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…     

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.     

Geochemical characteristics and source rock of Ordovician gas reservoir, Changqing Gasfield

Carbon isotopic composition of methane in Ordovician gas reservoir in the Changqing Gasfield can reflect the dominance of Upper Paleozoic coaltype gas despite its high mature degree. The¹²C-rich ethane in the Ordovician reservoir (δ¹³C₂ < −29%), known as a marker as oiltype gas, does not indicate the Ordovician marine carbonate as main source rock, it is because of the relative less ethane content in coaltype gas than in oiltyped gas due to generation and migration. The way of Upper Paleozoic coaltype gas migrating into the Ordovician reservoir is widely through the unconformlty instead of only through the erosion groove in the weathering crust.     

Stable carbon and oxygen isotopic compositions of carbonates in middle Mesoproterozoic Wumishan Formation and sea-level change

δ13C of dolostones from the Wumishan Formation (1 310-1 207 Ma) in the Ming Tombs area near Beijing ranges from - 1.5 to 1.5‰ (PDB), and generally, the δ18O ranges from - 4 to - 5‰ (PDB). The secular variation of stable carbon isotopic compositions is cyclic. δ13C displays positive shifts from a sequence boundary to 1.5 per mil (PDB), then a negative shifts to - 1.5 per mil (PDB). In some unit, where δ13C values of the rocks are negative, they have relatively high δ18O values close to -4.0‰ (PDB). These characteristics of the carbon and oxygen isotopic compositions may be associated with sea-level changes.     

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.     

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…     

Foliar δ^13C and δ^15N values of C3 plants in the Ethiopia Rift Valley and their environmental controls

The foliar C and N stable isotopic compositions （δ^13C and δ^15N） and the relationships between these compositions and environmental factors of C3 plants in the Ethiopia Rift Valley were investigated. There were three distribution patterns for foliar δ^13C with mean values of -26.7‰±0.4‰, -29.7‰ ±0.6‰ , and -26.9‰± 1.2‰ in cold-moist, temperate-moist, and arid-hot environments, respectively. The δ^15N values ranged from -1.4‰ ±1.7‰ to 14.3‰ ± 0.1‰, with higher values under arid-hot conditions and the lowest values in plants growing at higher altitudes under cold-moist conditions. A strong negative relationship between mean annual precipitation and δ^15N explained more than half of the observed variation in the δ^15N values （r2= 0.54, P 〈 0.001）; a modest positive relationship was also found between δ^15N and temperature （r2 = 0.32, P 〈 0.01）. A weakly positive relationship existed between δ^13C and temperature, and changes in δ^13C values with precipitation and altitude followed quadratic curves. This suggests a shift in the effects of water and heat conditions caused by altitude on carbon isotopic discrimination.     

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.     

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.     

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.     

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.     

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…     

Fatty-acids and their <Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C characteristics of seep carbonates from the northern continental slope of Gulf of Mexico

Here we reported the fatty-acids and their δ¹³C values in seep carbonates collected from Green Canyon lease block 185 (GC 185; Sample GC-F) at upper continental slope (water depth: ~540 m), and Alaminos Canyon lease block 645 (GC 645; Sample AC-E) at lower continental slope (water depth: ~2200 m) of the Gulf of Mexico. More than thirty kinds of fatty acids were detected in both samples. These fatty acids are maximized at C₁₆. There is a clear even-over-odd carbon number predominance in carbon number range. The fatty acids are mainly composed of n-fatty acids, iso-/anteiso-fatty acids and terminally branched odd-numbered fatty acids (iso/anteiso). The low δ¹³C values (−39.99‰ to −32.36‰) of n-C₁₂:0, n-C₁₃:0, i-C₁₄:0 and n-C₁₄:0 suggest that they may relate to the chemosynthetic communities at seep sites. The unsaturated fatty acids n-C_18:2 and C_18:1△⁹ have the same δ¹³C values, they may originate from the Beggiatoa/Thioploca. Unlike other fatty acids, the terminally branched fatty acids (iso/anteiso) show lower δ¹³C values (as low as −63.95‰) suggesting a possible relationship to sulfate reducing bacteria, which is common during anaerobic oxidation of methane at seep sites.     

Carbon isotopic composition,turnover and origins of soil CO<Subscript>2</Subscript> in a monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir,South China

Carbon isotopic compositions of soil CO2 in rainy season (July) from two natural soil profiles (DHLS & DHS) in the monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir (DBR), South China, are presented. Turnover and origins of soil CO₂ are preliminarily discussed in this paper. Results show that the content of soil CO2 varies between 6120 and 18718 ppmv, and increases with increasing depth until 75 cm, and then it declines. In DHLS, soil CO₂ δ¹³C ranges from −24.71‰ to −24.03‰, showing a significant inverse correlation (R²＝0.91) with the soil CO₂ content in the same layer. According to a model related to soil CO₂ δ¹³C, the soil CO₂ is mainly derived from the root respiration (>80%) in DHLS. While in DHS, where soil CO₂ ? 13C ranges from −25.19‰ to −22.82‰, soil CO₂ is primarily originated from the decomposition of organic matter (51%–94%), excluding the surface layer (20 cm, 90%). Radiocarbon data suggest that the carbon in soil CO₂ is modern carbon in both DHLS and DHS. Differences in ¹⁴C ages between the “oldest” and “youngest” soil CO₂ in DHLS and DHS are 8 months and 14 months, respectively, indicating that soil CO₂ in DHLS has a faster turnover rate than that in DHS. The ¹⁴C values of soil CO₂, which range between 100.0‰ and 107.2‰ and between 102.5‰ and 112.1‰ in DHLS and DHS, respectively, are obviously higher than those of current atmospheric CO₂ and SOC in the same layer, suggesting that soil CO₂ is likely an important reservoir for Bomb-¹⁴C in the atmosphere.     

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.     

The occurrence and significance of C25HBI in Cenozoic saline lacustrine source rocks from the Western Qaidam Basin,NW China

The saline lacustrine deposit of the Oligocene Lower Ganchaigou Formation is the main source rock for the Western Qaidam Basin,NW China.In this study,abundant highly branched isoprenoids with 25 carbon atoms (C25HBI) were detected in the upper section of the Lower Ganchaigou Formation.C25HBI is a biomarker for diatoms,and can provide information regarding biogeochemical processes during production and preservation of sedimentary organic matter.The carbon isotopic values of C25HBI in these source rocks were in the range of-18‰ to-20‰.The relative enrichment in 13C of C25HBI suggests that these isoprenoids were derived from diatom blooms.In this case,the diatoms used HCO3-as an additional carbon source to dissolved CO2 in water column due to their high biological productivity.Conversely,the diatom blooms indicated an abundant nutrient supply to the environment and high primary productivity.Thus,the occurrence of 13C-enriched C25HBI could be an ideal marker for good source rocks.The decreased concentration of CO2(aq) in the water column induced by diatom blooms can result in an enrichment in 13C of organic matter synthesized by primary producers.This may be a possible reason for the occurrence of 13C-enriched organic matter in the Cenozoic source rocks of the Western Qaidam Basin.Previous studies have shown that the high carbon number n-alkanes sourced from diatoms have no carbon preference.Hence,the sources of n-alkanes in regional source rocks are complex,and should be considered when discussing the sources of organic matter in future studies.     

Variability of snail growing season at the Chinese Loess Plateau during the last 75 ka

Knowledge of seasonal climate change is one of the key issues facing Quaternary paleoclimatic studies and estimating seasonal climate change is difficult,especially changes such as seasonal length on glacial-interglacial timescales.The stable isotope composition from seasonal land snail shells provides the potential to reveal seasonal climatic features.Two modern land snail species,cold-aridiphilous Pupilla aeoli and thermo-humidiphilous Punctum orphana,were collected from different climatic zones in 18 localities across the Chinese Loess Plateau,spanning 11 degrees of longitude and covering a range of 1000 km2.The duration of the snail growing season(temperature ≥10℃) was shorter(202 ± 6 d) in the eastern Loess Plateau compared with in the western Loess Plateau(162 ±7 d).The δ13C of P.aeoli shells was ?9.1‰ to ?4.7‰ and ?5.0‰ to 0.3‰ for δ18O.For P.orphana,the δ13C ranged from ?9.1‰ to ?1.9‰ and ?8.9‰ to ?2.9‰ for δ18O.Both the δ13C and δ18O differences between the two snail species were reduced from the east to the western Loess Plateau(2.8‰ to 0.2 ± 1.1‰ for δ13C and 4.7‰ to 2.9 ± 1.3‰ for δ18O).These isotopic differences roughly reflect the difference in the growing season lengths between the east and west Loess Plateau indicating that the duration of the snail growing season shortens by 15 d or 19 d if the difference decreases by 1‰ in δ13C or δ18O,respectively.Thus,the difference in δ13C and δ18O between both snail species can be used to reveal the length of the snail growing season in the past.Based on our investigation,the length of the snail growing seasons from the Xifeng region during the last 75 ka was reconstructed.During the mid-Holocene(8-3 ka),the mean isotopic difference from both snail species reached maximum values of 2.6 ± 0.7‰ and 2.1 ± 1.4‰ for δ13C and δ18O,respectively.This was followed by MIS 3 that ranged from 2.5 ± 0.4‰ for δ13C and 1.6 ± 0.8‰ for δ18O.The Last Glacial Maximum changed by only 0.2‰ and 0.4‰ for δ13C and δ18O,respectively.Therefore,we estimate that the duration of the snail growing seasons to be ～200 ± 10 d during the mid-Holocene,190 ± 6 d in MIS 3 and 160 ± 3 d during the last glacial period.     

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.     

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.