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PHOTOOXIDATION AND ITS EFFECTS ON THE CARBOXYL CONTENT OF DISSOLVED ORGANIC MATTER IN TWO COASTAL RIVERS IN THE SOUTHEASTERN UNITED STATES
Citation:
Xie, H., O. C. Zafiriou, W. J. Cai, Y. Wang, AND R G. Zepp. PHOTOOXIDATION AND ITS EFFECTS ON THE CARBOXYL CONTENT OF DISSOLVED ORGANIC MATTER IN TWO COASTAL RIVERS IN THE SOUTHEASTERN UNITED STATES. ENVIRONMENTAL SCIENCE & TECHNOLOGY 38(15):4113-4119, (2004).
Impact/Purpose:
The overall objective of this task is to develop quantitative relationships for assessing the vulnerability of aquatic resources to global change. The task will contribute experimental and modeling tools for assessments of the interactions of global climate and UV changes with coral reefs and selected watersheds and estuaries in the U.S. These activities are contributing primarily to two APGs in the ecosystems component of the Global Change Research Multiyear Plan: the 2006 APG (APG 3) on building the capacity to assess global change impacts on coastal aquatic ecosystems, including coral reefs and estuaries and the 2004 APG (APG 2) on building capacity to assess and respond to global change impacts on selected watersheds. One major task objective is to assess interactions of global warming and UV exposure that are contributing to the observed coral bleaching and disease. Our lab is working with scientists at the NHEERL Gulf Ecology Lab to characterize UV exposure and effects at several coral reef sites. Other research in this task is examining the interactions between UV-induced breakdown of refractory organic matter in estuaries and coastal areas that enhance UV penetration into the water and concurrently form biologically-labile nitrogen-, phosphorus- and carbon-containing substances that stimulate productivity and microbial activity. This task also involves research in central Brazil that is part of the Large Scale Biosphere Atmosphere Experiment (LBA). The objectives of this project are to assess the impacts of land use and climatic changes on soil nutrient cycles and microbiota, trace gas exchange and water quality in the Brazilian cerrado. This work involves a close collaboration between EPA and a group of scientists from the Department of Ecology, University of Brasilia, Brazil. Other objectives of this task are to assess the interactions of land use and climate changes with the ecological functioning of streams in watersheds of the Piedmont region of the southestern U.S.
Description:
Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 (ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the Southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals,hv) bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) non-decarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals,hv) bCO2 + cH2O2 + Cx-bHy'Oz' (COOH)m.