Carbon, sulfur, and oxygen isotope evidence for a strong depth gradient and oceanic oxidation after the Ediacaran Hankalchough glaciation

In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes (δ¹³C_carb), carbonate oxygen isotopes (δ¹⁸O_carb), carbonate associated sulfate sulfur (δ³⁴S_CAS) and oxygen isotopes (δ¹⁸O_CAS), and pyrite sulfur isotopes (δ³⁴S_py) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore-offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ¹³C_carb values decrease from −2‰ to −16‰ (VPDB), whereas δ¹⁸O_carb values increase from −4‰ to −1‰ (VPDB). Both δ³⁴S_CAS and δ³⁴S_py show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ¹⁸O_CAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ¹³C_carb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in ¹³C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation.     

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.     

Early cambrian carbon isotope stratigraphy in the tarim basin and a correlation with the yangtze platform

Carbon isotope chemostratigraphy has been used worldwide for stratigraphic correlation.In this study,δ13Ccarb values are estimated for the Early Cambrian Sugaitebulake section in the Tarim Basin,Xinjiang Autonomous Region,China.As a result,one positive and two negative carbon isotope excursions in the studied section were iden-tified.The δ13Ccarb values reached the maximum negative excursion(N1:-12.39‰) at the basal of the Yuertusi For-mation,and then increased to P1.After P1,δ13Ccarb values sharply decreased to about-7.06‰(N2) in the studied section.The pattern of δ13Ccarb in the Early Cambrian is comparable to the synchronous records of other sections,such as the Laolin section,the Xiaotan section and the Anjiahe section of the Yangtze Platform.It is concluded that the Early Cambrian Yuertusi Formation from the Tarim Basin is within the Nemakit-Daldynian stage,and the lower strata of the Yuertusi Formation may belong to the Zhujiaqing Formation(Meishucun Formation) of the Yangtze Platform.The Ediacaran/Cambrian boundary of the Tarim Block should be located in cherts and phosphorites suc-cessions at the basal of the Yuertusi Formation.The δ13Ccarb negative excursion N1 is just across the PC/C boundary,and may be related to certain biomass extinction due to anoxic sedimentary environment,transgression and/or the oceanic overturn.The second δ13Ccarb negative excursion N2 may account for the sea-level falling in the Early Cam-brian.     

Techniques for assessing spatial heterogeneity of carbonate δ13C values: Implications for craton‐wide isotope gradients

The sedimentary record of carbonate carbon isotopes (δ¹³C_carb) provides one of the best methods for correlating marine strata and understanding the long‐term evolution of the global carbon cycle. This work focuses on the Late Ordovician Guttenberg isotopic carbon excursion, a ca 2·5‰ positive δ¹³C_carb excursion that is found in strata globally. Substantial variability in the apparent magnitude and stratigraphic morphology of the Guttenberg excursion at different localities has hampered high‐resolution correlations and led to divergent reconstructions of ocean chemistry and the biogeochemical carbon cycle. This work investigates the magnitude, spatial scale and sources of isotopic variability of the Guttenberg excursion in two sections from Missouri, USA. Centimetre‐scale isotope transects revealed variations in δ¹³C_carb and δ¹⁸O_carb greater than 2‰ across individual beds. Linear δ¹³C_carb to δ¹⁸O_carb mixing lines, together with petrographic and elemental abundance data, demonstrate that much of the isotopic scatter in single beds is due to mixing of isotopically distinct components. These patterns facilitated objective sample screening to determine the ‘least‐altered’ data. A δ¹⁸O_carb filter based on empirical δ¹⁸O_carb values of well‐preserved carbonate mudstones allowed further sample discrimination. The resulting ‘least‐altered’ δ¹³C_carb profile improves the understanding of regional as well as continental‐scale stratigraphic relations in this interval. Correlations with other Laurentian sections strongly suggest that: (i) small‐scale variability in Guttenberg excursion δ¹³C_carb values may result in part from local diagenetic overprinting; (ii) peak‐Guttenberg excursion δ¹³C_carb values of the Midcontinent are not distinct from their Taconic equivalents; and (iii) no primary continental‐scale spatial gradient in δ¹³C_carb (for example, arising from chemically distinct ‘aquafacies’) is required during Guttenberg excursion‐time. This study demonstrates the importance of detailed petrographic and geochemical screening of samples to be used for δ¹³C_carb chemostratigraphy and for enhancing understanding of epeiric ocean chemistry.     

A large epeiric methanogenic Bambuí sea in the core of Gondwana supercontinent?

Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.     

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.     

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.     

Proterozoic (pre-Ediacaran) glaciation and the high obliquity,low-latitude ice,strong seasonality (HOLIST) hypothesis: Principles and tests

Sedimentological observations and palaeomagnetic data for Cryogenian glacial deposits present the climatic paradox of grounded glaciers and in situ cold climate near sea-level, glaciomarine deposition, and accompanying large (up to 40 °C) seasonal changes of temperature, all in low to near-equatorial (< 10°) palaeolatitudes (equated with geographic latitudes). Neither the “snowball Earth” nor the “slushball Earth” hypothesis can account for such strong seasonality near the palaeoequator, which together with findings from sedimentology, chemostratigraphy, biogeochemistry, micropalaeontology, geochronology and climate modelling argue against those scenarios. An alternative explanation of glaciation and strong seasonality in low palaeolatitudes is offered by a high (> 54°) obliquity of the ecliptic, which would render the equator cooler than the poles, on average, and amplify global seasonality. A high obliquity per se would not have been a primary trigger for glaciation, but would have strongly influenced the latitudinal distribution of glaciers. The principle of low-latitude glaciation on a terrestrial planet with high obliquity is validated by theoretical studies and observations of Mars. A high obliquity for the early Earth is a likely outcome of a single giant impact at 4.5 Ga, the widely favoured mechanism for lunar origin. This implies that a high obliquity could have prevailed during most of the Precambrian, controlling the low palaeolatitude of glaciations in the early and late Palaeoproterozoic and Cryogenian. It is postulated that the obliquity changed to < 54° between the termination of the last Cryogenian low-palaeolatitude glaciation at ≤ 635 Ma and the initiation of Late Ordovician–Early Silurian circum-polar glaciation at 445 Ma.The High Obliquity, Low-latitude Ice, STrong seasonality (HOLIST) hypothesis for pre-Ediacaran glaciation emerges favourably from numerous glacial and non-glacial tests. The hypothesis is in accord with such established or implied features of Cryogenian glaciogenic successions as extensive and long-lived open seas, an active hydrological cycle, aridity and palaeowesterly (reversed zonal) winds in low palaeolatitudes, and the apparent diachronism or non-correlation of some low-palaeolatitude glaciations. A pre-Ediacaran high obliquity also offers a viable solution of the faint young Sun paradox of a warm Archaean Earth. Furthermore, reduction of obliquity during the Ediacaran–early Palaeozoic would have yielded a more habitable globe with much reduced seasonal stresses and may have been an important factor influencing the unique evolutionary events of the Ediacaran and Cambrian. The palaeolatitudinal distribution of evaporites cannot discriminate unambiguously between high- and low-obliquity states for the pre-Ediacaran Earth. Intervals of true polar wander such as postulated by others for the Ediacaran and Early Cambrian imply major mass-redistributions within the Earth at those times, which may provide a potential mechanism for reducing the obliquity during the Ediacaran–early Palaeozoic.     

Ultra-high resolution multivariate record and multiscale causal analysis of Pridoli (late Silurian): Implications for global stratigraphy,turnover events,and climate-biota interactions

The upper Silurian, and especially Pridoli epoch is a critical interval for the understanding the evolution of Earth's biota, since it witnessed series of powerful extinction events, global reorganizations of paleocommunities, and expansion of new clades, which assumed dominance in the subsequent Devonian period. The stratigraphic record of the eastern part of the Silurian Baltic Basin represents an excellent candidate for the fine scale analysis of paleoecological and paleoceanographic dynamics. Therefore we presenting here stratigraphic record of the Milaičiai-103 core (south western Lithuania) of conodonts, brachiopods, δ¹³C_carb, δ¹⁸O_carb and a series of various geochemical and geophysical proxies, most of which were sampled at a very high resolution (~11 Ka), spanning uppermost Ludlow, Pridoli, and the lowermost Devonian. The analysis revealed that the Pridoli was characterized by four distinct long-term dynamic states here named: i) Normal Pridoli I, ii) Šilalė negative carbon isotopic excursion and extinction event, iii) Normal Pridoli II, and iv) Klonk positive stable carbon isotopic event and excursion. The most significant change in most variables is detected approximately in the middle of the Pridoli, at the beginning of the Delotaxis detorta Zone, at the recovery after Šilalė event of conodonts, and at the onset of collapse of brachiopod communities. The analysis of dynamic complexity revealed the strong evidence for the presence of ~405 Ka metronome Milankovitch cycles in the record of δ¹³C_carb, which constrains the duration of the Pridoli epoch to 4.3 ± 0.2 Ma. The recurrence plot analyses revealed deterministic coordination between δ¹³C_carb and conodont paleocommunity dynamics at all scales. Finally lead-lag analysis, using conditional joint recurrence, revealed that conodont dynamics, as a rule, were driven by perturbations in the carbon cycle, although Šilalė event interval shown opposite pattern, thus confirming the unusual nature of this previously unrecognized coordinated climatic and biotic event.     

Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

Paired δ13Ccarb and δ13Corg records of the Ordovician on the Yangtze platform,South China

During the Ordovician, huge biological revolutions and environmental changes happened in Earth’s history, including the Great Ordovician Biodiversification Event, global cooling and so on, but the cause of these events remains controversial. Herein, we conducted a paired carbon isotopic analysis of carbonate (δ¹³C_carb) and organic matter (δ¹³C_org) through the Ordovician in the Qiliao section on the Yangtze platform of South China. Our results showed that the δ¹³C_carb trend of the Qiliao section can be correlated with local and global curves. The δ¹³C_org trend seems is less clear than the δ¹³C_carb trend for stratigraphic correlations, but some δ¹³C_org positive excursions in the Middle and Upper Ordovician may be used for correlation studies. These carbon isotopic records may have global significance rather than local significance, revealing several fluctuations to the global carbon cycle during the Ordovician. Several known δ¹³C_carb and δ¹³C_org negative and positive excursions have been recognised in this study, including the early Floian Negative Inorganic Carbon (δ¹³C_carb) Excursion (EFNICE), as well as the early Floian Positive Organic Carbon (δ¹³C_carb) Excursion, the mid-Darriwilian Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (MDICE), and the early Katian Guttenberg Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (GICE). These positive excursions and a smooth decline trend of δ¹³C_org values during the early to mid-Floian may imply multiple episodes of enhanced organic carbon burial that began at the early Floian stage, probably resulting in further decline in atmospheric pCO₂ and then global cooling.     

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.     

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.     

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.     

Facies analysis and correlation of high-order sequences in middle–outer ramp successions: variations in exported carbonate on basin-wide δ13Ccarb (Kimmeridgian, NE Spain)

Carbonate mud that accumulated in the deep parts of a late Kimmeridgian carbonate ramp (Iberian Basin, NE Spain) was partly derived by resedimentation from shallow water production areas. High-frequency sea-level changes, probably driven by climatic changes in tune with precession and short-eccentricity cycles, affected carbonate production and the amount of exported sediment. Facies analysis and correlation of three outcrops located in middle and outer ramp settings allows a comparison of high-order sequences (bundles of beds and sets of bundles) across a ramp transect and an assessment of the carbonate factory. Analysis of the storm deposits found in middle ramp settings identifies deepening to shallowing high-frequency cycles based on the level of exported carbonate. In outer ramp areas, many of the bundles exhibit a thinning trend, indicating a progressive decrease of carbonate production and hence, carbonate export during periods of high-frequency sea-level rise. δ¹³C_carb values show a gradual increase through the studied long-term transgressive interval ranging from 1·5‰ to 2·8‰. Within this long-term evolutionary trend, short-term δ¹³C_carb fluctuations occur that correspond with some of the high-order cycles defined from sedimentary facies analysis. These short-term δ¹³C_carb shifts are interpreted as shifts in carbonate export from shallow reef regions to the outer ramp. A consequence of this study is that variation in δ¹³C_carb can be used for correlation in outer ramp successions, at least on a basin-wide scale.     

Palaeoecology and biostratigraphy of early Cretaceous (Aptian) calcareous nannofossils and the δCcarb isotope record from NE Iran

Upper Barremian-Lower Aptian sediments of the Sarcheshmeh and Sanganeh formations in the Kopet Dagh area, northeast Iran were studied with regard to their calcareous nannofossil content and their δ¹³C_carb signal. The sediments are composed mainly of marlstones, argillaceous limestones and limestones. Based on the occurrence of biostratigraphic index taxa, the calcareous nannofossil zones NC5, NC6 and the NC7A Subzone were recognised. The calcareous nannofossils and the δ¹³C_carb data enable recognition of the early Aptian Oceanic Anoxic Event 1a (OAE 1a). The deposits of the OAE 1a interval are characterised by the rarity of nannoconids and a sharp negative δ¹³C_carb excursion (1.36‰), followed by an abrupt positive δ¹³C_carb excursion of 4-5‰; both events have been recognised elsewhere in OAE 1a deposits in the Tethys. In the OAE 1a interval, the relative abundance of Watznaueria barnesiae/Watznaueria fossacincta is higher (more than 40%) than that of Biscutum spp., Discorhabdus spp. and Zeugrhabdotus spp., which indicates dissolution. In the upper part of the section, the higher relative abundance of mesotrophic and oligotrophic taxa (Watznaueria spp. and nannoconids respectively) and the enhanced relative abundance of eutrophic taxa (Biscutum spp., Discorhabdus spp., Zeugrhabdotus spp.) is indicative of an environment with slightly increased nutrient content. The presence of warm water taxa (Rhagodiscus asper and nannoconids) and the absence of cool water taxa (Repagulum and Crucibiscutum) suggest warm surface-water conditions.     

Coincident negative shifts in sulfur and carbon isotope compositions prior to the end-Permian mass extinction at Shangsi Section of Guangyuan, South China

Sulfur isotope composition of carbonate-associated sulfate (δ³⁴S_CAS) and carbon isotope composition of carbonate (δ¹³C_carb) were jointly investigated on the Late Permian rocks at Shangsi Section, Guanyuan, Northeast Sichuan, South China. Both δ³⁴S_CAS and δ¹³C_carb show gradual decline trends in Late Permian strata, inferring the occurrence of the long-term variation of marine environmental conditions. Associated with the long-term variation are the two coincident negative shifts in δ³⁴S_CAS and δ¹³C_carb, with one occurring at the boundary between Middle Permian Maokou Formation and Late Permian Wujiaping Formation and another at Middle Dalong Formation. Of significance is the second shift which clearly predates the regression and the biotic crisis at the end of Permian at Shangsi Section, providing evidence that a catastrophic event occurred prior to the biotic crisis. The frequent volcanisms indicated by the volcanic rocks or fragments, and the upwelling are proposed to cause the second negative excursion. An abrupt extreme negative δ³⁴S_CAS (ca. −20‰) associated with a low relative concentration of CAS and total organic carbon without large change in δ¹³C_carb is found at the end of the second shift, which might arise from the short-term oxygenation of bottom waters and sediments that resulted from the abrupt sea level drop.     

Middle–Upper Permian carbon isotope stratigraphy at Chaotian,South China: Pre-extinction multiple upwelling of oxygen-depleted water onto continental shelf

In order to examine the causal relationships between the carbon cycle in a shallow euphotic zone and the environmental changes in a relatively deep disphotic zone at the end-Guadalupian (Middle Permian), isotopic compositions of carbonate carbon (δ¹³C_carb) of the Guadalupian–Lopingian (Upper Permian) rocks were analyzed in the Chaotian section in northern Sichuan, South China. By analyzing exceptionally fresh drill core samples, a continuous chemostratigraphic record was newly obtained. The ca. 65 m-thick analyzed carbonate rocks at Chaotian comprise three stratigraphic units, i.e., the Limestone Unit of the Guadalupian Maokou Formation, the Mudstone Unit of the Maokou Formation, and the lower part of the Wuchiapingian (Lower Lopingian) Wujiaping Formation, in ascending order. The Limestone Unit of the Maokou Formation is characterized by almost constant δ¹³C_carb values of ca. +4‰ followed by an abrupt drop for 7‰ to −3‰ in the topmost part of the unit. In the Mudstone Unit of the Maokou Formation, the δ¹³C_carb values are rather constant around +2‰, although distinct three isotopic negative excursions for 3‰ from ca. +2 to −1‰ occurred in the upper part of the unit. In the lower part of the Wujiaping Formation, the δ¹³C_carb values monotonously increase for 5‰ from ca. 0 to +5‰. The present data newly demonstrated four isotopic negative excursions in the topmost part of the Maokou Formation in the Capitanian (Late Guadalupian) at Chaotian. It is noteworthy that these negative excursions are in accordance with the emergence of an oxygen-depleted condition on the relatively deep disphotic slope/basin on the basis of litho- and bio-facies characteristics. They suggest multiple upwelling of oxygen-depleted waters with dissolved inorganic carbon of relatively low carbon isotope values along the continental margin, from the deeper disphotic slope/basin to the shallower euphotic shelf, slightly before the end-Guadalupian extinction. Although the negative excursions at Chaotian are apparently correlated with the previously proposed large negative excursion in the middle Capitanian in South China, the age difference according to the biostratigraphic constraints clearly exclude this interpretation. The isotopic negative excursions at Chaotian are unique and no similar isotopic signal in the same period has been reported elsewhere. The multiple upwelling of oxygen-depleted waters onto the euphotic shelf may have represented local phenomena that occurred solely around northwestern South China.     

The Ediacaran radiogenic Sr isotope excursion in the Doushantuo Formation in the Three Gorges area,South China

The Ediacaran period was one of the most important times for the evolution of life. However, the scarcity of well-preserved outcrops of Ediacaran rocks still leaves ambiguity in decoding ambient surface environmental changes and biological evolution.The Ediacaran strata in South China are almost continuously exposed, comprise mainly carbonate rocks with subordinate black shales and sandstones, and they contain many fossils, suitable for study of environmental and biological changes in the Ediacaran. We conducted drilling through the Doushantuo Fm at four sites in the Three Gorges area to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed ⁸⁷Sr/⁸⁶Sr and ⁸⁸Sr/⁸⁶Sr ratios of the fresh carbonate rocks, selected on the basis of microscopic observations and the geochemical signatures of Sr contents, Mn/Sr and Rb/Sr ratios, and δ¹⁸O values, with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS).The chemostratigraphy of the ⁸⁷Sr/⁸⁶Sr ratios of the drilled samples displays a smooth curve and two large positive shifts during Ediacaran time. The combination of the detailed chemostratigraphies of δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values and Mn and Fe contents enables us to decode the surface environmental changes and their causes in the Ediacaran. The first large positive excursion of ⁸⁷Sr/⁸⁶Sr occurred together with negative δ¹³C and positive δ¹⁸O excursions. The higher ⁸⁷Sr/⁸⁶Sr values indicate an enhancement of continental weathering, whereas the positive δ¹⁸O excursion suggests global cooling. Global regression due to global cooling enhanced the oxidative decay of exposed marine organic sediments and continental weathering. Accelerated influx of nutrients promoted primary productivity, resulting in oxidation of dissolved organic carbon (DOC), whereas active sulfate reduction due to a higher sulfate influx from the continents caused remineralization of the large DOC, both of which caused a negative δ¹³C anomaly. The 580 Ma Gaskiers glaciation accounts for the close correlation among the positive ⁸⁷Sr/⁸⁶Sr, negative δ¹³C and positive δ¹⁸O excursions.The second large positive shift of ⁸⁷Sr/⁸⁶Sr firstly accompanied a positive δ¹³C excursion, and continued through the Shuram δ¹³C negative excursion. The positive correlation of δ¹³C and ⁸⁷Sr/⁸⁶Sr values is consistent with an enhanced continental weathering rate due to continental collisions that built Trans-Gondwana mountain chains, and with a higher primary activity due to the enhancement of continental weathering and consequent higher nutrient contents in seawater. The accompanied increase in Mn and Fe contents implies a gradual decline of the seawater oxygen content due to more active aerobic respiration and oxidation of reductive materials flowing in the oceans. In the Shuram excursion, higher ⁸⁷Sr/⁸⁶Sr values and a transition from increase to decrease in Mn and Fe contents were accompanied by the large negative δ¹³C excursion. The higher ⁸⁷Sr/⁸⁶Sr values are the first compelling evidence for enhanced continental weathering, which was responsible for the large δ¹³C anomaly through the remineralization of the DOC by more active sulfate reduction due to a higher sulfate influx. Higher Mn and Fe contents in the early and middle stages of the excursion suggest a decline in the oxygen content of seawater due to oxidative decay of the DOC, whereas in the late stages the decrease in Mn and Fe contents is consistent with oceanic oxygenation.The emergence of Ediacara biota after the Gaskiers glaciation and the prosperity of the latest Ediacaran is concomitant with the formation of more radiogenic seawater with high ⁸⁷Sr/⁸⁶Sr values, suggesting that enhanced continental weathering, and the consequent higher influx of nutrients, played an important role in biological evolution.     

Carbon isotope chemostratigraphy of a Precambrian/Cambrian boundary section in the Three Gorge area, South China: Prominent global-scale isotope excursions just before the Cambrian Explosion

Carbon isotope chemostratigraphy has been used for worldwide correlation of Precambrian/Cambrian (Pc/C) boundary sections, and has elucidated significant change of the carbon cycle during the rapid diversification of skeletal metazoa (i.e. the Cambrian Explosion). Nevertheless, the standard δ¹³C curve of the Early Cambrian has been poorly established mainly due to the lack of a continuous stratigraphic record. Here we report high-resolution δ¹³C chemostratigraphy of a drill core sample across the Pc/C boundary in the Three Gorge area, South China. This section extends from an uppermost Ediacaran dolostone (Dengying Fm.), through a lowermost Early Cambrian muddy limestone (Yanjiahe Fm.) to a middle Early Cambrian calcareous black shale (Shuijingtuo Fm.). As a result, we have identified two positive and two negative isotope excursions within this interval. Near the Pc/C boundary, the δ¹³C_carb increases moderately from 0 to + 2‰ (positive excursion 1: P1), and then drops dramatically down to − 7‰ (negative excursion 1: N1). Subsequently, the δ¹³C_carb increases continuously up to about + 5‰ at the upper part of the Nemakit–Daldynian stage. After this positive excursion, δ¹³C_carb sharply decreases down to about − 9‰ (N2) just below the basal Tommotian unconformity. These continuous patterns of the δ¹³C shift are irrespective of lithotype, suggesting a primary origin of the record. Moreover, the obtained δ¹³C profile, except for the sharp excursion N2, is comparable to records of other sections within and outside of the Yangtze Platform. Hence, we conclude that the general feature of our δ¹³C profile best represents the global change in seawater chemistry. The minimum δ¹³C of the N1 (− 7‰) is slightly lower than carbon input from the mantle, thus implying an enhanced flux of ¹³C-depleted carbon just across the Pc/C boundary. Hence, the ocean at that time probably became anoxic, which may have affected the survival of sessile or benthic Ediacaran biota. The subsequent δ¹³C rise up to + 5‰ (P2) indicates an increase of primary productivity or an enhanced rate of organic carbon burial, which should have resulted in lowering pCO₂ and following global cooling. This scenario accounts for the cause of the global-scale sea-level fall at the base of the Tommotian stage. The subsequent, very short-term, and exceptionally low δ¹³C (− 9‰) in N2 could have been associated with the release of methane from gas hydrates due to the sea-level fall. The inferred dramatic environmental changes (i.e., ocean anoxia, increasing productivity, global cooling and subsequent sea-level fall with methane release) appear to coincide with or occur just before the Cambrian Explosion. This may indicate synchronism between the environmental changes and rapid diversification of skeletal metazoa.