Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin

<p>Manganese (Mn) is an essential micronutrient and key redox intermediate in marine systems. The role of organically complexed dissolved Mn(III) (dMn(III)-L) as an electron acceptor and donor in marine environments is still incompletely understood. Here, we use geochemical depth profiles of s...

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Main Authors: R. Klomp, O. M. Żygadłowska, M. S. M. Jetten, V. E. Oldham, N. A. G. M. van Helmond, C. P. Slomp, W. K. Lenstra
Format: Article
Language:English
Published: Copernicus Publications 2025-02-01
Series:Biogeosciences
Online Access:https://bg.copernicus.org/articles/22/751/2025/bg-22-751-2025.pdf
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author R. Klomp
R. Klomp
O. M. Żygadłowska
M. S. M. Jetten
V. E. Oldham
N. A. G. M. van Helmond
N. A. G. M. van Helmond
C. P. Slomp
C. P. Slomp
W. K. Lenstra
W. K. Lenstra
author_facet R. Klomp
R. Klomp
O. M. Żygadłowska
M. S. M. Jetten
V. E. Oldham
N. A. G. M. van Helmond
N. A. G. M. van Helmond
C. P. Slomp
C. P. Slomp
W. K. Lenstra
W. K. Lenstra
author_sort R. Klomp
collection DOAJ
description <p>Manganese (Mn) is an essential micronutrient and key redox intermediate in marine systems. The role of organically complexed dissolved Mn(III) (dMn(III)-L) as an electron acceptor and donor in marine environments is still incompletely understood. Here, we use geochemical depth profiles of solutes and solids for the sediment and overlying waters and a reactive transport model to reconstruct the seasonality in sedimentary dMn(III)-L dynamics and benthic Mn release in a eutrophic, seasonally euxinic coastal basin (Lake Grevelingen, the Netherlands). Our model results suggest that dMn(III)-L is a major component of the dissolved Mn pool throughout the year. According to the model, there are three major sources of pore water dMn(III)-L when oxygen (O<span class="inline-formula"><sub>2</sub></span>) is present in the bottom water, namely reduction of Mn oxides coupled to the oxidation of Fe(II), reduction of Mn oxides coupled to organic matter degradation, and oxidation of Mn(II) with O<span class="inline-formula"><sub>2</sub></span>. Removal of pore water dMn(III)-L is inferred to primarily take place through reduction by dissolved Fe(II). When bottom waters are euxinic in summer, model-calculated rates of sedimentary Mn cycling decrease strongly because of a lower supply of Mn oxides. The dMn(III)-L transformations in summer mostly involve reactions with Fe(II) and organic matter. Modeled benthic release of Mn mainly occurs as dMn(III)-L when bottom waters are oxic, as Mn(II) upon initial bottom-water euxinia and as both Mn(II) and dMn(III)-L when the euxinia becomes persistent. Our model findings highlight strong interactions between the sedimentary Fe and Mn cycles. Dissolved Mn(III)-L is a relatively stable and mobile Mn species, compared to Mn(II), and is therefore more easily transported laterally throughout the coastal zone and possibly also to open marine waters.</p>
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spelling doaj-art-40dc133403c64b409a0b241f6a0640092025-02-11T10:58:14ZengCopernicus PublicationsBiogeosciences1726-41701726-41892025-02-012275176510.5194/bg-22-751-2025Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basinR. Klomp0R. Klomp1O. M. Żygadłowska2M. S. M. Jetten3V. E. Oldham4N. A. G. M. van Helmond5N. A. G. M. van Helmond6C. P. Slomp7C. P. Slomp8W. K. Lenstra9W. K. Lenstra10Department of Microbiology, Radboud Institute for Biological and Environmental Sciences, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsDepartment of Earth Sciences, Utrecht University, Princetonlaan 8a, 3584 CB Utrecht, the NetherlandsDepartment of Earth Sciences, Utrecht University, Princetonlaan 8a, 3584 CB Utrecht, the NetherlandsDepartment of Microbiology, Radboud Institute for Biological and Environmental Sciences, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsGraduate School of Oceanography, Rhode Island University, 215 S Ferry Rd, Narragansett, RI 02882, USADepartment of Microbiology, Radboud Institute for Biological and Environmental Sciences, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsDepartment of Earth Sciences, Utrecht University, Princetonlaan 8a, 3584 CB Utrecht, the NetherlandsDepartment of Microbiology, Radboud Institute for Biological and Environmental Sciences, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsDepartment of Earth Sciences, Utrecht University, Princetonlaan 8a, 3584 CB Utrecht, the NetherlandsDepartment of Microbiology, Radboud Institute for Biological and Environmental Sciences, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, the NetherlandsDepartment of Earth Sciences, Utrecht University, Princetonlaan 8a, 3584 CB Utrecht, the Netherlands<p>Manganese (Mn) is an essential micronutrient and key redox intermediate in marine systems. The role of organically complexed dissolved Mn(III) (dMn(III)-L) as an electron acceptor and donor in marine environments is still incompletely understood. Here, we use geochemical depth profiles of solutes and solids for the sediment and overlying waters and a reactive transport model to reconstruct the seasonality in sedimentary dMn(III)-L dynamics and benthic Mn release in a eutrophic, seasonally euxinic coastal basin (Lake Grevelingen, the Netherlands). Our model results suggest that dMn(III)-L is a major component of the dissolved Mn pool throughout the year. According to the model, there are three major sources of pore water dMn(III)-L when oxygen (O<span class="inline-formula"><sub>2</sub></span>) is present in the bottom water, namely reduction of Mn oxides coupled to the oxidation of Fe(II), reduction of Mn oxides coupled to organic matter degradation, and oxidation of Mn(II) with O<span class="inline-formula"><sub>2</sub></span>. Removal of pore water dMn(III)-L is inferred to primarily take place through reduction by dissolved Fe(II). When bottom waters are euxinic in summer, model-calculated rates of sedimentary Mn cycling decrease strongly because of a lower supply of Mn oxides. The dMn(III)-L transformations in summer mostly involve reactions with Fe(II) and organic matter. Modeled benthic release of Mn mainly occurs as dMn(III)-L when bottom waters are oxic, as Mn(II) upon initial bottom-water euxinia and as both Mn(II) and dMn(III)-L when the euxinia becomes persistent. Our model findings highlight strong interactions between the sedimentary Fe and Mn cycles. Dissolved Mn(III)-L is a relatively stable and mobile Mn species, compared to Mn(II), and is therefore more easily transported laterally throughout the coastal zone and possibly also to open marine waters.</p>https://bg.copernicus.org/articles/22/751/2025/bg-22-751-2025.pdf
spellingShingle R. Klomp
R. Klomp
O. M. Żygadłowska
M. S. M. Jetten
V. E. Oldham
N. A. G. M. van Helmond
N. A. G. M. van Helmond
C. P. Slomp
C. P. Slomp
W. K. Lenstra
W. K. Lenstra
Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin
Biogeosciences
title Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin
title_full Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin
title_fullStr Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin
title_full_unstemmed Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin
title_short Dissolved Mn(III) is a key redox intermediate in sediments of a seasonally euxinic coastal basin
title_sort dissolved mn iii is a key redox intermediate in sediments of a seasonally euxinic coastal basin
url https://bg.copernicus.org/articles/22/751/2025/bg-22-751-2025.pdf
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