Temporal changes in photoreactivity of dissolved organic carbon and implications for aquatic carbon fluxes from peatlands

Aquatic systems draining peatland catchments receive a high loading of dissolved organic carbon (DOC) from the surrounding terrestrial environment. Whilst photoprocessing is known to be an important process in the transformation of aquatic DOC, the drivers of temporal variability in this pathway are less well understood. In this study, 8h laboratory irradiation experiments were conducted on water samples collected from two contrasting peatland aquatic systems in Scotland: a peatland stream and a reservoir in a catchment with high percentage peat cover. Samples were collected monthly at both sites from May 2014 to May 2015 and from the stream system during two rainfall events. DOC concentrations, absorbance properties and fluorescence characteristics were measured to investigate characteristics of the photochemically labile fraction of DOC. CO2 and CO produced by irradiation were also measured to determine gaseous photoproduction and intrinsic sample photoreactivity. Significant variation was seen in the photoreactivity of DOC between the two systems, with total irradiation-induced changes typically 2 orders of magnitude greater at the highDOC stream site. This is attributed to longer water residence times in the reservoir rendering a higher proportion of the DOC recalcitrant to photo-processing. During the experimental irradiation, 7% of DOC in the stream water samples was photochemically reactive and direct conversion to CO2 accounted for 46% of the measured DOC loss. Rainfall events were identified as important in replenishing photoreactive material in the stream, with lignin phenol data indicating mobilisation of fresh DOC derived from woody vegetation in the upper catchment. This study shows that peatland catchments produce significant volumes of aromatic DOC and that photoreactivity of this DOC is greatest in headwater streams; however, an improved understanding of water residence times and DOC input-output along the source to sea aquatic pathway is required to determine the fate of peatland carbon.