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.     

Carbon isotope kinetics of gaseous hydrocarbons generated from different kinds of vitrinites

Kinetics study of gaseous hydrocarbons generated from vitrinites based on pyrolysis of gold tube closed system shows that the activation energies of methane generated from telocollinite are higher than that from desmocol-linite due to structure differences. But carbon isotope ratios of generated methane in pyrolysates of vitrinites at the same temperature points are similar. Carbon isotope ratio of methane may decrease in the early stage of gas generation and then increase in the later stage. But at higher temperature, δ13C1 decreases slightly or almost keeps stable with increasing temperature. Since it is known that carbon isotope distillation is controlled by time, temperature and carbon isotope ratio of bulk organic matter, the character of side chains connected to macromolecule of vitrinite and distribution of activation energies have no obvious effect on carbon isotope fraction. Decreasing trend of δ13C1 in the early stage may be caused by contagious structure of vitrinite or differences of activation energies between 12C-12C and 12C-13C are not strictly constant at different ranges of activation energy area.     

Stable isotopic evidence for methane seeps in Neoproterozoic postglacial cap carbonates

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.     

High CO2 levels in the Proterozoic atmosphere estimated from analyses of individual microfossils

Solar luminosity on the early Earth was significantly lower than today. Therefore, solar luminosity models suggest that, in the atmosphere of the early Earth, the concentration of greenhouse gases such as carbon dioxide and methane must have been much higher. However, empirical estimates of Proterozoic levels of atmospheric carbon dioxide concentrations have not hitherto been available. Here we present ion microprobe analyses of the carbon isotopes in individual organic-walled microfossils extracted from a Proterozoic ( approximately 1.4-gigayear-old) shale in North China. Calculated magnitudes of the carbon isotope fractionation in these large, morphologically complex microfossils suggest elevated levels of carbon dioxide in the ancient atmosphere--between 10 and 200 times the present atmospheric level. Our results indicate that carbon dioxide was an important greenhouse gas during periods of lower solar luminosity, probably dominating over methane after the atmosphere and hydrosphere became pervasively oxygenated between 2 and 2.2 gigayears ago.     

Increased terrestrial methane cycling at the Palaeocene-Eocene thermal maximum

The Palaeocene-Eocene thermal maximum (PETM), a period of intense, global warming about 55 million years ago, has been attributed to a rapid rise in greenhouse gas levels, with dissociation of methane hydrates being the most commonly invoked explanation. It has been suggested previously that high-latitude methane emissions from terrestrial environments could have enhanced the warming effect, but direct evidence for an increased methane flux from wetlands is lacking. The Cobham Lignite, a recently characterized expanded lacustrine/mire deposit in England, spans the onset of the PETM and therefore provides an opportunity to examine the biogeochemical response of wetland-type ecosystems at that time. Here we report the occurrence of hopanoids, biomarkers derived from bacteria, in the mire sediments from Cobham. We measure a decrease in the carbon isotope values of the hopanoids at the onset of the PETM interval, which suggests an increase in the methanotroph population. We propose that this reflects an increase in methane production potentially driven by changes to a warmer and wetter climate. Our data suggest that the release of methane from the terrestrial biosphere increased and possibly acted as a positive feedback mechanism to global warming.     

Evidence from fluid inclusions for microbial methanogenesis in the early Archaean era

Methanogenic microbes may be one of the most primitive organisms, although it is uncertain when methanogens first appeared on Earth. During the Archaean era (before 2.5 Gyr ago), methanogens may have been important in regulating climate, because they could have provided sufficient amounts of the greenhouse gas methane to mitigate a severely frozen condition that could have resulted from lower solar luminosity during these times. Nevertheless, no direct geological evidence has hitherto been available in support of the existence of methanogens in the Archaean period, although circumstantial evidence is available in the form of approximately 2.8-Gyr-old carbon-isotope-depleted kerogen. Here we report crushing extraction and carbon isotope analysis of methane-bearing fluid inclusions in approximately 3.5-Gyr-old hydrothermal precipitates from Pilbara craton, Australia. Our results indicate that the extracted fluids contain microbial methane with carbon isotopic compositions of less than -56 per thousand included within original precipitates. This provides the oldest evidence of methanogen (> 3.46 Gyr ago), pre-dating previous geochemical evidence by about 700 million years.     

High-resolution carbon isotope record for the Paleocene-Eocene thermal maximum from the Nanyang Basin,Central China

The Paleocene-Eocene thermal maximum (PETM) was a transient episode of global warming, associated with massive atmospheric greenhouse gas input that occurred at the Paleocene/Eocene boundary. Biostratigraphic and isotope stratigraphic studies indicate that the PETM event is well documented in the marl deposits of the Yuhuangding section in the Nanyang Basin, Central China, with a carbon isotope negative excursion of ~6.1‰ within 19-m-thick marl deposits. This is the highest resolution record of the PETM so far found in the world. The PETM event was triggered within 2-cm-thick marl sediments, with a decrease of δ¹³C (stable carbon isotope ratio) from –3.2‰ to –5.2‰, suggesting a massive methane hydrate release for a transient period that was possibly caused by a catastrophic event. A comparison between marine and terrestrial records indicates a “Three-Phase Model” for the PETM event. Initially there is a rapid negative excursion in the δ¹³C record, followed by a slowly decreasing trend, and then a gradual positive recovery, corresponding respectively to a rapid dissociation of oceanic methane hydrate, followed by a slow release of methane and then the consumption of the released methane.     

A humid climate state during the Palaeocene/Eocene thermal maximum

An abrupt climate warming of 5 to 10 degrees C during the Palaeocene/Eocene boundary thermal maximum (PETM) 55 Myr ago is linked to the catastrophic release of approximately 1,050-2,100 Gt of carbon from sea-floor methane hydrate reservoirs. Although atmospheric methane, and the carbon dioxide derived from its oxidation, probably contributed to PETM warming, neither the magnitude nor the timing of the climate change is consistent with direct greenhouse forcing by the carbon derived from methane hydrate. Here we demonstrate significant differences between marine and terrestrial carbon isotope records spanning the PETM. We use models of key carbon cycle processes to identify the cause of these differences. Our results provide evidence for a previously unrecognized discrete shift in the state of the climate system during the PETM, characterized by large increases in mid-latitude tropospheric humidity and enhanced cycling of carbon through terrestrial ecosystems. A more humid atmosphere helps to explain PETM temperatures, but the ultimate mechanisms underlying the shift remain unknown.     

吐哈盆地北部山前带下侏罗统天然气气源与成藏模式

为了明确山前带柯柯亚下侏罗统气藏,对于这套位于中上侏罗统油气藏之下的天然气性质、来源及成藏模式,运用地球化学分析和天然气气藏解剖方法进行研究.研究结果表明:本区天然气甲烷碳同位素分布在-44.0‰～－38.7‰,乙烷碳同位分布在-29.0‰～－27.5‰,属于偏腐泥型的腐殖气,伴生原油的物理性质和生物标志物呈现出典型的成熟煤系油特征,并与中上侏罗统油气来源不同,即地质条件和地球化学数据都证明天然气母质处于成熟演化阶段,垂向运移距离短,来自八道湾组煤系泥岩;天然气大量充注前大面积致密储层的形成、下侏罗统异常超压的发育以及源储的紧密叠置,都是形成致密砂岩气藏的地质条件.     

A marine microbial consortium apparently mediating anaerobic oxidation of methane

A large fraction of globally produced methane is converted to CO2 by anaerobic oxidation in marine sediments. Strong geochemical evidence for net methane consumption in anoxic sediments is based on methane profiles, radiotracer experiments and stable carbon isotope data. But the elusive microorganisms mediating this reaction have not yet been isolated, and the pathway of anaerobic oxidation of methane is insufficiently understood. Recent data suggest that certain archaea reverse the process of methanogenesis by interaction with sulphate-reducing bacteria. Here we provide microscopic evidence for a structured consortium of archaea and sulphate-reducing bacteria, which we identified by fluorescence in situ hybridization using specific 16S rRNA-targeted oligonucleotide probes. In this example of a structured archaeal-bacterial symbiosis, the archaea grow in dense aggregates of about 100 cells and are surrounded by sulphate-reducing bacteria. These aggregates were abundant in gas-hydrate-rich sediments with extremely high rates of methane-based sulphate reduction, and apparently mediate anaerobic oxidation of methane.     

Multi-origin alkanes related to CO2-rich, mantle-derived fluid in Dongying Sag, Bohai Bay Basin

With the newly obtained carbon isotope data for the natural gas, a pilot study of multiple-sourced alkanes related to the mantled-derived fluid is presented. The carbon isotope values of alkanes in the Dongying Sag possess thefea tures indicating a general organic origin. However, there are two sub-populations in the isotopic data set, which reflect two specific types of origins. In gene ral, the sub-population with high δ13CCH4 values is related to the CO2-rich, mantle-derived fluid, and it is distributed in the belts where mantle-derived fluid flow and basic volcanic activities have occurred. Geological and geochemical studies demonstrate that this variation of methane carbon isotope values in the Dongying Sag is unrelated with the basin bury and thermal histories, types of source rocks, and reactions between basin fluid and rocks. Mixing of mantle-derived fluid and organic sourced hydrocarbons is probably the cause for the variation .     

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.     

Ultraviolet-radiation-induced methane emissions from meteorites and the Martian atmosphere

Almost a decade after methane was first reported in the atmosphere of Mars there is an intensive discussion about both the reliability of the observations--particularly the suggested seasonal and latitudinal variations--and the sources of methane on Mars. Given that the lifetime of methane in the Martian atmosphere is limited, a process on or below the planet's surface would need to be continuously producing methane. A biological source would provide support for the potential existence of life on Mars, whereas a chemical origin would imply that there are unexpected geological processes. Methane release from carbonaceous meteorites associated with ablation during atmospheric entry is considered negligible. Here we show that methane is produced in much larger quantities from the Murchison meteorite (a type CM2 carbonaceous chondrite) when exposed to ultraviolet radiation under conditions similar to those expected at the Martian surface. Meteorites containing several per cent of intact organic matter reach the Martian surface at high rates, and our experiments suggest that a significant fraction of the organic matter accessible to ultraviolet radiation is converted to methane. Ultraviolet-radiation-induced methane formation from meteorites could explain a substantial fraction of the most recently estimated atmospheric methane mixing ratios. Stable hydrogen isotope analysis unambiguously confirms that the methane released from Murchison is of extraterrestrial origin. The stable carbon isotope composition, in contrast, is similar to that of terrestrial microbial origin; hence, measurements of this signature in future Mars missions may not enable an unambiguous identification of biogenic methane.     

树木年轮稳定碳同位素与气候变化的关系研究进展

树木的生长与立地环境密切相关并受气候变化的影响,树木年轮稳定碳同位素作为反映气 候与环境变化的一个重要参数,已被广大生态学家所重视并应用.综述了树木年轮稳定碳同位素的 测定方法,δ13C与CO2浓度、降水、温度、光照时间等气候因子的关系及其在古气候重建研究中的 应用,并针对该研究今后的发展方向提出了几点建议,为我国树木年轮稳定碳同位素研究的进一步 发展可提供理论参考.     

Calcium isotope fractionation and its controlling factors over authigenic carbonates in the cold seeps of the northern South China Sea

In this study, we analyzed stable calcium isotope results of authigenic carbonates from two cold seep areas of the Dongsha area and the Baiyun Sag in the northern South China Sea. The stable isotopes of carbon and oxygen as well as the mineral composition of authigenic carbonates were used to investigate control calcium isotope fractionation. The δ44/40Ca ratios of the southwestern Dongsha area samples ranged from 1.21‰ to 1.52‰ and the ratio of the Baiyun Sag sample was 1.55‰ of the SRM915a isotope standard. X-ray diffraction analysis showed that the carbonate samples consisted of dolomite, calcite and aragonite, with small amounts of high-Mg calcite and siderite. The δ13C values of the carbonates of the southwestern Dongsha area varied between δ49.21‰ and δ16.86‰ of the Vienna PeeDee Belemnite (VPDB) standard and the δ18O values ranged from 2.25‰ to 3.72‰ VPDB. The δ13C value of the Baiyun Sag sample was 2.36‰ VPDB and the δ18O value was 0.44‰ VPDB. The δ13C values of the carbonates of the southwestern Dongsha area revealed there is methane seeping into this area, with a variable contribution of methane-derived carbon. The sampled carbonates covered a range of δ13C values suggesting a dominant methane carbon source for the light samples and mixtures of δ13C values for the heavier samples, with possibly an organic or seawater carbon source. The δ18O values indicated that there is enrichment in 18O, which is related to the larger oxygen isotope fractionation in dolomite compared to calcite. The results of the Baiyun Sag sample exhibited normal seawater carbon and oxygen isotopic values, indicating that this sample is not related to methane seepage but instead to precipitation from seawater. The relatively high δ44/40Ca values indicated either precipitation at comparatively high rates in pore-water regimes with high alkalinity, or precipitation from an evolved heavy fluid with high degrees of Ca consumption (Raleigh type fractionation). The dolomite samples from the Dongsha area revealed a clear correlation between the carbon and calcium isotope composition, indicating a link between the amount and/or rate of carbonate precipitation and methane contribution to the bicarbonate source. The results of the three stable isotope systems, mineralogy and petrography, show that mineral composition, the geochemical environment of authigenic carbonates and carbon source can control the calcium isotope fractionation.     

Astronomical pacing of late Palaeocene to early Eocene global warming events

At the boundary between the Palaeocene and Eocene epochs, about 55 million years ago, the Earth experienced a strong global warming event, the Palaeocene-Eocene thermal maximum. The leading hypothesis to explain the extreme greenhouse conditions prevalent during this period is the dissociation of 1,400 to 2,800 gigatonnes of methane from ocean clathrates, resulting in a large negative carbon isotope excursion and severe carbonate dissolution in marine sediments. Possible triggering mechanisms for this event include crossing a threshold temperature as the Earth warmed gradually, comet impact, explosive volcanism or ocean current reorganization and erosion at continental slopes, whereas orbital forcing has been excluded. Here we report a distinct carbonate-poor red clay layer in deep-sea cores from Walvis ridge, which we term the Elmo horizon. Using orbital tuning, we estimate deposition of the Elmo horizon at about 2 million years after the Palaeocene-Eocene thermal maximum. The Elmo horizon has similar geochemical and biotic characteristics as the Palaeocene-Eocene thermal maximum, but of smaller magnitude. It is coincident with carbon isotope depletion events in other ocean basins, suggesting that it represents a second global thermal maximum. We show that both events correspond to maxima in the approximately 405-kyr and approximately 100-kyr eccentricity cycles that post-date prolonged minima in the 2.25-Myr eccentricity cycle, implying that they are indeed astronomically paced.     

鄂尔多斯盆地富县地区天然气地球化学特征及其成因

在对鄂尔多斯盆地富县地区奥陶系天然气地球化学特征研究的基础上,将其组分、烷烃气碳同位素、氦同位素、氩同位素等与盆地中部主要气田进行了对比,并结合区域地质背景综合分析了天然气的成因类型.指出该地区奥陶系天然气具有"干燥系数大、二氧化碳含量高、烷烃气碳同位素组成轻、热演化程度高"的特点,与靖边气田奥陶系天然气地球化学特征非常接近.应用国内学者建立的甲烷碳同位素与镜质体反射率关系方程式计算了富县地区奥陶系天然气的Ro约为3.33%,处于过成熟演化阶段.利用天然气成因判别图版综合分析,认为富县地区奥陶系天然气为油型气和煤成气的混合气体,且以油型气为主.     

Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation

Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide (P(CO2)) in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen. Our results suggest that P(CO2) was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results. We also find that the (17)O isotope anomalies of barites from Marinoan (approximately 635 million years ago) cap carbonates display a distinct negative spike (around -0.70 per thousand), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the P(CO2) was at its highest level in the past 750 million years. Our finding is consistent with the 'snowball Earth' hypothesis and/or a massive methane release after the Marinoan glaciation.     

Anaerobic oxidation of methane: Geochemical evidence from pore-water in coastal sediments of Qi’ao Island (Pearl River Estuary), southern China

The concentrations of CH4 and SO4^2- in pore-water and the carbon isotope compositions of total dissolved inorganic （TCO2） and OH4 were determined for three coastal sedimentary cores collected from Qi＇ao Island （Pearl River Estuary）, southern China. Results show that methane concentration changes dramatically at the base of the sulfate-reducing zone and sulfate concentration gradients are linear for all stations. In addition, the carbon isotope of methane becomes heavier at the sulfate-methane transition （SMT）, which causes ∑CO2-δ^13C to become the minimum. The geochemical profiles of pore-water render indirect evidence for anaerobic oxidation of methane （AOM）. Based on numerical modeling of AOM and sulfate-reducing rates, the portion of total sulfate reduction occurring via AOM is 9.0%, 84% and 45.5%, respectively, and the percentage of TCO2 added to the pore-water is 4.7%, 72.4% and 29.45% correspondingly for three sites. Furthermore, it is found that the methane concentration, methane diffusive flux and the depth of SMT are controlled by the quantity and quality of sedimentary organic matter incorporated into the sediments. The great amount of organic material is favorable for rapid depletion of sulfate via sedimentary organic matter degradation, and on the other hand, causes the increase of the methane flux in the SMT, which results in a portion of sulfate reduction supported by AOM. Accordingly, the SMT was shifted towards the sediment surface.     

Continental warming preceding the Palaeocene-Eocene thermal maximum

Marine and continental records show an abrupt negative shift in carbon isotope values at ～55.8?Myr ago. This carbon isotope excursion (CIE) is consistent with the release of a massive amount of isotopically light carbon into the atmosphere and was associated with a dramatic rise in global temperatures termed the Palaeocene-Eocene thermal maximum (PETM). Greenhouse gases released during the CIE, probably including methane, have often been considered the main cause of PETM warming. However, some evidence from the marine record suggests that warming directly preceded the CIE, raising the possibility that the CIE and PETM may have been linked to earlier warming with different origins. Yet pre-CIE warming is still uncertain. Disentangling the sequence of events before and during the CIE and PETM is important for understanding the causes of, and Earth system responses to, abrupt climate change. Here we show that continental warming of about 5?°C preceded the CIE in the Bighorn Basin, Wyoming. Our evidence, based on oxygen isotopes in mammal teeth (which reflect temperature-sensitive fractionation processes) and other proxies, reveals a marked temperature increase directly below the CIE, and again in the CIE. Pre-CIE warming is also supported by a negative amplification of δ(13)C values in soil carbonates below the CIE. Our results suggest that at least two sources of warming-the earlier of which is unlikely to have been methane-contributed to the PETM.