Several findings suggest that CO 2 emissions in lakes are not always directly linked to changes in metabolism but can be associated with interactions with the dissolved inorganic carbon equilibrium. Alkalinity has been described as a determining factor in regulating the relative contributions of biological and inorganic processes to carbon dynamics in lakes. Here we analyzed the relationship between metabolic changes in dissolved oxygen (DO) and dissolved inorganic carbon (DIC) at different timescales in eight lakes covering a wide range in alkalinity. We used high-frequency data from automatic monitoring stations to explore the sensitivity of DIC to metabolic changes inferred from oxygen. To overcome the problem of noisy data, commonly found in high-frequency measurements datasets, we used Singular Spectrum Analysis to enhance the diel signal-to-noise ratio. Our results suggest that in most of the studied lakes, a large part of the measured variability in DO and DIC reflects non-metabolic processes. Furthermore, at low alkalinity, DIC dynamics appear to be mostly driven by aquatic metabolism, but this relationship weakens with increasing alkalinity. The observed deviations from the metabolic 1:1 stoichiometry between DO and DIC were strongly correlated with the deviations expected to occur from calcite precipitation, with a stronger correlation when accounting also for the benthic contribution of calcite precipitation. This highlights the role of calcite precipitation as an important driver of CO 2 supersaturation in lakes with alkalinity above 1 meq L-1 , which represents 57% of the global area of lakes and reservoirs around the world.

The relevance of pelagic calcification in the global carbon budget of lakes and reservoirsCalcite precipitation acts as a carbon sink in the sediments and a short-term source of carbon dioxide (CO 2 ) to the atmosphere, as widely acknowledged in marine studies. However, pelagic calcite precipitation has received limited attention in lakes. Here we use the relationship between lake water alkalinity and reported calcification rates to provide the first global estimate of pelagic calcification in lakes. Global gross calcification rates amount to 0.03 Pg C yr -1 (0.01 -0.07) comparable to rates of organic carbon burial, whereas its related CO 2 release is largely buffered by the carbonate equilibria. Calcification occurs at water alkalinity above 1 meq/L corresponding to 57 % of global lake and reservoir surface area. Pelagic calcification therefore is a prevalent process in lakes and reservoirs at the global scale, with a potentially relevant role as a sedimentary inorganic carbon sink, comparable in magnitude to the total calcite accumulation rates in ocean sediments.

Pelagic calcification shapes the carbon budget of lakes and the sensitivity of dissolved inorganic carbon (DIC) responses to lake metabolism. This process, being tightly linked to primary production, needs to be understood within the context of summer eutrophication which is increasing due to human stressors and global change. Most lake carbon budget models do not account for calcification because the conditions necessary for its occurrence are not well constrained. This study aims at identifying ratios between calcification and primary production and the drivers that control these ratios in freshwater. Using in situ incubations in several European freshwater lakes, we identify a strong relationship between calcite saturation and the ratio between calcification and net ecosystem production (NEP) (p-value < 0.001, R2 = 0.95). NEP-induced calcification is a short-term process that is potentiated by the increase in calcite saturation occurring at longer time scales, usually reaching the highest levels in summer. The resulting summer calcification event has effects on the DIC equilibria, causing deviations from the metabolic 1:1 stoichiometry between DIC and dissolved oxygen (DO). The strong dependency of the ratio between NEP and calcification on calcite saturation can be used to develop a suitable parameterization to account for calcification in lake carbon budgets.