Super-hydration and reduction of manganese oxide minerals at shallow terrestrial depths

Seohee Yun; Huijeong Hwang; Gilchan Hwang; Yeongkyoo Kim; Douglas Blom; Thomas Vogt; Jeffrey E. Post; Tae Yeol Jeon; Tae Joo Shin; Dong Zhou Zhang; Hiroyuki Kagi; Yongjae Lee

doi:10.1038/s41467-022-29328-y

Super-hydration and reduction of manganese oxide minerals at shallow terrestrial depths

Seohee Yun, Huijeong Hwang, Gilchan Hwang, Yeongkyoo Kim, Douglas Blom, Thomas Vogt, Jeffrey E. Post, Tae Yeol Jeon, Tae Joo Shin, Dong Zhou Zhang, Hiroyuki Kagi, Yongjae Lee

Research output: Contribution to journal › Article › peer-review

Abstract

Manganese oxides are ubiquitous marine minerals which are redox sensitive. As major components of manganese nodules found on the ocean floor, birnessite and buserite have been known to be two distinct water-containing minerals with manganese octahedral interlayer separations of ~7 Å and ~10 Å, respectively. We show here that buserite is a super-hydrated birnessite formed near 5 km depth conditions. As one of the most hydrous minerals containing ca. 34.5 wt. % water, super-hydrated birnessite, i.e., buserite, remains stable up to ca. 70 km depth conditions, where it transforms into manganite by releasing ca. 24.3 wt. % water. Subsequent transformations to hausmannite and pyrochroite occur near 100 km and 120 km depths, respectively, concomitant with a progressive reduction of Mn⁴⁺ to Mn²⁺. Our work forwards an abiotic geochemical cycle of manganese minerals in subduction and/or other aqueous terrestrial environments, with implications for water storage and cycling, and the redox capacity of the region.

Original language	English
Article number	1942
Journal	Nature communications
Volume	13
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-29328-y
Publication status	Published - 2022 Dec

Bibliographical note

Funding Information:
This work was supported by the Leader Researcher program (NRF-2018R1A3B1052042) of the Korean Ministry of Science and ICT. Ex-situ synchrotron experiments were performed at the 3D and 6D beamlines at the Pohang Light Source II (PLS II) at the Pohang Accelerator Laboratory (PAL) with support in part by MSIP, POSTECH, and UNIST Central Research facilities, and BL-18C beamline at Photon Factory (PF). In-situ synchrotron experiments were performed 13-BM-C beamline at Advanced Photon Source (APS), which is supported by GSECARS (NSF EAR-1634415 and DOE DE-FG02-94ER14466) and COMPRES (NSF EAR-1606856).

Funding Information:
This work was supported by the Leader Researcher program (NRF-2018R1A3B1052042) of the Korean Ministry of Science and ICT. Ex-situ synchrotron experiments were performed at the 3D and 6D beamlines at the Pohang Light Source II (PLS II) at the Pohang Accelerator Laboratory (PAL) with support in part by MSIP, POSTECH, and UNIST Central Research facilities, and BL-18C beamline at Photon Factory (PF). In-situ synchrotron experiments were performed 13-BM-C beamline at Advanced Photon Source (APS), which is supported by GSECARS (NSF EAR-1634415 and DOE DE-FG02-94ER14466) and COMPRES (NSF EAR-1606856).

Publisher Copyright:
© 2022, The Author(s).

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
General
Physics and Astronomy(all)

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10.1038/s41467-022-29328-y

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@article{714cc15770654bf9aa70600017565dc6,

title = "Super-hydration and reduction of manganese oxide minerals at shallow terrestrial depths",

abstract = "Manganese oxides are ubiquitous marine minerals which are redox sensitive. As major components of manganese nodules found on the ocean floor, birnessite and buserite have been known to be two distinct water-containing minerals with manganese octahedral interlayer separations of ~7 {\AA} and ~10 {\AA}, respectively. We show here that buserite is a super-hydrated birnessite formed near 5 km depth conditions. As one of the most hydrous minerals containing ca. 34.5 wt. % water, super-hydrated birnessite, i.e., buserite, remains stable up to ca. 70 km depth conditions, where it transforms into manganite by releasing ca. 24.3 wt. % water. Subsequent transformations to hausmannite and pyrochroite occur near 100 km and 120 km depths, respectively, concomitant with a progressive reduction of Mn4+ to Mn2+. Our work forwards an abiotic geochemical cycle of manganese minerals in subduction and/or other aqueous terrestrial environments, with implications for water storage and cycling, and the redox capacity of the region.",

author = "Seohee Yun and Huijeong Hwang and Gilchan Hwang and Yeongkyoo Kim and Douglas Blom and Thomas Vogt and Post, {Jeffrey E.} and Jeon, {Tae Yeol} and Shin, {Tae Joo} and Zhang, {Dong Zhou} and Hiroyuki Kagi and Yongjae Lee",

note = "Funding Information: This work was supported by the Leader Researcher program (NRF-2018R1A3B1052042) of the Korean Ministry of Science and ICT. Ex-situ synchrotron experiments were performed at the 3D and 6D beamlines at the Pohang Light Source II (PLS II) at the Pohang Accelerator Laboratory (PAL) with support in part by MSIP, POSTECH, and UNIST Central Research facilities, and BL-18C beamline at Photon Factory (PF). In-situ synchrotron experiments were performed 13-BM-C beamline at Advanced Photon Source (APS), which is supported by GSECARS (NSF EAR-1634415 and DOE DE-FG02-94ER14466) and COMPRES (NSF EAR-1606856). Funding Information: This work was supported by the Leader Researcher program (NRF-2018R1A3B1052042) of the Korean Ministry of Science and ICT. Ex-situ synchrotron experiments were performed at the 3D and 6D beamlines at the Pohang Light Source II (PLS II) at the Pohang Accelerator Laboratory (PAL) with support in part by MSIP, POSTECH, and UNIST Central Research facilities, and BL-18C beamline at Photon Factory (PF). In-situ synchrotron experiments were performed 13-BM-C beamline at Advanced Photon Source (APS), which is supported by GSECARS (NSF EAR-1634415 and DOE DE-FG02-94ER14466) and COMPRES (NSF EAR-1606856). Publisher Copyright: {\textcopyright} 2022, The Author(s).",

year = "2022",

month = dec,

doi = "10.1038/s41467-022-29328-y",

language = "English",

volume = "13",

journal = "Nature Communications",

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AU - Yun, Seohee

AU - Hwang, Huijeong

AU - Hwang, Gilchan

AU - Kim, Yeongkyoo

AU - Blom, Douglas

AU - Vogt, Thomas

AU - Post, Jeffrey E.

AU - Jeon, Tae Yeol

AU - Shin, Tae Joo

AU - Zhang, Dong Zhou

AU - Kagi, Hiroyuki

AU - Lee, Yongjae

N1 - Funding Information: This work was supported by the Leader Researcher program (NRF-2018R1A3B1052042) of the Korean Ministry of Science and ICT. Ex-situ synchrotron experiments were performed at the 3D and 6D beamlines at the Pohang Light Source II (PLS II) at the Pohang Accelerator Laboratory (PAL) with support in part by MSIP, POSTECH, and UNIST Central Research facilities, and BL-18C beamline at Photon Factory (PF). In-situ synchrotron experiments were performed 13-BM-C beamline at Advanced Photon Source (APS), which is supported by GSECARS (NSF EAR-1634415 and DOE DE-FG02-94ER14466) and COMPRES (NSF EAR-1606856). Funding Information: This work was supported by the Leader Researcher program (NRF-2018R1A3B1052042) of the Korean Ministry of Science and ICT. Ex-situ synchrotron experiments were performed at the 3D and 6D beamlines at the Pohang Light Source II (PLS II) at the Pohang Accelerator Laboratory (PAL) with support in part by MSIP, POSTECH, and UNIST Central Research facilities, and BL-18C beamline at Photon Factory (PF). In-situ synchrotron experiments were performed 13-BM-C beamline at Advanced Photon Source (APS), which is supported by GSECARS (NSF EAR-1634415 and DOE DE-FG02-94ER14466) and COMPRES (NSF EAR-1606856). Publisher Copyright: © 2022, The Author(s).

PY - 2022/12

Y1 - 2022/12

N2 - Manganese oxides are ubiquitous marine minerals which are redox sensitive. As major components of manganese nodules found on the ocean floor, birnessite and buserite have been known to be two distinct water-containing minerals with manganese octahedral interlayer separations of ~7 Å and ~10 Å, respectively. We show here that buserite is a super-hydrated birnessite formed near 5 km depth conditions. As one of the most hydrous minerals containing ca. 34.5 wt. % water, super-hydrated birnessite, i.e., buserite, remains stable up to ca. 70 km depth conditions, where it transforms into manganite by releasing ca. 24.3 wt. % water. Subsequent transformations to hausmannite and pyrochroite occur near 100 km and 120 km depths, respectively, concomitant with a progressive reduction of Mn4+ to Mn2+. Our work forwards an abiotic geochemical cycle of manganese minerals in subduction and/or other aqueous terrestrial environments, with implications for water storage and cycling, and the redox capacity of the region.

AB - Manganese oxides are ubiquitous marine minerals which are redox sensitive. As major components of manganese nodules found on the ocean floor, birnessite and buserite have been known to be two distinct water-containing minerals with manganese octahedral interlayer separations of ~7 Å and ~10 Å, respectively. We show here that buserite is a super-hydrated birnessite formed near 5 km depth conditions. As one of the most hydrous minerals containing ca. 34.5 wt. % water, super-hydrated birnessite, i.e., buserite, remains stable up to ca. 70 km depth conditions, where it transforms into manganite by releasing ca. 24.3 wt. % water. Subsequent transformations to hausmannite and pyrochroite occur near 100 km and 120 km depths, respectively, concomitant with a progressive reduction of Mn4+ to Mn2+. Our work forwards an abiotic geochemical cycle of manganese minerals in subduction and/or other aqueous terrestrial environments, with implications for water storage and cycling, and the redox capacity of the region.

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Super-hydration and reduction of manganese oxide minerals at shallow terrestrial depths

Abstract

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