227 research outputs found
Inclination Dependence of Lyman-Alpha Properties in a Turbulent Disk Galaxy
We present simulations of Lyman-Alpha radiation transfer in an isolated disk
galaxy with a turbulence sub-grid model, multi-phase interstellar medium and
detailed star formation modelling. We investigate the influence of inclination
on the observed Lyman-Alpha properties for different snapshots. The Lyman-alpha
spectrum, equivalent width distribution and escape fractions vary significantly
with the detailed morphology of the disk, leading to variations from one
snapshot to another. In particular, we find that supernova-driven cavities near
star-forming regions in the simulation can dominate the transmitted Lyman-alpha
fraction, suggesting a variability of LAEs on the timescales of the star
formation activity.Comment: accepted for publication, 9 page
Hydrogen defects in feldspars: defect properties and implications for water solubility in feldspar
Hydrogen defects can strongly affect mechanical and chemical properties of feldspars. To get insight into the behavior of such defects, alkali feldspar and plagioclase of igneous origin were studied combining IR spectroscopy with heating experiments under well-controlled conditions. Near-infrared spectra show that OH groups are the predominant hydrous species in these feldspars but presence of minor amounts of molecular H2O cannot be excluded. Short-term annealing at 400–800 °C produces a small but significant irreversible change in the OH stretching vibration band which is attributed to relaxation of the feldspar structure. Polarized mid-infrared spectra of sanidine, adularia, and plagioclase recorded in situ at temperatures up to 600 °C show reversible shifts of maxima toward higher wavenumber and an overall decrease in integrated intensities. The pleochroic features of the OH vibration bands, i.e., the predominant orientation of OH dipoles along the crystallographic a axis in all feldspars and the additional band component perpendicular to the (010) plane in sanidine are still present in the high-temperature spectra. Different behavior during long-term annealing at high temperature was found for the alkali feldspars and the plagioclases. At 900–1000 °C, the Eifel sanidines rapidly lost about one quarter of the initial water content which is attributed to a weakly bound hydrogen species in the feldspar structure. The remaining hydrogen is very strongly bound and was still detectable in 0.7–0.9 mm thick sections after annealing for 108 days at 1000 °C in air dried by phosphorus pentoxide. In contrast, a 1-mm-thick section of plagioclase completely lost hydrogen during heating in air within 8 days at 1000 °C. After partial dehydration, the pleochroic behavior of the OH absorption bands of the feldspars was basically preserved except that the 3050 cm−1 band of the sanidine, oriented perpendicular to (010), becomes more pronounced than the 3400 cm−1 band, oriented parallel to the a direction. Annealing experiments at 1000 °C under controlled water pressures indicate equilibrium solubilities of several tens of ppm H2O in the plagioclases and more than 100 ppm H2O in the alkali feldspars already at 1 bar water pressure. The variation of the water content with H2O pressure and spectroscopic observations indicates that the water content in the feldspars is determined not only by the water pressure but also by already existing defects. Vacancies on alkali sites (VA1) may accommodate H2O molecules, possibly with subsequent hydrolysis of network bonds to minimize local stress. A likely explanation for the strongly bound hydrogen in the sanidine is a coupled substitution of H+ + Al3+ for Si4+ (AlOH defect) where the protons are located on interstitial sites. This incorporation model is supported by the complete recovery of the defects in H2O vapor after previous proton/alkali exchange in alkali chloride vapor at 1000 °C
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
Hydrogen defects in feldspars: kinetics of D/H isotope exchange and diffusion of hydrogen species in alkali feldspars
Diffusion of hydrogen in natural alkali feldspars (Eifel sanidine and adularia from unknown locality) containing strongly bonded OH defects was investigated by D/H isotope exchange in the T range 600–1050 °C at ambient pressure and at elevated pressures up to 8 kbar. Runs at 1 atm were performed in a fused silica tube connected to a liquid D2O reservoir at room temperature. In the high- pressure experiments samples were sealed with D2O in gold capsules and processed up to 4 kbar in externally heated pressure vessels using Ar/D2O as the pressure medium. Experiments at 6–8 kbar were performed in an internally heated gas pressure vessel using the double capsule technique to minimize isotopic contamination by the pressure medium. Diffusion coefficients were determined either by measuring concentration-distance profiles of OH and OD with an IR microscope or by measuring the total exchange of oriented plates after various run durations using a macroscopic IR technique. Both methods gave consistent data. D/H interdiffusion, DD/H, is almost identical in the adularia and in the sanidine implying that the chemical composition and the degree of Al/Si disorder have minor influence on the hydrogen isotope exchange in alkali feldspars. Furthermore, no effect of crystallographic orientation was found for DD/H in both feldspars. DD/H in sanidine, however, depends on the thermal pre-treatment. Heating for several days at 900 °C leads to a lowering of D by a factor of 2.3, indicating a corresponding decrease in mobile hydrogen species. Data for sanidine pre-annealed at 900 °C are well described in the T range 600–1050 °C by DD/H(m2/s)=6.9·10-6exp(-162kJ/molR·T)The diffusivity is strongly enhanced by water pressures (PH2O), i.e., in the range of 0–2 kbar. At PH2O = 2 kbar the following equation applies in the T-range of 645–800 °C: DD/H(m2/s)=1.2·10-6exp(-131kJ/molR·T)Experiments with D2O/CO2 mixture of ratio 1:1 gave smaller exchange rates compared to pure D2O fluids, confirming that that not the pressure but the water fugacity leads to the increase in the mobility of hydrogen species. At 720 °C and pressures of 4–8 kbar, chemical diffusivities of H2O, D~H2O, were determined by fitting the weighted sum of the absorbances of the OH and the OD band vs. distance. The D~H2O values are similar to those reported by Kronenberg et al. (Geochim Cosmochim Acta 60:4075–4094, 1996) for dehydration of Kristallina adularia at ambient pressure. It is concluded that in both cases high concentrations of H2O molecules on interstitial sites govern the transport of hydrogen. Comparison of D/H interdiffusion to O diffusion in sanidine (Freer et al. in Phil Mag A75:485–503, 1997) implies that not only interstitial H2O but also protons contribute to the transport of hydrogen under hydrothermal conditions. On the other hand, the high DD/H at ambient pressure is attributed to an interdiffusion of protons and Na+, which is supported by Na tracerdiffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363:79–84, 2015). A basic conclusion of this research is that hydrogen storage capacity and hydrogen diffusion in feldspars are largely determined by extrinsic defects, such as substitutional defects (i.e., Al3+ + H+ for Si4+) and associates of water molecules with vacancies. The bonding of hydrogen species to the defects can vary greatly, depending on the genesis of the feldspars, so that quantitative predictions are difficult
Hydrogen defects in feldspars: alkali-supported dehydrogenation of sanidine
In the first two papers of this series [Behrens, Phys Chem Minerals 48:8, 2021a; Behrens, Phys Chem Minerals 48:27, 2021b], incorporation of hydrogen in the feldspar structure, partitioning of hydrogen between feldspars and gases/fluids and self-diffusion of hydrogen in feldspars have been discussed, with particular focus on sanidine. Here, the results of reactions between sanidine containing strongly bonded hydrogen defects and (Na,K)Cl are presented. Experiments were performed at ambient pressure at temperatures of 605–1000 °C, and hydrogen profiles were measured by IR microspectroscopy. Profiles can be interpreted by an incomplete dehydrogenation at the crystal surface or a strong concentration dependence of hydrogen diffusivity. Both are consistent with hydrogen located on interstitial sites and difficult to substitute by the larger alkali ions. Chemical diffusivities of hydrogen derived from fitting of the profiles or Boltzmann–Matano analysis are similar to self-diffusivities determined by D/H exchange experiments. Activation energies are also comparable. Comparison to sodium and potassium diffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363: 79–84, 2015; Hergemöller et al. in Phys Chem Minerals 44:345–351, 2017) supports a mechanism of proton diffusion charge-compensated by Na+ diffusion for hydrogen removal in the sanidines under dry conditions
Recommended from our members
Quantification of H2O contents in silicate glasses using IR spectrocopy - a calibration based on hydrous glasses analyzed ba Karl-Fischer titration
Water-related IR absorption bands were investigated in hydrous soda-lime-silica glass (SLS) and float glass (FG). Glasses containing between 0.5 and 6 wt% H2O (corresponding to 0.7 and 8 mol/1) were synthesized in platinum capsules by re-melting glass powder to which water had been added. Synthesis were perfomed in an internally heated gas pressure vessel at temperatures of 1200 to 1250 °C and pressures 100 to 500 MPa. The total water content (Cwater) of glasses was analyzed by pyrolysis and subsequent Karl- Fischer titration.
Five bands at 3550, 2850, 2350, 1730 and 1635 cm-1 in the IR spectrum of an SLS glass containing 4 wt% H2O were identified as vibration modes of water-related species by comparison with a D2O-bearing glass. With increasing Cwater the absorbance band at 3550 cm-1 (OH stretch of weakly H-bonded hydrous species) grows in intensity relative to the band at 2850 cm-1 (OH Stretch of strongly H-bonded hydrous species). As a consequence, the practical absorption coefficient for the band at 3550 cm-1 (ε3550pract, defined by assigning the total water to this band) is 20 % lower at 0.1 wt% water than at 4 wt% water. The dependence of ε3550pract on Cwater is most pronounced above 0.5 wt% but appears to be present also in water-poor glasses. In contrast, ε2850pract does not noticeably depend on water content (FG: ε2850pract = (40.2 ± 2.4) l∙mol-1∙cm-1; SLS: ε2850pract = (50.8 ± 2.0) l∙mol-1∙cm-1) and, hence, it is preferred for water determination in float glass and soda-lime-silica glass. Scholze's two-band method [1] using the peak height of both bands at 3550 and 2850 cm-1 to quantify Cwater in glasses is a suitable first approach also for hydrous glasses, predicting the water content within 20 % relative. However, for a more precise determination the dependence of the ε-values on Cwater has to be considered. Α preliminary evaluation of the H2O bending vibration band at 1635 cm-1 shows that molecular H2O is a minor hydrous species in FG and SLS glasses with a maximum concentration of 2.0 wt% in FG glass containing 5.7 wt% total water. On the basis of the new spectroscopic results and data from literature the assignment of the so-called ABC triplet (bands 2850, 2350 and 1750 cm-1) is discussed
Lithium conductivity in glasses of the Li2O-Al2O3-SiO2 system
To improve the understanding of Li-dynamics in oxide glasses, i.e. the effect of [AlO4](-) tetrahedra and non-bridging oxygens on the potential landscape, electrical conductivity of seven fully polymerized and partly depolymerized lithium aluminosilicate glasses was investigated using impedance spectroscopy (IS). Lithium is the only mobile particle in these materials. Data derived from IS, i. e. activation energies, preexponential factors and diffusivities for lithium, are interpreted in light of Raman spectroscopic analyses of local structures in order to identify building units, which are crucial for lithium dynamics and migration. In polymerized glasses (compositional join LiAlSiO4-LiAlSi4O10) the direct current (DC) electrical conductivity continuously increases with increasing lithium content while lithium diffusivity is not affected by the Al/ Si ratio in the glasses. Hence, the increase in electrical conductivity can be solely assigned to lithium concentration in the glasses. An excess of Li with respect to Al, i.e. the introduction of non-bridging oxygen into the network, causes a decrease in lithium mobility in the glasses. Activation energies in polymerized glasses (66 to 70 kJ mol(-1)) are significantly lower than those in depolymerized networks (76 to 78 kJ mol(-1)) while pre-exponential factors are nearly constant across all compositions. Comparison of the data with results for lithium silicates from the literature indicates a minimum in lithium diffusivity for glasses containing both aluminium tetrahedra and non-bridging oxygens. The findings allow a prediction of DC conductivity for a large variety of lithium aluminosilicate glass compositions.DFG/FOR/1277DFG/FOR/127
Identification of low-frequency TRAF3IP2 coding variants in psoriatic arthritis patients and functional characterization
Introduction: In recent genome-wide association studies for psoriatic arthritis (PsA) and psoriasis vulgaris, common coding variants in the TRAF3IP2 gene were identified to contribute to susceptibility to both disease entities. The risk allele of p.Asp10Asn (rs33980500) proved to be most significantly associated and to encode a mutant protein with an almost completely disrupted binding property to TRAF6, supporting its impact as a main disease-causing variant and modulator of IL-17 signaling.
Methods: To identify further variants, exons 2-4 encoding both known TNF-receptor-associated factor (TRAF) binding domains were sequenced in 871 PsA patients. Seven missense variants and one three-base-pair insertion were identified in 0.06% to 1.02% of alleles. Five of these variants were also present in 931 control individuals at comparable frequency. Constructs containing full-length wild-type or mutant TRAF3IP2 were generated and used to analyze functionally all variants for TRAF6-binding in a mammalian two-hybrid assay.
Results: None of the newly found alleles, though, encoded proteins with different binding properties to TRAF6, or to the cytoplasmic tail of the IL-17-receptor α-chain, suggesting that they do not contribute to susceptibility.
Conclusions: Thus, the TRAF3IP2-variant p.Asp10Asn is the only susceptibility allele with functional impact on TRAF6 binding, at least in the German population
Water solubility in silica and quartzofeldspathic melts
Water solubility in silica melts was determined at 100–600 MPa, 1200–1350 °C, and at each temperature (T) was found to increase with pressure (P). At P £ 250 MPa, the effect of T on water solubility in silica melts is small and within analytical precision (±0.15 wt% H2O). A positive correlation with T was observed at 400 MPa. Increasing solubility of water with increasing T was observed when large amounts of water are dissolved in silica and quartzofeldspathic melts (i.e., when molecular water is the dominant species in the glasses at room temperature), as already observed for feldspar melts. Change in water solubility (expressed in mol%) with decreasing SiO2 content of the melt is nonlinear along the silica-albite join. In the compositional range Ab100 to Ab25 (100 to 25 mol% albite, respectively, compositions calculated on an eight-oxygen basis), the solubility of water at 200 MPa decreases only slightly with decreasing Ab content (–0.1 ± 0.01 mol% H2O per mol% albite). However, at Ab contents less than 25 mol%, water solubility decreases sharply with increasing Qz content. Similar behavior was observed at 500 MPa. These results suggest that two different incorporation mechanisms of water in quartzofeldspathic melts must be considered: one corresponding to an NaAlSi3O8-H2O mechanism, the other to an SiO2-H2O mechanism
Solubility of C-O-H mixtures in natural melts: new experimental data and application range of recent models
The effect of pressure, temperature, and melt composition on CO2 and H2O solubilities in aluminosilicate melts, coexisting with CO2-H2O fluids, is discussed on the basis of previously published and new experimental data. The datasets have been chosen so that CO2 and H2O are the main fluid components and the conclusions are only valid for relatively oxidizing conditions. The most important parameters controlling the solubilities of H2O and CO2 are pressure and composition of melt and fluid. On the other hand, the effect of temperature on volatile solubilities is relatively small. At pressures up to 200 MPa, intermediate compositions such as dacite, in which both molecular CO2 and carbonate species can be dissolved, show higher volatile solubilities than rhyolite and basalt. At higher pressures (0.5 to 1 GPa), basaltic melts can incorporate higher amounts of carbon dioxide (by a factor of 2 to 3) than rhyolitic and dacitic melts. Henrian behavior is observed only for CO2 solubility in equilibrium with H2O-CO2 fluids at pressures < 100 MPa, whereas at higher pressures CO2 solubility varies nonlinearly with CO2 fugacity. The positive deviation from linearity with almost constant CO2 solubility at low water activity indicates that dissolved water strongly enhances the solubility Of CO2. Water always shows non-Henrian solubility behavior because of its complex dissolution mechanism (incorporation of OH-groups and H2O molecules in the melt). The model of Newman and Lowenstern (2002), in which ideal mixing between volatiles in both fluid and melt phases is assumed, reproduces adequately the experimental data for rhyolitic and basaltic compositions at pressures below 200 MPa but shows noticeable disagreement at higher pressures, especially for basalt. The empirical model of Liu et al. (2004) is applicable to rhyolitic melts in a wide range of pressure (0-500 MPa) and temperature (700-1200 degrees C) but cannot be used for other melt compositions. The thermodynamic approach of Papale (1999) allows to calculate the effect of melt composition on volatile solubilities but needs an update to account for more recent experimental data. A disadvantage of this model is that it is not available as a program code. The review indicates a crucial need of new experimental data for scarcely investigated field of pressures and fluid compositions and new models describing evident non-ideality of H-C-O fluid solubility in silicate melts at high pressures
- …