ALBERT

Description: Coccoliths comprise a major fraction of the global carbonate sink. Therefore, changes in coccolithophores' Ca isotopic fractionation could affect seawater Ca isotopic composition, affecting interpretations of the global Ca cycle and related changes in seawater chemistry and climate. Despite this, a quantitative interpretation of coccolith Ca isotopic fractionation and a clear understanding of the mechanisms driving it are not yet available. Here, we address this gap in knowledge by developing a simple model (CaSri–Co) to track coccolith Ca isotopic fractionation during cellular Ca uptake and allocation to calcification. We then apply it to published and new δ44/40Ca and Sr/Ca data of cultured coccolithophores of the species Emiliania huxleyi and Gephyrocapsa oceanica. We identify changes in calcification rates, Ca retention efficiency and solvation–desolvation rates as major drivers of the Ca isotopic fractionation and Sr/Ca variations observed in cultures. Higher calcification rates, higher Ca retention efficiencies and lower solvation–desolvation rates increase both coccolith Ca isotopic fractionation and Sr/Ca. Coccolith Ca isotopic fractionation is most sensitive to changes in solvation–desolvation rates. Changes in Ca retention efficiency may be a major driver of coccolith Sr/Ca variations in cultures. We suggest that substantial changes in the water structure strength caused by past changes in temperature could have induced significant changes in coccolithophores' Ca isotopic fractionation, potentially having some influence on seawater Ca isotopic composition. We also suggest a potential effect on Ca isotopic fractionation via modification of the solvation environment through cellular exudates, a hypothesis that remains to be tested.

Description: Highlights • Six combined 231Pa/230Th and εNdεNd down-core profiles back to 25 ka are presented. • Increased influence of SCW and northward advection of deep waters during LGM/HS1. • Evidence for an active but shallower northern overturning cell during LGM/HS1. Abstract Reconstructing past modes of ocean circulation is an essential task in paleoclimatology and paleoceanography. To this end, we combine two sedimentary proxies, Nd isotopes (εNdεNd) and the 231Pa/230Th ratio, both of which are not directly involved in the global carbon cycle, but allow the reconstruction of water mass provenance and provide information about the past strength of overturning circulation, respectively. In this study, combined 231Pa/230Th and εNdεNd down-core profiles from six Atlantic Ocean sediment cores are presented. The data set is complemented by the two available combined data sets from the literature. From this we derive a comprehensive picture of spatial and temporal patterns and the dynamic changes of the Atlantic Meridional Overturning Circulation over the past ∼25 ka. Our results provide evidence for a consistent pattern of glacial/stadial advances of Southern Sourced Water along with a northward circulation mode for all cores in the deeper (〉3000 m) Atlantic. Results from shallower core sites support an active overturning cell of shoaled Northern Sourced Water during the LGM and the subsequent deglaciation. Furthermore, we report evidence for a short-lived period of intensified AMOC in the early Holocene.

Description: Oxygen isotope values of the extant Caribbean coralline sponge Ceratoporella nicholsoni are compared with published temperatures and δ18O of water calculated from salinities. The measured values from aragonitic sponge skeletons have a mean offset of 1.0 ± 0.1‰ from calculated calcite equilibrium values (αaragonite-calcite = 1.0010). This is in good agreement with published values from synthetic aragonite. They further agree with published near-equilibrium oxygen isotope values of temperate and cold water molluscs and foraminifera extrapolated to the temperature range of the coralline sponges. These results and the mode of skeleton formation of Ceratoporella nicholsoni suggest that these sponges precipitate aragonite close to isotopic equilibrium. The temperature dependence of oxygen isotopic fractionation between the aragonite of Ceratoporella nicholsoni and water is only roughly constrained by the available data, due to the narrow temperature range of the Caribbean reef sites. However, as the data suggest oxygen isotopic equilibrium, we can calculate a well constrained temperature equation combining temperate and cold water equilibrium values from molluscs and foraminifera with our sponge data: Full-size image (〈1 K) and Full-size image (〈1 K).

Description: Conflicting results have been reported for the stable Sr isotope fractionation, specifically with respect to the influence of temperature. In an experimental study we have investigated the stable Sr isotope systematics for inorganically precipitated and biogenic (coral) aragonite (natural and laboratory-cultured). Inorganic aragonite precipitation experiments were performed from natural seawater using the CO2 diffusion technique. The experiments were performed at different temperatures and different carbonate ion concentrations. 88Sr/86Sr of the inorganic aragonite precipitated in the experiments are 0.2‰ lighter than seawater, but showed no correlation to the water temperature or to CO32− concentration. Similar observations are made in different coral species (Cladocora caespitosa, Porites sp. and Acropora sp.), with identical fractionation from the bulk solution and no correlation to temperature or CO32− concentration. The lack of 88Sr/86Sr variability in corals at different environmental parameters and the similarity to the 88Sr/86Sr fractionation in inorganic aragonite may indicate a similar Sr incorporation mechanism in corals skeleton and inorganic aragonite, and therefore the previously proposed Rayleigh-based multi element model (Gaetani et al., 2011) cannot explain the process of Sr incorporation in the coral skeletal material. It is proposed that the relatively constant 88Sr/86Sr fractionation in aragonite can be used for paleo reconstruction of seawater 88Sr/86Sr composition. The seawater 88Sr/86Sr ratio reconstruction can be further used in calcite samples to reconstruct paleo precipitation rates.

Description: The aim of this study was the documentation of the molecular immune response of Suberites domuncula upon bacterial infection. Additionally, the bacteria that are naturally present in the sponge after prolonged aquarium maintenance were characterized. After 6 months of maintenance of S. domuncula in seawater aquaria, only one bacterial 16S rDNA sequence could be recovered, which belongs to the genus Pseudomonas. Concomitantly, morphologically uniform bacteria were found encapsulated in bacteriocytes. These findings indicate that certain bacteria, possibly of the genus Pseudomonas, are able to persist for long periods in host bacteriocytes. Subsequent to performing a previously established infection assay with S. domuncula, a potentially pathogenic Vibrio sp. was isolated from the tissues. Furthermore, the host tissue disintegrated and asexual propagation bodies (gemmules) were formed. In order to gain insights into the molecular events occurring after bacterial infection, the stress-response kinases, p38 protein kinase and JNK protein kinase, were analyzed. It is demonstrated that these two kinases are activated (phosphorylated) upon incubation of the tissue with the bacterial endotoxin lipopolysaccharide (LPS). Moreover, LPS strongly inhibits protein synthesis. It is concluded that there are many functionally different interactions between S. domuncula and bacteria and that the animal possesses mechanisms to differentiate between bacteria and to respond accordingly.

Description: The Kälberstein quarry at Berchtesgaden exposes Carnian-Norian deeper-water Hallstatt limestones. Conodont biostratigraphy, microfacies and stable isotopes of bulk carbonate matrix were investigated. The biostratigraphic results demonstrate a complete succession from the latest Carnian (Tuvalian 3/I) to the late Norian (Sevatian 2). As expected from the periplatform setting of the Hallstatt Zone, calculated mass accumulation rates conform partly to prograding sequences observed on the contemporary Dachstein platform. However, discrepancies exist, mainly for the middle Norian, pointing to an incomplete knowledge of the platform sequences. The sequence stratigraphic framework based on platform data should be complemented with data from the periplatform Hallstatt Zone. Diagenetic alteration of the limestones from Kälberstein quarry is low with a conodont alteration index (CAI)=1.0 throughout the section. Oxygen isotope values ranging from ± 1.2 to + 0.1½ (VPDB) point to stabilization and cementation at very shallow burial depths in contact with seawater in a deeper-water environment. Carbon isotope values display a clear stratigraphic trend with a rapid increase from 3.6 to 4.1½ (VPDB) during the basal Norian (Lacian 1), high values up to 4.2½ during the Lacian 2, and a slow decline starting in Lacian 3 to 2.6½ at the end of the Norian (Sevatian 1±2). These trends are best explained by variations in the global organic carbon/carbonate burial ratio with maximum organic carbon burial during the middle Lacian.

Description: The most important archive of Earth’s climate change through geologic history is the sedimentary rock record. Rhythmic sedimentary alternations are usually interpreted as a consequence of periodic variations in the orbital parameters of the Earth. This interpretation enables the application of cyclostratigraphy as a very precise chronometer, when based on the assumption that orbital frequencies are faithfully recorded in the sedimentary archive. However, there are numerous uncertainties with the application of this concept. Particularly in carbonates, sediment properties such as mineralogical composition and fossil associations are severely altered during post-depositional alteration (diagenesis). We here point out that the assumption of a 1:1 recording of orbital signals in many cases is questionable for carbonate rhythmites. We use computer simulations to show the effect of diagenetic overprint on records of orbital signals in the carbonate record. Such orbital signals may be distorted in terms of frequency, amplitude, and phase by diagenetic processes, and cycles not present in the insolation record may emerge. This questions the routine use of carbonate rhythmites for chronostratigraphic dating

Description: The nature of rhythmic carbonate-rich successions such as limestone^marl alternations has been, and still is, subject to controversy. The possibility of an entirely diagenetic origin for the rhythmic calcareous alternations is discarded by most authors. One problem with an entirely diagenetic, self-organized development of limestone^marl alternations is the fact that limestone and marl beds in many examples are laterally continuous over hundreds of meters or even kilometers. In an entirely self-organized system, lateral coupling would be very limited; thus one would expect that, rather than laterally continuous beds, randomly distributed elongate nodules would form. We address the origin of limestone^marl alternations using a computer model that simulates differential diagenesis of rhythmic calcareous successions. The setup uses a cellular automaton model to test whether laterally extensive, rhythmic calcareous alternations could develop from homogeneous sediments in a process of self-organization. Our model is a strong simplification of early diagenesis in fine-grained, partly calcareous sediments. It includes the relevant key mechanisms to the question whether an external trigger is required in order to obtain laterally extensive limestone^ marl alternations. Our model shows that diagenetic self-organization alone is not sufficient to produce laterally extensive, correlatable beds. Although an external control on bedding formation could be considered to have solved the problem as commonly assumed, we here suggest an interesting third possibility: the rhythmic alternations were formed through the interaction of both an external trigger and diagenetic self-organization. In particular we observe that a very limited external trigger, either in time or amplitude, readily forms correlatable beds in our otherwise diagenetic model. Remarkably, the resulting rhythmites often do not mirror the external trigger in a one-to-one fashion and may differ in phase, frequency and number of couplets. Therefore, the interpretation of calcareous rhythmites as a one-to-one archive of climate fluctuations may be misleading. Parameters independent of diagenetic alteration should be considered for unequivocal interpretation.

Description: We evaluate the potential of ophiolites as archives of paleoseawater and hydrothermal fluid compositions by analysing the chemical and isotopic composition of abiogenic carbonates, precipitated from fluids within the oceanic crust of the 91 Ma Troodos Ophiolite, Cyprus. Calculated variations in fluid Mg/Ca, Sr/Ca and Sr-87/ Sr-86 with temperature within the upper sections of the ophiolite are similar to those from drilled oceanic crust, and yield literature values for late Cretaceous seawater Mg/Ca, Sr/Ca and Sr-87/ Sr-86. This indicates that carbonates from ophiolites could be used to estimate the composition of ancient seawater at times before the age of the oldest preserved in-situ oceanic crust. Whereas most carbonates recovered from in-situ oceanic crust were precipitated at temperatures 〈 60 degrees C, abiogenic carbonates from the Troodos Ophiolite formed over a temperature range of 7 degrees C to 218 degrees C. These provide unique insights into the chemical and mineralogical processes that transform seawater into a high temperature hydrothermal fluid within the oceanic crust. We use 'hydrothermal variation diagrams' of Mg/Ca, Sr/Ca, Sr-87/ Sr-86 and delta(44)/Ca-40 versus calculated temperature (delta O-18) to trace this fluid evolution within the Troodos oceanic crust. We find that successive fluid-crust-interaction, the precipitation of Mg- and Ca-bearing minerals and the early formation of anhydrite (〉 44 degrees C) gradually transform Cretaceous seawater into a Troodos hydrothermal fluid. Comparison of the Troodos data with a global dataset of abiogenic carbonates from in-situ oceanic crust shows that the chemical pathways of low-temperature fluid evolution are similar for all Cretaceous sites. These different sites represent varied geotectonic settings (midocean ridge vs. suprasubduction zone), with different basement composition (basalt, basaltic andesite/boninite) and situated in different ocean basins (Atlantic, Pacific, Mediterranean [Tethys]). The similarity in the carbonate record indicates that these differences do not significantly influence seafloor weathering and hydrothermal alteration at low temperatures. However, abiogenic carbonates from younger oceanic crust differ from the Cretaceous trends and follow different fluid evolution pathways. This indicates, that temporal variations in the composition of seawater may control the nature and the extent of seafloor weathering and hydrothermal alteration at low temperatures. A thermodynamic model of fluid-crust interaction, in which modern and Cretaceous seawater are heated to 200 degrees C while an average Troodos basaltic andesite is successively added under otherwise identical conditions predicts that fluid evolution and alteration of the oceanic crust were different in the Cretaceous than they are today, and that initial seawater chemistry affects the nature and the extent of seafloor alteration up to moderate fluid temperatures. For example, twice the amount of carbonate formed during alteration of the oceanic crust in the Cretaceous compared to modern times, indicating that the flux of CO2 from the hydrosphere-atmosphere system into the oceanic crust was greater in the Cretaceous than it is nowadays, and that it probably varied throughout geologic time.

Description: The calcium isotope ratios (δ44Ca = [(44Ca/40Ca)sample/(44Ca/40Ca)standard −1] · 1000) of Orbulina universa and of inorganically precipitated aragonite are positively correlated to temperature. The slopes of 0.019 and 0.015‰ °C−1, respectively, are a factor of 13 and 16 times smaller than the previously determined fractionation from a second foraminifera, Globigerinoides sacculifer, having a slope of about 0.24‰ °C−1. The observation that δ44Ca is positively correlated to temperature is opposite in sign to the oxygen isotopic fractionation (δ18O) in calcium carbonate (CaCO3). These observations are explained by a model which considers that Ca2+-ions forming ionic bonds are affected by kinetic fractionation only, whereas covalently bound atoms like oxygen are affected by kinetic and equilibrium fractionation. From thermodynamic consideration of kinetic isotope fractionation, it can be shown that the slope of the enrichment factor α(T) is mass-dependent. However, for O. universa and the inorganic precipitates, the calculated mass of about 520 ± 60 and 640 ± 70 amu (atomic mass units) is not compatible with the expected ion mass for 40Ca and 44Ca. To reconcile this discrepancy, we propose that Ca diffusion and δ44Ca isotope fractionation at liquid/solid transitions involves Ca2+-aquocomplexes (Ca[H2O]n2+ · mH2O) rather than pure Ca2+-ion diffusion. From our measurements we calculate that such a hypothesized Ca2+-aquocomplex correlates to a hydration number of up to 25 water molecules (490 amu). For O. universa we propose that their biologically mediated Ca isotope fractionation resembles fractionation during inorganic precipitation of CaCO3 in seawater. To explain the different Ca isotope fractionation in O. universa and in G. sacculifer, we suggest that the latter species actively dehydrates the Ca2+-aquocomplex before calcification takes place. The very different temperature response of Ca isotopes in the two species suggests that the use of δ44Ca as a temperature proxy will require careful study of species effects.