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.     

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.     

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.     

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.     

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.     

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.     

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.     

Determination of anthropogenic CO2 in the North Atlantic Ocean using water mass ages and CO2 equilibrium chemistry

A new method to calculate the anthropogenic CO₂ (ΔDIC_ant) within the water column of the North Atlantic Ocean is presented. The method exploits the equilibrium chemistry of the carbonate system with reference to temperature, salinity and the partial pressure of atmospheric CO₂ (pCO_2,atm). ΔDIC_ant is calculated with reference to the ventilation ages of water masses derived from tracer data and to the time history of pCO_2,atm. The method is applied to data recorded during the WOCE program on the WHP A1/E transect in the North Atlantic Ocean, where we characterise six key water masses by their relationships of dissolved inorganic carbon (DIC) and apparent oxygen utilisation (AOU). The error in determining ΔDIC_ant is reduced significantly by minimising the number of values referred to, especially by avoiding any use of remineralisation ratios of particulate organic matter. The distribution of ΔDIC_ant shows highest values of up to 45 μmol kg⁻¹ in the surface waters falling to 28–33 μmol kg⁻¹ in the Irminger Sea west of the Mid-Atlantic Ridge. The eastern basin is imprinted by older water masses revealing decreasing values down to 10 μmol kg⁻¹ ΔDIC_ant in the Antarctic Bottom Water. These findings indicate the penetration of the whole water column of the North Atlantic Ocean by anthropogenic CO₂.     

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.     

内河船舶和国内海船CO2系统的异同分析

针对船舶现场检验中发现的固定式灭火系统的CO₂系统以及瓶头阀及其相关组件的各种缺陷,主要阐述内河船舶CO₂系统和国内海船CO₂系统的异同、瓶头阀的结构、释放总管的安装要求、泄放总管的安装要求、控制管路的安装要求,这也是验船师现场检验的难点,以期相关人员在遇到问题时了解如何处理。     

Distribution of suspended sediment in the coastal sea off the Ganges–Brahmaputra River mouth: observation from TM data

Remote sensing technique was applied to estimate suspended sediment concentration (SSC) and to understand transportation, distribution and deposition of suspended sediment in the estuary and throughout the coastal sea, off the Ganges–Brahmaputra River mouth. During low river discharge period, zone of turbidity maximum is inferred in the estuary near the shore. SSC map shows that maximum SSC reaches 1050 mg/l in this period. Magnitude of SSC is mainly owing to resuspension of the bottom surface sediments induced by tidal currents flowing over shallow water depths. The influence of depth on resuspension is farther revealed from the distribution and magnitude of SSC along the head of Swatch of No Ground (SNG) submarine canyon. During high river discharge period, huge river outflow pushed the salt wedge and flashes away the suspended sediments in the coastal sea off the river mouth. Zone of turbidity maximum is inferred in the coastal water approximately within 5–10 m depth of water, where the maximum SSC reaches 1700 mg/l. In this period, huge fluvial input of the suspended sediments including the resuspended bottom sediments and the particles remaining in suspension for longer period of time since their initial entry control mainly the magnitude of SSC. In the estuary near the shore, seasonal variation in the magnitude of SSC is not evident. In the coastal sea (>5 m water depth), seasonal influence in the magnitude of SSC could be concluded from the discrepancy between SSC values of two different seasons. Transportation and deposition of suspended sediments also experiences seasonal variations. At present, suspended sediments are being accumulated on the shallow shelf (between 5 and 10 m water depth) in low discharge period and on the mid-shelf (between 10 and 75 m water depth) during high discharge period. An empirical (exponential) relationship was found between gradual settle down of suspended sediments in the coastal sea and its lateral distance from the turbidity maximum.     

Annual uptake of atmospheric CO2 by the Weddell Sea derived from a surface layer balance, including estimations of entrainment and new production

Data from two cruises, one in April/May 1996 and one in December/January 1993, covering the same wide area in the offshore Weddell Sea, were used to derive the annual extent of entrainment and the capacity of the biological pump. The former property was obtained with the help of dissolved oxygen data, whereas the latter was approximated with nutrients. Especially the data from April/May, representing the initial state of the winter surface layer, were crucial to assess the annual extent of these processes. The results were applied to our carbon dioxide data. The annual increase of the Total CO₂ (TCO₂) concentration in the surface layer due to vertical transport amounts to 16.3 μmol kg⁻¹. An entrainment rate of deep water in the surface layer amounting to 35±10 m yr⁻¹ was deduced. The compensating, biologically mediated TCO₂ reduction was calculated to be larger than the TCO₂ increase due to vertical transport. Since the balance of these two processes determines whether the Weddell Sea is a source or a sink of CO₂, this indicates that the Weddell Sea, albeit upwelling area, is definitely a sink for atmospheric CO₂ on an annual basis. This conclusion is further supported by contemplations that the biological drawdown of CO₂ in the Weddell Sea as a whole is probably underestimated by our calculations. The new production for the Weddell Sea on a per unit area basis was found to be much higher than that for the Antarctic Ocean, when the latter value is being obtained by traditional biological methods. On the other hand, the CO₂ uptake by the Weddell Sea on a per unit area basis is somewhat smaller than the CO₂ uptake by the world ocean.     

Daily and seasonal variations of the partial pressure of CO2 in surface seawater along Belgian and southern Dutch coastal areas

The variations of the partial pressure of CO₂ (pCO₂) and related parameters were determined in surface seawater along the Belgian coast, from January 1995 to June 1996, at both daily and seasonal time scales. The distribution of pCO₂ in this area is regulated by river input from the Scheldt, biological activity and hydrodynamics. The contribution of each of these processes varies as a function of the considered time scale: (i) the daily variation of pCO₂ depends on the tide although modulated by the biological diel cycle; (ii) the seasonal variation of pCO₂ depends on the input from the Scheldt and the seasonal variations of phytoplanktonic biomass. During winter, the plume of the river Scheldt is oversaturated in pCO₂ with respect to the atmosphere. During spring and summer, phytoplankton blooms occur both in the lower Scheldt estuary and in the river plume and may lead to undersaturation of pCO₂ in the easternmost area of the river plume. However, the degradation of phytoplankton induces oversaturation of pCO₂, in the westernmost area of the plume. Furthermore, the inter-annual variation of pCO₂ depends partly on the fluctuations of the discharge of the Scheldt. Our preliminary results strongly suggest that, on an annual basis, the Scheldt plume behaves as a net source of CO₂ to the atmosphere.     

基于水力空化强化的ClO2脱硝研究

  目的   为提高过硫酸钠（Na₂S₂O₈）湿法氧化脱硝的效率以及药品利用率,利用水力空化强化Na₂S₂O₈开展湿法氧化脱硝实验。   方法   探究水力空化强化Na₂S₂O₈脱硝的可行性,研究溶液温度、Na₂S₂O₈浓度、氯离子（Cl⁻）等因素对脱硝效果的影响以及相关机理。   结果   实验结果表明：水力空化产生的特殊环境有利于活化Na₂S₂O₈,提高脱硝效率,但整体脱硝效果不佳;在实验条件下,当温度从30 ℃升到80 ℃时,一氧化氮(NO)去除率从7%提升至43%;提高Na₂S₂O₈的浓度有利于提高NO脱除率;在高温工况下,提高Na₂S₂O₈的浓度对提高整体脱硝率的促进作用更明显;Cl⁻的存在可以极大地提高NO的脱除率,当Cl⁻浓度与Na₂S₂O₈浓度配比达到0.15∶0.1时,NO的脱除率高达94%。   结论   水力空化可促进Na₂S₂O₈去除NO的反应速率,Cl⁻在水力空化创造的特殊反应环境中能产生更多的氧化性物质,提高脱硝效果。     

A study of the response of chlorophyll-a biomass to a winter upwelling event off Western Iberia using SeaWiFS and in situ data

Observations of a winter upwelling event off Western Iberia shelf/slope in the area of influence of the Western Iberia Buoyant Plume (WIBP) were conducted in February 2000. Spatial patterns and time evolution of the chlorophyll-a (chl-a) biomass are analysed, based on in situ and satellite data. SeaWiFS-derived chl-a concentration L2 products were used to track the chlorophyll front and estimate its westward migration velocity (maximum up to 29 km day⁻¹), as well as to characterize the frontal system and its evolution. A method associating the type of spectral signature of a pixel to the fraction of chlorophyll probed by SeaWiFS enabled the estimation of the chl-a biomass within error intervals. High chlorophyll concentrations (for wintertime) were observed over the shelf and slope, up to large distances to the coast. Due to the WIBP, a shallow Ekman layer developed, being nearly coincident with the stratified upper meters. The transport comprised westward advection and stretching of the plume, with little entrainment with the offshore deep mixed layer waters. The relative enlargement of the total area of the Inside-Front Zone (IFZ) during the upwelling event was roughly accompanied by the maintenance of the average biomass per unit of area, considering the water column up to depths of interest. This suggests that there was a net increase of chl-a biomass inside the water column associated with the IFZ, roughly proportional to the increase in the IFZ area. Retention of phytoplankton in the shallow stratified nutrient-rich waters of the WIBP was a key factor for this increase in chl-a biomass.     

紫外强化有效氯对船舶尾气同时脱硫脱硝试验

为提高有效氯溶液对船舶尾气同时脱硫、脱硝的性能,将紫外光(UV)辐照与有效氯溶液相结合,开展脱硫、脱硝试验。基于UV-鼓泡光催化反应器搭建模拟实验平台,进行UV辐照和无UV辐照环境下氧化溶液脱硫脱硝的对比试验和UV灯的功率、有效氯的浓度等因素对脱除率影响的试验。结果表明:在40℃的气液反应温度下,UV辐照能大幅度提高浓度为250 mg/L[CL2]的有效氯溶液对模拟烟气中NO、NOX和SO2的脱除能力;UV灯的功率从5W增加到16W,NO和NOX的脱除率近乎线性上升;将有效氯的浓度从250 mg/L[CL2]升高至1 500 mg/L[CL2],NO和NOX的脱除率缓慢上升;有效氯溶液对SO2的脱除率始终为100%。此外,对可能的反应机理进行了分析。