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Partition function corrections

The vibration-rotation interaction coupling in diatomic molecules is analyzed and first-order expressions for the energy levels are deduced. Corrections to the partition function to account for this coupling are derived. The effects of long-range intermolecular forces due to induced dipole-induced dipole interactions, dipole-induced dipole interactions, charge-dipole interactions, and charge-charge interactions are considered. London's quantized oscillator model of the induced dipole-induced dipole interaction is developed. The partition function including effects of such dispersion forces is derived and is shown to lead to the virial equation of state. For a model combining the hard sphere and long-range attractive type potentials, this is found to lead to the van der Waals equation of state. The equation of state near the critical point is presented in reduced form (thermodynamic variables expressed in units of critical point values). Finally, approximate corrections to the electronic partition functions are derived to account for perturbations of excited electronic states induced by neighboring neutral particles, heavy ions, and fast electron collisions.

Source record↗

Characterization of soil and postlaunch pad debris from Cape Canaveral launch complex and analysis of soil interaction with aqueous HCl

Soil samples were fractionated and analyzed in order to assess the physical and chemical interactions of entrained soil with solid-rocket exhaust clouds. The sandy soil consisted primarily of quartz (silica) particles, 30 to 500 microns in diameter, and also contained seashell fragments. Differential and cumulative soil-mass size distributions are presented along with mineralogy, elemental compositions, and solution pH histories. About 90 percent of the soil mass consisted of particles 165 microns in diameter. Characteristic reaction times in aqueous HC1 slurries varied from a few minutes to several days, and capacities for reaction under acidic conditions varied from 10 to 40 g HCl/kg soil, depending on particle size. Airborne lifetimes of particles 165 microns are conservatively 30 min, and this major grouping is predicted to represent a small short-term chemical sink for up to 5% of the total HC1. The smaller and more minor fractions, below a 165 micron diameter, may act as giant cloud condensation nuclei over much longer airborne lifetimes. Finally, the demonstrated time dependency of neutralization is a complicating factor; it can influence the ability to deduce in-cloud HCl scavenging with reaction and can affect the accuracy of measured chemical compositions of near-field wet deposition.

Pellett, G. L.↗

The interstellar gas experiment: Analysis in progress

The interstellar gas experiment (IGE) exposed thin metallic foils in order to collect neutral interstellar particles which penetrate the solar system due to their motion relative to the sun. These atoms were entrapped in the collecting foils along with precipitating magnetospheric ions and with ambient atmospheric atoms. For the entire duration of the LDEF mission, seven of the foils collected particles arriving from seven different directions as seen from the spacecraft. In the mass spectrometric analysis of the trapped noble gas component, we detected the He-3, He-4, Ne-20, and Ne-22 isotopes. In order to infer the isotopic ratios in the interstellar medium from the measured concentrations found in the foil piece, several lines of investigation had to be initiated. The flux of incident noble gas atoms from the ambient atmosphere was estimated by detailed calculations. The contributions proved to be negligible, supporting the experimental evidence. Foil and machine backgrounds for the four isotopes which were measured had to be assessed individually. While this was easy for He-4, spurious foil background of He-3 had to be monitored carefully by analyzing unflown foil pieces. Trapped Ne concentrations are not far above the background. During the flight, a stuck electrical relay precluded the foil-trays from sequencing as designed. Therefore, we could not use the seasonal variation of the direction of the incoming interstellar atoms to make the distinction between interstellar and magnetospheric components of the trapped particles. Instead, we had to try the method of stepwise heating to extract the interstellar component at lower temperatures than we use to extract the magnetospheric component (the interstellars hit the foil with lower energies than most of the magnetospherics). New limiting values for the isotopic composition of the interstellar medium, unavailable yet from any other method of measurement, are emerging from this analysis.

Buehler, F.↗

The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely <100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Blake, David Frederick↗

Large Abundances of Polycyclic Aromatic Hydrocarbons in Titan's Upper Atmosphere

In this paper, we analyze the strong unidentified emission near 3.28 micron in Titan's upper daytime atmosphere recently discovered by Dinelli et al.We have studied it by using the NASA Ames PAH IR Spectroscopic Database. The polycyclic aromatic hydrocarbons (PAHs), after absorbing UV solar radiation, are able to emit strongly near 3.3 micron. By using current models for the redistribution of the absorbed UV energy, we have explained the observed spectral feature and have derived the vertical distribution of PAH abundances in Titan's upper atmosphere. PAHs have been found to be present in large concentrations, about (2-3) × 10(exp 4) particles / cubic cm. The identified PAHs have 9-96 carbons, with a concentration-weighted average of 34 carbons. The mean mass is approx 430 u; the mean area is about 0.53 sq. nm; they are formed by 10-11 rings on average, and about one-third of them contain nitrogen atoms. Recently, benzene together with light aromatic species as well as small concentrations of heavy positive and negative ions have been detected in Titan's upper atmosphere. We suggest that the large concentrations of PAHs found here are the neutral counterpart of those positive and negative ions, which hence supports the theory that the origin of Titan main haze layer is located in the upper atmosphere.

PAH↗

The Comprehensive Inner Magnetosphere-Ionosphere Model

Simulation studies of the Earth's radiation belts and ring current are very useful in understanding the acceleration, transport, and loss of energetic particles. Recently, the Comprehensive Ring Current Model (CRCM) and the Radiation Belt Environment (RBE) model were merged to form a Comprehensive Inner Magnetosphere-Ionosphere (CIMI) model. CIMI solves for many essential quantities in the inner magnetosphere, including ion and electron distributions in the ring current and radiation belts, plasmaspheric density, Region 2 currents, convection potential, and precipitation in the ionosphere. It incorporates whistler mode chorus and hiss wave diffusion of energetic electrons in energy, pitch angle, and cross terms. CIMI thus represents a comprehensive model that considers the effects of the ring current and plasmasphere on the radiation belts. We have performed a CIMI simulation for the storm on 5-9 April 2010 and then compared our results with data from the Two Wide-angle Imaging Neutral-atom Spectrometers and Akebono satellites. We identify the dominant energization and loss processes for the ring current and radiation belts. We find that the interactions with the whistler mode chorus waves are the main cause of the flux increase of MeV electrons during the recovery phase of this particular storm. When a self-consistent electric field from the CRCM is used, the enhancement of MeV electrons is higher than when an empirical convection model is applied. We also demonstrate how CIMI can be a powerful tool for analyzing and interpreting data from the new Van Allen Probes mission.

Inner Magnetosphere↗

The Dipper Satellite: A Medium-Class Explorer Mission to the Threshold of Space

The Dipper satellite will carry out an unprecedented, systematic, and focused in-situ exploration of the Earth's lower ionosphere and thermosphere below 200 km that will produce a pivotal base of knowledge that will significantly advance our understanding of knowledge that will significantly advance our understanding of how our near-space environment works. The satellite will carry comprehensive in-situ probes to measure vector electric and magnetic fields, plasma density and temperature, ion velocities, ion and neutral composition and winds, energetic particles including suprathermal electrons, gravity waves, and lightning bursts. The satellite will include a propulsion system and tapered body that will provide over 10,000 excursions to altitudes below 200 km with over 3000 dips to altitudes below 150 km. With this instrument complement, spacecraft, and orbit, the Dipper mission will gather the necessary combined electrodynamics and neutral dynamics measurements to provide an understanding of the Earth's critical boundary region where the ionized gases of space and the neutral gases of the atmosphere are coupled, and where impinging forces and momentum are deposited from the magnetosphere above and from the troposphere, stratosphere, and mesosphere below. In exploring those physical processes in the lower ionosphere which can only be measured in-situ, the Dipper mission addresses four main science objectives. The Dipper will: 1) reveal how ion-neutral coupling creates a global system of dynamo electric fields and currents; 2) provide first-hand understanding of how magnetospheric currents close in the ionosphere and reveal the effects on the upper atmosphere of magnetospheric energy and momentum deposition; 3) discover the degree of upwards coupling and energy deposition due to thunderstorm electric fields and determine their significance; 4) determine the dynamics and composition of the Earth's lower thermosphere, including its response to gravity, tidal, and planetary waves on a range of spatial scales. A proposal to design, build, operate, and analyze data from instruments on the Dipper spacecraft within the schedule and budget constraints of NASA's MIDEX program was submitted to NASA in 1998. This presentation summarizes the main features of the mission.

Pfaff, R. F., Jr.↗

Discovery of Carbonate-Rich Outcrops in the Gusev Crater Columbia Hills by the MER Rover Spirit

The chemical composition, global abundance, distribution, and formation pathways of carbonates are central to understanding aqueous processes, climate, and habitability of early Mars. The Mars Exploration Rover (MER) Spirit analyzed a series of olivine-rich outcrops while descending from the summit region of Husband Hill into the Inner Basin of the Columbia Hills of Gusev Crater to the eastern edge of the El Dorado ripple field in late 2005. Reanalysis of Spirit s mineralogical data from the Moessbauer Spectrometer (MB) and the Miniature Thermal Emission Spectrometer (Mini-TES) and chemical data from the Alpha Particle X-Ray Spectrometer (APXS) in 2010, coupled with new laboratory data for carbonate-bearing samples, lead to identification of carbonate in one of the outcrops (Comanche) [Morris, R.V., et al., Science, 329, 421-424]. The carbonate is rich in magnesium and iron (Mc62Sd25Cc11Rh2, assuming all Ca and Mn is associated with the carbonate) and is a major component of the Comanche outcrops (16 to 34 wt.%). The mineralogical, chemical, and abundance data are constrained in multiple, mutually consistent ways by the MER analyses. For example, a low-Ca carbonate is required by the MB and APXS data and is consistent with Mini-TES data. Three spectral features attributable to fundamental infrared vibrational modes of low-Ca carbonate are present in the Mini-TES spectra of Comanche outcrops. The average composition of Comanche carbonate approximates the average composition of the carbonate globules in Martian meteorite ALH 84001. Analogy with ALH 84001, terrestrial, and synthetic carbonate globules suggests that Comanche carbonate precipitated from aqueous solutions under hydrothermal conditions at near neutral pH in association with volcanic activity during the Noachian era. Comanche outcrop morphology suggests they are remnants of a larger carbonate-bearing formation that evolved in ultramafic rock and then preferentially eroded by a combination of aeolian abrasion and chemical decomposition by exposure to acid-sulfate vapors/solutions. The high carbonate concentration in the Comanche outcrops supports climate models involving a CO2 greenhouse gas on a wet and warm early Mars and subsequent sequestering of at least part of that atmosphere in carbonate minerals.

Morris, Richard V.↗

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

Morris, Richard V.↗