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The effect of composition on chlorine solubility and behavior in silicate melts

  • Richard W. Thomas and Bernard J. Wood ORCID logo
Published/Copyright: May 9, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 5

Abstract

We have performed experiments at 1.5 GPa and 1400 °C on 25 different bulk compositions to determine the effects of major element compositions on the Cl contents of silicate melts at known fugacities of Cl2 and O2. The experimental method involved mixing a “sliding” Cl buffer, a mixture of AgCl, AgI, and Ag with the silicate bulk composition and performing the experiment in a graphite capsule together with a source of CO2 (AgCO3). The graphite capsules were sealed inside welded Pt tubes to maintain a CO2-CO atmosphere with oxygen fugacity fixed at the C-CO-CO2 (CCO) buffer. During the experiment, the Cl buffer segregates leaving a Cl-bearing melt, which quenches to a glass. We used the results to define chloride capacity CCl for each melt at the pressure and temperature of the experiment:

C C l = C l ( w t f C l 2 × f O 2 4

Chloride capacity was found to correlate positively with optical basicity and NBO/T and negatively with ionic porosity and the Larsen index. We combined our new data with the results of Thomas and Wood (2021) to derive an equation describing the composition, pressure and temperature dependence of the chloride capacity:

log C C l = 1.601 + 4470 X C a − 3430 X S i + 2592 X F e − 4092 X K − 894 P / T .

In this equation, XCa, XSi, and so on refer to the oxide mole fractions on a single-cation basis, P is in GPa and T in K. The equation reproduces 58 data points with an r2 of 0.96 and a standard error of 0.089. The addition of literature data on hydrous experiments indicates that the effects of <4.3 wt% H2O are small enough to be ignored. We also performed experiments aimed at determining the conditions of NaCl saturation in melts. When combined with literature data we obtained:

log C l − = log a N a C l + 0.06 − 2431 X C a + 3430 X S i − 2592 X F e + 3484 X N a + 4092 X K − 2417 / T

where (Cl–) is the Cl content of the melt in wt% aNaCl is the activity of NaCl (liquid) and the other symbols are the same as before. The results indicate that basalt dissolves ~8 times more Cl than rhyolite at a given NaCl activity i.e., Cl is ~8 times more soluble in basalt than in rhyolite.

Keywords: Basalt; rhyolite; Cl solubility in melts; compositional effects on Cl solubility; Cl degassing; chloride capacity; NaCl saturation in melts; Experimental Halogens in Honor of Jim Webster

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

Acknowledgments and Funding

We acknowledge the stimulation and guidance provided by Jim Webster’s numerous papers on halogen behavior in silicate melts. R.W.T. is grateful to the Natural Environmental Research Council, and the Oxford Doctoral Training Partnership in Environmental Research for studentship and funding (NE/L002612/1). B.J.W. acknowledges funding from Science and Technology Facilities Council grant ST/R000999/1 and the NERC FAMOS project NE/P017452/1. We thank Paula Antoschechkina of Caltech for advice in using AlphaMELTS. We acknowledge the thorough reviews of Bruno Scaillet and an anonymous reviewer, and discussions with Jon Blundy. Further thanks are owed to Dan Harlov as associate editor.

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Received: 2022-01-12
Accepted: 2022-04-28
Published Online: 2023-05-09
Published in Print: 2023-05-25

© 2023 by Mineralogical Society of America

Articles in the same Issue

  1. Eu speciation in apatite at 1 bar: An experimental study of valence-state partitioning by XANES, lattice strain, and Eu/Eu* in basaltic systems
  2. The effect of composition on chlorine solubility and behavior in silicate melts
  3. High-temperature phase relations of hydrous aluminosilicates at 22 GPa in the AlOOH-AlSiO3OH system
  4. Crystallization of spinel from coexisting silicate and sulfide immiscible liquids: An equilibrium case with postcumulus reactions
  5. X-ray absorption spectroscopy study of Mn reference compounds for Mn speciation in terrestrial surface environments
  6. Heterogeneous and retarded phase transformation of ferrihydrite on montmorillonite surface: The important role of surface interactions
  7. Atomic-scale characterization of the oxidation state of Ti in meteoritic hibonite: Implications for early solar system thermodynamics
  8. Structural behavior of C2/m tremolite to 40 GPa: A high-pressure single-crystal X-ray diffraction study
  9. Optimizing Raman spectral collection for quartz and zircon crystals for elastic thermobarometry
  10. Measuring H2O concentrations in olivine by secondary ion mass spectrometry: Challenges and paths forward
  11. Arsenic clustering in arsenian pyrite: A combined photoemission and theoretical modeling study
  12. High-pressure electrical conductivity and elasticity of iron-bearing δ-AlOOH
  13. Nudged elastic band calculations of the (4H)XSi hydrogarnet type defect in Mg2SiO4 forsterite
  14. Mn substitution and distribution in goethite and influences on its photocatalytic properties: A combined study using first-principles calculations and photocatalytic experiments
  15. Incorporating previously neglected excess oxygen associated with ferric iron in matrix corrections of microprobe data from cubic and rhombohedral Fe-Ti oxides
  16. Recycled carbonates in the mantle sources of natural kamafugites: A zinc isotope perspective
  17. Raman analysis of octocoral carbonate ion structural disorder along a natural depth gradient, Kona coast, Hawai‘i
  18. Memorial of Charles Wilson Burnham, 1933–2021
  19. Erratum
https://doi.org/10.2138/am-2022-8450
Keywords for this article
Basalt; rhyolite; Cl solubility in melts; compositional effects on Cl solubility; Cl degassing; chloride capacity; NaCl saturation in melts; Experimental Halogens in Honor of Jim Webster

Articles in the same Issue

  1. Eu speciation in apatite at 1 bar: An experimental study of valence-state partitioning by XANES, lattice strain, and Eu/Eu* in basaltic systems
  2. The effect of composition on chlorine solubility and behavior in silicate melts
  3. High-temperature phase relations of hydrous aluminosilicates at 22 GPa in the AlOOH-AlSiO3OH system
  4. Crystallization of spinel from coexisting silicate and sulfide immiscible liquids: An equilibrium case with postcumulus reactions
  5. X-ray absorption spectroscopy study of Mn reference compounds for Mn speciation in terrestrial surface environments
  6. Heterogeneous and retarded phase transformation of ferrihydrite on montmorillonite surface: The important role of surface interactions
  7. Atomic-scale characterization of the oxidation state of Ti in meteoritic hibonite: Implications for early solar system thermodynamics
  8. Structural behavior of C2/m tremolite to 40 GPa: A high-pressure single-crystal X-ray diffraction study
  9. Optimizing Raman spectral collection for quartz and zircon crystals for elastic thermobarometry
  10. Measuring H2O concentrations in olivine by secondary ion mass spectrometry: Challenges and paths forward
  11. Arsenic clustering in arsenian pyrite: A combined photoemission and theoretical modeling study
  12. High-pressure electrical conductivity and elasticity of iron-bearing δ-AlOOH
  13. Nudged elastic band calculations of the (4H)XSi hydrogarnet type defect in Mg2SiO4 forsterite
  14. Mn substitution and distribution in goethite and influences on its photocatalytic properties: A combined study using first-principles calculations and photocatalytic experiments
  15. Incorporating previously neglected excess oxygen associated with ferric iron in matrix corrections of microprobe data from cubic and rhombohedral Fe-Ti oxides
  16. Recycled carbonates in the mantle sources of natural kamafugites: A zinc isotope perspective
  17. Raman analysis of octocoral carbonate ion structural disorder along a natural depth gradient, Kona coast, Hawai‘i
  18. Memorial of Charles Wilson Burnham, 1933–2021
  19. Erratum
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