Multi‐proxy constraints on the significance of covariant δ13C values in carbonate and organic carbon during the early Mississippian

This study investigates the covariation between carbonate and organic δ¹³C values in a proximal to distal transect of four outcrops in the Madison Limestone in the Western United States Rockies, combined with δ³⁴S values of carbonate associated sulphate, the concentration of acid‐insoluble material and measurements of total organic carbon. These new geochemical datasets not only allow for an evaluation of carbon isotope covariance during one of the largest perturbations to the global carbon cycle over the past 550 Myr, but also constrain the cause of the excursion in carbonate δ¹³C values. The results support the hypothesis that a period of anoxia did not play a role in generating the positive carbonate δ¹³C values, but rather favour interpretations by previous workers that the proliferation of land plants destabilized the Carboniferous carbon cycle, setting the stage for a significant change in the carbonate δ¹³C values of contemporaneous marine carbonates. These results also demonstrate that one of the largest perturbations to the global carbon cycle did not produce synchronous variations in carbonate and organic δ¹³C values, emphasizing the importance of local depositional controls on carbon isotope covariance in the geological record in both modern and ancient environments.     

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.     

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.     

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.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Antarctic Ice‐Core Water (USGS49) – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ²H and δ¹⁸O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.     

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

Meteoric sphaerosiderite lines (MSLs), defined by invariant δ¹⁸O and variable δ¹³C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO₃ nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO₃) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca²⁺, Mg²⁺ and Mn²⁺ for Fe²⁺. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ¹⁸O and δ¹³C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ¹⁸O and δ¹³C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ¹⁸O vs. δ¹³C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ¹⁸O and δ¹³C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.     

Large variations of δ13C values in stalagmites from southeastern China during historical times: implications for anthropogenic deforestation

Variations in speleothem δ¹³C values can reflect changes in overlying surface vegetation, which, over historical time scales, may represent the influence of human activities. Here, we examined δ¹³C variations in two stalagmites growing for the last 2200 years in Shennong Cave, Jiangxi Province, SE China. The two δ¹³C records corroborate well one another and show a prominent 6‰ enrichment of the δ¹³C values from AD 700 to 1100. The isotopic equilibrium for modern calcite and negative correlation between δ¹⁸O and δ¹³C values along the growth axis suggest that the influences of kinetic fractionation are negligible. Varied correlations between Mg/Ca and Sr/Ca ratios and divergent changes between δ¹³C values and Mg/Ca and Sr/Ca ratios from AD 700 to 1100 reveal that the prior calcite precipitation (PCP) and water–rock interaction did not dominate the increase of δ¹³C values. It is plausible that the obvious δ¹³C variation was largely influenced by the changes in vegetation cover overlying the cave. Our δ¹³C results, together with the records of climate and human activity from historical documentary records, suggest that: (i) prior to AD 700, small fluctuations in relatively light δ¹³C values reflect the presence of lush forest coverage above the cave, which was minimally disturbed by human activities; (ii) during AD 700–1100, the drastic increase in δ¹³C values indicates persistent and massive deforestation associated with large‐scale immigration into northern Jiangxi after the Rebellion of An & Shi (AD 755–763) in the Tang Dynasty and the subsequent development of agriculture and economic activity; and (iii) since AD 1100, fluctuations in relatively high δ¹³C values suggest that local vegetation during the last millennium has been sparse. Since the Rebellion of An & Shi, southeastern China was progressively developed, coincident with deforestation and vegetation deterioration caused by human disturbance in the form of deforestation and cultivation.     

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.     

Assessment of δ13C and C/N ratios in bulk organic matter as palaeosalinity indicators in Holocene and Lateglacial isolation basin sediments,northwest Scotland

Carbon isotopes (δ¹³C) and C/N ratios from bulk organic matter have recently been used as alternative proxies for relative sea‐level (RSL) reconstruction where there are problems associated with conventional biological indictors. A previous study on a single isolation basin (Upper Loch nan Eala) in northwest Scotland has shown a clear relationship between δ¹³C, C/N ratios and palaeosalinity from Younger Dryas and Holocene aged sediments. In this paper we present results of δ¹³C and C/N ratio analyses from other isolation basins in northwest Scotland over the Holocene and the Lateglacial period in order to validate this technique. The results from the Holocene sequences support the earlier findings that this technique can be used to identify RSL change from isolation basins over the Holocene in this region. The relationship between δ¹³C, C/N ratios and RSL change is not apparent in sediments of Lateglacial age. Other environmental variables such as atmospheric CO₂ concentration, poor vegetation development and temperature influence δ¹³C values during this period. Copyright © 2007 John Wiley & Sons, Ltd.     

Holocene changes in precipitation seasonality in the western Mediterranean Basin: a multi‐species approach using δ13C of archaeobotanical remains

Precipitation has been of utmost importance in shaping the evolution of landscapes and human settlements in the Mediterranean. However, information on seasonal precipitation patterns through the Holocene is scarce. This study attempts to quantify the evolution of seasonal precipitation in the East Iberian Peninsula (5000 BC to AD 600) based on the carbon isotope composition (δ¹³C) of archaeobotanical remains. Data on Holm oak, Aleppo pine and small‐grain cereals were combined, and precipitation was inferred from models relating present‐day records to the δ¹³C of modern samples. Subsequently, charred grains were used as a proxy for ancient moisture during April–May, whereas oak and pine charcoals provided complementary rainfall estimates for September–December and January–August, respectively. The results reveal aridity changes throughout the Holocene in the western Mediterranean. Past spring–summer precipitation was consistently higher than at present. In contrast, autumn and early winter precipitation showed stronger fluctuations, particularly during the first millennium BC, and often exhibited values below those of the present. The high contribution of autumn precipitation to the annual water budget, typical of the present Mediterranean climate, was definitively established at the beginning of the current era. This study shows how a combination of species holding complementary environmental signals can contribute to a wider knowledge of local precipitation dynamics. Copyright © 2011 John Wiley & Sons, Ltd.     

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

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

δ98/95Mo values and Molybdenum Concentration Data for NIST SRM 610, 612 and 3134: Towards a Common Protocol for Reporting Mo Data

Molybdenum concentration and δ^98/95Mo values for NIST SRM 610 and 612 (solid glass), NIST SRM 3134 (lot 891307; liquid) and IAPSO seawater reference material are presented based on comparative measurements by MC‐ICP‐MS performed in laboratories at the Universities of Bern and Oxford. NIST SRM 3134 and NIST SRM 610 and 612 were found to have identical and homogeneous ⁹⁸Mo/⁹⁵Mo ratios at a test portion mass of 0.02 g. We suggest, therefore, that NIST SRM 3134 should be used as reference for the δ–Mo notation and to employ NIST SRM 610 or 612 as solid silicate secondary measurement standards, in the absence of an isotopically homogeneous solid geological reference material for Mo. The δ^98/95Mo_{JMC Bern} composition (Johnson Matthey ICP standard solution, lot 602332B as reference) of NIST SRM 3134 was 0.25 ± 0.09‰ (2s). Based on five new values, we determined more precisely the mean open ocean δ^98/95Mo_{SRM 3134} value of 2.09 ± 0.07‰, which equals the value of δ^98/95Mo_{JMC Bern} of 2.34 ± 0.07‰. We also refined the Mo concentration data for NIST SRM 610 to 412 ± 9 μg g^?1 (2s) and NIST SRM 612 to 6.4 ± 0.7 μg g^?1 by isotope dilution. We propose these concentration data as new working values, which allow for more accurate in situ Mo determination using laser ablation ICP‐MS or SIMS.     

Change of Organic δ13C in Ornithogenic Sediments of the Xisha Archipelago, South China Sea and its Implication for Ecological Development

Organic carbon isotopes in sediments have been frequently used to identify the source of organic matter.Here we present a study of organic δ~(13)C on two sediment profiles influenced by guano from Guangjin and Jinqing islands in the Xisha Archipelago,South China Sea.Organic matter from ornithogenic coral sand sediments has two main sources,guano pellets and plant residues,and their organic δ~(13)C(δ~(13)C_(OM)) are significantly different.Organic carbon δ~(13)C_(guano) is much higher thanδ~(13)C_(plants),and δ~(13)C_(OM)of bulk samples is intermediate.Based on a two-end-member mixing model,the proportions of guano-and plant-derived organic matter in the bulk samples were reconstructed quantitatively.The results showed that seabirds began to inhabit the islands around approximately1200-1400 AD,and that guano pellets have been an important source of soil organic matter since then.With the accumulation of guano-derived nutrients,plants began to develop prosperously on the islands in the last 200 years,which is reflected by the significant increase of plant-derived organic matter in the upper sediment layer.However,guano-derived organic matter decreased greatly in recent decades,indicating a rapid decrease in seabird population.Our results show that organic δ~(13)C can be effectively used to quantitatively determine different source contributions of OM to bulk ornithogenic coral sand sediments.