Sedimentary Sulphur:Iron Ratio Indicates Vivianite Occurrence: A Study from Two Contrasting Freshwater Systems

Rothe, Matthias; Kleeberg, Andreas; Grüneberg, Björn; Friese, Kurt; Pérez-Mayo, Manuel; Hupfer, Michael

doi:10.1371/journal.pone.0143737

Cited by 62 publications

(57 citation statements)

References 43 publications

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“…S5). The S:Fe-reactive ratios are also above 1.5, which is the upper threshold for vivianite occurrence according to Rothe et al (2015). As bottom waters were likely permanently sulfidic, vivianite may have formed in micro-environments in the sediments where S was in short supply relative to Fe, as suggested previously for the Fårö Deep sediments (Jilbert and Slomp, 2013a).…”

Section: The Importance Of the Fe Shelf-to-basin Shuttle For Vivianitsupporting

confidence: 62%

“…S6). This ratio between total S and reactive Fe in the sediments (as all Fe except silicates; S:Fe-reactive) can be used as a proxy for the occurrence of vivianite, whereby ratios below 1.5 are assumed to indicate that not all reactive Fe is captured as FeS x and vivianite formation is favoured (Rothe et al, 2015).…”

Section: The Importance Of the Fe Shelf-to-basin Shuttle For Vivianitmentioning

confidence: 99%

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Vivianite is a key sink for phosphorus in sediments of the Landsort Deep, an intermittently anoxic deep basin in the Baltic Sea

2016

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a b s t r a c t Phosphorus (P) is an essential nutrient for marine organisms. Its burial in hypoxic and anoxic marine basins is still incompletely understood. Recent studies suggest that P can be sequestered in sediments of such basins as reduced iron (Fe)-P but the exact phase and the underlying mechanisms that lead to its formation are unknown. In this study, we investigated sediments from the deepest basin in the Baltic Sea, the Landsort Deep (site M0063), that were retrieved during the Integrated Ocean Drilling Project (IODP) Baltic Sea Paleoenvironment Expedition 347. The record comprises the whole brackish/marine Littorina Sea stage including past intervals of extensive hypoxia in the Baltic Sea that occurred during the Holocene Thermal Maximum (HTM HI ) and the Medieval Climate Anomaly (MCA1 HI and MCA2 HI ). Various redox proxies (e.g. the presence of laminations and high Mo contents) suggest almost permanent bottom water hypoxia during the Littorina Sea stage in the Landsort Deep. The bottom waters were likely even seasonally anoxic or sulfidic during the MCA1 HI and MCA2 HI , and permanently sulfidic during the HTM HI . With the use of micro-analysis of sieved minerals (SEM-EDS, XRD and synchrotron-based XAS), we show that Mn-and Mgrich vivianite crystals are present at various depths in the Littorina Sea sediments. We also have indications for vivianite in the MCA1 HI , MCA2 HI and HTM HI deposits. The formation of vivianite thus likely explains the high Febound P fraction throughout the whole Littorina Sea stage. Shuttling of Fe and Mn from the shelves into the basin and high inputs of P in settling organic matter are likely key drivers for vivianite formation. Our study shows that vivianite can likely form in near-surface sediments under a broad range of bottom water redox conditions, varying from hypoxic and anoxic to sulfidic.

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Section: The Importance Of the Fe Shelf-to-basin Shuttle For Vivianitsupporting

confidence: 62%

Section: The Importance Of the Fe Shelf-to-basin Shuttle For Vivianitmentioning

confidence: 99%

Vivianite is a key sink for phosphorus in sediments of the Landsort Deep, an intermittently anoxic deep basin in the Baltic Sea

2016

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“…3b−e, g). This distinct morphology strongly resembles vivianite crystals identified from the Baltic Sea (Dijkstra et al, 2016;Egger et al, 2015a) and lacustrine sediments (Rothe et al, 2014(Rothe et al, , 2015.…”

Section: Morphology and Chemical Composition Of Mineral Aggregatessupporting

confidence: 71%

Vivianite formation in methane-rich deep-sea sediments from the South China Sea

Liu¹,

Wang²,

Izon³

et al. 2018

Preprint

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Phosphorus is often invoked as the ultimate limiting nutrient, modulating primary productivity on geological timescales. Consequently, along with nitrogen, phosphorus bioavailability exerts a fundamental control on organic carbon production, linking all the biogeochemical cycles across the Earth system. Unlike nitrogen that can be microbially fixed from 15 an essentially infinite atmospheric reservoir, phosphorus availability is dictated by the interplay between its sources and sinks.While authigenic apatite formation has received considerable attention as the dominant sedimentary phosphorus sink, the quantitative importance of reduced iron-phosphate minerals, such as vivianite, has only recently been acknowledged and their importance remains under-explored. Combining microscopic and spectroscopic analyses of handpicked mineral aggregates with sediment geochemical profiles we characterize the distribution and mineralogy of iron-phosphate minerals present in 20 methane-rich sediments recovered from the northern South China Sea. Here, we demonstrate that vivianite authigenesis is pervasive in the iron oxide-rich sediments below the sulfate-methane transition zone (SMTZ). We hypothesize that the downward migration of the SMTZ concentrated vivianite formation below the current SMTZ. Our observations support recent findings from non-steady state post-glacial coastal sedimentary successions, suggesting that iron reduction below the SMTZ, probably driven by iron-mediated anaerobic oxidation of methane (Fe-AOM), is coupled to phosphorus cycling on a much 25 greater spatial scale than previously assumed. Calculations reveal that vivianite acts as an important burial phase for both iron and phosphorus below the SMTZ, sequestering approximately half of the total reactive iron pool. By extension, sedimentary vivianite formation could serve as a mineralogical marker of Fe-AOM, signalling a low-sulfate availability against methanogenic and ferruginous backdrop. Given that similar conditions were likely present throughout vast swaths of Earth history, it is possible that Fe-AOM may have modulated phosphorus and methane availability on the early Earth. 30Biogeosciences Discuss., https://doi.

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“…The formation and burial of authigenic vivianite depends on the balance between dissolved HS − , iron (Fe 2+ ), and PO 4 in porewaters (Rothe et al 2015). In most marine sediments, Fe is mainly captured in Fe-sulfides and no Fe 2+ is left to precipitate with PO 4 , thereby preventing the precipitation of vivianite.…”

Section: Communicated By David Reide Corbettmentioning

confidence: 99%

Holocene Refreshening and Reoxygenation of a Bothnian Sea Estuary Led to Enhanced Phosphorus Burial

Dijkstra

Krupinski

Yamane

et al. 2017

Estuaries and Coasts

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Salinity variations in restricted basins like the Baltic Sea can alter their vulnerability to hypoxia (i.e., bottom water oxygen concentrations <2 mg/l) and can affect the burial of phosphorus (P), a key nutrient for marine organisms. We combine porewater and solid-phase geochemistry, microanalysis of sieved sediments (including XRD and synchrotron-based XAS), and foraminiferal δ 18 O and δ 13 C analyses to reconstruct the bottom water salinity, redox conditions, and P burial in the Ångermanälven estuary, Bothnian Sea. Our sediment records were retrieved during the Integrated Ocean Drilling Program (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013. We demonstrate that bottom waters in the Ångermanälven estuary became anoxic upon the intrusion of seawater in the early Holocene, like in the central Bothnian Sea. The subsequent refreshening and reoxygenation, which was caused by gradual isostatic uplift, promoted P burial in the sediment in the form of Mn-rich vivianite. Vivianite authigenesis in the surface sediments of the more isolated part of the estuary ultimately ceased, likely due to continued refreshening and an associated decline in productivity and P supply to the sediment. The observed shifts in environmental conditions also created conditions for postdepositional formation of authigenic vivianite, and possibly apatite formation, at ∼8 m composite depth. These salinityrelated changes in redox conditions and P burial are highly relevant in light of current climate change. The results specifically highlight that increased freshwater input linked to global warming may enhance coastal P retention, thereby contributing to oligotrophication in both coastal and adjacent open waters.

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Sedimentary Sulphur:Iron Ratio Indicates Vivianite Occurrence: A Study from Two Contrasting Freshwater Systems

Cited by 62 publications

References 43 publications

Vivianite is a key sink for phosphorus in sediments of the Landsort Deep, an intermittently anoxic deep basin in the Baltic Sea

Vivianite is a key sink for phosphorus in sediments of the Landsort Deep, an intermittently anoxic deep basin in the Baltic Sea

Vivianite formation in methane-rich deep-sea sediments from the South China Sea

Holocene Refreshening and Reoxygenation of a Bothnian Sea Estuary Led to Enhanced Phosphorus Burial

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