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.     

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.     

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.     

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.