

Pradesh, M. (2013) Occurrence of fluorine-bearing minerals in granite and a plausible mode of transport of fluorine into hydrological system: an example from Jabalpur District, M.P. India. Indian Journal of Geosciences, 66, 213–222.Suche in Google Scholar

Putnis, A. (1992) An Introduction to Mineral Sciences, 457 p. Cambridge University Press, U.K.10.1017/CBO9781139170383Suche in Google Scholar

—(2002) Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Mineralogical Magazine, 66, 689–708.10.1180/0026461026650056Suche in Google Scholar

—(2009) Mineral replacement reactions. Reviews in Mineralogy and Geochemistry, 70, 87–124.10.2138/rmg.2009.70.3Suche in Google Scholar

Putnis, C.V., and Mezger, K. (2004) A mechanism of mineral replacement: Isotope tracing in the model system KCl-KBr-H2O. Geochimica et Cosomochimica Acta, 68, 2039–2848.10.1016/j.gca.2003.12.009Suche in Google Scholar

Putnis, A., and Putnis, C.V. (2007) The mechanism of reequilibration of solids in the presence of a fluid phase. Journal of Solid State Chemistry, 180, 1783–1786.10.1016/j.jssc.2007.03.023Suche in Google Scholar

Putnis, C.V., Tsukamoto, K., and Nishimura, Y. (2005) Direct observations of pseudomorphism: compositional and textural evolution at a fluid-solid interface. American Mineralogist, 90, 1909–1912.10.2138/am.2005.1990Suche in Google Scholar

Richardson, C.K., and Holland, H.D. (1979) Fluorite deposition in hydrothermal systems. Geochimica et Cosmochimica Acta, 43, 1327–1335.10.1016/0016-7037(79)90122-4Suche in Google Scholar

Ruiz-Agudo, E., Putnis, C.V., and Putnis, A. (2014) Coupled dissolution and precipitation at mineral–fluid interfaces. Chemical Geology, 383, 132–146.10.1016/j.chemgeo.2014.06.007Suche in Google Scholar

Schwinn, G., and Markl, G. (2005) REE systematics in hydrothermal fluorite. Chemical Geology, 216, 225–248.10.1016/j.chemgeo.2004.11.012Suche in Google Scholar

Simonsson, D. (1979) Reduction of fluoride by reaction with limestone particles in a fixed bed. Industrial & Engineering Chemistry Process Design and Development, 18, 288–292.10.1021/i260070a019Suche in Google Scholar

Toft, P.C. (1986) Diagenetic fluorite in chalks from Stevns Klint and Møns Klint, Denmark. Sedimentary Geology, 46, 311–323.10.1016/0037-0738(86)90065-5Suche in Google Scholar

Trautz, O.R., and Zapanta, R.R. (1961) Experiments with calcium carbonate phosphates and the effect of topical application of sodium fluoride. Archives of Oral Biology, 4, 122–133.10.1016/0003-9969(61)90090-5Suche in Google Scholar

Turner, B.D., Binning, P., and Stipp, S.L.S. (2005) Fluoride removal by calcite: Evidence for fluorite precipitation and surface adsorption. Environmental Science and Technology, 39, 9561–9568.10.1021/es0505090Suche in Google Scholar

WHO (2011) Guidelines for drinking-water quality. World Health Organization (WHO), Geneva.Suche in Google Scholar

Xia, F., Chen, G., Ngothai, Y., O'Neill, B., Putnis, A., and Pring, A. (2009) Mechanism and kinetics of pseudomorphic mineral replacement reactions: a case study of the replacement of pentlandite by violarite. Geochimica et Cosmochimica Acta, 73, 1945–1969.10.1016/j.gca.2009.01.007Suche in Google Scholar

Yang, M., Hashimoto, T., Hoshi, N., and Myoga, H. (1999) Fluoride removal in a fixed bed packed with granular calcite. Water Research, 33, 3395–3402.10.1016/S0043-1354(99)00052-4Suche in Google Scholar

Yoshimura, M., Sujaridworakun, P., Koh, F., Fujiwara, T., Pongkao, D., and Ahniyaz, A. (2004) Hydrothermal conversion of calcite crystals to hydroxyapatite. Materials Science and Engineering C, 24, 521–525.10.1016/j.msec.2004.01.005Suche in Google Scholar

Received: 2016-2-16
Accepted: 2016-8-24
Published Online: 2017-1-3
Published in Print: 2017-1-1

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-5725
Schlagwörter für diesen Artikel
Calcite; fluorite; replacement; dissolution-precipitation; kinetics; porosity

Artikel in diesem Heft

  1. Highlights and Breakthroughs
  2. Periodic activity in continental magmatic arcs
  3. Highlights and Breakthroughs
  4. Early warning signs for mining accidents: Detecting crackling noise
  5. Review
  6. Fluids and trace element transport in subduction zones
  7. Solved: The enigma of labradorite feldspar with incommensurately modulated structure
  8. Solved: The enigma of labradorite feldspar with incommensurately modulated structure
  9. Special Collection: Earth Analogs for Martian Geological Materials and Processes
  10. Formation of the ferruginous smectite SWa-1 by alteration of soil clays
  11. Special Collection: Advances in Ultrahigh-Pressure Metamorphism
  12. Dissolving dolomite in a stable UHP mineral assemblage: Evidence from Cal-Dol marbles of the Dora-Maira Massif (Italian Western Alps)
  13. Special collection: Apatite: a common mineral, uncommonly versatile
  14. Hydroxyl, Cl, and F partitioning between high-silica rhyolitic melts-apatite-fluid(s) at 50–200 MPa and 700–1000 °C
  15. Special collection: Apatite: a common mineral, uncommonly versatile
  16. Apatite trace element and isotope applications to petrogenesis and provenance
  17. Special collection: Apatite: a common mineral, uncommonly versatile
  18. Raman and IR studies of the effect of Fe substitution in hydroxyapatites and deuterated hydroxyapatite
  19. Building Planets: The Dynamics and Geochemistry of Core Formation
  20. Carbon as the dominant light element in the lunar core
  21. Special collection: Olivine
  22. Formation of phosphorus-rich olivine in Dar al Gani 978 carbonaceous chondrite through fluid-assisted metamorphism
  24. Cobalt mineral ecology
  26. Deprotonation of Fe-dominant amphiboles: Single-crystal HT-FTIR spectroscopic studies of synthetic potassic-ferro-richterite
  28. The replacement of a carbonate rock by fluorite: Kinetics and microstructure
  30. An experimental kinetic study on the structural evolution of natural carbonaceous material to graphite
  32. Infrared spectra of carbonate apatites: Evidence for a connection between bone mineral and body fluids
  34. Experimental investigation into the substitution mechanisms and solubility of Ti in garnet
  36. XAFS spectroscopic study of Ti coordination in garnet
  38. Effect of composition on compressibility of skiagite-Fe-majorite garnet
  40. An integrated EPMA-EBSD study of metamorphic histories recorded in garnet
  42. A new formula and crystal structure for nickelskutterudite, (Ni,Co,Fe)As3, and occupancy of the icosahedral cation site in the skutterudite group
  44. Ab initio study of the structure and stability of CaMg(CO3)2 at high pressure
  46. Plastic deformation and post-deformation annealing in chromite: Mechanisms and implications
  47. Letter
  48. Bridgmanite-like crystal structure in the novel Ti-rich phase synthesized at transition zone condition
  49. Book Review
  50. Book Review: Geophysical Data Analysis: Discrete Inverse Theory (MATLAB Edition), Third edition
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