Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions
Abstract The interaction between rare earth element (REE)‐rich (La, Pr, Nd, Dy) aqueous solutions, dolomite (CaMg(CO3)2), and aragonite (CaCO3) at low temperature hydrothermal conditions (25–220 °C) is studied. The experiments result in the solvent‐mediated surface precipitation and subsequent pseud...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2023-02-01
|
| Series: | Global Challenges |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/gch2.202200085 |
| _version_ | 1811170706181849088 |
|---|---|
| author | Adrienn Maria Szucs Melanie Maddin Daniel Brien Paul Christopher Guyett Juan Diego Rodriguez‐Blanco |
| author_facet | Adrienn Maria Szucs Melanie Maddin Daniel Brien Paul Christopher Guyett Juan Diego Rodriguez‐Blanco |
| author_sort | Adrienn Maria Szucs |
| collection | DOAJ |
| description | Abstract The interaction between rare earth element (REE)‐rich (La, Pr, Nd, Dy) aqueous solutions, dolomite (CaMg(CO3)2), and aragonite (CaCO3) at low temperature hydrothermal conditions (25–220 °C) is studied. The experiments result in the solvent‐mediated surface precipitation and subsequent pseudomorphic mineral replacement of the dolomite and aragonite seeds by newly formed REE‐carbonates. The host grains are replaced from periphery inward. The newly formed REE‐bearing carbonates in La‐, Pr‐, and Nd‐doped systems follow the crystallization sequence: lanthanite [REE2(CO3)3·8H2O] → kozoite [orthorhombic REECO3(OH)] → hydroxylbastnasite [hexagonal REECO3(OH)]. The interaction of Dy‐bearing solutions with dolomite results only in the crystallization of kozoite [orthorhombic DyCO3(OH)]. However, experiments with aragonite reveal a two‐step crystallization pathway: tengerite [Dy2(CO3)3·2‐3(H2O)] → kozoite [orthorhombic DyCO3(OH)]. The temperature, the dissolution rate of the host mineral, and the ionic radii of the REE3+ in question are found to control the kinetics of the replacement reaction, the polymorph selection, and the crystallization pathways toward bastnasite. The findings allow to gain a more in‐depth understanding of the formation REE‐bearing carbonates, particularly the mineral bastnasite, which is the main source of REEs for industry. This knowledge can be used to improve REE separation, exploration, exploitation methods, as well to produce carbonate minerals with tailored structures. |
| first_indexed | 2024-04-10T17:02:07Z |
| format | Article |
| id | doaj.art-b35f720f342747d79c7984b4915bf62e |
| institution | Directory Open Access Journal |
| issn | 2056-6646 |
| language | English |
| last_indexed | 2024-04-10T17:02:07Z |
| publishDate | 2023-02-01 |
| publisher | Wiley |
| record_format | Article |
| series | Global Challenges |
| spelling | doaj.art-b35f720f342747d79c7984b4915bf62e2023-02-06T12:07:22ZengWileyGlobal Challenges2056-66462023-02-0172n/an/a10.1002/gch2.202200085Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement ReactionsAdrienn Maria Szucs0Melanie Maddin1Daniel Brien2Paul Christopher Guyett3Juan Diego Rodriguez‐Blanco4Department of Geology School of Natural Sciences Trinity College Dublin Dublin 2 IrelandDepartment of Geology School of Natural Sciences Trinity College Dublin Dublin 2 IrelandDepartment of Geology School of Natural Sciences Trinity College Dublin Dublin 2 IrelandiCRAG Department of Geology School of Natural Sciences Trinity College Dublin Dublin 2 IrelandiCRAG Department of Geology School of Natural Sciences Trinity College Dublin Dublin 2 IrelandAbstract The interaction between rare earth element (REE)‐rich (La, Pr, Nd, Dy) aqueous solutions, dolomite (CaMg(CO3)2), and aragonite (CaCO3) at low temperature hydrothermal conditions (25–220 °C) is studied. The experiments result in the solvent‐mediated surface precipitation and subsequent pseudomorphic mineral replacement of the dolomite and aragonite seeds by newly formed REE‐carbonates. The host grains are replaced from periphery inward. The newly formed REE‐bearing carbonates in La‐, Pr‐, and Nd‐doped systems follow the crystallization sequence: lanthanite [REE2(CO3)3·8H2O] → kozoite [orthorhombic REECO3(OH)] → hydroxylbastnasite [hexagonal REECO3(OH)]. The interaction of Dy‐bearing solutions with dolomite results only in the crystallization of kozoite [orthorhombic DyCO3(OH)]. However, experiments with aragonite reveal a two‐step crystallization pathway: tengerite [Dy2(CO3)3·2‐3(H2O)] → kozoite [orthorhombic DyCO3(OH)]. The temperature, the dissolution rate of the host mineral, and the ionic radii of the REE3+ in question are found to control the kinetics of the replacement reaction, the polymorph selection, and the crystallization pathways toward bastnasite. The findings allow to gain a more in‐depth understanding of the formation REE‐bearing carbonates, particularly the mineral bastnasite, which is the main source of REEs for industry. This knowledge can be used to improve REE separation, exploration, exploitation methods, as well to produce carbonate minerals with tailored structures.https://doi.org/10.1002/gch2.202200085aragonitebastnasitedolomitekozoitelanthaniterare earth carbonate |
| spellingShingle | Adrienn Maria Szucs Melanie Maddin Daniel Brien Paul Christopher Guyett Juan Diego Rodriguez‐Blanco Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions Global Challenges aragonite bastnasite dolomite kozoite lanthanite rare earth carbonate |
| title | Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions |
| title_full | Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions |
| title_fullStr | Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions |
| title_full_unstemmed | Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions |
| title_short | Targeted Crystallization of Rare Earth Carbonate Polymorphs at Hydrothermal Conditions via Mineral Replacement Reactions |
| title_sort | targeted crystallization of rare earth carbonate polymorphs at hydrothermal conditions via mineral replacement reactions |
| topic | aragonite bastnasite dolomite kozoite lanthanite rare earth carbonate |
| url | https://doi.org/10.1002/gch2.202200085 |
| work_keys_str_mv | AT adriennmariaszucs targetedcrystallizationofrareearthcarbonatepolymorphsathydrothermalconditionsviamineralreplacementreactions AT melaniemaddin targetedcrystallizationofrareearthcarbonatepolymorphsathydrothermalconditionsviamineralreplacementreactions AT danielbrien targetedcrystallizationofrareearthcarbonatepolymorphsathydrothermalconditionsviamineralreplacementreactions AT paulchristopherguyett targetedcrystallizationofrareearthcarbonatepolymorphsathydrothermalconditionsviamineralreplacementreactions AT juandiegorodriguezblanco targetedcrystallizationofrareearthcarbonatepolymorphsathydrothermalconditionsviamineralreplacementreactions |