C－isotope composition and significance of the Sinian on the Tarim plate

102 samples of limestones,mudrocks shales and tillites from the Sinian in Kuluketage have been analyzed ,Four formations in the Sinian belong to glacial deposits in which the differences in δ^13C are distinct (-14.7‰- 4.2‰),Distinctly negative δ^13C excursions for three times support the viwe of three glacial deposits in this area suggested by previous authors,except for the durations of them ,δ^13C values are generally positive in the Beiyixi Formation of lower part of the Lower Sinian ,representing probably the rock records of a continental rift related to break-up of the Rodinian supercontinent,There are three times of distinct excursions of δ^13C curve in all strata,The first one is from positive values at the bottom to about -5‰ at the top of the Beiyixi Formation ,The second one,from 0‰-3‰ in the Arletonggou Formation of upper part of the Lower Sinian to -3.4‰---14.4‰ in the Teruiaiken Formation.The third one,from positive values in the Zhamoketi Formation of lower part of the Upper Sinian to negative values in glacial varves at the top of the Hankeerqiaoke Formation.     

Analysis of carbon isotopes in airborne carbonate and implications for aeolian sources

Methods were developed to determine the mass ratios of carbon isotopes in trace amounts of aerosol carbonate. A Finnigan MAT 252 mass spectrometer fitted with an on-line Kiel device was to determine the ^13C/^12C ratio in CO2 produced from the carbonate. A study using these methods was conducted to characterize the carbonate carbon isotopes in aerosol samples collected in Xi‘an on dusty and normal days during March and April 2002. Results of the study demonstrate that insights into the origin of the dust can be deduced from its isotopic composition. That is, the δ^13C ofcarbonate for dust storm samples ranged from -1.4‰ to -4.2‰, and this is consistent with sandy materials in dust source regions upwind. In contrast, for non-dusty days δ^13C ranged from -7.5% to -9.3‰, which is more similar to fine particles emitted from local surface soils. Comparisons of dust storm aerosols with surface soils from source regions and with aerosol samples collected downwind indicate that the δ^13C values did not change appreciably during longrange transport. Therefore, carbon isotopes have the potential for distinguishing among source materials, and this approach provides a powerful new tool for identifying dust provenance.     

Abrupt climate change of EastAsian Monsoon at 130 kaBP inferred from a high resolu-tion stalagmite δ18O record

^230Th ages and oxygen isotope data of a stalagmite from Shanbao Cave in Hubei Province characterize the East Asian Monsoon precipitation from 133 to 127ka. The decadal-scale high-resolution δ^18O record reveals a detailed transitional process from the Penultimate Glaciation to the Last Interglaciation. As established with ^230Th dates, the age of the Termination Ⅱ is determined to be 129.5±1.0 kaBP, which supports the Northern Hemisphere insolation as the triggers for the ice-age cycles. In our δ^18O record, the glacial/interglacial fluctuation reaches about 4‰, almost the same level as in other Asian Monsoon cave stalagmite δ^18O records. The transition of the glacial/interglacial period in our record can be recognized as four stepwise stages, among which, a rapid rise of monsoon precipitation follows the stage of “Termination Ⅱ pause”. The rapid rise is synchronous with the abrupt change of global methane concentration, which reflects that an increase in both Asian Monsoon precipitation and tropical wetland plays an important role in the global climate changes.     

Changes in the content of eolian iron during the past 900 ka and the implications

In this study, total Fe2O3 content (Fet) in two parallel sections from the central Loess Plateau (Xifeng and Changwu) is analyzed to address the variations of eolian iron in the past 900 ka. The obtained timeseries indicate that Fet Vvalues in some glacial intervals are comparable to that of interglacial periods and its oscillations do not generally correspond to the long-term glacial-interglacial changes. Rather,it exhibits higher frequency fluctuations without detectable 100 ka period, but with a strong 20 ka period and a clear 40ka period. The combination of 20 ka and 40 ka periods suggest that eolian iron content was relatively independent of glacial-interglacial changes, but more strongly influenced by the insolation changes in the northern hemisphere. Higher iron content was observed for the S5-1 soil that is correlative to marine δ^18O stage 13. In marine records, this stage is characterized by higher δ^13C values, suggesting that the event is of global significance.     

δ13CSC values of the loess-paleosol sequence in Dali area, Shaanxi Province, China, and paleoenvironmental implications

The carbon isotopic ratios of carbonate in the two profiles of the Dali area were analyzed and some new understandings on the influencing factors of the δ^13Csc value of the Iocss-paleosol sequence and its paleoenvironmental implications were discussed preliminarily in this report. The δ^13Csc value of the Dali Ioess-paleasol sequence is synchronizing with the variance of magnetic susceptibility basically and the negative peaks of the δ^13Csc curves are corresponding to the different developmental periods of the paleosol. It is believed that the intervention of the CO2 produced by plants will cause the decrease of the δ^13Csc value, the amplitude of which may be relevant to the paleovegetation density and the ancient humidity. The relative biomass of C4 plants in the vegetation will affect the sublevel change of the δ^13Csc. Low δ^13Csc value by and large indicates the environmental conditions of the relatively abundant vegetation and humid climate. During the last 250000 years, the period with the sparsest vegetation and the most arid climate is the phase of the loess in L2 depositing and the period with the most abundant vegetation and the most humid climate is the last interglacial period. The δ^13Csc curves of Dali also show that the High Temperature and Large Precipitation Event of the Qinghai-Tibetan Plateau during 40-30 kaBP had affected the Central Shaanxi Plain with relatively humid climate, and had apparent influence on the local vegetation and humidity.     

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.     

Determination of trophic relationships within a Bohai Bay food web using stable δ15N and δ13C analysis

This study measured stable carbon and nitrogen isotope ratios in phytoplankton, zooplankton, five invertebrates species, eight fishes species and three seabirds species collected in Bohai Bay. δ^13C ranged from -25.38‰ to -11.08‰ showing a relative low enrichment in the food web from Bohai Bay. The mean δ^13C of mullet is higher than that of other organisms, and this might be due to that mullet is migration fish and feeds mainly on inshore sources. δ^15N ranged from 4.08‰ to 13.98‰, and showed a step-wise enrichment with trophic level of 3.8‰. The δ^15N enrichment factor was used to construct an isotopic food web model to establish trophic relationships within this marine food web. According to this model, exact trophic levels of all organisms were estimated as 1.46-2.10, 1.91-3.32, 2.55-4.23 and 2.98-4.28 for plankton, invertebrates, fishes, and seabirds.     

Sulfur and carbon isotopic variations in Neoproterozoic sedimentary rocks from southern China

A new set of δ34Ssulfide, δ34Ssulfate and δ13Ccarbonate values has been reported from Neoproterozoic sedimentary rocks in southern China. The interglacial black shales of the Datangpo Fm. display higher δ34Ssulfide values with >+20‰ average, but the postglacial black shales from the Doushantuo Fm. show negative δ34Ssulfide values. However, the Jinjiadong Fm., the same post-glaciation as the Doushantuo Fm., has positive δ34Ssulfide values, implying that the δ34S value of sedimentary sulfides would be controlled by lithofacies and paleogeographic environments. The δ34Ssulfate values relative to δ13Ccarbonate were obtained by extraction of trace sulfate from the successive carbonate sequences in the Yangtze Gorges sections. A preliminary interpretation suggests that the oceanic environment may fluctuate dramatically at the post-glacial Doushantuo stage and, then, recover its stability at the Dengying stage on the basis of the high resolution δ34S and δ13C curves of seawater.     

Petrographic and geochemical characterization of seep carbonate from Alaminos Canyon,Gulf of Mexico

Seep carbonates were collected from the Alaminos Canyon lease area, Gulf of Mexico. The carbonates are present as slabs and blocks. Bivalve shell and foraminifer are the dominant bioclasts in carbonate. Pores are common and usually filled with acicular aragonite crystals. XRD investigation shows that aragonite is the dominate mineral （98%）. Peloids, clotted microfabirc and botryoidal aragonite are developed in carbonate and suggest a genesis linked with bacterial degradation of the hydrocarbons. The δ^13C value of bioclasts in carbonate is from -4.9‰ to -0.6‰, indicating that the carbon source is mainly from sea water as well as the small portion incorporation of the seep hydrocarbon. The microcrystalline and sparite aragonite shows the δ^13C value from -31.3‰ to -23.4‰, suggesting that their carbon is derived mainly from microbial degradation of crude oil. ^14C analyses give the radiocarbon age of about 10 ka. Rare earth elements （REE） analyses of the 5% HNO3-treated solution of the carbonates show that the total REE content of the carbonates is low, that is from 0.752 to 12.725 μg·g^-1. The shale-normalized REE patterns show significantly negative Ce anomalies. This suggests that cold seep carbonate is most likely formed in a relatively aerobic environment.     

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.     

The possible contribution of a mantle-derived fluid to the Ningwu porphyry iron deposits-Evidence from carbon and strontium isotopes of apatites

Apatite is a characteristic mineral for the iron deposits in the Ningwu region. Apatite shows a range of δ^13CPDB values from -9.6‰ to -0.6‰, and most of them with the δ^13CPDB values distributed in a range of mantle carbon （i.e., -2‰to -9‰）, except for samples T-06-1 and J-06-3. Apatites in the Ningwu porphyry iron deposits yield a narrow variation range of ^87Sr/^86Sr values from 0.706326 to 0.707577, similar to those of the volcanic and subvolcanic rocks and higher than that of a typical mantle-derived magmatic apatite （i.e., about 0.7040）, indicating that formation of the apatites was involved with crust material contamination.δ^13CPDBand ^87Sr/^86Sr values of the apatite indicate a possible contribution of mantle-derived fluid and material to formation of the Ningwu porphyry iron deposits, supported by regional geology, regional gravities and geochemistry of the volcanic and subvolcanic rocks in the Ningwu region.     

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.     

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.     

Indicators of δ13C and δ18O of gas hydrate-associated sediments

The analyses of δ13C and δ18O of gas hydrate-associated sediments from two cores on Hydrate Ridge in Cascadia convergent margin offshore Oregon, eastern North Pacific show the values of d 13C from -29.81‰ to -48.28‰ (PDB) and d 18O from 2.56‰ to 4.28‰ (PDB), which could be plotted into a group called typical carbonate minerals influenced by the methane in cold venting. Moreover, the values of d 13C and d 18O show a consistent trend in both cores from top to bottom with increasing of d 13C and decreasing of d 18O. This trend could be explained as an effect caused by the anaerobic oxidation of methane (AOM) in depth and the oxygen fraction during the formation of gas hydrate in depth together. These characteristics of d 13C and d 18O indicate that the gas hydrate-associated sediments are significantly different from the normal marine carbonates, and they are deeply influenced by the formation and evolution of gas hydrate. So, the distinct characteristics of d 13C and d 18O of gas hydrate-associated sediments could be undoubtedly believed as one of parameters to determine the presence of gas hydrates in other unknown marine sediment cores.     

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.     

Vegetation evolution on the central Chinese Loess Plateau since late Quaternary evidenced by elemental carbon isotopic composition

There are many controversial issues in loess studies such as natural vegetation types on the Chinese Loess Plateau during the historical periods and the spatial and temporal evolution of C3/C4 plants. Elemental carbon isotopic composition （δ^13Cec） in the loess section may offer new evidence for these problems. Elemental carbon （EC） is produced by incomplete combustion of vegetation, and its carbon isotopic composition has a very small difference from that of the formal vegetation, then δ^13Cec can be used as a record to recover the changes of vegetation. Elemental carbon was extracted by applying the oxidation method from the Ioess-paleosol sequence in the central Chinese Loess Plateau, and its car- bon isotope composition was analyzed by the isotope mass spectrometer. The results showed that the vegetation in this region was a mixed type of C3 and C4 plants, dominated with C3 plants in most of the time. Since late Quaternary, C3/C4 plants may not follow a simple glacial-interglacial cycle mode on the Chinese Loess Plateau, but showing fluctuations. C3 plants increased gradually in L4 period, and more C3 plants occurred during $3 period, and C4 plants increased again during L3-- L2 periods, after that, Cs plants dominated again during S1 --S0 periods. During periods of paleosol development, C3 plants were abundant in S3 and S1, and there were more Ca plants in S2 and SO. During periods of loess sedimen- tation, there were more C3 plants in L4 and L1, and there were more C4 plants in L3 and L2. On the orbital timescale, the vegetation variations revealed by δ^13Cec record are consistent with the results of pollen data and also similar to the results obtained by organic carbon isotopic composition since the last glacial period.     

Preliminary study of microscale zircon oxygen isotopes for Dabie-Sulu metamorphic rocks： Ion probe in situ analyses

151 in situ analyses of oxygen isotopes were carried out by ion micro-probe for zircons from 8 localities of HP-UHP metamorphic rocks including eclogites in the Dabie-Sulu terrane. The results show significant heterogeneity in δ^18O values, with variation in different rocks from -8.5‰ to 9.7‰ and within one sample from 2‰ to 12‰. No measurable difference in δ^18O was observed between protolith magmatic (detrital) zircons and metamorphic recrystallized zircons within analytical uncertainties from the ion micro-probe measurements. This indicates that the metamorphic zircons have inherited the oxygen isotopic compositions of protolith zircons despite the HP to UHP metamorphism. According to their protolith ages from zircon U-Pb in situ dating by the same ion micro-probe, two groups of oxygen isotope composition are recognized, with one having δ^18O values of 6‰-7‰ for old protolith of 1.9-2.5 Ga ages and the other 0‰-2‰ for young protolith of 0.7-0.8 Ga ages. The latter anomalously low δ^18O values of zircons indicate that the magma has had the obvious involvement of meteoric water when forming the young protolith of high-grade metamorphic rocks. This may be correlated with the snowball Earth event occurring in South China and the world elsewhere during the Neoproterozoic.     

Origin and nature of cold seep in northeastern Dongsha area, South China Sea: Evidence from chimney-like seep carbonates

The occurrence of seep carbonates is one of the characteristic features for cold seep sites at continental margins.The carbonates documented the venting history of methane-rich fluid.Compared to the chemoherm carbonates and carbonate pavements which formed on the sediment-water interface,chimney-like seep carbonates precipitated around fluid conduits below the sediment-water interface therefore better recording information of the past fluid flow and composition.Here the chimney-like seep carbonate samples from the northeastern Dongsha area of the South China Sea were studied to understand the origin and nature of the venting fluids and their potential relationship with gas hydrate deposits underneath the seafloor.Based on the occurrence,morphology,petrology,mineralogy and C-and O-isotope compositions,combined with present and past bottom water temperatures and the timing of methane release events,the oxygen isotopic fractionation between calcite and water were used to estimate the equilibriumδ18O values of the precipitating fluids.Theδ13C values ranging from 56.33‰to 42.70‰V-PDB and thus clearly show that the studied chimneys were mainly derived from biogenic methane oxidation.The calculated equilibriumδ18O values of the precipitating fluids ranged from 1.9‰0.3‰to 0.6‰0.3‰V-SMOW,with an average of 1.4‰0.3‰V-SMOW which is heavier than those of seawater even at the last glacial maximum.It is considered that the formation of chimney-like carbonates was closely related to methane hydrate dissociation in the area.The methane hydrates contributed as much as45.7%of water to the venting fluids.It is suggested that the climate and environmental changes(e.g.sea-level lowering,down-cutting canyons and mass wasting)are the major mechanisms maybe responsible for the destabilization of methane hydrates in the study area.The extensive occurrence of seep carbonates indicates that a large amount of the methane released from methane hydrate dissociation has been effectively captured and sequestered by microbial anaerobic oxidation of methane(AOM)before it escapes into the water column.     

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.     

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.