The role of humic and fulvic acids in the phototransformation of phenolic compounds in seawater

Humic substances (HS) are known to act as photosensitizers toward the transformation of pollutants in the surface layer of natural waters. This study focused on the role played by HS toward the transformation of xenobiotics in seawater, with the purpose of assessing the prevailing degradation routes. Phenol was chosen as model xenobiotic and its transformation was investigated under simulated sunlight in the presence of terrestrial or marine humic and fulvic acids, in pure water at pH 8, artificial seawater (ASW) or natural seawater (NSW). The following parameters were determined: (1) the phenol degradation rate; (2) the variation in HS concentration with irradiation time; (3) the production of transformation products; (4) the influence of iron species on the transformation process. Faster transformation of phenol was observed with humic acids (HA) compared to fulvic acids (SRFA), and transformation induced by both HA and SRFA was faster in ASW than that in pure water. These observations can be explained by assuming an interplay between different competing and sometimes opposite processes, including the competition between chloride, bromide and dissolved oxygen for reaction with HS triplet states. The analysis of intermediates formed in the different matrices under study showed the formation of several hydroxylated (hydroquinone, 1,4-benzoquinone, resorcinol) and condensed compounds (2,2'-bisphenol, 4,4'-bisphenol, 4-phenoxyphenol). Although 1,4-benzoquinone was the main transformation product, formation of condensed molecules was significant with both HA and SRFA. Experiments on natural seawater spiked with HS confirmed the favored formation of condensed products, suggesting a key role of humic matter in dimerization reactions occurring in saline water. (C) 2014 Elsevier B.V. All rights reserved.