Decreasing Photoreactivity and Concurrent Change in Dissolved Organic Matter Composition with Increasing Inland Water Residence Time

Abstract

Photochemical degradation of dissolved organic matter (DOM) has been the subject of numerous studies, however, its regulation along the inland water continuum is still unclear. We aimed to unravel the DOM photoreactivity and concurrent DOM compositional changes across 30 boreal aquatic ecosystems including peat waters, streams, rivers, and lakes distributed along a water retention time (WRT) gradient. Samples were subject to a standardized exposure of simulated sunlight. We measured the apparent quantum yield (AQY), which corresponds to DOM photomineralization per photon absorbed, and the compositional change in DOM at bulk and individual compound levels in the original samples and after irradiation. AQY increased with the abundance of terrestrially-derived DOM and decreased at higher WRT. Additionally, the photochemical change in both DOM optical properties and molecular composition resembled changes along the natural boreal WRT gradient at low WRT (< 3 yr). Accordingly, mass spectrometry revealed that the abundance of photolabile and photoproduced molecules decreased with WRT along the boreal aquatic continuum. Our study highlights the tight link between DOM composition and DOM photodegradation. We suggest that photodegradation is an important driver of DOM composition change in waters with low WRT, where DOM is highly photoreactive.