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Titan's atmospheric composition and dynamical state have previously been studied over numerous epochs by both ground- and space-based facilities. However, stratospheric measurements remain sparse during Titan's northern summer and fall. The lack of seasonal symmetry in observations of Titan's temperature field and chemical abundances raises questions about the nature of the middle atmosphere's meridional circulation and evolution over Titan's 29-yr seasonal cycle that can only be answered through long-term monitoring campaigns. Here, we present maps of Titan's stratospheric temperature, acetonitrile (or methyl cyanide; CH$_3$CN), and monodeuterated methane (CH$_3$D) abundances following Titan's northern summer solstice obtained with Band 9 ($\sim0.43$ mm) ALMA observations. We find that increasing temperatures towards high-southern latitudes, currently in winter, resemble those observed during Titan's northern winter by the Cassini mission. Acetonitrile abundances have changed significantly since previous (sub)millimeter observations, and we find that the species is now highly concentrated at high-southern latitudes. The stratospheric CH$_3$D content is found to range between 4-8 ppm in these observations, and we infer the CH$_4$ abundance to vary between $\sim0.9-1.6\%$ through conversion with previously measured D/H values. A global value of CH$_4=1.15\%$ was retrieved, lending further evidence to the temporal and spatial variability of Titan's stratospheric methane when compared with previous measurements. Additional observations are required to determine the cause and magnitude of stratospheric enhancements in methane during these poorly understood seasons on Titan., Comment: Accepted for publication in the Planetary Science Journal. 9 Figures, 1 table

Measuring the abundances of C- and O-bearing species in exoplanet atmospheres enables us to constrain the C/O ratio, that contains indications about the planet formation history. With a wavelength coverage going from 0.95 to 2.5 microns, the high-resolution (R$\sim$70 000) spectropolarimeter SPIRou can detect spectral lines of major bearers of C and O in exoplanets. Here we present our study of SPIRou transmission spectra of WASP-76 b acquired for the ATMOSPHERIX program. We applied the publicly available data analysis pipeline developed within the ATMOSPHERIX consortium, analysing the data using 1-D models created with the petitRADTRANS code, with and without a grey cloud deck. We report the detection of H$_2$O and CO at a Doppler shift of around -6 km.s$^{-1}$, consistent with previous observations of the planet. Finding a deep cloud deck to be favoured, we measured in mass mixing ratio (MMR) log(H$_2$O)$_{MMR}$ = -4.52 $\pm$ 0.77 and log(CO)$_{MMR}$ = -3.09 $\pm$ 1.05 consistent with a sub-solar metallicity to more than 1$\sigma$. We report 3$\sigma$ upper limits for the abundances of C$_2$H$_2$, HCN and OH. We estimated a C/O ratio of 0.94 $\pm$ 0.39 ($\sim$ 1.7 $\pm$ 0.7 x solar, with errors indicated corresponding to the 2$\sigma$ values) for the limbs of WASP-76 b at the pressures probed by SPIRou. We used 1-D ATMO forward models to verify the validity of our estimation. Comparing them to our abundance estimations of H$_2$O and CO, as well as our upper limits for C$_2$H$_2$, HCN and OH, we found that our results were consistent with a C/O ratio between 1 and 2 x solar, and hence with our C/O estimation. Finally, we found indications of asymmetry for both H$_2$O and CO when investigating the dynamics of their signatures, pointing to a complex scenario involving possibly both a temperature difference between limbs and clouds being behind the asymmetry this planet is best known for., Comment: 20 pages, 19 figures, accepted for publication in A&A

Precise measurements of chemical abundances in planetary atmospheres are necessary to constrain the formation histories of exoplanets. A recent study of WASP-127b, a close-in puffy sub-Saturn orbiting its solar-type host star in 4.2 d, using HST and Spitzer revealed a feature-rich transmission spectrum with strong excess absorption at 4.5 um. However, the limited spectral resolution and coverage of these instruments could not distinguish between CO and/or CO2 absorption causing this signal, with both low and high C/O ratio scenarios being possible. Here we present near-infrared (0.9--2.5 um) transit observations of WASP-127 b using the high-resolution SPIRou spectrograph, with the goal to disentangle CO from CO2 through the 2.3 um CO band. With SPIRou, we detect H2O at a t-test significance of 5.3 sigma and observe a tentative (3 sigma) signal consistent with OH absorption. From a joint SPIRou + HST + Spitzer retrieval analysis, we rule out a CO-rich scenario by placing an upper limit on the CO abundance of log10[CO]<-4.0, and estimate a log10[CO2] of -3.7^(+0.8)_(-0.6), which is the level needed to match the excess absorption seen at 4.5um. We also set abundance constraints on other major C-, O-, and N-bearing molecules, with our results favoring low C/O (0.10^(+0.10)_(-0.06)), disequilibrium chemistry scenarios. We further discuss the implications of our results in the context of planet formation. Additional observations at high and low-resolution will be needed to confirm these results and better our understanding of this unusual world., Comment: 23 pages, 13 figures, Submitted for publication in the Monthly Notice of the Royal Astronomical Society

In response to ESA Voyage 2050 announcement of opportunity, we propose an ambitious L-class mission to explore one of the most exciting bodies in the Solar System, Saturn largest moon Titan. Titan, a "world with two oceans", is an organic-rich body with interior-surface-atmosphere interactions that are comparable in complexity to the Earth. Titan is also one of the few places in the Solar System with habitability potential. Titan remarkable nature was only partly revealed by the Cassini-Huygens mission and still holds mysteries requiring a complete exploration using a variety of vehicles and instruments. The proposed mission concept POSEIDON (Titan POlar Scout/orbitEr and In situ lake lander DrONe explorer) would perform joint orbital and in situ investigations of Titan. It is designed to build on and exceed the scope and scientific/technological accomplishments of Cassini-Huygens, exploring Titan in ways that were not previously possible, in particular through full close-up and in situ coverage over long periods of time. In the proposed mission architecture, POSEIDON consists of two major elements: a spacecraft with a large set of instruments that would orbit Titan, preferably in a low-eccentricity polar orbit, and a suite of in situ investigation components, i.e. a lake lander, a "heavy" drone (possibly amphibious) and/or a fleet of mini-drones, dedicated to the exploration of the polar regions. The ideal arrival time at Titan would be slightly before the next northern Spring equinox (2039), as equinoxes are the most active periods to monitor still largely unknown atmospheric and surface seasonal changes. The exploration of Titan northern latitudes with an orbiter and in situ element(s) would be highly complementary with the upcoming NASA New Frontiers Dragonfly mission that will provide in situ exploration of Titan equatorial regions in the mid-2030s., Comment: arXiv admin note: substantial text overlap with arXiv:1908.01374

Thanks to the Cassini-Huygens mission, Titan, the pale orange dot of Pioneer and Voyager encounters has been revealed to be a dynamic, hydrologically-shaped, organic-rich ocean world offering unparalleled opportunities to explore prebiotic chemistry. And while Cassini-Huygens revolutionized our understanding of each of the three layers of Titan--the atmosphere, the surface, and the interior--we are only beginning to hypothesize how these realms interact. In this paper, we summarize the current state of Titan knowledge and discuss how future exploration of Titan would address some of the next decade's most compelling planetary science questions. We also demonstrate why exploring Titan, both with and beyond the Dragonfly New Frontiers mission, is a necessary and complementary component of an Ocean Worlds Program that seeks to understand whether habitable environments exist elsewhere in our solar system., Comment: Submitted to the PSJ Focus Issue on Ocean World Exploration

This study presents a 13 years survey of haze UV extinction profiles, monitoring the temporal evolution of the detached haze layer (DHL) in Titan's upper atmosphere (350-600 km). As reported by West et al. 2011 (GRL vol.38, L06204) at the equator, we show that the DHL is present at all latitudes below 55{\deg}N during the northern winter (2004-2009). Then, it globally sunk and disappeared in 2012. No permanent DHL was observed between 2012 and 2015. It's only in late-2015, that a new structure emerged from the Northern hemisphere and propagated to the equator. This new DHL is not as pronounced as in 2004 and is much more complex than the one observed earlier. In one specific sequence, in 2005, we were able to investigate the short time scale variability of the DHL and no major changes was observed. When both side of the limb were visible (dawn/dusk), we notice that the extinction of the DHL is slightly higher on the dawn side. Additionally, during a polar flyby in 2009, we observed the longitudinal variability of the DHL and spotted some local inhomogeneities. Finally, comparisons with UVIS stellar occultations and General Climate Models (GCMs) are both consistent with our findings. However, we noticed that the timing of the DHL main pattern predicted by the GMCs can be off by up to 30{\deg} in solar longitude. All these observations bring new perspectives on the seasonal cycle of Titan's upper atmosphere, the evolution of the DHL and its interaction with the dynamics.

We outline a flagship-class mission concept focused on studying Titan as a global system, with particular emphasis on the polar regions. Investigating Titan from the unique standpoint of a polar orbit would enable comprehensive global maps to uncover the physics and chemistry of the atmosphere, and the topography and geophysical environment of the surface and subsurface. The mission includes two key elements: (1) an orbiter spacecraft, which also acts as a data relay, and (2) one or more small probes to directly investigate Titan's seas and make the first direct measurements of their liquid composition and physical environment. The orbiter would carry a sophisticated remote sensing payload, including a novel topographic lidar, a long-wavelength surface-penetrating radar, a sub-millimeter sounder for winds and for mesospheric/thermospheric composition, and a camera and near-infrared spectrometer. An instrument suite to analyze particles and fields would include a mass spectrometer to focus on the interactions between Titan's escaping upper atmosphere and the solar wind and Saturnian magnetosphere. The orbiter would enter a stable polar orbit around 1500 to 1800 km, from which vantage point it would make global maps of the atmosphere and surface. One or more probes, released from the orbiter, would investigate Titan's seas in situ, including possible differences in composition between higher and lower latitude seas, as well as the atmosphere during the parachute descent. The number of probes, as well as the instrument complement on the orbiter and probe, remain to be finalized during a mission study that we recommend to NASA as part of the NRC Decadal Survey for Planetary Science now underway, with the goal of an overall mission cost in the "small flagship" category of ~$2 bn. International partnerships, similar to Cassini-Huygens, may also be included for consideration., Comment: 13 pages, white paper submitted to the NRC Decadal Survey for Planetary Science and Astrobiology

The Cassini/Composite InfraRed Spectrometer (CIRS) instrument has been observing the middle atmosphere of Titan over almost half a Saturnian year. We used the CIRS dataset processed through the up-to-date calibration pipeline to characterize seasonal changes of temperature and abundance profiles in the middle atmosphere of Titan, from mid-northern winter to early northern summer all around the satellite. We used limb spectra from 590 to 1500 cm$^{-1}$ at 0.5-cm$^{-1}$ spectral resolution, which allows us to probe different altitudes. We averaged the limb spectra recorded during each flyby on a fixed altitude grid to increase the signal-to-noise ratio. These thermal infrared data were analyzed by means of a radiative transfer code coupled with an inversion algorithm, in order to retrieve vertical temperature and abundance profiles. These profiles cover an altitude range of approximately 100 to 600 km, at 10- or 40-km vertical resolution (depending on the observation). Strong changes in temperature and composition occur in both polar regions where a vortex is in place during the winter. At this season, we observe a global enrichment in photochemical compounds in the mesosphere and stratosphere and a hot stratopause located around 0.01 mbar, both linked to downwelling in a pole-to-pole circulation cell. After the northern spring equinox, between December 2009 and April 2010, a stronger enhancement of photochemical compounds occurred at the north pole above the 0.01-mbar region, likely due to combined photochemical and dynamical effects. During the southern autumn in 2015, above the South pole, we also observed a strong enrichment in photochemical compounds that contributed to the cooling of the stratosphere above 0.2 mbar. Close to the northern spring equinox, in December 2009, the thermal profile at 74{\deg}N exhibits an oscillation that we interpret in terms of an inertia-gravity wave.

We have analyzed spectra recorded between 50 and 650 cm$^{-1}$ by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft at low and high emission angles to determine simultaneously the H$_2$ mole fraction and ortho-to-para ratio in Titan's troposphere. We used constraints from limb spectra between 50 and 900 cm$^{-1}$ and from in situ measurements by the Huygens probe to characterize the temperature, haze and gaseous absorber profiles. We confirm that the N$_2$-CH$_4$ collision-induced absorption (CIA) coefficients used up to now need to be increased by about 52% at temperatures of 70-85 K. We find that the N$_2$-N$_2$ CIA coefficients are also too low in the N$_2$ band far wing, beyond 110 cm$^{-1}$, in agreement with recent quantum mechanical calculations. We derived a H$_2$ mole fraction equal to (0.88 $\pm$ 0.13) $\times$ 10$^{-3}$, which pertains to the $\sim$1-34 km altitude range probed by the S$_0$(0) and S$_0$(1) lines. The H$_2$ para fraction is close to equilibrium in the 20-km region. We have investigated different mechanisms that may operate in Titan's atmosphere to equilibrate the H$_2$ o-p ratio and we have developed a one-dimensional model that solves the continuity equation in presence of such conversion mechanisms. We conclude that exchange with H atoms in the gas phase or magnetic interaction of H$_2$ in a physisorbed state on the surface of aerosols are too slow compared with atmospheric mixing to play a significant role. On the other hand, magnetic interaction of H$_2$ with CH$_4$, and to a lesser extent N$_2$, can operate on a timescale similar to the vertical mixing time in the troposphere. This process is thus likely responsible for the o-p equilibration of H$_2$ in the mid-troposphere implied by CIRS measurements.

The atmosphere of Titan, the largest moon of Saturn, is rich in organic molecules, and it has been suggested that the moon may serve as an analog for the pre-biotic Earth due to its highly reducing chemistry and existence of global hazes. Photochemical models of Titan have predicted the presence of propadiene (historically referred to as allene), CH$_{2}$CCH$_{2}$, an isomer of the well-measured propyne (also called methylacetylene) CH$_{3}$CCH, but its detection has remained elusive due to insufficient spectroscopic knowledge of the molecule - which has recently been remedied with an updated spectral line list. Here we present the first unambiguous detection of the molecule in any astronomical object, observed with the Texas Echelle Cross Echelle Spectrograph (TEXES) on the NASA Infrared Telescope Facility (IRTF) in July 2017. We model its emission line near 12 $\mu$m and measure a volume mixing ratio (VMR) of (6.9 $\pm$ 0.8) $\times$10$^{-10}$ at 175 km, assuming a vertically increasing abundance profile as predicted in photochemical models. Cassini measurements of propyne made during April 2017 indicate that the abundance ratio of propyne to propadiene is 8.2$\pm$1.1 at the same altitude. This initial measurement of the molecule in Titan's stratosphere paves the way towards constraining the amount of atomic hydrogen available on Titan, as well as future mapping of propadiene on Titan from 8 meter and larger ground based observatories, and future detection on other planetary bodies.

In this white paper, we present a cross-section of important scientific questions that remain partially or completely unanswered, ranging from Titan exosphere to the deep interior, and we detail which instrumentation and mission scenarios should be used to answer them. Our intention is to formulate the science goals for the next generation of planetary missions to Titan in order to prepare the future exploration of the moon. The ESA L-class mission concept that we propose is composed of a Titan orbiter and at least an in situ element (lake lander and/or drone(s))., Comment: White Paper submission to the call for ESA Voyage 2050 long-term plan

From 2004 to 2017, the Cassini spacecraft orbited Saturn, completing 127 close flybys of its largest moon, Titan. Cassini's Composite Infrared Spectrometer (CIRS), one of 12 instruments carried on board, profiled Titan in the thermal infrared (7-1000 microns) throughout the entire 13-year mission. CIRS observed on both targeted encounters (flybys) and more distant opportunities, collecting 8.4 million spectra from 837 individual Titan observations over 3633 hours. Observations of multiple types were made throughout the mission, building up a vast mosaic picture of Titan's atmospheric state across spatial and temporal domains. This paper provides a guide to these observations, describing each type and chronicling its occurrences and global-seasonal coverage. The purpose is to provide a resource for future users of the CIRS data set, as well as those seeking to put existing CIRS publications into the overall context of the mission, and to facilitate future inter-comparison of CIRS results with those of other Cassini instruments, and ground-based observations., Comment: 62 pages, 31 figures, 10 tables. CSV format table data included

Titan's middle atmosphere is currently experiencing a rapid change of season after northern spring arrived in 2009. A large cloud was observed for the first time above Titan's southern pole in May 2012, at an altitude of 300 km. This altitude previously showed a temperature maximum and condensation was not expected for any of Titan's atmospheric gases. Here we show that this cloud is composed of micron-sized hydrogen cyanide (HCN) ice particles. The presence of HCN particles at this altitude, together with new temperature determinations from mid-infrared observations, indicate a very dramatic cooling of Titan's atmosphere inside the winter polar vortex in early 2012. Such a cooling is completely contrary to previously measured high-altitude warming in the polar vortex, and temperatures are a hundred degrees colder than predicted by circulation models. Besides elucidating the nature of Titan's mysterious polar cloud, these results thus show that post-equinox cooling at the winter pole is much more efficient than previously thought., Comment: Published in Nature on 2 October 2014. This is the author version, before final editing by Nature

The Voyager 1 flyby of Titan in 1980 gave a first glimpse of the chemical complexity of Titan's atmosphere, detecting many new molecules with the infrared spectrometer (IRIS). These included propane (C3H8) and propyne (CH3C2H), while the intermediate-sized C3Hx hydrocarbon (C3H6) was curiously absent. Using spectra from the Composite Infrared Spectrometer (CIRS) on Cassini, we show the first positive detection of propene (C3H6) in Titan's stratosphere (5-sigma significance), finally filling the three-decade gap in the chemical sequence. We retrieve a vertical abundance profile from 100-250 km, that varies slowly with altitude from ~2 ppbv at 100 km, to ~5 ppbv at 200 km. The abundance of C3H6 is less than both C3H8 and CH3C2H, and we remark on an emerging paradigm in Titan's hydrocarbon abundances whereby: alkanes > alkynes > alkenes within the C2Hx and C3Hx chemical families in the lower stratosphere. More generally, there appears to be much greater ubiquity and relative abundance of triple-bonded species than double-bonded, likely due to the greater resistance of triple bonds to photolysis and chemical attack., Comment: 16 pages; 4 figures; 1 table. Withdrawn due to journal policy

In this chapter we describe the remote sensing measurement of nitrogen-bearing species in Titan's atmosphere by the Composite Infrared Spectrometer (CIRS) on the Cassini spacecraft. This instrument, which detects the thermal infrared spectrum from 10-1500 cm-1 (1000-7 microns) is sensitive to vibrational emissions of gases and condensates in Titan's stratosphere and lower mesosphere, permitting the measurement of ambient temperature and the abundances of gases and particulates. Three N-bearing species are firmly detected: HCN, HC3N and C2N2, and their vertical and latitudinal distributions have been mapped. In addition, ices of HC3N and possibly C4N2 are also seen in the far-infrared spectrum at high latitudes during the northern winter. The HC(15)N isotopologue has been measured, permitting the inference of the 14N/15N ratio in this species, which differs markedly (lower) than in the bulk nitrogen reservoir (N2). We also describe the search in the CIRS spectrum, and inferred upper limits, for NH3 and CH3CN. CIRS is now observing seasonal transition on Titan and the gas abundance distributions are changing accordingly, acting as tracers of the changing atmospheric circulation. The prospects for further CIRS science in the remaining five years of the Cassini mission are discussed., Comment: 19 pages, 9 figures, 1 table

In this paper we describe a first quantitative search for several molecules in Titan's stratosphere in Cassini CIRS infrared spectra. These are: ammonia (NH3), methanol (CH3OH), formaldehyde (H2CO), and acetonitrile (CH3CN), all of which are predicted by photochemical models but only the last of which observed, and not in the infrared. We find non-detections in all cases, but derive upper limits on the abundances from low-noise observations at 25{\deg}S and 75{\deg}N. Comparing these constraints to model predictions, we conclude that CIRS is highly unlikely to see NH3 or CH3OH emissions. However, CH3CN and H2CO are closer to CIRS detectability, and we suggest ways in which the sensitivity threshold may be lowered towards this goal., Comment: 11 pages plus 6 figure files