Due to the detection of phosphine PH3 in the Solar System gas giants Jupiter and Saturn, PH3 has long been suggested to be detectable in exosolar substellar atmospheres too. However, to date, a direct detection of phosphine has proven to be elusive in exoplanet atmosphere surveys. We construct an updated phosphorus-hydrogen-oxygen (PHO) photochemical network suitable for simulation of gas giant hydrogen-dominated atmospheres. Using this network, we examine PHO photochemistry in hot Jupiter and warm Neptune exoplanet atmospheres at Solar and enriched metallicities. Our results show for HD 189733b-like hot Jupiters that HOPO, PO and P2 are typically the dominant P carriers at pressures important for transit and emission spectra, rather than PH3. For GJ1214b-like warm Neptune atmospheres our results suggest that at Solar metallicity PH3 is dominant in the absence of photochemistry, but is generally not in high abundance for all other chemical environments. At 10 and 100 times Solar, small oxygenated phosphorus molecules such as HOPO and PO dominate for both thermochemical and photochemical simulations. The network is able to reproduce well the observed PH3 abundances on Jupiter and Saturn. Despite progress in improving the accuracy of the PHO network, large portions of the reaction rate data remain with approximate, uncertain or missing values, which could change the conclusions of the current study significantly. Improving understanding of the kinetics of phosphorus-bearing chemical reactions will be a key undertaking for astronomers aiming to detect phosphine and other phosphorus species in both rocky and gaseous exoplanetary atmospheres in the near future.
UV radiation can induce photochemical processes in exoplanet atmospheres and produce haze particles. Recent observations suggest that haze and/or cloud layers could be present in the upper atmospheres of exoplanets. Haze particles play an important role in planetary atmospheres and may provide a source of organic material to the surface which may impact the origin or evolution of life. However, very little information is known about photochemical processes in cool, high-metallicity exoplanetary atmospheres. Previously, we investigated haze formation and particle size distribution in laboratory…
We investigate the impact of photochemical hazes and disequilibrium gases on the thermal structure of hot-Jupiters, using a detailed 1-D radiative-convective model. We find that the inclusion of photochemical hazes results in major heating of the upper and cooling of the lower atmosphere. Sulphur containing species, such as SH, S$_2$ and S$_3$ provide significant opacity in the middle atmosphere and lead to local heating near 1 mbar, while OH, CH, NH, and CN radicals produced by the photochemistry affect the thermal structure near 1 $μ$bar. Furthermore we show that the modifications on the the…
Refractive indices of photochemical haze analogs for Solar System and exoplanet applications : a cross-laboratory comparative study between the PAMPRE and COSmIC experimental set-ups
Spectral slopes in optical transmission spectra of exoplanetary atmospheres encapsulate information on the properties of exotic clouds. The slope is usually attributed to the Rayleigh scattering caused by tiny aerosol particles, whereas recent retrieval studies have suggested that the slopes are often steeper than the canonical Rayleigh slopes. Here, we propose that photochemical haze formed in vigorously mixing atmospheres can explain such super-Rayleigh slopes. We first analytically show that the spectral slope can be steepened by the vertical opacity gradient in which atmospheric opacity in…
Photochemical Production of CS2 in Temperate-to-Warm Gas Giant Exoplanet Atmospheres
University of Chicago（芝加哥大学）；Arizona State University（亚利桑那州立大学）；University of California, Santa Cruz（加州大学圣克鲁兹分校）；Carnegie Institution for Science（卡内基科学机构）
A Fast, Parallelized, GPU-Accelerated Photochemical Model, XODIAC, with Built-in Equilibrium Chemistry and Multiple Chemical Networks for Exoplanetary Atmospheres
Photochemical CS$_2$ Gas Detected on a 20-Myr-old Exoplanet
University of California Los Angeles（加州大学洛杉矶分校）；Arizona State University（亚利桑那州立大学）；Tsinghua University（清华大学）；Imperial College London（伦敦帝国理工学院）；Osaka University（大阪大学）；Institute for Astronomy, University of Hawai‘i at Mānoa（夏威夷大学马诺阿分校天体物理研究所）；NASA Ames Research Center（美国宇航局艾姆斯研究中心）；University of Kansas（堪萨斯大学）
利用JWST/NIRSpec透射光谱，在年轻行星V1298 Tau e的大气中以>8σ置信度探测到CS$_2$，表明强紫外辐射下H/He主导大气中硫光化学的复杂性。
About 2.5 billion years ago, microbes learned to harness plentiful solar energy to reduce CO$_2$ with H$_2$O, extracting energy and producing O$_2$ as waste. O$_2$ production from this metabolic process was so vigorous that it saturated its photochemical sinks, permitting it to reach "runaway" conditions and rapidly accumulate in the atmosphere despite its reactivity. Here we argue that O$_2$ may not be unique: diverse gases produced by life may experience a "runaway" effect similar to O$_2$. This runaway occurs because the ability of an atmosphere to photochemically cleanse itself of trace ga…
Hydrocarbon complexity and photochemical shielding of prebiotic feedstock molecules in exoplanet atmospheres
Center for Space and Habitability, University of Bern（伯尔尼大学太空与宜居性中心）；Centre for Exoplanet Science, University of Edinburgh（爱丁堡大学系外行星科学中心）；Department of Earth and Planetary Sciences, University of California Riverside（加州大学河滨分校地球与行星科学系）；Institute of Astronomy & Astrophysics, Academia Sinica（中央研究院天文及天文物理研究所）
Photochemical hazes are suspected to obscure molecular features, such as water, from detection in the transmission spectra of exoplanets with atmospheric temperatures < 800 K. The opacities of laboratory produced organic compounds (tholins) from Khare et al. (1984) have become a standard for modeling haze in exoplanet atmospheres. However, these tholins were grown in an oxygen-free, Titan-like environment that is very different from typical assumptions for exoplanets, where C/O~0.5. This work presents the 0.13-10 micron complex refractive indices derived from laboratory transmission measuremen…
Atmospheric chemistry models have shown molecular oxygen can build up in CO2-dominated atmospheres on potentially habitable exoplanets without an input of life. Existing models typically assume a surface pressure of 1 bar. Here we present model scenarios of CO2-dominated atmospheres with the surface pressure ranging from 0.1 to 10 bars, while keeping the surface temperature at 288 K. We use a one-dimensional photochemistry model to calculate the abundance of O2 and other key species, for outgassing rates ranging from a Venus-like volcanic activity up to 20x Earth-like activity. The model maint…
Three dimensional temporal evolution of photochemical haze in exoplanet atmospheres I. Description and test application to HD 189733b
Center for Space and Habitability, University of Bern（伯尔尼大学太空与宜居性中心）；University of Chicago（芝加哥大学）；National Astronomical Observatory of Japan（日本国立天文台）；University of California, Santa Cruz（加州大学圣克鲁兹分校）
Photochemistry is expected to change the chemical composition of the upper atmospheres of irradiated exoplanets through the dissociation of species, such as methane and ammonia, and the association of others, such as hydrogen cyanide. Although primarily the high altitude day side should be affected by photochemistry, it is still unclear how dynamical processes transport photochemical species throughout the atmosphere, and how these chemical disequilibrium effects scale with different parameters. In this work we investigate the influence of photochemistry in a two-dimensional context, by synthe…
Assessing the Impact of Varying HSO Cross Sections on Photochemical Models: Implications for the Spectral Characterization of Terrestrial Exoplanets
Institute of Astrophysics and Space Sciences, Universidade do Porto（波尔图大学天体物理与空间科学研究所）；Departamento de Física e Astronomia, Faculdade de Ciências, Universidade do Porto（波尔图大学理学院物理与天文系）；Bard College（巴德学院）；Department of Earth and Planetary Sciences, University of California, Riverside（加州大学河滨分校地球与行星科学系）；Blue Marble Space Institute of Science（蓝大理石空间科学研究所）；University of Arizona, Lunar and Planetary Laboratory/Department of Planetary Sciences（亚利桑那大学月球与行星实验室/行星科学系）
Photochemistry induced by stellar UV flux should produce haze particles in exoplanet atmospheres. Recent observations indicate that haze and/or cloud layers exist in the atmospheres of exoplanets. However, photochemical processes in exoplanetary atmospheres remain largely unknown. We performed laboratory experiments with the PHAZER chamber to simulate haze formation in a range of exoplanet atmospheres (hydrogen-rich, water-rich, and carbon dioxide-rich at 300, 400, and 600 K), and observed the gas phase compositional change (the destruction of the initial gas and the formation of new gas speci…
Photochemical hazes have been frequently used to interpret exoplanet transmission spectra that show an upward slope towards shorter wavelengths and weak molecular features. While previous studies have only considered spherical haze particles, photochemical hazes composed of hydrocarbon aggregate particles are common throughout the solar system. We use an aerosol microphysics model to investigate the effect of aggregate photochemical haze particles on transmission spectra of warm exoplanets. We find that the wavelength dependence of the optical depth of aggregate particle hazes is flatter than …
Exoplanets orbiting M-dwarfs within habitable zones are exposed to stellar environments more extreme than that terrestrial planets experience in our Solar System, which can significantly impact the atmospheres of the exoplanets and affect their habitability and sustainability. This study provides the first prediction of hot oxygen corona structure and the associated photochemical loss from a 1 bar CO2-dominated atmosphere of a Venus-like rocky exoplanet, where dissociative recombination of O2+ ions is assumed to be the major source reaction for the escape of neutral O atoms and formation of th…
Following the discovery of the first exoplanet candidate transiting a white dwarf (WD), a "white dwarf opportunity" for characterizing the atmospheres of terrestrial exoplanets around WDs is emerging. Large planet-to-star size ratios and hence large transit depths make transiting WD exoplanets favorable targets for transmission spectroscopy - conclusive detection of spectral features on an Earth-like planet transiting a close-by WD can be achieved within a medium James Webb Space Telescope (JWST) program. Despite the apparently promising opportunity, however, the post-main sequence (MS) evolut…
Oxygen and methane are considered to be the canonical biosignatures of modern Earth, and the simultaneous detection of these gases in a planetary atmosphere is an especially strong biosignature. However, these gases may be challenging to detect together in the planetary atmospheres because photochemical oxygen radicals destroy methane. Previous work has shown that the photochemical lifetime of methane in oxygenated atmospheres is longer around M dwarfs, but M dwarf planet habitability may be hindered by extreme stellar activity and evolution. Here, we use a 1-D photochemical-climate model to s…
Oxygenated False Positive Biosignatures in Mars-like Exoplanet Atmospheres
Southeastern Universities Research Association（东南大学研究协会）；NASA Goddard Space Flight Center（美国国家航空航天局戈达德太空飞行中心）；Mary W. Jackson NASA Headquarters（玛丽·W·杰克逊 NASA 总部）；Johns Hopkins University（约翰斯·霍普金斯大学）；Johns Hopkins Applied Physics Laboratory（约翰斯·霍普金斯大学应用物理实验室）
Photochemical escape is an important process for oxygen escape from present Mars. In this work, a 1-D Monte-Carlo Model is developed to calculate escape rates of energetic oxygen atoms produced from O2+ dissociative recombination reactions (DR) under 1, 3, 10, and 20 times present solar XUV fluxes. We found that although the overall DR rates increase with solar XUV flux almost linearly, oxygen escape rate increases from 1 to 10 times present solar XUV conditions but decreases when increasing solar XUV flux further. Analysis shows that atomic species in the upper thermosphere of early Mars incr…
Most exoplanets detected so far have atmospheric T significantly higher than 300K. Often close to their star, they receive an intense UV photons flux that triggers important photodissociation processes. The T dependency of VUV absorption cross sections are poorly known, leading to an undefined uncertainty in atmospheric models. Similarly, data measured at low T similar to that of the high atmosphere of Mars, Venus, and Titan are often lacking. Our aim is to quantify the T dependency of the abs. cross section of important molecules in planetary atmospheres. We want to provide both high-resoluti…
Cloudy mornings and clear evenings on a gas giant exoplanet
Johns Hopkins University（约翰斯·霍普金斯大学）；University of California, Santa Cruz（加州大学圣克鲁兹分校）；Johns Hopkins Applied Physics Laboratory（约翰斯·霍普金斯大学应用物理实验室）；University of Exeter（埃克塞特大学）；University of Oxford（牛津大学）；Max Planck Institute for Astronomy（马克斯·普朗克天文学研究所）
We present a comprehensive photochemistry model for exploration of the chemical composition of terrestrial exoplanet atmospheres. The photochemistry model is designed from the ground up to have the capacity to treat all types of terrestrial planet atmospheres, ranging from oxidizing through reducing, which makes the code suitable for applications for the wide range of anticipated terrestrial exoplanet compositions. The one-dimensional chemical transport model treats up to 800 chemical reactions, photochemical processes, dry and wet deposition, surface emission and thermal escape of O, H, C, N …
Sub-Neptunes (Rp~1.25-4 REarth) remain the most commonly detected exoplanets to date. However, it remains difficult for observations to tell whether these intermediate-sized exoplanets have surfaces and where their surfaces are located. Here we propose that the abundances of trace species in the visible atmospheres of these sub-Neptunes can be used as proxies for determining the existence of surfaces and approximate surface conditions. As an example, we used a state-of-the-art photochemical model to simulate the atmospheric evolution of K2-18b and investigate its final steady-state composition…
We investigate the abiotic production of oxygen and its photochemical byproduct ozone through water vapor photolysis in moist atmospheres of temperate terrestrial exoplanets. The amount of water vapor available for photolysis in the middle atmosphere of a planet can be limited by an atmospheric cold-trap, the formation of which largely depends on the amount of non-condensable gases. We study this effect using a photochemical model coupled to a 1D radiative-convective equilibrium model in atmospheres with N2, CO2 and H2O as the main constituents. We find that in atmospheres with a low N2 invent…
Ultraviolet (UV) absorption cross sections are an essential ingredient of photochemical atmosphere models. Exoplanet searches have unveiled a large population of short-period objects with hot atmospheres, very different from what we find in our solar system. Transiting exoplanets whose atmospheres can now be studied by transit spectroscopy receive extremely strong UV fluxes and have typical temperatures ranging from 400 to 2500 K. At these temperatures, UV photolysis cross section data are severely lacking. Our goal is to provide high-temperature absorption cross sections and their temperature…
(Abridged) Super Earth exoplanets are being discovered with increasing frequency and some will be able to retain stable H2-dominated atmospheres. We study biosignature gases on exoplanets with thin H2 atmospheres and habitable surface temperatures, by using a model atmosphere with photochemistry, and biomass estimate framework for evaluating the plausibilty of a range of biosignature gas candidates. We find that photochemically produced H atoms are the most abundant reactive species in H2 atmospheres. In atmospheres with high CO2 levels, atomic O is the major destructive species for some molec…
UV absorption cross sections are an essential ingredient of photochemical atmosphere models. Exoplanet searches have unveiled a large population of short-period objects with hot atmospheres, very different from what we find in our solar system. Transiting exoplanets whose atmospheres can now be studied by transit spectroscopy receive extremely strong UV fluxes and have typical temperatures ranging from 400 to 2500 K. At these temperatures, UV photolysis cross section data are severely lacking. Aims. Our goal is to provide high-temperature absorption cross sections and their temperature depende…
Spectral characterization of Super-Earth atmospheres for planets orbiting in the Habitable Zone of M-dwarf stars is a key focus in exoplanet science. A central challenge is to understand and predict the expected spectral signals of atmospheric biosignatures (species associated with life). Our work applies a global-mean radiative-convective-photochemical column model assuming a planet with an Earth-like biomass and planetary development. We investigated planets with gravities of 1g and 3g and a surface pressure of one bar around central stars with spectral classes from M0 to M7. The spectral si…
Understanding the chemistry of temperate exoplanets atmospheres through experimental and numerical simulations
UVSQ Université Paris-Saclay, Sorbonne Université, CNRS（凡尔赛大学巴黎萨克雷大学、索邦大学、法国国家科学研究中心）；ETH University, Center for Origin and Prevalence of Life, Department of Earth and Planetary Sciences（苏黎世联邦理工学院，生命起源与普遍性中心，地球与行星科学系）；ENS-Paris-Saclay（巴黎萨克雷高等师范学校）
Thanks to the \textit{Cassini} spacecraft onboard instruments, it has been known that Titan's ionospheric chemistry is complex and the molecular growth is initiated through the photolysis of the most abundant species directly in the upper atmosphere. Among the pool of chemical compounds formed by the photolysis, N-bearing species are involved in the haze formation but the chemical incorporation pathways need to be better constrained.}\\ In this work, we performed low-pressure EUV photochemical laboratory experiments. The APSIS reactor was filled with a N$_2$/CH$_4$ (90/10\%) gas mixture releva…
Photochemical hazes are important opacity sources in temperate exoplanet atmospheres, hindering current observations from characterizing exoplanet atmospheric compositions. The haziness of an atmosphere is determined by the balance between haze production and removal. However, the material-dependent removal physics of the haze particles is currently unknown under exoplanetary conditions. Here we provide experimentally-measured surface energies for a grid of temperate exoplanet hazes to characterize haze removal in exoplanetary atmospheres. We found large variations of surface energies for haze…
Neptune remains a mysterious world that deserves further exploration and is a high-priority objective for a future planetary mission in order to better understand the formation and evolution of ice giant planets. We have developed a coupled ion-neutral 1D photochemical model of Neptune's atmosphere to study the origin and evolution of the hydrocarbons and the oxygen species. The up-to-date chemical scheme is derived from one used for Titan's atmosphere, which led to good agreements with the Cassini-CIRS observations for oxygen species and the main hydrocarbons. The main results we obtain are t…
Sulfur gases significantly affect the photochemistry of planetary atmospheres in our Solar System, and are expected to be important components in exoplanet atmospheres. However, sulfur photochemistry in the context of exoplanets is poorly understood due to a lack of chemical-kinetics information for sulfur species under relevant conditions. Here, we study the photochemical role of hydrogen sulfide (H2S) in warm CO2-rich exoplanet atmospheres (800 K) by carrying out laboratory simulations. We find that H2S plays a significant role in photochemistry, even when present in the atmosphere at relati…
Numerous solar system atmospheres possess aerosols including the characteristic organic hazes of Titan and Pluto. Haze particles substantially impact atmospheric temperatures structures and may provide organic material to the surface of a world, thereby affecting its habitability. Observations of exoplanet atmospheres suggest the presence of aerosols, especially in cooler (<800 K), smaller (<0.3 times Jupiter's mass) exoplanets. It remains unclear if the aerosols muting the spectroscopic features of exoplanet atmospheres are condensate clouds or photochemical hazes, which is difficult to predi…
We study the properties of photochemical hazes in super-Earths/mini-Neptunes atmospheres with particular focus on GJ1214b. We evaluate photochemical haze properties at different metallicities between solar and 10000$\times$solar. Within the four orders of magnitude change in metallicity, we find that the haze precursor mass fluxes change only by a factor of $\sim$3. This small diversity occurs with a non-monotonic manner among the different metallicity cases, reflecting the interaction of the main atmospheric gases with the radiation field. Comparison with relative haze yields at different met…
In situ exploration of the planetary atmospheres requires the development of laboratory experiments to understand the molecular growth pathways initiated by photochemistry in the upper layers of the atmospheres. Major species and dominant reaction pathways are used to feed chemical network models that reproduce the chemical and physical processes of these complex environments. Energetic UV photons initiate very efficient chemistry by forming reactive species in the ionospheres of planets and satellites. Here we present a laboratory experiment based on a new photoreactor with an irradiation bea…
The isotopic signature of atmospheric carbon offers a unique tracer for the history of the Martian atmosphere and the origin of organic matter on Mars. Photolysis of CO$_{2}$ is known to induce strong isotopic fractionation of carbon between CO$_{2}$ and CO. However, its effect on the carbon isotopic compositions in the Martian atmosphere remains uncertain. Here we develop a 1-D photochemical model considering isotopic fractionation via photolysis of CO$_{2}$ to estimate the vertical profiles of the carbon isotopic compositions of CO and CO$_{2}$ in the Martian atmosphere. We find that CO is d…
Hazes are common in known planet atmospheres, and geochemical evidence suggests early Earth occasionally supported an organic haze with significant environmental and spectral consequences. The UV spectrum of the parent star drives organic haze formation through methane photochemistry. We use a 1D photochemical-climate model to examine production of fractal organic haze on Archean Earth-analogs in the habitable zonesof several stellar types: the modern and early Sun, AD Leo (M3.5V), GJ 876 (M4V), $ε$ Eridani (K2V), and $σ$ Boötis (F2V). For Archean-like atmospheres, planets orbiting stars with …
Methane has been proposed as an exoplanet biosignature. Imminent observations with the James Webb Space Telescope may enable methane detections on potentially habitable exoplanets, so it is essential to assess in what planetary contexts methane is a compelling biosignature. Methane's short photochemical lifetime in terrestrial planet atmospheres implies that abundant methane requires large replenishment fluxes. While methane can be produced by a variety of abiotic mechanisms such as outgassing, serpentinizing reactions, and impacts, we argue that, in contrast to an Earth-like biosphere, known …
The detections of atomic hydrogen, heavy atoms and ions surrounding the extrasolar giant planet (EGP) HD209458b constrain the composition, temperature and density profiles in its upper atmosphere. Thus the observations provide guidance for models that have so far predicted a range of possible conditions. We present the first hydrodynamic escape model for the upper atmosphere that includes all of the detected species in order to explain their presence at high altitudes, and to further constrain the temperature and velocity profiles. This model calculates the stellar heating rates based on recen…
The hot Jupiter WASP-12b is a heavily irradiated exoplanet in a short period orbit around a G0-star with twice the metallicity of the Sun. A recent thermochemical equilibrium analysis based on Spitzer and ground-based infrared observations suggests that the presence of $\ch4$ in its atmosphere and the lack of $\h2o$ features can only be explained if the carbon-to-oxygen ratio in the planet's atmosphere is much greater than the solar ratio ($\ctoo = 0.54$). Here, we use a 1-D photochemical model to study the effect of disequilibrium chemistry on the observed abundances of $\h2o, \com, \co2$ and…
A recent study by Ramirez et al. (2014) demonstrated that an atmosphere with 1.3-4 bar of CO2 and H2O, in addition to 5-20% H2, could have raised the mean annual and global surface temperature of early Mars above the freezing point of water. Such warm temperatures appear necessary to generate the rainfall (or snowfall) amounts required to carve the ancient martian valleys. Here, we use our best estimates for early martian outgassing rates, along with a 1-D photochemical model, to assess the conversion efficiency of CO, CH4, and H2S to CO2, SO2, and H2. Our outgassing estimates assume that Mars…
Triton is the largest satellite of Neptune and probably a Kuiper Belt Object that was captured by the planet. It has a tenuous nitrogen atmosphere similar to the one of Pluto and may be an ocean world. The Neptunian system has only been visited by Voyager 2 in 1989. Over the last few years, the demand for a new mission to the Ice Giants and their systems has increased so that a theoretical basis to prepare for such a mission is important. We aim to develop a photochemical model of Triton's atmosphere with an up-to-date chemical scheme, as previous photochemical models date back to the post-fly…
The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium(IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water i…
Observations of exoplanet atmospheres have shown that aerosols, like in the Solar System, are common across a variety of temperatures and planet types. The formation and distribution of these aerosols are inextricably intertwined with the composition and thermal structure of the atmosphere. At the same time, these aerosols also interfere with our probes of atmospheric composition and thermal structure, and thus a better understanding of aerosols lead to a better understanding of exoplanet atmospheres as a whole. Here we review the current state of knowledge of exoplanet aerosols as determined …
A Comprehensive Sulfur Chemistry Network Including Excited S(1D) and SO(1Δ) for the XODIAC Photochemical Model: Accounting for Missing Sulfur Processes in Venus and Exo-Venus Analogs
National Institute of Science Education and Research（国家科学教育研究中心）；Homi Bhabha National Institute（霍米·巴巴国立研究所）
