ALBERT

Description: The stable (δ18O and δ13C) and clumped (Δ47) isotope compositions of coral carbonate are valuable archives for paleoclimate reconstructions. However, the Δ47-temperature relationships of warm and cold-water corals deviate from that of inorganic carbonate precipitated at equilibrium. Dual clumped isotope thermometry of carbonates (i.e., simultaneous Δ47 and Δ48 measurements on a single carbonate) has the potential to achieve more accurate paleotemperature reconstruction, identifying and correcting for kinetically driven isotopic disequilibrium. Here we present the first extensive dual clumped isotope dataset of coral carbonate, spanning a broad range of cold and warm-water coral species. We confirm that corals are enriched in Δ47 and depleted in Δ48 relative to equilibrium, a pattern corresponding to the mixing of an equilibrium DIC pool with kinetically derived HCO3– produced by hydration and hydroxylation of CO2. Dual clumped isotope measurements of cold-water corals fall on the initial linear portion of model (IsoDIC) predicted departure from equilibrium. The dual clumped isotope composition of cold-water corals, corrected by the model-predicted Δ47/Δ48 offset slope (−0.78), yield accurate reconstruction of coral growth temperature with a precision of 〈3 °C at the 68% confidence level. In contrast, disequilibrium offsets in the Δ47 and Δ48 of warm-water corals correspond to precipitation from a more equilibrated DIC pool, which we attribute to the action of carbonic anhydrase in the calcifying fluid. It may be possible to correct warm-water coral growth temperatures, using an empirically derived correction (Δ47/ Δ48 offset slope of −0.4). Dual clumped isotope thermometry of coral carbonate opens new possibilities to reconstruct both sea surface temperatures and ocean dynamics of intermediate to deep water masses.

Description: Synchrotron-based powder diffraction measurements in combination with inductively coupled plasma optical emission spectrometry, Raman and fluorescence spectroscopy show that (Ba,Ca)2 can incorporate significant amounts (up to 6 ​mol%) of europium. This solid solution is therefore of potential interest for the solidification of nuclear waste streams involving aqueous nitrate solutions of lanthanides. Europium replaces Ba/Ca on lattice sites and is not incorporated as an interstitial defect. Charge compensation is likely due to the presence of OH−-groups as we could exclude a coupled substitution involving Na+. The Eu-containing compound is stable to at least 723 ​K. We show that the one-phase-field of (Bax,Ca(1−x))CO3 solid solutions at ambient conditions is larger (0.36 0.51) than previously thought. The synthesis routes employed here lead to compounds which have similar molar volumes than those of the naturally occurring (Ba,Ca)-double carbonates, in noted contrast to another synthetic phase, “balcite”.

Description: Due to their large heat and moisture storage capabilities, the tropics are fundamental in modulating both regional and global climate. Furthermore, their thermal response during past extreme warming periods, such as super interglacials, is not fully resolved. In this regard, we present high-resolution (analytical) foraminiferal geochemical (δ18O and Mg/Ca) records for the last 1800 kyr from the shallow (487 m) Inner Sea drift deposits of the Maldives archipelago in the equatorial Indian Ocean. Considering the diagenetic susceptibility of these proxies, in carbonate-rich environments, we assess the integrity of a suite of commonly used planktonic and benthic foraminifera geochemical datasets (Globigerinoides ruber (white), Globigerinita glutinata (with bulla), Pulleniatina obliquiloculata (with cortex) and Cibicides mabahethi) and their use for future paleoceanographic reconstructions. Using a combination of spot Secondary Ion Mass Spectrometer, Electron Probe Micro-Analyzer and Scanning Electron Microscope image data, it is evident that authigenic overgrowths are present on both the external and internal test (shell) surfaces, yet the degree down-core as well as the associated bias is shown to be variable across the investigated species and proxies. Given the elevated authigenic overgrowth Mg/Ca (∼12–22 mmol/mol) and δ18O values (closer to the benthic isotopic compositions) the whole-test planktonic G. ruber (w) geochemical records are notably impacted beyond ∼627.4 ka (24.7 mcd). Yet, considering the setting (i.e. bottom water location) for overgrowth formation, the benthic foraminifera δ18O record is markedly less impacted with only minor diagenetic bias beyond ∼790.0 ka (28.7 mcd). Even though only the top of the G. ruber (w) and C. mabahethi records (whole-test data) would be suitable for paleo-reconstructions of absolute values (i.e. sea surface temperature, salinity, seawater δ18O), the long-term cycles, while dampened, appear to be preserved. Furthermore, planktonic species with thicker-tests (i.e. P. obliquiloculata (w/c)) might be better suited, in comparison to thinner-test counter-parts (i.e. G. glutinata (w/b), G. ruber (w)), for traditional whole-test geochemical studies in shallow, carbonate-rich environments. A thicker test equates to a smaller overall bias from the authigenic overgrowth. Overall, if the diagenetic impact is constrained, as done in this study, these types of diagenetically altered geochemical records can still significantly contribute to studies relating to past tropical seawater temperatures, latitudinal scale ocean current shifts and South Asian Monsoon dynamics

Description: IODP Expedition 307 made it for the first time possible to investigate the entire body of a cold-water coral carbonate mound. Here we provide new insights into the long-term history of Challenger Mound on the European continental margin off Ireland. This study is based on age determinations (230Th/U, 87Sr/86Sr) and geochemical signals (Mg/Li and Ba/Ca) measured in the scleractinian cold-water coral Lophelia pertusa from IODP Site 1317 in the Porcupine Seabight. The paleoceanographic reconstructions reveal that coral growth in the Porcupine Seabight was restricted to specific oceanographic conditions such as enhanced export of primary production and Bottom-Water Temperatures (BWT) between ∼8–10 °C, related to the water mass stratification of the Mediterranean Outflow Water (MOW) and Eastern North Atlantic Water (ENAW). The geochemical signals from the coral skeletons can be explained by the close interaction between cold-water coral growth, sea-surface productivity and the surrounding water masses - the boundary layer between MOW and ENAW. Enhanced sea-surface productivity and the build-up of a stable water mass stratification between ENAW and MOW caused enhanced nutrient supply at intermediate water depths and facilitated a steady mound growth between∼3.0 - 2.1 Ma. With the decrease in sea-surface productivity and related reduced export productivity the food supply was insufficient for rapid coral mound growth between∼1.7 - 1 Ma. During the late Pleistocene (over the last∼0.5 Myr) mound growth was restricted to interglacial periods. During glacials the water mass boundary between ENAW/MOW probably was below the mound summit and hence food supply was not sufficient for corals to grow.

Description: The aragonitic skeletons of scleractinian cold-water corals can serve as valuable archives in paleoceanographic studies. The potential of δ88/86Sr, Sr/Ca, Mg/Ca, Li/Ca and Mg/Li ratios of the cold-water coral Lophelia pertusa to record intermediate water mass properties has been investigated. Here we used samples from several locations along the European continental margin spanning a large temperature range from 6 to 14 °C. Stable strontium isotope measurements were carried out with the recently developed double spike TIMS technique and our results differ from those obtained with less precise methods. In contrast to the strong positive relationship with temperature of previous studies, our results suggest that δ88/86Sr measured in scleractinian cold-water corals is not controlled by seawater temperature, but reflects the Sr isotopic composition of seawater with an offset of Δ88/86Sr = − 0.196‰. As found in previous studies, the elemental ratios Sr/Ca, Li/Ca and Mg/Li measured in corals are significantly related to water temperature and do not correlate with salinity. Moreover, Sr/Ca ratios in L. pertusa display the expected inverse correlation with temperature. However, the variance in the Sr/Ca data severely limits the accuracy of paleotemperature estimates. The Li/Ca and Mg/Ca ratios reveal other influences besides temperature such as pH and/or growth or calcification rate. However, corresponding Mg/Li ratios in L. pertusa are more tightly related to temperature as they remove these secondary effects. In particular, the Mg/Li ratio in L. pertusa may serve as a new promising paleotemperature proxy for intermediate water masses. Our dataset represents the most extensive geochemical examination of L. pertusa to date, revealing a temperature sensitivity of 0.015 mol/mmol/°C for Mg/Li. However, using this temperature dependence and the precision of 5.3% (2SD) only temperature variations larger than ~ 1.5 °C can be resolved with 95% confidence.

Description: The understanding of the paleoenvironment during initiation and early development of deep cold-water coral carbonate mounds in the NE Atlantic is currently a focus of international research. The Integrated Ocean Drilling Program (IODP) Expedition 307 drilled the 155 m high Challenger Mound in the Porcupine Seabight (SW off Ireland) in order to investigate for the first time sediments from the base of a giant carbonate mound. In this study we focus in high resolution on 12 m of sediments from Site 1317 encompassing the mound base. The mound initiation and start-up phase coincide with the intensification of the Northern Hemisphere Glaciation (INHG) at around 2.7 Ma. Further carbonate mound development seems to be strongly dependent on rapid changes in paleoceanographic and climatic conditions at the Pliocene–Pleistocene boundary, especially characterized and caused by the interaction of intermediate water masses, the Mediterranean Outflow Water (MOW), the Eastern North Atlantic Water (ENAW) and the influence of Southern Component Water (SCW). This study is based on well-established proxies such as δ18O and δ13C of planktonic (Globigerina bulloides) and benthic foraminifera (Fontbotia wuellerstorfi, Discanomalina coronata, Lobatula lobatula, Lobatula antarctica, and Planulina ariminensis) as well as grain size parameters to identify the paleoenvironmental and paleoecological setting favourable for the initial coral colonization on the mound. Stable oxygen and carbon isotope records of benthic foraminiferal species indicate that L. lobatula provides a reliable isotopic signature for paleoenvironmental reconstructions. In particular, δ18O values of L. lobatula indicate that initial mound growth started in a glacial mode with moderate excursions in δ18O values. Carbon isotope values of D. coronata are significantly offset compared to other epibenthic species. This offset may be related to vital effects. Bottom water temperatures, calculated using standard equations based on δ18O of foraminiferal tests, range between 7 and 11 °C, consistent with the known temperature range conducive for cold-water coral growth and development. Bottom currents transporting intermediate water masses of southern origin (Mediterranean and Bay of Biscay) enhanced at 2.6 Ma supporting first coral settlements with the INHG. The benthic δ13C and the sortable silt records indicate that the early Pleistocene hydrodynamic regime was characterized by weaker current intensities associated with vertical movements of MOW or its replacement by SCW at intermediate depth. After these sluggish phases enhanced MOW flow dominated again and led to stronger current intensities and most probably sediment erosion on Challenger Mound. Erosion in combination with early diagenetic (oxidation) processes overprinted the sediment layers as indicated by dissolved coral skeletons, the increase in Ca-content and sediment density, minimum δ13Cplanktonic values, as well as the occurrence of gypsum and pyrite, implying a careful evaluation of original and overprinted geochemical signals. We conclude that the Challenger Mound development was already influenced by short-term variability of water masses from southern origin and possible erosional events comparable to the late Pleistocene setting.

Description: Highlights • Re-organization of the West Pacific Warm Pool at ~ 1.7 – 1.35 Ma. • West Pacific Warm Pool and South Pacific Convergence Zone located further to the NE prior to ~ 1.5 Ma. • High amplitude variations at thermocline and deep thermocline depths after ~ 1.5 Ma. • West Pacific Warm Pool thermocline dynamics linked to southern-sourced mode waters. Abstract The internal development of the tropical West Pacific Warm Pool and its interaction with high latitude ocean regions on geological timescales is only poorly constrained. Based on two newly recovered sediment cores from the southeastern margin of the West Pacific Warm Pool (northern and southern Manihiki Plateau), we provide new aspects on the dynamically interacting ocean circulation at surface, subsurface, thermocline, and deep thermocline levels during the Pleistocene (~ 2.5–0.5 Ma). Notably, the variability of thermocline and deep thermocline (~ 150–400 m water depth) foraminiferal Mg/Ca-based temperatures with up to ~ 6 °C amplitude variations exceeds those at shallower depths (down to ~ 120 m) with only ~ 2–3 °C temperature variations. A major gradual reorganization of the West Pacific Warm Pool oceanography occurred during the transitional time period of ~ 1.7–1.35 Ma. Prior to ~ 1.7 Ma, pronounced meridional and latitudinal gradients in sea-surface to subsurface ocean properties point to the eastward displacement of the West Pacific Warm Pool boundaries, with the South Pacific Convergence Zone being shifted further northeastward across Manihiki Plateau. Simultaneously, the low amplitude variations of thermocline and deep thermocline temperatures refer to an overall deep and stable thermocline. The meridional and zonal gradients in sea-surface and subsurface ocean properties within the West Pacific Warm Pool reveal a pronounced change after 1.5 Ma, leading to a more southward position of the warm South Pacific Convergence Zone between ~ 1.35–0.9 Ma and ~ 0.75–0.5 Ma. Synchronous to the changes in the upper ocean, the deeper water masses experienced high amplitude variations in temperature, most prominently since ~ 1.5 Ma. This and the dynamically changing thermocline were most likely associated to the impact of southern-sourced mode waters, which might have developed coincidently with the emergence of the East Pacific Cold Tongue and high latitude sea-surface cooling.

Description: Highlights • First apparent calcification depth assessment of living foraminifera in the SE WPWP • Deep surface mixed layer causes deep apparent calcification depths. • Deep-dwelling G. hexagonus traces nutrient conditions in equatorial water masses. Abstract Insight into past changes of upper ocean stratification, circulation, and nutrient signatures rely on our knowledge of the apparent calcification depth (ACD) and ecology of planktonic foraminifera, which serve as archives for paleoceanographic relevant geochemical signals. The ACD of different species varies strongly between ocean basins, but also regionally. We constrained foraminiferal ACDs in the Western Pacific Warm Pool (Manihiki Plateau) by comparing stable oxygen and carbon isotopes (δ18Ocalite, δ13Ccalcite) as well as Mg/Ca ratios from living planktonic foraminifera to in-situ physical and chemical water mass properties (temperature, salinity, δ18Oseawater, δ13CDIC). Our analyses point to Globigerinoides ruber as the shallowest dweller, followed by Globigerinoides sacculifer, Neogloboquadrina dutertrei, Pulleniatina obliquiloculata and Globorotaloides hexagonus inhabiting increasing greater depths. These findings are consistent with other ocean basins; however, absolute ACDs differ from other studies. The uppermost mixed-layer species G. ruber and G. sacculifer denote mean calcification depths of ~ 95 m and ~ 120 m, respectively. These Western Pacific ACDs are much deeper than in most other studies and most likely relate to the thick surface mixed layer and the deep chlorophyll maximum in this region. Our results indicate that N. dutertrei appears to be influenced by mixing waters from the Pacific equatorial divergence, while P. obliquiloculata with an ACD of ~ 160 m is more suitable for thermocline reconstructions. ACDs of G. hexagonus reveal a deep calcification depth of ~ 450 m in oxygen-depleted, but nutrient-rich water masses, consistent to other studies. As the δ13C of G. hexagonus is in near-equilibrium with ambient seawater, we suggest this species is suitable for tracing nutrient conditions in equatorial water masses originating in extra-topical regions.

Description: High-latitude cold-water coral reefs are particularly vulnerable to climate change due to enhanced CO2 uptake in these regions. To evaluate their physiological functioning and potential application as pH archives, we retrieved both recent and fossil samples of Lophelia pertusa along the Norwegian margin from Oslofjord (59°N), over to Trondheimsfjord, Sula and Lopphavet (70.6°N). Boron isotope analyses (δ11B) were undertaken using solution-based and laser ablation multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS; LA-ICP-MS), and secondary ion mass spectrometry (SIMS). Epi-fluorescence microscopy was employed to provide a rapid pre-screening routine for structure-specific subsampling in the coral skeleton. This integrated approach enabled us to assess heterogeneities within single specimens, as well as to investigate the role of local environmental influences including recent and past variations. All three mass spectrometry methods show substantial differences in the δ11B of the theca wall (TW) and the centres of calcification (COC's). Micro-bulk subsamples milled from the theca wall of modern specimens originating from different habitats but with comparable seawater pH (8–8.16) gave consistent δ11B values averaging 26.7 (±0.2‰, 2σ, n = 4), while COC subsamples systematically deviated towards lower B/Ca (by ~40%) and depleted δ11B values (minimum 22.7 ± 0.3‰, 2σ), implying a difference of at least 4‰ between TW and COC. SIMS and LA-ICP-MS measurements identified much larger internal heterogeneities with maximum variation of ~10‰ between the distinct skeletal structures; minimal SIMS δ11B values of ~17.3 ± 1.2‰ (2σ) were associated with the pure COC material. Our findings may be interpreted in terms of the occurrence of two main, but likely different, biomineralisation mechanisms in L. pertusa, with the COC's generally exhibiting minimal pH up-regulation, potentially supporting the use of bicarbonate in the early stages of biomineralisation. Furthermore, we highlight the potential utility of L. pertusa for palaeo-proxy studies if targeting the compositionally homogenous TW zones devoid of COC admixtures, which appear to provide highly reproducible measurements.

Description: The isotopic composition of Phanerozoic marine sediments provides important information about changes in seawater chemistry. In particular, the radiogenic strontium isotope (87Sr/86Sr) system is a powerful tool for constraining plate tectonic processes and their influence on atmospheric CO2 concentrations. However, the 87Sr/86Sr isotope ratio of seawater is not sensitive to temporal changes in the marine strontium (Sr) output flux, which is primarily controlled by the burial of calcium carbonate (CaCO3) at the ocean floor. The Sr budget of the Phanerozoic ocean, including the associated changes in the amount of CaCO3 burial, is therefore only poorly constrained. Here, we present the first stable isotope record of Sr for Phanerozoic skeletal carbonates, and by inference for Phanerozoic seawater (δ88/86Srsw), which we find to be sensitive to imbalances in the Sr input and output fluxes. This δ88/86Srsw record varies from ∼0.25‰ to ∼0.60‰ (vs. SRM987) with a mean of ∼0.37‰. The fractionation factor between modern seawater and skeletal calcite Δ88/86Srcc-sw, based on the analysis of 13 modern brachiopods (mean δ88/86Sr of 0.176±0.016‰, 2 standard deviations (s.d.)), is -0.21‰ and was found to be independent of species, water temperature, and habitat location. Overall, the Phanerozoic δ88/86Srsw record is positively correlated with the Ca isotope record (δ44/40Casw), but not with the radiogenic Sr isotope record ((87Sr/86Sr)sw). A new numerical modeling approach, which considers both δ88/86Srsw and (87Sr/86Sr)sw, yields improved estimates for Phanerozoic fluxes and concentrations for seawater Sr. The oceanic net carbonate flux of Sr (F(Sr)carb) varied between an output of -4.7x1010mol/Myr and an input of +2.3x1010mol/Myr with a mean of -1.6x1010mol/Myr. On time scales in excess of 100Myrs the F(Sr)carb is proposed to have been controlled by the relative importance of calcium carbonate precipitates during the “aragonite” and “calcite” sea episodes. On time scales less than 20Myrs the F(Sr)carb seems to be controlled by variable combinations of carbonate burial rate, shelf carbonate weathering and recrystallization, ocean acidification, and ocean anoxia. In particular, the Permian/Triassic transition is marked by a prominent positive δ88/86Srsw-peak that reflects a significantly enhanced burial flux of Sr and carbonate, likely driven by bacterial sulfate reduction (BSR) and the related alkalinity production in deeper anoxic waters. We also argue that the residence time of Sr in the Phanerozoic ocean ranged from ∼1Myrs to ∼20Myrs.