Calcium isotope fractionation and its controlling factors over authigenic carbonates in the cold seeps of the northern South China Sea

In this study, we analyzed stable calcium isotope results of authigenic carbonates from two cold seep areas of the Dongsha area and the Baiyun Sag in the northern South China Sea. The stable isotopes of carbon and oxygen as well as the mineral composition of authigenic carbonates were used to investigate control calcium isotope fractionation. The δ 44/40Ca ratios of the southwestern Dongsha area samples ranged from 1.21‰ to 1.52‰ and the ratio of the Baiyun Sag sample was 1.55‰ of the SRM915a isotope standard. X-ray diffraction analysis showed that the carbonate samples consisted of dolomite, calcite and aragonite, with small amounts of high-Mg calcite and siderite. The δ 13C values of the carbonates of the southwestern Dongsha area varied between −49.21‰ and −16.86‰ of the Vienna PeeDee Belemnite (VPDB) standard and the δ 18O values ranged from 2.25‰ to 3.72‰ VPDB. The δ 13C value of the Baiyun Sag sample was 2.36‰ VPDB and the δ 18O value was 0.44‰ VPDB. The δ 13C values of the carbonates of the southwestern Dongsha area revealed there is methane seeping into this area, with a variable contribution of methane-derived carbon. The sampled carbonates covered a range of δ 13C values suggesting a dominant methane carbon source for the light samples and mixtures of δ 13C values for the heavier samples, with possibly an organic or seawater carbon source. The δ 18O values indicated that there is enrichment in 18O, which is related to the larger oxygen isotope fractionation in dolomite compared to calcite. The results of the Baiyun Sag sample exhibited normal seawater carbon and oxygen isotopic values, indicating that this sample is not related to methane seepage but instead to precipitation from seawater. The relatively high δ 44/40Ca values indicated either precipitation at comparatively high rates in pore-water regimes with high alkalinity, or precipitation from an evolved heavy fluid with high degrees of Ca consumption (Raleigh type fractionation). The dolomite samples from the Dongsha area revealed a clear correlation between the carbon and calcium isotope composition, indicating a link between the amount and/or rate of carbonate precipitation and methane contribution to the bicarbonate source. The results of the three stable isotope systems, mineralogy and petrography, show that mineral composition, the geochemical environment of authigenic carbonates and carbon source can control the calcium isotope fractionation.This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (KZCX2-YW-GJ03-01), the National Natural Science Foundation of China (40706022, U0733003 and 41176052), the National Basic Research Program of China (2009CB219502-4) and the Knowledge Innovation Program of South China Sea Institute of Oceanology, Chinese Academy of Sciences (LYQY200806). The authors thank the University of Aveiro and Universität Münster for the facilities provided for this research. We appreciate the thoughtful and constructive comments provided by editors and reviewers, which improve the manuscript.publishe

Ancient Nursery Area for the Extinct Giant Shark Megalodon from the Miocene of Panama

BACKGROUND: As we know from modern species, nursery areas are essential shark habitats for vulnerable young. Nurseries are typically highly productive, shallow-water habitats that are characterized by the presence of juveniles and neonates. It has been suggested that in these areas, sharks can find ample food resources and protection from predators. Based on the fossil record, we know that the extinct Carcharocles megalodon was the biggest shark that ever lived. Previous proposed paleo-nursery areas for this species were based on the anecdotal presence of juvenile fossil teeth accompanied by fossil marine mammals. We now present the first definitive evidence of ancient nurseries for C. megalodon from the late Miocene of Panama, about 10 million years ago. METHODOLOGY/PRINCIPAL FINDINGS: We collected and measured fossil shark teeth of C. megalodon, within the highly productive, shallow marine Gatun Formation from the Miocene of Panama. Surprisingly, and in contrast to other fossil accumulations, the majority of the teeth from Gatun are very small. Here we compare the tooth sizes from the Gatun with specimens from different, but analogous localities. In addition we calculate the total length of the individuals found in Gatun. These comparisons and estimates suggest that the small size of Gatun's C. megalodon is neither related to a small population of this species nor the tooth position within the jaw. Thus, the individuals from Gatun were mostly juveniles and neonates, with estimated body lengths between 2 and 10.5 meters. CONCLUSIONS/SIGNIFICANCE: We propose that the Miocene Gatun Formation represents the first documented paleo-nursery area for C. megalodon from the Neotropics, and one of the few recorded in the fossil record for an extinct selachian. We therefore show that sharks have used nursery areas at least for 10 millions of years as an adaptive strategy during their life histories

Direct measurement of 44Ca/40Ca ratios by MC-ICP-MS using the cool plasma technique

Here, we present a new technique for the direct measurement of 44Ca/40Ca isotope ratios on a Multicollector Inductively Coupled Plasma Mass Spectrometer (MC–ICP–MS, AXIOM) using the “cool plasma” technique. By reducing the plasma energy to about 400 W, the isobaric effect resulting from 40Ar+ can be significantly reduced, enabling the simultaneous and precise measurement of 44Ca and 40Ca beam intensities in different Faraday cups. In contrast to the TIMS technique requiring a 43Ca/48Ca double spike, the isotope measurements on MC–ICP–MS can be performed by bracketing standards. We express the calcium isotope variation relative to NIST SRM 915a (δ44/40Ca [‰]=[((44Ca/40Ca)sample/(44Ca/40Ca)NIST SRM 915a)−1]*1000). Isobaric effects of 24Mg16O+ and 23Na16OH+ interfering with 40Ca and 26Mg16OH2+ with 44Ca can be neglected by measuring calcium isotopes near the low-mass edge of the peaks. No influence of 87Sr2+ monitored on 43.5 atomic mass units (amu) was found. Repeated measurements of two Johnson Matthey CaCO3 standards (lot No. 4064 and lot No. 9912) revealed values of about −11.29 (‰ SRM 915a) and 0.57 (‰ SRM 915a). These values are in accordance with previous values published by Russell et al. [Geochim. Cosmochim. Acta 42 (1978) 1075], Heuser et al. [Int. J. Mass Spectrom. 220 (2002) 385], Hippler et al. [Geostand. Newsl. 27 (2003) 267] and Schmitt et al. [Geochim. Cosmochim. Acta 67 (2003) 2607]. Repeated measurement of the NIST SRM 915a CaCO3 standard showed that the variance of a single δ44/40Ca measurement is about 0.14‰ RSD being comparable with TIMS. MC–ICP–MS-based δ44/40Ca values measured on inorganically precipitated aragonite samples are indistinguishable from earlier measurements based on TIMS, confirming the positive correlation of δ44/40Ca and temperature. MC–ICP–MS-based δ44/40Ca measurements on cultured Orbulina universa showed a slope of about 0.026‰/°C being similar to the TIMS-based δ44/40Ca measurements showing a slope of about 0.019‰/°C. The large offset of about 5‰ between the two techniques is shown to be caused by a “matrix” effect, indicating that any δ44/40Ca measurements on MC–ICP–MS are sensitively controlled by the Ca concentration and the acidity of the solution. Our study demonstrates the possibility to measure the whole dispersion of calcium isotopes with MC–ICP–MS, showing that 40Ca can be used for normalization of 44Ca

Untersuchungen ueber den Einfluss konkurrierender Vegetationen auf die Wirtschaftsbaumarten in Forstkulturen und Naturverjuengungen Anlage

SIGLETIB Hannover: D.Dt.F./AC 1000 (14,53) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekDEGerman

The Pacific Equatorial Age Transect, IODP Expeditions 320 and 321: Building a 50-Million-Year-Long Environmental Record of the Equatorial Pacific

In March 2009, the R/V JOIDES Resolution returned to operations after its extended refit and began with a drilling program ideally suited to its drilling strengths, the Pacific Equatorial Age Transect (PEAT, IODP Exp 320/321; Fig. 1A). The PEAT drilling program was developed to understand how a major oceanic region evolved over the Cenozoic Era(65–0 Ma) and how it interacted with global climate. It specifically targeted the interval between 52 Ma and 0 Ma and drilled a series of sites that originated on the paleoequator. These sites have since been moved to the northwest by plate tectonics.The equatorial Pacific is an important target for paleocean ographic study because it is a significant ‘cog’ in the Earth’s climate machine, representing roughly half of the total tropical oceans that in turn represent roughly half of the total global ocean area. Prior drilling in both the Deep Sea Drilling Project (DSDP) and the Ocean Drilling Program (ODP) outlined the changes that have occurred through the Cenozoic (e.g., van Andel et al., 1975; Pisias et al., 1995). Not only did the earlier work fail to cover sufficient timeintervals but also many of the sites were cored with ‘first-generation’ scientific drilling technology with incomplete and disturbed sediment recovery and thus cannot be used for detailed studies

Coccolith strontium to calcium ratios in Emiliania huxleyi: The dependence on seawater strontium and calcium concentrations.

In recent studies the Sr/Ca ratio of coccolithophore calcite was used as a proxy for past coccolithophore growth and calcification rates. Since Sr and Ca concentrations in seawater have not remained constant through time, interpretation of Sr/Ca data from the coccolith-dominated sedimentary record requires knowledge about the incorporation of seawater Sr into coccolith calcite during coccolithogenesis. Here we show that Sr/Ca of Emiliania huxleyi coccoliths is linearly related to seawater Sr/Ca, meaning that the Sr exchange coefficient does not change with changing seawater Sr/Ca. The exchange coefficient for Sr in this study, 0.39, is close to values presented in the literature and is high compared with values obtained by inorganic precipitation experiments. This suggests a strong effect of cell physiology on biogenic calcite precipitation in coccolithophores. We present a conceptual model, based on the transmembrane transport of Sr and Ca, which explains the offset