Variability of carbon monoxide and carbon dioxide apparent quantum yield spectra in three coastal estuaries of the South Atlantic Bight

Abstract. The photochemical oxidation of oceanic dissolved organic carbon (DOC) to carbon monoxide (CO) and carbon dioxide (CO₂) has been estimated to be a significant process with global photoproduction transforming petagrams of DOC to inorganic carbon annually. To further quantify the importance of these two photoproducts in coastal DOC cycling, 38 paired apparent quantum yield (AQY) spectra for CO and CO₂ were determined at three locations along the coast of Georgia, USA over the course of one year. The AQY spectra for CO₂ were considerably more varied than CO. CO AQY spectra exhibited a seasonal shift in spectrally integrated (260 nm–490 nm) AQY from higher efficiencies in the autumn to less efficient photoproduction in the summer. While full-spectrum photoproduction rates for both products showed positive correlation with pre-irradiation UV-B sample absorption (i.e. chromophoric dissolved organic matter, CDOM) as expected, we found no correlation between AQY and CDOM for either product at any site. Molecular size, approximated with pre-irradiation spectral slope coefficients, and aromatic content, approximated by the specific ultraviolet absorption of the pre-irradiated samples, were also not correlated with AQY in either data set. The ratios of CO₂ to CO photoproduction determined using both an AQY model and direct production comparisons were 23.2 ± 12.5 and 22.5 ± 9.0, respectively. Combined, both products represent a loss of 2.9 to 3.2% of the DOC delivered to the estuaries and inner shelf of the South Atlantic Bight yearly, and 6.4 to 7.3% of the total annual degassing of CO₂ to the atmosphere. This result suggests that direct photochemical production of CO and CO₂ is a small, yet significant contributor to both DOC cycling and CO₂ gas exchange in this coastal system.