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Young oceanic plateaus are important for fluid exchange between the lithosphere and the ocean. Increased heat fluxes can lead to a large-scale upwelling of fluids that play a role in global elemental cycles. In addition, variations in fluid chemistries can potentially influence the biomass and species compositions of microbial and benthic communities in sediments exposed to subsurface fluid flow. Yet, the present understanding of these young oceanic plateaus in terms of their fluid dynamics and their biogeochemical local and global impacts is limited. The goal of RV Meteor Expedition M186 in December 2022 was to investigate how subsurface fluids on the young Azores Plateau, Central North Atlantic, vary with respect to their flow rates, chemical compositions, and the prevalent on microbial and benthic communities at and below the seafloor. First data from the São Jorge Channel (Azores Plateau) show that fluid dynamics here are diffuse rather than focused, and that fluid chemical compositions nonetheless show strong local variations, over a small spatial scale of 65 km2, that could be related to differences in fluid origins and fluid flow paths. However, the connection of fluid conduits, heat flow data and biogeochemical data as well as their relation to faults visible in seismic data are rather complex. Our first results thus indicate that diffuse fluid flow on young oceanic plateaus is highly heterogeneous despite occurring over large sediment-covered areas. Thus, the role of fluids at young oceanic plateaus as an important intermediate between the lithosphere and the ocean cannot be generalized over large spatial and possibly temporal scales.

The release of potentially toxic metals, such as copper (Cu), into the water column is of concern during polymetallic nodule mining. The bioavailability and thus toxicity of Cu is strongly influenced by its speciation which is dominated by organic ligand (L) complexation in seawater, with L-complexes being considered less bioavailable than free Cu2+. The presence of CuL-complexes in deep-sea sediments has, however, not been systematically studied in the context of deep-sea mining. We thus analyzed the Cu-binding L concentration ([L]) in deep-sea pore waters of two polymetallic nodule provinces in the Pacific Ocean, the Peru Basin and the Clarion-Clipperton-Zone, using competitive ligand equilibration–adsorptive stripping voltammetry. The pore-water dissolved Cu concentration ([dCu]) ranged from 3 to 96 nM, generally exceeding bottom water concentrations (4–44 nM). Based on fitting results from ProMCC and Excel, Cu was predominantly complexed by L (3–313 nM) in bottom waters and undisturbed pore waters. We conclude that processes like deep-sea mining are unlikely to cause a release of toxic Cu2+ concentrations ([Cu2+]) to the seawater as > 99% Cu was organically complexed in pore waters and the [Cu2+] was 2+ likely remains beneath toxic thresholds.

Copper (Cu) is a naturally occurring micronutrient of eco-toxicological concern in aquatic ecosystems. Current knowledge of Cu-speciation and bioavailability in natural saline environments is insufficient to adequately inform environmental protection policy for estuarine systems. We assessed the combined effect of two of the main drivers of metal bioavailability, salinity and natural dissolved organic carbon (DOC), on Cu-speciation and associated Cu-toxicity to blue mussel (Mytilus galloprovincialis) embryos in a standard 48-h bioassay. We placed special emphasis on measurement of Cu-speciation rather than modelling. Cu-toxicity was found to be a function of DOC and salinity. The varying protective effect of different DOC-types suggests that estuarine DOC is more protective against Cu-toxicity than oceanic DOC. Salinity was negatively correlated with [Cu48-h-EC50], indicating a salinity-induced alteration in the physiology of the exposed mussel embryos and/or Cu-DOC-reactivity. These two assumptions were supported by (1) the relative uniformity of bioavailable copper ([Cu']) across similar salinity treatments despite considerable variation in [Cu48-h-EC50] and DOC-concentrations, and (2) the fact that Cu-toxicity and [Cu'] were slightly higher in the 35 salinity treatment compared to the 25 salinity treatment. Stripping voltammetry studies determined the presence of only one strong Cu-binding ligand class (i.e., L1), either actively or passively released by the exposed embryos. [L1] was found to be proportional to the total dissolved Cu-concentration ([CuT]), suggesting a protective effect of Cu-binding-ligands, in addition to the protective effect of DOC. There was also a strong positive correlation between [L1] and [Cu48-h-EC50], implying that electrochemically defined ligand concentrations along with measurements of [Cu'], DOC-quality, and salinity can be used as proxies for 48-h-EC50 Cu-values in estuarine waters, which may result in a significant improvement to risk assessments of Cu in estuarine systems.

Capacity building efforts in Small Island Developing States (SIDS) are indispensable for the achievement of both individual and collective ocean-related 2030 agenda priorities for sustainable development. Knowledge of the individual capacity building and research infrastructure requirements in SIDS is necessary for national and international efforts to be effective in supporting SIDS to address nationally-identified sustainable development priorities. Here, we present an assessment of human resources and institutional capacities in SIDS United Nations (UN) Member States to help formulate and implement durable, relevant, and effective capacity development responses to the most urgent marine issues of concern for SIDS. The assessment highlights that there is only limited, if any, up-to-date information publicly available on human resources and research capacities in SIDS. A reasonable course of action in the future should, therefore, be the collection and compilation of data on educational, institutional, and human resources, as well as research capacities and infrastructures in SIDS into a publicly available database. This database, supported by continued, long-term international, national, and regional collaborations, will lay the foundation to provide accurate and up-to-date information on research capacities and requirements in SIDS, thereby informing strategic science and policy targets towards achieving the UN sustainable development goals (SDGs) within the next decade.

Organic ligands play a key role in the marine biogeochemical cycle of copper (Cu), a bio-essential element, regulating its solubility and bioavailability . However, the sources, abundance, and distribution of these ligands are still poorly understood. In this study, we examined vertical Cu speciation profiles from the South-East Atlantic (GEOTRACES section GA08). Profiles were collected from a range of ocean conditions, including the Benguela upwelling region, the oligotrophic South Atlantic Gyre , and the Congo River outflow. In general, the lack of a significant correlation between most of the parameters assessed here with Cu speciation data obscures the provenance of Cu-binding ligands, suggesting that Cu speciation in the South-East Atlantic is influenced by a complex interplay between biotic and abiotic processes. Nevertheless, the total dissolved Cu (CuT) illustrated an allochthonous origin in the working area, while Cu-binding ligands showed both an allochthonous and a biogenic, autochthonous origin. Pigment concentrations showed that the phylogeography of different microorganisms influenced the spatial features of the Cu-binding ligand pool in the South-East Atlantic. Allochthonous Cu-binding ligand sources in the upper water column are likely associated with dissolved organic matter which originated from the Congo River and the Benguela upwelling system. Deep water ligand sources could include refractory dissolved organic carbon (DOC), resuspended benthic inputs, and lateral advected inputs from the shelf margin. The degradation of L1-type ligands and/or siderophores in low oxygen conditions may also be a source of L2-type ligands in the deep. Free Cu ion levels (1.7 to 156 fM), the biologically available form of CuT, were below the putative biolimiting threshold of many marine organisms. Two classes of ligands were found in this study with total ligand concentrations ([LT]) ranging from 2.5 to 283.0 nMand conditional stability constants (logKCuL, Cu2+ cond) ranging from 10.7 to 14.6. The Cu speciation values were spatially variable across the three subregions, suggesting that biogeochemical processes and sources strongly influence Cu speciation.

Pollution from the grounding or sinking of ships can have long lasting effects on the recovery and dynamics of coastal ecosystems. Research on the impact of copper (Cu) pollution from the 2011 MV Rena shipwreck at the Astrolabe Reef (Otaiti), New Zealand, 5 years after the grounding, followed a multi-method and multi-disciplinary approach. Three independent measures of aqueous Cu using trace-element-clean-techniques substantiate the presence of high total, total dissolved (

The naturally occurring radium (Ra) isotope quartet was measured for the first time at an intraoceanic arc hydrothermal setting along the Kermadec Island Arc (SW Pacific). 224Ra (3.7 d half life) and 223Ra (11.4 d half life) are assumed to be tracers solely originating from hydrothermal discharge and have been used to resolve near-field hydrothermal plume dynamics by applying both advection and eddy diffusion-based dispersion models. Assuming dominant advective processes, we identified different horizontal plume age structures at Brothers volcano, with a slow moving plume inside the caldera (0.060 cm/s) and a faster moving plume outside the caldera (0.323 cm/s), indicating a longer plume residence time within the caldera structure. The decreasing trend in Ra activity also allows the calculation of horizontal eddy diffusion coefficients inside and outside of the caldera, with 0.164 m2/s and 3.545 m2/s for 224Ra, respectively. These trends are in accordance with the radial horizontal eddy diffusion model. Our results reveal that net advection might not necessarily play a major role at Brothers, as radial horizontal eddy diffusion reproduces the observed Ra activity distribution to the same degree. Additional model simulations based on a combination of advection and diffusion, favor slow net advection to explain the Ra activity distribution. Within the rising non-buoyant plume, Ra isotopes suggested constant dilution along the first 170 m of the vertical water column and a vertical transport velocity on the order of 0.156 cm/s for altitudes up to 150 m above the vent and around 0.004 cm/s for altitudes above 150 m. When a common source of diffuse and focused venting is assumed and only small amounts of Ra are added to the ascending plume, due to recoil originating from high water to rock ratios, fluids from diffuse vents show a slower migration rate through the subsurface than fluids from focused vents. Our data imply that the fluids from diffuse vents needed approximately five days longer to percolate through the underlying subsurface to reach the water column plume, compared to the fluids from direct vents which emanate through chimney structures. This study demonstrates the potential of short-lived Ra isotopes as tracers of near-field plume dynamics, which will improve our understanding of hydrothermal vents as sources for various trace elements to the global ocean.

In situ effects of ocean acidification are increasingly studied at submarine CO2 vents. Here we present a preliminary investigation into the water chemistry and biology of cool temperate CO2 vents near Whakaari–White Island, New Zealand. Water samples were collected inside three vent shafts, within vents at a distance of 2m from the shaft and at control sites. Vent samples contained both seawater pH on the total scale (pHT) and carbonate saturation states that were severely reduced, creating conditions as predicted for beyond the year 2100. Vent samples showed lower salinities, higher temperatures and greater nutrient concentrations. Sulfide levels were elevated and mercury levels were at concentrations considered toxic at all vent and control sites, but stable organic and inorganic ligands were present, as deduced from Cu speciation data, potentially mediating harmful effects on local organisms. The biological investigations focused on phytoplankton, zooplankton and macroalgae. Interestingly, we found lower abundances but higher diversity of phytoplankton and zooplankton at sites in the direct vicinity of Whakaari. Follow-up studies will need a combination of methods and approaches to attribute observations to specific drivers. The Whakaari vents represent a unique ecosystem with considerable biogeochemical complexity, which, like many other vent systems globally, require care in their use as a model of ‘future oceans’.

During the R/V Sonne cruise SO253 in 2016/2017, hydrothermal vent sites along the Kermadec intraoceanic arc were sampled for hydrothermal fluids at four active volcanoes: Macauley, Haungaroa, Brothers and Rumble III, respectively. Water depths ranged between 290 m and 1700 m. A new vent field was discovered at Haungaroa. The samples were taken from diffuse-flow sites as well as from white and black smokers – rich in metals and gases – with discharge temperatures as high as 311 °C. Their fluid composition is very variable but basically divides into two types: one that indicates distinct magmatic input and another that shows evidence for intense water-rock interaction under hot, acidic conditions. Fluid samples from Macauley, the shallowest sampling site (~300 m), had Fe concentrations as high as 1.7 mM, Al concentrations up to 122 μM and H2S up to 10 mM at a pH of only 1.2. At Brothers, the deepest sampling site (down to 1600 m), we identified two different fluid types: 1) A magmatically-influenced type at the Upper and Lower Cone with highest temperatures of 115 °C, up to 95.6 mM Mg (the highest Mg concentration measured in fluids from intraoceanic arc systems so far), elevated SO42− (76.9 mM), high H2S (5.0 mM), but Fe concentrations of only 15 μM and 2) A fluid with low Mg (5.4 mM), low H2S (1.1 mM), temperatures reaching 311 °C and high Fe contents (12.4 mM) at the Upper Caldera and NW Caldera Wall, typical of a black smoker fluid. Chloride concentrations in all fluids were similar, or highly enriched when compared to seawater (e.g. up to 787 mM, brine fluids), with also one low-chlorinity vapor-phase fluid sample recovered, indicating that phase separation is occurring at Brothers. Unusual highly elevated Mg concentrations in fluids from the Brothers Lower Cone (95.6 mM, compared to 53.2 mM in ambient seawater) combined with highly elevated concentrations of SO42− (76.9 mM, compared to 29.0 mM in ambient seawater) indicate dissolution of Mg- and SO42−-bearing minerals in the subsurface, such as caminite. Our data show how highly diverse and variable island arc systems can be with respect to their fluid chemistry, both spatially and temporally. It adds to the still limited data set of arc systems compared to mid-ocean ridges and supplies an important contribution towards a better understanding of geochemical processes along arc volcanoes. The higher range in fluid chemistry together with shallower water depth implies that the fluids from intraoceanic arcs may contribute a significant fraction of dissolved metals not only to the global oceanic biogeochemical cycle but also into the photic zone, the area of highest bioproductivity.

The production of accurate and reliable data on metal toxicity during ecotoxicological bioassays is important for credible environmental risk assessments and management in aquatic environments. Actual measurements and reporting of contaminant concentrations in bioassays are, however, often disregarded; and potential contaminant loss attributable to adsorption processes (e.g., wall adsorption) in bioassays is widely omitted, which can have detrimental effects on calculated metal toxicity thresholds. In the present we assessed copper (Cu) mass balance during a standard 48-h bioassay test with blue mussel (Mytilus galloprovincialis) embryos to evaluate effects on calculated toxicity endpoints. We demonstrated that measured Cu concentrations at the test conclusion need to be used to quantify the risk of Cu toxicity because nominal Cu and initial Cu concentrations underestimate overall Cu toxicity by up to 1.5-fold, owing to Cu loss in solution attributable to adsorption and bioaccumulation processes. For the first time we provide evidence that extracellular adsorption to the biological surface of the embryos is the most important sink for total dissolved Cu in a bioassay. We also established that adsorbed extracellular Cu accumulation reduces Cu toxicity to embryos, potentially by inhibiting Cu from entering the cell of the mussel embryo. Environmental factors (e.g., salinity and dissolved organic carbon) did not influence the partitioning of Cu within the laboratory-based bioassay. The present results 1) demonstrate the importance of differentiating extra- and intracellular Cu pools to improve our understanding of Cu toxicity and associated processes, 2) reveal the potential for bias with respect to calculated Cu toxicity thresholds when results are based on nominal and initial Cu concentrations, and 3) point out the need to follow current guidelines for the testing of chemicals to standardize toxicity tests and data reporting. Environ Toxicol Chem 2019;38:561-574. © 2019 SETAC.

Copper (Cu) is a naturally occurring micronutrient of eco-toxicological concern in aquatic ecosystems. Current knowledge of Cu-speciation and bioavailability in natural saline environments is insufficient to adequately inform environmental protection policy for estuarine systems. We assessed the combined effect of two of the main drivers of metal bioavailability, salinity and natural dissolved organic carbon (DOC), on Cu-speciation and associated Cu-toxicity to blue mussel (Mytilus galloprovincialis) embryos in a standard 48-h bioassay. We placed special emphasis on measurement of Cu-speciation rather than modelling. Cu-toxicity was found to be a function of DOC and salinity. The varying protective effect of different DOC-types suggests that estuarine DOC is more protective against Cu-toxicity than oceanic DOC. Salinity was negatively correlated with [Cu