An approach to estimation of near-surface turbulence and CO2 transfer velocity from remote sensing data

The air–sea CO₂ exchange is primarily determined by the boundary-layer processes in the near-surface layer of the ocean since it is a water-side limited gas. As a consequence, the interfacial component of the CO₂ transfer velocity can be linked to parameters of turbulence in the near-surface layer of the ocean. The development of remote sensing techniques provides a possibility to quantify the dissipation of the turbulent kinetic energy in the near-surface layer of the ocean and the air–sea CO₂ transfer velocity on a global scale. In this work, the dissipation rate of the turbulent kinetic energy in the near-surface layer of the ocean and its patchiness has been linked to the air–sea CO₂ transfer velocity with a boundary-layer type model. Field observations of upper ocean turbulence, laboratory studies, and the direct CO₂ flux measurements are used to validate the model. The model is then forced with the TOPEX POSEIDON wind speed and significant wave height to demonstrate its applicability for estimating the distribution of the near-surface turbulence dissipation rate and gas transfer velocity for an extended (decadal) time period. A future version of this remote sensing algorithm will incorporate directional wind/wave data being available from QUIKSCAT, a now-cast wave model, and satellite heat fluxes. The inclusion of microwave imagery from the Special Sensor Microwave Imager (SSM/I) and the Synthetic Aperture Radar (SAR) will provide additional information on the fractional whitecap coverage and sea surface turbulence patchiness.     

Parameterization of air–sea gas fluxes at extreme wind speeds

Air–sea flux measurements of O₂ and N₂ obtained during Hurricane Frances in September 2004 [D'Asaro, E. A. and McNeil, C. L., 2006. Measurements of air–sea gas exchange at extreme wind speeds. Journal Marine Systems, this edition.] using air-deployed neutrally buoyant floats reveal the first evidence of a new regime of air–sea gas transfer occurring at wind speeds in excess of 35 m s^− 1. In this regime, plumes of bubbles 1 mm and smaller in size are transported down from near the surface of the ocean to greater depths by vertical turbulent currents with speeds up to 20−30 cm s^− 1. These bubble plumes mostly dissolve before reaching a depth of approximately 20 m as a result of hydrostatic compression. Injection of air into the ocean by this mechanism results in the invasion of gases in proportion to their tropospheric molar gas ratios, and further supersaturation of less soluble gases. A new formulation for air–sea fluxes of weakly soluble gases as a function of wind speed is proposed to extend existing formulations [Woolf, D.K, 1997. Bubbles and their role in gas exchange. In: Liss, P.S., and Duce, R.A., (Eds.), The Sea Surface and Global Change. Cambridge University Press, Cambridge, UK, pp. 173–205.] to span the entire natural range of wind speeds over the open ocean, which includes hurricanes. The new formulation has separate contributions to air–sea gas flux from: 1) non-supersaturating near-surface equilibration processes, which include direct transfer associated with the air–sea interface and ventilation associated with surface wave breaking; 2) partial dissolution of bubbles smaller than 1 mm that mix into the ocean via turbulence; and 3) complete dissolution of bubbles of up to 1 mm in size via subduction of bubble plumes. The model can be simplified by combining “surface equilibration” terms that allow exchange of gases into and out of the ocean, and “gas injection” terms that only allow gas to enter the ocean. The model was tested against the Hurricane Frances data set. Although all the model parameters cannot be determined uniquely, some features are clear. The fluxes due to the surface equilibration terms, estimated both from data and from model inversions, increase rapidly at high wind speed but are still far below those predicted using the cubic parameterization of Wanninkhof and McGillis [Wannikhof, R. and McGillis, W.R., 1999. A cubic relationship between air–sea CO₂ exchange and wind speed. Geophysical Research Letters, 26:1889–1892.] at high wind speed. The fluxes due to gas injection terms increase with wind speed even more rapidly, causing bubble injection to dominate at the highest wind speeds.     

Air–sea gas exchange at extreme wind speeds measured by autonomous oceanographic floats

Measurements of the air–sea fluxes of N₂ and O₂ were made in winds of 15–57 m s^− 1 beneath Hurricane Frances using two types of air-deployed neutrally buoyant and profiling underwater floats. Two “Lagrangian floats” measured O₂ and total gas tension (GT) in pre-storm and post-storm profiles and in the actively turbulent mixed layer during the storm. A single “EM-APEX float” profiled continuously from 30 to 200 m before, during and after the storm. All floats measured temperature and salinity. N₂ concentrations were computed from GT and O₂ after correcting for instrumental effects. Gas fluxes were computed by three methods. First, a one-dimensional mixed layer budget diagnosed the changes in mixed layer concentrations given the pre-storm profile and a time varying mixed layer depth. This model was calibrated using temperature and salinity data. The difference between the predicted mixed layer concentrations of O₂ and N₂ and those measured was attributed to air–sea gas fluxes F_BO and F_BN. Second, the covariance flux F_CO(z) = wO₂′(z) was computed, where w is the vertical motion of the water-following Lagrangian floats, O₂′ is a high-pass filtered O₂ concentration and (z) is an average over covariance pairs as a function of depth. The profile F_CO(z) was extrapolated to the surface to yield the surface O₂ flux F_CO(0). Third, a deficit of O₂ was found in the upper few meters of the ocean at the height of the storm. A flux F_SO, moving O₂ out of the ocean, was calculated by dividing this deficit by the residence time of the water in this layer, inferred from the Lagrangian floats. The three methods gave generally consistent results. At the highest winds, gas transfer is dominated by bubbles created by surface wave breaking, injected into the ocean by large-scale turbulent eddies and dissolving near 10-m depth. This conclusion is supported by observations of fluxes into the ocean despite its supersaturation; by the molar flux ratio F_BO/F_BN, which is closer to that of air rather than that appropriate for Schmidt number scaling; by O₂ increases at about 10-m depth along the water trajectories accompanied by a reduction in void fraction as measured by conductivity; and from the profile of F_CO(z), which peaks near 10 m instead of at the surface.At the highest winds O₂ and N₂ are injected into the ocean by bubbles dissolving at depth. This, plus entrainment of gas-rich water from below, supersaturates the mixed layer causing gas to flux out of the near-surface ocean. A net influx of gas results from the balance of these two competing processes. At lower speeds, the total gas fluxes, F_BO, F_BN and F_CO(0), are out of the ocean and downgradient.     

Surface CO2 measurements in the English Channel and Southern Bight of North Sea using voluntary observing ships

Ships of opportunity have been used to investigate ocean–atmosphere CO₂ fluxes in the English Channel and Southern Bight of the North Sea. Continuous underway measurements of the fugacity of seawater carbon dioxide (fCO₂^sw), chlorophyll, temperature and salinity have been performed along 26 transects during the spring and autumn periods. The spatial fCO₂^sw distribution along the Channel and Southern Bight is modulated by the photosynthetic activity, temperature changes and water mixing between inputs from the North Atlantic Ocean and riverine discharges. The seasonal variability of fCO₂^sw is assessed and discussed in terms of the biology and temperature effects, these having similar impacts. The variation of fCO₂^sw shows similar interannual patterns, with lower values in spring. The annual average of air–sea CO₂ fluxes places the English Channel as neutral area of CO₂ uptake. The spring and autumn data allow differentiating between distal and proximal continental areas. The Southern Bight shows a tendency towards net CO₂ uptake on the distal continental shelf, whereas the Scheldt and Thames Plumes show a CO₂ source behaviour on the proximal continental shelves.     

Evaluating transfer velocity-wind speed relationship using a long-term series of direct eddy correlation CO2 flux measurements

Long-term observations of the marine atmospheric boundary layer were performed by an eddy correlation system, which was set-up on a platform in the Baltic Sea. In this experiment the three-dimensional wind vector and the turbulent fluxes of momentum, sensible and latent heat and CO₂ were measured for one and a half years. Simultaneously the CO₂ partial pressure p_CO2 in surface water was measured by a submersible autonomous moored instrument for CO₂ at the platform in 7-m depth. The high-resolution eddy correlation measurements of the atmospheric CO₂ flux F_CO2, together with the measurements of the CO₂ partial pressure differences between air and sea Δp_CO2 led to a long-term data set which provided the possibility to investigate the parameterization of the CO₂ transfer velocity k as a function of 10-m wind speed u in a statistical manner. From half-hour mean CO₂ fluxes and CO₂ partial pressure differences, k was calculated using k = F_CO2 / (K₀Δp_CO2), with K₀ the CO₂ solubility. The half-hour mean data points, used for the determination of the k–u parameterization, show large scatter. However, assuming a linear, quadratic dependency the analysis yields: k₆₆₀ = 0.365u² + 0.46u (k at 20 °C and salinity 35 psu) with a correlation coefficient of r² = 0.81. The large scatter indicates that the kinetics of the air–sea CO₂ transfer velocity is not only a function of the wind speed alone, but might also be controlled by other environmental parameters and mechanisms, such as sea state and surface coverage with surfactants.     

Air–sea CO2 fluxes in the Caribbean Sea from 2002–2004

Air–sea fluxes in the Caribbean Sea are presented based on measurements of partial pressure of CO₂ in surface seawater, pCO_2sw, from an automated system onboard the cruise ship Explorer of the Seas for 2002 through 2004. The pCO_2sw values are used to develop algorithms of pCO_2sw based on sea surface temperature (SST) and position. The algorithms are applied to assimilated SST data and remotely sensed winds on a 1° by 1° grid to estimate the fluxes on weekly timescales in the region. The positive relationship between pCO_2sw and SST is lower than the isochemical trend suggesting counteracting effects from biological processes. The relationship varies systematically with location with a stronger dependence further south. Furthermore, the southern area shows significantly lower pCO_2sw in the fall compared to the spring at the same SST, which is attributed to differences in salinity. The annual algorithms for the entire region show a slight trend between 2002 and 2004 suggesting an increase of pCO_2sw over time. This is in accord with the increasing pCO_2sw due the invasion of anthropogenic CO₂. The annual fluxes of CO₂ yield a net invasion of CO₂ to the ocean that ranges from − 0.04 to − 1.2 mol m^− 2 year^− 1 over the 3 years. There is a seasonal reversal in the direction of the flux with CO₂ entering into the ocean during the winter and an evasion during the summer. Year-to-year differences in flux are primarily caused by temperature anomalies in the late winter and spring period resulting in changes in invasion during these seasons. An analysis of pCO_2sw before and after hurricane Frances (September 4–6, 2004), and wind records during the storm suggest a large local enhancement of the flux but minimal influence on annual fluxes in the region.     

Measurement of air–water CO2 transfer at four coastal sites using a chamber method

We measured the air–water CO₂ flux in four coastal regions (two coral reefs, one estuary, and one coastal brackish lake) using a chamber method, which has the highest spatial resolution of the methods available for measuring coastal air–water gas flux. Some of the measurements were considerably higher than expected from reported wind-dependent relationships. The average k₆₀₀ values for Shiraho Reef, Fukido Reef, Fukido River, and Lake Nakaumi were 1.5 ± 0.6, 3.2 ± 0.3, 0.69 ± 0.26, and 2.2 ± 0.9 (mean ± S.D.) times larger than the wind-dependent relationships. Results were compared with current-dependent relationships and vertical turbulence intensity (VTI). VTI is an index of water-surface stirring and is calculated from near-surface vertical velocity. Although some measurements from the reefs and river closely matched those expected from wind-dependent relationships, others were considerably higher. All data were correlated with VTI and were qualitatively explained by bottom macro-roughness enhancement. In Lake Nakaumi, results tended to differ from the wind-dependent relationships, and the difference between the measured and expected gas-transfer velocity was correlated with biological DO changes and/or the intensity of density stratification. We found these factors to have important effects on coastal gas flux. In addition, the chamber method was an effective tool for evaluating coastal gas flux.     

Gas transfer velocities of CO2 and CH4 in a tropical reservoir and its river downstream

We have measured simultaneously the methane (CH₄) and carbon dioxide (CO₂) surface concentrations and water–air fluxes by floating chambers (FC) in the Petit-Saut Reservoir (French Guiana) and its tidal river (Sinnamary River) downstream of the dam, during the two field experiments in wet (May 2003) and dry season (December 2003). The eddy covariance (EC) technique was also used for CO₂ fluxes on the lake. The comparison of fluxes obtained by FC and EC showed little discrepancies mainly due to differences in measurements durations which resulted in different average wind speeds. When comparing the gas transfer velocity (k₆₀₀) for a given wind speed, both methods gave similar results. On the lake and excluding rainy events, we obtained an exponential relationship between k₆₀₀ and U₁₀, with a significant intercept at 1.7 cm h^− 1, probably due to thermal effects. Gas transfer velocity was also positively related to rainfall rates reaching 26.5 cm h⁻¹ for a rainfall rate of 36 mm h^− 1. During a 24-h experiment in dry season, rainfall accounted for as much as 25% of the k₆₀₀. In the river downstream of the dam, k₆₀₀ values were 3 to 4 times higher than on the lake, and followed a linear relationship with U₁₀.     

Seasonal study of dissolved CH4, CO2 and N2O in a shallow tidal system of the bay of Cádiz (SW Spain)

During 2004, 10 samplings were performed in order to measure dissolved methane (CH₄), carbon dioxide (CO₂) and nitrous oxide (N₂O) in the surface waters of Río San Pedro, a tidal creek in the salt marsh area of the Bay of Cádiz (SW Spain). The inner partvs of the creek is affected by the inputs coming from an intensive fish farm and the drainage of an extensive salt marsh area.Dissolved CH₄, CO₂ and N₂O concentrations ranged from 11 to 88 nM, 36 to 108 μM and 14 to 50 nM, respectively. Surface waters were in all cases oversaturated with respect to the atmosphere, reaching values of up to 5000% for CH₄, 1240% for CO₂ and 840% for N₂O. Dissolved CH₄, CO₂ and N₂O showed a significant tidal and seasonal variability. Over a tidal cycle, concentrations were always highest during low tide, which points to the influence of the inputs from the fish farm effluent and the drainage of the adjacent salt marsh area, as well as in situ production within the system. Dissolved CH₄, CO₂ and N₂O seasonal patterns were similar and showed maximum concentrations in summer conditions. Using four different parameterizations to calculate the gas transfer coefficients [Liss, P.S. and Merlivat, L., 1986. Air-sea exchange rates: introduction and synthesis. In P. Buat-Ménard (Ed.), The Role of Air-Sea Exchanges in Geochemical Cycling. Reidel, Dordrecht, The Netherlands, p. 113–127.; Clark, J.F., Schlosser, P., Simpson, H.J., Stute, M., Wanninkhof, R., and Ho, D.T., 1995. Relationship between gas transfer velocities and wind speeds in the tidal Hudson River determined by the dual tracer technique. In: B. Jähne and E. Monahan (Eds.), Air-Water Gas Transfer: AEON Verlag and Studio, Hanau, Germany, pp. 785–800.; Carini, S., Weston, N., Hopkinson, G., Tucker, J., Giblin, A. and Vallino, J., 1996. Gas exchanges rates in the Parker River estuary, Massachusetts. Biol. Bull., 191: 333–334.; Kremer, J.N., Reischauer, A. and D'Avanzo, C., 2003. Estuary-specific variation in the air-water gas exchange coefficient for oxygen. Estuaries, 26: 829–836.], the averaged air–water fluxes of CH₄, CO₂ and N₂O from the creek to the atmosphere ranged between 34 and 150 μmol CH₄ m^− 2 day^− 1, 73 and 177 mmol CO₂ m^− 2 day^− 1 and 24 and 62 μmol N₂O m⁻² day⁻¹, respectively.     

Application of new parameterizations of gas transfer velocity and their impact on regional and global marine CO2 budgets

One of the dominant sources of uncertainty in the calculation of air–sea flux of carbon dioxide on a global scale originates from the various parameterizations of the gas transfer velocity, k, that are in use. Whilst it is undisputed that most of these parameterizations have shortcomings and neglect processes which influence air–sea gas exchange and do not scale with wind speed alone, there is no general agreement about their relative accuracy.The most widely used parameterizations are based on non-linear functions of wind speed and, to a lesser extent, on sea surface temperature and salinity. Processes such as surface film damping and whitecapping are known to have an effect on air–sea exchange. More recently published parameterizations use friction velocity, sea surface roughness, and significant wave height. These new parameters can account to some extent for processes such as film damping and whitecapping and could potentially explain the spread of wind-speed based transfer velocities published in the literature.We combine some of the principles of two recently published k parameterizations [Glover, D.M., Frew, N.M., McCue, S.J. and Bock, E.J., 2002. A multiyear time series of global gas transfer velocity from the TOPEX dual frequency, normalized radar backscatter algorithm. In: Donelan, M.A., Drennan, W.M., Saltzman, E.S., and Wanninkhof, R. (Eds.), Gas Transfer at Water Surfaces, Geophys. Monograph 127. AGU,Washington, DC, 325–331; Woolf, D.K., 2005. Parameterization of gas transfer velocities and sea-state dependent wave breaking. Tellus, 57B: 87–94] to calculate k as the sum of a linear function of total mean square slope of the sea surface and a wave breaking parameter. This separates contributions from direct and bubble-mediated gas transfer as suggested by Woolf [Woolf, D.K., 2005. Parameterization of gas transfer velocities and sea-state dependent wave breaking. Tellus, 57B: 87–94] and allows us to quantify contributions from these two processes independently.We then apply our parameterization to a monthly TOPEX altimeter gridded 1.5° × 1.5° data set and compare our results to transfer velocities calculated using the popular wind-based k parameterizations by Wanninkhof [Wanninkhof, R., 1992. Relationship between wind speed and gas exchange over the ocean. J. Geophys. Res., 97: 7373–7382.] and Wanninkhof and McGillis [Wanninkhof, R. and McGillis, W., 1999. A cubic relationship between air−sea CO2 exchange and wind speed. Geophys. Res. Lett., 26(13): 1889–1892]. We show that despite good agreement of the globally averaged transfer velocities, global and regional fluxes differ by up to 100%. These discrepancies are a result of different spatio-temporal distributions of the processes involved in the parameterizations of k, indicating the importance of wave field parameters and a need for further validation.     

Fluxes of dissolved inorganic carbon in three estuarine systems of the Cantabrian Sea (north of Spain)

The diffusive and in situ fluxes of dissolved inorganic carbon (DIC) and total alkalinity (TA) have been measured and an estimation has been made of the water–atmosphere fluxes of CO₂ in three estuarine systems of the Cantabrian Sea during the spring of 1998. Each of these systems undergoes a different anthropogenic influence. The diffusive fluxes of dissolved inorganic carbon and total alkalinity obtained present values ranging between 0.54–2.65 and 0.0–2.4 mmol m⁻² day⁻¹, respectively. These ranges are in agreement with those of other coastal systems. The in situ fluxes are high and extremely variable (35–284 mmol TA m⁻² day⁻¹, 43–554 mmol DIC m⁻² day⁻¹ and 22–261 mmol dissolved oxygen (DO) m⁻² day⁻¹), because the systems studied are very heterogeneous. The values of the ratio of the in situ fluxes of TA and DIC show on average that the rate of dissolution of CaCO₃ is 0.37 times that of organic carbon oxidation. Equally, the interval of variation of the relationship between the benthic fluxes of inorganic carbon and oxygen (F_DIC/F_DO) is very wide (0.3–13.9), which demonstrates the different contributions made by the processes of aerobic and anaerobic degradation of the organic matter, as well as by the dissolution–precipitation of CaCO₃. The water–atmosphere fluxes of CO₂ present a clear dependence on the salinity. The brackish water of these systems (salinity<20), where maximum fluxes of 989 mmol m⁻² day⁻¹ have been estimated, act as a source of CO₂ to the atmosphere. The more saline zones of the estuary (salinity>30) act as a sink of CO₂, with fluxes between −5 and −10 mmol m⁻² day⁻¹.     

Air–sea gas transfer velocity estimates from the Jason-1 and TOPEX altimeters: Prospects for a long-term global time series

Estimation of global and regional air–sea fluxes of climatically important gases is a key goal of current climate research programs. Gas transfer velocities needed to compute these fluxes can be estimated by combining altimeter-derived mean square slope with an empirical relation between transfer velocity and mean square slope derived from field measurements of gas fluxes and small-scale wave spectra [Frew, N.M., Bock, E.J., Schimpf, U., Hara, T., Hauβecker, H., Edson, J.B., McGillis, W.R., Nelson, R.K., McKenna, S.P., Uz, B.M., Jähne, B., 2004. Air–sea gas transfer: Its dependence on wind stress, small-scale roughness and surface films, J. Geophys. Res., 109, C08S17, doi: 10.1029/2003JC002131.]. We previously reported initial results from a dual-frequency (Ku- and C-band) altimeter algorithm [Glover, D.M., Frew, N.M., McCue, S.J., Bock, E.J., 2002. A Multi-year Time Series of Global Gas Transfer Velocity from the TOPEX Dual Frequency, Normalized Radar Backscatter Algorithm, In: Gas Transfer at Water Surfaces, editors: Donelan, M., Drennan, W., Saltzman, E., and Wanninkhof, R., Geophysical Monograph 127, American Geophysical Union, Washington, DC, 325–331.] for estimating the air–sea gas transfer velocity (k) from the mean square slope of short wind waves (40–100 rad/m) and derived a 6-year time series of global transfer velocities based on TOPEX observations. Since the launch of the follow-on altimeter Jason-1 in December 2001 and commencement of the TOPEX/Jason-1 Tandem Mission, we have extended this time series to 12 years, with improvements to the model parameters used in our algorithm and using the latest corrected data releases. The prospect of deriving multi-year and interdecadal time series of gas transfer velocity from TOPEX, Jason-1 and follow-on altimeter missions depends on precise intercalibration of the normalized backscatter. During the Tandem Mission collinear phase, both satellites followed identical orbits with a mere 73-s time separation. The resulting collocated, near-coincident normalized radar backscatter (σ°) data from both altimeters present a unique opportunity to intercalibrate the two instruments, compare derived fields of transfer velocity and estimate the precision of the algorithm. Initial results suggest that the monthly gas transfer velocity fields generated from the two altimeters are very similar. Comparison of along-track Ku-band and C-band σ° during the collinear phase indicates that observed discrepancies are due primarily to small offsets between TOPEX and Jason-1 σ°. The Jason-1 k values have an apparent bias of + 4% relative to TOPEX, while the precision estimated from the two observation sets is 5–7% and scales with k. The resultant long-term, global, mean k is 16 cm/h.     

Lengthscales of motions that control air–water gas transfer in grid-stirred turbulence

The relationship between the gas transfer velocity and turbulent lengthscales is investigated experimentally in a grid-stirred turbulent flow. The horizontal velocity field at the water surface is measured using particle image velocimetry (PIV). The gas transfer velocity for oxygen is obtained through reaeration experiments. In addition, the gas transfer process by surface-renewal eddies is visualized using laser-induced fluorescence (LIF) technique, in which carbon dioxide is used as the tracer gas. The definition of the Taylor microscale holds that the root-mean-square (RMS) of the surface divergence is expressed by the square root of the turbulent kinetic energy divided by the Taylor microscale. Experimentally obtained data support this scaling. They show the gas transfer velocity to be proportional to the square root of the RMS of the surface divergence. These experimental results imply that the Taylor microscale is an important parameter for gas transfer velocity at the air–water interface. These relations indicate that a nondimensional gas transfer velocity is proportional to the − 1/4 power of a turbulent-macroscale Reynolds number, which is similar to a small-eddy model, assuming that turbulent eddies with the Kolmogorov scale control the gas transfer process. However, this Reynolds number dependence does not necessarily mean the superiority of turbulent eddies with the Kolmogorov scale in the gas transfer. The LIF visualizations in horizontal and vertical planes close to the air–water interface indicate that the horizontal CO₂-concentration field has a fine spatial pattern, which resembles that of the surface divergence field, and that surface-renewal motions observed in the vertical plane have a larger lengthscale than the Kolmogorov scale. We infer from both PIV and LIF results that the Taylor microscale is an important lengthscale for air–water gas transfer.     

Atmospheric CO2 measurements and error analysis on seasonal air–sea CO2 fluxes in the Bay of Biscay

Atmospheric molar fraction of CO₂ (xCO₂^atm) measurements obtained on board of ships of opportunity are used to parameterize the seasonal cycle of atmospheric xCO₂ (xCO₂^atm) in three regions of the eastern North Atlantic (Galician and French offshore and Bay of Biscay). Three selection criteria are established to eliminate spurious values and identify xCO₂^atm data representative of atmospheric background values. The filtered data set is fitted to seasonal curve, consisting of an annual trend plus a seasonal cycle. Although the fitted curves are consistent with the seasonal evolution of xCO₂^atm data series from land meteorological stations, only ship-board measurements can report the presence of winter xCO₂^atm minimum on Bay of Biscay. Weekly air–sea CO₂ flux differences (mmol C·m^− 2 day^− 1) produced by the several options of xCO₂^atm usually used (ship-board measurements, data from land meteorological stations and annually averaged values) were calculated in Bay of Biscay throughout 2003. Flux error using fitted seasonal curve relative to on board measurements was minimal, whereas land stations and annual means yielded random (− 0.2 ± 0.3 mmol C·m^− 2·day^− 1) and systematic (− 0.1 ± 0.4 mmol C·m^− 2 day^− 1), respectively. The effect of different available sources of sea level pressure, wind speed and transfer velocity were also evaluated. Wind speed and transfer velocity parameters are found as the most critical choice in the estimate of CO₂ fluxes reaching a flux uncertainty of 7 mmol C·m^− 2·day^− 1 during springtime. The atmospheric pressure shows a notable relative effect during summertime although its influence is quantitatively slight on annual scale (0.3 ± 0.2 mmol C·m^− 2·day^− 1). All results confirms the role of the Bay of Biscay as CO₂ sink for the 2003 with an annual mean CO₂ flux around − 5 ± 5 mmol C m^− 2 day^− 1.     

Sail–sail and sail–hull interaction effects of hybrid-sail assisted bulk carrier

In a previously reported study, wind tunnel experiments were undertaken to investigate the aerodynamic characteristics of hybrid-sails in isolation. Such sails are seen as providing a worthwhile reduction in the delivered power to the propeller and hence the engine generated thrust, with a corresponding reduction in the CO₂ production of diesel engine exhaust. In this paper, wind tunnel testing is used to investigate sail–sail interaction effects for two sets of four identical hybrid-sails, and the sail–hull interaction effects for the same two sets of four identical sails in the presence of a bulk carrier hullform. The analysis presented suggests that to build a sail-assisted ship requires an appreciation of the sail–sail and sail–hull interaction effects.     

Inorganic carbon fluxes through the boundaries of the Greenland Sea Basin based on in situ observations and water transport estimates

A carbon budget for the exchange of total dissolved inorganic carbon C_T between the Greenland Sea and the surrounding seas has been constructed for winter and summer situations. An extensive data set of C_T collected over the years 1994–1997 within the European Sub-polar Ocean Programmes (ESOP1 and ESOP2) are used for the budget calculation. Based on these data, mean values of C_T in eight different boxes representing the inflow and outflow of water through the boundaries of the Greenland Sea Basin are estimated. The obtained values are then combined with simulated water transports taken from the ESOP2 version of the Miami Isopycnic Coordinate Ocean Model (MICOM). The fluxes of inorganic carbon are presented for three layers; a surface mixed layer, an intermediate layer and a deep layer, and the imbalance in the fluxes are attributed to air–sea exchange, biological fixation of inorganic carbon, and sedimentation. The main influx of carbon is found in the surface and the deep layers in the Fram Strait, and in the surface waters of direct Atlantic origin, whereas the main outflux is found in the surface layer over the Jan Mayen Fracture Zone and the Knipovich Ridge, transporting carbon into the Atlantic Ocean via the Denmark Strait and towards the Arctic Ocean via the Norwegian Sea, respectively. The flux calculation indicates that there is a net transport of carbon out of the Greenland Sea during wintertime. In the absence of biological activity, this imbalance is attributed to air sea exchange, and requires an oceanic uptake of CO₂ of 0.024±0.006 Gt C yr⁻¹. The flux calculations from the summer period are complicated by biological fixation of inorganic carbon, and show that data on organic carbon is required in order to estimate the air–sea exchange in the area.     

Carbonate chemistry dynamics and carbon dioxide fluxes across the atmosphere–ice–water interfaces in the Arctic Ocean: Pacific sector of the Arctic

Climatic changes in the Northern Hemisphere have led to remarkable environmental changes in the Arctic Ocean, which is surrounded by permafrost. These changes include significant shrinking of sea-ice cover in summer, increased time between sea-ice break-up and freeze-up, and Arctic surface water freshening and warming associated with melting sea-ice, thawing permafrost, and increased runoff. These changes are commonly attributed to the greenhouse effect resulting from increased atmospheric carbon dioxide (CO₂) concentration and other non-CO₂ radiatively active gases (methane, nitrous oxide). The greenhouse effect should be most pronounced in the Arctic where the largest air CO₂ concentrations and winter–summer variations in the world for a clean background environment were detected. However, the air–land–shelf interaction in the Arctic has a substantial impact on the composition of the overlying atmosphere; as the permafrost thaws, a significant amount of old terrestrial carbon becomes available for biogeochemical cycling and oxidation to CO₂. The Arctic Ocean's role in determining regional CO₂ balance has been ignored, because of its small size (only  4% of the world ocean area) and because its continuous sea-ice cover is considered to impede gaseous exchange with the atmosphere so efficiently that no global climate models include CO₂ exchange over sea-ice. In this paper we show that: (1) the Arctic shelf seas (the Laptev and East-Siberian seas) may become a strong source of atmospheric CO₂ because of oxidation of bio-available eroded terrestrial carbon and river transport; (2) the Chukchi Sea shelf exhibits the strong uptake of atmospheric CO₂; (3) the sea-ice melt ponds and open brine channels form an important spring/summer air CO₂ sink that also must be included in any Arctic regional CO₂ budget. Both the direction and amount of CO₂ transfer between air and sea during open water season may be different from transfer during freezing and thawing, or during winter when CO₂ accumulates beneath Arctic sea-ice; (4) direct measurements beneath the sea ice gave two initial results. First, a drastic pCO₂ decrease from 410 μatm to 288 μatm, which was recorded in February–March beneath the fast ice near Barrow using the SAMI-CO₂ sensor, may reflect increased photosynthetic activity beneath sea-ice just after polar sunrise. Second, new measurements made in summer 2005 beneath the sea ice in the Central Basin show relatively high values of pCO₂ ranging between 425 μatm and 475 μatm, values, which are larger than the mean atmospheric value in the Arctic in summertime. The sources of those high values are supposed to be: high rates of bacterial respiration, import of the Upper Halocline Water (UHW) from the Chukchi Sea (CS) where values of pCO₂ range between 400 and 600 μatm, a contribution from the Lena river plume, or any combination of these sources.     

Organic carbon budget for the Gulf of Bothnia

We calculated input of organic carbon to the unproductive, brackish water basin of the Gulf of Bothnia from rivers, point sources and the atmosphere. We also calculated the net exchange of organic carbon between the Gulf of Bothnia and the adjacent marine system, the Baltic Proper. We compared the input with sinks for organic carbon; permanent incorporation in sediments and mineralization and subsequent evasion of CO₂ to the atmosphere. The major fluxes were riverine input (1500 Gg C year^− 1), exchange with the Baltic Proper (depending on which of several possible DOC concentration differences between the basins that was used in the calculation, the flux varied between an outflow of 466 and an input of 950 Gg C year^− 1), sediment burial (1100 Gg C year^− 1) and evasion to the atmosphere (3610 Gg C year^− 1). The largest single net flux was the emission of CO₂ to the atmosphere, mainly caused by bacterial mineralization of organic carbon. Input and output did not match in our budget which we ascribe uncertainties in the calculation of the exchange of organic carbon between the Gulf of Bothnia and the Baltic Proper, and the fact that CO₂ emission, which in our calculation represented 1 year (2002) may have been overestimated in comparison with long-term means. We conclude that net heterotrophy of the Gulf of Bothnia was due to input of organic carbon from both the catchment and from the Baltic Proper and that the future degree of net heterotrophy will be sensible to both catchment export of organic carbon and to the ongoing eutrophication of the Baltic Proper.     

pH variability and CO2 induced acidification in the North Sea

A coupled carbonate system–marine ecosystem–hydrodynamic model is used to simulate the temporal and spatial variability in pH across the southern North Sea as it relates to the environmental and biological processes affecting CO₂, namely, photosynthesis and respiration, riverine boundary conditions and atmospheric CO₂ concentrations. Annual pH ranges are found to vary from < 0.2 in areas of low biological activity to > 1.0 in areas influenced by riverine signals, consistent with observations and previous studies. It is shown that benthic, as well as pelagic, activity is an important factor in this variability. The acidification of the region due to increased fluxes of atmospheric CO₂ into the marine system is calculated and shown to exceed, on average, 0.1 pH units over the next 50 years and result in a total acidification of 0.5 pH units below pre-industrial levels at atmospheric CO₂ concentrations of 1000 ppm. The potential for measurable changes in biogeochemistry are demonstrated by simulating the observed inhibition of pelagic nitrification with decreasing pH. However, we conclude that there is a lack of knowledge of how acidification might affect the complex interaction of processes that govern marine biogeochemical cycles and a consequent need for further research and observations.