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Eu speciation in apatite at 1 bar: An experimental study of valence-state partitioning by XANES, lattice strain, and Eu/Eu* in basaltic systems

  • Nicholas D. Tailby ORCID logo , Dustin Trail , E. Bruce Watson , Antonio Lanzirotti ORCID logo , Matthew Newville and Yanling Wang
Published/Copyright: May 9, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 5

Abstract

Partition coefficients for rare earth elements (REEs) between apatite and basaltic melt were determined as a function of oxygen fugacity (fO2; iron-wüstite to hematite-magnetite buffers) at 1 bar and between 1110 and 1175 °C. Apatite-melt partitioning data for REE3+ (La, Sm, Gd, Lu) show near constant values at all experimental conditions, while bulk Eu becomes more incompatible (with an increasing negative anomaly) with decreasing fO2. Experiments define three apatite calibrations that can theoretically be used as redox sensors. The first, a XANES calibration that directly measures Eu valence in apatite, requires saturation at similar temperature-composition conditions to experiments and is defined by:

(Eu3+∑Eu)Apatite =11+10−0.10±0.01×log(fo2)−1.63±0.16.

The second technique involves analysis of Sm, Eu, and Gd in both apatite and coexisting basaltic melt (glass), and is defined by:

(EuEu∗)DSm×Gd=11+10−0.15±0.03×log(fo2)−2.46±0.41.

The third technique is based on the lattice strain model and also requires analysis of REE in both apatite and basalt. This calibration is defined by

(EuEu∗)Dlattice strain =11+10−0.20±0.03×log(fo2)−3.03±0.42.

The Eu valence-state partitioning techniques based on (Sm×Gd) and lattice strain are virtually indistinguishable, such that either methodology is valid. Application of any of these calibrations is best carried out in systems where both apatite and coexisting glass are present and in direct contact with one another. In holocrystalline rocks, whole rock analyses can be used as a guide to melt composition, but considerations and corrections must be made to either the lattice strain or Sm×Gd techniques to ensure that the effect of plagioclase crystallization either prior to or during apatite growth can be removed. Similarly, if the melt source has an inherited either a positive or negative Eu anomaly, appropriate corrections must also be made to lattice strain or (Sm×Gd) techniques that are based on whole rock analyses. This being the case, if apatite is primary and saturates from the parent melt early during the crystallization sequence, these corrections may be minimal.

The partition coefficients for the REE between apatite and melt range from a maximum DEu3+ = 1.67 ± 0.25 (as determined by lattice strain) to DLu3+ = 0.69 ± 0.10. The REE partition coefficient pattern, as observed in the Onuma diagram, is in a fortuitous situation where the most compatible REE (Eu3+) is also the polyvalent element used to monitor fO2. These experiments provide a quantitative means of assessing Eu anomalies in apatite and how they be used to constrain the oxygen fugacity of silicate melts.

Keywords: Apatite; europium; Eu/Eu*; XANES; oxygen fugacity; fO2; valence; anomaly; KREEP; basalt; lunar; merrillite; Experimental Halogens in Honor of Jim Webster

* Present address: Division of Earth Science, School of Environmental and Rural Science, University of New England, Armidale, NSW, Australia.

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

Funding statement: This research was partially funded under the NASA Astrobiology Institute grant no. NNA09DA80A to RPI. Portions of this work were performed at Geo-SoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation, Earth Sciences (EAR-1634415) and Department of Energy-GeoSciences (DE-FG02-94ER14466). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work was partially supported by EAR-1751903.

Acknowledgments

The authors thank Daniel Harlov and Justin Filiberto for organizing this special volume in memory of our friend and colleague Jim Webster. N.D.T. enjoyed numerous discussions with Jim during the development of this study, and we hope the paper promotes further experimental work on apatite, something we believe Jim would appreciate and approve of. The authors thank Adrian Fiege for assistance with Virtual WDS software and general awesomeness, Antony Burnham for assistance with Eu valence fityk code, and John Hughes and George Harlow for providing apatite structural models. The various reviewers of this paper are also thanked for improving on earlier versions.

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Received: 2021-11-14
Accepted: 2022-03-02
Published Online: 2023-05-09
Published in Print: 2023-05-25

© 2023 Mineralogical Society of America

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  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-2022-8388
Keywords for this article
Apatite; europium; Eu/Eu*; XANES; oxygen fugacity; fO2; valence; anomaly; KREEP; basalt; lunar; merrillite; 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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