In this study, we present first results from an ongoing investigation on the stable barium (Ba) isotope fractionation in the natural barium cycle. Stable Ba isotope signatures of international IAEA reference materials (synthetic barium sulfate, IAEA-SO-5, -6, and barium carbonate, IAEA-CO-9), natural Ba minerals and experimental Ba precipitates have been analyzed as a first approach to evaluate potential discriminating processes in the global geochemical barium cycle. Ba = − 0.5‰ was found in a diagenetic barite sample from ODP Leg 207. The observed natural discriminations are clearly larger than the analytical uncertainty of the stable isotope measurements, indicating significant isotope discrimination in the natural barium cycle. Precipitation experiments from aqueous barium chloride solutions at temperatures of~21°C and 80°C indicate that the light Ba isotope is enriched in pure barium carbonate and barium sulfate compared to the aqueous solution. A maximum isotope fractionation of − 0.3‰ is observed for both barium carbonate and sulfate, that -in the case of BaCO 3 -seems to be influenced by precipitation rate and/or the aqueous speciation, but less by temperature.

We investigate the redox-sensitive isotope system of molybdenum (Mo) in marine carbonates to evaluate their potential as archive of the Mo isotopic composition of coeval seawater. We present Mo isotope data (δ 98/95 Mo) of modern skeletal and non-skeletal carbonates as well as a variety of precipitates from the mid and late Carboniferous. The external reproducibility is determined by repeated analyses of two commercially available carbonate standards. The resulting uncertainty of the low concentration samples is ±0.1‰ (2σ). Analysis of modern ooid sands from the Bahamas shows a consistently heavy Mo isotopic composition (δ 98/95 Mo between 2 and 2.2‰), approaching modern mean seawater values (δ 98/95 Mo = 2.3‰ ± 0.1‰ (2σ)). This suggests that isotope fractionation during Mo uptake into non-skeletal carbonate precipitates is small. In contrast, modern skeletal carbonates show variable isotopic compositions (0.1 to 2.2‰) which suggests a biologically controlled fractionation process. The varying Mo signatures found in Carboniferous cement phases point to a strong response to local changes in fluid composition from which they precipitated. Overall, we recognized three important factors to cause an offset relative to ocean water: Mo derived from skeletal components, input of detrital Mo and admixture of light, hydroxide derived Mo via diagenetic fluids. All of these factors cause a lighter Mo isotopic composition relative to seawater. Due to the apparent small isotope fractionation during Mo uptake into non-skeletal carbonates, their δ 98/95Mo closely reflects the ambient fluid composition. From these results we conclude that carbonates represent a promising new tool to characterize the water mass Mo isotopic composition of marine paleo-environments.

We present a barium (Ba) isotope fractionation study of marine biogenic carbonates (aragonitic corals). The major aim is to provide first constraints on the Ba isotope fractionation between modern surface seawater and coral skeleton. Mediterranean surface seawater was found to be enriched in the heavy Ba isotopes compared to previously reported values for marine open ocean authigenic and terrestrial minerals. In aquarium experiments with a continuous supply of Mediterranean surface water, the Ba isotopic composition of the bulk sample originating from cultured, aragonitic scleractinian corals (d 137/134 Ba between +0Á16 AE 0Á12& and +0Á41 AE 0Á12&) were isotopically identical or lighter than that of the ambient Mediterranean surface seawater (d 137/134 Ba = +0Á42 AE 0Á07&, 2SD), which corresponds to an empirical maximum value of Ba isotope fractionation of D 137/134Ba coral-seawater = À0Á26 AE 0Á14& at 25°C. This maximum Ba isotope fractionation is close and identical in direction to previous results from inorganic precipitation experiments with aragonitestructured pure BaCO 3 (witherite). The variability in measured Ba concentrations of the cultured corals is at odds with a uniform distribution coefficient, D (Ba/Ca) , thus indicating stronger vital effects on isotope than element discrimination. This observation supports the hypothesis that the Ba isotopic compositions of these corals do not result from simple equilibrium between the skeleton and the bulk seawater. Complementary coral samples from natural settings (tropical shallowwater corals from the Bahamas and Florida and cold-water corals from the Norwegian continental shelf) show an even wider range in d 137/134 Ba values (+0Á14 AE 0Á08 to +0Á77 AE 0Á11&), most probably due to additional spatial and/ or temporal seawater heterogeneity, as indicated by recent publications.

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Mid- to late-Holocene sea-level records from low-latitude regions serve as an important baseline of natural variability in sea level and global ice volume prior to the Anthropocene. Here, we reconstruct a high-resolution sea-level curve encompassing the last 6000 years based on a comprehensive study of coral microatolls, which are sensitive low-tide recorders. Our curve is based on microatolls from several islands in a single region and comprises a total of 82 sea-level index points. Assuming thermosteric contributions are negligible on millennial time scales, our results constrain global ice melting to be 1.5–2.5 m (sea-level equivalent) since ~5500 years before present. The reconstructed curve includes isolated rapid events of several decimetres within a few centuries, one of which is most likely related to loss from the Antarctic ice sheet mass around 5000 years before present. In contrast, the occurrence of large and flat microatolls indicates periods of significant sea-level stability lasting up to ~300 years.

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Well-exposed mounds are common in limestone of the Late Carboniferous San Emiliano Formation, Cantabrian Mountains (Northern Spain). They occur as obvious primary topographic features. Careful study of the mound intervals and surrounding strata revealed the internal structures of mounds and the factors controlling their growth. The substrate (2 -3 m) of the mounds consists of greyish to reddish, bedded oolitic and oncolithic packstone and grainstone. Crinoids, fragments of the alga Epimastopora, and, rarely, bryozoans are present. Ooids and oncoids indicate a wave-dominated high-energy environment. Presence of quartz indicates the influence of terrigenous siliciclastic input. Mound intervals (6 -12 m thick) are characterized by skeletal -microbial boundstone. Donezellid algae, agglutinated worm tubes, and calcisponges are the dominant fossils. Smaller foraminifers, gastropods, and brachiopods are also present. A peloidal-clotted matrix is characteristic and accounts for more than 30% of the mound volume. Intraframe pores are mainly filled by peloidal sediment and early marine cement. Intermound strata are approximately one-third as thick as time equivalent mounds. Mound fossils (algae, agglutinated worm tubes, and sponges) are uncommon. However, intermound strata are generally more diverse than the mounds, containing fusulinids, smaller foraminifers, bryozoans, gastropods, crinoids, and bioclasts. Some of these fossils have micritic envelopes. Bedded packstone and grainstone, 3 -6 m thick, with siliciclastic debris, rugose corals, and chaetetid sponges characterize the capping facies. Coated grains and small ooids are uncommon. This facies indicates shallowing to a higher energy environment and/or a higher input of siliciclastics, inhibiting mound growth. Mounds are interpreted to have accreted in a quiet environment below wave base. This position is comparable to the depositional environment inferred for many Late Paleozoic mounds described elsewhere, e.g., from Texas and New Mexico, Canadian Archipelago, and Carnic Alps in Austria. Mound relief is explained by (1) accumulation of peloidal-clotted sediments limited to boundstone and probably related to microbial activities, (2) widespread marine cementation within this area, and (3) low export of mound fossils to intermound areas. The position of the mounds within the sequence, and their initiation, size and termination, seem to be mainly controlled by sea-level fluctuations and siliciclastic input. D