Description: Large quantities of methane are stored in hydrates and permafrost within shallow marine sediments in the Arctic Ocean. These reservoirs are highly sensitive to climate warming, but the fate of methane released from sediments is uncertain. Here, we review the principal physical and biogeochemical processes that regulate methane fluxes across the seabed, the fate of this methane in the water column, and potential for its release to the atmosphere. We find that, at present, fluxes of dissolved methane are significantly moderated by anaerobic and aerobic oxidation of methane. If methane fluxes increase then a greater proportion of methane will be transported by advection or in the gas phase, which reduces the efficiency of the methanotrophic sink. Higher freshwater discharge to Arctic shelf seas may increase stratification and inhibit transfer of methane gas to surface waters, although there is some evidence that increased stratification may lead to warming of sub-pycnocline waters, increasing the potential for hydrate dissociation. Loss of sea-ice is likely to increase wind speeds and sea-air exchange of methane will consequently increase. Studies of the distribution and cycling of methane beneath and within sea ice are limited, but it seems likely that the sea-air methane flux is higher during melting in seasonally ice-covered regions. Our review reveals that increased observations around especially the anaerobic and aerobic oxidation of methane, bubble transport, and the effects of ice cover, are required to fully understand the linkages and feedback pathways between climate warming and release of methane from marine sediments.

Description: Large amounts of the greenhouse gas methane are released from the seabed but liberation of methane to the atmosphere is mitigated by aerobic methanotrophs in the water column. The size and activity of methanotrophic communities are thought to be mainly determined by nutrient and redox dynamics, but little is known about the effects of water mass transport. Here, we show that cold bottom waters at methane seeps west off Svalbard, which contained a large number of aerobic methanotrophs, were rapidly displaced by warmer waters with a considerably smaller methanotrophic community. This water mass exchange, caused by short-term variations of the West Spitsbergen Current strongly reduced methanotrophic activity. Currents are common at many methane seeps and could thus be a globally important control on methane oxidation in the water column.

Description: © The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in PLoS Biology 10 (2012): e1001234, doi:10.1371/journal.pbio.1001234.

Description: Since the first discovery of deep-sea hydrothermal vents along the Galápagos Rift in 1977, numerous vent sites and endemic faunal assemblages have been found along mid-ocean ridges and back-arc basins at low to mid latitudes. These discoveries have suggested the existence of separate biogeographic provinces in the Atlantic and the North West Pacific, the existence of a province including the South West Pacific and Indian Ocean, and a separation of the North East Pacific, North East Pacific Rise, and South East Pacific Rise. The Southern Ocean is known to be a region of high deep-sea species diversity and centre of origin for the global deep-sea fauna. It has also been proposed as a gateway connecting hydrothermal vents in different oceans but is little explored because of extreme conditions. Since 2009 we have explored two segments of the East Scotia Ridge (ESR) in the Southern Ocean using a remotely operated vehicle. In each segment we located deep-sea hydrothermal vents hosting high-temperature black smokers up to 382.8°C and diffuse venting. The chemosynthetic ecosystems hosted by these vents are dominated by a new yeti crab (Kiwa n. sp.), stalked barnacles, limpets, peltospiroid gastropods, anemones, and a predatory sea star. Taxa abundant in vent ecosystems in other oceans, including polychaete worms (Siboglinidae), bathymodiolid mussels, and alvinocaridid shrimps, are absent from the ESR vents. These groups, except the Siboglinidae, possess planktotrophic larvae, rare in Antarctic marine invertebrates, suggesting that the environmental conditions of the Southern Ocean may act as a dispersal filter for vent taxa. Evidence from the distinctive fauna, the unique community structure, and multivariate analyses suggest that the Antarctic vent ecosystems represent a new vent biogeographic province. However, multivariate analyses of species present at the ESR and at other deep-sea hydrothermal vents globally indicate that vent biogeography is more complex than previously recognised.

Description: The ChEsSo research programme was funded by a NERC Consortium Grant (NE/DO1249X/1) and supported by the Census of Marine Life and the Sloan Foundation, and the Total Foundation for Biodiversity (Abyss 2100)(SVTH) all of which are gratefully acknowledged. We also acknowledge NSF grant ANT-0739675 (CG and TS), NERC PhD studentships NE/D01429X/1(LH, LM, CNR), NE/H524922/1(JH) and NE/F010664/1 (WDKR), a Cusanuswerk doctoral fellowship, and a Lesley & Charles Hilton-Brown Scholarship, University of St. Andrews (PHBS).

Description: © The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Geochimica et Cosmochimica Acta 139 (2014): 47-71, doi:10.1016/j.gca.2014.04.024.

Description: The East Scotia Ridge is an active back-arc spreading centre located to the west of the South Sandwich island arc in the Southern Ocean. Initial exploration of the ridge by deep-tow surveys provided the first evidence for hydrothermal activity in a back-arc setting outside of the western Pacific, and we returned in 2010 with a remotely operated vehicle to precisely locate and sample hydrothermal sites along ridge segments E2 and E9. Here we report the chemical and isotopic composition of high- and low-temperature vent fluids, and the mineralogy of associated high-temperature chimney material, for two sites at E2 (Dog’s Head and Sepia), and four sites at E9 (Black & White, Ivory Tower, Pagoda and Launch Pad). The chemistry of the fluids is highly variable between the ridge segments. Fluid temperatures were ∼350 °C at all vent sites except Black & White, which was significantly hotter (383 °C). End-member chloride concentrations in E2 fluids (532–536 mM) were close to background seawater (540 mM), whereas Cl in E9 fluids was much lower (98–220 mM) indicating that these fluids are affected by phase separation. Concentrations of the alkali elements (Na, Li, K and Cs) and the alkaline earth elements (Ca, Sr and Ba) co-vary with Cl, due to charge balance constraints. Similarly, concentrations of Mn and Zn are highest in the high Cl fluids but, by contrast, Fe/Cl ratios are higher in E9 fluids (3.8–8.1 × 10−3) than they are in E2 fluids (1.5–2.4 × 10−3) and fluids with lowest Cl have highest Cu. Although both ridge segments are magmatically inflated, there is no compelling evidence for input of magmatic gases to the vent fluids. Fluid δD values range from 0.2‰ to 1.5‰, pH values (3.02–3.42) are not especially low, and F concentrations (34.6–54.4 μM) are lower than bottom seawater (62.8 μM). The uppermost sections of conjugate chimney material from E2, and from Ivory Tower and Pagoda at E9, typically exhibit inner zones of massive chalcopyrite enclosed within an outer zone of disseminated sulphide, principally sphalerite and pyrite, in an anhydrite matrix. By contrast, the innermost part of the chimneys that currently vent fluids with lowest Cl (Black & White and Launch Pad), is dominated by anhydrite. By defining and assessing the controls on the chemical composition of these vent fluids, and associated mineralisation, this study provides new information for evaluating the significance of hydrothermal processes at back-arc basins for ocean chemistry and the formation of seafloor mineral deposits.

Description: This work was funded by the Natural Environment Research Council consortium grant NE/D01249X/1. C.R.G. acknowledges further support from the National Science Foundation’s Office of Polar Programs grant ANT-0739675. N.R.B. acknowledges funding from the National Sciences and Engineering Research Council of Canada, Ontario Ministry of Research and Innovation, and the Academic Development Fund at Western University.

Description: Constraints on the variability of chromium (Cr) isotopic compositions in the modern ocean are required to validate the use of Cr isotopic signatures in ancient authigenic marine sediments for reconstructing past levels of atmospheric and ocean oxygenation. This study presents dissolved Cr concentrations (Cr-T, where Cr-T = Cr(VI) + Cr(III)) and Cr isotope data (delta Cr-53) for shelf, slope and open ocean waters within the oxygen minimum zone (OMZ) of the eastern sub-tropical Atlantic Ocean. Although dissolved oxygen concentrations were as low as 44-90 mu mol kg(-1) in the core of the OMZ, there was no evidence for removal of Cr(VI). Nonetheless, there was significant variability in seawater delta Cr-53, with values ranging from 1.08 to 1.72 parts per thousand. Shelf Cr-T concentrations were slightly lower (2.21 +/- 0.07 nmol kg(-1)) than in open ocean waters at the same water depth (between 0 and 160 m, 2.48 +/- 0.07 nmol kg(-1)). The shelf waters also had higher delta Cr-53 values (1.41 +/- 0.14 parts per thousand compared to 1.18 +/- 0.05 parts per thousand for open ocean waters shallower than 160 m). This is consistent with partial reduction of Cr(VI) to Cr(III), with subsequent removal of isotopically light Cr(III) onto biogenic particles. We also provide evidence for input of relatively isotopically heavy Cr from sediments on the shelf. Intermediate and deep water masses (AAIW and NADW) show a rather limited range of delta Cr-53 values (1.19 +/- 0.09 parts per thousand) and inputs of Cr from remineralisation of organic material or re-oxidation of Cr (III) appear to be minimal. Authigenic marine precipitates deposited in deep water in the open ocean therefore have the potential to faithfully record seawater delta Cr-53, whereas archives of seawater delta Cr-53 derived from shelf sediments must be interpreted with caution.

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: The East Scotia subduction zone, located in the Atlantic sector of the Southern Ocean, hosts a number of hydrothermal sites in both back-arc and island-arc settings. High temperature (〉348 °C) ‘black smoker’ vents have been sampled at three locations along segments E2 and E9 of the East Scotia back-arc spreading ridge, as well as ‘white smoker’ (〈212 °C) and diffuse (〈28 °C) hydrothermal fluids from within the caldera of the Kemp submarine volcano. The composition of the endmember fluids (Mg = 0 mmol/kg) is markedly different, with pH ranging from 〈1 to 3.4, [Cl−] from ∼90 to 536 mM, [H2S] from 6.7 to ∼200 mM and [F−] from 35 to ∼1000 μM. All of the vent sites are basalt- to basaltic andesite-hosted, providing an ideal opportunity for investigating the geochemical controls on rare earth element (REE) behaviour. Endmember hydrothermal fluids from E2 and E9 have total REE concentrations ranging from 7.3 to 123 nmol/kg, and chondrite-normalised distribution patterns are either light REE-enriched (LaCN/YbCN = 12.8–30.0) with a positive europium anomaly (EuCN/Eu∗CN = 3.45–59.5), or mid REE-enriched (LaCN/NdCN = 0.61) with a negative Eu anomaly (EuCN/Eu∗CN = 0.59). By contrast, fluids from the Kemp Caldera have almost flat REE patterns (LaCN/YbCN = 2.1–2.2; EuCN/Eu∗CN = 1.2–2.2). We demonstrate that the REE geochemistry of fluids from the East Scotia back-arc spreading ridge is variably influenced by ion exchange with host minerals, phase separation, competitive complexation with ligands, and anhydrite deposition, whereas fluids from the Kemp submarine volcano are also affected by the injection of magmatic volatiles which enhances the solubility of all the REEs. We also show that the REE patterns of anhydrite deposits from Kemp differ from those of the present-day fluids, potentially providing critical information about the nature of hydrothermal activity in the past, where access to hydrothermal fluids is precluded.

Description: Widespread seepage of methane from seafloor sediments offshore Svalbard close to the landward limit of the gas hydrate stability zone (GHSZ) may, in part, be driven by hydrate destabilization due to bottom water warming. To assess whether this methane reaches the atmosphere where it may contribute to further warming, we have undertaken comprehensive surveys of methane in seawater and air on the upper slope and shelf region. Near the GHSZ limit at ∼400 m water depth, methane concentrations are highest close to the seabed, reaching 825 nM. A simple box model of dissolved methane removal from bottom waters by horizontal and vertical mixing and microbially mediated oxidation indicates that ∼60% of methane released at the seafloor is oxidized at depth before it mixes with overlying surface waters. Deep waters are therefore not a significant source of methane to intermediate and surface waters; rather, relatively high methane concentrations in these waters (up to 50 nM) are attributed to isopycnal turbulent mixing with shelf waters. On the shelf, extensive seafloor seepage at 〈100 m water depth produces methane concentrations of up to 615 nM. The diffusive flux of methane from sea to air in the vicinity of the landward limit of the GHSZ is ∼4-20 μmol m-2 d-1, which is small relative to other Arctic sources. In support of this, analyses of mole fractions and the carbon isotope signature of atmospheric methane above the seeps do not indicate a significant local contribution from the seafloor source.

Description: Large quantities of methane are stored in hydrates and permafrost within shallow marine sediments in the Arctic Ocean. These reservoirs are highly sensitive to climate warming, but the fate of methane released from sediments is uncertain. Here, we review the principal physical and biogeochemical processes that regulate methane fluxes across the seabed, the fate of this methane in the water column, and potential for its release to the atmosphere. We find that, at present, fluxes of dissolved methane are significantly moderated by anaerobic and aerobic oxidation of methane. If methane fluxes increase then a greater proportion of methane will be transported by advection or in the gas phase, which reduces the efficiency of the methanotrophic sink. Higher freshwater discharge to Arctic shelf seas may increase stratification and inhibit transfer of methane gas to surface waters, although there is some evidence that increased stratification may lead to warming of sub-pycnocline waters, increasing the potential for hydrate dissociation. Loss of sea-ice is likely to increase wind speeds and seaair exchange of methane will consequently increase. Studies of the distribution and cycling of methane beneath and within sea ice are limited, but it seems likely that the sea-air methane flux is higher during melting in seasonally ice-covered regions. Our review reveals that increased observations around especially the anaerobic and aerobic oxidation of methane, bubble transport, and the effects of ice cover, are required to fully understand the linkages and feedback pathways between climate warming and release of methane from marine sediments.