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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 < 6 pM for 8 of 9 samples. Moreover, the excess of L found especially in shallow pore waters implied that even with a Cu release through mining activities, Cu2+ likely remains beneath toxic thresholds. [ABSTRACT FROM AUTHOR]

The microbial community composition and its functionality was assessed for hydrothermal fluids and volcanic ash sediments from Haungaroa and hydrothermal fluids from the Brothers volcano in the Kermadec island arc (New Zealand). The Haungaroa volcanic ash sediments were dominated by epsilonproteobacterial Sulfurovum sp. Ratios of electron donor consumption to CO2 fixation from respective sediment incubations indicated that sulfide oxidation appeared to fuel autotrophic CO2 fixation, coinciding with thermodynamic estimates predicting sulfide oxidation as the major energy source in the environment. Transcript analyses with the sulfide-supplemented sediment slurries demonstrated that Sulfurovum prevailed in the experiments as well. Hence, our sediment incubations appeared to simulate environmental conditions well suggesting that sulfide oxidation catalyzed by Sulfurovum members drive biomass synthesis in the volcanic ash sediments. For the Haungaroa fluids no inorganic electron donor and responsible microorganisms could be identified that clearly stimulated autotrophic CO2 fixation. In the Brothers hydrothermal fluids Sulfurimonas (49%) and Hydrogenovibrio/Thiomicrospira (15%) species prevailed. Respective fluid incubations exhibited highest autotrophic CO2 fixation if supplemented with iron(II) or hydrogen. Likewise catabolic energy calculations predicted primarily iron(II) but also hydrogen oxidation as major energy sources in the natural fluids. According to transcript analyses with material from the incubation experiments Thiomicrospira/Hydrogenovibrio species dominated, outcompeting Sulfurimonas. Given that experimental conditions likely only simulated environmental conditions that cause Thiomicrospira/Hydrogenovibrio but not Sulfurimonas to thrive, it remains unclear which environmental parameters determine Sulfurimonas' dominance in the Brothers natural hydrothermal fluids. [ABSTRACT FROM AUTHOR]

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 mass‐balance of a closed 48‐h bioassay with Mytilus galloprovincialis embryos. [ABSTRACT FROM AUTHOR]

Hydrothermal venting is an important transfer process of energy and elements between the Earth's solid material and the oceans. Compared to mid-ocean-ridge hydrothermal vent fields, those at intra-oceanic island arcs are typically in shallower water depth and have a more variable geochemical fluid composition. Biologically essential trace elements (such as Fe and Mn) are generally elevated in fluids of both deep and shallow hydrothermal vent fields, while vents at shallower water depth influence the photic zone more directly and thus are potentially more relevant for marine primary productivity. However, fluid flux estimations of island arc hydrothermal systems into the surrounding water column are scarce. This study (I) presents a method based on short-lived radium isotopes to estimate submarine hydrothermal discharge (SHD), (II) applies this method at Brothers volcano in the southern Kermadec arc, located northeast of New Zealand, and (III) gives dissolved Fe, Mn and He isotope flux estimates for the Earth´s longest intra-oceanic island arc, the Kermadec arc. The comparison between measured inert He isotope concentrations in the plume with calculated concentrations based on Ra isotopes matched reasonably well, which supports the use of a Ra-based discharge model. Overall, this study represents a novel approach to assess fluid and thus trace element fluxes from one hydrothermal vent field, which can be applied in future studies on various hydrothermal systems to improve geochemical models of element cycling in the ocean. [ABSTRACT FROM AUTHOR]