Barium isotopes in mid-ocean ridge hydrothermal vent fluids : a source of isotopically heavy Ba to the ocean

Funding: These field and related experimental studies were supported through US NSF grants: 0549547, 0751771, 0813861, 0961188 and 1736679 (WES).Mid-ocean ridge (MOR) hydrothermal vent fluids are enriched with dissolved barium, but due to barite (BaSO4) precipitation during mixing between Ba-bearing vent fluids and SO4-bearing seawater, the magnitude of hydrothermal Ba input to the ocean remains uncertain. Deep-ocean Ba isotopes show evidence for non-conservative behavior, which might be explained by input of isotopically heavy hydrothermal Ba. In this study we present the first Ba isotope data in mid-ocean ridge hydrothermal vent fluids and particles from systems on the Mid-Atlantic Ridge (Rainbow 36°N and TAG 26°N), the East Pacific Rise (EPR9–10°N and 13°N) and the Juan de Fuca Ridge (MEF and ASHES). The vent fluids display a wide range of dissolved Ba concentrations from 0.43 to 97.9 μmol/kg and δ138/134Ba values from −0.26 to +0.91‰, but are modified relative to initial composition due to precipitation of barite. Calculated endmember vent fluid δ138/134Ba values, prior to barite precipitation, are between −0.17 and +0.09‰, consistent with the values observed in oceanic basalts and pelagic sediments. Water-rock interaction at depth in the oceanic crust appears to occur without Ba isotope fractionation. During subsequent venting and mixing with seawater, barite precipitation preferentially removes isotopically light Ba from vent fluids with a fractionation factor of Δ138/134Bahyd-barite-fluid = −0.35 ± 0.10‰ (2SE, n = 2). Based on knowledge of barite saturation and isotope fractionation during precipitation, the effective hydrothermal Ba component that mixes with seawater after barite precipitation has completed can be calculated: δ138/134Bahyd = +1.7 ± 0.7‰ (2SD). This value is isotopically heavier than deep ocean waters and may explain the observed non-conservative of Ba isotopes in deep waters. These new constraints on hydrothermal Ba compositions enable the hydrothermal input of Ba to Atlantic deep waters to be assessed at ≈3–9% of the observed Ba. Barium isotopes might be used as a tracer to reconstruct the history of hydrothermal Ba inputs and seawater SO4 concentrations in the past.PostprintPeer reviewe

Crystal-Chemical Origins of the Ultrahigh Conductivity of Metallic Delafossites

Despite their highly anisotropic complex-oxidic nature, certain delafossite compounds (e.g., PdCoO2, PtCoO2) are the most conductive oxides known, for reasons that remain poorly understood. Their room-temperature conductivity can exceed that of Au, while their low-temperature electronic mean-free-paths reach an astonishing 20 microns. It is widely accepted that these materials must be ultrapure to achieve this, although the methods for their growth (which produce only small crystals) are not typically capable of such. Here, we first report a new approach to PdCoO2 crystal growth, using chemical vapor transport methods to achieve order-of-magnitude gains in size, the highest structural qualities yet reported, and record residual resistivity ratios (>440). Nevertheless, the first detailed mass spectrometry measurements on these materials reveal that they are not ultrapure, typically harboring 100s-of-parts-per-million impurity levels. Through quantitative crystal-chemical analyses, we resolve this apparent dichotomy, showing that the vast majority of impurities are forced to reside in the Co-O octahedral layers, leaving the conductive Pd sheets highly pure (~1 ppm impurity concentrations). These purities are shown to be in quantitative agreement with measured residual resistivities. We thus conclude that a previously unconsidered "sublattice purification" mechanism is essential to the ultrahigh low-temperature conductivity and mean-free-path of metallic delafossites

Deep high-temperature hydrothermal circulation in a detachment faulting system on the ultra-slow spreading ridge

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Tao, C., Seyfried, W. E., Jr., Lowell, R. P., Liu, Y., Liang, J., Guo, Z., Ding, K., Zhang, H., Liu, J., Qiu, L., Egorov, I., Liao, S., Zhao, M., Zhou, J., Deng, X., Li, H., Wang, H., Cai, W., Zhang, G., Zhou, H., Lin, J., & Li, W. Deep high-temperature hydrothermal circulation in a detachment faulting system on the ultra-slow spreading ridge. Nature Communications, 11(1), (2020): 1300, doi:10.1038/s41467-020-15062-w.Coupled magmatic and tectonic activity plays an important role in high-temperature hydrothermal circulation at mid-ocean ridges. The circulation patterns for such systems have been elucidated by microearthquakes and geochemical data over a broad spectrum of spreading rates, but such data have not been generally available for ultra-slow spreading ridges. Here we report new geophysical and fluid geochemical data for high-temperature active hydrothermal venting at Dragon Horn area (49.7°E) on the Southwest Indian Ridge. Twin detachment faults penetrating to the depth of 13 ± 2 km below the seafloor were identified based on the microearthquakes. The geochemical composition of the hydrothermal fluids suggests a long reaction path involving both mafic and ultramafic lithologies. Combined with numerical simulations, our results demonstrate that these hydrothermal fluids could circulate ~ 6 km deeper than the Moho boundary and to much greater depths than those at Trans-Atlantic Geotraverse and Logachev-1 hydrothermal fields on the Mid-Atlantic Ridge.This work was supported by National Key R&D Program of China under contract no. 2018YFC0309901, 2017YFC0306603, 2017YFC0306803, and 2017YFC0306203, COMRA Major Project under contract No. DY135-S1-01-01 and No. DY135-S1-01-06

Kinetics of H2–O2–H2O redox equilibria and formation of metastable H2O2 under low temperature hydrothermal conditions

Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 75 (2011): 1594-1607, doi:10.1016/j.gca.2010.12.020.Hydrothermal experiments were conducted to evaluate the kinetics of H2(aq) oxidation in the homogeneous H2-O2-H2O system at conditions reflecting subsurface/near-seafloor hydrothermal environments (55-250 oC and 242-497 bar). The kinetics of the water-forming reaction that controls the fundamental equilibrium between dissolved H2(aq) and O2(aq), are expected to impose significant constraints on the redox gradients that develop when mixing occurs between oxygenated seawater and high- temperature anoxic vent fluid at near-seafloor conditions. Experimental data indicate that, indeed, the kinetics of H2(aq)-O2(aq) equilibrium become slower with decreasing temperature, allowing excess H2(aq) to remain in solution. Sluggish reaction rates of H2(aq) oxidation suggest that active microbial populations in near-seafloor and subsurface environments could potentially utilize both H2(aq) and O2(aq), even at temperatures lower than 40 oC due to H2(aq) persistence in the seawater/vent fluid mixtures. For these H2-O2 disequilibrium conditions, redox gradients along the seawater/hydrothermal fluid mixing interface are not sharp and microbially-mediated H2(aq) oxidation coupled with a lack of other electron acceptors (e.g. nitrate) could provide an important energy source available at low-temperature diffuse flow vent sites. More importantly, when H2(aq)-O2(aq) disequilibrium conditions apply, formation of metastable hydrogen peroxide is observed. The yield of H2O2(aq) synthesis appears to be enhanced under conditions of elevated H2(aq)/O2(aq) molar ratios that correspond to abundant H2(aq) concentrations. Formation of metastable H2O2 is expected to affect the distribution of dissolved organic carbon (DOC) owing to the existence of an additional strong oxidizing agent. Oxidation of magnetite and/or Fe++ by hydrogen peroxide could also induce formation of metastable hydroxyl radicals (•OH) through Fenton-type reactions, further broadening the implications of hydrogen peroxide in hydrothermal environments.This research was conducted with partial support from the NSF OCE-0752221 and the Geophysical Laboratory Postdoctoral Fellowship. We would also like to acknowledge contributions by the W.M. Keck Foundation and Shell towards supporting the hydrothermal lab at the Geophysical Lab. SMS acknowledges support from NSF OCE-0452333 and the Alfried-Krupp Wissenschaftskolleg Greifswald (Germany), while WES acknowledges support from NSF grants OCE-0549457 and OCE- 0813861

Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics Progress Report

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory-measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between lab and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO{sub 2} injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the first year of the project, we have successfully developed a sample preparation method and completed three batch feldspar dissolution experiments at 200 C and 300 bars. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and pressure. These data allow calculating overall apparent feldspar dissolution rates and secondary mineral precipitation rates as a function of saturation states. State-of-the-art atomic resolution transmission electron microscopy (TEM), scanning electron microscopy, and electron microprobe was used to characterize the reactants (feldspars before experiments). We experimented with different sample preparation methods for TEM study, and found excellent images and chemical resolution with reactants, which shows promise of the technology and establishes the baseline for comparison with products (feldspars after the experiments). Preliminary electron microscopic characterization shows that the reacted feldspars have etch pits and are covered with secondary sheet silicate phases. Reaction-path geochemical modeling is used to interpret the experimental results. We have established the software and database, and are making great progress. Also during the first year, our education goal of graduate student training has been achieved. A Ph. D. student at Indiana University is progressing well in the degree program and has taken geochemical modeling, SEM, and TEM courses, which will facilitate research in the second and third year. A Ph. D. student at University of Minnesota is progressing well in conducting the experiments, and is near graduation. With the success of training of graduate students and excellent experimental data in the first year, we anticipate a more fruitful year in the second year

Geochemistry, description and mineralogy of sediments at DSDP Holes 92-597B and 92-597C

B, Li, and other trace elements were analyzed in samples from 12 celadonite and smectite-rich veins from oxidative and non-oxidative alteration zones in basalts from Holes 597B and 597C. The oxidative alteration zones are characterized by celadonite and Fe-oxyhydroxide and conspicuously high K, Rb, and B concentrations. In contrast, the non-oxidative alteration zones are characterized by Mg-rich smectite (saponite), talc, and calcite and high Li concentrations. Neither B nor Li reaches high concentrations in high-Al high-Ti veins that appear to have formed by replacement of basalt. B, Li, and Rb enrichments in vein assemblages of low-temperature origin reflect an important removal mechanism from seawater for these species. The alteration zones characterized by Mg-smectite and talc are strikingly enriched in Ni. There is a correlation between the Ni-enriched smectite and the presence of olivine in the host basalt; the correlation indicates that olivine alteration may be the source of the Ni. Other transition elements, including Cr, Mn, Co, Cu, and Zn, are often found in significant concentrations in the celadonite and high-Mg smectite veins, but their enrichments are neither as large nor as consistent as the enrichment of Ni in the Mg-smectite veins. Two high-Al, high-Ti vein assemblages of smectite and noncrystalline phases have transition element abundances similar to those of the host basalts but are relatively depleted in Cu and Cr. The material in these veins may have formed by replacement with concomitant release of Cu and Cr to circulating aqueous fluids