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Experimental determination of quartz solubility in H2O-CaCl2 solutions at 600–900 °C and 0.6–1.4 GPa

  • Adam R. Makhluf , Robert C. Newton and Craig E. Manning
Published/Copyright: October 4, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 10

Abstract

Fluid-mediated calcium metasomatism is often associated with strong silica mobility and the presence of chlorides in solution. To help quantify mass transfer at lower crustal and upper mantle conditions, we measured quartz solubility in H2O-CaCl2 solutions at 0.6–1.4 GPa, 600–900 °C, and salt concentrations to 50 mol%. Solubility was determined by weight loss of single-crystals using hydrothermal piston-cylinder methods. All experiments were conducted at salinity lower than salt saturation. Quartz solubility declines exponentially with added CaCl2 at all conditions investigated, with no evidence for complexing between silica and Ca. The decline in solubility is similar to that in H2O-CO2 but substantially greater than that in H2O-NaCl at the same pressure and temperature. At each temperature, quartz solubility at low salinity (XCaCl2 < 0.1) depends strongly on pressure, whereas at higher XCaCl2 it is nearly pressure independent. This behavior is consistent with a transition from an aqueous solvent to a molten salt near XCaCl2 ~0.1. The solubility data were used to develop a thermodynamic model of H2O-CaCl2 fluids. Assuming ideal molten-salt behavior and utilizing previous models for polymerization of hydrous silica, we derived values for the activity of H2O (aH2O), and for the CaCl2 dissociation factor (α), which may vary from 0 (fully associated) to 2 (fully dissociated). The model accurately reproduces our data along with those of previous work and implies that, at conditions of this study, CaCl2 is largely associated (<0.2) at H2O density <0.85 g/cm3. Dissociation rises isothermally with increasing density, reaching ~1.4 at 600 °C, 1.4 GPa. The variation in silica molality with aH2O in H2O-CaCl2 is nearly identical to that in H2O-CO2 solutions at 800 °C and 1.0 GPa, consistent with the absence of Ca-silicate complexing. The results suggest that the ionization state of the salt solution is an important determinant of aH2O, and that H2O-CaCl2 fluids exhibit nearly ideal molecular mixing over a wider range of conditions than implied by previous modeling. The new data help interpret natural examples of large-scale Ca-metasomatism in a wide range of lower crustal and upper mantle settings.

Keywords: Metasomatism, quartz; silica; experimental; brines; fluids; halogens; solubility; Experimental Halogens in Honor of James Webster

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Received: 2021-11-15
Accepted: 2022-12-15
Published Online: 2023-10-04
Published in Print: 2023-10-26

© 2023 by Mineralogical Society of America

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  2. Compositional trends in Ba-, Ti-, and Cl-rich micas from metasomatized mantle rocks of the Gföhl Unit, Bohemian Massif, Austria
  3. Experimental determination of quartz solubility in H2O-CaCl2 solutions at 600–900 °C and 0.6–1.4 GPa
  4. The use of boron nitride to impose reduced redox conditions in experimental petrology
  5. Structures and transport properties of supercritical SiO2-H2O and NaAlSi3O8-H2O fluids
  6. Hydrologic regulation of clay-mineral transformations in a redoximorphic soil of subtropical monsoonal China
  7. Witness to strain: Subdomain boundary length and the apparent subdomain boundary density in large strained olivine grains
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  9. Crystal vs. melt compositional effects on the partitioning of the first-row transition and high field strength elements between clinopyroxene and silicic, alkaline, aluminous melts
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  13. Crocobelonite, CaFe23+(PO4)2O, a new oxyphosphate mineral, the product of pyrolytic oxidation of natural phosphides
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https://doi.org/10.2138/am-2022-8387
Keywords for this article
Metasomatism, quartz; silica; experimental; brines; fluids; halogens; solubility; Experimental Halogens in Honor of James Webster

Articles in the same Issue

  1. Heavy halogen compositions of lamprophyres derived from metasomatized lithospheric mantle beneath eastern North China Craton
  2. Compositional trends in Ba-, Ti-, and Cl-rich micas from metasomatized mantle rocks of the Gföhl Unit, Bohemian Massif, Austria
  3. Experimental determination of quartz solubility in H2O-CaCl2 solutions at 600–900 °C and 0.6–1.4 GPa
  4. The use of boron nitride to impose reduced redox conditions in experimental petrology
  5. Structures and transport properties of supercritical SiO2-H2O and NaAlSi3O8-H2O fluids
  6. Hydrologic regulation of clay-mineral transformations in a redoximorphic soil of subtropical monsoonal China
  7. Witness to strain: Subdomain boundary length and the apparent subdomain boundary density in large strained olivine grains
  8. Libyan Desert Glass: New evidence for an extremely high-pressure-temperature impact event from nanostructural study
  9. Crystal vs. melt compositional effects on the partitioning of the first-row transition and high field strength elements between clinopyroxene and silicic, alkaline, aluminous melts
  10. Microbially induced clay weathering: Smectite-to-kaolinite transformation
  11. Hydrous wadsleyite crystal structure up to 32 GPa
  12. Multiple fluid sources in skarn systems: Oxygen isotopic evidence from the Haobugao Zn-Fe-Sn deposit in the southern Great Xing’an Range, NE China
  13. Crocobelonite, CaFe23+(PO4)2O, a new oxyphosphate mineral, the product of pyrolytic oxidation of natural phosphides
  14. Tetrahedrite-(Ni), Cu6(Cu4Ni2)Sb4S13, the first nickel member of tetrahedrite group mineral from Luobusa chromite deposits, Tibet, China
  15. New Mineral Names: Heavy metal and minerals from China
  16. Book Review
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