| 1. |
- Van Helmond, Niels A.G.M., et al.
(author)
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Removal of phosphorus and nitrogen in sediments of the eutrophic Stockholm archipelago, Baltic Sea
- 2020
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In: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 17:10, s. 2745-2766
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Journal article (peer-reviewed)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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| 2. |
- Hermans, Martijn, et al.
(author)
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Coupled dynamics of iron, manganese, and phosphorus in brackish coastal sediments populated by cable bacteria
- 2021
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In: Limnology and Oceanography. - : Wiley. - 1939-5590 .- 0024-3590. ; 66:7, s. 2611-2631
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Journal article (peer-reviewed)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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| 3. |
- Hermans, Martijn, et al.
(author)
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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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In: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 246, s. 174-196
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Journal article (peer-reviewed)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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| 4. |
- Kubeneck, L. Joëlle, et al.
(author)
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Phosphorus burial in vivianite-type minerals in methane-rich coastal sediments
- 2021
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In: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 231
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Journal article (peer-reviewed)abstract
- Sediments are a key sink for phosphorus (P) in coastal systems. This allows coastal areas to act as a filter for P that is transported from land to sea. Recent work suggests that vivianite-type ferrous iron (Fe(II))-P minerals may be more important as a sink for P in coastal sediments than previously thought. Here, we investigate the occurrence of such vivianite-type minerals in sediments of three eutrophic coastal sites with contrasting dynamics with respect to iron (Fe) and sulfur (S), covering a salinity range of 0 to 7. We only find authigenic vivianite-type minerals at the low and intermediate salinity sites, where Fe is available in excess over sulfide production. Sequential extractions combined with SEM-EDS and μXRF analysis point towards substitution of Fe in vivianite-type minerals by other transition metal cations such as magnesium and manganese, suggesting potentially different formation pathways modulated by metal cation availability. Our results suggest that vivianite-type minerals may act as a key sink for P in sediments of many other brackish coastal systems. Climate change-driven modulations of coastal bottom water salinity, and hence, Fe versus S availability in the sediment, may alter the role of vivianite-type minerals as a P burial sink over the coming decades. Model projections for the Baltic Sea point towards increased river input and freshening of coastal waters, which could enhance P burial. In contrast, sea level rise in the Chesapeake Bay area is expected to lead to an increase in bottom water salinity and this could lower rates of P burial or even liberate currently buried P, thereby enhancing eutrophication.
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| 5. |
- Lenstra, Wytze K., et al.
(author)
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Gene-based modeling of methane oxidation in coastal sediments : constraints on the efficiency of the microbial methane filter
- 2023
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 57:34, s. 12722-12731
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Journal article (peer-reviewed)abstract
- Methane is a powerful greenhouse gas that is produced in large quantities in marine sediments. Microbially mediated oxidation of methane in sediments, when in balance with methane production, prevents the release of methane to the overlying water. Here, we present a gene-based reactive transport model that includes both microbial and geochemical dynamics and use it to investigate whether the rate of growth of methane oxidizers in sediments impacts the efficiency of the microbial methane filter. We focus on iron- and methane-rich coastal sediments and, with the model, show that at our site, up to 10% of all methane removed is oxidized by iron and manganese oxides, with the remainder accounted for by oxygen and sulfate. We demonstrate that the slow growth rate of anaerobic methane-oxidizing microbes limits their ability to respond to transient perturbations, resulting in periodic benthic release of methane. Eutrophication and deoxygenation decrease the efficiency of the microbial methane filter further, thereby enhancing the role of coastal environments as a source of methane to the atmosphere.
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| 6. |
- Lenstra, Wytze K., et al.
(author)
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Large variations in iron input to an oligotrophic Baltic Sea estuary : Impact on sedimentary phosphorus burial
- 2018
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In: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 15:22, s. 6979-6996
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Journal article (peer-reviewed)abstract
- Estuarine sediments are key sites for removal of phosphorus (P) from rivers and the open sea. Vivianite, an Fe(II)-P mineral, can act as a major sink for P in Fe-rich coastal sediments. In this study, we investigate the burial of P in the Öre Estuary in the northern Baltic Sea. We find much higher rates of P burial at our five study sites (up to ĝ1/4 0.145 molĝ€†mĝ'2ĝ€†yrĝ'1) when compared to more southern coastal areas in the Baltic Sea with similar rates of sedimentation. Detailed study of the sediment P forms at our site with the highest rate of sedimentation reveals a major role for P associated with Fe and the presence of vivianite crystals below the sulfate methane transition zone. By applying a reactive transport model to sediment and porewater profiles for this site, we show that vivianite may account for up to ĝ1/4 40 % of total P burial. With the model, we demonstrate that vivianite formation is promoted in sediments with a low bottom water salinity and high rates of sedimentation and Fe oxide input. While high rates of organic matter input are also required, there is an optimum rate above which vivianite formation declines. Distinct enrichments in sediment Fe and sulfur at depth in the sediment are attributed to short periods of enhanced input of riverine Fe and organic matter. These periods of enhanced input are linked to variations in rainfall on land and follow dry periods. Most of the P associated with the Fe in the sediment is likely imported from the adjacent eutrophic Baltic Proper. Our work demonstrates that variations in land-to-sea transfer of Fe may act as a key control on burial of P in coastal sediments. Ongoing climate change is expected to lead to a decrease in bottom water salinity and contribute to continued high inputs of Fe oxides from land, further promoting P burial as vivianite in the coastal zone of the northern Baltic Sea. This may enhance the role of this oligotrophic area as a sink for P imported from eutrophic parts of the Baltic Sea.
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