Organic carbon isotope gradient and ocean stratification across the late Ediacaran-Early Cambrian Yangtze Platform

Organic carbon isotope(δ13Corg) data from two well-preserved sections across a shallow-to-deep water transect of the late Ediacaran-Early Cambrian Yangtze Platform in South China show significant temporal and spatial variations. In the shallow-water Jiulongwan-Jijiapo section, δ13Corg values of the late Ediacaran Dengying Formation range from -29‰ to -24‰. In the deep-water Longbizui section, δ13Corg values from time-equivalent strata of the Dengying Formation are mostly between –35‰ and -32‰. These new data, in combination with δ13Corg data reported from other sections in South China, reveal a 6‰–8‰ shallow-to-deep water δ13Corg gradient. High δ13Corg values(-30‰) occur mostly in shallow-water carbonate rocks, whereas low δ13Corg values(-32‰) dominate the deep-water black shale and chert. The large temporal and spatial δ13Corg variations imply limited buffering effect from a large dissolved organic carbon(DOC) reservoir that was inferred to have existed in Ediacaran-Early Cambrian oceans. Instead, δ13Corg variations between platform and basin sections are more likely caused by differential microbial biomass contribution to total organic matter. High δ13Corg values(-30‰) documented from shallow-water carbonates are within the range of typical Phanerozoic δ13Corg data and may record the isotope signature of organic matter from primary(photosynthetic) production. In contrast, low δ13Corg values(-32‰) from deep-water sections may have resulted from higher chemoautotrophic or methanotrophic biomass contribution to bulk organic matter in anoxic environments. The δ13Corg data provide indirect evidence for ocean stratification and episodic chemocline fluctuations in the Ediacaran-Early Cambrian Yangtze Platform.     

Natural gas geochemistry and its origins in Kuqa depression

According to gas compositional and carbon isotopic measurement of 114 gas samples from the Kuqa depression, accumulation of the natural gases in the depression is dominated by hydrocarbon gases, with high gas dryness (C₁/C_1–4) at the middle and northern parts of the depression and low one towards east and west sides and southern part. The carbon isotopes of methane and its homologues are relatively enriched in ¹³C, and the distributive range of δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ is ?32‰–?36‰, ?22‰–?24‰ and ?20‰–?22‰, respectively. In general, the carbon isotopes of gaseous alkanes become less negative with the increase of carbon numbers. The δ ¹³ \(C_{CO_2 } \) value is less than ?10‰ in the Kuqa depression, indicating its organogenic origin. The distributive range of ³He/⁴He ratio is within n × 10^?8 and a decrease in ³He/⁴He ratio from north to south in the depression is observed. Based on the geochemical parameters of natural gas above, natural gas in the Kuqa depression is of characteristics of coal-type gas origin. The possible reasons for the partial reversal of stable carbon isotopes of gaseous alkanes involve the mixing of gases from one common source rock with different thermal maturity or from two separated source rock intervals of similar kerogen type, multistages accumulation of natural gas under high-temperature and over-pressure conditions, and sufficiency and diffusion of natural gas.     

Light carbon isotope events of foraminifera attributed to methane release from gas hydrates on the continental slope,northeastern South China Sea

In 2013, the China Geological Survey and Guangzhou Marine Geological Survey conducted the second Chinese gas hydrate expedition in the northern South China Sea(SCS) and successfully obtained visible gas hydrate samples. Five of the thirteen drilling sites were cored for further research. In this work, Site GMGS2-08 is selected for the stable isotopic analysis of foraminifera present in the boreholes in order to reveal the carbon isotopic characteristics of the foraminifera and their response to methane release in the gas hydrate geological system. Our results show that the methane content at Site GMGS2-08 is extremely high, with headspace methane concentrations up to 39300 μmol L~(-1). The hydrocarbon δ~(13)C values, ranging from-69.4‰ to-72.3‰ PDB, distinctly indicate biogenic generation. Based on the δD analytical results(~(-1)83‰ to~(-1)85‰ SMOW), headspace methane is further discriminated to be microbial gas, derived from CO_2 reduction. By isotopic measurement, five light δ~(13)C events are found in the boreholes from Site GMGS2-08, with foraminiferal δ~(13)C values being apparently lower than the normal variation range found in the glacial-interglacial cycles of the SCS. The δ~(13)C values of benthic Uvigerina peregrina are extremely depleted(as low as~(-1)5.85‰ PDB), while those of planktonic Globigerinoides ruber reach-5.68‰ PDB. Scanning electron micrograph(SEM) studies show that foraminiferal tests have experienced post-depositional alteration, infilled with authigenic carbonate, and the diagenetic mineralization is unlikely to be related to the burial depths. The correlation calculation suggests that the anaerobic oxidation of organic matter has only weak influences on the δ~(13)C composition of benthic foraminifera. This means that the anomalous δ~(13)C depletions are predominantly attributed to the overprinting of secondary carbonates derived from the anaerobic oxidation of methane(AOM). Furthermore, the negative δ~(13)C anomalies, coupled with the positive δ18O anomalies observed at Site GMGS2-08, are most likely the critical pieces of evidence for gas hydrate dissociation in the geological history of the study area.     

Preliminary study on the origin identification of natural gas by the parameters of light hydrocarbon

The light hydrocarbon composition of 209 natural gas samples and individual light hydrocarbon carbon isotopes of 53 natural gas samples from typical humic-sourced gas and sapropelic-sourced gas in the four basins of China have been determined and analyzed. Some identification parameters for humic-sourced gas and sapropelic-sourced gas are proposed or corrected. The differences of compound-specific δ ¹³C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded. The humic-sourced gas has the distribution of δ ¹³C_benzene> ?24‰, δ ¹³C_toluene >?23‰, δ ¹³C_cyclohexane > ?24‰ and δ ¹³C_{methyl cyclohexane}> ?24‰, while the sapropelic-sourced gas has the distribution of δ ¹³C_benzene <?24‰, δ ¹³C_toluene< ?24‰, δ ¹³C_cyclohexane< ?24‰ and δ ¹³C_{methyl cyclohexane}< ?24‰. Among the components of C₇ light hydrocarbon compound, such as normal heptane (nC₇), methyl cyclohexane (MCH) and dimethyl cyclopentane (ΣDMCP), etc, relative contents of nC₇ and MCH are influenced mainly by the source organic matter type of natural gas. Therefore, it is suggested that the gas with relative content of nC₇ of more than 30% and relative content of MCH of less than 70% is sapropelic-sourced gas, while gas with relative content of nC₇ of less than 35% and relative content of MCH of more than 50% is humic-sourced gas. Among components of C_5–7 aliphatics, the gas with relative content of C_5–7 normal alkane of more than 30% is sapropelic-sourced gas, while the gas with relative content of C_5–7 normal alkane of less than 30% is humic-sourced gas. These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.     

Nitrogen and carbon isotopic composition in the diamonds of Mbuji Mayi (Zaïre)

The concentration and isotopic composition of nitrogen, measured in large diamonds (gram size) from the Mbuji Mayi kimberlite district (Zaïre) show a large range of variation (100<N<2100 ppm, ?11.2<δ¹⁵N< +6.0). The¹⁵N-depleted nitrogen is associated with the higher nitrogen concentrations. The large diamonds are individually rather homogeneous in¹³C (range ofδ¹³C < 0.9‰) while variations occur within small octahedral diamonds from the same district (range up to 5.8‰). The total range ofδ¹³C variation is about the same for the large diamonds (?10.5 <δ¹³C < ?5.5), the small octahedral diamonds (?10 <δ¹³C < ?4.6), and the carbonates from local kimberlites (?11.8 < δ¹³C < ?5.5). The diamond carbon isotopic data could indicate a complex story of crystallization within a deep-seated system fractionating its carbon isotopes.The nitrogen results indicate that nitrogen in diamonds is, on the average, markedly depleted in¹⁵N (weighted average ?5.15‰) relative to atmosphere, sediments and upper mantle.     

13C/12C ratios of rocks and inclusions in popping rocks of the Mid-Atlantic Ridge and their bearing on the problem of isotopic composition of deep-seated carbon

CO₂-rich inclusions recovered from “popping” and related tholeiitic rocks from the Mid-Atlantic Ridge have δ¹³C values of ?7.6 ± 0.5%. relative to PDB. δ¹³C values of total carbon in the same rocks range from ?12 to ?13.7‰. These values are discussed in the light of the known δ¹³C variations in rocks of deep-seated origin. The ?7.6‰ value is interpreted as a reasonable estimate of the primary value of δ¹³C of deep-seated carbon in the ridge area.     

Carbon isotopic compositions of organic matter across continental Cretaceous–Tertiary (K–T) boundary sections: Implications for paleoenvironment after the K–T impact event

To assess the environmental perturbation induced by the impact event that marks the Cretaceous–Tertiary (K–T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K–T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record δ¹³C values of plant-derived organic matter, reflecting the δ¹³C value of atmospheric CO₂, whereas siliceous sedimentary rocks record the δ¹³C values of organic matter derived from plants and microbiota. The microbiota δ¹³C value reflects not only the δ¹³C value of atmospheric CO₂, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds.Across the freshwater K–T boundary at Brownie Butte, the δ¹³C values decrease by 2.6‰ (from − 26.15‰ below the boundary clay to − 28.78‰ above the boundary clay), similar to the trend in carbonate at marine K–T sites. This means that the organic δ¹³C values reflect the variation of δ¹³C of atmospheric CO₂, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in δ¹³C values is observed across the K–T boundary at Dogie Creek (from − 25.32‰ below the boundary clay to − 26.11‰ above the boundary clay), the degree of δ¹³C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate.About 2‰ decrease in δ¹³C of atmospheric CO₂ was expected from the δ¹³C variation of marine carbonate at the K–T boundary. This δ¹³C-decrease of atmospheric CO₂ should affect the δ¹³C values of organic matter derived from plant tissue. As such a decrease in δ¹³C value was not observed at Dogie Creek, a process that compensates the δ¹³C-decrease of atmospheric CO₂ should be involved. For example, the enhanced contribution of ¹³C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The δ¹³C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO₃⁻ becomes an important carbon source, as well as dissolved CO₂. As the δ¹³C-decrease of atmospheric CO₂ reflected a reduction of marine productivity, the compensation of the δ¹³C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment.A distinct positive δ¹³C excursion of 2‰ in the K–T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K–T boundary clays include ¹³C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K–T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K–T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10 yr) respond to the impact-related environmental perturbations.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Natural gas leakage of Mizhi gas reservoir in Ordos Basin,recorded by natural gas fluid inclusion

Abundant natural gas inclusions were found in calcite veins filled in fractures of Central Fault Belt across the centre of Ordos Basin. Time of the calcite veins and characteristics of natural gas fluid inclusion were investigated by means of dating of thermolum luminescence (TL) and analyzing stable isotope of fluid inclusion. Results show that natural gas inclusion formed at 130–140°C with salinity of 5.5 wt%–6.0 wt% NaCl. It indicates that natural gas inclusion is a kind of thermal hydrocarbon fluid formed within the basin. Method of opening inclusion by heating was used to analyze composition of fluid inclusion online, of which the maximal hydrocarbon gas content of fluid inclusion contained in veins is 2.4219 m³/t rock and the maximal C₁/ΣC _i ratio is 91%. Laser Raman spectroscopy (LRS) was used to analyze chemistry of individual fluid inclusion in which the maximal hydrocarbon gas content is 91.6% compared with little inorganic composition. Isotope analysis results of calcite veins show that they were deposited in fresh water, in which the δ ¹³C_PDB of calcite veins is from ?5.75‰ to 15.23‰ and δ ¹⁸O_SMOW of calcite veins is from 21.33‰ to 21.67‰. Isotope results show that δ ¹³C_{1 PDB} of natural gas fluid inclusion is from ?21.36‰ to ?29.06‰ and δD_SMOW of that is from ?70.89‰ to ?111.03‰. It indicates that the gas of fluid inclusion formed from coal source rocks and it is the same as that of natural gas of Mizhi gas reservoir. Results of TL dating show that time of calcite vein is (32.4±3.42)×10⁴ a, which is thought to be formation time of gas inclusion. It indicated that natural gas inclusion contained in calcite veins recorded natural gas leakage from Mizhi gas reservoir through the Central Fault Belt due to Himalayan tectonic movement.     

The distribution of13C in the Atlantic Ocean

Individual vertical profiles and north-south sections for the distribution of theδ¹³C of total dissolved inorganic carbon are presented for the Atlantic stations of the GEOSECS program. In most cases theδ¹³C data parallel the distribution of dissolved O₂. Differences are attributed to in-situ oxidation of organic matter and dissolution of particles of CaCO₃. Antarctic Bottom and Intermediate Waters have aδ¹³C value of near 0.5‰ relative to the PDB isotopic standard. The lowest values in the Atlantic ocean were found in the Antarctic Circumpolar waters which haveδ¹³C values as low as 0.2‰. The core of the North Atlantic Deep Water has aδ¹³C value of 1.0‰.     

Correlations between13C and ΣCO2 in surface waters and atmospheric CO2

¹³C and ΣCO₂ data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ¹³C of the ΣCO₂ in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO₂ per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO₂, while the remainder is attributed to dissolution of calcium carbonate.The δ¹³C of the dissolved CO₂ in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO₂ at a mean temperature of 16°C. The δ¹³C and ΣCO₂ values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.     

Modern stable isotopic (δ18O, δ2H, δ13C) variation in terrestrial,fluvial, estuarine and marine waters from north‐central Sarawak,Malaysian Borneo

Stable isotope data on humid tropical hydrology are scarce and, at present, no such data exist for Borneo. Delta¹⁸O, δ²H and δ¹³C were analysed on 22 water samples from different parts of the Sungai (river) Niah basin (rain, cave drip, rainforest pool, tributary stream, river, estuary, sea) in north‐central Sarawak, Malaysian Borneo. This was done to improve understanding of the modern stable isotope systematics of the Sungai Niah basin, essential for the palaeoenvironmental interpretation of the Late Quaternary stable isotope proxies preserved in the Great Cave of Niah. The Niah hydrology data are put into a regional context using the meteoric water line for Southeast Asia, as derived from International Atomic Energy Agency/World Meteorological Organization isotopes in precipitation network data. Although the Niah hydrological data‐set is relatively small, spatial isotopic variability was found for the different subenvironments of the Sungai Niah basin. A progressive enrichment occurs towards the South China Sea (δ¹⁸O ?4·6‰; δ²H ?29·3‰; δ¹³C ?4·8‰) from the tributary stream (δ¹⁸O ?8·4‰; δ²H ?54·7‰; δ¹³C ?14·5‰) to up‐river (δ¹⁸O c. ?8‰; δ²H c. ?51‰; δ¹³C c. ?12‰) and down‐river values (δ¹⁸O c. ?7·5‰; δ²H c. ?45‰; δ¹³C c. ?11‰). This is thought to reflect differential evaporation and mixing of different components of the water cycle and a combination of depleted biogenic δ¹³C (plant respiration and decay) with enriched δ¹³C values (due to photosynthesis, atmospheric exchange, mixing with limestone and marine waters) downstream. Cave drip waters are relatively enriched in δ¹³C as compared to the surface waters. This may indicate rapid degassing of the cave drips as they enter the cave atmosphere. Copyright © 2005 John Wiley & Sons, Ltd.     

Diagenetic fluid evolution and water-rock interaction model of carbonate cements in sandstone: An example from the reservoir sandstone of the Fourth Member of the Xujiahe Formation of the Xiaoquan-Fenggu area,Sichuan Province,China

Carbonate cement is the most abundant cement type in the Fourth Member of the Xujiahe Formation in the Xiaoquan-Fenggu area of the West Sichuan Depression. Here we use a systematic analysis of carbonate cement petrology, mineralogy, carbon and oxygen isotope ratios and enclosure homogenization temperatures to study the precipitation mechanism, pore fluid evolution, and distribution of different types of carbonate cement in reservoir sand in the study area. Crystalline calcite has relatively heavy carbon and oxygen isotope ratios(δ13C = 2.14‰, δ18O = -5.77‰), and was precipitated early. It was precipitated directly from supersaturated alkaline fluid under normal temperature and pressure conditions. At the time of precipitation, the fluid oxygen isotope ratio was very light, mainly showing the characteristics of a mixed meteoric water-seawater fluid(δ18O = -3‰), which shows that the fluid during precipitation was influenced by both meteoric water and seawater. The calcite cement that fills in the secondary pores has relatively lighter carbon and oxygen isotope ratios(δ13C = -2.36‰, δ18O = -15.68‰). This cement was precipitated late, mainly during the Middle and Late Jurassic. An important material source for this carbonate cement was the feldspar corrosion process that involved organic matter. The Ca2+, Fe3+ and Mg2+ ions released by the clay mineral transformation process were also important source materials. Because of water-rock interactions during the burial process, the oxygen isotope ratio of the fluid significantly increased during precipitation, by about 3‰. The dolomite cements in calcarenaceous sandstone that was precipitated during the Middle Jurassic have heavier carbon and oxygen isotope ratios, which are similar to those of carbonate debris in the sandstone(δ13C = 1.93‰, δ18O = -6.11‰), demonstrating that the two are from the same source that had a heavier oxygen isotope ratio(δ18O of about 2.2‰). The differences in fluid oxygen isotope ratios during cement precipitation reflect the influences of different water-rock interaction systems or different water-rock interaction strengths. This is the main reason why the sandstone containing many rigid particles(lithic quartz sandstone) has a relatively negative carbon isotope ratio and why the precipitation fluid in calcarenaceous sandstone has a relatively heavier oxygen isotope ratio.     

Characteristics of bleaching of sandstone in northeast of Ordos Basin and its relationship with natural gas leakage

Bleaching of sandstone has significant applications to tracing hydrocarbon pathways and evaluating the scale of natural gas seepage. Bleaching of sandstones in the northeast of Ordos Basin is mainly distributed in the Mesozoic Yan’an Formation. Studying on petrology, major elements, REEs and trace elements of bleached sandstones and comparing with adjacent sandstones, combining with geologic-geochemical evidences of gas seepage in the northeast of the basin, the bleached sandstones are formed in the acid environment and reducing fluids. Characteristics of petrology show that the contents of kaolinite are high and the color of margin of ferric oxide minerals is lighter than that of the center. Major elements of sandstone samples show high contents of Al₂O₃ and low ratio of Fe³⁺/Fe²⁺. The TFe₂O₃ content of the bleached sandstone is lower than that of red rock. REE data show that bleached sandstones have low ΣREE contents and Eu-depleted and slightly Ce-enriched. Trace elements show that the bleached sandstones enrich in Co, deplete in Sr, and slightly enrich in Zr and Hf which are close to the values for the green alteration sandstones, and slightly lower than ore-bearing sandstones. Geochemical characteristics of oil-bearing sandstone in the northern basin suggest that the oil-shows are formed by matured Carboniferous-Permian coal bed methane escaping to the surface, and natural gas in field could migrate to the north margin of the basin. The δ ¹³C (PDB) and δ ¹⁸O(PDB) values of calcite cement in the study area range from ?11.729‰ to ?10.210‰ and ?14.104‰ to ?12.481‰, respectively. The δ ¹³C (PDB) values less than ?10‰ imply the carbon sources part from organic carbon. Comprehensive study suggests that the gas leakage has occurred in the northeastern basin, which is responsible for bleaching of the sandstone on top of the Yan’an Formation.     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than ?44‰, ?29‰ and ?26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \(C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than ?10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.     

Extraction of soluble collagen and its feasibility in the palaeodietary research

In current palaeodietary research, gelatinization is the main method to extract insoluble collagen(ISC) from ancient bones. However, the degradation products of ISC, i.e., soluble collagen(SC), is often neglected and abandoned. In this work, we try to separate the extracts of ancient bones using gel chromatography and compare the contents of carbon and nitrogen, atomic C/N ratio, and stable carbon and nitrogen isotopic values of the extracts from three peaks to determine which peak can be attributed to SC. At last, the potential application of SC in palaeodietary research is discussed based on the comparison of stable isotopic values between ISC and SC. Among the three peaks, the second with the retention time between 17.5 min and 27.5 min had the most broad peak shape, indicating that the molecular weights of proteins collected were most variable. Besides, the contents of carbon and nitrogen and atomic C/N ratio of extracts in this peak were closest to the corresponding ISC. Based on the above, we conclude that the extract in second peak is SC. More important, the δ 13C and δ 15N values of ISC and SC are very similar. For ISC and SC with atomic C/N ratios within the normal range(2.9–3.6), the mean difference of δ 13C value was only(0.3±0.2)‰(n=2) while δ 15N value was(0.6±0.1)‰(n=2). Although the atomic C/N ratios of some SC are slightly beyond the normal range, the mean differences of δ 13C and δ 15N values were still only(0.4±0.1)‰ and(0.3±0)‰(n=2) respectively. These isotopic differences are quite below the isotope fractionation in one trophic level(δ 13C values of 1‰–1.5‰ and δ 15N values of 3‰–5‰), suggesting that SC had great application potentials in palaeodietary research.     

Water isotope characteristics of a flood: Brisbane River,Australia

Flooding associated with tropical storms can cause extreme perturbations in riverine and coastal ecosystems. Measuring isotope variability of tropical storm events can help investigate the impacts of flooding. We measured the water isotope composition (δD and δ¹⁸O) of rain and associated floodwater collected during two storms and subsequent major and minor flooding events in the subtropical coast of eastern Australia. Compared with baseline regional rainfall isotope values of ?15.0 ± 1.9‰ for δD and ?3.3 ± 0.2‰ for δ¹⁸O, floodwater had lower values with ?33.8 ± 2.5‰ δD and ?5.1 ± 0.4‰ δ¹⁸O for the major flood and ?29.4 ± 1.0‰ δD and ?4.6 ± 0.1‰ δ¹⁸O for the minor flood. The low isotope composition of the floodwater was associated with the transport of large quantities of suspended sediments, with sediment loads 30 to 70 times larger than during base flow conditions. Floods carried up to 35% of the annual phosphorus and up to 208% of the currently calculated average annual nitrogen load of the Brisbane River. The dramatic changes caused by a rapid increase in discharge from 2 to 2015 m³ s^?1 over 2 days in the major flood would have major consequences in riverine and coastal ecosystems of the region. These changes could potentially be traced using the isotope composition of the floodwaters. Copyright © 2015 John Wiley & Sons, Ltd.     

Rare gases,water, and carbon in kaersutites

Kaersutites from Kakanui, New Zealand and from three localities in the southwestern United States have been analyzed for rare gases, water and carbon to investigate the volatile signature of the sub-continental mantle. This study does not confirm the high ³He/⁴He and ²¹Ne/²²Ne ratios reported by Saito et al. [1] for the Kakanui kaersutite. Instead, a ³He/⁴He ratio of 6 R_A and atmospheric ²¹Ne/²²Ne ratios were measured which are consistent with our current knowledge of the earth's mantle. A low ⁴⁰Ar/³⁶Ar of 320 and more than 10^?8 cm³/g of ³⁶Ar confirms the argon results of Saito et al. and indicates that significant quantities of ³⁶Ar reside in this portion of the mantle. Kaersutites from the southwestern United States (Arizona) have a heterogeneous helium isotope signature, ranging from 8.8 R_A at San Carlos to 0.46 at Hoover Dam. All D/H ratios for the water in kaersutites (?56‰ to ?78‰) represent typical mantle values with no apparent correlation with ³He/⁴He. The correlation of increasing carbon content (140–400 ppm) with increasing δ¹³C (?24.5‰ to ?16.7‰) may reflect differences in the proportions of oxidized and reduced carbon in these samples.     

Characteristics and accumulation mechanisms of the Dongfang 13-1 high temperature and overpressured gas field in the Yinggehai Basin,the South China Sea

The Dongfang 13-1 is located in the diapiric structure belt of the Yinggehai Basin. The formation pressure of its main gas reservoir in the Miocene Huangliu Formation is up to 54.6 MPa(pressure coefficient=1.91) and the temperature is as high as 143°C(geothermal gradient 4.36°C/100 m), indicating that it is a typical high-temperature and overpressured gas reservoir. The natural gas is interpreted to be coal-type gas derived from the Miocene mature source rocks containing type II2-III kerogens as evidenced by high dryness index of up to 0.98 and heavy carbon isotopes, i.e., the δ13C1 ranging from -30.76‰ to -37.52‰ and δ13C2 ranging from -25.02‰ to -25.62‰. The high temperature and overpressured Miocene petroleum system is related mainly to diapir in the Yinggehai Basin and contains more pore water in the overpressured reservoirs due to undercompaction process. The experimental and calculated results show that the solubility of natural gas in formation water is as high as 10.5 m3/m3 under the temperature and pressure conditions of the Sanya Formation, indicating that at least part of the gas may migrate in the form of water-soluble phase. Meanwhile, the abundant gas source in the Basin makes it possible for the rapid saturation of natural gas in formation water and exsolution of soluble gas. Therefore, the main elements controlling formation of the Dongfang 13-1 gas pool include that(1) the diapir activities and accompanying changes in temperature and pressure accelerate the water-soluble gas exsolution and release a lot of free gas;(2) submarine fan fine sandstone in the Huangliu Formation provides good gas-water segregation and accumulation space; and(3) the overlying overpressured mud rocks act as effective caps. The accumulation mechanism reveals that the high temperatural and high pressure structure belt near the diapir structures has a good potential for large and medium-sized gas field exploration.     

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.