The Paleoproterozoic Lomagundi Event is an interval of 130-250 million years, ca. 2.3-2.1 billion years ago, in which extraordinarily 13 C enriched (>10‰) limestones and dolostones occur globally. The high levels of organic carbon burial implied by the positive δ 13 C values suggest the production of vast quantities of O 2 as well as an alkalinity imbalance demanding extremely low levels of weathering. The oxidation of sulfides has been proposed as a mechanism capable of ameliorating these imbalances: It is a potent sink for O 2 as well as a source of acidity. However, sulfide oxidation consumes more O 2 than it can supply CO 2 , leading to insurmountable imbalances in both carbon and oxygen. In contrast, the oxidation of siderite (FeCO 3 proper, as well as other Fe 2+ -bearing carbonate minerals), produces 4 times more CO 2 than it consumes O 2 and is a common-although often overlooked-constituent of Archean and Early Proterozoic sedimentary successions. Here we propose that following the initial rise of O 2 in the atmosphere, oxidation of siderite provided the necessary carbon for the continued oxidation of sulfides, burial of organic carbon, and, most importantly, accumulation of free O 2 . The duration and magnitude of the Lomagundi Event were determined by the size of the preexisting Archean siderite reservoir, which was consumed through oxidative weathering. Our proposal helps resolve a long-standing conundrum and advances our understanding of the geologic history of atmospheric O 2 .carbon isotopes | oxygen | siderite | carbon cycle | Great Oxidation Event R econstructing the geologic history of atmospheric oxygen is among the foremost scientific challenges of our time (1). The level of atmospheric oxygen (pO 2 ) without doubt played a key role in the evolution of the Earth System (2), exerting a major influence on the biosphere, especially the evolution of metazoans (3). With no direct way of measuring oxygen concentrations in deep geologic time, the stable isotopes of carbon recorded in marine limestones provide key constraints (4). Carbon enters the ocean−atmosphere system through volcanoes and weathering of carbon-bearing sedimentary rocks and can exit in one of two ways: (i) uptake during photosynthesis and burial of organic carbon leading to O 2 production and (ii) reaction during weathering and formation of CaCO 3 in the ocean. The carbon isotopic record tells us how carbon was partitioned between these two sinks: A δ 13 C value of 0‰ indicates that ∼80% of incoming carbon was buried as carbonate carbon and 20% as organic carbon. Positive excursions in δ 13 C are unusual and indicate that a larger fraction of carbon was fixed and buried as organic carbon and, with it, a larger amount of O 2 was produced.Following the indications for the first rise of O 2 in the atmosphere (5, 6) is the largest and most protracted period of 13 C enrichment in the geologic record, known as the Lomagundi Event (Fig. 1). Limestones and dolostones with extreme carbon isotopic values of + 8‰ to greater than + 15‰ occur g...