Description: © The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Philosophical Transactions of the Royal Society A 374 (2016): 20160035, doi:10.1098/rsta.2016.0035.

Description: Hydrothermal activity occurs in all ocean basins, releasing high concentrations of key trace elements and isotopes (TEIs) into the oceans. Importantly, the calculated rate of entrainment of the entire ocean volume through turbulently mixing buoyant hydrothermal plumes is so vigorous as to be comparable to that of deep-ocean thermohaline circulation. Consequently, biogeochemical processes active within deep-ocean hydrothermal plumes have long been known to have the potential to impact global-scale biogeochemical cycles. More recently, new results from GEOTRACES have revealed that plumes rich in dissolved Fe, an important micronutrient that is limiting to productivity in some areas, are widespread above mid-ocean ridges and extend out into the deep-ocean interior. While Fe is only one element among the full suite of TEIs of interest to GEOTRACES, these preliminary results are important because they illustrate how inputs from seafloor venting might impact the global biogeochemical budgets of many other TEIs. To determine the global impact of seafloor venting, however, requires two key questions to be addressed: (i) What processes are active close to vent sites that regulate the initial high-temperature hydrothermal fluxes for the full suite of TEIs that are dispersed through non-buoyant hydrothermal plumes? (ii) How do those processes vary, globally, in response to changing geologic settings at the seafloor and/or the geochemistry of the overlying ocean water? In this paper, we review key findings from recent work in this realm, highlight a series of key hypotheses arising from that research and propose a series of new GEOTRACES modelling, section and process studies that could be implemented, nationally and internationally, to address these issues.

Description: his paper represents the outcomes from a series of break-out group discussions held at Chicheley Hall, UK, on 9 and 10 December 2015, as part of a Quantifying Fluxes and Processes in Trace-Metal Cycling in the Oceans science meeting sponsored by the Royal Society. C.R.G. also acknowledges further support from NSF grant OCE-1130870.

Description: Hydrocarbon-rich fluids expelled at mud volcanoes (MVs) may contribute significantly to the carbon budget of the oceans, but little is known about the long-term variation in fluid fluxes at MVs. The Darwin MV is one of more than 40 MVs located in the Gulf of Cadiz, but it is unique in that its summit is covered by a thick carbonate crust that has the potential to provide a temporal record of seepage activity. In order to test this idea, we have conducted petrographic, chemical and isotopic analyses of the carbonate crust. In addition a 1-D transport-reaction model was applied to pore fluid data to assess fluid flow and carbonate precipitation at present. The carbonate crusts mainly comprise of aragonite, with a chaotic fabric exhibiting different generations of cementation and brecciation. The crusts consist of bioclasts and lithoclasts (peloids, intraclasts and extraclasts) immersed in a micrite matrix and in a variety of cement types (microsparite, botryoidal, isopachous acicular, radial and splayed fibrous). The carbonates are moderately depleted in 13C (δ13C = − 8.1 to − 27.9‰) as are the pore fluids (δ13C = − 19.1 to − 28.7‰), which suggests that their carbon originated from the oxidation of methane and higher hydrocarbons, like the gases that seep from the MV today. The carbonate δ18O values are as high as 5.1‰, and it is most likely that the crusts formed from 18O-rich fluids derived from dehydration of clay minerals at depth. Pore fluid modelling results indicate that the Darwin MV is currently in a nearly dormant phase (seepage velocities are 〈 0.09 cm yr− 1). Thus, the thick carbonate crust must have formed during past episodes of high fluid flow, alternating with phases of mud extrusion and uplift. Highlights ► Results of pore fluid modelling indicate low seepage activity at localised sites. ► Pore fluids are supersaturated with respect to hydrocarbons of thermogenic origin. ► AOM supports vent fauna and results in the formation of authigenic carbonates. ► The carbonate crust has a brecciated appearance and mainly consists of aragonite. ► The crust formation seems to be regulated by changes in fluid and mudflow activity.

Description: Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment–seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34–180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr−1 at the apex of the MV but they rapidly decrease to 0.4 cm yr−1 at the periphery. The associated fluxes of boron, lithium and methane vary between 7–301, 0.5–6 and 0–806 mmol m−2 yr−1, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.