Nitrogen isotope chemostratigraphy of the Ediacaran and Early Cambrian platform sequence at Three Gorges,South China

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ¹⁵N_TN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ¹⁵N_TN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ¹⁵N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the ¹⁵N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ¹³C_carb and δ¹⁵N_TN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO₂ with recycled organic nitrogen. After the Shuram event, the δ¹⁵N value continued to decrease despite that δ¹³C_carb rose back to + 4‰. The continued δ¹⁵N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ¹³C_carb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ¹³C_carb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.     

A pronounced negative δ13C excursion in an Ediacaran succession of western Yangtze Platform: A possible equivalent to the Shuram event and its implication for chemostratigraphic correlation in South China

A pronounced negative δ¹³C shift that can be potentially correlated with the Shuram excursion has been reported from middle Ediacaran strata in the Yangtze Gorges area of South China. Whether it represents a perturbation to the ocean carbon cycle or a record of post-depositional alteration is still open to debate. Resolving this controversy will help clarify if δ¹³C variations can be used for chemostratigraphic correlation of Ediacaran successions. To further understand the regional pattern of Ediacaran carbon isotopic excursions in the Yangtze platform, we carried out a detailed δ¹³C analysis of the Lianghong section in the western part of the Yangtze platform. The Ediacaran System at Lianghong is overlain by the Maidiping Formation yielding early Cambrian small shelly fossils and underlain by the Cryogenian Lieguliu Formation diamictite and tuffaceous siltstones. It comprises the Guanyinya and Hongchunping formations, which have been traditionally correlated with the Doushantuo and Dengying formations, respectively, in the Yangtze Gorges area. Two negative δ¹³C excursions occur in the Lianghong section. The lower one at the uppermost Guanyinya Formation, with a nadir at − 8.6‰, may be correlated with the pronounced negative δ¹³C shift (EN3) in the uppermost Doushantuo Formation in the Yangtze Gorges area and possibly with the well known Shuram event in Oman. The upper negative δ¹³C excursion occurs in the upper Hongchunping Formation and may be correlated with negative excursions (EN4) near the Ediacaran/Cambrian boundary. Other negative δ¹³C excursions (e.g., EN1 and EN2) are not expressed in the Lianghong section because the lower Guanyinya Formation is dominated by siliciclastic rocks. Combined with previously published Ediacaran δ¹³C profiles, our results indicate that the EN3 excursion (likely a Shuram equivalent) may occur widely in South China and can be a useful chemostratigraphic feature for regional and global stratigraphic correlation.     

Carbon and sulfur isotopic fluctuations associated with the end-Guadalupian mass extinction in South China

Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ¹³C_carb, δ¹³C_org), and sulfur isotopic compositions of carbonate associated sulfate (δ³⁴S_sulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ¹³C_carb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ¹³C_carb values, Δ¹³C_carb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ³⁴S_sulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

SHRIMP zircon U–Pb geochronology,geochemistry and H–O–Si–S–Pb isotope systematics of the Kanggur gold deposit in Eastern Tianshan,NW China: Implication for ore genesis

The Kanggur gold deposit is located in the southern margin of the Central Asia Orogenic Belt and in the western segment of the Kanggur–Huangshan ductile shear belt in Eastern Tianshan, northwestern China. The orebodies of this deposit are hosted in the Lower Carboniferous volcanic rocks of the Aqishan Formation and mainly consist of andesite, dacite and pyroclastic rocks. The SHRIMP zircon U–Pb age data of the andesite indicate that the volcanism in the Kanggur area might have occurred at ca. 339 Ma in the Early Carboniferous, and that the mineralization age of the Kanggur gold deposit was later than the age of volcanic rocks in the area. Geochemically, the andesite rocks of the Aqishan Formation belong to low-tholeiite and calc-alkaline series and display relative depletions in high field strength elements (HFSEs; i.e. Nb, Ta and Ti). The δ¹⁸O_w and δD_w values vary from − 9.1‰ to + 3.8‰ and − 66.0‰ to − 33.9‰, respectively, indicating that the ore-forming fluids were mixtures of metamorphic and meteoric waters. The δ³⁰Si values of 13 quartz samples range from − 0.3‰ to + 0.1‰ with an average of − 0.15‰, and the δ³⁴S values of 18 sulphide samples range from − 0.9‰ to + 2.2‰ with an average of + 0.54‰. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values of 10 sulphide samples range from 18.166 to 18.880, 15.553 to 15.635 and 38.050 to 38.813, respectively, showing similarities to orogenic Pb; these values are consistent with those of the andesite from the Kanggur area, suggesting a common lead source. All of the silicon, sulphur and lead isotopic systems indicate that the ore-forming fluids and materials were mainly derived from the Aqishan Formation, and that the host volcanic rocks of the Aqishan Formation probably played a significant role in the Kanggur gold mineralization. Integrating the data obtained from studies on geology, geochronology, petro-geochemistry and H–O–Si–S–Pb isotope systematics, we suggest that the Kanggur gold deposit is an orogenic-type deposit formed in Eastern Tianshan orogenic belt during the Permian post-collisional tectonism.     

Chemostratigraphy and detrital zircon geochronology of the Neoproterozoic Khorbusuonka Group,Olenek Uplift,Northeastern Siberian platform

This study provides ⁸⁷Sr/⁸⁶Sr, δ¹³C and δ¹⁸O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.70822 and δ¹³C values between + 4.8 and + 6.0‰. ⁸⁷Sr/⁸⁶Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ¹³C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (⁸⁷Sr/⁸⁶Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of ⁸⁷Sr/⁸⁶Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean.     

Carbon isotope stratigraphy using carbonate cements in the Triassic Sherwood Sandstone Group: Corrib Field,west of Ireland

Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ¹³C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ¹³C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ¹³C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ¹³C correlates with indicators of aridity and biological stress such that the highest δ¹³C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ¹³C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.     

Carbon and oxygen isotope chemostratigraphies of the Yangtze platform,South China: Decoding temperature and environmental changes through the Ediacaran

Multicellular animals first appeared on the earth during the Ediacaran period. However, the relationship between the abrupt biological evolution and environmental changes is still ambiguous. In order to examine seawater temperature and the carbon cycle through the Ediacaran, we analyzed the carbon and oxygen isotope compositions of carbonate rocks from drill cores from the Three Gorges area, South China. Importantly, the core samples include the Nantuo tillite, corresponding to the Marinoan glaciation, through the Doushantuo to the lower Dengying Fms. in ascending order.The δ¹³C profile displays five positive and five negative anomalies (PI-1 to 5 and NI-1 to 5), and the oxygen isotopes display very high absolute values around 0‰ with the highest at + 1.83‰. The combined δ¹⁸O and δ¹³C chemostratigraphies display both positive and negative correlations between the δ¹⁸O and δ¹³C values. The occurrence of the negative correlations supports the preservation of primary δ¹⁸O and δ¹³C values.The sample NI-4 has a negative correlation of the δ¹⁸O and δ¹³C excursions. The correlation supports a primary signature for both δ¹⁸O and δ¹³C variations. The positive δ¹⁸O excursion, accompanied by evidence of a eustatic sea-level fall, provides direct evidence for global cooling in the mid-Ediacaran; the 580 Ma Gaskiers Glaciation is a potential candidate for this global cooling event. The negative δ¹³C excursion was possibly caused by an increase in remineralization of dissolved organic carbon (DOC) due to enhanced continental weathering during the glaciation.Sample NI-5 is characterized by very low δ¹³C values, down to ? 10‰, corresponding to the Shuram-Wonoka-Pertatataka Excursion. The cause of the δ¹³C negative excursion is still not clear. However, a ubiquitous occurrence in excursions worldwide, and the lower δ¹³C values in deeper sections favor the enhancement of remineralization and respiration rather than secondary alteration, a restricted sea environment and lithification in coastal areas.     

The nappe-hosted Hoshbulak MVT Zn–Pb deposit,Xinjiang, China: A review of the geological,elemental and stable isotopic constraints

The Hoshbulak Zn–Pb deposit is located in South Tianshan, Xinjiang, China. The Zn–Pb orebody is tabular and stratoid in form and it is hosted in calcareous rocks of the Upper Devonian Tan'gaitaer Formation which were thrust over the Carboniferous system. The ores are mineralogically simple and composed mainly of sphalerite, galena, pyrite, calcite, dolomite and exhibit massive, banded, veinlets, colloidal, metasomatic, eutectic, concentric ring and microbial-like fabrics. The Co/Ni ratios of pyrite in the ores range from 0.46 to 0.90 by electron microprobe, which suggested that the Hoshbulak Zn–Pb mineralization was formed in a sedimentary environment. The REE patterns of the hydrothermal calcite coincide well with those of recrystallized micritic limestones, suggesting that the Hoshbulak Pb–Zn mineralization was closely genetically related to limestones of the Tan'gaitaer Formation. The C-, H- and O-isotopic compositions of hydrothermal calcite and dolomite in the ores yield δ¹³C(VPDB) values ranging from − 1.9‰ to + 2.6‰ (mean 0.79‰), δ¹⁸O(VSMOW) values from 22.41‰ to 24.67‰ (mean 23.04‰) and δD values from − 77‰ to − 102‰ for fluid inclusions. It is suggested that the ore-forming fluids, including CO₂, were derived from the calcareous strata of the Tan'gaitaer Formation in association with hydrocarbon brines. The δ³⁴S(VCDT) ranges from − 22.3‰ to − 8.5‰ for early ore-stage sulfides and from 5.9‰ to 24.2‰ with a cluster between 14.4‰ and 24.2‰ for the sulfides (pyrite, sphalerite, galena) in the main ore-stage. The ore sulfur may have been derived from evaporite rocks by thermochemical sulfate reduction (TSR) as the predominant mechanism for H₂S generation. The Pb-isotopic compositions of the sulfide minerals from the Hoshbulak ores yield ²⁰⁶Pb/²⁰⁴Pb ratios from 17.847 to 18.173, ²⁰⁷Pb/²⁰⁴Pb ratios from 15.586 to 15.873 and ²⁰⁸Pb/²⁰⁴Pb ratios from 37.997 to 38.905, which indicate that the metals were sourced mainly from the Tan'gaitaer Formation. We conclude that the genesis of the Hoshbulak Mississippi Valley-type deposit was closely related to thrust faulting in the South Tianshan orogen of China.     

The δ13C excursions spanning the Cambrian explosion to the Canglangpuian mass extinction in the Three Gorges area,South China

A remarkable increase of the animal genera and a subsequent mass extinction in the late Early Cambrian are well known as the “Cambrian explosion” and the “Botomian–Toyonian crisis.” A composite global curve of the carbon isotope ratios for inorganic carbon (δ¹³C_carb) shows multiple fluctuations during the evolution events, and it indicates significant changes of the oceanic carbon cycle at that time. This study reveals a new continuous isotopic chemostratigraphy for inorganic carbon (δ¹³C_carb) from the bottom of the Shipai to the base of the Shilongdong formations in Three Gorges area, South China. This section covers the Canglangpuian to the Longwangmiaoian stages in the Lower Cambrian. The δ¹³C_carb variation exhibits three negative excursions: a remarkably negative excursion down to ca. − 12‰ in the middle Canglangpuian stage, a negative excursion to ca. − 1.0‰ in the upper Canglangpuian stage, and a negative excursion to ca. − 1.0‰ in the Longwangmiaoian stage, respectively. The largest negative δ¹³C_carb excursion and a positive excursion before the excursion are definitely consistent with the δ¹³C_carb negative shift (AECE) during the mass extinction and the δ¹³C_carb positive values (MICE) during the increase of animal genera, respectively. However, the minimum values of the negative shifts among South China, Siberia, and Canada sections are different from each other. The positive δ¹³C_carb excursion at the bottom of the Canglangpuian stage indicates that primary productivities and organic carbon burial were enhanced. A sea level rise in the Qiongzhusian to bottom of the Canglangpuian stages in South China corresponds to the Sinsk transgression event in Siberia and Canada. A eutrophication due to higher continental weathering during the transgression after the long-term retrogression enhanced the high primary production and consequently promoted the significant increase of animal diversity.On the other hand, deposition of laminated black shales without bioturbation signatures and a decline of trilobite diversity are observed during the negative δ¹³C_carb excursion in the Canglangpuian stage, indicating that the shallow water environment became anoxic at that time. The negative δ¹³C_carb shift indicates an influx of abundant ¹²CO₂ due to oxidation of organic carbons in seawater. The difference of the minimum values among sections implies the local difference in size of the organic carbon reservoirs and extent of the degradation of the carbons. The largest δ¹³C anomaly in South China suggests the presence of the largest OCPs due to higher activity of primary production and high degree of oxidation of the OCPs because of higher activity of animals. The coincidence of the timing of the negative δ¹³C excursions in the Canglangpuian stage among the sections indicates a global event, and suggests that the onset was caused by increase of oxygen contents of seawater and atmosphere. Abundant oxygen yielded by the increased primary productivity in the Atdabanian and the Qiongzhusian stages caused onset of the oxidation of OCP, and possibly led to the shallow water anoxia and the mass extinction of benthic animals in the Botomian and the Canglangpuian stage.     

Tracking connection and restriction of West Gondwana São Francisco Basin through isotope chemostratigraphy

C and Sr isotope compositions of carbonate rocks from the intracontinental São Francisco basin can track ocean connections and restriction. The lower three formations of the Bambuí Group can be grouped into three chemostratigraphic intervals (CI), recording different evolution stages of the basin. Lowermost CI-1 comprises the basal cap carbonates of the Sete Lagoas Formation displaying an initial C negative excursion, followed by a coeval C and Sr positive excursions (δ¹³C values from − 5 to 0‰ and ⁸⁷Sr/⁸⁶Sr ratios from 0.7074 to 0.7082) in 10 m of stratigraphic record. It marks a change from a restricted shallow basin influenced by freshwater to a basin connected to external seawaters due to marine transgression. CI-2 comprises carbonates of the middle portion of the Sete Lagoas Formation with δ¹³C values around 0‰ and ⁸⁷Sr/⁸⁶Sr ratios around 0.7082 that matches those observed worldwide for the Late Ediacaran. It records the onset of a Gondwana sea pathway connecting several epicontinental basins, allowing migration of index-fossil Cloudina sp. Uppermost CI-3 starts after a major positive excursion in the δ¹³C values reaching + 16‰ and a steepened decrease of ⁸⁷Sr/⁸⁶Sr ratios to 0.7075 which are lower than those expected for the Ediacaran-Cambrian boundary. This interval comprises the upper Sete Lagoas, Serra de Santa Helena and Lagoa do Jacaré formations and records the end of the connection of the São Francisco basin to the Gondwana sea pathway setting a restricted epeiric sea. Restriction was probably caused by Late Ediacaran uplifting of orogenic belts surrounding the basin. Other West Gondwana Cloudina bearing units also display the same mismatch in the Sr isotope ratios, suggesting that the establishment of intracontinental basins inside large continental masses may challenge the use of isotope chemostratigraphy for interbasinal correlations.     

Extremely negative and inhomogeneous sulfur isotope signatures in Cretaceous Chilean manto-type Cu–(Ag) deposits,Coastal Range of central Chile

Chilean manto-type (CMT) Cu(–Ag) hydrothermal deposits share a characteristic association of volcano-sedimentary Jurassic to Lower Cretaceous host rocks, style of mineralization, ore and associated mineralogy and geochemistry, with ore grades typically > 1%Cu, that make this family of deposits significant and interesting, both academically and economically. Although often stratabound, geological evidence supports an epigenetic origin for these deposits. We present a detailed stable isotope study of La Serena and Melipilla–Naltahua Lower Cretaceous deposits, central Chile, which reveals extremely negative δ³⁴S values, to − 50‰, which are among the lowest values found in any ore deposit. In addition, the range of δ³⁴S values from sulfides in the two areas is very wide: − 38.3 to − 6.9‰ in La Serena, and − 50.4 to − 0.6‰ in Melipilla–Naltahua. These new data significantly extended the reported range of δ³⁴S data for CMT deposits. Co-existing sulfates range from 7.9 to 14.3‰, and are exclusive to La Serena deposit. The wide sulfide isotopic range occurs at deposit and hand specimen scale, and suggests a polygenic sulfur source for these deposits, where bacteriogenic sulfide dominates. While sulfur isotope data for the bulk of Jurassic CMT deposits, northern Chile, suggests a predominant magmatic source in their origin (mean = − 2.7 ± 1.9‰, 1σ), contributions of a magmatic component is only likely to be involved at Melipilla–Naltahua deposit.The δ¹³C values obtained for calcites associated with the mineralization range from − 20.1 to 0.2‰ also suggesting polygenic carbon sources, with the likely strong involvement of degradation of organic matter and leaching of limestone.Two different genetic models, with involvement of hydrocarbon, are proposed for both areas. For Melipilla–Naltahua, a two-step model can be developed as follows: 1) Framboidal pyrite growth, with very low δ³⁴S, formed by bacterial sulfate reduction in an open system, and with diagenetic degradation of oil-related brines, leaving pyrobitumen. 2) Cu-bearing stage, replacing of framboidal pyrite, inheriting depleted sulfur as low as − 50.4‰, together with sulfides directly precipitated from a hydrothermal fluid with δ³⁴S close to 0‰. For La Serena, a single step model fits best, without framboidal pyrite generation. Cu-bearing sulfides were precipitated mainly in veins where Cu plus base metal-bearing hydrothermal fluids mixed with H₂S generated by bacterial sulfate reduction in the host rocks. Isotopic evidence clearly illustrates that bacterial activity, perhaps enhanced by hydrothermal activity, was fed by hydrocarbon brines and sulfate remobilized from continental evaporites. It is possible that variable ecological conditions led to different extents of isotopic fractionation, adding to the typical sulfur isotopic heterogeneity of such bacterial systems. For both areas, the Cu-bearing stage occurred during the peak to waning stages of the very low-grade metamorphism that affected the Lower Cretaceous sequence.     

Duration and synchroneity of the largest negative carbon isotope excursion on Earth: The Shuram/Wonoka anomaly

Carbonate δ¹³C values provide a useful monitor of changes in the global carbon cycle because they can record the burial ratio of organic to carbonate carbon. The most pronounced isotope excursions in the geologic record occur during the Neoproterozoic and have assumed a central role in the interpretation of biogeochemical events preceding the Ediacaran and Cambrian radiations. The most profound negative carbon isotope excursion is best recorded in the Ediacaran-aged Shuram Formation of Oman and has potential equivalents worldwide including the Wonoka Formation of South Australia and other sections in China, India, Siberia, Canada, Scandinavia and Brazil. All these excursions are less well understood than those in the Phanerozoic because of their unusual magnitude, long duration (> 1 Ma) and the difficulty in correlating Neoproterozoic basins to confirm independently that they do indeed record global change in the mixed ocean reservoir. Alternatively, these δ¹³C anomalies could reflect diachronous diagenetic processes. Currently none of these excursion are firmly time constrained and critical to their interpretation is a coherent reproducibility and synchroneity at the global ocean scale. Here we use available strontium isotope record as an independent chronometer to test the timing and synchroneity of the Shuram δ¹³C and its potential equivalents. The use of the ⁸⁶Sr/⁸⁷Sr ratio allows the reconstruction of a coherent, global δ¹³C record calibrated independently against time. The calibrated δ¹³C curve indicates that the Shuram negative anomaly spans several tens of millions of years and reaches values below −10‰. This carbon isotopic anomaly therefore represents a meaningful oceanographic event that fundamentally challenges our understanding of the carbon cycle as defined in the Phanerozoic.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Paleoproterozoic positive δ13Ccarb excursion in the northeastern Sino-Korean craton: Evidence of the Lomagundi Event

The 2.33–2.06 Ga positive δ¹³C_carb excursion, associated with environmental change and the breakup of the Kenorland or Superia supercontinent, is called the Lomagundi or Jatulian Event or Great Oxidation Event, and has been reported in many Early Precambrian cratons, but not yet in the Sino-Korean craton. The Guanmenshan Formation of the Liaohe Group occurs in the northeastern part of the Sino-Korean craton. δ¹³C_carb and δ¹⁸O values in 42 samples from this formation range from 3.5–5.9‰ (V-PDB), and 15.4–24.8‰ (V-SMOW), respectively, showing a clear positive δ¹³C_carb excursion that characterizes the Lomagundi Event. Thirty-five of the 42 samples with less hydrothermal alteration have higher δ¹³C_carb and δ¹⁸O_carb values than the other 7 samples obviously affected by fluid flow, confirming that it was fluid flow that reduced the δ¹³C_carb and δ¹⁸O_carb values. This positive δ¹³C_carb excursion places deposition of the Guanmenshan Formation within the age range of 2.33–2.06 Ga.     

Influence of maceral content on δ13C and δ15N in a Middle Pennsylvanian coal

Using density-gradient centrifugation, within-sample heterogeneity in C/N, δ¹³C, and δ¹⁵N was determined for a sample of the Blue Gem coal bed (Middle Pennsylvanian, Duckmantian (Westphalian B), Breathitt Formation) and related to maceral (petrographically identifiable organic component) composition. Relatively pure macerals were separated by density, with purities up to 99% in the case of vitrinite in fractions around 1.3 g/mL. Lower density fractions (∼ 1.2 g/mL) contain predominantly liptinite (∼ 75%) but also significant amounts of vitrinite (∼ 20%). Denser fractions contain increasing amounts of inertinite, with several fractions between 1.37 and 1.44 g/mL containing > 98% total inertinite. Within these denser fractions, semifusinite concentrated at lower densities than did fusinite. The separation of macerals by density allowed a more detailed evaluation of the isotopic composition of relatively pure macerals within a single coal. δ¹³C becomes increasingly heavy across the density gradient, with δ¹³C values being lightest in the liptinites, followed by vitrinite, and then semifusinite and fusinite; by contrast, δ¹⁵N becomes lighter across the same density range. C/H increases with density, reflecting a general decrease in aliphatic components and increase in aromatic components. C/N follows a similar pattern, ranging from < 40 to over 100, increasing significantly at densities > 1.32, the point at which inertinite macerals begin to predominate over vitrinite.The isotopic composition of macerals reflects chemical composition, which in turn reflects: 1) the original composition of plant tissues from which the macerals originated; 2) early diagenetic changes; and 3) changes during coalification. Macerals derived from lipid-rich precursor materials (liptinites) have more depleted δ¹³C values (∼ 2‰) relative to those derived from woody tissues (vitrinite). Fusinized material, derived from fossil charcoal, has δ¹³C values enriched by ∼ 0.5‰ compared with the vitrinite, consistent with the results from combustion experiments using modern plant tissues. Vitrinite fractions have enriched δ¹⁵N values relative to inertinite fractions, which may reflect early diagenetic changes in woody tissues involving preferential loss of ¹⁴N, possibly due to bacterial activity during the peat-forming stage. Due to the within-sample variability in carbon isotopic composition reported here, it is suggested that chemostratigraphic studies based on Type III kerogen (including both dispersed organic matter and coals) carefully consider the associated effects of variability in maceral composition.