The Hirnantian δ<Superscript>13</Superscript>C Positive Excursion in the Nabiullino Section (South Urals)

The upper Sandbian, Katian, and Hirnantian complexes of conodonts in the upper Ordovician section of the western slope of the Southern Urals near the village of Nabiullino were studied. The δ¹³C positive excursion with a maximum of 3.3‰ associated with the global Hirnantian isotopic event, HICE, was fixed for the first time. This excursion shows the beginning of the Hirnantian stage in the terrigenous–carbonate section of the upper Ordovician in the Southern Urals. It coincides with the first occurrence of the Hirnantian conodont species of Gamachignathus ensifer and the conodonts of shallow-water biophacies, Aphelognathus-Ozarkodina, reflecting the global glacio-eustatic event.     

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.     

Roller-coaster atmospheric-terrestrial-oceanic-climatic system during Ordovician-Silurian transition: Consequences of large igneous provinces

The Ordovician-Silurian transition (OST) hosted profound and frequent changes in the atmospheric-terrestrial-oceanic-climatic system (ATOCS). Previous studies have found contrasting stages for such changes, primarily based on hiatus-interrupted sections. However, the dominant driving factors and mechanisms reconciling such frequent changes remain controversial. Mercury isotopes, which undergo both mass-dependent and mass-independent fractionation, can provide critical insights into the deep-time ATOCSs, especially for those impacted by large igneous provinces (LIPs) events. Here, we build a high-resolution multi-proxy record of Hg (concentrations and isotopic compositions) combined with organic carbon isotopes (δ¹³C_org) and whole-rock geochemical data (including trace elements and phosphorus) from continuous cores in the Yangtze Platform, South China. Our data, combined with reported ones, indicate the occurrence of LIP eruptions against localized volcanism, and four successive, yet contrasting stages of ATOCSs during the OST. Moreover, we identified the coupling between two-pulse LIP magmatism and extreme ATOCSs, each with special pCO₂, weathering rate, primary productivity, redox condition, climatic mode, and biotic evolution. For stage I, the first pulse of LIP magmatism triggered global warming, enhanced terrestrial weathering, oceanic acidification, eutrophication, anoxia, P recycling, and thereby widespread deposition of black shales. During stage II, the Hirnantian glaciation and oxygenation arose from the intense chemical weathering and black shale deposition of stage I; slashed terrestrial weathering and oceanic oxygenation facilitated CO₂ accumulation. In stage III, another pulse of LIP magmatism triggered the de-glaciation, and the ATOCS was largely similar to that of stage I. This led to another round of oxygenation and positive δ¹³C_org excursion in stage IV. Compared with the environmental pressure by the peculiar ATOCS of each stage, their transitions might have been more devastating in triggering the prolonged Late Ordovician Mass Extinction (LOME). Moreover, limited biotic recovery was possible in the later portion of stages I and III. The multi-proxy study of continuous strata of the OST provides an excellent framework for better illuminating LIPs’ essential role in driving the “roller-coaster” behavior of the ATOCS and thus biotic crisis during the pivotal period of the OST.     

Distinguishing Cambrian from Upper Ordovician source rocks: Evidence from sulfur isotopes and biomarkers in the Tarim Basin

The reported source rocks for the abundant petroleum in the Tarim Basin, China range from Cambrian to Lower Ordovician and/or Upper Ordovician in age. However, the difference between the two groups of source rocks is not well characterized. In this study, pyrite was removed from eleven mature to over mature kerogen samples from source rocks using the method of CrCl₂ reduction and grinding. The kerogen and coexisting pyrite samples were then analyzed for δ³⁴S values. Results show that the kerogen samples from the Cambrian have δ³⁴S values between +10.4‰ and +19.4‰. The values are significantly higher than those from the Lower Ordovician kerogen (δ³⁴S of between +6.7‰ and +8.7‰), which in turn are generally higher than from the Upper Ordovician kerogen samples (δ³⁴S of between ?15.3 and +6.8‰). The associated pyrite shows a similar trend but with much lower δ³⁴S values. This stratigraphically controlled sulfur isotope variation parallels the evolving contemporary marine sulfate and dated oil δ³⁴S values from other basins, suggesting that seawater sulfate and source rock age have an important influence on kerogen and pyrite δ³⁴S values. The relatively high δ³⁴S values in the Cambrian to Lower Ordovician source rocks are associated with abundant aryl isoprenoids, gammacerane and C₃₅ homohopanes in the extractable organic matter, indicating that these source rocks were deposited in a bottom water euxinic environment with water stratification. Compared with the Upper Ordovician, the Cambrian to Lower Ordovician source rocks show abundance in C₂₈ 20R sterane, C₂₃ tricyclic terpanes, 4,23,24-trimethyl triaromatic dinosteroids and depletion in C₂₄ tetracyclic terpane, C₂₉ hopane. Thus, δ³⁴S values and biomarkers of source rock organic matter can be used for distinguishing the Cambrian and Upper Ordovician source rocks in the Tarim Basin.     

Trace elements indicating humid climatic events in the Ordovician–early Silurian

The chemical composition of the clay fraction separated from the carbonate rock of the north-eastern Baltoscandian Basin was analysed and interpreted. Increased contents of Rb, Zr, Nb, Ti and their Al₂O₃-normalised ratios were detected at several stratigraphical levels in the geological sections of the Middle Ordovician–Upper Llandovery. In the weathering areas, Rb, Zr, Nb, Ti and Al are sensitive to moist conditions in the clay-forming process. In the sedimentary basin, the contents of these elements in clay are preserved and allow to infer past climates. Humid events occurred in the Dapingian, Sandbian, early Katian and Hirnantian (Ordovician) and in the Middle and Late Llandovery (Silurian). Juxtaposition with the sea-level curve shows correlation of five humid climate intervals with eustatic transgressions, suggesting global causes for these climatic changes. The warm and humid events, lasting one to two million years, occurred as climaxes between ice ages. An exceptional humid event within the Hirnantian glacial time occurs during mid-Hirnantian transgression, i.e. at a time of relative warming, as well.     

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.     

Environmental changes and carbon cycle perturbations at the Triassic–Jurassic boundary in northern Switzerland

The Triassic–Jurassic boundary is characterized by strong perturbations of the global carbon cycle, triggered by massive volcanic eruptions related to the onset of the Central Atlantic Magmatic Province. These perturbations are recorded by negative carbon isotope excursions (CIEs) which have been reported worldwide. In this study, Triassic–Jurassic boundary sections from the southern margin of the Central European Basin (CEB) located in northern Switzerland are analyzed for organic carbon and nitrogen isotopes in combination with particulate organic matter (POM) analyses. We reconstruct the evolution of the depositional environment from Late Triassic to Early Jurassic in northern Switzerland and show that observed negative shifts in δ¹³C of the total organic carbon (δ¹³C_TOC) in the sediment are only subordinately influenced by varying organic matter (OM) composition and primarily reflect global changes in the carbon cycle. Based on palynology and the stratigraphic positions of isotopic shifts, the δ¹³C_TOC record of the studied sections is correlated with the GSSP section at Kuhjoch (Tethyan realm) in Austria and with the St. Audrie’s Bay section (CEB realm) in southwest England. We also show that in contrast to POM analyses the applicability of organic carbon/total nitrogen (OC/TN) atomic ratios and stable isotopes of total nitrogen (δ¹⁵N_TN) for detecting changes in source of OM is limited in marginal depositional environments with frequent changes in lithology and OM contents.     

2.0 Ga orogenic graphite deposits and associated 13C-enriched meta-carbonate rocks from South China Craton: Implications for global Lomagundi event

The Lomagundi (-Jatuli) event, characterized by extremely high positive global inorganic carbon isotope excursion at about 2.2 billion years ago, is pivotal in investigating the causes and consequences of great oxygenation event, inventory and sequestration of carbon on the Earth’s surface, evolution of life, and more profoundly tectonic control on Earth’s environment. However, the reasons that caused the isotopic excursion are not resolved yet. Herein, we report the discovery of meta-carbonate rocks with distinct positive carbon isotopic excursion from the Paleoproterozoic continental collision zone of the Kongling Complex, South China Craton. The δ¹³C_V-PDB values for meta-carbonate rocks show positive values in the range from +5.5‰ to +11.6‰, whereas the δ¹³C_V-PDB values of associated graphite deposits range from ?25.8‰ to ?9.5‰. Zircon U-Pb-Hf isotopes from zircon-bearing meta-carbonate sample yielded weighted average ²⁰⁷Pb/²⁰⁶Pb age of 2001.3 ± 9.5 Ma, with corresponding ε_Hf(t) range from ?7.05 to ?3.16, comparable to the values of local 2.9–2.6 Ga basement rocks. Geochemical characteristics of meta-carbonate rocks, such as their rare earth element patterns and the trace element parameters of La, Ce, Eu, and Gd anomalies and Y/Ho ratio, suggest that the carbonate deposition took place in passive continental margin in association with large volumes of organic carbon. The extensive graphite deposits from Kongling Complex in South China Craton, their equivalents in the North China Craton and elsewhere across the globe prove that the burial of ¹²C-enriched organic carbon has eventually resulted in the global enrichment of ¹³C in the atmospheric CO₂, which is recorded in the marine carbonate rocks. Isotopic mass balance estimates indicate that more than half of the organic carbon was buried during the oceanic closure. Hence, the observed global shift could be directly related to the continent collision event in greater China, thus resolving the long-standing paradox of the Lomagundi global positive carbon isotope excursion. Moreover, the present results suggest that orogenesis play a significant role in sequestration of carbon into the continental crust.     

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.     

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 carbon‐isotope record of shallow‐marine evaporative epicratonic basin carbonates,Ordovician Williston Basin,North America

Secular variations in stable carbon‐isotope values of marine carbonates are used widely to correlate successions that lack high‐resolution index fossils. Various environmental processes, however, commonly may affect and alter the primary marine carbon‐isotope signal in shallow epicratonic basins. This study focuses on the marine carbon‐isotope record from the carbonate–evaporite succession of the upper Katian (Upper Ordovician) Red River Formation of the shallow epicratonic Williston Basin, USA. It documents the carbon‐isotope signal between the two major Ordovician positive shifts in δ¹³C, the early Katian Guttenberg and the Hirnantian excursions. Eight δ¹³C stages are identified based on positive excursions, shifts from positive to negative values and relatively uniform δ¹³C_carb values. A correlation between carbon‐isotope trends and the relative sea‐level changes based on gross facies stacking patterns shows no clear relation. Based on the available biostratigraphy and δ¹³C trends, the studied Williston Basin curves are tied to the isotope curves from the North American Midcontinent, Québec (Anticosti Island) and Estonia, which confirm the Late Katian age (Aphelognathus divergens Conodont Zone) of the upper Red River Formation. The differences in the δ¹³C overall trend and absolute values, coupled with the petrographic and cathodoluminescence evidence, suggest that the carbon‐isotope record has been affected by the syndepositional environmental processes in the shallow and periodically isolated Williston Basin, and stabilized by later burial diagenesis under reducing conditions and the presence of isotopically more negative fluids.     

Seasonal water-column dynamics of dissolved inorganic carbon stable isotopic compositions (δCDIC) in small hardwater lakes in Minnesota and Montana

The carbon stable isotopic value of dissolved inorganic carbon (δ¹³C_DIC) was measured over several years at different depths in the water column in six carbonate-precipitating temperate lakes. δ¹³C_DIC behavior in three of these lakes departed from the conventional model wherein epilimnetic waters are seasonally enriched relative to all hypolimnetic waters, and in general δ¹³C_DIC values in the water column were not readily correlated to parameters such as lake stratification, algal productivity, hydraulic residence time, or water chemistry. Additionally, the processes implicated in generating the δ¹³C_DIC values of individual lakes differ between lakes with similar δ¹³C_DIC compositions. Each lake thus initially appears idiosyncratic, but when the effects of carbonate mineral equilibria, microbial activity, and lake residence time are viewed in terms of the magnitude of distinct DIC pools and fluxes in stratified lakes, generalizations can be made that allow lakes to be grouped by δ¹³C_DIC behavior. We recognize three modes in the relationship between δ¹³C_DIC values and DIC concentration ([DIC]) of individual lakes: (A) δ¹³C_DIC values decreasing with increasing [DIC]; (B) δ¹³C_DIC values increasing with increasing [DIC]; (C) δ¹³C_DIC values decreasing with increasing [DIC] but increasing again at the highest [DIC]. This approach is useful both in understanding δ¹³C_DIC dynamics in modern hardwater lakes and in reconstructing the environmental changes recorded by sedimentary δ¹³C components in the lacustrine paleorecord.     

Carbon isotope composition of organic seston and sediments in a Georgia salt marsh estuary

The distribution of δ¹³C values for organic seston and sediment was determined in three sounds in the Spartina marsh estuaries along the Georgia coast, which had high, moderate, and low inputs of freshwater. Organic matter in all three sounds had similar carbon isotope compositions, for the most part within the range of marine values (δ¹³C of ?18%. to ?24%.). It appears that river flow does not introduce significant quantities of particulate C₃ plant material (δ¹³C of ?25%. to ?28%.) to Georgia estuaries. Evaluation of δ¹³C values of estuarine seston and three size fractions of sediment indicated that while Spartina carbon (δ¹³C of ?13%.) can be an important component of organic matter in intertidal sediments (mean δ¹³C of ?14.3%. to ?20.0%.), it is less so in subtidal sediments (mean δ¹³C of ?18.8%. to ?21.2%.), and it is hardly present at all in the seston (mean δ¹³C of ?24.5%.). δ¹³C values of dissolved inorganic carbon (DIC) in several water samples ranged between ?2.5%. and ?5.6%., suggesting that the isotope composition of estuarine DIC is influenced by respiratory CO₂ derived from metabolism of ¹³C-depleted plant carbon. Phytoplankton production utilizing this comparatively light DIC could be a source of relatively negative δ¹³C carbon in the estuary. Additional origins of estuarine organic matter greatly depleted in ¹³C compared to Spartina carbon remain to be identified.     

Global significance of oxygen and carbon isotope compositions of pedogenic carbonates since the Cretaceous

Few global syntheses of oxygen and carbon isotope composition of pedogenic carbonates have been attempted,unlike marine carbonates.Pedogenic carbonates represent in-situ indicators of the climate conditions prevailing on land.The δ~(18)O and δ~(13)C values of pedogenic carbonates are controlled by local and global factors,many of them not affecting the marine carbonates largely used to probe global climate changes.We compile pedogenic oxygen and carbon isotopic data(N= 12,167) from Cretaceous to Quaternary-aged paleosols to identify potential trends through time and tie them to possible controlling factors.While discrete events such as the PaleoceneEocene Thermal Maximum are clearly evidenced,our analysis reveals an increasing complexity in the distribution of the δ~(18)O vs δ~(13)C values through the Cenozoic.As could be expected,the rise of C_4 plants induces a shift towards higher δ~(13)C values during the Neogene and Quaternary.We also show that the increase in global hypsometry during the Neogene plays a major role in controlling the δ~(18)O and δ~(13)C values of pedogenic carbonates by increasing aridity downwind of orographic barriers.Finally,during the Quaternary,an increase of 3‰ inδ~(18)O values is recorded both by the pedogenic carbonates and the marine foraminifera suggesting that both indicators may be used to track global climate signal.     

Carbon isotope composition of graptolite periderm and whole-rock from the Aeronian (Silurian, Llandovery) in Wales and Scotland and its use in chemostratigraphy

Here we show the use of graptolite periderm for chemostratigraphic study. Using material from the Aeronian (Silurian) interval from Wales and Scotland as examples, we show that the carbon isotope composition of the periderm (δ¹³C_grap.) provides a signal that is locally different but not consistently so from surrounding whole-rock samples (δ¹³C_whole-rock). Graptolite periderm δ¹³C seems not influenced by astogenetic stage of development or gross rhabdosome type and differences between δ¹³C_grap. from different metamorphic grades are minimal. Taken as a whole, the Aeronian interval examined shows little overall change, but large variations are seen on the small scale, possibly reflecting very local carbon cycling. For carbon isotope stratigraphy in such rocks, therefore, large-scale bulk sampling will likely reduce inhomogeneities and give more reproducible results. Furthermore, in situations (for instance associated with sea level fluctuations) where terrestrial organic matter has been incorporated into the sediment, then graptolite carbon may more faithfully reflect bulk marine organic matter.     

Lacustrine sedimentary record of early Aptian carbon cycle perturbation in western Liaoning,China

The early Aptian abrupt carbon isotope excursion in marine carbonate and sedimentary organic matter reflects a major perturbation in the global carbon cycle. However, until now almost all the evidences of this event came from marine deposits. Here we present organic-carbon isotope (δ¹³C_org) data from the non-marine Jehol Group in western Liaoning, China. The lacustrine δ¹³C_org curve is marked by a relative long-lasting δ¹³C_org minimum followed by two stages of positive δ¹³C_org excursions that are well correlated with contemporaneous marine records. The carbon isotope correlation shows that the lacustrine strata of the Jehol Group were deposited at the same time of the early Aptian Oceanic Anoxic Event (OAE1a). The relative long-lasting δ¹³C_org minimum supports the hypothesis that volcanic CO₂ emission may have played the main role in triggering the negative δ¹³C excursion and global warming at the onset of this event. In addition, the onset of δ¹³C_org minimum is concomitant with the radiation of the Jehol Biota, implying that the evolutionary radiation of the Jehol Biota may have been closely related with the increase in atmospheric CO₂ and temperature.     

Revised estimate of δ34S for marine sulfates from the Upper Ordovician: data from the Williston Basin,North Dakota,U.S.A.

Analyses for δ³⁴S of 13 bedded, marine anhydrite samples from the “C” anhydrite member of the Red River Formation (Upper Ordovician) in the North Dakota portion of the Williston basin represent an addition of δ³⁴S data to a portion of the S isotope age curve with few data. Previously published estimates of δ³⁴S for Upper Ordovician marine sulfates apparently are limited to 4 samples from the Saskatchewan portion of the same basin. An adjusted mean value of +25.5‰ was calculated for all known Upper Ordovician δ³⁴S determinations. This value is approximately 2 to 3‰ lighter than the previous estimate, which suggests that δ³⁴S of the world ocean during the Upper Ordovician may have been lighter than previously thought. However, because all δ³⁴S data are from one sedimentary basin, additional S isotopic data from several globally-distributed evaporite basins are needed to evaluate this hypothesis and further constrain δ³⁴S for the Upper Ordovician. Similar re-examination of other portions of the S isotope age curve with limited amounts of data may increase our understanding of the secular variation in δ³⁴S.     

Comparison of Michigan Basin crude oils

Michigan Basin oils from the Ordovician Trenton, Silurian Niagaran, and Devonian Dundee formations have been geochemically compared by GC, GC-MS, and carbon isotope mass spectrometry. One oil from each formation was selected for detailed analysis which included measurement of individual n-alkane δ¹³C values. The Ordovician and Devonian oils are strikingly similar to one another, yet clearly different from the Silurian oil. This pattern is unexpected because Ordovician and Devonian reservoirs are physically separated by the Silurian strata. From time-temperature considerations, the Devonian oil probably was formed in older strata and has migrated to its present location. Our analyses suggest a common source for the Devonian and Ordovician oils.     

Strontium and carbon isotope stratigraphy of the Late Jurassic shallow marine limestone in western Palaeo-Pacific,northwest Borneo

Strontium and carbon isotope stratigraphy was applied to a 202 m-thick shallow marine carbonate section within the Late Jurassic Bau Limestone at the SSF quarry in northwest Borneo, Malaysia, which was deposited in the western Palaeo-Pacific. Strontium isotopic ratios of rudist specimens suggest that the SSF section was formed between the latest Oxfordian (155.95 Ma) and the Late Kimmeridgian (152.70 Ma), which is consistent with previous biostratigraphy. The δ¹³C_carb values of bulk carbonate range from −0.10 to +2.28‰ and generally show an increasing upward trend in the lower part of the section and a decreasing upward trend in the upper part of the section. A comparable pattern is preserved in the δ¹³C_org isotope record. Limestone samples of the SSF section mainly preserve the initial δ¹³C_carb values, except for the interval 84–92 m, where an apparent negative anomaly likely developed as a result of meteoric diagenesis. Comparing with the Tethyan δ¹³C_carb profile, a negative anomaly in the lower SSF section can be correlated with the lowered δ¹³C values around the Oxfordian/Kimmeridgian boundary. In addition, δ¹³C_carb values of the Bau Limestone are generally ∼1‰ lower than the Tethyan values, but comparable with the values reported from Scotland and Russia, located in Boreal realm during the Late Jurassic. This suggests that either the Tethyan record or the other records have been affected by the δ¹³C values of regionally variable dissolved inorganic carbon (DIC). The Late Jurassic δ¹³C_DIC values are thought to have been regionally variable as a result of their palaeoceanographic settings. This study shows that δ¹³C chemostratigraphy of the Palaeo-Pacific region contributes to an improved understanding of global carbon cycling and oceanography during this time period.     

Hirnantian (Late Ordovician) δ13C HICE excursion in a North Gondwanan (NE Spain) periglacial setting and its relationship to glacioeustatic fluctuations

In the Iberian Chains of northeastern Spain, the Hirnantian Orea Shale comprises three erosive glaciogenic unconformities punctuating two transgressive glaciomarine sequences. These sequences represent ice retreat episodes of grounded ice on a North Gondwanan region of 50–60°S of estimated palaeolatitude. In contrast, the same formation recorded in the Hesperian Chains repeated episodes of extensional tectonic activity: diamictites were associated with slope-related debris flows and slumps commonly interrupted by truncating discontinuities.An analysis of δ¹³C_org in the Orea Shale has revealed that the lower Orea sequence displays isotopically light baseline values (∼ −27‰) punctuated by minor (2–3‰) shifts. In distal parts, the upper sequence is characterised by a rapid rise in δ¹³C_org values, which mark a positive excursion, in the range of 2.5‰ to 7‰ over 40 cm of thickness. The stratigraphic gap involved in the intra-Orea erosive unconformity appears to be greater both in proximal exposures and slope-related (Hesperian) areas, where the chemostratigraphic shift was not recorded. Upsection in the three studied sections, the δ¹³C values display upsection a sharp return to baseline values of −26‰ to −28‰.The Hirnantian strata of the Iberian and Hesperian Chains have recorded three major correlatable events: (i) a the karstic surface that caps upper Katian limestones and reflects the maximum glacial extension; (ii) a single δ¹³C_org positive peak of ∼6‰ that is recognisable in distal ramp settings, marking the beginning of the second ice retreat episode and probably representing the late Hirnantian HICE shift; and (iii) the erosive unconformity marked by the progradation of the Los Puertos shoreline complexes.