Direct and indirect photoreactions of chromophoric dissolved organic matter : roles of reactive oxygen species and iron

Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Civil and Environmental Engineering, and the Woods Hole Oceanographic Institution), 2002.Vita.Includes bibliographical references.Photochemical transformations of chromophoric dissolved organic matter (CDOM) are one of the principal processes controlling its fate in coastal waters. The photochemical decomposition of CDOM leads to the formation of a variety of biologically available carbon substrates. Photomineralization of CDOM to dissolved inorganic carbon may constitute a significant flux in the global carbon cycle. Photoreactions ultimately lead to the destruction of the chromophores and hence to the loss of absorption and fluorescence (bleaching), thus acting as a sink for CDOM. Photodecomposition may proceed both via direct photochemical reactions, following absorption of photons by CDOM, or via indirect processes, involving DOM reactions with photochemically generated intermediates such as reactive oxygen species (ROS). The reactions of CDOM with two important ROS, superoxide (02-) and hydroxyl radical (OH), have different consequences. Superoxide reactions with CDOM did not appear to degrade the CDOM. Instead, CDOM catalysed the dismutation of 02- to 02 and HOOH. This reactivity has the effect of limiting the steady-state concentration of 02- in most coastal waters. In contrast, reactions of CDOM with radiolytically produced OH formed CO2 and several low molecular weight carboxylic acids, as well as bleached both the absorption and fluorescence at slow rates. These reactions did not increase the bioavailability of this material to a microbial consortium. Both direct and indirect photochemical processes are expected to be accelerated by the presence of iron.(cont.) However, addition of iron to several coastal seawater samples neither increased the rate of photobleaching nor the apparent quantum yield (AQY) of CO. Similarly, the addition of the siderophore desferrioxamine B did not change the photobleaching rates or the CO AQYs. The addition of 2[mu]M Fe to solutions of Suwannee River Fulvic Acid did not increase the photobleaching rates. In combination with prior results, these findings suggest that indirect photoreactions do not increase the photobleaching rates of CDOM in coastal systems. A model of CDOM photobleaching based on the assumption of negligible indirect photobleaching processes and multiple non-interacting chromophores was created utilizing photobleaching data produced with monochromatic light to calculate the spectra and exponential decay rates of independent components. These components were then used to calculate bleaching spectra for broadband light and compared with actual bleaching spectra.by Jared Verrill Goldstone.Ph.D