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NASA NTRS1994

The use of multispectral thermal infrared image data to estimate the sulfur dioxide flux from volcanoes: A case study from Mount Etna, Sicily, July 29, 1986

We have found that image data acquired with NASA's airborne Thermal Infrared Multispectral Scanner (TIMS) can be used to make estimates of the SO2 content of volcanic plumes. TIMS image data are most applicable to the study of partially transparent SO2 plumes, such as those released during quiescent periods or nonexplosive eruptions. The estimation procedure is based on the LOWTRAN 7 radiative transfer code, which we use to model the radiance perceived by TIMS as it views the ground through an SO2 plume. The input to the procedure includes the altitudes of the aircraft and ground, the altitude and thickness of the SO2 plume, the emissivity of the ground, and altitude profiles of the atmospheric pressure, temperature, and relative humidity. We use the TIMS data to estimate both ground temperatures beneath a plume and SO2 concentrations within a plume. Applying our procedure to TIMS data acquired over Mount Etna, Sicily, on July 29, 1986, we estimate that the SO2 flux from the volcano was approximately 6700 t d(exp -1). The use of TIMS to study SO2 plumes represents a bridge between highly localized methods, such as correlation spectroscopy or direct sampling, and small-scale mapping techniques involving satellite instruments such as the Total Ozone Mapping Spectrometer or Microwave Limb Sounder. We require further airborne experiments to refine our estimation procedure. This refinement is a necessary preparation for the schedueled 1998 launch of the Advanced Spaceborne Thermal Emission and Reflectance Radiometer, which will allow large-scale multispectral thermal infrared image data to be collected over virtually any volcano on Earth at least once every 16 days.

Realmuto, Vincent J.↗
NASA NTRS2003

Radiation Synthesis of New Molecules on Jupiter's Icy Satellites

Spectra of Jupiter's icy satellites reveal surfaces dominated by water-ice, minor amounts of SO2 and CO2, and (for Europa) H2O2 along with hydrated materials. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons significantly modify the chemical composition of these moons' surfaces in times ranging from a few years for Europa to thousands of years for Callisto at micrometer depths. Appropriate laboratory studies examining relevant volatile and non-volatile materials under low-temperature radiation conditions can provide information on likely radiation chemical mechanisms, on the stability and evolution of species, and on new species awaiting detection. Although the molecules detected on the icy moons are relatively simple, predicting their responses to radiation in space remains difficult. One problem is that there is a dearth of fundamental data examining solid-phase reactions. Our laboratory experiments have focused on infrared studies (2.5 to 25 microns) of a few simple irradiated ices. We have measured the spectra of proton-irradiated H2O ice containing SO2, H2S, and/or CO2. Ices with H2O/SO2 or H2O/H2S ratios of 3 and 30 have been irradiated at 86 K, 110 K, and 132 K. In irradiated H2O + SO2 ices new ions have been identified: SO4(-2), HSO4(-) and H3O(+). After warming to 260 K the residual spectrum is similar to that of H2SO4. Ices with H2O + H2S form SO2. After warming to 175 K, the residual sample matches the spectrum of hydrated H2SO4. H2O + CO2 ice forms carbonic acid, H2CO3 which is stable to temperatures near 230 K. In addition, OCS has been detected in irradiated ices containing H2O + SO2 + CO2. The radiation half-life of SO2 and H2S in H2O has been calculated. Our results give compelling evidence for the presence of new species awaiting detection. Future experiments will examine the signatures of these ices and hydrated materials in the 1 to 5 micron region, where possible weaker overtone bands may occur. In addition, absolute strengths for both the fundamental and overtone bands will be determined. Finally, good arguments can be made, based on current information, for remote sensing observations that have spectral coverage to at least 5 microns on the long wavelength end. This range would include some of the characteristic bands of H2O, H2O2, CO2, SO2, H2CO3, H2S, and OCS.

Moore, M. H.↗
NASA NTRS1991

Laboratory studies of the newly discovered infrared band at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io: the tentative identification of CO2

We discuss over 120 laboratory experiments pertaining to the identification of the new absorption band discovered by Trafton et al. (1991) at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io. It is shown that this band is not due to overtones or combinations of the fundamental bands associated with the molecules (or their chemical complexes) already identified on Io, namely, SO2, H2S, and H2O. Thus, this band is due to a new, previously unidentified, component of Io. Experiments also demonstrate that the band is not due to molecular H2 frozen in SO2 frosts. Since the frequency of this band is very close to the first overtone of the nu 3 asymmetric stretching mode of CO2, we have investigated the spectral behavior of CO2 under a variety of conditions appropriate for Io. The profile of the Io band is not consistent with the rotational envelope expected for single, freely rotating, gaseous CO2 under Io-like conditions. It was found that pure, solid CO2 and CO2 intimately mixed in a matrix of solid SO2 and H2S produce bands with similar widths (5-10 cm-1), but that these bands consistently fall at frequencies about 10-20 cm-1 (approximately 0.007 micrometer) lower than the Io band. CO2 in SO2 : H2S ices also produces several additional bands that are not in the Io spectra. The spectral fit improves, however, as the CO2 concentration in SO2 increases, suggesting that CO2-CO2 interactions might be involved. A series of Ar : CO2 and Kr : CO2 matrix isolation experiments, as well as laboratory work done elsewhere, show that CO2 clustering shifts the band position to higher frequencies and provides a better fit to the Io band. Various laboratory experiments have shown that gaseous CO2 molecules have a propensity to cluster between 80 and 100 K, temperatures similar to those found on the colder regions of Io. We thus tentatively identify the newly discovered Io band at 4705.2 cm-1 (2.1253 micrometers) with CO2 multimers or "clusters" on Io. Whether these clusters are buried within an SO2 frost, reside on the surface, or are in a residual, steady-state "atmospheric aerosol" population over local coldtraps is not entirely clear, although we presently favor the latter possibility. The size of these clusters is not well defined, but evidence suggests groups of more than four molecules are required. The absorption strength of the 2 nu 3 CO2 cluster overtone determined in the laboratory, in conjunction with the observed strength of the Io band, suggests that the disk-integrated abundance of CO2 is less than 1% that of the SO2. Studies of the sublimation behavior of CO2 indicate that it probably resides predominantly in the cooler areas (< 100 K) of Io. The relative constancy of the Io feature over a variety of orbital phases suggests that the polar regions may contain much of the material. Some consequences of the physical properties of CO2 under conditions pertinent to Io are discussed. The presence of CO2 clusters on Io could be verified by the detection of any one of several other infrared bands associated with the CO2 molecule, of which the strongest are the nu 3 12CO2 asymmetric stretch fundamental near 2350 cm-1 (4.25 micrometers) and the nu 2 bending mode fundamental near 660 cm-1 (15.1 micrometers). Weaker bands that may also be detectable include the nu 3 13CO2 asymmetric stretch fundamental near 2280 cm-1 (4.39 micrometers), the 2 nu 2 + nu 3 combination/overtone band near 3600 cm-1 (2.78 micrometers), and the nu 1 + nu 3 combination band near 3705 cm-1 (2.70 micrometers).

NASA Center ARC↗
NASA NTRS2006

Compilation of a Global Emission Inventory from 1980 to 2000 for Global Model Simulations of the Long-term Trend of Tropospheric Aerosols

The approach to create a comprehensive emission inventory for the time period 1980 to 2000 is described in this paper. We have recently compiled an emission database, which we will use for a 21 year simulation of tropospheric aerosols with the GOCART model. Particular attention was paid to the time-dependent SO2, black carbon and organic carbon aerosol emissions. For the emission of SO2 from sporadically erupting volcanoes, we assembled emission data from the Global Volcanism Program of the Smithsonian Institution, using the VEI to derive the volcanic cloud height and the SO2 amount, and amended this dataset by the SO2 emission data from the TOMS instrument when available. 3-dimensional aircraft emission data was obtained for a number of years from the AEAP project, converted from burned fuel to SO2 and interpolated to each year, taking the sparsity of the flight patterns into account. Other anthropogenic SO2 emissions are based on gridded emissions from the EDGAR 2000 database (excluding sources from aircraft, biomass burning and international ship traffic), which were scaled to individual years with country/regional based emission inventories. Gridded SO2 emissions from international ship traffic for 2000 and the scaling factors for other years are from [Eyring et al., 2005]. We used gridded anthropogenic black and organic carbon emissions for 1996 [Bond et al., 2005], again excluding aircraft, biomass burning and ship sources. These emissions were scaled with regional based emission inventories from 1980 to 2000 to derive gridded emissions for each year. The biomass burning emissions are based on a climatology, which is scaled with regional scaling factors derived from the TOMS aerosol index and the AVHRR/ASTR fire counts to each year [Duncan et al., 2003]. Details on the integration of the information from the various sources will be provided and the distribution patterns and total emissions in the final product will be discussed.

Diehl, Thomas L.↗
NASA NTRS2007

Compilation of a Global Emission Inventory from 1980 to 2000 for Global Model Simulations of the Long-term Trend of Tropospheric Aerosols

The approach to create a comprehensive emission inventory for the time period 1980 to 2000 is described in this paper. We have recently compiled an emission database, which we will use for a 21 year simulation of tropospheric aerosols with the GOCART model. Particular attention was paid to the time-dependent SO2, black carbon and organic carbon aerosol emissions. For the emission of SO2 from sporadically erupting volcanoes, we assembled emission data from the Global Volcanism Program of the Smithsonian Institution, using the VEI to derive the volcanic cloud height and the SO2 amount, and amended this dataset by the SO2 emission data from the TOMS instrument when available. 3-dimensional aircraft emission data was obtained for a number of years from the AEAP project, converted from burned fuel to SO2 and interpolated to each year, taking the sparsity of the flight patterns into account. Other anthopogenic SO2 emissions are based on gridded emissions from the EDGAR 2000 database (excluding sources from aircraft, biomass burning and international ship traffic), which were scaled to individual years with country/regional based emission inventories. Gridded SO2 emissions from international ship traffic for 2000 and the scaling factors for other years are from [Eyring et al., 2005]. We used gridded anthropogenic black and organic carbon emissions for 1996 [Bond et al., 2005], again excluding aircraft, biomass burning and ship sources. These emissions were scaled with regional based emission inventories from 1980 to 2000 to derive gridded emissions for each year. The biomass burning emissions are based on a climatology, which is scaled with regional scaling factors derived from the TOMS aerosol index and the AVHRR/ATSR fire counts to each year [Duncan et al., 2003]. Details on the integration of the information from the various sources will be provided and the distribution patterns and total emissions in the final product will be discussed.

Diehl, T. L.↗
NASA NTRS2013

Evaluation of GEOS-5 Sulfur Dioxide Simulations During the Frostburg, MD 2010 Field Campaign.

Sulfur dioxide (SO2) is a major atmospheric pollutant with a strong anthropogenic component mostly produced by the combustion of fossil fuel and other industrial activities. As a precursor of sulfate aerosols that affect climate, air quality, and human health, this gas needs to be monitored on a global scale. Global climate and chemistry models including aerosol processes along with their radiative effects are important tools for climate and air quality research. Validation of these models against in-situ and satellite measurements is essential to ascertain the credibility of these models and to guide model improvements. In this study the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) module running on-line inside the Goddard Earth Observing System version 5 (GEOS-5) model is used to simulate aerosol and SO2 concentrations. Data taken in November 2010 over Frostburg, Maryland during an SO2 field campaign involving ground instrumentation and aircraft are used to evaluate GEOS-5 simulated SO2 concentrations. Preliminary data analysis indicated the model overestimated surface SO2 concentration, which motivated the examination of mixing processes in the model and the specification of SO2 anthropogenic emission rates. As a result of this analysis, a revision of anthropogenic emission inventories in GEOS-5 was implemented, and the vertical placement of SO2 sources was updated. Results show that these revisions improve the model agreement with observations locally and in regions outside the area of this field campaign. In particular, we use the ground-based measurements collected by the United States Environmental Protection Agency (US EPA) for the year 2010 to evaluate the revised model simulations over North America.

Air Quality Campaign↗
NASA NTRS2016

Constraining the Sulfur Dioxide Degassing Flux from Turrialba Volcano, Costa Rica Using Unmanned Aerial System Measurements

Observed sulfur dioxide (SO2)mixing ratios onboard unmanned aerial systems (UAS) duringMarch 11-13, 2013 are used to constrain the three-day averaged SO2 degassing flux fromTurrialba volcanowithin a Bayesian inverse modeling framework. A mesoscale model coupled with Lagrangian stochastic particle backward trajectories is used to quantify the source-receptor relationships at very high spatial resolutions (i.e., b1 km). The model shows better performance in reproducing the near-surface meteorological properties and observed SO2 variations when using a first-order closure non-local planetary boundary layer (PBL) scheme. The optimized SO2 degassing fluxes vary from 0.59 +/- 0.37 to 0.83 +/- 0.33 kt d−1 depending on the PBL scheme used. These fluxes are in good agreement with ground-based gas flux measurements, and correspond to corrective scale factors of 8-12 to the posteruptive SO2 degassing rate in the AeroCom emission inventory. The maximum a posteriori solution for the SO2 flux is highly sensitive to the specification of prior and observational errors, and relatively insensitive to the SO2 loss term and temporal averaging of observations. Our results indicate relatively low degassing activity but sustained sulfur emissions from Turrialba volcano to the troposphere during March 2013. This study demonstrates the utility of low-cost small UAS platforms for volcanic gas composition and flux analysis.

Xi, Xin↗
NASA NTRS1982

The atmospheres of Io and other satellites

Voyager measurements of gaseous SO2 in a hot spot region and of ions of sulfur, oxygen, and SO2(+) in the plasma torus, combined with the groundbased measurements of SO2 frost on the surface, indicate that SO2 is perhaps the dominant constituent of Io's atmosphere. Indeed the ionosphere of Io can be sustained by a pure SO2 atmosphere in thermal equilibrium with the surface. Upper limits on common volatiles H2O, CO2, NH3, and CH4 and exceedingly small, although S2 and Ar may still be present. Photochemistry of SO2 could lead to O2 as the major gas on the night side. Reasonable processes for loss to the torus include thermal escape, sputtering, and sweep-up of ions. The symmetry of the sodium cloud between eastern and western elongation is difficult to reconcile with any substantial, diurnally varying atmosphere. Europa, Ganymede, and Callisto may have oxygen atmospheres resulting from photolysis of water vapor. A pressure of approximately 10 to the -6th microbar is predicted, consistent with the Voyager upper limit for Ganymede. A much higher pressure might be present if the water vapor pressure is increased by a low albedo (Callisto) or sputtering (Europa).

Kumar, S.↗
NASA NTRS1984

Sulfur dioxide on Io - Spatial distribution and physical state

Observations of the 4-micron SO2 band on Jupiter's satellite Io and laboratory measurements of SO2 frost are presented. The observations confirm the existence of a large longitudinal variation in band strength, but show no evidence of temporal changes. Comparison of the band position and shape in Io's spectrum with those in the laboratory frost's suggests that the bulk of the absorption on Io is due to frost, not adsorbed gas. The derived SO2 coverage is large enough to require that SO2 be present in most terrain types on Io and not just in the white plains unit. To reconcile the infrared observations that indicate large amoutns of SO2 with the ultraviolet observations of Voyager and IUE that show little, the SO2 must be mixed intimately with the sulfur (or other material) so that at each wavelength the darker component dominates the spectrum.

Fanale, F. P.↗
NASA NTRS1988

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

Fegley, Bruce, Jr.↗
NASA NTRS1994

Hubble Space Telescope UV spectral observations of Io passing into eclipse

Time-resolved spectra of Io have been obtained with the Faint Object Spectrograph on the Hubble Space Telescope in January 1992 at times centered on the passage of Io into Jupiter's shadow. Two different eclipse observations covered 1100-1600 A and 2250-3300 A. In the far ultraviolet(far-UV) range, emission lines of atomic sulfur and oxygen from Io's atmosphere (similar to those previously detected with the International Ultraviolet Explorer (IUE)) have been observed from Io in sunlight, and the spatial extent of the emitting region has been resolved for the first time: this is 0.5-1 Io radii (R(sub Io)) above the surface. The emission lines are typically 1kR in brightness while Io is in sunlight, and decrease to a few hundred Rayleighs within 20 min or less of Io's passing into shadow. If the emissions are produced in Io's ionosphere, the decrease in shadow appears consistent with the collisional slowing and recombination of photoelectrons in 100-1000 s, with recombination an important quenching process if the dominant ion is molecular (i.e., SO2(+)) condensation, with the residual emission in shadow due either to plasma impact of gas above the hot volcanic calderas or electron impact on S and O. In the near-UV range, we have not detected any airglow emissions from Io's atmosphere in shadow, with the main limitation being a high level of scattered light from Jupiter. We derive a 3 sigma upper limit to the 2560 A SO emission feature of 1 KR, which is close to what is expected from electron impact on SO2 based on the obs erved brightness of the FUV S and O lines in shadow. A high signal-to-noise spectrum of Io's albedo in sunlight reveals a spectral shape similar to laboratory spectra of SO2 frost reflectivity, and the relative albedo spectrum changed as Io passed into eclipse and part of the disk was in shadow. No specific SO2 gas absorption features appear in the albedo spectrum, although there could be substantial gas absorption near 2800 A if the individual lines are narrow and saturated. Finally, we present preliminary models for the near-UV spectrum of Io as functions of SO2 frost areal coverage and SO2 gas density.

Clarke, John T.↗
NASA NTRS1995

H2SO4 photolysis: A souce of sulfur dioxide in the upper stratosphere

Numerous absoption lines of stratospheric sulfer dioxide (SO2) were identified in solar occulation spectra recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Science (ATLAS)-1 shuttle mission (March 24-April 2, 1992). based on their analysis, a volume mixing ratio profile of SO2 increasing from (13 +/- 4) p.p.t.v. (parts per 10(exp -12) by volume) at 16 mbar (approximately 28 km) to 455 +/- 90 p.p.t.v. at 0.63 mbar (approximately 52 km) was measured with no significant profile differences between 20 deg N and 60 deg S latitude. The increase in the SO2 mixing ratios with altitude indicates the presence of a source of SO2 in the upper stratosphere. Profiles retrieved from ATMOS spectra recorded during shuttle flights in April-May 1985 and April 1993 show similar vertical distributions but lower concentrations. Two-dimensional model calculations with SO2 assumed as the end product of H2SO4 photolysis produce SO2 profiles consistent with the ATMOS measuremnts to within about a factor 2.

Rinsland, C. P.↗
NASA NTRS1999

Trace Chemistry

The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and, in addition, of the pressure, temperature, and velocity. A near term goal of the experimental program should be to confirm the nonlinear effects of sulfur speciation, and if present, to provide an explanation for them. It is also desirable to examine if the particulate matter retains any sulfur. The recommendation is to examine the effects on SOx production of variations in fuel-bound sulfur and aromatic content (which may affect the amount of particulates formed). These experiments should help us to understand if there is a coupling between particulate formation and SO, concentration. Similarly, any coupling with NOx can be examined either by introducing NOx into the combustion air or by using fuel-bound nitrogen. Also of immediate urgency is the need to establish and validate a detailed mechanism for sulfur oxidation/aerosol formation, whose chemistry is concluded to be homogeneous, because there is not enough surface area for heterogeneous effects. It is envisaged that this work will involve both experimental and theoretical programs. The experimental work will require, in addition to the measurements described above, fundamental studies in devices such as flow reactors and shock tubes. Complementing this effort should be modeling and theoretical activities. One impediment to the successful modeling of sulfur oxidation is the lack of reliable data for thermodynamic and transport properties for several species, such as aqueous nitric acid, sulfur oxides, and sulfuric acid. Quantum mechanical calculations are recommended as a convenient means of deriving values for these properties. Such calculations would also help establish rate constants for several important reactions for which experimental measurements are inherently fraught with uncertainty. Efforts to implement sufficiently detailed chemistry into computational fluid dynamic codes should be continued. Zero- and one-dimensional flow models are also useful vehicles for elucidating the minimal set of species and reactions that must be included in two- and three-dimensional modeling studies.

Radhakrishnan, Krishnan↗
NASA NTRS2001

Pick-Up Ion Instabilities at Planetary Magnetospheres

This effort involved the analysis of low frequency waves as observed by the Galileo spacecraft near the Galilean moon, Io. Io is a significant source of material, especially SO2, and various products of dissociation, and further these atoms and molecules are readily ionized. The initial velocity of the ions is essentially that of the neutral species, i.e., the Keplerian velocity. The plasma, on the other hand is co-rotating, and there is a differential flow of the order 57 km/s between the plasma and the neutral particles. Thus pick-up ion instabilities are Rely to occur within the Jovian magnetosphere. Indeed, magnetometer observations from the Galileo spacecraft clearly show ion cyclotron waves that have been identified with a large variety of plasma species, such as O+, S++ (which has the same gyro-frequency as O+), S+, and SO2+. Typically, however, the dominant frequency is near the SO2+ gyro-frequency. The research effort was originally planned to be a team effort between Robert J. Strangeway as the Principal Investigator, and Debbie Huddleston, who was an Assistant Research Geophysicist at UCLA. Unfortunately, Dr. Huddleston took a position within Industry. The effort was therefore descoped, and Dr. Strangeway instead pursued a collaboration with Dr. Xochitl Blanco-Cano, of the Instituto de Geofisica, Universidad Nacional Autonoma de Mexico. This has proved to be a productive collaboration, with several papers and publications arising out of the effort. The magnetic field oscillations near lo generally fall into two types: ion cyclotron waves, with frequencies near an ion gyro-frequency, and lower frequency mirror-mode waves. The ion cyclotron waves are mainly transverse, and frequently propagate along the ambient magnetic field. The mirror-mode waves are compressional waves, and they have essentially zero frequency in the plasma rest frame. One of the purposes of our investigation is to understand what controls the types of wave modes that occur, since both wave modes can be drive unstable by the pressure anisotropy associated with the pick up ions. The pick ion velocity is perpendicular to the ambient magnetic field, and is generally much larger than the thermal velocity, at least initially. At its simplest, we found that the ion cyclotron waves are controlled by the parameters of the species in gyro-resonance with the wave. Thus, while the growth rates for the lower mass (higher gyro-frequency) pick-up ions are generally larger, we found that the heavier SO2+ ion cyclotron waves are generally preferred. This is because one of the effects of the wave instability is to diffuse the ions in pitch angle and energy. The lower mass ions therefore consist of both a ring of recently created pick-up ions, and a thermal background. This thermal background quenches the ion cyclotron instability. SO2+ is different, however. Being a molecule, the species can also dissociate. Our analysis suggests that the dissociation acts on a time scale comparable to or faster than the velocity space diffusion time scale. There are consequently no thermal SO2+ ions to quench the instability. We have also investigated the mirror-mode. This mode can at times grow more rapidly than the individual ion cyclotron waves. This is mainly because the mirror-mode can grow off the pressure anisotropy of the individual species with which the waves are in resonance. Lastly, as part of this effort we have begun to investigate the instability for obliquely propagating modes. Galileo observations show that at times the ion cyclotron waves are significantly elliptically polarized, and further the wave vector is at a large angle to the field, significant growth can occur for oblique propagation. Depending on the group velocity of the waves, it is possible that obliquely propagating modes have higher advective growth rate, but this has yet to be determined.

Strangeway, Robert J.↗
NASA NTRS2004

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗
NASA NTRS2010

NIRS-Derived Tissue Oxygen Saturation and Hydrogen Ion Concentration Following Bed Rest

Long-term bed rest (BR), a model of spaceflight, results in a decrease in aerobic capacity and altered submaximal exercise responses. The strongest BR-induced effects on exercise appear to be centrally-mediated, but longer BR durations may result in peripheral adaptations (e.g., decreased mitochondrial and capillary density) which are likely to influence exercise responses. PURPOSE: To measure tissue oxygen saturation (SO2) and hydrogen ion concentration ([H+]) in the vastus lateralis (VL) using near infrared spectroscopy (NIRS) during cycle ergometry before and after . 30 d of BR. METHODS: Eight subjects performed a graded exercise test on a cycle ergometer to volitional fatigue 7 d before (pre-BR) and at the end or 1 day after BR (post-BR). NIRS spectra were collected from a sensor adhered to the skin overlying the VL. Oxygen consumption (VO2) was measured by open circuit spirometry. Blood volume (BV) was measured before and after BR using the carbon monoxide rebreathing technique. Changes in pre- and post-BR SO2 and [H+] data were compared using mixed model analyses. BV and peak exercise data were compared using paired t-tests. RESULTS: BV (pre-BR: 4.3+/-0.3, post-BR: 3.7+/-0.2 L, mean+/-SE, p=.01) and peak VO2 (pre-BR: 1.98+/-0.24, post-BR: 1.48 +/-0.21 L/min, p<.01) were reduced after BR. As expected, SO2 decreased with exercise before and after BR. However, SO2 was lower post compared with pre-BR throughout exercise, including at peak exercise (pre-BR: 50+/-3, post-BR: 43+/-4%, p=.01). After BR, [H+] was higher at the start of exercise and did not increase at the same rate as pre-BR. Peak [H+] was not different from pre to post-BR (pre-BR: 36+/-2; post-BR: 38+/-2 nmol/L). CONCLUSIONS: Lower SO2 during exercise suggests that oxygen extraction in the VL is higher after BR, perhaps due to lower circulating blood volume. The higher [H+] after BR suggests a greater reliance upon glycolysis during submaximal exercise, although [H+] at peak exercise was unchanged. Taken together, these data suggest that longer duration BR induces a number of changes that result in peripheral adaptations which contribute to cardiovascular and muscular deconditioning as measured by NIRS-derived SO2 and [H+] in the VL and may contribute to lower post-BR exercise tolerance. Supported by the National Space Biomedical Research Institute through NASA NCC 9-58

Lee, S. M. C.↗
NASA NTRS2010

The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

DeWitt, H. Langley↗
NASA NTRS2011

Characterizing Volcanic Eruptions on Venus: Some Realistic (?) Scenarios

When Pioneer Venus arrived at Venus in 1978, it detected anomalously high concentrations of SO2 at the top of the troposphere, which subsequently declined over the next five years. This decline in SO2 was linked to some sort of dynamic process, possibly a volcanic eruption. Observations of SO2 variability have persisted since Pioneer Venus. More recently, scientists from the Venus Express mission announced that the SPICAV (Spectroscopy for Investigation of Characteristics of the Atmosphere of Venus) instrument had measured varying amounts of SO2 in the upper atmosphere; VIRTIS (Visible and Infrared Thermal Imaging Spectrometer) measured no similar variations in the lower atmosphere (ESA, 4 April, 2008). In addition, Fegley and Prinn stated that venusian volcanoes must replenish SO2 to the atmosphere, or it would react with calcite and disappear within 1.9 my. Fegley and Tremain suggested an eruption rate on the order of approx 1 cubic km/year to maintain atmospheric SO2; Bullock and Grinspoon posit that volcanism must have occurred within the last 20-50 my to maintain the sulfuric acid/water clouds on Venus. The abundance of volcanic deposits on Venus and the likely thermal history of the planet suggest that it is still geologically active, although at rates lower than Earth. Current estimates of resurfacing rates range from approx 0.01 cubic km/yr to approx 2 cubic km/yr. Demonstrating definitively that Venus is still volcanically active, and at what rate, would help to constrain models of evolution of the surface and interior, and help to focus future exploration of Venus.

Stofan, E. R.↗