Methyl Radical Detected on Titan with JWST/MIRI

(2025)

Authors:

Nicholas Teanby, Conor Nixon, Manuel López-Puertas, Brandon Coy, Véronique Vuitton, Panayotis Lavvas, Lucy Wright, Joshua Ford, Patrick Irwin

Abstract:

Saturn’s largest moon Titan has a nitrogen-methane atmosphere and a rich organic photochemistry. Dissociation of Titan’s molecular methane and nitrogen into N and methyl (CH3) radicals forms the basis of this photochemistry and results in a vast array of hydrocarbon and nitrile species. The abundance of CH3 is thus of critical importance to understanding Titan’s atmospheric chemistry. CH3 is predicted by photochemical models and must be present to explain Titan’s trace gas composition, but has never been directly observed. Cassini’s mass spectrometer was unable to make a detection as the extreme reactivity of radicals results in reactions on the instrument wall (e.g. recombination with H) before detection is possible. Emission features in the infra-red are also very weak, so detection from remote-sensing spectroscopy has previously not been possible. Here we use the very high sensitivity of the James Webb Space Telescope’s (JWST) Mid-InfraRed Instrument (MIRI) to detect emission from CH3 at 16.5 microns. We have used this to validate model predictions that underpin Titan’s rich atmospheric chemistry.JWST/MIRI observations were taken in Medium Resolution Spectroscopy (MRS) mode on 11th July 2023 as part of Guaranteed Time Observation programme 1251 [Nixon et al., 2025]. Observations were reduced using the standard pipeline and combined to give a disc-averaged spectrum (Fig 1). The observed spectrum was compared to a forward model generated with a reference Titan atmosphere using the NEMESIS radiative transfer suite [Irwin et al., 2008]. The reference atmospheric temperature profile was based on observation from Cassini half a Titan year previous, augmented with ground-based measurements from ALMA and in-situ measurements from the Huygens probe (Fig 2a). A baseline atmospheric composition was compiled from Cassini/Huygens measurements [Teanby et al., 2019]. For the CH3 profile, in the absence of measurements, we used the predicted abundance from a photochemical model [Vuitton et al., 2019] (Fig 2a).The abundance profile of CH3 is expected to be extremely steep with very high fractional abundances in the thermosphere (100 ppm at 1000km) and much lower abundances in the stratosphere and mesosphere (1 ppb at 300km). Peak emission under conditions of local thermodynamic equilibrium should originate from the mid-thermosphere at an altitude of ~800km (Fig 2b). However, our analysis shows that non-local thermodynamic equilibrium (non-LTE) emission is expected due to very low thermospheric pressures [Nixon et al., 2025]. This supresses emission below that expected from the Planck function and reduces infra-red emission from thermospheric CH3 to negligible levels. When non-LTE effects are considered, we find that the emission instead originates from the stratopause region (~300km) where CH3 abundances are predicted to be around 1 ppb (Fig 2c).Agreement between forward modelled non-LTE emission using the photochemical model profile and the JWST/MIRI observation match very well (Fig 1) – confirming the model predicted abundances are consistent with conditions in Titan’s middle atmosphere. Our initial results were presented in Nixon et al., (2025). Here we present an updated analysis using improved pipeline processing, more in-depth treatment of the disc-averaged nature of the observation, and provide formal limits on the CH3 abundance profiles. The consistency of our results with predictions from photochemical models gives confidence to current chemical schemes for Titan’s low-order chemistry, which provides a sound basis for a deeper analysis of Titan’s more exotic species such as high-order hydrocarbons and poly-aromatic hydrocarbons.ReferencesIrwin, P.G.J., et al., 2008. The NEMESIS planetary atmosphere radiative transfer and retrieval tool. Journal of Quantitative Spectroscopy and Radiative Transfer 109, 1136–1150.Nixon, C.A., et al., 2025., Titan’s Atmosphere in Late Northern Summer from JWST and Keck Observations. Nature Astronomy, in press.Teanby, N.A., et al., 2019. Seasonal Evolution of Titan’s Stratosphere During the Cassini Mission. Geophysical Research Letters 46, 3079–3089.Vuitton, V., et al., 2019. Simulating the density of organic species in the atmosphere of Titan with a coupled ion-neutral photochemical model. Icarus 324, 120–197.Fig 1: JWST/MIRI disc-average spectrum compared with forward models with and without CH3. The model including CH3 provides a much better fit to the observations.Fig 2: (a) Titan’s atmospheric temperature structure and uncertainty envelope from Nixon et al. (2025), along with photochemical model prediction of the CH3 profile from Vuitton et al. (2019). (b) Contribution functions for LTE case with nominal temperature profile (green), hot temperature limit (red) and cold temperature limit (blue). For LTE, peak emission would be from the thermosphere at ~800km, but this is not realistic. (c) Contribution functions for a more realistic non-LTE emission case peak at ~300km around the mesopause as non-LTE effects suppress emission at very low pressures. Our observations are thus most sensitive to abundances around the stratopause. 

Microphysical Modeling of Hydrogen Sulfide Clouds in the Atmospheres of the Ice Giants

(2025)

Authors:

Daniel Toledo, Pascal Rannou, Patrick Irwin, Bruno de Batz de Trenquelléon, Michael Roman, Noé Clément, Gwenael Milcareck, Victor Apestigue, Ignacio Arruego, Margarita Yela

Abstract:

Radiative transfer analyses of spectra obtained from Uranus and Neptune have revealed the presence ofa cloud layer at pressures greater than ~2 bar (1,2). The detection of hydrogen sulfide (H₂S) gas abovethis cloud layer on both planets (3,4) suggests that H₂S ice is the most likely main constituent. Thisinterpretation is further supported by the expectation that methane (CH₄) clouds condense at higheraltitudes (5). However, due to their depth and observational limitations, our understanding of theproperties of H₂S clouds on these planets remains very limited.To investigate the properties of H₂S clouds in the atmospheres of Uranus and Neptune, we employed aone-dimensional cloud microphysics model originally developed for Titan and Mars (6,7). The modelincludes nucleation, condensation, evaporation, coagulation, and precipitation processes, and haspreviously been used to simulate haze and CH₄ cloud microphysics in the Ice Giants (5,8,9).Figure 1 shows, as an example, simulated H₂S ice profiles for Uranus using this microphysical model.The vertical transport of H₂S gas is simulated using an eddy diffusion coefficient (Keddʏ), which controlsthe supply of vapor for cloud nucleation and particle growth. We employed the Keddʏ profiles derivedin [10] for H₂S abundances of 10× and 30× solar. Since several cloud microphysical parameters for H₂Sremain uncertain (e.g., the contact parameter), different values are tested in the simulations. In theexample shown, the model indicates cloud bases near 5.3 bar for 10× solar abundance and 6.4 bar for30× solar. Near the cloud base, particle mean radii range from 40 to 55 μm, depending on the assumedcontact parameter and abundance. At higher altitudes, particle sizes decrease; for instance, at ~3 bar,mean radii are around 20 μm. In general, H₂S cloud simulations produce higher opacities than CH₄clouds.In this work, we will present a series of cloud microphysical simulations of H₂S clouds in the Ice Giants.Various cloud properties, such as particle size distributions and precipitation rates, will be constrained.We will also discuss the implications of our results for the atmospheric circulation of these planets andfor the future exploration of Uranus.Figure 1. Vertical distributions of H2S ice (g/m³) for Uranus, simulated for different values of the cloudcontact parameter and deep H2S abundances. These simulations employ the Keddʏ profiles calculated in[10] for the corresponding H2S abundances.References: [1] P. G. Irwin, et al., JGR: Planets, 127, e2022JE007189. [2] L. Sromovsky, et al., Icarus,Volume 317, (2019) [3] P. G. Irwin, et al., Nature Astronomy 2, 420 (2018). [4] P. G. Irwin, et al.,Icarus 321, 550 (2019). [5] D. Toledo, et al., A&A, 694, A81 (2025). [6] P. Rannou, et al., Science 311,201 (2006). [7] F. Montmessin, et al., JGR: Planets 107, 4 (2002). [8] D. Toledo, et al., Icarus, 333, 1-11, (2019). [9] D. Toledo, et al., Icarus, Volume 350, (2020). [10] H. Ge, et al., The Planetary ScienceJournal,5, 101(2024). 

Modelling the Influence of Oxidative Chemistry on Trace Gases in Mars' Atmosphere.

(2025)

Authors:

Bethan Gregory, Kevin Olsen, Ehouarn Millour, Megan Brown

Abstract:

In this presentation, we will show efforts made to include accurate photochemical modelling of hydrogen chloride (HCl) and ozone (O3) in the Mars Planetary Climate Model in order to reconcile recent observations.The ExoMars Trace Gas Orbiter (TGO) has detected and characterised trace gases in the Martian atmosphere over several Mars years. With its data, upper limits of potential constituents have been constrained, the accuracy of species’ concentration measurements has been improved, and seasonal and spatial variations in the atmosphere have been observed. The wealth of data obtained has addressed several open questions about the nature of Mars’ atmosphere, while other measurements have revealed much that remains poorly understood. For example, models continue to struggle to reproduce ozone distributions, both spatially and temporally, as well as seasonal variations in atmospheric oxygen (O2), suggesting that some key photochemical interactions may be being overlooked. As another example, despite seven years of dedicated observations producing very low upper limits on atmospheric methane levels, there remains no unifying hypothesis that simultaneously explains the detections reported by other Mars assets at Gale Crater [e.g., 1-4].Hydrogen chloride—the first new gas detected by TGO [5,6]—has been investigated recently using the mid-infrared channel on TGO’s Atmospheric Chemistry Suite (ACS MIR) [7,8]. Observations show a strong seasonal dependence of HCl in the atmosphere, with almost all detections occurring during the latter half of the year between the start of dust activity and the southern hemisphere autumnal equinox. There are also unusual measurements of HCl, localised in both time and space, during the aphelion season. Chlorine-bearing species such as HCl are important to understand in the Mars atmosphere because on Earth they are involved in numerous processes throughout the planetary system, including volcanism, from which HCl on Earth ultimately originates. Further, chlorine species play a key role in atmospheric chemistry: they influence oxidative chemistry and variations in the aforementioned O2 and O3 concentrations (e.g., by catalysing the destruction of ozone), and by extension, potential CH4 in the Martian atmosphere [9]. However, much remains unknown about original source and sinks of HCl, as well as the factors controlling its distribution and variation.Here, we use the Mars Planetary Climate Model—a 3-D global climate model that includes a photochemical network—to investigate potential mechanisms accounting for patterns in ozone and HCl detections and interactions between them. We begin with the role of heterogeneous chemistry involving ice and dust aerosols, by implementing modelling developed for the Open University Mars Global Climate Model [10] and building on existing chlorine photochemical model networks [11,12,13]. Heterogeneous chemistry affects the abundances of oxidative species such as OH and HO2, and by extension, O and O3. In addition, we investigate how such processes can potentially serve as a mechanism for direct release and sequestration of HCl from the atmosphere. We also explore potential mechanisms behind the annual occurrence of spatially-constrained aphelion HCl, including volcanic sources, and we investigate the interplay between chlorine-bearing species and OH, HO2,O, and O3. Figure 1 shows the way that HCl appears during spring and summer in the southern hemisphere (solar longitudes 180-360°) when water vapour is present in the Martian atmosphere. Ozone behaves in the opposite manner and is present when water vapour abundances are low. As shown, these species are anti-correlated; we explore the important chemical pathways connecting them.Understanding the role of oxidative chemistry on HCl and other trace gases is key to achieving a more complete picture of processes occurring in the present-day Mars atmosphere, as well as processes that have shaped its evolution and habitability.Figure 1: Observations of CO, O2, O3 and HCl seasonally and across multiple Mars Years. Upper panel: CO and O2 observations from Curiosity’s Sample Analysis at Mars (SAM) instrument (stars; [14]) and the Mars Climate Database (lines; [15]). Lower panel: O3 and HCl observations from TGO’s ACS instrument [8]. MY=Mars Year; NH/SH=northern/southern hemisphere. Figure from Kevin Olsen.References:[1] Giuranna, M., et al. (2019). Nat. Geosci. 12, 326–332. [2] Korablev, O. et al. (2019). Nature 568, 517–520. [3] Montmessin, F. et al. (2021). Astron. Astrophys. 650, A140. [4] Webster, C. R. et al. (2015). Science 347, 415-417. [5] Korablev O. I. et al. (2021). Sci. Adv., 7, eabe4386. [6] Olsen K. S. et al. (2021). Astron. Astrophys., 647, A161. [7] Olsen K. S. et al. (2024a). JGR, 129, e2024JE008350. [8] Olsen K. S. et al. (2024b). JGR, 129, e2024JE008351. [9] Taysum, B. M. et al. (2024). Astron. Astrophys., 687, A191. [10] Brown M. A. J. et al. (2022). JGR, 127, e2022JE007346. [11] Rajendran, K. et al. (2025). JGR: Planets 130(3), p.e2024JE008537. [12] Streeter, P. M. et al. (2025). GRL 52(6), p.e2024GL111059. [13] Benne, B. et al. (2024). EPSC, pEPSC2024-1037. [14] Trainer, M. G. et al. (2019). JGR 124, 3000. [15] Millour, E. et al. (2022). Mars Atmosphere: Modelling and Observations, p. 1103.

Neptune's Latitudinal H2S Distribution: Reconciling Near-Infrared and Microwave Observations

Copernicus Publications (2025)

Authors:

Joseph Penn, Patrick Irwin, Jack Dobinson

Abstract:

In 2018, analysis of Gemini-NIFS near-infrared observations revealed the probable presence of H2S above the main cloud deck on Neptune [1]. The spectral signature of the gas was found to be much stronger at Neptune's south pole compared to regions nearer the equator.Conversely, analysis of Neptune's microwave emission with ALMA suggested strongly enhanced H2S abundances at midlatitudes [2], with much less at the south pole. Determining the true variation of H2S with latitude is crucial for understanding the tropospheric circulation of Neptune.We present our analysis of observations of Neptune from VLT-SINFONI in 2018. Using a limb-darkening approximation, we are able to fit the reflected solar radiance from multiple zenith angles, which allows us to discriminate between gas and aerosol opacity. Despite the lower spectral resolution of this instrument compared to Gemini-NIFS, we are able to detect the H2S spectral signature. With our radiative transfer retrieval code, archNEMESIS [3], we use nested sampling to fit a parameterised cloud model (similar to that of [4]) to these observations over a range of latitudes. We prescribe a latitudinally varying deep methane abundance derived from recent VLT-MUSE observations [5], which enables us to constrain the depth of the cloud top.Our retrieved results are in agreement with the results derived from ALMA [2] - we find a significant enhancement of deep H2S at Neptune's southern midlatitudes, decreasing towards the equator and the pole. Our results show a much deeper cloud top towards the pole, resulting in the increased cloud top column abundance of H2S observed here in the previous near-infrared analysis [1].Figure 1: A comparison of fits to a spectrum extracted from the 50°S to 60°S latitude band, with a model including H2S (blue) and a model without H2S (red). Note the significant discrepancy around 1.58 microns. The models are fitted to spectra at two zenith angles simultaneously.[1] Irwin, P. G., Toledo, D., Garland, R., Teanby, N. A., Fletcher, L. N., Orton, G. S., & Bézard, B. (2019). Probable detection of hydrogen sulphide (H2S) in Neptune’s atmosphere. Icarus, 321, 550-563.[2] Tollefson, J., de Pater, I., Luszcz-Cook, S., & DeBoer, D. (2019). Neptune's latitudinal variations as viewed with ALMA. The Astronomical Journal, 157(6), 251.[3] Alday, J., Penn, J., Irwin, P. G., Mason, J. P., & Yang, J. (2025). archNEMESIS: an open-source Python package for analysis of planetary atmospheric spectra. arXiv preprint arXiv:2501.16452.[4] Irwin, P. G., Teanby, N. A., Fletcher, L. N., Toledo, D., Orton, G. S., Wong, M. H., ... & Dobinson, J. (2022). Hazy blue worlds: a holistic aerosol model for Uranus and Neptune, including dark spots. Journal of Geophysical Research: Planets, 127(6), e2022JE007189.[5] Irwin, P. G., Dobinson, J., James, A., Wong, M. H., Fletcher, L. N., Roman, M. T., ... & de Pater, I. (2023). Latitudinal variations in methane abundance, aerosol opacity and aerosol scattering efficiency in Neptune's atmosphere determined from VLT/MUSE. Journal of Geophysical Research: Planets, 128(11), e2023JE007980.

Optically Observed Ammonia in the Northern Equatorial Zone

(2025)

Authors:

Steven M Hill, Patrick Irwin, John Rogers, Leigh Fletcher

Abstract:

IntroductionJupiter’s northern Equatorial Zone (EZn) and southern North Equatorial Belt (NEBs) are dominated by three features: five-micron hotspots (seen as North Equatorial Dark Features, NEDFs, in the optical), white cloud plumes, and complex local circulation. These features are influenced by the NEBs jet, which is modulated by a meridionally trapped Rossby wave, in conjunction with the high concentration of ammonia in the EZ and the ammonia depletion in the NEB. Numerous measurements have been made of the temperature, aerosol, and ammonia distributions in this region (c.f. Fletcher et al., 2020). And a number of models have been partially successful at explaining the interrelationships between the observed features (c.f Showman & Dowling, 2000). Here we explore the ammonia and cloud height distribution during 2024-25, when NEDFs and five-micron hotspots were prominent, using the optical band-average technique (Hill et al., 2024, Irwin et al., 2025). We show that while many sensing methods highlight the ammonia and aerosol depletion in five-micron hotspots, this band average method highlights enhancements in ammonia to the south of the hotspots.ObservationsMultiple observations on 2025-01-06 were made allowing coverage of a wide range of longitudes and coverage of a given longitude at several zenith angles. Figure 1 shows maps constructed using the method of Hill et al. (2024). An empirical limb correction is applied in addition to a weighted averaging scheme for overlapping observations. The data clearly show that enhanced ammonia regions lie to the south of NEDFs (labeled 1-4 in order of ascending longitude). For the ammonia enhancements we observe a planetary wave number of nine, within the range of hotspot and NEDF wavenumbers typically observed.DiscussionThe NEBs jet speed peaks at about  7° N, which in fact marks the boundary between the NEDFs and the ammonia enhancements. Anticyclonic gyres are a known feature seen in the same location as we show ammonia enhancements (c.f. Choi et al., 2013). We hypothesize that these gyres are regions of uplift and outflow, bringing up ammonia rich air from deeper levels of the atmosphere. The NEDFs are thought to be areas of subsidence, with cyclonic flow, where dryer air descends from above and results in a clearing of aerosols. Figure 1D shows this schematically with upwelling occurring at the gyres, horizontal winds carrying condensates from the upwelling source to the east and northeast as the visible cloud plumes, and descending clear air in the NEDFs.To further support this hypothesis, we analyze the ammonia mole fraction and cloud pressure at the NEDFs, gyres, and in the plumes through a regions-of-interest (ROI) approach. Figure 2 shows a longitudinal subset of the data in Figure 1, focusing on ammonia regions 3 and 4. Rectangles outline the ROIs which are analyzed for three observation times in Figure 2A. Figure 2B shows a time series of average values at each observation time for cloud pressure and ammonia mole fraction along with statistical errors. Finally, 2C shows scatter plots of the average cloud pressure versus the ammonia abundance. Note the very clear clustering of points where the NEB sample provides a consistent reference with relatively high pressure and very low ammonia abundance. Following the upwelling ammonia, eastward advection of plume aerosols, and NEDF subsidence from Figure 1, we can trace an ammonia cycle between its gaseous source and sink, with an intermediary aerosol state.Future WorkHundreds of observations of NEDFs and ammonia enhancements in the EZn have been made in 2024-25 using the Hill et al. (2024) technique. This data set will be analyzed and assessed for the statistical consistency of the results presented here. In addition, this data set will be compared to complementary multispectral observations to help discriminate why the optical method seems to so clearly detect ammonia enhancements at the 1-2 bar pressure level and why these enhancements appear broad enough to overlap NEDFs.Figure 1. Ammonia mole fraction, cloud pressure, and visual context maps created from observations on 2025-01-06 using an 11 inch Schmidt-Cassegrain telescope. A) Ammonia mole fraction (ppm) with enhanced areas labeled 1-4 in order of ascending longitude. The black circle at left shows the approximate spatial resolution of the data. B) Cloud pressure (mbar). C) Visual context image with selected contour overlays to show enhanced ammonia mole fraction and lowest pressure (highest) clouds. D) Same as C), but with arrows indicating presumed upwelling (black ⊙), downwelling (white ⦻), and horizontal flow (red arrows). Figure 2. Two ammonia enhancements (4 & 3 from Figure 1), associated plumes, and NEDFs are analyzed for cloud pressure and ammonia abundance. Three observations are assessed with the targets near nadir viewing. A) Ammonia mole fraction, cloud pressure, and visual context image with overlaid rectangles indicating regions-of-interest (ROIs). B) Time series of cloud pressure (left) and ammonia mole fraction (right) over the three observations. C) Scatter plot of all ammonia and cloud measurements in each ROI (left) and of the averages over the three observations. Note that the NEB data are provided as a stable reference.ReferencesChoi, D. S. et al. 2013. Icarus, 223, 832. Hill, S. M. et al. 2024. Earth and Space Science, 11(8), e2024EA003562.Fletcher, L. N. et al. 2020. Journal of Geophysical Research (Planets), 125, e06399. Irwin, P. G. J. et al. 2025. Journal of Geophysical Research: Planets, 130(1), e2024JE008622. Showman, A. P., & Dowling, T. E. 2000. Science, 289, 1737-1740.