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In a laboratory-based test series, seven experiments along a simulated Pacific hydrotherm at 152 degrees W, 40 degrees 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 parametrization by Chen et al. (Tellus 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 parametrizations recently suggested in the literature. In the experiments from 5.7 MPa, 4.8 oC to 11.9 MPa, 2.8 degrees 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 atthe same liquid CO2-seawater density difference (delta rho) 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 parametrization of CO2 droplet rise velocity, which in the past emerged partly from their scarcity and contradictions in constraints of earlier experiments.

Direct oceanic disposal of fossil fuel CO2 is being considered as a possible means to moderate the growth rate of CO2 in the atmosphere. We have measured the rise rate and dissolution rate of freely released CO2 droplets in the open ocean to provide fundamental data for carbon sequestration options. A small amount of liquid CO2 was released at 800 m, at 4.4 degrees C, and the rising droplet stream was imaged with a HDTV camera carried on a remotely operated vehicle. The initial rise rate for 0.9-cm diameter droplets was 10 cm/s at 800 m, and the dissolution rate was 3.0 micromol cm(-2) s(-1). While visual contact was maintained for 1 h and over a 400 m ascent, 90% of the mass loss occurred within 30 min over a 200 m ascent above the release point. Images of droplets crossing the liquid-gas-phase boundary showed formation of a gas head, pinching off of a liquid tail, and rapid gas bubble separation and dissolution.

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 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]

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 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]

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 of 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. Strong upwelling events 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 strong 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 and 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. 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 upwelling is an important and relevant process controlling trace gas dynamics in near-coastal environments in the Baltic Sea, and that SOOP data, especially when combined with other data sets, enable flux quantification and process studies on larger spatial and temporal scales. [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]

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]

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]

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 μm/s and between 9.0 and 10.6 · 10−2 μm/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ± 0.5 mmol CO2/m2s and 0.37 ± 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. [Copyright &y& Elsevier]

A fully automated measurement system for recording of the surface water CO 2 partial pressure, pCO 2 , was deployed on VOS (voluntary observation ship) “Finnpartner/Finnmaid” in 2003. Since 2009, an amendment of the system also allows for the continuous detection of the surface water partial pressure of methane, pCH 4 . The ship commutes regularly at 2–3 day intervals between the Gulf of Finland (Helsinki) and the Mecklenburg Bight (Lübeck) in the southwest of the Baltic Sea. The pCO 2 data in the central Gotland Sea showed a pronounced seasonality that was mainly controlled by the biological production and decomposition of organic matter in combination with stratification/mixing of the water column. CO 2 consumption in spring/summer caused pCO 2 that were by up to 300 μatm below the atmospheric level. In contrast, the pCO 2 exceeded the atmospheric values during autumn/winter when deep mixing transports CO 2 -enriched water to the surface. To identify the central Baltic Sea as a sink or source for atmospheric CO 2 , an air–sea CO 2 gas exchange balance was established for three selected years (2005, 2008 and 2009). During each year the surface water acted as a net sink for atmospheric CO 2 with uptake rates ranging between 0.60 and 0.89 mol m − 2 yr − 1 . The rates correspond approximately to the enhanced carbon burial in sediments during the last century and suggest a link between eutrophication and CO 2 uptake. The data of the surface methane concentration are used to focus on situations were extraordinarily high methane concentrations were observed. Temporary methane peaks were observed south of the Island of Gotland, which could clearly be attributed to frequent upwelling events. Between spring 2012 and 2013, Finnmaid went at a few occasions to St. Petersburg in the east of the Gulf of Finland. Methane concentration of up to 130 nmol L − 1 where found close to the River Neva mouth but decreased rapidly to the west. The plume of methane-enriched waters was observed farthest to the west during the winter period. This was attributed to air–sea gas exchange that was most effective during summer but inhibited during winter because of the ice coverage. [ABSTRACT FROM AUTHOR]

Abstract: The surface water CO2 partial pressure, pCO2, was measured during nine cruises in the Gulf of Bothnia at different seasons between 1999 and 2010, with continuous recording during most of the cruises using a bubble-type equilibrator and infrared CO2 detection. The data were used to construct the mean seasonality of the pCO2 in characteristic sub-areas. The low pCO2 measured in spring/summer and the high pCO2 measured in fall/winter indicated that biological production, stratification, mineralization and deep mixing, controlled the seasonal pCO2 cycle in both the Bothnian Bay and the Bothnian Sea. To calculate CO2 exchange with the atmosphere, the gas exchange transfer velocity was computed as a function of wind speed according to . Based on the mean seasonal pCO2 distribution, CO2 fluxes were calculated, taking into account the differing wind conditions and the varying ice coverage. The resulting mean annual flux of +140mmolm−2 yr−1 in the Bothnian Bay indicated that this area is a weak source for atmospheric CO2. In contrast, the Bothnian Sea was found to act as a sink for atmospheric CO2, with a mean flux of −730mmolm−2 yr−1. [Copyright &y& Elsevier]

Air–sea gas fluxes are commonly estimated using wind-based parametrizations of the gas transfer velocity. However, neglecting gas exchange forcing mechanisms – other than wind speed – may lead to large uncertainties in the flux estimates and the carbon budgets, in particular, in heterogeneous environments such as marginal seas and coastal areas. In this study we investigated the impact of including relevant processes to the air–sea CO 2 flux parametrization for the Baltic Sea. We used six parametrizations of the gas transfer velocity to evaluate the effect of precipitation, water-side convection, and surfactants on the net CO 2 flux at regional and sub-regional scale. The differences both in the mean CO 2 fluxes and the integrated net fluxes were small between the different cases. However, the implications on the seasonal variability were shown to be significant. The inter-annual and spatial variability were also found to be associated with the forcing mechanisms evaluated in the study. In addition to wind, water-side convection was the most relevant parameter controlling the air–sea gas exchange at seasonal and inter-annual scales. The effect of precipitation and surfactants seemed negligible in terms of the inter-annual variability. The effect of water-side convection and surfactants resulted in a reduction of the downward fluxes, while precipitation was the only parameter that resulted in an enhancement of the net uptake in the Baltic Sea. • Variability of air–sea CO 2 fluxes is modulated by mechanisms other than wind speed. • Gas transfer velocity parameterizations are not adequate for coastal/marginal seas. • Water-side convection enhances air–sea fluxes during winter in the Baltic Sea. • Surfactants suppress CO 2 downward fluxes during summer. • Precipitation represents a net increase of the carbon uptake. [ABSTRACT FROM AUTHOR]

A letter to the editor is presented in response to the article "Fate of Rising Carbon Dioxide Droplets in Seawater," by Y. Zhang in the December 2005 issue.