Assessing the source of the photochemical formation of hydroxylating species from dissolved organic matter using model sensitizers.

Dissolved organic matter (DOM) is ubiquitous in natural waters and can facilitate the chemical transformation of many contaminants through the photochemical production of reactive intermediates, such as singlet oxygen (1O2), excited triplet state DOM (3DOM*), and hydroxylating species (˙OH and other intermediates of similar reaction chemistry). The formation mechanism of most reactive intermediates is well understood, but this is not the case for the formation of hydroxylating species from DOM. To investigate this chemistry, DOM model sensitizers were irradiated with two different probe compounds (benzene and benzoic acid) at two irradiation wavelengths (254 and 320 nm). The ability of DOM model sensitizers to hydroxylate these arene probes was assessed by measuring rates of formation of the hydroxylated probe compounds (phenol and salicylic acid). Multiple classes of model sensitizers were tested, including quinones, hydroxybenzoic acids, aromatic ketones, and other triplet forming species. Of these classes of model sensitizers, only quinones and hydroxybenzoic acids had a hydroxylating capacity. Methanol quenching experiments were used to assess the reactivity of hydroxylating species. These results have several implications for the systems tested. First, they suggest that the hydroxylating intermediate produced from hydroxybenzoic acid photolysis may not be hydroxyl radical, but a different hydroxylating species. Also, these data prompted investigation of whether quinone photoproducts have a hydroxylating capacity. These results confirm that hydroxybenzoic acids and quinones are important to the photochemical production of hydroxylating species from DOM, but the mechanism by which this occurs for these classes of sensitizers is still elusive.

Investigation of the Coupled Effects of Molecular Weight and Charge-Transfer Interactions on the Optical and Photochemical Properties of Dissolved Organic Matter.

We studied the formation of photochemically produced reactive intermediates (RI) from dissolved organic matter (DOM). Specifically, we focused on the effects of variable molecular weight and chemical reduction on the optical properties of DOM (absorbance and fluorescence) and the formation of singlet oxygen ((1)O2), DOM triplet excited states ((3)DOM*), and the hydroxyl radical ((•)OH). The data are largely evaluated in terms of a charge-transfer (CT) model, but deficiencies in the model to explain the data are pointed out when evident. A total of two sets of samples were studied that were subjected to different treatments; the first set included secondary-treated wastewaters and a wastewater-impacted stream, and the second was a DOM isolate. Treatments included size fractionation and chemical reduction using sodium borohydride. Taken as a whole, the results demonstrate that decreasing molecular weight and borohydride reduction work in opposition regarding quantum efficiencies for (1)O2 and (3)DOM* production but in concert for fluorescence and (•)OH production. The optical and photochemical data provide evidence for a limited role of CT interactions occurring in lower-molecular-weight DOM molecules. In addition, the data suggest that the observed optical and photochemical properties of DOM are a result of multiple populations of chromophores and that their relative contribution is changed by molecular-weight fractionation and borohydride reduction.