Quantitatively unmixing method for complex mixed oil based on its fractions carbon isotopes: A case from the Tarim Basin, NW China

Deep mixed oils with secondary alterations have been widely discovered in the Tarim Basin,but current methods based on biomarkers and isotopes to de-convolute mixed oil cannot calculate the exact mixing proportion of different end-member oils,which has seriously hindered further exploration of deep hydrocarbons in the study area.To solve this problem,we constructed a novel method based on the carbon isotope(δ13C)of the group components to de-convolute mixed liquid hydrocarbons under the material balance principle.The results showed that the mixed oil in the Tazhong Uplift was dominantly contributed at an average proportion of 68% by an oil end-member with heavier d13C that was believed to be generated from the Cambrian-Lower Ordovician source rocks,whereas the mixed oil in the Tabei Uplift was predominantly contributed at an average proportion of 61% by an oil end-member with lighter d13C that was believed to be generated from the Middle-Upper Ordovician source rocks.This indicates that,on the basis of the detailed description of the distribution of effective source rocks,the proposed method will be helpful in realizing differential exploration and further improving the efficiency of deep liquid hydrocarbon exploration in the Tarim Basin.In addition,compared to traditional δ13C methods for whole oil and individual n-alkanes in de-convoluted mixed oil,the proposed method has a wider range of applications,including for mixed oils with variations in color and density,indicating potential for promoting the exploration of deep complex mixed oils in the Tarim Basin and even around the world.

Carbon isotopes of graphite:Implications on fluid history

Stable carbon isotope geochemistry provides important information for the recognition of funda- mental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elab- oration of models for the global carbon cycle. Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon （organic matter, mantle, or carbonates） and help to constrain the fluid history and the mechanisms involved in graphite deposition. Graphite precipitation in fluid-deposited occurrences results from C02- and/or CH4-bearing aqueous fluids. Fluid flow can be considered as both a closed （without replenishment of the fluid） or an open system （with renewal of the fluid by successive fluid batches）. In closed systems, carbon isotope systematics in graphite is mainly governed by Rayleigh precipi- tation and/or by changes in temperature affecting the fractionation factor between fluid and graphite. Such processes result in zoned graphite crystals or in successive graphite generations showing, in both cases, isotopic variation towards progressive 13C or 12C enrichment （depending upon the dominant carbon phase in the fluid, C02 or CH4, respectively）. In open systems, in which carbon is episodically introduced along the fracture systems, the carbon systematics is more complex and individual graphite crystals may display oscillatory zoning because of Rayleigh precipitation or heterogeneous variations of 613C values when mixing of fluids or changes in the composition of the fluids are the mechanisms responsible for graphite precipitation.

Carbon isotopes and lignin phenols for tracing the floods during the past 70 years in the middle reach of the Changjiang River

The Lake Tian E Zhou(TEZ,an oxbow lake)was formed during the rerouting of the Changjiang River in 1972,with strong influences from the main river channel and flood events.Herein,a sediment core was collected from the Lake TEZ for the measurements of carbon isotopes and biomarkers,including stable carbon isotopes(δ13C),radiocarbon composition(?14C),and lignin phenols,as well as lead-210 to reconstruct recent heavy flood events over the past 70 years.At the 24–26 cm interval,the sediment contained the highest OC%,TN%,and lignin phenols content,as well as significantly depleted 13C but enriched 14C,corresponding to the extreme flood event in 1998.In addition,statistics from t-test showed that lignin phenols normalized to OC(Λ8),the concentration of 3,5-dihydroxy benzoic acid(3,5-BD),and the ratio of p-hydroxy benzophenone to total hydroxyl phenols(PHB/HP)were all significantly different between the layers containing flood deposits and the layers deposited under normal non-flood conditions(p<0.05).These results indicate that the later three parameters are highly related to flood events and can be used as compelling proxies,along with sediment chronology,for hydrological changes and storm/flood events in the river basin and coastal marine environments.

A preliminary study on benthos food web structure oftidal zone in the Laoshan Bay by using stable carbon isotopes

By anayses of carbon isotopic composition (δ13C values) of the benthos collected in the Laoshan Bay in August 1993 and February and May 1994, it is found that the main food sources of the benthos can be divided into four groups in terms of carbon isotope composition: Particulate Organic Matter (POM), benthic diatoms, benthic macroalgae and the organic matter in sediments. The results show that the carbon isotopic composition of the benthic animals has a close relation with that of the food they take in. The Carbon isotopic compositions of benthos may be useful in elucidating their food sources. The carbon isotopic data have confirmed that POM is the main food source of the benthic filter feeders such as bivalves; crustaceans have a wide range of δ13C values, showing their food source has diversity; benthic diatoms are an important fraction of the food for most of gastropods. A preliminary investigation of the benthic-pelagic coupling in that region using the stable carban isotopic tracers has confirmed the importance of POM as a food source for benthos in this region, but the organic matter in sediments and benthic diatoms are also relatively important for a lot of benthic animals. The benthic-pelagic coupling in the Laoshan Bay temperate ecosystem is not so tight as that in ecosystems at higher latitudes such as northeastern water polynya.

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform, South China: Evidence from Biomarkers and Carbon Isotopes

The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province （China）. All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 （C 23 for sample Gzh00-1）. The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values （0.7） suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.

Effects of pretreatment procedures on fatty acid composition and stable carbon isotopes in the marine microalga Isochrysis zhanjiangenisis

This study aims to quantify the effects of different pretreatment methods on the stable carbon isotope values of fatty acids in marine microalgae（Isochrysis zhanjiangenisis）.To identify the effects of sample preparation on theδ^（13）C value and the fatty acid composition,we examined eight types of pretreatment methods including：（a） drying the sample followed by direct methyl esterification using HCl-CH3OH;（b） drying the sample followed by direct methyl esterification using H2SO4-CH3OH;（c） drying the sample by ultrasonic extraction and methylesterification using HCl-CH3OH;（d） drying the sample by ultrasonic extraction and methyl-esterification using H2SO4-CH3OH;（e） fresh sample followed by direct methyl-esterification using HCl-CH3OH;（f） fresh sample followed by direct methyl-esterification using H2SO4-CH3OH;（g） fresh sample with ultrasonic extraction followed by methyl-esterification using HCl-CH3OH,and（h） fresh sample with ultrasonic extraction followed by methylesterification using H2SO4-CH3 OH.The results show that the δ^（13）C values from Groups a-e,g and h fluctuated within 0.3‰,and the δ^（13）C values of Group f were approximately 0.7‰ lower than the other seven groups.Therefore,the different sample pretreatment methods used towards the extraction of fatty acids from marine microalgae may result in different results regarding the stable carbon isotope ratios,and if necessary a correction should be applied.

Origin of the Gas Hydrate and Free Gas in the Qilian Permafrost,Northwest China:Evidence from Molecular Composition and Carbon Isotopes

The Qilian permafrost of the South Qilian Basin(SQB)has become a research focus since gas hydrates were discovered in 2009.Although many works from different perspectives have been conducted in this area,the origin of gas from gas hydrate is still controversial.Molecular composition and carbon isotope of 190 samples related to gas hydrates collected from 11 boreholes allowed exploration of genetic type,thermal maturity,biodegradation,as well as gas-source correlation of alkane gases from gas hydrates and free gases.Results indicate that alkane gases biodegraded after the formation of natural gas.According to differences in carbon isotopes of methane and their congeners(CH4,C2H6,C3H8),the thermal maturity(vitrinite reflectance,VRo)of most alkane gases ranges from 0.6%to 1.5%,indicating a mature to high mature stage.The thermal maturity VRo of a small part of alkane gas(in boreholes DK5 and DK6)is higher than 1.3%,indicating a high mature stage.Alkane gases were mainly produced by secondary cracking,consisting of crude oilcracking gases and wet gases cracking to dry gases.Genetic types of alkane gases are primarily oil-type gases generated from shales and mudstones in the upper Yaojie Formation of Jurassic,with less coal-type gases originated from the mudstones in the Triassic Galedesi Formation and the lower Yaojie Formation of Jurassic.Carbon dioxides associated with alkanes from gas hydrates and free gases indicate the thermal decomposition and biodegradation of organic matter.The origins of natural gases from gas hydrates and free gases shed light on the evaluation of petroleum resource potential,deeply buried sediments,and petroleum resource exploration in the SQB.

Response to the Lomagundi-Jatuli Event in the southwestern margin of the Yangtze Plate:Evidence from the carbon and oxygen isotopes of the Paleoproterozoic Yongjingshao Formation

The Lomagundi-Jatuli Event(LJE)refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic(2.22-2.06 Ga).Theδ^(13)C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05‰-4.95‰(V-PDB;maximum:4.95‰)in this study,which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group.They are much higher than theδ^(13)C values of marine carbonates(-1.16‰on average).Theδ^(13)C values of other formations in the Paleoproterozoic Yimen Group are negative.The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block,which is reported for the first time.Furthermore,they are comparable to theδ^(13)C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton,the Wuzhiling Formation of the Songshan Group in the Xiong'er area,Henan Province,and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area,Liaoning Province.Therefore,it can be further concluded that the LJE is a global event.This study reveals that LJE occurred in Central Yunnan at 2.15-2.10 Ga,lasting for about 50 Ma.The macro-columnar,bean-shaped,and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group.They are the direct cause for the LJE and are also the oldest paleontological fossils ever found.The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event(first occurrence),the global Superiortype banded iron formations(BIFs),the Huronian glaciation,the Great Oxygenation Event(second occurrence),the explosion of multicellular eukaryotes,the positive carbon isotope excursion,and the global anoxic and selenium-rich sedimentary event.The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.

Effects of thinning and understory removal on water use efficiency of Pinus massoniana:evidence from photosynthetic capacity and stable carbon isotope analyses

Understanding the relationship between forest management and water use efficiency(WUE)is important for evaluating forest adaptability to climate change.However,the effects of thinning and understory removal on WUE and its key controlling processes are not well understood,which limits our comprehension of the physiological mechanisms of various management practices.In this study,four forest management measures(no thinning:NT;understory removal:UR;light thinning:LT;and heavy thinning:HT)were carried out in Pinus massoniana plantations in a subtropical region of China.Photosynthetic capacity and needle stable carbon isotope composition(δ^(13)C)were measured to assess instantaneous water use efficiency(WUE_(inst))and long-term water use efficiency(WUE_(i)).Multiple regression models and structural equation modelling(SEM)identified the effects of soil properties and physiological performances on WUE_(inst)and WUE_(i).The results show that WUE_(inst)values among the four treatments were insignificant.However,compared with the NT stand(35.8μmol·mol^(-1)),WUE_(i)values significantly increased to 41.7μmol·mol^(-1)in the UR,50.1μmol·mol^(-1)in the LT and 46.6μmol·mol^(-1)in HT treatments,largely explained by photosynthetic capacity and soil water content.Understory removal did not change physiological performance(needle water potential and photosynthetic capacity).Thinning increased the net photosynthetic rate(A_n)but not stomatal conductance(g_s)or predawn needle water potential(ψ_(pd)),implying that the improvement in water use efficiency for thinned stands was largely driven by radiation interception than by soil water availability.In general,thinning may be an appropriate management measure to promote P.massoniana WUE to cope with seasonal droughts under future extreme climates.

Characteristics of carbon isotopic composition of alkane gas in large gas fields in China

Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output to 1925×108m3in 2020,making it the fourth largest gas-producing country in the world.Based on 1696 molecular components and carbon isotopic composition data of alkane gas in 70 large gas fields in China,the characteristics of carbon isotopic composition of alkane gas in large gas fields in China were obtained.The lightest and average values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become heavier with increasing carbon number,while the heaviest values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become lighter with increasing carbon number.Theδ^(13)C_(1)values of large gas fields in China range from-71.2‰to-11.4‰(specifically,from-71.2‰to-56.4‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-18.9‰for coal-derived gas,and from-35.6‰to-11.4‰for abiogenic gas).Based on these data,theδ^(13)C_(1)chart of large gas fields in China was plotted.Moreover,theδ^(13)C_(1)values of natural gas in China range from-107.1‰to-8.9‰,specifically,from-1071%o to-55.1‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-13.3‰for coal-derived gas,and from-36.2‰to-8.9‰for abiogenic gas.Based on these data,theδ^(13)C_(1)chart of natural gas in China was plotted.

Carbon isotopic compositions of mono-, di-, tri-aromatics provide insights into the source of sulfur-rich crude oils in the Huanghekou Depression, Bohai Bay Basin

The stable carbon isotope compositions (δ13C) of individual aromatic hydrocarbons have been analyzed in sulfur-rich and sulfur-lean crude oils from the Huanghekou Depression, Bohai Bay Basin. The δ13C values of individual aromatic hydrocarbons, including alkylbenzenes, alkylnaphthalenes, alkylphenanthrenes, alkylfluorenes and alkyldibenzothiophenes, are reported. The main aims are to find out the origin of these oils and their relationship to paleoclimate. The distribution of aromatic hydrocarbons and maturity parameters show the oils all stay in the low-mature to mature stage. Meanwhile, aromatic hydrocarbons are mainly derived from the diagenetic/catagenetic origin. The δ13C values for 1,2,4-trimethylbenzene (−30.7‰ to −28.8‰) and 1,2,3,4-tetramethylbenzene (−32.4‰ to −26.3‰) indicate the algae-derived organic matter for alkylbenzenes. Some isomers, such as 1,7-+1,3-+1,6-dimethylnaphthalene, 1,2,5-trimethylnaphthalene, 1,2,5,6-+1,2,3,5-tetramethylnaphthalene, 1,10-+1,3-+3,10-+3,9-dimethylphenanthrenes, 1,6-+2,9-+2,5-dimethylphenanthrenes and 4,9-+4,10-+1,9- dimethylphenanthrenes show isotopic depletion (−34.9‰ to −25.2‰), indicating the major contribution of algae for these compounds. Meanwhile, isotopically depleted (−33.6‰ to −26.7‰) alkyldibenzothiophenes represent the algae input. δ13C values for mainly algae-derived naphthalene to trimethylnaphthalenes of sulfur-rich oils are more enriched than those of sulfur-lean oil, with the most significant difference of 4.4‰, indicating that the aridity of the environment and stratified water column result in the enrichment in 13C.

Carbon and Strontium Isotopes of Late Palaeozoic Marine Carbonates in the Upper Yangtze Platform,Southwest China

238 marine carbonate samples were collected from seven sedimentary sections ofthe entire late Palaeozoic (Permian, Carboniferous and Devonian) in the Upper Yangtze Plat-form, southwest China. Based on the absence of cathodoluminescence and very low Mn (gener-ally<50 ppm) contents of the samples, it is thought that they contain information on the orig-inal sea water geochemistry. The results of isotopic analyses of these samples are presented interms of δ^(13)C and ^(87)Sr/^(86)Sr ratios versus geological time. The strontium data, consistent withother similar data based on samples from North America, Europe, Africa and other areas inAsia, support the notion of a global consistency in strontium isotope composition of marinecarbonates. The strontium data exhibit three intervals of relatively low ^(87)Sr/^(86)Sr ratios in thelate Middle Devonian to early Late Devonian, Early Carboniferous and Early Permian, corre-sponding to global eustatic high sea level stands. The lowest ^(87)Sr/^(86)Sr ratio recorded in theLate Permian was probably caused by substantial basalt eruptions in the Upper Yangtze Plat-form at the time. Three corresponding periods of relatively high δ^(13)C values at roughly the samethe intervals were caused by a relatively high rate of accumulation of organic carbon duringsea level rises at these times. The deposition of coal was probably responsible for the increaseof sea water δ^(13)C at other times. The δ^(13)C values drop dramatically near theDevonian/Carboniferous, Carboniferous/Permian and Permian/Triassic boundaries, con-sistent with other similar data, which further support the notion that geological time boundariesare associated with mass extinction and subsequent rejuvenation.

Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the Tengchong magmatic component. Compared with MORB, this relative low 3He/4He ratio could be fully attributed to either deep crustal contamination, or radioactive aging, or past contamination of the local mantle by U- and Th-rich subducted crustal material. However, a combination of low 3He/4He, high radiogenic 4He/40Ar ratio and identical CO2/3He and δ13Cco2 relative to MORB may suggest addition of prior subductedd crsustal material (ca 1 %-2%) to the MORB reservoir around 1.3 Ga ago, which is essentially compatible with the LIL-elements, and Sr-Nd-Pb isotopes of volcanic rocks.

Sources of particulate organic matter in the Chukchi and Siberian shelves: clues from carbon and nitrogen isotopes

The stable isotopic composition(δ13C andδ15N)and carbon/nitrogen ratio(C/N)of particulate organic matter(POM)in the Chukchi and East Siberian shelves from July to September,2016 were measured to evaluate the spatial variability and origin of POM.Theδ13CPOC values were in the range of−29.5‰to−17.5‰with an average of−25.9‰±2.0‰,and theδ15NPN values ranged from 3.9‰to 13.1‰with an average of 8.0‰±1.6‰.The C/N ratios in the East Siberian shelf were generally higher than those in the Chukchi shelf,while theδ13C andδ15N values were just the opposite.Abnormally low C/N ratios(<4),lowδ13CPOC(almost−28‰)and highδ15NPN(>10‰)values were observed in the Wrangel Island polynya,which was attributed to the early bloom of small phytoplankton.The contributions of terrestrial POM,bloom-produced POM and non-bloom marine POM were estimated using a three end-member mixing model.The spatial distribution of terrestrial POM showed a high fraction in the East Siberian shelf and decreased eastward,indicating the influence of Russian rivers.The distribution of non-bloom marine POM showed a high fraction in the Chukchi shelf with the highest fraction occurring in the Bering Strait and decreased westward,suggesting the stimulation of biological production by the Pacific inflow in the Chukchi shelf.The fractions of bloom-produced POM were highest in the winter polynya and gradually decreased toward the periphery.A negative relationship between the bloom-produced POM and the sea ice meltwater inventory was observed,indicating that the net sea ice loss promotes early bloom in the polynya.Given the high fraction of bloom-produced POM,the early bloom of phytoplankton in the polynyas may play an important role on marine production and POM export in the Arctic shelves.

Organic carbon and nitrogen isotopes in surface sediments from the western Arctic Ocean and their implications for sedimentary environments

Surface sediments from the Chukchi Sea and adjacent arctic deep sea were investigated for organic carbon and nitrogen isotopes （in δ13Corg and δ15Norg） as well as biogeni＇c silica （BSiO2）. δ13Corg and δ15Norg values of surface sediments in the study area fall between the end-member values of marine and terrestrial organic matter from the surrounding lands and seas, their variations reflect the changes of marine productivity and terrestrial supply in the study area. BSiO2 shows a similar distribution pattern with δ13Corg and δ15Norg, and can be used as an indicator of marine productivity. In the central-west Chukchi Sea and the Chukchi Rise, sediments have higher δ13Corg, δ15Norg and BSiO2 values, indicating the region has high marine productivity influenced by the nutrient-rich branches of the Pacific waters. In the coastal zone off northwestern Alaska, δ13Corg and δ15Norg values become lighter, indicating a weakening marine productivity and an increasing terrigenous supply due to the effects of the least nutrient-rich branch of the Pacific waters. In the north and the northeast of the study area （including the Chukchi Plateau, the Canada Basin and the Beaufort shelf）, δ13Corg, δ15Norg and BSiO2 have the lowest values, and the terrigenous organic matter becomes dominant in surface sediments because this region has the longest ice-covered duration, the least nutrient-rich seawater and the increasing supply of terrestrial materials from the Mackenzie River and the northern Alaska under the action of the clockwise Beaufort gyre. Because the subarctic Pacific waters are continuously discharged into the central basin of the Arctic Ocean through the study area, the nutrient pool in the Chukchi Sea can be considered as a typical open system, the ratio of δ15Norg to BSiO2 content show some tracers that the level of nutrient utilization is contrary to nutrient supply and marine productivity formed in seawater.

Long chain n-alkanes and their carbon isotopes in lichen species from western Hubei Province： implication for geological records

Five coticolous lichen samples were collected from western Hubei Province of China to analyze the long chain n-alkanes and their carbon isotope compositions. The n-alkanes range in carbon number from C17 to C33 with strong odd-over-even predominance between C21 and C33. Lichens are dominated by n-C29 in the samples of Dajiuhu, Shennongjia Mountain, but by both n-C23 and n- C29 at Qizimei Mountain. This difference may result from the different environmental conditions in these two sites. The δ13C values of long chain n-alkanes in lichen samples show the signature of C3 plants. Based on compound- specific carbon isotopic values and previous results, we state that alkane homologs 〉 C23 mainly originate from the symbiotic fungi, while symbiotic algae only contribute trace amount of long chain alkanes. Of great interesting is the occurrence of long chain 3-methylalkanes in the Qizimei samples. These anteiso compounds range from C24 to C32, displaying obvious even-over-odd predomi- nance. This study reveals that the association of long chain 3-methylalkanes with n-C23 alkane might be used as proxies to reconstruct the paleoecological implications of lichens in Earth history.

Tracing the Methane Events by Stable Carbon Isotopes of Benthic Foraminifera at Glacial Periods in the Andaman Sea

Stable isotopes of carbon and oxygen variations in foraminiferal shells have been widely used in paleo-environment studies.However,studies about the shells of benthic foraminifera in methanehydrate-bearing sediments as reliable geochemical proxies to reconstruct the potential methane release events in the geologic past are rare.In this study,we present the stable carbon and oxygen isotopes of fossil benthic foraminifera including one epifaunal species(Cibicidoides wuellerstorfi)and two infaunal species(Bulimina mexicana and Uvigerina peregrina)from the Site U1447 of IODP 353 Expedition to trace methane events in the Andaman Sea,where one of the thickest and deepest gas hydrate stability zones was discovered.Theδ^(13)C values of benthic foraminifera show that there are eight distinct intervals with negative values in the last~10 Myr,interpreted as a record of long-term fluctuations in methane emission.Six of these methane events occurred during the glacial sea-level lowstands in the last~1.1 Myr.We,therefore,infer that the trigger mechanism for these events might be the hydrate destabilization caused by sea level fall.The methane events that occurred at~2.11 and~5.93 Ma are more likely related to the sudden changes in sedimentation,either slide events or marked variations in sedimentation rate.

Distribution of Carbon and Oxygen Isotopes in theSequence Stratigraphic Framework of the Middle andUpper Proterozoic in the Ming Tombs Area, Beijing

Abstract: This paper discusses the distribution pattern and geological significance of the carbon and oxygen isotopes (δ13C and δ18O) in the depositional sequences of Gaoyuzhuangian, Yangzhuangian and Wumishanian ages of the established Middle and Upper Proterozoic sequence stratigraphic framework in the Ming Tombs area lying in western Yanshan Mountain of Beijing. Besides, sketchy determination of δ13C and δ18O was also performed for other formations and members. The analytical results show the following: under the condition of clear-water carbonate sediments, δ13C and δ18O, featuring smaller variation of δ13C but larger variation of δ18O, can well delineate the relative change of sea level, which reflects the difference of primary sedimentary settings; in the presence of terrigenous substances, δ13C values vary greatly while δ18O slightly; the carbon and oxygen isotopes show marked changes at sequence boundaries. Besides, particular patterns can be found in regard to the distribution of carbon and oxygen isotopes within the sequences.

δ^(13)C_(org) perturbations preserved by the interglacial Datangpo Formation in South China with implications for stratigraphic correlation and carbon cycle

Palaeoclimatic and palaeoenvironmental reconstructions of the Cryogenian Period have attracted attention in relation to the debated“Snowball Earth”hypothesis and the early evolution of metazoan life.The carbon cycle and redox conditions of the Sturtian-Marinoan non-glacial interval have been subjected to much controversy in the past decades because of the lack of a high-resolution stratigraphic correlation scheme.As one of the typical Sturtian-Marinoan interglacial deposits,the Datangpo Formation was widely distributed in South China with shales continuously deposited.The previous zircon dating data of the Datangpo Formation provide important ages for global constrain of the Sturtian-Marinoan non-glacial interval.Here we present a high-resolution straitigraphic study of the organic carbon isotopes of the Datangpo Formation from a drill core section in northern Guizhou Province.Based on measured episodicδ^(13)C_(org) perturbations,three positive shifts and three negative excursions are identified.Aδ^(13)C_(org)-based chemostratigraphic correlation scheme is proposed herein that works well for the Datangpo Formation regionally.Meanwhile,theδ^(13)C_(org) vertical gradients changed dynamically throughout the formation.This discovery implies that a significant ocean circulation overturn might have occurred in the upper Datangpo Formation,coinciding with the potential oxygenation.

Origin of hydrocarbon fluids and discussion of abnormal carbon isotopic compositions in the Lishui-Jiaojiang Sag,East China Sea Shelf Basin

The hydrocarbon gases in the L1 gas field of the Lishui-Jiaojiang Sag have been commonly interpreted to be an accumulation of pure sapropelic-type thermogenic gas.In this study,chemical components,stable isotopic compositions,and light hydrocarbons were utilized to shed light on the origins of the hydrocarbon fluids in the L1gas pool.The hydrocarbon fluids in the L1 gas pool are proposed to be a mixture of three unique components:mid-maturity oil from the middle Paleocene coastal marine Lingfeng source rock,oil-associated(late oil window)gas generated from the lower Paleocene lacustrine Yueguifeng source rock,and primary microbial gas from the paralic deposits of the upper Paleocene Mingyuefeng source rock.Here,for the first time,the hydrocarbon gases in the L1 gas pool are diagnosed as mixed oil-associated sapropelic-type gas and microbial gas via four pieces of principal evidence:(1)The abnormal carbon isotopic distributions of all methane homologues from C_(1)(CH_(4)or methane)to C_(5)(C_(5)H_(12)or pentane)shown in the Chung plot;(2)the diagnostic~(13)C-depleted C_(1)compared with the thermogenic sapropelic-type gas model,whileδ^(13)C_(2)(C_(2)H_(6)or ethane)andδ^(13)C_(3)(C_(3)H_(8)or propane)both fit perfectly;(3)the excellent agreement of the calculated carbon isotopic compositions of the pure thermogenic gas with the results of the thermal simulated gas from the type-II1 kerogen-rich Yueguifeng source rock;and(4)the oil-associated gas inferred from various binary genetic diagrams with an abnormally elevated gas oil ratio.Overall,the natural gases of the L1 gas pool were quantified in this study to comprise approximately 13%microbial gas,nearly 48%oil-associated sapropelic-type gas,and 39%of nonhydrocarbon gas.The microbial gas is interpreted to have been codeposited and entrained in the humic-kerogen-rich Mingyuefeng Formation under favorable lowtemperature conditions during the late Paleocene-middle Eocene.The microbial gas subsequently leaked into the structurally and stratigraphically complex L1 trap with oil-associated sapropelic-type gas from the Yueguifeng source rock during the late Eocene-Oligocene uplifting event.A small amount of humic-kerogen-generated oil in the L1 gas pool is most likely to be derived from the underlying Lingfeng source rock.The detailed geological and geochemical considerations of source rocks are discussed to explain the accumulation history of hydrocarbon fluids in the L1 gas pool.This paper,therefore,represents an effort to increase the awareness of the pitfalls of various genetic diagrams,and an integrated geochemical and geological approach is required for hydrocarbonsource correlation.