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.     

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…     

The specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4‰— -39.0‰) and methanotrophic bacteria (-38.4‰— -46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied steranes, showing that the carbon source or growth condition for its precursor, dinoflageilate, may be different from that of regular steranes. The variation trend of δ^13C ValUes between isomers of hopanes shows that ^13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.     

A breakthrough of researching reservoir adsorption gas and its significance

GC-C-MS on linear isotope analysis equipment makes it possible to measure the hydrocarbon gases at the level of 10 -3-10 -2 μL- By applying this technique the carbon isotopes of C1-C3 of the adsorbed gas from the Triassic oil sand bed of the Aican-l Well in the Turpan-Hami basin were analysed. The δ13C values of C1-C3, are -55.1‰, -38.6‰ and -35.0‰ respectively. In terms of geochemical characteristics of natural gases and crude oils, in combination with basinal geological backgrounds, it is considered that the reservoir adsorbed gas was formed by crude-oil biodegradation, absorbed by reservoir rocks and its oil-gas source is related with the Permain (perhaps including the Carboniferous). The adsorbed gas is obviously different from the Jurassic coal-generated oil and gas.     

Natural gas geochemistry of low evolutionary stage of medium- and small-sized basins in Yunnan Province, southwestern China

The biogenic gas and premature-low mature associated gases in some medium and small-sized basins of Yannan Province, such as Luliang, Yanglin, Baoshan and Jinggu basins, have beed researched. The results show that the biogenic-gas consists mainly of methane which is more than 99% in gasous hydrocarbons and of lighter carbon isotopic composition with δ13C1 values from -60.0‰ to - 75.4‰. The methane carbon isotopic compositions in the Baoshan Basin is relatively heavy (δ13C1 - 60‰- - 65‰), but those in Luliang and Yanglin basins are lighter (δ13C1, less than -70‰), which implies that the gas field of the Baoshan Basin formed earlier than the others. In the Jinggu Basin, where crude oil is premature-lower mature, the natural gas of associated oil relatively wet and the relative content of methane about 58%-95% in gasous hydrocarbons. Constituently the gas composition is much similar to associated one, but the methane carbon isotopic compositions from - 53.8‰ to - 57.8‰ are obviously richer in 12C than those of general oil fields and similarly characterize the biothermo-catalytic transitional zone gas. Their ethane carbon isotopic compositions from - 34.6‰ to -29.0‰ show that they may be derived from type Ⅰ or Ⅱ source rock. But for the associated gas from lower evolutionary stage, the heavier ethane carbon isotopic composition as well as the reversed order among the carbon isotopic composition of ethane, propylane and butane also implies that some gases from the type Ⅲ organic matter are mixed. The δ13CCo2 of the samples essentially less than - 10‰ may be generated from organic matter.     

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.     

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.     

Distribution characteristics of soil organic carbon of alpine meadow in the Eastern Qinghai-Tibet Plateau

A study on the distribution characteristics of soil organic carbon (SOC) in the alpine meadow in the Eastern Qinghai-Tibet Plateau has been carried out. The results indicate that the content of soil organic carbon (C _SOC) in the topsoil of terrace meadow (TM) ((67.16 ± 1.02) g·kg⁻¹) is more than that in the soil of upland meadow (UM) ((63.42 ± 0.65) g·kg⁻¹), while the C _SOC in upland shrubland (US) ((67.49 ± 0.83) g·kg⁻¹) is the most abundant in the scoreh stage (September). From May to September, the C _SOC in the topsoil of UM and US tends to descend, but that of TM tends to ascend. As for the distribution of the C _SOC and the density of SOC in the soil in the three sample areas, the data show that the deeper the soil, the lesser the content and density of SOC. The C _SOC in US is higher than that in TM and UM; the C _SOC in UM is the lowest at 0–10 cm soil depth. The density of SOC in US is always the lowest among UM, TM, and US at 0–40 cm depth, which shows that the storage of carbon in UM is more than that in US in the same range; the carbon pool capacity in UM is higher than that in US in the same range. Biography: ZHANG Wei (1979–), male, Lecturer, research direction: ecology of environment.     

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.     

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…     

Hydrogen isotopic compositions and their environmental significance for individual n-alkanes in typical plants from land in China

Hydrogen isotopes of n-alkanes in grasses, tree leaves and reeds from six regions with latitudes of 20° to 39°N in China are measured by GC-TC-IRMS analytical technique in order to understand their hydrogen isotopic compositions and environmental significance. The results show that a difference in ° D values (from −42.1‰ to −66.6‰) of n-alkanes exists among the same kinds of plants from various regions. Hydrogen isotopic compositions of most even carbon numbered n-alkanes in every plant are slightly heavier than that of the odd homologues. A trend toward D-enrichment with increasing chain length of n-alkanes in most plant samples is observed. Mean ° D values of n-alkanes in the studied plants range from −202.6‰ to −130.7‰ and the reed from a salt marsh has the largest value. The mean ° D values of individual n-alkanes among the same kinds of plants from various regions have the characteristics of leaf > reed > grass. The hydrogen isotopic compositions of n-alkanes are apparently distinct among various kinds of plants from the same region and the mean ° D values exhibit a distribution of tree leaf > reed > grass. It is observed that the mean ° D values of n-alkanes and ° D values of C₂₇ and C₂₉ n-alkanes in the grasses and tree leaves from these studied regions correlate clearly negatively with latitude and positively with temperature, indicating that these values can be used as excellent indicators of environment and climate. These results provide important basic data for understanding the distributional law of hydrogen isotopes of individual n-alkanes and their applied research. Supported by National Natural Science Foundation of China (Grant Nos. 40642007 and 40772069), National Basic Research Program of China (Grant No. 2005CB422105) and Special Project for Winners of CAS President Award     

Groundbreaking gas source rock correlation research based on the application of a new experimental approach for adsorbed gas

Many years of experimentation have led to the development and improvement of equipment and methods used to make gas source rock correlations.By crushing samples using a ball mill and directly collecting adsorbed gases in the absence of aqueous media under high vacuum conditions,most possible interference factors,such as atmospheric pollution,crushing-induced pyrolysis,and gas collection by aqueous media are eliminated.This greatly enhances the volume percentage of hydrocarbon gas in the acquired adsorbed gases,with maxima up to more than 80%.The actual measurement of carbon isotopic series can be carried out to such an extent as to be δ13C1-δ13C5.A preliminary study using newly established equipment and methods has indicated the following.(1) The carbon isotopic composition of ethane in adsorbed gases on hydrocarbon source rocks can be used to distinguish the types of source rocks.This is consistent with results obtained by using organic geochemical parameters for source rocks,and illustrates that it is highly feasible to use the carbon isotopic composition of ethane in natural gases as a parameter for distinguishing the types of source rocks.(2) The thermal evolution degree(Ro) of hydrocarbon-source rocks calculated in terms of the carbon isotopic composition of methane in adsorbed gases on hydrocarbon source rocks agrees well with the vitrinite reflectance actually measured in the source rocks.This confirms the reliability of the relationship between the carbon isotopic composition of methane in natural gases and the thermal evolution degree determined using statistics.(3) Finally,a direct gas source correlation method for natural gases has been established,and the expression of log Ro vs.δ13C1 established in terms of actually measured δ13C1 values of methane in absorbed gases.Ro values of hydrocarbon source rocks have been established as well,thus creating favorable conditions for precise oil-and-gas source correlations in exploration areas.     

High molecular weight (C35 +) n-alkanes of Neogene heavily biodegraded oil in the Qianmiqiao region, North China

With wax content of 1.62%, heavy oil has been produced from the sandstone reservoirs of Neogene Guantao Formation (Ng1^Ⅲ). In the GC and GC-MS RIC profiles of its aliphatic fraction, n-alkanes are totally lost, which shows the result of heavy biodegradedation. However, the remaining trace C₁₃－C₃₆ n-alkanes can be still seen from its m/z 85 mass chromatogram. In addition, a complete series of C₃₅－C₇₃ high molecular weight (HMW) n-alkanes was detected by high-temperature gas chromatography (HTGC). The HMW n-alkane series shows a normal distribution pattern, a major peak at nC₄₃, obvious odd-carbon-number predominance, CP_I37—55 and OEP_45—49 values up to 1.17 and 1.16—1.20 respectively. The present study not only has conformed the strong resistibility of HMW n-alkanes to biodegradation in crude oils as concluded by previous researchers, but also has provided some significant information on source input and maturity for the heavily biodegraded oil in the Qianmiqiao region.     

Vast laminated diatom mat deposits from the west low-latitude Pacific Ocean in the last glacial period

Diatoms are one of the predominant contributors to global carbon fixation by accounting for over 40% of total oceanic primary production and dominate export production. They play a significant role in marine biogeochemistry cycle. The diatom mat deposits are results of vast diatoms bloom. By analysis of diatom mats in 136°00′--140°00′E, 15°00′--21°00′N, Eastern Philippines Sea, we identified the species of the diatoms as giant Ethmodiscus rex （Wallich） Hendey. AMS 14C dating shows that the sediments rich in diatom mats occurred during 16000--28600 a B.P., which means the bloom mainly occurred during the last glacial period, while there are no diatom mat deposits in other layers. Preliminary analysis indicates that Antarctic Intermediate Water （AAIW） expanded northward and brought silicate-rich water into the area, namely, silicon leakage processes caused the bloom of diatoms. In addition, the increase of iron input is one of the main reasons for the diatom bloom.     

The biomarkers of 2,6,10,15, 19-pentamethylicosenes and their carbon isotopic composition in the sediments from the Gulf of Mexico

The methanogenic archaea and sulfate reduction bacteria are flourishing in the sediments associated with gas venting and gas hydrate settings on the sea floor, where the anaerobic oxidation of methane (AOM) me-diated by these bacteria is the dominant path…     

Pure CO2 fluids in the Sarekoubu gold deposit at southern margin of Altai Mountains in Xinjiang, West China

Sarekoubu gold deposit occurs in metamorphosed acid volcanic rocks and volcaniclastic rocks of Devonian Kangbutiebao Formation along the southern margin of Altai Mountains in Xinjiang, West China. Pyritization, silicification and carbonatization are developed in wallrocks, and main gold mineralization stages are pyrite-quartz stage (Ⅱ)and polymetallic sulfide stage (Ⅲ). Primary fluid inclusions are often seen in main gold mineralization stages, which are almost pure CO2 liquid inclusions (Lco2) under room temperature with high densities of 0.85--1.07 g/cm^3. CO2-rich inclusions (Lco2-LH2O) and H2O-rich inclusions (LH2O-LCo2)are subordinate. Fluid inclusions in stage Ⅰ (polymetallic sulfide stage) are more complex than in stage Ⅱ, containing CO2-CH4 system with -78.1-61.9℃ of solid CO2 melting temperatures and -33.7-17.7℃ of partial homogenization temperatures. The trapping pressures of high densities are estimated to be 150-350 MPa. Laser Raman microprobe was used to confirm the composition of pure CO2 liquid inclusions. δ^13C values of CO2 inclusions range from -10.73‰ to -21.15‰, which are similar to some of fluids in the mantle-derived minerals that contain surface organic carbon by subduction recycling. These characteristics differ from many hydrothermal gold deposits. CO2 fluids have a regional source related to post-collisional orogeny.     

The elemental carbon record in Weinan loess section since the last 21 ka

We studied the records of elemental carbon (EC) of the last 21 ka in the Weinan loess section, Shanxi Province. The variations of EC abundance and δ¹³C_EC value along with depth (or age) were presented. There are four large peaks of EC abundance around the following years: 20.16 ka, 17.76 ka, 11.97 ka and 4.49 ka. Climatic situation was changed rapidly during these periods. The peaks around 11.97 ka and 20.16 ka are particularly sharp, occurring over intervals of tens to hundreds of years, which could represent short-duration intense events. δ¹³C_EC values in the upper 4 m of the Weinan loess section vary between −11.71‰ and −21.34‰, which suggests that the vegetation pattern of the last 21 ka on the Loess Plateau is C₄-dominated grasses.     

Potash-rich volcanic rocks and lamprophyres in western Shandong Province: 40Ar-39Ar dating and source tracing

Highly precise ⁴⁰Ar-³⁹Ar dating results demonstrate that the ages of potash-rich volcanic rocks in western Shandong Province are 114.7–124.3 Ma, and that of the lamprophyres is 119.6 Ma. The potash-rich volcanic rocks have relatively high (⁸⁷Sr÷⁸⁶Sr)_i ratios (0.708715–0.711418) and distinctly negative ε_nd values (−11.47–−17.54), and are enriched in radiogenic lead (²⁰⁶Pb÷²⁰⁴Pb=17.341−17.622, ²⁰⁷Pb÷²⁰⁴Pb=15.525−15.538, ²⁰⁸Pb÷²⁰⁴Pb = 37.563−37.684). Similarly, the lamprophyres also have quite low ε_nd values (−11.57–−19.64). Based on the fact that the Sr, Nd and Pb isotopic compositions of potash-rich volcanic rocks are very consistent with that of the clinopyroxene separates, and by integrating comprehensive analyses of their tectonic settings, and extensive comparisons of the Sr, Nd isotopic compositions with that of the related simultaneous rocks, it is concluded that the potash-rich volcanic rocks and lamprophyres in western Shandong Province were most possibly derived from the partial melting of enriched mantle which was caused by source contamination and metasomatism of subducted continental crustal materials.     

Formation, structure and properties of GeCn± and Ge2Cn± binary clusters

The binary cluster ions Ge₂C_n⁺/Ge₂C_n^- and GeC_n⁺ have been produced by laser ablation. The parity effect is present in the negative ions Ge₂C_n^-, though it is not very prominent. While the experiments tell that the parity effect is totally not shown in the positive ions Ge₂C_n⁺. An extensive theoretical investigation on GeCn/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂Cn/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) has been carried out by density functional theory at B3LPY level. The calculation shows that the low-lying states of GeC_n/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂C_n/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) are linear structure with germanium atoms locating at terminals respectively. The electronic distributions, ionization potential (IP_ad), elec-tron affinity (EA) and increasing bonding energy reveal that the parity effect of neutral species is much stronger than that of ions, which is attributed to the valence π-electrons. It is explained that the differences between experiments and cal-culations are due to the kinetic factor in the formation of Ge₂C_n^±.     

The impacts of “05.6” extreme flood event on riverine carbon fluxes in Xijiang River

An extreme flood event with a frequency of nearly 200 year occurred in June of 2005 in the Xijiang River, the main trunk stream of the Zhujlang River. Samples were systematically collected during the flood event, and water quality parameters, including total suspended sediment （TSS）, dissolved inorganic carbon （DIC）, dissolved organic carbon （DOC）, and particulate organic carbon （POC） were analyzed, and riverine carbon concentrations associated with its changing pattern through the flood process were discussed. These parameters reflect the changes in basin surface flow and subsurface flow during the flood. This flood event influenced annual flux estimations of POC, DOC, and DIC to great extents. Based on carbon flux estimations for the year 2005 and the flood event （June 21-28） in the Xijiang River, it was found that DIC, DOC, and POC fluxes during ＇05.6＇ flood event are 1.52×10^6g.km^-2.a^-1, 0.24×10^6 g.km^-2.a^-1, and 0.54×10^6 g.km^-2.a^-1, and account for 14.87%, 24.75% and 44.89% of the annual fluxes in 2005, respectively. The results suggested that carbon exports during extreme flood events had great contributions to the total carbon fluxes and composition of various carbon components, being important for accurate estimates of annual carbon fluxes in rivers with frequent floods.