Ni‑rich mineral nepouite explains the exceptional green color of speleothems

Martin Vlieghe; Gaetan Rochez; Stéphane Pire-Stevenne; Jean-Yves Storme; Augustin Dekoninck; Yves VANBRABANT; Olivier Namur; Yishen Zhang; Alicia Van Ham-Meert; Jean-Pierre Donnadieu; Michel Berbigé; Jean-Luc Hasbroucq; Johan Yans

doi:10.1038/s41598-023-41977-7

Ni‑rich mineral nepouite explains the exceptional green color of speleothems

Martin Vlieghe, Gaetan Rochez, Stéphane Pire-Stevenne, Jean-Yves Storme, Augustin Dekoninck, Yves VANBRABANT, Olivier Namur, Yishen Zhang, Alicia Van Ham-Meert, Jean-Pierre Donnadieu, Michel Berbigé, Jean-Luc Hasbroucq, Johan Yans

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Résumé

Speleothems are secondary mineral structures typically found in karstic caves and usually composedof calcite or aragonite. Despite being naturally white, some might exhibit unusual colors, such asblue, black, red, yellow or green. The causes of these exceptional colorations are poorly understood,especially for green speleothems, which are barely reported. Here we describe the occurrence of thegreen Ni‑bearing serpentine nepouite in green aragonite and calcite speleothems, in the Aven duMarcou (Hérault, France). Nepouite is mainly found as flat lamellar crystals in the outer rim of greenspeleothems and crystallized alongside radially grown aragonite crystals. This supports nepouitebeginning to crystallize recently, due to a change in the chemical composition of the water. Nepouitealso exhibits extensive substitution between Ni, Mg and Zn. The various elements responsible fornepouite precipitation are thought to come from the weathering of pyrite crystals in the overlyingrocks, which is consistent with the pH conditions of the cave and the Al‑free composition of nepouite.This study explains the crystallization mechanisms and stability conditions of silicate minerals incolored caves.

langue originale	Anglais
Numéro d'article	15017
journal	Scientific Reports
Volume	13
Numéro de publication	1
Les DOIs	https://doi.org/10.1038/s41598-023-41977-7
Etat de la publication	Publié - déc. 2023

Financement

This work was funded by an Institute of Life, Earth and Environment doctoral grant and a UNamur F.S.R. Grant both awarded to M.V. We thank RBINS and KULeuven for providing access to Raman and EPMA facilities respectively, as well as Jean-Claude Gayet and Anthony Alliès (Association Mont Marcou) for allowing sampling in the Aven du Marcou. We also thank University of Montpellier, and particularly Michel Lopez, for the realization of X-Ray Fluorescence analyses. We thank David Alford who agreed proof-reading the document to improve English language expression. We also thank Scientific Reports Editor Hiroaki Ohfuji for his help and support. This work was funded by an Institute of Life, Earth and Environment doctoral grant and a UNamur F.S.R. Grant both awarded to M.V. We thank RBINS and KULeuven for providing access to Raman and EPMA facilities respectively, as well as Jean-Claude Gayet and Anthony Alliès (Association Mont Marcou) for allowing sampling in the Aven du Marcou. We also thank University of Montpellier, and particularly Michel Lopez, for the realization of X-Ray Fluorescence analyses. We thank David Alford who agreed proof-reading the document to improve English language expression. We also thank Scientific Reports Editor Hiroaki Ohfuji for his help and support.

Bailleurs de fonds	Numéro du bailleur de fonds
KU Leuven
UNamur F.S.R.
Université de Montpellier

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10.1038/s41598-023-41977-7

Vlieghe_et_al-2023-Scientific_ReportsVersion finale publiée, 3,16 MBLicense: CC BY

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title = "Ni‑rich mineral nepouite explains the exceptional green color of speleothems",

abstract = "Speleothems are secondary mineral structures typically found in karstic caves and usually composedof calcite or aragonite. Despite being naturally white, some might exhibit unusual colors, such asblue, black, red, yellow or green. The causes of these exceptional colorations are poorly understood,especially for green speleothems, which are barely reported. Here we describe the occurrence of thegreen Ni‑bearing serpentine nepouite in green aragonite and calcite speleothems, in the Aven duMarcou (H{\'e}rault, France). Nepouite is mainly found as flat lamellar crystals in the outer rim of greenspeleothems and crystallized alongside radially grown aragonite crystals. This supports nepouitebeginning to crystallize recently, due to a change in the chemical composition of the water. Nepouitealso exhibits extensive substitution between Ni, Mg and Zn. The various elements responsible fornepouite precipitation are thought to come from the weathering of pyrite crystals in the overlyingrocks, which is consistent with the pH conditions of the cave and the Al‑free composition of nepouite.This study explains the crystallization mechanisms and stability conditions of silicate minerals incolored caves.",

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AU - Vlieghe, Martin

AU - Rochez, Gaetan

AU - Pire-Stevenne, Stéphane

AU - Storme, Jean-Yves

AU - Dekoninck, Augustin

AU - VANBRABANT, Yves

AU - Namur, Olivier

AU - Zhang, Yishen

AU - Van Ham-Meert, Alicia

AU - Donnadieu, Jean-Pierre

AU - Berbigé, Michel

AU - Hasbroucq, Jean-Luc

AU - Yans, Johan

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Ni‑rich mineral nepouite explains the exceptional green color of speleothems

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