The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

The effect of fluorine on viscosities in the system Na2O-Al2O3-SiO2: implications for phonolites, trachytes and rhyolites

The effect of fluorine on melt viscosities of five compositions in the system Na2O-Al2O3- SiO2h as been investigateda t one atmospherea nd 1000-1600'Cb y concentric-cylinder viscometry. The compositions chosen were albite, jadeite and nepheline on the join NaAlOlSiO2 and two others of the join at 75 mole percent SiO2, one peralkaline and one peraluminous. All melt viscosities were independent of shear rate over two orders of magnitude, indicating Newtonian behavior. All viscosity-temperature relationships were Arrhenian within error. Fluorine reduces the viscosities and activation energies of all melts investigated. The viscosity-reducing power of fluorine increases with the SiO2 content of melts on the join NaAlO2-SiO2 and is a maximum at Na/Al (molar) = I for melts containing 75 mole percent SiO2. Fluorine and water have similar effects on aluminosilicate melt viscosities, probably due to depolymerization of these melts by replacement of Si-O-(Si, Al) bridges with Si-OH and Si-F bonds, respectively. Evidence from slag systems shows that fluorine also reduces the viscosity of depolymerized silicate melts. The viscous flow of phonolites, trachytes and rhyolites will be strongly afected by fluorine. It appears that fluorine contents of igneous rocks may be combined with water in calculation schemes for determining the viscosity of natural melts

Energetics of the Charge-Coupled Substitution Si4+ Na++ T3+ in the-Glasses NaTO2–SiO2 (T = Al, Fe, Ga, B)

Heats of solution in molten 2PbO·B2O3 at 973 K are reported for glasses xNaT3+O2–(1 –x)SiO2 for T = Fe, Ga. These measurements, combined with previous data for T = Al, B, give a relative measure of the enthalpy of the charge-coupled substitution Si4+→ Na++ T3+. The heats of solution become more endothermic with increasing x for x→ 0.5 and exhibit a maximum near x= 0.5. This indicates an exothermic enthalpy for the substitution and an overall stabilization of the glasses. The degree to which the glasses are stabilized decreases in the order Al > Ga > Fe > B. On the basis of molecular orbital calculations, X-ray scattering, and Raman spectroscopy, it is argued that this trend is primarily due to a decrease in the range of energetically favorable T–O–T bond angles as Al, Ga, Fe, and B are substituted for Si

The solubility of rhenium in silicate melts: Implications for the geochemical properties of rhenium at high temperatures

The solubility of rhenium (Re) in a haplobasaltic melt (anorthite-diopside eutectic composition) has been experimentally determined using the mechanically assisted equilibration technique at 1400°C as a function of oxygen fugacity (10−12 < fO2 ≤ 10−7 bar), imposed by CO-CO2 gas mixtures. Samples were analysed by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). This is a true microanalytical technique, which allows small-scale sample heterogeneity to be detected, while providing a limit of detection of 2 ppb Re. Time-resolved LA-ICP-MS spectra revealed the presence of suboptically sized micronuggets of Re in all samples, which, because they are present at the 0.5 to 10 ppm level, dominate the true solubilities of Re (<1 ppm at the conditions of the experiment) in bulk analyses of the samples. Nevertheless, the micronuggets could be filtered out from the time-resolved spectra to reveal accurate values of the true Re solubility. A number of time series of samples were taken at constant fO2 to demonstrate that the solubilities converge to a constant value. In addition, solubilities were measured after increasing and decreasing the imposed fO2. The results show that Re dissolves in the silicate melt as ReO2 (Re4+) and ReO3 (Re6+) species, with the latter predominating at typical terrestrial upper-mantle oxygen fugacities. The total solubility of Re is described by the following expression (fO2 in bars): [Re/ppb] = 9.7(±1.9) × 109 (fO2) + 4.2 (±0.3) × 1014 (fO2)1.5Assuming an activity coefficient for Re in Fe-rich metal of 1, this gives a value of DRemet/sil of 5 × 1010 at log fO2 = IW-2, appropriate for metal-silicate partitioning in an homogenously accreting Earth. Thus, Re is indeed very highly siderophile, and the mantle’s abundance cannot be explained by homogenous accretion

Impact vesiculation – a new trigger for volcanic bubble growth and degassing

We highlight a potentially important trigger for bubble growth and degassing in volcanic bombs. We have successfully triggered bubble growth in previously unvesiculated samples of silicate melt during experiments to simulate volcanic bomb impact, by firing pellets at, and dropping weights onto, melt samples. We call this phenomenon "impact vesiculation". Further work is required on real volcanic bombs to establish the extent to which impact vesiculation occurs in nature. However, our experiments are sufficient to demonstrate that impact vesiculation is a viable processes and should be borne in mind in analysis of bubble populations and degassing histories of bombs and spatter-fed lava flows. Degassing caused by impact vesiculation can occur only at ground-level, so any attempt to calculate the amount of erupted gas available for transport high into the atmosphere by convection above the source of a fountain-fed lava flow that is based on subtracting the volatile content of fluid inclusions from the volatile content of the resulting lava flow would be an overestimate if significant impact vesiculation has occurred

The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

Design aspects of explosive mixtures in a vehcile interstage final report

Prevention and control of explosive mixture of hydrogen and oxygen within vehicle interstag

Comparison of walking overground and in a Computer Assisted Rehabilitation Environment (CAREN) in individuals with and without transtibial amputation

Background Due to increased interest in treadmill gait training, recent research has focused on the similarities and differences between treadmill and overground walking. Most of these studies have tested healthy, young subjects rather than impaired populations that might benefit from such training. These studies also do not include optic flow, which may change how the individuals integrate sensory information when walking on a treadmill. This study compared overground walking to treadmill walking in a computer assisted virtual reality environment (CAREN) in individuals with and without transtibial amputations (TTA). Methods Seven individuals with traumatic TTA and 27 unimpaired controls participated. Subjects walked overground and on a treadmill in a CAREN at a normalized speed. The CAREN applied optic flow at the same speed that the subject walked. Temporal-spatial parameters, full body kinematics, and kinematic variability were collected during all trials. Results Both subject groups decreased step time and control subjects decreased step length when walking in the CAREN. Differences in lower extremity kinematics were small (\u3c 2.5○) and did not exceed the minimal detectable change values for these measures. Control subjects exhibited decreased transverse and frontal plane range of motion of the pelvis and trunk when walking in the CAREN, while patients with TTA did not. Both groups exhibited increased step width variability during treadmill walking in the CAREN, but only minor changes in kinematic variability. Conclusions The results of this study suggest that treadmill training in a virtual environment should be similar enough to overground that changes should carry over. Caution should be made when comparing step width variability and step time results from studies utilizing a treadmill to those overground

Crystal plasticity as an indicator of the viscous-brittle transition in magmas

Understanding the flow of multi-phase (melt, crystals and bubbles) magmas is of great importance for interpreting eruption dynamics. Here we report the first observation of crystal plasticity, identified using electron backscatter diffraction, in plagioclase in andesite dome lavas from Volcán de Colima, Mexico. The same lavas, deformed experimentally at volcanic conduit temperature and load conditions, exhibit a further, systematic plastic response in the crystalline fraction, observable as a lattice misorientation. At higher stress, and higher crystal fraction, the amount of strain accommodated by crystal plasticity is larger. Crystal plastic distortion is highest in the intact segments of broken crystals, which have exceeded their plastic limit. We infer that crystal plasticity precludes failure and can punctuate the viscous-brittle transition in crystal-bearing magmas at certain shallow magmatic conditions. Since crystal plasticity varies systematically with imposed conditions, this raises the possibility that it may be used as a strain marker in well-constrained systems