An alternative model for positive shifts in shallow-marine carbonate δ13C and δ18O

Abstract Positive shifts in global seawater δ¹³C_DIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ¹⁸O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ¹³C and δ¹⁸O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and ¹³C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate ¹³C and ¹⁸O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.     

Evaluation of bulk carbonate δ13C data from Triassic hemipelagites and the initial composition of carbonate mud

Bulk carbonate samples of hemipelagic limestone–marl alternations from the Middle and Upper Triassic of Italy are analysed for their isotopic compositions. Middle Triassic samples are representative of the Livinallongo Formation of the Dolomites, while Upper Triassic hemipelagites were sampled in the Pignola 2 section, within the Calcari con Selce Formation of the Southern Apennines in Southern Italy. Triassic hemipelagites occur either as nodular limestones with chert nodules or as plane‐bedded limestone–marl alternations which are locally silicified. In the Middle Triassic Livinallongo Formation, diagenetic alteration primarily affected the stable isotopic composition of sediment surrounding carbonate nodules, whereas the latter show almost pristine compositions. Diagenesis lowered the carbon and oxygen isotope values of bulk carbonate and introduced a strong correlation between δ¹³C and δ¹⁸O values. In the Middle Triassic successions of the Dolomites, bulk carbonate of nodular limestone facies is most commonly unaltered, whereas carbonate of the plane‐bedded facies is uniformly affected by diagenetic alteration. In contrast to carbonate nodules, plane‐bedded facies often show compaction features. Although both types of pelagic carbonate rocks show very similar petrographic characteristics, scanning electron microscopy studies reveal that nodular limestone consists of micrite (< 5 μm in diameter), whereas samples of the plane‐bedded facies are composed of calcite crystals ca 10 μm in size showing pitted, polished surfaces. These observations suggest that nodular and plane‐bedded facies underwent different diagenetic pathways determined by the prevailing mineralogy of the precursor sediment, i.e. probably high‐Mg calcite in the nodular facies and aragonite in the case of the plane‐bedded facies. Similar to Middle Triassic nodular facies, Upper Triassic nodular limestones of the Lagonegro Basin are also characterized by uncorrelated δ¹³C and δ¹⁸O values and exhibit small, less than 5 μm size, crystals. The alternation of calcitic and aragonitic precursors in the Middle Triassic of the Dolomites is thought to mirror rapid changes in the type of carbonate production of adjacent platforms. Bioturbation and dissolution of metastable carbonate grains played a key role during early lithification of nodular limestone beds, whereby early stabilization recorded the carbon isotopic composition of sea water. The bulk carbonate δ¹³C values of Middle and Upper Triassic hemipelagites from Italy agree with those of Tethyan low‐Mg calcite shells of articulate brachiopods, confirming that Triassic hemipelagites retained the primary carbon isotopic composition of the bottom sea water. A trend of increasing δ¹³C from the Late Anisian to the Early Carnian, partly seen in the data set presented here, is also recognized in successions from tropical palaeolatitudes elsewhere. The carbon isotopic composition of Middle and Upper Triassic nodular hemipelagic limestones can thus be used for chemostratigraphic correlation and palaeoenvironmental studies.     

The origin of magnesite deposits from the Polish Foresudetic Block ophiolites: preliminary δ13C and δ18O investigations

Twenty-three magnesite samples from vein deposits, found in ultramafic rocks related to ophiolites in the north-east Bohemian Massif, have been examined for carbon and oxygen isotope ratios. In these rocks two stages of antigorite serpentinization took place prior to magnesite precipitation. δ¹⁸O_SMOW in magnesites ranges from 24.5 to 27.9%o (corrected for acid fractionation factor) which leads us to conclude a meteoric origin of the ore-forming solution. This inference is further supported by δ¹³C values (?18.7 to ?4.4%o) which point to a biogenic origin of carbon in the magnesites.     

Effect of sample pretreatment and size fraction on the δ18O and δ13C values of foraminifera in Arabian Sea sediments

Stable oxygen and carbon isotope ratios (δ¹⁸O and δ¹³C, respectively) of a planktonic foraminiferal species (Globigerinoides sacculifer) and marble carbonate were measured with and without a variety of pretreatments like ultrasonication, soaking in H₂O₂, methanol and roasting under vacuum. Additionally, organic matter - carbonate mixtures were also analysed with and without the above pretreatments. No significant difference was found in the isotope ratios of treated and untreated samples. It appears that most of the pretreatments may not be necessary when dealing with planktonic foraminifera, especially G. sacculifer. Analysis of two different size fractions (> 400 μm and 250–400 μm) of this species reveals that the smaller size fraction is enriched in ¹⁸O and depleted in ¹³C relative to the bigger size fraction. It is therefore necessary to choose a proper size fraction for isotopic analyses.     

Determination of Total Organic Carbon Content and δ13C in Carbonate-Rich Detrital Sediments

The determination of total organic carbon content and composition in detrital sediments requires careful removal of their carbonate minerals. In detrital sediments containing large amounts of carbonates, including dolomite, this can only be achieved by liquid acid leaching that may solubilise a significant proportion of the organic carbon. For a set of detrital sediments from the Himalayan system and the Amazon River as well as five geological reference materials, we determined the proportion of organic carbon (C_org) solubilised during acid leaching. This proportion is significant for all analysed sediments and generally tends to increase with the organic carbon content. Compared to other types of sediments analysed, clay fractions extracted from river sediments and bed sediments with very low organic carbon content have high and low proportions of acid soluble C_org respectively. In Himalayan and Amazon river sediments, the proportion of C_org solubilised during acid leaching was relatively constant with average values of 14 and 19 % respectively. Thus, it is possible to correct the C_org content for the dissolved organic carbon content measured after decarbonation. Data presented here show that C_org dissolved during liquid acid leaching must be taken into account. After careful calibration, the method presented here should, therefore, be applied to any carbonate-rich detrital sediment.     

Long-term (105) or short-term (103) δ13C excursion near the Palaeocene-Eocene transition: evidence from the Tethys

Expanded sedimentary records from the Tethys reveal unique faunal and isotopic changes across the Palaeocene-Eocene (P-E) transition. Unlike in the open oceans, the Tethys exhibits a gradual decrease of 1.5% in δ¹³C values prior to the rapid δ¹³C excursion. Associated with the 6¹³C excursion is a decrease in calcite burial, increase in detrital content and appearance of a unique opportunistic planktic foraminifera1 assemblage (e.g. compressed acarininids). The existence of a prelude decrease in δ¹³C values in the Tethys suggests that the P-E δ¹³C excursion may have occurred in two steps and over a few hundred thousand years, rather than as one step over a few thousand years as previously suggested. This slower excursion rate is readily explained by changing organic carbon weathering or burial rates and avoids the need of invoking ad hoc scenarios.     

Facies analysis and correlation of high-order sequences in middle–outer ramp successions: variations in exported carbonate on basin-wide δ13Ccarb (Kimmeridgian, NE Spain)

Carbonate mud that accumulated in the deep parts of a late Kimmeridgian carbonate ramp (Iberian Basin, NE Spain) was partly derived by resedimentation from shallow water production areas. High-frequency sea-level changes, probably driven by climatic changes in tune with precession and short-eccentricity cycles, affected carbonate production and the amount of exported sediment. Facies analysis and correlation of three outcrops located in middle and outer ramp settings allows a comparison of high-order sequences (bundles of beds and sets of bundles) across a ramp transect and an assessment of the carbonate factory. Analysis of the storm deposits found in middle ramp settings identifies deepening to shallowing high-frequency cycles based on the level of exported carbonate. In outer ramp areas, many of the bundles exhibit a thinning trend, indicating a progressive decrease of carbonate production and hence, carbonate export during periods of high-frequency sea-level rise. δ¹³C_carb values show a gradual increase through the studied long-term transgressive interval ranging from 1·5‰ to 2·8‰. Within this long-term evolutionary trend, short-term δ¹³C_carb fluctuations occur that correspond with some of the high-order cycles defined from sedimentary facies analysis. These short-term δ¹³C_carb shifts are interpreted as shifts in carbonate export from shallow reef regions to the outer ramp. A consequence of this study is that variation in δ¹³C_carb can be used for correlation in outer ramp successions, at least on a basin-wide scale.     

Low δ18O eclogites from the Kokchetav massif, northern Kazakhstan

Oxygen isotopic compositions of silicates in eclogites and whiteschists from the Kokchetav massif were analyzed by whole‐grain CO₂‐laser fluorination methods. Systematic analyses yield extremely low δ¹⁸O for eclogites, as low as ?3.9‰ for garnet; these values are comparable with those reported for the Dabie‐Sulu UHP eclogites. Oxygen isotopic compositions are heterogeneous in samples of eclogite, even on an outcrop scale. Schists have rather uniform oxygen isotope values compared to eclogites, and low δ¹⁸O is not observed. Isotope thermometry indicates that both eclogites and schists achieved high‐temperature isotopic equilibration at 500–800 °C. This implies that retrograde metamorphic recrystallization barely modified the peak‐metamorphic oxygen isotopic signatures. A possible geological environment to account for the low‐δ¹⁸O basaltic protolith is a continental rift, most likely subjected to the conditions of a cold climate. After the basalt interacted with low δ¹⁸O meteoric water, it was tectonically inserted into the surrounding sedimentary units prior to, or during subduction and UHP metamorphism.     

Palaeoproterozoic evaporites in Fennoscandia: implications for seawater sulphate, the rise of atmospheric oxygen and local amplification of the δ13C excursion

This paper addresses global oxygenation and establishment of a marine sulphate reservoir in the Palaeoproterozoic. We report syn-depositional, marine, anhydrite-containing pseudomorphs after Ca-sulphates as widespread throughout the Tulomozero Formation in the SE Fennoscandian Shield, implying that surface waters were oxidized and a large SO marine reservoir was developed as early as 2100 Ma. The Ca-sulphates and associated magnesite and halite precipitated syn-depositionally from oxidized, evolved and modified seawater in coastal playa, sabkha and intertidal flat settings. ⁸⁷Sr/⁸⁶Sr and δ¹³C of associated ¹³C-rich stromatolitic dolostones were environmentally controlled with the highest ratios occurring in playa and sabkha carbonates. The results imply that the Palaeoproterozoic δ¹³C_carb excursion was amplified by 8‰ by local environmental factors and calls into question many observations of putative δ¹³C global signals reported previously from similar Palaeoproterozoic, evaporitic, dolostones. The local environmental amplification can explain a large regional and intercontinental δ¹³C discrepancy observed in synchronous carbonates.     

13C/12C ratio double cyclicity in a Miocene browncoal: isotopic signals and orbital forcing

A detailed stable carbon isotopic profile of a late Miocene browncoal seam from the Lower Rhine Embayment, Germany, reveals two clear separate cycles of different frequency: this is the first instance of this type of isotopic signature being recognized within coals. The ratio of the two frequencies suggests this isotopic signal possibly resulted from climatic or vegetational responses to orbital forcing. The cyclicity has been enhanced by the application of conventional filtering methods on the data set. An analysis of the seam's palynology indicates a correlation between heavier isotopic compositions and the presence of Sequoiapollenites polyformosus , whose parent plant is believed to have favoured moist climates and higher groundwater tables.     

δ30Si and δ29Si Determinations on USGS BHVO-1 and BHVO-2 Reference Materials with a New Configuration on a Nu Plasma Multi-Collector ICP-MS

We report silicon isotopic determinations for USGS rock reference materials BHVO-1 and BHVO-2 using a Nu Plasma multi-collector (MC)-ICP-MS, upgraded with a new adjustable entrance slit, to obtain medium resolution, as well as a stronger primary pump and newly designed sampler and skimmer cones ("B" cones). These settings, combined with the use of collector slits, allowed a resolution to be reached that was sufficient to overcome the ¹⁴N¹⁶O and ¹⁴N₂ interferences overlying the ³⁰Si and the ²⁸Si peaks, respectively, in an earlier set-up. This enabled accurate measurement of both δ³⁰Si and δ²⁹Si. The δ value is expressed in per mil variation relative to the NBS 28 quartz reference material. Based on data acquired from numerous sessions spread over a period of six months, we propose a recommended average δ³⁰Si of −0.33 ± 0.05‰ and −0.29 ± 0.11‰ (2se) for BHVO-1 and BHVO-2, respectively. Our BHVO grand mean silicon isotope composition (δ³⁰Si =−0.31 ± 0.06‰) is significantly more negative than the only published value for BHVO-2, but is in very good agreement with the recently established average value of ocean island basalts (OIB), confirming the conclusion that the OIB reservoir has a distinct isotopic composition from the solar reservoir as sampled by chondrites.     

Tying platform drowning to perturbations of the global carbon cycle with a δ13COrg-curve from the Valanginian of DSDP Site 416

The carbonate carbon isotope record of the Phanerozoic is marked by repeated high-amplitude excursions towards more positive values. Although the interpretation of C-isotope events remains controversial, they are regarded as a proxy of the global C-cycle. Using δ¹³C_Org-measurements of samples from DSDP Site 416, it is shown that a classic example of platform drowning coincided with the onset of the mid-Valanginian carbon-cycle excursion. Widespread carbonate platform drowning would have contributed to the observed positive shift in the C-isotope record. As choking of carbonate production was compensated by increased organic production, both processes favoured a shift in marine carbon partitioning from the oxidized to the reduced carbon reservoir. This would have resulted in an increased flux of CO₂ from the atmosphere into the marine and sedimentary carbon reservoir.     

The role of inter-specific, micro-habitat and climatic factors on the carbon isotope (δ13C) variability of a modern leaf assemblage from northern Scandinavia: implications for climate reconstruction

To provide a basis for the interpretation of past climatic conditions from Quaternary leaf records, leaf carbon isotope (δ¹³C) results are presented for 12 northern European dwarf-shrub, shrub and tree species growing across a network of 18 sites in northern Scandinavia. The role of micro-habitat (hummock/hollow) on carbon isotope trends is explored in addition to a comparison of the carbon isotope composition of both cellulose and wholeleaf material. The data are also examined against local meteorological variables (temperature, precipitation and vapour pressure deficit) at both species and genus levels. Results exhibit only modest coherence between selected plant species and low-order correlations with external climate forcings consistent with accepted models for carbon isotope fractionation. Potential for the analysis and interpretation of stable isotopic time series may still be identified; however, factors such as inter-plant variability, senescence, diagenesis and homogeneity need to be thoroughly addressed before such an approach may be used for palaeoenvironmental reconstructions. These findings highlight the complexities and limitations of spatial calibration methods.     

δ 11B as tracer of slab dehydration and mantle evolution in Western Anatolia Cenozoic Magmatism

Boron isotope data are presented for Cenozoic Western Anatolia rocks, which define two main associations: (i) calc-alkaline, shoshonitic and ultra-potassic rocks (Early to Middle Miocene); and (ii) Late Miocene–Quaternary intraplate alkali basalts. Boron data, together with Sr–Nd isotope and other trace elements, are consistent with a progressive dehydration of the slab, producing fluid phases gradually depleted in B (and ¹¹B). These fluids were added to the supraslab mantle, triggering a partial melting that gave rise to orogenic magmatism. The stretching and tearing of the slab caused by the faster convergence of Greece over Africa with respect to Anatolia facilitated an interaction of the upwelling subslab asthenosphere with residual slab-fluids during the Late Miocene followed by production of typical intraplate magmas during the Pleistocene–Holocene, whose relatively high δ¹¹B (approximately −2‰) is considered representative of the local asthenosphere not affected by subduction contamination.     

Deglaciation history of the southwestern Fennoscandian Ice Sheet between 15 and 13 14C ka BP

Analysis of 2D and 3D seismic records from the continental shelf off western Norway, in combination with chronological constraints from ¹⁴C dates, has led to a model for the glacial development in these shelf areas between c. 15 and 13 ¹⁴C ka BP. On the shallow Måløy Plateau adjacent to the Norwegian Channel, iceberg scours are preserved below a prominent moraine ridge, which by correlation to the Norwegian Channel indicate ice retreat at c. 15 ¹⁴C ka BP. Subsequently, the ice advanced across the scoured surface and deposited a till sheet before stabilizing to deposit a prominent moraine, termed the Bremanger Moraine. Based on location on the shelf, seismic stratigraphy, morphology and C dates the Bremanger Moraine is correlated with a significant moraine on the continental shelf off Trøndelag. We suggest that these features are products of a regional glacial event, the Bremanger Event, dated to <15–13.3 ¹⁴C ka BP. The Bremanger Event is probably a result of the deteriorating climatic conditions in the NE Atlantic during Heinrich event 1.     

Biostratigraphical and palaeoenvironmental implications of isotopic studies (18O, 13C) of middle Miocene (Badenian) foraminifers in the Central Paratethys

The cause of the middle Miocene Badenian salinity crisis in the Central Paratethys is addressed by examining the palaeotemperature evolution of Badenian waters before and after the deposition of evaporites. Selected foraminifer taxa ( Globigerinoides spp., Globigerina bulloides , and Uvigerina ) characterizing, respectively, the near-surface, intermediate, and bottom layers of the water column, were studied in two boreholes of SW Poland. The δ¹⁸O and δ¹³C values for these taxa show distinct differences which can be explained by the temperature difference between surface and bottom waters during deposition. These values also show temporal changes corresponding to the water temperature evolution in the Badenian basin. Different and quickly changing environmental conditions have been inferred from changes in foraminifer assemblages. They explain why biostratigraphic subdivisions based on well-recognized assemblages are the most accurate approach for determining the biostratigraphy of middle Miocene deposits in the Central Paratethys. The results of isotopic studies indicate that evaporites occur in a part of the Badenian section that was characterized by the lowest temperatures in the studied sections.     

The 14C age of the Toten' mammoth, eastern Norway

A mammoth tusk find from Toten in Oppland, eastern Norway, has been re-dated by the EDTA method. On examining the tusk for heavy metals, the porous parts were found to have the highest concentration. This fact, together with earlier experience from selecting bone samples for ¹⁴C dating, favour the choice of the hard non-porous parts. The influence of possible minor contaminants remaining after pretreatment is discussed. Because of high cosmic-ray intensity the background deviated from the normal stable value. The variations were studied carefully. The final result is that the net activity of the bone is so close to zero that it is questionable whether the age is 'finite'. It is concluded that the tusk is older than 28,000 years.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

Refinements in BaSO4 to CO2 Preparation and δ18 O Calibration of the Sulfate Reference Materials NBS-127, IAEA SO-5 and IAEA SO-6

Refinements have been made to achieve over 99% yield in the conversion of CO to CO₂ in order to improve the reproducibility and accuracy of δ¹⁸ O measurements in sulfates. BaSO₄ (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO₂; the former gas was simultaneously converted to CO₂ by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ¹⁸ O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO₂ produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO₂ equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from ¹⁸O/¹⁶O of the working calibrator we used CO₂ gas prepared from ocean water sulfate for this purpose. The calibrated δ¹⁸ O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.