The cycles of carbon and oxygen at the Earth surface are intimately linked, where the burial of organic carbon into sediments represents a source of oxygen to the surface environment. This coupling is typically quantified through the isotope records of organic and inorganic carbon. Yet, the late Neoproterozoic Eon, the time when animals first evolved, experienced wild isotope fluctuations which do not conform to our normal understanding of the carbon cycle and carbon-oxygen coupling. We interpret these fluctuations with a new carbon cycle model and demonstrate that all of the main features of the carbonate and organic carbon isotope record can be explained by the release of methane hydrates from an anoxic dissolved organic carbon-rich ocean into an atmosphere containing oxygen levels considerably less than today.carbon isotope excursion | carbon monoxide | Shuram-Wonoka anomaly | earth evolution | atmospheric chemistry T he Neoproterozoic Eon was one of the most dynamic, yet enigmatic, times in Earth history. The Eon saw the breakup of super continent Rodinia and was punctuated by several glacial episodes, some of which were global in extent (1). The Eon saw the evolution and expansion of the first animals on Earth (2), as well as a rise in atmospheric oxygen and a major oxygenation of the deep ocean (3, 4). The isotopic composition* of carbonate (δ 13 C IC ) in sedimentary rocks reveals some of the largest isotope fluctuations in marine dissolved inorganic carbon (DIC) in Earth history (e.g., 4-6). Such isotope fluctuations are considered to reflect dynamics in the carbon cycle, and they have been used to reconstruct the history of atmospheric oxygen (e.g., 7, 8).The Neoproterozoic δ 13 C IC record, however, reveals excursions to less than mantle values (< − 5‰), and the assumed input value to the oceans (5, 9) ( Fig. 1). Prolonged negative δ 13 C IC excursions such as these cannot be explained by our normal understanding of the carbon cycle (e.g., 10, 11). While a diagenetic origin has been advocated to explain these excursions (12, 13), we will show that the major features of the carbon isotope records are consistent with a seawater origin through the action of the carbon cycle.Indeed, a nondiagenetic origin for the carbon isotope excursion is supported by the fact that in individual regions, an excursion may be observed over 100's of kilometers, mappable to the same stratigraphic horizon, and with isotope trends independent of sediment lithology (e.g., 14-16). The lateral extent and stratigraphic consistency of these excursions is difficult to reconcile with a diagenetic origin. Furthermore, modeling shows that the extent of isotopic alteration during diagenesis is highly dependant on the mineralogy of both the initial and the altered sediment (12). Isotope trends, however, transcend these differences (e.g., 6, 14, 17), further arguing against a diagenetic origin for the isotope signals.Many of the large Neoproterozoic isotope excursions display a relationship between the 18 O and 13 C of carbonate, which is...