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.

U-Pb Zircon Age,Geochemical and Sr-Nd-Hf Isotopic Compositions of Neoproterozoic Granitoids in Northwestern Margin of Yangtze Block (South China):Implications for Neoproterozoic Tectonic Evolution

ABSTRACT： The widespread Neoproterozoic magmatism along the Yangtze block carries critical in- formation for understanding the Neoproterozoic evolution of the Yangtze block. In the northwestern margin of the Yangtze block, the Hannan （汉南） intrusive complex includes the Wudumen （五堵门）, Erliba （二里坝） and Zushidian （祖师殿） granitoids. Using LA-ICP-MS U-Pb zircon dating method, the Wudumen and Erliba granitoids yielded magma crystallization ages of 785±4 and 778±3 Ma, respectively. Samples from these three granitoids show variable SiO2 contents ranging from 58.8% to 72.6%. They are characterized by enrichment of Al2O3（14.97%-17.87%）, Na2O（3.80%-5.33%） and Sr （504ppm-741 ppm）, and depletion of Y （〈19 ppm） and HREE （e.g., Yb〈1.6 ppm）, resulting in high Sr/Y （29-161） and （La/Yb）N （7.3-27.8） ratios. The geochemical features of the granitoids are comparable with those of adakite. The granitoids have zircon εHdt） values of ＋3.65 to ＋10.05, whole-rock εNd（t） values of -0.09 to ＋2.98 and whole-rock initial ^87Sr/^86Sr ratios of 0.7034-0.7039, indicating that their magma was derived from a juvenile crustal source. Together with geochemical and Hf-Sr-Nd isotopic compositions, it is suggested that the granitoids formed in island-arc setting and originated from partial melting of a subducted oceanic slab. The results support a model that the Yangtze block was surrounded by ocean and arc magmatism in its northern and northwestern margins in Neoproterozoic.

Petrogenesis and Tectonic Implications of the Early Triassic Nianzi Adakitic Granite Unit in the Yanshan Fold and Thrust Belt:New Constraints from U-Pb Geochronology and Sr-Nd-Hf Isotopes

The Nianzi granite unit,which includes the Nianzi,Xiaolianghou and Xiawopu granitic intrusions,is a significant component of the northern part of the North China Craton(NCC)and is situated in the Yanshan fold and thrust belt(YFTB).However,there is still debate regarding the tectonic evolutionary history of the YFTB during the late Permian to Triassic period,specifically regarding the timing of subduction and collision between the NCC and the Paleo-Asian Ocean.The Nianzi granite unit exhibits unique petrological,geochronological and geochemical signatures that shed light on the tectonic evolutionary history of the YFTB.This study presents detailed petrology,whole-rock geochemistry,together with Sr-Nd isotopic,zircon U-Pb dating and Lu-Hf isotopic data of the granites within the Nianzi granite unit.Our findings demonstrate that the granites primarily consist of subhedral K-feldspar,plagioclase,quartz,minor biotite and hornblende,with accessory titanite,apatite,magnetite and zircon.Zircon U-Pb dating indicates that the Xiaolianghou granite was emplaced at 247.5±0.62 Ma.Additionally,the adakitic characteristics of the Nianzi,Xiawopu and Xiaolianghou granitic intrusions,such as high Sr and Ba contents and high ratios of Sr/Y and(La/Yb)N,combined with negative Sr-Nd and Lu-Hf isotopes(87Sr/86Sr)i=0.705681–0.7057433,εNd(t)=−21.98 to−20.97,zirconεHf(t)=−20.26 to−9.92,as well as the I-type granite features of high SiO_(2),Na_(2)O and K_(2)O/Na_(2)O ratios,enriched Rb,K,Sr and Ba,along with depleted Th,U,Nb,Ta,P and Ti,suggest that the Nianzi granitic unit was mainly derived from the partial melting of a thickened lower crust containing hydrous,calc-alkaline to high-K calc-alkaline,mafic to intermediate metamorphic rocks.In light of these parameters,we further integrate our data with previous studies and conclude that the Nianzi granitic unit was generated in a post-collisional extensional environment during the Early Triassic.

VARIATIONS IN ISOTOPIC COMPOSITIONS OF CHLORINE IN EVAPORATION-CONTROLLED SALT LAKE BRINES OF QAIDAM BASIN,CHINA

The variations in the isotopic compositions of chlorine in evaporation controlled saline lake brines were determined by using an improved procedure for precise measurement of chlorine isotopes based on Cs 2Cl + ion by thermal ionization mass spectrometry. The results showed that variation in δ 37 Cl values in these evaporation controlled brines are attributable to evaporation of brine accompanied by the deposition of saline minerals. The isotopic fractionation of chlorine between the deposited saline mineral and the co existing brine caused the variation of δ 37 Cl values in the brine. In general the isotopic fractionation of chlorine in nature indicates enrichment of 3 7Cl in the solid phase relative to 3 5Cl. The reverse isotopic fractionation of chlorine in which 3 5Cl is enriched in the solid phase, was observed to some extent during quick deposition under laboratory conditions as well as in nature. The mechanism of isotopic fractionation of chlorine during evaporation deposition was studied.

Carbon and Oxygen Isotopic Composition of Surface-Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition （δ^13C） values of the carbonate sediment （-1‰ to -2‰） have no relation to the oxygen isotope composition of the carbonate （δ^18O） values （-7‰ to -8‰）, with both isotopes showing a low variability. The carbonate content is low （〈20%）. Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ^13C values between approximately ＋0.5‰ and ＋3‰, and δ^18O values between -1‰ and -5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg-calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg-calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.

High-Resolution Records of the Holocene Paleoenvironmental Variation Reflected by Carbonate and Its Isotopic Compositions in Bosten Lake and Response to Glacial Activities

The Early Holocene paleoclimate in Bosten Lake on the northern margin of the Tarim Basin, southern Xinjiang, is reconstructed through an analysis of a 953 cm long core （BSTC2000） taken from Bosten Lake. Multiple proxies of this core, including the mineral components of carbonate, carbonate content, stable isotopic compositions of carbonate, Ca/Sr, TOC and C/N and C/S of organic matter, are used to reconstruct the climatic change since 8500 a B.P. The chronology model is made by nine AMS 14C ages of leaves, seeds and organic matter contained in two parallel cores. The climate was cold and wet during 8500 to 8100 a B.P. Temperature increased from 8100 to 6400 a B.P., the climate was warm and humid, and the lake expanded. The lake level was highest during this stage. Then from 6400 to 5100 a B.P., the climate became cold and the lake level decreased slightly. During the late mid-Holocene, the climate was hot and dry from 5100 to 3100 a B.P., but there was a short cold period during 4400 to 3800 a B.P. At this temporal interval, a mass of ice and snow melting water supplied the lake at the early time and made the lake level rise. The second highest lake level stage occurred during 5200 to 3800 a B.P. The climate was cool and wet during 3100 to 2200 a B.P., when the lake expanded with decreasing evaporation. The lake had the last short-term high level during 3100 to 2800 a B.P. After this short high lake level period, the lake shrank because of the long-term lower temperature and reduced water supply. From 2200 to 1200 a B.P., the climate was hot and dry, and the lake shrank greatly. Although the temperature decreased somewhat from 1200 a B.P. to the present, the climate was warm and dry. The lake level began to rise a little again, but it did not reach the river bed altitude of the Konqi River, an outflow river of the Bosten Lake.

The Isotopic Composition of Noble Gases in Gold Deposits and the Source of Ore-Forming Materials in the Region of North Hebei, China

The source of ore\|forming materials has long been a controversial focus both in metallogenic theory and in ore\|searching practice. This study deals with the helium and argon isotopic characteristics of pyrites from 11 gold deposits and some country rocks in the gold mineralization\|concentrated areas within the three mantle\|branch structures in the region of North Hebei Province. It is indicated that \{\}\+3He/\+4He ratios in the gold deposits are within the range of \{0.93×10\+\{-6\}\}-\{7.3×10\+\{-6\}\}, with an average of \{3.55\} ×10\+\{-6\}; R/Ra=\{0.66\}-\{4.93\}, averaging \{2.53\}; \{\{\}\+\{40\}Ar/\+\{39\}Ar\} ratios vary between 426 and 2073, with the average value of \{\}\+\{40\}Ar being \{8.32\}; and the average of \{\}\+4He/\{\}\+\{40\}Ar ratios is 2.17. \{\}\+3He/ \{\}\+4He ratios in gneiss and granite in the periphery of the mining district are within the range of \{0.001×10\+\{-6\}\}-\{0.55×10\+\{-6\}\}, reflecting significant differences in their sources. \{\}\+3He and \{\}\+4He fall near the mantle, as is shown in the He concentration diagram. Studies have shown that the ore\|forming materials in this region should come from the deep interior of the Earth. With the multi\|stage evolution of mantle plume, ore\|forming fluids in the deep interior were moving upwards to shallow levels (crust). Under such circumstances, there would be inevitably occur crust/mantle fluid mixing, so their noble gas isotopic characteristics are intermediate between the mantle and the crust.

Isotopic Compositions of Sulfur in the Jinshachang Lead–Zinc Deposit, Yunnan, China, and its Implication on the Formation of Sulfur-Bearing Minerals

The Jinshachang lead-zinc deposit is mainly hosted in the Upper Neoproterozoic carbonate rocks of the Dengying Group and located in the Sichuan-Yunnan-Guizhou （SYG） Pb-Zn-Ag multi- metal mineralization area in China. Sulfides minerals including sphalerite, galena and pyrite postdate or coprecipitate with gangue mainly consisting of fluorite, quartz, and barite, making this deposit distinct from most lead-zinc deposits in the SYG. This deposit is controlled by tectonic structures, and most mineralization is located along or near faults zones. Emeishan basalts near the ore district might have contributed to the formation of orebodies. The j34S values of sphalerite, galena, pyrite and barite were estimated to be 3.6‰-13.4‰, 3.7‰-9.0‰, -6.4‰ to 29.2‰ and 32.1‰34.7‰, respectively. In view of the similar δ34S values of barite and sulfates being from the Cambrian strata, the sulfur of barite was likely derived from the Cambrian strata. The homogenization temperatures （T ≈ 134--383℃） of fluid inclusions were not suitable for reducing bacteria, therefore, the bacterial sulfate reduction could not have been an efficient path to generate reduced sulfur in this district. Although thermochemical sulfate reduction process had contributed to the production of reduced sulfur, it was not the main mechanism. Considering other aspects, it can be suggested that sulfur of sulfides should have been derived from magmatic activities. The δ34S values of sphalerite were found to be higher than those of coexisting galena. The equilibrium temperatures calculated by using the sulfur isotopic composition of mineral pairs matched well with the homogenization temperature of fluid inclusions, suggesting that the sulfur isotopic composition in ore-forming fluids had reached a partial equilibrium.

Hydrogen Isotopic Compositions of Pyroxenes in Nushan Peridotite Xenoliths,SE China

Hydrogen isotopic compositions of pyroxenes in peridotite xenoliths from the Nushan volcano, Anhui Province, SE China have been obtained using an ion probe (Cameca 1270). D/H ratios are constant within a single grain and among the different grains from the same sample. The lack of correlation between the D/H ratios and the hydrogen contents indicates that the hydrogen isotopic compositions are inherited from their mantle source. Combining with the δD values of coexisting amphiboles, it is inferred that the Nushan mantle experienced at least a two-stage metasomatic event. One was responsible for formation of amphiboles with extremely variable δD values, and the other was probably responsible for the high δD values (up to ?20‰) of some clinopyroxenes from peridotites, clinopyroxene and mica megacrysts. High δD values point to a subduction-related fluid being involved in one metasomatic event. The primary δD values (?90‰ to ?140‰) of the Nushan pyroxenes, together with data gleaned from the literature, suggest that the D/H ratios of the nominally anhydrous mineral reservoir might have differed from that of the other mantle hydrogen in being relatively depleted in D.

Ore Genesis of the Kalatongke Cu-Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.

Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater.Mg isotopes are significantly(up to 5%)fractionated during carbonate precipitation by preferential incorporation of ^(24)Mg,while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of^( 26)Mg.Thus,the marine Mg cycle could be reflected by seawater Mg isotopic composition(δ^(26)Mg_(sw)),which might be recorded in marine carbonate.However,carbonates are both texturally and compositionally heterogeneous,and it is unclear which carbonate component is the most reliable for reconstructing δ^(26)Mg_(sw).In this study,we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China.Based on petrographic studies,four carbonate components were recognized:micrite,marine cement,brachiopod shell,and mixture.The four components had distinct δ^(26)Mg:(1)micrite samples ranged from -2.86% to -2.97%;(2)pure marine cements varied from -3.40% to -3.54%,while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range(-3.27% to-3.75%);(3)values for the mixture component were-3.17% and -3.49%;and (4)brachiopod shells ranged from -2.20% to -3.07%,with the thickened hinge area enriched in ^( 24)Mg.Due to having multiple carbonate sources,neither the micrite nor the mixture component could be used to reconstruct δ^(26)Mg_(sw).In addition,the marine cement was homogenous in Mg isotopes,but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ^(26)Mg_(sw).Furthermore,brachiopod shells had heterogeneous C and Mg isotopes,suggesting a significant vital effect during growth.Overall,the heterogeneous δ^(26)Mg of the Huangjin limestone makes it difficult to reconstruct δ^(26)Mg_(sw)using bulk carbonate/calcareous sediments.Finally,δ^(26)Mg_(sw)was only slightly affected by the faunal composition of carbonate-secreting organisms,even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range(0.2%–4.8%)of fractionation during biogenic carbonate formation.

Lead Isotopic Composition and Lead Source of the Huogeqi Cu-Pb-Zn Deposit,Inner Mongolia,China

The Huogeqi orefield located on the northern side of Mt. Langshan, Inner Mongolia occurs in the Middle Proterozoic Langshan Group metamorphic rocks, and the orebodies arc stratiform. In the past twenty years, many Chinese geologists have conducted researches on the Huogeqi Cu-Pb-Zn deposit, but there has been still a controversy on its origin. Some advocate that the deposit is of sedimentary-metamorphic rcworking origin, some hold that it is of sea-floor SEDEX origin, and others have a preference for magmatic superimposition origin. The crux of the controversy is that there is no common understanding about the source of ore-forming materials. In this paper, the Pb isotopic compositions of regional Achaean-Early Proterozoic basement rocks, various types of sedimentary- metamorphic rocks and volcanic rocks in the mining district, Late Proterozoic and Hercynian magmatic rocks arc introduced and compared with the orc-lead composition, so as to constrain the source of the ore lead. The result indicates that （1） sulfides in the ores have homogeneous Pb isotopic compositions, showing a narrow variation range. Their ^206pb/^204pb ratios arc within a range of 17.027- 17.317; ^207Pb/^204pb ratios, 15.451-15.786 and ^208Pb/^204pb ratios, 36.747-37.669; （2） the Pb isotopic compositions of the regional Achaean-Early Proterozoic basement rocks arc characteristic of the old Pb isotopic composition at the early-stage evolution of the Earth, which varies over a wider range, reflecting significant differences in Pb isotopic compositions of the ores. All this indicates that the source of ore lead has no bearing on the basement rocks; （3） the sedimentary-metamorphic rocks in the mining district arc characterized by highly variable and more radiogenic Pb isotopic compositions and their Pb isotopic ratios arc obviously higher than those of ores, demonstrating that ore lead did not result from metamorphic rcworking of these rocks; （4） Pb isotopic compositions of Late Proterozoic diorite-gabbro and Hercynian granite are higher than those of ores. Meanwhile, the Pb isotopic compositions of sulfides in the small-sized strata-penetrating mineralized veinlets formed at later stages arc completely consistent with that of sulfides in stratiform-banded ores, suggesting that these veiniets arc the product of autochthonous rcworking of the stratiform-banded ores during the period of metamorphism and the late magmatic superimposition-mineralization can be excluded; （5） amphibolite, whose protolith is basic volcanic rocks, has the same Pb isotopic compositions as ores, implying that ore lead was derived probably from basic volcanism. So, the source of ore-forming materials for the Huogeqi deposit is like that of the volcanic massive sulfide （VMS） deposits. However, the orebodies do not occur directly within the volcanic rocks, and instead they overlie the volcanic rocks, showing some differences from those typical VMS-type deposits.

Sulfur isotopic composition of seafloor hydrothermal sediment from the Jade hydrothermal field in the central Okinawa Trough and its geological significance

Eighteen samples of hydrothermal sediments from the Jade hydrothermal field in the central Okinawa Trough have been analyzed. Sulfur isotopic values for 10 sulfide samples vary from 5.2× 10^(-3)to 7.2× 10^(-3), δ^(34)S values for 7 sulfate samples vary from 16.3 × 10^(-3) to 22.3 × 10^(-3), and 1 native sulphur sample has a δ^(34)S value of 8.2 × 10^(-3). The major sources of sulfur for hydrothermal sediment are intermediate to acid volcanic rocks and sea water sulfate, and it is possible that the partial sulfur of hydrothermal sediment is from the pelagic sediment by the interaction between hydrothermal fluid and sediment. The reasons of causing the distinct differences in sulfur isotopic values for sulfide samples from hydrothermal sediment ( compared with other hydrothermal fields), are the differences in the sources of sulfur, the magmatic activity and the tectonic evolution in different hydrothermal fields. The sulfur evolution is a long and complex process in the seafloor hydrothermal system, involving the ascending of heating sea water, the interaction between fluid and volcanic rocks, the mixing of sea water sulfate and sulfur from intermediate to acid volcanic rocks, and the fluid/pelagic-sediment interaction. And the interaction between sea water and intermediate to acid volcanic rocks is an important mechanism for the sulfur evolution in the Jade hydrothermal field.

Stable Carbon Isotopic Compositions of Methylated-MTTC in Crude Oils from Saline Lacustrine Depositional Environment:Source Implications

Significantly high abundant methyl-Methyl Trimethyl Tridecyl Chromans （MTTCs） have been detected in aromatic hydrocarbon fractions in crude oils from the Jizhong Depression and Jianghan Basin. The distribution of these compounds is dominated by methyl-MTTC and dimethyl- MTTC series, which indicate diagenetic products of a hypersaline depositional environment in the early stage and show a low degree of methylation. The occurrence of significantly high abundant methyl-MTTC depends mainly on good preservation conditions with a strongly reductive, hypersaline and water-columned depositional environment and subsequent non-intensive diagenetic transformations. The stable carbon isotopic compositions of the methyl-MTTCs and dimethyl-MTTCs in two samples are far different from the stable carbon isotopic composition of C30 hopane of apparent bacteria biogenesis （up to 4.11‰ and 5.75‰, respectively）. This obviously demonstrates that the methyl-MTTC and dimethyl-MTTCs cannot be of bacteria origin, which is different from the previous point of view about non-photosynthetic bacteria products or possible bacteria-reworked products. On the contrary, the stable carbon isotopic compositions of methyl-MTTC and dimethyl-MTTCs in the two samples were similar to that of the same carbon-numbered n-alkanes （nC27-nC28-nC29）, which indicates that they share the same source origin. Especially in the crude oil from the Zhao61 well, stable carbon isotopic compositions are also similar to that of the same carbon-numbered steranes with ααα- 20R isomer （mostly less than 0.4‰）. In consideration of the results of previous studies on saline lake ecological sedimentation, the authors hold that the methyl-MTTC and dimethyl-MTTCs in the saline lake sediments should be of algal biogenesis origin.

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

Noble gas isotopic compositions of various layers in three-layered （outer, porous and compact layers） cobalt-rich ferromanganese crusts and their basaltic and phosphorite substrates from the western Pacific Ocean were analyzed by using a high vacuum gas mass spectrum. The analytical results show that the noble gases in the Co-rich crusts have derived mainly from the ambient seawater, extraterrestrial grains such as interplanetary dust particles （IDPs） and wind-borne continental dust grains, and locally formation water in the submarine sediments, but different noble gases have different sources. He in the crusts derives predominantly from the extraterrestrial grains, with a negligible amount of radiogenic He from the eolian dust grains. Ar is sourced mainly from the dissolved air in the seawater and insignificantly from radiogenic Ar in the eolian continental dust grains or the formation water. Xe and Ne derive mainly from the seawater, with minor amounts of extraterrestrial Xe and Ne in the IDPs. Compared with the porous and outer layers, the compact layer has a relatively high 4He content and lower 3He/4He ratios, suggesting that marine phosphatization might have greatly modified the noble gas isotopic compositions of the crusts. Besides, the 3He/4He values of the basaltic substrates of the cobalt-rich crusts are very low and their R/R. ratios are mostly 〈0.1 R., which are similar to that of phosphorite substrates （0.087 R.）, but much lower than that of fresh submarine MORB （8.75±14 Ra） or seamount basalts （3-43 Ra）, implying that the basaltic substrates have suffered strong water/rock interaction and reacted with radiogenic ^4He and P-rich upwelling marine currents during phosphatization. The trace elements released in the basalt/seawater interaction might favor the growth of cobalt-rich crusts. The relatively low ^3He/^4He values in the seamount basalts may be used as an important exploration criterion for the cobalt-rich ferromanganese crusts.

Rare-earth and trace elements and hydrogen and oxygen isotopic compositions of Cretaceous kaolinitic sediments from the Lower Benue Trough, Nigeria: provenance and paleoclimatic significance

This study evaluated the Cretaceous(Campanian–Maastrichtian) kaolinitic sediments of the Ajali/Mamu and Enugu/Nkporo Formations from the Lower Benue Trough of Nigeria. A combined method of inductively coupled plasma–mass spectrometry and isotope ratio mass spectrometry was used to investigate trace and rareearth element geochemistry and hydrogen and oxygen isotopic compositions. These data were then used to infer the sediments' provenance and paleoclimatic conditions during their deposition. The sediments contained low concentrations of most trace elements, with the exceptions of Zr(651–1352 ppm), Ba(56–157 ppm), V(38–90 ppm),and Sr(15.1–59.6 ppm). Average values of Co and Ni were1.5 and 0.7 ppm, respectively. Trace and rare earth element values were lower than corresponding values for upper continental crust and Post-Archean Australian Shale, with the exception of Zr. The samples showed only slight light rare-earth enrichment and nearly flat heavy rare-earth depletion patterns, with negative Eu and Tm anomalies,typical of felsic sources. Geochemical parameters such as La/Sc, Th/Sc, and Th/Co ratios support that the kaolinitic sediments were derived from a felsic rock source, likely deposited in an oxic environment.^(18 )O values ranged from+ 15.4 to + 21.2% for the investigated samples, consistent with a residual material derived from chemicalweathering of felsic rock and redeposited in a sedimentary basin(typical values of + 19 to + 21.2%). While in the basin, the sediments experienced extended interactions with meteoric water enriched in d D and d16 O. However,the variation in d D and d16 O values for the investigated samples is attributed to the high temperature of formation(54–91 °C). The d D and d^(18 )O values suggest that the sediments, although obtained from different localities within the Lower Benue Trough, formed under similar hot,tropical climatic conditions.

Age and Origin of Paleogene Granitoids from Western Yunnan Province,China:Geochemistry,SHRIMP Zircon Ages,and Hf-in-Zircon Isotopic Compositions

We report geochemical data, SHRIMP zircon ages and Hf-in-zircon isotopic compositions for Cenozoic granitoids from major fault systems in the Tethyan belt in western Yunnan Province, southwestern China.Four magmatic pulses occurred in the Paleogene, namely at ca.57 Ma, ca.50 Ma, 45–40 Ma, and 38–34 Ma.Early magmatism of this episode（57–50 Ma） produced S-type granites whose zircons yielded εHf（t） values of-5.0 to-0.3.In contrast, late magmatism of this episode reflects heterogeneous sources.Zircons from a granite porphyry along the Ailaoshan-Red River fault system have slightly positive εHf（t） values suggesting derivation from relatively young crust and/or a juvenile source.However, zircons from a granite along the Gaoligong fault system have strongly negative εHf（t） values and suggest derivation from a Paleoproterozoic crustal source.The composition of the granitoids varies with age（from ca.57 Ma to ca.34 Ma） from peraluminous to metaluminous and also suggests a change from syn-collisional to late-orogenic tectonic setting.A new tectonic model, impacting lithospheric wedge（ILW） is shown for the origin of Paleogene granitoids in this paper.

Isotopic Composition of Dissolved Carbonates Meromictic Soda Lake Doroninskoe(Eastern Transbaikalia,Russia)

1 Introduction Meromictic soda Lake Doroninskoe localized in the intermountain area,filled with continental sediments of the Mesozoic,in the upper basin of the river Amur.Coordinates of its location are N51°14’42"E112°14’40",

Origin of natural sulfur-metal chimney in the Tangyin hydrothermal field,Okinawa Trough:constraints from rare earth element and sulfur isotopic compositions

For the first time,we present the rare earth element (REE)and sulfur isotopic composition of hydrothermal precipitates recovered from the Tangyin hydrothermal field (THF),Okinawa Trough at a water depth of 1206 m.The natural sulfur samples exhibit the lowest ∑REE concentrations (∑REE= 0.65×10^-6-4.580×10^-6)followed by metal sulfides (∑REE=1.71×10^-6-11.63×10^-6).By contrast,the natural sulfur-sediment samples have maximum ∑REE concentrations (∑REE=1 1.54×10^-6-33.06×10^-6), significantly lower than those of the volcanic and sediment samples.Nevertheless,the δEu,δCe,(La/Yb)N, La/Sm,(Gd/Yb)N and normalized patterns of the natural sulfur and metal sulfide show the most similarity to the sediment.Most hydrothermal precipitate samples are characterized by enrichments of LREE (LREE/HREE=10.09-24.53)arid slightly negative Eu anomalies or no anomaly (δEu=0.48-0.99),which are different from the hydrothermal fluid from sediment-free mid-oceanic ridges and back-are basins,but identical to the sulfides from the Jade hydrothermal field.The lower temperature and more oxidizing conditions produced by the mixing between seawater and hydrothermal fluids further attenuate the leaching ability of hydrothermal fluid,inducing lower REE concentrations for natural sulfur compared with metal sulfide;meanwhile,the negative Eu anomaly is also weakened or almost absent.The sulfur isotopic compositions of the natural sulfur (δ^34S=3.20‰-5.01‰,mean 4.23 ‰)and metal sulfide samples (δ34S=0.82‰-0.89‰,mean 0.85‰)reveal that the sulfur of the chimney is sourced from magmatic degassing.

Petrogenesis and Tectonic Significance of the Xiuwacu Two-Period Magmatism in Geza Arc of Yunnan Province： Constraints from Lithogeochemistry, Zircon U-Pb Geochronology and Hf isotopic Compositions

Objective The Late Cretaceous Xiuwacu ore-bearing porphyry is located in the Geza area of southern Yidun arc, SW China. In this area, the rock mass is mainly composed of three lithofacies： biotite granite porphyry, monzonitic granite and light alkali feldspar granite. As a part of the Yidun arc, the Geza arc has common structure and temporal- spatial evolution with the ~idun arc, which has experienced three stages of oceanic crust subduction, collision orogeny and intracontinent convergence stages. The molybdenite ores in the area are mainly hosted in monzonitic granite-porphyry and structural fracture zone, and the ore bodies are strictly controlled by faults. In recent years, great geological prospecting results have been achieved in Xiuwacu, and the deposit has reached a medium scale. However, there are few researches on the metallogenic porphyry. Based on the previous research, we determined the rock-forming and ore-forming age of the porphyry, and found that there were two stages of magmatism intrusion in Xiuwacu： Indosinian and Yanshanian. We also discussed the geochemical characteristics and source area of the rocks in the area.