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: The modern precipitation balance in southeastern (SE) Brazil is regulated by the South American summer Monsoon and threatened by global climate change. On glacial-interglacial timescales, monsoon intensity was strongly controlled by precession-forced changes in insolation. To date, relatively little is known about the spatiotemporal distribution of tropical precipitation in SE Brazil and the resulting variability of fluvial discharge on glacial-interglacial timescales. Here, we present X-ray diffraction-derived mineralogical data for the 150–70 ka period (marine isotope stage (MIS) 6 to MIS 5) from the Doce River basin. This area was sensitive to changes in monsoonal precipitation intensity due to its proximity to the South Atlantic Convergence Zone. The data, obtained from a marine sediment core (M125-55–7) close to the Doce river mouth (20°S), show pronounced changes in the Doce River suspension load’s mineralogical composition on glacial-interglacial and precessional timescales. While the ratio of silicates to carbonates displays precession-paced changes, the mineralogical composition of the carbonate-free fraction discriminates between two assemblages which strongly vary between glacial and interglacial time scales, with precession-forced variability only visible in MIS 5. The first assemblage, dominated by high contents of kaolinite and gibbsite, indicates intensified lowland erosion of mature tropical soils. The second one, characterized by higher contents of the well-ordered illite, quartz and albite, points to intensified erosion of immature soils in the upper Doce Basin. High kaolinite contents in the silicate fraction prevailed in late MIS 6 and indicate pronounced lowland soil erosion along a steepened topographic gradient. The illite-rich mineral assemblage was more abundant in MIS 5, particularly during times of high austral summer insolation, indicating strong monsoonal rainfall and intense physical erosion in the upper catchment. When the summer monsoon weakened in times of lower insolation, the mineral assemblage was dominated by kaolinite again, indicative of lower precipitation and runoff in the upper catchment and dominant lowland erosion.

Description: The Arctic Svalbard Archipelago hosts the world’s northernmost cold-water ‘carbonate factories’ thriving here despite of presumably unfavourable environmental conditions and extreme seasonality. Two contrasting sites of intense biogenic carbonate production, the rhodolith beds in Mosselbukta in the north of the archipelago and the barnacle-mollusc dominated carbonate sediments accumulating in the strong hydrodynamic regime of the Bjørnøy-Banken south of Spitsbergen, were the targets of the RV Maria S. Merian cruise 55 in June 2016. By integrating data from physical oceanography, marine biology, and marine geology, the present contribution characterises the environmental setting and biosedimentary dynamics of these two polar carbonate factories. Repetitive CTD profiling in concert with autonomous temperature/salinity loggers on a long-term settlement platform identified spatiotemporal patterns in the involved Atlantic and Polar water masses, whereas short-term deployments of a lander revealed fluctuations of environmental variables in the rhodolith beds in Mosselbukta and at same depth (46 m) at Bjørnøy-Banken. At both sites, dissolved inorganic nutrients in the water column were found depleted (except for elevated ammonium concentrations) and show an overall increase in concentration and N:P ratios toward deeper waters. This indicates that a recycling system was fuelling primary production after the phytoplankton spring bloom at the time of sampling in June 2016. Accordingly, oxygen levels were found elevated and carbon dioxide concentrations (pCO2) markedly reduced, on average only half the expected equilibrium values. Backed up by seawater stable carbon and oxygen isotope signatures, this is interpreted as an effect of limited air-sea gas exchange during seasonal ice cover in combination with a boost in community photosynthesis during the spring phytoplankton bloom. The observed trends are enhanced by the onset of rhodophyte photosynthesis in the rhodolith beds during the polar day upon retreat of sea-ice. Potential adverse effects of ocean acidification on the local calcifier community are thus predicted to be seasonally buffered by the marked drop in pCO2 during the phase of sea-ice cover and spring phyto-plankton bloom, but this effect will diminish should the seasonal sea-ice formation continue to decline. Among the 25 macrobenthos taxa identified from images captured by the lander’s camera system, all but three species were calcifiers contributing to the carbonate production. Biodiversity was found to be much higher in Mosselbukta (21 taxa) compared to Bjørnøy-Banken (8 taxa), which is considered as a result of enhanced habitat diversity provided in the rhodolith beds by the bioengineering crustose alga Lithothamnion glaciale. Filter-feeding activity of selected key species did reveal group-specific but no common activity patterns. Biotic disturbance of the filtering activity was common, in contrast to abiotic factors, with hermit crabs representing the primary trigger. Motion tracking of rhodoliths revealed a high frequency of dislocation, triggered not by abiotic factors but by the activity of benthic invertebrates, in particular echinoids ploughing below or moving over the rhodoliths. The echinoid Strongylocentrotus sp. is the most abundant component of the associated fauna, thereby considerably contributing both to carbonate production and to grazing bioerosion. Together, these results portray a high degree of seasonal as well as short-term dynamics in environmental conditions that despite many similarities support distinctly different communities and biodiversity patterns in the calcifying macrobenthos at the two studied polar carbonate factories.

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.