Abstract
We apply principles of Gibbs phase plane chemistry across the entire ocean-atmosphere interface to investigate aerosol generation and geophysical transfer issues. Marine surface tension differences comprise a tangential pressure field controlling trace gas fluxes, primary organic inputs, and sea spray salt injections, in addition to heat and momentum fluxes. Mapping follows from the organic microlayer composition, now represented in ocean system models. Organic functional variations drive the microforcing, leading to (1) reduced turbulence and (by extension) laminar gas-energy diffusion; plus (2) altered bubble film mass emission into the boundary layer. Interfacial chemical behaviors are, therefore, closely reviewed as the background. We focus on phase transitions among two dimensional “solid, liquid, and gaseous” states serving as elasticity indicators. From the pool of dissolved organic carbon (DOC) only proteins and lipids appear to occupy significant atmospheric interfacial areas. The literature suggests albumin and stearic acid as the best proxies, and we distribute them through ecodynamic simulation. Consensus bulk distributions are obtained to control their adsorptive equilibria. We devise parameterizations for both the planar free energy and equation of state, relating excess coverage to the surface pressure and its modulus. Constant settings for the molecular surrogates are drawn from laboratory study and successfully reproduce surfactant solid-to-gas occurrence in compression experiments. Since DOC functionality measurements are rare, we group them into super-ecological province tables to verify aqueous concentration estimates. Outputs are then fed into a coverage, tension, elasticity code. The resulting two dimensional pressure contours cross a critical range for the regulation of precursor piston velocity, bubble breakage, and primary aerosol sources plus ripple damping. Concepts extend the water-air adsorption theory currently embodied in our OCEANFILMS aerosol emissions package, and the two approaches could be inserted into Earth System Models together. Uncertainties in the logic include kinetic and thermochemical factors operating at multiple scales.
Highlights
Composition of the marine atmospheric interface determines the surface tension across most of the ocean [1,2,3,4,5,6,7,8,9] so that multiple climate-critical fluxes are influenced
Drawing on Langmuir surfactant concepts lately applied to marine organic aerosol emissions
([30,31,32,33]—the developing OCEANFILMS code), we extend toward a complete physicochemistry of global interfacial mass and energy transfer
Summary
Composition of the marine atmospheric interface determines the surface tension across most of the ocean [1,2,3,4,5,6,7,8,9] so that multiple climate-critical fluxes are influenced. During and after the World Wars it became clear that surfactant influence on upper ocean mixing must function on regional to planetary scales [47,48,49] and, that it extends to the turbulent eddy spectrum arising around the atmospheric interface [38,50]. This latter connection implies influence upon large-scale transfer of many other properties—e.g., ocean solute mass inclusive of dissolved gas concentration gradients, heat, energy and, via temperature dependence of the vapor pressure, water itself [2,46,51]. Effects on trace gas fluxes operating in the greenhouse and marine aerosol-cloud systems began to draw real attention only during the era of global change biogeochemistry [2,6,55]
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