Recent studies with closed-path eddy covariance (EC) systems have indicated that the attenuation of fluctuations of water vapor concentration is dependent upon ambient relative humidity, presumably due to sorption/desorption of water molecules at the interior surface of the tube. Previous studies of EC-related tube attenuation effects have either not considered this issue at all or have only examined it superficially. Nonetheless, the attenuation of water vapor fluctuations is clearly much greater than might be expected from a passive tracer in turbulent tube flow. This study reexamines the turbulent tube flow issue for both passive and sorbing tracers with the intent of developing a physically-based semi-empirical model that describes the attenuation associated with water vapor fluctuations. Toward this end, we develop a new model of tube flow dynamics (radial profiles of the turbulent diffusivity and tube airstream velocity). We compare our new passive-tracer formulation with previous formulations in a systematic and unified way in order to assess how sensitive the passive-tracer results depend on fundamental modeling assumptions. We extend the passive tracer model to the vapor sorption/desorption case by formulating the model's wall boundary condition in terms of a physically-based semi-empirical model of the sorption/desorption vapor fluxes. Finally we synthesize all modeling and observational results into a single analytical expression that captures the effects of the mean ambient humidity and tube flow (Reynolds number) on tube attenuation.
Atmospheric Chemistry and Physics, 2008, Vol 8, Issue 20, p. 6245-6259