H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Separation of H<Subscript>2</Subscript>S from CH<Subscript>4</Subscript> by polymeric membranes at different H<Subscript>2</Subscript>S concentrations

In this work, permeation of mixed gases H₂S/CH₄ through commercial polyphenylene oxide (PPO) hollow fiber and poly (ester urethane) urea (PEUU) flat membranes was studied at pressures of 345–689 kPa, at ambient temperature and at 313.15 K. Various H₂S concentrations of about 100–5000 ppm in CH₄ binary synthetic gas mixtures as well as a real natural gas sample obtained from a gas refinery containing 0.3360 mol.% H₂S (equivalent to 3360 ppm) were tested. It was observed that the permeance of components was affected by the balance between competitive sorption and plasticization effects. Separation factors of H₂S/CH₄ were in the range of 1.3–2.9, 1.8–3.1 and 2.2–4.3 at pressures of 345, 517 and 689 kPa, respectively. In the range of 101–5008 ppm of H₂S in CH₄, the effect of temperature on the separation factor was nearly negligible; however, permeances of both components of the mixtures increased with temperature. Additionally, the results obtained by PEUU membrane indicated that it was a better choice for hydrogen sulfide separation from H₂S/CH₄ mixtures than PPO. For PPO membrane, removal of hydrogen sulfide from high-concentration (up to 5008 ppm) binary mixtures of H₂S/CH₄ was compared with that of low concentration (as low as 101 ppm) through PPO. At concentrations of 101–968 ppm, plasticization was dominant compared with the competitive sorption, while for the H₂S feed concentrations of 3048 ppm, the competitive sorption effect was dominant. For H₂S concentration of 5008 ppm, the balance between these two effects played an important role for explanation of its trend.     

The effect of H<Subscript>2</Subscript>O on the olivine liquidus of basaltic melts: experiments and thermodynamic models

We designed and carried out experiments to investigate the effect of H₂O on the liquidus temperature of olivine-saturated primitive melts. The effect of H₂O was isolated from other influences by experimentally determining the liquidus temperatures of the same melt composition with various amounts of H₂O added. Experimental data indicate that the effect of H₂O does not depend on pressure or melt composition in the basaltic compositional range. The influence of H₂O on melting point lowering can be described as a polynomial function This expression can be used to account for the effect of H₂O on olivine-melt thermometers, and can be incorporated into fractionation models for primitive basalts. The non-linear effect of H₂O indicates that incorporation of H₂O in silicate melts is non-ideal, and involves interaction between H₂O and other melt components. The simple speciation approach that seems to account for the influence of H₂O in simple systems (albite-H₂O, diopside-H₂O) fails to describe the mixing behavior of H₂O in multi-component silicate melts. However, a non-ideal solution model that treats the effect of H₂O addition as a positive excess free energy can be fitted to describe the effect of melting point lowering.     

Crystal chemistry of selenates with mineral-like structures. III. Heteropolyhedral chains in the crystal structure of [Mg(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>(SeO<Subscript>4</Subscript>)]<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)

The crystal structure of a new compound [Mg(H₂O)₄(SeO₄)]₂(H₂O) (monoclinic, P2 ₁/a, a = 7.2549(12), b = 20.059(5), c = 10.3934(17) Å, β = 101.989(13), V = 1479.5(5) ų) has been solved by direct methods and refined to R ₁ = 0.059 for 2577 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure consists of [Mg(H₂O)₄(SeO₄)]⁰ chains formed by alternating corner-sharing Mg octahedrons and (SeO₄)^2? tetrahedrons. O atoms of Mg octahedrons that are shared with selenate tetrahedrons are in a trans orientation. The heteropoly-hedral octahedral-tetrahedral chains are parallel to the c axis and undulate within the (010) plane. The adjacent chains are linked by hydrogen bonds involving H₂O molecules not bound with M²⁺ cations.     

Experimental study of eclogite melting with participation of the H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-KCl fluid at 5 GPa

In order to model the processes of formation of the highly alkaline (potassic) melts during the partial melting of the eclogite nodules in kimberlites, experiments on the melting of the model and natural eclogites in presence of the H₂O-CO₂ and H₂O-CO₂-KCl fluids at 5 GPa and 1200 and 1300°C are performed. A comparative analysis of the phase relations in the systems with H₂O-CO₂ and H₂O-CO₂-KCl demonstrate that KCl in the fluid equilibrated with eclogites intensifies their melting. It is related to both high Cl concentration in the forming silicate melt (2.0–5.5 wt %) and its enrichment in K₂O owing to the K-Na exchange reactions with the immiscible chloride melt. Because of these reactions, the K₂O/Cl ratio in the melts increases with the KCl content in the system and reaches 2.5–3.5 in the silicate melts coexisting with the immiscible chloride liquid. However, the ratio KCl/(H₂O + CO₂ + KCl) in the fluid does not influence on the ratio K₂O/Cl in the melts. Thus, the solubility KCl in the melts, apparently, does not depend on presence of the H₂O-CO₂ fluid, at least, within the concentration range used in the experiments (up to 20 wt %). The experiments show that the deliberated chloride liquid is necessary to form the potassium-rich chlorine-bearing silicate melts during the eclogite melting. It corresponds to the KCl content in the system above 5 wt %.     

Triplet spectra of H<Subscript>2</Subscript>O masers and protoplanetary disks

An analysis of the H₂O maser emission associated with protoplanetary disks is presented. Triplet H₂O spectra can be formed at certain stages in the evolution of Keplerian disks. The dependence of the mass of the central star in the Keplerian disk on the disk radius is derived. The calculations are based on the distribution of the water-vapor molecules (maser spots). In S140, the observed elongated maser spots (chains) with a smoothly varying line-of-sight velocity are interpreted as protoplanetary structures with a small intrinsic rotation.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

The evolution of H<Subscript>2</Subscript>O maser spots in star-forming regions

Strong flares of the H₂O maser emission in sources associated with active star-forming regions are analyzed. The main characteristics of 13 flares in nine sources selected using special criteria are presented. The observed phenomena are explained as flares in double emission features. The approach of two emission features in the spectrum with increasing flux and their recession with decreasing flux is explained using a model with two physically related clumps of material that are partially superposed in the line of sight. Calculations have shown that, in this type of model, exponential amplification (unsaturated maser emission) in the overlapping parts of the clumps can produce the observed line narrowing with increasing flux. In most cases, the maser spots are inhomogeneous. During the evolution of some flares, the maser condensations may split into separate fragments. A less catastrophic evolutionary path may be an initial stage of formation of chainlike structures, which are fairly widespread in envelopes around ultracompact HII regions.     

Vibrational states of H<Subscript>2</Subscript>O in beryl: physical aspects

Single-crystal polarized Raman spectra (3,000–4,000 cm⁻¹ at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be₂Al₃Si₆O₁₈·xH₂O, to determine the behavior of H₂O molecules of both Type I and Type II in the cavities. At low temperature, the H₂O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice. The H₂O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the box” with a frequency of 6.3 cm⁻¹. Water Type II is characterized by a free rotation with respect to the C ₂ molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.

Chain-type structure in the H<Subscript>2</Subscript>O maser NGC 7538N

An analysis of the H₂O maser emission toward the source NGC 7538N, which is associated with an active star-forming region, is reported. The analysis is based on 24 years of monitoring in the 1.35-cm line using the the 22-m radio telescope of the Pushchino Radio Astronomy Observatory in 1981–2005 with a spectral resolution of 0.101 km/s. Individual spectral components have been isolated, and temporal drifts in their radial velocities found. From time to time, the drifts were accompanied by velocity jumps. This can be explained if there are chains consisting of clumps of material that are elongated in the radial direction toward the star and have a radial-velocity gradient. In 1982–2005, two maser activity cycles were observed, during which the chains were activated. We propose that shocks consecutively cross the chain elements and excite maser emission in them. The longest chain, at a radial velocity of ?58 km/s, has not fewer than 15 links. For a shock velocity of 15 km/s, the chain step is estimated to be ≤1.5 AU. The chains could be located in a circumstellar disk with a width of ≤10¹⁵ cm. A structure in the form of a rotating nonuniform vortex with the rotation period of about 1.6 years has also been detected. The translational motion of the vortex may be a consequence of its orbital motion within the protoplanetary disk.     

Evolution of the H<Subscript>2</Subscript>O Maser Emission Zone in ON2 N

Results of a multi-faceted study of the H₂O maser emission in the region ON2 N carried out on the Very Large Array (VLA, NRAO) and 22-m radio telescope of the Pushchino Radio Astronomy Observatory are reported. The envelope around the ultracompact HII region is fairly extended and has a composite, strongly fragmented structure. The maser emission zone consists of single spots and spot clusters arranged along an arc, which is associated with a ram shock front. This shock front is nonsta-tionary, and its position changes with time. The front position probably depends on the state of activity of the central star. There can be turbulent motions of material in clusters as well as individual maser spots (such as turbulent vortices). In the turbulent-vortex model, the size of an H₂O maser spot is estimated to be 0.07–0.1 AU. Flux-correlated radial-velocity drifts of emission features have been detected, which can be accompanied by spatial displacement (proper motion) of maser spots.     

Experimental multipole-refined and theoretical charge density study of LiGaSi<Subscript>2</Subscript>O<Subscript>6</Subscript> clinopyroxene at ambient conditions

The synthetic LiGaSi₂O₆ clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi₂O₆), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si₂O₆ group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

H<Subscript>2</Subscript>O storage capacity of MgSiO<Subscript>3</Subscript> clinoenstatite at 8–13 GPa, 1,100–1,400°C

We present H₂O analyses of MgSiO₃ pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H₂O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H₂O concentrations increase with pressure and range from 0.08 wt.% H₂O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H₂O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H₂O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H₂O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H₂O partitioning between olivine and clinoenstatite gives values of D ^ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D ^wd/CEn, gives a value of 2.8 ± 0.4.     

Evolution of selected components of the H<Subscript>2</Subscript>O maser in Sgr B2

We present the results of a variability study of some H₂O maser-emission components of Sgr B2, which is located in an active star-forming region. Our monitoring was conducted in 1982–2004 with the 22-m radio telescope of the Pushchino Radio Astronomy Observatory. We analyze brightness variations for the strongest groups of emission features in the H₂O spectra, mainly during periods of maser flaring activity. Each of these groups contains many components, whose radial velocities and fluxes we determined. Most of the components displayed radial-velocity drifts. We detected a correlation between the flux and radial-velocity variations for some of the components. Variability of the emission can be explained in a model in which the maser spots form elongated chains and filaments with radial-velocity gradients. During H₂O flares, the flux increases of some maser spots were accompanied by acceleration, while flux decreases were accompanied by deceleration of their motion in the dense circumstellar matter. Spectral groups of emission features are probably spatially compact structures.     

The H<Subscript>2</Subscript>O supermaser region in Orion KL: Epoch 1982.9

Radio interferometric observations of an H₂O maser flare in the Orion Nebula at epoch 1982.9 have been used to determine the flare’s spatial structure. Antennas in the Crimea, Effelsberg, and Onsala were used. The emission region consists of three groups of components. The angular sizes of the components are 0.2–0.9 mas, and the widths of the emitted lines are 0.2–0.7 km/s. The velocities of the components are correlated with their relative positions, which correspond to expanding concentric rings. Assuming a 1 M_⊙ protostar in a Keplerian approximation, the radius of the inner ring R is 15 AU, the velocity of its rotation V_rot is 8.98 km/s, and the radial component of the velocity V_rad is 1.79 km/s. For the outer ring, R=15.7 AU, V_rot=8.79 km/s, and V_rad=2.61 km/s.     

Diffusion-controlled spherulite growth in obsidian inferred from H<Subscript>2</Subscript>O concentration profiles

Spherulites are spherical clusters of radiating crystals that occur naturally in rhyolitic obsidian. The growth of spherulites requires diffusion and uptake of crystal forming components from the host rhyolite melt or glass, and rejection of non-crystal forming components from the crystallizing region. Water concentration profiles measured by synchrotron-source Fourier transform spectroscopy reveal that water is expelled into the surrounding matrix during spherulite growth, and that it diffuses outward ahead of the advancing crystalline front. We compare these profiles to models of water diffusion in rhyolite to estimate timescales for spherulite growth. Using a diffusion-controlled growth law, we find that spherulites can grow on the order of days to months at temperatures above the glass transition. The diffusion-controlled growth law also accounts for spherulite size distribution, spherulite growth below the glass transition, and why spherulitic glasses are not completely devitrified. An erratum to this article can be found at     

H<Subscript>2</Subscript>O masers and protoplanetary disk dynamics in IC 1396 N

We report H₂O maser line observations of the bright-rimmed globule IC 1396 N using a ground-space interferometer with the 10-m RadioAstron radio telescope as the space-based element. The source was not detected on projected baselines >2.3. Earth diameters, which indicates a lower limit on the maser size of L > 0.03 AU and an upper limit on the brightness temperature of 6.25 × 10¹² K. Fringe-rate maps are prepared based on data from ground-ground baselines. Positions, velocities and flux densities of maser spots were determined. Multiple low-velocity features from ?4.5 km/s to +0.7 km/s are seen, and two high-velocity features of V _LSR = ?9.4 km/s and V _LSR = +4.4 km/s are found at projected distances of 157 AU and 70 AU, respectively, from the strongest low-velocity feature at V _LSR = ~+0.3 km/s. Maser components from the central part of the spectrum fall into four velocity groups but into three spatial groups. Three spatial groups of low-velocity features detected in the 2014 observations are arranged in a linear structure about ~200 AU in length. Two of these groups were not detected in 1996 and possibly are jets which formed between 1996 and 2014. The putative jet seems to have changed direction in 18 years, which we explain by the precession of the jet under the influence of the gravity of material surrounding the globule. The jet collimation can be provided by a circumstellar protoplanetary disk. There is a straight line orientation in the “V _LSR-Right Ascension” diagram between the jet and the maser group at V _LSR = ~+0.3 km/s. However, the central group with the same position but at the velocity V _LSR ~ ?3.4 km/s falls on a straight line between two high-velocity components detected in 2014. Comparison of the low-velocity positions from 2014 and 1996, based on the same V _LSR-Right Ascension diagram for low-velocity features, shows that the majority of the masers maintain their positions near the central velocity V _LSR = ~0.3 km/s during the 18 year period.     

Phototrophic bacteria dominate consortia,potentially to remove CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>S from biogas under microaerophilic conditions

The use of microbial consortia to remove contaminants in industrial systems and in natural environments could be an alternative to the use of unique strains of microorganisms, since microbial consortia have greater robustness to environmental fluctuations. However, it is necessary to evaluate the relationship between the genetic structure and functionality of the consortia. In this work, the functional and structural stability over time of two bacterial consortia (C5 and C6) with the potential to remove CO₂ and H₂S from biogas was evaluated. Both consortia decreased the dissolved CO₂ by over 30% at the end of the incubation period, but C5 presented shorter removal kinetics (3.9 days) than C6 (6.4 days). Additionally, a chemical oxidation of H₂S could have occurred in the microcosms. Moreover, both consortia presented a stable genetic structure, measured by terminal restriction fragment length polymorphism profiles of the 16S rRNA gene, characterized by high homogeneity and prevalence of the genus Rhodopseudomonas throughout the incubation period, and an increasing abundance of Xanthobacter during the exponential phase of the growth curve in C5, which would account for the functionality of the consortia.