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A numerical scheme to calculate temperature and salinity dependent air-water transfer velocities for any gas

Martin Johnson

The transfer velocity determines the rate of exchange of a gas across the air-water interface for a given deviation from Henry's law equilibrium between the two phases. In the thin film model of gas exchange, which is commonly used for calculating gas exchange rates from measured concentrations of trace gases in the atmosphere and ocean/freshwaters, the overall transfer is controlled by diffusion-mediated films on either side of the air-water interface. Calculating the total transfer velocity (i.e. including the influence from both molecular layers) requires the Henry's law constant and the Schmidt number of the gas in question, the latter being the ratio of the viscosity of the medium and the molecular diffusivity of the gas in the medium. All of these properties are both temperature and (on the water side) salinity dependent and extensive calculation is required to estimate these properties where not otherwise available. The aim of this work is to standardize the application of the thin film approach to flux calculation from measured and modelled data, to improve comparability, and to provide a numerical framework into which future parameter improvements can be integrated. A detailed numerical scheme is presented for the calculation of the gas and liquid phase transfer velocities (ka and kw respectively) and the total transfer velocity, K. The scheme requires only basic physical chemistry data for any gas of interest and calculates K over the full range of temperatures, salinities and wind-speeds observed in and over the ocean. Improved relationships for the wind-speed dependence of ka and for the salinity-dependence of the gas solubility (Henry's law) are derived. Comparison with alternative schemes and methods for calculating air-sea flux parameters shows good agreement in general but significant improvements under certain conditions. The scheme is provided as a downloadable program in the supplementary material, along with input files containing molecular weight, solubility and structural data for 80 gases of general interest, enabling calculation of the total transfer velocity over ranges of temperature and salinity for each gas.

Ocean Science Discussions, 7, (1), 251-290

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