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At least 235 records · Page 13
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NASA NTRS1992

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.↗
NASA NTRS1992

The HITRAN molecular data base - Editions of 1991 and 1992

We describe in this paper the modifications, improvements, and enhancements to the HITRAN molecular absorption database that have occurred in the two editions of 1991 and 1992. The current database includes line parameters for 31 species and their isotopomers that are significant for terrestrial atmospheric studies. This line-by-line portion of HITRAN presently contains about 709,000 transitions between 0 and 23,000/cm and contains three molecules not present in earlier versions: COF2, SF6, and H2S. The HITRAN compilation has substantially more information on chlorofluorocarbons and other molecular species that exhibit dense spectra which are not amenable to line-by-line representation. The user access of the database has been advanced, and new media forms are now available for use on personal computers.

Rothman, Laurence S.↗
NASA NTRS1993

Effect of plasma ion bombardment on the reflectance of Io's trailing and leading hemispheres

The possible effect of a net difference in the ion bombardment flux to the surface of Io on the ratio of the reflectance spectra is investigated. Io's vapor-deposited surface layers are simulated by a laboratory-produced film of vapor-deposited SO2 with a small admixture (about 3 percent) of H2S and (about 0.1 percent) H2O. It is shown that the reflectance ratio in the UV/visible of the surface bombarded by keV ions to the unbombarded surface is surprisingly similar to the observed ratio of Io's trailing to leading hemispherical reflectance. The changes produced are either structural or involve products of species originally present in the sample.

Sack, N. J.↗
NASA NTRS1993

Sources of Na for the Io atmosphere

The physics and geology of Io have been extensively studied, but there has been little discussion of the chemistry. Relatively little is known about Io chemistry, but there are constraints. Further, it will be a long time before improvements will result from direct observation, given the severe difficulties with the Galileo mission. Via laboratory simulation experiments, plausible thermochemical and photochemical processes which determine the nature and amounts of surface constituents of Io are explored. The well-known density of Io shows that the planet overall is rocky. Because the orbit of Io is well within the magnetosphere of Jupiter and because Io only has a thin, transient SO2 atmosphere, the surface is continually sputtered with magnetospheric ions. Complex processes ionize and accelerate the Io surface atoms to keV and MeV energies. Remarkably, only S, O, and Na ions were found by Voyager. Sputtering also produces an atomic cloud of Na and S (O not observable) with a trace of K. Both gaseous and solid SO2 are known from spectroscopic studies. A trace of H2S and possibly CO2 are present. Geologic features are interpreted in terms of elemental S, but there is no direct evidence for this constituent. We thus have a rocky planet which does not have rocks on the surface. Our general goal is to understand the cycling of Na, S, and O through the crust and atmosphere on present-day Io and to understand how Io evolved to this state. A specific objective was to determine the phases on the surface which are the source of the Na in the atmosphere of Io.

Burnett, D. S.↗
NASA NTRS1992

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗
NASA NTRS1993

Magmatic volatiles and the weathering of Mars

The sources for volatiles on Mars have been the subject of many hypotheses for exogenous influences including late accretion of volatile-enriched material, impact devolatilization to create massive early atmospheres, and even major bombardment by comets. However, the inventory of chemically active volatiles observable at the contemporary surface of Mars is consistent with domination by endogenous, subsequent planetary processes, viz., persistent magmatic outgassing. Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the geochemical similarities are such that the suite of gases emitted from Martian volcanic activity should include H2O, CO2, S-containing gases (e.g. H2S and/or SO2), and Cl-containing gases (e.g., Cl2 and/or HCl). H2O and CO2 exist in the atmosphere of Mars. Both are also present as surface condensates. However, spectroscopic observations of the Martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted, with upper limits of less than or equal to 10(exp -7) the abundance of CO2. Likewise, there is no evidence of polar condensates of compounds of these elements as there is for CO2 and H2O. Within the soil, on the other hand, there has been direct measurement of incorporated H2O and abundant compounds containing S and Cl. Barring some as yet implausible geochemical sequestering process, the S/Cl ratio of about 6:1 in Martian soils implies a limit of 5% on the contribution of matter of solarlike composition (e.g., carbonaceous chondrite or cometary material) to these volatiles. Hence, exogenous sources are minor or not yet observed. From analysis of elemental trends in Martian soils, it has been recently shown that a simple two-component model can satisfy the Viking in situ measurements. Component A includes Si and most or all the Al, Ca, Ti, and Fe. Component B, taken as 16 +/- 3% by weight of the total, contains S and most or all the Cl and Mg. These results constrain several models of Martian soil mineralogy but are consistent with a mixture of silicates (such as Fe-rich clays and accessory minerals and soluble salts). The overall element profile is notably like shergottites, with significant incorporation of chemically reactive atmospheric gases from magmatic degassing.

Clark, B. C.↗
NASA NTRS1992

Gas exchange in wetlands: Controls and remote sensing

This project was directed toward the quantification of fluxes of gaseous biogenic sulfur compounds from freshwater wetlands. These compounds (primarily hydrogen sulfide (H2S), dimethyl sulfide (DMS), and carbonyl sulfide (OCS)) have been implicated in the regulation of planetary albedo by the formation of microscopic atmospheric aerosols when they oxidize, and the further role of these aerosols as cloud condensation nuclei (CCN). The role of continental sources and sinks for these compounds is poorly understood. The present study was undertaken to quantify the source and sink strength of high latitude wetlands, and to delineate factors that regulate this flux.

Hines, Mark E.↗
NASA NTRS1994

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.↗
NASA NTRS1995

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↗
NASA NTRS1993

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.↗
NASA NTRS1994

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.↗
NASA NTRS1993

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.↗
NASA NTRS1994

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.↗
NASA NTRS1995

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↗
NASA NTRS1996

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↗
NASA NTRS1993

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.↗
NASA NTRS1995

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.↗