ALBERT

Description: In this study we present the first combined investigation into the composition of the major matrices involved in calcification processes (surrounding water, extrapallial fluid, aragonite, and calcite) of Mytilus edulis with respect to their calcium isotope (d44/40Ca) and elemental compositions (Sr/Ca and Mg/Ca). Our aim was to examine the suitability of Mytilus edulis as a proxy archive and to contribute to the understanding of the process of biomineralization. Mytilus edulis specimens were live collected from the Schwentine Estuary, Kiel Fjord, and North Sea (Sylt). d44/40Ca was determined by thermal ionization mass spectrometry (TIMS) accompanied by measurements of Mg/Ca and Sr/Ca using inductively coupled plasma–optical emission spectroscopy (ICP-OES). The elemental and isotopic compositions of the investigated matrices showed systematic offsets. The carbonates are strongly depleted in their magnesium and strontium concentrations and fractionated toward lighter calcium isotope compositions relative to the surrounding Schwentine Estuary water. The opposite is observed for the extrapallial fluid (EPF). Our findings extend the results of previous studies reporting a strong biological control and the interaction of different environmental conditions influencing biomineralization. Future studies should focus on the temporal development of the interrelation between the different matrices.

Description: Recent studies comparing shipboard data between the 1950's and the 1990's have shown significant, heterogeneous adjustments of the temperature-salinity structure of the N. Atlantic Ocean. Here, we present proxy records of temperature and salinity from aragonite sclerosponge skeletons, extending existing records of the Salinity Maximum Waters (SMW) of the N. Atlantic back to 1890. These proxy records show secular temperature increases of 1.6–2.0°C, higher than published global averages, and salinity increases of 0.35–0.5 psu, smaller than short-term secular trends recently measured. Salinity reconstructions vary more significantly on the decadal scale, showing changes that are related to low-frequency variations of the North Atlantic Oscillation (NAO). On both secular and decadal time scales, the records indicate significant thermohaline changes in the SMW, either via forcing at the surface or increasing depths of density surfaces in the Bahamas.

Description: Stable strontium isotopes (here 88Sr/86Sr) are introduced as a new member of the nontraditional stable isotopes. We have developed a bracketing standard method for the determination of δ88/86Sr using an AXIOM MC-ICP-MS and normalizing to strontium SRM NBS987. For individual measurements the external reproducibility is better than about 25 ppm (1σ RSD). For the IAPSO seawater standard a δ88/86Sr value of 0. 381 ± 0.010‰ (2SEM) was determined. For the first time a temperature-dependent strontium isotope fractionation during calcium carbonate precipitation could be shown. Aragonite samples inorganically precipitated under temperature control between 10 and 50°C revealed a δ88/86Sr/temperature dependency of 0.0054(5)‰/°C (R2 = 0.987). In contrast, for natural coral samples (Pavona clavus) from a proxy calibration study (23 to 27°C) we did determine 0.033(5)‰/°C (R2 = 0.955). The processes causing this sixfold stronger temperature dependency for the natural coral samples have to be studied in more detail in future studies. In a first approach the different slopes can be interpreted as effects of kinetic fractionation of strontium ions with or without a hydrate shell of 22 to 29 water molecules.

Description: We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented.

Description: We reconstruct Caribbean seawater temperatures from sclerosponge Sr/Ca ratios using a specimen of Ceratoporella nicholsoni that grew at 20 m below sea level in a reef cave at Jamaica. We sample the time interval from 1620 to 1745 A.D. with almost monthly resolution. This interval includes the Maunder sunspot minimum, one of the coldest periods of the Little Ice Age. Reconstructed annual temperature amplitudes are on the order of about 1°C. The mean growth rate calculated from the annual Sr/Ca variations corresponds perfectly with U-Th-based growth rates. We find that the interannual climate variability is determined by El Niño–Southern Oscillation and by a decadal signal, most likely originating from the tropical North Atlantic. On a multidecadal timescale the Maunder Minimum is characterized by a 1°–2°C cooling and reduced amplitudes of the interannual and decadal temperature variations.

Description: [1] Recently, calcium isotope fractionation in the coccolithophore Emiliania huxleyi was shown to exhibit a significant temperature dependency. An important subsequent question in this context is whether the observed fractionation patterns are caused by temperature itself or related growth rate changes. In order to separate growth and calcification rate effects from direct temperature effects, batch culture experiments with the coccolithophore E. huxleyi were conducted under varying light intensities. Despite large changes in cellular growth and calcification rates, calcium isotope fractionation remained constant. Independence of calcium isotope fractionation on growth and calcification was also obtained in two additional sets of experiments in which growth rates changed in response to varying calcium concentration and seawater salinity. These experiments also showed no direct effects of calcium concentration and salinity on calcium isotope fractionation. Values for calcium isotope fractionation of E. huxleyi coccoliths fell within a range of −1.0 to −1.6 (1000 lnα), confirming earlier results. This range is similar to that observed in several foraminiferal species and coccolith oozes, suggesting a rather homogeneous calcium isotopic composition in marine biogenic calcite. Our data further show that the calcium isotope fractionation does not change with changing isotopic composition of seawater. This is a basic requirement for reconstructing the calcium isotopic composition of the ocean over time.

Description: The Mg/Ca temperature calibration of the polar to subpolar planktonic foraminifera Neogloboquadrina pachyderma (sinistral) (sinistral indicates left coiling) was refined by a multiproxy approach combining hydrographic temperature and salinity data with Mg/Ca, delta Ca-44/40, and delta O-18 values from Holocene Nordic seas core top samples. Reliable Mg/Ca-based temperature estimates are limited to foraminiferal tests that calcified in water masses with temperatures above similar to 3 degrees C at habitat depth. In these samples, Mg/Ca and delta Ca-44/40 values are positively correlated (Mg/Ca (mmol/mol) = 0.77 (+/- 0.22) x delta Ca-44/40 (parts per thousand SRM 915a) + 0.52 (+/- 0.12); n = 20, R-2 = 0.76). Both Mg/Ca- and delta Ca-44/40-derived temperatures projected onto their corresponding depth intervals reveal that the "apparent'' calcification depth of N. pachyderma (sinistral) averaging the specimens' whole life cycle is bound to an isopycnal layer defined by water densities (sigma(t)) between 27.7 and 27.8. This implies that N. pachyderma (sinistral) prefers gradually deeper habitats with increasing sea surface temperatures, thus counterbalancing absolute temperature variations. Consequently, the total temperature range recorded in this foraminiferal species is restricted and only partly reflects environmental changes. On the basis of the new Mg/Ca, delta Ca-44/40, and delta O-18 multiproxy data set, we propose a linear Mg/Ca temperature relation for high-latitude N. pachyderma (sinistral): Mg/Ca (mmol/mol) = 0.13 (+/- 0.037) T (degrees C) + 0.35 (+/- 0.17); T > 3 degrees C. In core top samples from polar waters with peak summer temperatures below similar to 3 degrees C, the temperature response in the Mg/Ca and delta Ca-44/40 proxy signal is inversed and poorly correlated. Both Mg/Ca- and delta Ca-44/40-derived temperature estimates pretend significantly higher calcification temperatures than maximum summer sea surface temperatures of these water masses.

Description: Measurements of the calcium isotopic composition (δ44/40Ca) of planktonic foraminifera from the western equatorial Pacific and the Indian sector of the Southern Ocean show variations of about 0.6‰ over the past 24 Myr. The stacked δ44/40Ca record of Globigerinoides trilobus and Globigerina bulloides indicates a minimum in δ44/40Casw (seawater calcium) at 15 to 16 Ma and a subsequent general increase toward the present, interrupted by a second minimum at 3 to 5 Ma. Applying a coupled calcium/carbon cycle model, we find two scenarios that can explain a large portion of the observed δ44/40Casw variations. In both cases, variations in the Ca input flux to the ocean without proportional changes in the carbonate flux are invoked. The first scenario increases the riverine calcium input to the ocean without a proportional increase of the carbonate flux. The second scenario generates an additional calcium flux from the exchange of Ca by Mg during dolomitization. In both cases the calcium flux variations lead to drastic changes in the seawater Ca concentrations on million year timescales. Our δ44/40Casw record therefore indicates that the global calcium cycle may be much more dynamic than previously assumed.