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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 and Andrew Putnis
Published/Copyright: January 3, 2017
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American Mineralogist
From the journal American Mineralogist Volume 102 Issue 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.

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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
Keywords for this article
Calcite; fluorite; replacement; dissolution-precipitation; kinetics; porosity

Articles in the same Issue

  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
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  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
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