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.     

An H<Subscript>2</Subscript>O maser in the infrared source IRAS 20126+4104

Results of monitoring of H₂O maser in the infrared source IRAS 20126+4104, which is associated with a cool molecular cloud, are presented. The observations were carried out on the 22-meter radio telescope of the Pushchino Radio Astronomy Observatory (Russia) between June 1991 and January 2006. The spectrum of the H₂O maser emission extends from ? 16.7 to 4.8 km/s and splits into separate groups of emission features. Cyclic variations of the integrated maser flux with a period from 3.4 to 5.5 years were detected, together with strong flares of up to 220 Jy in individual emission features. It is shown that large linewidths in periods of high maser activity are due to small-scale turbulent motions of the material. An expanding envelope around a young star is accepted as a model for the source. The protostar has a small peculiar velocity with respect to the molecular cloud (～2 km/s). Individual emission features form organized structures, including multi-link chains.     

Preferential dissolution of SiO<Subscript>2</Subscript> from enstatite to H<Subscript>2</Subscript> fluid under high pressure and temperature

Stability and phase relations of coexisting enstatite and H₂ fluid were investigated in the pressure and temperature regions of 3.1–13.9 GPa and 1500–2000 K using laser-heated diamond-anvil cells. XRD measurements showed decomposition of enstatite upon heating to form forsterite, periclase, and coesite/stishovite. In the recovered samples, SiO₂ grains were found at the margin of the heating hot spot, suggesting that the SiO₂ component dissolved in the H₂ fluid during heating, then precipitated when its solubility decreased with decreasing temperature. Raman and infrared spectra of the coexisting fluid phase revealed that SiH₄ and H₂O molecules formed through the reaction between dissolved SiO₂ and H₂. In contrast, forsterite and periclase crystals were found within the hot spot, which were assumed to have replaced the initial orthoenstatite crystals without dissolution. Preferential dissolution of SiO₂ components of enstatite in H₂ fluid, as well as that observed in the forsterite H₂ system and the quartz H₂ system, implies that H₂-rich fluid enhances Mg/Si fractionation between the fluid and solid phases of mantle minerals.     

Flares of the H<Subscript>2</Subscript>O Maser Emission in the Young Stellar Object GH<Subscript>2</Subscript>O 092.67+03.07 (IRAS 21078+5211)

The results of monitoring the H₂O maser observed toward the region GH₂O 092.67+03.07 (IRAS 21078+5211) located in the Giant Molecular Cloud Cygnus OB7 are presented. The observations were carried out with the 22-m radio telescope of the Pushchino Radio Astronomy Observatory in 2006–2017. Strong flares of the H₂O maser emission with flux densities up to 19 800 Jy were detected. The flares exhibited both global (over the source) and local characters. All the flares were accompanied by strong variations in the H₂O spectra within the corresponding radial-velocity ranges. Individual H₂O components form both compact clusters and chains 1–2-AU long. Analysis of the variations of the fluxes, radial velocities, and line shapes of features during the flares showed that the medium may be strongly fragmented, with small-scale turbulent motions taking place in the H₂Omaser region.     

The high-pressure stability of Mg-sursassite in a model hydrous peridotite: a possible mechanism for the deep subduction of significant volumes of H<Subscript>2</Subscript>O

The stability of the high-pressure phase Mg-sursassite, previously MgMgAl-pumpellyite, in ultramafic compositions has been determined in experiments in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). The breakdown of Mg-sursassite + forsterite + enstatite to pyrope + vapour with increasing temperature was bracketed at 6.0 and 7.0 GPa. Below 6.0 GPa, Mg-sursassite + forsterite + vapour reacts to chlorite + enstatite. This reaction provides a mechanism for transfer of water from chlorite- to Mg-sursassite-bearing assemblages. At pressures of 7.0 GPa and above, the assemblage Mg-sursassite + phase A + enstatite was found. Phase relations involving Mg-sursassite and phase A are considered. For bulk compositions with a low water content, the vapour-absent reaction Mg-sursassite + forsterite = pyrope + phase A + enstatite determines the upper-pressure stability of Mg-sursassite, and provides a mechanism for the complete transfer of water from Mg-sursassite to phase A-bearing assemblages. Mg-sursassite plays an important role in peridotite compositions in the subducting slab because, at temperatures below 700 °C, it can transfer water from hydrous phases such as antigorite and chlorite to high-pressure stable phases such as phase A.     

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.     

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.     

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 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.     

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.     

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 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.     

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.     

Dihedral angle measurements and infiltration property of SiO<Subscript>2</Subscript>-rich melts in mantle peridotite assemblages

Petrological and experimental studies demonstrated that nepheline-normative, SiO₂-rich melts can be present in the upper mantle at pressures 1.5 GPa. To evaluate the role of such melts in mantle processes and magma genesis, we carried out two types of experiments: (1) melt distribution experiments to characterize the grain-scale distribution of a small fraction of typical SiO₂-rich mantle melt (SRMM) in polycrystalline olivine (Ol) at 1,180°C, 1.2 GPa; and (2) an infiltration experiment to test the ability of SRMM to impregnate and metasomatise neighbouring non-molten mantle rocks. The median dihedral angles at Ol-Ol-SRMM contacts are equal to 50°, implying that melt should be interconnected at all melt fractions. Complications arise, however, in the investigated system because Ol–liquid interfacial energy is anisotropic, and we estimate that the connectivity threshold in the SRMM–Ol system is 0.3 vol%. Regarding the very low volume fraction of SRMM in peridotites, we conclude that these melts either occur as isolated pockets or form a network of grain edge channels with a low degree of connectivity due to a large number of dry grain edges. Even in the case where an interconnected network exists, their large viscosities should prohibit the extraction of SRMM from peridotite sources. The infiltration experiment also points to a very reduced mobility of SRMM in the upper mantle. In this experiment, a slice of synthetic dunite was immersed into a magma reservoir made of 60 wt% SRMM+40 wt% Ol, and subjected to 1,180°C-1.2 GPa for 113 h: despite this long duration, the SiO₂-rich liquid was unable to infiltrate measurably the dunite. Our experiments do not support the hypothesis that SRMM represent agents of mantle metasomatism.     

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 solubility of alkali basaltic melts: an experimental study

Experiments were conducted to determine the water solubility of alkali basalts from Etna, Stromboli and Vesuvius volcanoes, Italy. The basaltic melts were equilibrated at 1,200°C with pure water, under oxidized conditions, and at pressures ranging from 163 to 3,842 bars. Our results show that at pressures above 1 kbar, alkali basalts dissolve more water than typical mid-ocean ridge basalts (MORB). Combination of our data with those from previous studies allows the following simple empirical model for the water solubility of basalts of varying alkalinity and fO₂ to be derived: \textH ₂ \textO( \textwt% ) = \text H ₂ \textO_\textMORB ( \textwt% ) + ( 5.84 ×10 ^{- 5} *\textP - 2.29 ×10 ^{- 2} ) ×( \textNa₂ \textO + \textK₂ \textO )( \textwt% ) + 4.67 ×10 ^{- 2} ×\Updelta \textNNO - 2.29 ×10 ^{- 1} {\text{H}}_{ 2} {\text{O}}\left( {{\text{wt}}\% } \right) = {\text{ H}}_{ 2} {\text{O}}_{\text{MORB}} \left( {{\text{wt}}\% } \right) + \left( {5.84 \times 10^{ - 5} *{\text{P}} - 2.29 \times 10^{ - 2} } \right) \times \left( {{\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}}} \right)\left( {{\text{wt}}\% } \right) + 4.67 \times 10^{ - 2} \times \Updelta {\text{NNO}} - 2.29 \times 10^{ - 1} where H₂O_MORB is the water solubility at the calculated P, using the model of Dixon et al. (1995). This equation reproduces the existing database on water solubilities in basaltic melts to within 5%. Interpretation of the speciation data in the context of the glass transition theory shows that water speciation in basalt melts is severely modified during quench. At magmatic temperatures, more than 90% of dissolved water forms hydroxyl groups at all water contents, whilst in natural or synthetic glasses, the amount of molecular water is much larger. A regular solution model with an explicit temperature dependence reproduces well-observed water species. Derivation of the partial molar volume of molecular water using standard thermodynamic considerations yields values close to previous findings if room temperature water species are used. When high temperature species proportions are used, a negative partial molar volume is obtained for molecular water. Calculation of the partial molar volume of total water using H₂O solubility data on basaltic melts at pressures above 1 kbar yields a value of 19 cm³/mol in reasonable agreement with estimates obtained from density measurements.     

Amphibole stability in primitive arc magmas: effects of temperature,H<Subscript>2</Subscript>O content,and oxygen fugacity

The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO₂, 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200–800 MPa, temperature range of 915–1,070 °C, and oxygen fugacities varying from the nickel–nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO₂, 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515–533; 2003) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H₂O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H₂O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H₂O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H₂O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975–1,025 °C. With increasing H₂O pressure (\({P}_{\text {H}_2{\rm O}}\)), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and \(f_{\text {O}_2}\):

$$ P_{\text{H}_{2}{\rm O}}({\rm MPa})=\left[{\frac{{\rm Mg\#}}{52.7}}-0.014 * \Updelta {\rm NNO}\right]^{15.12} $$

This barometer gives a minimum \({P}_{\text{H}_{2}{\rm O}}\) recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H₂O pressures (500–900 MPa) and high pre-eruptive magmatic H₂O contents (10–14 wt% H₂O) are indicated for the primitive end members of magma mixing that are preserved in the Shasta lavas. We also use these new experimental data to explore and evaluate the empirical hornblende barometer of Larocque and Canil (2010).

     

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