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…     

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.     

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…     

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.     

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.     

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.     

Pyrolysis of oil at high temperatures: Gas potentials, chemical and carbon isotopic signatures

Although the gas cracked from oil has been believed to be one of the important sources in highly ma-tured marine basins, there are still some debates on its resource potentials and chemical and isotopic compositions. In this study a Cambrian-sourced marine oil sample from the Silurian reservoir of well TZ62 in the central Tarim basin was pyrolyzed using sealed gold tubes with two different pyrolysis schemes: continuous pyrolysis in a closed system and stepwise semi-open pyrolysis. The results show that the maximum weight yield of C_1–5 gases occurs at EasyRo=2.3% and the residual gas poten-tial after this maturity is only 43.4 mL/g, about 12% of the yield of 361 mL/g at EasyRo=2.3%. Combined with the results of kinetic modeling, the main stage of gas generation from oil cracking is believed within the EasyRo=1.6%―2.3%. The increase in the volume yield of C_1–5 gases at EasyRo>2.3% in a closed system is mainly related to the re-cracking of previously formed C_2–5 wet gases, not the direct cracking of oil. The stepwise pyrolysis experiments show that the gas from the cracking of residual oil at EasyRo>2.3% is characterized by very high dryness index (higher than 92%) and heavy methane carbon isotopes ranging from -28.7‰ to -26.7‰, which is quite different from the gases from the con-tinuous pyrolysis in a closed system. The kinetic modeling of methane carbon isotope fractionation shows that the carbon isotopes of methane within the main stage of gas generation (EasyRo<2.3%) are far lighter than the carbon isotopes of the precursor oils under a geological heating rate of 2 ℃/Ma. The above observations and results provide some new clues to the accurate recognition and objective re-source evaluation of oil cracking gas in highly mature marine basins.     

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.     

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.     

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.     

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.     

Experimental evidence for formation water promoting crude oil cracking to gas

Crude oil cracking to gas is the key to determining the exploration potential and strategy for deep hydrocarbon resources.Identifying the factors that affect the threshold and potential of crude oil cracking to gas as well as other possible influencing factors will provide the scientific basis for deep hydrocarbon exploration.A comparison of pyrolysis simulation experiments of crude oil,hydrous crude oil,and various water media under a constant temperature(350℃) and pressure(50 MPa) shows that water plays a large role in crude oil cracking to gas.(1) When water is added,the gas yields increase significantly,including those of alkane gases and non-hydrocarbon gases:the yield of alkane gases increases 1.8-3 times;the yields of H2 and CO2 also increase significantly.This means that water takes part in the process of crude oil cracking to gas,and supplies hydrogen.Therefore,the presence of water will dramatically enhance the potential of crude oil cracking to gas.(2) Mg2+ ions in the formation water promote the crude oil + water reaction to some extent and increase the total yield of alkane gases and the yields of both H2 and CO2 ;more interestingly,the i-C4/n-C4 and i-C5/n-C5 ratios increase significantly.This indicates that Mg2+ ions in formation water act as a catalyst,and a disproportionation reaction is involved in the crude oil + water reaction.This study helps us to understand the factors influencing crude oil cracked gas and to evaluate the hydrocarbon resources in deep sedimentary basins.     

Stable carbon and hydrogen isotopic fractionations of alkane compounds and crude oil during aerobically microbial degradation

Petroleum-related environmental pollution has be-come a global concern with the industrial and economicaldevelopment, causing serious ecological risks and threat-ening natural resources and human health. Therefore, it isimportant to characterize contaminants and thereby iden-tify unambiguously the sources of contaminants, not onlyfor the purpose of settling disputes related to liability butmore importantly, for selecting appropriate responses andtaking effective cleanup precautions[1]. Chemica…     

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‰.     

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.     

Preliminary Mo isotope data of Phanerozoic clastic sediments from the northern margin of the Yangtze block and its implication for paleoenvironmental conditions

Mo isotopes along with Nd isotopes and other geochemical characteristics of the Phanerozoic clastic sediments from the northern margin of the Yangtze block were analyzed by MC-ICP-MS and some other techniques, spanning the period from Cambrian to Jurassic. The δ 98Mo values and εNd(t ) in these sedimets were observed to exhibit a large range of variation (?0.65‰―+1.87‰, ?1.46―?10.90, respec-tively). Specifically, the sample from Late Permian Maokou Formation has relatively positive values in both δ 98Mo and...     

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.     

Oil cracking to gases： Kinetic modeling and geological significance

A Triassic oil sample from LN14 of Tarim Basin was pyrolyzed using the sealed gold tubes at 200-620℃under a constant pressure of 50 MPa. The gaseous and residual soluble hydrocarbons were analyzed. The results show that the cracking of oil to gas can be divided into two distinct stages: the primary generation of total C1-5 gases from liquid oil characterized by the dominance of C2-5 hydrocarbons and the secondary or further cracking of C2-5 gases to methane and carbon-rich matters leading to the progressive dryness of gases. Based on the experimental data, the kinetic parameters were determined for the primary generation and secondary cracking of oil cracking gases and extrapolated to geological conditions to predict the thermal stability and cracking extent of crude oil. Finally, an evolution model for the thermal destruction of crude oil was proposed and its implications to the migration and accumulation of oil cracking gases were discussed.     

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.