Photochemical production of polyols arising from significant photo-transformation of dissolved organic matter in the oligotrophic surface ocean

Ultrahigh resolution mass spectrometry of marine dissolved organic matter (DOM) has suggested the presence of many common molecular compositions throughout the open ocean. The majority of these supposedly ubiquitous molecules was concluded to represent the refractory marine DOM pool. This study demonstrates that 24 h of exposure of Atlantic and Pacific surface DOM to simulated sunlight causes phototransformation of about half of these supposedly refractory molecular compositions. It is suggested that these transformations are related to indirect photobleaching possibly involving reactive oxygen species (e.g. hydroxyl radicals), because very little change in the fluorescent component of the DOM (FDOM) was observed during the photo-degradation experiments. A significant decline in average mass with distinct decrease of average O/C ratios and concomitant increase of H/C ratios was observed. NMR spectra revealed a decrease in aromatic and olefinic unsaturation and the formation of a limited and near identical suite of oxygenated aliphatic compounds in both Atlantic and Pacific surface DOM. Their NMR characteristics indicated a mixture of about 10 polyols that are plausible products of convergent pathways of photochemical carbohydrate decomposition and oxidation of functionalized, branched aliphatic compounds. These prominent photochemical signature molecules amounted to ~ 2% of total proton NMR integral and are expected to be quickly consumed by various microorganisms in the open ocean. These results may suggest a fast photo-induced large-scale cycling of DOM within the surface ocean dynamic equilibrium of photo- and bio-transformations.