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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.

Submarine groundwater discharge (SGD) is an important source of nutrients and metals to the coastal ocean, affects coastal ecosystems, and is gaining recognition as a relevant water resource. SGD is usually quantified using geochemical tracers such as radon or radium. However, a few studies have also used dissolved silicon (DSi) as a tracer for SGD, as DSi is usually enriched in groundwater when compared to surface waters. In this study, we discuss the potential of DSi as a tracer in SGD studies based on a literature review and two case studies from contrasting environments. In the first case study, DSi is used to calculate SGD fluxes in a tropical volcanic-carbonate karstic region (southern Java, Indonesia), where SGD is dominated by terrestrial groundwater discharge. The second case study discusses DSi as a tracer for marine SGD (i.e., recirculated seawater) in the tidal flat area of Spiekeroog (southern North Sea), where SGD is dominantly driven by tidal pumping through beach sands. Our results indicate that DSi is a useful tracer for SGD in various lithologies (e.g., karstic, volcanic, complex) to quantify terrestrial and marine SGD fluxes. DSi can also be used to trace groundwater transport processes in the sediment and the coastal aquifer. Care has to be taken that all sources and sinks of DSi are known and can be quantified or neglected. One major limitation is that DSi is used by siliceous phytoplankton and therefore limits its applicability to times of the year when primary production of siliceous phytoplankton is low. In general, DSi is a powerful tracer for SGD in many environments. We recommend that DSi should be used to complement other conventionally used tracers, such as radon or radium, to help account for their own shortcomings.

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.