An empirical model has been developed to depict the ionic strength of concentrated NaCl aqueous solutions at high temperatures and pressures. The model adopts the solvation properties of electrolyte-bearing aqueous solutions that link ionic strength with relative permittivity:

A series of hydrothermal diamond anvil cell experiments was conducted to constrain the effect of anions (Cl-, F-) and cations (Mg+2, Na+) on the molecular structure of high temperature/-pressure fluids, and to express the extent of hydration as a function of solute's speciation and concentration at temperatures ranging from 400 to 800 degrees C and pressures of 1.7 to 30.1 kbar. Results reveal that hydrogen-bonding environments for H2O molecules in the first hydration shell of anions evolve from pure O-H center dot center dot center dot O to dynamic mixtures with O-H center dot center dot center dot X- (F-, Cl-). The distribution of the "O-H center dot center dot center dot X-" structures (O-H center dot center dot center dot O, O-H center dot center dot center dot X-) is proportional to the concentration of dissolved anions; strongly dependent, however, on ionic speciation. To this end, the O-H center dot center dot center dot O structures inside the hydration shell of F- are weaker than the O-H center dot center dot center dot Cl- and O-H center dot center dot center dot O in Cl- bearing solutions. On the contrary, cations (Na+, Mg2+) appear to impose a minimal effect on the Raman spectra of the O-H center dot center dot center dot O structures. The thermodynamic stability of "O-H center dot center dot center dot Cl-" environments shows a strong correlation with the activity of H2O, indicative of the localized effect of the C-l electric field that decouples the hydration from the bulk water molecules. The enthalpy change required to rupture these H-bonding environments (Delta HO-H center dot center dot center dot Cl-) provides a measure for the extent of ion hydration and constrains the solvation properties of supercritical electrolyte solutions. For example, the dominant presence of "O-H center dot center dot center dot Cl-" environments lowers the concentration of isolated water dipoles and contributes to the decrease in the dielectric constant of supercritical electrolyte solutions, which in turn, could suppress the solubility of hydrophobic non-polar aqueous species, such as SiO2(aq). (C) 2016 Elsevier B.V. All rights reserved.

NO3- reduction is a metabolism that is widespread among epsilon-Proteobacteria and Aquificae, two abundant classes of microorganisms found at deep-sea vents. In this study, we used Sulfurovum lithotrophicum, Caminibacter mediatlanticus and Thermovibrio ammonificans as representatives of these groups to study ecophysiological, metabolic and biogeochemical parameters associated with chemolithoautotrophic NO3- reduction under different temperature regimes. We observed that while S. lithotrophicum and C. mediatlanticus achieved higher cell densities than T. ammonificans, the overall NO3- consumption by the latter was on average similar to 9 and similar to 5 times faster on a per cell basis, respectively. Comparison with previously published data from other cultured vent epsilon-Proteobacteria and Aquificae suggests that the rate-yield trade-offs observed in our experiments are generally conserved between these two groups in line with their ecophysiologies. Kinetic isotope effects of N from NO3- reduction were 9.6 +/- 2.7 parts per thousand for S. lithotrophicum, 6.4 +/- 0.7 parts per thousand for C. mediatlanticus and 8.8 +/- 0.6 parts per thousand for T. ammonificans. Our results help evaluate how metabolic partitioning between growth efficiency and reaction kinetics during chemolithoautotrophic NO3- reduction affect the concentration and isotope composition of N compounds at deep-sea hydrothermal vents. (C) 2017 Elsevier Ltd. All rights reserved.

Microbial sulfur cycling in marine sediments often occurs in environments characterized by transient chemical gradients that affect both the availability of nutrients and the activity of microbes. High turnover rates of intermediate valence sulfur compounds and the intermittent availability of oxygen in these systems greatly impact the activity of sulfur-oxidizing micro-organisms in particular. In this study, the thiosulfate-oxidizing hydrothermal vent bacterium Thiomicrospira thermophila strain EPR85 was grown in continuous culture at a range of dissolved oxygen concentrations (0.04-1.9 mM) and high pressure (5-10 MPa) in medium buffered at pH 8. Thiosulfate oxidation under these conditions produced tetrathionate, sulfate, and elemental sulfur, in contrast to previous closed-system experiments at ambient pressure during which thiosulfate was quantitatively oxidized to sulfate. The maximum observed specific growth rate at 5 MPa pressure under unlimited O-2 was 0.25 hr(-1). This is comparable to the mu(max) (0.28 hr(-1)) observed at low pH (<6) at ambient pressure when T. thermophila produces the same mix of sulfur species. The half-saturation constant for O-2 (KO2) estimated from this study was 0.2 mM (at a cell density of 10(5) cells/ml) and was robust at all pressures tested (0.4-10 MPa), consistent with piezotolerant behavior of this strain. The cell-specific KO2 was determined to be 1.5 pmol O-2/cell. The concentrations of products formed were correlated with oxygen availability, with tetrathionate production in excess of sulfate production at all pressure conditions tested. This study provides evidence for transient sulfur storage during times when substrate concentration exceeds cell-specific KO2 and subsequent consumption when oxygen dropped below that threshold. These results may be common among sulfur oxidizers in a variety of environments (e.g., deep marine sediments to photosynthetic microbial mats).

In this study, we integrated geochemical measurements, microbial diversity surveys and physiological characterization of laboratory strains to investigate substrate-attached filamentous microbial biofilms at Tor Caldara, a shallow-water gas vent in the Tyrrhenian Sea. At this site, the venting gases are mainly composed of CO2 and H2S and the temperature at the emissions is the same as that of the surrounding water. To investigate the composition of the total and active fraction of the Tor Caldara biofilm communities, we collected established and newly formed filaments and we sequenced the 16S rRNA genes (DNA) and the 16S rRNA transcripts (cDNA). Chemoautotrophic sulfur-oxidizing members of the Gammaproteobacteria (predominantly Thiotrichales) dominate the active fraction of the established microbial filaments, while Epsilonproteobacteria (predominantly Sulfurovum spp.) are more prevalent in the young filaments. This indicates a succession of the two communities, possibly in response to age, sulfide and oxygen concentrations. Growth experiments with representative laboratory strains in sulfide gradient medium revealed that Sulfurovum riftiae (Epsilonproteobacteria) grew closer to the sulfide source than Thiomicrospira sp. (Gammaproteobacteria, Thiotrichales). Overall, our findings show that sulfur-oxidizing Epsilonproteobacteria are the dominant pioneer colonizers of the Tor Caldara biofilm communities and that Gammaproteobacteria become prevalent once the community is established. This succession pattern appears to be driven - among other factors - by the adaptation of Epsilon- and Gammaproteobacteria to different sulfide concentrations.

Ultramafic-hosted hydrothermal vent systems link the hydrosphere with the peridotitic mantle via serpentinization. Here, the fractionation and mobility of selected trace (Nd, Sm, Gd, Dy, Yb, Sr and Ba) and major cations (Si, Ca, Mg, Fe, Ni) during seawater-peridotite interaction was investigated through a series of experiments where natural olivine grains were reacted with an artificial seawater solution at a range of temperatures (15-90 degrees C) and grain size distributions. No evidence for any significant olivine dissolution or precipitation of carbonate and, Fe-oxy-hydroxide phases was observed in these experiments. Experimental data show a strong decoupling of REE (Nd, Sm, Gd, Dy, and Yb) from Sr and Ba under all experimental conditions, with Sr and Ba remaining quantitatively in solution. The REE were removed from the solution and were adsorbed onto olivine surface with kinetic rate constants (i.e. uptake over time) that increase with increasing temperature and increasing surface area (i.e. decreasing particle size). Dysprosium and Yb (heavy REE; HREE) were removed from solution with a faster rate than Nd and Sm (light REE; LREE). Gadolinium is decoupled from this trend, with a slower kinetic rate constant than Sm. The activation energies (E-a) of REE adsorption on olivine were higher for Nd and Sm than Dy and Yb. This suggests that the adsorbance of LREE is generally more dependent on temperature than the HREE. The E-a correlates well with the summed 1st, 2nd and 3rd ionization energies of REE suggesting a link between kinetic rates of element adsorption and electron configuration of the 4f-orbitals. Gadolinium has higher Ea than the other analyzed REE, consistent with the electron configuration of Gd3+ where all 4f-orbitals are filled with one electron each. These experimental data suggest that REE are adsorbed on the surface of olivine via inner sphere complexes under low-temperature hydrothermal conditions, when alteration processes are limited or extremely slow. Scavenging and fractionation of REE may occur within the recharge zone of peridotite-hosted hydrothermal systems at relatively low temperatures (<100 degrees C), leading to fluids with progressively higher LREE/HREE which could impose seawater-derived LREE enrichments in serpentinized peridotites during high temperature, high pressure water/rock interaction deeper in the oceanic lithosphere. (C) 2019 Elsevier B.V. All rights reserved.

A series of hydrothermal diamond anvil cell experiments was conducted to investigate the mobility of Os and Ir in saline and oxidizing hydrothermal fluids as function of fluid pH at temperatures ranging from 500 degrees C to 1000 degrees C and pressures resembling upper mantle/lower crust environments (29-1343 MPa). The composition of reactant fluids was monitored in real time and at in situ conditions by Raman vibrational spectroscopy. Results revealed the formation of Os=O volatile aqueous species under oxidizing redox conditions (similar to+5 Delta FMQ) and at temperatures exceeding 850 degrees C. These species were detected in an immiscible phase separated from the homogeneous fluid at low pressure conditions (<150 MPa). Based on previous experimental and theoretical studies, the Os-bearing species observed in situ are attributed to the presence of OsO4(g). Volatile transport of Os in high temperature/pressure magmatic fluids, therefore, may include oxide aqueous species along with Os-Cl complexation. Possible evidence of Ir oxidation was provided by the formation of H-2(aq) in Ir-H2O experiments at 700-800 degrees C and pressures of 543-793 MPa. Experimental data support the role of slab-derived fluids in yielding elevated Os/Ir ratios in metasomatized xenoliths relative to primitive upper mantle composition through the enhanced mobility of Os in the form of Cl- and oxygen-bearing volatile aqueous complexes. (C) 2019 Elsevier Ltd. All rights reserved.

Understanding the viscosity of mantle-derived magmas is needed to model their migration mechanisms and ascent rate from the source rock to the surface. High pressure-temperature experimental data are now available on the viscosity of synthetic melts, pure carbonatitic to carbonate-silicate compositions, anhydrous basalts, dacites and rhyolites. However, the viscosity of volatile-bearing melilititic melts, among the most plausible carriers of deep carbon, has not been investigated. In this study, we experimentally determined the viscosity of synthetic liquids with 31 and 39 wt% SiO2, 1.60 and 1.42 wt% CO2 and 5.7 and 1 wt% H2O, respectively, at pressures from 1 to 4.7 GPa and temperatures between 1265 and 1755 degrees C, using the falling-sphere technique combined with in situ X-ray radiography. Our results show viscosities between 0.1044 and 2.1221 Pas, with a clear dependence on temperature and SiO2 content. The atomic structure of both melt compositions was also determined at high pressure and temperature, using in situ multi-angle energy-dispersive X-ray diffraction supported by ex situ microFTIR and microRaman spectroscopic measurements. Our results yield evidence that the T-T and T-O (T = Si,Al) interatomic distances of ultrabasic melts are higher than those for basaltic melts known from similar recent studies. Based on our experimental data, melilititic melts are expected to migrate at a rate from 2 to 57 kmyr(-1) in the present-day or the Archaean mantle, respectively.

The speciation of water dissolved into and reacted with hydrous alumino-silicate glasses (of NaAlSi3O8 and "rhyolitic" compositions) quenched from high temperature is re-investigated where the predominant species are expected to be "X(Si and Al)-OH" and "H2O". Only, two analytical methods are capable of assessing such speciation: Near InfraRed (NIR) spectroscopy and solid-state H-1 Nuclear Magnetic Resonance (NMR) spectroscopy. It is observed that the apparent water speciation, as a function of total water content, as determined by NIR spectroscopy is nearly the opposite from what the H-1 NMR data reveal. Deuterium (H-2) NMR and silicon (Si-29) NMR report consistent trends in apparent speciation (depolymerization) with those indicated by the H-1 NMR data. Compared with four previous NMR studies of hydrous NaAlSi3O8 glasses it is shown that whereas NIR data always report the same apparent systematic variation in the intensity of the 4500 ("X-OH") and 5200 ("H2O") cm(-1) bands with total water content, multiple H-1 NMR studies of hydrous NaAlSi3O8 report a wide range in OH/H2O. The discrepancy between the various NMR studies likely reflects differences in how the various glasses were made. Specifically, quench rate (fast or slow) and synthesis pressure (higher or lower), might impose a strong effect on observed water speciation in glasses via H-1 NMR. It is concluded that the application of NIR spectroscopy, specifically the use of the intensities of the 4500 ("X-OH") and 5200 ("H2O") cm(-1) NIR bands, does not provide an accurate assessment of water speciation in hydrous alumino-silicate glasses. NIR spectroscopy does remain a very valuable analytical tool for determination of total water content. (C) 2020 Elsevier Ltd. All rights reserved.

On September 12, 2019 at 12:49:48 (UT) a bolide was observed by hundreds of eye-witnesses from the Netherlands, Germany, Belgium, Denmark and the UK. One day later a small meteorite stone was found by accident in Flensburg. The presence of short-lived cosmogenic radionuclides with half-lives as short as 16 days proves the recent exposure of the found object to cosmic rays in space linking it clearly to the bolide event. An exceptionally short exposure time of similar to 5000 years was determined. The 24.5 g stone has a fresh black fusion crust, a low density of <2 g/cm(3), and a magnetic susceptibility of log chi = 4.35 (chi in 10(-9) m(3)/kg). The rock consists of relict chondrules and clusters of sulfide and magnetite grains set in a fine-grained matrix. The most abundant phases are phyllosilicates. Carbonates (similar to 3.9 vol.%) occur as calcites, dolomites, and a Na-rich phase. The relict chondrules (often surrounded by sulfide laths) are free of anhydrous silicates and contain abundant serpentine. Lithic clasts are also surrounded by similar sulfide laths partly intergrown with carbonates. Mn-53-Cr-53 ages of carbonates in Flensburg indicate that brecciation and contemporaneous formation of the pyrrhotite-carbonate intergrowths by hydrothermal activities occurred no later than 4564.6 +/- 1.0 Ma (using the angrite D'Orbigny as the Mn-Cr age anchor). This corresponds to 2.6 +/- 1.0 or 3.4 +/- 1.0 Ma after formation of CAIs, depending on the exact absolute age of CAIs. This is the oldest dated evidence for brecciation and carbonate formation, which likely occurred during parent body growth and incipient heating due to decay of Al-26.