Many aspects of the carbon cycle can be assessed from temporal changes in the (13)C/(12)C ratio of oceanic bicarbonate. (13)C/(12)C can temporarily rise when large amounts of (13)C-depleted photosynthetic organic matter are buried at enhanced rates, and can decrease if phytomass is rapidly oxidized or if low (13)C is rapidly released from methane clathrates. Assuming that variations of the marine (13)C/(12)C ratio are directly recorded in carbonate rocks, thousands of carbon isotope analyses of late Precambrian examples have been published to correlate these otherwise undatable strata and to document perturbations to the carbon cycle just before the great expansion of metazoan life. Low (13)C/(12)C in some Neoproterozoic carbonates is considered evidence of carbon cycle perturbations unique to the Precambrian. These include complete oxidation of all organic matter in the ocean and complete productivity collapse such that low-(13)C/(12)C hydrothermal CO(2) becomes the main input of carbon. Here we compile all published oxygen and carbon isotope data for Neoproterozoic marine carbonates, and consider them in terms of processes known to alter the isotopic composition during transformation of the initial precipitate into limestone/dolostone. We show that the combined oxygen and carbon isotope systematics are identical to those of well-understood Phanerozoic examples that lithified in coastal pore fluids, receiving a large groundwater influx of photosynthetic carbon from terrestrial phytomass. Rather than being perturbations to the carbon cycle, widely reported decreases in (13)C/(12)C in Neoproterozoic carbonates are more easily interpreted in the same way as is done for Phanerozoic examples. This influx of terrestrial carbon is not apparent in carbonates older than approximately 850 Myr, so we infer an explosion of photosynthesizing communities on late Precambrian land surfaces. As a result, biotically enhanced weathering generated carbon-bearing soils on a large scale and their detrital sedimentation sequestered carbon. This facilitated a rise in O(2) necessary for the expansion of multicellular life.
A thick Neoproterozoic carbonate and glaciogenic succession of the southern Congo craton has yielded δ 13 C and 87 Sr/ 86 Sr records through the later Cryogenian (ca. 750-600 Ma) and earlier part of the Terminal Proterozoic (ca. 600-570 Ma). Sizeable negative δ 13 C excursions (to less than-5‰) occur above each of two glacial intervals and the 87 Sr/ 86 Sr values of marine carbonates shift from ~0.7072 to ~0.7079 at the upper glacial level. These geochemical constraints provide a Marinoan (younger Varanger) age for the upper glacial interval, previously regarded as a second phase of the Sturtian glaciation. The δ 13 C record from the Congo craton is therefore incompatible with recent global δ 13 C syntheses that have identified four or more separate ice ages during the Neoproterozoic. A cladistic analysis of geologic and geochemical characters of 12 Neoproterozoic glacial deposits identifies two distinct groups that are found in a consistent stratigraphic order whenever two glacial units occur within a single succession. We use δ 13 C and 87 Sr/ 86 Sr records from the Congo craton and other key successions to test the null hypothesis that there were only two global glaciations (Sturtian and Marinoan) during the Neoproterozoic. Placing the GSSP (global stratotype section and point) for the base of the Terminal Proterozoic within or just above a cap carbonate of the younger (Marinoan) glaciogenic succession would confine all known Neoproterozoic glaciations to the Cryogenian. The rapid shift in marine 87 Sr/ 86 Sr to more radiogenic values during the Marinoan glaciation is opposite that predicted by the snowball Earth scenario which calls for continental runoff to cease during glaciation, resulting in a shift to less radiogenic values.
The Earth's most severe glaciations are thought to have occurred about 600 million years ago, in the late Neoproterozoic era. A puzzling feature of glacial deposits from this interval is that they are overlain by 1-5-m-thick 'cap carbonates' (particulate deep-water marine carbonate rocks) associated with a prominent negative carbon isotope excursion. Cap carbonates have been controversially ascribed to the aftermath of almost complete shutdown of the ocean ecosystems for millions of years during such ice ages--the 'snowball Earth' hypothesis. Conversely, it has also been suggested that these carbonate rocks were the result of destabilization of methane hydrates during deglaciation and concomitant flooding of continental shelves and interior basins. The most compelling criticism of the latter 'methane hydrate' hypothesis has been the apparent lack of extreme isotopic variation in cap carbonates inferred locally to be associated with methane seeps. Here we report carbon isotopic and petrographic data from a Neoproterozoic postglacial cap carbonate in south China that provide direct evidence for methane-influenced processes during deglaciation. This evidence lends strong support to the hypothesis that methane hydrate destabilization contributed to the enigmatic cap carbonate deposition and strongly negative carbon isotopic anomalies following Neoproterozoic ice ages. This explanation requires less extreme environmental disturbance than that implied by the snowball Earth hypothesis.
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