Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects

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Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects. / Eichinger, Stefanie; Boch, Ronny; Baldermann, Andre et al.
in: Chemical geology, Jahrgang 2023, Nr. ??? Stand: 16. Oktober 2023, 121768, 09.10.2023.

Publikationen: Beitrag in FachzeitschriftArtikelForschung(peer-reviewed)

Harvard

Eichinger, S, Boch, R, Baldermann, A, Goetschl, K, Wenighofer, R, Hoffmann, R, Stamm, F, Hippler, D, Grengg, C, Immenhauser, A & Dietzel, M 2023, 'Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects', Chemical geology, Jg. 2023, Nr. ??? Stand: 16. Oktober 2023, 121768. https://doi.org/10.1016/j.chemgeo.2023.121768

APA

Eichinger, S., Boch, R., Baldermann, A., Goetschl, K., Wenighofer, R., Hoffmann, R., Stamm, F., Hippler, D., Grengg, C., Immenhauser, A., & Dietzel, M. (2023). Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects. Chemical geology, 2023(??? Stand: 16. Oktober 2023), Artikel 121768. Vorzeitige Online-Publikation. https://doi.org/10.1016/j.chemgeo.2023.121768

Vancouver

Eichinger S, Boch R, Baldermann A, Goetschl K, Wenighofer R, Hoffmann R et al. Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects. Chemical geology. 2023 Okt 9;2023(??? Stand: 16. Oktober 2023):121768. Epub 2023 Okt 9. doi: 10.1016/j.chemgeo.2023.121768

Author

Eichinger, Stefanie ; Boch, Ronny ; Baldermann, Andre et al. / Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects. in: Chemical geology. 2023 ; Jahrgang 2023, Nr. ??? Stand: 16. Oktober 2023.

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@article{478f40800d2c47999b9086161c951c3b,
title = "Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects",
abstract = "Calcite-aragonite alternations are documented in sedimentary deposits worldwide, but their formation is still poorly understood and individual CaCO3 precipitation pathways are rarely confirmed experimentally. Therefore, (sub)recent CaCO3 sinter formation in a historic subsurface adit at Erzberg (Austria) was used as a natural laboratory to monitor and assess the calcite-to-aragonite evolution pathway and intergrowth mechanism in terms of solid-liquid-atmosphere dynamics and their relevance for solid-liquid interface reactions and nucleation effects. Our results indicate an initial homogeneous nucleation of low-Mg calcite (LMC: ~3 ± 1 mol% MgCO3), induced by CO2 degassing from the percolating geogenic fluid, which is originated from seepage of local meteoric water and incongruent dissolution of Mg-Ca-Fe-bearing minerals from the host rock. Progressive LMC growth leads to an increase in the aqueous molar ratio of Mg/Ca, causing a Mg/Ca zonation pattern with transitions to high-Mg calcite (HMC: up to 7 mol% MgCO3). At a critical Mg concentration, the available Mg calcite crystal surfaces are acting as a nucleation site for heterogenous aragonite formation. In this way, fast growing acicular aragonite crystals are initiated, which impede further calcite growth. The calcite-to-aragonite transition is thus controlled by the reaction kinetics and mechanisms of Mg-calcite formation and the chemical evolution of the precipitating solution at the nano- to micro-spatial scale, creating Mg-enriched HMC surface sites for aragonite to be nucleated and preferentially grown. In the present case, the dynamics of the formation of calcite-aragonite sequences are triggered by distinct local environmental changes, in particular seasonal variations in seepage fluid flow behavior and progress in CO2 degassing. These considerations are relevant for a better understanding of proxy signal development and preservation in calcareous sedimentary sequences forming under highly dynamic environmental conditions.",
author = "Stefanie Eichinger and Ronny Boch and Andre Baldermann and Katja Goetschl and Robert Wenighofer and Rene Hoffmann and Franziska Stamm and Dorothee Hippler and Cyrill Grengg and Adrian Immenhauser and Martin Dietzel",
year = "2023",
month = oct,
day = "9",
doi = "10.1016/j.chemgeo.2023.121768",
language = "English",
volume = "2023",
journal = "Chemical geology",
issn = "0009-2541",
publisher = "Elsevier",
number = "??? Stand: 16. Oktober 2023",

}

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TY - JOUR

T1 - Unravelling calcite-to-aragonite evolution from a subsurface fluid - Formation pathway, interfacial reactions and nucleation effects

AU - Eichinger, Stefanie

AU - Boch, Ronny

AU - Baldermann, Andre

AU - Goetschl, Katja

AU - Wenighofer, Robert

AU - Hoffmann, Rene

AU - Stamm, Franziska

AU - Hippler, Dorothee

AU - Grengg, Cyrill

AU - Immenhauser, Adrian

AU - Dietzel, Martin

PY - 2023/10/9

Y1 - 2023/10/9

N2 - Calcite-aragonite alternations are documented in sedimentary deposits worldwide, but their formation is still poorly understood and individual CaCO3 precipitation pathways are rarely confirmed experimentally. Therefore, (sub)recent CaCO3 sinter formation in a historic subsurface adit at Erzberg (Austria) was used as a natural laboratory to monitor and assess the calcite-to-aragonite evolution pathway and intergrowth mechanism in terms of solid-liquid-atmosphere dynamics and their relevance for solid-liquid interface reactions and nucleation effects. Our results indicate an initial homogeneous nucleation of low-Mg calcite (LMC: ~3 ± 1 mol% MgCO3), induced by CO2 degassing from the percolating geogenic fluid, which is originated from seepage of local meteoric water and incongruent dissolution of Mg-Ca-Fe-bearing minerals from the host rock. Progressive LMC growth leads to an increase in the aqueous molar ratio of Mg/Ca, causing a Mg/Ca zonation pattern with transitions to high-Mg calcite (HMC: up to 7 mol% MgCO3). At a critical Mg concentration, the available Mg calcite crystal surfaces are acting as a nucleation site for heterogenous aragonite formation. In this way, fast growing acicular aragonite crystals are initiated, which impede further calcite growth. The calcite-to-aragonite transition is thus controlled by the reaction kinetics and mechanisms of Mg-calcite formation and the chemical evolution of the precipitating solution at the nano- to micro-spatial scale, creating Mg-enriched HMC surface sites for aragonite to be nucleated and preferentially grown. In the present case, the dynamics of the formation of calcite-aragonite sequences are triggered by distinct local environmental changes, in particular seasonal variations in seepage fluid flow behavior and progress in CO2 degassing. These considerations are relevant for a better understanding of proxy signal development and preservation in calcareous sedimentary sequences forming under highly dynamic environmental conditions.

AB - Calcite-aragonite alternations are documented in sedimentary deposits worldwide, but their formation is still poorly understood and individual CaCO3 precipitation pathways are rarely confirmed experimentally. Therefore, (sub)recent CaCO3 sinter formation in a historic subsurface adit at Erzberg (Austria) was used as a natural laboratory to monitor and assess the calcite-to-aragonite evolution pathway and intergrowth mechanism in terms of solid-liquid-atmosphere dynamics and their relevance for solid-liquid interface reactions and nucleation effects. Our results indicate an initial homogeneous nucleation of low-Mg calcite (LMC: ~3 ± 1 mol% MgCO3), induced by CO2 degassing from the percolating geogenic fluid, which is originated from seepage of local meteoric water and incongruent dissolution of Mg-Ca-Fe-bearing minerals from the host rock. Progressive LMC growth leads to an increase in the aqueous molar ratio of Mg/Ca, causing a Mg/Ca zonation pattern with transitions to high-Mg calcite (HMC: up to 7 mol% MgCO3). At a critical Mg concentration, the available Mg calcite crystal surfaces are acting as a nucleation site for heterogenous aragonite formation. In this way, fast growing acicular aragonite crystals are initiated, which impede further calcite growth. The calcite-to-aragonite transition is thus controlled by the reaction kinetics and mechanisms of Mg-calcite formation and the chemical evolution of the precipitating solution at the nano- to micro-spatial scale, creating Mg-enriched HMC surface sites for aragonite to be nucleated and preferentially grown. In the present case, the dynamics of the formation of calcite-aragonite sequences are triggered by distinct local environmental changes, in particular seasonal variations in seepage fluid flow behavior and progress in CO2 degassing. These considerations are relevant for a better understanding of proxy signal development and preservation in calcareous sedimentary sequences forming under highly dynamic environmental conditions.

U2 - 10.1016/j.chemgeo.2023.121768

DO - 10.1016/j.chemgeo.2023.121768

M3 - Article

VL - 2023

JO - Chemical geology

JF - Chemical geology

SN - 0009-2541

IS - ??? Stand: 16. Oktober 2023

M1 - 121768

ER -