ALBERT

Description: Trace metal micronutrients are integral to the functioning of marine ecosystems and the export of particulate carbon to the deep ocean. Although much progress has been made in mapping the distributions of metal micronutrients throughout the ocean over the last 30 years, there remain information gaps, most notable during seasonal transitions and in remote regions. The next challenge is to develop in situ sensing technologies necessary to capture the spatial and temporal variabilities of micronutrients characterized with short residence times, highly variable source terms, and sub-nanomolar concentrations in open ocean settings. Such an effort will allow investigation of the biogeochemical processes at the necessary resolution to constrain fluxes, residence times, and the biological and chemical responses to varying metal inputs in a changing ocean. Here, we discuss the current state of the art and analytical challenges associated with metal micronutrient determinations and highlight existing and emerging technologies, namely in situ chemical analyzers, electrochemical sensors, passive preconcentration samplers, and autonomous trace metal clean samplers, which could form the basis of autonomous observing systems for trace metals within the next decade. We suggest that several existing assets can already be deployed in regions of enhanced metal concentrations and argue that, upon further development, a combination of wet chemical analyzers with electrochemical sensors may provide the best compromise between analytical precision, detection limits, metal speciation, and longevity for autonomous open ocean determinations. To meet this goal, resources must be invested to: (1) improve the sensitivity of existing sensors including the development of novel chemical assays; (2) reduce sensor size and power requirements; (3) develop an open-source “Do-It-Yourself” infrastructure to facilitate sensor development, uptake by end-users and foster a mechanism by which scientists can rapidly adapt commercially available technologies to in situ applications; and (4) develop a community-led standardized protocol to demonstrate the endurance and comparability of in situ sensor data with established techniques. Such a vision will be best served through ongoing collaborations between trace metal geochemists, analytical chemists, the engineering community, and commercial partners, which will accelerate the delivery of new technologies for in situ metal sensing in the decade following OceanObs’19.

Description: Competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV) is a widely used technique to determine dissolved iron (Fe) speciation in seawater, and involves competition for Fe of a known added ligand (AL) with natural organic ligands. Three different ALs were used, 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-napthol (NN). The total ligand concentrations ([L t ]) and conditional stability constants (log K ′ Fe’L ) obtained using the different ALs are compared. The comparison was done on seawater samples from Fram Strait and northeast Greenland shelf region, including the Norske Trough, Nioghalvfjerdsfjorden (79N) Glacier front and Westwind Trough. Data interpretation using a one-ligand model resulted in [L t ] SA (2.72 ± 0.99 nM eq Fe) > [L t ] TAC (1.77 ± 0.57 nM eq Fe) > [L t ] NN (1.57 ± 0.58 nM eq Fe); with the mean of log K ′ Fe’L being the highest for TAC (log ′ K Fe’L(TAC) = 12.8 ± 0.5), followed by SA (log K ′ Fe’L(SA) = 10.9 ± 0.4) and NN (log K ′ Fe’L(NN) = 10.1 ± 0.6). These differences are only partly explained by the detection windows employed, and are probably due to uncertainties propagated from the calibration and the heterogeneity of the natural organic ligands. An almost constant ratio of [L t ] TAC /[L t ] SA = 0.5 – 0.6 was obtained in samples over the shelf, potentially related to contributions of humic acid-type ligands. In contrast, in Fram Strait [L t ] TAC /[L t ] SA varied considerably from 0.6 to 1, indicating the influence of other ligand types, which seemed to be detected to a different extent by the TAC and SA methods. Our results show that even though the SA, TAC and NN methods have different detection windows, the results of the one ligand model captured a similar trend in [L t ], increasing from Fram Strait to the Norske Trough to the Westwind Trough. Application of a two-ligand model confirms a previous suggestion that in Polar Surface Water and in water masses over the shelf, two ligand groups existed, a relatively strong and relatively weak ligand group. The relatively weak ligand group contributed less to the total complexation capacity, hence it could only keep part of Fe released from the 79N Glacier in the dissolved phase.

Description: Hydrothermal vents are a source of many trace metals to the oceans. Compared to mid-ocean ridges, hydrothermal vent systems at arcs occur in shallower water depth and are much more diverse in fluid composition, resulting in highly variable water column trace metal concentrations. However, only few studies have focused on trace metal dynamics in hydrothermal plumes at volcanic arcs. During R/V Sonne cruise SO253 in 2016/2017, hydrothermal plumes from two hydrothermally active submarine volcanoes along the Kermadec arc in the Southwest Pacific Ocean were sampled: (1) Macauley, a magmatic dominated vent site located in water depths between 300 and 680 m, and (2) Brothers, located between 1,200 and 1,600 m water depth, where hydrothermalism influenced by water rock interactions and magmatically influenced vent sites occur near each other. Surface currents estimated from satellite-altimeter derived currents and direct measurements at the sites using lowered acoustic Doppler current profilers indicate the oceanic regime is dominated by mesoscale eddies. At both volcanoes, results indicated strong plumes of dissolved trace metals, notably Mn, Fe, Co, Ni, Cu, Zn, Cd, La, and Pb, some of which are essential micronutrients. Dissolved metal concentrations commonly decreased with distance from the vents, as to be expected, however, certain element/Fe ratios increased, suggesting a higher solubility of these elements and/or their stronger stabilization (e.g., for Zn compared to Fe). Our data indicate that at the magmatically influenced Macauley and Brothers cone sites, the transport of trace metals is strongly controlled by sulfide nanoparticles, while at the Brothers NW caldera wall site iron oxyhydroxides seem to dominate the trace metal transport over sulfides. Solution stabilization of trace metals by organic complexation appears to compete with particle adsorption processes. As well as extending the generally sparse data set for hydrothermal plumes at volcanic arc systems, our study presents the first data on several dissolved trace metals in the Macauley system, and extends the existing plume dataset of Brothers volcano. Our data further indicate that chemical signatures and processes at arc volcanoes are highly diverse, even on small scales.