• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.303-312
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• 2023

The determination of the oxidation states of metal elements in manganese nodules sheds light on the understanding of the formation mechanism of nodules, providing insights into the paleo-environmental conditions such as the redox potential of the aqueous system. This study aims to reveal the oxidation states and chemical bonding of manganese in the natural polymetallic nodules, utilizing conventional X-ray photoelectron spectroscopy (XPS). Specifically, shallow manganese nodules from the Siberian Arctic Sea, effectively recording mineralogical variations, were used in this study. Detailed analysis of XPS Mn 2p spectra showed changes in the manganese oxidation state from the center to the outer parts of the nodules. The central part of the nodules showed a higher Mn⁴⁺ content, approximately 67.9%, while the outermost part showed about 63% of Mn⁴⁺ due to an increase in the Mn³⁺+Mn²⁺. The decrease in the Mn oxidation state with the growth is consistent with the previously reported mineralogical variations from todorokite to birnessite with growth. Additionally, the O 1s spectra presented a predominance of Mn-O-H bonds in the outer layers compared to the center, suggesting hydration by water in the layered manganates of outer layers. The results of this study demonstrate that XPS can be directly applied to understand changes in paleo-environmental conditions such as the redox states during the growth of manganese nodules. Finally, future studies using high-resolution synchrotron-based XPS experiments could achieve details in oxidation states of manganese and trace metal elements.