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We examine Saturn's non-auroral (dayglow) emissions at Lyman-$\alpha$ observed by the {Cassini/UVIS} instrument from 2004 until 2016, to constrain meridional and seasonal trends in the upper atmosphere. We separate viewing geometry effects from trends driven by atmospheric properties, by applying a multi-variate regression to the observed emissions. The Lyman-$\alpha$ dayglow brightnesses depend on the incident solar flux, solar incidence angle, emission angle, and observed latitude. The emissions across latitudes and seasons show a strong dependence with solar incidence angle, typical of resonantly scattered solar flux and consistent with no significant internal source. We observe a bulge in Ly-$\alpha$ brightness that shifts with the summer season from the southern to the northern hemisphere. We estimate atomic hydrogen optical depths above the methane homopause level for dayside disk observations (2004-2016) by comparing observed Lyman-$\alpha$ emissions to a radiative transfer model. We model emissions from resonantly scattered solar flux and a smaller but significant contribution by scattered photons from the interplanetary hydrogen (IPH) background. During northern summer, inferred hydrogen optical depths steeply decrease with latitude towards the winter hemisphere from a northern hemisphere bulge, as predicted by a 2D seasonal photochemical model. The southern hemisphere mirrors this trend during its summer. However, inferred optical depths show substantially more temporal variation between 2004 and 2016 than predicted by the photochemical model.

The incredible longevity of Cassini's orbital mission at Saturn has provided the most comprehensive exploration of a seasonal giant planet to date. This review explores Saturn's changing global temperatures, composition, and aerosol properties between northern spring and summer solstice (2015-2017), extending our previous review of Cassini's remote sensing investigations (2004-14, Fletcher et al., 2018) to the grand finale. The result is an unprecedented record of Saturn's climate that spans almost half a Saturnian year, which can be used to test the seasonal predictions of radiative climate models, neutral and ion photochemistry models, and atmospheric circulation models. Hemispheric asymmetries in tropospheric and stratospheric temperatures were observed to reverse from northern winter to northern summer; spatial distributions of hydrocarbons and para-hydrogen shifted in response to atmospheric dynamics (e.g., seasonally-reversing Hadley cells, polar stratospheric vortex formation, equatorial stratospheric oscillations, and inter-hemispheric transport); and upper tropospheric and stratospheric aerosols exhibited changes in optical thickness that modulated Saturn's visible colours (from blue hues to a golden appearance in the north near solstice), reflectivity, and near-infrared emission. Numerical simulations of radiative balance and photochemistry do a good job in reproducing the observed seasonal change and phase lags, but discrepancies between models and observations still persist, indicating a crucial role for atmospheric dynamics and the need to couple chemical and radiative schemes to the next generation of circulation models. With Cassini's demise, an extended study of Saturn's seasons, from northern summer to autumn, will require the capabilities of ground- and space-based observatories, as we eagerly await the next orbital explorer at Saturn., Comment: 24 pages, 17 figures, accepted for publication by Cambridge University Press as part of a multi-volume work edited by Kevin Baines, Michael Flasar, Norbert Krupp, and Thomas Stallard, entitled "Cassini at Saturn: The Grand Finale." The copy of the Chapter, as displayed on this website, is a draft, pre-publication copy only

Comparatively little is known about atmospheric chemistry on Uranus and Neptune, because remote spectral observations of these cold, distant ``Ice Giants'' are challenging, and each planet has only been visited by a single spacecraft during brief flybys in the 1980s. Thermochemical equilibrium is expected to control the composition in the deeper, hotter regions of the atmosphere on both planets, but disequilibrium chemical processes such as transport-induced quenching and photochemistry alter the composition in the upper atmospheric regions that can be probed remotely. Surprising disparities in the abundance of disequilibrium chemical products between the two planets point to significant differences in atmospheric transport. The atmospheric composition of Uranus and Neptune can provide critical clues for unravelling details of planet formation and evolution, but only if it is fully understood how and why atmospheric constituents vary in a three-dimensional sense and how material coming in from outside the planet affects observed abundances. Future mission planning should take into account the key outstanding questions that remain unanswered about atmospheric chemistry on Uranus and Neptune, particularly those questions that pertain to planet formation and evolution, and those that address the complex, coupled atmospheric processes that operate on Ice Giants within our solar system and beyond., Comment: review paper accepted in Philos. Trans. R. Soc. A

The past decade has seen significant progress on the direct detection and characterization of young, self-luminous giant planets at wide orbital separations from their host stars. Some of these planets show evidence for disequilibrium processes like transport-induced quenching in their atmospheres; photochemistry may also be important, despite the large orbital distances. These disequilibrium chemical processes can alter the expected composition, spectral behavior, thermal structure, and cooling history of the planets, and can potentially confuse determinations of bulk elemental ratios, which provide important insights into planet-formation mechanisms. Using a thermo/photochemical kinetics and transport model, we investigate the extent to which disequilibrium chemistry affects the composition and spectra of directly imaged giant exoplanets. Results for specific "young Jupiters" such as HR 8799 b and 51 Eri b are presented, as are general trends as a function of planetary effective temperature, surface gravity, incident ultraviolet flux, and strength of deep atmospheric convection. We find that quenching is very important on young Jupiters, leading to CO/CH4 and N2/NH3 ratios much greater than, and H2O mixing ratios a factor of a few less than, chemical-equilibrium predictions. Photochemistry can also be important on such planets, with CO2 and HCN being key photochemical products. Carbon dioxide becomes a major constituent when stratospheric temperatures are low and recycling of water via the H2 + OH reaction becomes kinetically stifled. Young Jupiters with effective temperatures <~ 700 K are in a particularly interesting photochemical regime that differs from both transiting hot Jupiters and our own solar-system giant planets., Comment: Accepted in The Astrophysical Journal

Mid-infrared spectral observations Uranus acquired with the Infrared Spectrometer (IRS) on the Spitzer Space Telescope are used to determine the abundances of C2H2, C2H6, CH3C2H, C4H2, CO2, and tentatively CH3 on Uranus at the time of the 2007 equinox. For vertically uniform eddy diffusion coefficients in the range 2200-2600 cm2 s-1, photochemical models that reproduce the observed methane emission also predict C2H6 profiles that compare well with emission in the 11.6-12.5 micron wavelength region, where the nu9 band of C2H6 is prominent. Our nominal model with a uniform eddy diffusion coefficient Kzz = 2430 cm2 sec-1 and a CH4 tropopause mole fraction of 1.6x10-5 provides a good fit to other hydrocarbon emission features, such as those of C2H2 and C4H2, but the model profile for CH3C2H must be scaled by a factor of 0.43, suggesting that improvements are needed in the chemical reaction mechanism for C3Hx species. The nominal model is consistent with a CH3D/CH4 ratio of 3.0+-0.2x10-4. From the best-fit scaling of these photochemical-model profiles, we derive column abundances above the 10-mbar level of 4.5+01.1/-0.8 x 10+19 molecule-cm-2 for CH4, 6.2 +- 1.0 x 10+16 molecule-cm-2 for C2H2 (with a value 24% higher from a different longitudinal sampling), 3.1 +- 0.3 x 10+16 molecule-cm-2 for C2H6, 8.6 +- 2.6 x 10+13 molecule-cm-2 for CH3C2H, 1.8 +- 0.3 x 10+13 molecule-cm-2 for C4H2, and 1.7 +- 0.4 x 10+13 molecule-cm-2 for CO2 on Uranus. Our results have implications with respect to the influx rate of exogenic oxygen species and the production rate of stratospheric hazes on Uranus, as well as the C4H2 vapor pressure over C4H2 ice at low temperatures.

Motivated by recent spectroscopic evidence for carbon-rich atmospheres on some transiting exoplanets, we investigate the influence of the C/O ratio on the chemistry, composition, and spectra of extrasolar giant planets both from a thermochemical-equilibrium perspective and from consideration of disequilibrium processes like photochemistry and transport-induced quenching. We find that although CO is predicted to be a major atmospheric constituent on hot Jupiters for all C/O ratios, other oxygen-bearing molecules like H2O and CO2 are much more abundant when C/O < 1, whereas CH4, HCN, and C2H2 gain significantly in abundance when C/O > 1. Disequilibrium processes tend to enhance the abundance of CH4, NH3, HCN, and C2H2 over a wide range of C/O ratios. We compare the results of our models with secondary-eclipse photometric data from the Spitzer Space Telescope and conclude that (1) disequilibrium models with C/O ~ 1 are consistent with spectra of WASP-12b, XO-1b, and CoRoT-2b, confirming the possible carbon-rich nature of these planets, (2) spectra from HD 189733b are consistent with C/O ~< 1, but as the assumed metallicity is increased above solar, the required C/O ratio must increase toward 1 to prevent too much H2O absorption, (3) species like HCN can have a significant influence on spectral behavior in the 3.6 and 8.0 um Spitzer channels, potentially providing even more opacity than CH4 when C/O > 1, and (4) the very high CO2 abundance inferred for HD 189733b from near-infrared observations cannot be explained through equilibrium or disequilibrium chemistry in a H2-dominated atmosphere. We discuss possible formation mechanisms for carbon-rich hot Jupiters. The C/O ratio and bulk atmospheric metallicity provide important clues regarding the formation and evolution of the giant planets., Comment: accepted in the Astrophysical Journal

A dedicated mission to investigate exoplanetary atmospheres represents a major milestone in our quest to understand our place in the universe by placing our Solar System in context and by addressing the suitability of planets for the presence of life. EChO -the Exoplanet Characterisation Observatory- is a mission concept specifically geared for this purpose. EChO will provide simultaneous, multi-wavelength spectroscopic observations on a stable platform that will allow very long exposures. EChO will build on observations by Hubble, Spitzer and groundbased telescopes, which discovered the first molecules and atoms in exoplanetary atmospheres. EChO will simultaneously observe a broad enough spectral region -from the visible to the mid-IR- to constrain from one single spectrum the temperature structure of the atmosphere and the abundances of the major molecular species. The spectral range and resolution are tailored to separate bands belonging to up to 30 molecules to retrieve the composition and temperature structure of planetary atmospheres. The target list for EChO includes planets ranging from Jupiter-sized with equilibrium temperatures Teq up to 2000 K, to those of a few Earth masses, with Teq ~300 K. We have baselined a dispersive spectrograph design covering continuously the 0.4-16 micron spectral range in 6 channels (1 in the VIS, 5 in the IR), which allows the spectral resolution to be adapted from several tens to several hundreds, depending on the target brightness. The instrument will be mounted behind a 1.5 m class telescope, passively cooled to 50 K, with the instrument structure and optics passively cooled to ~45 K. EChO will be placed in a grand halo orbit around L2. We have also undertaken a first-order cost and development plan analysis and find that EChO is easily compatible with the ESA M-class mission framework., Comment: Accepted for publication in Experimental Astronomy, 23 pages, 15 figures

We use a 1D model to address photochemistry and possible haze formation in the irradiated warm Jupiter 51 Eridani b. The intended focus was to be carbon, but sulfur photochemistry turns out to be important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If they form, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the regions where methane and water are photolyzed. The more novel result is that photochemistry turns H2S into elemental sulfur, here treated as S8. In the cooler models, S8 is predicted to condense in optically thick clouds of solid sulfur particles, whilst in the warmer models S8 remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we have discussed is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650-750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.

The past decade has seen significant progress on the direct detection and characterization of young, self-luminous giant planets at wide orbital separations from their host stars. Some of these planets show evidence for disequilibrium processes like transport-induced quenching in their atmospheres; photochemistry may also be important, despite the typically large orbital distances. Disequilibrium chemical processes such as these can alter the expected composition, spectral behavior, thermal structure, and cooling history of the planets, and can potentially confuse determinations of bulk elemental ratios, which provide important insights into planet-formation mechanisms. Using a thermo/photochemical kinetics and transport model, we investigate the extent to which disequilibrium chemical processes affect the composition and spectra of directly imaged giant exoplanets. Results for specific "young Jupiters" such as HR 8799 b and c and 51 Eri b are presented, as are general trends as a function of planetary effective temperature, surface gravity, incident ultraviolet flux, and strength of deep atmospheric convection. We find that quenching is very important on young Jupiters, leading to CO/CH4 and N2/NH3 ratios much greater than; and H2O mixing ratios a factor of a few less than chemical equilibrium predictions. Photochemistry can also be important on such planets, with CO2 and HCN being key photochemical products. Carbon dioxide becomes a particularly major constituent when stratospheric temperatures are low and recycling of water following H2O photolysis becomes stifled. Young Jupiters with effective temperatures less than 700 degrees Kelvin are in a particularly interesting photochemical regime that differs from both transiting hot Jupiters and our own solar-system giant planets.

We have developed a realistic, time-variable, one-dimensional, seasonal model for stratospheric photochemistry on Saturn using the Caltech/ JPL KINETICS code [1,2,3]. The model accounts for variations in ultraviolet flux due to orbital position, solar-cycle variations, and ring-shadowing effects. The results for two Saturnian years, starting at Ls = 0 in 1950 and running until the upcoming northern vernal equinox in 2009, are presented for numerous latitudes. The same two model years are run over and over again until the model convergences to make sure that high-altitude effects have had a chance to propagate down through the atmosphere. We use the SOLAR2000 model [4,5], in combination with the spectra presented in [6], to predict the ultraviolet flux at any wavelength and any point in time during the simulation. Saturn's orbital position during the simulation was taken from the ephemeris calculator at http://ssd.jpl.nasa.gov/horizons.html [7]. The photochemical model is derived from "Model C" of [8] and uses a hydrocarbon reaction list that has been extensively updated from that presented in [3].

To date, approximately 120 planet-sized objects have been discovered around other stars, mostly through the radial-velocity technique. This technique can provide information about a planet s minimum mass and its orbital period and distance; however, few other planetary data can be obtained at this point in time unless we are fortunate enough to find an extrasolar giant planet that transits its parent star (i.e., the orbit is edge-on as seen from Earth). In that situation, many physical properties of the planet and its parent star can be determined, including some compositional information. Our prospects of directly obtaining spectra from extrasolar planets may improve in the near future, through missions like NASA's Terrestrial Planet Finder. Most of the extrasolar giant planets (EGPs) discovered so far have masses equal to or greater than Jupiter's mass, and roughly 16% have orbital radii less than 0.1 AU - extremely close to the parent star by our own Solar-System standards (note that Mercury is located at a mean distance of 0.39 AU and Jupiter at 5.2 AU from the Sun). Although all EGPs are expected to have hydrogen-dominated atmospheres similar to Jupiter, the orbital distance can strongly affect the planet's temperature, physical, chemical, and spectral properties, and the abundance of minor, detectable atmospheric constituents. Thermochemical equilibrium models can provide good zero-order predictions for the atmospheric composition of EGPs. However, both the composition and spectral properties will depend in large part on disequilibrium processes like photochemistry, chemical kinetics, atmospheric transport, and haze formation. We have developed a photochemical kinetics, radiative transfer, and 1-D vertical transport model to study the atmospheric composition of EGPs. The chemical reaction list contains H-, C-, O-, and N-bearing species and is designed to be valid for atmospheric temperatures ranging from 100-3000 K and pressures up to 50 bar. Here we examine the effect of stellar distance (e.g., incident ultraviolet flux, atmospheric temperature) on the chemical properties of EGPs. The model is applied to two generic Class II and III intermediate temperature EGPs located at 3.3 and 0.27 AU from a solar-like parent star, and the results are compared with a model for Jupiter at 5.2 AU.