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Hydrothermal mineral replacement reactions for an apatite-monazite assemblage in alkali-rich fluids at 300–600 °C and 100 MPa

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Published/Copyright: November 30, 2016
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American Mineralogist
From the journal American Mineralogist Volume 101 Issue 12

Abstract

Mineral replacement reactions are common in the various environments where rocks have undergone re-equilibration with geologic fluids. Replacement reactions commonly take the form of fluid-aided, coupled dissolution-precipitation and often result in pseudomorph formation. One class of environment that frequently shows significant examples of mineral replacements is hydrothermal ore deposit systems. The goal of this study was to test the simultaneous reactivity of fluorapatite and monazite in Na- and Si-rich hydrothermal fluids, which partially mimic the mineralogy and fluid chemistry of the Llallagua tin deposit in Bolivia. A series of experiments were performed at 300 to 600 °C and 100 MPa, utilizing various combinations of monazite, fluorapatite, and H2O + Na2Si2O5. Reaction products were evaluated using scanning electron microscopy, electron microprobe analysis, and single-crystal X-ray diffraction. The results of this experimental study show that fluorapatite and monazite are differentially reactive under the conditions studied. The reaction products, pathways, and kinetics have a large temperature dependence. The 300 and 400 °C experiments show variable amounts of monazite replacement and only minor, if any, dissolution or reactivity of fluorapatite. The high-temperature 500 and 600 °C experiments are characterized by massive replacement of monazite by vitusite and britholite. Exclusively at 600 °C, monazite alteration takes the form of symplectite development at the reaction front as vermicular intergrowths of vitusite and britholite. The higher-temperature experiments also show substantially more reactivity by fluorapatite, which is partially pseudomorphically altered into britholite. This is an example of regenerative mineral replacement where both fluorapatite and britholite share the same atomic structure and are crystallographically coherent after the partial replacement. The britholite replacement is characterized by the presence of oriented nanochannels, which facilitate fluid-based mass transfer between the bulk solution and the reaction front. The fluorapatite replacement is enhanced by monazite alteration through a self-perpetuating, positive feedback mechanism between these two reactions, which enhance the REE mobility in alkali-bearing fluids and further drives bulk re-equilibration. These results have potential geochronologic implications and may be significant in the evaluation of monazite and fluorapatite as potential solid nuclear waste forms. They also give us deeper insights into the mechanism of mineral replacement reactions and porosity development.

Keywords: Selective mineral replacement; dissolution-precipitation; fluorapatite; monazite; britholite; pseudomorphism; multi-phase reaction

Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

Acknowledgments

We thank Dieter Rhede of the GeoForschungsZentrum, Potsdam, for his expertise with the electron microprobe and helpful comments. Richard Edelman and Mat Duley are thanked for assistance with the SEM. We thank Jaroslaw Majka and an anonymous reviewer for their insightful comments on an earlier version on this manuscript. Support for this work was provided by the National Science Foundation through grant EAR-0952298 to J.R. We also thank Tresa Foster and Brian Kosnar for the Llallagua monazites used in these experiments.

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Received: 2016-3-13
Accepted: 2016-7-25
Published Online: 2016-11-30
Published in Print: 2016-12-1

© 2016 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2016-5765
Keywords for this article
Selective mineral replacement; dissolution-precipitation; fluorapatite; monazite; britholite; pseudomorphism; multi-phase reaction

Articles in the same Issue

  1. Review
  2. Physical basis of trace element partitioning: A review
  3. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  4. A mineralogical view of apatitic biomaterials
  5. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  6. Radionuclide removal by apatite
  7. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  8. Hydrothermal mineral replacement reactions for an apatite-monazite assemblage in alkali-rich fluids at 300–600 °C and 100 MPa
  9. Chemistry and Mineralogy of Earth’s Mantle
  10. Raman spectroscopy of siderite at high pressure: Evidence for a sharp spin transition
  11. Chemistry and Mineralogy of Earth’s Mantle
  12. Electron diffraction determination of 11.5 Å and HySo structures: Candidate water carriers to the Upper Mantle
  13. Special collection: Mechanisms, Rates, and Timescales of Geochemical Transport Processes in the Crust and Mantle
  14. Influence of grain size, water, and deformation on dolomite reaction rim formation
  15. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  16. Dissolution-reprecipitation and self-assembly of serpentine nanoparticles preceding chrysotile formation: Insights into the structure of proto-serpentine
  17. Research Article
  18. Submicrometer-scale spatial heterogeneity in silicate glasses using aberration-corrected scanning transmission electron microscopy
  19. Research Article
  20. Growth of hydrothermal baddeleyite and zircon in different stages of skarnization
  21. Research Article
  22. Structural incorporation of W6+ into hematite and goethite: A combined study of natural and synthetic iron oxides developed from precursor ferrihydrite and the preservation of ancient fluid compositions in hematite
  23. Research Article
  24. Morphological and chemical evolution of corundum (ruby and sapphire): Crystal ontogeny reconstructed by EMPA, LA-ICP-MS, and Cr3+ Raman mapping
  25. Research Article
  26. High-pressure compressibility and vibrational properties of (Ca,Mn)CO3
  27. Research Article
  28. Transformation of pyrite to pyrrhotite in the presence of Au-Ag alloys at 500 °C
  29. Research Article
  30. An alternative method of calculating cleavage energy: The effect of compositional domains in micas
  31. Research Article
  32. 10.2138/am-2016-5717
  33. Research Article
  34. Collapsing minerals: Crackling noise of sandstone and coal, and the predictability of mining accidents
  35. Research Article
  36. Magnetite exsolution in ilmenite from the Fe-Ti oxide gabbro in the Xinjie intrusion (SW China) and sources of unusually strong remnant magnetization
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  38. Statistical petrology reveals a link between supercontinents cycle and mantle global climate
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  40. An improved clinopyroxene-based hygrometer for Etnean magmas and implications for eruption triggering mechanisms
  41. Research Article
  42. New Mineral Names
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