Minimum estimates of the amount and timing of gases released into the martian atmosphere from volcanic eruptions

Volcanism has been a major process during most of the geologic history of Mars. Based on data collected from terrestrial basaltic eruptions, we assume that the volatile content of martian lavas was typically ∼0.5 wt.% water, ∼0.7 wt.% carbon dioxide, ∼0.14 wt.% sulfur dioxide, and contained several other important volatile constituents. From the geologic record of volcanism on Mars we find that during the late Noachian and through the Amazonian volcanic degassing contributed ∼0.8 bar to the martian atmosphere. Because most of the outgassing consisted of greenhouse gases (i.e., CO₂ and SO₂) warmer surface temperatures resulting from volcanic eruptions may have been possible. Our estimates suggest that ∼1.1 × 10²¹ g (∼8 ± 1 m m⁻²) of juvenile water were released by volcanism; slightly more than half the amount contained in the north polar cap and atmosphere. Estimates for released CO₂ (1.6 × 10²¹ g) suggests that a large reservoir of carbon dioxide is adsorbed in the martian regolith or alternatively ∼300 cm cm⁻² of carbonates may have formed, although these materials would not occur readily in the presence of excess SO₂. Up to ∼120 cm cm⁻² (2.2 × 10²⁰ g) of acid rain (H₂SO₄) may have precipitated onto the martian surface as the result of SO₂ degassing. The hydrogen flux resulting from volcanic outgassing may help explain the martian atmospheric D/H ratio. The amount of outgassed nitrogen (∼1.3 mbar) may also be capable of explaining the martian atmospheric ¹⁵N/¹⁴N ratio. Minor gas constituents (HF, HCl, and H₂S) could have formed hydroxyl salts on the surface resulting in the physical weathering of geologic materials. The amount of hydrogen fluoride emitted (1.82 × 10¹⁸ g) could be capable of dissolving a global layer of quartz sand ∼5 mm thick, possibly explaining why this mineral has not been positively identified in spectral observations. The estimates of volcanic outgassing presented here will be useful in understanding how the martian atmosphere evolved over time.     

Excitation of the oxygen nightglow on the terrestrial planets

A scheme of excitation, quenching, and energy transfer processes in the oxygen nightglow on the Earth, Venus, and Mars has been developed based on the observed nightglow intensities and vertical profiles, measured reaction rate coefficients, and photochemical models of the nighttime atmospheres of the Venus and Mars. The scheme involves improved radiative lifetimes of some band systems, calculated yields of the seven electronic states of O₂ in termolecular association, and rate coefficients of seven processes of electronic quenching of the Herzberg states of O₂, which are evaluated by fitting to the nightglow observations. Electronic quenching of the vibrationally excited Herzberg states by O₂ and N₂ in the Earth's nightglow is a quarter of total collisional removal of the O₂(A, A′) states and a dominant branch for the O₂(c) state. The scheme supports the conclusion by Steadman and Thrush (1994) that the green line is excited by energy transfer from the O₂(A³Σ_u⁺, v≥6) molecules, and the inferred rate coefficient of this transfer is 1.5×10⁻¹¹ cm³ s⁻¹. The O₂ bands at 762 nm and 1.27 μm are excited directly, by quenching of the Herzberg states, and by energy transfer from the O₂(⁵Π_g) state. Quenching of the O₂ band at 762 nm excites the band at 1.27 μm as well. Effective yield of the O₂(a¹Δ_g) state in termolecular association on Venus and Mars is ∼0.7. Quantitative assessments of all these processes have been made. A possible reaction of O₂(c¹Σ_u⁻)+CO is a very minor branch of recombination of CO₂ on Venus and Mars. Night airglow on Mars is calculated for typical conditions of the nighttime atmosphere. The calculated vertical intensity of the O₂ band at 1.27 μm is 13 kR, far below the recently reported detections.     

Methane evolution from UV-irradiated spacecraft materials under simulated martian conditions: Implications for the Mars Science Laboratory (MSL) mission

Fifteen organic and three inorganic compounds were tested for methane (CH₄) evolution under simulated martian conditions of 6.9 mbar; UVC (200-280 nm) flux of 4 W m⁻²; 20 °C; simulated optical depth of 0.1; and a Mars gas composition of CO₂ (95.3%), N₂ (2.7%), Ar (1.7%), O₂ (0.13%), and water vapor (0.03%). All three inorganic compounds (i.e., NaCl, CaCO₃, graphite) failed to evolve methane at the minimum detection level 0.5 ppm, or above. In contrast, all organic compounds evolved methane when exposed to UV irradiation under simulated martian conditions. The polycyclic aromatic hydrocarbon, pyrene, released the most methane per unit of time at 0.175 nmol CH₄ g⁻¹ h⁻¹, and a spectral reflectance target material used for the MER rovers and Phoenix lander released the least methane at 0.00065 nmol CH₄ cm⁻² h⁻¹. Methane was also released from UV-killed bacterial endospores of Bacillus subtilis. Although all organic compounds evolved methane when irradiated with UV photons under martian conditions, the concentrations of residual organics, biogenic signature molecules, and dead microbial cells should be relatively low on the exterior surfaces of the MSL rover, and, thus, not significant sources of methane contamination. In contrast, kapton tape was found to evolve methane at the rate of 0.00165 nmol CH₄ cm⁻² h⁻¹ (16.5 nmol m⁻² h⁻¹) under the UV and martian conditions tested. Although the evolution of methane from kapton tape was found to decline over time, the large amount of kapton tape used on the MSL rover (lower bound estimated at 3 m²) is likely to create a significant source of terrestrial methane contamination during the early part of the mission.     

The Unusual Absorption Line Spectrum of Quasar SDSS J2220+0109

We report the Balmer broad absorption lines (BALs) in the quasar SDSS J2220 + 0109 discovered from the SDSS data, and present a detailed analysis of the peculiar absorption line spectrum, including the He I* multiplet at λλ3189, 3889 arising from the metastable 2³s-state helium and the Balmer Hα and Hβ lines from the excited hydrogen H I of n = 2 level, which are rarely seen in quasar spectra, as well as many absorption lines arising from the excited Fe II* of the levels 7 955 cm⁻¹, 13 474 cm⁻¹ and 13 673 cm⁻¹ in the wavelength range 3100∼3300 Å. Ca II H, K absorption line doublets also clearly appear in the SDSS spectrum. All absorption lines show a similar blueshifted velocity structure of Δv ≈ − 1500 ∼ 0 km·s⁻¹ relative to the quasar's systematic redshift determined from the emission lines. Detailed analysis suggests that the Balmer absorption lines should arise from the partially ionized region with a column density of N_HI ≈ 10²¹ cm⁻² for an electron density of ne ∼ 10⁶ cm⁻³; and that the hydrogen n = 2 level may be populated via collisional excitation with Lyα pumping.     

Hydrogen peroxide on Mars: evidence for spatial and seasonal variations

Hydrogen peroxide (H₂O₂) has been suggested as a possible oxidizer of the martian surface. Photochemical models predict a mean column density in the range of 10¹⁵-10¹⁶ cm⁻². However, a stringent upper limit of the H₂O₂ abundance on Mars (9×10¹⁴ cm⁻²) was derived in February 2001 from ground-based infrared spectroscopy, at a time corresponding to a maximum water vapor abundance in the northern summer (30 pr. μm, Ls=112°). Here we report the detection of H₂O₂ on Mars in June 2003, and its mapping over the martian disk using the same technique, during the southern spring (Ls=206°) when the global water vapor abundance was ∼10 pr. μm. The spatial distribution of H₂O₂ shows a maximum in the morning around the sub-solar latitude. The mean H₂O₂ column density (6×10¹⁵ cm⁻²) is significantly greater than our previous upper limit, pointing to seasonal variations. Our new result is globally consistent with the predictions of photochemical models, and also with submillimeter ground-based measurements obtained in September 2003 (Ls=254°), averaged over the martian disk (Clancy et al., 2004, Icarus 168, 116-121).     

Core-collapse supernovae and the Younger Dryas/terminal Rancholabrean extinctions

Early predictions that some supernovae release large quantities of prompt high energy photons are now corroborated by optical identification of core-collapse supernovae associated with extragalactic GRBS (beamed γ-ray bursts) and XRFS (beamed or un-beamed X-ray flashes). Given the in-galaxy supernova frequency and GRB and XRF recurrence statistics, significant Earth-incident events during the past several million years very likely occurred and nearby events should have affected the Earth and other planetary atmospheres, including terrestrial surface solar UV, the Earth’s climate, and its ecology. The Younger Dryas Stadial (∼12,900 to 11,550 calendar yr BP) began with sharply cooler temperatures in the Earth’s northern hemisphere, regional drought, paleoecological evidence compatible with increased UV, and abrupt increases in cosmogenic ¹⁴C and ¹⁰Be in ice and marine cores and tree rings. In North America, stratigraphic and faunal sequences indicate that a major pulse of mammalian extinctions (at least 23-31 genera) began very close to 12,830 calendar yr BP and was sudden: deposits one century younger are devoid of diverse extinct fauna remains. A 10 s beamed GRB within 2 kpc of the Earth delivers 100 kJ m⁻² fluence to the Earth’s atmosphere, where it causes spallation and catalytic reactions depleting 35-50% O³, and producing excess NO_x species (which favor cooling, drought, and surface fertility), ¹⁴C, and ¹⁰Be. An un-beamed, 10⁵⁰ erg hard photon impulse at ∼250 pc produces similar terrestrial atmospheric effects. A well-characterized massive star supernova, the unusually close Vela event (d = 250 ± 30 pc; total energy of 1-2 × 10⁵¹ erg; age constrained from remnant nebula shock velocities considerations at 13,000-16,000 yr and from the pulsar characteristic age at ∼11,400 yr) may have initiated the Younger Dryas climate change, and caused the extinction of the terminal Rancholabrean fauna.     

Venus night airglow: Ground-based detection of OH, observations of O2 emissions, and photochemical model

Venus nightglow was observed at NASA IRTF using a high-resolution long-slit spectrograph CSHELL at LT = 21:30 and 4:00 on Venus. Variations of the O₂ airglow at 1.27 μm and its rotational temperature are extracted from the observed spectra. The mean O₂ nightglow is 0.57 MR at 21:30 at 35°S-35°N, and the temperature increases from 171 K near the equator to ∼200 K at ±35°. We have found a narrow window that covers the OH (1-0) P1(4.5) and (2-1) Q1(1.5) airglow lines. The detected line intensities are converted into the (1-0) and (2-1) band intensities of 7.2 ± 1.8 kR and <1.4 kR at 21:30 and 15.5 ± 2 kR and 4.7 ± 1 kR at 4:00. The f-component of the (1-0) P1(4.5) line has not been detected in either observation, possibly because of resonance quenching in CO₂. The observed Earth’s OH (1-0) and (2-1) bands were 400 and 90 kR at 19:30 and 250 and 65 kR at 9:40, respectively. A photochemical model for the nighttime atmosphere at 80-130 km has been made. The model involves 61 reactions of 24 species, including odd hydrogen and chlorine chemistries, with fluxes of O, N, and H at 130 km as input parameters. To fit the OH vibrational distribution observed by VEX, quenching of OH (v > 3) in CO₂ only to v ? 2 is assumed. According to the model, the nightside-mean O₂ emission of 0.52 MR from the VEX and our observations requires an O flux of 2.9 × 10¹² cm⁻² s⁻¹ which is 45% of the dayside production above 80 km. This makes questionable the nightside-mean O₂ intensities of ∼1 MR from some observations. Bright nightglow patches are not ruled out; however, the mean nightglow is ∼0.5 MR as observed by VEX and supported by the model. The NO nightglow of 425 R needs an N flux of 1.2 × 10⁹ cm⁻² s⁻¹, which is close to that from VTGCM at solar minimum. However, the dayside supply of N at solar maximum is half that required to explain the NO nightglow in the PV observations. The limited data on the OH nightglow variations from the VEX and our observations are in reasonable agreement with the model. The calculated intensities and peak altitudes of the O₂, NO, and OH nightglow agree with the observations. Relationships for the nightglow intensities as functions of the O, N, and H fluxes are derived.     

Eclipse reappearances of Io: Time-resolved spectroscopy (1.9-4.2 μm)

We obtained time-resolved, near-infrared spectra of Io during the 60-90 min following its reappearance from eclipse by Jupiter on five occasions in 2004. The purpose was to search for spectral changes, particularly in the well-known SO₂ frost absorption bands, that would indicate surface-atmosphere exchange of gaseous SO₂ induced by temperature changes during eclipse. These observations were a follow-on to eclipse spectroscopy observations in which Bellucci et al. [Bellucci et al., 2004. Icarus 172, 141-148] reported significant changes in the strengths of two strong SO₂ bands in data acquired with the VIMS instrument aboard the Cassini spacecraft. One of the bands (4.07 μm [ν₁ + ν₃]) observed by Bellucci et al. is visible from ground-based observatories and is included in our data. We detected no changes in Io’s spectrum at any of the five observed events during the approximately 60-90 min during which spectra were obtained following Io’s emergence from Jupiter’s shadow. The areas of the three strongest SO₂ bands in the region 3.5-4.15 μm were measured for each spectrum; the variation of the band areas with time does not exceed that which can be explained by the Io’s few degrees of axial rotation during the intervals of observation, and in no case does the change in band strength approach that seen in the Cassini VIMS data. Our data are of sufficient quality and resolution to show the weak 2.198 μm (4549.6 cm⁻¹) 4ν₁ band of SO₂ frost on Io for what we believe is the first time. At one of the events (June 22, 2004), we began the acquisition of spectra ∼6 min before Io reappeared from Jupiter’s shadow, during which time it was detected through its own thermal emission. No SO₂ bands were superimposed on the purely thermal spectrum on this occasion, suggesting that the upper limit to condensed SO₂ in the vertical column above Io’s surface was ∼4 × 10⁻⁵ g cm⁻².     

Spatially-resolved high-resolution spectroscopy of Venus 2. Variations of HDO, OCS, and SO2 at the cloud tops

While CO, HCl, and HF, that were considered in the first part of this work, have distinct absorption lines in high-resolution spectra and were detected four decades ago, the lines of HDO, OCS, and SO₂ are either very weak or blended by the telluric lines and have not been observed previously by ground-based infrared spectroscopy at the Venus cloud tops. The H₂O abundance above the Venus clouds is typically below the detection limit of ground-based IR spectroscopy. However, the large D/H ratio on Venus facilitates observations of HDO. Converted to H₂O with D/H ≈ 200, our observations at 2722 cm⁻¹ in the Venus afternoon show a H₂O mixing ratio of ∼1.2 ppm at latitudes between ±40° increasing to ±60° by a factor of 2. The observations in the early morning reveal the H₂O mixing ratio that is almost constant at 2.9 ppm within latitudes of ±75°. The measured H₂O mixing ratios refer to 74 km. The observed increase in H₂O is explained by the lack of photochemical production of sulfuric acid in the night time. The recent observations at the P-branch of OCS at 4094 cm⁻¹ confirm our detection of OCS. Four distributions of OCS along the disk of Venus at various latitudes and local times have been retrieved. Both regular and irregular components are present in the variations of OCS. The observed OCS mixing ratio at 65 km varies from ∼0.3 to 9 ppb with the mean value of ∼3 ppb. The OCS scale height is retrieved from the observed limb darkening and varies from 1 to 4 km with a mean value of half the atmospheric scale height. SO₂ at the cloud tops has been detected for the first time by means of ground-based infrared spectroscopy. The SO₂ lines look irregular in the observed spectra at 2476 cm⁻¹. The SO₂ abundances are retrieved by fitting by synthetic spectra, and two methods have been applied to determine uncertainties and detection limits in this fitting. The retrieved mean SO₂ mixing ratio of 350 ± 50 ppb at 72 km favors a significant increase in SO₂ above the clouds since the period of 1980-1995 that was observed by the SOIR occultations at Venus Express. Scale heights of OCS and SO₂ may be similar, and the SO₂/OCS ratio is ∼500 and may be rather stable at 65-70 km under varying conditions on Venus.     

FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

An experimental study of the reaction kinetics of C2(XΣg) with hydrocarbons (CH4, C2H2, C2H4, C2H6 and C3H8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

The reactivity of C₂(X¹Σ⁺_g) with simple saturated (CH₄, C₂H₆ and C₃H₈) and unsaturated (C₂H₂ and C₂H₄) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ?10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ with the exception of methane for which the rate coefficient is one order of magnitude lower: ∼10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These results have been analyzed in terms of potential destruction sources of C₂(X¹Σ⁺_g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction ¹C₂ + CH₄ should be updated with our new data and that reactions with C₂H₂, C₂H₄ and C₂H₆ should also be included in the existing photochemical models.     

Neutron Capture Isotopes in the Martian Regolith and Implications for Martian Atmospheric Noble Gases

Impact-produced glasses in some martian meteorites have trapped significant amounts of the recent martian atmosphere. From literature data, we estimate that ∼9% of the trapped ⁸⁰Kr in these meteorites was produced from neutron capture on ⁷⁹Br. Estimates of neutron fluences made from ⁸⁰Kr and ¹⁴⁹Sm for bulk samples of meteorite EET79001 indicate that ⁸⁰Kr excesses in the impact glass were not produced in situ. Theoretical calculations independently predict production of a large neutron-capture component of ⁸⁰Kr and ³⁶Ar in the martian regolith, and part of this component presumably escaped into the martian atmosphere. These calculations were made by using the Los Alamos High-Energy Transport Code to calculate the fluxes of galactic cosmic ray (GCR)-produced thermal neutrons as a function of depth in the uppermost 500 g cm⁻² of the martian surface, and by adopting average Cl, Br, and I concentrations of the upper martian surface of ∼0.3%, ∼20 ppm, and ∼0.5 ppm, respectively. Combining these data with the appropriate neutron-capture cross sections, we calculate Mars global production rates of ⁸⁰Kr_n=2.4×10¹⁶atoms sec⁻¹, ³⁶Ar_n=5.5×10¹⁸ atoms sec⁻¹, and ¹²⁸Xe_n=3×10¹³ atoms sec⁻¹. Calculated global production rates of spallogenic ⁸⁰Kr_sp, and ³⁶Ar_sp, are smaller by factors of ∼770 and ∼29, respectively. It would require ∼330 Myr to produce an amount of ⁸⁰Kr_n equivalent to the amount inferred to be present today in the martian atmosphere (∼2.5×10³² atoms). Production of these neutron-capture components probably has occurred over the past ∼4 Gyr, as only an atmospheric pressure substantially higher than today's would appreciably decrease the neutron flux in the regolith. Thus, most of the neutron-capture noble gases produced over time probably remain in the martian regolith and would make sensitive indicators of the time period a sample has resided near the martian surface. Assuming mixing of the martian surface to an average depth of 100 m, the predicted average regolith concentrations of ⁸⁰Kr_n, ³⁶Ar_n, and ¹²⁸Xe_n are ∼4×10⁻⁹ cm⁻³ g⁻¹, ∼1×10⁻⁶ cm³ g⁻¹, and ∼5×10⁻¹² cm³ g⁻¹, respectively. If similar fractions of these neutron-capture isotopes have escaped into the atmosphere, they would comprise ∼3% and ∼0.2% of the present atmospheric inventories of ³⁶Ar and ¹²⁸Xe, respectively. The fractional excess of ⁸⁰Kr_n in ancient martian meteorite ALH84001 appears similar to that in shock-glass phases of young shergottite meteorites. If ALH84001 acquired its atmospheric gases ∼4 Gyr ago, this implies that, prior to that time, halogens were greatly concentrated at the martian surface by crustal formational and weathering processes, impacts efficiently degassed the regolith, and Mars did not have a significant atmosphere to shield the surface.     

Vertical profile of H2SO4 vapor at 70-110 km on Venus and some related problems

The vertical profile of H₂SO₄ vapor is calculated using current atmospheric and thermodynamic data. The atmospheric data include the H₂O profiles observed at 70-112 km by the SOIR solar occultations, the SPICAV-UV profiles of the haze extinction at 220 nm, the VeRa temperature profiles, and a typical profile of eddy diffusion. The thermodynamic data are the saturated vapor pressures of H₂O and H₂SO₄ and chemical potentials of these species in sulfuric acid solutions. The calculated concentration of sulfuric acid in the cloud droplets varies from 85% at 70 km to a minimum of 70% at 90 km and then gradually increasing to 90-100% at 110 km. The H₂SO₄ vapor mixing ratio is ∼10⁻¹² at 70 and 110 km with a deep minimum of 3 × 10⁻¹⁸ at 88 km. The H₂O-H₂SO₄ system matches the local thermodynamic equilibrium conditions up to 87 km. The column photolysis rate of H₂SO₄ is 1.6 × 10⁵ cm⁻² s⁻¹ at 70 km and 23 cm⁻² s⁻¹ at 90 km. The calculated abundance of H₂SO₄ vapor at 90-110 km and its photolysis rate are smaller than those presented in the recent model by Zhang et al. (Zhang, X., Liang, M.C., Montmessin, F., Bertaux, J.L., Parkinson, C., Yung, Y.L. [2010]. Nat. Geosci. 3, 834-837) by factors of 10⁶ and 10⁹, respectively. Assumptions of 100% sulfuric acid, local thermodynamic equilibrium, too warm atmosphere, supersaturation of H₂SO₄ (impossible for a source of SO_X), and cross sections for H₂SO₄·H₂O (impossible above the pure H₂SO₄) are the main reasons of this huge difference. Significant differences and contradictions between the SPICAV-UV, SOIR, and ground-based submillimeter observations of SO_X at 70-110 km are briefly discussed and some weaknesses are outlined. The possible source of high altitude SO_X on Venus remains unclear and probably does not exist.     

Characteristics of Saturn’s FUV airglow from limb-viewing spectra obtained with Cassini-UVIS

This study reports the analysis of far ultraviolet (FUV) limb spectra of the airglow of Saturn in the 1150-1850 Å spectral window, obtained with the Ultraviolet Imaging Spectrograph (UVIS) onboard Cassini, spanning altitudes from −1200 to 4000 km. The FUV limb emission consists of three main contributions: (1) H Ly-α peaking at 1100 km with a brightness of 0.8 kilo-Rayleighs (kR), (2) reflected sunlight longward of 1550 Å which maximizes at −950 km with 16.5 kR and (3) H₂ bands in the 1150-1650 Å bandwidth, peaking at 1050 km reaching a maximum of 3.9 kR.A vertical profile of the local H₂ volume emission rate has been derived using the hydrocarbon density profiles from a model of the Saturn equatorial atmosphere. It is well matched by a Chapman function, characterized by a maximum value of 3.5 photons cm⁻³ s⁻¹ in the 800-1650 Å UV bandwidth, peaking at 1020 km.Comparisons between the observed spectra and a first-order synthetic airglow H₂ model in the 1150-1650 Å bandwidth show that the spectral shape of the H₂ bands is accounted for by solar fluorescence and photoelectron excitation. The best fits are obtained with a combination of H₂ fluorescence lines and 20 eV electron impact spectra, the latter contributing ∼68% of the total H₂ airglow emission.     

New laboratory measurements of CH4 in Titan's conditions and a reanalysis of the DISR near-surface spectra at the Huygens landing site

Laboratory spectra of methane-nitrogen mixtures have been recorded in the near-infrared range (1.0-1.65 μm) in conditions similar to Titan's near surface, to facilitate the interpretation of the DISR/DLIS (DISR—Descent Imager/Spectral Radiometer) spectra taken during the last phase of the descent of the Huygens Probe, when the surface was illuminated by a surface-science lamp. We used a 0.03 cm⁻¹ spectral resolution, adequate to resolve the lines at high pressure (p_N2∼1.5 bar). By comparing the laboratory spectra with synthetic calculations in the well-studied ν₂+2ν₃ band (7515-7620 cm⁻¹), we determine a methane absorption column density of 178±20 cm atm and a temperature of 118±10 K in our experiment. From this, we derive the methane absorption coefficients over 1.0-1.65 μm with a 0.03 cm⁻¹ sampling, allowing for the extrapolation of the results to any other methane column density under the relevant pressure and temperature conditions. We then revisit the calibration and analysis of the Titan “lamp-on” DLIS spectra. We infer a 5.1±0.8% methane-mixing ratio in the first 25 m of Titan's atmosphere. The CH₄ mixing ratio measured 90 s after landing from a distance of 45 cm is found to be 0.92±0.25 times this value, thus showing no post-landing outgassing of methane in excess of ∼20%. Finally, we determine the surface reflectivity as seen between 25 m and 45 cm and find that the 1500 nm absorption band is deeper in the post-landing spectrum as compared to pre-landing.     

Molecular hydrogen in Titan’s atmosphere: Implications of the measured tropospheric and thermospheric mole fractions

The third most abundant species in Titan’s atmosphere is molecular hydrogen with a tropospheric/lower stratospheric mole fraction of 0.001 derived from Voyager and Cassini infrared measurements. The globally averaged thermospheric H₂ mole fraction profile from the Cassini Ion Neutral Mass Spectrometer (INMS) measurements implies a small positive gradient in the H₂ mixing ratio from the tropopause region to the lower thermosphere (∼950-1000 km), which drives a downward H₂ flux into Titan’s surface comparable to the H₂ escape flux out of the atmosphere (∼2 × 10¹⁰ cm⁻² s⁻¹ referenced to the surface) and requires larger photochemical production rates of H₂ than obtained by previous photochemical models. From detailed model calculations based on known photochemistry with eddy, molecular, and thermal diffusion, the tropospheric and thermospheric H₂ mole fractions are incompatible by a factor of ∼2. The measurements imply that the downward H₂ surface flux is in substantial excess of the speculative threshold value for methanogenic life consumption of H₂ (McKay, C.P., Smith, H.D. [2005], Icarus 178, 274-276. doi:10.1016/j.icarus.2005.05.018), but without the extreme reduction in the surface H₂ mixing ratio.     

High-resolution spectroscopy of Venus: Detection of OCS, upper limit to H2S, and latitudinal variations of CO and HF in the upper cloud layer

Venus was observed at 2.4 and 3.7 μm with a resolving power of 4×¹⁰⁴ using the long-slit high-resolution spectrograph CSHELL at NASA IRTF. The observations were made along a chord that covered a latitude range of ± 60° at a local time near 8:00. The continuous reflectivity and limb brightening at 2.4 μm are fitted by the clouds with a single scattering albedo 1−a=0.01 and a pure absorbing layer with τ=0.09 above the clouds. The value of 1−a agrees with the refractive index of H₂SO₄ (85%) and the particle radius of 1 μm. The absorbing layer is similar to that observed by the UV spectrometer at the Pioneer Venus orbiter. However, its nature is puzzling. CO₂ was measured using its R32 and R34 lines. The retrieved product of the CO₂ abundance and airmass is constant at 1.9 km-atm along the instrument slit in the latitude range of ± 60°. The CO mixing ratio (measured using the P21 line) is rather constant at 70 ppm, and its variations of ∼10% may be caused by atmospheric dynamics. The observed value is higher than the 50 ppm retrieved previously from a spectrum of the full disk, possibly, because of some downward extension of the mesospheric morningside bulge of CO. The observations of the HF R3 line reveal a constant HF mixing ratio of 3.5±0.5 ppb within ± 60° of latitude, which is within the scatter in the previous measurements of HF. OCS has been detected for the first time at the cloud tops by summing 17 lines of the P-branch. The previous detections of OCS refer to the lower atmosphere at 30-35 km. The retrieved OCS mixing ratio varies with a scale height of 1 to 3 km. The mean OCS mixing ratio is ∼2 ppb at 70 km and ∼14 ppb at 64 km. Vertical motions in the atmosphere may change the OCS abundance. The detected OCS should significantly affect Venus' photochemistry. A sensitive search for H₂S using its line at 2688.93 cm⁻¹ results in a 3 sigma upper limit of 23 ppb, which is more restrictive than the previous limit of 100 ppb.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Europa's Oxygen Exosphere and Its Magnetospheric Interaction

The newly detected oxygen atmosphere of Europa is modeled by invoking charged particle sputtering with H₂O and O₂molecules as the main ejecta. The magnetospheric corotating ions could provide the required source strength (∼3 × 10²⁶sec⁻¹) of O₂molecules if a fraction (∼20%) of the exospheric ions were recycled to Europa's surface where they produce additional sputtering product. Two exospheric components are expected to form: an extended corona with a size of a few satellite radii which is composed of sputtered molecules in ballistic motion, and a thermal population with a surface density of 10⁸–10⁹cm⁻³and a scale height of about 20 km. The electron impact ionization of this exosphere would lead to an Io-like interaction with the jovian magnetosphere with a field-aligned Birkeland current of about 5 × 10⁵A.     

H2O2 production by high-energy electrons on icy satellites as a function of surface temperature and electron flux

Chemistry on the icy surface of Europa is heavily influenced by the incident energetic particle flux from the jovian magnetosphere. The majority (>75%) of this energy is in the form of high energy electrons (extending to >10 MeV). We have simulated the electron irradiation environment of Europa with a vacuum system containing a high-energy electron gun for irradiation of ice samples formed on a gold mirror cooled with a cryostat. Pure water films of ∼2.6 μm thickness were grown at 100 K and then either cooled (to 80 K), warmed (to 120 K) or left at 100 K and subsequently irradiated with 10 keV electrons. The production of hydrogen peroxide (H₂O₂) was monitored by observation of the 2850 cm⁻¹ (3.5 μm) band. Equilibrium concentrations of H₂O₂, in units of percent by number H₂O₂ relative to water, were found to be 0.043% (80 K), 0.029% (100 K), and 0.0063% (120 K). These values are 33%, 22%, and 5%, respectively, that of the reported surface concentration on the leading hemisphere of Europa (Carlson, R.W., Anderson, M.S., Johnson, R.E., Smythe, W.D., Hendrix, A.R., Barth, C.A., et al. [1999]. Science 283(5410), 2062-2064) and less than the equilibrium concentrations formed by ion irradiation. In addition to the ice film temperature, the current of electrons was varied between different experiments to determine the production and destruction of H₂O₂ as a function of both electron flux and ice temperature. Variation in current was found to have little effect on the results other than accelerating arrival at radiolytic equilibrium.