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.

Diverse transformations of sulfur in seabird-affected sediments revealed by microbial and stable isotope analyses

Microbial communities,sulfur isotope of sulfides(δ^(34)S_(AVS)and δ^(34)S_(CRS)),and sulfur and oxygen isotopes of sulfate(δ^(34)S_(SO_(4))and δ^(18)O_(SO_(4)))in sediments were analyzed to reveal the biogeochemical transformations of sulfur in a seabird-affected lake Y2 and a se abird-free YO from Fildes Peninsula,Antarctic Peninsula.The microbial communities in Y2 were mainly associated with penguin activities,while those in YO were limited by nutrients.The much enriched δ^(34)S_(SO_(4))recorded at depth of 30,41,and 52 cm in Y2indicates very strong sulfate reduction therein.The sulfur-degrading bacteria Pseudomonas in 0-23 cm of Y2 was 3.5 time s as abundant as that of sulfur oxidizing bacteria(SOB),indicating remarkable remineralization of organic sulfur.The abundant SOB and ^(34)S-depleted sulfate indicate considerable sulfur oxidation in 34-56-cm layer in Y2.In YO sediments,the highest abundance of Desulfotalea and the most enriched δ^(34)S_(SO_(4))(35.2‰)and δ^(34)S_(CRS)(2.5‰)indicate the strongest sulfate reduction in 28-cm layer.High abundance of Pseudomonas indicates active remineralization of organic sulfur in 3-5-cm layer in YO.The medium δ^(34)S_(SO_(4))and considerable abundance of SOB and sulfate-reducing bacteria(SRB)indicate concurrence of sulfur oxidation and sulfate reduction in other layers in YO.Therefore,a high level of organic matter input from penguin populations supported the diverse microbial community and transformations of sulfur in aquatic ecosystems in Antarctica.

Preparation of nitrogen and sulfur co-doped ultrathin graphitic carbon via annealing bagasse lignin as potential electrocatalyst towards oxygen reduction reaction in alkaline and acid media

Renewable lignin used for synthesizing materials has been proven to be highly potential in specific electrochemistry.Here,we report a simple method to synthesize nitrogen and sulfur co-doped carbon nanosheets by using bagasse lignin,denoted as lignin-derived carbon(LC).By adjusting the ratio of nitrogen source and annealing temperature,we obtained the ultrathin graphitic lignin carbon(LC-4-1000)with abundant wrinkles with high surface area of 1208 m2g_1 and large pore volume of 1.40 cm3g_1.In alkaline medium,LC-4-1000 has more positive half-wave potential and nearly current density compared to commercial Pt/C for oxygen reduction reaction(ORR).More importantly,LC-4-1000 also exhibits comparable activity and superior stability for ORR in acid medium due to its high graphitic N ratio and a direct four electron pathway for ORR.This study develops a cost-effective and highly efficient method to prepare biocarbon catalyst for ORR in fuel cells.

Coupled carbon and sulfur isotope behaviors and other geochemical perspectives into marine methane seepage

Methane seepage is the signal of the deep hydrocarbon reservoir. The determination of seepage is significant to the exploration of petroleum, gas and gas hydrate. The seepage habits microbial and macrofaunal life which is fueled by the hydrocarbons, the metabolic byproducts facilitate the precipitation of authigenic minerals. The study of methane seepage is also important to understand the oceanographic condition and local ecosystem. The seepage could be active or quiescent at different times. The geophysical surveys and the geochemical determinations reveal the existence of seepage. Among these methods, only geochemical determination could expose message of the dormant seepages. The active seepage demonstrates high porewater methane concentration with rapid SO42- depleted, low HaS and dissolved inorganic carbon （DIC）, higher rates of sulfate reduction （SR） and anaerobic oxidation of methane （AOM）. The quiescent seepage typically develops authigenic carbonates with specific biomarkers, with extremely depleted 13C in gas, DIC and carbonates and with enriched 34S sulfate and depleted 34S pyrite. The origin of methane, minerals precipitation, the scenario of seepage and the possible method of immigration could be determined by the integration of solutes concentration, mineral composition and isotopic fractionation of carbon, sulfur. Numerical models with the integrated results provide useful insight into the nature and intensity of methane seepage occurring in the sediment and paleo- oceanographic conditions. Unfortunately, the intensive investigation of a specific area with dormant seep is still limit. Most seepage and modeling studies are site-specific and little attempt has been made to extrapolate the results to larger scales. Further research is thus needed to foster our understanding of the methane seepage.

Power-law patterns in the Phanerozoic sedimentary records of carbon, oxygen, sulfur,and strontium isotopes

Power-law patterns appear in a variety of natural systems on the modern Earth;nevertheless,whether such behaviors appeared in the deep-time environment has rarely been studied. Isotopic records in sedimentary rocks, which are widely used to reconstruct the geological/geochemical conditions in paleoenvironments and the evolutionary trajectories of biogeochemical cycles, offer an opportunity to investigate power laws in ancient geological systems. In this study, I focus on the Phanerozoic sedimentary records of carbon, oxygen, sulfur, and strontium isotopes, which have well documented and extraordinarily comprehensive datasets. I perform statistical analyses on these datasets and show that the variations in the sedimentary records of the four isotopes exhibit power-law behaviors. The exponents of these power laws range between 2.2 and 2.9;this narrow interval indicates that the variations in carbon, oxygen, sulfur, and strontium isotopes likely belong to the same universality class, suggesting that these systematic power-law patterns are governed by universal, scale-free mechanisms. I then derive a general form for these power laws from a minimalistic model based on basic physical principles and geosystem-specific assumptions, which provides an interpretation for the power-law patterns from the perspective of thermodynamics. The fundamental mechanisms regulating such patterns might have been ubiquitous in paleoenvironments, implying that similar power-law behaviors may exist in the sedimentary records of other isotopes.

Stable Carbon and Oxygen Isotopes of Pedogenic Carbonates in Ustic Vertisols: Implications for Paleoenvironmental Change

Pedogenic carbonates, found extensively in arid and semiarid regions, are important in revealing regional climatic and environmental changes as well as the carbon cycle. In addition, stable carbon and oxygen isotopic compositions of pedogenic carbonates have been used to rebuild paleoecology (biomass and vegetation) and to estimate paleotemperature and paleoprecipitation during past geological time. By utilizing the stable carbon and oxygen isotopic compositions (δ13C and (δ18O) of secondary nodules in Ustic Vertisols, this study looked into the climatic and environmental changes in the dry valleys of the Yuanmou Basin, Yunnan Province, in southwestern China. The results showed that during the early Holocene, a warm-humid or hot-humid climate existed in the Yuanmou Basin, but since then fluctuations in climate have occurred, with a dry climate prevailing. A highly significant correlation (r = 0.92, n = 9) between δ13C and δ18O values of carbonates illustrated that there had been a continual shifting between cold-humid and warm-dry climates in southwestern China including the Yuanmou Basin since the early Holocene.

Characteristics and Implications Significance for Carbon and Oxygen Isotope Continuous Change of Zhenjia1 Well in The Northern Shaanxi Salt Basin

Zhenjia1 well located in the 2nd salt depression of the Northern Shaanxi Salt Basin(Zhang et al,2013),is the basis potash exploration wells,and its main purpose is marine potash prospection,combining with gas exploration.Drilling completion depth is 3443.6m,

Research on carbon and oxygen isotopes in phosphorus-bearing rock series of the Late Neoproteroic-Early Cambrian Taozichong Formation in Qingzhen City, Guizhou Province, Southwest China

In the study of the phosphate-bearing stratum at the bottom of the Cambrian system, the authors found that there occurred carbon isotope negative anomalies in the Taozichong section phosphate-bearing stratum in Qingzhen, Guizhou Province; they can be correspondingly compared with other synsedimentary carbon isotope negative anomalies both at home and abroad. The results showed that there occurred three negative anomalies of carbon isotopes in the Neoproterozoic-Early Cambrian Taozichong Formation, indicating that the temporal palaeo-oceanographical environment changed significantly, in which there happened two times of intensive carbon isotope variation, corresponding to creature extinction. Meanwhile, it is believed that the carbon isotope negative anomalies in phosphorites were caused by the ascending water mass of ocean current with the negative carbon isotopic composition of deep-ocean hydrothermal deposits.

Estimation of Residence Times and Recharge Area of Groundwater in the Moulares Mining Basin by Using Carbon and Oxygen Isotopes (South Western Tunisia)

Radiogenic carbon (14C) of the DIC (Dissolved Inorganic Carbon) and oxygen-18 were used to understand the hydro- dynamic functioning of the multilayer aquifer system in the Moulares mining basin, southern Tunisia. The results of this study permits identify two groundwater types. A- an old paleoclimatic groundwater, marked by low carbon-14 (14C) activities. B - a recent groundwater, was distinguished by relatively high carbon-14 activities. In addition to these two water types, other groundwater, indicating a mixing effect, is resulting presumably from upward movement from the deeper groundwater. Based on 14C activity and the piston flow type theory the groundwater residence time varies from 5 Kyear to 35 Kyear. Carbon-14 activity and oxygen-18 in Groundwater are active since Mio-Plio-Quaternary and Upper Cretaceous aquifers lead to the identification of paleorecharged water probably during Late Pleistocene and Early to Middle Holocene. The water feedings of these aquifers are mainly provided by infiltration of precipitations, infiltration of irrigation water, lateral feeding from cretaceous relieves from the South and the North and along recent and fossil drainage networks that constitute major fresh water sources in groundwater tables.

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.

The Geochemical Characteristics of Stable Carbon and Oxygen Isotope and Analysis of Diagenetic Environment --A Case Study of Upper Permian Changxing Formation Dolostone in Northeast of Sichuan

四川盆地东北部上二叠统长兴组白云岩为重要的优质储层,近年来,长兴组白云岩成岩环境或成因问题成为研究者讨论的热点话题。在岩石学研究的基础上,运用稳定碳、氧同位素,对研究区长兴组白云岩进行综合研究表明,白云石化具有多期次的特点,按照成岩环境划分为蒸发环境下的准同生白云岩和埋藏条件下的早、中、晚期成岩白云岩。并划分为早、中、晚成岩阶段,结合碳、氧同位素分析结果进一步表明晚成岩阶段白云岩是构造热液白云石化的结果。

Riverine sulfate sources and behaviors in arid environment,Northwest China:Constraints from sulfur and oxygen isotopes

The fate of riverine sulfate ion (SO_(4)^(2-)) and its environmental effects in arid environment are difficult to evaluate due to its complicated sources and strongly coupled behaviors with water cycle which is significantly modified by humans.To understand the sulfur cycle in aquatic systems in arid environment,the chemical and sulfur and oxygen isotopic compositions (δ^(34)S_(SO4)and δ^(18)O_(SO4)) of major rivers around the Badain Jaran Desert,northwestern China,were investigated.These rivers had averaged SO_(4)^(2-)content at 1336μmol/L,over 10times higher than the global average.The δ^(34)S_(SO4)and δ^(18)O_(SO4)values ranged from-5.3‰to+11.8‰and+1.6‰to+12.8‰,respectively.The end-member analysis and the inverse model showed that riverine sulfate was mainly derived from evaporites dissolution (0-87%),sulfide oxidation (13%-100%) and precipitation (0-33%),indicating heterogeneity in sulfur sources and behaviors along the river drainage with the lithology variations and climate gradients.Multiple isotopic tools combining with hydro-chemistry compositions could be applied to reveal sulfur cycle in arid environment.Based on the calculation,sulfide oxidation plays the primary role in the headwater and upstream in the Qilian-Mountains area,where sulfide is widely exposed.While the proportion of evaporites dissolution contributing to riverine sulfate is much higher in downstream in a drier environment.Besides,less precipitation and higher temperature can lead to more intensive evaporation,affecting the process of sulfide oxidation and enhancing the rates of evaporites dissolution and sulfate precipitation in the basin.

Sulfate sources constrained by sulfur and oxygen isotopic compositions in the upper reaches of the Xijiang River,China

While it is critical to accurately understand the sources and transformation of sulfate based on time-series analysis, there are limited studies on temporal variation of sulfate in rivers and on rock weathering by sulfuric acids.We conducted a monthly sampling campaign in the Beipan, Nanpan, and Hongshui Rivers over the course of one hydrological year. This study examined seasonal variations in riverine sulfate impacted by the monsoon climate in the upper reaches of the Xijiang River basin. In general, the SO_4^(2-) contents in these rivers dropped from relatively high levels to low values during the high-flow season, in response to increasing discharge. The sulfate was generally enriched in heavy isotopes during the low-flow season compared to the high-flow season. The calculated results indicate that the riverine sulfate was mainly derived from sulfide oxidation, but that evaporite dissolution could be an important source during the low-flow season, based on isotopic evidence. Mine drainage is likely an important source of sulfate to these rivers during the high-flow season due to contributions from fast surface flow, which responds to frequent heavy rain in monsoonal climate regions. Arelatively high proportion of HCO_3^- was found to be derived from rock weathering by sulfuric acid during the high-flow season when compared to that observed during the low-flow season. The results suggest that approximately one quarter of the HCO_3^- in the Hongshui River originated from carbonate weathering by sulfuric acid derived from the oxidation of sulfide. Such information on the specific dual isotopic characteristics of riverine sulfate throughout a hydrological year can provide unique evidence for understanding the temporal variability of sulfate concentrations and weathering processes in rivers.

Unveil the Redox Evolution of Ore-forming Fluids using Sulfur Isotope:A Case Study of the Zhengguang Intermediate Sulfidation Epithermal Au-Zn Deposit,NE China

Oxygen fugacity(fO_(2))is a key intensity variable during the entire magmatic-hydrothermal mineralization courses.The redox state and its variations between different stages of the ore-forming fluids of intermediate sulfidation epithermal deposits are rarely deciphered due to the lack of appropriate approaches to determine fO_(2)of the fluids.Here,we reported theδ^(34)S of the sulfides from three different stages(stageⅠ,Ⅱ,Ⅲ)of Zhengguang,an Early Ordovician Au-rich intermediate sulfidation(IS)epithermal deposit,to decipher the redox evolution of the ore-forming fluids.The increasingδ^(34)S values from stageⅠpyrite(pyl,average-2.6‰)through py2(average-1.9‰)to py3(average-0.2‰)indicates a decrease of the oxygen fugacity of the ore-forming fluids.A compilation ofδ^(34)S values of sulfides from two subtypes of IS deposits(Au-rich and Ag-rich)from NE China shows that theδ^(34)S values of sulfides from Au-rich IS deposits are systematically lighter than those of Ag-rich IS Ag-Pb-Zn deposit,indicating the ore-forming fluids of the former are more oxidized than the latter.We highlight that sulfur isotopic composition of hypogene sulfides is an efficacious proxy to fingerprint the oxygen fugacity fluctuations of epithermal deposits and could potentially be used to distinguish the subtypes of IS deposits.

Effective exposure of nitrogen heteroatoms in 3D porous graphene framework for oxygen reduction reaction and lithium–sulfur batteries

The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.

Sulfur-encapsulated in heteroatom-doped hierarchical porous carbon derived from goat hair for high performance lithium–sulfur batteries

Biomass-derived carbon materials have aroused widespread concern as host material of sulfur to enhance electrochemical performances for lithium–sulfur batteries. Herein, goat hair, as a low-cost and eco-friendly precursor, is employed to fabricate cauliflower-like in-situ nitrogen, oxygen and phosphorus tri-doped porous biomass carbon(NOPC) by a facile activation with H_3PO_4 and carbonization process.The morphology and microstructure of NOPC can be readily tuned by altering pyrolysis temperature. The as-prepared NOPC matrix material carbonized at 600 °C possesses 3D hierarchical porous structure, high specific surface area(535.352 m^2 g^(-1)), and appropriate pore size and pore size distribution. Encapsulating sulfur into the NOPC depends on a stem-melting technology as cathode materials of Li–S batteries. Due to the synergistic effect of special physical structure and inherent tri-doping of N, O and P, electrons and ions transfer and utilization of active sulfur in the materials are improved, and the shuttle behaviors of soluble lithium polysulfides are also mitigated. Consequently, the S/NOPC-600 composite exhibits excellent electrochemical performance, giving a high initial discharge capacity of 1185 mA h g^(-1) at 0.05 C and maintaining a relatively considerable capacity of 489 m A h g^(-1) at 0.2 C after 300 cycles. Our work shows that a promising candidate for cathode material of Li–S batteries can be synthesized using low-cost and renewable biomass materials by a facile process.

Carbon isotopes, sulfur isotopes, and trace elements of the dolomites from the Dengying Formation in Zhenba area, southern Shaanxi: Implications for shallow water redox conditions during the terminal Ediacaran

Carbon isotope, sulfur isotope, and trace element(including Rare Earth Elements, REE) analyses were conducted on the carbonates of the Dengying Formation at Lianghekou section in southern Shaanxi to reconstruct the terminal Ediacaran shallow-water environment on the northwestern margin of the Yangtze Platform. At Lianghekou section, samples in the middle 50-m of the Beiwan Member show characteristics of low ΣREE concentrations, no MREE-enriched REE distribution patterns, high Ce/Ce* values close to 1, and enriched redox-sensitive elements, whereas samples in the lower 30-m and upper 10-m show opposite characteristics of high ∑REE concentrations, MREE-enriched REE distribution patterns, low Ce/Ce* values around 0.6, and no redox-sensitive elements enriched, indicating that oxygenation did occur in the shallow water on the northwestern margin of the Yangtze Platform and redox conditions of the shallow water fluctuated from relatively oxygenated to anoxic and then back to oxygenated again. We propose that the anoxia appeared in middle of the Beiwan time may associate with the anoxic upwelled water. On one hand, abundant nutrients were brought in by this upwelling event, which stimulated the photosynthetic carbon fixation and increased the organic carbon burial under this anoxic condition, causing a peak of 3.6‰ in δ 13 C. On the other hand, because the anoxic upwelled water replaced the oxic shallow water, together with the increasing organic matter in the water column, bacterial sulfate reduction was enhanced and therefore quickly reduced the sulfate concentration, which eventually caused δ 34 S increasing to 50‰. However, as the upwelling gradually disappeared, δ 13 C and δ 34 SCAS values decreased as well in the late Beiwan time, indicating the shallow water went back to suboxic or oxic again.

Multiple sulfur and oxygen isotope compositions in Beijing aerosol

Multiple sulfur isotopes （32S, 335, 345, 365） and oxygen isotopes （160, 180） in Beijing aerosols were measured with MAT-253 isotope mass spectrometer. The δ345 values of Beijing aerosol samples range from 1.68%o to 12.57%o with an average value of 5.86%0, indicating that the major sulfur source is from direct emission during coal combustion. The c5180 values vary from -5.29%0 to 9.02%0 with an average value of 5.17%o, revealing that the sulfate in Beijing aerosols is mainly composed of the secondary sulfate. The main heterogeneous oxidation of SO2 in atmosphere is related to H202 in July and August, whereas H202 oxidation and Fe3＋ catalytic oxidation with SO2 exist simultaneously in September and October. Remarkable sulfur iso- tope mass-independent fractionation effect is found in Beijing aerosols, which is commonly attributed to the photochemical oxidation of SO2 in the stratosphere. In addition, thermochemical reactions of sulfur-bearing compounds might be also a source of sulfur isotope anomalies based on the correlation between A335 and CAPE.