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The temperature structure of Titan's upper atmosphere exhibits large variability resulting from numerous spatially and temporally irregular external energy sources, seasonal changes, and the influence of molecular species produced via photochemistry. In particular, Titan's relatively abundant HCN is thought to provide substantial cooling to the upper atmosphere through rotational emission, balancing UV/EUV heating and thermal conduction. Here, we present the analysis of ALMA observations of Titan from 2012, 2014, 2015, and 2017, corresponding to planetocentric solar longitudes of ~34-89$^{\circ}$, including vertical HCN and temperature profiles retrieved from the lower mesosphere through the thermosphere (~350-1200 km; $3\times10^{-2}$-$2\times10^{-8}$ mbar). Throughout the atmosphere, temperature profiles differ by 10 to 30 K between observations approximately one Earth year apart, particularly from 600-900 km. We find evidence for a large imbalance in Titan's upper atmospheric energy budget between 2014 and 2015, where the mesospheric thermal structure changes significantly and marks the transition between a mesopause located at ~600 km ($2\times10^{-4}$ mbar) and at ~800 km ($3\times10^{-6}$ mbar). The retrieved HCN abundances vary dramatically during the 2012 to 2017 time period as well, showing close to 2 orders of magnitude difference in abundance at 1000 km. However, the change in HCN abundance does not appear to fully account for the variation in mesospheric temperatures over the $L_S\sim$34-89$^{\circ}$ period. These measurements provide additional insight into the variability of Titan's mesospheric composition and thermal structure following its 2009 vernal equinox, and motivate continued investigation of the origins of such rapid changes in Titan's atmosphere throughout its seasonal cycle., Comment: Published in the Planetary Science Journal. 25 pages, 11 figures, 1 table

Similar to Earth, Saturn's largest moon, Titan, possesses a system of high-altitude zonal winds (or jets) that encircle the globe. Using the Atacama Large Millimeter/submillimeter Array (ALMA) in August 2016, Lellouch et al. (2019) discovered an equatorial jet at much higher altitudes than previously known, with a surprisingly fast speed of up to ~340 m/s, but the origin of such high velocities is not yet understood. We obtained spectrally and spatially resolved ALMA observations in May 2017 to map Titan's 3D global wind field and compare our results with a reanalysis of the August 2016 data. Doppler wind velocity maps were derived in the altitude range ~300-1000 km (from the upper stratosphere to the thermosphere). At the highest, thermospheric altitudes, a 47% reduction in the equatorial zonal wind speed was measured over the 9-month period (corresponding to L_s = 82-90 degrees on Titan). This is interpreted as due to a dramatic slowing and loss of confinement (broadening) of the recently-discovered thermospheric equatorial jet, as a result of dynamical instability. These unexpectedly-rapid changes in the upper-atmospheric dynamics are consistent with strong variability of the jet's primary driving mechanism.

We present a reanalysis of visible/near-infrared (480-930 nm) observations of Neptune, made in 2018 with the MUSE instrument at the Very Large Telescope (VLT) in Narrow Field Adaptive Optics mode, reported by Irwin et al., Icarus, 311, 2019. We find that the inferred variation of methane abundance with latitude in our previous analysis, which was based on central meridian observations only, underestimated the retrieval errors when compared with a more complete assessment of Neptune's limb darkening. In addition, our previous analysis introduced spurious latitudinal variability of both the abundance and its uncertainty, which we reassess here. Our reanalysis of these data incorporates the effects of limb-darkening based upon the Minnaert approximation, which provides a much stronger constraint on the cloud structure and methane mole fraction, makes better use of the available data and is more computationally efficient. We find that away from discrete cloud features, the observed reflectivity spectrum from 800-900 nm is very well approximated by a background cloud model that is latitudinally varying, but zonally symmetric, consisting of a H$_2$S cloud layer, based at 3.6-4.7 bar with variable opacity and scale height, and a stratospheric haze. The background cloud model matches the observed limb darkening seen at all wavelengths and latitudes and we find that the mole fraction of methane at 2-4 bar, above the H$_2$S cloud, but below the methane condensation level, varies from 4-6\% at the equator to 2-4\% at near the south pole, consistent with previous analyses, with a equator/pole ratio of $1.9 \pm 0.2$ for our assumed cloud/methane model. The spectra of discrete cloudy regions are fitted, to a very good approximation, by the addition of a single vertically thin methane ice cloud with opacity ranging from 0 - 0.75 and pressure less than $\sim 0.4$ bar.

Titan harbors a dense, organic-rich atmosphere primarily composed of N$_2$ and CH$_4$, with lesser amounts of hydrocarbons and nitrogen-bearing species. As a result of high sensitivity observations by the Atacama Large Millimeter/submillimeter Array (ALMA) in Band 6 ($\sim$230-272 GHz), we obtained the first spectroscopic detection of CH$_3$C$_3$N (methylcyanoacetylene or cyanopropyne) in Titan's atmosphere through the observation of seven transitions in the $J = 64\rightarrow63$ and $J = 62\rightarrow61$ rotational bands. The presence of CH$_3$C$_3$N on Titan was suggested by the Cassini Ion and Neutral Mass Spectrometer detection of its protonated form: C$_4$H$_3$NH$^+$, but the atmospheric abundance of the associated (deprotonated) neutral product is not well constrained due to the lack of appropriate laboratory reaction data. Here, we derive the column density of CH$_3$C$_3$N to be (3.8-5.7)$\times10^{12}$ cm$^{-2}$ based on radiative transfer models sensitive to altitudes above 400 km Titan's middle atmosphere. When compared with laboratory and photochemical model results, the detection of methylcyanoacetylene provides important constraints for the determination of the associated production pathways (such as those involving CN, CCN, and hydrocarbons), and reaction rate coefficients. These results also further demonstrate the importance of ALMA and (sub)millimeter spectroscopy for future investigations of Titan's organic inventory and atmospheric chemistry, as CH$_3$C$_3$N marks the heaviest polar molecule detected spectroscopically in Titan's atmosphere to date., Comment: 17 pages, 6 figures, 2 tables. Accepted in ApJ Letters

The Cassini mission performed 127 targeted flybys of Titan during its 13-year mission to Saturn, culminating in the Grand Finale between April-September 2017. Here we demonstrate the use of the Atacama Large Millimeter/submillimeter Array (ALMA) to continue Cassini's legacy for chemical and climatological studies of Titan's atmosphere. Whole-hemisphere, interferometric spectral maps of HCN, HNC, HC3N, CH3CN, C2H3CN, C2H5CN and C3H8 were obtained using ALMA in May 2017 at moderate (~0.2'', or 1300 km) spatial resolution, revealing the effects of seasonally-variable chemistry and dynamics on the distribution of each species. The ALMA sub-mm observations of HCN and HC3N are consistent with Cassini infrared data on these species, obtained in the same month. Chemical/dynamical lifetimes of a few years are inferred for C2H3CN and C2H5CN, in reasonably close agreement with the latest chemical models incorporating sticking of C2H5CN to stratospheric aerosol particles. ALMA radial limb flux profiles provide column density information as a function of altitude, revealing maximum abundances in the thermosphere (above 600 km) for HCN, HNC, HC3N and C2H5CN. This constitutes the first detailed measurement of the spatial distribution of HNC, which is found to be confined predominantly to altitudes above 730 $\pm$ 60 km. The HNC emission map shows an east-west hemispheric asymmetry of (13$\pm$3)%. These results are consistent with very rapid production (and loss) of HNC in Titan's uppermost atmosphere, making this molecule an effective probe of short-timescale (diurnal) ionospheric processes., Comment: AJ; submitted March 2019; accepted for publication June 2019

The Cassini mission offered us the opportunity to monitor the seasonal evolution of Titan's atmosphere from 2004 to 2017, i.e. half a Titan year. The lower part of the stratosphere (pressures greater than 10 mbar) is a region of particular interest as there are few available temperature measurements, and because its thermal response to the seasonal and meridional insolation variations undergone by Titan remains poorly known. In this study, we measure temperatures in Titan's lower stratosphere between 6 mbar and 25 mbar using Cassini/CIRS spectra covering the whole duration of the mission (from 2004 to 2017) and the whole latitude range. We can thus characterize the meridional distribution of temperatures in Titan's lower stratosphere, and how it evolves from northern winter (2004) to summer solstice (2017). Our measurements show that Titan's lower stratosphere undergoes significant seasonal changes, especially at the South pole, where temperature decreases by 19 K at 15 mbar in 4 years.

Submillimeter emission lines of carbon monoxide (CO) in Titan's atmosphere provide excellent probes of atmospheric temperature due to the molecule's long chemical lifetime and stable, well constrained volume mixing ratio. Here we present the analysis of 4 datasets obtained with the Atacama Large Millimeter/Submillimeter Array (ALMA) from 2012 to 2015 that contain strong CO rotational transitions. Utilizing ALMA's high spatial resolution in the 2012, 2014, and 2015 observations, we extract spectra from 3 separate regions on Titan's disk using datasets with beam sizes of ~0.3''. Temperature profiles retrieved by the NEMESIS radiative transfer code are compared to Cassini Composite Infrared Spectrometer (CIRS) and radio occultation science results from similar latitude regions. Small seasonal variations in atmospheric temperature are present from 2012 to 2015 in the stratosphere and mesosphere (~100-500 km) of spatially resolved regions. We measure the stratopause (320 km) to increase in temperature by 5 K in northern latitudes from 2012-2015, while temperatures rise throughout the stratosphere at lower latitudes. While retrieved temperature profiles cover a range of latitudes in these observations, deviations from CIRS nadir maps and radio occultation measurements convolved with the ALMA beam-footprint are not found to be statistically significant, and discrepancies are often found to be less than 5 K throughout the atmosphere. ALMA's excellent sensitivity in the lower stratosphere (60-300 km) provides a highly complementary dataset to contemporary CIRS and radio science observations. The demonstrated utility of CO emission lines in the submillimeter as a tracer of Titan's atmospheric temperature lays the groundwork for future studies of other molecular species, as temperature profiles are found to consistently vary with latitude in all three years by up to 15 K., Comment: 11 pages, 9 figures, 3 tables

Previous investigations have employed more than 100 close observations of Titan by the Cassini orbiter to elucidate connections between the production and distribution of Titan's vast, organic-rich chemical inventory and its atmospheric dynamics. However, as Titan transitions into northern summer, the lack of incoming data from the Cassini orbiter presents a potential barrier to the continued study of seasonal changes in Titan's atmosphere. In our previous work (Thelen et al., 2018), we demonstrated that the Atacama Large Millimeter/submillimeter Array (ALMA) is well suited for measurements of Titan's atmosphere in the stratosphere and lower mesosphere (~100-500 km) through the use of spatially resolved (beam sizes <1'') flux calibration observations of Titan. Here, we derive vertical abundance profiles of four of Titan's trace atmospheric species from the same 3 independent spatial regions across Titan's disk during the same epoch (2012 to 2015): HCN, HC$_3$N, C$_3$H$_4$, and CH$_3$CN. We find that Titan's minor constituents exhibit large latitudinal variations, with enhanced abundances at high latitudes compared to equatorial measurements; this includes CH$_3$CN, which eluded previous detection by Cassini in the stratosphere, and thus spatially resolved abundance measurements were unattainable. Even over the short 3-year period, vertical profiles and integrated emission maps of these molecules allow us to observe temporal changes in Titan's atmospheric circulation during northern spring. Our derived abundance profiles are comparable to contemporary measurements from Cassini infrared observations, and we find additional evidence for subsidence of enriched air onto Titan's south pole during this time period. Continued observations of Titan with ALMA beyond the summer solstice will enable further study of how Titan's atmospheric composition and dynamics respond to seasonal changes., Comment: 15 pages, 16 figures, 2 tables. Accepted for publication in Icarus, September 2018

We present the first maps of cyanoacetylene isotopologues in Titan's atmosphere, including H$^{13}$CCCN and HCCC$^{15}$N, detected in the 0.9 mm band using the Atacama Large Millimeter/submillimeter array (ALMA) around the time of Titan's (southern winter) solstice in May 2017. The first high-resolution map of HC$_3$N in its $v_7=1$ vibrationally excited state is also presented, revealing a unique snapshot of the global HC$_3$N distribution, free from the strong optical depth effects that adversely impact the ground-state ($v=0$) map. The HC$_3$N emission is found to be strongly enhanced over Titan's south pole (by a factor of 5.7 compared to the north pole), consistent with rapid photochemical loss of HC$_3$N from the summer hemisphere combined with production and transport to the winter pole since the April 2015 ALMA observations. The H$^{13}$CCCN/HCCC$^{15}$N flux ratio is derived at the southern HC$_3$N peak, and implies an HC$_3$N/HCCC$^{15}$N ratio of $67\pm14$. This represents a significant enrichment in $^{15}$N compared with Titan's main molecular nitrogen reservoir, which has a $^{14}$N/$^{15}$N ratio of 167, and confirms the importance of photochemistry in determining the nitrogen isotopic ratio in Titan's organic inventory., Comment: Accepted for publication in ApJL, May 2018

Vinyl cyanide (C$_2$H$_3$CN) is theorized to form in Titan's atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C$_2$H$_3$CN on Titan by Palmer et al. (2017) with the detection of three new C$_2$H$_3$CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C$_2$H$_3$CN on Titan. We present simultaneous observations of C$_2$H$_5$CN, HC$_3$N, and CH$_3$CN emission, and obtain the first (tentative) detection of C$_3$H$_8$ (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC$_3$N and C$_2$H$_5$CN, which are theorized to be short-lived in Titan's atmosphere, C$_2$H$_3$CN is most abundant over the southern (winter) pole, whereas the longer-lived CH$_3$CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan's atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C$_2$H$_3$CN and C$_2$H$_5$CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C$_2$H$_3$CN is found to be $3.03\pm0.29$ ppb, with a C$_2$H$_5$CN/C$_2$H$_3$CN abundance ratio of $2.43\pm0.26$. Our HC$_3$N and CH$_3$CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of $2.05\pm0.16$ and $1.63\pm0.02$, respectively., Comment: Accepted for publication in the Astronomical Journal

We study the seasonal evolution of Titan's lower stratosphere (around 15~mbar) in order to better understand the atmospheric dynamics and chemistry in this part of the atmosphere. We analysed Cassini/CIRS far-IR observations from 2006 to 2016 in order to measure the seasonal variations of three photochemical by-products: $\mathrm{C_4H_2}$, $\mathrm{C_3H_4}$, and $\mathrm{C_2N_2}$. We show that the abundances of these three gases have evolved significantly at northern and southern high latitudes since 2006. We measure a sudden and steep increase of the volume mixing ratios of $\mathrm{C_4H_2}$, $\mathrm{C_3H_4}$, and $\mathrm{C_2N_2}$ at the south pole from 2012 to 2013, whereas the abundances of these gases remained approximately constant at the north pole over the same period. At northern mid-latitudes, $\mathrm{C_2N_2}$ and $\mathrm{C_4H_2}$ abundances decrease after 2012 while $\mathrm{C_3H_4}$ abundances stay constant. The comparison of these volume mixing ratio variations with the predictions of photochemical and dynamical models provides constraints on the seasonal evolution of atmospheric circulation and chemical processes at play., Comment: 14 pages, 12 figures

We have developed a new retrieval approach to modelling near-infrared spectra of Uranus that represents a significant improvement over previous modelling methods. We reanalysed IRTF/SpeX observations of Uranus observed in 2009 covering the wavelength range 0.8 to 1.8 microns and reported by Tice et al. (2013). By retrieving the imaginary refractive index spectra of cloud particles we are able to consistently define the real part of the refractive index spectra, through a Kramers-Kronig analysis, and thus determine self-consistent extinction cross-section, single-scattering and phase-function spectra for the clouds and hazes in Uranus' atmosphere. We tested two different cloud-modelling schemes used in conjunction with the temperature/methane profile of Baines et al. (1995), a reanalysis of the Voyager-2 radio-occultation observations performed by Sromovsky, Fry and Tomasko (2011), and a recent determination from Spitzer (Orton et al., 2014). We find that both cloud-modelling schemes represent the observed centre-of-disc spectrum of Uranus well, and both require similar cloud scattering properties of the main cloud residing at approximately 2 bars. However, a modified version of the Sromovsky, Fry and Tomasko (2011) model, with revised spectral properties of the lowest cloud layer, fits slightly better at shorter wavelengths and is more consistent with the expected vertical position of Uranus' methane cloud. We find that the bulk of the reflected radiance from Uranus arises from a thick cloud at approximately the 2 bar level, composed of particles that are significantly more absorbing at wavelengths > 1.0 micron than they are at wavelengths < 1.0 micron. This spectral information provides a possible constraint on the identity of the main particle type., Comment: 52 Pages, 14 Figures

We report the first spectroscopic detection of ethyl cyanide (C$_2$H$_5$CN) in Titan's atmosphere, obtained using spectrally and spatially resolved observations of multiple emission lines with the Atacama Large Millimeter/submillimeter array (ALMA). The presence of C$_2$H$_5$CN in Titan's ionosphere was previously inferred from Cassini ion mass spectrometry measurements of C$_2$H$_5$CNH$^+$. Here we report the detection of 27 rotational lines from C$_2$H$_5$CN (in 19 separate emission features detected at $>3\sigma$ confidence), in the frequency range 222-241 GHz. Simultaneous detections of multiple emission lines from HC$_3$N, CH$_3$CN and CH$_3$CCH were also obtained. In contrast to HC$_3$N, CH$_3$CN and CH$_3$CCH, which peak in Titan's northern (spring) hemisphere, the emission from C$_2$H$_5$CN is found to be concentrated in the southern (autumn) hemisphere, suggesting a distinctly different chemistry for this species, consistent with a relatively short chemical lifetime for C$_2$H$_5$CN. Radiative transfer models show that most of the C$_2$H$_5$CN is concentrated at altitudes 300-600 km, suggesting production predominantly in the mesosphere and above. Vertical column densities are found to be in the range (2-5)$\times10^{14}$ cm$^{-2}$., Comment: Published in 2015, ApJL, 800, L14

We present spectrally and spatially-resolved maps of HNC and HC$_3$N emission from Titan's atmosphere, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) on 2013 November 17. These maps show anisotropic spatial distributions for both molecules, with resolved emission peaks in Titan's northern and southern hemispheres. The HC$_3$N maps indicate enhanced concentrations of this molecule over the poles, consistent with previous studies of Titan's photochemistry and atmospheric circulation. Differences between the spectrally-integrated flux distributions of HNC and HC$_3$N show that these species are not co-spatial. The observed spectral line shapes are consistent with HNC being concentrated predominantly in the mesosphere and above (at altitudes $z\gtrsim 400$ km), whereas HC$_3$N is abundant at a broader range of altitudes ($z\approx70$-600 km). From spatial variations in the HC$_3$N line profile, the locations of the HC$_3$N emission peaks are shown to be variable as a function of altitude. The peaks in the integrated emission from HNC and the line core (upper-atmosphere) component of HC$_3$N (at $z\gtrsim300$ km) are found to be asymmetric with respect to Titan's polar axis, indicating that the mesosphere may be more longitudinally-variable than previously thought. The spatially-integrated HNC and HC$_3$N spectra are modeled using the NEMESIS planetary atmosphere code and the resulting best-fitting disk-averaged vertical mixing ratio (VMR) profiles are found to be in reasonable agreement with previous measurements for these species. Vertical column densities of the best-fitting gradient models for HNC and HC$_3$N are $1.9\times10^{13}$ cm$^{-2}$ and $2.3\times10^{14}$ cm$^{-2}$, respectively., Comment: Accepted for publication in ApJ Letters

In this paper we select large spectral averages of data from the Cassini Composite Infrared Spectrometer (CIRS) obtained in limb-viewing mode at low latitudes (30S--30N), greatly increasing the path length and hence signal-to-noise ratio for optically thin trace species such as propane. By modeling and subtracting the emissions of other gas species, we demonstrate that at least six infrared bands of propane are detected by CIRS, including two not previously identified in Titan spectra. Using a new line list for the range 1300-1400cm -1, along with an existing GEISA list, we retrieve propane abundances from two bands at 748 and 1376 cm-1. At 748 cm-1 we retrieve 4.2 +/- 0.5 x 10(-7) (1-sigma error) at 2 mbar, in good agreement with previous studies, although lack of hotbands in the present spectral atlas remains a problem. We also determine 5.7 +/- 0.8 x 10(-7) at 2 mbar from the 1376 cm-1 band - a value that is probably affected by systematic errors including continuum gradients due to haze and also an imperfect model of the n6 band of ethane. This study clearly shows for the first time the ubiquity of propane's emission bands across the thermal infrared spectrum of Titan, and points to an urgent need for further laboratory spectroscopy work, both to provide the line positions and intensities needed to model these bands, and also to further characterize haze spectral opacity. The present lack of accurate modeling capability for propane is an impediment not only for the measurement of propane itself, but also for the search for the emissions of new molecules in many spectral regions., Comment: 7 Figures, 3 Tables. Typeset in Latex with elsart.cls. In press for Planetary and Space Science

Since its first measurement 20 years ago by the Infrared Space Observatory (ISO), the water (H2O) mole fraction in Titan’s stratosphere remains uncertain due to large differences between the determinations from available measurements. More particularly, the recent measurements made from the Herschel observatory (PACS (Photodetector Array Camera and Spectrometer) and HIFI (Heterodyne Instrument for the Far Infrared)) estimated the H2O mole fraction to be 0.023 parts per billion at 12.1 millibars. A mixing ratio of 0.14 parts per billion at 10.7 millibars was, however, retrieved from nadir spatially-resolved observations of Cassini/CIRS (Composite Infrared Spectrometer). At the same pressure level (10.7 millibars), this makes a difference of a factor of 5.5 between PACS and CIRS measurements, and this has notably prevented current models from fully constraining the oxygen flux flowing into Titan’s atmosphere. In this work, we try to understand the differences between the H2O mole fractions estimated from Herschel/PACS and Cassini/CIRS observations. The strategy for this is to 1) analyse recent disc-averaged observations of CIRS to investigate if the observation geometry could explain the previous observed differences, and 2) (re)analyse the three types of observation with the same retrieval scheme to assess if previous differences in retrieval codes/methodology could be responsible for the previous discrepancies. With this analysis, we show that using the same retrieval method better reconcile the previous measurements of these instruments. However, the addition of the disc-averaged CIRS observations, instead of confirming the consistency between the different datasets, reveals discrepancies between one of the CIRS disc-averaged set of observations and PACS measurements. This raises new questions regarding the possibility of latitudinal variations of H2O, which could be triggered by seasonal changes of the meridional circulation. As it has already been shown for nitriles and hydrocarbons, this circulation could potentially impact the latitudinal distribution of H2O through the subsidence or up- welling of air rich in H2O. The possible influence of spatial/time variations of the OH/H2O input flux in Titan’s atmosphere is also discussed. The analysis of more observations will be needed in future work to address the questions arising from this work and to improve the understanding of the sources of H2O in Titan’s atmosphere.

Submillimeter emission lines of carbon monoxide (CO) in Titan's atmosphere provide excellent probes of atmospheric temperature due to the molecule's long chemical lifetime and stable, well constrained volume mixing ratio. Here we present the analysis of 4 datasets obtained with the Atacama Large Millimeter/Submillimeter Array (ALMA) in 2012, 2013, 2014, and 2015 that contain strong CO rotational transitions. Utilizing ALMA's high spatial resolution in the 2012, 2014, and 2015 observations, we extract spectra from 3 separate regions on Titan's disk using datasets with beam sizes ranging from 0.35 ×0.28'' to 0.39 ×0.34''. Temperature profiles retrieved by the NEMESIS radiative transfer code are compared to Cassini Composite Infrared Spectrometer (CIRS) and radio occultation science results from similar latitude regions. Disk-averaged temperature profiles stay relatively constant from year to year, while small seasonal variations in atmospheric temperature are present from 2012 to 2015 in the stratosphere and mesosphere ( approx. 100-500 km) of spatially resolved regions. We measure the stratopause (320 km) to in- crease in temperature by 5 K in northern latitudes from 2012 to 2015, while temperatures rise throughout the stratosphere at lower latitudes. We observe generally cooler temperatures in the lower stratosphere ( approx. 100 km) than those obtained through Cassini radio occultation measurements, with the notable exception of warming in the northern latitudes and the absence of previous instabilities; both of these results are indicators that Titan's lower atmosphere responds to seasonal effects, particularly at higher latitudes. While retrieved temperature profiles cover a range of latitudes in these observations, deviations from CIRS nadir maps and radio occultation measurements convolved with the ALMA beam-footprint are not found to be statistically significant, and discrepancies are often found to be less than 5 K throughout the atmosphere. ALMA's excellent sensitivity in the lower stratosphere (60-300 km) provides a highly complementary dataset to contemporary CIRS and radio science observations, including altitude regions where both of those measurement sets contain large uncertainties. The demonstrated utility of CO emission lines in the submillimeter as a tracer of Titan's atmospheric temperature lays the groundwork for future studies of other molecular species -particularly those that exhibit strong polar abundance enhancements or are pressure-broadened in the lower atmosphere, as temperature profiles are found to consistently vary with latitude in all three years by up to 15 K.

We present sub-millimeter spectra of HCN isotopologues on Titan, derived from publicly available ALMA flux calibration observations of Titan taken in early 2014. We report the detection of a new HCN isotopologue on Titan, H13C15N, and confirm an earlier report of detection of DCN. We model high signal-to-noise observations of HCN, H13CN, HC15N, DCN, and H13C15N to derive abundances and infer the following isotopic ratios: 12C/13C = 89.8 +/- 2.8, 14N/15N = 72.3 +/- 2.2, D/H = (2.5 +/- 0.2) × 10−4, and HCN/H13C15N = 5800 +/- 270 (1sigma errors). The carbon and nitrogen ratios are consistent with and improve on the precision of previous results, confirming a factor of approximately 2.3 elevation in 14N/15N in HCN compared to N2 and a lack of fractionation in 12C/13C from the protosolar value. This is the first published measurement of D/H in a nitrile species on Titan, and we find evidence for a factor of approximately 2 deuterium enrichment in hydrogen cyanide compared to methane. The isotopic ratios we derive may be used as constraints for future models to better understand the fractionation processes occurring in Titan's atmosphere.

We report interferometric observations of carbon monoxide (CO) and its isotopologues in Titan's atmosphere using the Atacama Large Millimeter/submillimeter Array (ALMA). The following transitions were detected: CO (J = 1-0, 2-1, 3-2, 6-5), C-13 O (J = 2-1, 3-2, 6-5), C-18 O (J = 2-1, 3-2), and C-17 O (J = 3-2). Molecular abundances and the vertical atmospheric temperature profile were derived by modeling the observed emission line profiles using NEMESIS, a line-by-line radiative transfer code. We present the first spectroscopic detection of O-17 in the outer solar system with C-17 O detected at greater than 8 sigma confidence. The abundance of CO was determined to be 49.6 +/- 1.8 ppm, assumed to be constant with altitude, with isotopic ratios C-12/C-13 = 89.9 +/- 3.4, O-16/O-18 = 486 +/- 22, and O-16/O-17 = 2917 +/- 359. The measurements of C-12/C-13 and O-16/O-18 ratios are the most precise values obtained in Titan's atmospheric CO to date. Our results are in good agreement with previous studies and suggest no significant deviations from standard terrestrial isotopic ratios.

A condensate cloud on Titan identified by its 220 cm−1 far-infrared signature continues to undergo seasonal changes at both the north and south poles. In the north, the cloud, which extends from 55 N to the pole, has been gradually decreasing in emission intensity since the beginning of the Cassini mission with a half-life of 3.8 years. The cloud in the south did not appear until 2012 but its intensity has increased rapidly, doubling every year. The shape of the cloud at the south pole is very different from that in the north. Mapping in 2013 December showed that the condensate emission was confined to a ring with a maximum at 80 S. The ring was centered 4deg from Titanʼs pole. The pattern of emission from stratospheric trace gases like nitriles and complex hydrocarbons (mapped in 2014 January) was also offset by 4deg, but had a central peak at the pole and a secondary maximum in a ring at about 70 S with a minimum at 80 S. The shape of the gas emission distribution can be explained by abundances that are high at the atmospheric pole and diminish toward the equator, combined with correspondingly increasing temperatures. We discuss possible causes for the condensate ring. The present rapid build up of the condensate cloud at the south pole is likely to transition to a gradual decline from 2015 to 2016. Key words: molecular processes - planets and satellites: atmospheres - planets and satellites: composition - planets and satellites: individual (Titan) - radiation mechanisms: thermal

Saturn׳s moons, Titan and Enceladus, are two of the Solar System׳s most enigmatic bodies and are prime targets for future space exploration. Titan provides an analogue for many processes relevant to the Earth, more generally to outer Solar System bodies, and a growing host of newly discovered icy exoplanets. Processes represented include atmospheric dynamics, complex organic chemistry, meteorological cycles (with methane as a working fluid), astrobiology, surface liquids and lakes, geology, fluvial and aeolian erosion, and interactions with an external plasma environment. In addition, exploring Enceladus over multiple targeted flybys will give us a unique opportunity to further study the most active icy moon in our Solar System as revealed by Cassini and to analyse in situ its active plume with highly capable instrumentation addressing its complex chemistry and dynamics. Enceladus׳ plume likely represents the most accessible samples from an extra-terrestrial liquid water environment in the Solar system, which has far reaching implications for many areas of planetary and biological science. Titan with its massive atmosphere and Enceladus with its active plume are prime planetary objects in the Outer Solar System to perform in situ investigations. In the present paper, we describe the science goals and key measurements to be performed by a future exploration mission involving a Saturn-Titan orbiter and a Titan balloon, which was proposed to ESA in response to the call for definition of the science themes of the next Large-class mission in 2013. The mission scenario is built around three complementary science goals: (A) Titan as an Earth-like system; (B) Enceladus as an active cryovolcanic moon; and (C) Chemistry of Titan and Enceladus - clues for the origin of life. The proposed measurements would provide a step change in our understanding of planetary processes and evolution, with many orders of magnitude improvement in temporal, spatial, and chemical resolution over that which is possible with Cassini-Huygens. This mission concept builds upon the successes of Cassini-Huygens and takes advantage of previous mission heritage in both remote sensing and in situ measurement technologies.