The effect of the ionization rate on the chemical composition of dense cores of dark molecular clouds

The effect of variations in the rate of ionization of neutral chemical species by cosmic rays, ζ, on the abundances of some observed molecules in the dense cores of dark molecular clouds is studied. Changes in molecular abundances accompanying an increased (decreased) ionization rate have a single origin: the acceleration (deceleration) of processes that are affected directly or indirectlybychemical reactions with charged species. In addition to affecting the gas-phase chemistry, an increased cosmic-ray flux leads to the more efficient destruction of dust-grain mantles and also accelerates the freezing of some components onto dust. In particular, in a model with an increased ζ, the destruction of the volatile N₂ molecule by ionized helium leads to the rapid accumulation of nitrogen atoms in dust-phase ammonia, which has a higher desorption energythan N₂. As a result, the gas-phase abundance of NH₃ and N₂H⁺ decreases significantly. This mechanism can explain the unusual chemical structures of some dense globules, such as B68, where surprisingly low abundances of nitrogen-bearing molecules are observed together with a central drop in the NH₃ and N₂H⁺ column densities. Observations of clouds in HCN and HNC lines can discriminate between the two possible origins of the reduced NH3 and N₂H⁺ abundances: an increased cosmic-ray flux or N₂ freezing due to the higher desorption energy of this molecule.     

Experimental study of incongruent evaporation kinetics of enstatite in vacuum and in hydrogen gas

Variations in bulk Mg/Si ratios in the various groups of chondritic meteorites indicate that Mg/Si fractionation occurred in the primitive solar nebula. Enstatite (MgSiO₃) evaporates incongruently forming forsterite (Mg₂SiO₄) as an evaporation residue; therefore, evaporation of enstatite produces Mg/Si variations in solid (Mg-rich) and gas (Si-rich) and must be considered as a probable process responsible for Mg/Si fractionation recorded in chondrites. To understand the evaporation kinetics of enstatite, incongruent evaporation experiments on enstatite single crystals have been carried out in vacuum and in hydrogen gas at temperatures of 1300 to 1500°C. A polycrystalline forsterite layer is formed on the surface of enstatite by preferential evaporation of the SiO₂ component, both in vacuum and in hydrogen gas. The thickness of the forsterite layer in vacuum increases with time in the early stage of evaporation and later the thickness of the forsterite layer remains constant (several microns). This is due to the change in the rate limiting process from surface reaction plus nucleation and growth to diffusion in the surface forsterite layer. The activation energy of the diffusion-controlled evaporation rate constant of enstatite is 457 (±58) kJ/mol. A thinner forsterite layer is formed on the surface of enstatite in hydrogen gas than in vacuum. Evaporation of enstatite in hydrogen gas is also considered to be controlled by diffusion of ions through the forsterite layer. The thin forsterite layer formed in hydrogen gas is ascribed to the enhanced evaporation rate of forsterite in the presence of hydrogen gas.The results are applied to incongruent evaporation under the solar nebular conditions. The steady thickness of the forsterite of nebular pressure-temperature conditions is estimated to be submicron because of the enhanced evaporation rate of forsterite under hydrogen-rich nebular conditions if evaporated gases are taken away immediately and no back reaction occurs (an open system). Because enstatite grains in the solar nebula would be comparable to the estimated steady thickness of forsterite, evaporation of such enstatite grains under kinetic conditions could play an important role in producing variations in Mg/Si ratios between solid and gas in the solar nebula.     

CaO-MgO-Al2o3-SiO2 liquids: chemical and isotopic effects of Mg and Si evaporation in a closed system of solar composition

A method is shown for calculating vapor pressures over a CMAS droplet in a gas of any composition. It is applied to the problem of the evolution of the chemical and Mg and Si isotopic composition of a completely molten droplet having the composition of a likely refractory inclusion precursor during its evaporation into the complementary, i.e. modified solar, gas from which it originally condensed, a more realistic model than previous calculations in which the ambient gas is pure H_2(g). Because the loss rate of Mg is greater than that of Si, the vapor pressure of Mg_(g) falls and its ambient pressure rises faster than those of SiO_(g) during isothermal evaporation, causing the flux of Mg_(g) to approach zero faster and MgO to approach its equilibrium concentration sooner than SiO₂. As time passes, δ²⁵Mg and δ²⁹Si increase in the droplet and decrease in the ambient gas. The net flux of each isotope crossing the droplet/gas interface is the difference between its outgoing and incoming flux. δ²⁵Mg and δ²⁹Si of this instantaneous gas become higher, first overtaking their values in the ambient gas, causing them to increase with time, and later overtaking their values in the droplet itself, causing them to decrease with time, ultimately reaching their equilibrium values. If the system is cooling during evaporation and if mass transfer ceases at the solidus temperature, 1500 K, final MgO and SiO₂ contents of the droplet are slightly higher in modified solar gas than in pure H_2(g), and the difference increases with decreasing cooling rate and increasing ambient pressure. During cooling under some conditions, net fluxes of evaporating species become negative, causing reversal of the evaporation process into a condensation process, an increase in the MgO and/or SiO₂ content of the droplet with time, and an increase in their final concentrations with increasing ambient pressure and/or dust/gas ratio. At cooling rates <∼3 K/h, closed-system evaporation at P^tot ∼ 10⁻³ bar in a modified solar gas, or at lower pressure in systems with enhanced dust/gas ratio, can yield the same δ²⁵Mg in a residual CMAS droplet for vastly different evaporated fractions of Mg. The δ²⁵Mg of a refractory residue may thus be insufficient to determine the extent of Mg loss from its precursor. Evaporation of Mg into an Mg-bearing ambient gas causes δ²⁶Mg and δ²⁵Mg of the residual droplet to fall below values expected from Rayleigh fractionation for the amount of ²⁴Mg evaporated, with the degree of departure increasing with increasing fraction evaporated and ambient pressure of Mg. δ²⁶Mg and δ²⁵Mg do not depart proportionately from Rayleigh fractionation curves, with δ²⁵Mg being less than expected on the basis of δ²⁶Mg by up to ∼1.2‰. Such departures from Rayleigh fractionation could be used in principle to distinguish heavily from lightly evaporated residues with the same δ²⁵Mg.     

Photodissociative absorption by H 2 + in the solar photosphere

Photoabsorption by systems of hydrogen atoms and protons in the solar photosphere is studied. Analytical formulas for the partial cross sections for photodissociation of the H ₂ ⁺ molecular ion are derived for the cases of fixed vibrational-rotational energy levels and averaging over a Boltzmann distribution for a given temperature. The photoabsorption coefficients for bound-free and free-free transitions of H-H⁺ in the solar photosphere are calculated. These are compared with the absorption coefficients for photo-ejection of an electron from a negative hydrogen ion H^? and free-free transitions of an electron in the field of a hydrogen atom H. Results can be applied to the Sun and hotter stars.     

Effects of clay minerals and biosurfactants on isotopic and molecular characteristics of methane encaged in pressure vessel gas hydrates

The stable isotope values of carbon (δ¹³C_methane) and hydrogen (δ²H_methane) from methane molecules trapped in gas hydrates are useful for differentiation of methane from microbial and thermal origins, providing valuable information during hydrocarbon exploration. Recent studies have reported catalysis of methane hydrates when smectite clays and biosurfactants are present in hydrate-hosting sediments, but catalytic influences on the values of δ¹³C_methane and δ²H_methane are not well documented. In this study, pressure vessel methane hydrates were formed from solutions in contact with smectite clays (montmorillonite and nontronite) and biosurfactants (rhamnolipids and surfactin). Experiments show less than 1‰ differences in values of δ¹³C_methane between free and encaged molecules and up to 10‰ variations in values of δ²H_methane between free and encaged molecules. Notably, methane consumption increased in methane hydrates formed from solutions containing biosurfactants and biosurfactant–smectite mixtures. Results presented here indicate that a hydrate formed in the presence of smectite clays and biosurfactants are characterized by small shifts in free and encaged values of δ¹³C_methane and δ²H_methane and do not complicate interpretation of gas origin. In contrast, methane consumption in hydrates formed under the catalytic effect of smectite clays and biosurfactants modifies gas wetness, obscures gas origin and complicates interpretation of thermal maturity.     

Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO₄²⁻-CH₄ transition where H₂S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H₂S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe²⁺ diffusing up from below. The H₂S-Fe²⁺ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO₄²⁻ and 10 yr for H₂S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO₄²⁻-CH₄ and H₂S-Fe²⁺ cause the trapping of isotopically heavy iron sulfide with δ³⁴S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO₄²⁻ diffusing downward into the SO₄²⁻-CH₄ transition has an isotopic composition of +19‰, close to the +23‰ of H₂S diffusing upward. These isotopic compositions are, however, very different from the porewater SO₄²⁻ (+43‰) and H₂S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H₂S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.     

Fractionation of oxygen and hydrogen isotopes in evaporating water

Variations in oxygen and hydrogen isotope ratios of water and ice are powerful tools in hydrology and ice core studies. These variations are controlled by both equilibrium and kinetic isotope effects during evaporation and precipitation, and for quantitative interpretation it is necessary to understand how these processes affect the isotopic composition of water and ice. Whereas the equilibrium isotope effects are reasonably well understood, there is controversy on the magnitude of the kinetic isotope effects of both oxygen and hydrogen and the ratio between them. In order to resolve this disagreement, we performed evaporation experiments into air, argon and helium over the temperature range from 10 to 70 °C. From these measurements we derived the isotope effects for vapor diffusion in gas phase (ε_{diff(HD¹⁶O)} for D/H and ε_{diff(H2¹⁸O)} for ¹⁸O/¹⁶O). For air, the ratio ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} at 20 °C is 0.84, in very good agreement with Merlivat (1978) (0.88), but in considerable inconsistency with Cappa et al. (2003) (0.52). Our results support Merlivat’s conclusion that measured ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} ratios are significantly different than ratios calculated from simplified kinetic theory of gas diffusion. On the other hand, our experiments with helium and argon suggest that this discrepancy is not due to isotope effects of molecular collision diameters. We also found, for the first time, that the ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} ratio tends to increase with cooling. This new finding may have important implications to interpretations of deuterium excess (d-excess = δD − 8δ¹⁸O) in ice core records, because as we show, the effect of temperature on d-excess is of similar magnitude to glacial interglacial variations in the cores.     

Distribution and Geochemical Characteristics of Hydrogen in Natural Gas from the Jiyang Depression, Eastern China

Hydrogen gas accelerates hydrocarbon generation, but little is known about its distribution and origin in petroliferous basins, which has hindered the further exploration.Taken the Jiyang Depression in eastern China as an example, this study collected natural gas from different tectonic units, and analyzed various geochemical characters including gas contents, and carbon and hydrogen isotopic composition.The result shows that:(1) hydrogen gas is widespread distributed, but its content is very low, which typically ranges from 0.01% to 0.1% in this region;(2) the ratios of H2/3He, indicative of the origins of hydrogen gas, suggest that mantle-derived hydrogen is dominant.Even in tectonically stable areas absent with deep fluid activities, there is also mantle-derived;(3) the isotopic composition of hydrogen falls in the range of –798‰ to –628‰(relative to VSMOW standard).In areas with deep-derived fluids, the hydrogen gas has a similar isotopic composition with the previously documented deep-sourced gas, with lighter isotopic composition.In contrast, hydrogen gas has a heavier isotopic composition in relatively stable areas.The isotopic signatures suggest that there is a mixture of mantle- and crust-derived hydrogen gas in the relatively stable area, which is consistent with the H2/3He ratios.Therefore, it is clear that the hydrogen gas has a much wider distribution than found in the deep-derived fluid area, resulting in a much broader area with hydrogenating effect for resource rock.This understanding will provide new insights for hydrocarbon generation research and resource assessment in petroliferous basins.     

The system NaAlSi3O8−H2O−H2 (1200° C, 2 kbar): the solubility and interaction mechanism of fluid species with melt

The H₂O and H₂ solubilities in an albite melt at 1200° C and 2 kbar over the entire range of gas phase composition, from pure hydrogen to pure water were studied in gas-media pressure vessels. The water solubility initially increases with increasing hydrogen content until a maximum of 9.19 wt% H₂O atXH ₂ ^v =0.1 is reached, withXH ₂ ^v >0.1 the water solubility decreases. The hydrogen solubility curve has a maximum atXH ₂ ^v =0.42 where the concentration reaches 0.206 wt% H₂O. Over the entire compositional range¹H NMR (nuclear magnetic resonance) spectra show distinct absorption lines due to protons bound to OH groups and to isolated firmly bound water molecules. In NMR and Raman spectra there were no bands attributable to the H–H vibrations of molecular hydrogen. The X-ray photo-electronic spectra of hydrogen-bearing glasses show the Si2p (99 eV) band which corresponds to the zero-valency silicon. The formation of OH groups and molecular water during interaction between hydrogen-bearing fluids and melts under reducing conditions has a qualitative effect, the same as for water dissolution. Another point of interest is that hydrogen-bearing melts undergo more depolymerization than do hydrous melts.     

Surface properties of the Orgueil meteorite: implications for the early history of solar system volatiles

Dehydration of Orgueil by stepwise calcination produced more than a tenfold change in its Kr B.E.T. surface area, which increased to 120 m²/g, then fell to 40 m²/g. This phenomenon characterizes structures of the montmorillonite type, but not other plausible constituents of Orgueil. It results from vacating of interlayer sites by H₂O molecules which are replaced by Kr until finally the sheets collapse, excluding Kr. Differential calorimetric scans of Orgueil also gave a better match for montmorillonite than for other minerals. However, a simple identification as montmorillonite conflicts with chemical analyses of Orgueil phyllosilicates.Exchangeability of H₂O in Orgueil was shown by water regain from lab air between calcination cycles and similarily of the cycles. Room temperature dehydration revealed up to 6 per cent free surface adsorbed water. High D/H ratios in CI's may result from D enrichment in OH^? groups during equilibration of dispersed phyllosilicate dust with nebula gas at temperatures ?0°C. Adsorption on the very large free and interlayer surface areas of this dust was the major mechanism by which volatiles still uncondensed at the time of gas-dust separation (including planetary primordial Ar, Kr and Xe) were incorporated into solid solar system material.     

Interaction between sulphide and H2O in silicate melts

Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na₂S; 1500-2000 ppm S by weight) and the other with H₂O (∼3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H₂O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H₂O) demonstrate that H₂O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H₂O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments.In Raman spectra a band at 2576 cm⁻¹ appears in the sulphide - H₂O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm⁻¹ (on expense of the combination band of molecular H₂O at 5225 cm⁻¹) and at 3400 cm⁻¹ was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H₂O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S²⁻ - H₂O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple experiments. On the contrary, XANES spectra from experiments conducted with a free H₂O fluid show complete transformation of sulphide to sulphate near the melt surface and coexistence of sulphate and sulphide in the center of the melt. This can be explained by a lower H₂O activity in the diffusion couple experiments or by the need of a sink for hydrogen (e.g., a fluid which can dissolve high concentration of hydrogen) to promote oxidation of sulphide by H₂O via the reaction S²⁻ + 4H₂O = SO₄²⁻ + 4H₂. Sulphite could not be detected in any of the XANES spectra implying that this species, if it exists in the melt, it is a subordinate or transient species only.     

Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts

The behavior of Na and K during evaporation from chondrule composition melts was studied using a vacuum furnace. Though Na is the less volatile of the two as an element, it is lost more rapidly than K from silicate melts. Mass fractionation of K isotopes was measured by ion microprobe and Rayleigh fractionation is observed for vacuum evaporation (10⁻⁵ atm). With higher pressures of air, the K loss rate decreases but with increasing hydrogen pressure, K is lost more rapidly. δ⁴¹K decreases with higher pressures, because of back reaction between melt and K in the gas. With long heating duration, the release of light K condensed within the furnace leads to interaction with the K-depleted melt and a further reduction of δ⁴¹K. Natural chondrules differ in some ways from our experimental residues. Some (especially type IIA) have superchondritic Na and K, despite their assumed formation in nebular hydrogen, which enhances volatile loss, and chondrules do not show K isotopic fractionation. Type I chondrules in Semarkona (LL3.0) either plot on our evaporation trend, or are depleted in K but slightly enriched in Na, relative to K. In Bishunpur (LL3.1), type I chondrules are mostly K-depleted but moderately to strongly enriched in Na. In petrologic type 3.2 to 3.4 chondrites they are enriched in both K and Na, like type II chondrules. The alkali contents suggest type I chondrules experienced evaporation and subsequent metasomatism. Their normal δ⁴¹K values suggest closed-system evaporation of a chondritic precursor in a gas with relatively high K pressures due to vaporization of dust accompanying chondrule precursor aggregates. Type II chondrules are volatile-rich, as well as unfractionated in K isotopes. They probably formed in a gas with higher pK than in the case of type I chondrules, due to heating of a more dust-rich parcel of gas.     

Dust formation in binaries with OB and WR components in a two-phase stellar-wind model

We describe the formation of carbon dust in binary systems with hot components as a result of the collisions of clouds in a two-phase stellar-wind model. Calculations are made for the well studied system WR 140. The collisions lead to the formation of composite clouds and shock waves, with the temperature at the shock front equal to about 3×10⁸ K along both sides of the interface boundary. During isobaric deexcitation to (0.5–0.7)×10⁴ K, the cloud density increases by a factor of several thousand; its thickness in the direction of the shock decreases by the same factor. After deexcitation, the hydrogen inside the composite cloud is in its atomic state, while the carbon remains ionized. The deexcitation is followed by expansion of the cloud, which moves away from both stars. During the first 10⁶ s, its thickness remains relatively small, so that the expansion is one-dimensional. The radiation field inside the cloud decays, resulting in the recombination of the carbon. Further expansion of the cloud leads to adiabatic cooling, and the formation of dust particles becomes possible. After the dimensions of the cloud have become roughly the same in all directions, its expansion is isotropic, so that it becomes transparent within approximately 10⁶ s, and the dust is heated to (1.0–1.4)×10³ K, observed as an IR “lare.” The time required for the cloud to move from the exciting star and heat the dust is comparable to the observed delay in the increased IR emission relative to the time of periastron.     

Collective supernova outbursts and the growth of supershells: Observational manifestations

Numerous supernova outbursts that are correlated in time and space are the main mechanism for the formation of powerful galactic winds and supershells of ionized hydrogen. Information about the dynamics and thermal properties of the gas in shells (bubbles) can be obtained from spectral observations, including those of optical recombination lines. The emission properties of the Hα and Hβ recombination lines and the velocity dispersion of the gas in bubbles formed by numerous supernova outbursts are studied. The appearance of the intensity vs. velocity dispersion (I(H _α)_?σ) diagram depends on the supernova rate and the age of the bubble. The temperature dependence of the I(H_α)/I(H _β) line-intensity ratio (the Balmer decrement) can be used to obtain additional constraints on the evolutionary status of a collective remnant formed by numerous supernova outbursts.     

Galaxies with anomalously high abundances of molecular hydrogen

A sample of 66 galaxies from the catalog of Bettoni et al. (CISM) with anomalously high molecular-to-atomic hydrogen mass ratios (M _mol/M _HI > 2) is analyzed. The sample galaxies do not differ systematically from the other galaxies in the catalog with the same morphological types, in terms of their photometric parameters, rotational velocities, dust contents, or the integrated masses of gas (for galaxies with the same linear sizes and disk angular momenta). This suggests that the overabundances of H₂ are due to the molecularization of HI. Galaxies with bars and active nuclei are found more frequently among galaxies with M _mol estimates in CISM. In a small fraction of cases, high M _mol/M _HI ratios are due to overestimation of M _mol due to overstimating of the conversion factor for the translation of CO-line intensities into the number of H₂ molecules along the line of sight. It is argued that the molecularization of the bulk of the gas mass could be due to the concentration of gas in the inner regions of the galactic disks and the resulting high gas pressures and relative low star-formation efficiencies, as is indeed observed in galaxies with high M _mol/M _HI ratios.     

The structure of shocks in the atmospheres of pulsating stars

The structure of shocks propagating through partially ionized hydrogen gas with characteristics typical of the atmospheres of RR Lyr, W Vir, and RV Tau type variables is analyzed in terms of a self-consistent solution of the equations of gas dynamics, atomic kinetics, and radiation transfer. The solutions were obtained for shock waves with velocities 20 km/s≤U ₁≤90 km/s and unperturbed hydrogen gas with temperatures 3000 K≤T ₁≤9000 K and density ρ₁=10^?10 g/cm³. The fraction of the energy of the gas-dynamic flux converted into radiation increases with the shock amplitude, and the ratio of the radiation flux emitted by the shock to the gas kinetic energy flux is 0.4???0.8 for the velocities U ₁ considered. This ratio also increases slightly with the ambient gas temperature T ₁ due to an increase in hydrogen ionization in the radiative precursor. The flux emitted by the leading edge of the shock opposite to the gas flow is several percent higher than the flux emitted in the opposite direction by the trailing edge of the shock. Radiation is mostly concentrated in the Balmer continuum, and the region of efficient Lyman radiation transfer includes gas layers located near the viscous jump (δX=±10⁴ cm). The final gas-compression ratio in units of the limiting compression corresponding to an isothermal approximation is virtually independent of the shock amplitude, and increases with the unperturbed gas temperature from r≈0.5 at T ₁=3000 K to r≈0.9 at T ₁=9000 K.     

Rates of microbial hydrogen oxidation and sulfate reduction in Opalinus Clay rock

Hydrogen gas (H₂) may be produced by the anoxic corrosion of steel components in underground structures, such as geological repositories for radioactive waste. In such environments, hydrogen was shown to serve as an electron donor for autotrophic bacteria. High gas overpressures are to be avoided in radioactive waste repositories and, thus, microbial consumption of H₂ is generally viewed as beneficial. However, to fully consider this biological process in models of repository evolution over time, it is crucial to determine the in situ rates of microbial hydrogen oxidation and sulfate reduction. These rates were estimated through two distinct in situ experiments, using several measurement and calculation methods. Volumetric consumption rates were calculated to be between 1.13 and 1.93 μmol cm⁻³ day⁻¹ for H₂, and 0.14 and 0.20 μmol cm⁻³ day⁻¹ for sulfate. Based on the stoichiometry of the reaction, there is an excess of H₂ consumed, suggesting that it serves as an electron donor to reduce electron acceptors other than sulfate, and/or that some H₂ is lost via diffusion. These rate estimates are critical to evaluate whether biological H₂ consumption can negate H₂ production in repositories, and to determine whether sulfate reduction can consume sulfate faster than it is replenished by diffusion, which could lead to methanogenic conditions.     

The Spatial–Kinematic Structure of the Region of Massive Star Formation S255N on Various Scales

The results of a detailed analysis of SMA, VLA, and IRAM observations of the region of massive star formation S255N in CO(2–1), N₂H⁺(3–2), NH₃(1, 1), C¹⁸O(2–1) and some other lines is presented. Combining interferometer and single-dish data has enabled a more detailed investigation of the gas kinematics in the moleclar core on various spatial scales. There are no signs of rotation or isotropic compression on the scale of the region as whole. The largest fragments of gas (≈0.3 pc) are located near the boundary of the regions of ionized hydrogen S255 and S257. Some smaller-scale fragments are associated with protostellar clumps. The kinetic temperatures of these fragments lie in the range 10–80 K. A circumstellar torus with inner radius R_in ≈ 8000 AU and outer radius R_out ≈ 12 000 AU has been detected around the clump SMA1. The rotation profile indicates the existence of a central object with mass ≈8.5/ sin²(i) M_⊙. SMA1 is resolved into two clumps, SMA1–NE and SMA1–SE, whose temperatures are≈150Kand≈25 K, respectively. To all appearances, the torus is involved in the accretion of surrounding gas onto the two protostellar clumps.     

Structure and kinematics of the interstellar medium near WR 137 and supernova remnants CTB 87 and G73.9+0.9

Using the results of our Hα interferometric observations and observational data on the 21 cm and CO lines, we have analyzed the structure and kinematics of the interstellar medium in the extended vicinity of the star WR 137 and the supernova remnants CTB 87 and G73.9+0.9. A shell structure with a radius of up to 40′ observable in optical lines has been discovered around WR 137. The high-velocity motions of ionized hydrogen inside this shell can be interpreted as expansion of the gas swept out by the wind of WR 137 at velocities of up to 60 km/s. The ionized hydrogen near WR 137 emits at the systematic velocity V _LSR ∼ 6–18 km/s. The expansion ofG73.9+0.9 at a velocity of up to 55 km/s has been confirmed. The systematic velocities of the ionized hydrogen toward this supernova remnant are V _LSR ≃ −14…+14 km/s. An HI shell around G73.9+0.9 has been detected at velocities V _LSR≃−14…−8 km/s. A very faint optical shell of CTB 87 with a size of about 20′ has also been detected. Evidence that CTB 87 is located in the Cygnus Arm is presented.     

Crystallization of melilite from CMAS-liquids and the formation of the melilite mantle of Type B1 CAIs: Experimental simulations

Type B CAIs are subdivided into B1s, with well-developed melilite mantles, and B2s, with randomly distributed melilite. Despite intensive study, the origin of the characteristic melilite mantle of the B1s remains unclear. Recently, we proposed that formation of the melilite mantle is caused by depletion of the droplet surface in volatile magnesium and silicon due to higher evaporation rates of volatile species compared to their slow diffusion rates in the melt, thus making possible crystallization of melilite at the edge of the CAI first, followed by its crystallization in the central parts at lower temperatures. Here, we present the results of an experimental study that aimed to reproduce the texture observed in natural Type B CAIs. First, we experimentally determined crystallization temperatures of melilite for three melt compositions, which, combined with literature data, allowed us to find a simple relationship between the melt composition, crystallization temperature, and composition of first crystallizing melilite. Second, we conducted a series of evaporation and cooling experiments exposing CAI-like melts to gas mixtures with different oxygen fugacities (f_O2). Cooling of the molten droplets in gases with logf_O2?IW-4 resulted in crystallization of randomly distributed melilite, while under more reducing conditions, melilite mantles have been formed. Chemical profiles through samples quenched right before melilite started to crystallize showed no chemical gradients in samples exposed to relatively oxidizing gases (logf_O2?IW-4), while the near-surface parts of the samples exposed to very reducing gases (logf_O2?IW-7) were depleted in volatile MgO and SiO₂, and enriched in refractory Al₂O₃. Using these experimental results and the fact that the evaporation rate of magnesium and silicon from CAI-like melts is proportional to , we estimate that Type B1 CAIs could be formed by evaporation of a partially molten precursor in a gas of solar composition with . Type B2 CAIs could form by slower evaporation of the same precursors in the same gas with .