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.     

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.     

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.     

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.     

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.     

Carbon and oxygen isotopes in the Frasnian–Famennian section of the Kuznetsk basin (southern West Siberia)

The first detailed isotope-geochemical study of carbonate deposits has been performed in the Lower Famennian stratotype section of the northwestern Kuznetsk Basin (Kosoy Utyos), which was localized in the middle latitudes of the Northern Hemisphere in the Late Devonian. The δ¹³C_carb, δ¹³C_org, and δ¹⁸O variation curves were constructed for the section deposits. Geochemical and petrographic studies of carbonates allowed allocation of samples that underwent postsedimentation alteration and exclude them from further interpretation. Compared with coeval sections in the other world's regions, the Kosoy Utyos section is characterized by higher δ¹³C_carb values, up to 5.4‰, whereas the maximum value in subequatorial area sections is 4‰. The isotope shift amplitude of the studied section reaches 4.6‰, which is 1.5‰ higher than those in other regions. The δ¹⁸O values are 3‰ lower than the ones of the world's coeval sections. The results obtained show that δ¹³C and δ¹⁸O variation trends differ from those of coeval subequatorial sections. The high shift amplitude and maximum δ¹³C_carb values in the Kosoy Utyos section are due to the shallow-water carbonate sedimentation environments on the Siberian continental shelf and, probably, the lower temperatures of waters in the middle latitudes as compared with the subequatorial areas.     

Spatial variability of watermass conditions within the European Epicontinental Seaway during the Early Jurassic (Pliensbachian–Toarcian)

In order to constrain spatial variability in watermass conditions within the European Epicontinental Seaway prior to, during and after the Toarcian Oceanic Anoxic Event, carbon (δ¹³C_bel, δ¹³C_carb) and oxygen (δ¹⁸O_bel, δ¹⁸O_carb) isotope records were obtained from three sections in the Grands Causses Basin (southern France). These data were then compared with similar records along a north–south transect across the European Epicontinental Seaway. As the conclusions reached here strongly depend on the reliability of belemnite calcites as archives of palaeoceanographic changes, an attempt was made to improve the understanding of isotope signals recorded in belemnite calcite. Intra‐rostral carbon and oxygen‐isotope data from six belemnite specimens belonging to the genus Passaloteuthis were collected. Intra‐rostral carbon‐isotopes are influenced by vital effects, whereas oxygen‐isotopes reflect relative changes in temperature and salinity. Palaeotemperatures calculated from δ¹⁸O_bel‐isotope records from the Grands Causses Basin confirm relatively low temperatures throughout the Late Pliensbachian. Similar cool water conditions have previously been shown in Germany, England, Spain and Portugal. A temperature increase of up to 6 °C is observed across the Pliensbachian–Toarcian boundary. A pronounced negative shift of at least ?3‰ (Vienna‐Pee Dee Belemnite) is recorded in bulk carbonate carbon during the lower Harpoceras serpentinum zone, typical of the Toarcian Oceanic Anoxic Event. Before and after the Toarcian Oceanic Anoxic Event, a good correlation between δ¹³C_carb and δ¹³C_bel exists, indicating well‐ventilated bottom‐waters and normal marine conditions. Instead, data for the Toarcian Oceanic Anoxic Event indicate the development of a strong north–south gradient in salinity stratification and surface‐water productivity for the Western Tethyan realm. This study thus lends further support to a pronounced regional overprint on carbon and oxygen‐isotope records in epicontinental seaways.     

Correlation of 13C12C and 34S32S secular variations

Statistical evaluation of 3056 δ¹³C measurements in carbonate rocks and fossils shows that they record a 2‰ ¹³C depletion from the late Proterozoic to the early Paleozoic, a 2.5‰ enrichment to the Permian, and a 1.5‰ depletion to the Cenozoic. These variations, not controlled primarily by facies or alteration phenomena, correlate negatively with the δ³⁴S sulfate secular trend, as confirmed by collation of 1083 δ³⁴S measurements. The correlation suggests that the biologically mediated redox fluxes of the C and S cycles have been approximately balanced through this long span of geological time, generally levelling available oxygen. Such a redox system is consistent with the controlling mechanism proposed by Garrels and Perry (1974). Consequently, the sedimentary reservoirs of C_organic as well as S_{bacteriological'}have varied through geological time.     

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.     

A carbon‐isotopic study of an end‐Permian mass‐extinction horizon,Bulla, northern Italy: a negative δ13C shift prior to the marine extinction

Palaeontological data from the Permian‐Triassic Bulla section, northern Italy, demonstrate a rapid extinction at this site. This occurs after a negative carbonate carbon‐isotope (δ¹³C_carb) shift, consistent with two other northern Italian sites (Val Badia and Tesero). However, conclusion goes against recent reporting that the extinction occurs before the δ¹³C_carb shift. We agree that the shift occurs after the extinction at Jameson Land, east Greenland (a high latitude palaeolocation). However, all other sections show the shift before, or coincident with, the extinction. We suggest that the simplest explanation is a coeval shift in carbonate carbon‐isotope shifts, and it follows that the extinction was not. This suggests that the end‐Permian extinction crept from region to region. It also suggests that the marine extinction occurred first in high northern latitudes.     

The Mid-Cenomanian Event in shallow marine environments: Influence on carbonate producers and depositional sequences (northern Aquitaine Basin,France)

The Mid-Cenomanian Event was a positive carbon-isotope (δ¹³C) excursion recorded in hemipelagic basins of the western Tethyan Sea, North to Tropical Atlantic Ocean, and Japan. It is thought of as a prelude to the Oceanic Anoxic Event 2. However, the Mid-Cenomanian Event has never been studied in detail in shallow marine platform deposits and it is not known how it relates to carbonate production and stratigraphic geometry. To better understand how this carbon cycle disruption influenced the neritic biological communities in shallow carbonates during the Cenomanian, a facies, geochemical, diagenetic, and sequence stratigraphic study of the northern Aquitaine platform has been conducted. Seventy-six δ¹³C and δ¹⁸O measurements have been made on micrite, rudists, and diagenetic cements. Fifteen sedimentary facies have been arranged into four depositional environments. Three third-order sequences (C_B, C_C, C_D) are defined from late early Cenomanian to early late Cenomanian and are well correlated with eustatic cycles in European basins. Two peaks of the Mid-Cenomanian Event (MCE1a, +1.2‰, and MCE1b, +1.7‰) have been identified for the first time in shallow marine carbonates. Analysis of diagenetic blocky calcite cements suggests that diagenesis did not affect the δ¹³C of micrite, which can be discussed in terms of the initial signal. The Mid-Cenomanian Event was synchronous with a turnover in neritic carbonate producers marking a transition from photozoan to heterozoan facies. This facies change resulted from the establishment of mesotrophic to eutrophic conditions at the early/mid-Cenomanian transition, reflecting a clear connection between the Mid-Cenomanian Event and neritic biological communities. Depositional geometry and carbonate production varied with δ¹³C during the Mid-Cenomanian Event on the Aquitaine platform. When δ¹³C values were between 2.5‰ and 3‰, the geometry was a flat platform with a high carbonate sedimentation rate leading to the formation of sandbars and rudist bioherms (Accommodation/Sedimentation ratio less than 1, A/S < 1). When the δ¹³C value exceeded 3‰, a carbonate demise occurred and clays and marls were deposited in the lower offshore environment (A/S >> 1). The general carbonate demise affecting the northern Aquitaine platform during the mid-Cenomanian can be explained by both a eustatic sea-level rise and the establishment of eutrophic conditions. The coincidence of the Mid-Cenomanian Event with both (1) the occurrence of mesotrophic to eutrophic conditions marked by carbonate producer turnover from photozoan to heterozoan facies and (2) the transgressive cycles, suggests that eustatic sea-level rise leading to high trophic conditions could explain this positive δ¹³C excursion in the Atlantic and western Tethyan domain. During the mid-Cenomanian, carbon cycle perturbations largely controlled the neritic biological communities on shallow carbonate platforms in a part of the western Tethyan domain.     

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.     

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.     

Effect of pedogenesis on the stable isotopic composition of calcretes and n‐alkanes: Implications for palaeoenvironmental reconstruction

In a fluvial system, depending on sub‐aerial exposure, non‐pedogenic pond calcretes can be modified into pedogenic calcretes. The present study attempts to understand the effect of sub‐aerial exposure and pedogenesis on calcretes using carbon and oxygen isotopic composition. For this purpose, two profiles (profile‐A and profile‐B) from the same stratigraphic level in Rayka from the western part of India were selected. The profiles are separated by a distance of 500 m and showed differences in calcrete characteristics. In profile‐A, the calcretes showed pedogenic features (root traces and void filling spar) whereas calcretes in profile‐B showed non‐pedogenic characteristics (fine laminations). However, some of the calcretes in profile‐A exhibited remnants of fine laminations suggesting that initially the calcretes had a non‐pedogenic origin but were modified due to pedogenesis. In profile‐A, the carbon and oxygen isotope values of pedogenic calcrete (δ¹³C_PC and δ¹⁸O_PC) showed more variation compared with non‐pedogenic pond calcretes (δ¹³C_SPC and δ¹⁸O_SPC) in profile‐B. The δ¹³C_PC and δ¹³C_SPC values exhibited a spread of 3·0‰ and 1·3‰, respectively, and δ¹⁸O_PC and δ¹⁸O_SPC values showed a spread of 2·3‰ and 1·3‰, respectively. The differences in the isotopic composition between the two profiles suggest that pedogenesis controlled the isotopic inheritance in calcretes. In addition, the carbon isotopic composition of organic matter (δ¹³C_OM) and n‐alkanes (δ¹³C_n‐alk) that forms the basis of palaeovegetational reconstruction have also been measured to understand the effect of pedogenesis on organic matter in both of the profiles. The average δ¹³C_OM values in profile‐A and profile‐B are ?23·4‰ and ?21·1‰, respectively. The disparity in δ¹³C_OM values is a result of the difference in the sources and preservation of organic matter. However, the δ¹³C_n‐alk values show a similar trend in profile‐A and profile‐B, indicating that sources of n‐alkanes are the same in both of the profiles and δ¹³C_n‐alk values are unaffected by the pedogenic modifications.     

Lipid Biomarkers and Their Stable Carbon Isotopes inAncient Seep Carbonates from SW Taiwan,China

Four massive brecciated, chimney-like, and slender pipe network carbonate samples(JA-4, JA-5, JX-8 and BG-12) were collected from southwestern Taiwan, which were suggested to have formed as a result of anaerobic oxidization of methane(AOM). Considering that the environmental conditions of the carbonates precipitation and the sources of carbon and organic matter need to be further declared, molecular fossils and compound-specific carbon isotopic investigations of the carbonates were conducted in this study. According to lipid biomarkers of 2,6,10,15,19-pentamethyleicosane(PMI) and squalane diagnostic to methanotrophic archaea, as well as the extremely low δ¹³C values(as low as -1¹³.4‰) detected in samples JA-4, JA-5 and JX-8, these carbonates were revealed to be a result of AOM. Based on the varied δ¹³C values of characteristic archaea biomarkers in specific samples, biogenic methane was proposed to be responsible for the formation of samples JA-4 and JA-5, whereas a mixed carbon source of ¹³C-depleted methane and ¹³C-enriched residual CO_2 from methanogenesis was suggested for the carbonate of JX-8 due to the co-occurrence of a highly positive δ¹³ C_carb value(+8‰) and a moderate ¹³C depletion of PMI. The low content of AOM-related biomarkers and the absence of indicators for ANME-2 suggested that these carbonates were formed in weak seep settings. By comparison, no typical lipid biomarkers for methanotrophic archaea was detected in carbonate BG-12. The short-chain and long-chain n-alkanes accounted for 30% and 45% of all hydrocarbons, respectively, with a CPI value of 1.2, suggesting that the n-alkanes were derived from both marine organisms and terrestrial inputs. A low thermal maturity could be revealed by the incomplete equilibrium value of the C³¹αβ 22S/(22S+22R) ratio(0.5), and the carbonate BG-12 was probably deposited in a suboxic condition indicated by a value of Pr/Ph ratio(2.5).     

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.     

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.     

Geochemical Characteristics of the Upper Triassic Xujiahe Formation in Sichuan Basin, China and its Significance for Hydrocarbon Accumulation

The alternative development of coal-bearing hydrocarbon source rocks and low-porosity and low-permeability tight sandstone reservoirs of the Triassic Xujiahe Formation in the Sichuan Basin is favorable for near-source hydrocarbon accumulation. The natural gas composition of the Xujiahe Formation in the Sichuan Basin is dominated by hydrocarbon gases, of which the methane content is80.16%-98.67%. Typically, the C_2~+ content is larger than 5% in main wet gas. The dry gas is mainly distributed in the western and northern regions of the basin. The non-hydrocarbon gases mainly contain nitrogen, carbon dioxide, hydrogen, and helium, with a total content of 2%. The carbon isotope ranges of methane and its homologues in natural gas are: δ~(13)C_1 of-43.8‰ to-29.6‰, δ~(13)C_2 of-35.4‰ to-21.5‰, δ~(13)C_3 of-27.6‰ to-19.8‰,and δ~(13)C_4 of-27.7‰ to-18.8‰. δ~(13)C_3δ~(13)C_4 occurs in some natural gas with a low evolution degree; such gas is mainly coal-related gas from humic-type source rocks of the Xujiahe Formation. As for the natural gas, δ~2 H_(CH4) values ranged from-195‰ to-161‰,δ~2 H_(C2H6) values ranged from-154‰ to-120‰, and δ~2 H_(C3H8) values ranged from-151‰ to-108‰. The dry coefficient,δ~(13)C and δ~2 H_(CH4) are all positively correlated with the maturity of source rocks. The higher the maturity of source rocks is, the larger the natural gas dry coefficient is and the larger the δ~(13)C and δ~2 H_(CH_4) values are, indicative of the characteristic of near-source accumulation. The δ~2 H_(C2H6) value of natural gas is influenced by paleosalinity to a relatively large extent; the higher the paleosalinity is, the larger the δ~2 H_(C2H6) value is. The Pr/Ph value of the condensate oil ranged from 1.60 to 3.43, illustrating light oxidization-light reduction and partial-oxidization characteristics of the depositional environment of coal-bearing source rocks of the Xujiahe Formation. The natural gas light hydrocarbon(C_5-C_7) from the Xujiahe Formation presented two characteristics: the first was the relatively high aromatic hydrocarbon content(19%-32.1%), which reveals the characteristic of natural gas with humic substances of high-maturity; the second was the low content of aromatic hydrocarbon(0.4%-9.3%),reflecting water-washing during the accumulation of the natural gas. The reported research outcomes indicate a potential mechanism for natural gas accumulation in the Xujiahe Formation, which will further guide natural gas exploration in this region.     

Stable carbon and oxygen isotopic study of carbonate along a loess/paleosol section in Lantian County, Shaanxi Province, on the southeastern edge of the Chinese Loess Plateau

Studies of carbonate carbon isotope of loess/paleosol (δ¹³C_carb) in the Chinese Loess Plateau (CLP) have shown δ¹³C_carb less negative in loess and more negative in paleosol, which is opposite to that of bulk organic matter. Although some mechanisms have been proposed to explain this inconsistency, few studies have been conducted to investigate how carbonate migration could affect the reliability of utilizing δ¹³C_carb as an effective indicator. Here, a loess/paleosol profile with a nodule horizon intercalated in the loess layer, located on the southeastern edge of the CLP, was investigated to understand the influence of carbonate eluviation and reprecipitation on δ¹³C_carb along the section. The mean grain size and magnetic susceptibility generally conform to the field observed loess/paleosol stratigraphy. However, carbonate content shows distinct differences in the two sides of the nodule horizon, clearly indicating eluviation along the section. The variation of carbon and oxygen isotopic compositions of soil carbonate (δ¹³C_SC and δ¹⁸O_SC) and nodule carbonate (δ¹³C_NC and δ¹⁸O_NC) along the profile does not present a clearly meaningful picture. Generally, δ¹³C_SC and δ¹⁸O_SC have a similar change trend along the profile and are positively correlated, but there is no apparent relationship between δ¹³C_NC and δ¹⁸O_NC. More importantly, δ¹⁸O_NC values fall in the range of δ¹⁸O_SC, whereas δ¹³C_NC values are much more positive than δ¹³C_SC. Detailed analyses of the data indicate migration of carbonate along the profile, which is an important factor that determines that loess/paleosol δ¹³C_carb could not be employed as a high-resolution paleovegetational and paleoenvironmental indicator in the CLP, at least on or below the glacial/interglacial scales.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).