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.     

Effect of wave boundary layer on sea-to-air dimethylsulfide transfer velocity during typhoon passage

A full-spectral third-generation ocean wind–wave model (Wavewatch-III) implemented in the South China Sea is used to investigate the effects of the wave boundary layer on the drag coefficient and the sea-to-air transfer velocity of dimethylsulfide (DMS) during passage of Typhoon Wukong (September 5–11, 2000) with a maximum sustained wind speed of 38 m s^− 1. The model is driven by the reanalyzed surface winds (1° × 1°, four times daily) from the National Centers for Environmental Prediction. It is found that the wave boundary layer evidently enhances (16.5%) the drag coefficient (in turn increases the momentum flux across the air–sea interface), and reduces (13.1%) the sea-to-air DMS transfer velocity (in turn decreases the sea-to-air DMS flux). This indicates the possibility of important roles of wave boundary layer in atmospheric DMS contents and global climate system.     

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.     

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.     

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.     

The combined effect of rain and wind on air–water gas exchange: A feasibility study

A series of experiments were conducted at University of Delaware's Air–Sea Interaction Laboratory to examine the combined effects of rain and wind on air–water gas exchange. During this study, ASIL WRX I, a combination of 3 rain rates and 4 wind speeds were used, for a total of 12 different environmental conditions. The SF₆ evasion method was used to determine the bulk gas transfer velocities, and airside profiles of wind and CO₂ were used to estimate flux–profiles of momentum and carbon dioxide. In addition to measurements of fluxes with and without rain in a wind–wave boundary layer, measurements of wave properties were also obtained. Rain is shown to alter the wind profile in the flume, and dampen surface waves. Also, SF₆ evasion indicates that with the present experimental setup, for most of the experimental conditions, rain and wind combine linearly to influence air–water gas exchange. Flux–profile relationships for marine atmospheric boundary layers, which were performed to scale up to field measurements, were explored by a comparison between SF₆-derived bulk fluxes and airside CO₂ profile measurements.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Whitecap coverage in coastal environment for steady and unsteady wave field conditions

Breaking waves represent a “key” parameter for many applications involved with a large number of environmental phenomena. In particular, it is well recognized that the whitecap cover induced by breaking waves allows substantial enhancement of heat, momentum, gas and particle transfer at the air–sea interface. A large number of studies were conducted during the last decades on the variation of the whitecap fraction, commonly noted W. The results presented in this paper deal with the evolution of the whitecap coverage in coastal zone. In such areas, the wave field is often unsteady with an important variety of sea state developments. The present analysis is based on an extensive series of data obtained during an experimental campaign which took place on the Mediterranean coast in 2001. The results allow observation of the influence of the sea state conditions of the wave field on the whitecap coverage. In addition, this paper confirms the occurrence of a peak in the variations of the whitecap fraction with the wave age for coastal areas as suggested by Lafon et al. [Lafon, C., Piazzola, J., Forget, P., Le Calvé, O. and Despiau, S., 2004. Analysis of the variations of the whitecap fraction as measured in a coastal zone. Boundary-Layer Meteorol., 111: 339-360.]. A wave age dependent model for the whitecap fraction is then proposed, which takes into account both the wind and the wave influence, and hence, is characteristics of the different sea state conditions.     

非均衡湍流边界层脉动压力测试研究

通过建立非均衡湍流边界层脉动压力测试技术及可提供较高测试信噪比的低噪声风洞试验装置,采用表面贴装式硅微传声器线列阵,测量获得了不同压力梯度模型的湍流边界层脉动压力特性,压力梯度模型表面湍流边界层脉动压力低频平台区幅值增加3-5 dB;回归得到了非均衡湍流边界层流脉动压力频谱与Strauhal数及Re数和压力梯度相关的拟合模型,具有一定的适用性;压力梯度对湍流边界层脉动压力频率—波数谱的影响主要集中在300 Hz以下的低频段,传输波数附近峰脊区谱级增加3-5 dB。     

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.     

Coupled renewal model of ocean viscous sublayer, thermal skin effect and interfacial gas transfer velocity

A previously developed renewal model included parameterizations for the thermal skin effect and interfacial gas transfer velocity. The more readily available cool skin data were used for an adjustment of the gas transfer parameterization. In this work, the renewal concept is extended to include the velocity difference across the viscous sublayer and to account for the stage of surface wave development. As a result, the empirical coefficients that enter the renewal model have been specified more accurately using laboratory data on the surface wind drift current. In addition, the coefficient linking the cool skin and gas transfer parameterization formulas has been determined from the probability distribution function for renewal events. A comparison of the upgraded renewal model with the thermal skin data collected during the COARE and more recent field programs and with gas transfer data collected during GasEx-01 experiment suggests that the renewal model can be a useful tool for producing a physically based parameterization for the interfacial CO₂ transfer velocity. Model uncertainties associated with the effect of surface films are discussed.     

The biogeochemical cycling of methane in Ria de Vigo, NW Spain: Sediment processing and sea–air exchange

Methane (CH₄) concentrations were measured in the water column, in sediment porewaters, and in atmospheric air, in the Ría de Vigo, NW Spain, during both the onset (April 2003) and at the end of (September 2004) seasonal upwelling. In addition, CH₄ concentration and stable isotopic signatures (δ¹³CH₄) were measured in porewaters, and sediment methanogenesis and aerobic oxidation of CH₄ were determined in sediment incubations. Surface water column CH₄ (2 m depth) was in the range 3–180 nmol l^− 1 (110–8500% saturation) and followed a generally landward increase but with localised maxima in both the inner and middle Ría. These maxima were consistent with CH₄ inputs from underlying porewaters in which CH₄ concentrations were up to 3 orders of magnitude higher (maximum 350 μmol l^− 1). Surface water CH₄ concentrations were approximately three times higher in September than in April, consistent with a significant benthic CH₄ flux driven by enhanced sediment methanogenesis following the summer productivity maximum. CH₄ and δ¹³CH₄ in sediment porewaters and in incubated sediment slurries (20 °C) revealed significant sediment CH₄ oxidation, with an apparent isotopic fractionation factor (r_c) of  1.004. Using turbulent diffusion models of air–sea exchange we estimate an annual emission of atmospheric CH₄ from the Ría de Vigo of 18–44 × 10⁶ g (1.1–2.7 × 10⁶ mol). This estimate is approximately 1–2 orders of magnitude lower than a previous estimate based on a bubble transport model.