| 1. |
- Hermans, Martijn, et al.
(författare)
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Coupled dynamics of iron, manganese, and phosphorus in brackish coastal sediments populated by cable bacteria
- 2021
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Ingår i: Limnology and Oceanography. - : Wiley. - 1939-5590 .- 0024-3590. ; 66:7, s. 2611-2631
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Tidskriftsartikel (refereegranskat)abstract
- Coastal waters worldwide suffer from increased eutrophication and seasonal bottom water hypoxia. Here, we assess the dynamics of iron (Fe), manganese (Mn), and phosphorus (P) in sediments of the eutrophic, brackish Gulf of Finland populated by cable bacteria. At sites where bottom waters are oxic in spring, surface enrichments of Fe and Mn oxides and high abundances of cable bacteria were observed in sediments upon sampling in early summer. At one site, Fe and P were enriched in a thin layer (~ 3 mm) just below the sediment–water interface. X-ray absorption near edge structure and micro X-ray fluorescence analyses indicate that two-thirds of the P in this layer was associated with poorly crystalline Fe oxides, with an additional contribution of Mn(II) phosphates. The Fe enriched layer was directly overlain by a Mn oxide-rich surface layer (~ 2 mm). The Fe oxide layer was likely of diagenetic origin, formed through dissolution of Fe monosulfides and carbonates, potentially induced by cable bacteria in the preceding months when bottom waters were oxic. Most of the Mn oxides were likely deposited from the water column as part of a cycle of repeated deposition and remobilization. Further research is required to confirm whether cable bacteria activity in spring indeed promotes the formation of distinct layers enriched in Fe, Mn, and P minerals in Gulf of Finland sediments. The temporal variations in biogeochemical cycling in this seasonally hypoxic coastal system, potentially controlled by cable bacteria activity, have little impact on permanent sedimentary Fe, Mn, and P burial.
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| 2. |
- Hermans, Martijn, et al.
(författare)
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Impact of natural re-oxygenation on the sediment dynamics of manganese, iron and phosphorus in a euxinic Baltic Sea basin
- 2019
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 246, s. 174-196
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Tidskriftsartikel (refereegranskat)abstract
- The Baltic Sea is characterized by the largest area of hypoxic (oxygen (O2) < 2 mg L−1) bottom waters in the world’s ocean induced by human activities. Natural ventilation of these O2-depleted waters largely depends on episodic Major Baltic Inflows from the adjacent North Sea. In 2014 and 2015, two such inflows led to a strong rise in O2 and decline in phosphate (HPO42−) in waters below 125 m depth in the Eastern Gotland Basin. This provided the opportunity to assess the impact of such re-oxygenation events on the cycles of manganese (Mn), iron (Fe) and phosphorus (P) in the sediment for the first time. We demonstrate that the re-oxygenation induced the activity of sulphur (S)-oxidising bacteria, known as Beggiatoaceae in the surface sediment where a thin oxic and suboxic layer developed. At the two deepest sites, strong enrichments of total Mn and to a lesser extent Fe oxides and P were observed in this surface layer. A combination of sequential sediment extractions and synchrotron-based X-ray spectroscopy revealed evidence for the abundant presence of P-bearing rhodochrosite and Mn(II) phosphates. In contrast to what is typically assumed, the formation of Fe oxides in the surface sediment was limited. We attribute this lack of Fe oxide formation to the high flux of reductants, such as sulphide, from deeper sediments which allows Fe(II) in the form of FeS to be preserved and restricts the penetration of O2 into the sediment. We estimate that enhanced P sequestration in surface sediments accounts for only ∼5% of water column HPO42− removal in the Eastern Gotland Basin linked to the recent inflows. The remaining HPO42− was transported to adjacent areas in the Baltic Sea. Our results highlight that the benthic O2 demand arising from the accumulation of organic-rich sediments over several decades, the legacy of hypoxia, has major implications for the biogeochemical response of euxinic basins to re-oxygenation. In particular, P sequestration in the sediment in association with Fe oxides is limited. This implies that artificial ventilation projects that aim at removing water column HPO42− and thereby improving water quality in the Baltic Sea will likely not have the desired effect.
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| 3. |
- Jilbert, Tom, et al.
(författare)
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Iron-Phosphorus Feedbacks Drive Multidecadal Oscillations in Baltic Sea Hypoxia
- 2021
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Ingår i: Geophysical Research Letters. - : American Geophysical Union (AGU). - 0094-8276 .- 1944-8007. ; 48:24
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Tidskriftsartikel (refereegranskat)abstract
- Hypoxia has occurred intermittently in the Baltic Sea since the establishment of brackish-water conditions at ∼8,000 years B.P., principally as recurrent hypoxic events during the Holocene Thermal Maximum (HTM) and the Medieval Climate Anomaly (MCA). Sedimentary phosphorus release has been implicated as a key driver of these events, but previous paleoenvironmental reconstructions have lacked the sampling resolution to investigate feedbacks in past iron-phosphorus cycling on short timescales. Here we employ Laser Ablation (LA)-ICP-MS scanning of sediment cores to generate ultra-high resolution geochemical records of past hypoxic events. We show that in-phase multidecadal oscillations in hypoxia intensity and iron-phosphorus cycling occurred throughout these events. Using a box model, we demonstrate that such oscillations were likely driven by instabilities in the dynamics of iron-phosphorus cycling under preindustrial phosphorus loads, and modulated by external climate forcing. Oscillatory behavior could complicate the recovery from hypoxia during future trajectories of external loading reductions.
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| 4. |
- Paul, K. Mareike, et al.
(författare)
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Revisiting the applicability and constraints of molybdenum- and uranium-based paleo redox proxies : comparing two contrasting sill fjords
- 2023
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Ingår i: Biogeosciences Discussions. - 1810-6277 .- 1810-6285. ; 20:24, s. 5003-5028
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Tidskriftsartikel (refereegranskat)abstract
- Sedimentary molybdenum (Mo) and uranium (U) enrichments are often used as redox proxies to reconstruct bottom water redox changes. However, these redox proxies may not be equally reliable across a range of coastal settings due to varying depositional environments. Fjords vary greatly in their depositional conditions, due to their unique bathymetry and hydrography, and are highly vulnerable to anthropogenic and climatic pressures. Currently, it is unknown to what extent Mo and U sequestration is affected by variable depositional conditions in fjords. Here, we use pore water and sequential extraction data to investigate Mo and U enrichment pathways in sediments of two sill fjords on the Swedish west coast with contrasting depositional environments and bottom water redox conditions. Our data suggest that sedimentary authigenic Mo and U pools differ between the two fjords. At the (ir)regularly dysoxic (oxygen = 0.2–2 mL L−1) Gullmar Fjord, authigenic Mo largely binds to manganese (Mn) oxides and to a lesser extent to iron (Fe) oxides; Mo sulfides do not play a major role due to low sulfate reduction rates, which limits the rate of Mo burial. Authigenic U largely resides in carbonates. At the (ir)regularly euxinic (oxygen = 0 mL L−1; total hydrogen sulfide ≥ 0 mL L−1) Koljö Fjord, authigenic Mo is significantly higher due to binding with more refractory organic matter complexes and Mo-Fe-sulfide phases. Uranium is moderately enriched and largely bound to organic matter. We found no direct evidence for temporal changes in bottom water redox conditions reflected in Mo and U enrichments at either Gullmar Fjord or Koljö Fjord. While sulfidic bottom waters favor Mo sequestration at Koljö Fjord, enrichment maxima reflect a combination of depositional conditions rather than short-term low-oxygen events. Our data demonstrate that secondary pre- and post-depositional factors control Mo and U sequestration in fjords to such an extent that bottom water redox conditions are either not being systematically recorded or overprinted. This explains the large variability in trace metal enrichments observed in fjords and has implications for applying Mo and U as proxies for environmental redox reconstructions in such systems.
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| 5. |
- Rydin, Emil, et al.
(författare)
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Contrasting distribution and speciation of sedimentary organic phosphorus among different basins of the Baltic Sea
- 2023
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Ingår i: Limnology and Oceanography. - : John Wiley & Sons. - 0024-3590 .- 1939-5590. ; 68:4, s. 767-779
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Tidskriftsartikel (refereegranskat)abstract
- Recycling of phosphorus (P) from deoxygenated sediments perpetuates eutrophic conditions in parts of the Baltic Sea. Sedimentary organic P is a major source of dissolved P to the water column, but also a sink for permanent P burial. The mechanisms behind these two pathways are, however, largely unknown. Using new methods, we determined P in DNA and phospholipids, which are both found in all organisms. We also identified inositol phosphates that are particularly important in eukaryotes. Sediment cores were collected from contrasting basins in the Baltic Sea to study their relative contribution to the total P pool. We found high DNA-P/phospholipid-P ratios in surface sediments from the Bothnian Bay and Bothnian Sea. However, these ratios were low throughout profiles in euxinic Baltic Proper sediments. The elevated ratios present in sediments overlain by oxic bottom waters might indicate the presence of a microbial community stimulated by bioturbation, whereas the low DNA-P/phospholipid-P ratios in Baltic Proper sediments likely indicate an energy-limited microbial community, typical to the "deep biosphere" environment. Inositol-P was almost absent in euxinic Baltic Proper sediments that had a low total P amount compared to those in the other basins. We suggest that variability in the composition of sedimentary microbial communities among the Baltic Sea basins might cause differences in organic P forms that in turn affects its turnover.
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| 6. |
- Van Helmond, Niels A.G.M., et al.
(författare)
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Removal of phosphorus and nitrogen in sediments of the eutrophic Stockholm archipelago, Baltic Sea
- 2020
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Ingår i: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 17:10, s. 2745-2766
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Tidskriftsartikel (refereegranskat)abstract
- Coastal systems can act as filters for anthropogenic nutrient input into marine environments. Here, we assess the processes controlling the removal of phosphorus (P) and nitrogen (N) for four sites in the eutrophic Stockholm archipelago. Bottom water concentrations of oxygen (O2) and P are inversely correlated. This is attributed to the seasonal release of P from iron-oxide-bound (Fe-oxidebound) P in surface sediments and from degrading organic matter. The abundant presence of sulfide in the pore water and its high upward flux towards the sediment surface (4 to 8 mmolm-2 d-1), linked to prior deposition of organic-rich sediments in a low-O2 setting ("legacy of hypoxia"), hinder the formation of a larger Fe-oxide-bound P pool in winter. This is most pronounced at sites where water column mixing is naturally relatively low and where low bottom water O2 concentrations prevail in summer. Burial rates of P are high at all sites (0.03 0.3 molm-2 yr-1), a combined result of high sedimentation rates (0.5 to 3.5 cm yr-1) and high sedimentary P at depth (30 to 50 mol g-1). Sedimentary P is dominated by Fe-bound P and organic P at the sediment surface and by organic P, authigenic Ca-P and detrital P at depth. Apart from one site in the inner archipelago, where a vivianite-type Fe(II)-P mineral is likely present at depth, there is little evidence for sink switching of organic or Feoxide- bound P to authigenic P minerals. Denitrification is the major benthic nitrate-reducing process at all sites (0.09 to 1.7 mmolm-2 d-1) with rates decreasing seaward from the inner to outer archipelago. Our results explain how sediments in this eutrophic coastal system can remove P through burial at a relatively high rate, regardless of whether the bottom waters are oxic or (frequently) hypoxic. Our results suggest that benthic N processes undergo annual cycles of removal and recycling in response to hypoxic conditions. Further nutrient load reductions are expected to contribute to the recovery of the eutrophic Stockholm archipelago from hypoxia. Based on the dominant pathways of P and N removal identified in this study, it is expected that the sediments will continue to remove part of the P and N loads.
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| 7. |
- Xu, Xiaoling, et al.
(författare)
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Cable bacteria regulate sedimentary phosphorus release in freshwater sediments
- 2023
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Ingår i: Water Research. - 0043-1354 .- 1879-2448. ; 242
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Tidskriftsartikel (refereegranskat)abstract
- Previous studies have demonstrated that e-SOx can regulate the sedimentary release of phosphorus (P) in brackish and marine sediments. When e-SOx is active, an iron (Fe) and manganese (Mn) oxide rich layer is formed near the sediment surface, which prevents P release. When e-SOx becomes inactive, the metal oxide layer is reduced via sulfide-mediated dissolution, and P is subsequently released to the water column. Cable bacteria have been shown to also occur in freshwater sediments. In these sediments, sulfide production is limited, and the metal oxide layer would thus dissolve less efficiently, leaving the P trapped at the sediment surface. This lack of an efficient dissolution mechanism implies that e-SOx could play an important role in the regulation of P availability in eutrophied freshwater streams. To test this hypothesis, we incubated sediments from a eutrophic freshwater river to investigate the impact of cable bacteria on sedimentary cycling of Fe, Mn and P. High-resolution depth profiling of pH, O2 and ΣH2S complemented with FISH analysis and high-throughput gene sequencing showed that the development of e-SOx activity was closely linked to the enrichment of cable bacteria in incubated sediments. Cable bacteria activity caused a strong acidification in the suboxic zone, leading to the dissolution of Fe and Mn minerals and consequently a strong release of dissolved Fe2+ and Mn2+ to the porewater. Oxidation of these mobilized ions at the sediment surface led to the formation of a metal oxide layer that trapped dissolved P, as shown by the enrichment of P-bearing metal oxides in the top layer of the sediment and low phosphate in the pore and overlying water. After e-SOx activity declined, the metal oxide layer did not dissolve and P remained trapped at the surface. Overall, our results suggested cable bacteria can play an important role to counteract eutrophication in freshwater systems.
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| 8. |
- Zhao, Siqi, et al.
(författare)
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Elevated internal phosphorus loading from shallow areas of eutrophic boreal lakes : Insights from porewater geochemistry
- 2024
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Ingår i: Science of the Total Environment. - 0048-9697 .- 1879-1026. ; 907
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Tidskriftsartikel (refereegranskat)abstract
- Internal phosphorus (P) loading is widely recognized as a major cause of lake eutrophication. One conventional paradigm states that the magnitude of internal loading through P diffusion is constrained by the presence of iron (Fe) oxides in surface sediments under oxic conditions near the sediment-water interface (SWI). However, biogeochemical P dynamics in Fe-rich sedimentary systems are still not fully understood, especially in eutrophic lakes where intensively coupled organic matter (OM) remineralization and reductive dissolution of Fe-bound P (Fe-P) exist concurrently. Here, we assess the diagenetic processes that govern sedimentary P cycling in two eutrophic Fe-rich lakes in southern Finland, Lake Hiidenvesi and Lake Kytäjärvi, using a combination of porewater and solid-phase analyses. Coupled reductive dissolution of Fe-P and OM remineralization controlled P regeneration in both lakes, with Fe-P acting as the dominant source for porewater P. Vivianite formation likely immobilized sedimentary P in the deepest basin of Hiidenvesi. Elevated P diffusion rates were observed at shallow sites under oxic bottom water conditions in summer in both lakes, stimulated by enhanced remineralization of both freshly- (mostly phytoplankton-origin) and earlier-deposited OM under elevated temperatures. Areas overlain by oxic bottom water contributed more benthic P fluxes to the water column compared to anoxic/hypoxic areas in both lakes during all sampling seasons. Our study suggests that in shallow eutrophic settings with high OM deposition and elevated temperatures, remineralization in upper sediments regenerates P efficiently enough to support a significant amount of P release to the water column even under sedimentary molar Fe/P ratios >20. We also discuss the implication of our findings for lake restoration strategies.
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