Photochemical mineralisation in a humic boreal lake: temporal variability and contribution to carbon dioxide production

Abstract. Sunlight induces photochemical mineralisation of chromophoric dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) in inland waters, resulting in carbon dioxide (CO2) emissions to the atmosphere. Photochemical rate modelling is used to determine sunlight-induced CO2 emissions on large spatial and temporal scales. A sensitive model parameter is the wavelength-specific photochemical CDOM reactivity, the apparent quantum yield (AQY). The modelling studies so far assume that AQY spectra determined for single lakes and on single occasions represent larger spatial and temporal scales. Here, we studied a humic boreal lake in Sweden. We measured AQY spectra for photochemical DIC production monthly between June and November 2014 and parameterised a photochemical rate model. Photochemical reactivity increased slightly during the open water period, likely due to a high rainfall event with consecutive mixing in autumn that increased availability of highly photoreactive CDOM. However, the variability in AQY spectra over time was much smaller than previously reported variability in AQY spectra across lakes. Yet, using either the AQY spectrum from the least or from the most photoreactive water sample resulted in a 5-fold difference in simulated annual DIC photoproduction (2.0 ± 0.1 and 10.3 ± 0.7 g C m−2 yr−1, respectively). Using the monthly measured AQY spectrum to simulate DIC photoproduction for month-long time periods resulted in an apparent time lag between irradiance and DIC photoproduction. This suggested that temporal variability in AQY spectra occurs on shorter time scales. Therefore, we parameterised the model with the pooled AQY spectrum of six monthly measurements. Simulated DIC photoproduction for three years (2012–2014) averaged 4.5 ± 0.2 g C m−2 yr−1, which represented 3 % of the mean CO2 emissions from this lake. We conclude that (1) it may be recommendable to conduct repeated AQY measurements across the season for more accurate simulation of annual photochemical DIC production in lakes and (2), in agreement with previous studies, direct CDOM photomineralisation makes only a minor contribution to mean CO2 emissions from Swedish humic lakes.