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.     

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.     

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.     

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.     

Oxygen and carbon isotope and Sr/Ca signatures of high-latitude Permian to Jurassic calcite fossils from New Zealand and New Caledonia

Calcite fossils from New Zealand and New Caledonia provide insight into the Permian to Jurassic climatic history of Southern High Latitudes (southern HL) and Triassic Southern Intermediate Latitudes (southern IL). These results permit comparison with widely studied, coeval sections in Low Latitudes (LL) and IL. Oxygen isotope ratios of well-preserved shell materials indicate a partially pronounced Sea Surface Temperature (SST) gradient in the Permian, whereas for the Triassic no indication of cold climates in the southern HL is found. The Late Jurassic of New Zealand is characterized by a slight warming in the Oxfordian–Kimmeridgian and a subsequent cooling trend in the Tithonian. Systematic variations in the δ¹³C values of southern HL samples are in concert with those from LL sections and confirm the global nature of the carbon isotope signature and changes in the long-term carbon cycle reported earlier.Systematic changes of Sr/Ca ratios in Late Triassic brachiopods, falling from 1.19 mmol/mol in the Oretian (early Norian) to 0.67 mmol/mol in the Warepan (late Norian) and subsequently increasing to 1.10 mmol/mol in the Otapirian (~ Rhaetian), are observed. Also Sr/Ca ratios of Late Jurassic belemnite genera Belemnopsis and Hibolithes show synchronous changes in composition that may be attributed to secular variations in the seawater Sr/Ca ratio. For the two belemnite genera an increase from 1.17 mmol/mol in the Middle Heterian (~ Oxfordian) to 1.78 mmol/mol in the Mangaoran (~ late Middle Tithonian) and a subsequent decrease to 1.51 mmol/mol in the Waikatoan (~ Late Tithonian) is documented.     

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.     

Tectonic and eustatic control on a mixed siliciclastic–carbonate platform during the Late Oxfordian–Kimmeridgian (La Rochelle platform,western France)

Boreal and Tethyan realms of Western Europe present significant sedimentological, paleontological, and stratigraphic differences. The purpose of this study is to constrain regional versus global controls on the dynamics of a sedimentary system located at the interface of these two realms in order to better understand the origin of their differences. Detailed sedimentological, palynofacies and calcareous nannofossil analyses were performed on two sections from the La Rochelle platform (western France). The Pas section includes part of the Late Oxfordian and Early Kimmeridgian, and the Rocher d'Yves section is assigned to the Late Kimmeridgian. They correspond to monotonous marl–argillaceous limestone alternations. Limestones are essentially mudstones with echinoderms, bivalves and foraminifera that suggest low-energy, open-marine conditions. Highly bioclastic and/or peloidal deposits occur commonly, and show wackestones to wacke-pack-grainstones textures. These deposits indicate frequent high-energy events, and are interpreted as storm deposits. Marls dominate in the most proximal depositional environments, while calcareous deposits are more important in more distal environments. The Rocher d'Yves section is globally more marly than the Pas section, suggesting a more proximal setting. Palynofacies are dominated by woody particles, suggesting shallow-water, proximal depositional environments. Calcareous nannofossils are ascidian spicules, coccoliths, and schizospheres. Watznaueria britannica dominate calcareous nannofossil assemblages in the Pas section. The Rocher d'Yves assemblages are quasi-exclusively composed of Cyclagelosphaera margerelii, and indicate more proximal paleoenvironments than those of the Pas section. Different orders of depositional sequences are defined, with sequence boundaries corresponding to the most rapid relative sea-level falls. They are hierarchically stacked, and correlate, on the basis of ammonite zones, with the sequences of contemporaneous sections from Tethyan and boreal realms. The stacking pattern of these sequences suggests an orbital control on sedimentation. Small-, medium- and large-scale sequences correspond to precession (20 ky) cycles and to 100 ky and 400 ky eccentricity cycles, respectively. The elementary sequences have durations shorter than 20 ky. The Kimmeridgian was a period of global sea-level rise that ended in the Late Kimmeridgian. More proximal depositional environments in the Rocher d'Yves section (Late Kimmeridgian) than in the Pas section (Early Kimmeridgian) imply a progradation of the La Rochelle platform during the Kimmeridgian. This progradation resulted from a slowdown of the subsidence in the Aquitaine Basin during the Kimmeridgian, corresponding to the first steps of Atlantic Ocean opening. High-frequency cycles on the La Rochelle platform formed in sync with Milankovitch orbital cycles, while tectonics controlled the formation of the low-frequency cycles.     

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.     

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ³⁴S_CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation.Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ³⁴S_CAS values near Miocene seawater sulfate (～+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ¹³C_carb (～?11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ³⁴S_CAS (up to ～+37‰), CAS concentrations of ～600 ppm, mildly depleted δ¹³C_carb (～?6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ¹³C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing methanogenesis in a highly reducing environment. This study highlights the promise in combining CAS analysis with more traditional techniques to differentiate among diagenetic reactions as preserved in the geologic record and shows potential for unraveling subsurface biospheric processes in ancient samples with a high degree of specificity.     

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.     

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.     

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

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

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

Zircon U–Pb age and Hf isotopic compositions of Mesozoic granitoids in southern Qiangtang,Tibet: Implications for the subduction of the Bangong–Nujiang Tethyan Ocean

The southern Qiangtang magmatic belt was formed by the north-dipping subduction of the Bangong–Nujiang Tethyan Ocean during Mesozoic. To better understand the petrogenesis, time–space distribution along the length of this belt, 21 samples of several granitoid bodies, from west to east, in the Bangong Co, Gaize, Dongqiao and Amdo areas were selected for in-situ zircon U–Pb dating, Hf isotopic and whole-rock chemical analyses. The results suggest a prolonged period of magmatic activity (185–84 Ma) with two major stages during the Jurassic (185–150 Ma) and the Early Cretaceous (126–100 Ma). Both the Jurassic and Cretaceous granitoids are high-K calc-alkaline I-type rocks, except the Cretaceous two-mica granite from Amdo in the east, which belongs to S-type. The granitoids are generated from different source materials as indicated by zircon Hf isotopic compositions. The Bangong Co and Dongqiao granitoids show high zircon ε_Hf(t) values of − 1.3–13.6 with younger T_DM^C ages of 293–1263 Ma, suggesting a relatively juvenile source; whereas the Gaize and Amdo granitoids have low ε_Hf(t) values of − 16.1–2.9 with older T_DM^C ages of 999–2024 Ma, indicating an old crustal contribution. These source rocks melt at different P–T conditions as suggested by Sr/Y ratio and T_Zr. The Sr/Y ratio of both stage granitoids increases with decreasing age. However, the T_Zr of the Jurassic granitoids decreases, whereas the T_Zr of the Cretaceous granitoids increases with decreasing age. The contrasting geochemical signatures of these granitoids may be controlled by the varying contribution of slab-derived fluids involved in the generation of the Jurassic and Cretaceous granitic magmas; i.e. increasing amount of fluids in the Jurassic, whereas decreasing amount of fluids in the Cretaceous. Therefore, it is proposed that the Jurassic and Cretaceous magmatism may be related to subduction and closure of the Bangong–Nujiang Tethyan Ocean, respectively. The age pattern of the Jurassic and Cretaceous granitoids suggests an oblique subduction of the Bangong–Nujiang Tethyan Ocean and a diachronous collision between the Lhasa and Qiangtang blocks.     

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

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

Tracking the fate of dung-derived carbohydrates in a temperate grassland soil using compound-specific stable isotope analysis

Carbohydrates are major organic components of dung and are likely to contribute substantially to increased carbon stocks in manured soils. To investigate this hypothesis, a field-scale experiment was conducted on a temperate grassland site in Devon, UK. C₄ dung (bulk δ¹³C value ?12.6‰) was applied to a temperate grassland C₃ soil (bulk δ¹³C value ?30.3‰) in April and the surface soil beneath cow pats sampled at seven dates over a year. Total carbohydrates were extracted as their monosaccharide components and analysed as the alditol acetates using gas chromatography. The δ¹³C values of the major monosaccharides glucose (?11.5 ±0.6‰), xylose (?10.4 ±0.4‰), arabinose (?10.4 ±0.5‰) and galactose (?8.3 ±1.6‰) extracted from the C₄ dung via acid hydrolysis were indicative of their source. Their weighted mean δ¹³C value was ?10.8‰, 1.8‰ more ¹³C-enriched than the bulk dung value. The δ¹³C values of individual monosaccharides recovered by acid hydrolysis in the 0–1 cm and 1–5 cm soil horizons beneath C₄ cow pats, compared with control soils determined over 372 days, allowed assessment of the extent of incorporation and fluxes of dung-derived monosaccharides. A maximum of 60% of the dung C in soil was derived from carbohydrates after 56 days, declining to around 20% after 372 days. Incorporation dynamics varied between monosaccharide species. Glucose, xylose and arabinose behaved in a similar manner because of their predominantly plant cell wall derived provenance in the dung, whilst dung-derived galactose and mannose appeared to have a microbial source in the soil. The dynamics of total dung-derived monosaccharides in the top 5 cm was comparable to incorporation and flux of bulk dung C, previously estimated using bulk δ¹³C values. The movement of dung-derived carbohydrates into the soil was inequivalent between the 0–1 cm and 1–5 cm horizons. The lack of a significant difference in concentration, but the evidence for the persistence of dung-derived monosaccharides in soil based on δ¹³C values, indicated replacement of existing pools in the soil, suggesting that the ability of this particular soil to sequester further C derived from carbohydrates was limited.     

Quantifying pyrogenic carbon from thermosequences of wood and grass using hydrogen pyrolysis

Previously studied thermosequences of wood (chestnut) and grass (rice straw) biochar were subjected to hydrogen pyrolysis (hypy) to evaluate the efficacy of the technique for determining pyrogenic carbon (C_P) abundance. As expected, biochar from both wood and grass produced at higher temperature had higher C_P amount. However, the trend was not linear, but more sigmoidal. C_P/C_T ratio values (C_T = total organic carbon) for the wood thermosequence were ⩽0.03 at biochar production temperature (T_CHAR) ⩽ 300 °C. They increased dramatically until 600 °C and remained relatively constant and near unity at higher biochar production temperature. Grass biochar was similar in profile, but C_P/C_T values rose dramatically after 400 °C. The findings are consistent with the hypothesis that hypy residues contain polycyclic aromatic hydrocarbons (PAHs) with a degree of condensation above at least 7–14 fused rings, with labile organic matter and pyrogenic PAHs below this degree of condensation removed by hypy.Both wood and grass thermosequences displayed δ¹³C_P values that decreased with increased T_CHAR, indicating that recalcitrant carbon compounds (pyrogenic aromatic PAHs with a relatively high degree of condensation) were first formed from structural components with relatively high δ¹³C values (e.g. cellulose). Relatively constant δ¹³C values at T_CHAR ⩾ 500 °C suggested the dominant pyrolysis reaction was condensation of PAHs with no additional fractionation. Comparison of hypy with benzene polycarboxylic acid (BPCA), ‘ring current’ NMR and pyrolysis gas chromatography–mass spectrometry (GC–MS) results from the same suite of samples indicated a consistent overview of the structure of C_P, but provided unique and complimentary information.     

Chronostratigraphy of Campanian–Maastrichtian platform carbonates and rudist associations of Salento (Apulia,Italy)

Late Cretaceous platform carbonates from the Salento peninsula (south Italy) were studied by strontium-isotope stratigraphy to improve their chronostratigraphy. Forty-three samples from nine localities were collected and the numerical ages were derived from fifteen geochemically well-preserved samples of rudist shells that were analyzed for ⁸⁷Sr/⁸⁶Sr values. Strontium isotope stratigraphy yielded new ages for the base of the Ciolo Limestone. The oldest successions studied in Salento are 85.9 Ma (+/− 0.6) and assigned to the Melissano Limestone. The youngest Cretaceous limestones observed at the Ciolo Limestone type locality (Ciolo cove) are 66.4 Ma (+/− 1.5), and the base of this formation is older than 72.8 Ma (+/− 0.4). Karstic cavities observed at the Cava Cocumola in the mid-Campanian S. Cesarea Limestone are tentatively interpreted to be linked to an intra-Campanian event which is related to a sea-level lowstand inferred also on the island of Brač (Adriatic coast of Croatia) and in the Boreal realm at 75–77 Ma. A new large recumbent rudist similar to Sabinia and Pseudosabinia is observed in the Ciolo and S. Cesarea Limestone and appears to be characteristic of the Apulian platform carbonates. Rudist associations from the S. Cesarea Limestone and the overlying Ciolo Limestone are remarkably similar, although they range over a time interval of more than 12 Ma.     

Global climate perturbations during the Permo-Triassic mass extinctions recorded by continental tetrapods from South Africa

Several studies of the marine sedimentary record have documented the evolution of global climate during the Permo-Triassic mass extinction. By contrast, the continental records have been less exploited due to the scarcity of continuous sections from the latest Permian into the Early Triassic. The South African Karoo Basin exposes one of the most continuous geological successions of this time interval, thus offering the possibility to reconstruct climate variations in southern Laurasia from the Middle Permian to Middle Triassic interval. Both air temperature and humidity variations were estimated using stable oxygen (δ¹⁸O_p) and carbon (δ¹³C_c) isotope compositions of vertebrate apatite. Significant fluctuations in both δ¹⁸O_p and δ¹³C_c values mimic those of marine records and suggest that stable isotope compositions recorded in vertebrate apatite reflect global climate evolution. In terms of air temperature, oxygen isotopes show an abrupt increase of about + 8 °C toward the end of the Wuchiapingian. This occurred during a slight cooling trend from the Capitanian to the Permo-Triassic boundary (PTB). At the end of the Permian, an intense and fast warming of + 16 °C occurred and kept increasing during the Olenekian. These thermal fluctuations may be related to the Emeishan (South China) and Siberian volcanic paroxysms that took place at the end of the Capitanian and at the end of the Permian, respectively. Vertebrate apatite δ¹³C_c partly reflects the important fluctuations of the atmospheric δ¹³C values, the differences with marine curves being likely due to the evolution of local humidity. Both the oxygen and carbon isotope compositions indicate that the PTB was followed by a warm and arid phase that lasted 6 Ma before temperatures decreased, during the Late Anisian, toward that of the end-Permian. Environmental fluctuations occurring around the PTB that affected both continental and marine realms with similar magnitude likely originated from volcanism and methane release.     

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

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