Autotrophic dissolved organic matter (DOM) is central to the carbon biogeochemistry of aquatic systems, and the full complexity of autotrophic DOM has not been extensively studied, particularly by high‐resolution mass spectrometry (HRMS). Terrestrial DOM tends to dominate HRMS studies in freshwaters due to the propensity of such compounds to ionize by negative mode electrospray, and possibly also because ionizable DOM produced...