Atmospheric implications of the lack of H3+ detection at Neptune.

H3+ has been detected at all of the solar system giant planets aside from Neptune. Current observational upper limits imply that there is far less H3+ emission at Neptune than rudimentary modelling would suggest. Here, we explore via modelling a range of atmospheric conditions in order to find some that could be consistent with observational constraints. In particular, we consider that the upper atmosphere might be much cooler than it was during the 1989 Voyager 2 encounter, and we examine the impact of an enhanced influx of external material that could act to reduce H3+ density. Resulting ionosphere models that are consistent with existing H3+ observational constraints have an exospheric temperature of 450 K or less, 300 K lower than the Voyager 2 value. Alternatively, if a topside CO influx of 2 × 108 cm-2 s-1 is imposed, the upper atmospheric temperature can be higher, up to 550 K. The potential cooling of Neptune's atmosphere is relevant for poorly understood giant planet thermospheric energetics, and would also impact aerobreaking manoeuvers for any future spacecraft. Such a large CO influx, if present, could imply Triton is a very active moon with prominent atmospheric escape, and/or that Neptune's rings significantly modify its upper atmosphere, and the introduction of so much exogenic material would complicate interpretation of the origin of species observed in Neptune's lower atmosphere. This article is part a discussion meeting issue 'Future exploration of ice giant systems'.

Neptune and Uranus: ice or rock giants?

Existing observations of Uranus and Neptune's fundamental physical properties can be fitted with a wide range of interior models. A key parameter in these models is the bulk rock:ice ratio and models broadly fall into ice-dominated (ice giant) and rock-dominated (rock giant) categories. Here we consider how observations of Neptune's atmospheric temperature and composition (H2, He, D/H, CO, CH4, H2O and CS) can provide further constraints. The tropospheric CO profile in particular is highly diagnostic of interior ice content, but is also controversial, with deep values ranging from zero to 0.5 parts per million. Most existing CO profiles imply extreme O/H enrichments of >250 times solar composition, thus favouring an ice giant. However, such high O/H enrichment is not consistent with D/H observations for a fully mixed and equilibrated Neptune. CO and D/H measurements can be reconciled if there is incomplete interior mixing (ice giant) or if tropospheric CO has a solely external source and only exists in the upper troposphere (rock giant). An interior with more rock than ice is also more compatible with likely outer solar system ice sources. We primarily consider Neptune, but similar arguments apply to Uranus, which has comparable C/H and D/H enrichment, but no observed tropospheric CO. While both ice- and rock-dominated models are viable, we suggest a rock giant provides a more consistent match to available atmospheric observations. This article is part of a discussion meeting issue 'Future exploration of ice giant systems'.

Atmospheric chemistry on Uranus and Neptune.

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. This article is part of a discussion meeting issue 'Future exploration of ice giant systems'.

Modelling H3+ in planetary atmospheres: effects of vertical gradients on observed quantities.

Since its detection in the aurorae of Jupiter approximately 30 years ago, the H3+ ion has served as an invaluable probe of giant planet upper atmospheres. However, the vast majority of monitoring of planetary H3+ radiation has followed from observations that rely on deriving parameters from column-integrated paths through the emitting layer. Here, we investigate the effects of density and temperature gradients along such paths on the measured H3+ spectrum and its resulting interpretation. In a non-isothermal atmosphere, H3+ column densities retrieved from such observations are found to represent a lower limit, reduced by 20% or more from the true atmospheric value. Global simulations of Uranus' ionosphere reveal that measured H3+ temperature variations are often attributable to well-understood solar zenith angle effects rather than indications of real atmospheric variability. Finally, based on these insights, a preliminary method of deriving vertical temperature structure is demonstrated at Jupiter using model reproductions of electron density and H3+ measurements. The sheer diversity and uncertainty of conditions in planetary atmospheres prohibits this work from providing blanket quantitative correction factors; nonetheless, we illustrate a few simple ways in which the already formidable utility of H3+ observations in understanding planetary atmospheres can be enhanced. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H3+, H5+ and beyond'.

ON THE COMPOSITION OF YOUNG, DIRECTLY IMAGED GIANT PLANETS.

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.

COMPOSITIONAL DIVERSITY IN THE ATMOSPHERES OF HOT NEPTUNES, WITH APPLICATION TO GJ 436b.

Neptune-sized extrasolar planets that orbit relatively close to their host stars - often called "hot Neptunes" - are common within the known population of exoplanets and planetary candidates. Similar to our own Uranus and Neptune, inefficient accretion of nebular gas is expected produce hot Neptunes whose masses are dominated by elements heavier than hydrogen and helium. At high atmospheric metallicities of 10-10,000× solar, hot Neptunes will exhibit an interesting continuum of atmospheric compositions, ranging from more Neptune-like, H2-dominated atmospheres to more Venus-like, CO2-dominated atmospheres. We explore the predicted equilibrium and disequilibrium chemistry of generic hot Neptunes and find that the atmospheric composition varies strongly as a function of temperature and bulk atmospheric properties such as metallicity and the C/O ratio. Relatively exotic H2O, CO, CO2, and even O2-dominated atmospheres are possible for hot Neptunes. We apply our models to the case of GJ 436b, where we find that a CO-rich, CH4-poor atmosphere can be a natural consequence of a very high atmospheric metallicity. From comparisons of our results with Spitzer eclipse data for GJ 436b, we conclude that although the spectral fit from the high-metallicity forward models is not quite as good as the best fit obtained from pure retrieval methods, the atmospheric composition predicted by these forward models is more physically and chemically plausible in terms of the relative abundance of major constituents. High-metallicity atmospheres (orders of magnitude in excess of solar) should therefore be considered as a possibility for GJ 436b and other hot Neptunes.

CHEMICAL CONSEQUENCES OF THE C/O RATIO ON HOT JUPITERS: EXAMPLES FROM WASP-12b, COROT-2b, XO-1b, AND HD 189733b.

Motivated by recent spectroscopic evidence for carbon-rich atmospheres on some transiting exo-planets, 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. Other notable species like N2 and NH3 that do not contain carbon or oxygen are relatively unaffected by the C/O ratio. 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 µm 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 hydrogen-dominated atmosphere. We discuss possible formation mechanisms for carbon-rich hot Jupiters, including scenarios in which the accretion of CO-rich, H2O-poor gas dominates the atmospheric envelope, and scenarios in which the planets accrete carbon-rich solids while migrating through disk regions inward of the snow line. The C/O ratio and bulk atmospheric metallicity provide important clues regarding the formation and evolution of the giant planets.

Volcanically emitted sodium chloride as a source for Io's neutral clouds and plasma torus.

The atmosphere of Jupiter's satellite Io is extremely tenuous, time variable and spatially heterogeneous. Only a few molecules--SO2, SO and S2--have previously been identified as constituents of this atmosphere, and possible sources include frost sublimation, surface sputtering and active volcanism. Io has been known for almost 30 years to be surrounded by a cloud of Na, which requires an as yet unidentified atmospheric source of sodium. Sodium chloride has been recently proposed as an important atmospheric constituent, based on the detection of chlorine in Io's plasma torus and models of Io's volcanic gases. Here we report the detection of NaCl in Io's atmosphere; it constitutes only approximately 0.3% when averaged over the entire disk, but is probably restricted to smaller regions than SO2 because of its rapid photolysis and surface condensation. Although the inferred abundance of NaCl in volcanic gases is lower than predicted, those volcanic emissions provide an important source of Na and Cl in Io's neutral clouds and plasma torus.

Hydrocarbon nucleation and aerosol formation in Neptune's atmosphere.

Photodissociation of methane at high altitude levels in Neptune's atmosphere leads to the production of complex hydrocarbon species such as acetylene (C2H2), ethane (C2H6), methylacetylene (CH3C2H), propane (C3H8), diacetylene (C4H2), and butane (C4H8). These gases diffuse to the lower stratosphere where temperatures are low enough to initiate condensation. Particle formation may not occur readily, however, as the vapor species become supersaturated. We present a theoretical analysis of particle formation mechanisms at conditions relevant to Neptune's troposphere and stratosphere and show that hydrocarbon nucleation is very inefficient under Neptunian conditions: saturation ratios much greater than unity are required for aerosol formation by either homogeneous, heterogeneous, or ion-induced nucleation. Homogeneous nucleation will not be important for any of the hydrocarbon species considered; however, both heterogeneous and ion-induced nucleation should be possible on Neptune for most of the above species. The relative effectiveness of heterogeneous and ion-induced nucleation depends on the physical and thermodynamic properties of the particular species, the abundance of the condensable species, the temperature at which the vapor becomes supersaturated, and the number and type of condensation nuclei or ions available. Typical saturation ratios required for observable particle formation rates on Neptune range from approximately 3 for heterogeneous nucleation of methane in the upper troposphere to greater than 1000 for heterogeneous nucleation of methylacetylene, diacetylene, and butane in the lower stratosphere. Thus, methane clouds may form slightly above, and stratospheric hazes far below, their saturation levels. When used in conjunction with the results of detailed models of atmospheric photochemistry, our nucleation models place realistic constraints on the altitude levels at which we expect hydrocarbon hazes or clouds to form on Neptune.

Hydrogen and deuterium loss from the terrestrial atmosphere: a quantitative assessment of nonthermal escape fluxes.

A comprehensive one-dimensional photochemical model extending from the middle atmosphere (50 km) to the exobase (432 km) has been used to study the escape of hydrogen and deuterium from the Earth's atmosphere. The model incorporates recent advances in chemical kinetics as well as atmospheric observations by satellites, especially the Atmosphere Explorer C satellite. The results suggest: (1) the escape fluxes of both H and D are limited by the upward transport of total hydrogen and total deuterium at the homopause (this result is known as Hunten's limiting flux theorem); (2) about one fourth of total hydrogen escape is thermal, the rest being nonthermal; (3) escape of D is nonthermal; and (4) charge exchange and polar wind are important mechanisms for the nonthermal escape of H and D, but other nonthermal mechanisms may be required. The efficiency to escape from the terrestrial atmosphere for D is 0.74 of the efficiency for H. If the difference between the D/H ratio measured in deep-sea tholeiite glass and that of standard sea water, delta D = -77%, were caused by the escape of H and D, we estimate that as much water as the equivalent of 36% of the present ocean might have been lost in the past.