Distribution and evolution of manganese minerals in polymetallic nodules from the Clarion-Clipperton Fracture Zone: implications for nickel and copper enrichment
Abstract
Mn oxides in polymetallic nodules act as pivotal reservoirs for Ni and Cu, governing the biogeochemical cycling of these metals in marine environments. However, accurate identification of Mn-oxide phases—such as buserite, asbolane, and todorokite—remains challenging due to their similar X-ray diffraction characteristics. By applying an integrated mineralogical approach, this study elucidates the distribution and mineralogical controls of Ni and Cu in two diagenetic nodules from the Clarion-Clipperton Fracture Zone. Our results demonstrate a distinct mineralogical zonation: todorokite is predominantly concentrated in the inner layers (constituting up to ∼ 68% of the Mn-oxide assemblage), while the outer layers are dominated by 10 Å vernadite (buserite) and asbolane. XANES analysis reveals a significantly higher proportion of Mn(III) in the inner layers (15–25%) compared to the outer layers (8–10%). This Mn(III) enrichment, which we interpret as resulting from early nodule growth under high-productivity-driven suboxic conditions, likely promotes the transformation of 10 Å vernadite into todorokite. This mineralogical transition induces to a 40–50% decrease in Ni content in the inner layer, consistent with the lower compatibility of Ni in the todorokite structure. In contrast, Cu2+, as a Jahn–Teller active element, appears to be compatible with the todorokite structure and exhibits similar contents in both todorokite and asbolane. As nodule growth proceeds into more oxic environments, the Increased Stability of Mn(IV), most likely inhibited tectomanganate formation and may have favored the phyllomanganate stability. Furthermore, the precipitation metal (hydr)oxides in phyllomanganate interlayers could have led to the asbolane formation. Collectively, our findings underscore that fine-scale mineralogical characterization is indispensable for deciphering the distinct biogeochemical behaviors of Ni and Cu governed by specific Mn oxides.
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BibTeX
@article{fan2026distribution,
title = {{Distribution and evolution of manganese minerals in polymetallic nodules from the Clarion-Clipperton Fracture Zone: implications for nickel and copper enrichment}},
author = {Zedong Fan and Xiaohu Li and Yanhui Dong and Bruno Lanson and Zhongkuan Wu and Weilin Ma and Zhenggang Li and Junming Zhou and Yi Ding and Hao Wang and Zhimin Zhu and Jie Li and Xingwei Meng and Huaiming Li and Fengyou Chu},
journal = {Geochimica et Cosmochimica Acta},
year = {2026},
month = oct,
doi = {10.1016/j.gca.2026.04.016},
url = {https://insu.hal.science/insu-05795857v1},
note = {CC BY-NC-SA 4.0},
}
RIS
TY - JOUR
TI - Distribution and evolution of manganese minerals in polymetallic nodules from the Clarion-Clipperton Fracture Zone: implications for nickel and copper enrichment
AU - Zedong Fan
AU - Xiaohu Li
AU - Yanhui Dong
AU - Bruno Lanson
AU - Zhongkuan Wu
AU - Weilin Ma
AU - Zhenggang Li
AU - Junming Zhou
AU - Yi Ding
AU - Hao Wang
AU - Zhimin Zhu
AU - Jie Li
AU - Xingwei Meng
AU - Huaiming Li
AU - Fengyou Chu
PY - 2026
DA - 2026/10/15
JO - Geochimica et Cosmochimica Acta
DO - 10.1016/j.gca.2026.04.016
UR - https://insu.hal.science/insu-05795857v1
AB - Mn oxides in polymetallic nodules act as pivotal reservoirs for Ni and Cu, governing the biogeochemical cycling of these metals in marine environments. However, accurate identification of Mn-oxide phases—such as buserite, asbolane, and todorokite—remains challenging due to their similar X-ray diffraction characteristics. By applying an integrated mineralogical approach, this study elucidates the distribution and mineralogical controls of Ni and Cu in two diagenetic nodules from the Clarion-Clipperton Fracture Zone. Our results demonstrate a distinct mineralogical zonation: todorokite is predominantly concentrated in the inner layers (constituting up to ∼ 68% of the Mn-oxide assemblage), while the outer layers are dominated by 10 Å vernadite (buserite) and asbolane. XANES analysis reveals a significantly higher proportion of Mn(III) in the inner layers (15–25%) compared to the outer layers (8–10%). This Mn(III) enrichment, which we interpret as resulting from early nodule growth under high-productivity-driven suboxic conditions, likely promotes the transformation of 10 Å vernadite into todorokite. This mineralogical transition induces to a 40–50% decrease in Ni content in the inner layer, consistent with the lower compatibility of Ni in the todorokite structure. In contrast, Cu2+, as a Jahn–Teller active element, appears to be compatible with the todorokite structure and exhibits similar contents in both todorokite and asbolane. As nodule growth proceeds into more oxic environments, the Increased Stability of Mn(IV), most likely inhibited tectomanganate formation and may have favored the phyllomanganate stability. Furthermore, the precipitation metal (hydr)oxides in phyllomanganate interlayers could have led to the asbolane formation. Collectively, our findings underscore that fine-scale mineralogical characterization is indispensable for deciphering the distinct biogeochemical behaviors of Ni and Cu governed by specific Mn oxides.
SN - 0016-7037
SN - 1872-9533
ER -