A hydrothermal origin for isotopically anomalous cap dolostone cements from south China

The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan 'snowball Earth' ice age, ～635?Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ(13)C(PDB) down to -48‰; ref. 8) in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, (87)Sr/(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the (13)C-depleted signatures crystallized more than 1.6?Myr after deposition of the cap dolostone. Our results indicate that highly (13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly (13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly (13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the 'snowball' state, it would not have left extreme carbon isotope signals in cap dolostones.     

Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H2

Molecular hydrogen (H2) is the second most abundant trace gas in the atmosphere after methane (CH4). In the troposphere, the D/H ratio of H2 is enriched by 120 per thousand relative to the world's oceans. This cannot be explained by the sources of H2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H2 from its single largest source--the photochemical oxidation of methane--has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440 per thousand, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H2 produced from CH4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H2 from CH4 concentrates D in the product H2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H2.     

Oxygen-isotope evidence for recycled crust in the sources of mid-ocean-ridge basalts

Mid-ocean-ridge basalts (MORBs) are the most abundant terrestrial magmas and are believed to form by partial melting of a globally extensive reservoir of ultramafic rocks in the upper mantle. MORBs vary in their abundances of incompatible elements (that is, those that partition into silicate liquids during partial melting) and in the isotopic ratios of several radiogenic isotope systems. These variations define a spectrum between 'depleted' and 'enriched' compositions, characterized by respectively low and high abundances of incompatible elements. Compositional variations in the sources of MORBs could reflect recycling of subducted crustal materials into the source reservoir, or any of a number of processes of intramantle differentiations. Variations in (18)O/(16)O (principally sensitive to the interaction of rocks with the Earth's hydrosphere) offer a test of these alternatives. Here we show that (18)O/(16)O ratios of MORBs are correlated with aspects of their incompatible-element chemistry. These correlations are consistent with control of the oxygen-isotope and incompatible-element geochemistry of MORBs by a component of recycled crust that is variably distributed throughout their upper mantle sources.     

Coupling of surface temperatures and atmospheric CO2 concentrations during the Palaeozoic era

Atmospheric carbon dioxide concentrations seem to have been several times modern levels during much of the Palaeozoic era (543-248 million years ago), but decreased during the Carboniferous period to concentrations similar to that of today. Given that carbon dioxide is a greenhouse gas, it has been proposed that surface temperatures were significantly higher during the earlier portions of the Palaeozoic era. A reconstruction of tropical sea surface temperatures based on the delta18O of carbonate fossils indicates, however, that the magnitude of temperature variability throughout this period was small, suggesting that global climate may be independent of variations in atmospheric carbon dioxide concentration. Here we present estimates of sea surface temperatures that were obtained from fossil brachiopod and mollusc shells using the 'carbonate clumped isotope' method-an approach that, unlike the delta18O method, does not require independent estimates of the isotopic composition of the Palaeozoic ocean. Our results indicate that tropical sea surface temperatures were significantly higher than today during the Early Silurian period (443-423 Myr ago), when carbon dioxide concentrations are thought to have been relatively high, and were broadly similar to today during the Late Carboniferous period (314-300 Myr ago), when carbon dioxide concentrations are thought to have been similar to the present-day value. Our results are consistent with the proposal that increased atmospheric carbon dioxide concentrations drive or amplify increased global temperatures.