Factors affecting the efficiency of carbon monoxide photoproduction in the St. Lawrence estuarine system (Canada).

This study examined the effects of water temperature and the origin (terrestrial vs marine) and light history of chromophoric dissolved organic matter (CDOM) on the apparent quantum yields of carbon monoxide (CO) photoproduction for water samples collected along a salinity gradient (salinity range: 0-33) in the St. Lawrence estuarine system (Canada). The solar insolation-weighted mean apparent quantum yield of CO (phico) decreased as much as fourfold with increasing salinity and showed a strong positive correlation with the dissolved organic carbon-specific absorption coefficient at 254 nm. This suggests that terrestrial CDOM is more efficient at photochemically producing CO than is marine algae-derived CDOM and that aromatic moieties are likely involved in this photoprocess. CDOM photobleaching, mainly at the very early stage, dramatically decreased phico (by up to 6.4 times) for low-salinity samples, but photobleaching had little effect on the most marine sample. For a 20 degree C increase in temperature, phico increased by approximately 70% for low-salinity samples and 30-40% for saline samples. This study demonstrates that water temperature, as well as the CDOM's origin and light history, strongly affect the efficiency of CO photoproduction. These factors should be taken into account in modeling the photochemical fluxes of CO and other related CDOM photoproducts on varying spatiotemporal scales.