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At least 199 records · Page 11

Surface ices in the outer solar system

Planetary volatile inventories are products of several factors: (1) condensation-accretion of pre-planetary material which determines the bulk volatile inventory; (2) energy history of a planet, including timing, causes, and mechanisms of degassing; (3) the volatile sinks, including temporary, long term, and permanent; and (4) external processes operating on the volatile inventory. Information regarding the current surface compositions provide insight into both internal and surface-atmosphere evolutionary history. Our discussion focuses upon the surface composition of outer solar system planets and satellites as determined by spacecraft and telescopic spectral observations. We provide a review and an update of the recent work by Cruikshank and Brown that includes more recent observations and interpretations. In the context of formation and evolution of solar system bodies, the interesting ices typically considered are simple molecules formed from elements having high cosmic abundances. These mainly include ices of H2O, NH3, SO2, H2S, CH4, CO, CO2, and N2. In the solid state, these ices have vibrational spectral features, analogous to their gaseous counterparts but rotational transitions are quenched, that lie in the near- and mid-infrared. The overtone and combination modes, occurring in the visible and near-IR region, are of particular importance as standard observational techniques used to identify these ices rely upon reflected solar energy. Table I summarizes the ices found on various bodies in the outer solar system. H2O is most abundant surface material in the inner and middle regions while more volatile species appear to dominate surfaces in the outermost edge of the outer solar system.

Roush, Ted L.↗

Analyses of TIMS and AVIRIS data, integrated with field and laboratory spectra, for lithological and mineralogical interpretation of Vulcano Island, Italy

Vulcano Island is part of the Eolian archipelago, located about 25 km from the northeast coast of Sicily. The archipelago comprises seven major volcanic islands, two of which are active volcanoes (Vulcano and Stromboli). Vulcano covers an area of about 50 square km, and is about 10 km long. Explosive volcanic activity has predominated in the geological evolution of Vulcano Island, and there is no evidence that this pattern has ceased. Rather, the current situation is one of unrest, so a strict regimen of continuous geophysical and geochemical monitoring has been undertaken over the last decade. Though the year-round population of Vulcano is small (under 1000), during the summer the island becomes a very popular resort, and has thousands of additional tourists at any time throughout the high season, thus substantially increasing the number of people potentially at risk from an explosive eruption or other hazards such as noxious gas emissions (e.g., CO2, H2S, SO2). During the past ten years, remote sensing data have been repetitively acquired with optical and microwave airborne sensors. The present work shows the preliminary results of a study based on the integration of various remote sensing data sets with field spectroscopy, and other laboratory analyses, for the geological and geomorphological mapping of the island. It is hoped that such work will also usefully contribute to the evaluation of the volcanic hazard potential of the islands as well as to the evaluation of the status of its current activity.

Buongiorno, M. Fabrizia↗

Condensation and vaporization studies of CH3OH and NH3 ices: Major implications for astrochemistry

In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

Sandford, Scott A.↗

Molecular abundances and low-mass star formation. 1: Si- and S-bearing species toward IRAS 16293-2422

Results from millimeter and submillimeter spectral line surveys of the protobinary source Infrared Astronomical Satellite (IRAS) 16293-2422 are presented. Here we outline the abundances of silicon- and sulfur-containing species. A combination of rotation diagram and full statistical equilibrium/radiative transfer calculations is used to constrain the physical conditions toward IRAS 16293 and to construct its beam-averaged chemical composition over a 10 to 20 sec (1600 to 3200 AU) scale. The chemical complexity as judged by species such as SiO, OCS, and H2S, is intermediate between that of dark molecular clouds such as L134N and hot molecular cloud cores such as Orion KL. From the richness of the spectra compared to other young stellar objects of similar luminosity, it is clear that molecular abundances do not scale simply with mass; rather, the chemistry is a strong function of evolutionary state, i.e., age.

Blake, Geoffrey A.↗

Operational overview of the NASA GTE/CITE 3 airborne instrument intercomparisons for sulfur dioxide, hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, and carbon disulfide

This paper reports the overall experimental design and gives a brief overview of results from the third airborne Chemical Instrumentation Test and Evaluation (CITE 3) mission conducted as part of the National Aeronautics and Space Administration's Global Tropospheric Experiment. The primary objective of CITE 3 was to evaluate the capability of instrumentation for airborne measurements of ambient concentrations of SO2, H2S, CS, dimethyl sulfide, and carbonyl sulfide. Ancillary measurements augmented the intercomparison data in order to address the secondary objective of CITE 3 which was to address specific issues related to the budget and photochemistry of tropospheric sulfur species. The CITE 3 mission was conducted on NASA's Wallops Flight Center Electra aircraft and included a ground-based intercomparison of sulfur standards and intercomparison/sulfur science flights conducted from the NASA Wallops Flight Facility, Wallops Island, Virginia, followed by flights from Natal, Brazil. Including the transit flights, CITE 3 included 16 flights encompassing approximately 96 flight hours.

Hoell, James M., Jr.↗

Physical and chemical structure of the IC 63 nebula. 1: Millimeter and far-infrared observations

We present results of a (sub)millimeter and far-infrared study of the reflection/emission nebula IC 63, located close to the BO.5p star gamma Cas. The source has been mapped in the (12)CO 2 - 1 and 3 - 2, (13)CO 2 - 1, and CS 2 - 1 lines and shows a small molecular cloud less than 1'x 2' in extent, which coincides with the brightest optical nebulosity and IRAS 100 micrometer emission. IC 63 is therefore an excellent example of a nearby (d approximately = 230 pc), edge-on photon-dominated region (PDR). Various other molecules have been observed at the peak position through their rotational transitions, in order to probe the physical parameters and to derive abundances. The measured CO, HCO(+) HCN, CS and H2CO line ratios suggest that the cloud is warm, T approximately = 50 K, and dense, n (H2) approximately = 5 x 10(exp 4)/cu cm. Excitation of molecules by electrons may play a significant role in this PDR. On the basis of these physical conditions, column densities have been determined from the observed line strengths. Several different methods are discussed to constrain the H2 column density, including the use of measured submillimeter continuum fluxes. The resulting abundances of species such as CN and CS are similar to those found in cold, dark clouds like TMC-1 and L134N. However, the abundances of other simple molecules such as HNC, HCO(+) and possibly C2H are lower by factors of at least three, probably because of the enhanced photodissociation rates at a distance of 1.3 pc from a B star. Surprisingly, only the abundance of the H2S molecule appears enhanced. More complex, volatile molecules such as CH3OH CH3CN and HNCO, and the sulfur-oxides SO and SO2 have not been found in this cloud. Limited observations of molecules in the reflection nebulea NGC 2023 are presented as well, and the resulting molecular abundances are compared with those found for IC 63.

Jansen, David J.↗

Sulfur Chemistry in the Wake of Comet Shoemaker-Levy 9

A curious and unexpected result of the impact of P/Shoemaker Levy 9 with Jupiter was the production of enormous amounts of molecular sulfur (S2). Here we show that S2 is the natural product of disequilibrium chemistry at low pressures in shocked Jovian air, its formation a byproduct of hydrogen recombination. The species observed by the Hubble Space Telescope (HST) - S2, CS2, and H2S - imply that the G fragment penetrated the NH4SH cloud but did not reach the water table. A typical impact within or below the NH4SH clouds produces about 0.03 - 0.1 impactor masses of S2. Because comets are relatively hydrogen-poor, SO2, not S2, is the major product of shocking a water-rich comet, while S2, CS2 and OCS are major products of a dessicated comet. In all cases we find that as the gas cools, S2 converts to the stable low temperature allotrope S8, although other chemical fates not modeled here might intervene first.

Zahnle, Kevin↗

Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

McBee, Joshua↗

Condensation and Vaporization Studies of CH3OH and NH3 Ices: Major Implications for Astrochemistry

In an extension of previously reported work on ices containing H20, CO, CO2, SO2, H2S, and H2, We present measurements of the physical and infrared spectral properties of ices containing CH30H and NH3.The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed 87 of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

Sandford, Scott A.↗

Degradation of Coflon in Methanol at Temperatures Around 140 C

An unexpected and significant physico-chemical degradation of Coflon PVDF specimens was observed at the end of 1994 during routine scheduled exposure exercises on strained material. The intent was to age various samples, including some strained in a 4-point bend configuration, in methanol at 140 C and subsequently submit the aged samples to various tests including dynamic fatigue and fracture toughness. However, the samples deteriorated to such an extent that such testing was not possible: only when conditions were made less severe was it found possible to perform such testing. The purpose of the current report is to describe the nature of the PVDF deterioration observed during a number of tests performed to examine this phenomenon. This report also records, as Appendix 1, some SEM/X-ray microanalysis data on Coflon samples exposed to a methanol/amine mixture, and to other amine or H2S-aged samples.

Campion, R. P.↗

Chemical and Thermal Analysis

Thermal decomposition activation energies have been determined using two methods of Thermogravimetric Analysis (TGA), with good correlation being obtained between the two techniques. Initial heating curves indicated a two-component system for Coflon (i.e. polymer plus placticizer) but a single component system for Tefzel. Two widely differing activation energies were for Coflon supported this view, 15 kcl/mol being associated with plasticizer, and 40 kcal/mol with polymer degradation. With Tefzel, values were 40-45 kcal/mol, the former perhaps being associated with a low molecular weight fraction. Appropriate acceleration factors have been determined. Thermomechanical Analysis (TMA) has shown considerable dimensional change during temperature cycles. For unaged pipe sections heating to 100 C and then holding the temperature resulted in a stable thickness increase of 2%, whereas the Coflon thickness decreased continuously, reaching -4% in 2.7 weeks. Previously strained tensile bars of Tefzel expanded on cooling during TMA. SEM performed on H2S-aged Coflon samples showed significant changes in both physical and chemical nature. The first may have resulted from explosive decompression after part of the aging process. Chemically extensive dehydrofluorination was indicated, and sulfur was present as a result of the aging. These observations indicate that chemical attack of PVDF can occur in some circumstances.

Bulluck, J. W.↗

High-Resolution Temperature-Dependent Photoabsorption Cross Section Measurements of S2, with Application to HST UV Spectra of SL9/Jupiter

The Hubble Space Telescope (HST) UV spectra of Jupiter after the collision of Comet SL9 show predominantly molecular features of S2, CS2, NH3, and H2S in the 1800-3200 A region. The HST observations were made under various phases of impact conditions which gave temperatures higher than 1000 K. It is thus clear that temperature-dependent laboratory cross section data are required in order to determine the molecular abundances in Jupiter's atmosphere after the impact of Comet Shoemaker-Levy 9. The required high-resolution temperature dependent S2 absorption cross sections have not been directly measured in the laboratory. To provide the required data for modelers our objective is to accurately measure the high-resolution (FWHM = 0.003 A) and medium resolution (FWHM - 0.08 A) temperature dependent S2 in the 2450-3200 A region. Using the experimental setup we have obtained absorbtion spectra of S2 under various temperature conditions.

Wu, C. Y. Robert↗

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Kress, M. E.↗

Endogenous Synthesis of Prebiotic Organic Molecules

The necessary condition for the synthesis of organic compounds on the primitive earth is the presence of reducing conditions. This means an atmosphere of CH4, CO, or CO2 + H2. The atmospheric nitrogen can be N2 with a trace of NH3, but NH4(+) is needed in the ocean at least for amino acid synthesis. Many attempts have been made to use CO2 + H2O atmospheres for prebiotic synthesis, but these give at best extremely low yields of organic compounds, except in the presence of H2. Even strong reducing agents such as FeS + H2S or the mineral assemblages of the submarine vents fail to give significant yields of organic compounds with CO2. There appears to be a high kinetic barrier to the non-biological reduction of CO2 at low temperatures using geological reducing agents. The most abundant source of energy for prebiotic synthesis is ultraviolet light followed by electric discharges, with electric discharges being more efficient, although it is not clear which was the important energy source. Photochemical process would also make significant contributions. In an atmosphere Of CO2, N2, and H2O with no H2, the production rates of HCN and H2CO would be very low, 0.001 or less than that of a relatively reducing atmosphere. The concentration of organic compounds under these non-reducing conditions would be so low that there is doubt whether the concentration mechanism would be adequate for further steps toward the origin of life. A number of workers have calculated the influx of comets and meteorites on the primitive earth as a source of organic compounds. We conclude that while some organic material was added to the earth from comets and meteorites the amount available from these sources at a given time was at best only a few percent of that from earth bases syntheses under reducing conditions.

Miller, Stanley L.↗

Improved Chromatographic Techniques for Sulfur Pollutants

This paper describes several improvements in instrumental techniques for the analysis of low ppb concentrations of sulfur gases using gas chromatography (G.C.). This work has focused on the analytical problem of ambient air monitoring of the two main sulfur gas pollutants, hydrogen sulfide and sulfur dioxide. The most significant technical improvement that will be reported here is the newly developed silica gel column for ppb concentrations of the light sulfur gases (COS, H2S, CS2, SO2, CH3SH). A simplified inlet system will be described which improves reliability of the GC system. The flame photometric detector is used as the means of selectively and sensitively detecting the low concentrations of sulfur gases. Improvements will be described which have yielded better performance than previously reported for this application of the detector. Also included in this paper will be a report of field monitoring using this improved GC system. Reliability and repeatability of performance at the low ppb concentrations of sulfur gases will be demonstrated.

Hartmann, C. H.↗

Contributions of Nimbus 7 TOMS Data to Volcanic Study and Hazard Mitigation

Nimbus TOMS data have led to advancements among many volcano-related scientific disciplines, from the initial ability to quantify SO2 clouds leading to derivations of eruptive S budgets and fluxes, to tracking of individual clouds, assessing global volcanism and atmospheric impacts. Some of the major aspects of TOMS-related research, listed below, will be reviewed and updated: (1) Measurement of volcanic SO2 clouds: Nimbus TOMS observed over 100 individual SO2 clouds during its mission lifetime; large explosive eruptions are now routinely and reliably measured by satellite. (2) Eruption processes: quantification of SO2 emissions have allowed assessments of eruption sulfur budgets, the evaluation of "excess" sulfur, and inferences of H2S emissions. (3) Detection of ash: TOMS data are now used to detect volcanic particulates in the atmosphere, providing complementary analyses to infrared methods of detection. Paired TOMS and AVHRR studies have provided invaluable information on volcanic cloud compositions and processes. (4) Cloud tracking and hazard mitigation: volcanic clouds can be considered gigantic tracers in the atmosphere, and studies of the fates of these clouds have led to new knowledge of their physical and chemical dispersion in the atmosphere for predictive models. (5) Global trends: the long term data set has provided researchers an unparalleled record of explosive volcanism, and forms a key component in assessing annual to decadal trends in global S emissions. (6) Atmospheric impacts: TOMS data have been linked to independent records of atmospheric change, in order to compare cause and effect processes following a massive injection of SO2 into the atmosphere. (7) Future TOMS instruments and applications: Nimbus TOMS has given way to new satellite platforms, with several wavelength and resolution modifications. New efforts to launch a geostationary TOMS could provide unprecedented observations of volcanic activity.

Krueger, Arlin J.↗

NASA GRC's High Pressure Burner Rig Facility and Materials Test Capabilities

The High Pressure Burner Rig (HPBR) at NASA Glenn Research Center is a high-velocity. pressurized combustion test rig used for high-temperature environmental durability studies of advanced materials and components. The facility burns jet fuel and air in controlled ratios, simulating combustion gas chemistries and temperatures that are realistic to those in gas turbine engines. In addition, the test section is capable of simulating the pressures and gas velocities representative of today's aircraft. The HPBR provides a relatively inexpensive. yet sophisticated means for researchers to study the high-temperature oxidation of advanced materials. The facility has the unique capability of operating under both fuel-lean and fuel-rich gas mixtures. using a fume incinerator to eliminate any harmful byproduct emissions (CO, H2S) of rich-burn operation. Test samples are easily accessible for ongoing inspection and documentation of weight change, thickness, cracking, and other metrics. Temperature measurement is available in the form of both thermocouples and optical pyrometery. and the facility is equipped with quartz windows for observation and video taping. Operating conditions include: (1) 1.0 kg/sec (2.0 lbm/sec) combustion and secondary cooling airflow capability: (2) Equivalence ratios of 0.5- 1.0 (lean) to 1.5-2.0 (rich), with typically 10% H2O vapor pressure: (3) Gas temperatures ranging 700-1650 C (1300-3000 F): (4) Test pressures ranging 4-12 atmospheres: (5) Gas flow velocities ranging 10-30 m/s (50-100) ft/sec.: and (6) Cyclic and steady-state exposure capabilities. The facility has historically been used to test coupon-size materials. including metals and ceramics. However complex-shaped components have also been tested including cylinders, airfoils, and film-cooled end walls. The facility has also been used to develop thin-film temperature measurement sensors.

Robinson, R. Craig↗

Volcanic Degassing of Hydrogen Compounds on Io

Thermodynamic calculations show that hydrogen, recently detected in Io's ionosphere by the Galileo spacecraft, can degas from high-temperature silicate magmas on Io in the form of H2O, H2S, HS, NaOH, H2, KOH, and HCl in order of decreasing abundance.

Zolotov, M. Yu.↗