Description: The concentration of 230Th in Mn crust VA13-2 (146°W, 9°25′S, 4830 m) from the Pacific Ocean was measured with high depth resolution (0.02 mm) to a depth of 1.4 mm corresponding to an age of ∼226 ka B.P. The mean growth rate estimated from these results is 6.2 ± 0.4 mm/Ma. However, the exponential curve obtained shows two drastic events in the 230Th concentration record with durations of41 ± 4 ka and 37 ± 6 ka which are interpreted as growth standstills. The decay-corrected 230Th concentration is inversely correlated with those of Mn, Fe and Co indicating that the 230Th flux into the crust has been constant throughout time and that the observed fluctuations in 230Th are due to dilution by the main components. By applying a constant 230Th flux model, high-resolution growth rates were derived from every sample investigated. A detailed comparison of the growth pattern with the SPECMAP time table reveals that the VA13-2 growth rates tend to be higher during interglacial than during glacial periods. In particular, the observed growth standstills are associated with glacial stages 6 and 8. Further investigation of Mn crust 72 DK 9 taken from shallower water (170°35′W, 20°13′N, 1550 m) tend to confirm that there is a link between the growth rates of hydrogenetic crusts and the climate of the Late Quaternary.

Description: In order to study Strontium (Sr) partitioning and isotope fractionation of Sr and Calcium (Ca) in calcite we performed precipitation experiments decoupling temperature and precipitation rate (R∗). Calcite was precipitated at 12.5, 25.0 and 37.5 °C by diffusing NH3 and CO2 gases into aqueous solutions closely following the experimental setup of Lemarchand et al (2004). The precipitation rate (R∗) for every sample was determined applying the initial rate method and from the specific surface area of almost all samples for each reaction. The order of reaction with respect to Ca2+ ions was determined to be one and independent of T. However, the order of reaction with respect to HCO3- changed from three to one as temperature increases from 12.5, 25 °C and 37.5 °C. Strontium incorporated into calcite (expressed as DSr= [Sr/Ca] calcite/ [Sr/Ca] solution) was found to be R∗ and T dependent. As a function of increasing R∗ the Δ88/86Sr-values become more negative and as temperature increases the Δ88/86Sr values also increase at constant R∗. The DSr and Δ88/86Sr-values are correlated to a high degree and depend only on R∗ being independent of temperature, complexation and varying initial ratios. Latter observation may have important implications for the study of diagenesis, the paleo-sciences and the reconstruction of past environmental conditions. Calcium isotope fractionation (Δ44/40Ca) was also found to be R∗ and T dependent. For 12.5 and 25.0 °C we observe a general increase of the Δ44/40Ca values as a function of R∗ (Lemarchand et al type behavior, Lemarchand et al (2004)). Whereas at 37.5 °C a significant decreasing Δ44/40Ca is observed relative to increasing R∗ (Tang et al type behavior, Tang et al. (2008)). In order to reconcile the discrepant observations we suggest that the temperature triggered change from a Ca2+-NH3-aquacomplex covalent controlled bonding to a Ca2+-H2O-aquacomplex van-der-Waals controlled bonding caused the change in sign of the R∗ - Δ44/40Ca slope due to the switch of an equilibrium type of isotope fractionation related to the covalent bonding during lower temperatures to a kinetic type of isotope fractionation at higher temperatures. This is supported by the observation that the Δ44/40Ca ratios are independent from the [Ca]: [DIC] ratio at 12.5 and 25°C but highly dependent at 37.5°C. Our observations imply the chemical fluid composition and temperature dependent complexation controls the amount and direction of Ca isotope fractionation in contrast to the Sr isotopes which do not show any change of its fractionation behaviour as a function of complexation in the liquid phase.

Description: The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (δ44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the δ44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of δ44/40Ca ranges from 0.6 to 0.1‰, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and δ44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by δ18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's δ44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean. Highlights ► Corals cultured in aquaria or from natural environment show the same Ca isotopic composition. ► δ44/40Ca of coral skeleton is independent of depositional setting environment. ► Strong influence of vital effects on coral skeleton δ44/40Ca composition and calcification mechanisms

Description: The recrystallisation (dissolution–precipitation) of carbonate sediments has been successfully modelled to explain profiles of pore water Sr concentration and radiogenic Sr isotope composition at different locations of the global ocean. However, there have been few systematic studies trying to better understand the relative importance of factors influencing the variability of carbonate recrystallisation. Here we present results from a multi-component study of recrystallisation in sediments from the Integrated Ocean Drilling Program (IODP) Expedition 320/321 Pacific Equatorial Age Transect (PEAT), where sediments of similar initial composition have been subjected to different diagenetic histories. The PEAT sites investigated exhibit variable pore water Sr concentrations gradients with the largest gradients in the youngest sites. Radiogenic Sr isotopes suggest recrystallisation was relative rapid, consistent with modelling of other sediment columns, as the 87Sr/86Sr ratios are indistinguishable (within 2σ uncertainties) from contemporaneous seawater 87Sr/86Sr ratios. Bulk carbonate leachates and associated pore waters of Site U1336 have lower 87Sr/86Sr ratios than contemporaneous seawater in sediments older than 20.2 Ma most likely resulting from the upward diffusion of Sr from older recrystallised carbonates. It seems that recrystallisation at Site U1336 may still be on-going at depths below 102.5 rmcd (revised metres composite depth) suggesting a late phase of recrystallisation. Furthermore, the lower Sr/Ca ratios of bulk carbonates of Site U1336 compared to the other PEAT sites suggest more extensive diagenetic alteration as less Sr is incorporated into secondary calcite. Compared to the other PEAT sites, U1336 has an inferred greater thermal gradient and a higher carbonate content. The enhanced thermal gradient seems to have made these sediments more reactive and enhanced recrystallisation. In this study we investigate stable Sr isotopes from carbonate-rich deep sea sediments for the first time. Pore water δ88/86Sr increases with depth (from 0.428‰ to values reaching up to 0.700‰) at Site U1336 documenting an isotope fractionation process during recrystallisation. Secondary calcite preferentially incorporates the lighter Sr isotope (86Sr) leaving pore waters isotopically heavy. The δ88/86Sr values of the carbonates themselves show more uniform values with no detectable change with depth. Carbonates have a much higher Sr content and total Sr inventory than the pore waters meaning pore waters are much more sensitive to fractionation processes than the carbonates. The δ88/86Sr results indicate that pore water stable Sr isotopes have the potential to indicate the recrystallisation of carbonate sediments.

Description: Dust is a relatively unconstrained flux in the geochemical cycle of Ca. The isotopic composition of dust-derived Ca has not been studied, though it is an important part of any attempt at deciphering Ca isotope-based proxy records. Accordingly, this study reports the elemental and calcium isotope geochemistry of 30 surface (upper ∼0.5 cm) sediments from an arid dust producer, the Black Rock Desert in northwestern Nevada. Geochemical data for sequential water and 0.5 N HCl leaches, meant to sample mobile Ca, and selected leached residues are presented, along with X-ray diffraction (XRD) determinations of major mineralogy. Bulk playa sediments have Ca concentrations between 0.28 and 40 wt.% (median: 6.8 wt.%) and calcite concentrations of 2–32%. Isotopically, Ca sampled by water leaches (〈1% of total Ca) are, on average, +0.33 ± 0.16‰ (1 SD) heavier than acid leaches (〉60% of total Ca), though the degree of fractionation (Δw-a) varies between 0‰ and 0.6‰. Acid leaches, which are the primary component of mobile Ca in the sediments, have δ44CaSRM-915a values of 0.78 ± 0.08‰, similar to the δ44Ca of modern nannofossil ooze and modern rivers. This means that dust produced in closed continental basins likely has little isotopic leverage to change the ocean’s isotopic composition, and suggests that the Ca isotopic composition of dust is tied to rivers/weathering. In addition, while the Ca concentration data in the water leach suggest that evaporative evolution controls the amount of Ca in this reservoir, the isotope data are inconsistent with this conclusion. Instead, we hypothesize that adsorption of Ca on clays controls the Ca isotope systematics in the water leach. This hypothesis requires that there is no significant isotopic fractionation during evaporite mineral precipitation and may suggest that sorption at rates appropriate for natural systems might fractionate differently than sorption at laboratory rates.

Description: Tropical coral reefs are among the most diverse marine ecosystems. In order to better understand temporal and spatial variation in late Quaternary biodiversity, foraminiferal faunas of two fossil, raised reef terraces at the southern Sinai Peninsula were studied and compared to modern coral reef faunas. Eleven U-series dates of shell fragments of the giant clam Tridacna sp. indicates deposition largely during marine isotope stage 5 (MIS 5), 77–129 kyr BP, for the two raised terraces. In these terraces, Amphistegina (A. lessonii and A. lobifera) dominates the five fossil foraminiferal associations. The fossil reef-flat association 1 has common Gypsina plana, Homotrema rubra and Acervulina spp., and fossil reef-flat association 2 consists of Amphistegina spp. Of the three fossil fore-reef associations, one has abundant porcelaneous taxa including Sorites, Amphisorus, Peneroplis and Borelis, one has a mix of porcelaneous taxa and attached-arborescent taxa (Homotrema and Placopsilina) and one has abundant attached and arborescent taxa (Miniacina, Gypsina, Acervulina and Planogypsina). The modern fringing reef is dominated by porcelaneous foraminifera, and three modern associations are identified. These include a lagoonal association with abundant Peneroplis pertusus, a reef-flat association dominated by Sorites orbiculus and a fore-reef association with porcelaneous taxa plus common H. rubra, Amphistegina lessonii and A. lobifera. Based on our data and including additional published information on regional biodiversity it appears that during MIS 5 foraminiferal biodiversity was higher and community structure was different than within the modern reefs. These data and regional paleo-climate patterns indicate that oceanographic conditions in the Red Sea were probably closer to normal marine conditions during the last interglacial than they are today.

Description: A multi-isotope approach has been used in the Marano lagoon (NE Italy) and parts of its catchment area to identify causes of increased NO3- pollution. The hydrogeochemical features of different water types and potential sources of NO3- were characterized using the isotopic composition of NO3- (delta N-15, delta O-18, and Delta O-17) and other source-related species such as B (delta B-11), water (delta H-2 and delta O-18) and SO42- (delta S-34 and delta O-18). Water samples from the lagoon, its tributary rivers, the groundwater up-welling line, groundwater, sewer pipes, and open sea water have been collected at quarterly intervals in the years 2009-2010. The results indicate that the NO3- load in the lagoon was not only derived from agricultural activities but also from other sources such as urban waste water, in situ nitrification and atmospheric deposition. The delta S-34 signature in the lagoon clearly denotes the largely prevailing origin of aqueous SO42- from seawater, and practically points to the absence of any appreciable redox process involving S species in the lagoon. It also supports the existence of a connection between the lagoon and the nearby Tagliamento river

Description: Highlights • δ44Ca was measured in bulk carbonate and barite at two sites over the PETM. • Diagenetic effects on δ44Ca are observed associated with ocean acidification. • Multiple sites and proxy archives necessary to reconstruct the past accurately. Abstract Carbonates are used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. However, these archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the possible effects of diagenesis on proxy fidelity, the impacts of diagenesis on the calcium isotopic composition (δ44Ca) of carbonates are unclear. To shed light on this issue, bulk carbonate δ44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene–Eocene Thermal Maximum (PETM, ∼55 Ma∼55 Ma). The δ44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large variations (∼0.8‰∼0.8‰) in bulk carbonate δ44Ca occur in the deeper of the two sites at depths corresponding to the peak carbon isotope excursion, which correlate with a large drop in carbonate weight percent. Such an effect is not observed in either the 1221 barite record or the bulk carbonate record at the shallower Site 1212, which is also less affected by dissolution. We contend that ocean chemical changes associated with abrupt and massive carbon release into the ocean–atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate δ44Ca record via diagenesis in the sedimentary column. Such effects are considerable, and need to be taken into account when interpreting Ca isotope data and, potentially, other geochemical proxies over extreme climatic events that drive sediment dissolution.

Description: Chemical (Sr, Mg) and isotopic (δ18O, 87Sr/86Sr) compositions of calcium carbonate veins (CCV) in the oceanic basement were determined to reconstruct changes in Sr/Ca and Mg/Ca of seawater in the Cenozoic. We examined CCV from 10 basement drill sites in the Atlantic and Pacific, ranging in age between 165 and 2.3 Ma. Six of these sites are from cold ridge flanks in basement 〈46 Ma, which provide direct information about seawater composition. CCV of these young sites were dated, using the Sr isotopic evolution of seawater. For the other sites, temperature-corrections were applied to correct for seawater–basement exchange processes. The combined data show that a period of constant/low Sr/Ca (4.46–6.22 mmol/mol) and Mg/Ca (1.12–2.03 mol/mol) between 165 and 30 Ma was followed by a steady increase in Mg/Ca ratios by a factor of three to modern ocean composition. Mg/Ca–Sr/Ca relations suggest that variations in hydrothermal fluxes and riverine input are likely causes driving the seawater compositional changes. However, additional forcing may be involved in explaining the timing and magnitude of changes. A plausible scenario is intensified carbonate production due to increased alkalinity input to the oceans from silicate weathering, which in turn is a result of subduction-zone recycling of CO2 from pelagic carbonate formed after the Cretaceous slow-down in ocean crust production rate.

Description: Mg/Ca and Sr/Ca ratios were determined on a single species of planktonic foraminiferan, Globigerinoides ruber (white), collected from the Gulf of Eilat and cultured in seawater at five different salinities (32 to 44), five temperatures (18 to 30 °C) and four pH values (7.9 to 8.4). The Mg/Ca-temperature calibration of cultured G. ruber (with an exponential slope of 8 ± 3%/°C) agrees well with previously published calibrations from core-tops and sediment traps. However, the dependence of Mg/Ca on salinity (with an exponential slope of 5 ± 3%/psu) is also significant and should be included in the calibration equation. With this purpose, we calculated a calibration equation for G. ruber dependent on both temperature and salinity within the 95% confidence limits: Mg/Ca(mmol/mol)=exp[0.06(±0.02)*S(psu)+0.08(±0.02)*T(°C)−2.8(±1.0)],R2=0.95 The influence of pH on Mg/Ca ratios is negligible at ambient seawater pH (8.1 to 8.3). However, we observe a dominating pH control on shell Mg/Ca when the pH of seawater is lower than 8.0. Sr/Ca in G. ruber shows a significant positive correlation with average growth rate. Presumably, part of the variability in shell Sr/Ca in the geological record is linked to changes in growth rates of foraminifera as a response to changing environmental conditions.