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: Highlights • Calcification fluid pH and [precipitating DIC] are positively correlated in all corals. • [Precipitating DIC] and coral calcification rate are positively correlated in all but one outlier coral. • Corals cultured at high seawater pCO2 usually have low fluid pH and [precipitating DIC]. • Maintaining high [precipitating DIC] at high seawater pCO2 is at the expense of other calcification processes. Abstract Ocean acidification typically reduces calcification in tropical marine corals but the mechanism for this process is not understood. We use skeletal boron geochemistry (B/Ca and δ11B) to reconstruct the calcification fluid DIC of corals cultured over both high and low seawater pCO2 (180, 400 and 750 μatm). We observe strong positive correlations between calcification fluid pH and concentrations of the DIC species potentially implicated in aragonite precipitation (be they CO32−, HCO3− or HCO3− + CO32−). Similarly, with the exception of one outlier, the fluid concentrations of precipitating DIC species are strongly positively correlated with coral calcification rate. Corals cultured at high seawater pCO2 usually have low calcification fluid pH and low concentrations of precipitating DIC, suggesting that a reduction in DIC substrate at the calcification site is responsible for decreased calcification. The outlier coral maintained high pHCF and DICCF at high seawater pCO2 but exhibited a reduced calcification rate indicating that the coral has a limited energy budget to support proton extrusion from the calcification fluid and meet other calcification demands. We find no evidence that increasing seawater pCO2 enhances diffusion of CO2 into the calcification site. Instead the overlying [CO2] available to diffuse into the calcification site appears broadly comparable between seawater pCO2 treatments, implying that metabolic activity (respiration and photosynthesis) generates a similar [CO2] in the vicinity of the calcification site regardless of seawater pCO2.

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.