Chemical and environmental stability of monazite-cheralite solid solutions Ln1-2xCaxThxPO4 (Ln = Pr, Nd; x = 0–0.15): A thermodynamic study

Qin, Danwen; Shelyug, Anna; Szenknect, Stéphanie; Mesbah, Adel; Clavier, Nicolas; Dacheux, Nicolas; Navrotsky, Alexandra

doi:10.1016/j.apgeochem.2022.105504

Chemical and environmental stability of monazite-cheralite solid solutions Ln_1-2xCa_xTh_xPO₄ (Ln = Pr, Nd; x = 0–0.15): A thermodynamic study

Journal Article · Sun Nov 13 23:00:00 EST 2022 · Applied Geochemistry

DOI:https://doi.org/10.1016/j.apgeochem.2022.105504· OSTI ID:2419595

Qin, Danwen ^[1]; Shelyug, Anna ^[2]; Szenknect, Stéphanie ^[3]; Mesbah, Adel ^[4]; Clavier, Nicolas ^[3]; Dacheux, Nicolas ^[3]; Navrotsky, Alexandra ^[5]

Montpellier Univ. 2 (France); Centre National de la Recherche Scientifique (CNRS) (France); Sun Yat-Sen Univ., Zhuhai (China); OSTI
Institute of Solid State Chemistry, Yekaterinburg (Russian Federation)
Montpellier Univ. 2 (France); Centre National de la Recherche Scientifique (CNRS) (France)
Montpellier Univ. 2 (France); Centre National de la Recherche Scientifique (CNRS) (France); Univ. of Lyon (France); Université Claude-Bernard Lyon 1 (UCBL) (France)
Arizona State Univ., Tempe, AZ (United States)

Monazite-cheralite ceramics are a promising waste form for actinides. To elucidate the long-term behavior of this matrix in aqueous solutions, this study measured thermodynamic data for Th-rhabdophanes Ln_1-2xCa_xTh_xPO₄·nH₂O (with Ln = Pr, Nd; x = 0–0.15) and the associated anhydrous monazite-cheralites Ln_1-2xCa_xTh_xPO₄. Further, solubility experiments at 298K and high temperature oxide melt solution calorimetry were combined for calculation of ΔG$$^°_f$$, ΔH$$^°_f$$ and S$$^°_m$$ of Th-rhabdophanes and associated monazite-cheralites. Standard solubility constants were employed in a geochemical simulation using the PHREEQC software, the results of which confirmed the high chemical stability of the monazite-cheralite phases and supported their use as a specific conditioning matrix for the long-term immobilization of actinides.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001089

OSTI ID:: 2419595

Alternate ID(s):: OSTI ID: 1900545

Journal Information:: Applied Geochemistry, Journal Name: Applied Geochemistry Journal Issue: C Vol. 148; ISSN 0883-2927

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Determination of the Solubility of Rhabdophanes LnPO ₄ ·0.667H ₂ O (Ln = La to Dy) : Determination of the Solubility of Rhabdophanes LnPO Gausse, Clémence; Szenknect, Stéphanie; Qin, Dan Wen European Journal of Inorganic Chemistry, Vol. 2016, Issue 28 https://doi.org/10.1002/ejic.201600517	journal	August 2016
Progress and new directions in high temperature calorimetry Navrotsky, Alexandra Physics and Chemistry of Minerals, Vol. 2, Issue 1-2 https://doi.org/10.1007/BF00307526	journal	January 1977
Thermochemistry of monazite-(La) and dissakisite-(La): implications for monazite and allanite stability in metapelites Janots, E.; Brunet, F.; Goffé, B. Contributions to Mineralogy and Petrology, Vol. 154, Issue 1 https://doi.org/10.1007/s00410-006-0176-2	journal	January 2007
Solubilities of some hydrous REE phosphates with implications for diagenesis and sea water concentrations Jonasson, R. G.; Bancroft, G. M.; Nesbitt, H. W. Geochimica et Cosmochimica Acta, Vol. 49, Issue 10 https://doi.org/10.1016/0016-7037(85)90071-7	journal	October 1985
Influence of the pH on the dissolution of TPD and associated solid solutions Robisson, A. C.; Dacheux, N.; Aupiais, J. Journal of Nuclear Materials, Vol. 306, Issue 2-3 https://doi.org/10.1016/S0022-3115(02)01246-1	journal	December 2002
Andra thermodynamic database for performance assessment: ThermoChimie Giffaut, E.; Grivé, M.; Blanc, Ph. Applied Geochemistry, Vol. 49 https://doi.org/10.1016/j.apgeochem.2014.05.007	journal	October 2014
Dissolution kinetics of monazite LnPO 4 (Ln = La to Gd): A multiparametric study Gausse, Clémence; Szenknect, Stéphanie; Mesbah, Adel Applied Geochemistry, Vol. 93 https://doi.org/10.1016/j.apgeochem.2018.04.005	journal	June 2018
Formation enthalpy of ThSiO4 and enthalpy of the thorite → huttonite phase transition Mazeina, Lena; Ushakov, Sergey V.; Navrotsky, Alexandra Geochimica et Cosmochimica Acta, Vol. 69, Issue 19 https://doi.org/10.1016/j.gca.2005.03.053	journal	October 2005
The solubility of monazite (CePO4), SmPO4, and GdPO4 in aqueous solutions from 100 to 250 °C Gysi, Alexander P.; Harlov, Daniel; Miron, George D. Geochimica et Cosmochimica Acta, Vol. 242 https://doi.org/10.1016/j.gca.2018.08.038	journal	December 2018
The solubility of monazite (LaPO4, PrPO4, NdPO4, and EuPO4) endmembers in aqueous solutions from 100 to 250 °C Van Hoozen, Christopher J.; Gysi, Alexander P.; Harlov, Daniel E. Geochimica et Cosmochimica Acta, Vol. 280 https://doi.org/10.1016/j.gca.2020.04.019	journal	July 2020
The low temperature heat capacity of LaPO4 and GdPO4, the thermodynamic functions of the monazite-type LnPO4 series Thiriet, C.; Konings, R. J. M.; Javorský, P. The Journal of Chemical Thermodynamics, Vol. 37, Issue 2 https://doi.org/10.1016/j.jct.2004.07.031	journal	February 2005
The heat capacity of NdPO4 Popa, K.; Jutier, F.; Wastin, F. The Journal of Chemical Thermodynamics, Vol. 38, Issue 11 https://doi.org/10.1016/j.jct.2006.02.006	journal	November 2006
Thermodynamics of solid phases containing rare earth oxides Navrotsky, Alexandra; Lee, Wingyee; Mielewczyk-Gryn, Aleksandra The Journal of Chemical Thermodynamics, Vol. 88 https://doi.org/10.1016/j.jct.2015.04.008	journal	September 2015
Thermochemistry of La1−xLnxPO4-monazites (Ln= Gd, Eu) Neumeier, Stefan; Kegler, Philip; Arinicheva, Yulia The Journal of Chemical Thermodynamics, Vol. 105 https://doi.org/10.1016/j.jct.2016.11.003	journal	February 2017
Solubility product of the thorium phosphate hydrogen-phosphate hydrate (Th 2 (PO 4 ) 2 (HPO 4 )·H 2 O, TPHPH) Qin, Danwen; Gausse, Clémence; Szenknect, Stéphanie The Journal of Chemical Thermodynamics, Vol. 114 https://doi.org/10.1016/j.jct.2017.01.003	journal	November 2017
Thermochemistry of rare-earth aluminate and aluminosilicate glasses Zhang, Yahong; Navrotsky, Alexandra Journal of Non-Crystalline Solids, Vol. 341, Issue 1-3 https://doi.org/10.1016/j.jnoncrysol.2004.04.027	journal	August 2004
Actinide solubility-controlling phases during the dissolution of phosphate ceramics Du Fou de Kerdaniel, E.; Clavier, N.; Dacheux, N. Journal of Nuclear Materials, Vol. 362, Issue 2-3 https://doi.org/10.1016/j.jnucmat.2007.01.132	journal	May 2007
Incorporation of thorium in the rhabdophane structure: Synthesis and characterization of Pr 1-2x Ca x Th x PO 4 ·nH 2 O solid solutions Qin, Danwen; Mesbah, Adel; Gausse, Clémence Journal of Nuclear Materials, Vol. 492 https://doi.org/10.1016/j.jnucmat.2017.05.019	journal	August 2017
Energetics of La1−xAxCrO3−δ perovskites (A=Ca or Sr) Cheng, Jihong; Navrotsky, Alexandra Journal of Solid State Chemistry, Vol. 178, Issue 1 https://doi.org/10.1016/j.jssc.2004.11.028	journal	January 2005
Structural, vibrational, and thermochemical properties of the monazite-type solid solution La1–Pr PO4 Hirsch, A.; Kegler, P.; Alencar, I. Journal of Solid State Chemistry, Vol. 245 https://doi.org/10.1016/j.jssc.2016.09.032	journal	January 2017
Synthesis, Crystal Structure, and Enthalpies of Formation of Churchite-type REPO ₄ ·2H ₂ O (RE = Gd to Lu) Materials Subramani, Tamilarasan; Rafiuddin, Mohamed Ruwaid; Shelyug, Anna Crystal Growth & Design, Vol. 19, Issue 8 https://doi.org/10.1021/acs.cgd.9b00524	journal	June 2019
Monoclinic Form of the Rhabdophane Compounds: REEPO ₄ ·0.667H ₂ O Mesbah, Adel; Clavier, Nicolas; Elkaim, Erik Crystal Growth & Design, Vol. 14, Issue 10 https://doi.org/10.1021/cg500707b	journal	September 2014
Densities of binary aqueous solutions of 306 inorganic substances Novotny, P.; Sohnel, O. Journal of Chemical & Engineering Data, Vol. 33, Issue 1 https://doi.org/10.1021/je00051a018	journal	January 1988
Energetic Effects of Substitution of La-Nd and Si-Ge Oxyapatite-Type Materials Hosseini, Seyedeh Mahboobeh; Navrotsky, Alexandra Journal of the American Ceramic Society, Vol. 96, Issue 12 https://doi.org/10.1111/jace.12705	journal	November 2013
Progress and New Directions in Calorimetry: A 2014 Perspective Navrotsky, Alexandra Journal of the American Ceramic Society, Vol. 97, Issue 11 https://doi.org/10.1111/jace.13278	journal	October 2014
Monazite from mountain to ocean: a case study from Trolognaro (Fort-Dauphin), Madagascar [Monazite from mountain to ocean: a case study from Trolognaro (Fort-Dauphin), Madagascar] Montel, Jean -Marc; Razafimahatratra, Dieudonné; Ralison, Bruno European Journal of Mineralogy, Vol. 23, Issue 5 https://doi.org/10.1127/0935-1221/2011/0023-2149	journal	December 2011
Low-temperature heat capacity and thermodynamic properties of PrPO4 Gavrichev, K. S.; Gurevich, V. M.; Ryumin, M. A. Geochemistry International, Vol. 54, Issue 4 https://doi.org/10.1134/S001670291602004X	journal	April 2016
The heat capacity and thermodynamic functions of EuPO4 over the temperature range 0–1600 K Gavrichev, K. S.; Ryumin, M. A.; Tyurin, A. V. Russian Journal of Physical Chemistry A, Vol. 83, Issue 6 https://doi.org/10.1134/S0036024409060053	journal	January 2009
Thermochemistry of rare-earth orthophosphates Ushakov, S. V.; Helean, K. B.; Navrotsky, A. Journal of Materials Research, Vol. 16, Issue 9 https://doi.org/10.1557/JMR.2001.0361	journal	September 2001
Thermodynamic properties of CaTh(PO4)2 synthetic cheralite Popa, K.; Shvareva, T.; Mazeina, L. American Mineralogist, Vol. 93, Issue 8-9 https://doi.org/10.2138/am.2008.2794	journal	August 2008
Versatile Monazite: Resolving geological records and solving challenges in materials science: Monazite as a promising long-term radioactive waste matrix: Benefits of high-structural flexibility and chemical durability Dacheux, N.; Clavier, N.; Podor, R. American Mineralogist, Vol. 98, Issue 5-6 https://doi.org/10.2138/am.2013.4307	journal	May 2013
Synthesis, Structure, and Properties of Monazite, Pretulite, and Xenotime Boatner, L. A. Reviews in Mineralogy and Geochemistry, Vol. 48, Issue 1 https://doi.org/10.2138/rmg.2002.48.4	journal	January 2002
Thermodynamics and Stability of Rhabdophanes, Hydrated Rare Earth Phosphates REPO4 · n H2O Shelyug, Anna; Mesbah, Adel; Szenknect, Stéphanie Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00604	journal	December 2018

Similar Records

A low-temperature, one-step synthesis for monazite can transform monazite into a readily usable advanced nuclear waste form

Journal Article · Fri Mar 21 00:00:00 EDT 2025 · Science Advances · OSTI ID:2998822

Synthesis of nuclear waste monazites, ideal actinide hosts for geologic disposal

Journal Article · Tue Oct 31 23:00:00 EST 1978 · Mater. Res. Bull.; (United States) · OSTI ID:6441395

Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

Journal Article · Sun Dec 14 23:00:00 EST 2014 · Journal of Solid State Chemistry · OSTI ID:22451121

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
58 GEOSCIENCES
Calorimetry
Cheralite
Monazite
Rhabdophane
Solubility
Stability
Thorium

Chemical and environmental stability of monazite-cheralite solid solutions Ln1-2xCaxThxPO4 (Ln = Pr, Nd; x = 0–0.15): A thermodynamic study

Citation Formats

References (33)

Similar Records

Related Subjects

Chemical and environmental stability of monazite-cheralite solid solutions Ln_1-2xCa_xTh_xPO₄ (Ln = Pr, Nd; x = 0–0.15): A thermodynamic study