Hydroxyl Radical Photoproduction in the Sea and Its Potential Impact on Marine Processes

Photochemical production rates and steady-state concentrations of hydroxyl radicals (.OH) were measured in sunlight-irradiated seawater. Values ranged from 110 nanomolar per hour and 12 x 10(-18) molar in coastal surface water to 10 nanomolar per hour and 1.1 x 10(-18) molar in open ocean surface water. The wavelengths responsible for this production are in the ultraviolet B region (280 to 320 nanometers) of the solar spectrum. Dissolved organic matter (DOM) appears to be the main source for .OH over most of the oceans, but in upwelling areas nitrite and nitrate photolysis may also be important. DOM in the deep sea is degraded more readily by .OH (and its daughter radicals), by a factor of 6 to 15, than is DOM in open-ocean surface water. This finding may in part bear on major discrepancies among current methods for measuring dissolved organic carbon in seawater.