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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Bibliographic Details
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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Summary:<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>
ISSN:1726-4170
1726-4189