Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutrient cycles

Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link between iron oxyhydroxide dissolution and release of P from Baltic Sea sediments, we show that preferential remineralization of P with respect to carbon (C) and nitrogen (N) during degradation of organic matter plays a key role in determining the surplus of bioavailable P in the water column. Preferential remineralization of P takes place both in the water column and upper sediments and its rate is shown to be redox-dependent, increasing as reducing conditions become more severe at greater water-depth in the deep basins. Existing Redfield-based biogeochemical models of the Baltic may therefore underestimate the imbalance between N and P availability for primary production, and hence the vulnerability of the Baltic to sustained eutrophication via the fixation of atmospheric N. However, burial of organic P is also shown to increase during multidecadal intervals of expanded hypoxia, due to higher net burial rates of organic matter around the margins of the deep basins. Such intervals may be characterized by basin-scale acceleration of all fluxes within the P cycle, including productivity, regeneration and burial, sustained by the relative accessibility of the water column P pool beneath a shallow halocline

The analysis of freshwater pearl mussel shells using mu-XRF (micro-x-ray fluorescence) and the applicability for environmental reconstruction

Freshwater pearl mussel is a highly threatened species, and many populations are currently on the brink of local extinction. For example, in south Finland, only two populations are currently viable. Even though the reasons for the mussels' demise are relatively well known, the long-term impacts of water quality are not completely resolved. Here, mu-XRF analysis and historical records were used to evaluate whether the differences in water chemistry or past environmental changes in three rivers in southern Finland are visible in mussel shell chemistry. The results show that the cracks inside mussel shells, invisible to the naked eye, may greatly affect the elemental composition results. Further, anomalies which could be related to inclusion of detrital matter inside the shells were detected. Manganese (Mn) seems to be related to mussel growth dynamics, especially in the nacreous layer, while high values of iron (Fe) and Mn are also present at the top sections of the prismatic layer. Line scan analysis revealed high variation between replicates. The mu-XRF method could be used as prescreening method in mussel sclerochemistry studies, but more studies are needed to clarify the ability of FPM shells to reliably record the environmental conditions

Effects of the 2014 major Baltic inflow on methane and nitrous oxide dynamics in the water column of the Central Baltic Sea

Peer reviewe

Terrestrial organic matter input drives sedimentary trace metal sequestration in a human-impacted boreal estuary

Coastal sediments play a fundamental role in processing anthropogenic trace metal inputs. Previous studies have shown that terrestrial organic matter (OM) is a significant vector for trace metal transport across the land-to-sea continuum, but little is known about the fate of land-derived metal-OM complexes in coastal sediments. Here, we use a comprehensive set of sediment pore water and solid-phase analyses to investigate how variations in terrestrial OM delivery since the 1950s have influenced trace metal accumulation and diagenesis in a human-impacted boreal estuary in the northern Baltic Sea. A key feature of our dataset is a strong correlation between terrestrial OM deposition and accumulation of metal-OM complexes in the sediments. Based on this strong coupling, we infer that the riverine input of terrestrial metal-OM complexes from the hinterland, followed by flocculation-induced settling in the estuary, effectively modulates sedimentary trace metal sequestration. While part of the trace metal pool associated with these complexes is efficiently recycled in the surface sediments during diagenesis, a substantial fraction is permanently buried as refractory metal-OM complexes or through incorporation into insoluble sulfides, thereby escaping further biological processing. These findings suggest that terrestrial OM input could play a more pivotal role in trace metal processing in coastal environments than hitherto acknowledged.</p

Coupled Dynamics of Iron and Phosphorus in Sediments of an Oligotrophic Coastal Basin and the Impact of Anaerobic Oxidation of Methane

Studies of phosphorus (P) dynamics in surface sediments of lakes and coastal seas typically emphasize the role of coupled iron (Fe), sulfur (S) and P cycling for sediment P burial and release. Here, we show that anaerobic oxidation of methane (AOM) also may impact sediment P cycling in such systems. Using porewater and sediment profiles for sites in an oligotrophic coastal basin (Bothnian Sea), we provide evidence for the formation of Fe-bound P (possibly vivianite; Fe3(PO4)2.8H2O) below the zone of AOM with sulfate. Here, dissolved Fe2+ released from oxides is no longer scavenged by sulfide and high concentrations of both dissolved Fe2+ (>1 mM) and PO4 in the porewater allow supersaturation with respect to vivianite to be reached. Besides formation of Fe(II)-P, preservation of Fe-oxide bound P likely also contributes to permanent burial of P in Bothnian Sea sediments. Preliminary budget calculations suggest that the burial of Fe-bound P allows these sediments to act as a major sink for P from the adjacent eutrophic Baltic Proper

Anthropogenic and climatic impacts on a coastal environment in the Baltic Sea over the last 1000 years

Coastal environments have experienced large ecological changes as a result of human activities over the last 100-200 years. To understand the severity and potential consequences of such changes, paleoenvironmental records provide important contextual information. The Baltic Sea coastal zone is naturally a vulnerable system and subject to significant human-induced impacts. To put the recent environmental degradation in the Baltic coastal zone into a long-term perspective, and to assess the natural and anthropogenic drivers of environmental change, we present sedimentary records covering the last 1000 years obtained from a coastal inlet (Gasfjarden) and a nearby lake (Lake Storsjon) in Sweden. We investigate the links between a pollen-based land cover reconstruction from Lake Storsjon and paleoenvironmental variables from Gasfjarden itself, including diatom assemblages, organic carbon (C) and nitrogen (N) contents, stable C and N isotopic ratios, and biogenic silica contents. The Lake Storsjon record shows that regional land use was characterized by small-scale agricultural activity between 900 and 1400 CE, which slightly intensified between 1400 and 1800 CE. Substantial expansion of cropland was observed between 1800 and 1950 CE, before afforestation between 1950 and 2010 CE. From the Gasfjarden record, prior to 1800 CE, relatively minor changes in the diatom and geochemical proxies were found. The onset of cultural eutrophication in Gasfjarden can be traced to the 1800s and intensified land use is identified as the main driver. Anthropogenic activities in the 20th century have caused unprecedented ecosystem changes in the coastal inlet, as reflected in the diatom composition and geochemical proxies. (c) 2018 Elsevier Ltd. All rights reserved.Peer reviewe

A 1500-year multiproxy record of coastal hypoxia from the northern Baltic Sea indicates unprecedented deoxygenation over the 20th century

The anthropogenically forced expansion of coastal hypoxia is a major environmental problem affecting coastal ecosystems and biogeochemical cycles throughout the world. The Baltic Sea is a semi-enclosed shelf sea whose central deep basins have been highly prone to deoxygenation during its Holocene history, as shown previously by numerous paleoenvironmental studies. However, long-term data on past fluctuations in the intensity of hypoxia in the coastal zone of the Baltic Sea are largely lacking, despite the significant role of these areas in retaining nutrients derived from the catchment. Here we present a 1500-year multiproxy record of near-bottom water redox changes from the coastal zone of the northern Baltic Sea, encompassing the climatic phases of the Medieval Climate Anomaly (MCA), the Little Ice Age (LIA), and the Modern Warm Period (MoWP). Our reconstruction shows that although multicentennial climate variability has modulated the depositional conditions and delivery of organic matter (OM) to the basin the modern aggravation of coastal hypoxia is unprecedented and, in addition to gradual changes in the basin configuration, it must have been forced by excess human-induced nutrient loading. Alongside the anthropogenic nutrient input, the progressive deoxygenation since the beginning of the 1900s was fueled by the combined effects of gradual shoaling of the basin and warming climate, which amplified sediment focusing and increased the vulnerability to hypoxia. Importantly, the eutrophication of coastal waters in our study area began decades earlier than previously thought, leading to a marked aggravation of hypoxia in the 1950s. We find no evidence of similar anthropogenic forcing during the MCA. These results have implications for the assessment of reference conditions for coastal water quality. Furthermore, this study highlights the need for combined use of sedimentological, ichnological, and geochemical proxies in order to robustly reconstruct subtle redox shifts especially in dynamic, non-euxinic coastal settings with strong seasonal contrasts in the bottom water quality.</p

Long-Term Consequences of Water Pumping on the Ecosystem Functioning of Lake Seksu, Latvia

Cultural eutrophication, the process by which pollution due to human activity speeds up natural eutrophication, is a widespread and consequential issue. Here, we present the 85-year history of a small, initially Lobelia-Isoetes dominated lake. The lake's ecological deterioration was intensified by water pumping station activities when it received replenishment water for more than 10 years from a eutrophic lake through a pipe. In this study, we performed a paleolimnological assessment to determine how the lake's ecosystem functioning changed over time. A multi-proxy (pollen, Cladocera, diatoms, and Chironomidae) approach was applied alongside a quantitative reconstruction of total phosphorus using diatom and hypolimnetic dissolved oxygen with chironomid-based transfer functions. The results of the biotic proxy were supplemented with a geochemical analysis. The results demonstrated significant changes in the lake community's structure, its sediment composition, and its redox conditions due to increased eutrophication, water level fluctuations, and erosion. The additional nutrient load, particularly phosphorus, increased the abundance of planktonic eutrophic-hypereutrophic diatoms, the lake water's transparency decreased, and hypolimnetic anoxia occurred. Cladocera, Chironomidae, and diatoms species indicated a community shift towards eutrophy, while the low trophy species were suppressed or disappeared

№ 109. Протокол допиту Миколи Чехівського від 13 жовтня 1929 р.

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Metaschoepite Dissolution in Sediment Column Systems-Implications for Uranium Speciation and Transport

Metaschoepite is commonly found in U-contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO3 center dot nH(2)O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield Ltd. site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6- and 12-months for analysis. Solution chemistry, extractions, and bulk and micro/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO22+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially mediated sulfate reduction, significant amounts of UO2-like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), noncrystalline U(IV), and biogenic UO2, with UO2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.Peer reviewe