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The incorporation of chlorine into calcium amphibole

  • David M. Jenkins EMAIL logo
Veröffentlicht/Copyright: 24. März 2019
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 104 Heft 4

Abstract

The exchange of halogens between fluids and solid silicates holds considerable potential to shed light on fluid-rock interactions associated with various geological processes, including seawater-ocean-crust interaction, crustal and mantle metasomatism, and economic deposit formation. This study reports on how variations in formation conditions (temperature, pressure, hydrogen fugacity), bulk composition (Na and K ratio), and choice of starting material salts affect the Cl contents of calcium amphiboles synthesized specifically from ferro-pargasite and hastingsite bulk compositions. Syntheses were attempted over the range of 600–950 °C and 0.1–0.45 GPa at logfH2 of 1.4 to 2.4 (equivalent to –0.9 to –2.1 log fO2 below the fayalite-magnetite-β-quartz oxygen buffer, or ΔFMβQ) for durations of 111–672 h. Amphiboles were characterized by powder X-ray diffraction and electron microprobe, with cation proportions calculated on the basis of an assumed 18% ferric iron content. Amphiboles formed from the ferro-chloro-pargasite bulk composition [NaCa2(Fe4.0Al)(Al2Si6)O22Cl2] had Cl contents of only about 0.5 atoms per formula unit (apfu), compared to the intended 2.0, and whose stabilities were about 70 °C lower at 0.1–0.2 GPa than reported in a previous study of Cl-free (OH-bearing) ferro-pargasite. Syntheses on the ferro-pargasite bulk composition in the presence of a brine with a nominal mole fraction of Cl (XCl) of 0.3 over the range of 700–950 °C at 0.2 GPa showed that temperature had less effect on the Cl content of the amphibole than small variations in the brine concentration assessed after treatment. For the chloro-hastingsite bulk composition [NaCa2(Fe4.0Fe3+)(Al2Si6)O22Cl2], the Cl content of the product amphibole was unaffected by the specific choice of chloride salt or salt combinations (NaCl, CaCl2, FeCl2), but showed a direct correlation with the substitution of K for Na. Experiments done over the range of 0.10–0.45 GPa at 700 °C and at –1.3 log fO2 ΔFMβQ showed an increased rate of nucleation of amphibole with increasing pressure for a hastingsite bulk composition with 40% substitution of K for Na, but no variation in the Cl content of the amphibole. Classification of the amphiboles formed in this study showed that several were well outside their intended field, with some of those formed from the ferro-pargasite bulk composition straddling the boundary between hastingsite and ferro-pargasite, while several formed from the hastingsite bulk composition were actually ferro-ferri-hornblendes. These results confirm that K more so than Na is important for the incorporation of Cl into calcium amphiboles, and that Cl-bearing ferro-ferri-hornblende, with low A-site Na + K, can form even from mixtures with abundant Na + K. Combining these observations with the strong correlation between Cl content and Fe# [= Fe2+/(Fe2++Mg)] noted in previous studies, a general correlation was found to exist between the Cl content and the FeAlK index, defined as Fe#(TAl + K), which combines the effects of Fe#, tetrahedrally coordinated Al (TAl), and K content. A linear trend is observed once a minimum value of about 0.34 in the FeAlK index is reached. The implication is that the crystal-chemical controls for Cl incorporation in calcium amphiboles are dominated by substitution of Fe2+ for Mg, TAl for Si, and K for Na into the crystallographic A site with a linear dependence at the rate of 0.45 Cl per FeAlK index above a minimum value of about 0.34.

Keywords: Ferro-pargasite; hastingsite; chlorine; chloro-amphibole; synthesis; ferro-ferri-hornblende

  1. Funding Financial support for this study comes from NSF grants EAR-1347463 and EAR-1725053 to D.M.J.

Acknowledgments

The manuscript benefitted from the careful reviews of P. Ulmer and an anonymous reviewer. David Collins assisted with the electron microprobe analyses.

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Received: 2018-07-30
Accepted: 2018-12-21
Published Online: 2019-03-24
Published in Print: 2019-04-24

© 2019 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Introduction
  2. Deep carbon cycle through five reactions
  3. Earth in five reactions: Grappling with meaning and value in science
  4. In-situ iron isotope analyses reveal igneous and magmatic-hydrothermal growth of magnetite at the Los Colorados Kiruna-type iron oxide-apatite deposit, Chile
  5. Carbon and nitrogen isotopes and mineral inclusions in diamonds from chromitites of the Mirdita ophiolite (Albania) demonstrate recycling of oceanic crust into the mantle
  6. Geochronology and trace element mobility in rutile from a Carboniferous syenite pegmatite and the role of halogens
  7. The incorporation of chlorine into calcium amphibole
  8. Crystal size distribution of amphibole grown from hydrous basaltic melt at 0.6–2.6 GPa and 860–970 °C
  9. Role of micropores, mass transfer, and reaction rate in the hydrothermal alteration process of plagioclase in a granitic pluton
  10. Lead diffusion in CaTiO3: A combined study using Rutherford backscattering and TOF-SIMS for depth profiling to reveal the role of lattice strain in diffusion processes
  11. On growth and form of etched fission tracks in apatite: A kinetic approach
  12. High-pressure behavior of liebenbergite: The most incompressible olivine-structured silicate
  13. Phase transition of wadsleyite-ringwoodite in the Mg2SiO4-Fe2SiO4 system
  14. Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): X-ray diffraction and photoelectron spectroscopy studies and mechanisms of Nb enrichment
  15. Meyrowitzite, Ca(UO2)(CO3)2⋅5H2O, a new mineral with a novel uranyl-carbonate sheet
  16. Letter
  17. Discovery of the first natural hydride
  18. Synthesis of pigeonites for spectroscopic studies
  19. Presentation of the 2018 Roebling Medal of the Mineralogical Society of America to E. Bruce Watson
  20. Acceptance of the 2018 Roebling Medal of the Mineralogical Society of America
  21. Presentation of the Dana Medal of the Mineralogical Society of America for 2018 to Jörg Hermann
  22. Acceptance of the Dana Medal of the Mineralogical Society of America for 2018
  23. New Mineral Names
  24. Book Review
https://doi.org/10.2138/am-2019-6768
Schlagwörter für diesen Artikel
Ferro-pargasite; hastingsite; chlorine; chloro-amphibole; synthesis; ferro-ferri-hornblende

Artikel in diesem Heft

  1. Introduction
  2. Deep carbon cycle through five reactions
  3. Earth in five reactions: Grappling with meaning and value in science
  4. In-situ iron isotope analyses reveal igneous and magmatic-hydrothermal growth of magnetite at the Los Colorados Kiruna-type iron oxide-apatite deposit, Chile
  5. Carbon and nitrogen isotopes and mineral inclusions in diamonds from chromitites of the Mirdita ophiolite (Albania) demonstrate recycling of oceanic crust into the mantle
  6. Geochronology and trace element mobility in rutile from a Carboniferous syenite pegmatite and the role of halogens
  7. The incorporation of chlorine into calcium amphibole
  8. Crystal size distribution of amphibole grown from hydrous basaltic melt at 0.6–2.6 GPa and 860–970 °C
  9. Role of micropores, mass transfer, and reaction rate in the hydrothermal alteration process of plagioclase in a granitic pluton
  10. Lead diffusion in CaTiO3: A combined study using Rutherford backscattering and TOF-SIMS for depth profiling to reveal the role of lattice strain in diffusion processes
  11. On growth and form of etched fission tracks in apatite: A kinetic approach
  12. High-pressure behavior of liebenbergite: The most incompressible olivine-structured silicate
  13. Phase transition of wadsleyite-ringwoodite in the Mg2SiO4-Fe2SiO4 system
  14. Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): X-ray diffraction and photoelectron spectroscopy studies and mechanisms of Nb enrichment
  15. Meyrowitzite, Ca(UO2)(CO3)2⋅5H2O, a new mineral with a novel uranyl-carbonate sheet
  16. Letter
  17. Discovery of the first natural hydride
  18. Synthesis of pigeonites for spectroscopic studies
  19. Presentation of the 2018 Roebling Medal of the Mineralogical Society of America to E. Bruce Watson
  20. Acceptance of the 2018 Roebling Medal of the Mineralogical Society of America
  21. Presentation of the Dana Medal of the Mineralogical Society of America for 2018 to Jörg Hermann
  22. Acceptance of the Dana Medal of the Mineralogical Society of America for 2018
  23. New Mineral Names
  24. Book Review
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