In situ Raman investigation of Dy complexation in Cl-bearing aqueous solutions at 20–300 °C

Smith-Schmitz, Sarah E.; Hurtig, Nicole C.; Gysi, Alexander P.

doi:10.1039/d4dt02170c

Title: In situ Raman investigation of Dy complexation in Cl-bearing aqueous solutions at 20–300 °C

Journal Article · 09 February 2025 · Dalton Transactions

DOI: https://doi.org/10.1039/d4dt02170c · OSTI ID:2522092

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New Mexico Institute of Mining and Technology, Socorro, NM (United States)

Raman spectroscopy provides a versatile tool for in situ characterization of aqueous rare earth elements (REE) speciation at the molecular level. Complexation of REE with ligands such as Cl^– and OH^– is of particular interest for understanding the mobility of REE in NaCl-bearing hydrothermal fluids responsible for enriching REE to economic levels in nature. Raman spectroscopic studies of REE speciation in Cl-bearing aqueous fluids are primarily conducted at ambient temperature, whereas natural systems indicate temperatures of >100–600 °C. In this study, the speciation of Dy in acidic chloride-bearing hydrothermal solutions was investigated using confocal Raman spectroscopy with a new capillary Raman heating stage at 20–300 °C. Background solutions (pure water, NaCl-solutions) and solutions with 0.14–1.8 mol kg^–1 dissolved DyCl₃ were sealed in quartz capillary cells. Comparison of the spectra for Dy chloride solutions with those for background solutions and the spectra for reference Dy-bearing solids was used to identify Raman bands specific to Dy–O and Dy–Cl bonds. The Raman band for the Dy–O stretching mode of hydrated Dy³⁺ aqua ions was measured at 365–384 cm^–1 and a Raman band for the Dy–Cl stretching modes of Dy chloride complexes was measured near 240 cm^–1. The Dy–O band decreases systematically with temperature, whereas the Dy–Cl band systematically increases, indicating a systematic increase in the stability of Dy chloride complexes with temperature. Here, this study provides the framework for expanding the use of in situ Raman spectroscopy to investigate the speciation of REE in aqueous solutions to hydrothermal conditions.

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Research Organization:: New Mexico Institute of Mining and Technology, Socorro, NM (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0022269

OSTI ID:: 2522092

Report Number(s):: DOE-NMT--0022269

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Vol. 54; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Raman and Resonance Raman Spectroscopy of Selected Rare-Earth Sesquioxides Tucker, L. A.; Carney, F. J.; McMillan, P. Applied Spectroscopy, Vol. 38, Issue 6 https://doi.org/10.1366/0003702844554657	journal	November 1984
Non-Complexing Anions for Quantitative Speciation Studies Using Raman Spectroscopy in Fused Silica High-Pressure Optical Cells under Hydrothermal Conditions Applegarth, Lucas M. S. G. A.; Alcorn, Christopher; Bissonette, Katherine Applied Spectroscopy, Vol. 69, Issue 8 https://doi.org/10.1366/14-07825	journal	August 2015
On Polymorphism of Dysprosium Trichloride Zakirýanova, Irina D.; Khokhlov, Vladimir A.; Salyulev, Alexander B. Zeitschrift für Naturforschung A, Vol. 70, Issue 3 https://doi.org/10.1515/zna-2014-0276	journal	February 2015
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Lithogeochemical Vectors for Hydrothermal Processes in the Strange Lake Peralkaline Granitic REE-Zr-Nb Deposit Gysi, Alexander P.; Williams-Jones, Anthony E.; Collins, Patrick Economic Geology, Vol. 111, Issue 5 https://doi.org/10.2113/econgeo.111.5.1241	journal	May 2016
X-ray spectroscopic investigations of fluids in the hydrothermal diamond anvil cell: The hydration structure of aqueous La³⁺up to 300 °C and 1600 bars Anderson, Alan J.; Jayanetti, Sumedha; Mayanovic, Robert A. American Mineralogist, Vol. 87, Issue 2-3 https://doi.org/10.2138/am-2002-2-307	journal	February 2002
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Rare Earth Permanent Magnets: Supply Chain Deep Dive Assessment Smith, Braeton J.; Riddle, Matthew E.; Earlam, Matthew R. https://doi.org/10.2172/1871577	report	February 2022
Theoretical prediction of the thermodynamic behavior of aqueous electrolytes by high pressures and temperatures; IV, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 degrees C and 5kb Helgeson, H. C.; Kirkham, D. H.; Flowers, G. C. American Journal of Science, Vol. 281, Issue 10 https://doi.org/10.2475/ajs.281.10.1249	journal	December 1981
Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures; revised equations of state for the standard partial molal properties of ions and electrolytes Tanger, J. C.; Helgeson, H. C. American Journal of Science, Vol. 288, Issue 1 https://doi.org/10.2475/ajs.288.1.19	journal	January 1988
The convex programming minimization of five thermodynamic potentials other than Gibbs energy in geochemical modeling Karpov, I. K. American Journal of Science, Vol. 302, Issue 4 https://doi.org/10.2475/ajs.302.4.281	journal	April 2002
Global Potential of Rare Earth Resources and Rare Earth Demand from Clean Technologies Zhou, Baolu; Li, Zhongxue; Chen, Congcong Minerals, Vol. 7, Issue 11 https://doi.org/10.3390/min7110203	journal	October 2017
Hydration and Ion Pair Formation in Aqueous Lu3+- Solution Rudolph, Wolfram; Irmer, Gert Molecules, Vol. 23, Issue 12 https://doi.org/10.3390/molecules23123237	journal	December 2018
On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study Rudolph, Wolfram; Irmer, Gert Molecules, Vol. 24, Issue 10 https://doi.org/10.3390/molecules24101953	journal	May 2019
GEM-SELEKTOR GEOCHEMICAL MODELING PACKAGE: TSolMod LIBRARY AND DATA INTERFACE FOR MULTICOMPONENT PHASE MODELS Wagner, T.; Kulik, D. A.; Hingerl, F. F. The Canadian Mineralogist, Vol. 50, Issue 5 https://doi.org/10.3749/canmin.50.5.1173	journal	October 2012
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