Effects of F, B2O3 and P2O5 on the solubility of water in haplogranite melts compared to natural silicate melts

The effects of F, B2O3 and P2O5 on the H2O solubility in a haplogranite liquid (36 wt. % SiO2, 39 wt. % NaAlSi3O8, 25 wt. % KAlSi3O8) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H2O solubility increases with increasing F and B content of the melt. The H2O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H2O solubility increases from 5.94 to 8.22 wt. % H2O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H2O solubility increase of 0.53 mol H2O/mol F. With addition of 4.35 wt. % B2O3, the H2O solubility increases up to 6.86 wt. % H2O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H2O/mol B2O3. The results allow to define the individual effects of fluorine and boron on H2O solubility in haplogranitic melts with compositions close to that of H2O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H2O solubility was found to be negligible in natural melt compositions. The concominant increase in H2O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts

Water solubility in aluminosilicate melts of haplogranite composition at 2 kbar

The compositional dependence of H2O solubility was investigated at 2 kbar and 800°C in haplogranite melts (system SiO2---1bNaAlSi3O8---1bKAlSi3O8 or Qz---1bAb---1bOr). The sixteen investigated compositions contained 25, 35 or 45 wt.% normative Qz and various Ab/(Ab+Or) ratios (0.15–0.92). Starting solid materials were anhydrous bubble-free glasses to which 10 wt.% H2O was added. The H2O contents of the isobarically quenched melts (glasses) were measured by Karl-Fischer titration. The results show that H2O solubility in aluminosilicate melts depends significantly upon anhydrous composition. The highest solubility values are obtained for the most Ab-rich melts. At a constant normative quartz content, the solubility of water decreases from 6.49 ± 0.20 wt.% H2O for a composition Qz35Ab60Or05 (normative composition expressed in wt.%) to 5.50 ± 0.15 wt.% H2O for a composition Qz35Ab10Or55. Along this join, the most significant changes are observed for Ab-rich melts whereas H2O solubility in Or-rich melts remains almost constant. The H2O solubility data imply that H2O is preferentially associated with the Ab component in aluminosilicate melts. Application of the results to natural granitic melts suggests that Na-rich, H2O-saturated melts may be significantly less viscous than H2O-saturated, K-rich melts. The temperature dependence of H2O solubility, investigated for composition Qz28Ab38Or34 at 2 kbar, is low. Increasing temperature from 750° to 1150°C only causes a decrease in H2O solubility from 6.00 to 5.41 wt.% H2O. These data are in agreement with previous data obtained for albite melts

Effects of CO2 on H2O band profiles and band strengths in mixed H2O:CO2 ices

H2O is the most abundant component of astrophysical ices. In most lines of sight it is not possible to fit both the H2O 3 um stretching, the 6 um bending and the 13 um libration band intensities with a single pure H2O spectrum. Recent Spitzer observations have revealed CO2 ice in high abundances and it has been suggested that CO2 mixed into H2O ice can affect relative strengths of the 3 um and 6 um bands. We used laboratory infrared transmission spectroscopy of H2O:CO2 ice mixtures to investigate the effects of CO2 on H2O ice spectral features at 15-135 K. We find that the H2O peak profiles and band strengths are significantly different in H2O:CO2 ice mixtures compared to pure H2O ice. In all H2O:CO2 mixtures, a strong free-OH stretching band appears around 2.73 um, which can be used to put an upper limit on the CO2 concentration in the H2O ice. The H2O bending mode profile also changes drastically with CO2 concentration; the broad pure H2O band gives way to two narrow bands as the CO2 concentration is increased. This makes it crucial to constrain the environment of H2O ice to enable correct assignments of other species contributing to the interstellar 6 um absorption band. The amount of CO2 present in the H2O ice of B5:IRS1 is estimated by simultaneously comparing the H2O stretching and bending regions and the CO2 bending mode to laboratory spectra of H2O, CO2, H2O:CO2 and HCOOH.Comment: 12 pages, 11 figures, accepted by A&

Magnetic behavior of lamellar mnps3 and cdps3 composites with a paramagnetic manganese(iii) macrocyclic guest

Indexación: ScieloSix new composites derived from the intercalation of the MPS3 phases (M = MnII, CdIII) with the macrocyclic manganese(III) complex [MnL(H2O)2].NO3(H2O) (LH2 = Schiff base macrocyclic ligand derived from the condensation of 2-hydroxy-5-methy1-1,3-benzene-dicarbaldehyde and 1,2-diamine-benzene) were obtained by two different synthetic procedures: a conventional and a microwave assisted method. The composites [MnL]0.25K0.15Mn0.80 PS3(H2O)~1.0 (1), and [MnL]0.25K0.15Cd 0. 80PS3(H2O)~0.5 (2) were obtained by the conventional method, after stirring a suspension of the corresponding potassium precursor and the macrocyclic complex for two weeks, while [MnL]0.35K0.15Mn0.80 PS3(H2O)~1.0 (3) and [MnL]0.25K0.15Cd 0. 80PS3(H2O)~0.5 (4) after stirring for four weeks at room temperature. Using a microwave assisted reaction permitted to obtain in a shorter period of time as compared with the conventional method, composites [MnL]0.20K0.15Mn0.80 PS3(H2O)~1.0 (5) and [MnL]0.15K0.15Cd 0. 80PS3(H2O)~0.5 (6). All the M = MnII, MnIII composites show a bulk antiferromagnetic behavior. However, the spontaneous magnetization present at low temperature in the potassium precursor K0.40Mn0.80 PS3(H2O)~1.0 is observable in composite [MnL]0.20K0.15Mn0.80 PS3(H2O)~1.0 (5), while it is completely absent in composites [MnL]0.25K0.15Mn0.80 PS3(H2O)~1.0 (1) and [MnL]0.35K0.15Mn0.80 PS3(H2O)~1.0 (3). Keywords: Intercalation; MPS3 phases; MnIII macrocyclic complex; microwave assisted synthesis; magnetic properties

H2O line mapping at high spatial and spectral resolution - Herschel observations of the VLA1623 outflow

Apart from being an important coolant, H2O is known to be a tracer of high-velocity molecular gas. Recent models predict relatively high abundances behind interstellar shockwaves. The dynamical and physical conditions of the H2O emitting gas, however, are not fully understood yet. We aim to determine the abundance and distribution of H2O, its kinematics and the physical conditions of the gas responsible for the H2O emission. The observed line profile shapes help us understand the dynamics in molecular outflows. We mapped the VLA1623 outflow, in the ground-state transitions of o-H2O, with the HIFI and PACS instruments. We also present observations of higher energy transitions of o-H2O and p-H2O obtained with HIFI and PACS towards selected outflow positions. From comparison with non-LTE radiative transfer calculations, we estimate the physical parameters of the water emitting regions. The observed water emission line profiles vary over the mapped area. Spectral features and components, tracing gas in different excitation conditions, allow us to constrain the density and temperature of the gas. The H2O emission originates in a region where temperatures are comparable to that of the warm H2 gas (T\gtrsim200K). Thus, the H2O emission traces a gas component significantly warmer than the gas responsible for the low-J CO emission. The H2O column densities at the CO peak positions are low, i.e. N(H2O) \simeq (0.03-10)x10e14 cm-2. The H2O abundance with respect to H2 in the extended outflow is estimated at X(H2O)<1x10e-6, significantly lower than what would be expected from most recent shock models. The H2O emission traces a gas component moving at relatively high velocity compared to the low-J CO emitting gas. However, other dynamical quantities such as the momentum rate, energy and mechanical luminosity are estimated to be the same, independent of the molecular tracer used, CO or H2O.Comment: 14 pages, 13 figures, 4 table

Modeling the H2O submillimeter emission in extragalactic sources

Recent observational studies have shown that H2O emission at (rest) submillimeter wavelengths is ubiquitous in infrared galaxies, both in the local and in the early Universe, suggestive of far-infrared pumping of H2O by dust in warm regions. In this work, models are presented that show that (i) the highest-lying H2O lines (E_{upper}>400 K) are formed in very warm (T_{dust}>~90 K) regions and require high H2O columns (N_{H2O}>~3x10^{17} cm^{-2}), while lower lying lines can be efficiently excited with T_{dust}~45-75 K and N_{H2O}~(0.5-2)x10^{17} cm^{-2}; (ii) significant collisional excitation of the lowest lying (E_{upper}<200 K) levels, which enhances the overall L_{H2O}-L_{IR} ratios, is identified in sources where the ground-state para-H2O 1_{11}-0_{00} line is detected in emission; (iii) the H2O-to-infrared (8-1000 um) luminosity ratio is expected to decrease with increasing T_{dust} for all lines with E_{upper}<~300 K, as has recently been reported in a sample of LIRGs, but increases with T_{dust} for the highest lying H2O lines (E_{upper}>400 K); (iv) we find theoretical upper limits for L_{H2O}/L_{IR} in warm environments, owing to H2O line saturation; (v) individual models are presented for two very different prototypical galaxies, the Seyfert 2 galaxy NGC 1068 and the nearest ultraluminous infrared galaxy Arp 220, showing that the excited submillimeter H2O emission is dominated by far-infrared pumping in both cases; (vi) the L_{H2O}-L_{IR} correlation previously reported in observational studies indicates depletion or exhaustion time scales, t_{dep}=Sigma_{gas}/Sigma_{SFR}, of <~12 Myr for star-forming sources where lines up to E_{upper}=300 K are detected, in agreement with the values previously found for (U)LIRGs from HCN millimeter emission...Comment: 13 pages, 13 figure

Microwave spectra of van der Waals complexes of importance in planetary atmospheres

The Fourier-transform Fabry-Perot pulsed-molecular-beam microwave spectrometer at NIST was used to study the microwave spectra of a number of molecular dimers and trimers that may be present in planetary atmospheres. The weak van der Waals bonds associated with these species usually give rise to rotational-tunneling splittings in the microwave spectra. The microwave spectrum of the water dimer species was used to illustrate the complications that can arise in the study of the rotational spectra of these loosely bound species. In addition to the water dimer species, the microwave spectra of the following hydrogen-bonded and van der Waals complexes were studied: (CO2)2-H2O, CO2-(H2O)2, CO2-H2S, N2-H2O, CO-H2O, SO2-H2O, and O3-H2O

Stabilities of nanohydrated thymine radical cations: insights from multiphoton ionization experiments and ab initio calculations

Multi-photon ionization experiments have been carried out on thymine-water clusters in the gas phase. Metastable H2O loss from T+(H2O)n was observed at n ≥ 3 only. Ab initio quantum-chemical calculations of a large range of optimized T+(H2O)n conformers have been performed up to n = 4, enabling binding energies of water to be derived. These decrease smoothly with n, consistent with the general trend of increasing metastable H2O loss in the experimental data. The lowest-energy conformers of T+(H2O)3 and T+(H2O)4 feature intermolecular bonding via charge-dipole interactions, in contrast with the purely hydrogen-bonded neutrals. We found no evidence for a closed hydration shell at n = 4, also contrasting with studies of neutral clusters

Submillimeter vibrationally excited water emission from the peculiar red supergiant VY CMa

Vibrationally excited emission from the SiO and H2O molecules probes the innermost circumstellar envelopes of oxygen-rich red giant and supergiant stars. VY CMa is the most prolific known stellar emission source in these molecules. Observations were made to search for rotational lines in the lowest vibrationally excited state of H2O. The APEX telescope was used for observations of H2O lines at frequencies around 300 GHz. Two vibrationally excited H2O lines were detected, a third one could not be found. In one of the lines we find evidence for weak maser action, similar to known (sub)millimeter H2O lines. We find that the other line's intensity is consistent with thermal excitation by the circumstellar infrared radiation field. Several SiO lines were detected together with the H2O lines.Comment: APEX A&A special issue, accepte