In this study, we examine the role of the hydroxyl (OH*) radical as a mechanism for the photodecomposition of chromophoric dissolved organic matter (CDOM) in sunlit surface waters. Using gamma-radiolysis of water, OH* was generated in solutions of standard humic substances in quantities comparable to those produced on time scales of days in sunlit surface waters. The second-order rate coefficients of OH* reaction with Suwannee River fulvic (SRFA; 2.7 x 10(4) s(-1) (mg of C/L)(-1)) and humic acids (SRHA; 1.9 x 10(4) s(-1) (mg of C/L)(-1)) are comparable to those observed for DOM in natural water samples and DOM isolates from other sources but decrease slightly with increasing OH* doses. OH* reactions with humic substances produced dissolved inorganic carbon (DIC) with a high efficiency of approximately 0.3 mol of CO2/mol of OH*. This efficiency stayed approximately constant from early phases of oxidation until complete mineralization of the DOM. Production rates of low molecular weight (LMW) acids including acetic, formic, malonic, and oxalic acids by reaction of SRFA and SRHA with OH* were measured using HPLC. Ratios of production rates of these acids to rates of DIC production for SRHA and for SRFA were similar to those observed upon photolysis of natural water samples. Bioassays indicated that OH* reactions with humic substances do not result in measurable formation of bioavailable carbon substrates other than the LMW acids. Bleaching of humic chromophores by OH* was relatively slow. Our results indicate that OH* reactions with humic substances are not likely to contribute significantly to observed rates of DOM photomineralization and LMW acid production in sunlit waters. They are also not likely to be a significant mechanism of photobleaching except in waters with very high OH* photoformation rates.
This study examines the importance of several possible mechanisms causing sunlight-mediated changes in the amounts of bacterial utilization and biomass growth on dissolved organic matter (DOM) from allochthonous sources. Our results demonstrate that, while hydroxyl radical reactions with DOM can be an important process increasing its bioavailability, other photoreactions will cause most of the sunlight-induced increases unless hydroxyl production rates are high (Ͼϳ7 mol L Ϫ1 d Ϫ1 ). Low molecular weight carboxylic acids could not account for most of the observed sunlight and hydroxyl-induced increases in DOM bioavailability. Both sunlight and hydroxyl-mediated reactions significantly decreased the bacterial growth efficiency of DOM, indicating that photochemical reactions affect not only the fraction of the total DOM pool available to bacteria on ecologically relevant timescales but also the substrate quality and ultimately the environmental fate of this material. Extrapolation of these results to field conditions suggests that photochemical and biochemical mineralization could be an important sink of DOC and source of bioavailable carbon in the Plum Island estuary during the summer months.Dissolved organic matter (DOM) is a heterogeneous mixture of natural organic compounds that is present in all natural waters. The sources of this carbon in freshwater systems include both in situ biological production (autochthonous sources) and detrital carbon from the surrounding terrestrial watershed (allochthonous sources). At one time, relatively labile autochthonous material was thought to be the dominant source of substrates for bacterial growth in these systems (Cole et al. 1982). More recently, it has become clear that relatively recalcitrant allochthonous (or humic) organic matter can also be a major source of energy and carbon for bacterial growth in many freshwaters (Tranvik 1988;Moran and Hodson 1990).One important environmental factor that may change the utilization of DOM by bacteria is exposure to light. A variety of studies have shown that irradiation of DOM by natural and/or simulated sunlight can increase both the amount of DOM that is susceptible to bacterial utilization and the abil- AcknowledgmentsThis research was funded by the National Science Foundation (Chemical Oceanography, grant OCE-9819089) and by postdoctoral fellowships to M.J.P. and S.B. through the National Science Foundation (Earth Sciences) and the Knut and Alice Wallenberg Foundation, respectively. The authors thank Phil Gschwend for the use of the HPLC equipment; Bob Chen, Chuck Hopkinson, and Pete Raymond for assistance in field sampling; Joe Vallino for background information on the Parker River; and Barbara Southworth for lab assistance and estimates of hydroxyl radical production rates.
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