Fossil shark teeth record a microscale pathway for ferromanganese oxide nucleation and Li–Ni enrichment in deep-sea biogenic substrates
Abstract
Marine ferromanganese crusts and nodules are major reservoirs of critical metals considered essential for a low-carbon economy, yet the mechanisms governing their initial formation remain poorly documented. Here, we integrate Micro-CT, SEM-EDS, EPMA, LA-ICP-MS, TEM, Raman spectroscopy, and XANES to reconstruct the initial stages of Fe–Mn oxide (FMO) formation in fossil shark teeth from the Rio Grande Rise (southwestern Atlantic Ocean). We document a four-stage FMO mineralization sequence preserved within dentin tubules: (1) bioapatite alteration and organic matter degradation, potentially associated with endolithic bioerosion; (2) precipitation of nanoscale goethite onto dentin tubule walls, associated with phosphate release and pH buffering; (3) Mn oxidation and precipitation of lithiophorite, a layered Mn(III–IV) oxide enriched in Li (~ 650 µg g –1 ) and Ni (~ 37,000 µg g –1 ) overgrowing goethite, with lithiophorite-bearing domains characterized by a high average Mn oxidation state of ~ 3.6; and (4) selective redistribution of REY into altered bioapatite, while Ce remains preferentially associated with FMO, followed by late clay-rich infilling. These results highlight the importance of biogenic substrates and confined dentin microenvironments in early FMO nucleation and phase-specific metal redistribution and retention, providing a microscale model for metal partitioning during the initial stages of deep-sea FMO mineralization.
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BibTeX
@article{felipe2026fossil,
title = {{Fossil shark teeth record a microscale pathway for ferromanganese oxide nucleation and Li–Ni enrichment in deep-sea biogenic substrates}},
author = {Thales C. Felipe and Alexandre Henrique Ferraz and Simone Bernardini and Anthony Chappaz and Bruno Becker-Kerber and Douglas Galante and Luigi Jovane and Carina Ulsen and Omid H. Ardakani and Janina Czas and Victoria Duarte Moreno and Véronique Caradec and Christian Millo},
journal = {Scientific Reports},
year = {2026},
month = oct,
doi = {10.1038/s41598-026-75019-9},
url = {https://www.nature.com/articles/s41598-026-75019-9},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Fossil shark teeth record a microscale pathway for ferromanganese oxide nucleation and Li–Ni enrichment in deep-sea biogenic substrates
AU - Thales C. Felipe
AU - Alexandre Henrique Ferraz
AU - Simone Bernardini
AU - Anthony Chappaz
AU - Bruno Becker-Kerber
AU - Douglas Galante
AU - Luigi Jovane
AU - Carina Ulsen
AU - Omid H. Ardakani
AU - Janina Czas
AU - Victoria Duarte Moreno
AU - Véronique Caradec
AU - Christian Millo
PY - 2026
DA - 2026/10/22
JO - Scientific Reports
DO - 10.1038/s41598-026-75019-9
UR - https://www.nature.com/articles/s41598-026-75019-9
AB - Marine ferromanganese crusts and nodules are major reservoirs of critical metals considered essential for a low-carbon economy, yet the mechanisms governing their initial formation remain poorly documented. Here, we integrate Micro-CT, SEM-EDS, EPMA, LA-ICP-MS, TEM, Raman spectroscopy, and XANES to reconstruct the initial stages of Fe–Mn oxide (FMO) formation in fossil shark teeth from the Rio Grande Rise (southwestern Atlantic Ocean). We document a four-stage FMO mineralization sequence preserved within dentin tubules: (1) bioapatite alteration and organic matter degradation, potentially associated with endolithic bioerosion; (2) precipitation of nanoscale goethite onto dentin tubule walls, associated with phosphate release and pH buffering; (3) Mn oxidation and precipitation of lithiophorite, a layered Mn(III–IV) oxide enriched in Li (~ 650 µg g –1 ) and Ni (~ 37,000 µg g –1 ) overgrowing goethite, with lithiophorite-bearing domains characterized by a high average Mn oxidation state of ~ 3.6; and (4) selective redistribution of REY into altered bioapatite, while Ce remains preferentially associated with FMO, followed by late clay-rich infilling. These results highlight the importance of biogenic substrates and confined dentin microenvironments in early FMO nucleation and phase-specific metal redistribution and retention, providing a microscale model for metal partitioning during the initial stages of deep-sea FMO mineralization.
SN - 2045-2322
ER -