Increases in the longwave photobleaching of chromophoric dissolved organic matter in coastal waters

Abstract

Salinity effects on the photobleaching of chromophoric dissolved organic matter (CDOM) due to coastal mixing were investigated through a comparative study of surrogate and surface-water CDOM. Suwannee River humic acid (SRHA) and ultrafiltered river dissolved organic matter (UDOM) added to mixtures of river and seawater permeates (,1 kDa) that varied in salinity from 0 to 33 to mimic coastal mixing. Surface-water CDOM was collected from the Chesapeake Bay in January, June, and September 2002. Shortwave CDOM absorption loss (e.g., 280 nm) did not change with salinity; however, longwave CDOM absorption loss (e.g., 440 nm) often decreased by 10% to 40% with salinity. Apparent quantum yields for average absorption loss from 280 to 550 nm (Qavg) increased with salinity for both surrogate and surface-water CDOM, providing evidence for an effect of salinity independent of light absorption among different samples. Further, hydrogen peroxide photoproduction from UDOM increased from 15 to 368 nmol L 21 h 21 with salinity, even though pH values were circumneutral. A kinetic model demonstrated that, at circumneutral pH and iron concentrations expected for the Chesapeake Bay, photo-Fenton chemistry could not explain the increase in hydrogen peroxide production quantum yields (Qhp) with salinity. Using Qavg for the SRHA and UDOM surrogates, a model of the change in surface-water CDOM photoreactivity in the Chesapeake Bay as a function of salinity suggested additional CDOM inputs for the lower Chesapeake Bay. Because estuarine mixing increases photobleaching of longwave CDOM absorption, the modeling of absorption coefficients above 400 nm may underestimate dissolved organic matter in coastal waters.