Investigation of extractable organic compounds in deep-sea hydrothermal vent fluids along the Mid-Atlantic Ridge

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 156 (2015): 122-144, doi:10.1016/j.gca.2015.02.022.The possibility that deep-sea hydrothermal vents may contain organic compounds produced by abiotic synthesis or by microbial communities living deep beneath the surface has led to numerous studies of the organic composition of vent fluids. Most of these studies have focused on methane and other light hydrocarbons, while the possible occurrence of more complex organic compounds in the fluids has remained largely unstudied. To address this issue, the presence of higher molecular weight organic compounds in deep-sea hydrothermal fluids was assessed at three sites along the Mid-Atlantic Ridge that span a range of temperatures (51 to >360 °C), fluid compositions, and host-rock lithologies (mafic to ultramafic). Sample were obtained at several sites within the Lucky Strike, Rainbow, and Lost City hydrothermal fields. Three methods were employed to extract organic compounds for analysis, including liquid:liquid extraction, cold trapping on the walls of a coil of titanium tubing, and pumping fluids through cartridges filled with solid phase extraction (SPE) sorbents. The only samples to consistently yield high amounts of extractable organic compounds were the warm (51-91 °C), highly alkaline fluids from Lost City, which contained elevated concentrations of C8, C10, and C12 n-alkanoic acids and, in some cases, trithiolane, hexadecanol, squalene, and cholesterol. Collectively, the C8-C12 acids can account for about 15% of the total dissolved organic carbon in the Lost City fluids. The even-carbon-number predominance of the alkanoic acids indicates a biological origin, but it is unclear whether these compounds are derived from microbial activity occurring within the hydrothermal chimney proximal to the site of fluid discharge or are transported from deeper within the system. Hydrothermal fluids from the Lucky Strike and Rainbow fields were characterized by an overall scarcity of extractable dissolved organic compounds. Trace amounts of aromatic hydrocarbons including phenanthrenes and benzothiophene were the only compounds that could be identified as indigenous components of these fluids. Although hydrocarbons and fatty acids were observed in some samples, those compounds were likely derived from particulate matter or biomass entrained during fluid collection. In addition, extracts of some fluid samples from the Rainbow field were found to contain an unresolved complex mixture (UCM) of organic compounds. This UCM shared some characteristics with organic matter extracted from bottom seawater, suggesting that the organic matter observed in these samples might represent seawater-derived compounds that had persisted, albeit with partial alteration, during circulation through the hydrothermal system. While there is considerable evidence that Rainbow and Lost City vent fluids contain methane and other light hydrocarbons produced through abiotic reduction of inorganic carbon, we found no evidence for more complex organic compounds with an abiotic origin in the same fluids.This research was supported by the NSF Ocean Sciences directorate through grants MGG-OCE 0550800 to T.M.M. and MGG-OCE 0549829 to J.S.S. and C.R.G

Flow measurement using micro-PIV and related temperature distributions within evaporating sessile drops of self-rewetting mixtures of 1-pentanol and water

This paper was presented at the 4th Micro and Nano Flows Conference (MNF2014), which was held at University College, London, UK. The conference was organised by Brunel University and supported by the Italian Union of Thermofluiddynamics, IPEM, the Process Intensification Network, the Institution of Mechanical Engineers, the Heat Transfer Society, HEXAG - the Heat Exchange Action Group, and the Energy Institute, ASME Press, LCN London Centre for Nanotechnology, UCL University College London, UCL Engineering, the International NanoScience Community, www.nanopaprika.eu.Recently interest has arisen in the use of so-called self-rewetting mixtures for micro-scale heat transfer systems. Such fluids, in which the surface tension can increase with increasing temperature, are expected to offer superior evaporative cooling performance by extending the region of operation before dryout of the heated surface sets in. Whilst improved performance has been shown in some practical situations using these fluids, it is not entirely clear as to the mechanism of such improvements. We have studied the flow within evaporating sessile drops of 1-pentanol-water mixtures using micro-PIV and have observed three stages in the evaporation process. During the first stage there appears to be a single toroidal vortex with flow inwards along the base of the drop. The vortex only occupies the central region of the drop and appears to pulsate, reducing in size during evaporation. This is followed by a second transition stage to a third stage in which the flow is directed radially outward, as observed by us for pure water droplet evaporation and in the latter stages of ethanol/water drop evaporation. Temperature measurements, using IR thermography suggest that the initial stage of evaporation may be controlled by thermal Marangoni effects as opposed to the concentration driven Marangoni flows postulated for ethanol-water mixtures

Hydrogen and Oxygen Isotope Fractionation Between Brucite and Aqueous NaCl Solutions from 250 to 450°C

Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnαbr-sw) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18O/16O fractionation, 1000lnαbr-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18O/16O brucite-water fractionation factors from available calibrations of the salt-effect on 18O/16O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln αbr-w = 9.54 × 106T−2 − 3.53 × 104T−1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18O/16O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ18O composition of talc-brucite and serpentine-brucite pairs could be used as a geothermometer and that these coexisting phases should display the following order of 18O enrichment: talc \u3e serpentine \u3e brucite

Oxygen and hydrogen isotope fractionation in serpentine–water and talc–water systems from 250 to 450°C MPa

Oxygen and hydrogen isotope fractionation factors in the talc–water and serpentine–water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D–H exchange was much more rapid than 18O–16O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of 18O–16O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc–water and serpentine–water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln = 11.70 × 106/T2 − 25.49 × 103/T + 12.48 and 1000 ln = 3.49 × 106/T2 − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc–water D–H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 106/T2 − 41.52 × 103/T + 5.61 where T is temperature in Kelvin. Our D–H serpentine–water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D–H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln = 3.436 × 106/T2 − 34.736 × 103/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D–H and 18O–16O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings

Observations of bubbles in natural seep flares at MC 118 and GC 600 using in situ quantitative imaging

Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 121 (2016): 2203–2230, doi:10.1002/2015JC011452.This paper reports the results of quantitative imaging using a stereoscopic, high-speed camera system at two natural gas seep sites in the northern Gulf of Mexico during the Gulf Integrated Spill Research G07 cruise in July 2014. The cruise was conducted on the E/V Nautilus using the ROV Hercules for in situ observation of the seeps as surrogates for the behavior of hydrocarbon bubbles in subsea blowouts. The seeps originated between 890 and 1190 m depth in Mississippi Canyon block 118 and Green Canyon block 600. The imaging system provided qualitative assessment of bubble behavior (e.g., breakup and coalescence) and verified the formation of clathrate hydrate skins on all bubbles above 1.3 m altitude. Quantitative image analysis yielded the bubble size distributions, rise velocity, total gas flux, and void fraction, with most measurements conducted from the seafloor to an altitude of 200 m. Bubble size distributions fit well to lognormal distributions, with median bubble sizes between 3 and 4.5 mm. Measurements of rise velocity fluctuated between two ranges: fast-rising bubbles following helical-type trajectories and bubbles rising about 40% slower following a zig-zag pattern. Rise speed was uncorrelated with hydrate formation, and bubbles following both speeds were observed at both sites. Ship-mounted multibeam sonar provided the flare rise heights, which corresponded closely with the boundary of the hydrate stability zone for the measured gas compositions. The evolution of bubble size with height agreed well with mass transfer rates predicted by equations for dirty bubbles.Gulf of Mexico Research Initiativ

Dissolved organic carbon compounds in deep-sea hydrothermal vent fluids from the East Pacific Rise at 9°50′N

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 125 (2018): 41-49, doi:10.1016/j.orggeochem.2018.08.004.Deep-sea hydrothermal vents are unique ecosystems that may release chemically distinct dissolved organic matter to the deep ocean. Here, we describe the composition and concentrations of polar dissolved organic compounds observed in low and high temperature hydrothermal vent fluids at 9°50’N on the East Pacific Rise. The concentration of dissolved organic carbon was 46 μM in the low temperature hydrothermal fluids and 14 μM in the high temperature hydrothermal fluids. In the low temperature vent fluids, quantifiable dissolved organic compounds were dominated by water-soluble vitamins and amino acids. Derivatives of benzoic acid and the organic sulfur compound 2,3-dihydroxypropane-1-sulfonate (DHPS) were also present in low and high temperature hydrothermal fluids. The low temperature vent fluids contain organic compounds that are central to biological processes, suggesting that they are a by-product of biological activity in the subseafloor. These compounds may fuel heterotrophic and other metabolic processes at deep-sea hydrothermal vents and beyond.This project was funded by a grant from WHOI’s Deep Ocean Exploration Institute and WHOI’s Ocean Ridge Initiative (to EBK and SMS) and by NSF OCE-1154320 (to EBK and KL), OCE- 1136727 (to SMS and JSS), and OCE 1131095 (to SMS)

Clumped isotopologue constraints on the origin of methane at seafloor hot springs

Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 223 (2018): 141-158, doi:10.1016/j.gca.2017.11.030.Hot-spring fluids emanating from deep-sea vents hosted in unsedimented ultramafic and mafic rock commonly contain high concentrations of methane. Multiple hypotheses have been proposed for the origin(s) of this methane, ranging from synthesis via reduction of aqueous inorganic carbon (ΣCO2) during active fluid circulation to leaching of methane-rich fluid inclusions from plutonic rocks of the oceanic crust. To further resolve the process(es) responsible for methane generation in these systems, we determined the relative abundances of several methane isotopologues (including 13CH3D, a “clumped” isotopologue containing two rare isotope substitutions) in hot-spring source fluids sampled from four geochemically-distinct hydrothermal vent fields (Rainbow, Von Damm, Lost City, and Lucky Strike). Apparent equilibrium temperatures retrieved from methane clumped isotopologue analyses average 310−42 +53 °C, with no apparent relation to the wide range of fluid temperatures (96 to 370 °C) and chemical compositions (pH, [H2], [ΣCO2], [CH4]) represented. Combined with very similar bulk stable isotope ratios (13C/12C and D/H) of methane across the suite of hydrothermal fluids, all available geochemical and isotopic data suggest a common mechanism of methane generation at depth that is disconnected from active fluid circulation. Attainment of equilibrium amongst methane isotopologues at temperatures of ca. 270 to 360 °C is compatible with the thermodynamically-favorable reduction of CO2 to CH4 at temperatures at or below ca. 400 °C under redox conditions characterizing intrusive rocks derived from sub-ridge melts. Collectively, the observations support a model where methane-rich aqueous fluids, known to be trapped in rocks of the oceanic lithosphere, are liberated from host rocks during hydrothermal circulation and perhaps represent the major source of methane venting with thermal waters at unsedimented hydrothermal fields. The results also provide further evidence that water-rock reactions occurring at temperatures lower than 200 °C do not contribute significantly to the quantities of methane venting at mid-ocean ridge hot springs.Financial support from the U.S. National Science Foundation (NSF awards EAR-1250394 to S.O., and OCE-1061863 and OCE-0549829 to J.S.S.), the National Aeronautics and Space Administration (NASA) (NNX-327 09AB75G to J.S.S., and the NASA Astrobiology Institute “Rock- Powered Life” project under cooperative agreement NNA15BB02A to S.O.), the Alfred P. Sloan Foundation via the Deep Carbon Observatory (to S.O. and J.S.S.), the U.S. Department of Defense (DoD) through a National Defense Science & Engineering Graduate (NDSEG) Fellowship (to D.T.W.), a Shell-MIT Energy Initiative Fellowship, and the Kerr-McGee Professorship at MIT (to S.O.) is gratefully acknowledged

Cloud condensation nucleus activity comparison of dry- and wet-generated mineral dust aerosol: the significance of soluble material

This study examines the interaction of clay mineral particles and water vapor for determining the conditions required for cloud droplet formation. Droplet formation conditions are investigated for two common clay minerals, illite and sodium-rich montmorillonite, and an industrially derived sample, Arizona Test Dust. Using wet and dry particle generation coupled to a differential mobility analyzer (DMA) and cloud condensation nuclei counter, the critical activation of the clay mineral particles as cloud condensation nuclei is characterized. Electron microscopy (EM) is used in order to determine non-sphericity in particle shape. It is also used in order to determine particle surface area and account for transmission of multiply charged particles by the DMA. Single particle mass spectrometry and ion chromatography are used to investigate soluble material in wet-generated samples and demonstrate that wet and dry generation yield compositionally different particles. Activation results are analyzed in the context of both κ-Köhler theory (κ-KT) and Frenkel–Halsey–Hill (FHH) adsorption activation theory. This study has two main results: (1) κ-KT is the suitable framework to describe clay mineral nucleation activity. Apparent differences in κ with respect to size arise from an artifact introduced by improper size-selection methodology. For dust particles with mobility sizes larger than ~300 nm, i.e., ones that are within an atmospherically relevant size range, both κ-KT and FHH theory yield similar critical supersaturations. However, the former requires a single hygroscopicity parameter instead of the two adjustable parameters required by the latter. For dry-generated particles, the size dependence of κ is likely an artifact of the shape of the size distribution: there is a sharp drop-off in particle concentration at ~300 nm, and a large fraction of particles classified with a mobility diameter less than ~300 nm are actually multiply charged, resulting in a much lower critical supersaturation for droplet activation than expected. For wet-generated particles, deviation from κ-KT is likely a result of the dissolution and redistribution of soluble material. (2) Wet generation is found to be unsuitable for simulating the lofting of fresh dry dust because it changes the size-dependent critical supersaturations by fractionating and re-partitioning soluble material.United States. National Oceanic and Atmospheric Administration. Climate Program Office (award number NA11OAR4310159