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     

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…     

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 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.     

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.     

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…     

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.     

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.     

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.     

Climatic and environmental implications from n-alkanes in glacially eroded lake sediments in Tibetan Plateau: An example from Ximen Co

Gas chromatography-mass spectrometry was used to identify a series of n-alkanes in the sediments of a typical glacially eroded lake in the eastern Tibetan Plateau.By comparing the distribution patterns of n-alkanes in lake sediments,surface soils and cow manure,it was shown that n-C 27-n-C 33 alkanes in the soil ecosystem of Ximen Co are derived from vascular plant species and that the distribution pattern of n-C 27-n-C 33 alkanes remains unchanged during the feeding and digestion processes of herbivores.The relative percentage of C 27,C 29 and C 31 n-alkanes decreased from the bottom to the top of the sediment core showing a trend of degradation of higher plants in the Ximen Co lake region during the formation of the 44 cm core.210 Pb dating,combined with pre-existing AMS 14 C dating results showed that the depositional core reflects climatic and environmental variations since about 900 years before present.The n-alkane indexes (ACL 27-33,P aq,P wax) are comparable with regional temperature variation,especially recording the Little Ice Age event (LIA).This study highlights that n-alkanes are valid proxies for paleo-climate and paleo-environment reconstruction,despite the same distribution patterns in n-alkane molecular fossils derived from a typical glacially eroded lake.     

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.     

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.     

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.     

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^±.     

Treatment efficiency of integrated vertical-flow constructed wetland for saline wastewater

The integrated vertical-flow constructed wetland(IVCW) was simulated with three suits of designed experiment columns planted with Kandelia candel.Units A,B and C were irrigated with sewage of different salinity(A:10‰ B:20‰,C:30‰),respectively.The removal rates of dissolved organic carbon(DOC),NH3-N and NO3--N dropped 90.4%-48.6%,80.2%-40.3% and 84.8%-60.9%,respectively,when salinity increases from 10‰ to 30‰.The removal rate of TP increased 14%-31.2%,oppositely.A 20-day inflow salinity drastic change shock affective trial was done on units D and E.Unit D was used as a control and irrigated with saline sewage(20‰).Unit E was irrigated with sewage with low salinity(5‰) as a salinity drastic change shock on the third and fourth days.DOC,NH3-N and NO3--N removal efficiency of unit E showed a three-stage process of change,"rapidly decrease,increase beyond the normal standard,and then back to the normal standard".TP removal value was negative during the 2-day shock period.     

Characteristics of gas geochemistry in Yangbajing geothermal field, Tibet

CO 2 is a main component of gases in the Yangbajing geothermal field, usually higher than 85 in volume; others are N 2, H 2S, H 2, CH 4, etc. Helium R/R a ratios, ranging from 0.14 to 0.46, indicate a crustal component to be dominant in the gases. δ 13C-CO 2 values and δ 34S-H 2S values are in the range -7.72‰--11.33‰ and 0.2‰-8.3‰, respectively. The gases are inferred to mostly derive from the partial melting of the Nyainqentanglha core complex. The gases of shallow and deep reservoirs are distinctive in chemical compositions and δ 34S-H 2S values, which shows their different flowing paths and physical-chemical processes. Sulphur does not approach isotopic equilibrium between H 2S and SO 2- 4 species in both reservoirs. Significance of steam chemical monitoring is also discussed.     

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.     

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.     

Lipids of sulfate-reducing bacteria and sulfur-oxidizing bacteria found in the Dongsheng uranium deposit

U-bearing sandstones from the Dongsheng deposit in Ordos Basin contain abundant C15-C18 fatty acids. The fatty acids may have been derived from modern and ancient organisms including organisms from the intervals of U mineralization. A certain amount of i15:0, a15:0, a17:0 fatty acids coexist with small amounts of i17:1ω7c and 10me16:0, characteristic biomarkers of Desulfovibrio and Desulfobacter sp., respectively. This indicates the existence of sulfate-reducing bacteria (SRB) in the sandstones. The presence of sulfur-oxidizing bacteria (SOB), such as Beggiatoa and Thioploca, is indicated by significant amounts of 16:1ω7c and 18:1ω7c fatty acids. The existence of the SRB in the deposit, as inferred from the fatty acids, is consistent with results from fossilized microorganisms and isotopic compositions of ore-stage pyrite. This suggests that the environment may have been favorable for the SRB to grow since ore formation (9.8-22 Ma). The bacteria may have degraded hydrocarbons directly, or indirectly utilized hydrocarbons degraded by oxic microbes in the deposits. This process may have produced 12C-rich calcite and prominent baseline humps of unresolved complex mixtures (UCM), and 25-demethylated hopanes and tricyclic terpanes. The existence of sulfur-oxidizing bacteria and sulfate-reducing bacteria in the deposit may have resulted in bacterial sulfate reduction to sulfide, re-oxidization of the sulfide to sulfate and subsequent reduction of the sulfate to sulfide. This assertion is supported by ore-stage pyrite with δ34S values as low as-39.2‰, and the lightest sulfate (about 11‰) measured during the Phanerozoic, a difference of more than 46‰.     

Characteristics of strontium isotopes and their implications in the Qixing Cave of Guizhou,China

The strontium isotopic compositions (87Sr/86Sr) of samples including soils, bedrock, soil waters, drip waters and their corresponding speleothems in the Qixing Cave (QXC), Guizhou Province, China, were systemically measured and analyzed. The results indicate that there are significant Sr isotopic differences among samples. The mean 87Sr/86Sr ratios in drip water for the samples 1#, 4# and 9# were 0.709568, 0.709139 and 0.708761, respectively, which possibly result from different flow paths, residence times, and other hydrogeological processes in the unsaturated zone overlying QXC. Meanwhile, levels of 40.8%, 57.6% and 72.4% of Sr in drip waters for 1#, 4# and 9#, respectively, were derived from bedrock dissolution, which was calculated by the mixture model of the two end-members (soil and bedrock). There is, however, no positive correlation between the relative proportion from bedrock dissolution (δ13C value is 1.8‰) and drip water δ13CDIC values. The mean drip water δ13CDIC value in 1# is the heaviest (–4.5‰) with the lowest contribution rate of bedrock dissolution, whereas the value in 9# is the lightest (–9.3‰) with the highest contribution rate of bedrock dissolution. The proportion from host rock dissolution in 4# is higher than that in 1# and lower than that in 9#, while its mean drip water δ13CDIC value (–8.6‰) is higher than that of 9# and lower than that for 1#. This suggests that the prior calcite precipitation (PCP) processes in the unsaturated zone overlying the cave are responsible for the δ13CDIC value differences between different drip waters, and not bedrock dissolution. Furthermore, this study also demonstrates that the 87Sr/86Sr ratios of speleothems in the 1# and 4# mainly reflect the variation in the relative proportions from the soil system (soil water) and bedrock dissolution overlying the cave. It is, therefore, feasible to use the strontium isotopic signals of speleothems as an indicator for soil chemical weathering intensity, and consequently as a monsoon proxy in the study area.