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.     

Isotopic composition of organic carbon and elemental carbon in PM2.5 in Hangzhou, China

In order to identify the sources of organic carbon (OC) and elemental carbon (EC) in airborne PM2.5 in Hangzhou, OC and EC were oxidized to CO2 offline in two thermal steps, and their carbon isotope compositions were measured by mass spectrometer. Results showed that the average δ13COC values were -52.8‰, -48.1‰, -50.0‰ and -52.5‰ in spring, summer, autumn, and winter, respectively, and the annual average value was -50.9‰ (-85.0‰ to -35.6‰), whereas δ13CEC values were -26.4‰, -26.9‰, -26.7‰ and -25.9‰ in the four seasons, and its annual value was -26.5‰ (-30.5‰ to -23.8‰). Large differences were found between isotope compositions of the two types of carbon. δ13COC values were much smaller than those of δ13CEC, and varied in a large range, and the ratios in both spring and winter were the smallest. δ13CEC varied in a small range, and its mean values in four seasons were nearly the same. This suggests that the carbon isotope compositions of OC and EC in PM2.5 can provide useful information in distinguishing their sources.     

A reconnaissance of Cu isotopic compositions of hydrothermal vein-type copper deposit Jinman,Yunnan, China

The Jinman deposit is a low-temperature hydrothermal vein-type copper deposit, which occurs along faults and fractures within Middle Jurassic sandstone and mudstone units of the Lanping-Simao Mesozoic-Cenozoic basin of Yunnan Province. In this note, we report for the first time the Cu isotopic compositions of Cu-sulfides from the Jinman deposit. The data show large variations and low δ⁶⁵Cu values of -3.70‰ to +0.30‰, which are in sharp contrast to the δ⁶⁵Cu values of high-temperature magmatic-hydrothermal copper deposits (-0.62‰ to +0.40‰) and the modern ocean-floor massive sulfide deposits (-0.48‰ to +1.15‰). It is suggested that the Cu isotope fractionation at Jinman is affected mainly by the following factors, i.e. a low temperature of ore formation (150—286℃); a sedimentary source for ore materials; various stages of ore deposition; and involvement of organic matter in the ore-forming processes.     

Diet control on carbon isotopic composition of land snail shell carbonate

Carbon isotope compositions for both the carbonate shells and soft bodies (organic tissue) of living land snails collected mostly from the Loess Plateau, China have been measured. The result shows that δ 13C values range from -13.1‰ to -4.3‰ for the aragonite shell samples and from -26.8‰ to -18.0‰ for the soft body samples. Although the shells are enriched in 13C relative to the bodies averagely by 14.2(±0.8)‰, the shell δ 13Ca values are closely correlated to the body δ 13Corg values, expressed as δ 13Ca = 1.021 δ 13Corg 14.38 (R = 0.965; N = 31). This relationship indicates that δ 13Ca is primarily a function of the isotopic composition of the snail diets since previous studies have proved that the snail body is the same as their food in carbon isotope composition. In other words, carbon isotope compo-sition of the carbonate shell can be used as a proxy to estimate the dietary 13C abundance of the land snails. The data also support that the 13C enrichment of the carbonate shells results mainly from the equilibrium fractionations between the metabolic CO2, HCO3-in the hemolymph and shell aragonite, and partially from kinetic fractionations when snail shells form during their activity.     

Glycerol ether biomarkers and their carbon isotopic compositions in a cold seep carbonate chimney from the Shenhu area,northern South China Sea

At modern cold seeps,the anaerobic oxidation of methane(AOM)is the dominant pathway for methane consumption in marine sediments.AOM,which is mediated by a consortium of methane oxidizing archaea and sulfate reducing bacteria,is proposed to be responsible for authigenic carbonate formation.A methane-derived carbonate chimney was collected from the Shenhu area, northern South China Sea.The membrane lipids and their very low carbon isotopic compositions(?115‰to?104‰)in the Shenhu chimney suggest the presence of an AOM process.Three specific archaeal and bacterial biomarkers were detected,including Ar,DAGE 1f,and monocyclic MDGD.Their strongly depleted??13C values(?115‰to?104‰),which are lower than those of the normal marine lipids in sediments,reveal biogenic methane as their origin.The carbonate deposits exhibiting a chimney structure indicate that a vigorous methane-rich fluid expulsion may have occurred at the seafloor.We propose that the decomposition of gas hydrates at depth is the likely cause of seepage and cold seep carbonate formation in the Shenhu area.     

Analysis of carbon isotope in phytoliths from C3 and C4 plants and modern soils

The analysis of carbon isotope in phytoliths from modern plants and surface soils in China shows that the values of carbon isotope are consistent with those from C3 and C4 plants,and the processes of photosynthesis of the original plants can be clearly identified by carbon isotope in phytoliths.The value of carbon isotope varied from -23.8‰ to -28‰,with the maximum distributed in the latitude zone from 34° N to 40° N in North China and East China areas,and the minimum in the Northeast China and South China regions.The values of carbon of phytoliths tend to increase from low to high and then reduce to low value again as the latitude increases.In the same latitude zone,the carbon isotope in phytoliths from grassland soil under the trees is obviously lower than that from grassland soil without any trees with the difference of 1‰-2‰.     

Variations of organic carbon isotopic composition and its environmental significance during the last glacial on western Chinese Loess Plateau

The last glacial period is characterized by a cold and dry climate with low atmospheric CO2 concentration. The relatively arid climate and low CO2 concentration are favorable to the growth of C4 plants, but the low temperature limits the development of th…     

Variation of soil Δδ13C values in Xifeng loess-paleosol sequence and its paleoenvironmental implication

The carbon isotopic compositions of soil organic matter （SOM） and total carbonate （TC） in Xifeng Ioess-paleosol sequence have been studied. The δ^13CsoM values vary from -23.8‰ to -20.2‰, which are higher in interglacial than in glacial stages. Contrary to δ^13Csoi values, the δ^13CTc values vary from -8.5‰ to -3.6‰ and are lower in interglacial than in glacial stages. The differences （△δ^13C） between the δ^13CsoM and δ^13CTc values vary from 14.1‰ to 19.4‰. Our results from the Xifeng loesspaleosol sequence indicate that the △δ^13C values represent the ratio of primary carbonate （PC） to secondary carbonate （SC）. The △δ^13C values were high in the loess stages, and the maximal PC-to-SC ratio can reach 6：4. But in the paleosol stages, the △δ^13C values were low, with a small proportion of PC. The △δ^13C values in Ioess-paleosol sequence also indicate the contributions of the dust to the loess sediment in the Chinese Loess Plateau because the dust contains the PC.     

Discovery of seep carbonate nodules as new evidence for gas venting on the northern continental slope of South China Sea

The geotectonic evolution of the northern South China Sea (SCS) is controlled by the Eurasian, the Pa-cific and the Indian-Australian Plates. With regard to its tectonic evolution, the northern margin composed of faulted terraces and basins and deposited …     

Molybdenum isotopic composition as a tracer for low-medium temperature hydrothermal ore-forming systems: A case study on the Dajiangping pyrite deposit,western Guangdong Province,China

Little is known about the range or controls on the molybdenum isotopic composition of low-medium temperature hydrothermal ore-forming systems. We present molybdenum isotope data from 12 hydrothermal syndepositional silicalite and carbonaceous slate samples from the Dajiangping pyrite deposit in western Guangdong Province, South China. The δ ^97/95 Mo values from Orebody III range from −0.02‰ to 0.29‰, with an average of 0.18‰. In contrast, the composition values from Orebody IV display a larger variation from −0.70‰ to 0.62‰. However, the five samples from the main ore bed all show strong negative values. This indicates that the significant variation in molybdenum isotopic composition supports different hydrothermal ore-forming metallogenesis and a metallogenic environment between the two orebodies. Orebody III is likely to have been deposited from submarine exhalative hydrothermal fluids under a relatively strong reducing environment and Orebody IV may have also been influenced by hydrothermal superimposition in a more oxidized disequilibrium condition. In addition, the δ ^97/95 Mo values of Orebody IV are clearly negative, together with the values increasing stratigraphically upward in the ore beds, suggesting that the metallogenic environment of Orebody IV is different from the open oceanic systems. There might be dynamic fractionation in this restricted environment. Therefore, the molybdenum isotope can be used as an effective tracer for the ore-forming fluid and metallogenic environment.     

Compound-specific carbon isotope compositions of individual long-chain n-alkanes in severe Asian dust episodes in the North China coast in 2002

Asian dust storms originating from the arid regions of central and eastern Asia and from the Loess Plateau in China frequently occur in spring [1,2]. Driven by the East Asian monsoon, Asian dust can be transported to northern Pacific Ocean[2―8]. Asian du…     

Variation of δ13C in karst soil in Yaji Karst Experiment Site, Guilin

This study deals with δ₁₃ C variation in karst soil system of Yaji Karst Experiment Site, Guilin, a typical region of humid subtropical karst formations. Samples of near ground air, plant tissue, soil and water (soil solution and karst spring) were respectively collected on site in different seasons during 1996–1999. Considerable variation of δ₁₃ C values are not only found with different carbon pools of soil organic carbon, soil air CO₂ and soil water HCO₃⁻, but also with the soil depths and with different seasons during a year. The °₁₃ C values of CO₂ both of near ground air and soil air are lower in July than those in April by 1‰–4‰ PDB. Our results indicate that the δ₁₃ C values of carbon in the water and air are essentially dependent on interface carbon interaction of air-plant—soil-rock—water governed by soil organic carbon and soil CO₂ in the system.     

Oxygen and carbon isotope records of calcareous nannofossils for the past 1 Ma in the southern South China Sea

Oxygen and carbon isotopic analyses have been carried out on calcareous nannofossils from ODP Site 1143 in the southern South China Sea. The results demonstrate that the δ18O values of calcareous nannofossils for the past 1 Ma vary systematically with those of planktonic and benthic foraminifera from the same site. But the average δ18O value of nannofossils is 1.869‰ higher than that of planktonic foraminifera, and is 3.855‰ lower than that of benthic foarminifera. There are systematic differences between the δ13C values of nannofossils, planktonic foarminifera and benthic foraminifera. The average δ13C of nannofossils is 0.756‰ higher than that of benthic foraminifera, and is 0.460‰ lower than that of planktonic foraminifera. The δ13C values of nannofossils exhibit a significant positive shift beginning near isotope stage 14 and lasting until stage 8. This study also finds that there is a close ralationship between the δ13C of nannofossils and the percentage of Florisphaera profunda. This implies that the δ13C of nannofossils can be used as an indicator of sea water surface paleoproductivity.     

Methane seeps, methane hydrate destabilization, and the late Neoproterozoic postglacial cap carbonates

Natural gas (methane) hydrates, the crystalline solids composed mainly of methane and water, are present in marine sediments of the continental margins and polar permafrost under a delicate balance of temperature (< 7℃) and hydrostatic pressure (> 50×10…     

Large selenium isotopic variations and its implication in the Yutangba Se deposit, Hubei Province, China

The selenium isotopic ratios have been measured in the Yutangba Se deposit, Hubei Province, China. The results show that the δ 82/76SeNIST values vary from -12.77‰ to 4.93‰, which is the largest Se iso- topic variation found so far in natural terrestrial samples. The sample Ytb-5 of high-selenium carbona-ceous shale has the lightest Se isotopic composition with a δ 82/76SeNIST value of -12.77‰. On the basis of variations of Se isotope in the deposit along with other geological and geochemical evidence, the "redox model" is suggested to favor the explanation of the occurrence of native Se in the deposit. The application to the Yutangba Se deposit with the discovery of large Se isotopic fractionation for natural samples indicates the potential of Se isotope as a new geochemical tracer.     

Isotopic composition characteristics and identification of immature and lowmature oils

Isotopic composition characteristics and the significance of immature and low-mature oils are first systematically discussed. The carbon isotopes of the whole oil can be divided into two groups, one has δ¹³C main peak values ranging from -30‰ to -29 and the other from -27‰ to-25‰, they are related to lacustrine and salt-lake facies or swamp facies, respectively. The carbon isotopic fractionation among different group components is relatively small, usually less than 2‰ and the biggest difference in fractionation often occurs between saturated and aromatic fractions. Their δD values vary between -180‰ and -130‰ The main peak of their δD values concentrates between -170‰ and -150‰, suggesting a domination of lacustrine fades. However, the secondary peak ranges from -160‰ to -150‰, showing a frequent salinization of paleo-water bodies. The average δ¹³C values of the methane vary between -50‰ and -52‰, about 10‰ lighter than those of mature oils. There is a relatively good correlationship between immature and low-mature oils and their source rocks in carbon isotopic compositions of group fractions and monohydrocarbons; moreover, compared with the source rocks of mature oils, that of immature oils is often relatively depleted in¹³C, which is one of the characteristics of immature oils, differing from those of mature oils.     

Comparison of the carbon isotope composition of total organic carbon and long-chain <Emphasis Type="Italic">n</Emphasis>-alkanes from surface soils in eastern China and their significance

Surface soil samples collected over a high spatial resolution in eastern China were analyzed for carbon isotope composition （δ^13C） of total organic carbon （TOC） and higher plant-derived long-chain n-alkanes, with the latter reported as weighted mean values. The two sets of δ^13C values are significantly correlated and show similar trends in spatial variation. The spatial distribution of δ^13C shows less negative values in the mid-latitudes between 31°N and 40°N and more negative ones at higher and lower latitudes. This is consistent with previously reported carbon isotope data from surface soil phytoliths in the same region and suggests that the mid-latitude area provides relatively favorable growing condi- tions for C4 plants. Furthermore, δ^13C values of both TOC and long-chain n-alkanes from 12 surface soil samples collected from a small grassland in north China displayed similar carbon isotope values and the difference between paired δ^13C of a soil samples remains relatively constant. Our data demonstrate that in eastern China, soil δ^13C composition of both TOC and long-chain n-alkanes is effective indicators of C3/C4 ratios of the prevailing vegetation. This work suggests that -22‰ and -32‰ are good es- timated end members for the weighted mean δ^13C values of long-chain n-alkanes （C27, C29 and C31 n-alkanes） from soils under dominant C4 or C3 vegetation, allowing us to reconstruct paleovegetation trends.     

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.     

贵州拉也剖面下Kellwasser事件生物地层及化学地层特征研究

为研究下Kellwasser事件的生物地层及化学地层特征, 对贵州拉也剖面进行细致的牙形石生物地层学和高分辨率化学地层学研究。结果表明, 剖面底部无机碳同位素及有机碳同位素有显著正向偏移, 样品LY-8代表的层位为下Kellwasser事件的界线。Kellwasser事件碳同位素变化的主要原因是有机碳埋藏量的增加, 可能是由初级生产力增加和缺氧环境共同造成的。     

Two kinds of silicalites in Mount Ailao belt, Yunnan Province

Two kinds of radiolarian silicalites at the bottom and top of the ophiolite in the Mount (Mt.) Ailao belt, Yunnan Province, are dealt with in this work in terms of geology, micro-paleontology, isotope and REE. The first kind of silicalite was defined as the turbidite formation. In this category, the radiolarian species lived in the Late Devonian (D3). The corresponding ecologic assemblage, composed of δ 30Si (0.4‰-0.5‰, average 0.03‰), δ Ce (0.77- 0.97, average 0.85) and LaN /YbN (0.77-1.06, average 0.96) of silicalite, shows that it occurred in the abyssal environment. The second kind of silicalite was defined as the mud-siliceous formation. Contacting conformably with the basalt of the ophiolite suit, the radiolarian silicalite at the top of ophiolite was in the category of the component units of the ophiolite in the Mt. Ailao belt. In this category, the radiolarian species lived in the Early Carboniferous (C1-). The corresponding ecologic assemblage, composed of d 30Si (0.2‰-1.3‰, averaging 0.7‰), dδCe (0.88- 0.92, averaging 0.90) and LaN /YbN (0.77-1.45, averaging 1.22), of silicalites indicate that it occurred in the bathyal environment. All these facts domonstrate that the Mt. Ailao must have been a small ocean basin at that time.