Geochemistry of fluids from Earth's deepest ridge-crest hot-springs: Piccard hydrothermal field, Mid-Cayman Rise

Hosted in basaltic substrate on the ultra-slow spreading Mid-Cayman Rise, the Piccard hydrothermal field is the deepest currently known seafloor hot-spring (4957-4987 m). Due to its great depth, the Piccard site is an excellent natural system for investigating the influence of extreme pressure on the formation of submarine vent fluids. To investigate the role of rock composition and deep circulation conditions on fluid chemistry, the abundance and isotopic composition of organic, inorganic, and dissolved volatile species in high temperature vent fluids at Piccard were examined in samples collected in 2012 and 2013. Fluids from the Beebe Vents and Beebe Woods black smokers vent at a maximum temperature of 398 degrees C at the seafloor, however several lines of evidence derived from inorganic chemistry (Cl, SiO2, Ca, Br, Fe, Cu, Mn) support fluid formation at much higher temperatures in the subsurface. These high temperatures, potentially in excess of 500 degrees C, are attainable due to the great depth of the system. Our data indicate that a single deep-rooted source fluid feeds high temperature vents across the entire Piccard field. High temperature Piccard fluid H-2 abundances (19.9 mM) are even higher than those observed in many ultramafic-influenced systems, such as the Rainbow (16 mM) and the Von Damm hydrothermal fields (18.2 mM). In the case of Piccard, however, these extremely high H2 abundances can be generated from fluid-basalt reaction occurring at very high temperatures. Magmatic and thermogenic sources of carbon in the high temperature black smoker vents are described. Dissolved Sigma CO2 is likely of magmatic origin, CH4 may originate from a combination of thermogenic sources and leaching of abiotic CH4 from mineral-hosted fluid inclusions, and CO abundances are at equilibrium with the water-gas shift reaction. Longer-chained nalkanes (C2H6, C3H8, n-C4H10, i-C4H10) may derive from thermal alteration of dissolved and particulate organic carbon sourced from the original seawater source, entrainment of microbial ecosystems peripheral to high temperature venting, and/or abiotic mantle sources. Dissolved Sigma HCOOH in the Beebe Woods fluid is consistent with thermodynamic equilibrium for abiotic production via Sigma CO2 reduction with H2 at 354 degrees C measured temperature. A lack of Sigma HCOOH in the relatively higher temperature 398 degrees C Beebe Vent fluids demonstrates the temperature sensitivity of this equilibrium. Abundant basaltic seafloor outcrops and the axial location of the vent field, along with multiple lines of geochemical evidence, support extremely high temperature fluid-rock reaction with mafic substrate as the dominant control on Piccard fluid chemistry. These results expand the known diversity of vent fluid composition, with implications for supporting microbiological life in both the modern and ancient ocean. (C) 2018 Elsevier Ltd. All rights reserved.