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Significant research has been carried out in the last decade to describe the CO2 system dynamics in the Baltic Sea. However, there is a lack of knowledge in this field in the NE Baltic Sea, which is the main focus of the present study. We analysed the physical forcing and hydrographic background in the study year (2018) and tried to elucidate the observed patterns of surface water CO2 partial pressure (pCO2) and methane concentrations (cCH4). Surface water pCO2 and cCH4 were calculated from continuous measurements during six monitoring cruises onboard R/V Salme, covering the Northern Baltic Proper (NBP), the Gulf of Finland (GoF) and the Gulf of Riga (GoR) and all seasons in 2018. The general seasonal pCO2 pattern showed oversaturation in autumn-winter and undersaturation in spring-summer in all three areas, but it locally reached the saturation level during the cruises in April, May and August in the GoR and in August in the GoF. cCH4 was oversaturated during the entire study period, and the seasonal course was not well exposed on the background of high variability. Surface water pCO2 and cCH4 distributions showed larger spatial variability in the GoR and GoF than in the NBP for all six cruises. We linked the observed local maxima to river bulges, coastal upwelling events, fronts, and occasions when vertical mixing reached the seabed in shallow areas. Seasonal averaging over the CO2 flux based on our data suggest a weak sink for atmospheric CO2 for all basins, but high variability and the long periods between cruises (temporal gaps in observation) preclude a clear statement. [ABSTRACT FROM AUTHOR]

Ocean surface pCO 2 estimates are of great interest for the calculation of air–sea CO 2 fluxes, oceanic uptake of anthropogenic CO 2 , and eventually the Global Carbon Budget. They are accessible from direct observations, which are discrete in space and time and thus always sparse, or from biogeochemical models, which only approximate reality. Here, a combined method for the extrapolation of pCO 2 observations is presented that uses (1) model-based patterns of variability from an empirical orthogonal function (EOF) analysis of variability with (2) observational data to constrain EOF pattern amplitudes in (3) an ensemble approach, which locally adjusts the spatial scale of the mapping to the density of the observations. Thus, data-constrained, gap- and discontinuity-free mapped fields including local error estimates are obtained without the need for or dependence on ancillary data (e.g. satellite sea surface temperature maps). This extrapolation approach is generic in that it can be applied to any oceanic or coastal region covered by a suitable model and observations. It is used here to establish a regional pCO 2 climatology of the Baltic Sea (: 10.1594/PANGAEA.961119), largely based on ICOS-DE ship of opportunity (SOOP) Finnmaid surface pCO 2 observations between Lübeck-Travemünde (Germany) and Helsinki (Finland). The climatology can serve as improved input for atmosphere–ocean CO 2 flux estimation in this coastal environment. [ABSTRACT FROM AUTHOR]

Ocean surface pCO2 estimates are of great interest for the calculation of air-sea CO2 fluxes, oceanic uptake of anthropogenic CO2, and eventually the Global Carbon Budget. They are accessible from direct observations, which are discrete in space and time and thus always sparse, or from biogeochemical models, which only approximate reality. Here, a combined method for the extrapolation of pCO2 observations is presented that uses (1) model-based patterns of variability from an EOF analysis of variability with (2) observational data to constrain EOF pattern amplitudes in (3) an ensemble approach, 5 which locally adjusts the spatial scale of the mapping to the density of the observations. Thus, data-constrained, gap- and discontinuity-free mapped fields including local error estimates are obtained without the need for or dependence on ancillary data (like, e.g., satellite sea surface temperature maps). This extrapolation approach is generic in that it can be applied to any oceanic or coastal region covered by a suitable model and observations. It is used here to establish a regional pCO2 climatology of the Baltic Sea, largely based on ICOS-DE SOOP Finnmaid surface pCO2 observations between Lübeck-Travemünde 10 (Germany) and Helsinki (Finland). The climatology can serve as improved input for atmosphere-ocean CO2 flux estimation in this coastal environment. [ABSTRACT FROM AUTHOR]

The rewetting of drained peatlands supports long-term nutrient removal in addition to reducing emissions of carbon dioxide (CO 2) and nitrous oxide (N 2 O). However, rewetting may lead to short-term nutrient leaching into adjacent water and high methane (CH 4) emissions. The consequences of rewetting with brackish water on nutrient and greenhouse gas (GHG) fluxes remain unclear, although beneficial effects such as lower CH 4 emissions seem likely. Therefore, we studied the actively induced rewetting of a coastal peatland with brackish water, by comparing pre- and post-rewetting data from the peatland and the adjacent bay. Both the potential transport of nutrients into adjacent coastal water and the shift in GHG fluxes (CO 2 , CH 4 , and N 2 O) accompanying the change from drained to inundated conditions were analyzed based on measurements of the surface water concentrations of nutrients (dissolved inorganic nitrogen, DIN, and phosphate, PO 43-), oxygen (O 2), components of the CO 2 system, CH 4 , and N 2 O together with manual closed-chamber measurements of GHG fluxes. Our results revealed higher nutrient concentrations in the rewetted peatland than in the adjacent bay, indicating that nutrients leached out of the peat and were exported to the bay. A comparison of DIN concentrations of the bay with those of an unaffected reference station showed a significant increase after rewetting. The maximum estimated nutrient export (mean ± 95 % confidence level) out of the peatland was calculated to be 33.8 ± 9.6 t yr -1 for DIN-N and 0.24 ± 0.29 t yr -1 for PO 4 -P, depending on the endmember (bay vs. reference station). The peatland was also a source of GHG in the first year after rewetting. However, the spatial and temporal variability decreased, and high CH 4 emissions, as reported for freshwater rewetting, did not occur. CO 2 fluxes (mean ± SD) decreased slightly from 0.29 ± 0.82 g m -2 h -1 (pre-rewetting) to 0.26 ± 0.29 g m -2 h -1 (post-rewetting). The availability of organic matter (OM) and dissolved nutrients were likely the most important drivers of continued CO 2 production. Pre-rewetting CH 4 fluxes ranged from 0.13 ± 1.01 mg m -2 h -1 (drained land site) to 11.4 ± 37.5 mg m -2 h -1 (ditch). After rewetting, CH 4 fluxes on the formerly dry land increased by 1 order of magnitude (1.74 ± 7.59 mg m -2 h -1), whereas fluxes from the former ditch decreased to 8.5 ± 26.9 mg m -2 h -1. These comparatively low CH 4 fluxes can likely be attributed to the suppression of methanogenesis and oxidation of CH 4 by the available O 2 and sulfate in the rewetted peatland, which serve as alternative electron acceptors. The post-rewetting N 2 O flux was low, with an annual mean of 0.02 ± 0.07 mg m -2 h -1. Our results suggest that rewetted coastal peatlands could account for high, currently unmonitored, nutrient inputs into adjacent coastal water, at least on a short timescale such as a few years. However, rewetting with brackish water may decrease GHG emissions and might be favored over freshwater rewetting in order to reduce CH 4 emissions. [ABSTRACT FROM AUTHOR]

Marine biogeochemical models based on Redfield stoichiometry suffer from underestimating carbon fixation by primary production. The most pronounced indication of this is the overestimation of the dissolved inorganic carbon (DIC) concentration and, consequently, the partial pressure of carbon dioxide in surface waters. The reduced production of organic carbon will impact most biogeochemical processes. We propose a marine biogeochemical model allowing for a non-Redfieldian carbon fixation. The updated model is able to reproduce observed partial pressure of carbon dioxide and other variables of the ecosystem, like nutrients and oxygen, reasonably well. The additional carbon uptake is realized in the model by an extracellular release (ER) of dissolved organic matter (DOM) from phytoplankton. Dissolved organic matter is subject to flocculation and the sinking particles remove carbon from surface waters. This approach is mechanistically different from existing non-Redfieldian models which allow for flexible elemental ratios for the living cells of the phytoplankton itself. The performance of the model is demonstrated as an example for the Baltic Sea. We have chosen this approach because of a reduced computational effort which is beneficial for large-scale and long-term model simulations. Budget estimates for carbon illustrate that the Baltic Sea acts as a carbon sink. For alkalinity, the Baltic Sea is a source due to internal alkalinity generation by denitrification. Owing to the underestimated model alkalinity, an unknown alkalinity source or underestimated land-based fluxes still exist. [ABSTRACT FROM AUTHOR]

The rewetting of drained peatlands supports long-term nutrient removal in addition to reducing emissions of carbon dioxide (CO2) and nitrous oxide (N2O). However, rewetting may lead to short-term nutrient leaching into adjacent water and high methane (CH4) emissions. The consequences of rewetting with brackish water on nutrient and greenhouse gas (GHG) fluxes remain unclear, although beneficial effects such as lower CH4 emissions seem likely. Therefore, we studied the actively induced rewetting of a coastal peatland with brackish water, by comparing pre- and post-rewetting data from the peatland and the adjacent bay. Both the potential transport of nutrients into adjacent coastal water and the shift of GHG fluxes (CO2, CH4, N2O) accompanying the change from drained to inundated conditions were analyzed based on measurements of the surface water concentrations of nutrients (dissolved inorganic nitrogen (DIN), phosphate (PO43-)), oxygen (O2), components of the CO2 system, CH4, and N2O together with manual closed-chamber measurements of GHG fluxes. Our results revealed higher nutrient concentrations in the rewetted peatland than in the adjacent bay, indicating that nutrients leached out of the peat and were exported to the bay. A comparison of DIN concentrations of the bay with those of an unaffected reference station showed a significant increase after rewetting. The total nutrient export out of the peatland ranged between 12.5 and 36.5 t yr−1 for DIN-N and 0.2 ± 0.5 t yr−1 for PO4-P. The peatland was also a source of GHG in the first year after rewetting. However, the spatial and temporal variability decreased and high CH4 emissions, as reported for freshwater rewetting, did not occur. CO2 fluxes decreased slightly from 0.29 ± 0.74 g m−2 h−1 (pre-rewetting) to 0.26 ± 0.29 g m−2 h−1 (post-rewetting). The availability of organic matter (OM) and dissolved nutrients were likely the most important drivers of continued CO2 production. Pre-rewetting CH4 fluxes ranged from 0.13 ± 1.01 mg m−2 h−1 (drained land site) to 11.4 ± 37.5 mg m−2 h−1 (ditch). After rewetting, CH4 fluxes on the formerly dry land increased by 1 order of magnitude (1.74 ± 7.59 mg m−2 h−1 ), whereas fluxes from the former ditch decreased to 8.5 ± 26.9 mg m−2 h−1 . These comparatively low CH4 fluxes can likely be attributed to the suppression of methanogenesis by the available O2 and sulfate, which serve as alternative electron acceptors. The post-rewetting N2O flux was low, with an annual mean of 0.02 ± 0.07 mg m−2 h−1. Our results suggest that rewetted coastal peatlands could account for high, currently unmonitored nutrient inputs into adjacent coastal water, at least on a short time scale such as a few years. However, rewetting with brackish water may decrease GHG emissions and might be favored over freshwater rewetting in order to reduce CH4 emissions. [ABSTRACT FROM AUTHOR]

Location, specific topography, and hydrographic setting together with climate change and strong anthropogenic pressure are the main factors shaping the biogeochemical functioning and thus also the ecological status of the Baltic Sea. The recent decades have brought significant changes in the Baltic Sea. First, the rising nutrient loads from land in the second half of the 20th century led to eutrophication and spreading of hypoxic and anoxic areas, for which permanent stratification of the water column and limited ventilation of deep-water layers made favourable conditions. Since the 1980s the nutrient loads to the Baltic Sea have been continuously decreasing. This, however, has so far not resulted in significant improvements in oxygen availability in the deep regions, which has revealed a slow response time of the system to the reduction of the land-derived nutrient loads. Responsible for that is the low burial efficiency of phosphorus at anoxic conditions and its remobilization from sediments when conditions change from oxic to anoxic. This results in a stoichiometric excess of phosphorus available for organic-matter production, which promotes the growth of N2 -fixing cyanobacteria and in turn supports eutrophication. This assessment reviews the available and published knowledge on the biogeochemical functioning of the Baltic Sea. In its content, the paper covers the aspects related to changes in carbon, nitrogen, and phosphorus (C, N, and P) external loads, their transformations in the coastal zone, changes in organic-matter production (eutrophication) and remineralization (oxygen availability), and the role of sediments in burial and turnover of C, N, and P. In addition to that, this paper focuses also on changes in the marine CO2 system, the structure and functioning of the microbial community, and the role of contaminants for biogeochemical processes. This comprehensive assessment allowed also for identifying knowledge gaps and future research needs in the field of marine biogeochemistry in the Baltic Sea. [ABSTRACT FROM AUTHOR]

The direction and magnitude of carbon dioxide fluxes between the atmosphere and the sea are regulated by the gradient in the partial pressure of carbon dioxide (pCO2) across the air–sea interface. Typically, observations of pCO2 at the sea surface are carried out by using research vessels and ships of opportunity, which usually do not resolve the diurnal cycle of pCO2 at a given location. This study evaluates the magnitude and driving processes of the diurnal cycle of pCO2 in a coastal region of the Baltic Sea. We present pCO2 data from July 2018 to June 2019 measured in the vicinity of the island of Utö at the outer edge of the Archipelago Sea, and quantify the relevant physical, biological, and chemical processes controlling pCO2. The highest monthly median of diurnal pCO2 variability (31 µatm) was observed in August and predominantly driven by biological processes. Biological fixation and mineralization of carbon led to sinusoidal diurnal pCO2 variations, with a maximum in the morning and a minimum in the afternoon. Compared with the biological carbon transformations, the impacts of air–sea fluxes and temperature changes on pCO2 were small, with their contributions to the monthly medians of diurnal pCO2 variability being up to 12 and 5 µ atm, respectively. During upwelling events, short-term pCO2 variability (up to 500 µ atm within a day) largely exceeded the usual diurnal cycle. If the net annual air–sea flux of carbon dioxide at our study site and for the sampled period is calculated based on a data subset that consists of only one regular measurement per day, the bias in the net exchange depends on the sampling time and can amount up to ±12 %. This finding highlights the importance of continuous surface pCO2 measurements at fixed locations for the assessment of the short-term variability of the carbonate system and the correct determination of air–sea CO2 fluxes. [ABSTRACT FROM AUTHOR]

Organic matter production by cyanobacteria blooms is a major environmental concern for the Baltic Sea, as it promotes the spread of anoxic zones. Partial pressure of carbon dioxide (p CO2) measurements carried out on Ships of Opportunity (SOOP) since 2003 have proven to be a powerful tool to resolve the carbon dynamics of the blooms in space and time. However, SOOP measurements lack the possibility to directly constrain depth-integrated net community production (NCP) in moles of carbon per surface area due to their restriction to the sea surface. This study tackles the knowledge gap through (1) providing an NCP best guess for an individual cyanobacteria bloom based on repeated profiling measurements of p CO2 and (2) establishing an algorithm to accurately reconstruct depth-integrated NCP from surface p CO2 observations in combination with modelled temperature profiles. Goal (1) was achieved by deploying state-of-the-art sensor technology from a small-scale sailing vessel. The low-cost and flexible platform enabled observations covering an entire bloom event that occurred in July–August 2018 in the Eastern Gotland Sea. For the biogeochemical interpretation, recorded p CO2 profiles were converted to CT* , which is the dissolved inorganic carbon concentration normalised to alkalinity. We found that the investigated bloom event was dominated by Nodularia and had many biogeochemical characteristics in common with blooms in previous years. In particular, it lasted for about 3 weeks, caused a CT* drawdown of 90 µmolkg-1 , and was accompanied by a sea surface temperature increase of 10 ∘C. The novel finding of this study is the vertical extension of the CT* drawdown up to the compensation depth located at around 12 m. Integration of the CT* drawdown across this depth and correction for vertical fluxes leads to an NCP best guess of ∼1.2 molm-2 over the productive period. Addressing goal (2), we combined modelled hydrographical profiles with surface p CO2 observations recorded by SOOP Finnmaid within the study area. Introducing the temperature penetration depth (TPD) as a new parameter to integrate SOOP observations across depth, we achieve an NCP reconstruction that agrees to the best guess within 10 % , which is considerably better than the reconstruction based on a classical mixed-layer depth constraint. Applying the TPD approach to almost 2 decades of surface p CO2 observations available for the Baltic Sea bears the potential to provide new insights into the control and long-term trends of cyanobacteria NCP. This understanding is key for an effective design and monitoring of conservation measures aiming at a Good Environmental Status of the Baltic Sea. [ABSTRACT FROM AUTHOR]

Location, specific topography and hydrographic setting together with climate change and strong anthropogenic pressure are the main factors shaping the biogeochemical functioning and thus also the ecological status of the Baltic Sea. The recent decades have brought significant changes in the Baltic Sea. First, the rising nutrient loads from land in the second half of the 20th century led to eutrophication and spreading of hypoxic and anoxic areas, for which permanent stratification of the water column and limited ventilation of deep water layers made favourable conditions. Since the 1980s the nutrient loads to the Baltic Sea have been continuously decreasing. This, however, has so far not resulted in significant improvements in oxygen availability in the deep regions, which has revealed a slow response time of the system to the reduction of the land-derived nutrient loads. Responsible for that is the low burial efficiency of phosphorus at anoxic conditions and its remobilization from sediments when conditions change from oxic to anoxic. This results in a stoichiometric excess of phosphorus available for organic matter production, which promotes the growth of N2-fixing cyanobacteria and in turn supports eutrophication. This assessment reviews the available and published knowledge on the biogeochemical functioning of the Baltic Sea. In its content, the paper covers the aspects related to changes in carbon, nitrogen and phosphorus (C, N and P) external loads, their transformations in the coastal zone, changes in organic matter production (eutrophication) and remineralization (oxygen availability), and the role of sediments in burial and turnover of C, N and P. In addition to that, this paper focuses also on changes in the marine CO2 system, structure and functioning of the microbial community and the role of contaminants for biogeochemical processes. This comprehensive assessment allowed also for identifying knowledge gaps and future research needs in the field of marine biogeochemistry in the Baltic Sea. [ABSTRACT FROM AUTHOR]

Autonomous measurements aboard ships of opportunity (SOOP) provide in situ data sets with high spatial and temporal coverage. In this study, we use 8 years of carbon dioxide (CO2) and methane (CH4) observations from SOOP Finnmaid to study the influence of upwelling on trace gas dynamics in the Baltic Sea. Between spring and autumn, coastal upwelling transports water masses enriched with CO2 and CH4 to the surface of the Baltic Sea. We study the seasonality, regional distribution, relaxation, and interannual variability in this process. We use reanalysed wind and modelled sea surface temperature (SST) data in a newly established statistical upwelling detection method to identify major upwelling areas and time periods. Large upwelling-induced SST decrease and trace gas concentration increase are most frequently detected around August after a long period of thermal stratification, i.e. limited exchange between surface and underlying waters. We found that these upwelling events with large SST excursions shape local trace gas dynamics and often lead to near-linear relationships between increasing trace gas levels and decreasing temperature. Upwelling relaxation is mainly driven by mixing, modulated by air–sea gas exchange, and possibly primary production. Subsequent warming through air–sea heat exchange has the potential to enhance trace gas saturation. In 2015, quasi-continuous upwelling over several months led to weak summer stratification, which directly impacted the observed trace gas and SST dynamics in several upwelling-prone areas. Trend analysis is still prevented by the observed high variability, uncertainties from data coverage, and long water residence times of 10–30 years. We introduce an extrapolation method based on trace gas–SST relationships that allows us to estimate upwelling-induced trace gas fluxes in upwelling-affected regions. In general, the surface water reverses from CO2 sink to source, and CH4 outgassing is intensified as a consequence of upwelling. We conclude that SOOP data, especially when combined with other data sets, enable flux quantification and process studies addressing the process of upwelling on large spatial and temporal scales. [ABSTRACT FROM AUTHOR]

The Baltic Sea has a salinity gradient decreasing from fully marine (> 25) in the west to below 7 in the central Baltic Proper. Habitat-forming and ecologically dominant mytilid mussels exhibit decreasing growth when salinity < 11; however, the mechanisms underlying reduced calcification rates in dilute seawater are not fully understood. Both [HCO 3- ] and [Ca 2+ ] also decrease with salinity, challenging calcifying organisms through CaCO 3 undersaturation (Ω≤1) and unfavourable ratios of calcification substrates ([Ca 2+ ] and [HCO 3- ]) to the inhibitor (H +), expressed as the extended substrate–inhibitor ratio (ESIR). This study combined in situ monitoring of three southwest Baltic mussel reefs with two laboratory experiments to assess how various environmental conditions and isolated abiotic factors (salinity, [Ca 2+ ], [HCO 3- ] and pH) impact calcification in mytilid mussels along the Baltic salinity gradient. Laboratory experiments rearing juvenile Baltic Mytilus at a range of salinities (6, 11 and 16), HCO 3- concentrations (300–2100 µ mol kg -1) and Ca 2+ concentrations (0.5–4 mmol kg -1) reveal that as individual factors, low [HCO 3- ], pH and salinity cannot explain low calcification rates in the Baltic Sea. Calcification rates are impeded when Ωaragonite ≤ 1 or ESIR ≤ 0.7 primarily due to [Ca 2+ ] limitation which becomes relevant at a salinity of ca. 11 in the Baltic Sea. Field monitoring of carbonate chemistry and calcification rates suggest increased food availability may be able to mask the negative impacts of periodic sub-optimal carbonate chemistry, but not when seawater conditions are permanently adverse, as observed in two Baltic reefs at salinities < 11. Regional climate models predict a rapid desalination of the southwest and central Baltic over the next century and potentially a reduction in [Ca 2+ ] which may shift the distribution of marine calcifiers westward. It is therefore vital to understand the mechanisms by which the ionic composition of seawater impacts bivalve calcification for better predicting the future of benthic Baltic ecosystems. [ABSTRACT FROM AUTHOR]

The ocean and inland waters are two separate regimes, with concentrations in greenhouse gases differing on orders of magnitude between them. Together, they create the land–ocean aquatic continuum (LOAC), which comprises itself largely of areas with little to no data with regards to understanding the global carbon system. Reasons for this include remote and inaccessible sample locations, often tedious methods that require collection of water samples and subsequent analysis in the lab, and the complex interplay of biological, physical and chemical processes. This has led to large inconsistencies, increasing errors and has inevitably lead to potentially false upscaling. A set-up of multiple pre-existing oceanographic sensors allowing for highly detailed and accurate measurements was successfully deployed in oceanic to remote inland regions over extreme concentration ranges. The set-up consists of four sensors simultaneously measuring p CO 2 , p CH 4 (both flow-through, membrane-based non-dispersive infrared (NDIR) or tunable diode laser absorption spectroscopy (TDLAS) sensors), O 2 and a thermosalinograph at high resolution from the same water source. The flexibility of the system allowed for deployment from freshwater to open ocean conditions on varying vessel sizes, where we managed to capture day–night cycles, repeat transects and also delineate small-scale variability. Our work demonstrates the need for increased spatiotemporal monitoring and shows a way of homogenizing methods and data streams in the ocean and limnic realms. [ABSTRACT FROM AUTHOR]

We developed a simple method to refine existing open-ocean maps and extend them towards different coastal seas. Using a multi-linear regression we produced monthly maps of surface ocean f CO2 in the northern European coastal seas (the North Sea, the Baltic Sea, the Norwegian Coast and the Barents Sea) covering a time period from 1998 to 2016. A comparison with gridded Surface Ocean CO2 Atlas (SOCAT) v5 data revealed mean biases and standard deviations of 0 ± 26 µatm in the North Sea, 0 ± 16 µatm along the Norwegian Coast, 0 ± 19 µatm in the Barents Sea and 2 ± 42 µatm in the Baltic Sea. We used these maps to investigate trends in f CO2 , pH and air–sea CO2 flux. The surface ocean f CO2 trends are smaller than the atmospheric trend in most of the studied regions. The only exception to this is the western part of the North Sea, where sea surface f CO2 increases by 2 µatmyr-1 , which is similar to the atmospheric trend. The Baltic Sea does not show a significant trend. Here, the variability was much larger than the expected trends. Consistently, the pH trends were smaller than expected for an increase in f CO2 in pace with the rise of atmospheric CO2 levels. The calculated air–sea CO2 fluxes revealed that most regions were net sinks for CO2. Only the southern North Sea and the Baltic Sea emitted CO2 to the atmosphere. Especially in the northern regions the sink strength increased during the studied period. [ABSTRACT FROM AUTHOR]

The direction and magnitude of carbon dioxide exchange between the atmosphere and the sea is regulated by their difference in partial pressure of carbon dioxide (pCO2). Typically, observations of pCO2 are carried out by using research vessels and voluntary observing ships which cannot easily detect the diurnal cycle of pCO2 at a given location. This study evaluates the magnitude and driving processes of the diurnal cycle of pCO2 in a coastal region of the Baltic Sea during the different seasons.We present pCO2 data from July 2018-June 2019 carried out in the vicinity of the island of Utö in the Archipelago Sea and quantify the relevant physical, biological and chemical processes affecting pCO2. The highest monthly median diurnal pCO2 peak-to-peak amplitude (31 µatm) was observed in August. This high diurnal variation was found to be related predominantly to biological processes. The biological transformations of carbon generated a sinusoidal diurnal pCO2 variation, with a maximum in the morning and a minimum in the afternoon. Compared to the biological carbon transformations, the effect of air sea exchange of carbon dioxide and the effect of temperature changes on pCO2 are smaller, with their monthly median peak-to-peak amplitudes were up to 12 and 5 µatm, respectively. Single diurnal peak-to-peak amplitudes can be significantly larger (up to 500 µatm), during upwelling. If the net exchange of carbon dioxide between the sea and atmosphere on our study site and sampling period is calculated based on a data set that consists of only one measurement per day, the error in the budget depends on the sampling time and can be up to ±12 %. [ABSTRACT FROM AUTHOR]

The Baltic Sea has a salinity gradient decreasing from fully marine (> 25) in the West to below 7 in the Central Baltic Proper. Reef forming mytilid mussels exhibit decreasing growth when salinity <11, however the mechanisms underlying reduced calcification rates in dilute seawater are not fully understood. In fact, both [HCO3- ] and [Ca2+] also decrease with salinity, challenging calcifying organisms through CaCO3 undersaturation (Ω < 1) and unfavourable ratios of calcification substrate (Ca2+ and HCO3-) to inhibitor (H+). In this study we assessed the impact of isolated individual factors (salinity, [Ca2+], [HCO3"] and pH) on calcification and growth of mytilid mussel populations along the Baltic salinity gradient. Laboratory experiments rearing juvenile Baltic Mytilus at a range of salinities (6, 11 and 16), HCO3" concentrations (300-2100 μmol kg-1) and Ca2+ concentrations (0.5-4 mmol kg-1) were coupled with field monitoring in three Baltic mussel reefs. Results reveal that as individual factors, low [HCO3-], pH and salinity cannot explain low calcification rates in the Baltic Sea. Calcification rates are impeded when Ω^ω^ <1 or the substrate inhibitor ratio < 0.7, primarily due to [Ca2+] limitation which corresponds to a salinity of ca. 11. Increased food availability may be able to mask these negative impacts, but not when seawater conditions are permanently adverse, as observed in two Baltic reefs at salinities < 11. Future climatic models predict rapid desalination of the southwest and Central Baltic and potentially a reduction in [Ca2+] which may lead to a westward distribution shift of marine calcifiers. It is therefore vital to understand the mechanisms by which the ionic composition of seawater impacts bivalve calcification for better predicting the future of benthic Baltic ecosystems. [ABSTRACT FROM AUTHOR]

Comparatively the ocean and inland waters are two separate worlds, with concentrations in greenhouse gases having orders of magnitude in difference between the two. Together they create the Land-Ocean Aquatic Continuum (LOAC), which comprises itself largely of areas with little to no data in regards to understanding the global carbon system. Reasons for this include remote and inaccessible sample locations, often tedious methods that require collection of water samples and subsequent analysis in the lab, as well as the complex interplay of biological, physical and chemical processes. This has led to large inconsistencies, increasing errors and inevitably leading to potentially false upscaling. Here we demonstrate successful deployment in oceanic to remote inland regions, over extreme concentration ranges with multiple pre-existing oceanographic sensors combined set-up, allowing for highly detailed and accurate measurements. The set-up consists of sensors measuring pCO2, pCH4 (both flow-through, membrane-based NDIR or TDLAS sensors), O2, and a thermosalinograph at high-resolution from the same water source simultaneously. The flexibility of the system allowed deployment from freshwater to open ocean conditions on varying vessel sizes, where we managed to capture day-night cycles, repeat transects and also delineate small scale variability. Our work demonstrates the need for increased spatiotemporal monitoring, and shows a way to homogenize methods and data streams in the ocean and limnic realms. [ABSTRACT FROM AUTHOR]

The flow (flux) of climate-critical gases, such as carbon dioxide (CO2), between the ocean and the atmosphere is a fundamental component of our climate and an important driver of the biogeochemical systems within the oceans. Therefore, the accurate calculation of these air–sea gas fluxes is critical if we are to monitor the oceans and assess the impact that these gases are having on Earth's climate and ecosystems. FluxEngine is an open-source software toolbox that allows users to easily perform calculations of air–sea gas fluxes from model, in situ, and Earth observation data. The original development and verification of the toolbox was described in a previous publication. The toolbox has now been considerably updated to allow for its use as a Python library, to enable simplified installation, to ensure verification of its installation, to enable the handling of multiple sparingly soluble gases, and to enable the greatly expanded functionality for supporting in situ dataset analyses. This new functionality for supporting in situ analyses includes user-defined grids, time periods and projections, the ability to reanalyse in situ CO2 data to a common temperature dataset, and the ability to easily calculate gas fluxes using in situ data from drifting buoys, fixed moorings, and research cruises. Here we describe these new capabilities and demonstrate their application through illustrative case studies. The first case study demonstrates the workflow for accurately calculating CO2 fluxes using in situ data from four research cruises from the Surface Ocean CO2 ATlas (SOCAT) database. The second case study calculates air–sea CO2 fluxes using in situ data from a fixed monitoring station in the Baltic Sea. The third case study focuses on nitrous oxide (N2O) and, through a user-defined gas transfer parameterisation, identifies that biological surfactants in the North Atlantic could suppress individual N2O sea–air gas fluxes by up to 13 %. The fourth and final case study illustrates how a dissipation-based gas transfer parameterisation can be implemented and used. The updated version of the toolbox (version 3) and all documentation is now freely available. [ABSTRACT FROM AUTHOR]

Sediments play an important role in organic matter mineralisation and nutrient recycling, especially in shallow marine systems. Marine ecosystem models, however, often only include a coarse representation of processes beneath the sea floor. While these parameterisations may give a reasonable description of the present ecosystem state, they lack predictive capacity for possible future changes, which can only be obtained from mechanistic modelling. This paper describes an integrated benthic–pelagic ecosystem model developed for the German Exclusive Economic Zone (EEZ) in the western Baltic Sea. The model is a hybrid of two existing models: the pelagic part of the marine ecosystem model ERGOM and an early diagenetic model by Reed et al. (2011). The latter one was extended to include the carbon cycle, a determination of precipitation and dissolution reactions which accounts for salinity differences, an explicit description of the adsorption of clay minerals, and an alternative pyrite formation pathway. We present a one-dimensional application of the model to seven sites with different sediment types. The model was calibrated with observed pore water profiles and validated with results of sediment composition, bioturbation rates and bentho-pelagic fluxes gathered by in situ incubations of sediments (benthic chambers). The model results generally give a reasonable fit to the observations, even if some deviations are observed, e.g. an overestimation of sulfide concentrations in the sandy sediments. We therefore consider it a good first step towards a three-dimensional representation of sedimentary processes in coupled pelagic–benthic ecosystem models of the Baltic Sea. [ABSTRACT FROM AUTHOR]

Several methanogenic pathways in oxic surface waters were recently discovered, but their relevance in the natural environment is still unknown. Our study examines distinct methane (CH4) enrichments that repeatedly occur below the thermocline during the summer months in the central Baltic Sea. In agreement with previous studies in this region, we discovered differences in the methane distributions between the western and eastern Gotland Basin, pointing to in situ methane production below the thermocline in the latter (concentration of CH414.1±6.1 nM, δ13C CH4 -62.9 ‰). Through the use of a high-resolution hydrographic model of the Baltic Sea, we showed that methane below the thermocline can be transported by upwelling events towards the sea surface, thus contributing to the methane flux at the sea–air interface. To quantify zooplankton-associated methane production rates, we developed a sea-going methane stripping-oxidation line to determine methane release rates from copepods grazing on 14C -labelled phytoplankton. We found that (1) methane production increased with the number of copepods, (2) higher methane production rates were measured in incubations with Temora longicornis (125±49 fmol methane copepod -1 d -1) than in incubations with Acartia spp. (84±19 fmol CH4 copepod -1 d -1) dominated zooplankton communities, and (3) methane was only produced on a Rhodomonas sp. diet, and not on a cyanobacteria diet. Furthermore, copepod-specific methane production rates increased with incubation time. The latter finding suggests that methanogenic substrates for water-dwelling microbes are released by cell disruption during feeding, defecation, or diffusion from fecal pellets. In the field, particularly high methane concentrations coincided with stations showing a high abundance of DMSP/DMSO-rich Dinophyceae. Lipid biomarkers extracted from phytoplankton- and copepod-rich samples revealed that Dinophyceae are a major food source of the T. longicornis dominated zooplankton community, supporting the proposed link between copepod grazing, DMSP/DMSO release, and the build-up of subthermocline methane enrichments in the central Baltic Sea. [ABSTRACT FROM AUTHOR]

The rewetting of drained peatlands alters peat geochemistry and often leads to sustained elevated methane emission. Although this methane is produced entirely by microbial activity, the distribution and abundance of methanecycling microbes in rewetted peatlands, especially in fens, is rarely described. In this study, we compare the community composition and abundance of methane-cycling microbes in relation to peat porewater geochemistry in two rewetted fens in northeastern Germany, a coastal brackish fen and a freshwater riparian fen, with known high methane fluxes. We utilized 16S rRNA high-throughput sequencing and quantitative polymerase chain reaction (qPCR) on 16S rRNA, mcrA, and pmoA genes to determine microbial community composition and the abundance of total bacteria, methanogens, and methanotrophs. Electrical conductivity (EC) was more than 3 times higher in the coastal fen than in the riparian fen, averaging 5.3 and 1.5mScm-1, respectively. Porewater concentrations of terminal electron acceptors (TEAs) varied within and among the fens. This was also reflected in similarly high intra- and inter-site varia-tions of microbial community composition. Despite these differences in environmental conditions and electron acceptor availability, we found a low abundance of methanotrophs and a high abundance of methanogens, represented in particular by Methanosaetaceae, in both fens. This suggests that rapid (re)establishment of methanogens and slow (re)establishment of methanotrophs contributes to prolonged increased methane emissions following rewetting. [ABSTRACT FROM AUTHOR]

Several methanogenic pathways in oxic surface waters were recently discovered, but their relevance in the natural environment is still unknown. Our study examines distinct methane enrichments that repeatedly occur below the thermocline during the summer months in the central Baltic Sea. In agreement with previous studies in this region, we discovered differences in the methane distributions between the Western and Eastern Gotland Basin, pointing to in situ methane production below the thermocline in the latter (conc. CH4 14.1 ± 6.1 nM, δ13C CH4 -62.9 ‰). Through the use of a high resolution hydrographic model of the Baltic Sea, we showed that methane below the thermocline can be transported by upwelling events towards the sea surface thus contributing to the methane flux at the sea/air interface. To quantify zooplankton-associated methane production rates, we developed a sea-going methane stripping-oxidation line to determine methane release rates from copepods grazing on 14C-labelled phytoplankton. We found that: (1) methane production increased with the number of copepods, (2) higher methane production rates were measured in incubations with Temora longicornis (125 ± 49 fmol methane copepod-1 d-1) than incubations with Acartia spp. (84 ± 19 fmol CH4 copepod-1 d-1) dominated zooplankton communities, and (3) methane was only produced on a Rhodomonas sp. diet, but not on a cyanobacteria diet. Furthermore, copepod-specific methane production rates increased with incubation time. The latter finding suggests that methanogenic substrates for water-dwelling microbes are released by cell disruption during feeding, defecation, or diffusion from fecal pellets. In the field, particularly high methane concentrations coincided with stations showing a high abundance of DMSP-rich Dinophyceae. Lipid biomarkers extracted from phytoplankton- and copepod-rich samples revealed that Dinophyceae are a major food source of the T. longicornis dominated zooplankton community, supporting the proposed link between copepod grazing, DMSP release, and the buildup of subthermocline methane enrichments in the central Baltic Sea. [ABSTRACT FROM AUTHOR]

The rewetting of drained peatlands alters peat geochemistry and often leads to sustained elevated methane emission. Although this methane is produced entirely by microbial activity, the distribution and abundance of methane-cycling microbes in rewetted peatlands, especially in fens, is rarely described. In this study, we compare the community composition and abundance of methane-cycling microbes in relation to peat porewater geochemistry in two rewetted fens in northeastern Germany, a coastal brackish fen and a freshwater riparian fen, with known high methane fluxes. We utilized 16S rDNA high-throughput sequencing and quantitative polymerase chain reaction on 16S rDNA, mcrA, and pmoA genes to determine microbial community composition and the abundance of total bacteria, methanogens, and methanotrophs. Electrical conductivity was more than three times higher in the coastal fen than in the riparian fen, averaging 5.3 and 1.5 mS cm-1, respectively. Porewater concentrations of terminal electron acceptors varied within and among the fens. This was also reflected in similarly high intra- and inter-site variations of microbial community composition. Despite these differences in environmental conditions and electron acceptor availability, we found a low abundance of methanotrophs and a high abundance of methanogens, represented in particular by Methanosaetaceae, in both fens. This suggests that rapid re/establishment of methanogens and slow re/establishment of methanotrophs contributes to prolonged increased methane emissions following rewetting. [ABSTRACT FROM AUTHOR]

Abstract: Spectrophotometric pH measurements were first introduced for oceanic environments and they facilitated the determination of the marine CO2 system, including the direct observation of Ocean Acidification. Extended characterizations of the indicator dye m‐Cresol purple over the past two decades enabled the application of this method to natural waters ranging from brines to freshwaters. However, the required determination of the dye's dissociation constants and absorbance properties were exclusively performed in buffer solutions prepared with artificial seawater. Potential perturbations by substances that occur in natural waters, but are not included in the buffer solutions, have never been tested. Therefore, we studied the impact of elevated amounts of dissolved organic matter (DOM) and hydrogen sulfide (H2S) on spectrophotometric pH measurements. We did not observe an impact on spectrophotometric pH measurements by H2S concentrations up to 400 μmol kg−1, which reflect high levels such as those reported from the Black Sea. Likewise, natural DOM did not interfere with the spectrophotometric measurements at concentrations typical for oceanic environments and large estuarine systems. However, strongly colored river waters can cause spectral disturbances resulting in calculated pH values that are up to tenths of pH units too low. To circumvent such disturbances, we recommend using intense light sources, a shorter cuvette length or spectrophotometrically calibrated glass electrodes when performing spectrophotometric measurements under critical conditions. [ABSTRACT FROM AUTHOR]

Anthropogenic CO2 emissions currently decrease open ocean pH, but on multi-millennial time scales intensified continental weathering is expected to contribute to increasing oceanic alkalinity ( AT) and thus mitigate the acidification signal. The Baltic Sea is an ideal study site for such AT dynamics, due to its direct link to terrestrial processes, short water residence time and long history of AT measurements dating back to the early 20th century. We compiled an extensive AT data set that revealed the highest data quality and coverage for the past two decades. Within that period, surface water AT levels increased throughout the Baltic Sea. The rates of change were highest in the low-saline, northern areas and decreased gradually toward constant levels in the North Sea. The AT increase observed in the Central Baltic Sea (+3.4 µmol kg−1 yr−1) and the Gulf of Bothnia (+7 µmol kg−1 yr−1) has compensated CO2-induced acidification by almost 50% and 100%, respectively. Further, the AT trends enhanced the CO2 storage capacity and stabilized the CaCO3 saturation state of the Baltic Sea over the past two decades. We discuss the attribution of the AT trends to potential changes in precipitation patterns, continental weathering driven by acidic rain and increasing atmospheric CO2, agricultural liming and internal AT sources. [ABSTRACT FROM AUTHOR]

Cold seep ecosystems can support enormous biomasses of free-living and symbiotic chemoautotrophic organisms that get their energy from the oxidation of methane or sulfide. Most of this biomass derives from animals that are associated with bacterial symbionts, which are able to metabolize the chemical resources provided by the seeping fluids. Often these systems also harbor dense accumulations of non-symbiotic megafauna, which can be relevant in exporting chemosynthetically fixed carbon from seeps to the surrounding deep sea. Here we investigated the carbon sources of lithodid crabs (Paralomis sp.) feeding on thiotrophic bacterial mats at an active mud volcano at the Costa Rica subduction zone. To evaluate the dietary carbon source of the crabs, we compared the microbial community in stomach contents with surface sediments covered by microbial mats. The stomach content analyses revealed a dominance of epsilonproteobacterial 16S rRNA gene sequences related to the free-living and epibiotic sulfur oxidiser Sulfurovum sp. We also found Sulfurovum sp. as well as members of the genera Arcobacter and Sulfurimonas in mat-covered surface sediments where Epsilonproteobacteria were highly abundant constituting 10% of total cells. Furthermore, we detected substantial amounts of bacterial fatty acids such as i-C15∶0 and C17∶1ω6c with stable carbon isotope compositions as low as −53‰ in the stomach and muscle tissue. These results indicate that the white microbial mats at Mound 12 are comprised of Epsilonproteobacteria and that microbial mat-derived carbon provides an important contribution to the crab's nutrition. In addition, our lipid analyses also suggest that the crabs feed on other 13C-depleted organic matter sources, possibly symbiotic megafauna as well as on photosynthetic carbon sources such as sedimentary detritus. [ABSTRACT FROM AUTHOR]

Sediment-hosting hydrothermal systems in the Okinawa Trough maintain a large amount of liquid, supercritical and hydrate phases of CO2 in the seabed. The emission of CO2 may critically impact the geochemical, geophysical and ecological characteristics of the deep-sea sedimentary environment. So far it remains unclear whether microbial communities that have been detected in such high-CO2 and low-pH habitats are metabolically active, and if so, what the biogeochemical and ecological consequences for the environment are. In this study, RNA-based molecular approaches and radioactive tracer-based respiration rate assays were combined to study the density, diversity and metabolic activity of microbial communities in CO2-seep sediment at the Yonaguni Knoll IV hydrothermal field of the southern Okinawa Trough. In general, the number of microbes decreased sharply with increasing sediment depth and CO2 concentration. Phylogenetic analyses of community structure using reverse-transcribed 16S ribosomal RNA showed that the active microbial community became less diverse with increasing sediment depth and CO2 concentration, indicating that microbial activity and community structure are sensitive to CO2 venting. Analyses of RNA-based pyrosequences and catalyzed reporter deposition-fluorescence in situ hybridization data revealed that members of the SEEP-SRB2 group within the Deltaproteobacteria and anaerobic methanotrophic archaea (ANME-2a and -2c) were confined to the top seafloor, and active archaea were not detected in deeper sediments (13-30 cm in depth) characterized by high CO2. Measurement of the potential sulfate reduction rate at pH conditions of 3-9 with and without methane in the headspace indicated that acidophilic sulfate reduction possibly occurs in the presence of methane, even at very low pH of 3. These results suggest that some members of the anaerobic methanotrophs and sulfate reducers can adapt to the CO2-seep sedimentary environment; however, CO2 and pH in the deep-sea sediment were found to severely impact the activity and structure of the microbial community. [ABSTRACT FROM AUTHOR]

Within the German integrated project SUGAR, aiming for the development of new technologies for the exploration and exploitation of submarine gas hydrates, the option of gas transport by gas hydrate pellets has been comprehensively re-investigated. A series of pVT dissociation experiments, combined with analytical tools such as x-ray diffraction and cryo-SEM, were used to gather an additional level of understanding on effects controlling ice formation. Based on these new findings and the accessible literature, knowns and unknowns of the self-preservation effect important for the technology are summarized. A conceptual process design for methane hydrate production and pelletisation has been developed. For the major steps identified, comprising (i) hydrate formation; (ii) dewatering; (iii) pelletisation; (iv) pellet cooling; and (v) pressure relief, available technologies have been evaluated, and modifications and amendments included where needed. A hydrate carrier has been designed, featuring amongst other technical solutions a pivoted cargo system with the potential to mitigate sintering, an actively cooled containment and cargo distribution system, and a dual fuel engine allowing the use of the boil-off gas. The design was constrained by the properties of gas hydrate pellets, the expected operation on continental slopes in areas with rough seas, a scenario-defined loading capacity of 20,000 m3 methane hydrate pellets, and safety as well as environmental considerations. A risk analysis for the transport at sea has been carried out in this early stage of development, and the safety level of the new concept was compared to the safety level of other ship types with similar scopes, i.e., LNG carriers and crude oil tankers. Based on the results of the technological part of this study, and with best knowledge available on the alternative technologies, i.e., pipeline, LNG and CNG transportation, an evaluation of the economic competitiveness of the methane hydrate transport technology has been performed. The analysis considers capital investment as well as operational costs and comprises a wide set of scenarios with production rates from 20 to 800 103 Nm3.h-1 and transport distances from 200 to 10,000 km. In contrast to previous studies, the model calculations in this study reveal no economic benefit of methane hydrate transportation versus competing technologies. [ABSTRACT FROM AUTHOR]

In a laboratory-based test series, seven experiments along a simulated Pacific hydrotherm at 152°W, 40°N were carried out to measure the rise velocities of liquefied CO2 droplets under (clathrate) hydrate forming conditions. The impact of a hydrate skin on the rising behavior was investigated by comparing the results with those from outside the field of hydrate stability at matching buoyancy. A thermostatted high-pressure tank was used to establish conditions along the natural oceanic hydrotherm. Under P-/T-conditions allowing hydrate formation, the majority of the droplets quickly developed a skin of CO2 hydrate upon contact with seawater. Rise rates of these droplets support the parametrisation by Chen et al. (Tel/us 2003, 55B, 723-730), which is based on empirical equations developed to match momentum of hydrate covered, deformed droplets. Our data do not support other parametrisation recently suggested in the literature. In the experiments from 5.7 MPa, 4.8 °C to 11.9 MPa, 2.8°C positive and negative deviations from predicted rise rates occurred, which we propose were caused by lacking hydrate formation and reflect intact droplet surface mobility and droplet shape oscillations, respectively. This interpretation is supported by rise rates measured at P-/T- conditions outside the hydrate stability field at the same liquid CO2- seawater density difference (Δp) matching the rise rates of the deviating data within the stability field. The results also show that droplets without a hydrate skin ascend up to 50% faster than equally buoyant droplets with a hydrate skin. This feature has a significant impact on the vertical pattern of dissolution of liquid CO2 released into the ocean. The experiments and data presented considerably reduce the uncertainty of the parametrisation of CO2 droplet rise velocity, which in the past emerged partly from their scarcity and contradictions in constraints of earlier experiments. [ABSTRACT FROM AUTHOR]