The anomalous Ca cycle in the Ediacaran ocean: Evidence from Ca isotopes preserved in carbonates in the Three Gorges area,South China

The Ediacaran–Cambrian was one of the most important periods for the evolution of life. Recent studies have provided detailed chemostratigraphies that decipher the linkages between ambient surface environmental changes and biological evolution. The occurrence of skeletal fossils in Ediacaran rocks suggests that the possible onset of Ca-biomineralization started in the latest Neoproterozoic. Molecular clocks also predict the emergence of animals containing Ca-carbonate spicules in the Neoproterozoic. Therefore, it is important to estimate the transition of the Ca cycle in seawater. Ancient Ca cycles in the oceans are estimated from the calcium isotopic compositions of carbonate rocks. However, the lack of continuous Ca isotopic data in the Ediacaran leaves the Ca cycle unresolved.The almost continuously exposed, Ediacaran and Cambrian strata in South China mainly comprise carbonate rocks with subordinate black shales and sandstones, which contain many fossils, suitable for the study of environmental and biological changes. We conducted drilling from the Liantuo, via the Nantuo, Doushantuo, Dengying and Yanjiahe to the Shuijingtuo formation at four sites in the Three Gorges area in order to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed ⁴⁴Ca/⁴²Ca ratios in carbonate rocks with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) screened for diagenetic alteration.The resultant δ^44/42Ca ratios exhibit a smooth curve. The values of δ^44/42Ca are anomalously high relative to those in the Phanerozoic, and they gradually decrease towards the end of the Ediacaran. Our new Ca isotope chemostratigraphy suggests that a different Ca cycle had existed during the Ediacaran. The long-term, high δ^44/42Ca is not simply explicable by changes in temperature, differences in carbonate mineralogy, or changes in the input/output fluxes of Ca to the ocean. We propose three possible explanations for the observed high δ^44/42Ca ratios in the Ediacaran: high δ^44/42Ca ratios of Ca inputs, potential undiscovered sinks of Ca with low δ^44/42Ca values, and negligible isotope fractionation between carbonate and seawater; we consider that one or all of these contributed to the high δ^44/42Ca ratios. Of these, we prefer the small isotope fractionation, which implies that the Ca concentration in seawater was initially low in the early Ediacaran and increased throughout that period.     

A 16-Ma record of paleodiet using carbon and oxygen isotopes in fossil teeth from Pakistan

The Siwalik Sequence of northern Pakistan contains a 16-Ma record of paleosol carbonate and fossil teeth from which a record of paleovegetation can potentially be reconstructed and compared. The carbon isotopic composition of paleosol carbonate and organic matter from Siwalik strata reflects a major paleoecological change on the floodplains of major rivers beginning7.3 Ma ago. By 6 Ma C₃-dominated plant communities, probably composed of mostly trees and shrubs, were displaced by nearly continuous C₄ grassland. We find that the carbon isotopic ratios in herbivore tooth enamel reflect this dramatic ecologic shift. Carbonate in enamel older than 7 Ma averages −11‰ in δ¹³C_PDB, consistent with a largely C₃ diet. Enamel from the Plio-PIeistocene averages +1.9‰ in δ¹³C, similar to the value displayed by modern C₄ grazers. Analysis of post-burial carbonate cements, and the concordance with isotopic evidence from paleosols argues strongly against major isotopic alteration of the enamel, while coexisting bone may have been altered early in burial. This study confirms that enamel apatite is useful for paleodietary reconstruction much further back in the geologic record than was previously thought.     

A pronounced negative δ13C excursion in an Ediacaran succession of western Yangtze Platform: A possible equivalent to the Shuram event and its implication for chemostratigraphic correlation in South China

A pronounced negative δ¹³C shift that can be potentially correlated with the Shuram excursion has been reported from middle Ediacaran strata in the Yangtze Gorges area of South China. Whether it represents a perturbation to the ocean carbon cycle or a record of post-depositional alteration is still open to debate. Resolving this controversy will help clarify if δ¹³C variations can be used for chemostratigraphic correlation of Ediacaran successions. To further understand the regional pattern of Ediacaran carbon isotopic excursions in the Yangtze platform, we carried out a detailed δ¹³C analysis of the Lianghong section in the western part of the Yangtze platform. The Ediacaran System at Lianghong is overlain by the Maidiping Formation yielding early Cambrian small shelly fossils and underlain by the Cryogenian Lieguliu Formation diamictite and tuffaceous siltstones. It comprises the Guanyinya and Hongchunping formations, which have been traditionally correlated with the Doushantuo and Dengying formations, respectively, in the Yangtze Gorges area. Two negative δ¹³C excursions occur in the Lianghong section. The lower one at the uppermost Guanyinya Formation, with a nadir at − 8.6‰, may be correlated with the pronounced negative δ¹³C shift (EN3) in the uppermost Doushantuo Formation in the Yangtze Gorges area and possibly with the well known Shuram event in Oman. The upper negative δ¹³C excursion occurs in the upper Hongchunping Formation and may be correlated with negative excursions (EN4) near the Ediacaran/Cambrian boundary. Other negative δ¹³C excursions (e.g., EN1 and EN2) are not expressed in the Lianghong section because the lower Guanyinya Formation is dominated by siliciclastic rocks. Combined with previously published Ediacaran δ¹³C profiles, our results indicate that the EN3 excursion (likely a Shuram equivalent) may occur widely in South China and can be a useful chemostratigraphic feature for regional and global stratigraphic correlation.     

Primary and diagenetic isotopic signals in fossils and hemipelagic carbonates: the Lower Jurassic of northern Spain

Stable isotope and trace element analyses of 230 Jurassic (Pliensbachian–Toarcian) samples from northern Spain have been performed to test the use of geochemical variations in fossils (belemnites and brachiopods) and whole‐rock hemipelagic carbonates as palaeoceanographic indicators. Although the succession analysed (Reinosa area, westernmost Basque–Cantabrian Basin) has been subject to severe thermal alteration during burial diagenesis, the samples appear to be well preserved. The degree of diagenetic alteration of the samples has been assessed through the application of integrated petrographic, chemical and cathodoluminescence analyses. It is demonstrated that brachiopods and whole‐rock carbonates, although widely used for palaeoceanic studies, do not retain their primary marine geochemical composition after burial diagenesis. In contrast, there is strong evidence that belemnite rostra preserve original isotopic values despite pervasive diagenesis of the host rock. Well‐preserved belemnite shells (non‐luminescent to slightly luminescent) typically show stable isotope values of +4·3‰ to –0·7‰δ¹³C, +0·7‰ to –3·2‰δ¹⁸O, and trace element contents of <32 μg g^–1 Mn, <250 μg g^–1 Fe, >950 μg g^–1 Sr and Sr/Mn ratios >80. This study suggests that the degree to which diagenesis has affected the preservation of an original isotopic composition may differ for different low‐Mg calcite fossil shells and hemipelagic bulk carbonates, behaviour that should be considered when marine isotopic signatures from other ancient carbonate rocks are investigated. Multiple non‐luminescent contemporaneous belemnite samples passed the petrographic and geochemical tests to be considered as palaeoceanic recorders, yet their δ¹³C and δ¹⁸O values exhibited moderate scatter. Such variability is likely to be related to the palaeoecological behaviour of belemnites and/or high‐frequency secular variations in sea‐water chemistry superimposed on the long‐term isotopic trend. A pronounced positive carbon‐isotope excursion (up to +4·3‰) is documented in the early Toarcian serpentinus biozone, which correlates with the Toarcian δ¹³C maximum reported in other European and Tethyan regions.     

Did an extensive forest ever develop on the Chinese Loess Plateau during the past 130 ka?: a test using soil carbon isotopic signatures

Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ¹³C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ¹³C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C₃ and C₄ plants and can be distinguished from that in the patchy forest areas where exclusive C₃ trees yield a narrow δ¹³C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ¹³C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C₃ and C₄ contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.     

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO₂ components—atmospheric CO₂ and CO₂ from in situ oxidation of organic matter. The δ¹³C values measured for the Fe(CO₃)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most ¹³C-rich Fe(CO₃)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO₂ components. δ¹³C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco₂ value of about 1 × PAL, but the scatter in the measured δ¹³C values of organic matter permits a calculated maximum Pco₂ of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO₃)OH in MCGoeth and SAP correspond to soil CO₂ concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO₂ concentrations are similar to modern soils in warm, wet environments.The average δ¹³C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ¹³C value for all profiles of −5.4‰. Thus, the value of Δ¹³C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco₂ and organic matter δ¹³C values were the same for both paleosol types. Furthermore, the atmospheric Pco₂ calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco₂ (permitted by one standard deviation of the organic matter δ¹³C value) of ∼5 × PAL.If, however, measured average δ¹³C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of ¹³C-depleted, labile organic compounds, calculated Permian atmospheric Pco₂ using these ¹³C-enriched organic values would underestimate the actual atmospheric Pco₂ using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO₂ concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO₂.The Fe(CO₃)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in ¹³C relative to Fe(CO₃)OH in goethites from soils in which there are mixtures of two isotopic CO₂ components. Field-relationships and the δ¹³C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO₂ components at the time of goethite crystallization. The three components were probably atmospheric CO₂, CO₂ from in situ oxidation of organic matter and CO₂ from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO₂ components, as recorded by Fe(CO₃)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco₂.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

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

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

Chemostratigraphy and detrital zircon geochronology of the Neoproterozoic Khorbusuonka Group,Olenek Uplift,Northeastern Siberian platform

This study provides ⁸⁷Sr/⁸⁶Sr, δ¹³C and δ¹⁸O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.70822 and δ¹³C values between + 4.8 and + 6.0‰. ⁸⁷Sr/⁸⁶Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ¹³C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (⁸⁷Sr/⁸⁶Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of ⁸⁷Sr/⁸⁶Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean.     

Paleoenvironmental reconstruction from chemical and isotopic compositions of Permo-Pennsylvanian pedogenic minerals

Mineralogical and chemical analysis of Late Pennsylvanian and Early Permian paleosols from the eastern shelf of the Midland basin, north-central Texas, USA, are used to test hypothesized climate change in Late Paleozoic western equatorial Pangea, previously defined independently on the bases of sedimentologic and paleontologic proxies and climate models. The <0.2-μm size phyllosilicate fraction in the studied paleosols exhibits down-profile trends in mineralogy and chemical composition that are consistent with modern weathering profiles suggesting a dominantly pedogenic origin. A stratigraphic trend from kaolinite-dominated profiles in Upper Pennsylvanian paleosols to profiles dominated by smectite and hydroxy-interlayered 2:1 phyllosilicates in Lower Permian paleosols indicates a relatively rapid decrease in soil weathering and leaching in the latest Pennsylvanian followed by a more gradual decrease in leaching throughout the Early Permian. The chemical composition (cation ratios and exchange capacity) of these phyllosilicates further corroborates this shift toward less intensive leaching, presumably in response to climate change from humid to progressively more arid conditions.The phyllosilicates in the <0.2-μm size fraction and contemporaneous pedogenic calcites from the Permo-Pennsylvanian paleosols exhibit a long-term stratigraphic increase in their δ¹⁸O values of as much as ∼3.2‰ and ∼5.2‰, respectively. This long-term trend is consistent with a transition throughout the latest Pennsylvanian through Early Permian toward progressively more evaporatively enriched soil waters. Superimposed on the long-term trend is an apparent rapid enrichment (1.5 to 2‰) in phyllosilicate δ¹⁸O values immediately above the Pennsylvanian-Permian boundary. Observed oxygen isotope fractionation between the phyllosilicates and calcites within individual paleosols indicate isotopic disequilibrium between mineral pairs. This is attributed to a minor detrital component in the pedogenic clay-dominated phyllosilicate fraction coupled with the effects of seasonality of mineral formation. Inferred δ¹⁸O compositions of Late Paleozoic meteoric water (−2‰ to +4‰) are compatible with less intensive soil leaching under conditions of increasing aridity, possibly coupled with a shift in local precipitation from a continental source to a marine source.     

Early Cretaceous atmospheric pCO2 levels recorded from pedogenic carbonates in China

Pedogenic carbonates were collected from Early Cretaceous strata in Sichuan and Liaoning, China. These paleosol carbonates and calcareous paleosols were evaluated in order to reconstruct atmospheric CO₂ concentrations during the Early Cretaceous using a paleosol barometer. Using the isotopic ratios of pedogenic carbonates from Early Cretaceous (early-middle Berriasian, early Valanginian) strata in Sichuan Basin, averaged atmospheric pCO₂ is estimated to have been 360 ppmv in the early-middle Berriasian and a mean value of 241 ppmv in the early Valanginian. In the late Barremian in western Liaoning, however the average was 530 ppmv, with a range of 365 ppmv and 644 ppmv, lower than previous estimates of pCO₂ for these time periods, consistent with the suggestion of overall climate cooling and paleotemperature fluctuation during the Early Cretaceous. This indicates that not all of the Cretaceous was a high or continuous CO₂ greenhouse, especially during Early Cretaceous.     

Seasonal variation of the stable isotopic compositions of coastal marine plankton from Woods Hole,Massachusetts and Georges Bank

A study of the isotopic composition of plankton from Woods Hole Harbor was conducted to investigate seasonal variation in carbon and nitrogen stable isotopes in a shallow coastal environment. Stable isotopic ratios of carbon and nitrogen both showed temporal variation on the scale of weeks to months, with heaviest (most positive) values in summer to fall for both isotopes. Particulate organic matter (POM) δ¹³C values were highest (?19‰ to ?21‰) in August to November and lower (?21‰ to ?25‰) at other times of the year, while δ¹³N-POM values were highest (9.5‰ to 12‰) in March to September and lower (7.5‰ to 9.5‰) at other times of the year. Stable isotopic values were significantly correlated with temperature, DI¹³C, and C∶N ratios, but not with [DIC], [POC], [PN], [chlorophyll], or the taxonomic composition of the phytoplankton. There was no direct evidence of allochthonous inputs of carbon and nitrogen to the system. Woods Hole δ¹³C values were virtually identical to Georges Bank plankton values; similar POC: Chlorophyll and C∶N ratios in the two systems further suggest that Woods Hole Harbor is principally a marine system. The high δ¹³C values of net plankton (>20 μm) during summer and early fall are consistent with a smaller degree of photosynthetic isotopic fractionation at that time, related to temperature and/or [CO_2(aq)]. This pattern was not seen, however, in total POM. Plankton δ¹³N values were higher in Woods Hole Harbor than on Georges Bank, especially during warmer periods, possibly due to high rates of nitrification and organic matter recycling in Woods Hole waters. Relatively wide ranges of stable isotopic values from both Woods Hole Harbor and Georges Bank suggest that seasonality should be considered when attempting to establish endmember C and N isotopic values for temperate marine plankton. Preliminary results from size-fractionated samples suggest that cyanobacteria may fractionate carbon isotopes to a greater degree than net phytoplankton.     

Contrast in the isotopic composition of oxygen and carbon between the Mud Tank Carbonatite and the marbles in the granulite terrane of the Strangways Range,central Australia

Three samples from the Mud Tank Carbonatite have very similar isotopic ratios, averaging δ¹³C=‐4.3 and δ¹⁸O=+7.5(SMOW). These isotope values are distinct from those of nearby highly metamorphosed Carpentarian marbles, which have marine limestone values of δ¹³C=‐1.3±0.5, and δ¹⁸O=+17.6+0.7 with n=11. Minor variations in the values for the normal marbles show no correlation with stratigraphy or geographic location; however, somewhat lighter oxygen is found in some other marbles known to be affected by low‐temperature fluids within the Woolanga Lineament. Isotopes of C and O, if discretely used in conjunction with other geochemical features, not only may discriminate between deep‐seated carbona‐tites and marbles, but may also help to identify zones of carbonate metasomatism and define the isotopic characters of the fluids.     

Stable isotopic studies on chitin. III. The D/H and 18O/16O ratios in arthropod chitin

Stable hydrogen and oxygen isotope ratios are presented for carbon-bound hydrogen and for oxygen in chitin-derived substrates from 57 arthropod species collected in 50 different locations or grown under controlled conditions in the laboratory. No systematic isotopic differences were found among Insecta, Crustacea, and Merostomata. The determination of infra- and interindividual isotopic variabilities in a lobster and among individuals of crustacean populations yielded small variances of about ±3 per mil for δD values and ±0.3 per mil for δ¹⁸O values. Molting stage and sex of crustaceans showed no systematic effects on isotopic composition. The δD and δ¹⁸O values of ambient water showed only weak correlations with the respective δ values of chitin-derived substrates. Positive correlation was observed between δD values and trophic level. No temperature effects on δ¹⁸O and δD values from marine crustaceans were found that exceed the natural isotopic noise level. Taken together, these observations indicate that reconstruction of water isotopic composition from arthropod chitin δD and δ¹⁸O values will require specific information about the habits and habitats of the species involved in the analysis.     

Sea-land oxygen isotopic relationships from planktonic foraminifera and speleothems in the Eastern Mediterranean region and their implication for paleorainfall during interglacial intervals

The oxygen and carbon stable isotope compositions of cave speleothems provide a powerful method for understanding continental climate change. Here, we examine the question of the regionality of this isotopic record and its linkage with the marine isotopic record in the Eastern Mediterranean (EM) region. The study presents a new, accurately dated 250-kyr δ¹⁸O and δ¹³C record determined from speleothems of the Peqiin Cave, Northern Israel. Its comparison with the continuous 185-kyr isotopic record of the Soreq Cave speleothems from Central Israel reveals striking similarities. Thus, a strong regional climatic signal, brought about by variations in temperature and rainfall amount, is reflected in both cave records. Low δ¹⁸O minima in the Peqiin profile for the last 250- to 185-kyr period (interglacial marine isotopic stage 7) match the timing of sapropels 9 to 7 and are indicative of high rainfall in the EM region at these times. The combined Soreq and Peqiin δ¹⁸O record for the last 250 kyr excellently matches the published Globigerinoides ruber (G. ruber) marine δ¹⁸O record for the EM Sea, with the isotopic compositional difference Δ_{G.ruber-speleothems} remaining relatively constant at −5.6 ± 0.7‰, thus establishing for the first time a robust, exploitable link between the land and the marine isotopic records. The correspondence of low δ¹⁸O speleothem values and high cave water stands with low G. ruber δ¹⁸O values during interglacial sapropel events indicates that these periods were characterized by enhanced rainfall in the EM land and sea regions. By use of sea surface temperatures derived from alkenone data as a proxy for land temperatures at the Soreq Cave, we calculate the paleorainfall δ¹⁸O values and its amounts. Maximum rainfall and lowest temperature conditions occurred at the beginning of the sapropel events and were followed by decrease in rainfall and increase in temperatures, leading to arid conditions. The record for the last 7000 yr shows a trend toward increasing aridity and agrees well with climatic and archeological data from North Africa and the Middle East.     

A first Holocene leaf wax isotope-based paleoclimate record from the semi-humid to semi-arid south-eastern Caucasian lowlands

The Holocene paleoclimate of the Caucasus region is rather complex and not yet well understood: while existing studies are mainly based on pollen records from high-altitude and humid lowland regions, no records are available from the semi-humid to semi-arid south-eastern Caucasian lowlands. Therefore, this study investigated compound-specific δ²H and δ¹³C isotopes of leaf wax biomarkers from Holocene floodplain soils in eastern Georgia. Our results show that the leaf wax δ²H signal from the paleosols mostly reflects changes in the moisture source and its isotopic composition. Depleted δ²H values before ~8 cal ka bp change towards enriched values after ~5 cal ka bp and become again depleted after ~1.6 cal ka bp. This trend could be caused by Holocene changes of the isotopic compositions of the Black and eastern Mediterranean Sea, and/or by varying contribution of both moisture sources linked with the North Atlantic Oscillation. The leaf wax δ¹³C signal from the paleosols directly indicates varying local water availability and drought stress. Depleted δ¹³C values before ~8 and after ~5 cal ka bp indicate wetter local conditions with higher water availability, whereas more enriched values during the middle Holocene (~8 until at least 5 cal ka bp ) indicate drier conditions with increased drought stress.     

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.     

Fingerprinting groundwater salinity sources in the Gulf Coast Aquifer System,USA

Understanding groundwater salinity sources in the Gulf Coast Aquifer System (GCAS) is a critical issue due to depletion of fresh groundwater and concerns for potential seawater intrusion. The study objective was to assess sources of groundwater salinity in the GCAS using ～1,400 chemical analyses and ～90 isotopic analyses along nine well transects in the Texas Gulf Coast, USA. Salinity increases from northeast (median total dissolved solids (TDS) 340 mg/L) to southwest (median TDS 1,160 mg/L), which inversely correlates with the precipitation distribution pattern (1,370– 600 mm/yr, respectively). Molar Cl/Br ratios (median 540–600), depleted δ²H and δ¹⁸O (?24.7‰, ?4.5‰) relative to seawater (Cl/Br ～655 and δ²H, δ¹⁸O 0‰, 0‰, respectively), and elevated ³⁶Cl/Cl ratios (～100), suggest precipitation enriched with marine aerosols as the dominant salinity source. Mass balance estimates suggest that marine aerosols could adequately explain salt loading over the large expanse of the GCAS. Evapotranspiration enrichment to the southwest is supported by elevated chloride concentrations in soil profiles and higher δ¹⁸O. Secondary salinity sources include dissolution of salt domes or upwelling brines from geopressured zones along growth faults, mainly near the coast in the northeast. The regional extent and large quantities of brackish water have the potential to support moderate-sized desalination plants in this location. These results have important implications for groundwater management, suggesting a current lack of regional seawater intrusion and a suitable source of relatively low TDS water for desalination.     

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.