ALBERT

Description: In high-latitude continental shelf environments, late Pleistocene glacial overdeepening and early Holocene eustatic sea-level rise combined to create restricted marine basins with a high vulnerability to oxygen depletion. Here we show that ongoing glacio-isostatic rebound during the Holocene may have played an important role in determining the distribution of past hypoxia in these environments by controlling the physical exchange of water masses and the distribution of large-scale phosphorus (P) sinks. We focus on the Baltic Sea, where sediment records from a large, presently oxic sub-basin show evidence for intense hypoxia and cyanobacteria blooms during the Holocene Thermal Maximum. Using paleobathymetric modeling, we show that this period was characterized by enhanced deep-water exchange, allowing widespread phosphorus regeneration. Intra-basin sills then shoaled over a period of several thousand years, enhancing P burial in one of the sub-basins. Together with climate forcing, this may have caused the termination of hypoxia throughout the Baltic Sea. Similar rearrangements of physical and chemical processes likely occurred in response to glacio-isostatic rebound in other high-latitude shelf basins during the Holocene.

Description: Hypoxia (oxygen concentrations of 〈2 ml/L) and so-called "dead zones" are a growing concern in coastal marine environments. The Baltic Sea is a shelf sea that is highly sensitive to hypoxia, and may serve as a laboratory for studying the interplay between natural and anthropogenic forcing of redox conditions in the global coastal zone. Past occurrences of hypoxia in the Baltic Sea have been shown by previous studies, but high-resolution, quantitative reconstructions of past hypoxia intensity are lacking. Here we present bulk sediment geochemical records from the deep basins of the Baltic Sea that show multicentennial oscillations during intervals of past hypoxia, suggesting rapid alternations between hypoxic and relatively oxic conditions. While the onset of past hypoxic events was likely forced by climatic variability, these events intensified and terminated rapidly due to feedbacks in the phosphorus (P) cycle. The modern intensity of hypoxia is similar to several past events, suggesting that hypoxia in the Baltic Sea has a maximum potential intensity. However, using ultrahigh-resolution laser ablation–inductively coupled plasma–mass spectrometry scanning of sediment blocks, we show that modern hypoxia intensified more rapidly than any past event. This confirms the role of anthropogenic nutrient loading in driving this system into its current hypoxic state.

Description: 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 water-depth dependent, increasing with the severity of reducing conditions into 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.

Description: Expanding hypoxia in the Baltic Sea over the past century has led to anoxic and sulfidic (euxinic) deep basins that are only periodically ventilated by inflows of oxygenated waters from the North Sea. In this study, we investigate the consequences of the expanding hypoxia for manganese (Mn) burial in the Baltic Sea using a combination of pore water and sediment analyses of well-dated sediment cores from 8 locations. Diffusive fluxes of dissolved Mn from sediments to overlying waters at oxic and hypoxic sites are in line with an active release of Mn from these areas. However, this flux of Mn is only small when compared to the large pool of Mn already present in the hypoxic and anoxic water column. Our results highlight two modes of Mn carbonate formation in sediments of the deep basins. In the Gotland Deep area, Mn carbonates likely form from Mn oxides that are precipitated from the water column directly following North Sea inflows. In the Landsort Deep, in contrast, Mn carbonate and Mn sulfide layers form independent of inflow events, with pore water Mn produced in deeper layers of the sediment acting as a key Mn source. While formation of Mn enrichments in the Landsort Deep continues to the present, this does not hold for the Gotland Deep area. Here, increased euxinia, as evident from measured bottom water sulfide concentrations and elevated sediment molybdenum (Mo), goes hand in hand with a decline in sediment Mn and recent inflows of oxygenated water (since ca. 1995) are no longer consistently recorded as Mn carbonate layers. We postulate that the reduction of Mn oxides by hydrogen sulfide following inflows has become so rapid that Mn2+ is released to the water column before Mn carbonates can form. Our results have important implications for the use of Mn carbonate enrichments as a redox proxy in marine systems.

Description: 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.

Description: Expanding hypoxia in the Baltic Sea over the past century has led to the development of anoxic and sulfidic (euxinic) deep basins that are only periodically ventilated by inflows of oxygenated waters from the North Sea. In this study, we investigate the potential consequences of the expanding hypoxia for manganese (Mn) burial in the Baltic Sea using a combination of pore water and sediment analyses of dated sediment cores from eight locations. Diffusive fluxes of dissolved Mn from sediments to overlying waters at oxic, hypoxic and euxinic sites are consistent with an active release of Mn from these areas. Although the present-day fluxes are significant (ranging up to ca. 240 μmol m−2 d−1), comparison to published water column data suggests that the current benthic release of Mn is small when compared to the large pool of Mn already present in the hypoxic and anoxic water column. Our results highlight two modes of Mn carbonate formation in sediments of the deep basins. In the Gotland Deep area, Mn carbonates likely form from Mn oxides that are precipitated from the water column directly following North Sea inflows. In the Landsort Deep, in contrast, Mn carbonate and Mn sulfide layers appear to form independently of inflow events, and are possibly related to the much larger and continuous input of Mn oxides linked to sediment focusing. Whereas Mn-enriched sediments continue to accumulate in the Landsort Deep, this does not hold for the Gotland Deep area. Here, a recent increase in euxinia, as evident from measured bottom water sulfide concentrations and elevated sediment molybdenum (Mo), coincides with a decline in sediment Mn content. Sediment analyses also reveal that recent inflows of oxygenated water (since ca. 1995) are no longer consistently recorded as Mn carbonate layers. Our data suggest that eutrophication has not only led to a recent rise in sulfate reduction rates but also to a decline in reactive Fe input to these basins. We hypothesize that these factors have jointly led to higher sulfide availability near the sediment–water interface after inflow events. As a consequence, the Mn oxides may be reductively dissolved more rapidly than in the past and Mn carbonates may no longer form. Using a simple diagenetic model for Mn dynamics in the surface sediment, we demonstrate that an enhancement of the rate of reduction of Mn oxides is consistent with such a scenario. Our results have important implications for the use of Mn carbonate enrichments as a redox proxy in marine systems.

Description: Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.