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The role of sulfate in the hydrothermal replacement of aragonite single crystals by calcite

dc.contributor.authorForjanes Pérez, Pablo Cayetano
dc.contributor.authorAstilleros García-Monge, José Manuel
dc.contributor.authorFernández Díaz, María Lourdes
dc.date.accessioned2024-06-28T16:34:08Z
dc.date.available2024-06-28T16:34:08Z
dc.date.issued2024-08-01
dc.description.abstractAragonite (CaCO3) is a stable calcium carbonate phase under high pressure conditions. However, its formation in (sub)surface environments, where calcite is the stable polymorph, is widespread. Regardless of its origin, aragonite is expected to undergo transformation into calcite under moderate pressures and temperatures. However, this transformation does not always take place, which results in the presence of abundant aragonitic relics in the geological record. Traditionally, this preservation has been explained by the presence of chemical inhibitors that prevent the conversion of aragonite to calcite. While it is widely accepted that magnesium (Mg) plays a key role in the polymorphic selection of CaCO3, the influence of other ions has also been suggested. This work evaluates the effect that different concentrations of sulfate (SO42−) in the fluid has on the progress of the aragonite-to-calcite transformation at 220 °C. Our results show that, upon reaction with deionized water or sulfate-poor solutions ([SO42−]aq < 0.1 mM), aragonite single crystals are extensively replaced by calcite aggregates (crystal size > 15 µm) through an interface coupled dissolution-precipitation reaction. The replacement starts at the aragonite crystal surfaces and advances inwards thanks to the development of an extensive network of fractures. Contrarily, when the solution bears higher concentrations of sulfate ([SO42−]aq > 0.1 mM), only a thin layer of smaller crystals of calcite (< 10 µm) form on the aragonite substrates, without any further transformation taking place. We interpret that these smaller crystals exert too little crystallization pressure and fail to promote the development of a network of fractures. In the absence of this network, the aragonite-calcite transformation cannot take place. The transformation does not occur neither when the experiments are conducted with deionized water and fragments of gypsum or anhydrite together with the aragonite grains. The results of this study shed light on the influence of dissolved sulfate in the kinetics of the fluid-driven transformation of aragonite into calcite. These results are useful to understand the preservation of aragonite in a variety of current geological settings and provide valuable insights for better understanding the diagenesis of sedimentary carbonates.
dc.description.departmentDepto. de Mineralogía y Petrología
dc.description.facultyFac. de Ciencias Geológicas
dc.description.refereedTRUE
dc.description.sponsorshipMinisterio de Ciencia, Innovación y Universidades
dc.description.sponsorshipHelmholtz Recruitment Initiative
dc.description.sponsorshipMinisterio de Universidades
dc.description.statuspub
dc.identifier.citationForjanes, Pablo, et al. «The Role of Sulfate in the Hydrothermal Replacement of Aragonite Single Crystals by Calcite». Earth and Planetary Science Letters, vol. 639, agosto de 2024, n. 118771, https://doi.org/10.1016/j.epsl.2024.118771
dc.identifier.doi10.1016/j.epsl.2024.118771
dc.identifier.essn1385-013X
dc.identifier.issn0012-821X
dc.identifier.officialurlhttps://doi.org/10.1016/j.epsl.2024.118771
dc.identifier.urihttps://hdl.handle.net/20.500.14352/105371
dc.issue.number118771
dc.journal.titleEarth and Planetary Science Letters
dc.language.isoeng
dc.publisherElsevier
dc.relation.projectIDPID2021–125467NB-I00
dc.relation.projectIDgrant number I-044–16–01
dc.relation.projectIDFPU17/01689
dc.rightsAttribution-NonCommercial 4.0 Internationalen
dc.rights.accessRightsopen access
dc.rights.urihttp://creativecommons.org/licenses/by-nc/4.0/
dc.subject.cdu549.742
dc.subject.keywordAragonite
dc.subject.keywordCalcite
dc.subject.keywordCaCO3
dc.subject.keywordSulfate
dc.subject.keywordMineral replacement reaction
dc.subject.keywordDiagenesis
dc.subject.ucmMineralogía (Geología)
dc.subject.unesco2506.11 Mineralogía
dc.titleThe role of sulfate in the hydrothermal replacement of aragonite single crystals by calcite
dc.typejournal article
dc.type.hasVersionVoR
dc.volume.number639
dspace.entity.typePublication
relation.isAuthorOfPublication9cb9825d-0758-4388-8984-145d2b594906
relation.isAuthorOfPublication04510d2c-6771-46a3-a807-f37e2932fb09
relation.isAuthorOfPublication5283531a-5de9-4e87-bcc7-1c218b2d3a89
relation.isAuthorOfPublication.latestForDiscovery9cb9825d-0758-4388-8984-145d2b594906

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