Early Silurian positive δ13C excursions and their relationship to glaciations,sea‐level changes and extinction events

Evidence is presented from the upper Aeronian, lower Sheinwoodian and middle Homerian demonstrating that positive δ¹³C excursions in the lower Silurian are the result of increased carbonate weathering and probably also enhanced burial of organic carbon coincident with sea‐level falls resulting from growth of ice sheets on the South American part of Gondwana. Graptolite extinctions are coincident with the δ¹³C excursions, whereas major conodont extinction events (Ireviken and Mulde) are not, but conversely, occur at times of high sea level. This suggests very different controls on graptolite and conodont global diversity patterns. Palynological studies suggest that netromorph acritarchs may have been opportunists that flourished during positive δ¹³C excursion intervals. Copyright © 2007 John Wiley & Sons, Ltd.     

Foraminiferal and δ13C isotopic event‐stratigraphy across the Danian–Selandian transition at Zumaya (northern Spain): chronostratigraphic implications

The Zumaya section, northern Spain, is a suitable candidate to define the Global Stratotype Section and Point for the base of the Selandian Stage (Palaeocene) because of its excellent accessibility, exposure and stratigraphic continuity. Uncertainties exist, however, with regard to the stratigraphic horizon where to place the Danian/Selandian (D/S) boundary. Five potential stratigraphic horizons (HDS1 to HDS5) to define the D/S boundary have been identified at Zumaya, based on integrated stratigraphic studies that include quantitative planktic and benthic foraminiferal results, as well as δ¹³C isotopic and lithological data. Two of these horizons (HDS2 and HDS4) placed in Zone C26r appear to have particularly good potential for serving as the D/S boundary marker, because they may represent significant global palaeoceanographic, palaeoclimatic and eustatic events.     

50 Myr recovery from the largest negative δ13C excursion in the Ediacaran ocean

Sedimentary rocks deposited during the Ediacaran period (～630–542 Ma) contain carbonates whose carbon isotopic ratios show a marked negative excursion consisting of a precipitous drop from +5‰ to ?12‰, followed by a sub‐linear recovery to positive δ¹³C values. Isotopic ages (U/Pb) and thermal subsidence modelling are combined to constrain the excursion in time and indicate an onset at ～600 Ma, and duration of recovery of approximately 50 Myr. The excursion is widely recognized in Oman and has potential correlatives in Ediacaran strata elsewhere, and may thus represent a characteristic feature of the Ediacaran period. The amplitude of this carbon isotope excursion far exceeds those of other Neoproterozoic anomalies. The isotopic trend of negative excursion and long‐term recovery spanned at least one short‐lived glacial episode (at 580 Ma), but appears unrelated to glaciation, which indicates that negative anomalies in the Neoproterozoic marine carbon isotope record are not directly or uniquely linked to ice ages.     

Late Holocene stable isotopic (δ13C and δ15N) records of lacustrine organic matter in Guangdong Province,south China,and their palaeoenvironmental implications

This study presents the results of TOC/TN (C/N) ratio, δ¹³C and δ¹⁵N analyses of lake sedimentary organic matter (OM) from the Hedong section, western Guangdong Province in south China, with the objective to reveal the history of hydrological and ecological variations in the region influenced by both the Indian summer monsoon (ISM) and East Asian summer monsoon (EASM). Variations in δ¹³C and δ¹⁵N of sedimentary OM may be closely related to past climatic conditions, which results in variations in surface runoff, lake level, allochthonous and autochthonous sources of OM, and lake productivity. Based on the interpretation of these proxies, four periods, i.e. 4370–4100, 3700–2900, 2400–2100 and 1900–900 cal. a BP, are characterized by low lake level, weakened surface runoff and deteriorated status of terrestrial and aquatic ecosystems, whereas the periods 4100–3700, 2900–2400, 2100–1900 and 900–600 cal. a BP are dominated by high lake level, strengthened surface runoff, and flourishing terrestrial and aquatic plants. A remarkable positive correlation between the δ¹³C values of the section and the ENSO number record obtained from the tropical Pacific implies that the impact of the ISM is greater than that of the EASM in the study area. The abnormal correspondence between the δ¹³C and solar activity reconstructed from ¹⁰Be and ¹⁴C records in GRIP ice‐core occurred from 1500–800 and particularly from 4200–4000 cal. a BP, suggesting that these two cool and dry intervals may be caused by stronger volcanic activities that are recorded in the GISP2 and Dome C ice‐cores. This study reveals that changes in solar insolation and solar activity, as well as changes in oceanic–atmospheric circulation (e.g. the ENSO intensity) and intensive volcano eruptions may have exerted influence on late Holocene climate variability in the study area.     

The complex diagenetic history of discontinuities in shallow‐marine carbonate rocks: New insights from high‐resolution ion microprobe investigation of δ18O and δ13C of early cements

Sedimentary gaps are a major obstacle in the reconstruction of a carbonate platform's history. In order to improve the understanding of the early diagenesis and the succession of events occurring during the formation of discontinuity surfaces in limestones, secondary ion mass spectrometry was used for the first time to measure the δ ¹⁸O and δ ¹³C signatures of 11 early cement and fabric stages in several discontinuity surfaces from the Jurassic carbonate platform of the Paris Basin, France. Pendant cements show a high variability in δ ¹⁸O, which was impossible to detect by the less precise microdrilling method. The morphology of a given cement can be produced in various environments, and dogtooth cements especially can precipitate in marine phreatic and meteoric phreatic to vadose environments. Marine dogtooth cements and micritic microbially induced fabrics precipitated directly as low‐magnesium calcite in marine waters, as attested to by the preservation of their initial δ ¹⁸O and δ ¹³C signals. Five discontinuity types are recognized based on high‐resolution geochemical analyses, and their palaeoenvironmental history can be reconstructed. Two exposure surfaces with non‐ferroan pendant or meniscus cements formed in the oxidizing vadose zone. A hardground displays marine fibrous cements and non‐ferroan dogtooth cements that formed in a subtidal environment in oxidizing water. Two composite surfaces have undergone both marine and subaerial lithification. Composite surface 1 displays non‐luminescent ferroan dogtooth cements that precipitated in reduced conditions in seawater, followed by brown‐luminescent dogtooth cements characteristic of a meteoric phreatic environment. Composite surface 2 exhibits microbially induced fabrics that formed in marine water with abundant organic matter. The latter discontinuity, initially formed in a subtidal environment, was subsequently exposed to meteoric conditions, as evidenced by ferroan geopetal cements. A high‐resolution ion microprobe study is essential to precisely document the successive diagenetic environments that have affected carbonate rocks and discontinuities with a polygenic and intricate history.     

The Paleoceanography during the Time with High δ13C of Phanerozoic marine carbonates

Carbon isotopic composition of marine carbonates is a record for various important geological events in the process of earth development and evolution. The carbonates of Carboniferous, Permian and Triassic, as the transition from Paleozoic to Mesozoic-Cenozoic have very high ¹³C value. Taking this as the main point, and combined with the oxygen, strontium isotopic composition in carbonates, distribution of carbonate basin area through geologic time, the correlation of carbon isotopic composition of marine carbonates to sea level change, organic carbon burial flux, exchange of CO₂ content in atmosphere and ocean, and long cycle evolution of the earth ecosystems were approached. The results are shown as follows: ①The interval of ¹³C >3‰ during Phanerozoic was concentrated in Carboniferous, Permian and the beginning of Triassic, but the beginning of Triassic was characterized by higher frequency and larger fluctuations in ¹³C value during a short time, whereas the Carboniferous-Permian presented a continuously stable high ¹³C value, indicating a larger amount of organic carbon accumulation in this time interval. Relatively high ¹⁸O values during this time was also observed, showing a long time of glaciations and cold climate, which suggest a connection among rapid organic carbon burial, cold climate, as well as pCO₂ and pO₂ states of atmosphere. ②The over consumption of atmosphere CO₂ by green plants during the time with high ¹³C of seawater forced CO₂ being transferred from ocean to atmosphere for the balance, but the decrease in the seawater amount and water column pressure caused by the global cooling could weaken dissolution capacity of CO₂ in seawater and carbon storage of marine carbonates, and also reduce the carbonate sedimentary rate and decrease the carbonate basin area globally from Devonian to Carboniferous and Permian. During the middle-late Permian carbonate was widely replaced by siliceous sediments even though in shallow carbonate platform, which resulted in the decrease of marine invertebrates, suggesting the Permian chert event should be global. ③The Phanerozoic ⁸⁷Sr/⁸⁶Sr trend of seawater showed a sharp fall in Permian and drop to a minimum at the end of the Permian, indicting input of strontium from the submarine hydrothermal systems (mantle flux). Such process should accompany with a supplement of CO₂ from deep earth to atmosphere and ocean system, but the process associated with widespread volcanism and rises of earth’s surface temperature pricked up the mass extinction during the time of end Permian. ④Cold climate and increase of continental icecap volume, the amalgamation of northern Africa and Laurentia continentals were the main reasons responsible for the sea level drop, but the water consumption result from the significantly increased accumulation of organic carbon should also be one of the reasons for the sea level drop on the order of tens of meters. ⑤The mass extinction at the end Permian was an inevitable event in the process of earth system adjustment. It was difficult for marine invertebrates to survive because of the continuously rapid burial of organic carbon, and of the decrease of sea water amount and its dissolution ability to CO₂. At last, at the end of Paleozoic, the supplement of CO₂ to atmosphere and ocean by widely magma activities resulted in a high temperature of earth surface and intensified mass extinction.     

Influence of landscape evolution on the distribution of floristic patterns in northern Amazonia revealed by δ13C data

The Amazonian lowlands include large patches of open vegetation which contrast sharply with the rainforest, and the origin of these patches has been debated. This study focuses on a large area of open vegetation in northern Brazil, where δ¹³C and, in some instances, C/N analyses of the organic matter preserved in late Quaternary sediments were used to achieve floristic reconstructions over time. The main goal was to determine when the modern open vegetation started to develop in this area. The variability in δ¹³C data derived from nine cores ranges from ?32.2 to ?19.6‰, but with nearly 60% of data above ?26.5‰. The most enriched values were detected only in ecotone and open vegetated areas. The development of open vegetation communities was asynchronous, varying between estimated ages of 6400 and 3000 cal a BP. This suggests that the origin of the studied patches of open vegetation might be linked to sedimentary dynamics of a late Quaternary megafan system. As sedimentation ended, this vegetation type became established over the megafan surface. In addition, the data presented here show that the presence of C₄ plants must be used carefully as a proxy to interpret dry paleoclimatic episodes in Amazonian areas. Copyright © 2012 John Wiley & Sons, Ltd.     

Estimating past leaf-to-air vapour pressure deficit from terrestrial plant δ13C

δ¹³C was determined in lignin extracted from present-day cladodes of Phyllocladus alpinus (a small coniferous tree) from seven well-lit sites across New Zealand. The δ¹³C values ranged from −30.9‰ to −23.6‰ and were compared with monthly means of temperature, precipitation, relative humidity and vapour pressure deficit from the nearest recording stations. Of these parameters, the leaf-to-air vapour pressure deficit of the first month of cladode growth and expansion proved to be the most significantly correlated with lignin δ¹³C, over a range of 0.3 to 0.8 kPa, confirming the importance of atmospheric moisture content on stomatal conductance. The carbon isotopic signature of lignin from fossilised cladodes preserved under the Kawakawa Tephra (22.6 k ¹⁴C yr BP) on the North Island is identical to that of the whole tissue, suggesting that for this species at least, fossil material can be used to approximate the lignin δ¹³C. The δ¹³C of species- and organ-specific fossil terrestrial plant material therefore provides an excellent method to quantify past changes in leaf-to-air vapour pressure deficit. Copyright © 1999 John Wiley & Sons, Ltd.     

Elemental δ13C at Allen's Cave,Nullarbor Plain,Australia: assessing post‐depositional disturbance and reconstructing past environments

The degree to which post‐depositional disturbance can be assessed in archaeological sequences is critical for the development of robust chronologies for such deposits. A common approach is the identification of conjoined artefacts distributed through the sequence as a measure of disturbance following deposition, although this method is relatively labour intensive and does not provide a continuous record of disturbance through the entire sequence. Here we present δ¹³C values for different size fractions (<125 and >125 µm) of chemically resistant charcoal distributed through a sedimentary profile at Allen's Cave, South Australia. The curves generated from both size fractions parallel one another, indicating minimal disturbance through the entire profile and providing greater confidence in the luminescence and radiocarbon chronologies reported previously for the site. In addition, the elemental δ¹³C values provide an indication of greater aridity (compared with present) persisting in this area from ca. 45 to 12 ka, consistent with other proxy records. The onset of the Holocene is marked by a shift to wetter conditions, probably as a result of post‐glacial marine transgression and closer proximity to the coastline. Copyright © 2001 John Wiley & Sons, Ltd.     

Possible reasons for the δ13C anomaly of Lower Proterozoic sedimentary carbonates

Detailed isotopic study (δ¹³C, δ¹⁸O) of Lower Proterozoic sedimentary carbonates from biostratigraphically dated successions in Karelia (Russia) revealed a large positive δ¹³C anomaly (average δ¹³C-value constitutes approximately +10‰ PDB) at 2.3 Byr ago and a huge drop of δ¹³C-values in the subsequent ‘black shale period’(2.2 Byr ago). These data are interpreted to be a result of large-scale changes in the oxygen content of the atmosphere. According to this model the positive carbon isotopic anomaly of sedimentary carbonates at about 2.3 Byr ago reflects a very high O₂-content of the atmosphere at this time; the subsequent drop in δ¹³C-values equates with a sharp decrease of the O₂-content of the atmosphere.     

δ18O and δ13C in fossil shells of Radix sp. from the sediment succession of a dammed palaeo‐lake in the Yarlung Tsangpo valley,Tibet, China

A series of confirmed and suspected dammed palaeo‐lake sedimentary successions is scattered within the middle Yarlung Tsangpo valley in Tibet. However, the chronology, the genesis of the dam and its location, the water level of the dammed lake, the process of dam failure and the spatiotemporal relationships between the sedimentary successions remain controversial. Here, we focus on one sedimentary succession of the suspected dammed palaeo‐lake at Xigazê. We measured the grain‐size distribution, magnetic susceptibility, organic and inorganic carbon content, and δ¹³C_org and δ¹⁵N_total ratios of the sediments. In addition, we measured the δ¹⁸O_shell and δ¹³C_shell values of modern and fossil Radix sp. shells, and the δ¹⁸O_water and δ¹³C_DIC values of the ambient water with different hydrological regimes. The results indicate that the δ¹⁸O_shell values of modern Radix sp. and the δ¹⁸O_water of the ambient water body significantly depend on its hydrological status. In addition, a strong positive relationship was observed between δ¹⁸O_shell values of modern Radix sp. shells and the δ¹⁸O_water of the ambient water on the Tibetan Plateau. According to this correlation, the δ¹⁸O_water values of the palaeo‐water body are reconstructed using the δ¹⁸O_shell values of Radix sp. fossil shells in the Xigazê section. Further, based on the δ¹⁸O_shell values of fossil Radix sp., the reconstructed δ¹⁸O_water of the palaeo‐water body and the specific habitats of Radix sp., we infer that the sedimentary succession in the Xigazê broad valley was mainly formed within the backwater terminal zone of a dammed palaeo‐lake and that the elevation of the water level of the lake was approximately 3811 m a.s.l. AMS ¹⁴C dating indicates that the deposits of the dammed palaeo‐lake were formed at about 33–22 cal. ka BP. Finally, the presence of Radix sp. fossil shells within the Xigazê section suggests that Radix sp. survived the late Last Glacial Period on the Tibetan Plateau.     

SIMS Bias on Isotope Ratios in Ca‐Mg‐Fe Carbonates (Part III): δ18O and δ13C Matrix Effects Along the Magnesite–Siderite Solid‐Solution Series

This study explores the effects of cation composition on mass bias (i.e., the matrix effect), which is a major component of instrumental mass fractionation (IMF) in the microanalyses of δ¹³C and δ¹⁸O by SIMS in carbonates of the magnesite–siderite solid‐solution series (MgCO₃–FeCO₃). A suite of twelve calibration reference materials (RMs) was developed and documented (calibrated range: Fe# = 0.002–0.997, where Fe# = molar Fe/[Mg + Fe]), along with empirical expressions for regressing calibration data (affording residuals < 0.5‰ relative to certified reference material NIST‐19). The calibration curves of both isotope systems are non‐linear and have, over a 2‐year period, fallen into one of two distinct but largely self‐consistent shape categories (data from ten measurement sessions), despite adherence to well‐established analytical protocols for carbonate δ¹³C and δ¹⁸O analyses at WiscSIMS (CAMECA IMS 1280). Mass bias was consistently most sensitive to changes in composition near the magnesite end‐member (Fe# 0–0.2), deviating by up to 4.5‰ (δ¹³C) and 14‰ (δ¹⁸O) with increasing Fe content. The cause of variability in calibration curve shapes is not well understood at present and demonstrates the importance of having available a sufficient number of well‐characterised RMs so that potential complexities of curvature can be adequately delineated and accounted for on a session‐by‐session basis.     

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.     

Lower Triassic δC isotope curve from shallow-marine carbonates in Japan, Panthalassa realm: Confirmation of the Tethys δC curve

δ¹³C data from Tethyan sections provide evidence of profound changes in the carbon cycle during the Lower Triassic. Sections from the Panthalassa realm were investigated to establish whether these variations are also present there. In the Jurassic accretionary wedges in Japan, exotic blocks having a Panthalassan affinity, have been incorporated. The majority of the blocks are pelagic cherts but rare shallow-water carbonates are also present. We present a δ¹³C study on the Lower Triassic of a shallow-water carbonate succession deposited on a mid-oceanic seamount and accreted to the Chichibu Belt, Japan. Two sections have been measured at Kamura, central Kyushu Island. The carbon isotope curve shows depleted values across the Permian–Triassic boundary (PTB), subsequently followed by an increase to heavier values into the Dienerian, culminating in a maximum of almost +4‰ V-PDB, before a steep drop at a stratigraphic gap. Low values are recorded in the Smithian, but rise to enriched δ¹³C values > +3.5‰ near the Smithian–Spathian boundary. The observed trend of the stable carbon isotope curve from Japanese sediments mirrors the curves derived from sections in the Tethys (e.g. Italy, Iran, Turkey, Oman and the South China Nanpanjing Basin). Our results support the interpretation of this curve as representing a global trend across the PTB and in the Lower Triassic, although some distinct features are absent around the Dienerian/Smithian boundary. Profound variations of the carbon isotope curve in the Lower Triassic are presented for the first time from a marine section outside of the Tethys. They indicate severe, global changes in the Lower Triassic carbon cycle, and the causative processes must have significantly contributed to the delayed biotic recovery after the PTB. Large amounts of carbon were shifted between carbon reservoirs, most probably between shallow- and deep-ocean waters, and/or ocean and sediment. Anoxia followed by overturn of the ocean water masses may have been the mechanism which quickly altered ecological conditions in the ocean leading to variable availability of nutrients and oxygen, and changes in isotope composition of the available carbon in the surface waters that was incorporated in the precipitated carbonate.     

δ13C signature of early graphite and subsequently formed microdiamond from the Saxonian Erzgebirge,Germany

Microdiamond and graphite occur in quartzofeldspathic rocks (saidenbachites) of the central Erzgebirge in Saxony. Zircon from such rocks contains not only relatively high but also variable amounts of early formed graphite and later crystallized diamond, however no carbonate. Six purified zircon concentrates were analysed by mass spectrometry for δ₁₃C(PDB) values which were between −24 and −33‰. The carbon inclusions resulted in C contents of the concentrates as high as 0.5 wt%. It is hypothesized that the observed δ₁₃C signature results from organic material in the sedimentary protoliths of the saidenbachites probably deposited not earlier than Mid‐Devonian. This material was transformed to graphite during early metamorphism and subsequently to diamond after an anatectic event at great depths (>150 km). During these processes, the δ₁₃C signature of the carbon did not (significantly) change.