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Enhanced release of alkalinity from the seafloor, principally driven by anaerobic degradation of organic matter under low-oxygen conditions and associated secondary redox reactions, can increase the carbon dioxide (CO2) buffering capacity of seawater and therefore oceanic CO2 uptake. The Baltic Sea has undergone severe changes in oxygenation state and total alkalinity (TA) over the past decades. The link between these concurrent changes has not yet been investigated in detail. A recent system-wide TA budget constructed for the past 50 years using BALTSEM, a coupled physical–biogeochemical model for the whole Baltic Sea area revealed an unknown TA source. Here we use BALTSEM in combination with observational data and one-dimensional reactive-transport modeling of sedimentary processes in the Fårö Deep, a deep Baltic Sea basin, to test whether sulfate (SO42-) reduction coupled to iron (Fe) sulfide burial can explain the missing TA source in the Baltic Proper. We calculated that this burial can account for up to 26 % of the missing source in this basin, with the remaining TA possibly originating from unknown river inputs or submarine groundwater discharge. We also show that temporal variability in the input of Fe to the sediments since the 1970s drives changes in sulfur (S) burial in the Fårö Deep, suggesting that Fe availability is the ultimate limiting factor for TA generation under anoxic conditions. The implementation of projected climate change and two nutrient load scenarios for the 21st century in BALTSEM shows that reducing nutrient loads will improve deep water oxygen conditions, but at the expense of lower surface water TA concentrations, CO2 buffering capacities and faster acidification. When these changes additionally lead to a decrease in Fe inputs to the sediment of the deep basins, anaerobic TA generation will be reduced even further, thus exacerbating acidification. This work highlights that Fe dynamics plays a key role in the release of TA from sediments where Fe sulfide formation is limited by Fe availability, as exemplified by the Baltic Sea. Moreover, it demonstrates that burial of Fe sulfides should be included in TA budgets of low-oxygen basins.

In an enclosure experiment, we employed two levels of inorganic NP ratios (10 and 5) for three distinct plankton communities collected along the coast of central Chile (33ºS). Each combination of community and NP level was replicated three times. The experiment lasted 12 days, and the data set include inorganic nutrients (NO3, PO4, DSi), particular organic carbon (POC), nitrogen (PON) and phosphorus (POP), Chlorophyll a, a range of fluorescence based measurements such as photochemical efficiency (Fv/Fm) and community data. The primary effect of the NP treatment was related to different concentrations of NO3, which directly influenced the biomass of phytoplankton. Additionally, low inorganic NP ratio reduced the seston NP and Chl a-C ratios, and there were some effects on the plankton community composition, e.g. benefitting Synechococcus spp in some communities.

Arkona Basin (southwestern Baltic Sea) is a seasonally-hypoxic basin characterized by the presence of free methane gas in its youngest organic-rich muddy stratum. Through the use of reactive transport models, this study tracks the development of the methane geochemistry in Arkona Basin as this muddy sediment became deposited during the last 8 kyr. Four cores are modeled each pertaining to a unique geochemical scenario according to their respective contemporary geochemical profiles. Ultimately the thickness of the muddy sediment and the flux of particulate organic carbon are crucial in determining the advent of both methanogenesis and free methane gas, the timescales over which methanogenesis takes over as a dominant reaction pathway for organic matter degradation, and the timescales required for free methane gas to form.

Variability and long-term climate change in the Baltic Sea region is investigated for the pre-industrial period of the last millennium. For the first time dynamical downscaling covering the complete millennium is conducted with a regional climate model in this area. As a result of changing external forcing conditions, the model simulation shows warm conditions in the first centuries followed by a gradual cooling until ca. 1700 before temperature increases in the last centuries. This long-term evolution, with a Medieval Climate Anomaly (MCA) and a Little Ice Age (LIA), is in broad agreement with proxy-based reconstructions. However, the timing of warm and cold events is not captured at all times. We show that the regional response to the global climate anomalies is to a strong degree modified by the large-scale circulation in the model. In particular, we find that a positive phase of the North Atlantic Oscillation (NAO) simulated during MCA contributes to enhancing winter temperatures and precipitation in the region while a negative NAO index in the LIA reduces them. In a second step, the regional ocean model (RCO-SCOBI) is used to investigate the impact of atmospheric changes onto the Baltic Sea for two 100 yr time slices representing the MCA and the LIA. Besides the warming of the Baltic Sea, the water becomes fresher at all levels during the MCA. This is induced by increased runoff and stronger westerly winds. Moreover, the oxygen concentrations in the deep layers are slightly reduced during the MCA. Additional sensitivity studies are conducted to investigate the impact of even higher temperatures and increased nutrient loads. The presented experiments suggest that changing nutrient loads may be more important determining oxygen depletion than changes in temperature or dynamic feedbacks.

Computer models are necessary for understanding and predicting marine ice sheet behaviour. However, there is uncertainty over implementation of physical processes at the ice base, both for grounded and floating glacial ice. Here we implement several sliding relations in a marine ice sheet flow-line model accounting for all stress components and demonstrate that model resolution requirements are strongly dependent on both the choice of basal sliding relation and the spatial distribution of ice shelf basal melting.Sliding relations that reduce the magnitude of the step change in basal drag from grounded ice to floating ice (where basal drag is set to zero) show reduced dependence on resolution compared to a commonly used relation, in which basal drag is purely a power law function of basal ice velocity. Sliding relations in which basal drag goes smoothly to zero as the grounding line is approached from inland (due to a physically motivated incorporation of effective pressure at the bed) provide further reduction in resolution dependence.A similar issue is found with the imposition of basal melt under the floating part of the ice shelf: melt parameterisations that reduce the abruptness of change in basal melting from grounded ice (where basal melt is set to zero) to floating ice provide improved convergence with resolution compared to parameterisations in which high melt occurs adjacent to the grounding line.Thus physical processes, such as sub-glacial outflow (which could cause high melt near the grounding line), impact on capability to simulate marine ice sheets. If there exists an abrupt change across the grounding line in either basal drag or basal melting, then high resolution will be required to solve the problem. However, the plausible combination of a physical dependency of basal drag on effective pressure, and the possibility of low ice shelf basal melt rates next to the grounding line, may mean that some marine ice sheet systems can be reliably simulated at a coarser resolution than currently thought necessary.

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe)-oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ.Here we combine detailed geochemical analyses of the sediment and porewater with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P), and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. In line with previous studies in the Black Sea, we show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g., vivianite) are converted to sulfide phases, leading to an enrichment in solid-phase S and the release of phosphate to the porewater. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward-diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front.Our model results further demonstrate that downward-migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM ( ∼ 1–100 pmol cm−3 d−1) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction and reactivation of less reactive Fe oxides by methanogens, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the porewater at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate, and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

The analog method (AM) has found application to reconstruct gridded climate fields from the information provided by proxy data and climate model simulations. Here, we test the skill of different setups of the AM, in a controlled but realistic situation, by analysing several statistical properties of reconstructed daily high-resolution atmospheric fields for Northern Europe for a 50-yr period. In this application, station observations of sea-level pressure and air temperature are combined with atmospheric fields from a 50-yr high-resolution regional climate simulation. This reconstruction aims at providing homogeneous and physically consistent atmospheric fields with daily resolution suitable to drive high resolution ocean and ecosystem models. Different settings of the AM are evaluated in this study for the period 1958–2007 to estimate the robustness of the reconstruction and its ability to replicate high and low-frequency variability, realistic probability distributions and extremes of different meteorological variables. It is shown that the AM can realistically reconstruct variables with a strong physical link to daily sea-level pressure on both a daily and monthly scale. However, to reconstruct low-frequency decadal and longer temperature variations, additional monthly mean station temperature as predictor is required. Our results suggest that the AM is a suitable upscaling tool to predict daily fields taken from regional climate simulations based on sparse historical station data.

Methane and carbon dioxide were measured with an autonomous and continuous running system on a ferry line crossing the Baltic Sea on a 2–3 day interval from the Mecklenburg Bight to the Gulf of Finland in 2010. Surface methane saturations show great seasonal differences in shallow regions like the Mecklenburg Bight (103–507%) compared to deeper regions like the Gotland Basin (96–161%). The influence of controlling parameters like temperature, wind, mixing depth and processes like upwelling, mixing of the water column and sedimentary methane emissions on methane oversaturation and emission to the atmosphere are investigated. Upwelling was found to influence methane surface concentrations in the area of Gotland significantly during the summer period. In February 2010, an event of elevated methane concentrations in the surface water and water column of the Arkona Basin was observed, which could be linked to a wind-derived water level change as a potential triggering mechanism. The Baltic Sea is a source of methane to the atmosphere throughout the year, with highest fluxes occurring during the winter season. Stratification was found to promote the formation of a methane reservoir in deeper regions like Gulf of Finland or Bornholm Basin, which leads to long lasting elevated methane concentrations and enhanced methane fluxes, when mixed to the surface during mixed layer deepening in autumn and winter. Methane concentrations and fluxes from shallow regions like the Mecklenburg Bight are predominantly controlled by sedimentary production and consumption of methane, wind events and the change in temperature-dependent solubility of methane in the surface water. Methane fluxes vary significantly in shallow regions (e.g. Mecklenburg Bight) and regions with a temporal stratification (e.g. Bornholm Basin, Gulf of Finland). On the contrary, areas with a permanent stratification like the Gotland Basin show only small seasonal fluctuations in methane fluxes.

Coastal locations are highly influenced by input from freshwater river runoff, including sources of terrestrial carbon, which can be expected to modify the 14C reservoir age, or R (t), associated with marine water. In this Baltic Sea case study, pre-bomb museum collection mollusc shells of known calendar age, from 30 locations across a strategic salinity transect of the Baltic Sea, were analysed for 14C, δ13C and δ18O. R (t) was calculated for all 30 locations. Seven locations, of which six are within close proximity of the coast, were found to have relatively higher R (t) values, indicative of hard-water effects. Whenever possible, the Macoma genus of mollusc was selected from the museum collections, in order to exclude species specific reservoir age effects as much as possible. When the Macoma samples are exclusively considered, and samples from hard-water locations excluded, a statistically significant correlation between Macoma R (t) and average salinity is found, indicating a two end-member linear mixing model between 14Cmarine and 14Crunoff. A map of Baltic Sea Macoma aragonite R (t) for the late 19th and early 20th centuries is produced. Such a map can provide an estimate for contemporary Baltic Sea Macoma R (t), although one must exercise caution when applying such estimates back in time or to 14C dates obtained from different sample material. A statistically significant correlation is found between δ18Oaragonite and Macoma R (t), suggesting that δ18Oaragonite can be used to estimate Macoma palaeo-R (t), due to the δ18Oaragonite signal being dominated by the salinity gradient of the Baltic Sea. A slightly increased correlation can be expected when δ18Oaragonite is corrected for temperature fractionation effects. The results of this Baltic Sea case study, which show that R (t) is affected by hydrographic conditions and local carbon inputs, have important consequences for other coastal and estuarine locations, where R (t) is also likely to significantly vary on spatial and temporal bases.

In late 2014, a large, oxygen-rich salt water inflow entered the Baltic Sea and caused considerable changes in deep water oxygen concentrations. We studied the effects of the inflow on the concentration patterns of two greenhouse gases, methane and nitrous oxide, during the following year (2015) in the water column of the Gotland Basin. In the eastern basin, methane which had previously accumulated in the deep waters was largely removed during the year. Here, volume-weighted mean concentration below 70 m decreased from 108 nM in March to 16.3 nM over a period of 141 days (0.65 nM d−1), predominantly due to oxidation (up to 79 %) following turbulent mixing with the oxygen-rich inflow. In contrast nitrous oxide, which was previously absent from deep waters, accumulated in deep waters due to enhanced nitrification following the inflow. Volume-weighted mean concentration of nitrous oxide below 70 m increased from 11.8 nM in March to 24.4 nM in 141 days (0.09 nM d−1). A transient extreme accumulation of nitrous oxide (877 nM) was observed in the deep waters of the Eastern Gotland Basin towards the end of 2015, when deep waters turned anoxic again, sedimentary denitrification was induced and methane was reintroduced to the bottom waters. The Western Gotland Basin gas biogeochemistry was not affected by the inflow.