On the Use of Hydroxyl Radical Kinetics to Assess the Number-Average Molecular Weight of Dissolved Organic Matter

Dissolved organic matter (DOM) is involved in numerous environmental processes, and its molecular size is important in many of these processes, such as DOM bioavailability, DOM sorptive capacity, and the formation of disinfection byproducts during water treatment. The size and size distribution of the molecules composing DOM remains an open question. In this contribution, an indirect method to assess the average size of DOM is described, which is based on the reaction of hydroxyl radical (HO•) quenching by DOM. HO• is often assumed to be relatively unselective, reacting with nearly all organic molecules with similar rate constants. Literature values for HO• reaction with organic molecules were surveyed to assess the unselectivity of DOM and to determine a representative quenching rate constant (krep = 5.6 × 109 M–1 s–1). This value was used to assess the average molecular weight of various humic and fulvic acid isolates as model DOM, using literature HO• quenching constants, kC,DOM. The results obtained by this method were compared with previous estimates of average molecular weight. The average molecular weight (Mn) values obtained with this approach are lower than the Mn measured by other techniques such as size exclusion chromatography (SEC), vapor pressure osmometry (VPO), and flow field fractionation (FFF). This suggests that DOM is an especially good quencher for HO•, reacting at rates close to the diffusion-control limit. It was further observed that humic acids generally react faster than fulvic acids. The high reactivity of humic acids toward HO• is in line with the antioxidant properties of DOM. The benefit of this method is that it provides a firm upper bound on the average molecular weight of DOM, based on the kinetic limits of the HO• reaction. The results indicate low average molecular weight values, which is most consistent with the recent understanding of DOM. A possible DOM size distribution is discussed to reconcile the small nature of DOM with the large-molecule behavior observed in other studies.