ALBERT

Description: The ratio of sodium to calcium (Na/Ca) in foraminiferal calcite has been proposed as a proxy for salinity, yet relatively little is known about the incorporation of sodium into the shells of foraminifera. Ongoing debates include the location of Na in the calcite crystal lattice, the possibility that at least some Na might be complexed with organics, and the influence of spines/spine bases. We present new Na/Ca measurements, determined using both solution and laser ablation ICP-MS, of the planktonic foraminifera Globigerinoides ruber (white) from plankton tows and sediment traps spanning a wide salinity range (32.5–40.7 salinity units), laboratory cultures under varying carbonate chemistry, and globally-distributed core-top samples. Our results show that Na/Ca in recently living foraminifera measured by laser ablation ICP-MS is elevated by up to 5 mmol/mol (∼85%) relative to the same samples measured by solution ICP-MS (the same comparison for Mg/Ca shows excellent agreement between the techniques). Na/Ca in recently living foraminifera measured by laser ablation ICP-MS displays a significant relationship with salinity above ∼36 salinity units with a slope of ∼0.7 mmol/mol/salinity unit; however, only a weak relationship is observed between salinity and Na/Ca measured by solution ICP-MS. We propose that Na is incorporated in at least two discrete phases; a primary phase within the CaCO3 mineral, and a (or likely multiple) secondary phase(s). Possibilities for these secondary phases include residual metastable CaCO3, fluid inclusions, high Na/Ca spine bases, and organics. These secondary phases contribute to spatially-resolved analyses (i.e. laser ablation ICP-MS) of recently living foraminifera but are removed by crushing/oxidative cleaning for solution ICP-MS, and during early diagenesis, as evidenced by the agreement between laser analysis of coretop samples and Na/Ca measured by solution. The amount of one of these secondary phases, or the amount of Na within this phase, appears to vary as a function of salinity, and is likely the principal driver of the previously observed steep Na/Ca-salinity relationship in recently living foraminifera analysed by laser ablation. Overall, we find salinity, temperature, carbonate chemistry, and bottom water saturation state (Ωcalcite) all have a significant but relatively weak effect on Na/Ca in the primary calcite phase. As such, Na/Ca in planktonic foraminifera recovered from sediment cores is unlikely to find widespread utility as a salinity proxy.

Description: Seawater chemistry exerts an important control on the incorporation of trace elements into the shells of marine calcifying organisms. Variability in the major ion chemistry of seawater is a tracer of past geological processes, and the influence of seawater chemistry on trace element incorporation in calcium carbonate can be harnessed to determine changes in the composition of seawater through time. Here, we investigate whether key oceanographic parameters (temperature, salinity, and the carbonate system) affect the incorporation of potassium (K) into foraminiferal calcite, and explore the utility of K/Ca ratios in foraminifera as an indicator of past variability in the seawater Ca2+ concentration. We analysed both low-Mg and high-Mg modern foraminifera, including planktonic (Globigerinoides ruber) and shallow-dwelling larger benthic (Operculina ammonoides) species, using laser-ablation sector-field inductively-coupled plasma mass spectrometry (LA-SF-ICPMS). Both species show no resolvable influence of temperature, salinity, pH, or [CO32−] on K incorporation across the range that these vary at our samples sites. In order to determine the effect of the seawater Ca concentration ([Ca2+]sw) on K incorporation, we analysed laboratory-cultured O. ammonoides, the close living relative of the abundant Eocene Nummulites, grown at four different [Ca2+]sw. We find a significant relationship between seawater and shell K/Ca, albeit with a shallower slope compared to most other trace elements which we suggest is driven by a crystal growth rate effect on K incorporation, constrained using culture experiments of O. ammonoides grown at different pH. If the K+ concentration has remained relatively constant throughout the Phanerozoic Eon, our data may pave the way forward for the use of K/Ca as a direct proxy for past [Ca2+]sw variability. Alternatively, coupling K/Ca with the similar Na/Ca proxy would allow more accurate reconstruction of [Ca2+]sw or verification of whether [K+]sw and [Na+]sw have indeed remained within narrow bounds.

Description: We present kinematic, radiometric, geochemical and PT data, which help to constrain the tectonometamorphic evolution of the Tripolitza Unit (TPU). The age of both the metamorphic peak (P = 0.4 ±0.2 GPa, T = ca. 310 °C) and top-to-the WNW mylonitic thrusting, attributed to the emplacement of the hanging Pindos nappe, has been constrained at 19 ±2.5 Ma using Rb-Sr on synkinematic white mica of a basal mylonite of NW Crete. This early tectonic event is also documented by the oldest generation of veins, which cut through less metamorphic (T = 240 ±15 °C) late Bartonian/Priabonian Nummulite limestone exposed as olistolith in TPU flysch of central Crete. Calcite of these veins yielded a similar U-Pb age at 20 ±6 Ma. U-Pb dating of matrix calcite, on the other hand, reflect the time of sedimentation (38.4 ±5.7 Ma and 37.6 ±1.2 Ma), which is in line with the faunal content of the black limestone. Geochemical data and U-Pb calcite ages of fibres of the Nummulite test (32.3 ±3.1 Ma and 34.6 ±0.9 Ma) suggest unexpected pseudomorphic fibre replacement during late Priabonian/early Rupelian diagenesis. Additional calcite veins, which developed at ca. 10–11 and 7 – 9 Ma (U-Pb on calcite), are attributed to top-to-the S thrusting and subsequent extension, respectively. The resulting anticlockwise rotation of the shortening direction within the TPU from WNW-ESE at ca. 20 Ma to N-S at ca. 10 Ma has significant implications for the geodynamic evolution of the External Hellenides.

Description: The frequency of occurrence of extreme weather events, such as heat waves, severe storms, and extreme precipitation has increased dramatically in recent years and is expected to further increase with rising global temperatures. Extreme weather events and their changing characteristic due to rising global temperatures have a large societal impact. Exemplary, extremely warm summers can lead to severe health problems and are thus associated with an increased mortality. Furthermore, economic impacts, such as crop failure and water shortage, and political aspects, such as climate migration and general crisis management are associated with extremely warm summers. Reliable and precise predictability years in advance of these high-impact events would be crucial to reduce potential impacts. We use the demonstrated processes connecting the North Atlantic circulation and European temperatures (Hellmich et al., in review) to enhance the prediction skill of extremely warm European summers. The North Atlantic heat inertia can drive extremely warm European summers on sub-decadal time scales, thus acting as a precursor for the occurrence of such extreme events. Here we demonstrate how the sub-decadal North Atlantic heat inertia can be used to predict extremely warm European summers several years in advance, using a decadal hindcast ensemble based on the Max-Planck-Institute Earth system model.