Carbon Isotope Patterns Research Articles

New evidence for compaction-driven vertical fluid migration into the Upper Ordovician (Hirnantian) Guanyinqiao bed of south China

The Late Ordovician was a time of major climatic and sea-level changes linked to the Hirnantian Glaciation, marked by large positive excursions of δ13Ccarb and δ13Corg globally known as the Hirnantian carbon isotopic excursion (HICE). However, some Upper Ordovician sections in South China exhibit negative δ13Ccarb shifts within the Hirnantian-age Guanyinqiao Bed. We hypothesize that these unusual carbon-isotope patterns were due to influx of 13C-depleted dissolved inorganic carbon (DIC) from the underlying Wufeng and overlying Longmaxi black shales as a result of greater compaction of these fine-grained siliciclastic units compared to the coarse-grained carbonate Guanyinqiao Bed. The isotopically light DIC was generated through oxidation of organic matter by either microbial sulfate reduction (MSR) or methanogenesis (with subsequent anaerobic oxidation of methane, AOM) in the black shales. This hypothesis is supported by petrographic and geochemical evidence of vertical fluid migration within the Guanyinqiao Bed and across its contacts. In the Shiqiao drillcore, the Guanyinqiao Bed exhibits a V-shaped depression at its top that is connected to vertical channels filled with secondary carbonate cements having low δ13C values. In the Huanggexi section, both the base and top of the Guanyinqiao Bed are characterized by strong U enrichments, despite unambiguously oxic depositional conditions as inferred from other proxies (Fe speciation, Mo and V concentrations). These anomalous U enrichments resulted from oxidative remobilization of U along the Guanyinqiao-black shale contacts and subsequent transport into the Guanyinqiao Bed through compactional flow. This finding demonstrates the importance of recognizing remobilized trace metals in sedimentary successions in order to avoid potential errors in redox interpretations.

Three wood isotopic reference materials for δ2H and δ13C measurements of plant methoxy groups

Methoxy groups (OCH3) of plants show specific stable carbon and hydrogen isotope patterns that are used for applications in biogeochemical, atmospheric, paleoclimatic and food research. The method of choice for determining stable hydrogen and carbon isotope values of methoxy groups (δ2HOCH3 and δ13COCH3 values) is the conversion to gaseous iodomethane (CH3I) and subsequent measurement by stable isotope ratio mass spectrometry. However, comparative measurements particularly for stable hydrogen isotopes of plant methoxy groups are limited due to the lack of suitable reference materials. We have prepared three batches of powdered wood samples (birch HUBG3, beech HUBG4, and tineo HUBG5) collected from different geographical locations to serve as long-term reference materials for normalization of δ2HOCH3 but also δ13COCH3 values. Methoxy contents of the three wood samples range between 4.7 and 5.4%. Methoxy groups from subsamples of the three homogenized wood samples were quantitatively converted to CH3I and δ2HOCH3 and δ13COCH3 values of this CH3I were calibrated against international reference substances by high-temperature conversion- and elemental analyzer isotope ratio mass spectrometry. The δ2HOCH and δ13COCH3 values of HUBG3 and HUBG4 at 1σ uncertainty calibrated to the VSMOW and VPDB isotopic δ-scale, respectively are −272.9 ± 1.5 mUr and −29.40 ± 0.13 mUr; and −239.1 ± 1.4 mUr and −30.17 ± 0.13 mUr, respectively. In addition, the calibrated δ2HOCH value of HUBG5 is −191.7 ± 0.8 mUr. Whilst the δ2HOCH3 values of the three wood samples span a relatively wide range (~−280 to −190 mUr) suitable for normalization of δ2HOCH3 values of most plant samples that have been reported so far, δ13COCH3 values are restricted to a composition (~−30 mUr) typical of wood methoxy groups. We suggest that the three investigated wood materials HUBG3–5 are ideally suited for long-term usage, inter-laboratory comparison, and together with the two recently reported methyl sulfate salts (HUBG1 and HUBG2) complete a new set of solid methoxy reference materials that cover almost the full range of plant methoxy groups reported so far. Therefore, we recommend replacing liquid CH3I and instead use the solid reference materials set HUBG1–5 for normalizing δ2HOCH3 and δ13COCH3 values to the respective δ-scales.

Origin of Au-Rich Carbonate-Hosted Replacement Deposits of the Kassandra Mining District, Northern Greece: Evidence for Late Oligocene, Structurally Controlled, and Zoned Hydrothermal Systems

Abstract The Au-rich polymetallic massive sulfide orebodies of the Kassandra mining district belong to the intrusion-related carbonate-hosted replacement deposit class. Marble lenses contained within the Stratoni fault zone host the Madem Lakkos and Mavres Petres deposits at the eastern end of the fault system, where paragenetically early skarn and massive sulfide are spatially associated with late Oligocene aplitic and porphyritic dikes. Skarn transitions into predominant massive and banded replacement sulfide bodies, which are overprinted by a younger assemblage of boulangerite-bearing, quartz-rich sulfide and late quartz-rhodochrosite vein breccias. The latter style of mineralization is most abundant at the Piavitsa prospect at the western end of the exposed fault system. The sulfide orebodies at the Olympias deposit are hosted by marble in association with the Kassandra fault, where textural and mineralogical similarities to the sulfide bodies within the Stratoni fault zone suggest a genetic relationship. Estimated trapping temperatures and pressures based on fluid inclusion data indicate that carbonate replacement mineralization took place at depths less than about 5.9 km. Carbon and oxygen isotope patterns in carbonate from the Stratoni fault zone support isotopic exchange principally through fluid–wall-rock interaction, whereas decarbonation and fluid-rock exchange reactions were important at the Olympias deposit. Carbonate minerals associated with skarn and replacement sulfide throughout the district have isotopic compositions that are consistent with formation from a hydrothermal fluid of magmatic origin. Lower homogenization temperatures and salinities in the younger quartz-rich sulfide assemblage and quartz-rhodochrosite vein breccias, together with low δ18O values of gangue carbonate, suggest dilution of a primary magmatic fluid with meteoric water late in the evolution of the hydrothermal system in both the Olympias area and the Stratoni fault zone. The replacement sulfide orebodies in the district likely inherited their uniform Pb isotope composition from a late Oligocene igneous source and the isotopically heterogeneous metamorphic basement units. Metal distribution patterns at the scale of the Stratoni fault zone show diminishing Cu concentration with decreasing Pb/Zn and Ag/Au ratios from Madem Lakkos to Mavres Petres and the Piavitsa prospect in the west. The sulfide orebodies at the Olympias deposit exhibit elevated Cu values in the east with increasing Pb/Zn and Ag/Au ratios down-plunge to the south-southwest. Metal concentration and ratios support zoning related to temperature and solubility changes with increasing distance from a probable magmatic source. Structural and igneous relationships, together with fluid inclusion microthermometric and carbon-oxygen isotope data and metal distribution patterns, are supportive of a zoned hydrothermal system that exceeded 12 km along the Stratoni fault zone, sourced by an igneous intrusion to the southeast of the Madem Lakkos deposit. The Olympias replacement sulfide orebodies, associated with the Kassandra fault, resulted from a local hydrothermal system that was likely derived from a concealed igneous intrusion to the east of the deposit.

Carbon-isotope record and paleoceanographic changes prior to the OAE 1a in the Eastern Tethys: Implication for the accumulation of organic-rich sediments

Abstract The Barremian and Aptian correspond to periods of marked changes in the atmosphere-ocean system, and offer valuable information about global tectonic events. Here, we present integrated high-resolution carbonate carbon-isotope (δ13Ccarb) and geochemical data that precede the Early Aptian oceanic anoxic event (OAE 1 a) in the Qiangtang Basin (Eastern Tethys). We identified a characteristic and well-correlatable Barremian-Lower Aptian carbon-isotope pattern that can be categorized into 10 Segments. The most notable features of the δ13Ccarb record are multiple negative carbon-isotope excursions in the Barremian-Aptian, and each is possibly linked to environmental changes. Two carbon isotopic plateaus are observed in the Upper Barremian, which are generally related to increased primary productivity, and to the concomitant development of dys-to anaerobic conditions. Our data indicate the development of anoxic conditions during shale deposition, which occurred under the conditions of a semi-enclosed lagoon environment. Such conditions, were likely localized, and not the primary mechanism responsible for the deposition of organic-rich sediments within the Shenglihe succession. The deposition of organic-rich shales was very likely due to global/regional warming. Rising temperatures and hydrological cycle strengthening during shale deposition are believed to have increased primary productivity, and thus resulted in the expansion of the local oxygen minimum zone within the water column.

Isotopic Composition of Abiogenic Gas Produced in Closed-System Fischer-Tropsch Synthesis: Implications for the Origins of the Deep Songliao Basin Gases in China

In this study, closed-system Fischer-Tropsch synthesis was conducted at 380°C and 30 MPa for 72 h with magnetite as a catalyst. The isotopic composition of the closed-system Fischer-Tropsch synthesis gas and the composition of known abiogenic gas were systematically studied, and the deep Songliao Basin gas was also investigated. The results show that closed-system Fischer-Tropsch synthesis of gaseous hydrocarbon isotopes exhibits a partial reverse order, which includes the reverse order of methane and ethane such as δ13C-C1>δ13C-C2<δ13C-C3 and δ2H-C1>δ2H-C2<δ2H-C3. Furthermore, experimental data on the control of NaBH4 content indicates that the carbon isotopes demonstrate a reverse order on condition that the H2/CO2 (mole ratio) is equal to or greater than 4.0; meanwhile, the hydrogen isotopes show a normal order. The deep Songliao Basin hydrocarbon gas component is similar to thermogenic gas and has a trend of a transition to oceanic hydrothermal system abiogenic gas. In addition, the deep Songliao Basin gas isotopic pattern is different from both Lost City and Kidd Creek where the deep Basin gas carbon isotopic pattern has a reverse order, and the hydrogen isotopic pattern has a normal order. Therefore, the deep Basin gas might be a mixture of the oil-type gas and the coal-formed gas, which could be the cause of the isotopic reverse.

Stable carbon and hydrogen isotopic characteristics of natural gas from Taibei sag, Turpan-Hami Basin, NW China

Abstract Turpan-Hami Basin is a major petroliferous basin in China. To date the natural gas exploration is concentrated in the Taibei sag. The origin and source of natural gas in the Taibei sag has long been controversial. To further investigate the origin and source of the natural gas in the Taibei sag, combined with previous studies and the local geological backgrounds, this study collected 23 gas samples from the Baka, Qiuling, Shanshan and Wenmi oil fields in the Taibei sag and analyzed the sample composition, stable carbon and hydrogen isotopes of all the gas samples. The results show that, gases from the four oil fields in the Taibei sag are dominated by hydrocarbon gas and belong to wet gas. Methane accounts for 65.84% to 97.94%, the content of heavy hydrocarbon (C2-5) can be up to 34.98%, while the content of nonhydrocarbon (CO2, N2) is trace. The δ13C1 value is –44.9‰ to –40.4‰, δ13C2 is –28.2‰ to –24.9‰, δ13C3 is –27.1‰ to –18.0‰ and δ13C4 is –26.7‰ to –22.1; while the variation of δD1 is not significant from –272‰ to –252‰, δD2 is –236‰ to –200‰ and δD3 is –222‰ to –174‰. Methane and its homologues (C2-5) are characterized by normal stable carbon and hydrogen isotopic distribution pattern, i.e., with the increase of carbon number, methane and its homologues become more and more enriched in 13C or D (δ13C1

Compound-specific carbon isotope patterns in needles of conifer tree species from the Swiss National Park under recent climate change

Elevated CO2 along with rising temperature and water deficits can lead to changes in tree physiology and leaf biochemistry. These changes can increase heat- and drought-induced tree mortality. We aim to reveal the impacts of climatic drivers on individual compounds at the leaf level among European larch (Larix decidua) and mountain pine (Pinus mugo) trees, which are widely distributed at high elevations. We investigated seasonal carbon isotope composition (δ13C) and concentration patterns of carbohydrates and organic acids in needles of these two different species from a case study in the Swiss National Park (SNP). We found that average and minimum air temperatures were the main climatic drivers of seasonal variation of δ13C in sucrose and glucose as well as in concentrations of carbohydrates and citric acid/citrate in needles of both tree species. The impact of seasonal climatic drivers on larch and mountain pine trees at the needle level is in line with our earlier study in this region for long-term changes at the tree-ring level. We conclude that the species-specific changes in δ13C and concentrations of carbohydrates and organic acids are sensitive indicators of changes in the metabolic pathways occurring as a result of climatic changes.

Arido-eustasy: A new example of non-glacial eustatic sea level change

Sea level fluctuation is common in the stratigraphical record and is partly explained by periodic polar glaciation. Such fluctuation in the absence of polar glaciation, during the warm periods of Earth's history, is poorly understood and currently under discussion. Here, I reconsider the palaeo-environmental information extracted from the variation in the carbon-isotope record and explain the phenomenon by coupling the levels of marine and fresh-water reservoirs through long-term wet and arid climate modes. The arido-eustasy model produces a standard anti-covariation pattern of marine organic and carbonate carbon-isotope records, which may appear throughout the geochemical record of the last 200 Myr. Under the model, orbitally forced periods of extremely wet climate result in environmental crisis, sea level falls, and carbon cycle perturbations, during which negative excursions in the marine organic carbon-isotope record of sediments containing matter from terrestrial vegetation should be understood as a proxy reporting periods of high precipitation rather than changes in the global carbon reservoir. I propose that the early Toarcian oceanic anoxic event is an example of arido-eustasy.

Fueled by methane: deep-sea sponges from asphalt seeps gain their nutrition from methane-oxidizing symbionts

Sponges host a remarkable diversity of microbial symbionts, however, the benefit their microbes provide is rarely understood. Here, we describe two new sponge species from deep-sea asphalt seeps and show that they live in a nutritional symbiosis with methane-oxidizing (MOX) bacteria. Metagenomics and imaging analyses revealed unusually high amounts of MOX symbionts in hosts from a group previously assumed to have low microbial abundances. These symbionts belonged to the Marine Methylotrophic Group 2 clade. They are host-specific and likely vertically transmitted, based on their presence in sponge embryos and streamlined genomes, which lacked genes typical of related free-living MOX. Moreover, genes known to play a role in host–symbiont interactions, such as those that encode eukaryote-like proteins, were abundant and expressed. Methane assimilation by the symbionts was one of the most highly expressed metabolic pathways in the sponges. Molecular and stable carbon isotope patterns of lipids confirmed that methane-derived carbon was incorporated into the hosts. Our results revealed that two species of sponges, although distantly related, independently established highly specific, nutritional symbioses with two closely related methanotrophs. This convergence in symbiont acquisition underscores the strong selective advantage for these sponges in harboring MOX bacteria in the food-limited deep sea.

The Working Group on the Anthropocene: Summary of evidence and interim recommendations

Abstract Since 2009, the Working Group on the ‘Anthropocene’ (or, commonly, AWG for Anthropocene Working Group), has been critically analysing the case for formalization of this proposed but still informal geological time unit. The study to date has mainly involved establishing the overall nature of the Anthropocene as a potential chronostratigraphic/geochronologic unit, and exploring the stratigraphic proxies, including several that are novel in geology, that might be applied to its characterization and definition. A preliminary summary of evidence and interim recommendations was presented by the Working Group at the 35th International Geological Congress in Cape Town, South Africa, in August 2016, together with results of voting by members of the AWG indicating the current balance of opinion on major questions surrounding the Anthropocene. The majority opinion within the AWG holds the Anthropocene to be stratigraphically real, and recommends formalization at epoch/series rank based on a mid-20th century boundary. Work is proceeding towards a formal proposal based upon selection of an appropriate Global boundary Stratotype Section and Point (GSSP), as well as auxiliary stratotypes. Among the array of proxies that might be used as a primary marker, anthropogenic radionuclides associated with nuclear arms testing are the most promising; potential secondary markers include plastic, carbon isotope patterns and industrial fly ash. All these proxies have excellent global or near-global correlation potential in a wide variety of sedimentary bodies, both marine and non-marine.

Stable carbon isotopic composition of light hydrocarbons and n-alkanes of condensates in the Tarim Basin, NW China

The carbon isotope ratios of individual light hydrocarbons and the n-alkanes of twenty-one condensates from the Tarim Basin, as well as 47 condensates and oils from other petroliferous basins (Ordos Basin, Sichuan Basin, Turpan-Harmi Basin, Qiongdongnan Basin, Beibu Gulf Basin and Bohai Bay Basin) in China, were analyzed. We investigated the oil–oil correlation, the effects of gas washing and maturity, as well as the distinguishing parameters of humic and sapropelic condensates, and have come to the following conclusion. The carbon isotopic patterns of condensates and oils in the Ordovician strata of Tarim Basin are very similar, indicating they originate from the same type of source rocks. The condensates from Dawanqi oil field and Yinan 2, as well as Ti'ergen and Yitikelike gas fields, have similar carbon isotopic patterns. Thus, they probably have originated from the same terrestrial Jurassic source rock. The carbon isotopic patterns of the condensates from the Dabei, Kela 2, and Keshen gas fields are also similar, indicating they are of the same oil family and sourced from the Triassic and Jurassic terrestrial source rock. The carbon isotopic ratios of 2-MP, 3-MP, 3-MH, and nC5-8 are much more susceptible to maturity level than other light hydrocarbons. Gas washing has minor effects on the δ13C compositions of individual light hydrocarbons and n-alkanes, although it causes <2‰ shifts. The δ13C compositions of MCP, CH, MCH, benzene, and toluene can be used as identification parameters for humic and sapropelic condensates. Humic condensates generally have δ13CMCP > −25‰, δ13CCH > −24‰, δ13CMCH > −24‰, δ13Cbenzene > −25‰, and δ13Ctoluene > −24‰, whereas sapropelic condensates mainly have δ13CMCP < −26‰, δ13CCH < −26‰, δ13CMCH < −24‰, δ13Cbenzene < −25‰ and δ13Ctoluene < −24‰. Moreover, the mixing humic and sapropelic condensates usually show intermediate values.

Geochemical characteristics of gases from the largest tight sand gas field (Sulige) and shale gas field (Fuling) in China

This study performed a detailed geochemical analyses of the components, stable carbon isotopes of alkane gas and CO2, stable hydrogen isotopes of alkane gas and helium isotopes of reproducing gas from the largest tight gas field (Sulige) and shale gas (Fuling) field in China. The comparative study shows that tight gas from the Sulige gas field in the Ordos Basin is of coal-derived origin, which is characterized by a positive carbon and hydrogen isotopic distribution pattern (δ13C1 > δ13C2 > δ13C3 > δ13C4; δ2H1 > δ2H2 > δ2H3), i.e., the carbon and hydrogen isotopes increase with increasing carbon numbers. Carbon dioxide from this field are of biogenic origin and the helium is crust-derived. Shale gas from the Fuling shale gas field belongs to oil-derived gas which has complete carbon and hydrogen isotopic reversal of secondary alteration origin (δ13C1 < δ13C2 < δ13C3; δ2H1 < δ2H2 < δ2H3), i.e., the carbon and hydrogen isotopes decrease with increasing carbon numbers. Such complete isotopic reversal distribution pattern is due to the secondary alteration like oil or gas cracking, diffusion and so on under high temperature. In that case, positive carbon or hydrogen isotopic distribution pattern will change into complete isotopic reversal as the temperature increases. Carbon dioxide is of abiogenic origin resulting from the thermal metamorphism of carbonates and helium is crust-derived.

Elemental geochemistry and strontium-isotope stratigraphy of Cenomanian to Santonian neritic carbonates in the Zagros Basin, Iran

A Neo-Tethyan upper Cenomanian–Santonian neritic carbonate ramp succession (Sarvak and Ilam formations), drilled in the Zagros Basin in southwest Iran, was investigated via detailed sedimentology, microfacies analysis, elemental geochemistry and Sr-isotope stratigraphy (SIS). The succession contains two exposure surfaces, which are known as the CT-ES and mT-ES (Cenomanian–Turonian and middle Turonian, respectively), and associated prominent negative carbon-isotope excursions that represent important regional stratigraphic marker horizons. Precise knowledge about the onset of platform exposure and the duration of the exposure-related hiatus, however, is currently lacking due to a rather low-resolved shallow-water biostratigraphic framework and a bulk carbonate carbon-isotope pattern that clearly differs from global Late Cretaceous reference curves. Therefore, the existing bio-chemostratigraphic framework was complemented by bulk carbonate strontium-isotope stratigraphy (SIS). As bulk carbonate material is in particular prone to diagenetic alteration, a careful selection of least altered samples has been carried out by means of elemental geochemistry and petrography. In contrast to what could be expected, the meteoric alteration of limestones beneath both exposure surfaces is not clearly expressed by increasing iron and manganese and coeval decreasing strontium contents. On the contrary, the impact of meteoric diagenesis is well illustrated via pronounced increases in Rb concentrations and concomitant prominent positive shifts to radiogenic strontium-isotope values, an observation that clearly reflects the decay of continentally derived 87Rb into 87Sr. Rubidium corrected strontium-isotope values place the CT-ES around the Cenomanian–Turonian boundary and point to an exposure duration of less than 0.4Myr. This rather short-term CT-ES related hiatus is supported by petrographic evidence, which indicates a youth karstification stage of strata beneath the CT-ES. Following SIS, the Ilam–Sarvak transition at the top of Nezzazatinella–Dicyclina interval zone coincides with the mT-ES. Carbonates placing above this transition (Ilam Formation) are ascribed to the earliest to latest early Santonian, while carbonates immediately beneath the mT-ES (Sarvak Formation) are dated as late Turonian. SIS thus indicates a long-lasting hiatus of 4.5Myr associated with the mT-ES. Emergence represented by the CT-ES is here proposed as harbinger of the mT-ES in the Zagros Basin, which most likely resulted from stepwise peripheral bulging due to ophiolite obduction in combination with a small-scale global sea level fall around 94Ma.

Turkeys on the fringe: Variable husbandry in “marginal” areas of the prehistoric American Southwest

Previous research reporting stable carbon (δ13C) and nitrogen (δ15N) isotope values of prehistoric turkey (Meleagris gallopavo) remains from the American Southwest indicates that these birds were husbanded in consistent ways: the majority of samples suggest a diet dominated by maize, a domesticate that uses the C4 photosynthetic pathway. However, most of these studies have focused on turkey remains from locations where maize would likely have been readily available. Here we present isotope and mitochondrial DNA (mtDNA) haplotype data from turkey remains from the relatively high-elevation site of Tijeras Pueblo (LA 581), a location where maize production may have been marginal. The Tijeras Pueblo turkeys display a unique carbon isotope pattern in both bone collagen and bone apatite, with half the samples indicating a predominately C3 diet (a signature characteristic of modern wild turkeys) and the other half predominately C4, even though the majority of samples belong to the Southwestern domestic turkey mtDNA lineage identified by Speller et al. (2010). Comparative collagen samples from the Albuquerque Basin and the Gallina region do not follow this pattern. Apatite-collagen δ13C spacing in the Tijeras turkeys suggests these birds were acquiring carbohydrates and protein from a mixture of C3- and C4-based resources. We propose that the C3 Tijeras turkeys were free-ranged, and that the presence of two distinct turkey husbandry regimes at Tijeras Pueblo may reflect Tijeras' geographic location on a cultural boundary between the Plains and Pueblo regions.

Geochemical characteristics of marine and terrestrial shale gas in China

Although the annual production of shale gas in China was 13 × 108 m3 in 2014, a systematic study on geochemical and isotopic characteristics of these unconventional gases has not been well addressed. In the present study, almost all shale gas samples available in China, including marine shale gas from the Wufeng-Longmaxi Formation in the Sichuan Basin (O3w–S1l) and terrestrial shale gas from Chang 7 Member (T3y7) in the Ordos Basin, were collected and analyzed for their geochemical and isotopic compositions. The shale gas from the Wufeng-Longmaxi Shale is dry gas with an average methane content of 98.38% and records a highest content of CH4 in the world (99.59%), which is consistent with the very high thermal maturity levels of the gas shales that have equivalent vitrinite reflectance (EqVRo) values between 2.4 and 3.6%. The δ13C1 values are correspondingly heavy and record a heaviest δ13C1 values (−26.7‰) for the shale gases found in the world as well. The average values of δ13C1, δ13C2 and δ13C3 for the Wufeng-Longmaxi shale gas are −31.3‰, −35.6‰, and −47.2‰, respectively, displaying a complete carbon isotopic reversal (i.e., δ13C1 > δ13C2 > δ13C3). δ2HCH4 and δ2HC2H6 has an average value of −148‰ and −173‰, respectively, also yielding a hydrogen isotopic reversal (i.e., δ2HCH4 > δ2HC2H6). The Chang 7 shale has an average TOC content of 13.81% with vitrinite reflectance (VRo) values between 0.7 and 1.2%. The Chang 7 shale gas is wet gas with an average methane content of 84.90% and is rich in heavy gaseous hydrocarbons (C2–C5). The respective values of δ13C1, δ13C2 and δ13C3 are −48.7‰, −36.4‰ and −31.3‰, displaying a positive carbon isotopic distribution pattern (i.e., δ13C1 < δ13C2 < δ13C3). The average δ2HCH4, δ2HC2H6 and δ2HC3H8 values are −256‰, −244‰ and −188‰, respectively, and are characterized by a positive distribution pattern (i.e., δ2HCH4 < δ2HC2H6 < δ2HC3H8). The differences in gas wetness and carbon and hydrogen isotopic distribution patterns between the shale gases from the Wufeng-Longmaxi and Chang 7 shale are attributed to variations in thermal maturity levels. CO2 is present in low content in both the Wufeng-Longmaxi and Chang 7 shale gases, mostly less than 1%. δ13C values for the CO2 in the Wufeng-Longmaxi Formation are between 8.9 and −9.2‰, indicating an inorganic origin from the cracking of carbonate mineral in the shales under high temperatures. In contrast, δ13C values of the CO2 in the Chang 7 shale gas range from −8.2 to −22.7‰, indicating an organic origin from the thermal degradation of organic matter. Helium in both the Wufeng-Longmaxi and Chang 7 shale gases is dominantly of curst origin in terms of their R/Ra ratios that vary from 0.01 to 0.08. Positive carbon isotopic distribution pattern is typical of primitive thermogenic gas. However, it can be converted into complete or partial carbon isotopic reversal patterns due to secondary alteration. The causes that yield carbon isotopic reversal include (1) mixing of gases with the same source but different thermal maturity levels; (2) secondary cracking of oil or wet gas; (3) formation water-involved reactions; (4) gas diffusion; and (5) carbon isotope exchange between alkane gases at high temperature. Among them, carbon isotopic exchange between alkane gases at high temperature is a key factor. Nine plots have been drawn based on the shale gases from China, USA and Canada. Among them, the plot of δ13C2 versus wetness demonstrates a “lying-S” shape with two inflection points on the gas wetness axis. The wetness value of 1.4% represents a critical point from pyrolytic gas (primary cracking gas) to cracking gas (secondary cracking gas) and whereas the wetness value of 6% marks the end of oil generation. On the diagram of wetness versus δ13C, shale gases with wetness values greater than 1.6% are characterized by positive carbon isotopic distribution pattern, whereas a complete or partial carbon isotopic reversals are observed for shale gases with wetness values less than 1.6%.

Thermal Cracking of Oil under Water Pressure up to 900 bar at High Thermal Maturities. 1. Gas Compositions and Carbon Isotopes

In this study, a C9+ fraction of saturate-rich Tertiary source rock-derived oil from the South China Sea basin was pyrolyzed in normal and supercritical water using a 25 mL vessel at a range of temperature from 350 to 425 °C for 24 h, to probe pressure effects up to 900 bar on gas yields and their stable carbon isotopic compositions during thermal cracking. Pressure generally retards oil cracking, as evidenced by reduced gas yields, but the trends depend upon the level of thermal evolution. In the early stages of cracking (350 and 373 °C, equivalent vitrinite reflectance of 1.3% R0), pressure still has a strong suppression effect from 200 to 470 bar, which then levels off or is reversed as the pressure is increased further to 750 and 900 bar. Interestingly, the stable carbon isotopic composition of the generated methane becomes enriched in 13C as the pressure increases from 200 to 900 bar. A maximum fractionation effect of ∼3‰ is observed over this pressure range. Due to pressure retardation, the isotopically heaviest methane signature does not coincide with the maximum gas yield, contrary to what might be expected. In contrast, pressure has little effect on ethane, propane, and butane carbon isotope ratios, which show a maximum variation of ∼1‰. The results suggest that the rates of methane-forming reactions affected by pressure control methane carbon isotope fractionation. Based on distinctive carbon isotope patterns of methane and wet gases from pressurized oil cracking, a conceptual model using “natural gas plot” is constructed to identify pressure effect on in situ oil cracking providing other factors excluded. The transition in going from dry conditions to normal and supercritical water does not have a significant effect on oil-cracking reactions as evidenced by gold bag hydrous and anhydrous pyrolysis results at the same temperatures as used in the pressure vessel.

Stable isotope and high precision concentration measurements confirm that all humans produce and exhale methane

Mammalian formation of methane (methanogenesis) is widely considered to occur exclusively by anaerobic microbial activity in the gastrointestinal tract. Approximately one third of humans, depending on colonization of the gut by methanogenic archaea, are considered methane producers based on the classification terminology of high and low emitters. In this study laser absorption spectroscopy was used to precisely measure concentrations and stable carbon isotope signatures of exhaled methane in breath samples from 112 volunteers with an age range from 1 to 80 years. Here we provide analytical evidence that volunteers exhaled methane levels were significantly above background (inhaled) air. Furthermore, stable carbon isotope values of the exhaled methane unambiguously confirmed that this gas was produced by all of the human subjects studied.Based on the emission and stable carbon isotope patterns of various age groups we hypothesize that next to microbial sources in the gastrointestinal tracts there might be other, as yet unidentified, processes involved in methane formation supporting the idea that humans might also produce methane endogenously in cells. Finally we suggest that stable isotope measurements of volatile organic compounds such as methane might become a useful tool in future medical research diagnostic programs.

Assessing the potential of amino acid &amp;lt;sup&amp;gt;13&amp;lt;/sup&amp;gt;C patterns as a carbon source tracer in marine sediments: effects of algal growth conditions and sedimentary diagenesis

Abstract. Burial of organic carbon in marine sediments has a profound influence in marine biogeochemical cycles and provides a sink for greenhouse gases such as CO2 and CH4. However, tracing organic carbon from primary production sources as well as its transformations in the sediment record remains challenging. Here we examine a novel but growing tool for tracing the biosynthetic origin of amino acid carbon skeletons, based on naturally occurring stable carbon isotope patterns in individual amino acids (δ13CAA). We focus on two important aspects for δ13CAA utility in sedimentary paleoarchives: first, the fidelity of source diagnostic of algal δ13CAA patterns across different oceanographic growth conditions, and second, the ability of δ13CAA patterns to record the degree of subsequent microbial amino acid synthesis after sedimentary burial. Using the marine diatom Thalassiosira weissflogii, we tested under controlled conditions how δ13CAA patterns respond to changing environmental conditions, including light, salinity, temperature, and pH. Our findings show that while differing oceanic growth conditions can change macromolecular cellular composition, δ13CAA isotopic patterns remain largely invariant. These results emphasize that δ13CAA patterns should accurately record biosynthetic sources across widely disparate oceanographic conditions. We also explored how δ13CAA patterns change as a function of age, total nitrogen and organic carbon content after burial, in a marine sediment core from a coastal upwelling area off Peru. Based on the four most informative amino acids for distinguishing between diatom and bacterial sources (i.e., isoleucine, lysine, leucine and tyrosine), bacterially derived amino acids ranged from 10 to 15 % in the sediment layers from the last 5000 years, and up to 35 % during the last glacial period. The greater bacterial contributions in older sediments indicate that bacterial activity and amino acid resynthesis progressed, approximately as a function of sediment age, to a substantially larger degree than suggested by changes in total organic nitrogen and carbon content. It is uncertain whether archaea may have contributed to sedimentary δ13CAA patterns we observe, and controlled culturing studies will be needed to investigate whether δ13CAA patterns can differentiate bacterial from archeal sources. Further research efforts are also needed to understand how closely δ13CAA patterns derived from hydrolyzable amino acids represent total sedimentary proteineincous material, and more broadly sedimentary organic nitrogen. Overall, however, both our culturing and sediment studies suggest that δ13CAA patterns in sediments will represent a novel proxy for understanding both primary production sources, and the direct bacterial role in the ultimate preservation of sedimentary organic matter.

Stable hydrogen and carbon isotopic ratios of coal-derived gases from the Turpan-Hami Basin, NW China

Natural gases from the Qiudong and Hongtai gas fields in the Taibei sag in the Turpan-Hami Basin of China were analyzed for stable hydrogen and carbon isotopic characteristics, to investigate the origin of the gas and the gas-source correlation. Natural gases from the two gas fields are dominated by alkane gases with methane content varying from 81.61% to 92.57%. Dryness ranges from 0.76 to 0.93, indicating an abundance of wet gas. The carbon and hydrogen isotopic compositions of the methane vary from −39.8‰ to −42.6‰ and from −263‰ to −279‰ in the Qiudong gas field, respectively, and from −37.7‰ to −39.0‰ and from −250‰ to −257‰ in the Hongtai gas field, respectively. All gases have a characteristic carbon and hydrogen isotopic distribution pattern among the C1–C5 alkanes, in which δ13CCH4<δ13CC2H6<δ13CC3H8<δ13CC4H10<δ13CC5H12 and δ2HCH4<δ2HC2H6<δ2HC3H8. Both the stable carbon and hydrogen isotopic compositions of the gases and the hydrogen isotopic value of the formation water suggest that gases in the two gas fields are coal-derived without admixtures with gases of other origin. According to the calculation with empirical δ13CCH4–Ro% relationship, the thermal maturity (vitrinite reflectance Ro%) of the source rocks is up to 0.76% in the Qiudong area and up to 0.86% in the Hongtai area, which are in the oil window and approaching the start of major thermogenesis at the top of the maturity range. Since the gases in the Hongtai gas field are relatively more enriched in 13C and 2H, combined with the local geological thermal evolution history, it is concluded that the gases in the two gas fields were derived from the Lower Jurassic Badaowan source rocks. The heavier hydrogen and carbon isotopes of the gases from the Hongtai gas field are interpreted as a product of higher thermal maturity of the source rocks. This is in consistent with the thermal maturity of the local source rocks. The modern thermal maturity of the top of the Badaowan Formation is around 0.8% in the Qiudong area and around 1.0% in the Hongtai area. The combined use of both carbon and hydrogen isotopes is of high value in providing information on gas origin and gas-source correlation, which will be very useful for future gas exploration.

Composition of Closed-System Fischer-Tropsch Synthesis Gases and the Constraint Factors

Biogenic gases were reported to exhibit a ‘‘normal’’ carbon isotope order, whereas abiogenic gaseous hydrocarbons in igneous rocks and meteorites exhibit a reversed order. In this study, closed-system Fischer–Tropsch synthesis was conducted at 350°C and 380°C under 30 MPa and 390°C under 30, 100, and 200 MPa, respectively, with magnetite as a catalyst. The results do not show an expected reversed order, even though the features of partially reversed order in carbon isotope values can still be commonly observed. Studies have shown that the essential constraint factor on the carbon isotopic pattern of abiogenic gases is the molar ratio of H2/CO2.