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Abstract: The new ESA Venus Express orbiter is the first mission applying the probing technique of solar and stellar occultation to the atmosphere of Venus, with the SPICAV/SOIR instrument. SOIR is a new type of spectrometer used for solar occultations in the range 2.2–4.3 μm. Thanks to a high spectral resolving power (unprecedented in planetary space exploration), a new gaseous absorption band was soon detected in the atmospheric transmission spectra around 2982 cm−1, showing a structure resembling an unresolved Q branch and a number of isolated lines with a regular wave number pattern. This absorption could not be matched to any species contained in HITRAN or GEISA databases, but was found very similar to an absorption pattern observed by a US team in the spectrum of solar light reflected by the ground of Mars [Villanueva, G.L., Mumma, M.J., Novak, R.E., Hewagama, T., 2008. Icarus 195 (1), 34–44]. This team then suggested to us that the absorption was due to an uncatalogued transition of the 16O12C18O molecule. The possible existence of this band was soon confirmed from theoretical considerations by Perevalov and Tashkun. Some SOIR observations of the atmospheric transmission are presented around 2982 cm−1, and rough calculations of line strengths of the Q branch are produced, based on the isotopic ratio measured earlier in the lower atmosphere of Venus. This discovery emphasizes the role of isotopologues of CO2 (as well as H2O and HDO) as important greenhouse gases in the atmosphere of Venus. [Copyright &y& Elsevier]

We present here vertically resolved measurements of the carbon isotopic composition of CO 2 in the Martian atmosphere between the surface and 50 km of altitude. The results are based on data taken by the ExoMars Trace Gas Orbiter with the NOMAD instrument and have been aggregated to derive an average vertical profile of 13C/12C. We find no seasonal or spatial trends with variabilities beyond the sensitivity of the measurements. For the analysis, we developed a method that allows us to estimate whether the observed variability of isotopic measurements is beyond their intrinsic accuracy, by exploiting ab-initio spectroscopy and the radiometric noise of the instrument. Applying this method to our data, we find that atmospheric CO 2 is depleted in 13C compared to the Earth standard by 30‰ to 45‰, in line with previous ground-based measurements values of the atmosphere and in contrast with the average value obtained by Curiosity at the surface (46 ± 4‰). These differences in isotopic signatures of CO 2 as measured across the atmosphere and near-surface pose new questions when inferring the evolution and history of carbon on Mars, and suggest that processes such as a strong atmosphere-surface interactions may be fractionating the carbon reservoirs on the planet. • The 13C/12C isotopic ratio in CO 2 is derived in the lower atmosphere of Mars with NOMAD data. • There is indication that CO 2 at 20–35 km of altitude is depleted in 13C compared to Earth Standard. • A quantitative method to characterize retrieval uncertainty with spectroscopy is presented. • Surface-atmosphere processes should be investigated to explain the discrepancies between values from NOMAD and Curiosity. [ABSTRACT FROM AUTHOR]

Highlights • A complete spectral in-flight calibration of NOMAD is presented. • A model to compute spectral continuum is produced as a function of instrument properties. • NOMAD sensitivity to atmospheric CH 4 is evaluated with different aerosol loads. • NOMAD sensitivity to CH 4 in Solar Occultation is on sub-ppbv level. • NOMAD will be able to trace seasonal trends for CH 4 with nadir observations. Abstract The Nadir and Occultation for MArs Discovery instrument (NOMAD), onboard the ExoMars Trace Gas Orbiter (TGO) spacecraft was conceived to observe Mars in solar occultation, nadir, and limb geometries, and will be able to produce an outstanding amount of diverse data, mostly focused on properties of the atmosphere. The infrared channels of the instrument operate by combining an echelle grating spectrometer with an Acousto-Optical Tunable Filter (AOTF). Using in-flight data, we characterized the instrument performance and parameterized its calibration. In particular: an accurate frequency calibration was achieved, together with its variability due to thermal effects on the grating. The AOTF properties and transfer function were also quantified, and we developed and tested a realistic method to compute the spectral continuum transmitted through the coupled grating and AOTF system. The calibration results enabled unprecedented insights into the important problem of the sensitivity of NOMAD to methane abundances in the atmosphere. We also deeply characterized its performance under realistic conditions of varying aerosol abundances, diverse albedos and changing illumination conditions as foreseen over the nominal mission. The results show that, in low aerosol conditions, NOMAD single spectrum, 1σ sensitivity to CH 4 is around 0.33 ppbv at 20 km of altitude when performing solar occultations, and better than 1 ppbv below 30 km. In dusty conditions, we show that the sensitivity drops to 0 below 10 km. In Nadir geometry, results demonstrate that NOMAD will be able to produce seasonal maps of CH 4 with a sensitivity around 5 ppbv over most of planet's surface with spatial integration over 5 × 5° bins. Results show also that such numbers can be improved by a factor of ~10 to ~30 by data binning. Overall, our results quantify NOMAD's capability to address the variable aspects of Martian climate. [ABSTRACT FROM AUTHOR]

Hubble Space Telescope Imaging Spectrograph (HST/STIS) UV observations of Venus’ upper cloud tops were obtained between 20N and 40S latitude on December 28, 2010; January 22, 2011 and January 27, 2011 in coordination with the Venus Express (VEx) mission. The high spectral (0.27 nm) and spatial (40–60 km/pixel) resolution HST/STIS data provide the first direct and simultaneous record of the latitude and local time distribution of Venus’ 70–80 km SO and SO 2 (SO x ) gas density on Venus’ morning quadrant. These data were obtained simultaneously with (a) VEx/SOIR occultation and/or ground-based James Clerk Maxwell Telescope sub-mm observations that record respectively, Venus’ near-terminator SO 2 and dayside SO x vertical profiles between ∼75 and 100 km; and (b) 0.36 μm VEx/VMC images of Venus’ cloud-tops. Updating the (Marcq, E. et al. [2011]. Icarus 211, 58–69) radiative transfer model SO 2 gas column densities of ∼2–10 μm-atm and ∼0.4–1.8 μm-atm are retrieved from the December 2010 and January 2011 HST observations, respectively on Venus’ dayside (i.e., at solar zenith angles (SZA) < 60°); SO gas column densities of 0.1–0.11 μm-atm, 0.03–0.31 μm-atm and 0.01–0.13 μm-atm are also retrieved from the respective December 28, 2010, January 22, 2011 and January 27, 2011 HST observations. A decline in the observed low-latitude 0.24 and 0.36 μm cloud top brightness paralleled the declining SO x gas densities. On December 28, 2010 SO 2 VMR values ∼280–290 ppb are retrieved between 74 and 81 km from the HST and SOIR data obtained near Venus’ morning terminator (at SZAs equal to 70° and 90°, respectively); these values are 10× higher than the HST-retrieved January 2011 near terminator values. Thus, the cloud top SO 2 gas abundance declined at all local times between the three HST observing dates. On all dates the average dayside SO 2 /SO ratio inferred from HST between 70 and 80 km is higher than that inferred from the sub-mm the JCMT data above 84 km confirming that SO x photolysis is more efficient at higher altitudes. The direct correlation of the SO x gases provides the first clear evidence that SO x photolysis is not the only source for Venus’ 70–80 km sulfur reservoir. The cloud top SO 2 gas density is dependent in part on the vertical transport of the gas from the lower atmosphere; and the 0.24 μm cloud top brightness levels are linked to the density of the sub-micron haze. Thus, the new results may suggest a correlation between Venus’ cloud-top sub-micron haze density and the vertical transport rate. These new results must be considered in models designed to simulate and explore the relationship between Venus’ sulfur chemistry cycle, H 2 SO 4 cloud formation rate and climate evolution. Additionally, we present the first photochemical model that uniquely tracks the transition of the SO 2 atmosphere from steady to non-steady state with increasing SZA, as function of altitude within Venus’ mesosphere, showing the photochemical and dynamical basis for the factor of ∼2 enhancements in the SO x gas densities observed by HST near the terminator above that observed at smaller SZA. These results must also be considered when modeling the long-term evolution of Venus’ atmospheric chemistry and dynamics. [ABSTRACT FROM AUTHOR]

Highlights: [•] First determination of the CO2-broadening of lines in the ν 4 band of methane were realized. [•] CO2-broadening of lines in the ν 4 band of methane were measured accurately. [•] The line parameters were measured by high resolution diode-laser spectroscopy. [•] The line parameters were deduced from Voigt, Rautian–Sobel’man and Galatry fits. [•] Impact of the line parameters to CO2-rich planetary atmospheres were addressed. [Copyright &y& Elsevier]

Abstract: The variability of the aerosol loading in the mesosphere of Venus is investigated from a large data set obtained with SOIR, a channel of the SPICAV instrument suite onboard Venus Express. Vertical profiles of the extinction due to light absorption by aerosols are retrieved from a spectral window around 3.0μm recorded in many solar occultations (∼200) from September 2006 to September 2010. For this period, the continuum of light absorption is analyzed in terms of spatial and temporal variations of the upper haze of Venus. It is shown that there is a high short-term (a few Earth days) and a long-term (∼80 Earth days) variability of the extinction profiles within the data set. Latitudinal dependency of the aerosol loading is presented for the entire period considered and for shorter periods of time as well. [Copyright &y& Elsevier]

Abstract: Using the SPICAV-UV spectrometer aboard Venus Express in nadir mode, we were able to derive spectral radiance factors in the middle atmosphere of Venus in the 170–320nm range at a spectral resolution of R ≃200 during 2006 and 2007 in the northern hemisphere. By comparison with a radiative transfer model of the upper atmosphere of Venus, we could derive column abundance above the visible cloud top for SO2 using its spectral absorption bands near 280 and 220nm. SO2 column densities show large temporal and spatial variations on a horizontal scale of a few hundred kilometers. Typical SO2 column densities at low latitudes (up to 50°N) were found between 5 and 50μm-atm, whereas in the northern polar region SO2 content was usually below 5μm-atm. The observed latitudinal variations follow closely the cloud top altitude derived by SPICAV-IR and are thought to be of dynamical origin. Also, a sudden increase of SO2 column density in the whole northern hemisphere has been observed in early 2007, possibly related to a convective episode advecting some deep SO2 into the upper atmosphere. [ABSTRACT FROM AUTHOR]

Abstract: Line parameters for water vapour in natural abundance have recently been determined for the 9250–13000cm−1 region [M.-F. Mérienne, A. Jenouvrier, C. Hermans, A.C. Vandaele, M. Carleer, C. Clerbaux, P.-F. Coheur, R. Colin, S. Fally, M. Bach, J. Quant. Spectrosc. Radiat. Transfer 82 (2003) 99] and the 13000–26000cm−1 region [P.-F. Coheur, S. Fally, M. Carleer, C. Clerbaux, R. Colin, A. Jenouvrier, M.-F. Mérienne, C. Hermans, A.C. Vandaele, J. Quant. Spectrosc. Radiat. Transfer 74 (2002) 493] using a high-resolution Fourier-transform spectrometer with a long-path absorption cell. These spectra are analysed using several techniques including variational line lists and assignments made. In total, over 15000 lines were assigned to transitions involving more than 150 exited vibrational states of H2 16O. Twelve new vibrational band origins are determined and estimates for a further 16 are presented. [Copyright &y& Elsevier]

Abstract: This work presents new measurements of HDO line parameters in the near-infrared and visible regions (11500–23000cm−1). The measurements consist in high-resolution Fourier transform absorption spectra of H2O/HDO/D2O vapor mixtures, obtained using a long absorption path. Spectra with and without nitrogen as the buffer gas were recorded. Due to the simultaneous presence of the three isotopologues H2O, D2O, and HDO, the H2O lines removal and the D2O lines identification were two necessary preliminary steps to derive the HDO line parameters. The D2O contribution was small and confined to the well-known 4ν 1 + ν 3 band. An extensive listing of HDO spectroscopic parameters was obtained, for the first time, by fitting some 3256 observed lines to Voigt line profiles. The list contains calibrated line positions, absorption cross-sections and, for many of the lines, N2-broadening coefficients, as well as N2-induced frequency shifts. As a result of the low HDO vapor pressures, it was not possible to retrieve the self-broadening parameters. The list is available on the http://www.ulb.ac.be/cpm website. [Copyright &y& Elsevier]

More than a full Martian year of observations have now been made by the Nadir Occultation for MArs Discovery (NOMAD) instrument suite on-board the ExoMars Trace Gas Orbiter. Radiative transfer modeling of NOMAD observations taken in the nadir geometry enable the seasonal and global-scale variations of carbon monoxide gas in the Martian atmosphere to be characterized. These retrievals show the column-averaged volume mixing ratio of carbon monoxide to be about 800 ppmv, with significant variations at high latitudes caused by the condensation and sublimation of the background CO 2 gas. Near summer solstice in each hemisphere, the CO volume mixing ratio falls to 400 ppmv in the south and 600 ppmv in the north. At low latitudes, carbon monoxide volume mixing ratio inversely follows the annual cycle of surface pressure. Comparison of our retrieved CO volume mixing ratio against that computed by the GEM-Mars general circulation model reveals a good match in their respective seasonal and spatial trends, and can provide insight into the physical processes that control the distribution of CO gas in the current Martian atmosphere. • The global, seasonal distribution of CO gas is retrieved from NOMAD nadir observations. • Globally averaged CO abundance is ~800 ppm, but with strong seasonal variations. • GCM modeling can provide insight into physical processes behind retrieved abundances. [ABSTRACT FROM AUTHOR]

Methane (CH 4) on Mars has attracted a great deal of attention since it was first detected in January 2003. As methane is considered a potential marker for past/present biological or geological activity, any possible detection would require evidence with strong statistical significance. Ethane (C 2 H 6) and ethylene (C 2 H 4) are also relevant chemical species as their shorter lifetimes in the Martian atmosphere make them excellent tracers for recent and ongoing releases. If detected, a CH 4 /C 2 H n ratio could aid in constraining the potential source of organic production. Here we present the results of an extensive search for hydrocarbons in the Martian atmosphere in 240,000 solar occultation measurements performed by the ExoMars Trace Gas Orbiter/NOMAD instrument from April 2018 to April 2019. The observations are global, covering all longitudes and latitudes from 85°N to 85°S, and sampled from 6 to 100 km altitude with a typical vertical resolution of 2 km. There were no statistically significant detections of organics and new stringent upper limits for global ethane and ethylene were set at 0.1 ppbv and 0.7 ppbv, respectively. No global background level of methane was observed, obtaining an upper limit of 0.06 ppbv, in agreement with early results from ExoMars (Korablev et al., 2019). Dedicated searches for localized plumes at more than 2000 locations provided no positive detections, implying that if methane were released in strong and rapid events, the process would have to be sporadic. • A full year of Mars observation with global coverage yield no methane detections. • Search for global background level as well as localized plumes were conducted. • Methane upper limits down to 0.06 ppbv, lower than previous detections, were obtained above an altitude of 6 km. • Search for ethane and ethylene gave upper limits of 0.1 and 0.7 ppbv respectively. [ABSTRACT FROM AUTHOR]