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Evolved Gas Analyses of Mudstones from the Vera Rubin Ridge

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) rover has been essential in understanding volatile-bearing phases in Gale Crater materials. SAM’s evolved gas analysis mass spectrometry (EGA-MS) has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, in many samples. The identity and evolution temperature of evolved gases can support CheMin instrument mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with X-ray diffraction (e.g., amorphous phases). For the past ~500 sols, MSL has been exploring the Vera Rubin Ridge (VRR), which exhibits a striking hematite signature in orbital remote sensing data, in order to understand the depositional and diagenetic history recorded in the rocks and how it relates to the underlying Murray Formation. Four rock samples were drilled, one from the Blunts Point Member (Duluth, DU), one from the Pettegrrove Point Member (Stoer, ST), and two from the Jura Member. The Jura Member displays differences in color, summarized as grey and red, and a key goal was to constrain the cause of this color difference and the associated implications for depositional or post-depositional conditions. To investigate, a grey (Highfield, HF) and a red (Rock Hall, RH) Jura sample were drilled. Here we will give an overview of results from SAM EGA-MS analyses of VRR materials, with some comparisons to analyses of samples of the underlying Murray.

McAdam, A. C.↗

Investigation of the Glen Torridon Clay-Bearing Unit and Overlying Greenheugh Pediment by the Sample Analysis at Mars Instrument Suite

Exploring the Glen Torridon (GT) clay-bearing unit in Gale crater has long been a prime goal for the Mars Science Laboratory (MSL) because of spectral signatures of smectite identified from orbit. Smectite clay minerals can indicate habitable environments [1,2] and possibly facilitate the preservation of organic compounds [e.g., 3-7].Also, sulfate-bearing layers overlie GT and this sequence may record a large-scale change in aqueous conditions overtime [8].The Sample Analysis at Mars (SAM) instrument suitehas been essential in understanding volatile-bearing phases in Gale crater materials. SAM EGA has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, evolved from many samples on heating. The identity and evolution temperature of evolved gases can support mineral detection by CheMin instrument X-ray diffraction (XRD)and place constraints on trace volatile-bearing phases, clay mineral compositions, and X-ray amorphous materials. In GT, SAM analyzed the sample Kilmarie (KM) from the Jura member, Glen Etive (GE), Mary Anning (MA) and Groken (GR)from the Knockfarril Hill member (KHm), Glasgow (GG) and Hutton (HU) from the fractured Intermediate Unit (fIU), and Edinburgh (EB) from the Stimson formation rocks of the Greenheugh Pediment (GP). The Jura, KHm and fIU are all members of the Murray formation. HU was sampled near the basal Siccar Point group (SPg) unconformity between the fIU and GP, in an area that exhibits a brighter tone and differences in geochemistry compared to Murray materials down-section [9,10]. CheMin XRD of most samples (except for HU and EB)showed large abundances of smectite clay minerals (~25-35%) and all samples showed X-ray amorphous materials and relatively low amounts of well-crystalline hematite[11]. SAM evaluated mineralogy through evolved gas analysis mass spectrometry (EGA) while detailed organic chemistry of several samples was examined by pyrolysis gas chromatography mass spectrometry and wet chemistry experiments [12,13].Here we discuss data and interpretations from SAM EGA analyses.

Mars↗

Observations of cometary parent molecules with the IRAM radio telescope

Several rotational transitions of HCN, H2S, H2CO, and CH3OH were detected in comets P/Brorsen-Metcalf 1989 X, Austin (1989c1) and Levy (1990c) with the Institute for Millimeter Radioastronomy (IRAM) 30-m radio telescope. This allows us to determine the production rates of these molecules and to probe the physical conditions of the coma.

Colom, P.↗

Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analyzed several subsamples of <150 micron fines from ten sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform (RN) and drilled Sheepbed mudstone from sites John Klein (JK) and Cumberland (CB). One was drilled from the Windjana (WJ) site on a sandstone of the Kimberly formation. Four were drilled from sites Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP) and Buckskin (BK) of the Murray Formation at the base of Mt. Sharp. Two were drilled from sandstones of the Stimson formation targeting relatively unaltered (Big Sky, BY) and then altered (Greenhorn, GH) material associated with a light colored fracture zone. CheMin analyses provided quantitative sample mineralogy. SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases. This contribution will focus on evolved SO2. All samples evolved SO2 above 500 C. The shapes of the SO2 evolution traces with temperature vary between samples but most have at least two "peaks' within the wide high temperature evolution, from approx. 500-700 and approx. 700-860 C (Fig. 1). In many cases, the only sulfur minerals detected with CheMin were Ca sulfates (e.g., RN and GH), which should thermally decompose at temperatures above those obtainable by SAM (>860 C). Sulfides or Fe sulfates were detected by CheMin (e.g., CB, MJ, BK) and could contribute to the high temperature SO2 evolution, but in most cases they are not present in enough abundance to account for all of the SO2. This additional SO2 could be largely associated with x-ray amorphous material, which comprises a significant portion of all samples. It can also be attributed to trace S phases present below the CheMin detection limit, or to reactions which lower the temperatures of SO2 evolution from sulfates that are typically expected to thermally decompose at temperatures outside the SAM temperature range (e.g., Ca and Mg sulfates). Here we discuss the results of SAM-like laboratory analyses targeted at understanding this last possibility, focused on understanding if reactions of HCl or an HCl evolving phase (oxychlorine phases, chlorides, etc.) and Ca and Mg sulfates can result in SO2 evolution in the SAM temperature range.

McAdam, A. C.↗

The production and sputtering of S2 by keV ion bombardment

The ion bombardment of S-containing molecules in comets is simulated experimentally. Mass-analyzed 30-keV beams of Ar(+) and He(+) are directed at solid S, H2S, and CS2 targets at temperatures 15 K, and the neutral molecular species produced are ionized and analyzed using a quadrupole mass spectrometer. The dominant species detected are S1 and S2 for the S target, H2S and S2 for the H2S target, and S, CS, S2, and CS2 for the CS2 target. In the latter case, it is found that after about 10 to the 14th He(+) ions/sq cm have struck the target, further sputtering is prevented by formation of a dark brown deposit which is stable at room temperature; the residue forms more slowly when Ar(+) ions are used. These results, indicating relatively efficient S2 production by ion bombardment, are applied to theoretical models of S2 production and/or ejection by solar-wind, solar-flare, or cosmic-ray ions striking comets. It is found that direct solar-wind production of S2 by sputtering is unlikely at realistic bombardment rates, but that H2S-S2 conversion by energetic ions could be significant, with less stringent ice-temperature and irradiation-flux constraints than in the case of S2 production by photons.

Boring, J. W.↗

Measurements of atmospheric dimethylsulfide, hydrogen sulfide, and carbon disulfide during GTE/CITE 3

Measurements of atmospheric dimethylsulfide (DMS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were made over the North and South Atlantic Ocean as part of the Global Tropospheric Experiment/Chemical Instrumentation Test and Evaluation (GTE/CITE 3) project. DMS and CS2 samples were collected and analyzed using an automated gas chromatography/flame photometric detection system with a sampling frequency of 10 min. H2S samples were collected using silver nitrate impregnated filters and analyzed by fluorescence quenching. The DMS data from both hemispheres have a bimodal distribution. Over the North Atlantic this reflects the difference between marine and continental air masses. Over the South Atlantic it may reflect differences in the sea surface source of DMS, corresponding to different air mass source regions. The median boundary layer H2S and CS2 levels were significantly higher in the northern hemisphere than the southern hemisphere, reflecting the higher frequency of samples influenced by pollutant and/or coastal emissions. Composite vertical profiles of DMS and H2S are similar to each other, are consistent with a sea surface source. Vertical profiles of CS2 have maxima in the free troposphere, implicating a continental source. The low levels of H2S and CS2 found in the southern hemisphere constrain the role of these compounds in global budgets to significantly less than previously estimated.

Cooper, David J.↗

Carbonyl Sulfide (OCS): Detections in Comets C/2002 T7 (LINEAR), C/2015 ER61 (PanSTARRS), and 21P/Giacobini-Zinner and Stringent Upper Limits in 46P/Wirtanen

Carbonyl sulfide(OCS)is one of the sulfur-bearing molecules detected in different astronomical environments, including comets. The present-day sulfur chemistry in comets may reveal much about the origin of these ices and their subsequent processing history. Cometary sulfur molecules such as H2S, H2CS, SO2, SO, CS, CS2,S2, and NShave been detected in many comets. However, OCS, the only sulfur-bearing species with fluorescence emission lines at infrared wavelengths, is under-represented in comet volatile studies, having been reported in only six comets so far. We targeted OCS with the NASA Infrared Telescope Facility in comets 46P/Wirtanen, 21P/Giacobini–Zinner, and C/2015 ER61(Pan STARRS)in 2017–2018 using the high-resolution iSHELL spectrograph, and in C/2002 T7(LINEAR)in 2004 using the heritage CSHELL spectrograph. In comet C/2015 ER61, the OCS abundance was similar to those measured in bright comets such as comets C/2012 S1(ISON)and C/1996 B2(Hyakutake), whereas in C/2002 T7 it was relatively depleted. Our OCS measurement in21P/Giacobini–Zinner is the first definitive detection of this molecule in a Jupiter-family comet from a ground-based facility and is close to the average OCS abundance determined in comet 67P/ Churyumov–Gerasimenko by the Rosetta mission. Our 3σupper limit for comet 46P/Wirtanen is the lowest reported OCS abundance in any comet. We present production rates and mixing ratios(with respect to H2O)for these comets and place our results in the context of comets measured to date

Mohammad Saki↗

Centimeter, Millimeter, and Submillimeter Observations of Comet l03P/Hartley 2

The close approach (0.12 AU) of Comet 103P/Hartley 2 to the Earth only 8 days prior to perihelion provided a unique opportunity to probe the chemical composition of this object. Additionally, supporting data was acquired during the EPOXI (Extrasolar Planet Observation and Deep Impact Extended Investigation) flyby mission [1], which provided high resolution infrared spectra and images. Observations were conducted from four facilities, contributing to the large ground-based consortium organized in support of the EPOXI mission [2]. The Arizona Radio Observatory's 12m telescope, Kitt Peak, AZ, and Submillimeter telescope, Mt. Graham, AZ, as well as the James Clerk Maxwell Telescope, Mauna Kea, HI and the Greenbank 100m telescope, Greenbank, WV, were employed for this study covering 20 cm, 3 cm, and 0.8-3 mm. Data were obtained, collectively, from 12 October 2010 to 5 November 2010 [3]. HCN, CH3OH, H2CO, HNC, OH, and CS were detected, and upper limits on the abundance of H2S, SO2, c-C3H2, and deuterated isotopologues of HCN, H2CO, and H2O were measured. Upper limits on the D/H ratio derived from DCN gave D/H less than 0.01[3]. Detailed analysis of these data will help constrain the temperature, abundances, variance or periodicity of a given species, and can be compared to results from other comets, as well as support the data obtained from the EPOXI mission. The full analysis and comparison will be presented.

Milam, Stefanie N.↗

Carbonyl Sulfide (OCS): Detections in Comets C/2002 T7 (LINEAR), C/2015 ER61 (PanSTARRS), and 21P/Giacobini-Zinner and Stringent Upper Limits in 46P/Wirtanen

Carbonyl sulfide (OCS) is one of the sulfur-bearing molecules detected in different astronomical environments, including comets. The present-day sulfur chemistry in comets may reveal much about the origin of these ices and their subsequent processing history. Cometary sulfur molecules such as H2S, H2CS, SO2, SO, CS, CS2, S2, and NS have been detected in many comets. However, OCS, the only sulfur-bearing species with fluorescence emission lines at infrared wavelengths, is under-represented in comet volatile studies, having been reported in only six comets so far. We targeted OCS with the NASA Infrared Telescope Facility in comets 46P/Wirtanen, 21P/Giacobini–Zinner, and C/2015 ER61 (PanSTARRS) in 2017–2018 using the high-resolution iSHELL spectrograph, and in C/2002 T7 (LINEAR) in 2004 using the heritage CSHELL spectrograph. In comet C/2015 ER61, the OCS abundance was similar to those measured in bright comets such as comets C/2012 S1 (ISON) and C/1996 B2 (Hyakutake), whereas in C/2002 T7 it was relatively depleted. Our OCS measurement in 21P/Giacobini–Zinner is the first definitive detection of this molecule in a Jupiter-family comet from a ground-based facility and is close to the average OCS abundance determined in comet 67P/Churyumov–Gerasimenko by the Rosetta mission. Our 3σ upper limit for comet 46P/Wirtanen is the lowest reported OCS abundance in any comet. We present production rates and mixing ratios (with respect to H2O) for these comets and place our results in the context of comets measured to date.

Mohammad Saki↗

Identification of gaseous SO2 and new upper limits for other gases on Io

The identification of gaseous sulfur dioxide on Io by Voyager 1 is reported, and preliminary upper limits for other atmospheric gases are presented. Averaged spectra taken by the Voyager IRIS experiment in the range of 1,000 to 1,200/cm are interpreted as containing three fundamental sulfur dioxide bands, with intensities most nearly corresponding to an atmospheric model with a sulfur dioxide abundance of 0.2 cm atm. Upper limits for COS, CS2, SO3, H2S, CO2, O3, N2O, H2O, CH4, NH3 and HC1, not detected in the spectra, were calculated on the basis of the radiative transfer equation for temperatures of 130 and 250 K; a depletion of hydrogen, carbon and nitrogen is noted. It is suggested that a SO2 outgassing from a cooling sulfur extrusion is the major source of the observed atmospheric SO2.

Pearl, J.↗

Millimetre observations of comets P/Brorsen-Metcalf (1989o) and Austin (1989c1) with the IRAM 30-m radio telescope

Millimeter observations with the IRAM 30 m telescope were conducted in comet P/Brorsen-Metcalf (1989o) on September 1989 and Austin (1989c1) on April and May 1990. The HCN J(1-0) and J(3-2) lines were detected in both comets. The HCN production rate relative to water in P/Brorsen-Metcalf is comparable to that previously measured in comet P/Halley, while that inferred in comet Austin might be smaller by a factor of two. The H2CO(3 sub 12 - 2 sub 11) transition, marginally observed in comet P/Brorsen-Metcalf, was firmly detected in May 1990 in comet Austin. Observations performed at offset positions suggest that the source of H2CO might be distributed. The H2CO abundance is on the order of 0.5 percent that of water for both comets, assuming a scalelength of 10(exp 4) km at 1 AU from the Sun for the distributed source. During the May observing period of comet Austin, two new species were detected for the first time in a comet: hydrogen sulfide (H2S) through its 1(sub 10) - 1(sub 01) ortho line at 169 GHz, and methanol (CH3OH) through J(3-2) delta K = 0 transitions at 145 GHz. Preliminary estimates of their abundances are 1.5 x 10(exp -3) for H2S and 8 x 10(exp -3) for CH3OH.

Colom, P.↗

Primordial Synthesis of Amines and Amino Acids in a 1958 Miller H2S-Rich Spark Discharge Experiment

Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordia! environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.

Parker, Eric T.↗

Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P3/2) + H2S yields SH + HBr and Br((sup 2)P3/2) + CH3SH yields CH3S + HBr. Heats of Formation of SH and CH3S Radicals

Time resolved resonance fluorescence detection of Br(sup 2)P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P3/2) + H2S = SH + HBr (1,-1) and Br((sup2)P3/2) + CH3SH = CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(exp -12) cu cm/molecule/s which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T],(k-1) = (4.40 +/- 0.92) exp[(-971 +/- 73)/T],k(2) = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and k(-2) = (1.46 +/-0.21) exp[(-399 +/-41)/T; errors are 2 sigma and represent precision only. By examining Br((sup 2)P3/2) equilibrium kinetics following 355nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(exp -10) cu cm/molecule/s has been obtained for the reaction CH3S + Br2 yields CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr,Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: for reaction 1, Delta-H(298) = 3.64 +/- 0.43 and Delta-H(0) = 3.26 +/-0.45; for reaction 2, Delta-H(298) = -0.14 +/- 0.28 and Delta-H(0) = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the following heats of formation for the RS radicals in units of kcal/mol: Delta-H(sub f)(sub 0)(SH) = 34.07 +/- 0.72, Delta-H(sub f)(sub 298)(SH) = 34.18 +/- 0.68, Delta-H(sub f)(sub 0)(CH3S) = 31.44 +/- 0.54, Delta-H(sub f)(sub 298)(CH3S) = 29.78 +/- 0.44; errors are 2 sigma and represent estimates of absolute accuracy. The SH heat of formation determined from our data agrees well with literature values but has reduced error limits compared to other available values. The CH3S heat of formation determined from our date is near the low end of the range of previous estimates and is 3-4 kcal/mol lower than values derived from recent molecular beam photofragmentation studies.

Nicovich, J. M.↗

Regolith Volatile Characterization (RVC) in RESOLVE

Resource investigation in the lunar poles is of importance to the potential impact of in-situ resource utilization (ISRU). The RESOLVE project developed a payload to investigate the permanently shadowed areas of the lunar poles and demonstrate ISRU technology. As a part of the RESOLVE project, the regolith volatile characterization (RVC) subsystem was designed to examine the release of volatiles from sample cores. The test sample was heated in the reactor to release the volatiles where they were analyzed with gas chromatography. Subsequently, the volatile sample was introduced into the lunar water resource demonstration (LWRD) subsystem where the released hydrogen and water were selectively captured. The objective of the Regolith Volatile Characterization (RVC) subsystem was to heat the crushed core sample and determine the desorption of volatile species of interest. The RVC subsystem encompasses the reactor and the system for volatile analysis. The system was designed to analyze H2, He, CO, CO2, N2, 02, CH4, H2S and H2O. The GC chosen for this work is a Siemens MicroSAM process GC with 3 columns and 8 TCD detectors. Neon was chosen as the carrier gas to enhance the analysis of hydrogen and helium.The limit of detection for the gases is approx.1000ppm for H2, CO. CO2 , N2, O2 and H2 S. The limit of detection for CH4 is approx.4000ppm and the water limit of detection is -10000 ppm with a sample analysis time of 2-3 minutes. These values (with the exception of water and H2S) were determined by dilution of a six gas mixture from Scott Gas (5% CO2, CO, O2, N2, 4% CH4 and H2) using mass flow controllers (MFC5). Water was calibrated at low levels using an in house relative humidity (RH) generator. H 2S and high concentrations of H2 were calibrated by diluting a pure stream of gas with MFCs. Higher concentrations of N2 and 02 were calibrated using Air again diluting with MFCs. There were three modification goals for the GC in EBU2 that would allow this process GC to be used in the field demo for RESOLVE. The first modification was to decrease the weight associated with the GC, this included eliminating the explosion proof case (Figure 1) and replacing it with a lightweight case as well as using an on board COPV tank for the neon carrier gas. The next goal was to add a second oven for the molecular sieve column to allow for dual temperature control during GC operation; the separation of hydrogen and helium is optimum at lower temperatures while the water analysis required higher temperatures creating a competing design requirement. The second oven also allows a lower limit of detection for water quantification and avoids the possibility of water condensing in the GC which could ruin the column characteristics. The final goal was to modify the column arrangement to optimize the system for our specific application. Figure 2 shows the internal details of the module optimized optimized for our field application. The modifications and performance of the gas analysis system will be discussed in detail.

Captain, Janine↗

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.↗

Chemistry Related to Possible Outgassing Sources on Mars

An earlier paper, Chemical markers of possible hot spots on Mars by A. S. Wong, S. K. Atreya and Th. Encrenaz, explored the modification of the atmosphere of Mars following an influx of methane, sulfur dioxide and hydrogen sulfide (CH4, SO2, H2S) from any outgassing sources which are referred to as hot spots. The feasibility of detection of the new species by Planetary Fourier Spectrometer on Mars Express is reported in a subsequent paper, Atmospheric photochemistry above possible martian hot spots by A. S. Wong, S. K. Atreya, V. Formisano, Th. Encrenaz and N. Ignatiev. This abstract is a follow-up on the previous two papers. Here we treat the effect of any outgassed halogens rigorously. We also make estimates of dilution factors relative to the source location following convection and meridional transport.

A S Wong↗

Mass Wasting and Ground Collapse in Terrains of Volatile-Rich Deposits as a Solar System-Wide Geological Process: The Pre-Galileo View

The polar terrains of Mars are covered in many places with irregular pits and retreating scarps, as are some of the surfaces of the outer-planet satellites. These features are interpreted by us as diagnostic of exogenic degradation due to the loss of a volatile rock-forming matrix or cement. In this study we propose that sublimation degradation is a plausible Solar Systemwide geological process. Candidate examples have been identified on Mars, Io, and Triton, and possibly Europa and Ganymede. We envision this process as having two end-member expressions (pits and scarps), for which we hypothesize two end-member mechanisms (massive localized lenses and areally extensive basal layers). In this study we focus on the role this process may play on the surfaces of the galilean satellites. Our principle modeling results are that for these satellites, H2S, CO2, and NH3 are the only viable candidate volatiles for sublimation degradation of landforms, in light of galilean satellite cosmochemistry. For Io's polar regions only H2S, and then only from slopes that face the Sun and have thin lags, is volatile enough to cause the observed sublimation-induced erosion at those latitudes. SO2 is not a viable candidate as an agent of erosion, especially for these polar landforms. In the case of Europa, only CO2 and H2S are viable candidates (given surface age constraints). Both species could be efficient eroders in nonpolar regions. H2S could generate erosion within the polar regions if the deposition and erosion conditions were essentially identical as those we invoked for Io's polar regions. For Ganymede (and Callisto) NH3 might be an agent of erosion in equatorial terrains of great age. The sublimation of CO2 and H2S is much more robust than NH3. The much slower rate of sublimation degradation from NH3 might be detectable by Galileo and used as a compositional indicator.

Moore, Jeffrey M.↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗