ALBERT

Description: Seaweeds and their bioactive compounds, particularly polysaccharides and phenolics can be regarded as great dietary supplements with gut health benefits and prebiotics. These components are resistant to digestion by enzymes present in the human gastrointestinal tract, also selectively stimulate the growth of beneficial gut bacteria and the production of fermentation products such as short chain fatty acids. Commonly, the health benefits of seaweed components are assessed by including them in an in vitro anaerobic fermentation system containing human fecal inocula that mimics the environment of the human large bowel. Regarding to the complex interactions between dietary components, gastrointestinal physiological processes, and gut microbiota are difficult to model in vitro. Consequently it is important to follow up the promising in vitro results with in vivo animal or human testing. The aim of this chapter is to have a comprehensive review on the application of seaweeds and seaweed-derived metabolites as prebiotics, and understand the trends, gaps and future directions of both scientific and industrial developments. This work contributes to develop and expand new platform of seaweed utilization for higher-value products, particularly to functional food and nutraceutical industries in order to serve the social demand for health awareness and support economic development.

Description: Subduction zone volcanoes may show irregular bursts of high-frequency or high-magnitude activity. The andesitic Mt. Tongariro (New Zealand) experienced an unusual 〈200 year-long magmatic flare-up at ~11 ka that produced seven eruption episodes of a higher magnitude (M = 4–5) than seen before or since. This brief sequence produced a total of 4.5 km3 of dominantly tephra fall (Mangamate Formation) sourced by multiple vents aligned along the NNE trending axis of the tectonic Tongariro Graben. The magmatic system responsible for sporadic M = 1–2 eruptions underwent extensive change to feed the flare-up. Petrography and phase equilibria suggest that a coalesced network of magma mush zones formed along the N-S graben axis extending down to ~11 km during the episode. Recharge, mingling and mixing of formerly isolated heterogenous magmas within the plumbing system well before these eruptions is indicated by crystal zonation patterns. Mafic end members are evidenced by Fo86–89 olivine, clinopyroxene with Mg# 〉 85 and calcic plagioclase (An73–89), while evolved magma end members contained Mg# 〈 75 clinopyroxene and An56–63 plagioclase. Rim-zoning of these phases reflect timespans for equilibration of evolved and mafic crystals to a hybrid melt. The whole-rock compositions of lapilli reflect the hybrid basaltic andesite to andesite, but show diverse glass compositions (56–72 wt% SiO2) implying that magma homogenisation was incomplete before eruption. Crystal-melt equilibria of olivine and clinopyroxene rims reveal polybaric crystallisation, showing mean depths of ~8.5 km (230 ± 70 MPa) at temperatures between 1000 and 1150 °C. At the northern margins of the system, volatile-rich amphibole-bearing magmas were erupted for the first and last eruption of the series, creating stable Plinian eruption styles. This flare-up was previously interpreted as tectonically controlled, however, there were low tectonic extension rates at that time. Hence, we propose instead that magma pressure build-up and recharge beneath Mt. Tongariro drove the inflation and homogenisation of the magma system, fueling the ~200 year-long flare-up. Subsequently, the magma supply system returned to pre-Mangamate activity levels, so that vigorous recharge would be required for a return to 〉M 4 eruptions.

Description: Highlights: • Mnemiopsis leidyi is capable of catching and digesting herring yolk-sac larvae. • Predation on herring larvae is decreasing with prey age and increasing with predator size. • Predation of M. leidyi on herring larvae is not affected by the presence of alternative natural prey represented by the copepod Acartia tonsa. • Substantial predation of M. leidyi on yolk-sac herring larvae may occur in the field, when both overlap spatially and temporarily. Western Baltic spring spawning herring (Clupea harengus, L.) is a commercially important fish stock currently suffering a strong decline. Larval survival is essential for stock recruitment and can be substantially decreased by predation. The comb jelly Mnemiopsis leidyi A. Agassiz, 1865, is a lobate ctenophore which is invasive to the Baltic Sea and a known ichthyoplankton predator. However, predation on herring larvae in the Baltic Sea by M. leidyi has not been studied since its initial establishment in 2006. To address this knowledge gap, we conducted feeding experiments to investigate (1) the predation capability of M. leidyi on herring yolk-sac larvae, and (2) the influence of larval age, (3) predator size and (4) the presence of alternative prey on the clearance rate of M. leidyi on herring yolk-sac larvae. Our results showed that M. leidyi exhibited the ability to capture and digest herring larvae. The clearance rates of M. leidyi on herring larvae decreased with larval age and increased with predator size, while the presence of alternative prey had no effect on clearance rates. This finding suggests that M. leidyi can efficiently consume herring yolk-sac larvae under laboratory conditions. However, further investigations using mesocosm or field studies are necessary to evaluate the potential impact of M. leidyi on the mortality and recruitment of herring yolk-sac larvae under Baltic Sea field conditions.

Description: Highlights • Development of an autonomous DIC analyzer based on Conductometric technique using a cell with 4 hollow brass electrodes. • CO2 extraction from seawater using a gas diffusion cell with a “Tube In A Tube” configuration and a gas permeable membrane. • Formulation of mathematical temperature and salinity correction to determine accurate DIC concentration. • Demonstration of the analyzer performance in the southwest Baltic Sea. Abstract Background The increase in anthropogenic CO2 concentrations in the Earth's atmosphere since the industrial revolution has resulted in an increased uptake of CO2 by the oceans, leading to ocean acidification. Dissolved Inorganic Carbon (DIC) is one of the key variables to characterize the seawater carbonate system. High quality DIC observations at a high spatial-temporal resolution is required to improve our understanding of the marine carbonate system. To meet the requirements, autonomous DIC analyzers are needed which offer a high sampling frequency, are cost-effective and have a low reagent and power consumption. Results We present the development and validation of a novel analyzer for autonomous measurements of DIC in seawater using conductometric detection. The analyzer employs a gas diffusion sequential injection approach in a “Tube In A Tube” configuration that facilitates diffusion of gaseous CO2 from an acidified sample through a gas permeable membrane into a stream of an alkaline solution. The change in conductivity in the alkaline medium is proportional to the DIC concentration of the sample and is measured using a detection cell constructed of 4 hollow brass electrodes. Physical and chemical optimizations of the analyzer yielded a sampling frequency of 4 samples h−1 using sub mL reagent volumes for each measurement. Temperature and salinity effects on DIC measurements were mathematically corrected to increase accuracy. Analytical precision of ±4.9 μmol kg−1 and ±9.7 μmol kg−1 were achieved from measurements of a DIC reference material in the laboratory and during a field deployment in the southwest Baltic Sea, respectively. Significance This study describes a simple, cost-effective, autonomous, on-site benchtop DIC analyzer capable of measuring DIC in seawater at a high temporal resolution as a step towards an underwater DIC sensor. The analyzer is able to measure a wide range of DIC concentrations in both fresh and marine waters. The achieved accuracy and precision offer an excellent opportunity to employ the analyzer for ocean acidification studies and CO2 leakage detection in the context of Carbon Capture and Storage operations.

Description: Highlights • The Okorusu complex in NE Etendeka have Gough-type isotopic composition. • Messum igneous complex in SW Etendeka show a Doros/Tafelkop-type composition. • Both Gough- and Doros-type components derived from the Tristan-Gough plume. • Doros-type volcanism is surrounded by Gough-type volcanism. • The head-stage of Tristan-Gough plume coincide with the concentric zonation model. Abstract The Etendeka large igneous province in central Namibia is believed to be caused by widespread melting of the Tristan/Gough mantle plume head between ∼137 and 123 Ma ago. To explain the observed compositional variations of the Etendeka flood basalts, a laterally-zoned plume head has been proposed. Here we present new (major and trace element and Sr-Nd-Pb-O-C isotope) geochemical data from the Okorusu and Messum carbonatitic and silica-undersaturated rocks. Okorusu carbonatites, located at the far eastern end of the Etendeka province, have a Gough-type enriched mantle one (EM1) composition, consistent with derivation from a common source with the northern Etendeka flood basalts, Walvis Ridge and Gough (southern) hotspot subtrack of the southern Atlantic Guyot Province including Gough Island. The Messum basanite, erupted directly after the Etendeka event near the central coast of western Namibia, has a different EM1 type flavor (with more radiogenic Nd, less radiogenic Sr and thorogenic Pb isotopes), similar to the Doros, Tafelkop and Horingbaai formations of the Etendeka flood basalts. Combining our new findings with published data from flood basalts, carbonatites and silica-undersaturated rocks from the region, we propose a concentric zonation model for the postulated plume head with the isotopically Gough-type EM1 plume mantle enclosing a blob of Doros-type EM1 plume mantle.

Description: Highlights: • The interactions between vortices in a four-vortex flow field using a rotating water tank. • Driven by the strain field, non-ideal vortices stretch along the centerline, and manifest an asymmetric stretching pattern. • Non-ideal vortices disperse vorticity, accumulate filaments, and exhibit distinctive variations in anti-symmetric vorticity distribution, impacting respective merging efficiency. Abstract: Oceanic vortex merging is an important physical process for the vortex evolution and its impact on marine environment. However, limitation of the in-situ oceanic observational data of vortex merging inhabits its better understanding. This study investigates the interactions between non-ideal vortices in a four-vortex flow field in a rotating tank. We examine the merging stages of anticyclonic vortices, influenced by two other cyclonic vortices and their respective dynamical behaviors and quantify the effects of merging on vortex characteristics. The results indicate a strong shear flow between two counter-rotating vortices, which accelerates the motion of the anticyclonic vortex, while cyclonic ones exhibit greater stability. Subsequently, different stages of non-ideal vortex merging in a co-rotating framework are defined, primarily the encircling stage, rapid approaching stage, and merging vortex stage. In addition, we quantify and compare variations in morphological parameters and anti-symmetric vorticity distribution of non-ideal vortices across these stages. The stretching of vortices primarily occurs along the line connecting their centers due to the strain field exerted by neighboring vortices, resulting in an asymmetric stretching pattern in the interactions among non-ideal vortices. Furthermore, during the merging process, non-ideal vortices disperse vorticity outward and accumulate vortex filaments in the surrounding environment, leading to distinctive variations in anti-symmetric vorticity distribution, affecting their respective merging efficiency.

Description: In the past three decades, altimeter-based remote sensing has been a widely used system to estimate ocean surface currents. However, it remains a great challenge to effectively resolve scales below ∼100 km at high latitudes and ∼ 300 km at mid-latitudes. In this study, we propose a scheme that utilizes geostrophic equilibrium and surface quasigeostrophy theory (SQG) to improve surface current resolution by incorporating remote sensing sea surface temperature (SST), sea surface height (SSH), and sea surface salinity (SSS) observations. The scheme separately characterizes the larger-scale flows and smaller-scale motions of surface currents. A case study encompassing the Agulhas surface current demonstrates that the smaller-scale motions associated with temperature fronts are well captured by introducing high spatial-temporal resolution SST data. Furthermore, the reconstructed surface current is systemically evaluated by using surface drogued drifters and a Lagrangian synthetic particle tracking tool throughout the South Indian Ocean (SIO) for 2011–2015. Notably, the reconstructed zonal velocity component is closer to the drifter observations than the meridional counterpart and corresponding velocity phase. Regionally, the Antarctic Circumpolar Current (ACC) showcases superior reconstruction performance, with higher skill scores and lower Lagrangian separation distances. However, a relatively large uncertainty is observed around the Agulhas Retroflection (AR) and Greater Agulhas System (GAS), which are linked to complicated regional dynamic regimes. We finally conduct four simulation experiments to explore the effect of different SST products on surface current reconstruction within the subdomain AR. The results indicate the varying potentials of the four evaluated SST products for informing surface current applications. Specifically, the MWIRSST enhances the likelihood of particles reaching the target field, while DMI OI shortens the average deviation distance of the arrived particles.

Description: Marine imaging studies have unique constraints on the data collected requiring a tool for defining the biological scope to facilitate data discovery, quality evaluation, sharing and reuse. Defining the ‘target population’ is way of scoping biological sampling or observations by setting the pool of organisms to be observed or sampled. It is used in survey design and planning, to determine statistical inference, and is critical for data interpretation and reuse (both images and derived data). We designed a set of attributes for defining and recording the target population in biological studies using marine photography, incorporating ecological and environmental delineation and marine imaging method constraints. We describe how this definition may be altered and recorded at different phases of a project. The set of attributes records the definition of the target population in a structured metadata format to enhance data FAIRness. It is designed as an extension to the image FAIR Digital Objects metadata standard, and we map terms to other biological data standards where possible. This set of attributes serves a need to update ecological metadata to align with new remotely-sensed data, and can be applied to other remotely-sensed ecological image data.

Description: Fishes occur in a wider range of habitats than any other vertebrate or invertebrate group, from the upper reaches of streams in high mountain ranges to the mouths of temperate and tropical rivers, and from the intertidal zone to the ocean's abyss. Fish grow in size, spawn and die, either from natural causes (predation, diseases, ageing) or from being caught in fishing nets if the population is exploited. These dynamical processes are expressed with mathematical equations and are used in population models to estimate fisheries reference points (stock assessment), which in turn provide the basis for fisheries management. Fish populations subjected to fisheries exploitation are called fish “stocks”. Fishing has been increasingly affecting fish stocks and ecosystems both directly and indirectly, and along with the human-induced climate change they pose major threats to fish biodiversity worldwide. Using the available data stored in local or global databases to assess the status of all stocks, even the data-poor fish stocks, and following an ecosystem approach to fisheries management that incorporates effort reduction through marine protected areas, may contribute to the sustainable exploitation of fisheries resources.

Description: Cadmium (Cd) has a nutrient-like distribution in the ocean, similar to the macronutrient phosphate. Significant isotope fractionation induced by the biological cycling of Cd makes it a potential tracer for nutrients and productivity. However, the Cd flux and Cd isotope composition of marine sediments can also be influenced by local redox conditions and partial remineralization of organically hosted Cd. These confounding factors are under-constrained and render it challenging to use Cd as a reliable paleoproxy. To understand the relative importance of each of these processes, we examined the Cd isotope systematics of 69 modern sediments deposited across a wide range of environments. We complement these data with four profiles of particulate Cd isotope compositions from the Southern Ocean. We report three main results. First, we show that the sedimentary flux of Cd is tightly coupled to that of organic matter. Second, most Cd burial occurs in regions with some bottom-water oxygen, and the flux of CdS to anoxic regions is, globally, minor. Finally, we find that remineralization can substantially modify sedimentary Cd isotope compositions, though it is challenging to relate pelagic and sedimentary processes. For example, we find that the relationship between sedimentary Cd isotope compositions and surface seawater [Cd] is the reverse of that predicted by isotope reactor models. Likewise, sedimentary Cd isotope compositions are anti-correlated with bottom-water oxygen. While this pattern is consistent with preferential remineralization of isotopically heavy Cd, profiles of marine particulate matter reveal the reverse, whereby the Cd isotope composition of large particles, which are most likely to reach the seafloor, becomes increasingly ‘heavy’ with depth. These results highlight how productivity, redox, and remineralization all influence the flux and isotope composition of Cd to marine sediments. While our study suggests that there is no simple way to relate sedimentary Cd isotopes to surface nutrient utilization, our data point toward several potential controls that could form the basis of novel proxies for local redox conditions and remineralization.

Description: Trace metals (TMs) manganese (Mn), cobalt (Co), and aluminium (Al) have important geochemical and biological roles in the ocean. Here, we present full depth profiles of dissolved (d) and particulate Al, Mn, and Co along the latitude of 40 °S in the South Atlantic Ocean from the GEOTRACES GA10 cruises that operated in austral spring 2010 and summer 2011. The region is characterized by enhanced primary productivity and forms a key transition zone between the Southern Ocean and South Atlantic Subtropical Gyre. The mean concentrations of dAl, dCo, and dMn (±standard deviation) were 3.36 ± 2.65 nmol kg−1, 35.3 ± 17.6 pmol kg−1, and 0.624 ± 1.08 nmol kg−1, respectively. Their distributions in surface waters were determined by external sources and complex internal biogeochemical processes. Specifically, surface ocean dCo was controlled by the interplay between phytoplankton uptake, remineralization and external inputs; dMn was likely determined by the formation and photoreduction of Mn-oxides; and dAl was supplied by atmospheric deposition and removed by scavenging onto particles. Fluvial and sedimentary inputs near the Rio de La Plata estuary and benthic sources from the Agulhas Bank resulted in elevated dTM concentrations in near-shore surface waters. These externally sourced dTMs were effectively delivered to the open ocean by offshore diffusion and/or advection, and potentially facilitated enhanced primary productivity along the transect. The distributions of dTMs at depth were predominantly controlled by the mixing of North Atlantic Deep Water (NADW) and waters of Antarctic origin (e.g., Upper Circumpolar Water (UCDW) and Antarctic Bottom Water (AABW)). The calculated endmember concentrations of dAl and dCo in NADW showed minor decreases in the SASTG following north–south transport, suggesting removal rates of 0.064 nM/year and 0.035–0.075 pM/year, respectively. The endmember concentration of dCo in AABW was maintained at ∼30 pmol kg−1 without evidence for scavenging removal in the Southern Ocean and SASTG (time frame 〉400 years). The concentrations of dMn in NADW and AABW were between 0.1 and 0.16 nmol kg−1, and any elevated dMn concentrations were ascribed to local external inputs (e.g., from sediments in the Argentine Basin and hydrothermal activity near the Mid-Atlantic Ridge). Hence, four controlling factors (sources, internal cycling, water mass mixing and time) need to be considered when assessing TM distributions in the global ocean, even for TMs that are vulnerable to scavenging removal processes. Because the deep waters formed in high latitude oceans are crucial components of the global thermohaline overturning system, any processes (e.g., glacier melting, upwelling and sinking, and biological activity) that impact the preformed dTM concentrations in high latitude oceans will determine the downstream dTM distributions. Therefore, the sources and sinks of TMs and associated biological activity in high latitude oceans could engender basin to global scale impacts on seawater distributions of Al, Co, and Mn and their stoichiometric relationships with macronutrients, and the global biogeochemical cycles of these scavenged-type TMs.

Description: The overriding physicochemical controls in seawater discussed here are the chemical composition and the state of master variables including temperature, pressure, salinity, pH and redox status. Dissolved Organic Matter also plays a major role, but since its properties are not sufficiently well quantified it is described as an emergent master variable at this stage. The theoretical basis for the treatment of equilibrium chemistry and kinetics is presented, together with projections of the future development of seawater chemistry resulting from climate change. Key points • Composition of seawater • Master variables (temperature, pressure, pH, oxygen/redox state) • The role of Dissolved Organic Matter • Equilibrium chemistry • Kinetics • The consequences of ongoing global changes

Description: Highlights • Developed an innovative weighted outlier detection function that adaptively selects the best outlier detection technique, markedly improving precision and robustness in multibeam echosounder data analysis. • Demonstrated superior performance of the weighted function over traditional methods, achieving higher precision, recall, and F1 scores, pivotal for accurate seafloor mapping. • Enhanced data quality for geoscientific applications by effectively identifying and removing outliers without introducing data voids, preserving the integrity of multibeam sonar data. • The function’s significance extends to supporting sustainable environmental and resource management practices through improved accuracy in seabed mapping. • Discussed the adaptability of the method to various outlier patterns and its limitations, highlighting the need for further research and validation across different marine environments and data types. Abstract Multibeam sonar data are a valuable tool for seafloor mapping and geological studies. However, the presence of outliers in multibeam data can distort the results of analyses and reduce the accuracy of seafloor maps. In this paper, we define a weighting function based on the performance of various outlier detection techniques (OTDs) for detecting outliers in multibeam data, which calculates an outlier probability score for each sounding. Our results show that each OTD has its own strengths and weaknesses, and that a combination of outlier detection techniques is promising to improve reproducibility, explainability and the accuracy of the detection process. To address the challenge of detecting outliers in multibeam data, we propose a weighted outlier detection function that outperforms individual outlier detection techniques in terms of precision, recall and F1 scores by considering their strengths and combining them in a way that accounts for variations in the data. The function detects various types of outliers with high precision and recall values, resulting in valuable improvements in outlier detection performance for multibeam data. Overall, our proposed workflow has the potential to significantly improve the way multibeam data cleaning is performed, with the weighted outlier detection function being applied first, detecting most of the outlier automatically, followed by a domain-expert review of a small group of soundings whose automatic outlier labelling is not unequivocal.

Description: For the past 50 years it has been assumed that the principal pathway for the deep limb of the Atlantic Meridional Overturning Circulation (AMOC) is the Deep Western Boundary Current (DWBC). However, recent observations of Lagrangian floats have shown that the DWBC is not necessarily a unique, dominant, or continuous pathway for these deep waters. A significant portion of the deep water export from the subpolar to the subtropical gyres follows a pathway through the interior of the Newfoundland and subtropical basins, which is constrained by the western boundary and the western flank of the Mid-Atlantic Ridge. The hypothesis that deep eddy-driven recirculation gyres are a mechanism for partitioning the deep limb of the AMOC into the DWBC and this interior pathway is investigated here. Eulerian and Lagrangian analyses of the output of ocean general circulation models at eddy-resolving, eddy-permitting, and non-eddy permitting resolutions are used to test this hypothesis. Eddy-driven recirculation gyres, simulated in the eddy-resolving and eddy-permitting models and similar to recirculations inferred from hydrographic data, are shown to shape the export pathways of deep water from the subpolar to the subtropical gyres.

Description: Highlights • Accurate age model during Pliocene for site U1490 established • Co-variant nutricline depth and productivity in WPWP throughout Pliocene • Deeper nutricline and lower productivity during 4.8–3.5 Ma linked to CAS closure • Nutricline shoaling during 3.5–3.0 Ma due to restriction of Indonesian Seaway Abstract The tropical Pacific played an important role in modulating global climate change during the Pliocene. Studies of tropical Pacific sea surface temperatures covering the period from the Pliocene onwards indicate that changes in the thermal mean state over the tropical Pacific can significantly influence global climate feedbacks and connect the high- and low-latitude climates. Tropical productivity fluctuations are a significant mechanism with respect to the operation of the global carbon cycle. Yet, temporal changes in primary productivity are not well constrained in the western Pacific warm pool (WPWP), where the ocean–climate system is not dominated by upwelling systems. Furthermore, the role of nutricline dynamics in forcing productivity over tectonic timescales remains uncertain. Here we use relatively high-resolution foraminiferal carbon isotope records combined with Ba/Ti ratios obtained from International Ocean Discovery Program (IODP) Site U1490 in the WPWP to reconstruct nutricline depth and paleoproductivity over the period 5.1–2.6 Ma. Our records imply that nutricline and productivity variations were closely coupled over tectonic timescales, implying that the dynamics of the nutricline play a significant role in regulating productivity in the WPWP. The deeper nutricline and lower productivity during 4.8–3.5 Ma might have been fostered by the closure of the Central American Seaway through the thickening of the mixed layer in the WPWP. We relate the overall shallower nutricline and increased productivity during 3.5–3.0 Ma to the restriction of the Indonesian Seaway via the enhanced influence and upwelling of high-latitude southern-source waters.

Description: Highlights • Present day infiltration conditions in an monsoonal environment are studied. • Noble gas concentrations in groundwater are fixed near the soil surface. • Noble gas temperatures represent seasonal infiltration conditions in the monsoon. • Holocene and modern infiltration conditions are quite similar in southern Oman. Abstract Comparing directly measured soil temperatures with noble gas recharge temperatures (NGTs) inferred from noble gas concentrations indicates that the infiltrating soil water equilibrates with soil air near the soil surface during the rainy season. Therefore, NGTs of groundwater recently recharged by the Indian Summer Monsoon (ISM) in the Dhofar Mountains in southern Oman reflect the soil temperatures of the 3-month period and do not represent an annual mean. This finding highlights the need to account for seasonality when interpreting NGT data in regions with pronounced dry and wet seasons. We extend the observations from the southern flank of the Dhofar Mountains to three wells situated on the northern flank of the Dhofar Mountains. Two of these wells yield water of Holocene age that was recharged by the monsoon, their NGT signals are therefore classified as seasonal. The NGT calculated from a third well for recharge conditions during the Last Glacial Maximum (LGM), when the ISM was absent, is approximately 3 °C lower than that of the two Holocene wells. The lower LGM noble gas temperature corresponds well with the lower annual Sea Surface Temperature (SST) in the nearby Arabian Sea. NGTs from published studies from northern Oman are 1–3 °C higher when compared with our data of the same period in the southern Oman. We explain this regional difference of reconstructed temperatures for the LGM and Holocene groundwater with a more continental climatic influence on the infiltration conditions further to the north. The published NGTs from northern Oman show a large temperature difference between the late Holocene and the LGM. In view of our finding of seasonal NGT signals under monsoonal climate, part of this difference may reflect a change in the precipitation regime rather than in air temperature.

Description: Highlights • This study simulates the sedimentation-driven development of multiple stacked BSRs in the Danube paleo-delta, Black Sea. • Formation of multiple BSRs in the Black Sea is controlled by the sequence of sedimentation events of the levees induced by sea-level changes. • Kinetics of phase transitions plays a key role in the coexistence, location, and timing of the multiple BSRs. • Development of multiple stacked BSRs is possible only under a narrow range of parameters, unique for the Danube delta setting. Abstract The gas hydrate stability zone (GHSZ) is defined by pressure-temperature-salinity (pTS) constraints of natural gas hydrate (GH) system. It refers to a depth interval which usually extends several hundred meters into the sediment column at sufficient water depths. The lower boundary of the GHSZ often coincides in seismic reflection data with a bottom simulating reflector (BSR), which indicates the transition between the underlying free gas and the overlying no-free gas zone at the thermodynamic stability boundary. The GHSZ in geological systems is dynamic and can shift in response to sedimentation processes and/or changes in environmental conditions such as bottom water temperatures, hydrostatic pressure, and water salinity. The appearance of multiple BSRs has been interpreted as remnants of former GHSZ shifts which have persisted over geological timescales. In this study, we numerically simulate the sedimentation-driven development of multiple stacked BSRs in the Danube deep-sea fan in the Black Sea. We show that in this dynamic sediment depositional regime sufficient amounts of residual gas remain trapped in the former GHSZ, given sufficiently high initial gas hydrate saturations, so that paleo-BSRs could persist over long time scales (similar to 300 kyr). In particular, the formation and persistence of multiple BSRs in the Danube Delta is controlled by the sequence of sedimentation events of the levees induced by sea-level change. The kinetics of methane phase transitions between gas hydrate, dissolved methane, and free gas plays a key role in the coexistence, location and timing of the multiple BSRs. Thus, For a given permeability, distinct multiple BSRs appear only for a narrow range of GH formation (10(-14) 〈 k(f) [mol/m(2) Pa s] 〈= 10(-12)) and dissociation rates (10(-16) 〈 k(d) [mol/m(2) Pa s] 〈 10(-14)).

Description: Multiple stressors often act concomitantly on ecosystems but detection of species responses follows the “single species-single driver” strategy, and cumulative impacts are seldom considered. During 1990–2010, multiple perturbations in the Caspian Sea, led to the decline of kilka, sturgeon and Caspian seal populations. Specific causes for their collapse were identified but a cumulative assessment has never been carried out. Using loop analysis, a qualitative modelling technique suitable in poor-data contexts, we show how multiple drivers can be combined to assess their cumulative impact. We confirm that the decline of kilka, sturgeon and Caspian seal populations is compatible with a net effect of the concomitant perturbations. Kilkas collapse was certainly due to the outburst of M. leidyi and overfishing. In addition, the excess nutrient might have conspired to reduce these populations. The interplay between concurrent drivers produces trade-offs between opposite effects and ecosystem management must face this challenge

Description: Highlights • Four rhyolitic explosive eruption events were distinguished from 13.1 Ma to 11.6 Ma. • Silicic volcanism occurred at termination of subduction in a thinning lithosphere. • Rhyolites show extreme magma differentiation and reduced-dry character. • Zircon trace element and Hf isotope fingerprint is an effective correlation tool. Abstract The Tokaj Mts. volcanism occurred in a thinning continental lithosphere regime at the final stage of the subduction process. Using high-precision zircon U-Pb dating, four major explosive eruption events were distinguished. Among them the 13.1 Ma Sátoraljaújhely and the 12.0 Ma Szerencs eruptions could have yielded large amount of volcanic material (possibly 〉 100 km3) and they were associated with caldera collapse as shown by the several hundred-metre-thick pyroclastic deposits and the long (〉100 km) runout pyroclastic flow in case of the 13.1 Ma eruption. The 12.3 Ma Hegyköz and the 11.6 Ma Vizsoly eruptions were relatively smaller. The volcanic products can be readily distinguished by zircon and glass trace elements and trace element ratios, which can be used for fingerprinting and to correlate with distal deposits. The Rb, Ba, Sr content and strong negative Eu-anomaly of the glasses reflect extreme crystal fractionation, particularly for the Szerencs rhyolitic magma. The silicic volcanic products of the Tokaj Mts. show compositional similarities with the so-called ‘dry–reduced–hot’ rhyolite type consistent with an origin in an extensional environment, where the primary magmas were formed by near-adiabatic decompression melting in the mantle with subordinate fluid flux. In contrast, some of the older Bükkalja rhyolitic magmas evolved via more hydrous evolutionary paths, where amphibole played a role in the control of the trace element budget. The significant increase of zircon ε Hf values from −8.8 to + 0.2 in the rhyolitic pyroclastic rocks of Tokaj Mts. with time implies that mantle-derived magmas became more dominant. This can be explained by the specific tectonic setting, i.e. the final stage of subduction when the descending subducted slab became almost vertical, which exerted a pull in the upper lithosphere leading to thinning and accelerated subsidence as well as asthenospheric mantle flow just before the slab detachment.

Description: This review has been undertaken to understand the effectiveness of ocean acidification on oceanic micronutrient metal cycles (iron, copper and zinc) and its potential impacts on marine biota. Ocean acidification will slow down the oxidation of Fe(II) thereby retarding Fe(III) formation and subsequent hydrolysis/precipitation leading to an increase in iron bioavailability. Further, the increased primary production sustains enzymatic bacteria assisted Fe(III) reduction and subsequently the binding of weaker ligands favours the dissociation of free Fe(II) ions, thus increasing the bioavailability. The increasing pCO2 condition increases the bioavailability of copper ions by decreasing the availability of free CO32− ligand concentration. The strong complexation by dissolved organic matter may decrease the bioavailable iron and zinc ion concentration. Since ocean acidification affects the bioavailability of essential metals, studies on the uptake rates of these elements by phytoplankton should be carried out to reveal the future scenario and its effect on natural environment.

Description: The Red Sea is an important example of a continental rift transitioning slowly to an oceanic basin. However, structures that can inform us of how that transition occurred have been poorly reported because deep seismic reflection data capable of imaging basement under the rift sediments are generally lacking publicly. Three lines of multichannel seismic reflection data have recently been published revealing structures on the Nubian side of the central part of the basin. In this study, we reassess these data in the light of recent studies of the central Red Sea. Over continental crust, the data reveal reflection sequences likely due to strata at or near the base of the evaporites, in two cases with varied dips suggesting the presence of syn-rift growth stratigraphy. Almost all of those reflections dip downwards towards the rift axis, not away as would be expected from tilted fault blocks of bookshelf faulting types. That observation, and low relief of basement, confirm inferences made earlier based on gravity anomalies that this part of the Red Sea lacks large-relief fault escarpments and is most likely a syn-rift sag basin. In the transition to oceanic crust, an abnormally broad magnetic anomaly of estimated Chron 5 age is found not to be associated with structures such as sills, so it likely arises from deeper sources. One of the seismic lines traverses a ridge in Bouguer gravity anomalies that runs across the axis. This feature has previously been interpreted as a volcanic ridge similar to those observed at other ultra-slow spreading ridges. The seismic data reveal diffuse basement reflections and confirm that the record immediately above basement lacks reflections typical of sedimentary strata. Both observations are consistent with the presence of oceanic crust. Modelling of gravity anomalies suggests the ridge is likely underlain by igneous intrusive rocks displacing mantle rocks, as expected for a volcanic ridge. The seismic data, combined with recently updated multibeam and high-resolution sparker seismic results, further suggest how the evaporite movements have been modulated by basement topography. These results add to our knowledge of the evaporite movements and continent-ocean transition structures in the central Red Sea.

Description: The impact of oxygen on the preservation of organic matter in marine surface sediments is still controversial. We revisited this long-standing debate by determining the burial efficiency of sedimentary organic matter in the Black Sea, the largest anoxic and euxinic basin in the modern ocean. Surface sediments were sampled in the Danube paleodelta on the northwestern margin of the Black Sea at 420–1550 m water depth. Steady-state modeling of solid species (particulate organic carbon and nitrogen) and solutes (ammonium, sulfate, and total alkalinity) in sediments was performed to quantify rates of mass accumulation, particulate organic matter (POM) degradation, and POM burial. We develop a novel analytical model to quantify these rates applying an inverse modelling approach to down core data accounting for molecular diffusion, sediment burial and compaction. Our model results indicate that 56.7 ± 6.6 % of the particulate organic matter deposited in the study area is not degraded in surface sediments but accumulates below 10 cm sediment depth. This burial efficiency is substantially higher than those previously derived for seafloor areas underlying oxygenated bottom waters. Hence, our study confirms previous studies showing that euxinic bottom water conditions promote the preservation of particulate organic matter in marine sediments.

Description: The TetraEther indeX of 86 carbon atoms (TEX86) is widely used as a proxy to reconstruct past sea surface temperatures. Most current applications of TEX86 are primarily based on analyzing the composition of isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) that comprise TEX86 in sediments, with the assumption that the sedimentary isoGDGTs are mainly derived from the surface mixed layer. Here we report on the variations in the isoGDGT distribution, archaeal abundance and community through the water column of the Western Pacific Ocean, directly testing the export depth of isoGDGTs and constraining the temperature records of TEX86. Our data show that maximum isoGDGT concentrations occurred in subsurface waters (150–200 m) with maximum archaeal abundances. The ratio between isoGDGTs bearing 2 vs. 3 cyclopentane moieties, i.e. [2/3] ratio, increased with depth, which is likely related to the shift of the archaeal community from Ca. Nitrosopelagicus-dominance to norank_f__Nitrosopumilaceae-dominance. Models based on the [2/3] ratios in the water column predicted an average export depth of isoGDGTs to sediments of around 150–200 m, consistent with the robust relationship between the compiled sedimentary TEX86 and the annual mean subsurface temperature. Taken together, our findings support that TEX86 records subsurface rather than surface temperatures in the open ocean.

Description: The ocean region along the latitude of 40oS in the South Atlantic, characterized by enhanced primary productivity, forms a transition zone between the nutrient replete but iron depleted Southern Ocean, and the nitrate and iron depleted Subtropical Gyre. Here, we present distributions of nutrient-type dissolved and particulate trace metals (dTMs and pTMs) including cadmium (Cd), nickel (Ni), copper (Cu), and zinc (Zn) in the South Atlantic from the GEOTRACES GA10 cruises. Phytoplankton uptake, riverine and atmospheric inputs shaped dTM and pTM concentrations in surface waters (dCd 27.8±36.0 pmol kg-1, n=222; dCu 0.732±0.429 nmol kg-1, n=222; dNi 3.38±0.52 nmol kg-1, n=219; dZn 0.332±0.398 nmol kg-1, n=214). Subsurface nutrients and dTMs (dCd 563±184 pmol kg-1, n=335; dCu 1.819±0.773 nmol kg-1, n=334; dNi 6.19±1.06 nmol kg-1, n=330; dZn 3.71±2.10 nmol kg-1, n=333) were controlled by the mixing of Antarctic origin waters and North Atlantic Deep Waters (NADW) with negligible contributions from local remineralization. Dissolved and particulate TMs in the Argentine Basin showed elevated concentrations towards the seafloor because of benthic inputs. Direct hydrothermal inputs of dTMs and pTMs to deep waters were not observed along the transect. The Cd-Cu-Zn-phosphate stoichiometries of Antarctic origin waters were set by a combination of dynamic physical circulation and preferential uptake of Cd, Cu, and Zn relative to phosphate in surface waters because of a dominance by diatoms in the Southern Ocean. Water mass mixing subsequently produced convoluted dCu-P and dZn-P relationships and apparent linear dCd-P and dNi-P relationships in the South Atlantic. More importantly, endmember characteristics of Antarctic waters and NADW are largely fixed in their formation regions in high latitude oceans. Therefore, the highly dynamic high latitude oceans are key regions that supply nutrients and TMs at specific ratios to low latitude oceans via the thermohaline circulation. Changes to processes in the high latitude oceans may have consequences for marine primary productivity downstream, and hence the global carbon cycle.

Description: Highlights • Investigation into the potential of Porites microatolls for SST reconstruction. • Comparison between recent and more conventional coral paleoclimatology methods. • Application of Srsingle bondU and Li/Mg paleothermometer. • Accuracy and reproducibility of Sr/Ca proved to be the most suitable proxy for SST reconstruction. Abstract Massive dome-shaped coral Porites are the predominant choice for paleoclimate studies due to their consistent and reliable growth. When growing close to sea level, they become limited in their vertical growth and form so-called ‘microatolls’. Microatolls have not yet been extensively explored for paleoclimate reconstruction. Here, we investigate how reliable modern Porites microatolls are against empirical sea-surface temperature using Sr/Ca, δ18O, Li/Mg and Srsingle bondU paleothermometry methods on samples from the Society Islands, French Polynesia. Our results show Sr/Ca ratios have the lowest Standard Error of the Inverse Prediction (SEIP) at 0.415 °C (N = 41) with a calibration of Sr/Ca (mmol mol−1) = −0.082 ± 0.006 SST (°C) + 11.256 ± 0.170 and with high reproducibility across multiple corals. The reproducibility of δ18O was less good, with SEIP increasing to 0.829 °C (N = 41). Considering methods directly from the literature, Li/Mg ratio empirically corrected for Sr/Ca had the best balance between bias and precision where no local calibration could be available. This study independently evaluates and confirms the suitability of Porites microatolls from well-flushed environments for paleoclimate studies. Fossil dome-shaped Porites grow anywhere between near-surface and roughly 20 m depths which inherently incorporates uncertainty into any sea surface temperature reconstruction. This uncertainty is significantly reduced for microatolls due to their well-constrained bathymetry. The study represents a fundamental step in paleoclimate research targeting consistently near the water-air interface bringing reliability and, especially when combined with their ability to reconstruct past sea-level changes, microatolls have the potential to be central for future paleoenvironmental studies.

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.

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 dissolved iron (dFe) concentrations of the order of 10-100 nmol L-1 are a feature of waters influenced by sedimentary inputs in oxygen minimum zones (OMZ). However, the temporal development of dFe concentrations is poorly defined due to a general reliance on snapshot cross-shelf sections to study marine trace metal dynamics. Multiple cruise campaigns since the 1980s have investigated Fe dynamics over the Peruvian shelf, particularly between 9-17°S where the shelf is broad, extremely productive and known to feature benthic dFe effluxes which are amongst the highest measured globally. This extensive long-term dataset uniquely allows us to study the interannual variability in dFe concentrations and their response to El Niño–Southern Oscillation (ENSO) events. By combining data from 11 cruises during the period 1984-2017 we are able to evaluate dFe dynamics on interannual timescales in a major OMZ. The region where average dFe concentrations are sensitive to variations in ENSO is confined to a subsurface layer at depths between 50-150 m, particularly in the narrow coastal region within 50 km of the coastline. Subsurface dFe concentrations were generally low during El Niño events (0.7-15.4 nmol L-1) and relatively high with a wider range of variability during the cold ENSO phase (1.1-52.1 nmol L-1). Inverse relationships between wind speed and surface/subsurface dFe were evident. In the subsurface layer, this may be attributable to enhanced dFe offshore transport along isopycnals when upwelling-favorable winds relax in accordance with previously outlined theories. Surface layer (〈40 m) dFe variability was likely associated with a dilution and/or oxidation effect depending on the strength of wind driven water column mixing. Upwelling brings macronutrient-rich water into the euphotic zone, but its intensity had a limited impact on upper layer dFe concentrations possibly due to the influence of an onshore geostrophic flow. Interannual variability in surface chlorophyll-a (Chl-a) was found to correlate with dFe concentration in the offshore zone of northern Peru. This is consistent with bioassay experiments and climatological residual nitrate concentrations which both indicate proximal Fe limitation of phytoplankton growth over and beyond the northern Peruvian shelf. Overall, our work highlights the importance of physical factors driving short-term variations in Fe availability in one of the world’s most economically important fishery regions and suggests that, despite pronounced spatial and temporal variability in dFe concentrations, the ENSO phase has an impact on dFe availability.

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: Underwater image restoration has been a challenging problem for decades since the advent of underwater photography. Most solutions focus on shallow water scenarios, where the scene is uniformly illuminated by the sunlight. However, the vast majority of uncharted underwater terrain is located beyond 200 meters depth where natural light is scarce and artificial illumination is needed. In such cases, light sources co-moving with the camera, dynamically change the scene appearance, which make shallow water restoration methods inadequate. In particular for multi-light source systems (composed of dozens of LEDs nowadays), calibrating each light is time-consuming, error-prone and tedious, and we observe that only the integrated illumination within the viewing volume of the camera is critical, rather than the individual light sources. The key idea of this paper is therefore to exploit the appearance changes of objects or the seafloor, when traversing the viewing frustum of the camera. Through new constraints assuming Lambertian surfaces, corresponding image pixels constrain the light field in front of the camera, and for each voxel a signal factor and a backscatter value are stored in a volumetric grid that can be used for very efficient image restoration of camera-light platforms, which facilitates consistently texturing large 3D models and maps that would otherwise be dominated by lighting and medium artifacts. To validate the effectiveness of our approach, we conducted extensive experiments on simulated and real-world datasets. The results of these experiments demonstrate the robustness of our approach in restoring the true albedo of objects, while mitigating the influence of lighting and medium effects. Furthermore, we demonstrate our approach can be readily extended to other scenarios, including in-air imaging with artificial illumination or other similar cases.

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: Highlights: • Niche conservatism among reservoirs was generally higher in invertebrates. • Niche conservatism was not based on reservoir condition (i.e. presence or absence of pollution and/or invasion). • Invasion coupled with organic pollution may cause subtle yet differing effects on food web components. • Results provide baseline measure in carp invasions and organic pollution detection and response strategies. Abstract: Environmental pollution and biological invasions are key drivers of biodiversity change. However, the effects of invasion and pollution on food webs remain largely unexplored. Here, we used stable isotopes to examine the effects of common carp Cyprinus carpio and pollution on trophic dynamics in six small reservoirs. Our results revealed that the trophic niche widths of invertebrates, vertebrates, and invasive carp did not significantly differ among reservoirs with different pollution statuses. However, we found low niche conservatism among reservoirs, suggesting that while niche width may remain consistent, there is a shift in the position of the niches in isotopic space under both pollution and invasion scenarios. Niche conservatism among reservoirs was generally higher in invertebrates, but this was also regardless of reservoir condition (i.e. presence or absence of pollution and invasion). These results suggest that invasion by species coupled with organic pollution may cause subtle yet differing effects on components of a food web (basal end-members, invertebrates and vertebrates). Our findings provide a baseline measure of the potential in the development of detection and response strategies for carp invasions and organic pollution.

Description: Plate tectonic processes introduce oceanic crust (as eclogite) into the sources of oceanic island basalts (OIB). The fate of this recycled material in the deep mantle is still poorly understood. Here we present a systematic study of Zn isotopes on well-characterized alkaline basalts (〈5 Ma) from the Madeira Islands in the eastern North Atlantic. Our analyses show that the δ66Zn values of alkaline basalts range from 0.25‰ to 0.34‰, with an average of 0.30 ± 0.05‰ (2SD, N = 15), which is similar to the average of mid-ocean ridge basalts (MORB) (0.28 ± 0.03‰, 2SD), and ∼ 0.14‰ higher than that of the asthenospheric mantle (0.16 ± 0.06‰, 2SD). However, these alkaline basalts have higher Zn/Fe ratios (up to 14.20) than MORB (generally less than 12). Model calculations show that the partial melting of mantle peridotite cannot simultaneously produce the observed MORB-like δ66Zn values and trace element ratios. After excluding the effects of post-eruption alteration, crystal fractionation, and the assimilation of crustal materials during magma upwelling on Zn isotopic compositions of the studied samples, we suggest that the MORB-like δ66Zn values reflect the mixing of peridotite melt and eclogite/pyroxenite-derived melt in the magma source of the Madeira hotspot. This is supported by trace element ratios and radiogenic isotopes, such as high Zn/Fe and Dy/Yb ratios and 206Pb/204Pb values. Our new data provide independent evidence in support of the important role of recycled oceanic crust in the source and generation of alkaline OIBs, and also highlight that such sources are not ubiquitously carbonated.

Description: Highlights: • Huidobria chilensis is an endemic shrub distributed in the south of the Atacama Desert with a disjunct population at the northern coast. • Population and genetic structure correlate with geographic distance and geological factors. • Rain fall and fog, as well as ground water, must be regarded as important factors for populations at the coast and the Andean valleys, respectively. • A combination of different software tool to analyze GBS data allowed a good understanding of the population structure and genetic diversity. Abstract: Survival in hyperarid deserts is a major challenge for life in general and for plants in particular. The Atacama Desert presents harsh conditions such as limited rainfall, crusted soils, high soil salinity, high altitude, and intense solar radiation. These conditions, together with paleoclimatic variations over the last 10 million years, have influenced the genetic structure and connectivity of plant populations, resulting in a diverse flora with high endemism. However, the diversification of most lineages appears to be relatively recent, in contrast to the reported age of the Atacama Desert and the onset and expansion of hyperarid conditions since the late Oligocene and early Miocene. A prominent exception is Huidobria chilensis (Loasaceae), which is thought to be endemic to the Atacama since the Eocene. However, it is still not understood why this plant has been successful in adapting to the harshening environmental conditions. To investigate its genetic structure in relation to the history of the Atacama Desert, we studied 186 individuals from 11 populations using genotyping-by-sequencing (GBS). A total of nearly 56 k genome-wide single nucleotide polymorphisms (SNPs) were analyzed for population structure and genetic diversity. We identified four genetic clusters corresponding to geographic regions: the coastal region south of Tocopilla, the Cordillera de la Costa around Chañaral, and the Copiapó catchment 1 and 2. Genetic diversity within and between these clusters was analyzed along with rainfall, altitude, and landscape data. Although the genetic data support `isolation by distance’ as a major factor for genetic divergence between populations, the study also reveals the influence of topography on the distribution of H. chilensis and highlights the role of hydrologically connected watersheds and rivers in plant migration and colonization. This shapes the species' evolutionary trajectory and genetic diversity. Understanding these patterns in H chilensis lets one draw general conclusions about adaptation and survival strategies of plants in extreme desert environments such as the Atacama.

Description: Highlights: • Microphytobenthos contributed to the particulate organic matter in both beaches. • Allochthonous materials provide relevant contributions to the POM in surf zones. • Estuarine subsidies' availability determines changes in consumers' isotopic niches. • Higher estuarine trophic subsidies resulted in narrower niches of dominant species. Abstract: Benthic invertebrates in the surf zone of exposed sandy beaches represent important links for energy circulation between benthic and pelagic food webs. This work assesses the trophic ecology of co-occurring epi- and hyper-benthic invertebrates inhabiting the surf zone of sandy beaches located close to an estuarine mouth. It illustrates that different sources of organic matter induce changes in resource utilization. The trophic positions, and the niche width and overlap of species were described using δ13C and δ15N stable isotope analysis. The contribution of different sources to the particulate organic matter was quantified through stable isotopes analysis and fatty acids profiles. Shifts in the trophic niches of dominant species reflected a decrease in the contribution of estuarine carbon to the diets along the coast. This change in contribution of estuarine carbon also influenced trophic niche properties: more diverse resources availability resulted in narrower niches without overlap while less diverse resources resulted in broad isotopic niches and a highest overlap. Results show that spatial variations in the availability of resources can modify carbon pathways and trophic interactions in coastal food webs. Whenever resources are abundant, species display a more specialized diet while food scarcity leads to broader diets, a pattern consistent with the optimal foraging theory. This resource maximization behavior commonly observed in nature is also occurring in surf zone ecosystems.

Description: The Amazon and the Pará are two major rivers that carry dissolved and suspended particulate trace metals to the Atlantic Ocean. In the dynamic mixing zone of the estuary, competing processes of trace metal sorption and release play a role, which might affect transport to the open ocean. Here we investigate the behavior of dissolved (〈0.2 μm), soluble (〈0.015 μm) and truly dissolved (〈10 kDa and 〈 1 kDa) molybdenum (Mo), uranium (U), and vanadium (V) during estuarine mixing between river water (S 〈 1) and seawater (S 〉 35) end members during the high discharge period, as well as during aging of the plume in its northward flow along the coast. Molybdenum behaved conservatively during estuarine mixing and showed no colloidal fraction, suggesting Mo is solely present in the soluble or even truly dissolved fraction. Uranium behaved mostly conservatively but showed removal in the low salinity range (ca. S 〈 9). This is potentially due to colloidal flocculation at low salinities, as indicated by colloidal (0.015–0.2 μm) fractions of up to 30% for U but decreasing with increasing salinity until no significant difference could be discerned at S 〉 10. Vanadium shows a general conservative mixing, but with more scatter in the data than for Mo and U and potential removal at low to mid-salinities. Removal of V to the sediments is also indicated by surface sediment data from the mid-salinity region of the estuary but no size fractionation in the dissolved phase could be observed. Hence, V seems to be predominantly present in the soluble or even truly dissolved phase and export to the sediments might take place through particles 〉0.2 μm. No considerable removal or release of Mo, U and V was observed in their water column depth profiles, indicating a conservative behavior in the water column of the estuaries studied here. Additionally, we present a comparison of differential pulse adsorptive stripping voltammetry and inductively coupled plasma – mass spectrometry analyses for Mo and V, which showed excellent agreement within analytical uncertainty in this challenging sample material covering the full salinity range from freshwater to seawater.

Description: Abundance and composition of beach litter and microplastics (20–5000 μm, excluding fibres) were assessed in spring and autumn 2018 at various beaches along the Baltic Sea coast of Schleswig-Holstein, Northern Germany. The beach litter survey followed the OSPAR guidelines, while microplastics were extracted from sediment samples using density separation and were then identified with Raman μ-spectroscopy. We observed seasonality in the abundance and composition, but not in the mass of beach litter. The median microplastic abundance was 2 particles per 500 g of dry sediment in spring as well as in autumn, while six different synthetic polymers (PE, PP, PS, PET, PVC, POM) were detected. We found no correlation between the abundances of beach litter and microplastics. Our data represent the first systematic co-assessment of macro- and micro beach litter along the Baltic Sea coast of Schleswig-Holstein.

Description: Marine litter can be found along coasts, continental shelves and slopes, down into the abyss. The absence of light, low temperatures and low energy regimes characterising the deeper habitats ensure the persistence of litter over time. Therefore, manmade items within the deep sea will likely accumulate to increasing quantities. Here we report the litter abundance encountered at the Pacific abyssal nodule fields from the Peru Basin at 4150 m depth. An average density of 2.67 litter items/ha was observed. Litter composed of plastic was the most abundant followed by metal and glass. At least 58 % of the items observed could be linked to the research expeditions conducted in the area and appeared to be mostly accidental disposals from ships. The data gathered was used to address temporal trends in litter abundance as well as the impact of human on-site presence and return cruises in the context of future deep-sea mining efforts.

Description: Marine heatwaves (MHWs) are widely recognized as prolonged periods of significantly elevated sea surface temperatures, leading to substantial adverse impacts on marine ecosystems. However, a comprehensive understanding of their characteristics and potential changes under climate change in the South China Sea (SCS, 0 ∼ 25°N, 105 ∼ 125°E) remains insufficient. Here, utilizing the OISST V2.0 reanalysis dataset, our study first examines MHW characteristics and their trends in the SCS during the historical period (1982 ∼ 2014). Then, in accordance with the criteria established in this study, GFDL-ESM4, EC-Earth3-Veg, NESM3, EC-Earth3, and GFDL-CM4 are identified from the CMIP6 ensemble of 19 models for their enhanced simulations of historical MHW characteristics. Moreover, considering that the fixed and sliding threshold methods offer distinct perspectives on the future evolution of MHWs, we employ both approaches to evaluate MHW characteristics under projected scenarios for the future period (2015 ∼ 2100) and subsequently compare the disparities between the two methodologies. The outcomes obtained using these methods consistently indicate that MHWs in the SCS are anticipated to intensify and persist for longer durations in the future. Besides, addressing seasonal variability, the peak intensity of MHWs falls in May during both the historical period and the four projected future scenarios. This study provides valuable insights into the behavior of MHWs in the SCS within the context of climate change, underscoring the urgency of adopting effective mitigation strategies. Especially, the use of two definition methods provides a more comprehensive set of information for understanding the future changes of MHWs in the SCS.

Description: Highlights • Mercury methylation in sediment rapidly transported into water and diatoms. • CH3Hg flux was highest for sediments with higher sulfide and organic content. • Mineral and compressed sediment released minor Hg and CH3Hg. • Higher sediment Hg species flux does not correlate with high sediment content. • Stable isotope incubations provide substantial insight to environmental Hg cycling. Abstract Mercury (Hg) is a conspicuous and persistent global pollutant. Ionic Hg can be methylated into noxious methylmercury (CH3Hg), which biomagnifies in marine tropic webs and poses a health risk to humans and organisms. Sediment Hg methylation rates are variable, and the output flux of created CH3Hg are dependent on sediment characteristics and environmental factors. Thus, uncertainties remain about the formation and flux of CH3Hg from sediment, and how this could contribute to the bioaccumulative burden for coastal organisms in shallow ecosystems. Cores were collected from 3 estuarine locations along the Eastern USA to examine how sediments characteristics influence the introduction of Hg and CH3Hg into the base of the food chain. Stable isotopes of inorganic 200Hg and CH3199Hg were injected into sediments of individual cores, with cultured diatoms constrained to overlying waters. Five different treatments were done on duplicate cores, spiked with: (1) no Hg isotopes (control); (2) inorganic 200Hg; (3) CH3199Hg; (4) both 200Hg and CH3199Hg isotopes, (5) both 200Hg and CH3199Hg into overlying waters (not sediment). Experimental cores were incubated for 3 days under temperature and light controlled conditions. These results demonstrate that upper sediments characteristics lead to high variability in Hg cycling. Notably, sediments which contained abundant and peaty organic material (∼28 %LOI), had the highest pore water DOC (3206 μM) and displayed bands of sulfur reducing bacteria yielded the greatest methylation rate (1.97 % day−1) and subsequent diatom uptake of CH3200Hg (cell quota 0.18 amol/cell) in the overlying water.

Description: Highlights • Solutions to the climate crisis are not ahistorical. • Both social and technical processes explain their rise (or fall) on the agenda. • Thinking about ocean CDR closely co-evolved with scientific understandings of global climate change. • Ocean CDR methods have followed cycles of hype, controversy and disappointment. • Key sociotechnical configurations and narrative changes explain the new hype around ocean CDR. Abstract While the ocean has long been portrayed as a victim of climate change, threatened by ocean warming and acidification, it is now increasingly framed as a key solution to the climate crisis. In particular, the promising carbon sequestration potential of the ocean is being emphasised. In this paper, we seek to historicise the practices, discourses and actors that have constructed the ocean as a climate change solution space. We conceptualise the debate about the mitigation potential of the ocean as a contested site of governance, where varying actors form alliances and different sociotechnical narratives about climate action play out. Using an innovative quali-quantitative methodology which combines scientometrics with document analysis, observational fieldwork, and interviews, we outline three historical phases in the history of ocean carbon sequestration that follow recurring cycles of hype, controversy and disappointment. We argue that the most recent hype around ocean carbon sequestration was not triggered by a technological breakthrough or a reduction in scientific uncertainty, but by new socio-technical configurations and coalitions. We conclude by showing that how climate change solutions are put on the agenda and become legitimised is both a scientific and political process, linked to how science frames the climate crisis, and ultimately, its governance.

Description: The Zhenbei and Huangyan seamounts located close to the extinct spreading ridge (ESR) in the South China Sea (SCS) have provided fundamental insight into postspreading magmatism. Long debates on the source and evolutional process of the postspreading seamounts are due to the lack of detailed structural crustal constraints. Here, we present three-dimensional (3D) crustal thickness and the Moho geometry of the Zhenbei and Huangyan seamounts and their surrounding area by forwarding and interpolating P-wave forward velocity structures along 14 seismic refraction and wide-angle profiles. We analyzed the variation in crustal velocity and thickness from the waning stage of seafloor spreading to the postspreading magmatism stage. Results show that the original oceanic crust, with an average thickness of 4.5 ± 0.7 km, is characterized by thin lower crust, thick upper crust, and low crustal velocity, compared with Atlantic oceanic crust, reflecting reduced magma supply and intense tectonic fracturing. Both the Zhenbei and Huangyan seamounts show high extrusion to intrusion ratio (2.6 and 2.7) and low P-wave velocities in the upper crust, indicating that extrusive processes are dominant during the postspreading volcanism in the SCS. The total magma volumes for building Zhenbei and Huangyan seamounts are estimated to be 4995 km3 and 3674 km3, respectively, with a related volume flux of ~0.032 m3/s and ~ 0.023 m3/s. These values are larger than those of Longnan seamount (2884 km3, 0.018 m3/s) but smaller than those of plume-derived seamounts. The relationship between average lower crustal velocity and crustal thickness also indicates that the postspreading magma may not be caused by the higher degree of mantle melting driven by elevated temperature, but by multiple lower degree of melting caused partly by the enriched mantle.

Description: Climate change is driving compositional shifts in ecological communities directly by affecting species and indirectly through changes in species interactions. For example, competitive hierarchies can be inversed when competitive dominants are more susceptible to climate change. The brown seaweed Fucus vesiculosus is a foundation species in the Baltic Sea, experiencing novel interactions with the invasive red seaweed Gracilaria vermiculophylla, which is known for its high tolerance to environmental stress. We investigated the direct and interactive effects of warming and co-occurrence of the two algal species on their performance, by applying four climate change-relevant temperature scenarios: 1) cooling ) 2 °C below ambient – representing past conditions), 2) ambient summer temperature (18 °C), 3) IPCC RCP2.6 warming scenario (1 °C above ambient), and 4) RCP8.5 warming (3 °C above ambient) for 30 days and two compositional levels (mono and co-cultured algae) in a fully-crossed design. The RCP8.5 warming scenario increased photosynthesis, respiration, and nutrients' uptake rates of mono- and co-cultured G. vermiculophylla while growth was reduced. An increase in photosynthesis and essential nutrients' uptake and, at the same time, a growth reduction might result from increasing stress and energy demand of G. vermiculophylla under warming. In contrast, the growth of mono-cultured F. vesiculosus significantly increased in the highest warming treatment (+3 °C). The cooling treatment (−2 °C) exerted a slight negative effect only on co-cultured F. vesiculosus photosynthesis, compared to the ambient treatment. Interestingly, at ambient and warming (RCP2.6 and RCP8.5 scenarios) treatments, both F. vesiculosus and G. vermiculophylla appear to benefit from the presence of each other. Our results suggest that short exposure of F. vesiculosus to moderate or severe global warming scenarios may not directly affect or even slightly enhance its performance, while G. vermiculophylla net performance (growth) could be directly hampered by warming.

Description: Highlights: • Transcriptomic immune response assessments in seahorse (Hippocampus erectus). • Seahorses exposed in two phases to heat-killed Vibrio and Tenacibaculum strains. • Adaptive immune memory evidence (double-exposed) and increased naivety to Tenacibaculum. • Upregulated gene expression pertaining to potential innate ‘trained immunity’. • Trained immunity potential compensator for deduced MHC II loss of function. Evolutionary adaptations in the Syngnathidae teleost family (seahorses, pipefish and seadragons) culminated in an array of spectacular morphologies, key immune gene losses, and the enigmatic male pregnancy. In seahorses, genome modifications associated with immunoglobulins, complement, and major histocompatibility complex (MHC II) pathway components raise questions concerning their immunological efficiency and the evolution of compensatory measures that may act in their place. In this investigation heat-killed bacteria (Vibrio aestuarianus and Tenacibaculum maritimum) were used in a two-phased experiment to assess the immune response dynamics of Hippocampus erectus. Gill transcriptomes from double and single-exposed individuals were analysed in order to determine the differentially expressed genes contributing to immune system responses towards immune priming. Double-exposed individuals exhibited a greater adaptive immune response when compared with single-exposed individuals, while single-exposed individuals, particularly with V. aestuarianus replicates, associated more with the innate branch of the immune system. T. maritimum double-exposed replicates exhibited the strongest immune reaction, likely due to their immunological naivety towards the bacterium, while there are also potential signs of innate trained immunity. MHC II upregulated expression was identified in selected V. aestuarianus-exposed seahorses, in the absence of other pathway constituents suggesting a possible alternative or non-classical MHC II immune function in seahorses. Gene Ontology (GO) enrichment analysis highlighted prominent angiogenesis activity following secondary exposure, which could be linked to an adaptive immune process in seahorses. This investigation highlights the prominent role of T-cell mediated adaptive immune responses in seahorses when exposed to sequential foreign bacteria exposures. If classical MHC II pathway function has been lost, innate trained immunity in syngnathids could be a potential compensatory mechanism.

Description: Highlights • Alkaline rocks including nepheline syenites, monzogabbros and nepheline-monzosyenites are abundant in NW Iran. • 40Arsingle bond39Ar data show ages of 39.2–43.6 Ma for plutonic rocks and 41.8 Ma for crosscutting trachy-andesitic dikes. • Isotope modelling suggests mixing between depleted mantle and sediment melts for the formation of these rocks. Abstract High Na- to K- alkaline magmatism is common in the rear-arc region of the Cenozoic Urumieh-Dokhtar Magmatic Belt of Iran, but their geochemical signatures, as well as their formation mechanisms, have been poorly studied thus far. In the Kleybar area of NW Iran, Middle Eocene magmatic activity comprises silica-undersaturated to -saturated gabbros, monzogabbros, monzosyenites to nepheline-monzosyenites, and nepheline syenite as well as tephritic to trachy-basaltic and trachy-andesitic dikes. New 40Arsingle bond39Ar results show a restricted age range (39.2–43.6 Ma) for the intrusive rocks (43.16 ± 0.43 and 43.34 ± 0.43 Ma for gabbros, 43.56 ± 0.44 for monzogabbros, 39.22 ± 0.48 and 42.09 ± 0.42 Ma for nepheline syenites, 42.17 ± 0.42 Ma for nepheline-monzosyenites), whereas a cross-cutting trachy-andesitic dike yielded an 40Arsingle bond39Ar age of 41.78 ± 0.42 Ma. The Kleybar rocks are enriched in alkalis (K2O and Na2O) with variable K2O/Na2O ratios (0.14 to 2.93), light rare earth elements and large ion lithophile elements such as Th, Rb, K, U and Pb. High field strength elements such as Nbsingle bondTa are depleted in these rocks. The isotopic compositions of the different rock types are quite variable: gabbros and monzogabbros have 87Sr/86Sr(t) = 0.70419–0.70436, εNd(t) = +3.1 to +3.8 and εHf(t) = + 7.8 to +10.1; nepheline monzosyenites and nepheline syenites have 87Sr/86Sr(t) = 0.70359–0.70566 (except a nepheline syenite with a ratio of 0.74833 and very high Rb/Sr), εNd(t) = +1.5 to +4.2 and εHf(t) = +4.6 to +8.8; and trachy-basaltic to trachy-andesitic to tephritic dikes have 87Sr/86Sr(t) = 0.70437–0.70469, εNd(t) = +2.8 to +4.2 and εHf(t) = +8.3 to +10. In the thorogenic-Pb isotope diagram, the Kleyber igneous rocks define an array above the Northern Hemisphere Reference Line (NHRL), with ∆8/4 (deviation from the NHRL) of ~40–60. These samples also plot above the NHRL in uranogenic Pb space (∆7/4–5-10). The positive ∆8/4 Pb and ∆7/4 Pb may reflect the involvement of subducted terrigenous sediments in their mantle source during the subduction of the Neotethyan oceanic lithosphere. Two nepheline syenite samples have significantly higher thorogenic and uranogenic Pb isotopic compositions, that may reflect assimilation of surrounding clay-rich sedimentary rocks. Modelling of trace elements compositions using less fractionated Kleybar trachybasalt and fine-grained monzogabbro samples indicate that a 96:4 mixture of the depleted mantle and subducting (trench)-sediment melts with 6% aggregated fractional melting closely matches the trace-element abundances of the Kleybar trachybasalt and monzogabbro. Together with previous studies on high-K volcanic rocks from NW Iran, our results indicate that Neotethyan slab retreat and related extension of the Iranian continental lithosphere in the rear-arc region of the Urumieh-Dokhtar Magmatic Belt generated alkali-rich magmatic rocks throughout the NW Iran rear-arc during Middle-Late Eocene.

Description: Highlights • The developed joint inversion quantifies both free gas and hydrate concentration. • The robust method uses sonic and conductivity logs as main input parameters. • For the test site it reveals two hydrate accumulations with very different characteristics. • The whole range of concentrations is shown that can explain the observed data. • The method is applicable to most continental margins when there is borehole control. Abstract Quantification of gas hydrates in marine sediments is crucial for understanding gas hydrate systems. By empirical relationships or effective medium modelling, gas hydrate concentrations can be derived from velocity and/or conductivity logs. However, these approaches do not take the co-occurrence of free gas and gas hydrate into account leading to large uncertainties in the calculated free gas and gas hydrate concentrations. To overcome this issue we adopt a joint elastic and electric self-consistent/differential effective medium model as the basis for a new joint inversion scheme that distinguishes between both phases. We apply this scheme to p-wave velocity and electric induction data measured by downhole-logging of boreholes at Formosa Ridge off Taiwan - a known hydrate province with an active gas conduit. Gaussian Mixture Modeling separates the background signal of the host medium from anomalies and allows to determine a background porosity as a probability density function of depth. We use this derived porosity to jointly invert electrical conductivity and velocity data for hydrate and free gas concentrations. At Formosa Ridge, we find two resistive anomalies, one in the shallow and another in the deep part of the borehole. Only the deep anomaly in conductivity coincides with a high-velocity anomaly. This is consistent with ∼30% hydrate with ∼1% free gas concentration. For the shallow anomaly, increased velocities due to hydrate concentrations of ∼15% are compensated by a decrease in velocity due to ∼1% of free gas. The method reconciles the different sensitivities of the two data types and yields hydrate and free gas concentrations that are largely consistent with geochemically derived values.

Description: Highlights • Negligible Ba removal observed in the Rainbow hydrothermal system. • Insignificant modification of Ba isotope composition of the vent fluid endmember. • Rainbow vent introduces isotopically light Ba (−0.17) to the deep Atlantic Ocean. • Hydrothermal inputs contribute 4.6 ± 2.2 Gmol/yr Ba to the ocean. Abstract The marine barium (Ba) cycle is closely connected to the short-timescale carbon cycle, and Ba serves as a valuable paleo proxy for export production, ocean alkalinity, and terrestrial inputs. However, the marine Ba budget is poorly constrained, particularly regarding the fluxes of hydrothermally sourced Ba, which hinders our understanding of the Ba cycle and use of Ba-based proxies. Recent studies have suggested a modern source-sink imbalance of Ba isotopes in the global ocean, with sources being overall isotopically heavier than the sinks, and the hydrothermal Ba inputs were considered isotopically heavy sources. In this study, we present the first investigation of Ba and its isotopes in a non-buoyant hydrothermal plume based on dissolved and particulate samples collected from the Rainbow hydrothermal vent field on the Mid-Atlantic Ridge. Our data reveal strong hydrothermal signals at near-field stations, as evidenced by helium isotopes, accompanied by elevated concentrations of dissolved and particulate Ba. Dissolved Ba isotope compositions (δ138Ba) in hydrothermally influenced deep waters (∼0.3 ) are lighter than at similar depths of far-field stations (∼0.45 ) in the Atlantic Ocean. The concentrations and isotopic compositions of dissolved and labile particulate Ba in the non-buoyant hydrothermal plume can be explained by conservative mixing between a Ba-enriched hydrothermal component and North Atlantic Deep Water. By extrapolating the correlations to the vent fluid endmember, our results suggest that there is negligible removal of Ba, and insignificant modification of Ba isotopic signatures, from the vent fluid endmember to the non-buoyant hydrothermal plume. This indicates that the Rainbow hydrothermal system introduces isotopically light Ba (−0.17 ± 0.05 ) to the deep Atlantic Ocean. We estimate that global hydrothermal inputs of Ba are 4.6 ± 2.2 Gmol/yr. These observations highlight the potential of hydrothermal Ba to be an isotopically light source component of the marine Ba isotope budget.

Description: The burial of organic carbon (OC) in marine sediments is a considerable sink for carbon, removing OC from the active ocean-atmosphere system. Both the total OC buried, and the proportion of OC retained in sediments after burial, varies by location, with some areas of the ocean floor known to be 'hotspots' of OC sequestration. Two potential such hotspots may be sediments containing high proportions of tephra (the unconsolidated products of explosive volcanism), and locations of turbidite deposition, but knowledge of specific burial regimes in such locations remains poorly constrained. To fully investigate these processes, we performed a holistic (organic and inorganic) geochemical analysis of samples from the Aegir Ridge, which contain both tephra layers and material from the Storegga Slide, a large turbidite. We show sediments found between the Storegga Slide and the tephra are a location of high OC preservation, linked to reducing conditions caused by the rapidly deposited slide layer sealing the sediments from overlying water column O2. We see little evidence for tephra positively affecting OC preservation at our site, but this is likely a feature of specific burial conditions, with the responsible mechanisms depending highly on the nature of the tephra. Our findings demonstrate how even in locations proposed as OC burial hotpots, the processes controlling this burial are highly complex, and that levels of sedimentary OC burial must be assessed on a case-by-case basis.

Description: An increasing number of monitoring studies have confirmed the occurrence of antibiotic residues in the marine environment. Antibiotics have mostly been detected in coastal waters, but also in marine sediments and a diversity of aquatic organisms, raising concern on potential risks to the environment and human health. This chapter critically discusses antibiotic sources and prevalence in marine ecosystems, as well as potential adverse impacts on aquatic life. Current methodologies for the wide-scope analysis of antibiotics in the environment, alongside with novel ecotoxicological approaches, are also tackled. Lastly, a particular focus was given to the related emergence of antibiotic resistant bacteria in the marine environment and their implications for public health, as well as future trends and strategies for the mitigation of antibiotic pollution and effects.

Description: Highlights • Well-defined periodic states are embedded within the steady-state hydrate dynamics. • Periodic states lead to cyclic formation and dissociation of massive hydrate layers. • Periodic states are fully self-sustaining even in the absence of external triggers. • Spontaneous gas migration & pressure release occur in supposedly unperturbed systems. • Existence of periodic states implies an irreducible uncertainty in hydrate dynamics. Abstract Gas hydrates are one of the largest marine carbon reservoirs on Earth. The conventional understanding of hydrate dynamics assumes that the system, in the absence of external triggers, converges to a steady-state over geological time-scales, achieving fixed concentrations of gas hydrate and free gas phase. However, using a high-fidelity numerical model and consistently resolving phase states across multiple fluid-fluid and fluid-solid phase boundaries, we have identified well-defined periodic states embedded within hydrate system dynamics. These states lead to cyclic formation and dissolution of massive hydrate layers that is self-sustaining for the majority of natural marine settings. This previously unresolved characteristic could manifest as spontaneous gas migration and pressure release in, supposedly, unperturbed systems. Our findings show that the gas hydrate systems are not bound to have unique steady-state solutions. Instead, existence of periodic states introduces an irreducible, but, quantifiable uncertainty in gas hydrate dynamics which adds significant error bars to global gas hydrate inventory estimates.

Description: Marine gravity data can provide information on the distribution of mass anomalies in the oceanic crust and upper mantle. Computing corresponding gravity anomalies, especially so-called ‘residual’ gravity anomalies that directly reflect variations in the crustal structure, relies on gravity corrections of both seafloor relief and lithospheric thermal structure. The lithospheric thermal gravity correction involves either a plate cooling approximation or a mantle flow model with the latter typically done using simplified assumptions on mantle rheology. However, a detailed study of how differing rheological models affect the computed gravity anomalies is still missing. Here, we systematically examine the differences in residual mantle Bouguer anomalies (RMBA) caused by differing assumptions on mantle rheology for 16 mid-ocean ridge – transform fault systems. Our calculations show that isoviscous models tend to underpredict RMBA values within the transform deformation zone and overpredict them in the far field at older plate ages, when compared to plate cooling and nonlinear viscoplastic models. This discrepancy stems from isoviscous models failing to capture plate-like deformation, as well as their inability to resolve brittle failure and the associated strain localization that leads to warm upwelling beneath the transform fault. By exploring a wide parameter range, we find that the importance of mantle rheology scales with plate tectonic parameters at the mid-ocean ridge – transform fault system such as transform age offset, spreading rate, and transform fault length. These findings suggest that gravity thermal corrections at the intrinsically three-dimensional ridge – transform systems should employ mantle flow models that resolve plate-like deformation and brittle failure.

Description: Continental-arc igneous rock compositions change in response to the transition from subduction to collision and these changes can reveal how the crust, lithosphere and magma sources evolved. Neotethys-related Late Cretaceous to Pleistocene subduction- and collision-related magmatic rocks from the ~350 km long southeast Urumieh-Dokhtar Magmatic Belt (UDMB) of Iran provide an excellent natural laboratory to better understand these changes. These igneous rocks are well-exposed and moderately eroded to reveal a nearly complete record since subduction initiation at ~95 Ma. We analyzed new samples for major and trace elements (83 samples), Srsingle bondNd isotopic compositions (47 samples), and Usingle bondPb zircon ages (26 samples) and compiled geochemical and geochronological data on the southeast segment of the UDMB. The geochronological data reveal two magmatic pulses at ~80–70 Ma and ~50–0 Ma. Important changes in magmatic compositions reflect initial collision with Arabia at ~32 Ma, changing from normal calc-alkaline to increasingly adakitic immediately after collision began. Five stages can be identified: 1) normal continental-arc magmatism during the Late Cretaceous; 2) arc quiescence in Paleocene and Early Eocene time; 3) Middle-Late Eocene extensional arc magmatism related to slab rollback; 4) early collision and crustal thickening during the Early Oligocene; and 5) slab breakoff, asthenospheric upwelling, and associated adakitic magmatism from Middle Miocene onward. Temporal changes in UDMB magmas reflect the response of the overriding plate to changes in the geometry of the subducting Neotethyan lithosphere and to collision between Arabia and Iran. Crustal thickening and arc narrowing during Miocene to Pleistocene post-collisional magmatism caused adakitic magmatism and associated Cu mineralization. Zircon Osingle bondHf and apatite O isotopes as well as bulk-rock Nd isotopes of Cu-bearing adakitic rocks are similar to other barren rocks, but nearly all fertile rocks have higher Hf/Y, Eu/Eu⁎(n) in zircon and higher Sr/Y, V/Y, Eu/Eu⁎(n) in apatite than barren rocks.

Description: Highlights • An unprecedented detailed tectono-thermal history of a magma-poor margin is revealed. • Deformation mechanisms laterally vary across active faults during extreme extension. • Mantle hydration occurs through brittle deformation in the footwalls of active faults. • Detachments form through ductile shearing in the hangingwalls of active faults. • Detachment formation is a byproduct but not a root cause of margin asymmetry. Abstract A long-standing problem in solid Earth science is to understand how low-angle normal faults form, their role in the development of tectonic asymmetry of conjugate margins, and how they relate to mantle hydration during continental breakup. The latter requires water to reach the mantle through active brittle faults, but low angle slip on faults is mechanically difficult. Here, we incorporate observations from high-resolution multichannel seismic data along the West Iberia-Newfoundland margins into a 2D forward thermo-mechanical model to understand the relationship between evolving rift asymmetry, detachment tectonics, and mantle hydration. We show that, during extreme extension, slip on active faults bifurcates at depth into brittle and ductile deformation branches, as a result of the cooling of the faults' footwall and heating of their hangingwall. The brittle deformation penetrates the Moho and leads to mantle hydration, while ductile deformation occurs in localized shear zones and leads to the formation of detachment-like structures in the distal margin sections. Such structures, as for example ‘S’ in the West Iberia-Newfoundland margins, are thus composed of several shear zones, active at low-angles, ∼25°-20°, and merging with the Moho at depth. The final sub-horizontal geometry of these structures is the result of subsequent back-rotation of these shear zones by new oceanward faults. Our results reproduce remarkably well the final sedimentary, fault, crustal architecture, and serpentinisation pattern observed at the West Iberia-Newfoundland margins. However, they challenge widely accepted ideas that such detachment-like structures formed by brittle processes, separate crust from mantle and caused conjugate margin asymmetry. Our model provides a quantitative framework to study hydrothermal systems related to serpentinization during extreme extension, their associated hydrogen, methane production, and the chemosynthetic life they sustain.

Description: Highlights: • Ca. 418 ka Pauzhetka tephra from South Kamchatka was found in 11 marine sediment cores. • New major and trace element analyses allow identification of tephra glasses. • K/Ti and K/Fe maxima mark the Pauzhetka tephra presence in marine sediments. • The tephra occurs at Marine Isotope Stages 12 to 11c and below the Bermuda excursion. • The revised ash dispersal covers vast areas in the NW Pacific and Okhotsk Sea. Abstract: The distal Pauzhetka tephra, formed by a large caldera-forming volcanic eruption in South Kamchatka, has been identified in eleven recently recovered marine sediment cores based on major and trace element compositions of tephra glass. Ten SO264 cores form a transect along the Emperor Seamount Chain (ESC) in the Northwest (NW) Pacific between ∼50.3° and ∼45°N, 800–1200 km southeast of the Pauzhetka caldera. One additional core LV28-41-4 was retrieved in the Okhotsk Sea, ∼600 km west of the caldera. The Pauzhetka tephra glass shards have a characteristic medium-K rhyolite composition and trace element content compatible with the rear-arc position of the source volcano that ensures their identification. In the NW Pacific SO264 cores, the tephra is preserved as layers in cores 33, 47, 49, 53, 55, 56 and 62, as a lens in core 45, and as cryptotephra in cores 57 and 66. It forms a cryptotephra in the Okhotsk Sea core LV28-41-4. Distinctively high XRF-retrieved K/Ti and K/Fe ratios compared to those for the host sediments help identify the Pauzhetka tephra. According to our refined stable oxygen isotope (δ18O)- and magneto-stratigraphy of two studied and two reference cores, the Pauzhetka tephra occurs within a local δ18O maximum during a transition from marine isotope stage 12 to 11c (Termination V) and below a paleointensity minimum referred to as the Bermuda excursion, at ca. 418 ka. Using the tephra age as an isochron, we show that average linear sedimentation rates decrease southward along a transect of the SO264 cores, except in core 55. It partially reflects an intensification of mid-depth currents causing winnowing, erosion or non-deposition along the ESC over the past 418 kyr. An increased linear sedimentation rate in core 55, recovered from the southern leeward side of the Minnetonka Seamount, appears to record the pelagic accumulation protected from the mid-depth current influence. Our findings expand the former ash dispersal area farther southeast in the NW Pacific and southwest in the Okhotsk Sea. The new data on the tephra thickness supports the axis direction of the fallout zone southeast of the Pauzhetka caldera. Our results suggest the Pauzhetka tephra as a key middle Pleistocene isochron for the stratigraphy and correlation of the NW Pacific and Okhotsk Sea sediments.

Description: Highlights • More diverse non-native taxa generally include more economically costly species. • Chordates, nematodes and pathogens are among significantly over-represented taxa. • Monetary cost magnitude links positively to numbers of costly invasive species. • Costs are biased towards a few ‘hyper-costly’ invasive species groups. • Future invasion rates will continue to harbour new economically costly species. Abstract A dominant syndrome of the Anthropocene is the rapid worldwide spread of invasive species with devastating environmental and socio-economic impacts. However, the dynamics underlying the impacts of biological invasions remain contested. A hypothesis posits that the richness of impactful invasive species increases proportionally with the richness of non-native species more generally. A competing hypothesis suggests that certain species features disproportionately enhance the chances of non-native species becoming impactful, causing invasive species to arise disproportionately relative to the numbers of non-native species. We test whether invasive species with reported monetary costs reflect global numbers of established non-native species among phyla, classes, and families. Our results reveal that numbers of invasive species with economic costs largely reflect non-native species richness among taxa (i.e., in 96 % of families). However, a few costly taxa were over- and under-represented, and their composition differed among environments and regions. Chordates, nematodes, and pathogenic groups tended to be the most over-represented phyla with reported monetary costs, with mammals, insects, fungi, roundworms, and medically-important microorganisms being over-represented classes. Numbers of costly invasive species increased significantly with non-native richness per taxon, while monetary cost magnitudes at the family level were also significantly related to costly invasive species richness. Costs were biased towards a few ‘hyper-costly’ taxa (such as termites, mosquitoes, cats, weevils, rodents, ants, and asters). Ordination analysis revealed significant dissimilarity between non-native and costly invasive taxon assemblages. These results highlight taxonomic groups which harbour disproportionately high numbers of costly invasive species and monetary cost magnitudes. Collectively, our findings support prevention of arrival and containment of spread of non-native species as a whole through effective strategies for mitigation of the rapidly amplifying impacts of invasive species. Yet, the hyper- costly taxa identified here should receive greater focus from managers to reduce impacts of current invasive species.

Description: Highlights • We identify the largest active fault systems of the Alboran Basin. • Characterization of faults is key for accurate tsunamigenic potential estimations. • Alboran largest fault systems may generate Mw 〉 7 earthquakes. • These earthquakes have the potential to generate significant tsunami waves approaching the coast. Abstract The westernmost Mediterranean hosts part of the plate boundary between the European and African tectonic plates. Based on the scattered instrumental seismicity, this boundary has been traditionally interpreted as a wide zone of diffuse deformation. However, recent seismic images and seafloor mapping studies support that most of the plate convergence may be accommodated in a few tectonic structures, rather than in a broad region. Historical earthquakes with magnitudes Mw 〉 6 and historical tsunamis support that the low-to-moderate instrumental seismicity might also have led to underestimation of the seismogenic and tsunamigenic potential of the area. We evaluate the largest active faults of the westernmost Mediterranean: the reverse Alboran Ridge, and the strike-slip Carboneras, Yusuf and Al-Idrissi fault systems. For the first time, we use a dense grid of modern seismic data to characterize the entire dimensions of the main fault systems, accurately describe the geometry of these structures and estimate their seismic source parameters. Tsunami scenarios have been tested based on 3D-surfaces and seismic source parameters, using both uniform and heterogeneous slip distributions. The comparison of our results with previous studies, based on limited information on the fault geometry and kinematics, indicates that accurate fault geometries and heterogeneous slip distributions are needed to properly assess the seismic and tsunamigenic potential in this area. Based on fault scaling relations, the four fault systems have a large seismogenic potential, being able to generate earthquakes with Mw 〉 7. The reverse Alboran Ridge Fault System has the largest tsunamigenic potential, being able to generate a tsunami wave amplitude greater than 3 m in front of the coasts of Southern Spain and Northern Africa.

Description: Highlights • A new numerical model for permafrost in alpine regions. • Importance of lateral fluxes in mountain permafrost modeling. • Influence of unsaturated conditions on freezing processes. • Development of mountain permafrost during warming scenario. Abstract Alpine permafrost environments are highly vulnerable and sensitive to changes in regional and global climate trends. Thawing and degradation of permafrost has numerous adverse environmental, economic, and societal impacts. Mathematical modeling and numerical simulations provide powerful tools for predicting the degree of degradation and evolution of subsurface permafrost as a result of global warming. A particularly significant characteristic of alpine environments is the high variability in their surface geometry which drives large lateral thermal and fluid fluxes along topographic gradients. The combination of these topography-driven fluxes and unsaturated ground makes alpine systems markedly different from Arctic permafrost environments and general geotechnical ground freezing applications, and therefore, alpine permafrost demands its own specialized modeling approaches. In this work, we present a multi-physics permafrost model tailored to subsurface processes of alpine regions. In particular, we resolve the ice–water phase transitions, unsaturated conditions, and capillary actions, and account for the impact of the evolving pore space through freezing and thawing processes. Moreover, the approach is multi-dimensional, and therefore, inherently resolves the topography-driven horizontal fluxes. Through numerical case studies based on the elevation profiles of the Zugspitze (DE) and the Matterhorn (CH), we show the strong influence of lateral fluxes in 2D on active layer dynamics and the distribution of permafrost.

Description: Highlights • Collision-related, Oligocene magmatic rocks are abundant in the SE segment of the Urumieh-Dokhtar magmatic belt of Iran. • Zircon U-Pb data show ages of 34-25 Ma for plutonic rocks and 34-27 Ma for volcanic rocks from SE UDMB. • Isotope modelling suggests mixing between the mantle and Cadomian crust for the formation of these rocks. Abstract Despite diverse geochronological-geochemical studies on Cenozoic igneous rocks from the SE segment of the Urumieh-Dokhtar Magmatic Belt (UDMB) of Iran, the nature of the Oligocene magmatic rocks from the farthermost end of the SE segment- where it is linked to the Makran magmatic belt- has been ignored due to the difficulty of access. In this study, we focus on syn-collisional mafic to felsic igneous rocks of calc-alkaline and high-K calc-alkaline affinities from the SE segment of the Urumieh-Dokhtar Magmatic Belt (UDMB) near Nagisun, south of Bam. The Nagisun rocks have low Sr/Y and La(n)/Yb(n), similar to igneous rocks from typical arcs. Zircon Usingle bondPb ages show comparable ages for plutonic (~ 34–25 Ma) and volcanic (~34–27 Ma) rocks. The εHf(t) values for zircons from plutonic rocks range from −0.3 to +12.8, whereas the εHf(t) values for the volcanic rocks vary from −2.6 to +13. Modelling of trace elements compositions using Nagisan basaltic samples indicate that an 87:2:11 mixture of the depleted MORB mantle, subducting (trench)-sediments and altered oceanic crust with 5% aggregated fractional melting closely matches the trace-element abundances of the Nagisun basaltic rocks. Indeed, the modelling of Sr and Nd isotopic data emphasizes that the Nagisun magmatic rocks could be products of bulk mixing between a depleted MORB mantle and/or a mixed, fertilized mantle with the Cadomian lower and upper continental crust. Furthermore, our compiled data display that the magmatism in the SE segment of the UDMB changed through time from normal calc-alkaline magmatism to adakitic magmatism at ~20 Ma, after the collision with Arabia began ca 27 Ma.

Description: Highlights • Plinian eruptions linked to rheologically different mingling andesite magmas. • Magma decompression regimes producing variable degassing/crystallization kinetics. • Least explosive eruptions at slowest decompression, ascent and strain rates. • Plinian phases at rapid/intermittent magma decompression, ascent and strain rates. Abstract Estimating the kinetics of andesite magma vesiculation and crystallization inside volcanic plumbing systems is key for unraveling andesite Plinian eruption dynamics. The conduit kinetics provide the necessary input data for estimating the magma flow rates driving magma ascent and the fragmentation mechanisms controlling shifts in eruption explosivity and style. This information is crucial for increasing knowledge on expected hazards and for developing realistic eruption scenarios. In this work, we estimate conduit magma vesiculation and crystallization kinetics during the 3300 cal BP Upper Inglewood Plinian eruptive episode of Mount Taranaki, New Zealand. This episode comprised (i) low-intensity, conduit-opening phases of dome-collapse PDCs; (ii) pre-climactic, highly explosive phases of diverse PDCs, of up to violent 18-km-runout lateral blasts; (iii) climactic phases of steady 22-km-high Plinian eruption columns; and (iv) waning phases of column-collapse PDCs. By employing synchrotron microtomography, combined with mineral/glass chemistry and electron-microscopy, we quantified 3D vesicle and crystal size and shape distributions in juvenile pyroclasts over time, and corresponding number densities ranging from 1.1 × 105 to 2.5 × 106 mm−3 for vesicles, and from 8.0 × 104 to 5.1 × 106 mm−3 for crystals. Our results indicate that tapping of chemically alike yet rheologically contrasting magmas over a multi-phase andesite eruptive episode is linked to: (a) mafic magma recharge and differentiation in multiple storage reservoirs at distinct crustal levels, (b) stepwise to rapid magma decompression while mingling, producing variable pre- and syn-eruptive degassing and crystallization, and (c) syn-eruptive changes in melt viscosity, strain rate, localized shear deformation, and conduit geometry. The earliest and least explosive eruptive phases (≈ 2 × 106 kg s−1) were produced at the slowest rates of magma decompression (0.3–0.6 MPa s−1), ascent (0.01–0.02 m s−1) and strain (〈 0.002 s−1), driven by volatile diffusion and exsolution. All subsequent pre-climactic and Plinian phases (4 × 107–1 × 108 kg s−1) were produced at either rapid or intermittent rates of magma decompression (2.0–6.0 MPa s−1), ascent (0.06–0.2 m s−1) and strain (〉 0.003–0.010 s−1), powered by combined magma volatile supersaturation and delayed disequilibrium degassing, decompression-induced microlite crystallization and rapid heterogeneous vesiculation kinetics, shear deformation and magma mingling. These processes enabled complex fragmentation mechanisms of the rheologically most homogeneous magmas.

Description: Alteration of volcanogenic aluminosilicates (VAs) in marine sediments is recognized as critical in regulating geochemical cycles and sustaining the oceanic deep biosphere, but rates of VA alteration and its associated authigenic mineral formation are not commonly reported. Here we present results on analyses of sediments and pore water recovered from the upper 150 mbsf of four sites drilled on the northern Hikurangi margin during IODP Expeditions 372 and 375. Petrographic analyses show that volcanogenic materials (glass shards, feldspar, volcanic lithoclasts) constitute important components (15–45 wt%) of the hemipelagic mud, and reveal ongoing glass alteration with accompanying authigenic phase formation. A reaction-transport model constrained by pore water Sr, 87Sr/86Sr, Ca, Mg, and Si was applied to simulate VA diagenetic reactions. Our model results yield VA alteration rates of 0.047–0.64 mmol Sr m−2 yr−1, with substantially higher values at Sites U1517 and U1520 that experienced rapid sediment emplacement. In addition, our simulations show that 〉99% of the dissolved Si generated by VA alteration is fixed in silica cement and authigenic clay, and that ∼50% of Ca incorporated in the authigenic carbonate is supplied by VA alteration. First-order estimates suggest that, in addition to authigenic carbonate precipitation, authigenic clay formation may represent an important sink for dissolved Mg. This study quantitatively examines the linkage between VA alteration and formation of authigenic phases, highlights its role in subsurface geochemical cycles, and indicates that slope instability may play an important role in promoting VA diagenesis.

Description: The Toba Caldera on Sumatra, Indonesia is the host of the Young Toba eruption (~74 ka), globally one of the largest and most recognized eruptions during the Quaternary and regionally concentrated in the eastern Indian Ocean. Three older deposits (Middle, and Old Toba Tuff as well as Haranggaol Dacite Tuff) are also attributed to Toba caldera, with their eruption products distributed over the Indian Ocean. We present the Quaternary marine tephra record from an array of 14 sites and 28 holes from deep ocean drilling programs, complementing earlier work on distal to ultra-distal Indian Ocean sediment cores and terrestrial distribution data of Toba deposits. A unique set of major and trace element glass-shard compositions on 115 primary ash layers together with glass shard morphologies, core pictures and statistical analysis support geochemical fingerprinting between marine tephra layers and known deposits from Toba and five so far unidentified medium to large eruptions assigned to northern Sumatra. Additionally, zircon crystallization ages have been determined for the Haranggaol Dacite Tuff resulting in a new maximum eruption age of 1.42 ± 0.034 Ma. Tephra volumes and magma masses for the (co-ignimbrite) fallout are estimated based on the compiled marine tephra distribution that are complemented by published proximal ignimbrite volumes. For YTT the resulting tephra and DRE volumes of 5600 km3 and 3600 km3, respectively, are in between the previous estimates. For MTT (253 km3 DRE), ODT (1550 km3 DRE), HDT (129 km3 DRE), and the five additionally identified eruptions from Northern-Sumatran volcanoes, new magma volumes have been determined. Overall, the Indian Ocean tephra record reveals in one large eruption every 200 kyr in the Quaternary that is derived from northern Sumatra.

Description: Provenance studies of widely distributed tephra deposits are important to deduce systematic changes in the source, size, distribution, and temporal variation of regional explosive volcanism. Long-term deep ocean drilling sedimentary records are particularly useful for these kind of studies. In this study, we establish a robust tephrochronostratigraphy for 235 primary marine tephra layers collected during International Ocean Discovery Program Expeditions 353, 354, and 362, complemented by older drill cores from Deep Sea Drilling Program and Ocean Drilling Program Legs 22, 119, 120, 121, and 183. We infer at least two major phases of highly explosive arc volcanism during the Early Miocene to Pleistocene, as well as three episodes related to explosive ocean island volcanism located in the Kerguelen plateau, the Broken Ridge, and close to Réunion reaching back to the Paleogene. Twenty-two widespread arc-derived tephra layers from individual eruptions can be correlated by geochemical fingerprinting between multiple holes. These provide nine Quaternary and 13 Neogene temporal tie points in the sedimentary sequence including four new Usingle bondPb zircon ages. Provenance analysis of the marine tephra layers, which is based on glass composition, assign eleven of these layers to a Toba-like source, ranging from 24 Ma to 75 ka, with the youngest correlative being Young Toba Tuff. Based on distribution pattern, thickness decay, and compositional evidence another eleven tephra layers can be assigned to a northern Sumatran Arc or to an Andaman Arc provenance. First-order minimum eruptive volume estimates for the Neogene tephra layers imply eruptive magnitudes ranging from M = 6.5 to M = 7.5, proving a continuous history of large explosive eruptions from the Sumatran/Andaman Arc since the Neogene, as previously known from the Quaternary.

Description: Highlights: • The global economic costs of invasive aquatic crustaceans totalled US$ 271 million. • Invasive crayfish and crabs had the highest costs, US$ 120.5 and US$ 150.2 million, respectively. • The signal crayfish was the costliest species (US$ 103.9 million), as seen in Europe. • Among crabs, the European green crab and the Chinese mitten crab had the highest costs. • Taxonomic, geographical, and temporal gaps mean that these costs are severely underestimated. Abstract: Despite voluminous literature identifying the impacts of invasive species, summaries of monetary costs for some taxonomic groups remain limited. Invasive alien crustaceans often have profound impacts on recipient ecosystems, but there may be great unknowns related to their economic costs. Using the InvaCost database, we quantify and analyse reported costs associated with invasive crustaceans globally across taxonomic, spatial, and temporal descriptors. Specifically, we quantify the costs of prominent aquatic crustaceans — crayfish, crabs, amphipods, and lobsters. Between 2000 and 2020, crayfish caused US$ 120.5 million in reported costs; the vast majority (99%) being attributed to representatives of Astacidae and Cambaridae. Crayfish-related costs were unevenly distributed across countries, with a strong bias towards European economies (US$ 116.4 million; mainly due to the signal crayfish in Sweden), followed by costs reported from North America and Asia. The costs were also largely predicted or extrapolated, and thus not based on empirical observations. Despite these limitations, the costs of invasive crayfish have increased considerably over the past two decades, averaging US$ 5.7 million per year. Invasive crabs have caused costs of US$ 150.2 million since 1960 and the ratios were again uneven (57% in North America and 42% in Europe). Damage-related costs dominated for both crayfish (80%) and crabs (99%), with management costs lacking or even more under-reported. Reported costs for invasive amphipods (US$ 178.8 thousand) and lobsters (US$ 44.6 thousand) were considerably lower, suggesting a lack of effort in reporting costs for these groups or effects that are largely non-monetised. Despite the well-known damage caused by invasive crustaceans, we identify data limitations that prevent a full accounting of the economic costs of these invasive groups, while highlighting the increasing costs at several scales based on the available literature. Further cost reports are needed to better assess the true magnitude of monetary costs caused by invasive aquatic crustaceans.

Description: The origin of broad intraplate volcanic provinces has been related to deep mantle plumes or shallow lithospheric processes, e.g., underlying large fault systems. One example of an understudied intraplate volcanic province is the Bathymetrists Seamounts (BSM) in the central-eastern Atlantic, an area with dense and extended fracture zones, but the BSM has been associated with a mantle plume origin. Extensive bathymetric mapping and seafloor sampling show that most BSM-seamounts resemble flat-topped guyots capped by carbonate platforms. Vesicular, volcanoclastic samples imply that their tops formed near sea level, followed by reef formation during cessation of volcanism and crustal subsidence. Erosion determines the seamount irregularity proportional to their sizes. Strong ellipticity of some seamounts is related to multiple vents that erupted along fractures. The orientation of the volcanoes, carbonate platforms, and morphological lineaments of the BSM show particular trends that reveal information on their origin and formation mechanisms. Geomorphological analyses indicate a structural control on volcano emplacement related to underlying lithospheric faults resembling a Riedel shear pattern. The stress field corresponding to their orientations is related to a NE-SW tensional setting, fitting to the prevalent tectonic setting ~56–38 Ma years ago that coincides with the BSM formation and an increase in spreading rates. A change in movement of the African plate during this time, together with the reactivation of fracture zones of the strongly sheared equatorial Atlantic, created pathways in the lithosphere and possibly enhanced magmatism. The seamounts do not show distinct differences in erosion state, morphology, carbonate platform depth, or Mn-crust thickness, in contrast to what would be expected for an age progression within the seamount chain. Our observations, therefore, do not support a plume mantle source. While the magmatic source remains undefined, we show that tectonic pathways determined the shape of the seamounts and enabled the broad emplacement of the Bathymetrists seamount chain.

Description: The increasing global demand for seafood, coupled with the limitations of current fish stocks and aquaculture practices, requires the development of sustainable aquaculture solutions. In this context, this study explores the potential of a novel cage technology - Flow2Vortex - for the cultivation of jellyfish, a low-trophic-level organism with increasing market demand. The unique cage design creates a laminar and circular water flow, providing optimal conditions for cultivating fragile planktonic species. Indoor experiments demonstrated the successful growth of jellyfish in the cage, with growth rates of up to 11.6% per day. In addition, field tests in open waters confirmed the cage's ability to maintain a diffuse and controlled flow inside, even under strong external currents. The cage also maintained significantly higher zooplankton concentrations than the surrounding environment, offering a consistent food source for the cultivated jellyfish. These findings highlight the potential of the Flow2Vortex cage for scalable indoor and outdoor cultivation of low-trophic-level organisms, such as jellyfish, contributing to the diversification and sustainability of aquaculture practices.

Description: This study investigates the historical characteristics and future trends of marine heatwaves (MHWs) in the Western North Pacific (WNP) region. During the historical period from 1982 to 2014, the WNP region experiences an average MHW frequency of 0.89 ± 0.18 count/year. These events have an average duration of 8.64 ± 1.39 days/count. Annually, the cumulative MHW days amount to 7.76 ± 2.23 days, with an accumulated intensity of 15.73 ± 6.43 °C days. The maximum intensity recorded during this period reaches 2.04 ± 0.54 °C, while the average intensity stands at 1.74 ± 0.48 °C/count. In the evaluation of 14 CMIP6 models, five optimal models, namely GFDL-ESM4, EC-Earth3-Veg, EC-Earth3, BCC-CSM2-MR, and MRI-ESM2-0, are selected for simulating future MHWs. Based on the simulation results of these five models under the SSP2-4.5 and SSP5-8.5 scenarios for the future period (2015–2100), it is found that under the SSP2-4.5, the frequency of MHWs is slightly higher compared to the SSP5-8.5. However, under the SSP5-8.5, MHWs exhibit higher accumulated intensity, maximum intensity, and average intensity, with a predominance of high-intensity MHWs in the Kuroshio Extension region. The occurrence area ratio in the future is significantly larger than in the historical period. Moreover, MHWs intensity displays a seasonal variation, with stronger during summer and weaker during winter. This study provides important insights into MHWs in the WNP region, offering valuable information for decision-makers in formulating response measures and reducing economic losses.

Description: The Cretaceous Twihinate carbonatite in the Moroccan Sahara is a ~ 5 km diameter ring-shaped intrusion made of an inner core preserving sparse occurrences of medium- to coarse-grained calcite carbonatite encircled by a ring of vuggy siliceous breccia. The Twihinate carbonatite is enriched in large ion lithophile elements (Cs, Rb, Ba, U and Th) and light rare earth elements (LREE), but shows negative anomalies in high field strength elements (particularly Ta, Zr, Hf and Ti). Stable and radiogenic isotope ratios vary in the range of δ13Cv-PDB = −10.5 to −1.6‰, δ18OV-SMOW = 6.4–28.3‰, initial 87Sr/86Sr = 0.7034–0.7043 (εSri between −14.5 and − 1.8), 143Nd/144Nd = 0.51282–0.51283 (εNdi between 2.8 and 3.6), 206Pb/204Pbi = 19.52–23.78, 207Pb/204Pbi = 15.56–15.69 and 208Pb/204Pbi = 38.69–39.02). Altogether, these isotopic compositions reflect compositional mantle heterogeneity, and are interpreted to reflect partial melting of heterogenous mantle sources with a potential eclogite component in an intraplate, rift-controlled tectonic setting. From a geodynamic perspective, the time span ascribed to age emplacement of Twihinate carbonatite shortly follows the Upper Jurassic hyper-extension event which ultimately resulted in mantle exhumation and subsequent onset of drifting in the Central Atlantic Ocean and Maghrebian Tethys.

Description: Highlights: • Change in sea urchin species composition from RBC and NRBC habitats. • Sand coverage is an important factor that influences the sea urchin species composition. • The relationship between sea urchins and their habitat is species-specific. Sea urchins are important components of marine ecosystems and can act as bioindicators, reflecting the health of reefs. The spatial patterns of sea urchins are largely shaped by the type of habitat. In Hong Kong, coral communities are divided into two distinct types: reef -building coral habitats and non -reef -building coral habitats. In summer 2020, a qualitative survey was conducted using SCUBA at 56 sites across eastern and western waters, recording a total of 11 species from 6 families of sea urchins. Out of these 56 sites, 14 were selected for a quantitative survey to investigate the relationship between sea urchin assemblages and the two types of coral habitat. We found that the species composition of sea urchins differed significantly between the two habitats, and the presence of sand was a critical factor influencing the species composition of sea urchins. Sand coverage had a positive effect on Salmasic sphaeroides abundance but a negative effect on the abundance of Diadema setosum and Heliocidaris crassispina. The distribution of sea urchins across different degrees of sand coverage may be associated with food availability or species -specific adaptive behaviour, likely due to niche preferences.

Description: Highlights • East Asian climate evolution was dependent on the latitude of the proto-Tibetan Plateau in the deep past; • Global warming induced wetting at mid-latitude East Asian in the mid-Cretaceous; • The proto-Tibetan Plateau uplift led to drying in the subtropical East Asian in the mid-Cretaceous. Abstract Sedimentary records indicate that subtropical and mid-latitude East Asia exhibited considerable drying and wetting, respectively, during the mid-Cretaceous, which is considered to be relevant to much higher atmospheric carbon dioxide (pCO2) concentrations and/or proto-Tibetan Plateau (proto-TP) uplift. In order to explore and compare their roles on the East Asian climate evolution, we conducted simulations of the mid-Cretaceous climate system with different atmospheric pCO2 levels and varying topographies. The results show that both factors had significant influences on the East Asian climate. As the increase in atmospheric pCO2 levels from ∼560–1120 ppmv to ∼1120–2240 ppmv, the precipitation increases considerably over mid-latitude East Asia, but only small changes in the subtropical portion of East Asia occur. Simultaneously, the effects of the proto-TP uplift are opposite to those of global warming trend during that period. Generally, it leads to a precipitation decrease over subtropical East Asia, but rather minor changes over mid-latitude East Asia. These changes are qualitatively consistent with the deduction based on the geological records, but the magnitudes of the modeled precipitation changes are relatively smaller. Therefore, we can conclude that the subtropical East Asian drying during the mid-Cretaceous can be partly explained by the proto-TP uplift, while the mid-latitude East Asian wetting was partly due to global warming. However, additional factor(s) also played a significant role in the East Asian climate evolution during the mid-Cretaceous.

Description: Carbon dioxide removal (CDR) – the creation, enhancement, and upscaling of carbon sinks – has become a pillar of national and corporate commitments towards Net Zero emissions, as well as pathways towards realizing the Paris Agreement's ambitious temperature targets. In this perspective, we explore CDR as an emerging issue of Earth System Governance (ESG). We draw on the results of a workshop at the 2022 Earth System Governance conference that mapped a range of actors, activities, and issues relevant to carbon removal, and refined them into research questions spanning four intersecting areas: modeling and systems assessment, societal appraisal, policy, and innovation and industry. We filter these questions through the five lenses of the ESG framework and highlight several key ‘cross-cutting’ issues that could form the basis of an integrated ESG research agenda on CDR.

Description: Highlights • Cu complexation was measured for the first time in the Fram Strait region. • Cu-binding ligand concentrations and binding strength varied longitudinally in the Fram Strait. • More than 99 % of dCu was organically complexed by strong ligands. • On the Greenland shelf the Transpolar Drift and the coastal processes were the main sources of Cu ligands. Abstract The Fram Strait represents the major gateway of Arctic Ocean waters towards the Nordic Seas and North Atlantic Ocean and is a key region to study the impact of climate change on biogeochemical cycles. In the region, information about trace metal speciation, such as copper, is scarce. This manuscript presents the concentrations and conditional stability constants of copper-binding ligands (LCu and log KcondCu2+L) in the water column of Fram Strait and the Greenland shelf (GEOTRACES cruise GN05). Cu-binding ligands were analysed by Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) using salicylaldoxime (SA) as competitive ligand. Based on water masses and the hydrodynamic influences, three provinces were considered (coast, shelf, and Fram Strait) and differences were observed between regions and water masses. The strongest variability was observed in surface waters, with increasing LCu concentrations (mean values: Fram Strait = 2.6 ± 1.0 nM; shelf = 5.2 ± 1.3 nM; coast = 6.4 ± 0.8 nM) and decreasing log KcondCu2+L values (mean values: Fram Strait = 15.7 ± 0.3; shelf = 15.2 ± 0.3; coast = 14.8 ± 0.3) towards the west. The surface LCu concentrations obtained above the Greenland shelf indicate a supply from the coastal environment to the Polar Surface Water (PSW) which is an addition to the ligand exported from the central Arctic to Fram Strait. The significant differences (in terms of LCu and log KcondCu2+L) between shelf and coastal samples were explained considering the processes which modify ligand concentrations and binding strengths, such as biological activity in sea-ice, phytoplankton bloom in surface waters, bacterial degradation, and meltwater discharge from 79NG glacier terminus. Overall, the ligand concentration exceeded those of dissolved Cu (dCu) and kept the free copper (Cu2+) concentrations at femtomolar levels (0.13–21.13 fM). This indicates that Cu2+ toxicity limits were not reached and dCu levels were stabilized in surface waters by organic complexes, which favoured its transport to the Nordic Seas and North Atlantic Ocean and the development of microorganism.

Description: Highlights: • Ecological impacts of Pontogammarus maeoticus increased with temperature • Salinity effects were non-significant across temperatures (14–2 ppt; 18–22 °C) • Gammarids displayed hyperbolic Type II functional responses in all treatments • Future salinity regime shifts will not lessen ecological impacts via predation • Warming will heighten the ecological impacts of this emerging invasive species Abstract: Biological invasions are a growing ecological and socioeconomic problem worldwide. While robust predictions of impactful future invaders are urgently needed, understandings of invader impacts have been challenged by context-dependencies. In aquatic systems in particular, future climate change could alter the impacts of invasive non-native species. Widespread warming coupled with sea freshening may exacerbate ecological impacts of invaders in marine environments, compromising ecosystem structure, function and stability. We examined how multiple abiotic changes affect the potential ecological impact of an emerging invasive non-native species from the Ponto-Caspian region — a notorious origin hotspot for invaders, characterised by high salinity and temperature variation. Using a comparative functional response (feeding rates across prey densities) approach, the potential ecological impacts of the gammarid Pontogammarus maeoticus towards native chironomid prey were examined across a range of current and future temperature (18, 22°C) and salinity (14, 10, 6, 2 ppt) regimes in a factorial design. Feeding rates of P. maeoticus on prey significantly increased with temperature (by 60 %), but were not significantly affected by salinity regime. Gammarids displayed significant Type II functional responses, with attack rates not significantly affected by warming across all salinities. Handling times were, however, shortened by warming, and thus maximum feeding rates significantly increased, irrespective of salinity regime. Functional responses were significantly different following warming at high prey densities under all salinities, except under the ambient 10 ppt. Euryhalinity of invasive non-native species from the Ponto-Caspian region thus could allow sustained ecological impacts across a range of salinity regimes. These results corroborate high invasion success and field impacts of Ponto-Caspian gammarids in brackish through to freshwater ecosystems. Climate warming will likely worsen the potential ecological impact of P. maeoticus. With invasions growing worldwide, quantifications of how combined elements of climate change will alter the impacts of emerging invasive non-native species are needed.

Description: Highlights: • Predators displayed a Type II functional response towards prey • Microplastics had no effect on predator feeding efficiency • Functional responses are a useful tool for microplastic exposure studies • An environmentally relevant approach is needed in future microplastic exposure studies Abstract: Microplastics may affect the physiology, behaviour and populations of aquatic and terrestrial fauna through many mechanisms, such as direct consumption and sensory disruption. However, the majority of experimental studies have employed questionably high dosages of microplastics that have little environmental relevance. Predation, in particular, is a key trophic interaction that structures populations and communities and influences ecosystem functioning, but rarely features in microplastic research. Here, we quantify the effects of low (~65-114 MP/L) and high (~650-1140 MP/L) microplastic concentrations on the feeding behaviour of a ubiquitous and globally representative key marine predator, the shore crab, Carcinus maenas. We used a functional response approach (predator consumption across prey densities) to determine crab consumption rates towards a key marine community prey species, the blue mussel Mytilus edulis, under low and high microplastic concentrations with acute (8h) and chronic (120 h) microplastic exposure times. For both the acute and chronic microplastic exposure experiments, proportional prey consumption by crabs did not differ with respect to microplastic concentration, but significantly decreased over increasing prey densities. The crabs thus displayed classical, hyperbolic Type II functional responses in all experimental groups, characterised by high consumption rates at low prey densities. Crab attack rates, handling times and maximum feeding rates (ie functional response curves) were not significantly altered under lower or higher microplastics concentrations, or by acute or chronic microplastic exposures. Here, we show that functional response analyses could be widely employed to ascertain microplastic impacts on consumer-resource interactions. Furthermore, we suggest that future studies should adopt both acute and chronic microplastic exposure regimes, using environmentally-relevant microplastic dosages and types as well as elevated future scenarios of microplastic concentrations.

Description: Highlights • Core-log-seismic correlation allows to assign ages to the Scotia Sea seismic record. • Major implications are derived on the relation between regional and global events. • The main stratigraphic events are much younger than previously proposed. • Three major phases for the regional oceanography are observed from late Miocene. • These phases appear to be closely linked to the Antarctic Ice Sheet dynamics. Scotia Sea and the Drake Passage is key towards understanding the development of modern oceanic circulation patterns and their implications for ice sheet growth and decay. The sedimentary record of the southern Scotia Sea basins documents the regional tectonic, oceanographic and climatic evolution since the Eocene. However, a lack of accurate age estimations has prevented the calibration of the reconstructed history. The upper sedimentary record of the Scotia Sea was scientifically drilled for the first time in 2019 during International Ocean Discovery Program (IODP) Expedition 382, recovering sediments down to ∼643 and 676 m below sea floor in the Dove and Pirie basins respectively. Here, we report newly acquired high resolution physical properties data and the first accurate age constraints for the seismic sequences of the upper sedimentary record of the Scotia Sea to the late Miocene. The drilled record contains four basin-wide reflectors – Reflector-c, -b, -a and -a' previously estimated to be ∼12.6 Ma, ∼6.4 Ma, ∼3.8 Ma and ∼2.6 Ma, respectively. By extrapolating our new Scotia Sea age model to previous morpho-structural and seismic-stratigraphic analyses of the wider region we found, however, that the four discontinuities drilled are much younger than previously thought. Reflector-c actually formed before 8.4 Ma, Reflector-b at ∼4.5/3.7 Ma, Reflector-a at ∼1.7 Ma, and Reflector-a' at ∼0.4 Ma. Our updated age model of these discontinuities has major implications for their correlation with regional tectonic, oceanographic and cryospheric events. According to our results, the outflow of Antarctic Bottom Water to northern latitudes controlled the Antarctic Circumpolar Current flow from late Miocene. Subsequent variability of the Antarctic ice sheets has influenced the oceanic circulation pattern linked to major global climatic changes during early Pliocene, Mid-Pleistocene and the Marine Isotope Stage 11.

Description: Marine mammals and the ecological functions they provide to coastal and pelagic ecosystems are increasingly threatened by the intensification of anthropogenic impacts. The Uruguayan coastline throughout the 20th century, like other coastal environments worldwide, has been the sink of a variety of trace metals derived from the rapid urbanization and industrialization of related land areas. This coastline is inhabited by two species of pinnipeds trophically and spatially segregated. Otaria byronia feeds in coastal environments while Arctocephalus australis preysmainly offshore. The present study aimed to analyze historic changes in concentrations of trace elements in teeth of both species from 1941 to the present day. We analyzed the dentin of 94 canine teeth using stable isotope analysis (delta C-13) and ICP-MS to determine their feeding areas and the concentration of 10 trace elements (Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) respectively. The concentration of Cr was significantly higher during '70-'80s, in both species coinciding with tannery industry development. Both species of pinnipeds have been differentially exposed to trace elements depending on their feeding area. A pelagic diet, possibly based on squid, increased the concentration of Cd in A. australis, while O. byronia has been more exposed to anthropogenic Pb and Cu associated to a costal and more benthic diet. Our results highlight dentin as a reliable matrix for historic studies on the exposure to trace elements. In light of our results, the O. byronia's declining population could be the result of the synergistic effects of trace elements together with other ecological pressures faced in their environment.

Description: Highlights • India is industrializing rapidly with significant releases of Pb. • Increase in anthropogenic Pb input to Indian shelf occurred over last 40 years. • Sediment leachate Pb isotopes used to assess anthropogenic Pb inputs • Sources of Pb in eastern and western shelves of India were different. • Inland coal combustion and heavy industries are major sources of Pb. India is industrializing rapidly and with this there comes higher releases of contaminants into the environment. Change in Pb deposition over the last century on the eastern (off Andhra Pradesh) and western (off Karnataka) shelves of India was investigated based on the data extracted from two sediment cores covering the past ~114 and ~145 yrs. The variations of the total Pb content, its enrichment factor, and concentrations of non-residual Pb in both the sediment cores document that there was a gradual increase in anthropogenic Pb input into the coastal sediments of India over the last century. Sediment leachates were used to monitor the increase in anthropogenic Pb input and its Pb isotope composition. The anthropogenic end member composition of the western shelf sediment location (206Pb/207Pb: 1.105; 206Pb/208Pb: 2.149) was significantly less radiogenic than the eastern shelf isotopic composition (206Pb/207Pb: 1.145; 206Pb/208Pb:2.120). A binary mixing model suggests that Pb emitted from the heavy industries (e.g., ore mining, Pb processing and smelting plants) of India has been the major source of anthropogenic Pb to the sediments of western continental shelf. In contrast, the isotopic signatures suggest that coal combustion is responsible for elevated anthropogenic Pb levels in the sediments from the eastern shelf of India.

Description: Highlights • Atlantic and Mediterranean water-mass interface depth affected coral mound growth. • Sapropel derived events had a detrimental influence on coral mound development. • A shift in the reef-building dominating coral species occurred during the Holocene. • The southern mound has been subjected to less favourable environmental conditions. Abstract Cold-water coral mounds are key hot-spots of deep ocean biodiversity and also important archives of past climatic conditions. Nonetheless, the paleo-oceanographic setting in which coral mounds developed in the Mediterranean Sea during the last 500 ka still needs to be properly understood. This study describes the coral deposits and corresponding ages of two on-mound gravity cores acquired from opposite sectors of the newly discovered Cabliers Coral Mound Province (CMP, Alboran Sea, W Mediterranean). U–Th data revealed Pleistocene-aged corals covering mound formation periods from 〉389 to 9.3 ka BP and from 13.7 to 0.3 ka BP in the southern and northern mounds respectively. The coral-rich deposits of the cores were mainly dominated by Desmophyllum pertusum, although in some sections concurrent with the Middle Pleistocene and the Holocene, other corals such as Dendrophyllia cornigera and Madrepora oculata also appeared as dominating species. Coral mound formation stages generally occurred during deglacials and temperate interstadial (3.5–4.1 δ18O‰) periods, whereas during interglacials (〈3.5 δ18O‰) coral mound formation only occurred in the northern and shallower mound. We interpret this to indicate that the shoaling of the interface between Atlantic (AW) and Levantine Intermediate Waters (LIW) during interglacial periods prevented the corals in the southern CMP from acquiring sufficient food supply, thus causing periods of coral mound stagnation. Similarly, the interruption in LIW formation throughout sapropel events also coincides with coral mound stagnation phases. This suggests that sapropel-derived processes, which originated in the eastern Mediterranean, likely affected the entire Mediterranean basin and further supports the role of LIW as a conveyor belt facilitating cold-water coral growth in the Mediterranean Sea. Overall, we show that these coral mounds yield important insights into how local changes in oceanographic conditions can influence coral mound development.

Description: The facies distribution in time and space of sedimentary successions is controlled by a complex interplay between physical, chemical and biological processes, which are nowadays difficult to construe from the geological record. Numerical models constitute a valuable tool to identify and quantify such controlling factors permitting a reliable 3D extrapolation and prediction of stratigraphic and facies architectures beyond outcropping rock strata. This study assesses the roles of three controlling parameters being carbonate production rate, relative sea-level changes and terrigenous clastic sediment supply, on the evolution of an Aptian carbonate system. The SIMSAFADIM-CLASTIC, a 3D process-based sedimentary-stratigraphic forward model, was used for this evaluation. The carbonate succession modelled crops out in the western Maestrat Basin (E Iberia), and corresponded to a platform-to-basin transition comprising three depositional environment-related facies assemblages: platform top, slope and basin. Testing of geological parameters in forward modelling results in a wide range of possible 3D geological scenarios. The documented distribution of facies and sequence-stratigraphic framework combined with a virtual outcrop model were used as a reference to perform geometric (quantitative) and architectural and stacking pattern (qualitative) research by model-data comparison. The time interval modelled spans 1450 ky. The best-fit simulation run characterizes and quantifies (1) relative sea-level fluctuations recording five different genetic types of deposit (systems tracts) belonging to two depositional sequences as expected from field-data analysis, (2) a rate of terrigenous clastic sediment input ranging between 0.5 and 2.5 gr/s, and (3) a mean autochthonous carbonate production maximum rate of 0.08 m/ky. Furthermore, the quantitative and qualitative sensitivity tests carried out highlight that the fluctuation of relative sea level exerted the main control on the resulting stratigraphic and facies architectures, whereas the effect of inflowing terrigenous clastic sediment is less pronounced. Facies assemblages show different sensitivities to each parameter, being the slope carbonates more sensitive than the platform top facies to inflowing fine terrigenous sediments. On slope depositional settings, siliciclastic input also controls stratal stacking patterns and the dimensions of the carbonate bodies formed. The final 3D model allows to spot architectural features such as stacking patterns that can be misinterpreted by looking at the resulting record in the outcrop or by using other 2D approaches, and facilitates the comprehension of reservoir connectivity highlighting the occurrence of initial disconnected regressive platforms, which were later connected during a transgressive stage.

Description: Highlights • In-situ temperature measurements were conducted at the Danube deep sea fan. • Operations were performed with the MARUM-MeBo200 seafloor drill rig. • The BSR is located ∼20 m below the current gas hydrate stability zone. • Seismic data suggest presence of shallower BSR-like events. Abstract Coring, geophysical logging, and in-situ temperature measurements were performed with the MARUM-MeBo200 seafloor rig to characterize gas hydrate occurrences in sediments of the Danube deep sea fan, off Romania, Black Sea. The new drilling data showed no evidence for significant gas hydrate saturations within the sediments but the presence of free gas at the depth of the bottom-simulating reflector (BSR). In-situ temperature and core-derived geochemical data suggest that the current base of the gas hydrate stability zone (BGHSZ) is ∼20 m shallower than the BSR. Investigation of the seismic data around the drill sites shows several locations where free gas previously trapped at a former BGHSZ migrated upwards forming a new reflection above the BSR. This shows that the gas hydrate system in the Danube deep sea fan is still responding to climate changes initiated at the end of the last glacial maximum.

Description: Body condition and energy reserves are important indicators of organism health, habitat suitability and predictors for the reproductive success in fish. In Greenland waters, Atlantic cod (Gadus morhua) inhabits different habitats in shallow and deep parts on top of the shelf and along slopes, where diet composition differs. We investigated the influence of habitat heterogeneity and trophic niche on body condition using organosomatic indicators, e.g. the morphometric index K, hepatosomatic and gonadosomatic indices, and biochemical indicators, e.g. lipid content and fatty acid compositions, of mature female cod. Body condition differed between sites and peaked in north-eastern regions in depths below 300 m towards the slope of the northern Irminger Sea. Trophic niches as indicated by stable isotope values and stomach composition data varied between sites, which was likely related to depth and differences between benthic and pelagic feeding regimes. Total lipid content and fatty acid profiles important for reproduction were associated with a pelagic diet comprised of mesopelagic fish and crustaceans. Interestingly, consumption of capelin was not linked to highest energy reserves as indicated by traditional body condition indices, such as K and the hepatosomatic index, but lowest ratios of eicosapentaenoic acid to arachidonic acid in gonads, which are known to be beneficial for high egg production. This shows that body condition on biochemical level can differ from conventionally used indices, which emphasizes the need to take fatty acid composition into account, when investigating condition and reproductive potential in cod. Our results emphasize that the factor habitat cannot be ignored for population replenishment of the cod stocks in Greenland waters and indicate that capelin as part of an Arcto-boreal diet benefits reproductive success in cod.

Description: Highlights • First dissolved Nd/Hf isotope and REE data from the Congo River Plume. • High REE and Hf fluxes from the Congo River to the southeast Atlantic. • Conservative river and surface seawater mixing of Nd/Hf isotopes and REEs/Hf at S 〉 23. • Congo River particles impact intermediate and deep water signals of NE Angola Basin. Abstract The Congo River is the second largest river by discharge in the world and a major source of element inputs into the South Atlantic Ocean. Yet, the element fluxes and transport mechanisms across and beyond its estuary and their impacts on the marine distribution and cycling of many major and trace elements are not well understood. We present the first combined dissolved neodymium (Nd) and hafnium (Hf) isotope and rare earth element (REE) concentration distributions following the Congo River plume along its flow path off the West African coast and along a connected offshore latitudinal section at 3°S. The Congo River freshwater itself is characterized by extraordinarily high Nd and Hf concentrations of up to 4000 pmol/kg and 54 pmol/kg, and by Nd (εNd) and Hf (εHf) isotope compositions that range between −15.6 and −16.4 and between 0.35 and −1.4, respectively. Our near- and offshore data indicate that at salinities above 23 conservative mixing of Congo-derived Nd and Hf concentrations and isotopic signatures with ambient surface seawater occurs for at least 1000 km to the northwest of the river mouth. This demonstrates a large spatial extent of the influence of the Congo plume on trace metal distributions in the eastern south Atlantic surface waters. A comparison between dissolved Nd and Hf fluxes from the Congo River and the shelf zone estimated based on radium isotope compositions indicate that release from Congo-derived particulate phases likely balances strong estuarine REE and Hf removal in the low salinity zone. The combined riverine and shelf zone flux for Nd is almost twice as high as that estimated for the Amazon River, despite that the Amazon discharge is about five times higher than that of the Congo River. Even the offshore Nd flux estimated for the 3 °S transect based on radium isotope compositions still corresponds to ∼40% of the Congo-shelf-zone flux and reaches 150 ± 50 Mg/year for Nd. Moreover, intermediate waters below the plume are strongly affected by exchange with particulate inputs from the Congo River given that Nd isotope signatures are inconsistent with values expected from large-scale water mass mixing and instead support unradiogenic Nd release either from sinking or deposited Congo-derived detrital material. Deep and bottom water isotopic signatures are also slightly affected by interaction with particles and benthic Nd release.

Description: Carbon Capture and Storage (CCS) is a potential significant mitigation strategy to combat climate change and ocean acidification. The technology is well understood but its current implementation must be scaled up nearly by a hundredfold to become an effective tool that helps meet mitigation targets. Regulations require monitoring and verification at storage sites, and reliable monitoring strategies for detection and quantification of seepage of the stored carbon need to be developed. The Cseep method was developed for reliable determination of CO2 seepage signal in seawater by estimating and filtering out natural variations in dissolved inorganic carbon (C). In this work, we analysed data from the first-ever subsea CO2 release experiment performed in the north-western North Sea by the EU STEMM-CCS project. We successfully demonstrated the ability of the Cseep method to (i) predict natural C variations around the Goldeneye site over seasonal to interannual time scales; (ii) establish a process-based baseline C concentration with minimal variability; (iii) determine CO2 seepage detection threshold (DT) to reliably differentiate released- CO2 signal from natural variability and quantify released- CO2 dissolved in the sampled seawater. DT values were around 20 % of the natural C variations indicating high sensitivity of the method. Moreover, with the availability of DT value, the identification of released- CO2 required no preknowledge of seepage occurrence, but we used additional available information to assess the confidence of the results. Overall, the Cseep method features high sensitivity, automation suitability, and represents a powerful future monitoring tool both for large and confined marine areas.

Description: Marine sediments are an important source and sink of bio-essential trace metals to the ocean. However, the different mechanisms leading to trace metal release or burial are not fully understood and the associated fluxes are not well quantified. Here, we present sediment, pore water, sequential extraction and benthic flux data of Mn, Co, Ni, Cu, Zn and Cd along a latitudinal depth transect across the Peruvian oxygen minimum zone at 12°S. Sediments are depleted in Mn and Co compared to the lithogenic background. Diffusive Mn fluxes from the sediments into the bottom water (−26 to −550 μmol m−2 y−1) are largely consistent with the rate of Mn loss from the solid phase (−100 to −1160 μmol m−2 yr−1) suggesting that 50% or more of the sedimentary Mn depletion is attributed to benthic efflux. In contrast, benthic Co fluxes (~ −3 μmol m−2 yr−1) are lower than the rate of Co loss from the solid phase (up to −120 μmol m−2 yr−1), implying Co dissolution in the water column. The trace metals Ni, Cu, Zn and Cd are enriched within the sediments with respect to the lithogenic background. Uptake of Ni by phytoplankton in the photic zone and delivery with organic matter to the sediment surface can account for up to 100% of the excess Ni accumulation (87 to 180 μmol m−2 y−1) in shelf sediments near the coast, whereas at greater water depth additional scavenging by Mn- and Fe-oxides may contribute to Ni accumulation. Up to 20% of excess Cu (33 to 590 μmol m−2 y−1) and generally less than 20% of excess Zn (58 to 2170 μmol m−2 y−1) and Cd (6 to 260 μmol m−2 y−1) can be explained by delivery with fresh organic matter. Sequential extraction data suggest that the discrepancies between the known sources of Cd (and Cu) and their excess accumulation may be driven by the delivery of allochthonous sulphide minerals precipitated from the water column. Additionally, Cu may be scavenged by downward sinking organic material. In contrast, precipitation of Zn sulphide chiefly takes place in the sediment. Diffusive Zn fluxes into the sediment (21 to 1990 μmol m−2 y−1) match the excess Zn accumulation suggesting that Zn delivery is mediated by molecular diffusion from bottom waters. Considering the diverse behavioural pattern of trace metals observed in this study, we argue that declining oxygen and increasing hydrogen sulphide concentrations in a future ocean will modify trace metal fluxes at the seafloor and the trace metal stoichiometry of seawater.

Description: The numerous chemical and isotopic studies of oceanic basalts have shaped our perception of mantle geochemistry over the last six decades. As partial melts of Earth’s mantle, basalts are indirect tracers of mantle composition. Because the scale of isotopic heterogeneity is smaller than the scale of melt production, melts from isotopically heterogeneous mantle ingredients mix into variable blends on their way to eruption. Basalts are therefore isotopically less variable than their mantle sources. Decrypting “the message from oceanic volcanism” thus necessitates developing strategies to see through this ubiquitous sampling bias, but also acknowledging the inherent limitations imposed by investigating mantle composition through basalts. Understanding how large the bias between melts and mantle actually is requires decoding process versus source-related causes for the isotopic variability of basalts. Ultimately, deciphering the effective range of isotopic variability in Earth’s mantle is crucial for connecting isotopic signals in basalts to different materials and thus, the geologic processes that govern silicate earth evolution. Invariably, however, basalts are weighted averages of melts from isotopically different mantle constituents. As such, their incompatible element and isotopic composition is inherently biased towards the incompatible element enriched source components. The incompatible element depleted components of Earth’s mantle must therefore range to more extreme compositions than the basalts. But although isotope data from peridotites and olivine-hosted melt inclusions have extended the bounds of mantle heterogeneity, the overall extent of incompatible element depletion and mass fraction of incompatible element depleted mantle is still elusive. Mantle depletion is driven by the rate of melt extraction, or mantle processing, and thus interconnects the geochemical and geodynamical evolution of Earth’s mantle. Better constraining mantle depletion is therefore at the root of understanding our planet’s principal mode of operation.

Description: The Amazon is Earth's largest river by volume output, making it an important source of trace metals and dissolved organic matter (DOM) to the Atlantic Ocean. Despite major recent anthropogenic disruptions to the Amazon catchment area, data for trace metals such as copper (Cu) in the Amazon River estuary and associated mixing plume are still rare. Furthermore, there is currently no existing data in this region for Cu-binding ligands, which govern the amount of bioavailable Cu. To understand trace metal mixing and transport processes, the GEOTRACES process study GApr11 (cruise M147 with RV Meteor) was conducted in 2018 in the Amazon and Pará River estuaries and mixing plume in the tropical North Atlantic Ocean during high river discharge. Size-fractionated surface samples were collected along the full salinity gradient for concentrations of Cu, apparent Cu-binding organic ligands (LCu) and corresponding conditional stability constants (K′CuL, Cu2+cond), electroactive humic substances (eHS), solid phase extractable organic Cu (SPE[sbnd]Cu), dissolved organic carbon (DOC), chlorophyll a (Chl a) and macronutrients. Dissolved (〈0.2 μm) and soluble (〈0.015 μm) Cu correlated negatively with salinity and largely followed values expected from conservative mixing. Cu was primarily in the soluble fraction, with the exception of a minor fraction of large colloidal Cu at low salinity (S ≤ 10). Organic ligands (log K′CuL, Cu2+cond = 12.6–15.6) were present in excess of Cu and likely played a role in solubilizing Cu and preventing Cu being affected by colloidal flocculation. Cu-associated DOM (measured as LCu, eHS and SPE[sbnd]Cu) correlated negatively with salinity and appeared to be primarily governed by river input and mixing with seawater. However, an increase in the colloidal fraction for LCu and eHS observed at S ~ 6–10 was attributed to possible additional autochthonous (phytoplankton) ligand production. In all dissolved samples, organic complexation kept free Cu below levels potentially toxic for phytoplankton (〈1 pmol L−1). Despite increasing anthropogenic activity over the past century, we find Cu concentrations remained similar to the 1970s, suggesting that the large overall river flow may so far minimize the impact of Cu pollution.

Description: Highlights: • A single Saksunarvatn Ash layer was detected in two varved lake cores from N-Germany. • The ash layers in the two cores are dated to 10,282 ± 45 and 10,264 ± 24 cal. BP. • Palynological and geochemical analysis were conducted in proximity of the ash layers. • Environmental disturbance, possibly linked to volcanism, predates the ash fallout. • Evidence for a ca. 15-year-long cooling is recognizable after tephra deposition. Abstract Estimating the environmental and societal impact of recent volcanic eruptions is a task aided by direct measurements and historical sources. Beyond the reach of first-hand accounts, our understanding of pre-historic volcanism is often hindered by dating uncertainties inherent to geological archives. Here, we minimize dating errors by analyzing the annually laminated sequences of two Central European lakes, Poggensee and Woseriner See. We focus on environmental transformations that occurred in the decades preceding and following the deposition of the Icelandic Saksunarvatn tephra, dated between ca. 10,300 and 10,200 cal. BP. As a first result, we provide two new independent age determinations for the ash layer detected in both sequences. Our estimates (10,264 ± 24 cal. BP at Poggensee and 10,282 ± 45 cal. BP at Woseriner See) place the age of this tephra deposit closer to Greenland estimates than to continental ones, possibly reducing the chronological gap between the multiple fallout events that characterize the Saksunarvatn Ash. A high resolution palaeoenvironmental characterization was carried out via pollen, thin sections and geochemical analysis. Both sequences show traces of a contemporaneous disturbance event dated to ca. 18 years before tephra deposition. In addition, environmental impact compatible with a cooling event is discernible for ca. 15 years following tephra deposition. While independent climate mechanisms can be responsible for the observed trends, we explicitly focus on exploring volcanic eruptions as a possible leading driver. A consistent agreement across all proxies is lacking in the pre-tephra record, yet sulfur enrichment and acidification processes allow us to suggest volcanism as a plausible trigger. Combined with the post-tephra cooling, the two sedimentary records depict a possible scenario of multi-decadal, continuous volcanic impact.