Accurate and High-Precision Measurement of Lithium Isotopes in Two Reference Materials by MC-ICP-MS

We report here a newly developed method for measurement of Li isotopes by use of multi-collector ICP-MS (Neptune) allowing rapid and high precision determination of Li isotope ratios at low levels of lithium (15–20 ng). The lithium reference sample solution IRMM-016 was analysed over a period of ten months with an external reproducibility of 0.24% (2s, n = 52). Chemical separation of Li from matrix was performed on the seawater sample IRMM BCR-403, for which a mean δ⁷Li value of + 31.0 ± 0.1 % (2s/√n, n = 31) was obtained. This mean value is in good agreement with those previously published for other seawater samples. BCR-403 seawater being readily available, we propose that this seawater sample be used as a reference sample for Li isotope measurements.     

Three Secondary Reference Materials for Lithium Isotope Measurements: Li7-N, Li6-N and LiCl-N Solutions

The CRPG (Nancy, France) has prepared secondary reference materials for Li isotope measurements by mixing ⁷Li or ⁶Li spikes and either L-SVEC or IRMM-016 certified reference materials to produce solutions having a known Li concentration and isotopic composition. The Li7-N and Li6-N solution samples (1.5 mol l⁻¹ HNO₃) have nominal δ⁷Li isotopic compositions of 30.1‰ and -9.7‰ respectively relative to L-SVEC and concentrations of 100 mg l⁻¹. Repeated measurement of these samples using the QUAD-ICP-MS at the CRPG yielded δ⁷Li of 30.4 ± 1.1‰ (n = 13) and -8.9 ± 0.9‰ (n = 9) at the 2s level of confidence. An additional LiCl-N solution was measured and yielded a delta value of 9.5 ± 0.6‰ (n = 3). Identical results were obtained at the BRGM (Orléans, France) from determinations performed with a Neptune MC-ICP-MS (30.2 ± 0.3‰, n = 89 for the Li7-N, -8.0 ± 0.3‰, n = 38 for the Li6-N and 10.1 ± 0.2‰, n = 46 for LiCl-N at the 2s level of confidence). The deviation of measured composition relative to the nominal value for the Li6-N solution might be explained by either contamination during preparation or an error during sample weighing. These secondary reference materials, previously passed through ion exchange resin or directly analysed, may be used for checking the accuracy of Li isotopic measurements over a range of almost 40‰ and will be available to the scientific community upon request to J. Carignan or N. Vigier, CRPG.     

Boron Isotopic Composition and Concentration of Ten Geological Reference Materials

We present boron isotope and concentration data from magmatic (komatiitic to rhyolitic) and sedimentary geological silicate and artificial glass reference materials that cover a wide spectrum of boron isotope compositions and boron concentrations. Boron isotope compositions were determined by TIMS (Cs₂BO₂⁺ -graphite and BO₂^- method) and boron concentrations by ICP-AES. Boron concentrations ranged from 7 to 159μ g^-1 and agree within 14% with published values. Based on replicate analyses of individually prepared sample aliquots an overall external reproducibility of better than 10% was determined. The obtained δ¹¹B values ranged from -12.6 to +13.6% and were reproducible within 1.1 % (2 RSD; excluding NTIMS) on the basis of individually prepared sample aliquots. The δ¹¹B values of JA-1 (+5.3%), JB-3 (+5.9%) and JR-2 (+2.9%) overlap the published data within analytical uncertainty. For the first time δ¹¹B values for the TB (-12.6%) and the MPI-DING glasses GOR-128-G (+13.6%), GOR-132-G (+7.1 %) and StHs6/80-G (-4.5%) are reported. The δ¹¹B values obtained by the Cs₂BO₂⁺ -graphite and the BO₂^- method as well as the majority of δ¹¹B values obtained using different sample preparation methods agree within analytical uncertainty. Therefore, we conclude that none of these analytical methods introduce any systematic error on the obtained δ¹¹B values.     

Chemical Separation and Isotopic Variations of Cu and Zn From Five Geological Reference Materials

This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ⁶⁵Cu = 0.52 ± 0.15‰ (n = 10) and δ⁶⁶Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ⁶⁶Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ⁶⁶Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ⁶⁵Cu = 0.46 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ⁶⁵Cu = -0.018 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ⁶⁶Zn and δ⁶⁵Cu.     

Stable chlorine isotope evidence for non-marine chloride in Badenian evaporites, Carpathian mountain region

Routine trace-element geochemistry suggests that components in putative marine halite evaporites may be partly of nonmarine origin, but such interpretations are commonly ambiguous. Stable chlorine isotopes may provide a less-ambiguous marker of chloride origin where δ³⁷Cl departs from the range predicted for evaporite formation from seawater. Bedded halite with primary sedimentary textures preserves original δ³⁷Cl values. Measurable change in δ³⁷Cl can be generated by incongruent dissolution of halite, but only if less than half the original halite remains. Badenian (middle Miocene) halite from the Forecarpathian and from the East Slovakian and Transcarpathian basins has a δ³⁷Cl range of – 0.2 to 0.8‰. Two phenomena cannot be explained by simple evaporation of 0.0‰ seawater. At Wieliczka, the Shaft Salt has distinctive δ³⁷Cl values (– 0.2 to 0.0‰) relative to neighbouring salt beds (0.2 to  0.6‰), requiring a large, abrupt input of brine with negative δ³⁷Cl. Halite with high (0.6 – 0.8‰) δ³⁷Cl near the base of the East Slovakian and Transcarpathian evaporites requires a large input of chloride with positive δ³⁷Cl into the basins. Expulsion of basin brine with non-0‰δ³⁷Cl into the evaporite basins may account for the nonmarine chloride sources.     

Quantitative Separation of Molybdenum and Rhenium from Geological Materials for Isotopic Determination by MC-ICP-MS

We have developed a new chemical procedure for the quantitative separation of molybdenum (Mo) and rhenium (Re) from a wide variety of geological samples. A single pass anion exchange separation provided complete recovery of pure Mo and Re in a form that was ideal for subsequent isotope and abundance determination by multi-collector inductively coupled plasma-mass spectroscopy (MC-ICP-MS). An enriched ¹⁰⁰Mo-⁹⁷Mo solution, mixed with the sample before digestion, enabled natural mass-dependant isotopic fractionation of Mo to be determined with an external reproducibility of < 0.12‰ (δ⁹⁸Mo/⁹⁵Mo, 2 s ). Determination of the concentration of Mo and Re in the same sample was achieved by isotope dilution, with instrumental mass-fractionation of Re being corrected by the simultaneous measurement of the ¹⁹¹Ir/¹⁹³Ir ratio. We have applied the new procedure to a variety of samples, including seawater, basalt and organic-rich mudrock. The procedure is ideally suited to palaeoredox studies requiring the precise determination of the Mo isotope composition and the Re/Mo ratio from the same sample.     

Determination of Lithium Contents in Silicates by Isotope Dilution ICP-MS and its Evaluation by Isotope Dilution Thermal Ionisation Mass Spectrometry

A precise and simple method for the determination of lithium concentrations in small amounts of silicate sample was developed by applying isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Samples plus a Li spike were digested with HF-HClO₄, dried and diluted with HNO₃, and measured by ICP-MS. No matrix effects were observed for ⁷Li/⁶Li in rock solutions with a dilution factor (DF) of 97 at an ICP power of 1.7 kW. By this method, the determination of 0.5 μg g^-1 Li in a silicate sample of 1 mg can be made with a blank correction of < 1%. Lithium contents of ultrabasic to acidic silicate reference materials (JP-1, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1 and JR-2 from the Geological Survey of Japan, and PCC-1 from the US Geological Survey) and chondrites (three different Allende and one Murchison sample) of 8 to 81 mg were determined. The relative standard deviation (RSD) was typically < 1.7%. Lithium contents of these samples were further determined by isotope dilution-thermal ionisation mass spectrometry (ID-TIMS). The relative differences between ID-ICP-MS and ID-TIMS were typically < 2%, indicating the high accuracy of ID-ICP-MS developed in this study.     

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.     

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.     

Calcium Isotopic Composition of Various Reference Materials and Seawater

A compilation of δ^44/40Ca (δ^44/40Ca) data sets of different calcium reference materials is presented, based on measurements in three different laboratories (Institute of Geological Sciences, Bern; Centre de Géochimie de la Surface, Strasbourg; GEOMAR, Kiel) to support the establishment of a calcium isotope reference standard. Samples include a series of international and internal Ca reference materials, including NIST SRM 915a, seawater, two calcium carbonates and a CaF₂ reference sample. The deviations in δ^44/40Ca for selected pairs of reference samples have been defined and are consistent within statistical uncertainties in all three laboratories. Emphasis has been placed on characterising both NIST SRM 915a as an internationally available high purity Ca reference sample and seawater as representative of an important and widely available geological reservoir. The difference between δ^44/40Ca of NIST SRM 915a and seawater is defined as -1.88 O.O4%o (δ^44/42Ca_{NISTSRM915a/Sw}= -0.94 0.07%o). The conversion of values referenced to NIST SRM 915a to seawater can be described by the simplified equation δ^44/40Ca_Sa/Sw=δ^44/40Ca_{Sa/NIST SRM 915a} - 1.88 (δ^44/42Ca_Sa/Sw=δ^44/42Ca_{Sa/NIST SRM 915a} - 0.94). We propose the use of NIST SRM 915a as general Ca isotope reference standard, with seawater being defined as the major reservoir with respect to oceanographic studies.     

Stable isotopic and fluid inclusion evidence for meteoric fluid penetration into an active mountain belt; Alpine Schist, New Zealand

Calcite and quartz veins have formed, and are forming, in steeply dipping fissures in the actively rising Alpine Schist metamorphic belt of New Zealand. The fluids that deposited these minerals were mostly under hydrostatic pressure almost down to the brittle-ductile transition, which has been raised to 5-6 km depth by rapid uplift. Some fluids were trapped under lithostatic pressures. Fluids in the fissure veins were immiscible H₂O + NaCl-CO₂ mixtures at 200-350 C. Bulk fluid composition is 15-20 mol% CO₂ and <4.3 total mol CH₄+ N₂+ Ar/100mol H₂O. Water hydrogen isotopic ratio δD_H2O in the fissure veins spans -29 to -68‰, δ¹⁸O_H2O -0.7 to 8.5‰, and bulk carbon isotopic ratio δ¹³C ranges from -3.7 to -11.7‰. The oxygen and hydrogen isotopic data suggest that the water has a predominantly meteoric source, and has undergone an oxygen isotope shift as a result of interaction with the host metamorphic rock. Similar fluids were present during cooling and uplift. Dissolved carbon is not wholly derived from residual metamorphic fluids; part may be generated by oxidation of graphite.     

Isotope geochemistry, petrology and depositional environments of the diatomite-dominated Tripoli Formation (Lower Messinian), Sicily

ABSTRACT The Tripoli Formation (Lower Messinian) in Sicily includes diatomites irregularly alternating with marl and carbonate beds and lies, stratigraphically, between the Tortonian pelagic marls and the evaporitic Calcare di base. The relationships between mineralogy, textural features and oxygen-carbon isotopic compositions of carbonate components point to a wide variability of depositional conditions and suggest that Tripoli sedimentation occurred in small basins characterized by periodic and marked restriction from the open sea.
The isotopic values of calcite and dolomite in the diatomites suggest an evolution from normal marine towards more restricted environments. Evaporating conditions are also indicated by the occurrence of anhydrite, length-slow chalcedonic quartz and moulds of gypsum. In a more advanced stage, the precipitation of heavy δ¹⁸0 dolomite in the interstitial pores of fossil-poor diatomites denotes an environment with highly evaporated water. Mixing of meteoric and marine waters, on the other hand, might have favoured the precipitation of a dolomite characterized by relatively low δ¹⁸0 and δ¹³C values.
The deposition of marl and carbonate beds alternating with or overlying the diatomites took place in an environment with highly evaporated marine waters on the basis of δl¹⁸O values of dolomite (up to + 9.10‰) and aragonite (up to + 5.83‰), occurrence of evaporitic minerals and lack of fossils. The presence at these levels of calcite with extremely negative δ¹³C values (down to - 38.40‰), filling gypsum moulds, suggests activity of sulphate-reducing bacteria. Some aragonitic marls, however, bear evidence of deposition in relatively normal marine conditions.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

Boron isotope composition of melt inclusions from porphyry systems of the Central Andes: a reconnaissance study

Quartz-hosted melt inclusions from latite dykes of the Eocene El Salvador copper porphyry system in northern Chile display wide ranges in both boron concentration (15–155 p.p.m. B) and isotope composition (δ¹¹B −7 to +12‰; n  = 10), likely reflecting slab-derived fluid input from seawater-altered oceanic crust. In contrast, the major Miocene tin-silver and tin porphyry systems in the Bolivian back-arc region (Cerro Rico de Potosi, Chorolque, Llallagua) have distinctly different melt inclusion compositions with δ¹¹B of −11.4 ± 2.7‰ ( n  = 10), and magmatic boron enrichment up to several hundred p.p.m. B. The `seawater' signature in the El Salvador melt inclusions explains the oxidized mineral assemblage of the copper porphyry system, as opposed to the more reduced nature of the Bolivian tin porphyry systems, which reflect intracrustal melting of pelitic rocks.     

Stable isotope study of carbonate sediments from the Coorong Area, South Australia

ABSTRACT
The mineralogy and isotope geochemistry of carbonate minerals in the Coorong area are determined by the water chemistry of different depositional environments ranging from seawater to evaporitically modified continental water. The different isotopic compositions of coexisting calcite and dolomite suggest that each of the above two minerals was formed from water of composition and origin unique to that specific mineral. In addition, the dolomite was not formed by simple solid state cation exchange.
The occurrence of two types of dolomite was shown by isotope analysis and SEM observations. The dolomite, which is isotopically light (δ¹³C = -1 to -2% 0 ; δ¹⁸O=+3 to +5%₀) and of fine grain size (˜ 0·5 μm) probably precipitated under the influence of evaporitically modified continental water. Coarser grained dolomite (up to 4 μm) is isotopically heavier (δ¹³C=+3 to +4%₀; δ¹⁸O=+5 to + 6%₀) contains Mg in excess of Ca and was formed in or close to equilibrium with atmospheric CO² probably by the dolomitization of aragonite.     

Heavy Sulfur-isotope Enrichment in Middle Miocene Onnagawa Mudstones in the Green Tuff Region, Northeastern Japan

Abstract. Sulfur isotope ratios are analyzed for a series of mudstones in a successive section in the Taiheizan area in the central Green Tuff region, northeast Japan. The δ³⁴S values for the Uyashinai Mudstone Member (Nishikurosawa stage), the Onnagawa Formation and the Funakawa Formation range from -45 to -14%, -20 to +4% and -30 to -10%, respectively. There is a marked positive shift in δ³⁴S values at the Nishikurosawa/Onnagawa boundary and an upward δ³⁴S-decreasing trend in the Onnagawa and Funakawa Formations. The present data provides evidence for environmental change in the form of stratification of the seawater, initiated at the Nishikurosawa/Onnagawa boundary and persisting during deposition of the Onnagawa Formation, followed by gradual oxygenation during deposition of the Funakawa Formation.     

Seasonal and interannual variability of Siberian river discharge in the Laptev Sea inferred from stable isotopes in modern bivalves

Stable oxygen and carbon isotope profiles from modern bivalve shells were investigated in order to reconstruct short-term hydrographical changes in the river-shelf system of the Laptev Sea. Oxygen isotopic profiles obtained from the aragonitic species Astarte borealis exhibit amplitude cycles interpreted as annual hydrographical cycles. These records reflect the strong contrast between summer and winter bottom water conditions in the Laptev Sea. The seasonal variations in δ¹⁸O are mainly controlled by the riverine freshwater discharge during summer with 0.5‰ per salinity unit. Corrected for a defined species-dependent fractionation offset of -0.37‰, time-dependent salinity records were reconstructed from these δ¹⁸O profiles. They indicate a good correspondence to seasonal hydrographic changes and synoptical data. Persistent trends with shell growth towards more negative δ¹³C values are observed in all specimens and appear to be related to metabolic changes of the bivalves during ontogeny. In contrast, short-term fluctuations are likely linked to seasonal variabilities of the river water outflow patterns and enhanced phytoplankton productivity during summer. This is corroborated by a clear watermass-related distinction of the various δ¹³C records made on the basis of water depth and distance from the riverine source.     

Sulfur Content and Isotopic Ratio of Cambro-Ordovician Carbonate Rocks from South Korea: A Possible Source for Mesozoic Magmatic-hydrothermal Ore Sulfur

Abstract: Carbonate rocks of Cambrian (18 samples) and lower-middle Ordovician (11 samples) ages from South Korea were analyzed for sulfur contents of structurally substituted sulfate (SSS) and sulfides and their δ³⁴S values. The δ³⁴S values of SSS ranging from +25.9 to +45.2 permil, are averaged as +33.6 and +33.5 permil for the Cambrian and Ordovician rocks, respectively, which indicate high δ³⁴S values of the Cambro-Ordovician seawater. The SSS contents in the carbonate rocks are low being 2.9 to 17.3 ppm S (averaged as 7.0 ppm S). Sulfide sulfur, on the contrary, is much abundant containing 3 to 1,880 ppm S and the δ³⁴S values range widely between –17.6 and +31.1 permil. Sulfide sulfur of the studied rocks excluding impure carbonates has an average content of 187 ppm S and δ³⁴S value of +12.8 permil (n=24). The estimated δ³⁴S (sulfate–sulfide) values, which range from 13.8 to 25.4 permil in general with a few exceptions from 36.5 up to 52.3 permil for some impure carbonates, may provide evidence for the persistent oceanic anoxia with its temporary recovery during the Cambro-Ordovician time.
The SSS and sulfide sulfurs have often higher δ³⁴S values than the Mesozoic-Cenozoic ore sulfur (Ishihara et al., 2000). Since carbonate rocks are very reactive with circulating hydrothermal ore solution, high δ³⁴S values of the Korean ore deposits might be caused to some extent by ³⁴S enrichment from the host carbonates, resulting in the low SSS contents observed.     

Anthropogenic CO2 in Southern Ocean surface waters: evidence from stable organic carbon isotopes

We present an approach for tracing the fate of anthropogenic CO₂, compiling a large data set of stable organic carbon isotope ratios from surface sediments, plankton, and sinking matter in the Atlantic Ocean. The δ¹³C values of sinking matter are generally lower by 0.5–4.6‰ compared to the surface sediments. This difference increases with increasing latitude, which is explained by a stronger modern increase in surface water [CO₂ (aq)] in the Southern Ocean relative to the Tropical/Subtropical Ocean. Preindustrial dissolved CO₂ concentrations in Atlantic surface waters, estimated from the δ¹³C_org of surface sediments, are compared to recently measured surface water [CO₂ (aq)] values taken from literature. We obtain only a slight increase in [CO₂ (aq)] at lower latitudes but a significant change of about 7 ± 2 μ m in high latitudinal surface waters which we attribute to anthropogenic perturbation. Our results suggest that CO₂ released by human activities has been stored in Southern Ocean surface waters.     

Terrestrial carbon-isotope records from coastal deposits (Algarve, Portugal): a tool for chemostratigraphic correlation on an intrabasinal and global scale

ABSTRACT The carbon-isotope signature of terrestrial organic matter (OM) offers a valuable tool to develop stratigraphic correlations for near-shore deposits. A mid-Cretaceous coastal succession of the western Algarve Basin, Portugal, displays a marked negative δ¹³C excursion ranging from − 21.2‰ to − 27.8‰ in the Early Aptian followed by two shifts towards higher values (up to − 19.3‰) during the Early and Late Aptian, respectively. The dominance of cuticle and leaf debris in the bulk OM fraction is confirmed by optical studies, Rock-Eval pyrolysis and by comparison with the δ¹³C signature of four different types of fossilized land-plant particles. Correlation of two terrestrial δ¹³C_bulk OM records from different study sites leads to a significant enhancement of the intrabasinal stratigraphic correlation within the Algarve Basin. Three prominent excursions in the Portuguese records can be correlated with existing δ¹³C curves from pelagic and terrestrial environments. The general carbon-isotope pattern is superimposed by small-scale fluctuations which can be explained by compositional variations within the OM.