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At least 685 records · Page 38

Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

Kashiwagi, Takashi↗

A far wing line shape theory and its application to the foreign-broadened water continuum absorption. III

The far wing line shape theory developed previously and applied to the calculation of the continuum absorption of pure water vapor is extended to foreign-broadened continua. Explicit results are presented for H2O-N2 and H2O-CO2 in the frequency range from 0 to 10,000/cm. For H2O-N2 the positive and negative resonant frequency average line shape functions and absorption coefficients are computed for a number of temperatures between 296 and 430 K for comparison with available laboratory data. In general the agreement is very good.

Ma, Q.↗

Implications for volcanogenic volatile release on the weathering of Mars

Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the similarities are such that the suite of gases emitted from martian volcanic activity surely includes gases such as H2O, CO2, S-containing gases (H2S, SO3, or SO2), and Cl-containing gases (e.g. Cl or HCl). Both H2O and CO2 are present in the atmosphere of Mars; both are also present as surface condensates. Spectroscopic observations of the martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted. Likewise, there is no evidence of surface condensates of compounds of these elements. Within the soil, there is direct evidence of incorporation of H2O and some compounds of sulfur and chlorine. None of the resultant weathering products have been directly identified, but both clays and salts have been indirectly implicated. Other aspects of the implications for volcanogenic volatile release on the weathering of Mars are discussed.

Clark, Benton C.↗

Mapping Mars water vapor with the Very Large Array

This paper presents the first radio measurements of Mars atmospheric water, retrieved from interferometric spectral line observations with the NRAO VLA. Large atmospheric path lengths on the limb of Mars lead to an annulus of H2O line emission which provides a measure of the diurnal and latitudinal variability of atmospheric water on Mars. The measured line shapes of the observed H2O emission yield the first direct measurements of the vertical mixing profile of H2O in the Mars atmosphere. The observations indicate a very dry Mars atmosphere in which the globally averaged water column is approximately 3 pr micron.

Clancy, R. T.↗

The chemical effects of auroral oxygen precipitation at Jupiter

A numerical model of the auroral ionosphere and thermosphere of Jupiter, which includes odd oxygen species, is presented. Density profiles of neutral species O, OH, and H2O and the ion species H2(+), H3(+), H(+), H2O(+), H3O(+), O(+), and OH(+) are calculated. The total neutral odd oxygen density is found to be about 10 exp 5/cu cm near the auroral ionosphere peak. The major ionospheric ion, H(+) reacts rapidly with both O and H2O and the presence of these species in the model calculations significantly reduces the H(+) density and thus the electron density. The chemical lifetime against reaction of H(+) with odd oxygen is about 1000 s near the peak, whereas the radiative recombination lifetime is roughly 10,000 s.

Cravens, T. E.↗

Velocity distributions of hydrogen atoms and hydroxyl radicals produced through solar photodissociation of water

The velocity distributions of H and OH fragments produced through solar photodissociation of gaseous H2O molecules under collisionless conditions are presented. The calculations are carried out using: the most recently available absolute partial cross sections for the production of H and OH through photodissociation of H2O from its absorption onset at 1860 A down to 500 A; the newly available vibrational and rotational energy distributions of both the excited and ground state OH photofragments; the calculated cross sections for the total dissociation processes; and the integrated solar flux in 10 A increments from 500 to 1860 A in the continuum regions and the specific wavelength and flux at the bright solar lines. The calculated results show that the H atoms and the OH radicals produced exhibit multiple velocity groups. Since most current cometary modeling uses a single velocity of 20 km/sec associated with the photodissociation of H2O, the present results may be useful in interpreting the many peaks observed in the velocity distributions of the H Lyman alpha and H alpha of comets.

Wu, C. Y. R.↗

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Leu, Ming-Taun↗

An experimental study of the organic molecules produced in cometary and interstellar ice analogs by thermal formaldehyde reactions

Results of an experimental study tracing thermal formaldehyde reactions in astrophysically relevant ices in dense molecular clouds are reported. The formaldehyde chemistry during warm-up of ices containing H2CO and one or more of the molecules H2O, CH3OH, CO, O2, and NH3 were monitored using IR spectroscopy. Conversion of H2CO into residues was observed to start at about 40 K for NH3:H2CO ices and at about 80 K in H2O-rich ices. A total of five different organic products of these reactions were distinguished: POM and reaction products of H2CO and H2O, CH3OH, and NH3. Given the measured reaction paths and efficiencies, it is estimated that on the order of 1 percent of the organics found in the coma of Comet P/Halley could have been produced by thermal formaldehyde reactions taking place in the nucleus.

Schutte, W. A.↗

Analysis of hydrogen H-alpha observations of the coma of Comet P/Halley

The Monte Carlo Particle Trajectory Model of Combi and Smyth (1988) is used here to analyze observations of the H-alpha coma of Comet Halley. The solar excitation mechanism for the H-alpha emissions line is described. The H2O production rates derived for the H-alpha brightness measurements are shown to be very consistent with the H2O production rates determined from other Comet Halley observations of the H, O, and OH comae. Revised H2O production rates determined from 6300 A brightness measurements are presented.

Smyth, William H.↗

An observational search for CO2 ice clouds on Mars

CO2 ice clouds were first directly identified on Mars by the Mariner 6 and 7 infrared spectrometer limb scans. These observations provided support for early theoretical modeling efforts of CO2 condensation. Mariner 9 IRIS temperature profiles of north polar hood clouds were interpreted as indicating that these clouds were composed of H2O ice at lower latitudes and CO2 ice at higher latitudes. The role of CO2 condensation on Mars has recently received increased attention because (1) Kasting's model results indicated that CO2 cloud condensation limits the magnitude of the proposed early Mars CO2/H2O greenhouse, and (2) Pollack el al.'s GCM results indicated that the formation of CO2 ice clouds is favorable at all polar latitudes during the fall and winter seasons. These latter authors have shown that CO2 clouds play an important role in the polar energy balance, as the amount of CO2 contained in the polar caps is constrained by a balance between latent heat release, heat advected from lower latitudes, and thermal emission to space. The polar hood clouds reduce the amount of CO2 condensation on the polar caps because they reduce the net emission to space. There have been many extensive laboratory spectroscopic studies of H2O and CO2 ices and frosts. In this study, we use results from these and other sources to search for the occurrence of diagnostic CO2 (and H2O) ice and/or frost absorption features in ground based near-infrared imaging spectroscopic data of Mars. Our primary goals are (1) to try to confirm the previous direct observations of CO2 clouds on Mars; (2) to determine the spatial extent, temporal variability, and composition (H2O/CO2 ratio) of any clouds detected; and (3) through radiative transfer modeling, to try to determine the mean particle size and optical depth of polar hood clouds, thus, assessing their role in the polar heat budget.

Bell, James F., III↗

The role of the geothermal gradient in the emplacement and replenishment of ground ice on Mars

Knowledge of the mechanisms by which ground ice is emplaced, removed, and potentially replenished, are critical to understanding the climatic and hydrologic behavior of water on Mars, as well as the morphologic evolution of its surface. Because of the strong temperature dependence of the saturated vapor pressure of H2O, the atmospheric emplacement or replenishment of ground ice is prohibited below the depth at which crustal temperatures begin to monotonically increase due to geothermal heating. In contrast, the emplacement and replenishment of ground ice from reservoirs of H2O residing deep within the crust can occur by at least three different thermally-driven processes, involving all three phases of water. In this regard, Clifford has discussed how the presence of a geothermal gradient as small as 15 K/km can give rise to a corresponding vapor pressure gradient sufficient to drive the vertical transport of 1 km of water from a reservoir of ground water at depth to the base of the cryosphere every 10(exp 6) - 10(exp 7) years. This abstract expands on this earlier treatment by considering the influence of thermal gradients on the transport of H2O at temperatures below the freezing point.

Clifford, Stephen M.↗

Was Martian mantle wet? A possible consequence of rapid core formation

Degassing of H2O in the planetary interior possibly plays an important role in the evolution of surface environment as well as geologic activity on the terrestrial planets. Mars may be such a planet that well preserves the materials and the geologic features directly related to early evolution of H2O. H2O content in the interior of proto-Mars during accretion and also core formation were investigated. Geodetic data shows that Mars has a dense core. The existence of iron-rich core on Mars may be also supported by the depletion of siderophile elements in SNC meteorites assuming that these samples came from Mars. Isotope systematics of these meteorites indicate that the core formation occurred very early, probably concurrently with Mars formation. Considering the kinetics of metal segregation from silicate, the melting of silicate is likely to precede the core formation. Once the core formation occurs, substantial amount of gravitational energy is released and thus the planetary interior is heated. This energy may be large enough to keep the silicate material in partially molten state along with the accretional heating. Under such circumstances, the silicate melt probably migrates to the surface. Early crustal formation, therefore, is also likely to be associated with the core formation.

Kuramoto, Kiyoshi↗

Eddy mixing coefficient upper limit derived from the photochemical balance of O2

This work is based on the study of the photochemical balance of molecular oxygen in the martian atmosphere by using a one-dimensional model of photochemical reactions involving species derived from CO2 and H2O. The model is basically similar to one used previously for the study of the regulation of CO on a global scale, but the chemical rates are taken from another source. In the present scheme, the regulation of molecular oxygen is studied over timescales of the order of its photochemical lifetime (approximately equals 30 yr), which is much shorter than typical escape timescales. Thus, the escape fluxes are fixed to the values given by 3 and 4. We examine the calculated equilibrium abundances of O2 for given thermal, eddy diffusion coefficients and H2O profiles. The thermal profile is taken from in the lower atmosphere. At higher levels, in order to include the diurnal and seasonal thermal profile variability, we have also used the IRTM data. In order to study the influence of both temperature and pressure profiles on the O2 mixing ratio, we have made several tests corresponding to different martian seasons. The results show that the influence of pressure and temperature is quantitatively weak compared to the one of K and of the water vapor density (H2O). Thus, in the following we have fixed the pressure at the surface to a value of 7 mbar and we have used unique standard thermal profile corresponding to a profile roughly averaged over the year, the season, and the day: T equal 205 K at 0 km altitude, 175 K at 25 km, and 145 K at 50 km.

Rosenqvist, J.↗

Temporal changes in the geographic distribution, elevation, and potential origin of the Martian outflow channels

Observational evidence of outflow channel activity on Mars suggests that water was abundant in the planet's early crust. However, with the decline in the planet's internal heat flow, a freezing front developed within the regolith that propagated downward with time and acted as a thermodynamic sink for crustal H2O. One result of this thermal evolution is that, if the initial inventory of water on Mars was small, the cryosphere may have grown to the point where all the available water was taken up as ground ice. Alternatively, if the inventory of H2O exceeds the current pore volume of the cryosphere, then Mars has always possessed extensive bodies of subpermafrost groundwater. We have investigated the relative age, geographic distribution, elevation, and geologic setting of the outflow channels in an effort to accomplish the following: (1) identify possible modes of origin and evolutionary trends in their formation; (2) gain evidence regarding the duration and spatial distribution of groundwater in the crust; and (3) better constraint estimates of the planetary inventory of H2O.

Tribe, S.↗

Impact of stratospheric aircraft on calculations of nitric acid trihydrate cloud surface area densities using NMC temperatures and 2D model constituent distributions

A parameterization of NAT (nitric acid trihydrate) clouds is developed for use in 2D models of the stratosphere. The parameterization uses model distributions of HNO3 and H2O to determine critical temperatures for NAT formation as a function of latitude and pressure. National Meteorological Center temperature fields are then used to determine monthly temperature frequency distributions, also as a function of latitude and pressure. The fractions of these distributions which fall below the critical temperatures for NAT formation are then used to determine the NAT cloud surface area density for each location in the model grid. By specifying heterogeneous reaction rates as functions of the surface area density, it is then possible to assess the effects of the NAT clouds on model constituent distributions. We also consider the increase in the NAT cloud formation in the presence of a fleet of stratospheric aircraft. The stratospheric aircraft NO(x) and H2O perturbations result in increased HNO3 as well as H2O. This increases the probability of NAT formation substantially, especially if it is assumed that the aircraft perturbations are confined to a corridor region.

Considine, David B.↗

Numerical Study of Contaminant Effects on Combustion of Hydrogen, Ethane, and Methane in Air

A numerical study was performed to assess the effects of vitiated air on the chemical kinetics of hydrogen, ethane, and methane combustion with air. A series of calculations in static reacting systems was performed, where the initial temperature was specified and reactions occurred at constant pressure. Three different types of test flow contaminants were considered: NP, H2O, and a combustion of H2O and CO2. These contaminants are present in the test flows of facilities used for hypersonic propulsion testing. The results were computed using a detailed reaction mechanism and are presented in terms of ignition and reaction times. Calculations were made for a wide range of contaminant concentrations, temperatures and pressures. The results indicate a pronounced kinetic effect over a range of temperatures, especially with NO contamination and, to a lesser degree, with H2O contamination. In all cases studied, CO2 remained kinetically inert, but had a thermodynamic effect on results by acting as a third body. The largest effect is observed with combustion using hydrogen fuel, less effect is seen with combustion of ethane, and little effect of contaminants is shown with methane combustion.

Lai, H. T.↗

Kinematics of the ion tail of comet P/Swift-Tuttle

We have obtained long-slit high resolution spectra of the H2O(+) 6199 A complex in the near tail of comet P/Swift-Tuttle. The observations were made using the Hamilton echelle spectrometer fed by the Lick Observatory 0.6 m coude auxiliary telescope. For most of our observations, the spectral slit was aligned along the Sun-tail axis and the cometary nucleus was placed at one end of the slit, giving us spectra having the spatial and spectral resolution needed to measure the radial velocity and velocity dispersion continuously down the cometary tail out to a distance of 4X10(exp 5) km. The radial velocities confirm the earlier more restricted observations by Rauer & Jockers (1993) and by Wyckoff & Lindholm (1994) showing that the tail motions are indeed bulk flows in the antisolar direction. Out to 3X10(exp 5) km in the tail typical bulk flows are at a speed of approximately 30 km/s. The velocity dispersion, (sigma(sub r)), of the H2O(+) lines follows a pattern that is quite systematic; sigma(sub r) is smallest near the cometary nucleus, and steadily increases down the tail. The highest velocity dispersions are found ahead of the nucleus and off the tail axis. These velocity dispersions are equivalent to ion temperatures ranging from 10(exp 5) to 10(exp 6) K. We note a clear anticorrelation between the H2O(+) line intensities (related to the ion density) and the bulk flow and dispersion velocities; direct mass loading of the solar wind by the observed water ions may be responsible. We discuss several approximate equipartition methods used to infer local magnetic fields induced by the interaction of the cometary ions with the solar wind particle/field stream. Typical fields derived are near 50 nT. The measured tailward accelerations are consistent with this order of magnitude B field.

Spinrad, Hyron↗

Aerosol effects and corrections in the Halogen Occultation Experiment

The eruptions of Mt. Pinatubo in June 1991 increased stratospheric aerosol loading by a factor of 30, affecting chemistry, radiative transfer, and remote measurements of the stratosphere. The Halogen Occultation Experiment (HALOE) instrument on board Upper Atmosphere Research Satellite (UARS) makes measurements globally for inferring profiles of NO2, H2O, O3, HF, HCl, CH4, NO, and temperature in addition to aerosol extinction at five wavelengths. Understanding and removing the aerosol extinction is essential for obtaining accurate retrievals from the radiometer channels of NO2, H2O and O3 in the lower stratosphere since these measurements are severely affected by contaminant aerosol absorption. If ignored, aerosol absorption in the radiometer measurements is interpreted as additional absorption by the target gas, resulting in anomalously large mixing ratios. To correct the radiometer measurements for aerosol effects, a retrieved aerosol extinction profile is extrapolated to the radiometer wavelengths and then included as continuum attenuation. The sensitivity of the extrapolation to size distribution and composition is small for certain wavelength combinations, reducing the correction uncertainty. The aerosol corrections extend the usable range of profiles retrieved from the radiometer channels to the tropopause with results that agree well with correlative measurements. In situations of heavy aerosol loading, errors due to aerosol in the retrieved mixing ratios are reduced to values of about 15, 25, and 60% in H2O, O3, and NO2, respectively, levels that are much less than the correction magnitude.

Hervig, Mark E.↗