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Insertion of apoLp-III into a lipid monolayer is more favorable for saturated, more ordered, acyl-chains
Abstract not provided
Ab initio thermodynamics of magnesium carbonates and hydrates in water-saturated supercritical CO2 and CO2-rich regions
ab initio thermodynamics is used to determine how free energies of magnesium carbonates and hydrates in a CO2–rich environment change with water concentration across a range of temperature and pressure relevant to geochemistry and carbon sequestration (275 K to 375 K and pCO2 of 1 to 210 bar). The methodology is based on first principles density-functional theory (DFT) calculations of the total energies and vibrational entropy of periclase, magnesite, brucite, nesquehonite, and hydromagnesite coupled to the experimental chemical potentials of CO2 and H2O. The impact of water in supercritical CO2 (scCO2), even though less than 1% at saturation, is found to have a significant impact on the stability of hydrated carbonate minerals. Hydromagnesite and nesquehonite are found to be more thermodynamically stable than periclase and brucite in water-saturated scCO2 and hence may be expected to result kinetically from carbonation of these minerals during CO2 sequestration. Under dehydrating conditions nesquehonite destabilizes rapidly, whereas hydromagnesite is much more likely to persist in a CO2-rich environment, consistent with the observations that hydromagnesite is widespread in nature and nesquehonite is relatively rare.
In-Situ 27Al NMR Spectroscopy of Aluminate in Sodium Hydroxide Solutions Above and Below Saturation with Respect to Gibbsite
Aluminum hydroxide (Al(OH)3, gibbsite) dissolution and precipitation processes in alkaline environments play a commanding role in aluminum refining and nuclear waste processing, yet mechanistic aspects underlying sluggish kinetics during crystallization have remained obscured due to a lack of in situ probes capable of isolating incipient ion pairs. At a molecular level Al is cycling between tetrahedral (Td) coordination in solution to octahedral (Oh) in the solid. We explored dissolution of Al(OH)3 that prepared variably saturated aluminate (Al(OH)4 -)-containing solutions under alkaline conditions (pH > 13) with in-situ 27Al magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy, and interrogated the results with ab initio molecular dynamics (AIMD) simulations complemented with chemical shift calculations based on high level theory. The collective results highlight the overall stability of the solvation structure for Td Al in the Al(OH)4 - oxyanion as a function of both temperature and Al concentration. The observed chemical shift did not change significantly even when the Al concentration in solution became supersaturated upon cooling and limited precipitation of the octahedral Al(OH)3 phase occurred. However, subtle changes in Al(OH)4 - speciation correlated with the dissolution/precipitation reaction were found. AIMDinformed chemical shift calculations indicate that measurable perturbations should begin when the Al(OH)4 -?Na+ distance is less than 6 Å, increasing dramatically at shorter distances, coinciding with appreciable changes to the electrostatic interaction and reorganization of the Al(OH)4 - solvation shell. The integrated findings thus suggest that, at conditions incipient to and concurrent with gibbsite crystallization, nominally expected contact ion pairs are insignificant and instead medium-range (4 – 6 Å) solvent-separated Al(OH)4 -?Na+ pairs predominate. Moreover, the fact that these medium-range interactions bear directly on resulting gibbsite characteristics was demonstrated by detailed microscopic and X-ray diffraction analysis, and by progressive changes in the FWHM of the Oh resonance, as measured by in-situ NMR. Sluggish gibbsite crystallization may arise from the activation energy associated with disrupting this robust medium-range ion pair interaction.
Femtosecond all-optical parallel logic gates based on tunable saturable to reverse saturable absorption in graphene-oxide thin films
A detailed theoretical analysis of ultrafast transition from saturable absorption (SA) to reverse saturable absorption (RSA) has been presented in graphene-oxide thin films with femtosecond laser pulses at 800 nm. Increase in pulse intensity leads to switching from SA to RSA with increased contrast due to two-photon absorption induced excited-state absorption. Theoretical results are in good agreement with reported experimental results. Interestingly, it is also shown that increase in concentration results in RSA to SA transition. The switching has been optimized to design parallel all-optical femtosecond NOT, AND, OR, XOR, and the universal NAND and NOR logic gates.
The Variable Saturation Hydraulic Conductivity Method for Improving Soil Water Content Simulation in EPIC and APEX Models
Core Ideas We propose VSHC for calculating soil water percolation in continuous models. VSHC relates permeability to daily hydraulic properties to estimate hydraulic conductivity. VSHC performed well at field scale and improved estimates of peak streamflows. Soil water percolation is a key process in the life cycle of water in fields, watersheds, and river basins. The Environmental Policy Integrated Climate (EPIC) and the Agricultural Policy/Environmental eXtender (APEX) are continuous models developed for evaluating the environmental effects of agricultural management. Traditionally, these models have simulated soil water percolation processes using a tipping‐bucket approach, with the rate of flow limited by the saturated hydraulic conductivity. This simple approach often leads to inaccuracy in simulating elevated soil water conditions where soil water content (SWC) levels may remain above field capacity under prolonged wet weather periods or limited drainage. To overcome this deficiency, a new submodel, the variable saturation hydraulic conductivity (VSHC) method, was developed for simulating soil water percolation processes using a nonlinear equation to estimate the effective hydraulic conductivity as a function of the SWC and soil properties. The VSHC method was evaluated at three sites in the United States and two sites in Europe. In addition, a numerical solution of the Richards equation was used as a benchmark for SWC comparison. Results show that the VSHC method substantially improves the accuracy of the SWC simulation in long‐term simulations, particularly during wet periods. At the watershed scale, results on the Riesel Y2 watershed indicate that the VSHC method enhances model performance in the high‐flow regime of channel peak flows because of the improved estimation of SWC, which implies that the improved SWC simulation at the field scale is beneficial to hydrologic modeling at the watershed scale.
The mobility of Nb in rutile-saturated NaCl- and NaF-bearing aqueous fluids from 1–6.5 GPa and 300–800 °C
Rutile (TiO₂) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 °C). In this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300–500 °C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at ~1 GPa and 700–800 °C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 μg/g as temperature increases from 300 to 500 °C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 μg/g at 300 to 500 °C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. The Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 μg/g as temperature increases from 300 to 500 °C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 °C at ≥2 GPa, but there is no observed dependence on pressure. Together, the data demonstrate that the hydrothermal mobility of Nb is strongly controlled by the composition of the fluid, consistent with published data for Ti. At all experimental conditions, however, the concentration of Nb in the fluid is always lower than coexisting rutile, consistent with a role for rutile in moderating the Nb budget of arc rocks.
Interpreting HSE Contents of Planetary Basalts: The Importance of Sulfide Saturation and Under-Saturation
Highly siderophile elements provide important constraints on planetary differentiation due to their siderophile behavior. Their interpretation in terms of planetary differentiation models has so far overlooked the importance of sulfide saturation and under-saturation.
An Interpolation Method for Obtaining Thermodynamic Properties Near Saturated Liquid and Saturated Vapor Lines
The two most common approaches used to formulate thermodynamic properties of pure substances are fundamental (or characteristic) equations of state (Helmholtz and Gibbs functions) and a piecemeal approach that is described in Adebiyi and Russell (1992). This paper neither presents a different method to formulate thermodynamic properties of pure substances nor validates the aforementioned approaches. Rather its purpose is to present a method to generate property tables from existing property packages and a method to facilitate the accurate interpretation of fluid thermodynamic property data from those tables. There are two parts to this paper. The first part of the paper shows how efficient and usable property tables were generated, with the minimum number of data points, using an aerospace industry standard property package. The second part describes an innovative interpolation technique that has been developed to properly obtain thermodynamic properties near the saturated liquid and saturated vapor lines.
An Interpolation Method for Obtaining Thermodynamic Properties Near Saturated Liquid and Saturated Vapor Lines
The availability and proper utilization of fluid properties is of fundamental importance in the process of mathematical modeling of propulsion systems. Real fluid properties provide the bridge between the realm of pure analytiis and empirical reality. The two most common approaches used to formulate thermodynamic properties of pure substances are fundamental (or characteristic) equations of state (Helmholtz and Gibbs functions) and a piecemeal approach that is described, for example, in Adebiyi and Russell (1992). This paper neither presents a different method to formulate thermodynamic properties of pure substances nor validates the aforementioned approaches. Rather its purpose is to present a method to be used to facilitate the accurate interpretation of fluid thermodynamic property data generated by existing property packages. There are two parts to this paper. The first part of the paper shows how efficient and usable property tables were generated, with the minimum number of data points, using an aerospace industry standard property package (based on fundamental equations of state approach). The second part describes an innovative interpolation technique that has been developed to properly obtain thermodynamic properties near the saturated liquid and saturated vapor lines.
EGS rock reactions with Supercritical CO2 saturated with water and water saturated with Supercritical CO2
EGS using CO2 as a working fluid will likely involve hydro-shearing low-permeability hot rock reservoirs with a water solution. After that process, the fractures will be flushed with CO2 that is maintained under supercritical conditions (> 70 bars). Much of the injected water in the main fracture will be flushed out with the initial CO2 injection; however side fractures, micro fractures, and the lower portion of the fracture will contain connate water that will interact with the rock and the injected CO2. Dissolution/precipitation reactions in the resulting scCO2/brine/rock systems have the potential to significantly alter reservoir permeability, so it is important to understand where these precipitates form and how are they related to the evolving ‘free’ connate water in the system. To examine dissolution / precipitation behavior in such systems over time, we have conducted non-stirred batch experiments in the laboratory with pure minerals, sandstone, and basalt coupons with brine solution spiked with MnCl2 and scCO2. The coupons are exposed to liquid water saturated with scCO2 and extend above the water surface allowing the upper portion of the coupons to be exposed to scCO2 saturated with water. The coupons were subsequently analyzed using SEM to determine the location of reactions in both in and out of the liquid water. Results of these will be summarized with regard to significance for EGS with CO2 as a working fluid.
Evaluation of a commercially available passively Q-switched Nd:YAG laser with LiF:F-2(-) saturable absorber for laser-induced breakdown spectroscopy
Interest in passively Q-switched microchip lasers as a means for miniaturization of laser-induced breakdown spectroscopy (LIBS) apparatus has rapidly grown in the last years. To explore the possibility of using a comparatively UV-Vis transparent absorber, we herein present the first report on the evaluation of a commercially available flash lamp-pumped passively Q-switched Nd:YAG laser with LiF:F 2 - saturable absorber as an excitation source in LIBS. Quantitative measurements of barium, strontium, rubidium and lithium in granite, rhyolite, basalt and syenite whole-rock glass samples were performed. Ablation craters produced on a rock glass sample were characterized using a computerized X-ray tomography. Using a gated intensified benchtop spectrometer, limits of detection of 0.97, 23, 37, and 144 ppm were obtained for Li, Sr, Rb, and Ba, respectively. Finally, we discuss the advantages of using such a laser unit for LIBS applications in terms of ablation efficiency, analytical performances, output energy, and standoff capabilities.
Saturation current spikes eliminated in saturable core transformers
Unsaturating composite magnetic core transformer, consisting of two separate parallel cores designed so impending core saturation causes signal generation, terminates high current spike in converter primary circuit. Simplified waveform, demonstrates transformer effectiveness in eliminating current spikes.
Saturation current protection apparatus for saturable core transformers Patent
Magnetic current regulator for saturable core transformer
Saturation and beaming in astrophysical masers. II - The fully saturated limit
Radiative transfer in fully saturated maser clouds has been investigated using the 'four-stream' model equations of Alcock and Ross (1985). It is shown that a modest elongation of the maser cloud produces a substantial asymmetry in the maser output. The ratio of output fluxes in different directions is a strong function of the ratio of the corresponding chord lengths across the cloud. Arguments are presented that the asymmetries reported here for the 'four-stream' models closely mimic the asymmetries that should be expected in a real master cloud.