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

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.

Department dc:contributor.department

Joint Program in Oceanography

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2002

Author dc:creator

• Goldstone, Jared Verrill, 1971-

Advisor dc:contributor.advisor

• Bettina M. Voelker.

• Joint Program in Oceanography.
• Civil and Environmental Engineering.
• Woods Hole Oceanographic Institution.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/29053

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/29053