Ice as a kinetic and mechanistic driver of oxalate-promoted iron oxyhydroxide dissolution.
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| Title: | Ice as a kinetic and mechanistic driver of oxalate-promoted iron oxyhydroxide dissolution. |
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| Authors: | Sebaaly, Angelo P.1, van Rijn, Frank1, Hanna, Khalil2, Boily, Jean-François1 jean-francois.boily@umu.se |
| Source: | Proceedings of the National Academy of Sciences of the United States of America. 9/2/2025, Vol. 122 Issue 35, p1-9. 15p. |
| Subjects: | Ice, Oxalates, Geochemical modeling, Freeze-thaw cycles, Ferric hydroxides, Cryosphere, Dissolution (Chemistry), Liquid iron |
| Abstract: | Ice often mediates unexpected reactions in the Cryosphere, acting as a fascinating geochemical reactor. Mineral-organic interactions in frozen environments, such as soils and permafrost, are crucial for explaining the flux of soluble iron during melting events, yet the mechanisms remain misunderstood. This study elucidates the unique roles of freezing in the dissolution of iron oxyhydroxide nanoparticles (α-FeOOH) by oxalate, a low molecular weight dicarboxylate, under acidic conditions. From time-resolved experiments conducted over 4 d, we demonstrate that soluble iron was released through reactions in minute volumes of liquid water trapped between ice micrograins. Freeze concentration of nanoparticles, oxalate, and protons into this liquid water drove oxalate-and proton-promoted dissolution reactions at temperatures as low as -30 °C. Remarkably, ice at -10 °C dissolved more iron than liquid water at 4 °C under high oxalate loadings, and even more than at 25 °C under low oxalate loadings. In contrast, high salinity subdued dissolution. Also, sequential freeze-thaw cycles enhanced dissolution by releasing unreacted oxalate that was previously locked in ice. By resolving the chemical controls on mineral dissolution in ice, this work can help explain how freeze-thaw events are supplying new fluxes of soluble iron to nature. [ABSTRACT FROM AUTHOR] |
| Copyright of Proceedings of the National Academy of Sciences of the United States of America is the property of National Academy of Sciences and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 187988939 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Ice as a kinetic and mechanistic driver of oxalate-promoted iron oxyhydroxide dissolution. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Sebaaly%2C+Angelo+P%2E%22">Sebaaly, Angelo P.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22van+Rijn%2C+Frank%22">van Rijn, Frank</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Hanna%2C+Khalil%22">Hanna, Khalil</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Boily%2C+Jean-François%22">Boily, Jean-François</searchLink><relatesTo>1</relatesTo><i> jean-francois.boily@umu.se</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Proceedings+of+the+National+Academy+of+Sciences+of+the+United+States+of+America%22">Proceedings of the National Academy of Sciences of the United States of America</searchLink>. 9/2/2025, Vol. 122 Issue 35, p1-9. 15p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Ice%22">Ice</searchLink><br /><searchLink fieldCode="DE" term="%22Oxalates%22">Oxalates</searchLink><br /><searchLink fieldCode="DE" term="%22Geochemical+modeling%22">Geochemical modeling</searchLink><br /><searchLink fieldCode="DE" term="%22Freeze-thaw+cycles%22">Freeze-thaw cycles</searchLink><br /><searchLink fieldCode="DE" term="%22Ferric+hydroxides%22">Ferric hydroxides</searchLink><br /><searchLink fieldCode="DE" term="%22Cryosphere%22">Cryosphere</searchLink><br /><searchLink fieldCode="DE" term="%22Dissolution+%28Chemistry%29%22">Dissolution (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Liquid+iron%22">Liquid iron</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Ice often mediates unexpected reactions in the Cryosphere, acting as a fascinating geochemical reactor. Mineral-organic interactions in frozen environments, such as soils and permafrost, are crucial for explaining the flux of soluble iron during melting events, yet the mechanisms remain misunderstood. This study elucidates the unique roles of freezing in the dissolution of iron oxyhydroxide nanoparticles (α-FeOOH) by oxalate, a low molecular weight dicarboxylate, under acidic conditions. From time-resolved experiments conducted over 4 d, we demonstrate that soluble iron was released through reactions in minute volumes of liquid water trapped between ice micrograins. Freeze concentration of nanoparticles, oxalate, and protons into this liquid water drove oxalate-and proton-promoted dissolution reactions at temperatures as low as -30 °C. Remarkably, ice at -10 °C dissolved more iron than liquid water at 4 °C under high oxalate loadings, and even more than at 25 °C under low oxalate loadings. In contrast, high salinity subdued dissolution. Also, sequential freeze-thaw cycles enhanced dissolution by releasing unreacted oxalate that was previously locked in ice. By resolving the chemical controls on mineral dissolution in ice, this work can help explain how freeze-thaw events are supplying new fluxes of soluble iron to nature. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Proceedings of the National Academy of Sciences of the United States of America is the property of National Academy of Sciences and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1073/pnas.2507588122 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 15 StartPage: 1 Subjects: – SubjectFull: Ice Type: general – SubjectFull: Oxalates Type: general – SubjectFull: Geochemical modeling Type: general – SubjectFull: Freeze-thaw cycles Type: general – SubjectFull: Ferric hydroxides Type: general – SubjectFull: Cryosphere Type: general – SubjectFull: Dissolution (Chemistry) Type: general – SubjectFull: Liquid iron Type: general Titles: – TitleFull: Ice as a kinetic and mechanistic driver of oxalate-promoted iron oxyhydroxide dissolution. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Sebaaly, Angelo P. – PersonEntity: Name: NameFull: van Rijn, Frank – PersonEntity: Name: NameFull: Hanna, Khalil – PersonEntity: Name: NameFull: Boily, Jean-François IsPartOfRelationships: – BibEntity: Dates: – D: 02 M: 09 Text: 9/2/2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 00278424 Numbering: – Type: volume Value: 122 – Type: issue Value: 35 Titles: – TitleFull: Proceedings of the National Academy of Sciences of the United States of America Type: main |
| ResultId | 1 |
