An approach to quantify depth-resolved marine photochemical fluxes using remote sensing: Application to carbon monoxide (CO) photoproduction

This paper presents a model to calculate depth-resolved marine photochemical fluxes from remotely sensed ocean color and modeled solar irradiance. The basic approach uses three components: 1) below-sea-surface spectral downward scalar irradiance calculated from a radiative transfer model (STAR) and corrected for clouds using TOMS UV reflectivities; 2) surface-ocean spectral diffuse attenuation coefficients and absorption coefficients for chromophoric dissolved organic matter retrieved from SeaWiFS ocean color using the SeaUV/SeaUVc algorithms: and (3) spectral apparent quantum yield for the photochemical reaction considered. The output of the model is a photochemical rate profile, Psi(PR)(z), where z represents depth. We implemented the model for carbon monoxide (CO) photochemistry using an average apparent quantum yield spectrum and generated a monthly climatology of depth-resolved CO photoproduction rates in the global ocean. The climatology was used to compute global budgets and investigate the spatial and seasonal variabilities of CO photoproduction in the ocean. The model predicts a global CO photoproduction rate of about 41 TgC yr(-1), in good agreement with other recent published estimates ranging from 30 to 84 TgC yr(-1). The fate of photochemically derived CO and its role in global biogeochemical cycles remains uncertain however, with biological consumption and sea-air exchange competing for its removal in the surface ocean. Knowledge of the vertical distribution of CO photoproduction is critical in the quantification of the relative magnitudes of these sink mechanisms. The depth-resolution capabilities of this model, together with US Naval Research Laboratory climatology for mixed layer depths allowed further estimation that >95% of the total water-column CO photoproduction occurs within the mixed layer on a global, yearly basis. Despite this compelling figure, the model also suggests significant spatio-temporal variability in the vertical distribution of CO photoproduction in the subtropical gyres, where up to 40% of water-column CO can be produced below the mixed layer during summertime. While the approach can be applied to other photochemical fluxes (e.g. DIC formation or DMS removal), accurate quantification of such processes with remote sensing will be limited until the mechanisms regulating observed oceanic variability in the apparent quantum yields are better understood. Minor modification to this model can also make it applicable for the determination of the effects of UV and visible solar radiation on sensitive biological systems. (C) 2010 Elsevier Inc. All rights reserved.