Hydrothermal transport, deposition, and fractionation of the REE

experimental data and thermodynamic calculations

A. Migdisov, A. E. Williams-Jones, Joel Brugger, F. A. Caporuscio

Research output: Contribution to journalReview ArticleResearchpeer-review

Abstract

For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C (Haas et al., 1995; Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

Original languageEnglish
Pages (from-to)13-42
Number of pages30
JournalChemical Geology
Volume439
DOIs
Publication statusPublished - 7 Nov 2016

Keywords

  • Deposition
  • Fractionation
  • Hydrothermal
  • Rare earth elements
  • Transport

Cite this

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title = "Hydrothermal transport, deposition, and fractionation of the REE: experimental data and thermodynamic calculations",
abstract = "For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C (Haas et al., 1995; Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.",
keywords = "Deposition, Fractionation, Hydrothermal, Rare earth elements, Transport",
author = "A. Migdisov and Williams-Jones, {A. E.} and Joel Brugger and Caporuscio, {F. A.}",
year = "2016",
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Hydrothermal transport, deposition, and fractionation of the REE : experimental data and thermodynamic calculations. / Migdisov, A.; Williams-Jones, A. E.; Brugger, Joel; Caporuscio, F. A.

In: Chemical Geology, Vol. 439, 07.11.2016, p. 13-42.

Research output: Contribution to journalReview ArticleResearchpeer-review

TY - JOUR

T1 - Hydrothermal transport, deposition, and fractionation of the REE

T2 - experimental data and thermodynamic calculations

AU - Migdisov, A.

AU - Williams-Jones, A. E.

AU - Brugger, Joel

AU - Caporuscio, F. A.

PY - 2016/11/7

Y1 - 2016/11/7

N2 - For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C (Haas et al., 1995; Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

AB - For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semi-empirical estimates involving extrapolation of thermodynamic data obtained at 25 °C (Haas et al., 1995; Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

KW - Deposition

KW - Fractionation

KW - Hydrothermal

KW - Rare earth elements

KW - Transport

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DO - 10.1016/j.chemgeo.2016.06.005

M3 - Review Article

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JO - Chemical Geology

JF - Chemical Geology

SN - 0009-2541

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